Biosorption of copper ions from aqueous solution using rape straw powders: Optimization, equilibrium and kinetic studies.

PubMed

Liu, Xin; Chen, Zhao-Qiong; Han, Bin; Su, Chun-Li; Han, Qin; Chen, Wei-Zhong

2018-04-15

In this paper, the adsorption behaviors of Cu(II) from the aqueous solution using rape straw powders were studied. The effects of initial Cu(II) concentration, pH range and absorbent dosage on the adsorption efficiency of Cu(II) by rape straw powder were investigated by Box-Behnken Design based on response surface methodology. The values of coefficient constant of the nonlinear models were 0.9997, 0.9984 and 0.9944 for removal Cu(II) from aqueous solution using rape straw shell, seed pods and straw pith core, respectively, which could navigate the design space for various factors on effects of biosorption Cu(II) from aqueous solution. The various factors of pH and biosorbents dosage were the key factors that affecting the removal efficiency of Cu(II) from aqueous solution. The biosorption equilibrium data presented its favorable monolayer adsorption Cu(II) onto shell, seed pods and straw pith core, respectively. The pseudo-second order kinetic model was the proper approach to determine the adsorption kinetics. The biosorption of Cu(II) onto surfaces of rape straw powders were confirmed and ion-exchanged in the adsorption process by energy dispersive spectrometer. The critical groups, -OH, -CH, -NH 3 + , -CH 3 , -NH and -C-O, exhibited by the infrared spectra results, changed to suggest that these groups played critical roles, especially -CH 3 in the adsorption of copper ions onto rape straw powders. The study provided evidences that rape straw powders can be used for removing Cu(II) from aqueous water. Copyright © 2017 Elsevier Inc. All rights reserved.

Photocatalytic hydrogen generation from hydriodic acid using methylammonium lead iodide in dynamic equilibrium with aqueous solution

NASA Astrophysics Data System (ADS)

Park, Sunghak; Chang, Woo Je; Lee, Chan Woo; Park, Sangbaek; Ahn, Hyo-Yong; Nam, Ki Tae

2017-01-01

The solar-driven splitting of hydrohalic acids (HX) is an important and fast growing research direction for H2 production. In addition to the hydrogen, the resulting chemicals (X2/X3-) can be used to propagate a continuous process in a closed cycle and are themselves useful products. Here we present a strategy for photocatalytic hydrogen iodide (HI) splitting using methylammonium lead iodide (MAPbI3) in an effort to develop a cost-effective and easily scalable process. Considering that MAPbI3 is a water-soluble ionic compound, we exploit the dynamic equilibrium of the dissolution and precipitation of MAPbI3 in saturated aqueous solutions. The I- and H+ concentrations of the aqueous solution are determined to be the critical parameters for the stabilization of the tetragonal MAPbI3 phase. Stable and efficient H2 production under visible light irradiation was demonstrated. The solar HI splitting efficiency of MAPbI3 was 0.81% when using Pt as a cocatalyst.

Biosorption of Ag(I) from aqueous solutions by Klebsiella sp. 3S1.

PubMed

Muñoz, Antonio Jesús; Espínola, Francisco; Ruiz, Encarnación

2017-05-05

This study investigated the potential ability of Klebsiella sp. 3S1 to remove silver cations from aqueous solutions. The selected strain is a ubiquitous bacterium selected from among several microorganisms that had been isolated from wastewaters. To optimise the operating conditions in the biosorption process, a Rotatable Central Composite Experimental Design was developed establishing pH, temperature and biomass concentration as independent variables. Interaction mechanisms involved were analysed through kinetic and equilibrium studies. The experimental results suit pseudo-second order kinetics with two biosorption stages, being the first almost instantly. The Langmuir equilibrium model predicted a maximum capacity of biosorption (q) of 114.1mg Ag/g biomass. The study of the mechanisms involved in the biosorption was completed by employing advanced techniques which revealed that both bacterium-surface interactions and intracellular bioaccumulation participate in silver removal from aqueous solutions. The ability of Klebsiella sp. 3S1 to form silver chloride nanoparticles with interesting potential applications was also discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

Theoretical isotopic fractionation between structural boron in carbonates and aqueous boric acid and borate ion

NASA Astrophysics Data System (ADS)

Balan, Etienne; Noireaux, Johanna; Mavromatis, Vasileios; Saldi, Giuseppe D.; Montouillout, Valérie; Blanchard, Marc; Pietrucci, Fabio; Gervais, Christel; Rustad, James R.; Schott, Jacques; Gaillardet, Jérôme

2018-02-01

The 11B/10B ratio in calcite and aragonite is an important proxy of oceanic water pH. However, the physico-chemical mechanisms underpinning this approach are still poorly known. In the present study, we theoretically determine the equilibrium isotopic fractionation properties of structural boron species in calcium carbonates, BO33-, BO2(OH)2- and B(OH)4- anions substituted for carbonate groups, as well as those of B(OH)4- and B(OH)3 species in vacuum. Significant variability of equilibrium isotopic fractionation properties is observed among these structural species which is related to their contrasted coordination state, Bsbnd O bond lengths and atomic-scale environment. The isotopic composition of structural boron does not only depend on its coordination number but also on its medium range environment, i.e. farther than its first coordination shell. The isotopic fractionation between aqueous species and their counterparts in vacuum are assessed using previous investigations based on similar quantum-mechanical modeling approaches. At 300 K, the equilibrium isotope composition of structural trigonal species is 7-15‰ lighter than that of aqueous boric acid molecules, whereas substituted tetrahedral borate ions are heavier than their aqueous counterparts by 10-13‰. Although significant uncertainties are known to affect the theoretical prediction of fractionation factors between solids and solutions, the usually assumed lack of isotopic fractionation during borate incorporation in carbonates is challenged by these theoretical results. The present theoretical equilibrium fractionation factors between structural boron and aqueous species differ from those inferred from experiments which may indicate that isotopic equilibrium, unlike chemical equilibrium, was not reached in most experiments. Further research into the isotopic fractionation processes at the interface between calcium carbonates and aqueous solution as well as long duration experiments aimed at investigating the kinetics of equilibration of boron environment and isotopic composition are therefore required to refine our understanding of boron coprecipitation in carbonates and thus the theory behind the use of boron isotopes as an ocean pH proxy.

Aluminum speciation in aqueous fluids at deep crustal pressure and temperature

NASA Astrophysics Data System (ADS)

Mookherjee, Mainak; Keppler, Hans; Manning, Craig E.

2014-05-01

We investigated aluminum speciation in aqueous fluids in equilibrium with corundum using in situ Raman spectroscopy in hydrothermal diamond anvil cells to 20 kbar and 1000 °C. We have studied aluminum species in (a) pure H2O, (b) 5.3 m KOH solution, and (c) 1 m KOH solution. In order to better understand the spectral features of the aqueous fluids, we used ab initio simulations based on density functional theory to calculate and predict the energetics and vibrational spectra for various aluminum species that are likely to be present in aqueous solutions. The Raman spectra of pure water in equilibrium with Al2O3 are devoid of any characteristic spectral features. In contrast, aqueous fluids with 5.3 m and 1 m KOH solution in equilibrium with Al2O3 show a sharp band at ˜620 cm-1 which could be attributed to the [ species. The band grows in intensity with temperature along an isochore. A shoulder on the high-frequency side of this band may be due to a hydrated, charge neutral Al(OH)3·H2O species. In the limited pressure, temperature and density explored in the present study, we do not find any evidence for the polymerization of the [ species to dimers [(OH)2-Al-(OH)2-Al(OH)2] or [(OH)3-Al-O-Al(OH)3]2-. This is likely due to the relatively low concentration of Al in the solutions and does not rule out significant polymerization at higher pressures and temperatures. Upon cooling of Al-bearing solutions to room temperatures, Raman bands indicating the precipitation of diaspore (AlOOH) were observed in some experiments. The Raman spectra of the KOH solutions (with or without dissolved alumina) showed a sharp OH stretching band at ˜3614 cm-1 and an in-plane OH bending vibration at ˜1068 cm-1, likely related to an OH- ion with the oxygen atom attached to a water molecule by hydrogen bonding. A weak feature at ˜935 cm-1 may be related to the out-of-plane bending vibration of the same species or to an OH species with a different environment.

Potential adsorption of methylene blue from aqueous solution using green macroalgaePosidonia oceanica.

NASA Astrophysics Data System (ADS)

Allouche, F.-N.; Yassaa, N.

2018-03-01

The use of inexpensive biological materials, such as marine algae for removing dyes from contaminated industrial effluents appears as a potential alternative method. The aim of this study is to investigate the aptitude of marine macroalgae Posidonia Oceanica local biomass abundant on the coasts of Algeria for selective sorption of methylene blue (MB) from an aqueous solution in batch experiments at 20 °C. A maximum percentage removal of Posidonia oceanica occurs at pH 5. Equilibrium isotherm data were analyzed using the Langmuir and the Freundlich isotherms. The adsorption equilibrium of methylene blue was best describe by Langmuir model than the Freundlich model. The maximum sorption capacity was 357 mgg-1at pH 5. The sorption data were very well described by the pseudo-second-order model. Keywords: Posidonia oceanica, Methylene blue (MB), Biosorption, Isotherm Equilibrium, Kinetics; Modelling.

Li2MoO4 crystal growth from solution activated by low-frequency vibrations

NASA Astrophysics Data System (ADS)

Barinova, Olga; Sadovskiy, Andrey; Ermochenkov, Ivan; Kirsanova, Svetlana; Sukhanova, Ekaterina; Kostikov, Vladimir; Belov, Stanislav; Mozhevitina, Elena; Khomyakov, Andrew; Kuchuk, Zhanna; Zharikov, Eugeny; Avetissov, Igor

2017-01-01

The possibility of Li2MoO4 crystal growth from aqueous solutions activated by axial vibrational control (AVC) technique was investigated. It was found out that a low-frequency mechanical activation of the solution led to an increase of Li2MoO4 equilibrium solubility in aqueous solution for 11 rel% in the 25-29 °C temperature range. The changes in solution structure were analyzed in situ by Raman study of the solution. The AVC activation of solution resulted in a re-faceting of growing crystals, a smoothing of a face surface morphology and reduction of water content in the crystal.

Borate-polyol complexes in aqueous solution: determination of enthalpies by thermometric titrimetry.

PubMed

Aruga, R

1985-06-01

Enthalpies for the reaction of borate with 1,2-ethanediol, 1,2-propanediol, 1,2,3-propanetriol and d-mannitol have been determined by thermometric titrimetry. From these enthalpies and equilibrium constants taken from the literature, corresponding entropies have been calculated. The data refer to aqueous solutions at 25 degrees and I = 1.0M (NaNO(3)). The results indicate reasons for the differences in the stabilities of the complexes.

SORPTION OF VOLATILE ORGANIC SOLVENTS FROM AQUEOUS SOLUTION ONTO SUBSURFACE SOLIDS

EPA Science Inventory

Sorption isotherms for tetrachloroethene on low-carbon subsurface core samples were linear to equilibrium solution concentrations of 2 mg L−1. Concentrations above this value produced pronounced curvature in the sorption isotherms. Sorption of tetrachloroethene, benzene, trichlor...

Rapid removal of uranium from aqueous solutions using magnetic Fe3O4@SiO2 composite particles.

PubMed

Fan, Fang-Li; Qin, Zhi; Bai, Jing; Rong, Wei-Dong; Fan, Fu-You; Tian, Wei; Wu, Xiao-Lei; Wang, Yang; Zhao, Liang

2012-04-01

Rapid removal of U(VI) from aqueous solutions was investigated using magnetic Fe(3)O(4)@SiO(2) composite particles as the novel adsorbent. Batch experiments were conducted to study the effects of initial pH, amount of adsorbent, shaking time and initial U(VI) concentrations on uranium sorption efficiency as well as the desorbing of U(VI). The sorption of uranium on Fe(3)O(4)@SiO(2) composite particles was pH-dependent, and the optimal pH was 6.0. In kinetics studies, the sorption equilibrium can be reached within 180 min, and the experimental data were well fitted by the pseudo-second-order model, and the equilibrium sorption capacities calculated by the model were almost the same as those determined by experiments. The Langmuir sorption isotherm model correlates well with the uranium sorption equilibrium data for the concentration range of 20-200 mg/L. The maximum uranium sorption capacity onto magnetic Fe(3)O(4)@SiO(2) composite particles was estimated to be about 52 mg/g at 25 °C. The highest values of uranium desorption (98%) was achieved using 0.01 M HCl as the desorbing agent. Fe(3)O(4)@SiO(2) composite particles showed a good selectivity for uranium from aqueous solution with other interfering cation ions. Present study suggested that magnetic Fe(3)O(4)@SiO(2) composite particles can be used as a potential adsorbent for sorption uranium and also provided a simple, fast separation method for removal of heavy metal ion from aqueous solution. Copyright © 2011 Elsevier Ltd. All rights reserved.

Effect of the cation model on the equilibrium structure of poly-L-glutamate in aqueous sodium chloride solution

NASA Astrophysics Data System (ADS)

Marchand, Gabriel; Soetens, Jean-Christophe; Jacquemin, Denis; Bopp, Philippe A.

2015-12-01

We demonstrate that different sets of Lennard-Jones parameters proposed for the Na+ ion, in conjunction with the empirical combining rules routinely used in simulation packages, can lead to essentially different equilibrium structures for a deprotonated poly-L-glutamic acid molecule (poly-L-glutamate) dissolved in a 0.3M aqueous NaCl solution. It is, however, difficult to discriminate a priori between these model potentials; when investigating the structure of the Na+-solvation shell in bulk NaCl solution, all parameter sets lead to radial distribution functions and solvation numbers in broad agreement with the available experimental data. We do not find any such dependency of the equilibrium structure on the parameters associated with the Cl- ion. This work does not aim at recommending a particular set of parameters for any particular purpose. Instead, it stresses the model dependence of simulation results for complex systems such as biomolecules in solution and thus the difficulties if simulations are to be used for unbiased predictions, or to discriminate between contradictory experiments. However, this opens the possibility of validating a model specifically in view of analyzing experimental data believed to be reliable.

Nickel(II) biosorption from aqueous solutions by shrimp head biomass.

PubMed

Hernández-Estévez, Alejandro; Cristiani-Urbina, Eliseo

2014-11-01

The present study evaluates the capacity of shrimp (Farfantepenaeus aztecus) head to remove toxic Ni(II) ions from aqueous solutions. Relevant parameters that could affect the biosorption process, such as shrimp head pretreatment, solution pH level, contact time and initial Ni(II) concentration, were studied in batch systems. An increase in Ni(II) biosorption capacity and a reduction in the time required to reach Ni(II) biosorption equilibrium was manifested by shrimp head biomass pretreated by boiling in 0.5 N NaOH for 15 min; this biomass was thereafter denominated APSH. The optimum biosorption level of Ni(II) ions onto APSH was observed at pH 7.0. Biosorption increased significantly with rising initial Ni(II) concentration. In terms of biosorption dynamics, the pseudo-second-order kinetic model described Ni(II) biosorption onto APSH best. The equilibrium data adequately fitted the Langmuir isotherm model within the studied Ni(II) ion concentration range. According to this isotherm model, the maximum Ni(II) biosorption capacity of APSH was 104.22 mg/g. Results indicate that APSH could be used as a low-cost, environmentally friendly, and promising biosorbent with high biosorption capacity to remove Ni(II) from aqueous solutions.

Population and size distribution of solute-rich mesospecies within mesostructured aqueous amino acid solutions.

PubMed

Jawor-Baczynska, Anna; Moore, Barry D; Lee, Han Seung; McCormick, Alon V; Sefcik, Jan

2013-01-01

Aqueous solutions of highly soluble substances such as small amino acids are usually assumed to be essentially homogenous systems with some degree of short range local structuring due to specific interactions on the sub-nanometre scale (e.g. molecular clusters, hydration shells), usually not exceeding several solute molecules. However, recent theoretical and experimental studies have indicated the presence of much larger supramolecular assemblies or mesospecies in solutions of small organic and inorganic molecules as well as proteins. We investigated both supersaturated and undersaturated aqueous solutions of two simple amino acids (glycine and DL-alanine) using Dynamic Light Scattering (DLS), Brownian Microscopy/Nanoparticles Tracking Analysis (NTA) and Cryogenic Transmission Electron Microscopy (Cryo-TEM). Colloidal scale mesospecies (nanodroplets) were previously reported in supersaturated solutions of these amino acids and were implicated as intermediate species on non-classical crystallization pathways. Surprisingly, we have found that the mesospecies are also present in significant numbers in undersaturated solutions even when the solute concentration is well below the solid-liquid equilibrium concentration (saturation limit). Thus, mesopecies can be observed with mean diameters ranging from 100 to 300 nm and a size distribution that broadens towards larger size with increasing solute concentration. We note that the mesospecies are not a separate phase and the system is better described as a thermodynamically stable mesostructured liquid containing solute-rich domains dispersed within bulk solute solution. At a given temperature, solute molecules in such a mesostructured liquid phase are subject to equilibrium distribution between solute-rich mesospecies and the surrounding bulk solution.

Adsorption of cesium on cement mortar from aqueous solutions.

PubMed

Volchek, Konstantin; Miah, Muhammed Yusuf; Kuang, Wenxing; DeMaleki, Zack; Tezel, F Handan

2011-10-30

The adsorption of cesium on cement mortar from aqueous solutions was studied in series of bench-scale tests. The effects of cesium concentration, temperature and contact time on process kinetics and equilibrium were evaluated. Experiments were carried out in a range of initial cesium concentrations from 0.0103 to 10.88 mg L(-1) and temperatures from 278 to 313 K using coupons of cement mortar immersed in the solutions. Non-radioactive cesium chloride was used as a surrogate of the radioactive (137)Cs. Solution samples were taken after set periods of time and analyzed by inductively coupled plasma mass spectroscopy. Depending on the initial cesium concentration, its equilibrium concentration in solution ranged from 0.0069 to 8.837 mg L(-1) while the respective surface concentration on coupons varied from 0.0395 to 22.34 μg cm(-2). Equilibrium test results correlated well with the Freundlich isotherm model for the entire test duration. Test results revealed that an increase in temperature resulted in an increase in adsorption rate and a decrease in equilibrium cesium surface concentration. Among several kinetic models considered, the pseudo-second order reaction model was found to be the best to describe the kinetic test results in the studied range of concentrations. The adsorption activation energy determined from Arrhenius equation was found to be approximately 55.9 kJ mol(-1) suggesting that chemisorption was the prevalent mechanism of interaction between cesium ions and cement mortar. Crown Copyright © 2011. Published by Elsevier B.V. All rights reserved.

Molecular simulations of diffusion in electrolytes

NASA Astrophysics Data System (ADS)

Wheeler, Dean Richard

This work demonstrates new methodologies for simulating multicomponent diffusion in concentrated solutions using molecular dynamics (MD). Experimental diffusion data for concentrated multicomponent solutions are often lacking, as are accurate methods of predicting diffusion for nonideal solutions. MD can be a viable means of understanding and predicting multicomponent diffusion. While there have been several prior reports of MD simulations of mutual diffusion, no satisfactory expressions for simulating Stefan-Maxwell diffusivities for an arbitrary number of species exist. The approaches developed here allow for the computation of a full diffusion matrix for any number of species in both nonequilibrium and equilibrium MD ensembles. Our nonequilibrium approach is based on the application of constant external fields to drive species diffusion. Our equilibrium approach uses a newly developed Green-Kubo formula for Stefan-Maxwell diffusivities. In addition, as part of this work, we demonstrate a widely applicable means of increasing the computational efficiency of the Ewald sum, a technique for handling long-range Coulombic interactions in simulations. The theoretical development is applicable to any solution which can be simulated using MD; nevertheless, our primary interest is in electrochemical applications. To this end, the methods are tested by simulations of aqueous salt solutions and lithium-battery electrolytes. KCl and NaCl aqueous solutions were simulated over the concentration range 1 to 4 molal. Intermolecular-potential models were parameterized for these transport-based simulations. This work is the first to simulate all three independent diffusion coefficients for aqueous NaCl and KCl solutions. The results show that the nonequilibrium and equilibrium methods are consistent with each other, and in moderate agreement with experiment. We simulate lithium-battery electrolytes containing LiPF6 in propylene carbonate and mixed ethylene carbonate-dimethyl carbonate solvents. As with the aqueous-solution work, potential parameters were generated for these molecules. These nonaqueous electrolytes demonstrate rich transport behavior, which the simulations are able to reproduce qualitatively. In a mixed-solvent simulation we regress all six independent transport coefficients. The simulations show that strong ion pairing is responsible for the increase in viscosity and maximum in conductivity as ion concentrations are increased.

Application potential of grapefruit peel as dye sorbent: kinetics, equilibrium and mechanism of crystal violet adsorption.

PubMed

Saeed, Asma; Sharif, Mehwish; Iqbal, Muhammad

2010-07-15

This study reports the sorption of crystal violet (CV) dye by grapefruit peel (GFP), which has application potential in the remediation of dye-contaminated wastewaters using a solid waste generated by the citrus fruit juice industry. Batch adsorption of CV was conducted to evaluate the effect of initial pH, contact time, temperature, initial dye concentration, GFP adsorbent dose, and removal of the adsorbate CV dye from aqueous solution to understand the mechanism of sorption involved. Sorption equilibrium reached rapidly with 96% CV removal in 60 min. Fit of the sorption experimental data was tested on the pseudo-first and pseudo-second-order kinetics mathematical equations, which was noted to follow the pseudo-second-order kinetics better, with coefficient of correlation > or = 0.992. The equilibrium process was well described by the Langmuir isotherm model, with maximum sorption capacity of 254.16 mg g(-1). The GFP was regenerated using 1 M NaOH, with up to 98.25% recovery of CV and could be reused as a dye sorbent in repeated cycles. GFP was also shown to be highly effective in removing CV from aqueous solution in continuous-flow fixed-bed column reactors. The study shows that GFP has the potential of application as an efficient sorbent for the removal of CV from aqueous solutions. 2010 Elsevier B.V. All rights reserved.

Applications of Brazilian pine-fruit shell in natural and carbonized forms as adsorbents to removal of methylene blue from aqueous solutions--kinetic and equilibrium study.

PubMed

Royer, Betina; Cardoso, Natali F; Lima, Eder C; Vaghetti, Julio C P; Simon, Nathalia M; Calvete, Tatiana; Veses, Renato Cataluña

2009-05-30

The Brazilian pine-fruit shell (Araucaria angustifolia) is a food residue, which was used in natural and carbonized forms, as low-cost adsorbents for the removal of methylene blue (MB) from aqueous solutions. Chemical treatment of Brazilian pine-fruit shell (PW), with sulfuric acid produced a non-activated carbonaceous material (C-PW). Both PW and C-PW were tested as low-cost adsorbents for the removal of MB from aqueous effluents. It was observed that C-PW leaded to a remarkable increase in the specific surface area, average porous volume, and average porous diameter of the adsorbent when compared to PW. The effects of shaking time, adsorbent dosage and pH on adsorption capacity were studied. In basic pH region (pH 8.5) the adsorption of MB was favorable. The contact time required to obtain the equilibrium was 6 and 4h at 25 degrees C, using PW and C-PW as adsorbents, respectively. Based on error function values (F(error)) the kinetic data were better fitted to fractionary-order kinetic model when compared to pseudo-first order, pseudo-second order, and chemisorption kinetic models. The equilibrium data were fitted to Langmuir, Freundlich, Sips and Redlich-Peterson isotherm models. For MB dye the equilibrium data were better fitted to the Sips isotherm model using PW and C-PW as adsorbents.

Effective removal of tetracycline from aqueous solution using activated carbon prepared from tomato (Lycopersicon esculentum Mill.) industrial processing waste.

PubMed

Sayğılı, Hasan; Güzel, Fuat

2016-09-01

Activated carbon (TAC) prepared under optimized conditions with ZnCl2 activation from a new precursor; tomato industrial processing waste (TW), was applied as an adsorbent to remove tetracycline (TC) from aqueous solution. The factors (TAC dosage, initial TC concentration, contact time, ionic strength and solution temperature) affecting the adsorption process were examined at natural pH (5.7) of TAC-TC system in aqueous solution. Kinetic data was found to be best complied by the pseudo-second order model. The isotherm analysis indicated that the equilibrium data could be represented by the Langmuir model. The maximum adsorption capacity was identified as 500.0mgg(-1) at 308K. Copyright © 2016 Elsevier Inc. All rights reserved.

Reaction paths and equilibrium end-points in solid-solution aqueous-solution systems

USGS Publications Warehouse

Glynn, P.D.; Reardon, E.J.; Plummer, Niel; Busenberg, E.

1990-01-01

Equations are presented describing equilibrium in binary solid-solution aqueous-solution (SSAS) systems after a dissolution, precipitation, or recrystallization process, as a function of the composition and relative proportion of the initial phases. Equilibrium phase diagrams incorporating the concept of stoichiometric saturation are used to interpret possible reaction paths and to demonstrate relations between stoichiometric saturation, primary saturation, and thermodynamic equilibrium states. The concept of stoichiometric saturation is found useful in interpreting and putting limits on dissolution pathways, but there currently is no basis for possible application of this concept to the prediction and/ or understanding of precipitation processes. Previously published dissolution experiments for (Ba, Sr)SO4 and (Sr, Ca)C??O3orth. solids are interpreted using equilibrium phase diagrams. These studies show that stoichiometric saturation can control, or at least influence, initial congruent dissolution pathways. The results for (Sr, Ca)CO3orth. solids reveal that stoichiometric saturation can also control the initial stages of incongruent dissolution, despite the intrinsic instability of some of the initial solids. In contrast, recrystallisation experiments in the highly soluble KCl-KBr-H2O system demonstrate equilibrium. The excess free energy of mixing calculated for K(Cl, Br) solids is closely modeled by the relation GE = ??KBr??KClRT[a0 + a1(2??KBr-1)], where a0 is 1.40 ?? 0.02, a1, is -0.08 ?? 0.03 at 25??C, and ??KBr and ??KCl are the mole fractions of KBr and KCl in the solids. The phase diagram constructed using this fit reveals an alyotropic maximum located at ??KBr = 0.676 and at a total solubility product, ???? = [K+]([Cl-] + [Br-]) = 15.35. ?? 1990.

Reactive solute transport in streams: 1. Development of an equilibrium- based model

USGS Publications Warehouse

Runkel, Robert L.; Bencala, Kenneth E.; Broshears, Robert E.; Chapra, Steven C.

1996-01-01

An equilibrium-based solute transport model is developed for the simulation of trace metal fate and transport in streams. The model is formed by coupling a solute transport model with a chemical equilibrium submodel based on MINTEQ. The solute transport model considers the physical processes of advection, dispersion, lateral inflow, and transient storage, while the equilibrium submodel considers the speciation and complexation of aqueous species, precipitation/dissolution and sorption. Within the model, reactions in the water column may result in the formation of solid phases (precipitates and sorbed species) that are subject to downstream transport and settling processes. Solid phases on the streambed may also interact with the water column through dissolution and sorption/desorption reactions. Consideration of both mobile (water-borne) and immobile (streambed) solid phases requires a unique set of governing differential equations and solution techniques that are developed herein. The partial differential equations describing physical transport and the algebraic equations describing chemical equilibria are coupled using the sequential iteration approach.

Studies on the concentration dependence of specific rotation of Alpha lactose monohydrate (α-LM) aqueous solutions and growth of α-LM single crystals

NASA Astrophysics Data System (ADS)

Vinodhini, K.; Divya Bharathi, R.; Srinivasan, K.

2018-02-01

Lactose is an optically active substance. As it is one of the reducing sugars, exhibits mutarotation in solution when it dissolves in any solvent. In solution, lactose exists in two isomeric forms, alpha-Lactose (α-L) and beta-lactose (β-L) through the mutarotation reaction. Mutarotation produces a dynamic equilibrium between two isomers in a solution and kinetics of this process determines the growth rate of alpha lactose monohydrate (α-LM) crystals. Since no data were available on the specific rotation of aqueous α-LM solutions at different concentrations at 33 °C, the initial experiments were carried out on the specific rotation of aqueous α-LM solutions at different concentrations at 33 °C. The specific rotations of the solutions were decreased with increasing time through the mutarotation reaction. The initial and final (equilibrium) specific rotations of the solutions were determined by using automatic digital polarimeter. The compositions of α and β-L in all prepared solutions were calculated from initial and final optical rotations by the method of Sharp and Doob. The composition of α-L decreased whereas, the composition of β-L increased in solutions with increasing concentration of α-LM at 33 °C. Experimental results revealed that this method could be easily and safely employed to study the dependence of specific rotation of solutions on their concentration. The effect of β-lactose on the morphology of nucleated α-LM single crystals has been studied at different experimental conditions.

Thermodynamic properties of potassium chloride aqueous solutions

NASA Astrophysics Data System (ADS)

Zezin, Denis; Driesner, Thomas

2017-04-01

Potassium chloride is a ubiquitous salt in natural fluids, being the second most abundant dissolved salt in many geological aqueous solutions after sodium chloride. It is a simple solute and strong electrolyte easily dissociating in water, however the thermodynamic properties of KCl aqueous solutions were never correlated with sufficient accuracy for a wide range of physicochemical conditions. In this communication we propose a set of parameters for a Pitzer-type model which allows calculation of all necessary thermodynamic properties of KCl solution, namely excess Gibbs free energy and derived activity coefficient, apparent molar enthalpy, heat capacity and volume, as well as osmotic coefficient and activity of water in solutions. The system KCl-water is one of the best studied aqueous systems containing electrolytes. Although extensive experimental data were collected for thermodynamic properties of these solutions over the years, the accurate volumetric data became available only recently, thus making possible a complete thermodynamic formulation including a pressure dependence of excess Gibbs free energy and derived properties of the KCl-water liquids. Our proposed model is intended for calculation of major thermodynamic properties of KCl aqueous solutions at temperatures ranging from freezing point of a solution to 623 K, pressures ranging from saturated water vapor up to 150 MPa, and concentrations up to the salt saturation. This parameterized model will be further implemented in geochemical software packages and can facilitate the calculation of aqueous equilibrium for reactive transport codes.

Alumino-silicate speciation in aqueous fluids at deep crustal conditions

NASA Astrophysics Data System (ADS)

Mookherjee, M.; Keppler, H.; Manning, C. E.

2014-12-01

Alumina and silica are major oxides in most crustal rocks. While SiO2 is quite soluble in aqueous fluids at metamorphic conditions, behavior of Al2O3 in crustal metamorphic fluids has been poorly understood. It is known that alumina is dramatically less soluble in aqueous fluids and hence it is difficult to explain the common occurrence of quartz with aluminous minerals in metamorphic veins. In order to understand this complex behavior of alumina, we investigated aluminum speciation in aqueous fluids in equilibrium with corundum using in situ Raman spectroscopy in hydrothermal diamond anvil cells to 20 kbar and 1000 oC. In order to better understand the spectral features of the aqueous fluids, we used first principles simulations based on density functional theory to calculate and predict the energetics and vibrational spectra for various aluminum species that are likely to be present in aqueous solutions. The Raman spectra of pure water in equilibrium with Al2O3 are devoid of any characteristic spectral features. In contrast, aqueous fluids with KOH solution in equilibrium with Al2O3 show a sharp band at ~620 cm-1 which could be attributed to the [Al(OH)4]1- species. The band grows in intensity with temperature along an isochore. In the limited pressure, temperature and density explored in the present study, we do not find any evidence for the polymerization of the [Al(OH)4]1- species to dimers [(OH)2-Al-O2-Al(OH)2]2- or [(OH)3-Al-O-Al(OH)3]2-. This is likely due to the relatively low concentration of Al in the solutions and does not rule out significant polymerization at higher pressures and temperatures. We are also investigating the effect of SiO2 on the solubility of Al2O3 and the relative energetics of formation of pure alumina dimer [(OH)3-Al-O-Al(OH)3]2- vs. the aluminosilicate dimers, [(OH)3-Al-O-Si(OH)3]2- at deep crustal conditions. Acknowledgement- MM is supported by the US National Science Foundation grant (EAR-1250477).

Adsorptive separation in bioprocess engineering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, E.W.Y.

1987-01-01

The invention and development of an energy-efficient separation technique for recovery of desired chemicals from biomass conversion would greatly enhance the economic viability of this bioprocess. Adsorptive separation of several chemicals from aqueous solution was studied in this thesis. The desired species were recovered from the dilute aqueous solution by using crosslinked polyvinylpyridine resin to effect selective sorption. The sorbed chemicals were then removed from the resin by either thermal regeneration or elution with some appropriate desorbents. The effects of temperature, pH value, and solute concentration on resin swelling were investigated. The adsorption equilibrium isotherms, resin capacities and resin selectivitiesmore » of methanol, ethanol, 1-propanol, isopropanol, glycerol, acetone, 1-butanol, tert-butanol, and 2,3-butanediol were determined to study the homologies. Furthermore, acetic acid, butyric acid, hydrochloric acid, lactic acid, and sulfuric acid were recovered from very dilute aqueous solutions. The concentration of the sorbed chemical in the stationary phase can be many times higher than in the mobile phase for some acids. Finally, different types of equilibrium isotherms were used to fit the experimental data. A mathematical model was developed by using the theory of interference to predict the breakthrough curves and the process efficiency to provide information for large-scale process design and development.« less

Sulfuric Acid and Water: Paradoxes of Dilution

ERIC Educational Resources Information Center

Leenson, I. A.

2004-01-01

On equilibrium properties of aqueous solutions of sulfuric acid, Julius Thomsen has marked that the heat evolved on diluting liquid sulfuric acid with water is a continuous function of the water used, and excluded absolutely the acceptance of definite hydrates as existing in the solution. Information about thermochemical measurement, a discussion…

Highly effective removal of basic fuchsin from aqueous solutions by anionic polyacrylamide/graphene oxide aerogels.

PubMed

Yang, Xiaoxia; Li, Yanhui; Du, Qiuju; Sun, Jiankun; Chen, Long; Hu, Song; Wang, Zonghua; Xia, Yanzhi; Xia, Linhua

2015-09-01

Novel anionic polyacrylamide/graphene oxide aerogels were prepared by a freeze drying method and used to remove basic fuchsin from aqueous solutions. These aerogels were sponge-like solid with lightweight, fluffy and porous structure. The batch adsorption experiments were carried out to study the effect of various parameters, such as the solution pH, adsorbent dose, contact time and temperature on adsorption properties of basic fuchsin onto anionic polyacrylamide/graphene oxide aerogels. The kinetics of adsorption corresponded to the pseudo-second-order kinetic model. The Langmuir adsorption isotherm was suitable to describe the equilibrium adsorption process. The maximum adsorption capacity was up to 1034.3 mg/g, which indicated that anionic polyacrylamide/graphene oxide aerogels were promising adsorbents for removing dyes pollutants from aqueous solution. Copyright © 2015 Elsevier Inc. All rights reserved.

Comment on “Isotopic fractionation between Fe(III) and Fe(II) in aqueous solutions” by Clark Johnson et al., [Earth Planet. Sci. Lett. 195 (2002) 141–153

USGS Publications Warehouse

Bullen, Thomas D.; White, Arthur F.; Childs, Cyril W.

2003-01-01

In a recent contribution [1], Johnson et al. reported the equilibrium isotope fractionation factor between dissolved Fe(II) and Fe(III) in aqueous solutions at pH=2.5 and 5.5. They suggest that because the iron isotope fractionation observed in their experiments spans virtually the entire range observed in sedimentary rocks, Fe(II)–Fe(III) aqueous speciation may play a major role in determining iron isotope variations in nature where Fe(II) and Fe(III) can become physically separated. They discounted earlier conclusions by us and others [2] ;  [3] that significant equilibrium fractionation between specific coexisting Fe(II)- or Fe(III)-aqueous complexes (e.g., between aqueous Fe(II)(OH)x(aq)and Fe(II)(aq) ion) is capable of producing iron isotope contrasts that can be preserved in nature. This is an important contribution not only because the authors recognize the importance of abiotic equilibrium iron isotope fractionation in nature in contrast to previous assertions [4], but also because it will help to focus discussion on the development and evaluation of experimental approaches that can reveal abiotic fractionation mechanisms. However, in this Comment we propose that the experiments presented in this paper cannot be interpreted as straightforwardly as Johnson et al. contend. In particular, we show that in one of their critical experiments attainment of either isotope mass balance or equilibrium was not demonstrated, and thus the results of that experiment cannot be used to calculate an Fe(II)–Fe(III) equilibrium fractionation factor.

Adsorption of leather dye onto activated carbon prepared from bottle gourd: equilibrium, kinetic and mechanism studies.

PubMed

Foletto, Edson Luiz; Weber, Caroline Trevisan; Paz, Diego Silva; Mazutti, Marcio Antonio; Meili, Lucas; Bassaco, Mariana Moro; Collazzo, Gabriela Carvalho

2013-01-01

Activated carbon prepared from bottle gourd has been used as adsorbent for removal of leather dye (Direct Black 38) from aqueous solution. The activated carbon obtained showed a mesoporous texture, with surface area of 556.16 m(2) g(-1), and a surface free of organic functional groups. The initial dye concentration, contact time and pH significantly influenced the adsorption capacity. In the acid region (pH 2.5) the adsorption of dye was more favorable. The adsorption equilibrium was attained after 60 min. Equilibrium data were analyzed by the Langmuir, Freundlich, Dubinin-Radushkevich and Temkin isotherm models. The equilibrium data were best described by the Langmuir isotherm, with maximum adsorption capacity of 94.9 mg g(-1). Adsorption kinetic data were fitted using the pseudo-first-order, pseudo-second-order, Elovich and intraparticle diffusion models. The adsorption kinetic was best described by the second-order kinetic equation. The adsorption process was controlled by both external mass transfer and intraparticle diffusion. Activated carbon prepared from bottle gourd was shown to be a promising material for adsorption of Direct Black 38 from aqueous solution.

Spectroscopic and calorimetric studies on the interaction between PAMAM G4-OH and 5-fluorouracil in aqueous solutions

NASA Astrophysics Data System (ADS)

Buczkowski, Adam; Urbaniak, Pawel; Piekarski, Henryk; Palecz, Bartlomiej

2017-01-01

The results of spectroscopic measurements (an increase in solubility, equilibrium dialysis, 1H NMR titration) and calorimetric measurements (isothermal titration ITC) indicate spontaneous (ΔG < 0) binding of 5-fluorouracil molecules by PAMAM G4-OH dendrimer with terminal hydroxyl groups in an aqueous solution. PAMAM G4-OH dendrimer bonds about n = 8 ± 1 molecules of the drug with an equilibrium constant of K = 70 ± 10. The process of saturating the dendrimer active sites by the drug molecules is exothermal (ΔH < 0) and is accompanied by an advantageous change in entropy (ΔS > 0). The parameters of binding 5-fluorouracil by PAMAM G4-OH dendrimer were compared with those of binding this drug by the macromolecules of PAMAM G3-OH and G5-OH.

Kinetic and mechanism of the oxidation of chromium(III) complex with anthranil- N, N-diacetic acid by periodate ion in acidic aqueous solutions

NASA Astrophysics Data System (ADS)

Ali, Ismat H.

2015-06-01

The kinetics of oxidation of [CrIII(atda)(H2O)2] (atda = anthranil- N, N-diacetato) complex by IO{4/-} was studied spectrophotometrically in aqueous solutions with pH range 2.20-3.34, 0.30 M ionic strength and in 20.0-40.0°C temperature range. The rate law of the reaction exhibited saturation kinetics. Values of the rate constant for the electron transfer process, the equilibrium constant for dissociation of [CrIII (atda)(H2O)2] to [CrIII (atda) (H2O)OH]+ + H+ and the pre-equilibrium formation constant were calculated. The thermodynamic activation parameters are reported. It is proposed that electron transfer proceeds through an inner-sphere mechanism via coordination of the IVII to chromium(III).

Zeolitic imidazolate framework-8 for efficient adsorption and removal of Cr(VI) ions from aqueous solution.

PubMed

Niknam Shahrak, Mahdi; Ghahramaninezhad, Mahboube; Eydifarash, Mohsen

2017-04-01

Heavy metals are emerging toxic pollutants in which the development of advanced materials for their efficient adsorption and separation is thus of great significance in environmental sciences point of view. In this study, one of the zinc-based zeolitic imidazolate framework materials, known as ZIF-8, has been synthesized and used for chromium(VI) contaminant removal from water for the first time. The as-synthesized ZIF-8 adsorbent was characterized with different methodologies such as powder X-ray diffraction (XRD), thermo-gravimetric analysis, FT-IR, nuclear magnetic resonance spectroscopy, and UV-Vis spectra of solid state. Various factors affecting removal percentage (efficiency) are experimentally investigated including pH of solution, adsorbent dosage, contact time and initial concentration of Cr(VI) to achieve the optimal condition. The obtained results indicate that the ZIF-8 shows good performance for the Cr(VI) removal from aqueous solution so that 60 min mixing of 2 g of ZIF-8 adsorbent with the 2.5 ppm of Cr(VI) solution in a neutral environment will result in the highest separation efficiency around 70%. The time needed to reach the equilibrium (maximum separation efficiency) is only 60 min for a concentration of 5 mg L -1 . Structure stability in the presence of water is also carefully examined by XRD determination of ZIF-8 under different contact times in aqueous solution, which suggests that the structure is going to be destructed after 60 min immersed in solution. Electrostatic interaction of Cr(VI) anions by positively charged ZIF-8 is responsible for Cr(VI) adsorption and separation. Moreover, equilibrium adsorption study reveals that the Cr(VI) removal process using ZIF-8 nicely fits the Langmuir and Toth isotherm models which mean the adsorbent has low heterogeneous surface with different distributions of adsorption energies during Cr(VI) adsorption. Equilibrium adsorption capacity is observed around 0.25 for 20 mg L -1 of initial Cr(VI) solutions.

End-Member Formulation of Solid Solutions and Reactive Transport

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lichtner, Peter C.

2015-09-01

A model for incorporating solid solutions into reactive transport equations is presented based on an end-member representation. Reactive transport equations are solved directly for the composition and bulk concentration of the solid solution. Reactions of a solid solution with an aqueous solution are formulated in terms of an overall stoichiometric reaction corresponding to a time-varying composition and exchange reactions, equivalent to reaction end-members. Reaction rates are treated kinetically using a transition state rate law for the overall reaction and a pseudo-kinetic rate law for exchange reactions. The composition of the solid solution at the onset of precipitation is assumed tomore » correspond to the least soluble composition, equivalent to the composition at equilibrium. The stoichiometric saturation determines if the solid solution is super-saturated with respect to the aqueous solution. The method is implemented for a simple prototype batch reactor using Mathematica for a binary solid solution. Finally, the sensitivity of the results on the kinetic rate constant for a binary solid solution is investigated for reaction of an initially stoichiometric solid phase with an undersaturated aqueous solution.« less

Adsorption of cadmium and lead onto oxidized nitrogen-doped multiwall carbon nanotubes in aqueous solution: equilibrium and kinetics

NASA Astrophysics Data System (ADS)

Perez-Aguilar, Nancy Veronica; Muñoz-Sandoval, Emilio; Diaz-Flores, Paola Elizabeth; Rangel-Mendez, Jose Rene

2010-02-01

Nitrogen-doped multiwall carbon nanotubes (CNx) were chemically oxidized and tested to adsorb cadmium and lead from aqueous solution. Physicochemical characterization of carbon nanotubes included morphological analysis, textural properties, and chemical composition. In addition, the cadmium adsorption capacity of oxidized-CNx was compared with commercially available activated carbon and single wall carbon nanotubes. Carboxylic and nitro groups on the surface of oxidized CNx shifted the point of zero charge from 6.6 to 3.1, enhancing their adsorption capacity for cadmium and lead to 0.083 and 0.139 mmol/g, respectively, at pH 5 and 25 °C. Moreover, oxidized-CNx had higher selectivity for lead when both metal ions were in solution. Kinetic experiments for adsorption of cadmium showed that the equilibrium was reached at about 4 min. Finally, the small size, geometry, and surface chemical composition of oxidized-CNx are the key factors for their higher adsorption capacity than activated carbon.

Atmospheric Pressure Non-Equilibrium Plasma as a Green Tool to Crosslink Gelatin Nanofibers

NASA Astrophysics Data System (ADS)

Liguori, Anna; Bigi, Adriana; Colombo, Vittorio; Focarete, Maria Letizia; Gherardi, Matteo; Gualandi, Chiara; Oleari, Maria Chiara; Panzavolta, Silvia

2016-12-01

Electrospun gelatin nanofibers attract great interest as a natural biomaterial for cartilage and tendon repair despite their high solubility in aqueous solution, which makes them also difficult to crosslink by means of chemical agents. In this work, we explore the efficiency of non-equilibrium atmospheric pressure plasma in stabilizing gelatin nanofibers. We demonstrate that plasma represents an innovative, easy and environmentally friendly approach to successfully crosslink gelatin electrospun mats directly in the solid state. Plasma treated gelatin mats display increased structural stability and excellent retention of fibrous morphology after immersion in aqueous solution. This method can be successfully applied to induce crosslinking both in pure gelatin and genipin-containing gelatin electrospun nanofibers, the latter requiring an even shorter plasma exposure time. A complete characterization of the crosslinked nanofibres, including mechanical properties, morphological observations, stability in physiological solution and structural modifications, has been carried out in order to get insights on the occurring reactions triggered by plasma.

Peach gum for efficient removal of methylene blue and methyl violet dyes from aqueous solution.

PubMed

Zhou, Li; Huang, Jiachang; He, Benzhao; Zhang, Faai; Li, Huabin

2014-01-30

This study investigated the potential use of natural peach gum (PG) as alternative adsorbent for the removal of dyes from aqueous solutions. The PG showed high adsorption capacities and selectivity for cationic dyes (e.g., methylene blue (MB) and methyl violet (MV)) in the pH range 6-10. 98% of MB and MV could be adsorbed within 5 min, and both of the adsorptions reached equilibrium within 30 min. The dye uptake process followed the pseudo-second-order kinetic model. The intraparticle diffusion was not the sole rate controlling step. Equilibrium adsorption isotherm data indicated a good fit to the Langmuir isotherm model. Regeneration study revealed that PG could be well regenerated in acid solution. The recovered PG still exhibited high adsorption capacity even after five cycles of desorption-adsorption. On the basis of its excellent adsorption performance and facile availability, PG can be employed as an efficient low cost adsorbent for environmental cleanup. Copyright © 2013 Elsevier Ltd. All rights reserved.

Effective removal of Congo red dye from aqueous solution using modified xanthan gum/silica hybrid nanocomposite as adsorbent.

PubMed

Ghorai, Soumitra; Sarkar, Amit Kumar; Panda, A B; Pal, Sagar

2013-09-01

The aim of this work is to study the feasibility of XG-g-PAM/SiO2 nanocomposite towards its potential application as high performance adsorbent for removal of Congo red (CR) dye from aqueous solution. The surface area, average pore size and total pore volume of the developed nanocomposite has been determined. The efficiency of CR dye adsorption depends on various factors like pH, temperature of the solution, equilibrium time of adsorption, agitation speed, initial concentration of dye and adsorbent dosage. It has been observed that the nanocomposite is having excellent CR dye adsorption capacity (Q0=209.205 mg g(-1)), which is considerably high. The dye adsorption process is controlled by pseudo-second order and intraparticle diffusion kinetic models. The adsorption equilibrium data correlates well with Langmuir isotherm. Desorption study indicates the efficient regeneration ability of the dye loaded nanocomposite. Copyright © 2013 Elsevier Ltd. All rights reserved.

Biosorption of metal ions from aqueous solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Jiaping; Yiacoumi, Sotira

1997-01-01

Copper biosorption from aqueous solutions by calcium alginate is reported in this paper. The experimental section includes potentiometric titrations of biosorbents, batch equilibrium and kinetic studies of copper biosorption, as well as fixed-bed biosorption experiments. The potentiometric titration results show that the surface charge increases with decreasing pH. The biosorption of copper strongly depends on solution pH; the metal ion binding increases from 0 to 90 percent in pH ranging from 1.5 to 5.0. In addition, a decrease in ionic strength results in an increase of copper ion removal. Kinetic studies indicate that mass transfer plays an important role inmore » the biosorption rate. Furthermore, a fixed-bed biosorption experiment shows that calcium alginate has a significant capacity for copper ion removal. The two-pK Basic Stem model successfully represents the surface charge and equilibrium biosorption experimental data. The calculation results demonstrate that the copper removal may result from the binding of free copper and its hydroxide with surface functional groups of the biosorbents.« less

Implementation of equilibrium aqueous speciation and solubility (EQ3 type) calculations into Cantera for electrolyte solutions.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moffat, Harry K.; Jove-Colon, Carlos F.

2009-06-01

In this report, we summarize our work on developing a production level capability for modeling brine thermodynamic properties using the open-source code Cantera. This implementation into Cantera allows for the application of chemical thermodynamics to describe the interactions between a solid and an electrolyte solution at chemical equilibrium. The formulations to evaluate the thermodynamic properties of electrolytes are based on Pitzer's model to calculate molality-based activity coefficients using a real equation-of-state (EoS) for water. In addition, the thermodynamic properties of solutes at elevated temperature and pressures are computed using the revised Helgeson-Kirkham-Flowers (HKF) EoS for ionic and neutral aqueous species.more » The thermodynamic data parameters for the Pitzer formulation and HKF EoS are from the thermodynamic database compilation developed for the Yucca Mountain Project (YMP) used with the computer code EQ3/6. We describe the adopted equations and their implementation within Cantera and also provide several validated examples relevant to the calculations of extensive properties of electrolyte solutions.« less

Supercritical separation process for complex organic mixtures

DOEpatents

Chum, Helena L.; Filardo, Giuseppe

1990-01-01

A process is disclosed for separating low molecular weight components from complex aqueous organic mixtures. The process includes preparing a separation solution of supercritical carbon dioxide with an effective amount of an entrainer to modify the solvation power of the supercritical carbon dioxide and extract preselected low molecular weight components. The separation solution is maintained at a temperature of at least about 70.degree. C. and a pressure of at least about 1,500 psi. The separation solution is then contacted with the organic mixtures while maintaining the temperature and pressure as above until the mixtures and solution reach equilibrium to extract the preselected low molecular weight components from the organic mixtures. Finally, the entrainer/extracted components portion of the equilibrium mixture is isolated from the separation solution.

Intermolecular interactions in aqueous solutions of gallic acid at 296-306 K according to spectrofluorimetry and densimetry data

NASA Astrophysics Data System (ADS)

Grigoryan, K. R.; Sargsyan, L. S.

2015-12-01

Features of intermolecular interactions in aqueous solutions of gallic acid (GA) are studied by means of densimetry and fluorescence spectroscopy (intrinsic fluorescence, 2D spectra, and excitation/ emission matrix fluorescence spectra, 3D) at 296.15, 301.15, and 306.15 K in the concentration range of 5.88 × 10-4-5.88 × 10-2 mol L-1. It is shown by analyzing the concentration and temperature dependences of the apparent molar volumes and fluorescence parameters of GA that the equilibrium between nonassociated and associated species in the solution and the hydration of these species undergo changes.

Pore Scale Dynamics of Microemulsion Formation.

PubMed

Unsal, Evren; Broens, Marc; Armstrong, Ryan T

2016-07-19

Experiments in various porous media have shown that multiple parameters come into play when an oleic phase is displaced by an aqueous solution of surfactant. In general, the displacement efficiency is improved when the fluids become quasi-miscible. Understanding the phase behavior oil/water/surfactant systems is important because microemulsion has the ability to generate ultralow interfacial tension (<10(-2) mN m(-1)) that is required for miscibility to occur. Many studies focus on microemulsion formation and the resulting properties under equilibrium conditions. However, the majority of applications where microemulsion is present also involve flow, which has received relatively less attention. It is commonly assumed that the characteristics of an oil/water/surfactant system under flowing conditions are identical to the one under equilibrium conditions. Here, we show that this is not necessarily the case. We studied the equilibrium phase behavior of a model system consisting of n-decane and an aqueous solution of olefin sulfonate surfactant, which has practical applications for enhanced oil recovery. The salt content of the aqueous solution was varied to provide a range of different microemulsion compositions and oil-water interfacial tensions. We then performed microfluidic flow experiments to study the dynamic in situ formation of microemulsion by coinjecting bulk fluids of n-decane and surfactant solution into a T-junction capillary geometry. A solvatochromatic fluorescent dye was used to obtain spatially resolved compositional information. In this way, we visualized the microemulsion formation and the flow of it along with the excess phases. A complex interaction between the flow patterns and the microemulsion properties was observed. The formation of microemulsion influenced the flow regimes, and the flow regimes affected the characteristics of the microemulsion formation. In particular, at low flow rates, slug flow was observed, which had profound consequences on the pore scale mixing behavior and resulting microemulsion properties.

Capillary electrophoresis investigation on equilibrium between polymer-related and surfactant-related species in aqueous polymer-surfactant solutions.

PubMed

Wu, Yefan; Chen, Miaomiao; Fang, Yun; Zhu, Meng

2017-03-17

It was inferred from aqueous solution behavior of nonionic polymers and anionic surfactants that the formation of charged polymer-bound surfactant micelle above critical aggregation concentration (cac) and the formation of free surfactant micelle beyond polymer saturation point (psp), but there was still a lack of direct experimental evidence for the considered equilibrium chemical species. Three modes of capillary electrophoresis are applied in this paper to study the complexation between nonionic polymers, polyvinylpyrrolidone (PVP) or polyethylene glycol (PEG), and sodium dodecylbenzenesulfonate (SDBS) by successfully distinguishing the imaginary charged polymer-bound SDBS micelle from nonionic polymer and SDBS molecule. Perhaps even more important, it is the action of SDBS as both a main surfactant and a UV probe that makes the free surfactant micelle emerged in electropherogram beyond psp, and thus makes it possible for the first time to provide the equilibrium relationship of the polymer-related and the surfactant-related species in the concentration regions divided into by cac and psp. Copyright © 2017 Elsevier B.V. All rights reserved.

Hydrolysis of Methylal Catalyzed by Ion Exchange Resins in Aqueous Media

NASA Astrophysics Data System (ADS)

He, Gaoyin; Dai, Fangfang; Shi, Midong; Li, Qingsong; Yu, Yingmin

2018-05-01

In the present work, the chemical equilibrium and kinetics of methylal (PODE1) hydrolysis catalyzed by ion-exchange resin in aqueous solutions were investigated. The study covers temperatures between 333.15 and 363.15 K at various starting compositions covering (PODE1 + MeOH)/water molar ratio ranges from 0.5 to 1.5 in a time scale. On the basis of the experimental results, a mole fraction-based model of the chemical equilibrium and a pseudohomogeneous model are proposed to fit data based on true amount of monomeric formaldehyde. It has been demonstrated that the hydrolysis of PODE1 is slightly endothermic with the enthalpy 8.19 kJ/mol and the rate determining step. Finally, a feed-forward artificial neural networks (ANN) model is developed to model the concentration change of methanol in aqueous solutions. The results showed that the predicted data from designed ANN model were in good agreement with the experimental data with the coefficient ( R 2) of 0.98. Designed ANN provides a reliable method for modeling the hydrolysis reaction of methylal (PODE1).

Concentrated aqueous sodium chloride solution in clays at thermodynamic conditions of hydraulic fracturing: Insight from molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Svoboda, Martin; Lísal, Martin

2018-06-01

To address a high salinity of flow-back water during hydraulic fracturing, we use molecular dynamics (MD) simulations and study the thermodynamics, structure, and diffusion of concentrated aqueous salt solution in clay nanopores. The concentrated solution results from the dissolution of a cubic NaCl nanocrystal, immersed in an aqueous NaCl solution of varying salt concentration and confined in clay pores of a width comparable to the crystal size. The size of the nanocrystal equals to about 18 Å which is above a critical nucleus size. We consider a typical shale gas reservoir condition of 365 K and 275 bar, and we represent the clay pores as pyrophyllite and Na-montmorillonite (Na-MMT) slits. We employ the Extended Simple Point Charge (SPC/E) model for water, Joung-Cheatham model for ions, and CLAYFF for the slit walls. We impose the pressure in the normal direction and the resulting slit width varies from about 20 to 25 Å when the salt concentration in the surrounding solution increased from zero to an oversaturated value. By varying the salt concentration, we observe two scenarios. First, the crystal dissolves and its dissolution time increases with increasing salt concentration. We describe the dissolution process in terms of the number of ions in the crystal, and the crystal size and shape. Second, when the salt concentration reaches a system solubility limit, the crystal grows and attains a new equilibrium size; the crystal comes into equilibrium with the surrounding saturated solution. After crystal dissolution, we carry out canonical MD simulations for the concentrated solution. We evaluate the hydration energy, density profiles, orientation distributions, hydrogen-bond network, radial distribution functions, and in-plane diffusion of water and ions to provide insight into the microscopic behaviour of the concentrated aqueous sodium chloride solution in interlayer galleries of the slightly hydrophobic pyrophyllite and hydrophilic Na-MMT pores.

Concentrated aqueous sodium chloride solution in clays at thermodynamic conditions of hydraulic fracturing: Insight from molecular dynamics simulations.

PubMed

Svoboda, Martin; Lísal, Martin

2018-06-14

To address a high salinity of flow-back water during hydraulic fracturing, we use molecular dynamics (MD) simulations and study the thermodynamics, structure, and diffusion of concentrated aqueous salt solution in clay nanopores. The concentrated solution results from the dissolution of a cubic NaCl nanocrystal, immersed in an aqueous NaCl solution of varying salt concentration and confined in clay pores of a width comparable to the crystal size. The size of the nanocrystal equals to about 18 Å which is above a critical nucleus size. We consider a typical shale gas reservoir condition of 365 K and 275 bar, and we represent the clay pores as pyrophyllite and Na-montmorillonite (Na-MMT) slits. We employ the Extended Simple Point Charge (SPC/E) model for water, Joung-Cheatham model for ions, and CLAYFF for the slit walls. We impose the pressure in the normal direction and the resulting slit width varies from about 20 to 25 Å when the salt concentration in the surrounding solution increased from zero to an oversaturated value. By varying the salt concentration, we observe two scenarios. First, the crystal dissolves and its dissolution time increases with increasing salt concentration. We describe the dissolution process in terms of the number of ions in the crystal, and the crystal size and shape. Second, when the salt concentration reaches a system solubility limit, the crystal grows and attains a new equilibrium size; the crystal comes into equilibrium with the surrounding saturated solution. After crystal dissolution, we carry out canonical MD simulations for the concentrated solution. We evaluate the hydration energy, density profiles, orientation distributions, hydrogen-bond network, radial distribution functions, and in-plane diffusion of water and ions to provide insight into the microscopic behaviour of the concentrated aqueous sodium chloride solution in interlayer galleries of the slightly hydrophobic pyrophyllite and hydrophilic Na-MMT pores.

Commercial Coffee Wastes as Materials for Adsorption of Heavy Metals from Aqueous Solutions

PubMed Central

Kyzas, George Z.

2012-01-01

This work aims to study the removal of Cu(II) and Cr(VI) from aqueous solutions with commercial coffee wastes. Materials with no further treatment such as coffee residues from café may act as adsorbents for the removal of Cu(II) and Cr(VI). Equilibrium data were successfully fitted to the Langmuir, Freundlich and Langmuir-Freundlich model (L-F). The maximum adsorption capacity of the coffee residues can reach 70 mg/g for the removal of Cu(II) and 45 mg/g for Cr(VI). The kinetic data were fitted to pseudo-first, -second and -third order equations. The equilibrium was achieved in 120 min. Also, the effect of pH on adsorption and desorption was studied, as well as the influence of agitation rate. Ten cycles of adsorption-desorption were carried out revealing the strong reuse potential of these low-cost adsorbents; the latter was confirmed from a brief economic approach.

Apiaceae Family Plants as Low-Cost Adsorbents for the Removal of Lead Ion from Water Environment

NASA Astrophysics Data System (ADS)

Boontham, W.; Babel, S.

2017-06-01

Adsorbents prepared from the three selected plants from Apiaceae famaily commonly known as parsley, coriander and culantro were observed to remove lead from aqueous solutions. Batch experiments were conducted to study the effect of dosage, pH, contact time and agitation speed at 10 mg L-1 initial Pb(II) concentration. Results revealed that three selected plants showed high adsorption capacity for removal of lead from aqueous solutions. The maximum biosorption of Pb2+ was found to be more than 97% with 1.0 g/l dosage for all three adsorbents under optimum pH of 3-5. The adsorption equilibrium was established after about 1 hr. The equilibrium adsorption capacity of parsley and coriander were found to fit well with the Langmuir isotherm whereas the Freundlich isotherm was better fit for culantro. The studies showed that the adsorbents can be used for removing lead ions from contaminated waters.

Effect of aging on aluminum hydroxide complexes in dilute aqueous solutions

USGS Publications Warehouse

Smith, Ross Wilbert; Hem, John David

1972-01-01

Aqueous aluminum solutions containing 4?10 -5 mole/liter aluminum and a constant total ionic strength of 10 -2, but with varying ratios of hydroxide to aluminum (OH:Al), were prepared. Progress of these solutions toward equilibrium conditions over aging periods of as much as 2 years was studied by determining the composition and pH of the solutions at various time intervals. The solutions, after mixing, were supersaturated with respect to both crystalline and amorphous forms of aluminum oxides and aluminum hydroxides. The compositions of the solutions were determined by use of a timed colorimetric analytical procedure which allowed the estimation of three separate forms of aluminum that have been designated Al a, Al b, and Al c. Form Al a appeared to be composed of monomeric species such as Al(H20)6+3, Al(OH)(H20)5+2, Al(OH)2(H20)4 +I and Al(OH)4-. Form Al b was polynuclear material containing perhaps 20-400 aluminum atoms per structure. It appeared to be a metastable material. Form Al c was composed of relatively large, microcrystalline, clearly solid AI(OH)3 particles. For each OH :Al ratio, the concentration of Al a remained constant with aging time, Al b decreased, and Al c increased. It appeared that Al b particles were increasing in size and ultimately were converted to Al c particles. After a few weeks' aging, Al c particles had the structure of gibbsite. In all solutions, equilibrium was only very slowly achieved, and the time required depended on the OH:Al ratio and how rapidly the solution was initially prepared (mixing time). Lower ratios caused a slower approach to equilibrium; sometimes equilibrium was not achieved even after several years' aging. The more slowly base was initially added (to obtain the proper OH:Al ratio), the more slowly was equilibrium approached. Ultimate equilibrium values of dissolved aluminum concentration and pH were consistent with known thermodynamic data on monomeric aluminum species. From data determined during the aging study and by considering Al b material to consist of extremely small solid gibbsite particles, it was possible to estimate the Gibbs free energy of the (001) crystal face (?F, the gibbsite 'face') and the. Gibbs free energy of the (110) and (100) crystal faces (?E, the gibbsite 'edge') of gibbsite in equilibrium with its saturated solution. These values were: ?F=1404 ? 24 ergs/cm 2, and ?E = 483 ?-84 ergs/cm 2.

Solid solution partitioning of Sr2+, Ba2+, and Cd2+ to calcite

USGS Publications Warehouse

Tesoriero, A.J.; Pankow, J.F.

1996-01-01

Although solid solutions play important roles in controlling the concentrations of minor metal ions in natural waters, uncertainties regarding their compositions, thermodynamics, and kinetics usually prevent them from being considered. A range of precipitation rates was used here to study the nonequilibrium and equilibrium partitioning behaviors of Sr2+, Ba2+, and Cd2+ to calcite (CaCO3(s)). The distribution coefficient of a divalent metal ion Me2+ for partitioning from an aqueous solution into calcite is given by DMe = (XMeCO3(s)/[Me2+])/(XCaCO3(s)/[Ca 2+]). The X values are solid-phase mole fractions; the bracketed values are the aqueous molal concentrations. In agreement with prior work, at intermediate to high precipitation rates R (nmol/mg-min), DSr, DBa, and DCd were found to depend strongly on R. At low R, the values of DSr, DBa, and DCd became constant with R. At 25??C, the equilibrium values for DSr, DBa, and DCd for dilute solid solutions were estimated to be 0.021 ?? 0.003, 0.012 ?? 0.005, and 1240 ?? 300, respectively. Calculations using these values were made to illustrate the likely importance of partitioning of these ions to calcite in groundwater systems. Due to its large equilibrium DMe value, movement of Cd2+ will be strongly retarded in aquifers containing calcite; Sr2+ and Ba2+ will not be retarded nearly as much.

Equilibrium, Kinetic, and Thermodynamic Studies on the Adsorption of Cadmium from Aqueous Solution by Modified Biomass Ash

PubMed Central

Zheng, Xuebo; Cui, Hongbiao; Zhu, Zhenqiu; Liang, Jiani

2017-01-01

Natural biomass ash of agricultural residuals was collected from a power plant and modified with hexagonal mesoporous silica and functionalized with 3-aminopropyltriethoxysilane. The physicochemical and morphological properties of the biomass ash were analyzed by ICP-OES, SEM, TEM-EDS, FTIR, and BET analysis. The adsorption behavior of the modified product for Cd2+ in aqueous solution was studied as a function of pH, initial metal concentration, equilibrium time, and temperature. Results showed that the specific surface area of the modified product was 9 times that of the natural biomass ash. The modified biomass ash exhibited high affinity for Cd2+ and its adsorption capacity increased sharply with increasing pH from 4.0 to 6.0. The maximum adsorption capacity was 23.95 mg/g in a pH 5 solution with an initial metal concentration of 50 mg/L and a contact time of 90 min. The adsorption of Cd2+ onto the modified biomass ash was well fitted to the Langmuir model and it followed pseudo-second-order kinetics. Thermodynamic analysis results showed that the adsorption of Cd2+ was spontaneous and endothermic in nature. The results suggest that the modified biomass ash is promising for use as an inexpensive and effective adsorbent for Cd2+ removal from aqueous solution. PMID:28348509

Acid-base equilibrium in aqueous solutions of 1,3-dimethylbarbituric acid as studied by 13C NMR spectroscopy

NASA Astrophysics Data System (ADS)

Gryff-Keller, A.; Kraska-Dziadecka, A.

2011-12-01

13C NMR spectra of 1,3-dimethylbarbituric acid in aqueous solutions of various acidities and for various solute concentrations have been recorded and interpreted. The spectra recorded at pH = 2 and below contain the signals of the neutral solute molecule exclusively, while the ones recorded at pH = 7 and above only the signals of the appropriate anion, which has been confirmed by theoretical GIAO-DFT calculations. The signals in the spectra recorded for solutions of pH < 7 show dynamic broadenings. The lineshape analysis of these signals has provided information on the kinetics of the processes running in the dynamic acid-base equilibrium. The kinetic data determined this way have been used to clarify the mechanisms of these processes. The numerical analysis has shown that under the investigated conditions deprotonation of the neutral solute molecules undergoes not only via a simple transfer of the C-H proton to water molecules but also through a process with participation of the barbiturate anions. Moreover, the importance of tautomerism, or association, or both these phenomena for the kinetics of the acid-base transformations in the investigated system has been shown. Qualitatively similar changes of 13C NMR spectra with the solution pH variation have been observed for the parent barbituric acid.

Three-Phase Melting Curves in the Binary System of Carbon Dioxide and Water

NASA Astrophysics Data System (ADS)

Abramson, E. H.

2017-10-01

Invariant, three-phase melting curves, of ice VI in equilibrium with solid CO2, of ice VII in equilibrium with solid CO2, and of solid CO2 in simultaneous equilibrium with a majority aqueous and a majority CO2 fluid, were explored in the binary system of carbon dioxide and water. Diamond-anvil cells were used to develop pressures of 5 GPa. Water exhibits a large melting temperature depression (73°C less than its pure melting temperature of 253°C at 5 GPa) indicative of large concentrations of CO2 in the aqueous solution. The melting point of water-saturated CO2 does not show a measureable departure from that of the pure system at temperatures lower than ∼200°C and only 10°C at 5 GPa (from 327°C).

Optimization of mesoporous carbons for efficient adsorption of berberine hydrochloride from aqueous solutions.

PubMed

Li, Yin; Fu, Jie; Deng, Shuguang; Lu, Xiuyang

2014-06-15

Sixteen mesoporous carbon adsorbents were synthesized by varying the ratio of soft to hard templates in order to optimize the pore textural properties of these adsorbents. The mesoporous carbon adsorbents have a high BET specific surface area (1590.3-2193.5 m(2)/g), large pore volume (1.72-2.56 cm(3)/g), and uniform pore size distribution with a median pore diameter ranging from 3.51 nm to 4.52 nm. It was observed that pore textural properties of the carbon adsorbents critically depend on the molar ratio of carbon sources to templates, and the hard template plays a more important role than the soft template in manipulating the pore textures. Adsorption isotherms of berberine hydrochloride at 303 K were measured to evaluate the adsorption efficacy of these adsorbents. The adsorption of berberine hydrochloride from aqueous solutions on the sixteen mesoporous carbon adsorbents synthesized in this work is very efficient, and the adsorption equilibrium capacities on all samples are more than double the adsorption capacities of berberine hydrochloride of the benchmark adsorbents (polymer resins and spherical activated carbons) at similar conditions. It was observed from the adsorption experiments that the equilibrium adsorption amounts of berberine hydrochloride are strongly correlated with the BET specific surface area and pore volume of the adsorbents. The adsorbent with the highest BET of 2193.5 m(2)/g displayed the largest adsorption capacity of 574 mg/g at an equilibrium concentration of 0.10mg/mL of berberine hydrochloride in an aqueous solution. Copyright © 2014 Elsevier Inc. All rights reserved.

Binary adsorption of copper(II) and cadmium(II) from aqueous solutions by biomass of marine alga Durvillaea potatorum

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Q.; Kaewsarn, P.

1999-06-01

Much work on the biosorption of heavy metals by low-cost, natural biomass has been on the uptake of single metals. In practice, wastewaters often contain multiple heavy metal ions. In this paper the binary adsorption of copper(II) and cadmium(II) by a pretreated biomass of the marine alga Durvillaea potatorum from aqueous solutions was studied. The results showed that the uptake capacities for each heavy metal of the binary system were lower when compared with the single metal biosorption for copper and cadmium, respectively, but the total capacities for the binary system were similar to those obtained for single metal biosorption.more » The uptake capacities for copper and cadmium increased as the equilibrium pH increased and reached a plateau at a pH around 5.0. The uptake process was relatively fast, with 90% of the adsorption completed within 10 minutes for copper and 30 minutes for cadmium, and equilibrium reached after about 60 minutes of stirring. The biosorption isotherms of binary systems were not significantly affected by equilibrium temperature. The presence of light metal ions in solution also did not affect adsorption significantly. The binary adsorption was successfully predicted by the extended Langmuir model, using parameters and capacities obtained from single component systems.« less

Removal of zinc (II) ion from aqueous solution by adsorption onto activated palm midrib bio-sorbent

NASA Astrophysics Data System (ADS)

Mulana, F.; Mariana; Muslim, A.; Mohibah, M.; Halim, K. H. Ku

2018-03-01

In this paper, palm midrib that was activated with mixed citric acid and tartaric acid as biosorbent was used to remove Zn (II) ion from aqueous solution. The aim of this research is to activate palm midrib by using a mixed citric acid and tartaric acid and to determine adsorption capacity of activated palm midrib biosorbent on Zn (II) ion uptake from aqueous solution. The effect of several parameters such as contact time, initial Zn (II) ion concentration and activator concentration on the degree of Zn (II) ion removal was examined. Atomic Absorption Spectroscopy method was performed to determine adsorbed amount of Zn (II) ion into activated biosorbent. The result showed that the adsorption process was relatively not so fast and equilibrium was reached after contact time of 120 min. The adsorption capacity of biosorbent reached a maximum when the concentration of mixed citric acid and tartaric acid was 1.6 M. The optimum adsorption capacity was 5.72 mg/g. The result was obtained on initial Zn (II) ion concentration of 80 ppm for 120-min contact time. Langmuir isotherm was found as the best fit for the equilibrium data indicating homogeneous adsorption of metal ions onto the biosorbent surface.

Adsorptive Removal of Cadmium (II) from Aqueous Solution by Multi-Carboxylic-Functionalized Silica Gel: Equilibrium, Kinetics and Thermodynamics

NASA Astrophysics Data System (ADS)

Li, Min; Meng, Xiaojing; Yuan, Jinhai; Deng, Wenwen; Liang, Xiuke

2018-01-01

In the present study, the adsorption behavior of cadmium (II) ion from aqueous solution onto multi-carboxylic-functionalized silica gel (SG-MCF) has been investigated in detail by means of batch and column experiments. Batch experiments were performed to evaluate the effects of various experimental parameters such as pH value, contact time and initial concentration on adsorption capacity of cadmium (II) ion. The kinetic data were analyzed on the basis of the pseudo-first-order kinetic and the pseudo-second-order kinetic models and consequently, the pseudo-second-order kinetic can better describe the adsorption process than the pseudo-first-order kinetic model. Equilibrium isotherms for the adsorption of cadmium (II) ion were analyzed by Freundlich and Langmuir isotherm models, the results indicate that Langmuir isotherm model was found to be credible to express the data for cadmium (II) ion from aqueous solution onto the SG-MCF. Various thermodynamics parameters of the adsorption process, including free energy of adsorption (ΔG0 ), the enthalpy of adsorption (ΔH0 ) and standard entropy changes (ΔS0 ), were calculated to predict the nature of adsorption. The positive value of the enthalpy change and the negative value of free energy change indicate that the process is endothermic and spontaneous process.

Mechanistic understanding and performance of biosorption of metal ions by grapefruit peel using FTIR spectroscopy, kinetics and adsorption isotherms modeling, alkali and alkaline metal displacement and EDX analysis

USDA-ARS?s Scientific Manuscript database

The performance and mechanism of the sorptive removal of Ni2+ and Zn2+ from aqueous solution using grapefruit peel (GFP) as a new sorbent was investigated. The sorption process was fast, equilibrium was established in 60 min. The equilibrium process was described well by the Langmuir isotherm model,...

Evaporation-based Ge/.sup.68 Ga Separation

DOEpatents

Mirzadeh, Saed; Whipple, Richard E.; Grant, Patrick M.; O'Brien, Jr., Harold A.

1981-01-01

Micro concentrations of .sup.68 Ga in secular equilibrium with .sup.68 Ge in strong aqueous HCl solution may readily be separated in ionic form from the .sup.68 Ge for biomedical use by evaporating the solution to dryness and then leaching the .sup.68 Ga from the container walls with dilute aqueous solutions of HCl or NaCl. The chloro-germanide produced during the evaporation may be quantitatively recovered to be used again as a source of .sup.68 Ga. If the solution is distilled to remove any oxidizing agents which may be present as impurities, the separation factor may easily exceed 10.sup.5. The separation is easily completed and the .sup.68 Ga made available in ionic form in 30 minutes or less.

Supercritical separation process for complex organic mixtures

DOEpatents

Chum, H.L.; Filardo, G.

1990-10-23

A process is disclosed for separating low molecular weight components from complex aqueous organic mixtures. The process includes preparing a separation solution of supercritical carbon dioxide with an effective amount of an entrainer to modify the solvation power of the supercritical carbon dioxide and extract preselected low molecular weight components. The separation solution is maintained at a temperature of at least about 70 C and a pressure of at least about 1,500 psi. The separation solution is then contacted with the organic mixtures while maintaining the temperature and pressure as above until the mixtures and solution reach equilibrium to extract the preselected low molecular weight components from the organic mixtures. Finally, the entrainer/extracted components portion of the equilibrium mixture is isolated from the separation solution. 1 fig.

Standard Electrode Potentials Involving Radicals in Aqueous Solution: Inorganic Radicals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Armstrong, David A.; Huie, Robert E.; Koppenol, Willem H.

2015-12-01

Recommendations are made for standard potentials involving select inorganic radicals in aqueous solution at 25 °C. These recommendations are based on a critical and thorough literature review and also by performing derivations from various literature reports. The recommended data are summarized in tables of standard potentials, Gibbs energies of formation, radical pK a’s, and hemicolligation equilibrium constants. In all cases, current best estimates of the uncertainties are provided. An extensive set of Data Sheets is appended that provide original literature references, summarize the experimental results, and describe the decisions and procedures leading to each of the recommendations

Ice crystallization in ultrafine water-salt aerosols: nucleation, ice-solution equilibrium, and internal structure.

PubMed

Hudait, Arpa; Molinero, Valeria

2014-06-04

Atmospheric aerosols have a strong influence on Earth's climate. Elucidating the physical state and internal structure of atmospheric aqueous aerosols is essential to predict their gas and water uptake, and the locus and rate of atmospherically important heterogeneous reactions. Ultrafine aerosols with sizes between 3 and 15 nm have been detected in large numbers in the troposphere and tropopause. Nanoscopic aerosols arising from bubble bursting of natural and artificial seawater have been identified in laboratory and field experiments. The internal structure and phase state of these aerosols, however, cannot yet be determined in experiments. Here we use molecular simulations to investigate the phase behavior and internal structure of liquid, vitrified, and crystallized water-salt ultrafine aerosols with radii from 2.5 to 9.5 nm and with up to 10% moles of ions. We find that both ice crystallization and vitrification of the nanodroplets lead to demixing of pure water from the solutions. Vitrification of aqueous nanodroplets yields nanodomains of pure low-density amorphous ice in coexistence with vitrified solute rich aqueous glass. The melting temperature of ice in the aerosols decreases monotonically with an increase of solute fraction and decrease of radius. The simulations reveal that nucleation of ice occurs homogeneously at the subsurface of the water-salt nanoparticles. Subsequent ice growth yields phase-segregated, internally mixed, aerosols with two phases in equilibrium: a concentrated water-salt amorphous mixture and a spherical cap-like ice nanophase. The surface of the crystallized aerosols is heterogeneous, with ice and solution exposed to the vapor. Free energy calculations indicate that as the concentration of salt in the particles, the advance of the crystallization, or the size of the particles increase, the stability of the spherical cap structure increases with respect to the alternative structure in which a core of ice is fully surrounded by solution. We predict that micrometer-sized particles and nanoparticles have the same equilibrium internal structure. The variation of liquid-vapor surface tension with solute concentration is a key factor in determining whether a solution-embedded ice core or vapor-exposed ice cap is the equilibrium structure of the aerosols. In agreement with experiments, we predict that the structure of mixed-phase HNO3-water particles, representative of polar stratospheric clouds, consists of an ice core surrounded by freeze-concentrated solution. The results of this work are important to determine the phase state and internal structure of sea spray ultrafine aerosols and other mixed-phase particles under atmospherically relevant conditions.

Development of tropine-salt aqueous two-phase systems and removal of hydrophilic ionic liquids from aqueous solution.

PubMed

Wu, Haoran; Yao, Shun; Qian, Guofei; Song, Hang

2016-08-26

A novel aqueous two-phase systems (ATPS) composed of a small molecule organic compound tropine and an organic or inorganic salt aqueous solution has been developed for the first time. The phase behavior of tropine-salt ATPS was systemically investigated and the phase equilibrium data were measured in different temperatures and concentrations and correlated by the Merchuk equation with satisfactory results. The detection of the conductivity and particle size proved the formation of micelle in the process of forming tropine-salt ATPS. The separation application of the ATPS was assessed with the removal of hydrophilic benzothiazolium-based ionic liquids (ILs) from aqueous solution. The result showed that ILs were effectively extracted into the top tropine-rich phase. Finally, ILs in the top tropine-rich phase were further separated by the means of adsorption-desorption with DM301 macroporous resin and ethanol. The method of novel tropine-salt ATPS combined with adsorption-desorption is demonstrated a promising alternative thought and approach for the removal or recovery of hydrophilic compounds from aqueous media and also could provide a potential application for bio-separation. Copyright © 2016. Published by Elsevier B.V.

Chemical and physical properties affecting strontium distribution coefficients of surficial-sediment samples at the Idaho National Engineering and Environmental Laboratory, Idaho

USGS Publications Warehouse

Liszewski, M.J.; Rosentreter, J.J.; Miller, Karl E.; Bartholomay, R.C.

2000-01-01

The U.S. Geological Survey and Idaho State University, in cooperation with the U.S. Department of Energy, conducted a study to determine strontium distribution coefficients (K(d)s) of surficial sediments at the Idaho National Engineering and Environmental Laboratory (INEEL). Batch experiments using synthesized aqueous solutions were used to determine K(d)s, which describe the distribution of a solute between the solution and solid phase, of 20 surficial-sediment samples from the INEEL. The K(d)s for the 20 surficial-sediment samples ranged from 36 to 275 ml/g. Many properties of both the synthesized aqueous solutions and sediments used in the experiments also were determined. Solution properties determined were initial and equilibrium concentrations of calcium, magnesium, and strontium, pH and specific conductance, and initial concentrations of potassium and sodium. Sediment properties determined were grain-size distribution, bulk mineralogy, whole-rock major-oxide and strontium and barium concentrations, and Brunauer-Emmett-Teller (BET) surface area. Solution and sediment properties were correlated with strontium K(d)s of the 20 surficial sediments using Pearson correlation coefficients. Solution properties with the strongest correlations with strontium K(d)s were equilibrium pH and equilibrium calcium concentration correlation coefficients, 0.6598 and -0.6518, respectively. Sediment properties with the strongest correlations with strontium K(d)s were manganese oxide (MnO), BET surface area, and the >4.75-mm-grain-size fraction correlation coefficients, 0.7054, 0.7022, and -0.6660, respectively. Effects of solution properties on strontium K(d)s were interpreted as being due to competition among similarly charged and sized cations in solution for strontium-sorption sites; effects of sediment properties on strontium K(d)s were interpreted as being surface-area related. Multivariate analyses of these solution and sediment properties resulted in r2 values of 0.8071 when all five properties were used and 0.8043 when three properties, equilibrium pH, MnO, and BET surface area, were used.

Gibbs Energy Changes during Cobalt Complexation: A Thermodynamics Experiment for the General Chemistry Laboratory

ERIC Educational Resources Information Center

DeGrand, Michael J.; Abrams, M. Leigh; Jenkins, Judith L.; Welch, Lawrence E.

2011-01-01

By adding a large quantity of Cl[superscript -] to an aqueous solution of CoCl[subscript 2][multiplied by]6H[subscript 2]O, a mixture containing a red octahedral cobalt complex and a blue tetrahedral complex is produced. When the solution temperature is modified, the equilibrium constant, K[subscript eq], of the complexation reaction is shifted…

Emulsification kinetics during quasi-miscible flow in dead-end pores

NASA Astrophysics Data System (ADS)

Broens, M.; Unsal, E.

2018-03-01

Microemulsions have found applications as carriers for the transport of solutes through various porous media. They are commonly pre-prepared in bulk form, and then injected into the medium. The preparation is done by actively mixing the surfactant, water and oil, and then allowing the mixture to stagnate until equilibrium is reached. The resulting microemulsion characteristics of the surfactant/oil/water system are studied at equilibrium conditions, and perfect mixing is assumed. But in applications like subsurface remediation and enhanced oil recovery, microemulsion formation may occur in the pore space. Surfactant solutions are injected into the ground to solubilize and/or mobilize the non-aqueous phase liquids (NAPLs) by in-situ emulsification. Flow dynamics and emulsification kinetics are coupled, which also contributes to in-situ mixing. In this study, we investigated the nature of such coupling for a quasi-miscible fluid system in a conductive channel with dead-end extensions. A microfluidic setup was used, where an aqueous solution of an anionic, internal olefin sulfonate 20-24 (IOS) surfactant was injected into n-decane saturated glass micromodel. The oil phase was coloured using a solvatochromatic dye allowing for direct visualization of the aqueous and oil phases as well as their microemulsions under fluorescent light. Presence of both conductive and stagnant dead-end channels in a single pore system made it possible to isolate different transport mechanisms from each other but also allowed to study the transitions from one to the other. In the conductive channel, the surfactant was carried with flow, and emulsification was controlled by the localized flow dynamics. In the stagnant zones, the driving force of the mass transfer was driven by the chemical concentration gradient. Some of the equilibrium phase behaviour characteristics of the surfactant/oil/water system were recognisable during the quasi-miscible displacement. However, the equilibrium tests alone were not sufficient to predict the emulsification process under dynamic conditions.

Equilibrium sorption and diffusion rate studies with halogenated organic chemical and sandy aquifer material

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ball, W.P.

1990-01-01

Concepts for rate limitation of sorptive uptake of hydrophobic organic solutes by aquifer solids are reviewed, emphasizing physical diffusion models and in the context of effects on contaminant transport. Data for the sorption of tetrachloroethene (PCE) and 1,2,4,5-tetrachlorobenzene (TeCB) on Borden sand are presented, showing that equilibrium is attained very slowly, requiring equilibration times on the order of tens of days for PCE and hundreds of days for TeCB. The rate of approach to equilibrium decreased with increasing particle size and sorption distribution coefficient, in accordance with retarded intragranular diffusion models. Pulverization of the samples significantly decreased the required timemore » to equilibrium without changing the sorption capacity of the solids. Batch sorption methodology was refined to allow accurate measurement of long-term distribution coefficients, using purified {sup 14}C-labelled solute spikes and sealed glass ampules. Sorption isotherms for PCE and TeCB were conducted with size fractions of Borden sand over four to five orders of magnitude in aqueous concentration, and were found to be slightly nonlinear (Freundlich exponent = 0.8). A concentrated set of data in the low concentration range (<50 ug/L) revealed that sorption in this range could be equally well described by a linear isotherm. Distribution coefficients of the two solutes with seven size fractions of Borden sand, measured at low concentration and at full equilibrium, were between seven and sixty times the value predicted on the basis of recent correlations with organic carbon content. Rate results for coarse size fractions support a simple pore diffusion model, with pore diffusion coefficients estimated to be approximately 3 {times} 10{sup {minus}8} cm{sup 2}/sec, more than 200{times} lower than the aqueous diffusivities.« less

Removal of Congo red dye from aqueous solutions using a halloysite-magnetite-based composite.

PubMed

Ferrarini, F; Bonetto, L R; Crespo, Janaina S; Giovanela, M

2016-01-01

Adsorption has been considered as one of the most effective methods to remove dyes from aqueous solutions due to its ease of operation, high efficiency and wide adaptability. In view of all these aspects, this study aimed to evaluate the adsorption capacity of a halloysite-magnetite-based composite in the removal of Congo red dye from aqueous solutions. The effects of stirring rate, pH, initial dye concentration and contact time were investigated. The results revealed that the adsorption kinetics followed the pseudo-second-order model, and equilibrium was well represented by the Brunauer-Emmett-Teller isotherm. The thermodynamic data showed that dye adsorption onto the composite was spontaneous and endothermic and occurred by physisorption. Finally, the composite could also be regenerated at least four times by calcination and was shown to be a promising adsorbent for the removal of this dye.

Formation of ion-pairs in aqueous solutions of diclofenac salts.

PubMed

Fini, A; Fazio, G; Gonzalez-Rodriguez, M; Cavallari, C; Passerini, N; Rodriguez, L

1999-10-05

In this work we studied the ability of the diclofenac anion to form ion-pairs in aqueous solution in the presence of organic and inorganic cations: ion-pairs have a polarity and hydrophobicity more suitable to the partition than each ion considered separately and can be extracted by a lipid phase. The cations considered were those of the organic bases diethylamine, diethanolamine, pyrrolidine, N-(2-hydroxyethyl) pyrrolidine and N-(2-hydroxyethyl) piperidine; the inorganic cations studied were Li(+), Na(+), K(+), Rb(+), Cs(+). Related to each cation we determined the equilibrium constant (K(XD)) for the ion-pair formation with the diclofenac anion in aqueous solution and the water/n-octanol partition coefficient (P(XD)) for each type of ion-pair formed. Among the alkali metal cations, only Li(+) shows some interaction with the diclofenac anion, in agreement with its physiological behaviour of increasing clearance during the administration of diclofenac. The influence of the ionic radius and desolvation enthalpy of the alkali metal cations on the ion-pair formation and partition was briefly discussed. Organic cations promote the formation of ion-pairs with the diclofenac anion better than the inorganic ones, and improve the partition of the ion-pair according to their hydrophobicity. The values of the equilibrium parameters for the formation and partition of ion-pairs are not high enough to allow the direct detection of their presence in the aqueous solution. Their formation can be appreciated in the presence of a lipid phase that continuously extracts the ion-pair. Extraction constants (E(XD)=P(XD) times K(XD)) increase passing from inorga to organic cations. This study could help to clarify the mechanism of the percutaneous absorption of diclofenac in the form of a salt, a route where the formation of ion-pairs appears to play an important role.

Transfer Kinetics at the Aqueous/Non-Aqueous Phase Liquid Interface. A Statistical Mechanic Approach

NASA Astrophysics Data System (ADS)

Doss, S. K.; Ezzedine, S.; Ezzedine, S.; Ziagos, J. P.; Hoffman, F.; Gelinas, R. J.

2001-05-01

Many modeling efforts in the literature use a first-order, linear-driving-force model to represent the chemical dissolution process at the non-aqueous/aqueous phase liquid (NAPL/APL) interface. In other words, NAPL to APL phase flux is assumed to be equal to the difference between the solubility limit and the "bulk aqueous solution" concentrations times a mass transfer coefficient. Under such assumptions, a few questions are raised: where, in relation to a region of pure NAPL, does the "bulk aqueous solution" regime begin and how does it behave? The answers are assumed to be associated with an arbitrary, predetermined boundary layer, which separates the NAPL from the surrounding solution. The mass transfer rate is considered to be, primarily, limited by diffusion of the component through the boundary layer. In fact, compositional models of interphase mass transfer usually assume that a local equilibrium is reached between phases. Representing mass flux as a rate-limiting process is equivalent to assuming diffusion through a stationary boundary layer with an instantaneous local equilibrium and linear concentration profile. Some environmental researchers have enjoyed success explaining their data using chemical engineering-based correlations. Correlations are strongly dependent on the experimental conditions employed. A universally applicable theory for NAPL dissolution in natural systems does not exist. These correlations are usually expressed in terms of the modified Sherwood number as a function of Reynolds, Peclet, and Schmidt numbers. The Sherwood number may be interpreted as the ratio between the grain size and the thickness of the Nernst stagnant film. In the present study, we show that transfer kinetics at the NAPL/APL interface under equilibrium conditions disagree with approaches based on the Nernst stagnant film concept. It is unclear whether local equilibrium assumptions used in current models are suitable for all situations.A statistical mechanic framework has been chosen to study the transfer kinetic processes at the microscale level. The rationale for our approach is based on both the activation energy of transfer of an ion and its velocity across the NAPL/APL interface. There are four major energies controlling the interfacial NAPL dissolution kinetics: (de)solvation energy, interfacial tension energy, electrostatic energy, and thermal fluctuation energy. Transfer of an ion across the NAPL/APL interface is accelerated by the viscous forces which can be described using the averaged Langevin master equation. The resulting energies and viscous forces were combined using the Boltzmann probability distribution. Asymptotic time limits of the resulting kinetics lead to instantaneous local equilibrium conditions that contradict the Nernst equilibrium equation. The NAPL/APL interface is not an ideal one: it does not conserve energy and heat. In our case the interface is treated as a thin film or slush zone that alters the thermodynamic variables. Such added zone, between the two phases, is itself a phase, and, therefore, the equilibrium does not occur between two phases but rather three. All these findings led us to develop a new non-linearly coupled flow and transport system of equations which is able to account for specific chemical dissolution processes and precludes the need for empirical mass-transfer parameters. Work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract W-7405-Eng-48.

Adsorption of methyl orange from aqueous solution using chitosan/diatomite composite.

PubMed

Zhao, Peng; Zhang, Runhu; Wang, Jianglin

2017-04-01

A novel chitosan/diatomite composite was prepared by a simple mixture in the mass ratio to remove methyl orange (MO) from aqueous media in this study. The composite adsorbent was characterized by Fourier transform infrared spectroscopy and scanning electron microscopy analysis. The parameters to influence the adsorption of MO were studied under such conditions as kinetics, adsorption isotherm, pH effect, and thermodynamics. The results revealed that adsorption of MO was initially rapid and the equilibrium time was reached after 40 min. The optimal value of the pH was 5.0 for better adsorption. The equilibrium data were well fitted to the Langmuir isotherm compared to the Freundlich isotherm, and exhibited the highest capacity and a removal rate of 88.37% under an initial dye concentration of 50 mg/L. The kinetic data were well described by the pseudo-second order model. The thermodynamic calculations revealed that the sorption was viable, spontaneous, and exothermic under the conditions studied. In addition, the chitosan/diatomite composite had good adsorption and desorption performance with respect to reusability after six cycles. These results showed that the chitosan/diatomite could be considered as a potential adsorbent for the removal of MO in aqueous solution.

Biosorption of neodymium on Chlorella vulgaris in aqueous solution obtained from hard disk drive magnets

PubMed Central

Kucuker, Mehmet Ali; Wieczorek, Nils; Kuchta, Kerstin; Copty, Nadim K.

2017-01-01

In recent years, biosorption is being considered as an environmental friendly technology for the recovery of rare earth metals (REE). This study investigates the optimal conditions for the biosorption of neodymium (Nd) from an aqueous solution derived from hard drive disk magnets using green microalgae (Chlorella vulgaris). The parameters considered include solution pH, temperature and biosorbent dosage. Best-fit equilibrium as well as kinetic biosorption models were also developed. At the optimal pH of 5, the maximum experimental Nd uptakes at 21, 35 and 50°C and an initial Nd concentration of 250 mg/L were 126.13, 157.40 and 77.10 mg/g, respectively. Analysis of the optimal equilibrium sorption data showed that the data fitted well (R2 = 0.98) to the Langmuir isotherm model, with maximum monolayer coverage capacity (qmax) of 188.68 mg/g, and Langmuir isotherm constant (KL) of 0.029 L/mg. The corresponding separation factor (RL) is 0.12 indicating that the equilibrium sorption was favorable. The sorption kinetics of Nd ion follows well a pseudo-second order model (R2>0.99), even at low initial concentrations. These results show that Chlorella vulgaris has greater biosorption affinity for Nd than activated carbon and other algae types such as: A. Gracilis, Sargassum sp. and A. Densus. PMID:28388641

Ammonium Removal from Aqueous Solutions by Clinoptilolite: Determination of Isotherm and Thermodynamic Parameters and Comparison of Kinetics by the Double Exponential Model and Conventional Kinetic Models

PubMed Central

Tosun, İsmail

2012-01-01

The adsorption isotherm, the adsorption kinetics, and the thermodynamic parameters of ammonium removal from aqueous solution by using clinoptilolite in aqueous solution was investigated in this study. Experimental data obtained from batch equilibrium tests have been analyzed by four two-parameter (Freundlich, Langmuir, Tempkin and Dubinin-Radushkevich (D-R)) and four three-parameter (Redlich-Peterson (R-P), Sips, Toth and Khan) isotherm models. D-R and R-P isotherms were the models that best fitted to experimental data over the other two- and three-parameter models applied. The adsorption energy (E) from the D-R isotherm was found to be approximately 7 kJ/mol for the ammonium-clinoptilolite system, thereby indicating that ammonium is adsorbed on clinoptilolite by physisorption. Kinetic parameters were determined by analyzing the nth-order kinetic model, the modified second-order model and the double exponential model, and each model resulted in a coefficient of determination (R2) of above 0.989 with an average relative error lower than 5%. A Double Exponential Model (DEM) showed that the adsorption process develops in two stages as rapid and slow phase. Changes in standard free energy (∆G°), enthalpy (∆H°) and entropy (∆S°) of ammonium-clinoptilolite system were estimated by using the thermodynamic equilibrium coefficients. PMID:22690177

Ammonium removal from aqueous solutions by clinoptilolite: determination of isotherm and thermodynamic parameters and comparison of kinetics by the double exponential model and conventional kinetic models.

PubMed

Tosun, Ismail

2012-03-01

The adsorption isotherm, the adsorption kinetics, and the thermodynamic parameters of ammonium removal from aqueous solution by using clinoptilolite in aqueous solution was investigated in this study. Experimental data obtained from batch equilibrium tests have been analyzed by four two-parameter (Freundlich, Langmuir, Tempkin and Dubinin-Radushkevich (D-R)) and four three-parameter (Redlich-Peterson (R-P), Sips, Toth and Khan) isotherm models. D-R and R-P isotherms were the models that best fitted to experimental data over the other two- and three-parameter models applied. The adsorption energy (E) from the D-R isotherm was found to be approximately 7 kJ/mol for the ammonium-clinoptilolite system, thereby indicating that ammonium is adsorbed on clinoptilolite by physisorption. Kinetic parameters were determined by analyzing the nth-order kinetic model, the modified second-order model and the double exponential model, and each model resulted in a coefficient of determination (R(2)) of above 0.989 with an average relative error lower than 5%. A Double Exponential Model (DEM) showed that the adsorption process develops in two stages as rapid and slow phase. Changes in standard free energy (∆G°), enthalpy (∆H°) and entropy (∆S°) of ammonium-clinoptilolite system were estimated by using the thermodynamic equilibrium coefficients.

Comment on “Hydromagnesite solubility product and growth kinetics in aqueous solution from 25 to 75 °C” by Gautier, Q., Benezeth, P., Mavromatis, V., and Schott, J

DOE PAGES

Xiong, Yongliang

2016-04-16

Here, Gautier et al. (2014) recently published their determination of hydromagnesite solubility constant and hydromagnesite growth kinetics. Although their raw data appear to be of high quality, there is an oversight in their calculations of the hydromagnesite solubility constants given the solution compositions in their experiments. The oversight lies in the fact that they did not consider the constraint of simultaneous equilibrium with brucite. This oversight causes their newly calculated equilibrium constant for hydromagnesite to be discordant with the literature values (Königsberger et al., 1992 and Xiong, 2011).

In vitro dynamic swelling behaviors of radiation synthesized polyacrylamide with crosslinkers in the simulated physiological body fluids

NASA Astrophysics Data System (ADS)

Saraydın, Dursun; Işıkver, Yasemin; Karadağ, Erdener; Sahiner, Nurettin; Güven, Olgun

2002-03-01

Acrylamide hydrogels, containing different amounts and types of crosslinkers, were synthesized via γ-irradiation technique. Their swellings in simulated body fluids, such as physiological saline (0.89% NaCl) isoosmotic phosphate buffer at pH 7.4, gastric fluid at pH 1.1 (glycine-HCl), protein (aqueous solution of bovine serum albumin), urine (aqueous solution of urea), glucose and distilled water, were studied. Equilibrium swellings of the hydrogels were changed in the range 27-85 depending upon the fluids, type and amount of crosslinkers. The diffusion exponents were found over half for all hydrogels.

Standard electrode potentials involving radicals in aqueous solution: inorganic radicals (IUPAC Technical Report)

DOE PAGES

Armstrong, David A.; Huie, Robert E.; Koppenol, Willem H.; ...

2015-01-01

We made recommendations for standard potentials involving select inorganic radicals in aqueous solution at 25 °C. These recommendations are based on a critical and thorough literature review and also by performing derivations from various literature reports. We also summarized the data in tables of standard potentials, Gibbs energies of formation, radical pKa’s, and hemicolligation equilibrium constants. In all cases, current best estimates of the uncertainties are provided. An extensive set of Data Sheets is appended that provide original literature references, summarize the experimental results, and describe the decisions and procedures leading to each of the recommendations.

Characterizations of strontium(II) and barium(II) adsorption from aqueous solutions using dolomite powder.

PubMed

Ghaemi, Ahad; Torab-Mostaedi, Meisam; Ghannadi-Maragheh, Mohammad

2011-06-15

In this research, adsorption technique was applied for strontium and barium removal from aqueous solution using dolomite powder. The process has been investigated as a function of pH, contact time, temperature and adsorbate concentration. The experimental data was analyzed using equilibrium isotherm, kinetic and thermodynamic models. The isotherm data was well described by Langmuir isotherm model. The maximum adsorption capacity was found to be 1.172 and 3.958 mg/g for Sr(II) and Ba(II) from the Langmuir isotherm model at 293 K, respectively. The kinetic data was tested using first and pseudo-second order models. The results indicated that adsorption fitted well with the pseudo-second order kinetic model. The thermodynamic parameters (ΔG°, ΔH°, and ΔS°) were also determined using the equilibrium constant value obtained at different temperatures. The results showed that the adsorption for both ions was feasible and exothermic. Copyright © 2011 Elsevier B.V. All rights reserved.

Adsorption of Ag (I) from aqueous solution by waste yeast: kinetic, equilibrium and mechanism studies.

PubMed

Zhao, Yufeng; Wang, Dongfang; Xie, Hezhen; Won, Sung Wook; Cui, Longzhe; Wu, Guiping

2015-01-01

One type of biosorbents, brewer fermentation industry waste yeast, was developed to adsorb the Ag (I) in aqueous solution. The result of FTIR analysis of waste yeast indicated that the ion exchange, chelating and reduction were the main binding mechanisms between the silver ions and the binding sites on the surface of the biomass. Furthermore, TEM, XRD and XPS results suggested that Ag(0) nanoparticles were deposited on the surface of yeast. The kinetic experiments revealed that sorption equilibrium could reach within 60 min, and the removal efficiency of Ag (I) could be still over 93 % when the initial concentration of Ag (I) was below 100 mg/L. Thermodynamic parameters of the adsorption process (ΔG, ΔH and ΔS) identified that the adsorption was a spontaneous and exothermic process. The waste yeast, playing a significant role in the adsorption of the silver ions, is useful to fast adsorb Ag (I) from low concentration.

Cow bones char as a green sorbent for fluorides removal from aqueous solutions: batch and fixed-bed studies.

PubMed

Nigri, Elbert M; Cechinel, Maria Alice P; Mayer, Diego A; Mazur, Luciana P; Loureiro, José M; Rocha, Sônia D F; Vilar, Vítor J P

2017-01-01

Cow bone char was investigated as sorbent for the defluoridation of aqueous solutions. The cow bone char was characterized in terms of its morphology, chemical composition, and functional groups present on the bone char surface using different analytical techniques: SEM, EDS, N 2 -BET method, and FTIR. Batch equilibrium studies were performed for the bone chars prepared using different procedures. The highest sorption capacities for fluoride were obtained for the acid washed (q = 6.2 ± 0.5 mg/g) and Al-doped (q = 6.4 ± 0.3 mg/g) bone chars. Langmuir and Freundlich models fitted well the equilibrium sorption data. Fluoride removal rate in batch system is fast in the first 5 h, decreasing after this time until achieving equilibrium due to pore diffusion. The presence of carbonate and bicarbonate ions in the aqueous solution contributes to a decrease of the fluoride sorption capacity of the bone char by 79 and 31 %, respectively. Regeneration of the F-loaded bone char using 0.5 M NaOH solution leads to a sorption capacity for fluoride of 3.1 mg/g in the second loading cycle. Fluoride breakthrough curve obtained in a fixed-bed column presents an asymmetrical S-shaped form, with a slow approach of C/C 0  → 1.0 due to pore diffusion phenomena. Considering the guideline value for drinking water of 1.5 mg F - /L, as recommended by World Health Organization, the service cycle for fluoride removal was of 71.0 h ([F - ] feed  ∼ 9 mg/L; flow rate = 1 mL/min; m sorbent  = 12.6 g). A mass transfer model considering the pore diffusion was able to satisfactorily describe the experimental data obtained in batch and continuous systems.

Rheology of Self-Assembling Silk Fibroin Solutions

NASA Astrophysics Data System (ADS)

Zhou, Rui; Chen, Song-Bi; Yuan, Xue-Feng

2008-07-01

A robust procedure for preparation of aqueous silk fibroin solutions with a range of concentration up to 25 wt% from domestic Bombyx mori cocoon shells has been established. We have carried out molecular and rheometric characterizations of silk fibroin solutions, and constructed an equilibrium phase diagram. The sharp sol-gel transition can be exploited for rapid solidification of micro-morphological structure. We will discuss the correlations between fluid formulation, rheological properties and processibility of silk fibroin in the talk.

[Adsorption of Congo red from aqueous solution on hydroxyapatite].

PubMed

Zhan, Yan-Hui; Lin, Jian-Wei

2013-08-01

The adsorption of Congo red (CR) from aqueous solution on hydroxyapatite was investigated using batch experiments. The hydroxyapatite was effective for CR removal from aqueous solution. The adsorption kinetics of CR on hydroxyapatite well followed a pseudo-second-order model. The equilibrium adsorption data of CR on hydroxyapatite could be described by the Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherm models. Thermodynamic parameters such as Gibbs free energy change, enthalpy change and entropy change were calculated and showed that the adsorption of CR on hydroxyapatite was spontaneous and exothermic in nature. The CR adsorption capacity for hydroxyapatite decreased significantly with increasing pH from 8 to 10. Thermal regeneration showed that hydroxyapatite could be used for six desorption-adsorption cycles with high removal efficiency for CR in each cycle. The mechanisms for CR adsorption on hydroxyapatite with pH value below the pH at point of zero charge (pH(PZC)) include electrostatic attraction, hydrogen bonding and Lewis acid-base interaction. The mechanisms for CR adsorption on hydroxyapatite with pH value above its pH(PZC) include hydrogen bonding and Lewis acid-base interaction. Results of this work indicate that hydroxyapatite is a promising adsorbent for CR removal from aqueous solution.

Metal-organic complexes in geochemical processes: Estimation of standard partial molal thermodynamic properties of aqueous complexes between metal cations and monovalent organic acid ligands at high pressures and temperatures

NASA Astrophysics Data System (ADS)

Shock, Everetr L.; Koretsky, Carla M.

1995-04-01

Regression of standard state equilibrium constants with the revised Helgeson-Kirkham-Flowers (HKF) equation of state allows evaluation of standard partial molal entropies ( overlineSo) of aqueous metal-organic complexes involving monovalent organic acid ligands. These values of overlineSo provide the basis for correlations that can be used, together with correlation algorithms among standard partial molal properties of aqueous complexes and equation-of-state parameters, to estimate thermodynamic properties including equilibrium constants for complexes between aqueous metals and several monovalent organic acid ligands at the elevated pressures and temperatures of many geochemical processes which involve aqueous solutions. Data, parameters, and estimates are given for 270 formate, propanoate, n-butanoate, n-pentanoate, glycolate, lactate, glycinate, and alanate complexes, and a consistent algorithm is provided for making other estimates. Standard partial molal entropies of association ( Δ -Sro) for metal-monovalent organic acid ligand complexes fall into at least two groups dependent upon the type of functional groups present in the ligand. It is shown that isothermal correlations among equilibrium constants for complex formation are consistent with one another and with similar correlations for inorganic metal-ligand complexes. Additional correlations allow estimates of standard partial molal Gibbs free energies of association at 25°C and 1 bar which can be used in cases where no experimentally derived values are available.

Determination of acidity constants of curcumin in aqueous solution and apparent rate constant of its decomposition

NASA Astrophysics Data System (ADS)

Bernabé-Pineda, Margarita; Ramírez-Silva, María. Teresa; Romero-Romo, Mario; González-Vergara, Enrique; Rojas-Hernández, Alberto

2004-04-01

The stability of curcumin (H 3Cur) in aqueous media is improved when the systems in which it is present are at high pH values (higher than 11.7), fitting a model describable by a pseudo-zero order with a rate constant k' for the disappearance of the Cur 3- species of 1.39 (10 -9) M min -1. There were three acidity constants measured for the curcumin as follows: p KA3=10.51±0.01 corresponding to the equilibrium HCur 2-=Cur 3-+H +, a p KA2=9.88±0.02 corresponding to the equilibrium H 2Cur -=HCur -2+H +. These p KA values were attributed to the hydrogen of the phenol part of the curcumin, while the p KA1=8.38±0.04 corresponds to the equilibrium H 3Cur=H 2Cur -+H + and is attributed the acetylacetone type group. Formation of quinoid structures play an important role in the tautomeric forms of the curcumin in aqueous media, which makes the experimental values differ from the theoretically calculated ones, depending on the conditions adopted in the study.

Calcium Isotope Geochemistry: Research Horizons and Nanoscale Fractionation Processes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, W; Simon, J I; DePaolo, D J

Interest in studies of calcium isotope variations in nature continues to increase. Investigations span human biology, plants and soils, oceanography and paleoclimate, early solar system processes, aqueous geochemistry, and silicate liquid structure. Variations in the 44Ca/40Ca ratio are generally small, about 5 {per_thousand}, but gradual small improvements in analytical capability now yield 0.05 to 0.1 {per_thousand} resolution. The field is still plagued by a lack of universal standards for isotope ratios and data representation, but these are secondary issues. Traditional isotopic systems have been based in equilibrium thermodynamics, which can explain the magnitude and sign of observed mass-dependent fractionation behavior.more » For Ca isotopes this is not the case. There is still no reliable way to estimate the equilibrium free energy associated with isotopic exchange between most phases of interest. Experiments are difficult to interpret because it is almost impossible to precipitate minerals from aqueous solution at equilibrium at low temperature. Some studies suggest that, for example, there is no equilibrium isotopic fractionation between calcite and dissolved aqueous Ca. There is good evidence that most Ca isotopic fractionation is caused by kinetic effects. The details of the controlling processes are still missing, and without this mechanistic understanding it is difficult to fully understand the implications of natural isotopic variations. Recent work on dissolved Ca, calcite, and sulfates in both laboratory and natural settings is shedding light on where the fractionation may arise. There is emerging evidence for mass dependent fractionation associated with aqueous diffusion, but probably the primary source of the effects is in the details of precipitation of minerals from solution. This makes the fractionation potentially dependent on a number of factors, including solution composition and mineral growth rate. The next challenge is to develop appropriate experimental tests and combine them with micro- and nano-scale characterization, and to capture the critical processes in mathematical models. Some of the largest fractionation effects have been observed for silicate liquids, where both chemical and thermal diffusion generate large isotopic variations. Intake and transport of Ca in plants is also associated with substantial fractionation. Continuing work is beginning to place the fractionation into the context of global Ca cycles.« less

Evaluation of BTEX and phenol removal from aqueous solution by multi-solute adsorption onto smectite organoclay.

PubMed

Carvalho, M N; da Motta, M; Benachour, M; Sales, D C S; Abreu, C A M

2012-11-15

The removal process of BTEX and phenol was evaluated. The smectite organoclay for single-solute system reached removal was evaluated by adsorption on smectite organoclay adsorbent by kinetic and equilibrium efficiencies between 55 and 90% while was reached between 30 and 90% for multi-solute system at 297 K and pH 9. The Langmuir-Freundlich model was used to fit the experimental data with correlation coefficient between 0.98 and 0.99 providing kinetic and equilibrium parameter values. Phenol and ethylbenzene presented high maximum adsorbed amount, 8.28 and 6.67 mg/g, respectively, compared to the other compounds for single-solute. Toluene and p-xylene presented high values of adsorption constant which indicates a high adsorption affinity of compounds to organoclay surface and high binding energy of adsorption. Phenol presented low kinetic adsorption constant value indicating slow rate of adsorption. Copyright © 2012 Elsevier B.V. All rights reserved.

Removal of selected pharmaceuticals from aqueous solution using magnetic chitosan: sorption behavior and mechanism.

PubMed

Zhang, Yalei; Shen, Zhe; Dai, Chaomeng; Zhou, Xuefei

2014-11-01

A novel-modified magnetic chitosan adsorbent was used to remove selected pharmaceuticals, i.e., diclofenac (DCF) and clofibric acid (CA) and carbamazepine (CBZ), from aqueous solutions. The characterization of magnetic chitosan was achieved by scanning electron and transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, vibrating sample magnetometer, and nitrogen sorption analysis. The magnetic chitosan had effective sorption affinity for DCF and CA but no sorption of CBZ was observed. The sorption capacities of CA and DCF in the individual solutions were 191.2 and 57.5 mg/g, respectively. While in mixed solution, DCF showed higher sorption affinity. Sorption kinetics indicated a quick equilibrium reached within 2 min. Lower solution pH values were found to be advantageous for the adsorption process. The sorption efficacy of CA declined significantly with increasing inorganic salt concentration. However, sorption performance of DCF was stable under different ionic strength conditions.

Effect of solute nature on the polyamorphic transition in glassy polyol aqueous solutions.

PubMed

Suzuki, Yoshiharu

2017-08-14

I examined the polyamorphic behavior of glassy dilute aqueous solutions of polyols (ethylene glycol, glycerol, meso-erythritol, xylitol, and D-sorbitol) under pressure at low temperatures. Although the volume change of the glassy aqueous solution varied continuously against pressure, the rate of the volume change appeared to vary discontinuously at the onset pressure of the gradual polyamorphic transition. It is thought that low-density liquid-like solvent water and high-density liquid-like solvent water coexist during the transition. Moreover, the existence of a solute induces the shift of polyamorphic transition to the lower-pressure side. The effect of a solute on the polyamorphic transition becomes larger in the order ethylene glycol, glycerol, meso-erythritol, xylitol, and D-sorbitol. Therefore, the solute can become a variable controlling the polyamorphic state of liquid water. This experimental result suggests that the metastable-equilibrium phase boundary between the low-density and the high-density amorphs for pure water is likely to be located at 0.22-0.23 GPa at about 150 K, which is slightly larger than the previously estimated pressure. Moreover, the solute-nature dependence on the polyamorphic transition seems to connect to that on the homogeneous nucleation temperature of polyol aqueous solution at ambient pressure. The region in which a low-density liquid appears coincides with the region in which the nucleus of ice Ih appears, suggesting that the formation of a low-density liquid is a precursory phenomenon of the nucleation of ice Ih.

Effect of solute nature on the polyamorphic transition in glassy polyol aqueous solutions

NASA Astrophysics Data System (ADS)

Suzuki, Yoshiharu

2017-08-01

I examined the polyamorphic behavior of glassy dilute aqueous solutions of polyols (ethylene glycol, glycerol, meso-erythritol, xylitol, and D-sorbitol) under pressure at low temperatures. Although the volume change of the glassy aqueous solution varied continuously against pressure, the rate of the volume change appeared to vary discontinuously at the onset pressure of the gradual polyamorphic transition. It is thought that low-density liquid-like solvent water and high-density liquid-like solvent water coexist during the transition. Moreover, the existence of a solute induces the shift of polyamorphic transition to the lower-pressure side. The effect of a solute on the polyamorphic transition becomes larger in the order ethylene glycol, glycerol, meso-erythritol, xylitol, and D-sorbitol. Therefore, the solute can become a variable controlling the polyamorphic state of liquid water. This experimental result suggests that the metastable-equilibrium phase boundary between the low-density and the high-density amorphs for pure water is likely to be located at 0.22-0.23 GPa at about 150 K, which is slightly larger than the previously estimated pressure. Moreover, the solute-nature dependence on the polyamorphic transition seems to connect to that on the homogeneous nucleation temperature of polyol aqueous solution at ambient pressure. The region in which a low-density liquid appears coincides with the region in which the nucleus of ice Ih appears, suggesting that the formation of a low-density liquid is a precursory phenomenon of the nucleation of ice Ih.

Ni(II) removal from aqueous solutions using cone biomass of Thuja orientalis.

PubMed

Malkoc, Emine

2006-09-21

The biomass of terrestrial-plant materials has high removal capacities for a number of heavy metal ions. The Ni(II) biosorption capacity of the cone biomass of Thuja orientalis was studied in the batch mode. The biosorption equilibrium level was determined as a function of contact time, pH, temperature, agitation speed at several initial metal ion and adsorbent concentrations. The removal of Ni(II) from aqueous solutions increased with adsorbent concentration, temperature and agitation speed of the solution were increased. The biosorption process was very fast; 90% of biosorption occurred within 3 min and equilibrium was reached at around 7 min. It is found that the biosorption of Ni(II) on the cone biomass was correlated well (R2 > 0.99) with the Langmuir equation as compared to Freundlich, BET Temkin and D-R isotherm equation under the concentration range studied. According to Langmuir isotherm, the monolayer saturation capacity (Q(o)) is 12.42 mg g(-1). The pseudo-first-order, pseudo-second-order and intraparticle diffusion kinetic models were applied to test the experimental data for initial Ni(II) and cone biomass concentrations. The pseudo-second-order kinetic model provided the best correlation of the used experimental data compared to the pseudo-first-order and intraparticle diffusion kinetic models. The activation energy of biosorption (E(a)) was determined as 36.85 kJ mol(-1) using the Arrhenius equation. This study indicated that the cone biomass of T. orientalis can be used as an effective and environmentally friendly adsorbent for the treatment of Ni(II) containing aqueous solutions.

Uptake of Cr3+ from aqueous solution by lignite-based humic acids.

PubMed

Arslan, G; Pehlivan, E

2008-11-01

Humic acid (HA) produced from brown coal, a relatively abundant and inexpensive material is currently being investigated as an adsorbent to remove toxic metals from aqueous solution. The influence of five parameters (contact time, solution pH, initial metal concentration, temperature and amount of adsorbent) on the removal at 20+/-1 degrees C was studied. HAs were prepared from lignites by using alkaline extraction, sedimentation and acidic precipitation. Adsorption equilibrium was achieved in about 60 min for Cr3+ ion. The Langmuir adsorption isotherm was used to describe observed sorption phenomena. The maximum adsorption capacity of 0.17 mmol for Ilgin (HA1), 0.29 mmol for Beysehir (HA2) and 0.18 mmol Ermenek (HA3) and 0.17 mmol of Cr3+/g for activated carbon (AC) was achieved, respectively at pH of 4.1. More than 84% of Cr3+ was removed by HA2, 54% by HA3 and 51% by HA1 and 50% by AC from aqueous solution. The adsorption was strongly dependent on pH but independent of ionic strength and metal ions. The adsorption of Cr3+ was higher between pH 4.1 and 5.1 for all HAs and maximum sorption was observed at pH 4.1. The rise in temperature caused a slight decrease in the value of the equilibrium constant (Kc) for the sorption of Cr3+ ion. Complex mechanisms including ion exchange, complexation and adsorption and size exclusion are possible for sorption of Cr3+ ion on HAs.

Comparative thermodynamic studies of aqueous glutaric acid, ammonium sulfate and sodium chloride aerosol at high humidity.

PubMed

Hanford, Kate L; Mitchem, Laura; Reid, Jonathan P; Clegg, Simon L; Topping, David O; McFiggans, Gordon B

2008-10-02

Aerosol optical tweezers are used to simultaneously characterize and compare the hygroscopic properties of two aerosol droplets, one containing inorganic and organic solutes and the second, referred to as the control droplet, containing a single inorganic salt. The inorganic solute is either sodium chloride or ammonium sulfate and the organic component is glutaric acid. The time variation in the size of each droplet (3-7 microm in radius) is recorded with 1 s time resolution and with nanometre accuracy. The size of the control droplet is used to estimate the relative humidity with an accuracy of better than +/-0.09%. Thus, the Kohler curve of the multicomponent inorganic/organic droplet, which characterizes the variation in equilibrium droplet size with relative humidity, can be determined directly. The measurements presented here focus on high relative humidities, above 97%, in the limit of dilute solutes. The experimental data are compared with theoretical treatments that, while ignoring the interactions between the inorganic and organic components, are based upon accurate representations of the activity-concentration relationships of aqueous solutions of the individual salts. The organic component is treated by a parametrized fit to experimental data or by the UNIFAC model and the water activity of the equilibrium solution droplet is calculated using the approach suggested by Clegg, Seinfeld and Brimblecombe or the Zdanovskii-Stokes-Robinson approximation. It is shown that such an experimental strategy, comparing directly droplets of different composition, enables highly accurate measurements of the hygroscopic properties, allowing the theoretical treatments to be rigorously tested. Typical deviations of the experimental measurements from theoretical predictions are shown to be around 1% in equilibrium size, comparable to the variation between the theoretical frameworks considered.

Solubilizing properties of new surface-active agents, products of catalytic oxyethylation of cholic acid.

PubMed

Kołodziejczyk, Michał Krzysztof; Nachajski, Michal Jakub; Lukosek, Marek; Zgoda, Marian Mikołaj

2013-01-01

Solubilizing properties of aqueous solutions of a series of surface-active agents, products of oxyethylation of cholic acid, were examined in the present study. The content of oxyethylated segments determined by means of the 1H NMR method enabled the verification of the molecular mass of surfactants along with the calculation of the structural hydrophilic-lipophilic balance (HLB), the solubility parameter delta1/2, and the required solubility level of balance HLB(R). Viscosimetric measurements enabled the calculation of the limiting viscosity number, the content-average molecular mass, the effective volume, the hydrodynamic radius of the surfactant micelle and their equilibrium adducts with rutin, diclofenac and loratadine (BCS Class II and III). By means of the spectrophotometric method (UV) the amount of the solubilized diclofenac, loratadine and rutin (rutoside) was determined in the equilibrium system (saturated solution) in the environment of aqueous solutions of cholic acid derivatives of n(TE) = 20-70. The obtained results serve as a basis for determining the solubilization mechanism of lipophilic therapeutic products and indirectly for estimating the influence of the above process on pharmaceutical as well as biological availability of a micellar adduct from model drug forms (Lindbladt lithogenolitic index).

Association of riboflavin, caffeine, and sodium salicylate in aqueous solution

NASA Astrophysics Data System (ADS)

Baranovskii, S. F.; Bolotin, P. A.

2007-03-01

We have used UV and visible spectrophotometry to study self-association of aromatic riboflavin molecules (RFN, vitamin B2, 7,8-dimethyl-10-N-(1'-D-ribityl)isoalloxazine) in aqueous solution (pH 6.86) at T = 298 K, using a dimer model. We have determined the equilibrium dimerization constant for riboflavin, KdB = 125 ± 40 M-1. We have studied heteroassociation in the system of molecules of 7,8-dimethyl-10-ribitylisoalloxazine with 1,3,7-trimethylxanthine (caffeine) and sodium salicylate (NAS) in aqueous solution (pH 6.86; T = 298 K). We have determined the heteroassociation constants for RFN-NAS and RFN-caffeine molecules in the absence and in the presence of urea in solutions using a modified Benesi-Hildebrand equation: 25 ± 4, 17 ± 3, and 74 ± 11, 53 ± 7 M-1 respectively. We have determined the dimerization constants for NAS (2.7 ± 0.5 M-1) and caffeine (17.0 ± 1.5 M-1). We conclude that heteroassociation of the aromatic molecules leads to a lower effective riboflavin concentration in solution, and the presence of urea in mixed solutions leads to an decrease in the complexation constants for the RFN-NAS and RFN-caffeine systems.

Equivalent Aqueous Phase Modulation of Domain Segregation in Myelin Monolayers and Bilayer Vesicles

PubMed Central

Oliveira, Rafael G.; Schneck, Emanuel; Funari, Sergio S.; Tanaka, Motomu; Maggio, Bruno

2010-01-01

Purified myelin can be spread as monomolecular films at the air/aqueous interface. These films were visualized by fluorescence and Brewster angle microscopy, showing phase coexistence at low and medium surface pressures (<20–30 mN/m). Beyond this threshold, the film becomes homogeneous or not, depending on the aqueous subphase composition. Pure water as well as sucrose, glycerol, dimethylsulfoxide, and dimethylformamide solutions (20% in water) produced monolayers that become homogeneous at high surface pressures; on the other hand, the presence of salts (NaCl, CaCl2) in Ringer's and physiological solution leads to phase domain microheterogeneity over the whole compression isotherm. These results show that surface heterogeneity is favored by the ionic milieu. The modulation of the phase-mixing behavior in monolayers is paralleled by the behavior of multilamellar vesicles as determined by small-angle and wide-angle x-ray scattering. The correspondence of the behavior of monolayers and multilayers is achieved only at high surface pressures near the equilibrium adsorption surface pressure; at lower surface pressures, the correspondence breaks down. The equilibrium surface tension on all subphases corresponds to that of the air/alkane interface (27 mN/m), independently on the surface tension of the clean subphase. PMID:20816062

Predicting the equilibrium solubility of solid polycyclic aromatic hydrocarbons and dibenzothiophene using a combination of MOSCED plus molecular simulation or electronic structure calculations

NASA Astrophysics Data System (ADS)

Phifer, Jeremy R.; Cox, Courtney E.; da Silva, Larissa Ferreira; Nogueira, Gabriel Gonçalves; Barbosa, Ana Karolyne Pereira; Ley, Ryan T.; Bozada, Samantha M.; O'Loughlin, Elizabeth J.; Paluch, Andrew S.

2017-06-01

Methods to predict the equilibrium solubility of non-electrolyte solids are important for the design of novel separation processes. Here we demonstrate how conventional molecular simulation free energy calculations or electronic structure calculations in a continuum solvent, here SMD or SM8, can be used to predict parameters for the MOdified Separation of Cohesive Energy Density (MOSCED) method. The method is applied to the solutes naphthalene, anthracene, phenanthrene, pyrene and dibenzothiophene, compounds of interested to the petroleum industry and for environmental remediation. Adopting the melting point temperature and enthalpy of fusion of these compounds from experiment, we are able to predict equilibrium solubilities. Comparing to a total of 422 non-aqueous and 193 aqueous experimental solubilities, we find the proposed method is able to well correlate the data. The use of MOSCED is additionally advantageous as it is a solubility parameter-based method useful for intuitive solvent selection and formulation.

Gas-liquid equilibrium in a CO{sub 2}-MDEA-H{sub 2}O system and the effect of piperazine on it

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, G.W.; Zhang, C.F.; Qin, S.J.

1998-04-01

Aqueous N-methyldiethanolamine (MDEA) solutions are widely used for removal of the acid gas (H{sub 2}S and CO{sub 2}) from natural gas synthesis and refinery gas streams. Solubility data of CO{sub 2} and vapor pressure of water in 3.04--4.28 kmol/m{sup 3} aqueous N-methyldiethanolamine (MDEA) solutions were obtained at temperatures ranging from 40 to 100 C and CO{sub 2} partial pressures ranging from 0.876 to 1,013 kPa. A thermodynamic model was proposed and used for predicting CO{sub 2} solubility and water vapor pressure. An enthalpy change of absorption of CO{sub 2} in 4.28 kmol/m{sup 3} MDEA solution was estimated. The effect ofmore » piperazine (PZ) concentration on CO{sub 2} loading in MDEA solutions was determined at piperazine concentration ranging from 0 to 0.515 kmol/m{sup 3}. The results show that piperazine is beneficial to the CO{sub 2} loading. The equilibrium partial pressure of piperazine in the PZ-MDEA-H{sub 2}O system was measured in an Ellis Cell. Results show that the PZ-MDEA-H{sub 2}O system is a typical negative deviation system, with the strength of deviation decreasing with MDEA solutions.« less

Synthesis of magnetic biocomposite for efficient adsorption of azo dye from aqueous solution.

PubMed

Sivashankar, R; Sathya, A B; Krishnakumar, Uma; Sivasubramanian, V

2015-11-01

A novel magnetic biocomposite was synthesized using metal chlorides and aquatic macrophytes by co-precipitation method. The resulting product, magnetic biocomposite was characterized by Fourier transform infrared spectra (FTIR), X-ray diffraction (XRD), Energy-dispersive X-ray spectroscopy (EDX) and Scanning electron microscope (SEM). The adsorption performance of the magnetic biocomposite was tested with removal of Metanil Yellow dye from aqueous solution. The effect of influencing parameters such as initial dye concentration, solution pH and agitation were investigated. The equilibrium isotherm was well described by the Langmuir model with the with maximum adsorption capacity of 90.91mg/g. Adsorption kinetics experiments were carried out and the data were well fitted by a pseudo-second-order equation. The results revealed that the magnetic biocomposite could efficiently adsorb the azo dyes from aqueous solution, and the spent adsorbents could be recovered completely by magnetic separation process. Therefore, the prepared magnetic biocomposite could thus be used as promising adsorbent for the removal of azo dyes from polluted water. Copyright © 2015 Elsevier Inc. All rights reserved.

Natural biosorbents (garlic stem and horse chesnut shell) for removal of chromium(VI) from aqueous solutions.

PubMed

Parlayıcı, Şerife; Pehlivan, Erol

2015-12-01

The biosorption of Cr(VI) by the garlic stem (GS)-Allium sativum L. and horse chesnut shell (HCS)-Aesculus hippocastanum plant residues in a batch type reactor was studied in detail for the purpose of wastewater treatment. The influence of initial Cr(VI) concentration, time, and pH was investigated to optimize Cr(VI) removal from aqueous solutions and equilibrium isotherms and kinetic data. This influence was evaluated. The adsorption capacity of the GS and the HCS for Cr(VI) was determined with the Langmuir and Freundlich isotherm models, and the data was fitted to the Langmuir. The adsorption capacity of the GS and the HCS was found to be 103.09 and 142.85 mg/g of adsorbent from a solution containing 3000 ppm of Cr(VI), respectively. The GS's capacity was considerably lower than that of the HCS in its natural form. Gibbs free energy was spontaneous for all interactions, and the adsorption process exhibited exothermic enthalpy values. The HCS was shown to be a promising biosorbent for Cr(VI) removal from aqueous solutions.

Kinetics and thermodynamics of Pb(II) adsorption onto modified spent grain from aqueous solutions

NASA Astrophysics Data System (ADS)

Li, Qingzhu; Chai, Liyuan; Yang, Zhihui; Wang, Qingwei

2009-01-01

Spent grain, a main by-product of the brewing industry, is available in large quantities, but its main application has been limited to animal feeding. Nevertheless, in this study, spent grain modified with 1 M NaCl solution as a novel adsorbent has been used for the adsorption of Pb(II) in aqueous solutions. Isotherms, kinetics and thermodynamics of Pb(II) adsorption onto modified spent grain were studied. The equilibrium data were well fitted with Langmuir, Freundlich and Dubinin-Radushkevick (D-R) isotherm models. The kinetics of Pb(II) adsorption followed pseudo-second-order model, using the rate constants of pseudo-second-order model, the activation energy ( Ea) of Pb(II) adsorption was determined as 12.33 kJ mol -1 according to the Arrhenius equation. Various thermodynamic parameters such as Δ Gads, Δ Hads and Δ Sads were also calculated. Thermodynamic results indicate that Pb(II) adsorption onto modified spent grain is a spontaneous and endothermic process. Therefore, it can be concluded that modified spent grain as a new effective adsorbent has potential for Pb(II) removal from aqueous solutions.

A potential low cost adsorbent for the removal of cationic dyes from aqueous solutions

NASA Astrophysics Data System (ADS)

Uddin, Md. Tamez; Rahman, Md. Arifur; Rukanuzzaman, Md.; Islam, Md. Akhtarul

2017-10-01

This study was aimed at using mango leaf powder (MLP) as a potential adsorbent for the removal of methylene blue (MB) from aqueous solutions. Characterization of the adsorbent was carried out with scanning electron microscopy, Fourier transform infrared spectroscopy, and nitrogen adsorption-desorption analysis. The pH at the point of zero charge of the adsorbent was determined by titration method and was found a value to be 5.6 ± 0.2. Batch studies were performed to evaluate the influence of various experimental parameters like initial solution pH, contact time, initial concentration of dye and adsorbent dosage on the removal of MB. An adsorption-desorption study was carried out resulting the mechanism of adsorption was carried out by electrostatic force of attraction. The adsorption equilibrium time required for the adsorption of MB on MLP was almost 2 h and 85 ± 5% of the total amount of dye uptake was found to occur in the first rapid phase (30 min). The Langmuir and Freundlich isotherm models were used for modeling the adsorption equilibrium. The experimental equilibrium data could be well interpreted by Langmuir isotherm with maximum adsorption capacity of 156 mg/g. To state the sorption kinetics, the fits of pseudo-first-order and pseudo-second-order kinetic models were investigated. It was obtained that the adsorption process followed the pseudo-second-order rate kinetics. The above findings suggest that MLP can be effectively used for decontamination of dye containing wastewater.

Application of zeolite-activated carbon macrocomposite for the adsorption of Acid Orange 7: isotherm, kinetic and thermodynamic studies.

PubMed

Lim, Chi Kim; Bay, Hui Han; Neoh, Chin Hong; Aris, Azmi; Abdul Majid, Zaiton; Ibrahim, Zaharah

2013-10-01

In this study, the adsorption behavior of azo dye Acid Orange 7 (AO7) from aqueous solution onto macrocomposite (MC) was investigated under various experimental conditions. The adsorbent, MC, which consists of a mixture of zeolite and activated carbon, was found to be effective in removing AO7. The MC were characterized by scanning electron microscopy (SEM), energy dispersive X-ray, point of zero charge, and Brunauer-Emmett-Teller surface area analysis. A series of experiments were performed via batch adsorption technique to examine the effect of the process variables, namely, contact time, initial dye concentration, and solution pH. The dye equilibrium adsorption was investigated, and the equilibrium data were fitted to Langmuir, Freundlich, and Tempkin isotherm models. The Langmuir isotherm model fits the equilibrium data better than the Freundlich isotherm model. For the kinetic study, pseudo-first-order, pseudo-second-order, and intraparticle diffusion model were used to fit the experimental data. The adsorption kinetic was found to be well described by the pseudo-second-order model. Thermodynamic analysis indicated that the adsorption process is a spontaneous and endothermic process. The SEM, Fourier transform infrared spectroscopy, ultraviolet-visible spectral and high performance liquid chromatography analysis were carried out before and after the adsorption process. For the phytotoxicity test, treated AO7 was found to be less toxic. Thus, the study indicated that MC has good potential use as an adsorbent for the removal of azo dye from aqueous solution.

Ternary liquid-liquid equilibrium for eugenol + tert-butanol + water system at 303.15 and 323.15K and atmospheric pressure

NASA Astrophysics Data System (ADS)

Sucipto, Retno Kumala Hesti; Kuswandi, Wibawa, Gede

2017-05-01

The objective of this study was to determine ternary liquid-liquid equilibrium for eugenol + tert-butanol + water system at 303.15 and 323.15K and atmospheric pressure. Using 25 mL equilibrium cell equipped jacketted water connected to water bath to maintain equilibrium temperature constant. The procedure of this experiment was conducted by inserting mixture of eugenol + tert-butanol + water system at certain composition into equilibrium cell. The solution was stirred for 4 hours and then was allowed for 20 hours in order to separate aqueous and organic phases completely. The temperature equilibrium cell of and the atmosphere pressure were recorded as equilibrium temperature and pressure for each measurenment. The equilibrium compositions of each phase were analyzed using Gas Chromatography. The experimental data obtained in this work were correlated with NRTL and UNIQUAC models with root mean square deviation between esperimental and calculated equilibrium compositions of 0.03% and 0.04% respectively.

Mechanism of 1,4,5,8-naphthalene tetracarboxylic acid dianhydride hydrolysis and formation in aqueous solution.

PubMed

Barros, T C; Cuccovia, I M; Farah, J P S; Masini, J C; Chaimovich, H; Politi, M J

2006-01-07

The study of highly conjugated, carbonyl-containing molecules such as 1,4,5,8-naphthalene tetracarboxylic dianhydride, III, is of interest since reactivity differences and transmission of electronic effects through the conjugated framework can be evidenced. The kinetics of hydrolysis of III in aqueous solution were determined from 5 M acid to pH 10. In basic solution hydrolysis of III yields, sequentially, 1,4,5,8-naphthalene diacid monoanhydride, II, and 1,4,5,8-naphthalene tetracarboxylic acid, I. The second order rate constant for alkaline hydrolysis is 200 fold higher for the first ring opening. The water-catalyzed hydrolysis of III yields a pH-dependent mixture of ionic forms of I and II. The rate constant for water-catalyzed hydrolysis of III is 25 fold higher than that for II. In concentrated acid the rates for reaching equilibrium (I, II and III) increase and III is the major product. The pK(a)s of I (3.24, 5.13 and 6.25) and II (3.05, 5.90) were determined by potentiometric, fluorescence and UV spectroscopy titrations and by quantitative fit of the kinetic and equilibrium data. The apparent, pH-dependent, equilibrium constants, K(EqII), for anhydride formation between I and II were obtained from the UV spectra. The quantitative fit of kinetic and equilibrium data are consistent with the assumption that anhydride formation only proceeds with the fully protonated species for both I and II and permitted the estimation of the equilibrium constants for anhydride formation, K(EqII). The value of K(EqII) (I <==> II) between pH 1 and 6 was ca. 5. Geometry optimization calculations in the gas phase of the reactions of III in alkaline, neutral and acid conditions, at the DFT level of theory, gave electronic distributions that were qualitatively consistent with the experimental results.

Diffusion of water-soluble sorptive drugs in HEMA/MAA hydrogels.

PubMed

Liu, D E; Dursch, T J; Taylor, N O; Chan, S Y; Bregante, D T; Radke, C J

2016-10-10

We measure and, for the first time, theoretically predict four prototypical aqueous-drug diffusion coefficients in five soft-contact-lens material hydrogels where solute-specific adsorption is pronounced. Two-photon fluorescence confocal microscopy and UV/Vis-absorption spectrophotometry assess transient solute concentration profiles and concentration histories, respectively. Diffusion coefficients are obtained for acetazolamide, riboflavin, sodium fluorescein, and theophylline in 2-hydroxyethyl methacrylate/methacrylic acid (HEMA/MAA) copolymer hydrogels as functions of composition, equilibrium water content (30-90%), and aqueous pH (2 and 7.4). At pH2, MAA chains are nonionic, whereas at pH7.4, MAA chains are anionic (pKa≈5.2). All studied prototypical drugs specifically interact with HEMA and nonionic MAA (at pH2) moieties. Conversely, none of the prototypical drugs adsorb specifically to anionic MAA (at pH7.4) chains. As expected, diffusivities of adsorbing solutes are significantly diminished by specific interactions with hydrogel strands. Despite similar solute size, relative diffusion coefficients in the hydrogels span several orders of magnitude because of varying degrees of solute interactions with hydrogel-polymer chains. To provide a theoretical framework for the new diffusion data, we apply an effective-medium model extended for solute-specific interactions with hydrogel copolymer strands. Sorptive-diffusion kinetics is successfully described by local equilibrium and Henry's law. All necessary parameters are determined independently. Predicted diffusivities are in good agreement with experiment. Copyright © 2016 Elsevier B.V. All rights reserved.

Batch sorption dynamics and equilibrium for the removal of lead ions from aqueous phase using activated carbon developed from coffee residue activated with zinc chloride.

PubMed

Boudrahem, F; Aissani-Benissad, F; Aït-Amar, H

2009-07-01

Lignocellulosic materials are good precursors for the production of activated carbon. In this work, coffee residue has been used as raw material in the preparation of powder activated carbon by the method of chemical activation with zinc chloride for the sorption of Pb(II) from dilute aqueous solutions. The influence of impregnation ratio (ZnCl2/coffee residue) on the physical and chemical properties of the prepared carbons was studied in order to optimize this parameter. The optimum experimental condition for preparing predominantly microporous activated carbons with high pore surface area (890 m2/g) and micropore volume (0.772 cm3/g) is an impregnation ratio of 100%. The developed activated carbon shows substantial capability to sorb lead(II) ions from aqueous solutions and for relative impregnation ratios of 75 and 100%, the maximum uptake is practically the same. Thus, 75% represents the optimal impregnation ratio. Batch experiments were conducted to study the effects of the main parameters such as contact time, initial concentration of Pb(II), solution pH, ionic strength and temperature. The maximum uptake of lead(II) at 25 degrees C was about 63 mg/g of adsorbent at pH 5.8, initial Pb(II) concentration of 10 mg/L, agitation speed of 200 rpm and ionic strength of 0.005 M. The kinetic data were fitted to the models of pseudo-first order and pseudo-second order, and follow closely the pseudo-second order model. Equilibrium sorption isotherms of Pb(II) were analyzed by the Langmuir, Freundlich and Temkin isotherm models. The Freundlich model gives a better fit than the others. Results from this study suggest that activated carbon produced from coffee residue is an effective adsorbent for the removal of lead from aqueous solutions and that ZnCl2 is a suitable activating agent for the preparation of high-porosity carbons.

Group additivity-Pourbaix diagrams advocate thermodynamically stable nanoscale clusters in aqueous environments

PubMed Central

Wills, Lindsay A.; Qu, Xiaohui; Chang, I-Ya; Mustard, Thomas J. L.; Keszler, Douglas A.; Persson, Kristin A.; Cheong, Paul Ha-Yeon

2017-01-01

The characterization of water-based corrosion, geochemical, environmental and catalytic processes rely on the accurate depiction of stable phases in a water environment. The process is aided by Pourbaix diagrams, which map the equilibrium solid and solution phases under varying conditions of pH and electrochemical potential. Recently, metastable or possibly stable nanometric aqueous clusters have been proposed as intermediate species in non-classical nucleation processes. Herein, we describe a Group Additivity approach to obtain Pourbaix diagrams with full consideration of multimeric cluster speciation from computations. Comparisons with existing titration results from experiments yield excellent agreement. Applying this Group Additivity-Pourbaix approach to Group 13 elements, we arrive at a quantitative evaluation of cluster stability, as a function of pH and concentration, and present compelling support for not only metastable but also thermodynamically stable multimeric clusters in aqueous solutions. PMID:28643782

Group additivity-Pourbaix diagrams advocate thermodynamically stable nanoscale clusters in aqueous environments

NASA Astrophysics Data System (ADS)

Wills, Lindsay A.; Qu, Xiaohui; Chang, I.-Ya; Mustard, Thomas J. L.; Keszler, Douglas A.; Persson, Kristin A.; Cheong, Paul Ha-Yeon

2017-06-01

The characterization of water-based corrosion, geochemical, environmental and catalytic processes rely on the accurate depiction of stable phases in a water environment. The process is aided by Pourbaix diagrams, which map the equilibrium solid and solution phases under varying conditions of pH and electrochemical potential. Recently, metastable or possibly stable nanometric aqueous clusters have been proposed as intermediate species in non-classical nucleation processes. Herein, we describe a Group Additivity approach to obtain Pourbaix diagrams with full consideration of multimeric cluster speciation from computations. Comparisons with existing titration results from experiments yield excellent agreement. Applying this Group Additivity-Pourbaix approach to Group 13 elements, we arrive at a quantitative evaluation of cluster stability, as a function of pH and concentration, and present compelling support for not only metastable but also thermodynamically stable multimeric clusters in aqueous solutions.

Pourbaix ("E"-pH-M) Diagrams in Three Dimensions

ERIC Educational Resources Information Center

Pesterfield, Lester L.; Maddox, Jeremy B.; Crocker, Michael S.; Schweitzer, George K.

2012-01-01

"E"-pH (Pourbaix) diagrams provide an important graphical link between the thermodynamic calculations of potential, pH, equilibrium constant, concentration, and changes in Gibbs energy and the experimentally observed behavior of species in aqueous solutions. The utility of "E"-pH diagrams is extended with the introduction of an additional…

Hybrid Vapor Stripping-Vapor Permeation Process for Recovery and Dehydration of 1-Butanol and Acetone/Butanol/Ethanol from Dilute Aqueous Solutions. Part 1. Process Simulations

EPA Science Inventory

BACKGROUND: Fermentative production of butanol is limited to low concentrations, typically less than 2 wt% solvent, due to product inhibition. The result is high separation energy demand by conventional distillation approaches, despite favorable vapor-liquid equilibrium and parti...

Hypercrosslinked poly(styrene-co-divinylbenzene) resin as a specific polymeric adsorbent for purification of berberine hydrochloride from aqueous solutions.

PubMed

Li, Yin; Cao, Ruofan; Wu, Xiaofei; Huang, Jianhan; Deng, Shuguang; Lu, Xiuyang

2013-06-15

A hypercrosslinked poly(styrene-co-divinylbenzene) resin (TEPA) was synthesized and characterized as a specific polymeric adsorbent for concentrating berberine hydrochloride from aqueous solutions. Three organic molecules of different sizes (2-naphthol, berberine hydrochloride, and Congo red) were used as target molecules to elucidate the molecular sieving effect of the TEPA adsorbent. Because the TEPA adsorbent has a pore structure consisting mainly of micropores and mesopores, the adsorption of 2-naphthol from aqueous solutions is very efficient due to the micropore filling effect. The adsorption of berberine hydrochloride mostly takes place in the mesopores as well as macropores, while the adsorption of Congo red mainly occurs in the macropores. The smaller adsorbate molecule (2-naphthol) reaches the adsorption equilibrium much faster than the larger ones (berberine hydrochloride and Congo red). An adsorption breakthrough experiment with an aqueous solution containing 2-naphthol and berberine hydrochloride demonstrated that the TEPA adsorbent could effectively remove 2-naphthol from berberine hydrochloride at 0-107 BV (bed volume, 1 BV=10 ml), and the berberine hydrochloride concentration was increased from 66.7% to 99.4%, suggesting that this polymeric adsorbent is promising for purifying berberine hydrochloride and similar alkaloids from herbal plant extracts. Copyright © 2013 Elsevier Inc. All rights reserved.

Effect of surfactant on kinetics of thinning of capillary bridges

NASA Astrophysics Data System (ADS)

Nowak, Emilia; Kovalchuk, Nina; Simmons, Mark

2015-11-01

Kinetics of thinning of capillary bridges is of great scientific and industrial interest being of vital importance for example in various emulsification and microfluidic processes. It is well known that the rate of bridge thinning is proportional to the interfacial tension. Therefore it is expected that the process should slow down by addition of surfactant. The kinetics of capillary bridges in the presence of surfactant was studied by the dripping of liquid from a capillary tip under conditions of nearly zero flow rate (We << 1). The tested liquids were aqueous solutions of sodium lauryl ether sulphate (SLES), which is broadly used in personal care products. The viscosity, surfactant activity and adsorption kinetics have been controlled by addition of glycerol and sodium chloride. The study has shown that the kinetics of capillary bridges are determined by dynamic surface tension rather than by its equilibrium value. In particular, the kinetics of the bridge thinning for the 0.1 g L-1 aqueous SLES solution is practically the same as that of pure water despite twice lower equilibrium surface tension. EPSRC Programme Grant, MEMPHIS, EP/K0039761/1.

Kinetic, equilibrium and thermodynamic studies on sorption of uranium and thorium from aqueous solutions by a selective impregnated resin containing carminic acid.

PubMed

Rahmani-Sani, Abolfazl; Hosseini-Bandegharaei, Ahmad; Hosseini, Seyyed-Hossein; Kharghani, Keivan; Zarei, Hossein; Rastegar, Ayoob

2015-04-09

In this work, the removal of uranium and thorium ions from aqueous solutions was studied by solid-liquid extraction using an advantageous extractant-impregnated resin (EIR) prepared by loading carminic acid (CA) onto Amberlite XAD-16 resin beads. Batch sorption experiments using CA/XAD-16 beads for the removal of U(VI) and Th(IV) ions were carried out as a function of several parameters, like equilibration time, metal ion concentration, etc. The equilibrium data obtained from the sorption experiments were adjusted to the Langmuir isotherm model and the calculated maximum sorption capacities in terms of monolayer sorption were in agreement with those obtained from the experiments. The experimental data on the sorption behavior of both metal ions onto the EIR beads fitted well in both Bangham and intra-particle diffusion kinetic models, indicating that the intra-particle diffusion is the rate-controlling step. The thermodynamic studies at different temperatures revealed the feasibility and the spontaneous nature of the sorption process for both uranium and thorium ions. Copyright © 2014 Elsevier B.V. All rights reserved.

Removal of 4-nitrophenol from aqueous solution by adsorption onto activated carbon prepared from Acacia glauca sawdust.

PubMed

Dhorabe, Prashant T; Lataye, Dilip H; Ingole, Ramakant S

2016-01-01

The present paper deals with a complete batch adsorption study of 4-nitrophenol (4NP) from aqueous solution onto activated carbon prepared from Acacia glauca sawdust (AGAC). The surface area of the adsorbent determined by methylene blue method is found to be 311.20 m(2)/g. The optimum dose of adsorbent was found to be 2 g/l with 4NP uptake of 25.93 mg/g. The equilibrium time was found to be 30 minutes with the percentage removal of 96.40 at the initial concentration of 50 ppm. The maximum removal of 98.94% was found to be at pH of 6. The equilibrium and kinetic study revealed that the Radke-Prausnitz isotherm and pseudo second order kinetics model fitted the respective data well. In the thermodynamic study, the negative value of Gibbs free energy change (-26.38 kJ/mol at 30°C) and enthalpy change (-6.12 kJ/mol) showed the spontaneous and exothermic nature of the adsorption process.

Stable supersaturated aqueous solutions of silatecan 7-t-butyldimethylsilyl-10-hydroxycamptothecin via chemical conversion in the presence of a chemically modified beta-cyclodextrin.

PubMed

Xiang, Tian-Xiang; Anderson, Bradley D

2002-08-01

A method for obtaining clear supersaturated aqueous solutions for parenteral administration of the poorly soluble experimental anti-cancer drug silatecan 7-t-butyldimethylsilyl-10-hydroxycamptothecin (DB-67) has been developed. Equilibrium solubilities of DB-67 were determined in various solvents and pH values, and in the presence of chemically modified water-soluble beta-cyclodextrins. The stoichiometry and binding constants for complexes of the lactone form of DB-67 and its ring-opened carboxylate with sulfobutyl ether and 2-hydroxypropyl substituted beta-cyclodextrins (SBE-CD and HP-CD) were obtained by solubility and circular dichroism spectroscopy, respectively. Kinetics for the reversible ring-opening of DB-67 in aqueous solution and for lactone precipitation were determined by HPLC with UV detection. Solubilities of DB-67 lactone in various injectable solvent systems were found to be at least one order of magnitude below the target concentration (2 mg/ml). DB-67 forms inclusion complexes with SBE-CD and HP-CD but the solubilization attainable is substantially less than the target concentration. Slow addition of DB-67/ DMSO into 22.2% (w/v) SBE-CD failed to yield stable supersaturated solutions due to precipitation. Stable supersatured solutions were obtained, however, by mixing a concentrated alkaline aqueous solution of DB-67 carboxylate with an acidified 22.2% (w/v) SBE-CD solution. Ring-closure yielded supersaturated solutions that could be lyophilized and reconstituted to clear, stable, supersaturated solutions. The method developed provides an alternative to colloidal dispersions (e.g., liposomal suspensions, emulsions, etc.) for parenteral administration of lipophilic camptothecin analogs.

Combined Homogeneous Surface Diffusion Model - Design of experiments approach to optimize dye adsorption considering both equilibrium and kinetic aspects.

PubMed

Muthukkumaran, A; Aravamudan, K

2017-12-15

Adsorption, a popular technique for removing azo dyes from aqueous streams, is influenced by several factors such as pH, initial dye concentration, temperature and adsorbent dosage. Any strategy that seeks to identify optimal conditions involving these factors, should take into account both kinetic and equilibrium aspects since they influence rate and extent of removal by adsorption. Hence rigorous kinetics and accurate equilibrium models are required. In this work, the experimental investigations pertaining to adsorption of acid orange 10 dye (AO10) on activated carbon were carried out using Central Composite Design (CCD) strategy. The significant factors that affected adsorption were identified to be solution temperature, solution pH, adsorbent dosage and initial solution concentration. Thermodynamic analysis showed the endothermic nature of the dye adsorption process. The kinetics of adsorption has been rigorously modeled using the Homogeneous Surface Diffusion Model (HSDM) after incorporating the non-linear Freundlich adsorption isotherm. Optimization was performed for kinetic parameters (color removal time and surface diffusion coefficient) as well as the equilibrium affected response viz. percentage removal. Finally, the optimum conditions predicted were experimentally validated. Copyright © 2017 Elsevier Ltd. All rights reserved.

Theoretical estimation of equilibrium sulfur isotope fractionations among aqueous sulfite species: Implications for isotope models of microbial sulfate reduction

NASA Astrophysics Data System (ADS)

Eldridge, D. L.; Farquhar, J.; Guo, W.

2015-12-01

Sulfite (sensu lato), an intermediate in a variety sulfur redox processes, plays a particularly important role in microbial sulfate reduction. It exists intracellularly as multiple species between sets of enzymatic reactions that transform sulfate to sulfide, with the exact speciation depending on pH, T, and ionic strength. However, the complex speciation of sulfite is ignored in current isotope partitioning models of microbial sulfate reduction and simplified solely to the pyramidal SO32- (sulfite sensu stricto), due to a lack of appropriate constraints. We theoretically estimated the equilibrium sulfur isotope fractionations (33S/32S, 34S/32S, 36S/32S) among all documented sulfite species in aqueous solution, including sulfite (SO32-), bisulfite isomers and dimers ((HS)O3-, (HO)SO2-, S2O52-), and SO2(aq), through first principles quantum mechanical calculations. The calculations were performed at B3LYP/6-31+G(d,p) level using cluster models with 30-40 water molecules surrounding the solute. Our calculated equilibrium fractionation factors compare well to the available experimental constraints and suggest that the minor and often-ignored tetrahedral (HS)O3- isomer of bisulfite strongly influences isotope partitioning behavior in the sulfite system under most environmentally relevant conditions, particularly fractionation magnitudes and unusual temperature dependence. For example, we predict that sulfur isotope fractionation between sulfite and bulk bisulfite in solution should have an apparent inverse temperature dependence due to the influence of (HS)O3- and its increased stability at higher temperatures. Our findings highlight the need to appropriately account for speciation/isomerization of sulfur species in sulfur isotope studies. We will also present similar calculation results of other aqueous sulfur compounds (e.g., H2S/HS-, SO42-, S2O32-, S3O62-, and poorly documented SO22- species), and discuss the implication of our results for microbial sulfate reduction models and other sulfur-redox processes in nature.

Thermodynamic Characterization of Iron Oxide-Aqueous Fe(2+) Redox Couples.

PubMed

Gorski, Christopher A; Edwards, Rebecca; Sander, Michael; Hofstetter, Thomas B; Stewart, Sydney M

2016-08-16

Iron is present in virtually all terrestrial and aquatic environments, where it participates in redox reactions with surrounding metals, organic compounds, contaminants, and microorganisms. The rates and extent of these redox reactions strongly depend on the speciation of the Fe2+ and Fe3+ phases, although the underlying reasons remain unclear. In particular, numerous studies have observed that Fe2+ associated with iron oxide surfaces (i.e., oxide-associated Fe2+) often reduces oxidized contaminants much faster than aqueous Fe2+ alone. Here, we tested two hypotheses related to this observation by determining if solutions containing two commonly studied iron oxides—hematite and goethite—and aqueous Fe2+ reached thermodynamic equilibrium over the course of a day. We measured reduction potential (EH) values in solutions containing these oxides at different pH values and aqueous Fe2+ concentrations using mediated potentiometry. This analysis yielded standard reduction potential (EH0) values of 768 ± 1 mV for the aqueous Fe2+–goethite redox couple and 769 ± 2 mV for the aqueous Fe2+–hematite redox couple. These values were in excellent agreement with those calculated from existing thermodynamic data, and the data could be explained by the presence of an iron oxide lowering EH values of aqueous Fe3+/Fe2+ redox couples.

Studies of Drug Delivery and Drug Release of Dendrimer by Dissipative Particle Dynamics

NASA Astrophysics Data System (ADS)

Lin, Chun-Min; Wu, Yi-Fan; Tsao, Heng-Kwong; Sheng, Yu-Jane

2008-02-01

Dendrimers, like unimolecular micelles, may encapsulate guest biomolecules (drug) and therefore are attractive candidates as carriers in drug delivery applications. Hydrophobic drugs can be complexed within the hydrophobic dendrimer interior to make them water-soluble. The equilibrium partition of hydrophobic solutes into a dendrimer with hydrophobic interior from aqueous solutions is studied by dissipative particle dynamics. The drug is mainly distributed in the vicinity of the interface between hydrophobic interior and hydrophilic exterior within a dendrimer. The partition coefficient, which is defined as the concentration ratio of the drug distributed within dendrimer to aqueous phases, depends on the interaction between drug and hydrophilic dendrimer exterior. Increasing the repulsion between them reduces the solubilization ability associated with the dendrimer.

Equilibrium of molybdenum in selected extraction systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tkac, Peter; Paulenova, Alena

2007-07-01

The concentration of molybdenum(VI) in dissolved irradiated nuclear fuel is comparable with the concentrations of Tc, Am and Np. Therefore it is of big interest to understand its behavior under conditions related to the UREX/TRUEX process. The effect of the poly-speciation of molybdenum in aqueous solution on its extraction by neutral solvents TBP and CMPO/TBP was studied. Extraction yields of molybdenum decreased significantly when AHA was added to aqueous phase. Our investigation confirmed a strong ability of the aceto-hydroxamic acid to form complexes with Mo in high acidic solutions. Spectroscopic data (UV-Vis) confirmed that a fraction of the Mo(VI)-AHA complexmore » is present in the organic phase after extraction. (authors)« less

Removal of Rhodamine B from aqueous solution using magnetic NiFe nanoparticles.

PubMed

Liu, Yan; Liu, Kaige; Zhang, Lin; Zhang, Zhaowen

2015-01-01

Surface-modified magnetic nano alloy particles Ni2.33Fe were prepared using a hydrothermal method and they were utilized for removing Rhodamine B (RhB) from aqueous solution. The magnetic nanoparticles were characterized by X-ray diffraction, scanning electron microscopy, thermogravimetric analysis and Fourier transform infrared spectroscopy, which confirmed that the surface of the magnetic product with a face-centered cubic-type structure was successfully modified by sodium citrate. Kinetics studies were conducted. The pseudo-second-order kinetic model was used for fitting the kinetic data successfully. The Freundlich and Langmuir adsorption models were employed for the mathematical description of adsorption equilibrium. It was found that the adsorption isotherm can be very satisfactorily fitted by the Freundlich model.

Removal of Pb(II) ions from aqueous solution by a waste mud from copper mine industry: equilibrium, kinetic and thermodynamic study.

PubMed

Ozdes, Duygu; Gundogdu, Ali; Kemer, Baris; Duran, Celal; Senturk, Hasan Basri; Soylak, Mustafa

2009-07-30

The objective of this study was to assess the adsorption potential of a waste mud (WM) for the removal of lead (Pb(II)) ions from aqueous solutions. The WM was activated with NaOH in order to increase its adsorption capacity. Adsorption studies were conducted in a batch system as a function of solution pH, contact time, initial Pb(II) concentration, activated-waste mud (a-WM) concentration, temperature, etc. Optimum pH was specified as 4.0. The adsorption kinetic studies indicated that the overall adsorption process was best described by pseudo-second-order kinetics. The equilibrium adsorption capacity of a-WM was obtained by using Langmuir and Freundlich isotherm models and both models fitted well. Adsorption capacity for Pb(II) was found to be 24.4 mg g(-1) for 10 g L(-1) of a-WM concentration. Thermodynamic parameters including the Gibbs free energy (Delta G degrees), enthalpy (Delta H degrees), and entropy (DeltaS degrees) indicated that the adsorption of Pb(II) ions on the a-WM was feasible, spontaneous and endothermic, at temperature range of 0-40 degrees C. Desorption studies were carried out successfully with diluted HCl solutions. The results indicate that a-WM can be used as an effective and no-cost adsorbent for the treatment of industrial wastewaters contaminated with Pb(II) ions.

Metal biosorption equilibria in a ternary system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chong, K.H.; Volesky, B.

Equilibrium metal uptake performance of a biosorbent prepared from Ascophyllum nodosum seaweed biomass was studied using aqueous solutions containing copper, cadmium, and zinc ions in binary and ternary mixtures. Triangular equilibrium diagrams can graphically represent all the ternary equilibrium sorption data. Application of the multicomponent Langmuir model to describe the three-metal system revealed its nonideal characteristics, whereby the value of apparent dissociation constants for the respective metals differed for each system. This restricted the prediction of the ternary equilibria from the binary systems. However, some predictions of the ternary system behavior from the model were consistent with experimental data andmore » with conclusions postulated from the three possible binary subsystems.« less

Utilization of unconventional lignocellulosic waste biomass for the biosorption of toxic triphenylmethane dye malachite green from aqueous solution.

PubMed

Selvasembian, Rangabhashiyam; P, Balasubramanian

2018-05-12

Biosorption potential of novel lignocellulosic biosorbents Musa sp. peel (MSP) and Aegle marmelos shell (AMS) was investigated for the removal of toxic triphenylmethane dye malachite green (MG), from aqueous solution. Batch experiments were performed to study the biosorption characteristics of malachite green onto lignocellulosic biosorbents as a function of initial solution pH, initial malachite green concentration, biosorbents dosage, and temperature. Biosorption equilibrium data were fitted to two and three parameters isotherm models. Three-parameter isotherm models better described the equilibrium data. The maximum monolayer biosorption capacities obtained using the Langmuir model for MG removal using MSP and AMS was 47.61 and 18.86 mg/g, respectively. The biosorption kinetic data were analyzed using pseudo-first-order, pseudo-second-order, Elovich and intraparticle diffusion models. The pseudo-second-order kinetic model best fitted the experimental data, indicated the MG biosorption using MSP and AMS as chemisorption process. The removal of MG using AMS was found as highly dependent on the process temperature. The removal efficiency of MG showed declined effect at the higher concentrations of NaCl and CaCl 2 . The regeneration test of the biosorbents toward MG removal was successful up to three cycles.

The sorption of lead, cadmium, copper and zinc ions from aqueous solutions on a raw diatomite from Algeria.

PubMed

Safa, Messaouda; Larouci, Mohammed; Meddah, Boumediene; Valemens, Pierre

2012-01-01

The adsorption of Cu(2+), Zn(2+), Cd(2+) and Pb(2+) ions from aqueous solution by Algerian raw diatomite was studied. The influences of different sorption parameters such as contact pH solution, contact time and initial metal ions concentration were studied to optimize the reaction conditions. The metals ions adsorption was strictly pH dependent. The maximum adsorption capacities towards Cu(2+), Zn(2+), Cd(2+) and Pb(2+) were 0.319, 0.311, 0.18 and 0.096 mmol g(-1), respectively. The kinetic data were modelled using the pseudo-first-order and pseudo-second-order kinetic equations. Among the kinetic models studied, the pseudo-second-order equation was the best applicable model to describe the sorption process. Equilibrium isotherm data were analysed using the Langmuir and the Freundlich isotherms; the results showed that the adsorption equilibrium was well described by both model isotherms. The negative value of free energy change ΔG indicates feasible and spontaneous adsorption of four metal ions on raw diatomite. According to these results, the high exchange capacities of different metal ions at high and low concentration levels, and given the low cost of the investigated adsorbent in this work, Algerian diatomite was considered to be an excellent adsorbent.

Removal of cadmium(II) ions from aqueous solution using Ni (15 wt.%)-doped α-Fe2O3 nanocrystals: equilibrium, thermodynamic, and kinetic studies.

PubMed

OuldM'hamed, Mohamed; Khezami, L; Alshammari, Abdulrahman G; Ould-Mame, S M; Ghiloufi, I; Lemine, O M

2015-01-01

The present publication investigates the performance of nanocrystalline Ni (15 wt.%)-doped α-Fe2O3 as an effective nanomaterial for the removal of Cd(II) ions from aqueous solutions. The nanocrystalline Ni-doped α-Fe2O3 powders were prepared by mechanical alloying, and characterized by X-ray diffraction and a vibrating sample magnetometer. Batch-mode experiments were realized to determine the adsorption equilibrium, kinetics, and thermodynamic parameters of toxic heavy metal ions by Ni (15 wt.%)-doped α-Fe2O3. The adsorption isotherms data were found to be in good agreement with the Langmuir model. The adsorption capacity of Cd(II) ion reached a maximum value of about 90.91 mg g(-1) at 328 K and pH 7. The adsorption process kinetics was found to comply with pseudo-second-order rate law. Thermodynamic parameters related to the adsorption reaction, free energy change, enthalpy change and entropy change, were evaluated. The found values of free energy and enthalpy revealed a spontaneous endothermic adsorption-process. Moreover, the positive entropy suggests an increase of randomness during the process of heavy metal removal at the adsorbent-solution interface.

Thermodynamic and kinetic studies of biosorption of iron and manganese from aqueous medium using rice husk ash

NASA Astrophysics Data System (ADS)

Adekola, F. A.; Hodonou, D. S. S.; Adegoke, H. I.

2016-11-01

The adsorption behavior of rice husk ash with respect to manganese and iron has been studied by batch methods to consider its application for water and waste water treatment. The optimum conditions of adsorption were determined by investigating the effect of initial metal ion concentration, contact time, adsorbent dose, pH value of aqueous solution and temperature. Adsorption equilibrium time was observed at 120 min. The adsorption efficiencies were found to be pH dependent. The equilibrium adsorption experimental data were found to fit the Langmuir, Freundlich and Temkin isotherms for iron, but fitted only Langmuir isotherm for manganese. The pseudo-second order kinetic model was found to describe the manganese and iron kinetics more effectively. The thermodynamic experiment revealed that the adsorption processes involving both metals were exothermic. The adsorbent was finally applied to typical raw water with initial manganese and iron concentrations of 3.38 mg/l for Fe and 6.28 mg/l, respectively, and the removal efficiency was 100 % for Mn and 70 % for Fe. The metal ions were desorbed from the adsorbent using 0.01 M HCl, it was found to quantitatively remove 67 and 86 % of Mn and Fe, respectively, within 2 h. The results revealed that manganese and iron are considerably adsorbed on the adsorbent and could be an economic method for the removal of these metals from aqueous solutions.

Thermodynamic studies of aqueous solutions of 2,2,2-cryptand at 298.15 K: enthalpy-entropy compensation, partial entropies, and complexation with K+ ions.

PubMed

Shaikh, Vasim R; Terdale, Santosh S; Ahamad, Abdul; Gupta, Gaurav R; Dagade, Dilip H; Hundiwale, Dilip G; Patil, Kesharsingh J

2013-12-19

The osmotic coefficient measurements for binary aqueous solutions of 2,2,2-cryptand (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8] hexacosane) in the concentration range of ~0.009 to ~0.24 mol·kg(-1) and in ternary aqueous solutions containing a fixed concentration of 2,2,2-cryptand of ~0.1 mol·kg(-1) with varying concentration of KBr (~0.06 to ~0.16 mol·kg(-1)) have been reported at 298.15 K. The diamine gets hydrolyzed in aqueous solutions and needs proper approach to obtain meaningful thermodynamic properties. The measured osmotic coefficient values are corrected for hydrolysis and are used to determine the solvent activity and mean ionic activity coefficients of solute as a function of concentration. Strong ion-pair formation is observed, and the ion-pair dissociation constant for the species [CrptH](+)[OH(-)] is reported. The excess and mixing thermodynamic properties (Gibbs free energy, enthalpy, and entropy changes) have been obtained using the activity data from this study and the heat data reported in the literature. Further, the data are utilized to compute the partial molal entropies of solvent and solute at finite as well as infinite dilution of 2,2,2-cryptand in water. The concentration dependent non-linear enthalpy-entropy compensation effect has been observed for the studied system, and the compensation temperature along with entropic parameter are reported. Using solute activity coefficient data in ternary solutions, the transfer Gibbs free energies for transfer of the cryptand from water to aqueous KBr as well as transfer of KBr from water to aqueous cryptand were obtained and utilized to obtain the salting constant (ks) and thermodynamic equilibrium constant (log K) values for the complex (2,2,2-cryptand:K(+)) at 298.15 K. The value of log K = 5.8 ± 0.1 obtained in this work is found to be in good agreement with that reported by Lehn and Sauvage. The standard molar entropy for complexation is also estimated for the 2,2,2-cryptand-KBr complex in aqueous medium.

Premicellar and micelle formation behavior of dye surfactant ion pairs in aqueous solutions: deprotonation of dye in ion pair micelles.

PubMed

Gohain, Biren; Dutta, Robin K

2008-07-15

The premicellar and micelle formation behavior of dye surfactant ion pairs in aqueous solutions monitored by surface tension and spectroscopic measurements has been described. The measurements have been made for three anionic sulfonephthalein dyes and cationic surfactants of different chain lengths, head groups, and counterions. The observations have been attributed to the formation of closely packed dye surfactant ion pairs which is similar to nonionic surfactants in very dilute concentrations of the surfactant. These ion pairs dominate in the monolayer at the air-water interface of the aqueous dye surfactant solutions below the CMC of the pure surfactant. It has been shown that the dye in the ion pair deprotonates on micelle formation by the ion pair surfactants at near CMC but submicellar surfactant concentrations. The results of an equilibrium study at varying pH agree with the model of deprotonated 1:1 dye-surfactant ion pair formation in the near CMC submicellar solutions. At concentrations above the CMC of the cationic surfactant the dye is solubilized in normal micelles and the monolayer at the air-water interface consists of the cationic surfactant alone even in the presence of the dyes.

Biosorption of cadmium (II) from aqueous solutions by natural and modified non-living leaves of Posidonia oceanica.

PubMed

Meseguer, Víctor F; Ortuño, Juan F; Aguilar, M Isabel; Pinzón-Bedoya, Martha L; Lloréns, Mercedes; Sáez, José; Pérez-Marín, Ana B

2016-12-01

Natural, HCl-treated, and formaldehyde-treated non-living leaves of Posidonia oceanica, a marine plant, were investigated as potential biosorbents to remove Cd 2+ from aqueous solutions. The studied biosorbents were characterized by elemental analysis and Fourier transform infrared spectroscopy (FTIR) and it was observed that the adsorption capacity of the biosorbents strongly depended on the pH, increasing as the pH rises. The adsorption process was fast. The adsorption kinetic was analyzed using five kinetic models: pseudo-first order, pseudo-second order, Elovich, intraparticle diffusion, and Bangham models. The adsorption isotherms were analyzed by the Langmuir, Freundlich, Dubinin-Radushkevich, Sips, Redlich-Peterson, and Toth models. The maximum biosorption capacity was attained by the biosorbent treated with HCl (1.11 mmol g -1 ). The distribution equilibrium constant and the Gibbs free energy change were calculated. The effects of the presence of Na + , K + , Mg 2+ , and Ca 2+ ions in the solution on Cd 2+ uptake were studied. Results indicate that non-living leaves of P. oceanica, natural or treated, can be considered as effective and low-cost biosorbents for the removal of cadmium from aqueous solutions.

Evaluation of PAN-based manganese dioxide composite for the sorptive removal of cesium-137 from aqueous solutions.

PubMed

Nilchi, A; Saberi, R; Garmarodi, S Rasouli; Bagheri, A

2012-02-01

Hydrous manganese dioxide-polyacrylonitrile (MnO(2)-PAN) was chemically synthesized and evaluated, as an organic-inorganic composite material, for the removal of radio-contaminant cesium-137 from aqueous solutions. The physico-chemical characterization was carried out by Fourier transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), CHN elemental analysis, scanning electron microscopy (SEM), nitrogen adsorption-desorption studies and thermogravimetry-differential scanning calorimetry (TGA-DSC). Batch experiments were carried out as a function of contact time, interference of the coexisting ions and initial pH of adsorptive solution applying a radiotracer technique. The effect of temperature on the distribution coefficient of cesium has been utilized in order to evaluate the changes in the standard thermodynamic parameters. The results indicated that Cs(+) ions could be efficiently removed using MnO(2)-PAN composite in the pH range of 4-9 from aqueous solutions and the uptake of cesium is affected to varying degrees by the presence of some diverse co-ions. The equilibrium isotherms have been determined and the sorption data were successfully modeled using Freundlich model. Copyright © 2011 Elsevier Ltd. All rights reserved.

Evaluation of mineral-aqueous chemical equilibria of felsic reservoirs with low-medium temperature: A comparative study in Yangbajing geothermal field and Guangdong geothermal fields

NASA Astrophysics Data System (ADS)

Li, Jiexiang; Sagoe, Gideon; Yang, Guang; Lu, Guoping

2018-02-01

Classical geothermometers are useful tools for estimating reservoir temperatures of geothermal systems. However, their application to low-medium temperature reservoirs is limited because large variations of temperatures calculated by different classical geothermometers are usually observed. In order to help choose the most appropriate classical geothermometer for calculating the temperatures of low-medium temperature reservoirs, this study evaluated the mineral-aqueous equilibria of typical low-medium temperature felsic reservoirs in the Yangbajing geothermal field and Guangdong geothermal fields. The findings of this study support that reservoirs in the Guangdong geothermal fields have no direct magma influence. Also, natural reservoirs may represent the intermediate steady state before reaching full equilibrium, which rarely occurs. For the low-medium temperature geothermal systems without the influence of magma, even with seawater intrusion, the process of minerals reaching mineral-aqueous equilibrium is sequential: chlorite and chalcedony are the first, then followed by K-feldspar, kaolinite and K-mica. Chlorite may reach equilibrium at varying activity values, and the equilibrium between K-feldspar and kaolinite or K-feldspar and K-mica can fix the contents of K and Al in the solutions. Although the SiO2 and Al attain equilibrium state, albite and laumontite remain unsaturated and thus may affect low-medium temperature calculations. In this study, the chalcedony geothermometer was found to be the most suitable geothermometer for low-medium temperature reservoirs. The results of K-Mg geothermometer may be useful to complement that of the chalcedony geothermometer in low-medium temperature reservoir systems. Na-K geothermometer will give unreliable results at low-medium temperatures; and Na-K-Ca will also be unsuitable to calculate reservoir temperatures lower than 180 °C, probably caused by the chemical imbalance of laumontite.

Pyridinium-functionalized magnetic mesoporous silica nanoparticles as a reusable adsorbent for phosphate removal from aqueous solution.

PubMed

Ma, Fang; Du, Hongtao; Li, Ronghua; Zhang, Zengqiang

In this work, pyridinium-functionalized silica nanoparticles adsorbent (PC/SiO2/Fe3O4) was synthesized for phosphate removal from aqueous solutions. The removal efficiency of phosphate on the PC/SiO2/Fe3O4 was carried out and investigated under various conditions such as pH, contact temperature and initial concentration. The results showed that the adsorption equilibrium could be reached within 10 min, which fitted a Langmuir isotherm model, with maximum adsorption capacity of 94.16 mg/g, and the kinetic data were fitted well by pseudo-second-order and intra-particle diffusion models. Phosphate loaded on the adsorbents could be easily desorbed with 0.2 mol/L of NaOH, and the adsorbents showed good reusability. The adsorption capacity was still around 50 mg/g after 10 times of reuse. All the results demonstrated that this pyridinium-functionalized mesoporous material could be used for the phosphate removal from aqueous solution and it was easy to collect due to its magnetic properties.

Application of carbon adsorbents prepared from Brazilian-pine fruit shell for the removal of reactive orange 16 from aqueous solution: Kinetic, equilibrium, and thermodynamic studies.

PubMed

Calvete, Tatiana; Lima, Eder C; Cardoso, Natali F; Vaghetti, Júlio C P; Dias, Silvio L P; Pavan, Flavio A

2010-08-01

Activated (AC-PW) and non-activated (C-PW) carbonaceous materials were prepared from the Brazilian-pine fruit shell (Araucaria angustifolia) and tested as adsorbents for the removal of reactive orange 16 dye (RO-16) from aqueous effluents. The effects of shaking time, adsorbent dosage and pH on the adsorption capacity were studied. RO-16 uptake was favorable at pH values ranging from 2.0 to 3.0 and from 2.0 to 7.0 for C-PW and AC-PW, respectively. The contact time required to obtain the equilibrium using C-PW and AC-PW as adsorbents was 5 and 4h at 298 K, respectively. The fractionary-order kinetic model provided the best fit to experimental data compared with other models. Equilibrium data were better fit to the Sips isotherm model using C-PW and AC-PW as adsorbents. The enthalpy and entropy of adsorption of RO-16 were obtained from adsorption experiments ranging from 298 to 323 K. Copyright 2010 Elsevier Ltd. All rights reserved.

Dissolution without disappearing: multicomponent gas exchange for CO2 bubbles in a microfluidic channel.

PubMed

Shim, Suin; Wan, Jiandi; Hilgenfeldt, Sascha; Panchal, Prathamesh D; Stone, Howard A

2014-07-21

We studied the dissolution dynamics of CO2 gas bubbles in a microfluidic channel, both experimentally and theoretically. In the experiments, spherical CO2 bubbles in a flow of a solution of sodium dodecyl sulfate (SDS) first shrink rapidly before attaining an equilibrium size. In the rapid dissolution regime, the time to obtain a new equilibrium is 30 ms regardless of SDS concentration, and the equilibrium radius achieved varies with the SDS concentration. To explain the lack of complete dissolution, we interpret the results by considering the effects of other gases (O2, N2) that are already dissolved in the aqueous phase, and we develop a multicomponent dissolution model that includes the effect of surface tension and the liquid pressure drop along the channel. Solutions of the model for a stationary gas bubble show good agreement with the experimental results, which lead to our conclusion that the equilibrium regime is obtained by gas exchange between the bubbles and liquid phase. Also, our observations from experiments and model calculations suggest that SDS molecules on the gas-liquid interface form a diffusion barrier, which controls the dissolution behaviour and the eventual equilibrium radius of the bubble.

Lead sorption by waste biomass of hazelnut and almond shell.

PubMed

Pehlivan, Erol; Altun, Türkan; Cetin, Serpil; Iqbal Bhanger, M

2009-08-15

The potential to remove Pb(2+) ion from aqueous solutions using the shells of hazelnut (HNS) (Corylus avellana) and almond (AS) (Prunus dulcis) through biosorption was investigated in batch experiments. The main parameters influencing Pb(2+) ion sorption on HNS and AS were: initial metal ion concentration, amount of adsorbent, contact time and pH value of solution. The influences of initial Pb(2+) ion concentration (0.1-1.0mM), pH (2-9), contact time (10-240 min) and adsorbent amount (0.1-1.0 g) have been investigated. Equilibrium isotherms have been measured and modelled. Adsorption of Pb(2+) ions was in all cases pH-dependent showing a maximum at equilibrium pH values between 6.0 and 7.0, depending on the biomaterial, that corresponded to equilibrium pH values of 6.0 for HNS and 7.0 for AS. The equilibrium sorption capacities of HNS and AS were 28.18 and 8.08 mg/g for lead, respectively after equilibrium time of 2h. The adsorption data fit well with the Langmuir isotherm model and the experimental result inferred that adsorption, chelation and ion exchange are major adsorption mechanisms for binding Pb(2+) ion to the sorbents.

Immobilized nickel hexacyanoferrate on activated carbons for efficient attenuation of radio toxic Cs(I) from aqueous solutions

NASA Astrophysics Data System (ADS)

Lalhmunsiama; Lalhriatpuia, C.; Tiwari, Diwakar; Lee, Seung-Mok

2014-12-01

The aim of this study is to immobilize nickel hexacyanoferrate onto the large surface of activated carbons (ACs) precursor to rice hulls and areca nut waste materials. These nickel hexacyanoferrate immobilized materials are then assessed in the effective attenuation of radio logically important cesium ions from aqueous solutions. The solid samples are characterized by the XRD analytical method and surface morphology is obtained from the SEM images. The batch reactor experiments show that an increase in sorptive pH (2.0-10.0) apparently not affecting the high percent uptake of Cs(I). Equilibrium modeling studies suggest that the data are reasonably and relatively fitted well to the Langmuir adsorption isotherm. Kinetic studies show that sorption process is fairly rapid and the kinetic data are fitted well to the pseudo-second order rate model. Increasing the background electrolyte concentration from 0.001 to 0.1 mol/L NaCl causes insignificant decrease in Cs(I) removal which infers the higher selectivity of these materials for Cs(I) from aqueous solutions. Further, the column reactor operations enable to obtain the breakthrough data which are then fitted to the Thomas non-linear equation as to obtain the loading capacity of column for Cs(I). The results show that the modified materials show potential applicability in the attenuation of radio toxic cesium from aqueous solution.

Geochemical modeling of reactions and partitioning of trace metals and radionuclides during titration of contaminated acidic sediments.

PubMed

Zhang, Fan; Luo, Wensui; Parker, Jack C; Spalding, Brian P; Brooks, Scott C; Watson, David B; Jardine, Philip M; Gu, Baohua

2008-11-01

Many geochemical reactions that control aqueous metal concentrations are directly affected by solution pH. However, changes in solution pH are strongly buffered by various aqueous phase and solid phase precipitation/dissolution and adsorption/desorption reactions. The ability to predict acid-base behavior of the soil-solution system is thus critical to predict metal transport under variable pH conditions. This studywas undertaken to develop a practical generic geochemical modeling approach to predict aqueous and solid phase concentrations of metals and anions during conditions of acid or base additions. The method of Spalding and Spalding was utilized to model soil buffer capacity and pH-dependent cation exchange capacity by treating aquifer solids as a polyprotic acid. To simulate the dynamic and pH-dependent anion exchange capacity, the aquifer solids were simultaneously treated as a polyprotic base controlled by mineral precipitation/ dissolution reactions. An equilibrium reaction model that describes aqueous complexation, precipitation, sorption and soil buffering with pH-dependent ion exchange was developed using HydroGeoChem v5.0 (HGC5). Comparison of model results with experimental titration data of pH, Al, Ca, Mg, Sr, Mn, Ni, Co, and SO4(2-) for contaminated sediments indicated close agreement suggesting that the model could potentially be used to predictthe acid-base behavior of the sediment-solution system under variable pH conditions.

Green Synthesis of Zinc Oxide Nanoparticles for Enhanced Adsorption of Lead Ions from Aqueous Solutions: Equilibrium, Kinetic and Thermodynamic Studies.

PubMed

Azizi, Susan; Mahdavi Shahri, Mahnaz; Mohamad, Rosfarizan

2017-06-08

In the present study, ZnO nanoparticles (NPs) were synthesized in zerumbone solution by a green approach and appraised for their ability to absorb Pb(II) ions from aqueous solution. The formation of as-synthesized NPs was established by X-ray diffraction (XRD), Transmission Electron Microscopy (TEM), and UV-visible studies. The XRD and TEM analyses revealed high purity and wurtzite hexagonal structure of ZnO NPs with a mean size of 10.01 ± 2.6 nm. Batch experiments were performed to investigate the impact of process parameters viz. Pb(II) concentration, pH of solution, adsorbent mass, solution temperature, and contact time variations on the removal efficiency of Pb(II). The adsorption isotherm data provided that the adsorption process was mainly monolayer on ZnO NPs. The adsorption process follows pseudo-second-order reaction kinetic. The maximum removal efficiencies were 93% at pH 5. Thermodynamic parameters such as enthalpy change (ΔH⁰), free energy change (ΔG⁰), and entropy change (ΔS⁰) were calculated; the adsorption process was spontaneous and endothermic. The good efficiency of the as-synthesized NPs makes them attractive for applications in water treatment, for removal of heavy metals from aqueous system.

Removal of lead (II) ions from aqueous solutions onto activated carbon derived from waste biomass.

PubMed

Erdem, Murat; Ucar, Suat; Karagöz, Selhan; Tay, Turgay

2013-01-01

The removal of lead (II) ions from aqueous solutions was carried out using an activated carbon prepared from a waste biomass. The effects of various parameters such as pH, contact time, initial concentration of lead (II) ions, and temperature on the adsorption process were investigated. Energy Dispersive X-Ray Spectroscopy (EDS) analysis after adsorption reveals the accumulation of lead (II) ions onto activated carbon. The Langmuir and Freundlich isotherm models were applied to analyze equilibrium data. The maximum monolayer adsorption capacity of activated carbon was found to be 476.2 mg g⁻¹. The kinetic data were evaluated and the pseudo-second-order equation provided the best correlation. Thermodynamic parameters suggest that the adsorption process is endothermic and spontaneous.

Equilibrium state at supersaturated drug concentration achieved by hydroxypropyl methylcellulose acetate succinate: molecular characterization using (1)H NMR technique.

PubMed

Ueda, Keisuke; Higashi, Kenjirou; Yamamoto, Keiji; Moribe, Kunikazu

2015-04-06

The maintenance mechanism of the supersaturated state of poorly water-soluble drugs, glibenclamide (GLB) and chlorthalidone (CLT), in hydroxypropyl methylcellulose acetate succinate (HPMC-AS) solution was investigated at a molecular level. HPMC-AS suppressed drug crystallization from supersaturated drug solution and maintained high supersaturated level of drugs with small amount of HPMC-AS for 24 h. However, the dissolution of crystalline GLB into HPMC-AS solution failed to produce supersaturated concentrations, although supersaturated concentrations were achieved by adding amorphous GLB to HPMC-AS solution. HPMC-AS did not improve drug dissolution and/or solubility but efficiently inhibited drug crystallization from supersaturated drug solutions. Such an inhibiting effect led to the long-term maintenance of the amorphous state of GLB in HPMC-AS solution. NMR measurements showed that HPMC-AS suppressed the molecular mobility of CLT depending on their supersaturation level. Highly supersaturated CLT in HPMC-AS solution formed a gel-like structure with HPMC-AS in which the molecular mobility of the CLT was strongly suppressed. The gel-like structure of HPMC-AS could inhibit the reorganization from drug prenuclear aggregates to the crystal nuclei and delay the formation of drug crystals. The prolongation subsequently led to the redissolution of the aggregated drugs in aqueous solution and formed the equilibrium state at the supersaturated drug concentration in HPMC-AS solution. The equilibrium state formation of supersaturated drugs by HPMC-AS should be an essential mechanism underlying the marked drug concentration improvement.

Biosorption of Cu(II) from aqueous solutions by mimosa tannin gel.

PubMed

Sengil, I Ayhan; Ozacar, Mahmut

2008-09-15

The biosorption of Cu(II) from aqueous solutions by mimosa tannin resin (MTR) was investigated as a function of particle size, initial pH, contact time and initial metal ion concentration. The aim of this study was to understand the mechanisms that govern copper removal and find a suitable equilibrium isotherm and kinetic model for the copper removal in a batch reactor. The experimental isotherm data were analysed using the Langmuir, Freundlich and Temkin equations. The equilibrium data fit well in the Langmiur isotherm. The experimental data were analysed using four sorption kinetic models -- the pseudo-first- and second-order equations, and the Elovich and the intraparticle diffusion equation -- to determine the best fit equation for the biosorption of copper ions onto mimosa tannin resin. Results show that the pseudo-second-order equation provides the best correlation for the biosorption process, whereas the Elovich equation also fits the experimental data well. Thermodynamic parameters such as the entropy change, enthalpy change and Gibb's free energy change were found out to be 153.0 J mol(-1)K(-1), 42.09 kJ mol(-1) and -2.47 kJ mol(-1), respectively.

Sorption kinetics and isotherm studies of a cationic dye using agricultural waste: broad bean peels.

PubMed

Hameed, B H; El-Khaiary, M I

2008-06-15

In this paper, broad bean peels (BBP), an agricultural waste, was evaluated for its ability to remove cationic dye (methylene blue) from aqueous solutions. Batch mode experiments were conducted at 30 degrees C. Equilibrium sorption isotherms and kinetics were investigated. The kinetic data obtained at different concentrations have been analyzed using pseudo-first-order, pseudo-second-order and intraparticle diffusion equations. The experimental data fitted very well the pseudo-first-order kinetic model. Analysis of the temportal change of q indicates that at the beginning of the process the overall rate of adsorption is controlled by film-diffusion, then at later stage intraparticle-diffusion controls the rate. Diffusion coefficients and times of transition from film to pore-diffusion control were estimated by piecewise linear regression. The experimental data were analyzed by the Langmuir and Freundlich models. The sorption isotherm data fitted well to Langmuir isotherm and the monolayer adsorption capacity was found to be 192.7 mg/g and the equilibrium adsorption constant Ka is 0.07145 l/mg at 30 degrees C. The results revealed that BBP was a promising sorbent for the removal of methylene blue from aqueous solutions.

Removal of barium and strontium from aqueous solution using zeolite 4A.

PubMed

Araissi, Manel; Ayed, Imen; Elaloui, Elimame; Moussaoui, Younes

2016-01-01

The adsorption efficiency of Sr(2+) and Ba(2+) from aqueous solutions by zeolite 4A was investigated. Adsorption studies were carried out both in single and binary component systems. The single ion equilibrium adsorption data were fitted to three isotherm models: Langmuir, Freundlich and Dubinin-Radushkevich. The Langmuir model represents the equilibrium data better than the Freundlich model in the studied initial metal concentration (0.3-25 mmol L(-1)) in both the single and binary component systems. The obtained RL (separation factor or Langmuir parameter) values were in the range of 0-1 indicating that Sr(2+) and Ba(2+) sorption were favorable. The obtained mean free energy value for adsorption of Ba(2+) and Sr(2+) was 8.45 kJ mol(-1) and 9.12 kJ mol(-1), respectively, indicating that both ions were uptaken through an ion exchange process. The maximum adsorption capacities (Qmax) were 2.25 mmol g(-1) and 2.34 mmol g(-1) for Ba(2+) and Sr(2+) ions, respectively. Also, the study of the competitive sorption of ions in the binary system showed that zeolite 4A preferentially adsorbs cations in the following order: Ba(2+) < Sr(2+).

Static and dynamic investigations of poly(aspartic acid) and Pluronic F127 complex prepared by self-assembling in aqueous solution

NASA Astrophysics Data System (ADS)

Nita, Loredana E.; Chiriac, Aurica P.; Bercea, Maria; Nistor, Manuela T.

2015-12-01

The present investigation is focused on evaluation of self-assembling ability in aqueous solutions of two water soluble polymers: poly(aspartic acid) (PAS) and Pluronic F127 (PL). The intermolecular complexes, realized between polyacid and neutral copolymer surfactant in different ratios, have been studied by combining various characterization techniques as rheology, DLS, spectroscopy, microscopy, chemical imaging, and zeta potential determination, measurements performed in static and/or dynamic conditions. In static conditions, when the equilibrium state between PAS/PL polymeric pair was reached, and depending on the polymers mixture composition, and of experimental rheological conditions, positive or negative deviations from the additive rule are registered. Conformational changes of the macromolecular chains and correspondingly physical interactions are generated between PL and PAS for self-assembly and the formation of interpolymer complex as suprastructure with micellar configuration. The phenomenon was better evidenced in case of 1/1 wt ratio between the two polymers. In dynamic conditions of determination, during ;in situ; evaluation of the hydrodynamic diameter, zeta potential and conductivity, when the equilibrium state is not reached and as result either the intermolecular bonds are not achieved, the self-assembling process is not so obvious evidenced.

Adsorption of a textile dye "Indanthrene Blue RS (C.I. Vat Blue 4)" from aqueous solutions onto smectite-rich clayey rock.

PubMed

Chaari, Islem; Feki, Mongi; Medhioub, Mounir; Bouzid, Jalel; Fakhfakh, Emna; Jamoussi, Fakher

2009-12-30

The adsorption of a textile dye, namely, Indanthrene Blue RS (C.I. Vat Blue 4) onto smectite-rich clayey rock (AYD) and its sulphuric acid-activated products (AYDS) in aqueous solution was studied in a batch system with respect to contact time, pH, and temperature. The adsorbents employed were characterized by X-ray diffraction, infrared spectroscopy and specific surface area, cation exchange capacity and point of zero charge were also estimated. The effect of contact time on dye adsorption showed that the equilibrium was reached after a contact time of 40 min for the both adsorbents. The optimum pH for dye retention was found 6.0 for AYDS and 7.3 for AYD. The equilibrium adsorption data were analysed using the Langmuir and Freundlich isotherms. The adsorption capacities (Q(m)) for AYD and AYDS were found 13.92 mg/g and 17.85 mg/g, respectively. The effect of temperature on the adsorption was also investigated; adsorption of Indanthrene Blue RS is an endothermic process. This study demonstrates that all the considered adsorbents can be used as an alternative emerging technology for water treatment.

Development of parthenium based activated carbon and its utilization for adsorptive removal of p-cresol from aqueous solution.

PubMed

Singh, Ravi Kant; Kumar, Shashi; Kumar, Surendra; Kumar, Arinjay

2008-07-15

The activated carbon was prepared from carbonaceous agriculture waste Parthenium hysterophorous by chemical activation using concentrated H2SO4 at 130+/-5 degrees C. The prepared activated carbon was characterized and was found as an effective adsorbent material. In order to test the efficacy of parthenium based activated carbon (PAC), batch experiments were performed to carryout the adsorption studies on PAC for the removal of highly toxic pollutant p-cresol from aqueous solution. The p-cresol adsorption studies were also carried out on commercial grade activated carbon (AC) to facilitate comparison between the adsorption capabilities of PAC and AC. For PAC and AC, the predictive capabilities of two types of kinetic models and six types of adsorption equilibrium isotherm models were examined. The effect of pH of solution, adsorbent dose and initial p-cresol concentration on adsorption behaviour was investigated, as well. The adsorption on PAC and on AC was found to follow pseudo-first order kinetics with rate constant 0.0016 min(-1) and 0.0050 min(-1), respectively. The highest adsorptive capacity of PAC and AC for p-cresol solution was attained at pH 6.0. Further, as an adsorbent PAC was found to be as good as AC for removal of p-cresol upto a concentration of 500 mg/l in aqueous solution. Freundlich, Redlich-Peterson, and Fritz-Schlunder models were found to be appropriate isotherm models for PAC while Toth, Radke-Prausnitz and Fritz-Schlunder were suitable models for AC to remove p-cresol from aqueous solution.

The removal of As(III) and As(V) from aqueous solutions by waste materials.

PubMed

Rahaman, M S; Basu, A; Islam, M R

2008-05-01

The use of different waste materials such as Atlantic Cod fish scale, chicken fat, coconut fibre and charcoal in removing arsenic [As(III) and As(V)] from aqueous solutions was investigated. Initial experimental runs, conducted for both As(III) and As(V) with the aforementioned materials, demonstrated the potential of using Atlantic Cod fish scale in removing both species of arsenic from aqueous streams. Therefore, the biosorbent fish scale was selected for further investigations and various parameters such as residence time, adsorbent dose, initial concentration of adsorbate, grain size of the adsorbent and pH of the bulk phase were studied to establish optimum conditions. The maximum adsorption capacity was observed at pH value 4.0. The equilibrium adsorption data were interpreted by using both Freundlich and Langmuir models. Rapid small-scale column tests (RSSCT) were also performed to determine the breakthrough characteristics of the arsenic species with respect to packed biosorbent columns.

Papaya Seeds as A Low-Cost Sorbent for Removing Cr(VI) from The Aqueous Solution

NASA Astrophysics Data System (ADS)

Rahmawati, Atik; Marwoto, Putut; Karunia Z, Anita

2016-08-01

The presence of chromium (VI) contaminants and their toxicity in aqueous streams important environmental problems. Adsorption is one of the effective techniques that can be used for removing metal from wastewater. This research was initiated by preparing sorbent from papaya seeds and determining its functional group contents by using FT-IR. The adsorption process was carried out in a batch method. The study of adsorption aspects involved the pH, initial Cr (VI) concentration and contact time between Cr (VI) and sorbent. FT IR analysis results showed that the main functional groups are carbonyl, hydroxyl, and carboxylic. It was also found that the effective pH for Cr (VI) uptake is 2.0 and increasing contact time would increase the Cr (VI) uptake. In addition, the equilibrium was reached after 40 minutes interaction and the increase of initial chromium (VI) concentration would increase the sorbent uptake percentage. All these results indicated that papaya seed is a potential sorbent for removing Cr (VI) from aqueous solutions.

Burkholderia tropica as a Potential Microalgal Growth-Promoting Bacterium in the Biosorption of Mercury from Aqueous Solutions.

PubMed

ZÁrate, Ana; Florez, July; Angulo, Edgardo; Varela-Prieto, Lourdes; Infante, Cherlys; Barrios, Fredy; Barraza, Beatriz; Gallardo, D I; Valdés, Jorge

2017-06-28

The use of microalgal biomass is an interesting technology for the removal of heavy metals from aqueous solutions owing to its high metal-binding capacity, but the interactions with bacteria as a strategy for the removal of toxic metals have been poorly studied. The goal of the current research was to investigate the potential of Burkholderia tropica co-immobilized with Chlorella sp. in polyurethane discs for the biosorption of Hg(II) from aqueous solutions and to evaluate the influence of different Hg(II) concentrations (0.041, 1.0, and 10 mg/l) and their exposure to different contact times corresponding to intervals of 1, 2, 4, 8, 16, and 32 h. As expected, microalgal bacterial biomass adhered and grew to form a biofilm on the support. The biosorption data followed pseudo-second-order kinetics, and the adsorption equilibrium was well described by either Langmuir or Freundlich adsorption isotherm, reaching equilibrium from 1 h. In both bacterial and microalgal immobilization systems in the coimmobilization of Chlorella sp. and B. tropica to different concentrations of Hg(II), the kinetics of biosorption of Hg(II) was significantly higher before 60 min of contact time. The highest percentage of biosorption of Hg(II) achieved in the co-immobilization system was 95% at pH 6.4, at 3.6 g of biosorbent, 30 ± 1°C, and a mercury concentration of 1 mg/l before 60 min of contact time. This study showed that co-immobilization with B. tropica has synergistic effects on biosorption of Hg(II) ions and merits consideration in the design of future strategies for the removal of toxic metals.

Theoretical studies of UO(2)(OH)(H(2)O)(n) (+), UO(2)(OH)(2)(H(2)O)(n), NpO(2)(OH)(H(2)O)(n), and PuO(2)(OH)(H(2)O)(n) (+) (n

PubMed

Cao, Zhiji; Balasubramanian, K

2009-10-28

Extensive ab initio calculations have been carried out to study equilibrium structures, vibrational frequencies, and the nature of chemical bonds of hydrated UO(2)(OH)(+), UO(2)(OH)(2), NpO(2)(OH), and PuO(2)(OH)(+) complexes that contain up to 21 water molecules both in first and second hydration spheres in both aqueous solution and the gas phase. The structures have been further optimized by considering long-range solvent effects through a polarizable continuum dielectric model. The hydrolysis reaction Gibbs free energy of UO(2)(H(2)O)(5) (2+) is computed to be 8.11 kcal/mol at the MP2 level in good agreement with experiments. Our results reveal that it is necessary to include water molecules bound to the complex in the first hydration sphere for proper treatment of the hydrated complex and the dielectric cavity although water molecules in the second hydration sphere do not change the coordination complex. Structural reoptimization of the complex in a dielectric cavity seems inevitable to seek subtle structural variations in the solvent and to correlate with the observed spectra and thermodynamic properties in the aqueous environment. Our computations reveal dramatically different equilibrium structures in the gas phase and solution and also confirm the observed facile exchanges between the complex and bulk solvent. Complete active space multiconfiguration self-consistent field followed by multireference singles+doubles CI (MRSDCI) computations on smaller complexes confirm predominantly single-configurational nature of these species and the validity of B3LYP and MP2 techniques for these complexes in their ground states.

Hexavalent chromium adsorption from aqueous solution using carbon nano-onions (CNOs).

PubMed

Sakulthaew, Chainarong; Chokejaroenrat, Chanat; Poapolathep, Amnart; Satapanajaru, Tunlawit; Poapolathep, Saranya

2017-10-01

The capacity of carbon nano-onions (CNOs) to remove hexavalent chromium (Cr(VI)) from aqueous solution was investigated. Batch experiments were performed to quantify the effects of the dosage rate, pH, counter ions, and temperature. The adsorption of Cr(VI) onto CNOs was best described by a pseudo-second order rate expression. The adsorption efficiency increased with increasing adsorbent dosage and contact time and reached equilibrium in 24 h. The equilibrium data showed better compliance with a Langmuir isotherm than a Freundlich isotherm. Effective removal of Cr(VI) was demonstrated at pH values ranging from 2 to 10. The adsorption capacity of Cr(VI) was found to be highest (82%) at pH 3.4 and greatly depended on the solution pH. We found that Cr(VI) adsorption decreased with increasing pH over the pH range of 3.4-10. The adsorption capacity increased dramatically when the temperature increased from 10 °C to 50 °C regardless of the amount of CNOs used. Cr(VI) removal decreased by ∼13% when Zn(II), Cu(II), and Pb(II) were present, while there were no significant changes observed when NO 3 - or SO 4 2- was present. The overall results support that CNOs can be used as an alternative adsorbent material to remove Cr(VI) in the water treatment industry. Copyright © 2017 Elsevier Ltd. All rights reserved.

Determination of Henry`s law constants by equilibrium partitioning in a closed system using a new in situ optical absorbance method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Allen, J.M.; Balcavage, W.X.; Ramachandran, B.R.

Currently, a great deal of interest exists in developing quantitative descriptions of the transport behavior for organic chemical compounds in the environment. Transport between water and air is of particular significance in this regard. A new method for measurement of thermodynamic Henry`s law constants (H) is reported. In this method, the optical absorbance of a dilute aqueous solution containing an organic compound is followed with time as the compound partitions into the air above the solution in a sealed vessel. The change in optical absorbance and the vapor to liquid volume ratio of the vessel are then used to calculatemore » the value for H. The concentration of the organic compound in the aqueous and vapor phases need not be known. This method allows the approach to equilibrium to be observed in real time so that attainment of equilibrium is readily apparent. This method works particularly well for water-soluble compounds having low vapor pressures. The applicability of this method is limited to compounds that exhibit significant optical absorbance in the ultraviolet and visible regions of the electromagnetic spectrum. Values for H and their temperature dependencies measured using this new method are reported for methacrolein, methyl vinyl ketone, benzaldehyde, and acetophenone. Values for H are also reported for benzene, toluene, and ethylbenzene at 298 K. All reported H data are compared with previously reported values.« less

A breakthrough biosorbent in removing heavy metals: Equilibrium, kinetic, thermodynamic and mechanism analyses in a lab-scale study.

PubMed

Abdolali, Atefeh; Ngo, Huu Hao; Guo, Wenshan; Lu, Shaoyong; Chen, Shiao-Shing; Nguyen, Nguyen Cong; Zhang, Xinbo; Wang, Jie; Wu, Yun

2016-01-15

A breakthrough biosorbent namely multi-metal binding biosorbent (MMBB) made from a combination of tea wastes, maple leaves and mandarin peels, was prepared to evaluate their biosorptive potential for removal of Cd(II), Cu(II), Pb(II) and Zn(II) from multi-metal aqueous solutions. FTIR and SEM were conducted, before and after biosorption, to explore the intensity and position of the available functional groups and changes in adsorbent surface morphology. Carboxylic, hydroxyl and amine groups were found to be the principal functional groups for the sorption of metals. MMBB exhibited best performance at pH 5.5 with maximum sorption capacities of 31.73, 41.06, 76.25 and 26.63 mg/g for Cd(II), Cu(II), Pb(II) and Zn(II), respectively. Pseudo-first and pseudo-second-order models represented the kinetic experimental data in different initial metal concentrations very well. Among two-parameter adsorption isotherm models, the Langmuir equation gave a better fit of the equilibrium data. For Cu(II) and Zn(II), the Khan isotherm describes better biosorption conditions while for Cd(II) and Pb(II), the Sips model was found to provide the best correlation of the biosorption equilibrium data. The calculated thermodynamic parameters indicated feasible, spontaneous and exothermic biosorption process. Overall, this novel MMBB can effectively be utilized as an adsorbent to remove heavy metal ions from aqueous solutions. Copyright © 2015 Elsevier B.V. All rights reserved.

Recovery of hydrogen iodide

DOEpatents

Norman, John H.

1983-01-01

A method of extraction of HI from an aqueous solution of HI and I.sub.2. HBr is added to create a two-phase liquid mixture wherein a dry phase consists essentially of HBr, I and HI and is in equilibrium with a wet phase having a far greater HBr:HI ratio. Using a countercurrent extractor, two solutions can be obtained: a dry HBr--HI--I.sub.2 solution and a wet essentially HBr solution. The dry and wet phases are easily separable, and HI is recovered from the dry phase, after first separating I.sub.2, as by distillation. Alternatively, the HI-HBr liquid mixture is treated to catalytically decompose the HI. HBr is recovered from the wet phase by suitable treatment, including high-pressure distillation, to produce an H.sub.2 O--HBr azeotrope that is not more than 25 mole percent HBr. The azeotrope may be returned for use in an earlier step in the overall process which results in the production of the aqueous solution of HI and I.sub.2 without major detriment because of the presence of HBr.

Recovery of hydrogen iodide

DOEpatents

Norman, J.H.

1983-08-02

A method is described for extraction of HI from an aqueous solution of HI and I[sub 2]. HBr is added to create a two-phase liquid mixture wherein a dry phase consists essentially of HBr, I and HI and is in equilibrium with a wet phase having a far greater HBr:HI ratio. Using a countercurrent extractor, two solutions can be obtained: a dry HBr--HI--I[sub 2] solution and a wet essentially HBr solution. The dry and wet phases are easily separable, and HI is recovered from the dry phase, after first separating I[sub 2], as by distillation. Alternatively, the HI-HBr liquid mixture is treated to catalytically decompose the HI. HBr is recovered from the wet phase by suitable treatment, including high-pressure distillation, to produce an H[sub 2]O--HBr azeotrope that is not more than 25 mole percent HBr. The azeotrope may be returned for use in an earlier step in the overall process which results in the production of the aqueous solution of HI and I[sub 2] without major detriment because of the presence of HBr. 1 fig.

A model for trace metal sorption processes at the calcite surface: Adsorption of Cd2+ and subsequent solid solution formation

USGS Publications Warehouse

Davis, J.A.; Fuller, C.C.; Cook, A.D.

1987-01-01

The rate of Cd2+ sorption by calcite was determined as a function of pH and Mg2+ in aqueous solutions saturated with respect to calcite but undersaturated with respect to CdCO3. The sorption is characterized by two reaction steps, with the first reaching completion within 24 hours. The second step proceeded at a slow and nearly constant rate for at least 7 days. The rate of calcite recrystallization was also studied, using a Ca2+ isotopic exchange technique. Both the recrystallization rate of calcite and the rate of slow Cd2+ sorption decrease with increasing pH or with increasing Mg2+. The recrystallization rate could be predicted from the number of moles of Ca present in the hydrated surface layer. A model is presented which is consistent with the rates of Cd2+ sorption and Ca2+ isotopic exchange. In the model, the first step in Cd2+ sorption involves a fast adsorption reaction that is followed by diffusion of Cd2+ into a surface layer of hydrated CaCO3 that overlies crystalline calcite. Desorption of Cd2+ from the hydrated layer is slow. The second step is solid solution formation in new crystalline material, which grows from the disordered mixture of Cd and Ca carbonate in the hydrated surface layer. Calculated distribution coefficients for solid solutions formed at the surface are slightly greater than the ratio of equilibrium constants for dissolution of calcite and CdCO3, which is the value that would be expected for an ideal solid solution in equilibrium with the aqueous solution. ?? 1987.

Eragrostis plana Nees as a novel eco-friendly adsorbent for removal of crystal violet from aqueous solutions.

PubMed

Filho, Augusto Cezar D; Mazzocato, Ana C; Dotto, Guilherme L; Thue, Pascal S; Pavan, Flávio A

2017-08-01

Eragrostis plana Nees (EPN) was used as new and eco-friendly adsorbent for the removal of crystal violet dye (CV) from aqueous solution. Specific surface area (BET), scanning electron microscopy (SEM), infrared spectroscopy (ATR-FTIR), point of zero charge (pH PZC ), and modified Boehm titration method were used to characterize the EPN material. The effects of initial pH of solution, adsorbent mass, contact time and initial dye concentration, and temperature were studied in batch adsorption mode. Kinetic data were evaluated by pseudo-first-order and pseudo-second-order models. The result exhibited that pseudo-second-order model well described the adsorption kinetics of CV onto EPN. Langmuir, Freundlich, and Sips isotherm models were used for analysis of the isothermal data. The equilibrium data of adsorption of CV onto EPN was better fitted with the Sips isotherm. Based on the Sips isotherm model, the maximum adsorption capacity was 76.20 ± 1.20 mg g -1 at 333 K. A high desorption of CV from EPN was obtained using 1.00 mol L -1 of CH 3 COOH as eluent. The thermodynamic data indicated that the adsorption was spontaneous, endothermic, and physical process. EPN can be used as alternative adsorbent to remove CV from aqueous solution.

Pelletized ponderosa pine bark for adsorption of toxic heavy metals from water

Treesearch

Miyoung Oh; Mandla A. Tshabalala

2007-01-01

Bark flour from ponderosa pine (Pinus ponderosa) was consolidated into pellets using citric acid as cross-linking agent. The pellets were evaluated for removal of toxic heavy metals from synthetic aqueous solutions. When soaked in water, pellets did not leach tannins, and they showed high adsorption capacity for Cu(ll), Zn(ll), Cd(ll). and Ni(ll) under both equilibrium...

Acid-Base Properties of Azo Dyes in Solution Studied Using Spectrophotometry and Colorimetry

NASA Astrophysics Data System (ADS)

Snigur, D. V.; Chebotarev, A. N.; Bevziuk, K. V.

2018-03-01

Colorimetry and spectrophotometry with chemometric data processing were used to study the acid-base properties of azo dyes in aqueous solution. The capabilities of both methods were compared. Ionization constants of all the functional groups of the azo compounds studied could be determined relative to the change in the specific color difference depending on the acidity of the medium. The colorimetric functions of ion-molecular forms of azo compounds used as an analytical signal allow us to obtain complete information on the acid-base equilibrium in a wide acidity range.

Liquid-liquid equilibria for water + ethanol + 2-methylpropyl ethanoate and water + ethanol + 1,2-dibromoethane at 298. 15 K

DOE Office of Scientific and Technical Information (OSTI.GOV)

Solimo, H.N.; Barnes de Arreguez, N.G.

1994-01-01

Liquid-liquid equilibrium, distribution coefficients, and selectivities of the systems water + ethanol + 2-methylpropyl ethanoate or + 1,2-dibromoethane have been determined at 298.15 K in order to evaluate their suitability in preferentially extracting ethanol from aqueous solution. Tie-line data were satisfactorily correlated by the Othmer and Tobias method, and the plait point coordinates for the two systems were estimated. The experimental data was compared with the values calculated by the NRTL and UNIQUAC models. The water + ethanol + 2-methylpropyl ethanoate system was also compared with the values predicted by the UNIFAC model. Poor qualitative agreement was obtained with thesemore » models. From the experimental results, they can conclude that both solvents are inappropriate for ethanol extraction processes from aqueous solutions.« less

Malachite green "a cationic dye" and its removal from aqueous solution by adsorption

NASA Astrophysics Data System (ADS)

Raval, Nirav P.; Shah, Prapti U.; Shah, Nisha K.

2017-11-01

Adsorption can be efficiently employed for the removal of various toxic dyes from water and wastewater. In this article, the authors reviewed variety of adsorbents used by various researchers for the removal of malachite green (MG) dye from an aqueous environment. The main motto of this review article was to assemble the scattered available information of adsorbents used for the removal of MG to enlighten their wide potential. In addition to this, various optimal experimental conditions (solution pH, equilibrium contact time, amount of adsorbent and temperature) as well as adsorption isotherms, kinetics and thermodynamics data of different adsorbents towards MG were also analyzed and tabulated. Finally, it was concluded that the agricultural solid wastes and biosorbents such as biopolymers and biomass adsorbents have demonstrated outstanding adsorption capabilities for removal of MG dye.

Activated carbon prepared from yerba mate used as a novel adsorbent for removal of tannery dye from aqueous solution.

PubMed

Linhares, Bruno; Weber, Caroline Trevisan; Foletto, Edson Luiz; Paz, Diego Silva; Mazutti, Marcio A; Collazzo, Gabriela Carvalho

2013-01-01

Activated carbon prepared from yerba mate (Ilex paraguariensis) was used as adsorbent for the removal of tannery dye from aqueous solution. The activated carbon was characterized, and it showed a mesoporous texture, with surface area of 537.4 m2 g(-1). The initial dye concentration, contact time and pH influenced the adsorption capacity. The equilibrium data were in good agreement with both Langmuir and Freundlich isotherms. The adsorption kinetics of the tannery dye on activated carbon prepared from yerba mate followed a pseudo-second-order model. The adsorption process was found to be controlled by both external mass-transfer and intraparticle diffusion, but the external diffusion was the dominating process. This work highlights the potential application of activated carbon produced from yerba mate in the field of adsorption.

Biosorption of Azo dyes by spent Rhizopus arrhizus biomass

NASA Astrophysics Data System (ADS)

Salvi, Neeta A.; Chattopadhyay, S.

2017-10-01

In the present study, spent Rhizopus arrhizus biomass was used for the removal of six azo dyes from aqueous solutions. The dye removal capacity of the biomass was evaluated by conducting batch tests as a function of contact time, biomass dosage, pH and initial dye concentrations. The pseudo-second-order kinetic model fitted well with the experimental data with correlation coefficients greater than 0.999, suggesting that chemisorptions might be the rate limiting step. The equilibrium sorption data showed good fit to the Langmuir isotherm model. Among the six dyes tested, the maximum monolayer adsorption capacity for fast red A and metanil yellow was found to be 108.8 and 128.5 mg/g, respectively. These encouraging results suggest that dead Rhizopus arrhizus biomass could be a potential biomaterial for the removal of azo dyes from aqueous dye solution.

Competitive adsorption of ibuprofen and amoxicillin mixtures from aqueous solution on activated carbons.

PubMed

Mansouri, Hayet; Carmona, Rocio J; Gomis-Berenguer, Alicia; Souissi-Najar, Souad; Ouederni, Abdelmottaleb; Ania, Conchi O

2015-07-01

This work investigates the competitive adsorption under dynamic and equilibrium conditions of ibuprofen (IBU) and amoxicillin (AMX), two widely consumed pharmaceuticals, on nanoporous carbons of different characteristics. Batch adsorption experiments of pure components in water and their binary mixtures were carried out to measure both adsorption equilibrium and kinetics, and dynamic tests were performed to validate the simultaneous removal of the mixtures in breakthrough experiments. The equilibrium adsorption capacities evaluated from pure component solutions were higher than those measured in dynamic conditions, and were found to depend on the porous features of the adsorbent and the nature of the specific/dispersive interactions that are controlled by the solution pH, density of surface change on the carbon and ionization of the pollutant. A marked roll-up effect was observed for AMX retention on the hydrophobic carbons, not seen for the functionalized adsorbent likely due to the lower affinity of amoxicillin towards the carbon adsorbent. Dynamic adsorption of binary mixtures from wastewater of high salinity and alkalinity showed a slight increase in IBU uptake and a reduced adsorption of AMX, demonstrating the feasibility of the simultaneous removal of both compounds from complex water matrices. Copyright © 2014 Elsevier Inc. All rights reserved.

Removal of trivalent chromium from aqueous solution using aluminum oxide hydroxide.

PubMed

Bedemo, Agaje; Chandravanshi, Bhagwan Singh; Zewge, Feleke

2016-01-01

Water is second most essential for human being. Contamination of water makes it unsuitable for human consumption. Chromium ion is released to water bodies from various industries having high toxicity which affects the biota life in these waters. In this study aluminum oxide hydroxide was tested for its efficiency to remove trivalent chromium from aqueous solutions through batch mode experiments. Chromium concentrations in aqueous solutions and tannery waste water before and after adsorption experiments were determined using flame atomic absorption spectrometry. The effects of pH, contact time, initial concentration and adsorbent dosage on the adsorption of Cr(III) were studied. The study revealed that more than 99 % removal of Cr(III) was achieved over wide range of initial pH (3-10). The optimum conditions for the removal of Cr(III) were found to be at pH 4-6 with 40 g/L adsorbent dose at 60 min of contact time. The adsorption capacity was assessed using Langmuir and Freundlich isotherms. The equilibrium data at varying adsorbent dose obeyed the two isotherms. The adsorbent was found to be efficient for the removal of Cr(III) from tannery waste effluent.

Biosorption characteristics of copper (II), chromium (III), nickel (II), and lead (II) from aqueous solutions by Chara sp. and Cladophora sp.

PubMed

Elmaci, Ayşe; Yonar, Taner; Ozengin, Nihan

2007-09-01

The aim of this research was to expose individual removals of copper, chromium, nickel, and lead from aqueous solutions via biosorption using nonliving algae species, Chara sp. and Cladophora sp. Optimum pH values for biosorption of copper (II), chromium (III), nickel (II), and lead (II) from aqueous solutions were determined to be 6, 7, 7, and 3 for Cladophora sp. and 5, 3, 5, and 4 for Chara sp. respectively. Maximum adsorption capacities of Chara sp. [10.54 for chromium (III) and 61.72 for lead (II)] and Cladophora sp. [6.59 for chromium (III) and 16.75 and 23.25 for lead (II)] for chromium (III) and lead (II) are similar. On the other hand, copper (II) and nickel (II) biosorption capacity of Cladophora sp. [14.28 for copper (II) and 16.75 for nickel (II)] is greater than Chara sp. [6.506 for copper (II) and 11.76 for nickel (II)]. Significantly high correlation coefficients indicated for the Langmuir adsorption isotherm models can be used to describe the equilibrium behavior of copper, chromium, nickel, and lead adsorption onto Cladophora sp. and Chara sp.

Geochemical Modeling of Reactions and Partitioning of Trace Metals and Radionuclides during Titration of Contaminated Acidic Sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Fan; Parker, Jack C.; Luo, Wensui

2008-01-01

Many geochemical reactions that control aqueous metal concentrations are directly affected by solution pH. However, changes in solution pH are strongly buffered by various aqueous phase and solid phase precipitation/dissolution and adsorption/desorption reactions. The ability to predict acid-base behavior of the soil-solution system is thus critical to predict metal transport under variable pH conditions. This study was undertaken to develop a practical generic geochemical modeling approach to predict aqueous and solid phase concentrations of metals and anions during conditions of acid or base additions. The method of Spalding and Spalding was utilized to model soil buffer capacity and pH-dependent cationmore » exchange capacity by treating aquifer solids as a polyprotic acid. To simulate the dynamic and pH-dependent anion exchange capacity, the aquifer solids were simultaneously treated as a polyprotic base controlled by mineral precipitation/dissolution reactions. An equilibrium reaction model that describes aqueous complexation, precipitation, sorption and soil buffering with pH-dependent ion exchange was developed using HydroGeoChem v5.0 (HGC5). Comparison of model results with experimental titration data of pH, Al, Ca, Mg, Sr, Mn, Ni, Co, and SO{sub 4}{sup 2-} for contaminated sediments indicated close agreement, suggesting that the model could potentially be used to predict the acid-base behavior of the sediment-solution system under variable pH conditions.« less

Study of sorption-retarded U(VI) diffusion in Hanford silt/clay material.

PubMed

Bai, Jing; Liu, Chongxuan; Ball, William P

2009-10-15

A diffusion cell method was applied to measure the effective pore diffusion coefficient (Dp) for U(VI) under strictly controlled chemical conditions in a silt/clay sediment from the U.S. Department of Energy Hanford site, WA. "Inward-flux" diffusion studies were conducted in which [U(VI)] in both aqueous and solid phases was measured as a function of distance in the diffusion cell under conditions of constant concentration at the cell boundaries. A sequential extraction method was developed to measure sorbed contaminant U(VI) in the solid phase containing extractable background U(VI). The effect of sorption kinetics on U(VI) interparticle diffusion was evaluated by comparing sorption-retarded diffusion models with sorption described either as equilibrium or intraparticle diffusion-limited processes. Both experimental and modeling results indicated that (1) a single pore diffusion coefficient can simulate the diffusion of total aqueous U(VI), and (2) the local equilibrium assumption (LEA) is appropriate for modeling sorption-retarded diffusion under the given experimental conditions. Dp of 1.6-1.7 x 10(-6) cm2/s was estimated in aqueous solution at pH 8.0 and saturated with respect to calcite, as relevant to some subsurface regions of the Hanford site.

Biosorption of hexavalent chromium from aqueous medium with Opuntia biomass.

PubMed

Fernández-López, José A; Angosto, José M; Avilés, María D

2014-01-01

The biosorption of hexavalent chromium from aqueous solutions by Opuntia cladodes and ectodermis from cactus fruits was investigated. Both types of biomass are considered low-cost, natural, and ecofriendly biosorbents. Batch experiments were carried out to determine Cr(VI) biosorption capacity and the efficiency of the biosorption process under different pH, initial Cr(VI) concentration, and sorbent dosage. The biosorption of Cr(VI) by Opuntia biomass was highly pH dependent, favoring higher metal uptake at low pH. The higher biosorption capacity was exhibited at pH 2. The optimal conditions were obtained at a sorbent dosage of 1 g L(-1) and initial metal concentration of 10 mg L(-1). Biosorption kinetic data were properly fitted with the pseudo-second-order kinetic model. The rate constant, the initial biosorption rate, and the equilibrium biosorption capacity were determined. The experimental equilibrium data obtained were analyzed using two-parameter isotherm models (Langmuir, Freundlich, and Temkin). The Langmuir maximum monolayer biosorption capacity (q max) was 18.5 mg g(-1) for cladodes and 16.4 mg g(-1) for ectodermis. The results suggest that Opuntia biomass could be considered a promising low-cost biosorbent for the ecofriendly removal of Cr(VI) from aqueous systems.

Inverse Kinetic and Equilibrium Isotope Effects on Self-Assembly and Supramolecular Chirality of Porphyrin J-Aggregates.

PubMed

Zagami, Roberto; Romeo, Andrea; Castriciano, Maria A; Monsù Scolaro, Luigi

2017-01-01

When mixtures of D 2 O/DCl are used to foster the self-assembly formation of TPPS 4 porphyrin J-aggregates in aqueous solutions, an inverse kinetic isotope effect of 0.4 and an inverse equilibrium isotope effect of 0.6 are clearly detected. Most importantly, the addition of at least 10 % D 2 O causes an inversion in the handedness of the final chiral J-aggregates, thus evidencing an important role of deuterium in driving the enantiomeric excess in the scalemic mixture of such supramolecular assemblies. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Equilibrium distribution of dissolved sulphur species in water at 25°C and 1 atm total pressure

USGS Publications Warehouse

Garrels, R.M.; Naeser, C.R.

1958-01-01

The Eh-pH diagrams for the equilibrium concentrations in aqueous solution at 25°C of native sulphur and all the various sulphur-containing ions and acids from which the ions are produced have been constructed for systems having a total sulphur concentration of 0.1 molar. The composite of these diagrams indicates that elemental sulphur, H2S, HS− HSO4− and SO4 are the species that predominate in the environments that might be found in nature. This indication is in agreement with the composition of all sulphur-containing minerals.

Concentration dependences of the physicochemical properties of a water-acetone system

NASA Astrophysics Data System (ADS)

Fedyaeva, O. A.; Poshelyuzhnaya, E. G.

2017-01-01

Concentration dependences of the UV spectrum, refractive index, specific electrical conductivity, boiling point, pH, surface tension, and heats of dissolution of a water-acetone system on the amount of acetone in the water are studied. It is found that the reversible protolytic interaction of the components occurs in all such solutions, resulting in the formation of hydroxyl and acetonium ions. It is shown that shifts of the equilibrium between the molecules and ions in the solution leads to extreme changes in their electrical properties. It is concluded that the formation of acetone solutions of water is accompanied by heat absorption, while the formation of aqueous solutions of acetone is accompanied by heat release.

Evaluation of an adsorbent based on agricultural waste (corn cobs) for removal of tyrosine and phenylalanine from aqueous solutions.

PubMed

Alves, Cibele C O; Franca, Adriana S; Oliveira, Leandro S

2013-01-01

Adsorption of phenolic amino acids, such as phenylalanine and tyrosine, is quite relevant for the production of protein hydrolysates used as dietary formulations for patients suffering from congenital disorders of amino acid metabolism, such as phenylketonuria. In this study, an adsorbent prepared from corn cobs was evaluated for the removal of tyrosine (Tyr) from both a single component solution and a binary aqueous solution with phenylalanine (Phe). The adsorption behavior of tyrosine was similar to that of phenylalanine in single component solutions, however, with a much lower adsorption capacity (14 mg g(-1) for Tyr compared to 109 mg g(-1) for Phe). Tyr adsorption kinetics was satisfactorily described by a pseudosecond-order model as it was for Phe. In adsorption equilibrium studies for binary mixtures, the presence of Tyr in Phe solutions favored Phe faster adsorption whereas the opposite behavior was observed for the presence of Phe in Tyr solutions. Such results indicate that, in binary systems, Phe will be adsorbed preferably to Tyr, and this is a welcome feature when employing the prepared adsorbent for the removal of Phe from protein hydrolysates to be used in dietary formulations for phenylketonuria treatment.

Using Basic Principles To Understand Complex Science: Nicotine Smoke Chemistry and Literature Analogies

NASA Astrophysics Data System (ADS)

Seeman, Jeffrey I.

2005-10-01

The Henderson Hasselbalch equation calculates the equilibrium distribution of 50:50 for nicotine in its nonprotonated (free base form), relative to its monoprotonated form, at pH of 8 in dilute aqueous solution. This ratio has then been used in the literature to predict the effect of ammonia compounds in tobacco and in smoke on nicotine pyrolysis and smoke chemistry. Experiments demonstrate that neither the thermal chemistry of tobacco alkaloids nor the transfer of nicotine from tobacco to smoke can be explained by the position of the nonprotonated versus monoprotonated form equilibrium in aqueous extracts of tobacco. The high thermal stability of nicotine in air allows nicotine salts to be converted to nonprotonated nicotine and volatilize during heating prior to any substantial decomposition of the nicotine moiety. In contrast, cocaine hydrochloride is thermally unstable and will rapidly decompose upon heating; cocaine hydrochloride must first be converted to its nonprotonated form prior to heating and volatilization.

Universal patterns of equilibrium cluster growth in aqueous sugars observed by dynamic light scattering.

PubMed

Sidebottom, D L; Tran, Tri D

2010-11-01

Dynamic light scattering performed on aqueous solutions of three sugars (glucose, maltose and sucrose) reveal a common pattern of sugar cluster formation with a narrow cluster size distribution. In each case, equilibrium clusters form whose size increases with increasing sugar content in an identical power law manner in advance of a common, critical-like, percolation threshold near 83 wt % sugar. The critical exponent of the power law divergence of the cluster size varies with temperature, increasing with decreasing temperature, due to changes in the strength of the intermolecular hydrogen bond and appears to vanish for temperatures in excess of 90 °C. Detailed analysis of the cluster growth process suggests a two-stage process: an initial cluster phase formed at low volume fractions, ϕ, consisting of noninteracting, monodisperse sugar clusters whose size increases ϕ(1/3) followed by an aggregation stage, active at concentrations above about ϕ=40%, where cluster-cluster contact first occurs.

Preparation and Characterization of Biochars from Eichornia crassipes for Cadmium Removal in Aqueous Solutions.

PubMed

Li, Feng; Shen, Kaixuan; Long, Xiaolin; Wen, Jiasheng; Xie, Xiaojie; Zeng, Xiangyun; Liang, Yanyan; Wei, Yansha; Lin, Zefeng; Huang, Wenrou; Zhong, Ruida

2016-01-01

The study investigated the preparation and characterization of biochars from water hyacinth at 300°C to 700°C for cadmium (Cd) removal from aqueous solutions. The adsorption process was dominated by oxygen-containing functional groups with irregular surfaces via esterification reactions. Furthermore, the mineral components in the biochars also contributed to Cd absorption through precipitation. Parameters such as the effects of solution pH, contact time, and initial concentration were studied. The optimum pH value was observed at 5.0, in which nearly 90% of Cd was removed. The maximum Cd adsorption capacities based on the Langmuir isotherm were calculated at 49.837, 36.899, and 25.826 mg g(-1). The adsorption processes of the biochars followed the pseudo-second-order kinetics, with the equilibrium achieved around 5 h. The biochar from E. crassipes is a promising adsorbent for the treatment of wastewater, which can in turn convert one environmental problem to a new cleaning Technology.

Preparation and Characterization of Biochars from Eichornia crassipes for Cadmium Removal in Aqueous Solutions

PubMed Central

Li, Feng; Shen, Kaixuan; Long, Xiaolin; Wen, Jiasheng; Xie, Xiaojie; Zeng, Xiangyun; Liang, Yanyan; Wei, Yansha; Lin, Zefeng; Huang, Wenrou; Zhong, Ruida

2016-01-01

The study investigated the preparation and characterization of biochars from water hyacinth at 300°C to 700°C for cadmium (Cd) removal from aqueous solutions. The adsorption process was dominated by oxygen-containing functional groups with irregular surfaces via esterification reactions. Furthermore, the mineral components in the biochars also contributed to Cd absorption through precipitation. Parameters such as the effects of solution pH, contact time, and initial concentration were studied. The optimum pH value was observed at 5.0, in which nearly 90% of Cd was removed. The maximum Cd adsorption capacities based on the Langmuir isotherm were calculated at 49.837, 36.899, and 25.826 mg g−1. The adsorption processes of the biochars followed the pseudo-second-order kinetics, with the equilibrium achieved around 5 h. The biochar from E. crassipes is a promising adsorbent for the treatment of wastewater, which can in turn convert one environmental problem to a new cleaning Technology. PMID:26882239

Reactive phosphorus removal from aquaculture and poultry productions systems using polymeric hydrogels.

PubMed

Kofinas, Peter; Kioussis, Dimitri R

2003-01-15

This work reports on the features of a sorption processes for the ultimate removal and recovery of reactive phosphorus from aquaculture and poultry production wastewater effluents. The sorbent used was a cross-linked polyamine (PAA-HCl) polymeric hydrogel. The PAA-HCl hydrogels were prepared by chemically cross-linking aqueous solutions of linear PAA-HCl chains with epichlorohydrin (EPI). The phosphorus binding capacity of the gels was measured in standard aqueous solutions as a function of ionic strength. Equilibrium PO4(3-), loadings of 100 mg anion/g gel were obtained. The regeneration ability of the gels was demonstrated by release of the bound phosphorus anions upon washing with 1-2 M NaOH solution, providing opportunities to recover and reuse the gel over multiple cycles. The ionic polyamine gels have been demonstrated to be appropriate materials for treating poultry and aquaculture wastewater effluents. Upon treatment phosphorus anion concentrations were reduced to levels suitable for discharge into natural surface waters.

Jute stick powder as a potential biomass for the removal of congo red and rhodamine B from their aqueous solution.

PubMed

Panda, Gopal C; Das, Sujoy K; Guha, Arun K

2009-05-15

Jute stick powder (JSP) has been found to be a promising material for adsorptive removal of congo red (C.I. 22120) and rhodamine B (C.I. 45170) from aqueous solutions. Physico-chemical parameters like dye concentration, solution pH, temperature and contact time have been varied to study the adsorption phenomenon. Favorable adsorption occurs at around pH 7.0 whereas temperature has no significant effect on adsorption of both the dyes. The maximum adsorption capacity has been calculated to be 35.7 and 87.7mg/g of the biomass for congo red and rhodamine B, respectively. The adsorption process is in conformity with Freundlich and Langmuir isotherms for rhodamine B whereas congo red adsorption fits well to Langmuir isotherm only. In both the cases, adsorption occurs very fast initially and attains equilibrium within 60min. Kinetic results suggest the intra-particle diffusion of dyes as rate limiting step.

A general nuclear magnetic resonance analysis of hetero-association of aromatic molecules in aqueous solution

NASA Astrophysics Data System (ADS)

Veselkov, Alexei N.; Evstigneev, Maxim P.; Veselkov, Dennis A.; Davies, David B.

2001-08-01

A general nuclear magnetic resonance analysis of a statistical-thermodynamical model of hetero-association of aromatic molecules in solution has been developed to take "edge effects" into consideration, i.e., the dependence of proton chemical shifts on the position of the molecule situated inside or at the edge of the aggregate. This generalized approach is compared with a previously published model, where an average contribution to proton shielding is considered irrespective of the position of the molecule in the stack. Association parameters have been determined from experimental concentration and temperature dependences of 500 MHz proton chemical shifts of the hetero-association of the acridine dye, proflavine, and the phenanthridinium dye, ethidium bromide, in aqueous solution. Differences in the parameters in the range 10%-30% calculated using the basic and generalized approaches have been found to depend substantially on the magnitude of the equilibrium hetero-association constant Khet—the larger the value of Khet, the higher the discrepancy between the two methods.

Adsorptive removal of Congo red from aqueous solutions using crosslinked chitosan and crosslinked chitosan immobilized bentonite.

PubMed

Huang, Ruihua; Zhang, Lujie; Hu, Pan; Wang, Jing

2016-05-01

Batch experiments were executed to investigate the removal of Congo red (CR) from aqueous solutions using the crosslinked chitosan (CCS) and crosslinked chitosan immobilized bentonite (CCS/BT composite). The CCS and CCS/BT composite were characterized by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) techniques. The removal of CR was examined as a function of pH value of CR solution, contact time, and inorganic sodium salt and ionic strength. The equilibrium data of CCS and CCS/BT composite agreed well with the Langmuir model. The adsorption capacities of CCS and CCS/BT composite at 298K and natural pH value were 405 and 500 mg/g, respectively. The kinetic data correlated well with the pseudo-second-order model. The adsorption of CR onto the CCS was mainly controlled by chemisorption while the adsorption of CR onto the CCS/BT composite was controlled by chemisorption and the electrostatic attraction. Copyright © 2016 Elsevier B.V. All rights reserved.

Removal of methyl orange and methylene blue dyes from aqueous solution using lala clam (Orbicularia orbiculata) shell

NASA Astrophysics Data System (ADS)

Eljiedi, Arwa Alseddig Ahmed; Kamari, Azlan

2017-05-01

Textile effluents are considered as potential sources of water pollution because they contain toxic dyes. In the present study, lala clam shell was used as an alternative low-cost adsorbent for the removal of two harmful dyes, namely methyl orange (MO) and methylene blue (MB) from aqueous solution. Batch adsorption studies were carried out by varying experimental parameters such as solution pH, initial concentration and adsorbent dosage. The optimum pH values for MO and MB removal were pH 2.0 and pH 8.0, respectively. At an initial MO and MB concentration of 20 mg/L, the maximum removal percentage of MO and MB were 18.9 % and 81.3 %, respectively. The adsorption equilibrium data were correlated with both Langmuir and Freundlich isotherm models. The biomass adsorbent was characterised using Field Emission Scanning Electron Microscope (FESEM) and Fourier Transform Infrared Spectrometer (FTIR). Results from this study suggest that lala clam shell, a fishery waste, can be beneficial for water treatment.

Nonflat equilibrium liquid shapes on flat surfaces.

PubMed

Starov, Victor M

2004-01-15

The hydrostatic pressure in thin liquid layers differs from the pressure in the ambient air. This difference is caused by the actions of surface forces and capillary pressure. The manifestation of the surface force action is the disjoining pressure, which has a very special S-shaped form in the case of partial wetting (aqueous thin films and thin films of aqueous electrolyte and surfactant solutions, both free films and films on solid substrates). In thin flat liquid films the disjoining pressure acts alone and determines their thickness. However, if the film surface is curved then both the disjoining and the capillary pressures act simultaneously. In the case of partial wetting their simultaneous action results in the existence of nonflat equilibrium liquid shapes. It is shown that in the case of S-shaped disjoining pressure isotherm microdrops, microdepressions, and equilibrium periodic films exist on flat solid substrates. Criteria are found for both the existence and the stability of these nonflat equilibrium liquid shapes. It is shown that a transition from thick films to thinner films can go via intermediate nonflat states, microdepressions and periodic films, which both can be more stable than flat films within some range of hydrostatic pressure. Experimental investigations of shapes of the predicted nonflat layers can open new possibilities of determination of disjoining pressure in the range of thickness in which flat films are unstable.

Metastable equilibria among dicarboxylic acids and the oxidation state during aqueous alteration on the CM2 chondrite parent body

NASA Astrophysics Data System (ADS)

McAlister, Jason A.; Kettler, Richard M.

2008-01-01

Linear saturated dicarboxylic acids are present in carbonaceous chondrite samples at concentrations that suggest aqueous alteration under conditions of metastable equilibrium. In this study, previously published values of dicarboxylic acid concentrations measured in Murchison, Yamato-791198, and Tagish Lake carbonaceous chondrites are converted to aqueous activities during aqueous alteration assuming water:rock ratios that range from 1:10 to 10:1. Logarithmic plots of the aqueous activities of any two dicarboxylic acids are proximal to lines whose slope is fixed by the stoichiometry of reactions describing the oxidation-reduction equilibrium between the two species. The precise position of any line is controlled by the equilibrium constant of the reaction relating the species and the hydrogen fugacity for the reaction of interest. Reactions among succinic (C4), glutaric (C5), and adipic (C6) acids obtained from CM2 chondrites show evidence of metastable equilibrium and yield logf values that agree to within 0.3 log units at 298.15 K and 0.6 log units at 473.15 K. At a water:rock ratio of 1:1, metastable equilibrium among succinic, glutaric, and adipic acids results in calculated logf values during aqueous alteration that range from -6.2 at 298.15 K to -3.3 at 373.15 K. These values are consistent with those obtained in previous work on carbonaceous chondrites and with metastable equilibrium at temperatures ranging from 300 to 355 K in contact with cronstedtite + magnetite.

The Thermochemical and Kinetic Properties of Ascorbate are Tuned by its Local Environment: Solution Chemistry and Biochemical Implications

PubMed Central

Warren, Jeffrey J.; Mayer, James M.

2010-01-01

Ascorbate (Vitamin C) is a ubiquitous biological cofactor. While its aqueous solution chemistry has long been studied, many in vivo reactions of ascorbate occur in enzyme active sites or at membrane interfaces, which have varying local environments. This report shows that the rate and driving force of oxidations of two ascorbate derivatives by the TEMPO radical (2,2′-6,6′-tetramethylpiperidine-1-oxyl) in acetonitrile are very sensitive to the presence of various additives. These reactions proceed by the transfer of a proton and an electron (a hydrogen atom), as is typical of biological ascorbate reactions. The measured rate and equilibrium constants vary substantially with added water or other polar solutes in acetonitrile solutions, indicating large shifts in the reducing power of ascorbate. The correlation of rate and equilibrium constants indicates that this effect has a thermochemical origin rather than being a purely kinetic effect. This contrasts with previous examples of solvent effects on hydrogen atom transfer reactions. Potential biological implications of this apparently unique effect are discussed. PMID:20476757

Removal of Hexavalent Chromium by Adsorption on Microwave Assisted Activated Carbon Prepared from Stems of Leucas Aspera

NASA Astrophysics Data System (ADS)

Shanmugalingam, A.; Murugesan, A.

2018-05-01

This study reports adsorption of Cr(VI) ions from aqueous solution using activated carbon that was prepared from stems of Leucas aspera. Eight hundred and fifty watts power of microwave radiation, 12 min of radiation time, 60% of ZnCl2 solution and 24 h of impregnation time are the optimal parameters to prepare efficient carbon effective activated carbon. It was designated as MWLAC (Microwave assisted Zinc chloride activated Leucas aspera carbon). Various adsorption characteristics such as dose of the adsorbent, agitation time, initial Cr(VI) ion concentration, pH of the solution and temperature on adsorption were studied for removal of Cr(VI) ions from aqueous solution by batch mode. Also the equilibrium adsorption was analyzed by the Langmuir, Freundlich, Tempkin and D-R isotherm models. The order of best describing isotherms was given based on R2 value. The pseudo-second-order kinetic model best fitted with the Cr(VI) adsorption data. Thermodynamic parameters were also determined and results suggest that the adsorption process is a spontaneous, endothermic and proceeded with increased randomness.

Determination of kinetic and equilibrium parameters of the batch adsorption of Mn(II), Co(II), Ni(II) and Cu(II) from aqueous solution by black carrot (Daucus carota L.) residues.

PubMed

Güzel, Fuat; Yakut, Hakan; Topal, Giray

2008-05-30

In this study, the effect of temperature on the adsorption of Mn(II), Ni(II), Co(II) and Cu(II) from aqueous solution by modified carrot residues (MCR) was investigated. The equilibrium contact times of adsorption process for each heavy metals-MCR systems were determined. Kinetic data obtained for each heavy metal by MCR at different temperatures were applied to the Lagergren equation, and adsorption rate constants (kads) at these temperatures were determined. These rate constants related to the adsorption of heavy metal by MCR were applied to the Arrhenius equation, and activation energies (Ea) were determined. In addition, the isotherms for adsorption of each heavy metal by MCR at different temperatures were also determined. These isothermal data were applied to linear forms of isotherm equations that they fit the Langmuir adsorption isotherm, and the Langmuir constants (qm and b) were calculated. b constants determined at different temperatures were applied to thermodynamic equations, and thermodynamic parameters such as enthalpy (Delta H), free energy (Delta G), and entropy (Delta S) were calculated and these values show that adsorption of heavy metal on MCR was an endothermic process and process of adsorption was favoured at high temperatures.

Simulating the reactions of CO2 in aqueous monoethanolamine solution by reaction ensemble Monte Carlo using the continuous fractional component method.

PubMed

Balaji, Sayee Prasaad; Gangarapu, Satesh; Ramdin, Mahinder; Torres-Knoop, Ariana; Zuilhof, Han; Goetheer, Earl L V; Dubbeldam, David; Vlugt, Thijs J H

2015-06-09

Molecular simulations were used to compute the equilibrium concentrations of the different species in CO2/monoethanolamine solutions for different CO2 loadings. Simulations were performed in the Reaction Ensemble using the continuous fractional component Monte Carlo method at temperatures of 293, 333, and 353 K. The resulting computed equilibrium concentrations are in excellent agreement with experimental data. The effect of different reaction pathways was investigated. For a complete understanding of the equilibrium speciation, it is essential to take all elementary reactions into account because considering only the overall reaction of CO2 with MEA is insufficient. The effects of electrostatics and intermolecular van der Waals interactions were also studied, clearly showing that solvation of reactants and products is essential for the reaction. The Reaction Ensemble Monte Carlo using the continuous fractional component method opens the possibility of investigating the effects of the solvent on CO2 chemisorption by eliminating the need to study different reaction pathways and concentrate only on the thermodynamics of the system.

Combining MOSCED with molecular simulation free energy calculations or electronic structure calculations to develop an efficient tool for solvent formulation and selection

NASA Astrophysics Data System (ADS)

Cox, Courtney E.; Phifer, Jeremy R.; Ferreira da Silva, Larissa; Gonçalves Nogueira, Gabriel; Ley, Ryan T.; O'Loughlin, Elizabeth J.; Pereira Barbosa, Ana Karolyne; Rygelski, Brett T.; Paluch, Andrew S.

2017-02-01

Solubility parameter based methods have long been a valuable tool for solvent formulation and selection. Of these methods, the MOdified Separation of Cohesive Energy Density (MOSCED) has recently been shown to correlate well the equilibrium solubility of multifunctional non-electrolyte solids. However, before it can be applied to a novel solute, a limited amount of reference solubility data is required to regress the necessary MOSCED parameters. Here we demonstrate for the solutes methylparaben, ethylparaben, propylparaben, butylparaben, lidocaine and ephedrine how conventional molecular simulation free energy calculations or electronic structure calculations in a continuum solvent, here the SMD or SM8 solvation model, can instead be used to generate the necessary reference data, resulting in a predictive flavor of MOSCED. Adopting the melting point temperature and enthalpy of fusion of these compounds from experiment, we are able to predict equilibrium solubilities. We find the method is able to well correlate the (mole fraction) equilibrium solubility in non-aqueous solvents over four orders of magnitude with good quantitative agreement.

Combining MOSCED with molecular simulation free energy calculations or electronic structure calculations to develop an efficient tool for solvent formulation and selection.

PubMed

Cox, Courtney E; Phifer, Jeremy R; Ferreira da Silva, Larissa; Gonçalves Nogueira, Gabriel; Ley, Ryan T; O'Loughlin, Elizabeth J; Pereira Barbosa, Ana Karolyne; Rygelski, Brett T; Paluch, Andrew S

2017-02-01

Solubility parameter based methods have long been a valuable tool for solvent formulation and selection. Of these methods, the MOdified Separation of Cohesive Energy Density (MOSCED) has recently been shown to correlate well the equilibrium solubility of multifunctional non-electrolyte solids. However, before it can be applied to a novel solute, a limited amount of reference solubility data is required to regress the necessary MOSCED parameters. Here we demonstrate for the solutes methylparaben, ethylparaben, propylparaben, butylparaben, lidocaine and ephedrine how conventional molecular simulation free energy calculations or electronic structure calculations in a continuum solvent, here the SMD or SM8 solvation model, can instead be used to generate the necessary reference data, resulting in a predictive flavor of MOSCED. Adopting the melting point temperature and enthalpy of fusion of these compounds from experiment, we are able to predict equilibrium solubilities. We find the method is able to well correlate the (mole fraction) equilibrium solubility in non-aqueous solvents over four orders of magnitude with good quantitative agreement.

Metals sorption from aqueous solutions by Kluyveromyces marxianus: process optimization, equilibrium modeling and chemical characterization.

PubMed

Pal, Rama; Tewari, Saumyata; Rai, Jai P N

2009-10-01

The dead Kluyveromyces marxianus biomass, a fermentation industry waste, was used to explore its sorption potential for lead, mercury, arsenic, cobalt, and cadmium as a function of pH, biosorbent dosage, contact time, agitation speed, and initial metal concentration. The equilibrium data fitted the Langmuir model better for cobalt and cadmium, but Freundlich isotherm for all metals tested. At equilibrium, the maximum uptake capacity (Qmax) was highest for lead followed by mercury, arsenic, cobalt, and cadmium. The RL values ranged between 0-1, indicating favorable sorption of all test metals by the biosorbent. The maximum Kf value of Pb showed its efficient removal from the solution. However, multi-metal analysis depicted that sorption of all metals decreased except Pb. The potentiometric titration of biosorbent revealed the presence of functional groups viz. amines, carboxylic acids, phosphates, and sulfhydryl group involved in heavy metal sorption. The extent of contribution of functional groups and lipids to biosorption was in the order: carboxylic>lipids>amines>phosphates. Blocking of sulfhydryl group did not have any significant effect on metal sorption.

Conformation and Dynamics of Human Urotensin II and Urotensin Related Peptide in Aqueous Solution.

PubMed

Haensele, Elke; Mele, Nawel; Miljak, Marija; Read, Christopher M; Whitley, David C; Banting, Lee; Delépée, Carla; Sopkova-de Oliveira Santos, Jana; Lepailleur, Alban; Bureau, Ronan; Essex, Jonathan W; Clark, Timothy

2017-02-27

Conformation and dynamics of the vasoconstrictive peptides human urotensin II (UII) and urotensin related peptide (URP) have been investigated by both unrestrained and enhanced-sampling molecular-dynamics (MD) simulations and NMR spectroscopy. These peptides are natural ligands of the G-protein coupled urotensin II receptor (UTR) and have been linked to mammalian pathophysiology. UII and URP cannot be characterized by a single structure but exist as an equilibrium of two main classes of ring conformations, open and folded, with rapidly interchanging subtypes. The open states are characterized by turns of various types centered at K 8 Y 9 or F 6 W 7 predominantly with no or only sparsely populated transannular hydrogen bonds. The folded conformations show multiple turns stabilized by highly populated transannular hydrogen bonds comprising centers F 6 W 7 K 8 or W 7 K 8 Y 9 . Some of these conformations have not been characterized previously. The equilibrium populations that are experimentally difficult to access were estimated by replica-exchange MD simulations and validated by comparison of experimental NMR data with chemical shifts calculated with density-functional theory. UII exhibits approximately 72% open:28% folded conformations in aqueous solution. URP shows very similar ring conformations as UII but differs in an open:folded equilibrium shifted further toward open conformations (86:14) possibly arising from the absence of folded N-terminal tail-ring interaction. The results suggest that the different biological effects of UII and URP are not caused by differences in ring conformations but rather by different interactions with UTR.

Deep ice and salty oceans of icy worlds, how high pressures influence their thermodynamics and provide constrains on extraterrestrial habitability

NASA Astrophysics Data System (ADS)

Journaux, B.; Brown, J. M.; Bollengier, O.; Abramson, E.

2017-12-01

As in Earth arctic and Antarctic regions, suspected extraterrestrial deep oceans in icy worlds (i.e. icy moons and water-rich exoplanets) chemistry and thermodynamic state will strongly depend on their equilibrium with H2O ice and present solutes. Na-Mg-Cl-SO4 salt species are currently the main suspected ionic solutes to be present in deep oceans based on remote sensing, magnetic field measurements, cryovolcanism ice grains chemical analysis and chondritic material aqueous alteration chemical models. Unlike on our planet, deep extraterrestrial ocean might also be interacting at depth with high pressure ices (e.g. III, V, VI, VI, X) which have different behavior compared to ice Ih. Unfortunately, the pressures and temperatures inside these hydrospheres differ significantly from the one found in Earth aqueous environments, so most of our current thermodynamic databases do not cover the range of conditions relevant for modeling realistically large icy worlds interiors. Recent experimental results have shown that the presence of solutes, and more particularly salts, in equilibrium with high pressure ices have large effects on the stability, buoyancy and chemistry of all the phases present at these extreme conditions. High pressure in-situ measurements using diamond anvil cell apparatus were operated both at the University of washington and at the European Synchrotron Radiation Facility on aqueous systems phase diagrams with Na-Mg-Cl-SO4 species, salt incorporation in high pressure ices and density inversions between the solid and the fluids. These results suggest a more complex picture of the interior structure, dynamic and chemical evolution of large icy worlds hydrospheres when solutes are taken into account, compared to current models mainly using pure water. Based on our in-situ experimental measurements, we propose the existence of new liquid environments at greater depths and the possibility of solid state transport of solute through the high pressure ices(s) layers suggesting that large icy worlds like Enceladus, Titan or water-rich exoplanets could have habitable deep oceans, even when high pressure ices are present.

New treatment method for boron in aqueous solutions using Mg-Al layered double hydroxide: Kinetics and equilibrium studies.

PubMed

Kameda, Tomohito; Oba, Jumpei; Yoshioka, Toshiaki

2015-08-15

Mg-Al layered double hydroxides (LDHs) intercalated with NO3(-) (NO3 · Mg - Al LDHs) and with Cl(-) (Cl · Mg - Al LDHs) were found to take up boron from aqueous solutions. Boron was removed by anion exchange of B(OH)4(-) in solution with NO3(-) and Cl(-) intercalated in the interlayer of the LDH. Using three times the stoichiometric quantity of NO3 · Mg-Al LDH, the residual concentration of B decreased from 100 to 1.9 mg L(-1) in 120 min. Using five times the stoichiometric quantity of Cl · Mg - Al LDH, the residual concentration of B decreased from 100 to 5.6 mg L(-1) in 120 min. It must be emphasized that, in both cases, the residual concentration of B was less than the effluent standards in Japan (10 mg L(-1)). The rate-determining step of B removal by the NO3 · Mg - Al and Cl · Mg - Al LDHs was found to be chemical adsorption involving anion exchange of B(OH)4(-) with intercalated NO3(-) and Cl(-). The removal of B was well described by a pseudo second-order kinetic equation. The adsorption of B by NO3 · Mg - Al LDH and Cl · Mg - Al LDH followed a Langmuir-type adsorption. The values of the maximum adsorption and the equilibrium adsorption constant were 3.6 mmol g(-1) and 1.7, respectively, for NO3 · Mg - Al LDH, and 3.8 mmol g(-1) and 0.7, respectively, for Cl · Mg-Al LDH. The B(OH)4(-) in B(OH)4 · Mg - Al LDH produced by removal of B was found to undergo anion exchange with NO3(-) and Cl(-) in solution. The NO3 · Mg - Al and Cl · Mg - Al LDHs obtained after this regeneration treatment were able to remove B from aqueous solutions, indicating the possibility of recycling NO3 · Mg - Al and Cl · Mg - Al LDHs for B removal. Copyright © 2015 Elsevier B.V. All rights reserved.

Preparation of fast response superabsorbent hydrogels by radiation polymerization and crosslinking of N-isopropylacrylamide in solution

NASA Astrophysics Data System (ADS)

Abd El-Mohdy, H. L.; Safrany, Agnes

2008-03-01

Macroporous temperature-responsive poly( N-isopropylacrylamide) (PNIPAAm) hydrogels with high equilibrium swelling and fast response rates were obtained by a 60Co γ- and electron beam (EB) irradiation of aqueous N-isopropylacrylamide (NIPAAm) monomer solutions. The effect of irradiation temperatures, the dose, the addition of a pore-forming agent on the swelling ratio, and the kinetics of swelling and shrinking of the PNIPAAm gels was studied. The gels synthesized above the LCST exhibited the highest equilibrium swelling (300-400) and fastest response rate measured by minutes. Scanning electron microscope (SEM) pictures revealed that the gels synthesized above the LCST have larger pores than those prepared at temperatures below the LCST. The gels showed a reversible response to cyclical changes in temperature and might be used in a pulsed drug delivery device. The gels synthesized above the LCST exhibited the highest testosterone propionate release.

Equilibrium and kinetic modelling of chromium(III) sorption by animal bones.

PubMed

Chojnacka, Katarzyna

2005-04-01

The paper discusses sorption of Cr(III) ions from aqueous solutions by animal bones. Animal bones were found to be an efficient sorbent with the maximum experimentally determined sorption capacity in the range 29-194 mg g(-1) that depended on pH and temperature. The maximum experimentally determined sorption capacity was obtained at 50 degrees C, pH 5. Batch kinetics and equilibrium experiments were performed in order to investigate the influence of contact time, initial concentration of sorbate and sorbent, temperature and pH. It was found that sorption capacity increased with increase of Cr(III) concentration, temperature and initial pH of metal solution. Mathematical models describing kinetics and statics of sorption were proposed. It was found that process kinetics followed the pseudo-second-order pattern. The influence of sorbent concentration was described with Langmuir-type equation and the influence of sorbate concentration was described with empirical dependence. The models were positively verified.

Modeling biosorption of Cr(VI) onto Ulva compressa L. from aqueous solutions.

PubMed

Aid, Asma; Amokrane, Samira; Nibou, Djamel; Mekatel, Elhadj; Trari, Mohamed; Hulea, Vasile

2018-01-01

The marine biomass Ulva compressa L. (ECL) was used as a low-cost biosorbent for the removal of Cr(VI) from contaminated aqueous solutions. The operating variables were optimized: pH ∼ 2, initial concentration of 25 mg/L, solid/liquid ratio of 6 g/L and a temperature of 50 °C, leading to an uptake elimination of 96%. A full factorial experimental design technique enabled us to obtain a mathematical model describing the Cr(VI) biosorption and to study the main effects and interactions among operational parameters. The equilibrium isotherm was analyzed by the Langmuir, Freundlich and Dubinin-Radushkevich (D-R) models; it has been found that the adsorption process follows well the Langmuir model. Kinetic studies showed that the pseudo-second order model describes suitably the experimental data. The thermodynamic parameters indicated an endothermic heat and a spontaneity of the Cr(VI) biosorption onto ECL.

Efficient Removal of Uranium from Aqueous Solution by Reduced Graphene Oxide-Zn0.5Ni0.5Fe2O4 Ferrite-Polyaniline Nanocomposite

NASA Astrophysics Data System (ADS)

Tran, Dat Quang; Pham, Hung Thanh; Do, Hung Quoc

2017-06-01

Reduced graphene oxide-Zn0.5Ni0.5Fe2O4 ferrite-polyaniline nanocomposite (RGO-ZNF-PANI) was synthesized by a three-step method. The prepared samples were characterized by x-ray diffraction, Raman spectroscopy, scanning electron microscopy and vibrating sample magnetometer. In particular, we found that this material is capable of effectively removing uranium from an aquatic environment. This is confirmed by our experimental results using the method of inductively coupled plasma mass spectrometry. Adsorptive behaviour of uranium from an aqueous solution on the RGO-ZNF-PANI nanocomposite was examined as a function of pH, contact time, and equilibrium. Uranium concentration was carried out by batch techniques. The adsorption isotherm agrees well with the Langmuir model, having a maximum sorption capacity of 1885 mg/g, at pH 5 and 25°C.

Adsorption of 2,4-dichlorophenoxyacetic acid and 4-chloro-2-metylphenoxyacetic acid onto activated carbons derived from various lignocellulosic materials.

PubMed

Doczekalska, Beata; Kuśmierek, Krzysztof; Świątkowski, Andrzej; Bartkowiak, Monika

2018-05-04

Adsorption of 2,4-dichlorophenoxyacetic acid (2,4-D) and 4-chloro-2-metylphenoxyacetic acid (MCPA) from aqueous solution onto activated carbons derived from various lignocellulosic materials including willow, miscanthus, flax, and hemp shives was investigated. The adsorption kinetic data were analyzed using two kinetic models: the pseudo-first order and pseudo-second order equations. The adsorption kinetics of both herbicides was better represented by the pseudo-second order model. The adsorption isotherms of 2,4-D and MCPA on the activated carbons were analyzed using the Freundlich and Langmuir isotherm models. The equilibrium data followed the Langmuir isotherm. The effect of pH on the adsorption was also studied. The results showed that the activated carbons prepared from the lignocellulosic materials are efficient adsorbents for the removal of 2,4-D and MCPA from aqueous solutions.

Linear free-energy relationships between a single gas-phase ab initio equilibrium bond length and experimental pKa values in aqueous solution.

PubMed

Alkorta, Ibon; Popelier, Paul L A

2015-02-02

Remarkably simple yet effective linear free energy relationships were discovered between a single ab initio computed bond length in the gas phase and experimental pKa values in aqueous solution. The formation of these relationships is driven by chemical features such as functional groups, meta/para substitution and tautomerism. The high structural content of the ab initio bond length makes a given data set essentially divide itself into high correlation subsets (HCSs). Surprisingly, all molecules in a given high correlation subset share the same conformation in the gas phase. Here we show that accurate pKa values can be predicted from such HCSs. This is achieved within an accuracy of 0.2 pKa units for 5 drug molecules. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Insight into biosorption equilibrium, kinetics and thermodynamics of crystal violet onto Ananas comosus (pineapple) leaf powder

NASA Astrophysics Data System (ADS)

Chakraborty, Sagnik; Chowdhury, Shamik; Saha, Papita Das

2012-06-01

Biosorption performance of pineapple leaf powder (PLP) for removal of crystal violet (CV) from its aqueous solutions was investigated. To this end, the influence of operational parameters such as pH, biosorbent dose, initial dye concentration and temperature were studied employing a batch experimental setup. The biosorption process followed the Langmuir isotherm model with high correlation coefficients ( R 2 > 0.99) at different temperatures. The maximum monolayer biosorption capacity was found to be 78.22 mg g-1 at 293 K. The kinetic data conformed to the pseudo-second-order kinetic model. The activation energy of the system was calculated as 58.96 kJ mol- 1 , indicating chemisorption nature of the ongoing biosorption process. A thermodynamic study showed spontaneous and exothermic nature of the biosorption process. Owing to its low cost and high dye uptake capacity, PLP has potential for application as biosorbent for removal of CV from aqueous solutions.

Adsorptive potential of cationic Basic Yellow 2 (BY2) dye onto natural untreated clay (NUC) from aqueous phase: Mass transfer analysis, kinetic and equilibrium profile

NASA Astrophysics Data System (ADS)

Öztürk, A.; Malkoc, E.

2014-04-01

In this work, natural untreated clay (NUC) was studied for the removal of Basic Yellow 2 (BY2) from aqueous solution in batch system. The effects of initial BY2 concentration, contact time, solution temperature and solution pH on BY2 adsorption were investigated. Nitrogen sorption measurements were employed to investigate the variation in surface and pore properties after dye adsorption. The adsorbent was characterized by means of FTIR, PSD, TEM, XRD and BET analysis. The equilibrium adsorption data were analyzed by Langmuir, Freundlich, Temkin and Scatchard isotherm models. The maximum monolayer adsorption capacity was found to be 833.33 mg/g at 25 °C (at room temperature). The pseudo-second-order kinetic model provided the best fit to the experimental datas compared with pseudo-first-order kinetic adsorption models. To explain mass transfer mechanism of BY2 adsorption, obtained experimental datas were applied Weber and Morris model, Body and Frusawa and Smith models. The results show that the adsorption process is controlled by film diffusion. The thermodynamic parameters such as, Gibbs free energy changes (ΔG°), standard enthalpy change (ΔH°) and standard entropy change (ΔS°) were determined. Adsorption of BY2 on NUC is exothermic and spontaneous in nature. The calculated activation energy of adsorption was found to be 5.24 kJ/mol for BY2. This value indicates that the adsorption process is a physisorption.

Ca and Fe modified biochars as adsorbents of arsenic and chromium in aqueous solutions.

PubMed

Agrafioti, Evita; Kalderis, Dimitrios; Diamadopoulos, Evan

2014-12-15

This work investigated the production of Ca and Fe modified biochars in order to use them for the removal of arsenic As(V) and chromium Cr(VI) from aqueous solutions. Rice husk was impregnated with CaO at an impregnation ratio 0.114, while both rice husk and the organic fraction of municipal solid wastes were impregnated with Fe(0) and Fe(3+) at impregnation ratios 0.114 and 0.23. The modified biochars exhibited high As(V) removal capacity (>95%), except for the case of rice husk impregnated with Fe(0), whose removal capacity reached only 58%. All modified biochars exhibited much better As(V) removal capacity compared to the non-impregnated biochars. However, the Cr(VI) removal rates were not as high as the As(V) ones. The maximum Cr(VI) removal was observed in the case of rice husk biochar impregnated with 2.3% w/w Fe(3+), whereas the majority of impregnation agents examined did not manage to enhance the biochars' Cr(VI) removal ability. The equilibrium study showed that the Freundlich model can adequately describe the sorption process for the majority of samples examined. Analysis of the amount of Fe present in the equilibrium solutions suggested that the main mechanisms of As(V) and Cr(VI) removal were possibly metal precipitation and electrostatic interactions between the modified biochars and the adsorbate. Copyright © 2014 Elsevier Ltd. All rights reserved.

Total reflection infrared spectroscopy of water-ice and frozen aqueous NaCl solutions.

PubMed

Walker, Rachel L; Searles, Keith; Willard, Jesse A; Michelsen, Rebecca R H

2013-12-28

Liquid-like and liquid water at and near the surface of water-ice and frozen aqueous sodium chloride films were observed using attenuated total reflection infrared spectroscopy (ATR-IR). The concentration of NaCl ranged from 0.0001 to 0.01 M and the temperature varied from the melting point of water down to 256 K. The amount of liquid brine at the interface of the frozen films with the germanium ATR crystal increased with salt concentration and temperature. Experimental spectra are compared to reflection spectra calculated for a simplified morphology of a uniform liquid layer between the germanium crystal and the frozen film. This morphology allows for the amount of liquid observed in an experimental spectrum to be converted to the thickness of a homogenous layer with an equivalent amount of liquid. These equivalent thickness ranges from a nanometer for water-ice at 260 K to 170 nm for 0.01 M NaCl close to the melting point. The amounts of brine observed are over an order of magnitude less than the total liquid predicted by equilibrium thermodynamic models, implying that the vast majority of the liquid fraction of frozen solutions may be found in internal inclusions, grain boundaries, and the like. Thus, the amount of liquid and the solutes dissolved in them that are available to react with atmospheric gases on the surfaces of snow and ice are not well described by thermodynamic equilibrium models which assume the liquid phase is located entirely at the surface.

Effect of mixing, concentration and temperature on the formation of mesostructured solutions and their role in the nucleation of DL-valine crystals.

PubMed

Jawor-Baczynska, Anna; Moore, Barry D; Sefcik, Jan

2015-01-01

We report investigations on the formation of mesostructured solutions in DL-valine-water-2-propanol mixtures, and the crystallization of DL-valine from these solutions. Mesostructured liquid phases, similar to those previously observed in aqueous solutions of glycine and DL-alanine, were observed using Dynamic Light Scattering and Brownian microscopy, in both undersaturated and supersaturated solutions below a certain transition temperature. Careful experimentation was used to demonstrate that the optically clear mesostructured liquid phase, comprising colloidal mesoscale clusters dispersed within bulk solution, is thermodynamically stable and present in equilibrium with the solid phase at saturation conditions. Solutions prepared by slow cooling contained mesoscale clusters with a narrow size distribution and a mean hydrodynamic diameter of around 200 nm. Solutions of identical composition prepared by rapid isothermal mixing of valine aqueous solutions with 2-propanol contained mesoscale clusters which were significantly larger than those observed in slowly cooled solutions. The presence of larger mesoscale clusters was found to correspond to faster nucleation. Observed induction times were strongly dependent on the rapid initial mixing step, although solutions were left undisturbed afterwards and the induction times observed were up to two orders of magnitude longer than the initial mixing period. We propose that mesoscale clusters above a certain critical size are likely to be the location of productive nucleation events.

Uranium biosorption by Padina sp. algae biomass: kinetics and thermodynamics.

PubMed

Khani, Mohammad Hassan

2011-11-01

Kinetic, thermodynamic, and equilibrium isotherms of the biosorption of uranium ions onto Padina sp., a brown algae biomass, in a batch system have been studied. The kinetic data were found to follow the pseudo-second-order model. Intraparticle diffusion is not the sole rate-controlling factor. The equilibrium experimental results were analyzed in terms of Langmuir isotherm depending with temperature. Equilibrium data fitted very well to the Langmuir model. The maximum uptakes estimated by using the Langmuir model were 434.8, 416.7, 400.0, and 370.4 mg/g at 10°C, 20°C, 30°C, and 40°C, respectively. Gibbs free energy was spontaneous for all interactions, and the adsorption process exhibited exothermic enthalpy values. Padina sp. algae were shown to be a favorable biosorbent for uranium removal from aqueous solutions.

Modelling of the acid-base properties of natural and synthetic adsorbent materials used for heavy metal removal from aqueous solutions.

PubMed

Pagnanelli, Francesca; Vegliò, Francesco; Toro, Luigi

2004-02-01

In this paper a comparison about kinetic behaviour, acid-base properties and copper removal capacities was carried out between two different adsorbent materials used for heavy metal removal from aqueous solutions: an aminodiacetic chelating resin as commercial product (Lewatit TP207) and a lyophilised bacterial biomass of Sphaerotilus natans. The acid-base properties of a S. natans cell suspension were well described by simplified mechanistic models without electrostatic corrections considering two kinds of weakly acidic active sites. In particular the introduction of two-peak distribution function for the proton affinity constants allows a better representation of the experimental data reproducing the site heterogeneity. A priori knowledge about resin functional groups (aminodiacetic groups) is the base for preliminary simulations of titration curve assuming a Donnan gel structure for the resin phase considered as a concentrated aqueous solution of aminodiacetic acid (ADA). Departures from experimental and simulated data can be interpreted by considering the heterogeneity of the functional groups and the effect of ionic concentration in the resin phase. Two-site continuous model describes adequately the experimental data. Moreover the values of apparent protonation constants (as adjustable parameters found by non-linear regression) are very near to the apparent constants evaluated by a Donnan model assuming the intrinsic constants in resin phase equal to the equilibrium constants in aqueous solution of ADA and considering the amphoteric nature of active sites for the evaluation of counter-ion concentration in the resin phase. Copper removal outlined the strong affinity of the active groups of the resin for this ion in solution compared to the S. natans biomass according to the complexation constants between aminodiacetic and mono-carboxylic groups and copper ions.

Removal of lindane from an aqueous solution by using aminopropyl silica gel-immobilized calix[6]arene.

PubMed

Tor, Ali; Aydin, Mehmet Emin; Aydin, Senar; Tabakci, Mustafa; Beduk, Fatma

2013-11-15

An aminopropyl silica gel-immobilized calix[6]arene (C[6]APS) has been used for the removal of lindane from an aqueous solution in batch sorption technique. The C[6]APS was synthesized with p-tert-butylcalix[6]arene hexacarboxylate derivative and aminopropyl silica gel in the presence of N,N'-diisopropyl carbodiimide coupling reagent. The sorption study was carried out as functions of solution pH, contact time, initial lindane concentration, C[6]APS dosage and ionic strength of solution. The matrix effect of natural water samples on the sorption efficiency of C[6]APS was also investigated. Maximum lindane removal was obtained at a wide pH range of 2-8 and sorption equilibrium was achieved in 2h. The isotherm analysis indicated that the sorption data can be represented by both Langmuir and Freundlich isotherm models. Increasing ionic strength of the solutions increased the sorption efficiency and matrix of natural water samples had no effect on the sorption of lindane. By using multilinear regression model, regression equation was also developed to explain the effects of the experimental variables. Copyright © 2013 Elsevier B.V. All rights reserved.

Biosorption of Copper (II) from Aqueous Solution Using Non-Living Mesorhizobium amorphae Strain CCNWGS0123

PubMed Central

Mohamad, Osama Abdalla; Hao, Xiuli; Xie, Pin; Hatab, Shaimaa; Lin, Yanbing; Wei, Gehong

2012-01-01

The mining industry generates huge amounts of wastewater, containing toxic heavy metals. Treatment to remove heavy metals is necessary and recent work has been focused on finding more environmentally friendly materials for removing heavy metals from wastewater. Biosorption can be an effective process for heavy metal removal from aqueous solutions. Our objectives were to investigate the removal of copper (II) from aqueous solutions using dead cells of Mesorhizobium amorphae CCNWGS0123 under differing levels of pH, agitation speed, temperature, initial copper concentration, biosorbent dose and contact time using flame atomic absorption spectroscopy for metal estimation. The maximum copper removal rate was achieved at pH 5.0, agitation speed 150×g, temperature 28°C and initial Cu (II) concentration of 100 mg L−1. Maximum biosorption capacity was at 0.5 g L−1 and equilibrium was attained within 30 min. Langmuir and Freundlich isotherms showed correlation coefficients of 0.958 and 0.934, respectively. Fourier transform-infrared spectroscopy (FT-IR) analysis indicated that many functional groups, such as O-H, N-H, C-H, C=O, -NH, -CN, C-N, C-O, amide -I, -II, -III and unsaturated alkenes, alkyls and aromatic groups on the cell surface were involved in the interaction between CCNWGS0123 and Cu. Scanning electron microscope and energy dispersive X-ray scanning results showed deformation, aggregation, and cell-surface damage due to the precipitation of copper on the cell surface. Dead cells of CCNWGS0123 showed potential as an efficient biosorbent for the removal of Cu2+ from aqueous solutions. PMID:22353770

Analysis of the (Trimethylsilyl)propionic Acid-β(12-28) Peptide Binding Equilibrium with NMR Spectroscopy.

PubMed

Jayawickrama, D A; Larive, C K

1999-06-01

The binding of a small molecule, (trimethylsilyl)propionic acid (TSP), to a 17-residue peptide, β(12-28), is examined using (1)H NMR spectroscopy. β(12-28) (VHHQKLVFFAEDVGSNK) is a central fragment of the 40-42-residue Alzheimer's-associated Aβ peptide. This peptide has been previously shown to form soluble aggregates in low-pH aqueous solution. The TSP resonance is broadened appreciably in solutions containing relatively high concentrations (∼2 mM) of the peptide. The changes in TSP line width measured by titration of a peptide solution with TSP indicate a 1:1 binding stoichiometry. If the concentrations of both the peptide and TSP are reduced by 1 order of magnitude, the resonances of both species are sharp, suggesting that TSP binds predominately to the aggregated peptide. Nuclear Overhauser effect experiments indicate that the TSP interacts predominately with the side chains of the aliphatic peptide residues Leu(17) and Val(18). Pulsed-field gradient NMR measurements of TSP and peptide diffusion coefficients provide a more quantitative picture of the TSP-peptide binding equilibrium. The measured diffusion coefficients were used to calculate the fractions of the free and bound TSP. These results substantiate the conclusion that the stoichiometry of the TSP-peptide binding equilibrium is essentially 1:1 and further indicate anticooperative behavior in solutions containing an excess of TSP resulting in a dissociation of the peptide aggregates.

Structural ensembles reveal intrinsic disorder for the multi-stimuli responsive bio-mimetic protein Rec1-resilin

PubMed Central

Balu, Rajkamal; Knott, Robert; Cowieson, Nathan P.; Elvin, Christopher M.; Hill, Anita J.; Choudhury, Namita R.; Dutta, Naba K.

2015-01-01

Rec1-resilin is the first recombinant resilin-mimetic protein polymer, synthesized from exon-1 of the Drosophila melanogaster gene CG15920 that has demonstrated unusual multi-stimuli responsiveness in aqueous solution. Crosslinked hydrogels of Rec1-resilin have also displayed remarkable mechanical properties including near-perfect rubber-like elasticity. The structural basis of these extraordinary properties is not clearly understood. Here we combine a computational and experimental investigation to examine structural ensembles of Rec1-resilin in aqueous solution. The structure of Rec1-resilin in aqueous solutions is investigated experimentally using circular dichroism (CD) spectroscopy and small angle X-ray scattering (SAXS). Both bench-top and synchrotron SAXS are employed to extract structural data sets of Rec1-resilin and to confirm their validity. Computational approaches have been applied to these experimental data sets in order to extract quantitative information about structural ensembles including radius of gyration, pair-distance distribution function, and the fractal dimension. The present work confirms that Rec1-resilin is an intrinsically disordered protein (IDP) that displays equilibrium structural qualities between those of a structured globular protein and a denatured protein. The ensemble optimization method (EOM) analysis reveals a single conformational population with partial compactness. This work provides new insight into the structural ensembles of Rec1-resilin in solution. PMID:26042819

Structural ensembles reveal intrinsic disorder for the multi-stimuli responsive bio-mimetic protein Rec1-resilin.

PubMed

Balu, Rajkamal; Knott, Robert; Cowieson, Nathan P; Elvin, Christopher M; Hill, Anita J; Choudhury, Namita R; Dutta, Naba K

2015-06-04

Rec1-resilin is the first recombinant resilin-mimetic protein polymer, synthesized from exon-1 of the Drosophila melanogaster gene CG15920 that has demonstrated unusual multi-stimuli responsiveness in aqueous solution. Crosslinked hydrogels of Rec1-resilin have also displayed remarkable mechanical properties including near-perfect rubber-like elasticity. The structural basis of these extraordinary properties is not clearly understood. Here we combine a computational and experimental investigation to examine structural ensembles of Rec1-resilin in aqueous solution. The structure of Rec1-resilin in aqueous solutions is investigated experimentally using circular dichroism (CD) spectroscopy and small angle X-ray scattering (SAXS). Both bench-top and synchrotron SAXS are employed to extract structural data sets of Rec1-resilin and to confirm their validity. Computational approaches have been applied to these experimental data sets in order to extract quantitative information about structural ensembles including radius of gyration, pair-distance distribution function, and the fractal dimension. The present work confirms that Rec1-resilin is an intrinsically disordered protein (IDP) that displays equilibrium structural qualities between those of a structured globular protein and a denatured protein. The ensemble optimization method (EOM) analysis reveals a single conformational population with partial compactness. This work provides new insight into the structural ensembles of Rec1-resilin in solution.

Removal of uranium from aqueous solution by a low cost and high-efficient adsorbent

NASA Astrophysics Data System (ADS)

Liu, Yun-Hai; Wang, You-Qun; Zhang, Zhi-Bin; Cao, Xiao-Hong; Nie, Wen-Bin; Li, Qin; Hua, Rong

2013-05-01

In this study, a low-cost and high-efficient carbonaceous adsorbent (HTC-COOH) with carboxylic groups was developed for U(VI) removal from aqueous solution compared with the pristine hydrothermal carbon (HTC). The structure and chemical properties of resultant adsorbents were characterized by Scanning electron microscope (SEM), N2 adsorption-desorption, Fourier transform-infrared spectra (FT-IR) and acid-base titration. The key factors (solution pH, contact time, initial U(VI) concentrations and temperature) affected the adsorption of U(VI) on adsorbents were investigated using batch experiments. The adsorption of U(VI) on HTC and HTC-COOH was pH-dependent, and increased with temperature and initial ion concentration. The adsorption equilibrium of U(VI) on adsorbents was well defined by the Langmuir isothermal equation, and the monolayer adsorption capacity of HTC-COOH was found to be 205.8 mg/g. The kinetics of adsorption was very in accordance with the pseudo-second-order rate model. The adsorption processes of U(VI) on HTC and HTC-COOH were endothermic and spontaneous in nature according to the thermodynamics of adsorption. Furthermore, HTC-COOH could selectively adsorption of U(VI) in aqueous solution containing co-existing ions (Mg2+, Co2+, Ni2+, Zn2+ and Mn2+). From the results of the experiments, it is found that the HTC-COOH is a potential adsorbent for effective removal of U(VI) from polluted water.

Removal of Ca2+ and Zn2+ from aqueous solutions by zeolites NaP and KP.

PubMed

Yusof, Alias Mohd; Malek, Nik Ahmad Nizam Nik; Kamaruzaman, Nurul Asyikin; Adil, Muhammad

2010-01-01

Zeolites P in sodium (NaP) and potassium (KP) forms were used as adsorbents for the removal of calcium (Ca2+) and zinc (Zn2+) cations from aqueous solutions. Zeolite KP was prepared by ion exchange of K+ with Na+ which neutralizes the negative charge of the zeolite P framework structure. The ion exchange capacity of K+ on zeolite NaP was determined through the Freundlich isotherm equilibrium study. Characterization of zeolite KP was determined using infrared spectroscopy and X-ray diffraction (XRD) techniques. From the characterization, the structure of zeolite KP was found to remain stable after the ion exchange process. Zeolites KP and NaP were used for the removal of Ca and Zn from solution. The amount of Ca2+ and Zn2+ in aqueous solution before and after the adsorption by zeolites was analysed using the flame atomic absorption spectroscopy method. The removal of Ca2+ and Zn2+ followed the Freundlich isotherm rather than the Langmuir isotherm model. This result also revealed that zeolite KP adsorbs Ca2+ and Zn2+ more than zeolite NaP and proved that modification of zeolite NaP with potassium leads to an increase in the adsorption efficiency of the zeolite. Therefore, the zeolites NaP and KP can be used for water softening (Ca removal) and reducing water pollution/toxicity (Zn removal).

Structural ensembles reveal intrinsic disorder for the multi-stimuli responsive bio-mimetic protein Rec1-resilin

NASA Astrophysics Data System (ADS)

Balu, Rajkamal; Knott, Robert; Cowieson, Nathan P.; Elvin, Christopher M.; Hill, Anita J.; Choudhury, Namita R.; Dutta, Naba K.

2015-06-01

Rec1-resilin is the first recombinant resilin-mimetic protein polymer, synthesized from exon-1 of the Drosophila melanogaster gene CG15920 that has demonstrated unusual multi-stimuli responsiveness in aqueous solution. Crosslinked hydrogels of Rec1-resilin have also displayed remarkable mechanical properties including near-perfect rubber-like elasticity. The structural basis of these extraordinary properties is not clearly understood. Here we combine a computational and experimental investigation to examine structural ensembles of Rec1-resilin in aqueous solution. The structure of Rec1-resilin in aqueous solutions is investigated experimentally using circular dichroism (CD) spectroscopy and small angle X-ray scattering (SAXS). Both bench-top and synchrotron SAXS are employed to extract structural data sets of Rec1-resilin and to confirm their validity. Computational approaches have been applied to these experimental data sets in order to extract quantitative information about structural ensembles including radius of gyration, pair-distance distribution function, and the fractal dimension. The present work confirms that Rec1-resilin is an intrinsically disordered protein (IDP) that displays equilibrium structural qualities between those of a structured globular protein and a denatured protein. The ensemble optimization method (EOM) analysis reveals a single conformational population with partial compactness. This work provides new insight into the structural ensembles of Rec1-resilin in solution.

Batch and continuous (fixed-bed column) biosorption of crystal violet by Artocarpus heterophyllus (jackfruit) leaf powder.

PubMed

Saha, Papita Das; Chakraborty, Sagnik; Chowdhury, Shamik

2012-04-01

In this study, batch and fixed-bed column experiments were performed to investigate the biosorption potential of Artocarpus heterophyllus (jackfruit) leaf powder (JLP) to remove crystal violet (CV) from aqueous solutions. Batch biosorption studies were carried out as a function of solution pH, contact time, initial dye concentration and temperature. The biosorption equilibrium data showed excellent fit to the Langmuir isotherm model with maximum monolayer biosorption capacity of 43.39 mg g(-1) at pH 7.0, initial dye concentration=50 mg L(-1), temperature=293 K and contact time=120 min. According to Dubinin-Radushkevich (D-R) isotherm model, biosorption of CV by JLP was chemisorption. The biosorption kinetics followed the pseudo-second-order kinetic model. Thermodynamic analysis revealed that biosorption of CV from aqueous solution by JLP was a spontaneous and exothermic process. In order to ascertain the practical applicability of the biosorbent, fixed-bed column studies were also performed. The breakthrough time increased with increasing bed height and decreased with increasing flow rate. The Thomas model as well as the BDST model showed good agreement with the experimental results at all the process parameters studied. It can be concluded that JLP is a promising biosorbent for removal of CV from aqueous solutions. Copyright © 2011 Elsevier B.V. All rights reserved.

Tautomeric and Microscopic Protonation Equilibria of Anthranilic Acid and Its Derivatives.

PubMed

Zapała, Lidia; Woźnicka, Elżbieta; Kalembkiewicz, Jan

2014-01-01

The acid-base chemistry of three zwitterionic compounds, namely anthranilic (2-aminobenzoic acid), N -methylanthranilic and N -phenylanthranilic acid has been characterized in terms of the macroconstants K a1 , K a2 , the isoelectric point p H I , the tautomerization constant K z and microconstants k 11 , k 12 , k 21 , k 22 . The potentiometric titration method was used to determine the macrodissociation constants. Due to the very poor water solubility of N -phenylanthranilic acid the dissociation constants p K a1 and p K a2 were determined in MDM-water mixtures [MDM is a co-solvent mixture, consisting of equal volumes of methanol (MeOH), dioxane and acetonitrile (MeCN)]. The Yasuda-Shedlovsky extrapolation procedure has been used to obtain the values of p K a1 and p K a2 in aqueous solutions. The p K a1 and p K a2 values obtained by this method are 2.86 ± 0.01 and 4.69 ± 0.03, respectively. The tautomerization constant K z describing the equilibrium between unionized form ⇌ zwitterionic form was evaluated by the K z method based on UV-VIS spectrometry. The method uses spectral differences between the zwitterionic form (found at isoelectric pH in aqueous solution) and the unionized form (formed in an organic solvent of low dielectric constant). The highest value of the K z constant has been observed in the case of N -methylantranilic acid (log 10 K z  = 1.31 ± 0.04). The values of log 10 K z for anthranilic and N -phenylanthranilic acids are similar and have values of 0.93 ± 0.03 and 0.90 ± 0.05, respectively. The results indicate that the tested compounds, in aqueous solution around the isoelectric point pH I , occur mainly in the zwitterionic form. Moreover, the influence of the type of substituent and pH of the aqueous phase on the equilibrium were analyzed with regard to the formation and the coexistence of different forms of the acids in the examined systems.

Removal of ibuprofen, naproxen and carbamazepine in aqueous solution onto natural clay: equilibrium, kinetics, and thermodynamic study

NASA Astrophysics Data System (ADS)

Khazri, Hassen; Ghorbel-Abid, Ibtissem; Kalfat, Rafik; Trabelsi-Ayadi, Malika

2017-10-01

This study aimed to describe the adsorption of three pharmaceuticals compounds (ibuprofen, naproxen and carbamazepine) onto natural clay on the basis of equilibrium parameters such as a function of time, effect of pH, varying of the concentration and the temperature. Adsorption kinetic data were modeled using the Lagergren's first-order and the pseudo-second-order kinetic equations. The kinetic results of adsorption are described better using the pseudo-second order model. The isotherm results were tested in the Langmuir, Freundlich and Dubinin-Radushkevich models. The thermodynamic parameters obtained indicate that the adsorption of pharmaceuticals on the clay is a spontaneous and endothermic process.

A CO2-Silica Geothermometer for Low Temperature Geothermal Resource Assessment, with Application to Resources in the Safford Basin, Arizona

DOE Office of Scientific and Technical Information (OSTI.GOV)

Witcher, James C.; Stone, Claudia

1983-11-01

Geothermics is the study of the earth's heat energy, it's affect on subsurface temperature distribution, it's physical and chemical sources, and it's role in dynamic geologic processes. The term, geothermometry, is applied to the determination of equilibrium temperatures of natural chemical systems, including rock, mineral, and liquid phases. An assemblage of minerals or a chemical system whose phase composition is a function of temperature and pressure can be used as a geothermometer. Thus a geothermometer is useful to determine the formation temperature of rock or the last equilibrium temperature of a flowing aqueous solution such as ground water and hydrothermalmore » fluids.« less

Removal of copper (II) ion from aqueous solution using zeolite Y synthesized from rice husk ash: Equilibrium and kinetic study

NASA Astrophysics Data System (ADS)

Tuyen, Nguyen Thi Kim; Nhan, Do Nguyen Thanh; Nhat, Trieu Thi; An, Ngo Thanh; Long, Nguyen Quang

2017-09-01

Zeolite Y was synthesized from silica of rice-husk ash using hydrothermal process. The crystalline structure FAU of zeolite Y was characterized by X-ray diffraction (XRD). Surface's area of the catalyst was determined by physic-adsorption method using BET model. The zeolite was examined for possibility of Cu2+ adsorbent by an ion-exchange mechanism. Various adsorption isotherm models, such as Langmuir, Freundlich and Dubinin-Radushkevich were tested for equilibrium study. The integration method was applied to find out the possible kinetic equation of the Cu2+ adsorption on the zeolite Y which obtained from cheap and locally available rice husk ash.

Stability and electronic properties of oxygen-doped ZnS polytypes: DFTB study

NASA Astrophysics Data System (ADS)

Popov, Ilya S.; Vorokh, Andrey S.; Enyashin, Andrey N.

2018-06-01

Synthesis from aqueous solutions is an affordable method for fabrication of II-VI semiconductors. However, application of this method often imposes a disorder of crystal lattice, manifesting as a rich variety of polytypes arising from wurtzite and zinc blende phases. The origin of this disordering still remains debatable. Here, the influence of the most likely impurity at water environment - substitutional oxygen - on the polytypic equilibrium of zinc sulphide is studied by means of density-functional tight-binding method. According to calculations, the inclusion of such oxygen does not affect the polytypic equilibrium. Apart of thermodynamic stability, the electronic and elastic properties of ZnS polytypes are studied as the function of oxygen distribution.

The temporal evolution of magnesium isotope fractionation during hydromagnesite dissolution, precipitation, and at equilibrium

NASA Astrophysics Data System (ADS)

Oelkers, Eric H.; Berninger, Ulf-Niklas; Pérez-Fernàndez, Andrea; Chmeleff, Jérôme; Mavromatis, Vasileios

2018-04-01

This study provides experimental evidence of the resetting of the magnesium (Mg) isotope signatures of hydromagnesite in the presence of an aqueous fluid during its congruent dissolution, precipitation, and at equilibrium at ambient temperatures over month-long timescales. All experiments were performed in batch reactors in aqueous sodium carbonate buffer solutions having a pH from 7.8 to 9.2. The fluid phase in all experiments attained bulk chemical equilibrium within analytical uncertainty with hydromagnesite within several days, but the experiments were allowed to continue for up to 575 days. During congruent hydromagnesite dissolution, the fluid first became enriched in isotopically light Mg compared to the dissolving hydromagnesite, but this Mg isotope composition became heavier after the fluid attained chemical equilibrium with the mineral. The δ26Mg composition of the fluid was up to ∼0.35‰ heavier than the initial dissolving hydromagnesite at the end of the dissolution experiments. Hydromagnesite precipitation was provoked during one experiment by increasing the reaction temperature from 4 to 50 °C. The δ26Mg composition of the fluid increased as hydromagnesite precipitated and continued to increase after the fluid attained bulk equilibrium with this phase. These observations are consistent with the hypothesis that mineral-fluid equilibrium is dynamic (i.e. dissolution and precipitation occur at equal, non-zero rates at equilibrium). Moreover the results presented in this study confirm (1) that the transfer of material from the solid to the fluid phase may not be conservative during stoichiometric dissolution, and (2) that the isotopic compositions of carbonate minerals can evolve even when the mineral is in bulk chemical equilibrium with its coexisting fluid. This latter observation suggests that the preservation of isotopic signatures of carbonate minerals in the geological record may require a combination of the isolation of fluid-mineral system from external chemical input and/or the existence of a yet to be defined dissolution/precipitation inhibition mechanism.

Methanol Uptake by Low Temperature Aqueous Sulfuric Acid Solutions

NASA Technical Reports Server (NTRS)

Iraci, L. T.; Essin, A. M.; Golden, D. M.; Hipskind, R. Stephen (Technical Monitor)

2001-01-01

The global methanol budget is currently unbalanced, with source terms significantly larger than the sinks terms. To evaluate possible losses of gaseous methanol to sulfate aerosols, the solubility and reactivity of methanol in aqueous sulfuric acid solutions representative of upper tropospheric and lower stratospheric aerosols is under investigation. Methanol will partition into sulfate aerosols according to its Henry's law solubility. Using standard uptake techniques in a Knudsen cell reactor, we have measured the effective Henry's law coefficient, H*, for cold (196 - 220 K) solutions ranging between 45 and 70 wt % H2SO4. We have found that methanol solubility ranges from approx. 10(exp 5) - 10(exp 7) M/atm for UT/LS conditions. Solubility increases with decreasing temperature and with increasing sulfuric acid content. Although methanol is slightly more soluble than are acetone and formaldehyde, current data indicate that uptake by clean aqueous sulfuric acid particles will not be a significant sink for methanol in the UT/LS. These solubility measurements include uptake due to physical solvation and any rapid equilibria which are established in solution. Reaction between primary alcohols and sulfuric acid does occur, leading to the production of alkyl sulfates. Literature values for the rate of this reaction suggest that formation of CH3OSO3H is not significant over our experimental time scale for solutions below 80 wt % H2SO4. To confirm this directly, results obtained using a complementary equilibrium measurement technique will also be presented.

Nonequilibrium gas absorption in rotating permeable media

NASA Astrophysics Data System (ADS)

Baev, V. K.; Bazhaikin, A. N.

2016-08-01

The absorption of ammonia, sulfur dioxide, and carbon dioxide by water and aqueous solutions in rotating permeable media, a cellular porous disk, and a set of spaced-apart thin disks has been considered. The efficiency of cleaning air to remove these impurities is determined, and their anomalously high solubility (higher than equilibrium value) has been discovered. The results demonstrate the feasibility of designing cheap efficient rotor-type absorbers to clean gases of harmful impurities.

Three-dimensional barium-sulfate-impregnated reduced graphene oxide aerogel for removal of strontium from aqueous solutions

NASA Astrophysics Data System (ADS)

Jang, Jiseon; Lee, Dae Sung

2018-06-01

A three-dimensional barium-sulfate-impregnated reduced graphene oxide (BaSO4-rGO) aerogel was successfully synthesized by a facile one-step hydrothermal method and was used as an adsorbent to remove strontium from aqueous solutions. The characterized elemental composition, crystal structure, and morphology of the prepared aerogel confirmed that barium sulfate particles were firmly anchored on the surface of the rGO sheets and exhibited a porous 3D structure with a high surface area of 129.37 m2/g. The mass ratio of BaSO4 in the BaSO4-rGO aerogel substantially affected strontium adsorption, and the optimal BaSO4/rGO ratio was found to be 1:1. The synthesized BaSO4-rGO aerogel not only reached adsorption equilibrium within 1 h, but also showed much higher adsorption capacity than an rGO aerogel. The experimental data were well fitted to a pseudo-second-order kinetic model and the adsorption behavior followed the Langmuir isotherm. The adsorption capacity of strontium on BaSO4-rGO aerogels remained relatively high even under ionic competition in simulated seawater. These results showed that the BaSO4-rGO aerogel is an efficient and promising adsorbent for the treatment of strontium in aqueous solutions.

Hydroxyapatite-gelatin nanocomposite as a novel adsorbent for nitrobenzene removal from aqueous solution

NASA Astrophysics Data System (ADS)

Wei, Wei; Sun, Rong; Jin, Zhu; Cui, Jing; Wei, Zhenggui

2014-02-01

A novel adsorbent of hydroxyapatite-gelatin (HAP-GEL) nanocomposite was developed for nitrobenzene removal from aqueous solution. The adsorbent was characterized and its performance in nitrobenzene removal was evaluated. The effects of contact time, adsorbent dosage, temperature, pH, ionic strength, humic acid, and the presence of solvent on nitrobenzene adsorption, as well as the thermodynamic parameters for adsorption equilibrium were also investigated. Results showed that HAP-GEL nanocomposite possessed good adsorption ability to nitrobenzene. The adsorption process was fast, and it reached a steady state after only 1 min. Nitrobenzene removal was increased with an increasing amount of adsorbent dosage but decreased as the temperature and pH increased. Meanwhile the amount of nitrobenzene adsorbed decreased with an increase of ionic strength from 0.01 to 1.0 mol/L and humic acid from 10 to 50 mg/L. The adsorption isotherm studies showed that both Langmuir and Freundlich models could fit the experimental data well, and the maximum adsorption capacity was estimated to be 42.373 mg/g. The thermodynamic parameters suggested that the adsorption of nitrobenzene on HAP-GEL nanocomposite was physisorption, spontaneous and exothermic in nature. Findings of this study demonstrated the potential utility of the HAP-GEL nanocomposite as an effective adsorbent for nitrobenzene removal from aqueous solution.

p-Chlorophenol adsorption on activated carbons with basic surface properties

NASA Astrophysics Data System (ADS)

Lorenc-Grabowska, Ewa; Gryglewicz, Grażyna; Machnikowski, Jacek

2010-05-01

The adsorption of p-chlorophenol (PCP) from aqueous solution on activated carbons (ACs) with basic surface properties has been studied. The ACs were prepared by two methods. The first method was based on the modification of a commercial CWZ AC by high temperature treatment in an atmosphere of ammonia, nitrogen and hydrogen. The second approach comprised the carbonization followed by activation of N-enriched polymers and coal tar pitch using CO 2 and steam as activation agent. The resultant ACs were characterized in terms of porous structure, elemental composition and surface chemistry (pH PZC, acid/base titration, XPS). The adsorption of PCP was carried out from an aqueous solution in static conditions. Equilibrium adsorption isotherm was of L2 type for polymer-based ACs, whereas L3-type isotherm was observed for CWZ ACs series. The Langmuir monolayer adsorption capacity was related to the porous structure and the amount of basic sites. A good correlation was found between the adsorption capacity and the volume of micropores with a width < 1.4 nm for polymer-based ACs. Higher nitrogen content, including that in basic form, did not correspond to the enhanced adsorption of PCP from aqueous solution. The competitive effect of water molecule adsorption on the PCP uptake is discussed.

Removal and recovery of p-phenylenediamines developing compounds from photofinishing lab-washwater using clinoptilolite tuffs from Greece.

PubMed

Vlessidis, A G; Triantafillidis, C S; Evmiridis, N P

2001-04-01

Clinoptilolite tuffs from areas in Thrace region of Greece are compared with synthetic zeolites NaY and NH4Y for the uptake of N4-ethyl-N4-(2-methansulphonamidoethyl)-2-methyl-1,4-phenylenediamin (sesquisulphate, monohydrate) with the trade name CD-3 for the purpose to be used for clean-up and recycling photo-finishing and photo-developing washwaters. The cation-exchange capacity is found to be 6.15-11.1 mg/g for zeoliferous tuffs at equilibrium concentration of 50 ppm CD-3 in aqueous solution compared to 65.0 mg/g of NaY and 48.2 mg/g for NH4Y synthetic zeolites corresponding to the removal of CD-3 from 120 to 2001 of 50 ppm aqueous solution per kg of natural zeoliferous tuff; this capacity is only 6-10 times lower than type-Y synthetic zeolite. Initial rates of uptake are 20.8 mg/l/min for natural and 38.5 mg/l/min for synthetic zeolites. Regeneration levels of 55, 23, 35, and 33% are obtained for MCH, SF, NaY, and NH4Y, respectively. The rapid and almost complete uptake of CD-3 from its aqueous solutions at low CD-3 concentrations by the natural zeolites is promising for such an application.

Potential Biosorbent Derived from Calligonum polygonoides for Removal of Methylene Blue Dye from Aqueous Solution

PubMed Central

Nasrullah, Asma; Khan, Hizbullah; Khan, Amir Sada; Man, Zakaria; Muhammad, Nawshad; Khan, Muhammad Irfan; Abd El-Salam, Naser M.

2015-01-01

The ash of C. polygonoides (locally called balanza) was collected from Lakki Marwat, Khyber Pakhtunkhwa, Pakistan, and was utilized as biosorbent for methylene blue (MB) removal from aqueous solution. The ash was used as biosorbent without any physical or chemical treatment. The biosorbent was characterized by using various techniques such as Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). The particle size and surface area were measured using particle size analyzer and Brunauer-Emmett-Teller equation (BET), respectively. The SEM and BET results expressed that the adsorbent has porous nature. Effects of various conditions such as initial concentration of methylene blue (MB), initial pH, contact time, dosage of biosorbent, and stirring rate were also investigated for the adsorption process. The rate of the adsorption of MB on biomass sample was fast, and equilibrium has been achieved within 1 hour. The kinetics of MB adsorption on biosorbent was studied by pseudo-first- and pseudo-second-order kinetic models and the pseudo-second-order has better mathematical fit with correlation coefficient value (R 2) of 0.999. The study revealed that C. polygonoides ash proved to be an effective, alternative, inexpensive, and environmentally benign biosorbent for MB removal from aqueous solution. PMID:25705714

Indian jujuba seed powder as an eco-friendly and a low-cost biosorbent for removal of acid blue 25 from aqueous solution.

PubMed

Krishna, L Sivarama; Reddy, A Sreenath; Zuhairi, W Y Wan; Taha, M R; Reddy, A Varada

2014-01-01

Indian jujuba seed powder (IJSP) has been investigated as a low-cost and an eco-friendly biosorbent, prepared for the removal of Acid Blue 25 (AB25) from aqueous solution. The prepared biomaterial was characterized by using FTIR and scanning electron microscopic studies. The effect of operation variables, such as IJSP dosage, contact time, concentration, pH, and temperature on the removal of AB25 was investigated, using batch biosorption technique. Removal efficiency increased with increase of IJSP dosage but decreased with increase of temperature. The equilibrium data were analyzed by the Langmuir and the Freundlich isotherm models. The data fitted well with the Langmuir model with a maximum biosorption capacity of 54.95 mg g(-1). The pseudo-second-order kinetics was the best for the biosorption of AB25 by IJSP, with good correlation. Thermodynamic parameters such as standard free energy change (ΔG(0)), standard enthalpy changes (ΔH(0)), and standard entropy changes (ΔS(0)) were analyzed. The removal of AB25 from aqueous solution by IJSP was a spontaneous and exothermic adsorption process. The results suggest that IJSP is a potential low-cost and an eco-friendly biosorbent for the AB25 removal from synthetic AB25 wastewater.

Biosorption of hexavalent chromium from aqueous solutions by Macadamia nutshell powder

NASA Astrophysics Data System (ADS)

Pakade, Vusumzi Emmanuel; Ntuli, Themba Dominic; Ofomaja, Augustine Enakpodia

2017-10-01

Macadamia nutshell biosorbents treated in three different activating agents [raw Macadamia nutshell powder (RMN), acid-treated Macadamia nutshell (ATMN) and base-treated Macadamia nutshell (BTMN)] were investigated for the adsorption of hexavalent chromium [Cr(VI)] from aqueous solutions. Fourier transform infrared spectroscopy spectra of free and Cr(VI)-loaded sorbents as well as thermogravimetric analysis revealed that the acid and base treatments modified the surface properties of the sorbent. Surface characteristics were also evaluated by the scanning electron microscopy and surface area analyzer. The optimum conditions for the adsorption of Cr(VI) by sorbents were pH 2, contact time 10 h, adsorbent mass 0.2 g and concentration 100 mg L-1. The equilibrium data were fitted into the Langmuir, Freundlich, Redlich-Peterson and Sips isotherms, and no single model could clearly explain the sorption mechanism. Maximum binding capacities of 45.23, 44.83 and 42.44 mg g-1 for RMN, ATMN and BTMN, respectively, were obtained. The kinetic data were analyzed using the pseudo-first, pseudo-second and Elovich kinetic models, and it was observed that the pseudo-second-order model produced the best fit for the experimental data. Macadamia nutshell sorbents showed potential as low-cost adsorbent for the removal of Cr(VI) from aqueous solution.

Indian Jujuba Seed Powder as an Eco-Friendly and a Low-Cost Biosorbent for Removal of Acid Blue 25 from Aqueous Solution

PubMed Central

Krishna, L. Sivarama; Reddy, A. Sreenath; Zuhairi, W. Y. Wan; Taha, M. R.; Reddy, A. Varada

2014-01-01

Indian jujuba seed powder (IJSP) has been investigated as a low-cost and an eco-friendly biosorbent, prepared for the removal of Acid Blue 25 (AB25) from aqueous solution. The prepared biomaterial was characterized by using FTIR and scanning electron microscopic studies. The effect of operation variables, such as IJSP dosage, contact time, concentration, pH, and temperature on the removal of AB25 was investigated, using batch biosorption technique. Removal efficiency increased with increase of IJSP dosage but decreased with increase of temperature. The equilibrium data were analyzed by the Langmuir and the Freundlich isotherm models. The data fitted well with the Langmuir model with a maximum biosorption capacity of 54.95 mg g−1. The pseudo-second-order kinetics was the best for the biosorption of AB25 by IJSP, with good correlation. Thermodynamic parameters such as standard free energy change (ΔG 0), standard enthalpy changes (ΔH 0), and standard entropy changes (ΔS 0) were analyzed. The removal of AB25 from aqueous solution by IJSP was a spontaneous and exothermic adsorption process. The results suggest that IJSP is a potential low-cost and an eco-friendly biosorbent for the AB25 removal from synthetic AB25 wastewater. PMID:25383360

Biosorption of Hexavalent Chromium from Aqueous Medium with Opuntia Biomass

PubMed Central

2014-01-01

The biosorption of hexavalent chromium from aqueous solutions by Opuntia cladodes and ectodermis from cactus fruits was investigated. Both types of biomass are considered low-cost, natural, and ecofriendly biosorbents. Batch experiments were carried out to determine Cr(VI) biosorption capacity and the efficiency of the biosorption process under different pH, initial Cr(VI) concentration, and sorbent dosage. The biosorption of Cr(VI) by Opuntia biomass was highly pH dependent, favoring higher metal uptake at low pH. The higher biosorption capacity was exhibited at pH 2. The optimal conditions were obtained at a sorbent dosage of 1 g L−1 and initial metal concentration of 10 mg L−1. Biosorption kinetic data were properly fitted with the pseudo-second-order kinetic model. The rate constant, the initial biosorption rate, and the equilibrium biosorption capacity were determined. The experimental equilibrium data obtained were analyzed using two-parameter isotherm models (Langmuir, Freundlich, and Temkin). The Langmuir maximum monolayer biosorption capacity (q max) was 18.5 mg g−1 for cladodes and 16.4 mg g−1 for ectodermis. The results suggest that Opuntia biomass could be considered a promising low-cost biosorbent for the ecofriendly removal of Cr(VI) from aqueous systems. PMID:24982975

The removal of fluoride from aqueous solution by a lateritic soil adsorption: Kinetic and equilibrium studies.

PubMed

Iriel, Analia; Bruneel, Stijn P; Schenone, Nahuel; Cirelli, Alicia Fernández

2018-03-01

The use of natural sorbents to remove fluoride from drinking water is a promising alternative because of its low-cost and easy implementation. In this article, fluoride adsorption on a latosol soil from Misiones province (Argentina) was studied regarding kinetic and equilibrium aspects. Experiments were conducted in batch at room temperature under controlled conditions of pH 4-8) and ionic strength (1-10mM KNO 3 ). Experimental data indicated that adsorption processes followed a PSO kinetic where initial rates have showed to be influenced by pH solution. The necessary time to reach an equilibrium state had resulted approximately 30min. Equilibrium adsorption studies were performed at pH 8 which is similar to the natural groundwater. For that, fluoride adsorption data were successfully adjusted to Dubinin-Ataskhov model determining that the fluoride adsorption onto soil particles mainly followed a physical mechanism with a removal capacity of 0.48mgg -1 . Finally, a natural groundwater was tested with laterite obtaining a reduction close to 30% from initial concentration and without changing significantly the physicochemical properties of the natural water. Therefore, it was concluded that the use of lateritic soils for fluoride removal is very promising on a domestic scale. Copyright © 2017 Elsevier Inc. All rights reserved.

Does shaking increase the pressure inside a bottle of champagne?

PubMed

Vreme, A; Pouligny, B; Nadal, F; Liger-Belair, G

2015-02-01

Colas, beers and sparkling wines are all concentrated solutions of carbon dioxide in aqueous solvents. Any such carbonated liquid is ordinarily conditioned inside a closed bottle or a metal can as a liquid-gas 2-phase system. At thermodynamic equilibrium, the partial pressure of carbon-dioxide in the gas phase and its concentration in the liquid are proportional (Henry's law). In practical conditions and use (transport, opening of the container, exterior temperature change, etc.), Henry's equilibrium can be perturbed. The goal of this paper is to describe and understand how the system responds to such perturbations and evolves towards a new equilibrium state. Formally, we investigate the dynamics around Henry's equilibrium of a closed system, through dedicated experiments and modeling. We focus on the response to a sudden pressure change and to mechanical shaking (the latter point inspired the article's title). Observations are rationalized through basic considerations including molecular diffusion, bubble dynamics (based on Epstein-Plesset theory) and chemi-convective hydrodynamic instabilities. Copyright © 2014 Elsevier Inc. All rights reserved.

Effect of synthesis parameters on polymethacrylic acid xerogel structures and equilibrium swelling

NASA Astrophysics Data System (ADS)

Panić, V.; Jovanović, J.; Adnadjević, B.; Velicković, S.

2009-09-01

Hydrogels based on crosslinked polymethacrylic acid were synthesized via free-radical polymerization in aqueous solution, using N,N'-methylene bisacrylamide as a crosslinking agent and 2,2'-azobis-[2-(2-imidazolin-2-yl)propane] dihydrochloride as an initiator. The influence of the reaction parameters (the neutralization degree of methacrylic acid and the initial monomer concentration) on the equilibrium swelling degree, the swelling kinetic parameters and the basic structural properties of xerogels was investigated. The change of synthesis parameters leads to the change of the basic structural parameters of xerogel, as well as the equilibrium swelling degree and the initial swelling rate of the hydrogels. It is found that there are power form relationships between the equilibrium swelling degree, the initial swelling rate and the structural xerogel’s properties and the change of the neutralization degree of monomer, i.e. the monomer concentration. The examined correlations proved that the crosslinking density is the crucial parameter which determines all the other investigated structural and swelling parameters.

A thermodynamic model for the prediction of phase equilibria and speciation in the H 2O-CO 2-NaCl-CaCO 3-CaSO 4 system from 0 to 250 °C, 1 to 1000 bar with NaCl concentrations up to halite saturation

NASA Astrophysics Data System (ADS)

Li, Jun; Duan, Zhenhao

2011-08-01

A thermodynamic model is developed for the calculation of both phase and speciation equilibrium in the H 2O-CO 2-NaCl-CaCO 3-CaSO 4 system from 0 to 250 °C, and from 1 to 1000 bar with NaCl concentrations up to the saturation of halite. The vapor-liquid-solid (calcite, gypsum, anhydrite and halite) equilibrium together with the chemical equilibrium of H+,Na+,Ca, CaHCO3+,Ca(OH)+,OH-,Cl-, HCO3-,HSO4-,SO42-, CO32-,CO,CaCO and CaSO 4(aq) in the aqueous liquid phase as a function of temperature, pressure and salt concentrations can be calculated with accuracy close to the experimental results. Based on this model validated from experimental data, it can be seen that temperature, pressure and salinity all have significant effects on pH, alkalinity and speciations of aqueous solutions and on the solubility of calcite, halite, anhydrite and gypsum. The solubility of anhydrite and gypsum will decrease as temperature increases (e.g. the solubility will decrease by 90% from 360 K to 460 K). The increase of pressure may increase the solubility of sulphate minerals (e.g. gypsum solubility increases by about 20-40% from vapor pressure to 600 bar). Addition of NaCl to the solution may increase mineral solubility up to about 3 molality of NaCl, adding more NaCl beyond that may slightly decrease its solubility. Dissolved CO 2 in solution may decrease the solubility of minerals. The influence of dissolved calcite on the solubility of gypsum and anhydrite can be ignored, but dissolved gypsum or anhydrite has a big influence on the calcite solubility. Online calculation is made available on www.geochem-model.org/model.

Removal and attenuation of sewage effluent combined tracer signals of phosphorus, caffeine and saccharin in soil.

PubMed

Richards, Samia; Withers, Paul J A; Paterson, Eric; McRoberts, Colin W; Stutter, Marc

2017-04-01

Contaminants in septic tank effluent (STE) are expected to be removed by the soil system before discharging to the environment. However, potential contaminants such as phosphorus (P), caffeine and artificial sweeteners do find their way to watercourses impacting aquatic eco systems. In this study, the attenuation of STE P, caffeine and saccharin were investigated in untreated soil and in soil with reduced microbial activity, in aqueous solutions and in the complex matrix of STE. Time series sorption and desorption experiments using batch equilibrium and a column experiment of STE P attenuation were conducted. The results revealed that the soil distribution coefficients (K d ) were: P 81.57 > caffeine 22.16 > saccharin 5.98 cm 3 /g, suggesting greater soil affinity to P adsorption. The data revealed that 80% of saccharin and 33% of caffeine attenuation was associated with microbial activities rather than adsorption processes. However, a complete removal of saccharin and caffeine did not occur during the equilibration period, suggesting their leaching potential. The dominant mechanism of P attenuation was adsorption (chemical and physical), yielding P retention of >73% and 35% for P in aqueous solution and in STE matrix, respectively, for batch equilibrium. The soil in the column acted as effluent P sink retaining 125 μg P/g soil of effluent P. The attenuation of P, caffeine and saccharin in the aqueous solution was greater than in STE, suggesting that the complex composition of STE reduced soil adsorption ability, and that other substances present in STE may be competing for soil binding sites. The data revealed that caffeine and P had similarities in the interaction with soils and thus caffeine may be considered as a STE tracer of anthropogenic source of P in receiving waters. Copyright © 2017 Elsevier Ltd. All rights reserved.

Valorization of aquaculture waste in removal of cadmium from aqueous solution: optimization by kinetics and ANN analysis

NASA Astrophysics Data System (ADS)

Aditya, Gautam; Hossain, Asif

2018-05-01

Cadmium is one of the most hazardous heavy metal concerning human health and aquatic pollution. The removal of cadmium through biosorption is a feasible option for restoration of the ecosystem health of the contaminated freshwater ecosystems. In compliance with this proposition and considering the efficiency of calcium carbonate as biosorbent, the shell dust of the economically important snail Bellamya bengalensis was tested for the removal of cadmium from aqueous medium. Following use of the flesh as a cheap source of protein, the shells of B. bengalensis made up of CaCO3 are discarded as aquaculture waste. The biosorption was assessed through batch sorption studies along with studies to characterize the morphology and surface structures of waste shell dust. The data on the biosorption were subjected to the artificial neural network (ANN) model for optimization of the process. The biosorption process changed as functions of pH of the solution, concentration of heavy metal, biomass of the adsorbent and time of exposure. The kinetic process was well represented by pseudo second order ( R 2 = 0.998), and Langmuir equilibrium ( R 2 = 0.995) had better fits in the equilibrium process with 30.33 mg g-1 of maximum sorption capacity. The regression equation ( R 2 = 0.948) in the ANN model supports predicted values of Cd removal satisfactorily. The normalized importance analysis in ANN predicts Cd2+ concentration, and pH has the most influence in removal than biomass dose and time. The SEM and EDX studies show clear peaks for Cd confirming the biosorption process while the FTIR study depicts the main functional groups (-OH, C-H, C=O, C=C) responsible for the biosorption process. The study indicated that the waste shell dust can be used as an efficient, low cost, environment friendly, sustainable adsorbent for the removal of cadmium from aqueous solution.

Silicon isotope fractionations in pure Si and Fe-Si systems and their geological implications

NASA Astrophysics Data System (ADS)

Zheng, X. Y.; Beard, B. L.; Reddy, T. R.; Roden, E. E.; Johnson, C.

2016-12-01

Amorphous Si or Si-bearing materials are ubiquitous in nature, and are likely precursors to various rock types, such as cherts and banded iron formations (BIFs). Si isotope exchange kinetics and fractionation factors between these materials and aqueous Si, however, are poorly constrained, preventing a mechanistic or quantitative understanding of geological δ30Si records. A series of laboratory experiments were conducted to provide better estimates on Si isotope exchange kinetics and fractionation factors. Equilibrium Si isotope fractionation factors between Fe(III)-Si gel and aqueous Si (Δ30Sigel-aq) in artificial Archean seawater (AAS), determined by a three-isotope method with a 29Si tracer, are -2.3‰ where Fe2+ is absent from the solution, and -3.2‰ where Fe2+ is present in the solution[1]. Aqueous Fe2+ catalyzes Si isotope exchange, and causes larger Si isotope fractionation due to incorporation into the solid that may have changed Si bonding. In contrast, our preliminary results show that Δ30Sigel-aq between pure Si gel and aqueous Si at equilibrium is -0.13‰. Ongoing experiments are intended to approach the isotope equilibrium from multiple directions to resolve potential kinetic effects, and to explore temperature dependence. Nonetheless, the contrast in Δ30Sigel-aq between Fe-Si and pure Si systems highlights a significant impact of Fe on Si isotope fractionations. These results have important implications for Si isotopes in Precambrian cherts and BIFs, as well as in weathering systems in general. Silicon isotope fractionation was also studied in experiments that involved dissimilatory iron reduction of Fe(III)-Si gel by Desulfuromonas acetoxidans in AAS[2], and was found to become larger with progression of Fe reduction. A Δ30Sigel-aq of -3.5‰ was observed at 32% reduction of Fe3+. This result explains lower δ30Si values in magnetite-associated quartz that those in hematite-associated quartz in some BIFs. The large Si isotope fractionation produced in the microbial experiment, even larger than that seen in our Fe(II)-bearing abiologic experiments, suggests that δ30Si can be a potential tracer for magnetite of a microbial origin, or, vice versa, for microbial activities in magnetite. [1] Zheng et al., 2016, GCA 187, 102-122. [2] Reddy et al., 2016, GCA 190, 85-99.

Effect of organic matter on CO(2) hydrate phase equilibrium in phyllosilicate suspensions.

PubMed

Park, Taehyung; Kyung, Daeseung; Lee, Woojin

2014-06-17

In this study, we examined various CO2 hydrate phase equilibria under diverse, heterogeneous conditions, to provide basic knowledge for successful ocean CO2 sequestration in offshore marine sediments. We investigated the effect of geochemical factors on CO2 hydrate phase equilibrium. The three-phase (liquid-hydrate-vapor) equilibrium of CO2 hydrate in the presence of (i) organic matter (glycine, glucose, and urea), (ii) phyllosilicates [illite, kaolinite, and Na-montmorillonite (Na-MMT)], and (iii) mixtures of them was measured in the ranges of 274.5-277.0 K and 14-22 bar. Organic matter inhibited the phase equilibrium of CO2 hydrate by association with water molecules. The inhibition effect decreased in the order: urea < glycine < glucose. Illite and kaolinite (unexpandable clays) barely affected the CO2 hydrate phase equilibrium, while Na-MMT (expandable clay) affected the phase equilibrium because of its interlayer cations. The CO2 hydrate equilibrium conditions, in the illite and kaolinite suspensions with organic matter, were very similar to those in the aqueous organic matter solutions. However, the equilibrium condition in the Na-MMT suspension with organic matter changed because of reduction of its inhibition effect by intercalated organic matter associated with cations in the Na-MMT interlayer.

GEOSURF: a computer program for modeling adsorption on mineral surfaces from aqueous solution

NASA Astrophysics Data System (ADS)

Sahai, Nita; Sverjensky, Dimitri A.

1998-11-01

A new program, GEOSURF, has been developed for calculating aqueous and surface speciation consistent with the triple-layer model of surface complexation. GEOSURF is an extension of the original programs MINEQL, MICROQL and HYDRAQL. We present, here, the basic algorithm of GEOSURF along with a description of the new features implemented. GEOSURF is linked to internally consistent data bases for surface species (SURFK.DAT) and for aqueous species (AQSOL.DAT). SURFK.DAT contains properties of minerals such as site densities, and equilibrium constants for adsorption of aqueous protons and electrolyte ions on a variety of oxides and hydroxides. The Helgeson, Kirkham and Flowers version of the extended Debye-Huckel Equation for 1:1 electrolytes is implemented for calculating aqueous activity coefficients. This permits the calculation of speciation at ionic strengths greater than 0.5 M. The activity of water is computed explicitly from the osmotic coefficient of the solution, and the total amount of electrolyte cation (or anion) is adjusted to satisfy the electroneutrality condition. Finally, the use of standard symbols for chemical species rather than species identification numbers is included to facilitate use of the program. One of the main limitations of GEOSURF is that aqueous and surface speciation can only be calculated at fixed pH and at fixed concentration of total adsorbate. Thus, the program cannot perform reaction-path calculations: it cannot determine whether or not a solution is over- or under-saturated with respect to one or more solid phases. To check the proper running of GEOSURF, we have compared results generated by GEOSURF with those from two other programs, HYDRAQL and EQ3. The Davies equation and the "bdot" equation, respectively, are used in the latter two programs for calculating aqueous activity coefficients. An example of the model fit to experimental data for rutile in 0.001 M-2.0 M NaNO 3 is included.

Monte Carlo simulations of the counter ion effect on the conformational equilibrium of the N, N'-diphenyl-guanidinium ion in aqueous solution

NASA Astrophysics Data System (ADS)

Nagy, Peter I.; Durant, Graham J.

1996-01-01

Results of calculations for the equilibrium of the syn-syn, anti-syn, and anti-anti conformers of the N, N'-diphenyl-guanidinium ion in aqueous solution are sensitive to whether a counter ion is considered. Relative internal free energies were calculated upon MP2/6-31G*//HF/4-31G energies (second order Møller-Plesset energies obtained when using the 6-31G* basis set at geometries optimized at the Hartree-Fock level and using the 4-31G basis set) and relative solvation free energy terms were obtained by Monte Carlo simulations. Without considering a counter ion only a small fraction of the solute has been predicted to adopt the anti-anti conformation in the solution. When considering acetate and chloride counter ions with salt concentration of 0.11 mol/l at 310 K, mimicking physiological conditions, the counter ion close to the cation stabilizes the anti-anti form significantly. Though there are not local free energy minima for the present systems with close counter ions because of the relatively weak ion-ion interaction due to the largely delocalized total charge and atomic charge alternation in the cation, the constraint for the C(guanidinium)...C(carboxylate) separation of 4.6 Å allows an insight into the arginine...aspartate or glutamate interactions commonly found in peptides. The N-H(guanidinium)...O(carboxylate) hydrogen bonds are not stable due to thermal motion in aqueous solution. The neighboring water molecules, however, move into the space in-between the charged groups and comprise a hydrogen bonded network. Interactions with a chloride counter ion may be significant for the drug delivery process to the receptor site. Close contact between the N, N'-diphenyl guanidinium and a chloride ion is also not favored, though it may occur temporarily and then would favor the anti-anti conformer. Deviation from the relative solvation free energy obtained for the conformational change of the single cation is still some tenths of a kcal/mol with ions separated as much as 12.4 Å. While solvation energetics is affected even at such a separation, solution structure around the ions can be basically characterized without considering the effect of a remote counterpart.

Comparison of alkaline industrial wastes for aqueous mineral carbon sequestration through a parallel reactivity study.

PubMed

Noack, Clinton W; Dzombak, David A; Nakles, David V; Hawthorne, Steven B; Heebink, Loreal V; Dando, Neal; Gershenzon, Michael; Ghosh, Rajat S

2014-10-01

Thirty-one alkaline industrial wastes from a wide range of industrial processes were acquired and screened for application in an aqueous carbon sequestration process. The wastes were evaluated for their potential to leach polyvalent cations and base species. Following mixing with a simple sodium bicarbonate solution, chemistries of the aqueous and solid phases were analyzed. Experimental results indicated that the most reactive materials were capable of sequestering between 77% and 93% of the available carbon under experimental conditions in four hours. These materials - cement kiln dust, spray dryer absorber ash, and circulating dry scrubber ash - are thus good candidates for detailed, process-oriented studies. Chemical equilibrium modeling indicated that amorphous calcium carbonate is likely responsible for the observed sequestration. High variability and low reactive fractions render many other materials less attractive for further pursuit without considering preprocessing or activation techniques. Copyright © 2014 Elsevier Ltd. All rights reserved.

Chapter A6. Section 6.5. Reduction-Oxidation Potential (Electrode Method)

USGS Publications Warehouse

Nordstrom, D. Kirk; Wilde, Franceska D.

2005-01-01

Reduction-oxidation (redox) potential--also referred to as Eh--is a measure of the equilibrium potential, relative to the standard hydrogen electrode, developed at the interface between a noble metal electrode and an aqueous solution containing electroactive chemical species. Measurements of Eh are used to evaluate geochemical speciation models, and Eh data can provide insights on the evolution and status of water chemistry in an aqueous system. Nevertheless, the measurement is fraught with inherent interferences and limitations that must be understood and considered to determine applicability to the aqueous system being studied. For this reason, Eh determination is not one of the field parameters routinely measured by the U.S. Geological Survey (USGS). This section of the National Field Manual (NFM) describes the equipment and procedures needed to measure Eh in water using a platinum electrode. Guidance as to the limitations and interpretation of Eh measurement also is included.

Droplets on liquid surfaces: Dual equilibrium states and their energy barrier

NASA Astrophysics Data System (ADS)

Shabani, Roxana; Kumar, Ranganathan; Cho, Hyoung J.

2013-05-01

Floating aqueous droplets were formed at oil-air interface, and two stable configurations of (i) non-coalescent droplet and (ii) cap/bead droplet were observed. General solutions for energy and force analysis were obtained for both configurations and were shown to be in good agreement with the experimental observations. The energy barrier obtained for transition from configuration (i) to configuration (ii) was correlated to the droplet release height and the probability of non-coalescent droplet formation.

Structural study of human growth hormone-releasing factor fragment (1?29) by vibrational spectroscopy

NASA Astrophysics Data System (ADS)

Carmona, P.; Molina, M.; Lasagabaster, A.

1995-05-01

The conformational structure of fragment 1-29 of human growth hormone releasing factor, hGHRF (1-29), in aqueous solution and in the solid state is investigated by infrared and Raman spectroscopy. The polypeptide backbone is found to be unordered in the solid state. However, the spectra of the peptide prepared as 5% (w/w) aqueous solutions show that approximately 28% of the peptide is involved in intermolecular β-sheet aggregation. The remainder of the peptide exists largely as disordered and β-sheet conformations with a small portion of α-helices. Tyrosine residues are found to be exposed to the solvent. The secondary structures are quantitatively examined through infrared spectroscopy, the conformational percentages being near those obtained by HONDAet al. [ Biopolymers31, 869 (1991)] using circular dichroism. The fast hydrogen/deuterium exchange in peptide groups and the absence of any NMR sign indicative of ordered structure [ G. M. CLOREet al., J. Molec. Biol.191, 553 (1986)] support that the solution conformations of the non-aggregated peptide interconvert in dynamic equilibrium. Some physiological advantages that may derive from this conformational flexibility are also discussed

Utilization of activated carbon produced from fruit juice industry solid waste for the adsorption of Yellow 18 from aqueous solutions.

PubMed

Angin, Dilek

2014-09-01

The use of activated carbon obtained from sour cherry (Prunus cerasus L.) stones for the removal of a basic textile dye, which is Yellow 18, from aqueous solutions at different contact times, pH values and solution temperatures was investigated. The surface area and micropore volume of chemically modified activated carbon were 1704 m(2) g(-1) and 0.984 cm(3) g(-1), respectively. The experimental data indicated that the adsorption isotherms were well described by the Langmuir equilibrium isotherm equation and the calculated adsorption capacity was 75.76 mg g(-1) at 318 K. The adsorption kinetic of Yellow 18 obeys the pseudo-second-order kinetic model. The thermodynamic parameters were calculated to estimate the nature of adsorption. The activation energy of the system was calculated as 0.71-2.36 kJ/mol. According to these results, prepared activated carbon could be used as a low-cost adsorbent to compare with the commercial activated carbon for the removal of Yellow 18 from wastewater. Copyright © 2014 Elsevier Ltd. All rights reserved.

Characterization of Chitin and Chitosan Molecular Structure in Aqueous Solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Franca, Eduardo D.; Lins, Roberto D.; Freitas, Luiz C.

Molecular dynamics simulations have been used to characterize the structure of chitin and chitosan fibers in aqueous solutions. Chitin fibers, whether isolated or in the form of a β-chitin nanoparticle, adopt the so-called 2-fold helix with Φ and φ values similar to its crystalline state. In solution, the intramolecular hydrogen bond HO3(n)•••O5(n+1) responsible for the 2-fold helical motif is stabilized by hydrogen bonds with water molecules in a well-defined orientation. On the other hand, chitosan can adopt five distinct helical motifs and its conformational equilibrium is highly dependent on pH. The hydrogen bond pattern and solvation around the O3 atommore » of insoluble chitosan (basic pH) are nearly identical to these quantities in chitin. Our findings suggest that the solubility and conformation of these polysaccharides are related to the stability of the intrachain HO3(n)•••O5(n+1) hydrogen bond, which is affect by the water exchange around the O3-HO3 hydroxyl group.« less

Chemical functionalization of diatom silica microparticles for adsorption of gold (III) ions.

PubMed

Yu, Yang; Addai-Mensah, Jonas; Losic, Dusan

2011-12-01

Diatom silica microparticles from natural diatomaceous earth (DE) silica have been functionalized with 3-mercaptopropyltrimethoxysilane (MPTMS) and their application for adsorption of gold (III) ions from aqueous solutions is demonstrated. Fourier transform infrared spectroscopy (FTIR) and X-ray Photoelectron spectroscopy (XPS) analyses of the MPTMS modified diatom microparticles revealed that the silane layer with functional group (-SH) was successfully introduced to the diatom surface. The adsorption study of Au(III) ions using MPTMS-DE indicated that the process depends on initial gold (III) concentration and pH showing maximum adsorption capacity at pH = 3. The Au(III) adsorption kinetics results showed that the adsorption was very fast and followed a pseudo-second-order reaction model. The Langmuir model was used to provide a sound mechanistic basis for the theoretical of the adsorption equilibrium data. Gold recovery from MPTMS-DE structures was also investigated by using acidified thiourea solution and found to be high (> 95%). These results show that chemically modified DE microparticles can be used as a new, cost effective and environmentally benign adsorbent suitable for adsorption of gold metal ions from aqueous solutions.

Removal of mercury from aqueous solutions using activated carbon prepared from agricultural by-product/waste.

PubMed

Rao, M Madhava; Reddy, D H K Kumar; Venkateswarlu, Padala; Seshaiah, K

2009-01-01

Removal of mercury from aqueous solutions using activated carbon prepared from Ceiba pentandra hulls, Phaseolus aureus hulls and Cicer arietinum waste was investigated. The influence of various parameters such as effect of pH, contact time, initial metal ion concentration and adsorbent dose for the removal of mercury was studied using a batch process. The experiments demonstrated that the adsorption process corresponds to the pseudo-second-order-kinetic models and the equilibrium adsorption data fit the Freundlich isotherm model well. The prepared adsorbents ACCPH, ACPAH and ACCAW had removal capacities of 25.88 mg/g, 23.66 mg/g and 22.88 mg/g, respectively, at an initial Hg(II) concentration of 40 mg/L. The order of Hg(II) removal capacities of these three adsorbents was ACCPH>ACPAH>ACCAW. The adsorption behavior of the activated carbon is explained on the basis of its chemical nature. The feasibility of regeneration of spent activated carbon adsorbents for recovery of Hg(II) and reuse of the adsorbent was determined using HCl solution.

Graphene oxide/Fe3O4/chitosan nanocomposite: a recoverable and recyclable adsorbent for organic dyes removal. Application to methylene blue

NASA Astrophysics Data System (ADS)

Tran, Hoang V.; Bui, Lieu T.; Dinh, Thuy T.; Le, Dang H.; Huynh, Chinh D.; Trinh, Anh X.

2017-03-01

In this research, the potential of chitosan/Fe3O4/graphene oxide (CS/Fe3O4/GO) nanocomposite for efficient removal of methylene blue (MB) as a cationic dye from aqueous solutions was investigated. For this purpose, first, graphene oxide (GO) was prepared from pencil’s graphite by Hummer’s method, then after, CS/Fe3O4/GO was synthesized via chemical co-precipitation method from a mixture solution of GO, Fe3+, Fe2+ and chitosan. The synthesized CS/Fe3O4/GO was characterized by XRD, VSM and SEM techniques. Also, the various parameters affecting dye removal were investigated. Dye adsorption equilibrium data were fitted well to the Langmuir isotherm rather than Freundlich isotherm. The maximum monolayer capacity (q max), was calculated from the Langmuir as 30.10 mg · g-1. The results show that, CS/Fe3O4/GO nanocomposite, can be used as a cheap and efficient adsorbent for removal of cationic dyes from aqueous solutions.

Reversible hydration and aqueous exfoliation of the acetate-intercalated layered double hydroxide of Ni and Al: Observation of an ordered interstratified phase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Manohara, G.V.; Vishnu Kamath, P., E-mail: vishnukamath8@hotmail.com; Milius, Wolfgang

2012-12-15

Acetate-intercalated layered double hydroxides (LDHs) of Ni and Al undergo reversible hydration in the solid state in response to the ambient humidity. The LDH with a high layer charge (0.33/formula unit) undergoes facile hydration in a single step, whereas the LDH with a lower layer charge (0.24/formula unit) exhibits an ordered interstratified intermediate, comprising the hydrated and dehydrated layers stacked alternatively. This phase, also known as the staged S-2 phase, coexists with the end members suggesting the existence of a solution-type equilibrium between the S-2 phase and the end members of the hydration cycle. These LDHs also undergo facile aqueousmore » exfoliation into 2-5 nm-thick tactoids with a radial dimension of 0.2-0.5 {mu}m. - Graphical abstract: Schematic of the hydrated, dehydrated and interstratified phases observed during the hydration-dehydration of Ni/Al-CH{sub 3}COO LDH. Highlights: Black-Right-Pointing-Pointer Ni/Al-acetate LDHs were synthesized by HPFS method by hydrolysis of acetamide. Black-Right-Pointing-Pointer Intercalated acetate ion shows reversible hydration with variation in humidity. Black-Right-Pointing-Pointer An ordered interstratified phase was observed during hydration/dehydration cycle. Black-Right-Pointing-Pointer A solution type equilibrium is observed between hydration-dehydration phases. Black-Right-Pointing-Pointer These LDHs undergo facile aqueous exfoliation.« less

Enzymatic oxidation of ethanol in the gaseous phase.

PubMed

Barzana, E; Karel, M; Klibanov, A M

1989-11-01

The enzymatic conversion of gaseous substrates represents a novel concept in bioprocessing. A critical parameter in such systems is the water activity, A(w) The present article reports the effect of A(w) on the catalytic performance of alcohol oxidase acting on ethanol vapors. Enzyme activity in the gas-phase reaction increases several orders of magnitude, whereas the thermostability decreases drastically when A(w) is increased from 0.11 to 0.97. The enzyme is active on gaseous substrates even at hydration levels below the monolayer coverage. Enhanced thermostability at lower hydrations results in an increase in the optimum temperature of the gas-phase reaction catalyzed by alcohol oxidase. The apparent activation energy decreases as A(w) increases, approaching the value obtained for the enzyme in aqueous solution. The formation of a pread-sorbed ethanol phase on the surface of the support is not a prerequisite for the reaction, suggesting that the reaction occurs by direct interaction of the gaseous substrate with the enzyme. The gas-phase reaction follows Michaelis-Menten kinetics, with a K(m) value almost 100 times lower than that in aqueous solution. Based on vapor-liquid equilibrium data and observed K(m) values, it is postulated that during the gas-phase reaction the ethanol on the enzyme establishes an equilibrium with the ethanol vapor similar to that between ethanol in water and ethanol in the gas phase.

Adsorptive removal of malachite green from aqueous solutions by almond gum: Kinetic study and equilibrium isotherms.

PubMed

Bouaziz, Fatma; Koubaa, Mohamed; Kallel, Fatma; Ghorbel, Rhoudha Ellouz; Chaabouni, Semia Ellouz

2017-12-01

This work aimed at investigating the potential of almond gum as low cost adsorbent for the removal of the cationic dye; malachite green from aqueous solutions. Almond gum was first analyzed by scanning electron microscopy (SEM) and Fourier transforms infrared spectroscopy (FTIR), and then the adsorption behavior was studied in batch system. The effects of the adsorption parameters (adsorbent dose, pH, contact time, particle size, initial dye concentration, temperature and agitation) on the dye removal have been studied. Adsorption equilibrium and isotherms were evaluated depending on temperature using the isotherms of Freundlich, Langmuir, and Tempkin. The obtained result showed that both Langmuir and Freundlich models were adapted to study the dye sorption. The maximum adsorption capacities were equal to 172.41mg/g, 181.81mg/g, and 196.07mg/g at 303.16K, 313.16K, and 323.16K, respectively. The kinetics of sorption were following the pseudo-second order model. The thermodynamic changes in enthalpy (ΔH), entropy (ΔS), and free energy (ΔG) indicated that the adsorption of malachite green at the surface of almond gum is endothermic and occurs spontaneously. Desorption experiments were conducted to regenerate almond gum, showing great desorption capacity when using HCl at pH 2. Copyright © 2017 Elsevier B.V. All rights reserved.

The removal of uranium (VI) from aqueous solutions onto activated carbon developed from grinded used tire.

PubMed

Belgacem, Ahmed; Rebiai, Rachid; Hadoun, Hocine; Khemaissia, Sihem; Belmedani, Mohamed

2014-01-01

In this study, activated carbon was prepared from waste tire by KOH chemical activation. The pore properties including the BET surface area, pore volume, pore size distribution, and average pore diameter were characterized. BET surface area of the activated carbon was determined as 558 m(2)/g. The adsorption of uranium ions from the aqueous solution using this activated carbon has been investigated. Various physico-chemical parameters such as pH, initial metal ion concentration, and adsorbent dosage level and equilibrium contact time were studied by a batch method. The optimum pH for adsorption was found to be 3. The removal efficiency has also been determined for the adsorption system as a function of initial concentration. The experimental results were fitted to Langmuir, Freundlich, and Dubinin-Radushkevich (D-R) isotherm models. A comparison of best-fitting was performed using the coefficient of correlation and the Langmuir isotherm was found to well represent the measured sorption data. According to the evaluation using the Langmuir equation, the saturated monolayer sorption capacity of uranium ions onto waste tire activated carbon was 158.73 mg/g. The thermodynamic equilibrium constant and the Gibbs free energy were determined and results indicated the spontaneous nature of the adsorption process. Kinetics data were best described by pseudo-second-order model.

Mercury(II) removal from aqueous solutions and wastewaters using a novel cation exchanger derived from coconut coir pith and its recovery.

PubMed

Anirudhan, T S; Divya, L; Ramachandran, M

2008-09-15

A new adsorbent (PGCP-COOH) having carboxylate functional group at the chain end was synthesized by grafting poly(hydroxyethylmethacrylate) onto coconut coir pith, CP (a coir industry-based lignocellulosic residue), using potassium peroxydisulphate as an initiator and in the presence of N,N'-methylenebisacrylamide as a cross-linking agent. The adsorbent was characterized with the help of infrared spectroscopy, powder X-ray diffraction, scanning electron microscopy, and potentiometric titrations. The ability of PGCP-COOH to remove Hg(II) from aqueous solutions was assessed using batch adsorption technique under kinetic and equilibrium conditions. Adsorbent exhibits very high adsorption potential for Hg(II) and more than 99.0% removal was achieved in the pH range 5.5-8.0. Adsorption process was found to follow first-order-reversible kinetics. An increase of ionic strength of the medium caused a decrease in metal removal, indicating the occurrence of outer-sphere surface complex mechanism. The equilibrium data were fitted well by the Freundlich isotherm model (R(2)=0.99; chi(2)=1.81). The removal efficiency was tested using chlor-alkali industry wastewater. Adsorption isotherm experiments were also conducted for comparison using a commercial carboxylate-functionalized ion exchanger, Ceralite IRC-50. Regeneration experiments were tried for four cycles and results indicate a capacity loss of <9.0%.

Dried powder of corn stalk as a potential biosorbent for the removal of iodate from aqueous solution.

PubMed

Zhang, Kui; Chen, Tao

2018-10-01

Removal of IO 3 - from environmental samples with low-cost methods and materials is very useful approach for especially large-scale applications. Corn stalk is highly abundant agriculture residual, which is employed as useful biosorbent in many studies. In the present work, dried powder of corn stalk is applied for the removal of IO 3 - under various conditions. The results indicate that the K d is 49.73 ml g -1 under general conditions (m/V = 8 g L -1 , t = 5 day, equilibrium pH = 7 ± 0.3, T = 298 K and C 0  = 15 mg L -1 ). The sorption kinetics follows the pseudo-second-order equation, and the isotherm is well described by the Langmuir model. The sorption reaction was non-spontaneous and endothermic. Hydroxyl and carbonyl groups of the corn stalk contribute to IO 3 - sorption by ion-exchange, electrostatic attraction and redox reactions. Spectroscopic analyses and the effect of equilibrium pH prove that corn stalk was not only removed IO 3 - from aqueous solution but also reduced IO 3 - into I 2 and I - . These results demonstrate that corn stalk is a promising biosorbent for the environmental remediation of radioactive iodine pollution. Copyright © 2018 Elsevier Ltd. All rights reserved.

Preparation of activated carbon from a renewable bio-plant of Euphorbia rigida by H 2SO 4 activation and its adsorption behavior in aqueous solutions

NASA Astrophysics Data System (ADS)

Gerçel, Özgül; Özcan, Adnan; Özcan, A. Safa; Gerçel, H. Ferdi

2007-03-01

The use of activated carbon obtained from Euphorbia rigida for the removal of a basic textile dye, which is methylene blue, from aqueous solutions at various contact times, pHs and temperatures was investigated. The plant material was chemically modified with H 2SO 4. The surface area of chemically modified activated carbon was 741.2 m 2 g -1. The surface characterization of both plant- and activated carbon was undertaken using FTIR spectroscopic technique. The adsorption process attains equilibrium within 60 min. The experimental data indicated that the adsorption isotherms are well described by the Langmuir equilibrium isotherm equation and the calculated adsorption capacity of activated carbon was 114.45 mg g -1 at 40° C. The adsorption kinetics of methylene blue obeys the pseudo-second-order kinetic model and also followed by the intraparticle diffusion model up to 60 min. The thermodynamic parameters such as Δ G°, Δ H° and Δ S° were calculated to estimate the nature of adsorption. The activation energy of the system was calculated as 55.51 kJ mol -1. According to these results, prepared activated carbon could be used as a low-cost adsorbent to compare with the commercial activated carbon for the removal textile dyes from textile wastewater processes.

Reuse of waste beer yeast sludge for biosorptive decolorization of reactive blue 49 from aqueous solution.

PubMed

Wang, Baoe; Guo, Xiu

2011-06-01

Reactive blue 49 was removed from aqueous solution by biosorption using powder waste sludge composed of Saccharomyces cerevisiae from the beer-brewing industry. The effect of initial pH, temperature and the biosorption thermodynamics, equilibrium, kinetics was investigated in this study. It was found that the biosorption capacity was at maximum at initial pH 3, that the effect of temperature on biosorption of reactive blue 49 was only slight in relation to the large biosorption capacity (25°C, 361 mg g(-1)) according as the biosorption capacity decreased only 43 mg g(-1) at the temperature increased from 25 to 50°C. The biosorption was spontaneous, exothermic in nature and the dye molecules movements decreased slightly in random at the solid/liquid interface during the biosorption of dye on biosorbents. The biosorption equilibrium data could be described by Freundich isotherm model. The biosorption rates were found to be consistent with a pseudo-second-order kinetics model. The functional group interaction analysis between waste beer yeast sludge and reactive blue 49 by the aid of Fourier transform infrared (abbr. FTIR) spectroscopy indicated that amino components involved in protein participated in the biosorption process, which may be achieved by the mutual electrostatic adsorption process between the positively charged amino groups in waste beer yeast sludge with negatively charged sulfonic groups in reactive blue 49.

Characterization of H3PO4-Treated Rice Husk Adsorbent and Adsorption of Copper(II) from Aqueous Solution

PubMed Central

Zheng, Ru; Zhao, Jiaying; Ma, Fang; Zhang, Yingchao; Meng, Qingjuan

2014-01-01

Rice husk, a surplus agricultural byproduct, was applied to the sorption of copper from aqueous solutions. Chemical modifications by treating rice husk with H3PO4 increased the sorption ability of rice husk for Cu(II). This work investigated the sorption characteristics for Cu(II) and examined the optimum conditions of the sorption processes. The elemental compositions of native rice husk and H3PO4-treated rice husk were determined by X-ray fluorescence (XRF) analysis. The scanning electron microscopic (SEM) analysis was carried out for structural and morphological characteristics of H3PO4-treated rice husk. The surface functional groups (i.e., carbonyl, carboxyl, and hydroxyl) of adsorbent were examined by Fourier Transform Infrared Technique (FT-IR) and contributed to the adsorption for Cu(II). Adsorption isotherm experiments were carried out at room temperature and the data obtained from batch studies fitted well with the Langmuir and Freundlich models with R 2 of 0.999 and 0.9303, respectively. The maximum sorption amount was 17.0358 mg/g at a dosage of 2 g/L after 180 min. The results showed that optimum pH was attained at pH 4.0. The equilibrium data was well represented by the pseudo-second-order kinetics. The percentage removal for Cu(II) approached equilibrium at 180 min with 88.9% removal. PMID:24678507

Kinetics, equilibrium and thermodynamic studies on biosorption of Ag(I) from aqueous solution by macrofungus Pleurotus platypus.

PubMed

Das, Devlina; Das, Nilanjana; Mathew, Lazar

2010-12-15

Reports are available on silver binding capacity of some microorganisms. However, reports on the equilibrium studies on biosorption of silver by macrofungi are seldom known. The present study was carried out in a batch system using dead biomass of macrofungus Pleurotus platypus for the sorption of Ag(I). P. platypus exhibited the highest silver uptake of 46.7 mg g(-1) of biomass at pH 6.0 in the presence of 200 mg L(-1) Ag(I) at 20°C. Kinetic studies based on fractional power, zero order, first order, pseudo-first order, Elovich, second order and pseudo-second order rate expressions have been carried out. The results showed a very good compliance with the pseudo-first order model. The experimental data were analyzed using two parameter isotherms (Langmuir, Freundlich, Dubinin-Radushkevich, Temkin and Halsey), three parameter isotherms (Redlich-Peterson, Sips, Khan, Koble-Corrigan, Hill, Toth, Radke-Prausmitz, Jossens, Langmuir-Freundlich), four parameter isotherms (Weber-van Vliet, Fritz-Schlunder, Baudu) and five parameter isotherm (Fritz-Schlunder). Thermodynamic parameters of the biosorption (ΔG, ΔH and ΔS) were also determined. The present study confirmed that macrofungus P. platypus may be used as a cost effective efficient biosorbent for the removal of Ag(I) ions from aqueous solution. Copyright © 2010 Elsevier B.V. All rights reserved.

Equilibrium isotherm and kinetic studies for the simultaneous removal of phenol and cyanide by use of S. odorifera (MTCC 5700) immobilized on coconut shell activated carbon

NASA Astrophysics Data System (ADS)

Singh, Neetu; Balomajumder, Chandrajit

2017-10-01

In this study, simultaneous removal of phenol and cyanide by a microorganism S. odorifera (MTCC 5700) immobilized onto coconut shell activated carbon surface (CSAC) was studied in batch reactor from mono and binary component aqueous solution. Activated carbon was derived from coconut shell by chemical activation method. Ferric chloride (Fecl3), used as surface modification agents was applied to biomass. Optimum biosorption conditions were obtained as a function of biosorbent dosage, pH, temperature, contact time and initial phenol and cyanide concentration. To define the equilibrium isotherms, experimental data were analyzed by five mono component isotherm and six binary component isotherm models. The higher uptake capacity of phenol and cyanide onto CSAC biosorbent surface was 450.02 and 2.58 mg/g, respectively. Nonlinear regression analysis was used for determining the best fit model on the basis of error functions and also for calculating the parameters involved in kinetic and isotherm models. The kinetic study results revealed that Fractal-like mixed first second order model and Brouser-Weron-Sototlongo models for phenol and cyanide were capable to offer accurate explanation of biosorption kinetic. According to the experimental data results, CSAC with immobilization of bacterium S. odorifera (MTCC 5700) seems to be an alternative and effective biosorbent for the elimination of phenol and cyanide from binary component aqueous solution.

Thermodynamics of magnesian calcite solid-solutions at 25°C and 1 atm total pressure

USGS Publications Warehouse

Busenberg, Eurybiades; Plummer, Niel

1989-01-01

The stability of magnesian calcites was reexamined, and new results are presented for 28 natural inorganic, 12 biogenic, and 32 synthetic magnesian calcites. The magnesian calcite solid-solutions were separated into two groups on the basis of differences in stoichiometric solubility and other physical and chemical properties. Group I consists of solids of mainly metamorphic and hydrothermal origin, synthetic calcites prepared at high temperatures and pressures, and synthetic solids prepared at low temperature and very low calcite supersaturations () from artificial sea water or NaClMgCl2CaCl2solutions. Group I solids are essentially binary s of CaCO2 and MgCO2, and are thought to be relatively free of structural defects. Group II solid-solutions are of either biogenic origin or are synthetic magnesian calcites and protodolomites (0–20 and ∼ 45 mole percent MgCO3) prepared at high calcite supersaturations () from NaClNa2SO4MgCl2CaCl2 or NaClMgCl2CaCl2 solutions. Group II solid-solutions are treated as massively defective solids. The defects include substitution foreign ions (Na+ and SO42−) in the magnesian calcite lattice (point defects) and dislocations (~2 · 109 cm−2). Within each group, the excess free energy of mixing, GE, is described by the mixing model , where x is the mole fraction of the end-member Ca0.5Mg0.5CO3 in the solid-solution. The values of A0and A1 for Group I and II solids were evaluated at 25°C. The equilibrium constants of all the solids are closely described by the equation ln , where KC and KD are the equilibrium constants of calcite and Ca0.5Mg0.5CO3. Group I magnesian calcites were modeled as sub-regular solid-solutions between calcite and dolomite, and between calcite and “disordered dolomite”. Both models yield almost identical equilibrium constants for these magnesian calcites. The Group II magnesian calcites were modeled as sub-regular solid-solutions between defective calcite and protodolomite. Group I and II solid-solutions differ significantly in stability. The rate of crystal growth and the chemical composition of the aqueous solutions from which the solids were formed are the main factors controlling stoichiometric solubility of the magnesian calcites and the density of crystal defects. The literature on the occurrence and behavior of magnesian calcites in sea water and other aqueous solutions is also examined.

Adsorption of direct dyes from aqueous solutions by carbon nanotubes: determination of equilibrium, kinetics and thermodynamics parameters.

PubMed

Kuo, Chao-Yin; Wu, Chung-Hsin; Wu, Jane-Yii

2008-11-15

This study examined the feasibility of removing direct dyes C.I. Direct Yellow 86 (DY86) and C.I. Direct Red 224 (DR224) from aqueous solutions using carbon nanotubes (CNTs). The effects of dye concentration, CNT dosage, ionic strength and temperature on adsorption of direct dyes by CNTs were also evaluated. Pseudo second-order, intraparticle diffusion and Bangham models were adopted to evaluate experimental data and thereby elucidate the kinetic adsorption process. Additionally, this study used the Langmuir, Freundlich, Dubinin and Radushkevich (D-R) and Temkin isotherms to describe equilibrium adsorption. The adsorption percentage of direct dyes increased as CNTs dosage, NaCl addition and temperature increased. Conversely, the adsorption percentage of direct dyes decreased as dye concentration increased. The pseudo second-order model best represented adsorption kinetics. Based on the regressions of intraparticle diffusion and Bangham models, experimental data suggest that the adsorption of direct dyes onto CNTs involved intraparticle diffusion, but that was not the only rate-controlling step. The equilibrium adsorption of DR86 is best fitted in the Freundlich isotherm and that of DR224 was best fitted in the D-R isotherm. The capacity of CNTs to adsorb DY86 and DR224 was 56.2 and 61.3 mg/g, respectively. For DY86, enthalpy (DeltaH(0)) and entropy (DeltaS(0)) were 13.69 kJ/mol and 139.51 J/mol K, respectively, and those for DR224 were 24.29 kJ/mol and 172.06 J/mol K, respectively. The values of DeltaH(0), DeltaG(0) and E all indicate that the adsorption of direct dyes onto CNTs was a physisorption process.

Corncob as an effective, eco-friendly, and economic biosorbent for removing the azo dye Direct Yellow 27 from aqueous solutions.

PubMed

Berber-Villamar, Nayda Karina; Netzahuatl-Muñoz, Alma Rosa; Morales-Barrera, Liliana; Chávez-Camarillo, Griselda Ma; Flores-Ortiz, César Mateo; Cristiani-Urbina, Eliseo

2018-01-01

The corncob is an agricultural waste generated in huge quantities during corn processing. In this paper, we tested the capacity of corncob particles for water purification by removing the azo dye Direct Yellow 27 (DY27) via biosorption. The biosorption process was investigated in terms of the kinetics, equilibria, and thermodynamics. Batch biosorption studies showed that the biosorption performance has strong inverse correlations to the solution pH and the corncob particle size, and it increases quickly with increasing contact time and initial dye concentration. The pseudo-second-order kinetic model provides the best fit to the experimental data, whereas the Redlich-Peterson isotherm model is most suitable for describing the observed equilibrium biosorption. The biosorption process is exothermic, spontaneous, and physisorption in character. Fourier transform infrared (FTIR) spectroscopy and confocal scanning laser microscopy (CSLM) studies suggest that lignocellulose and proteins play key roles in the biosorption of DY27 from aqueous solutions by corncob. Furthermore, after biosorption onto the corncob, the dye can be effectively desorbed using 0.1 M NaOH solution. Therefore, the corncob can be used as a promising biosorbent to remediate DY27-contaminated water and wastewater.

Surface functionalized composite nanofibers for efficient removal of arsenic from aqueous solutions.

PubMed

Mohamed, Alaa; Osman, T A; Toprak, M S; Muhammed, M; Uheida, A

2017-08-01

A novel composites nanofiber was synthesized based on PAN-CNT/TiO 2 -NH 2 nanofibers using electrospinning technique followed by chemical modification of TiO 2 NPs. PAN-CNT/TiO 2 -NH 2 nanofiber were characterized by XRD, FTIR, SEM, and TEM. The effects of various experimental parameters such as initial concentration, contact time, and solution pH on As removal were investigated. The maximum adsorption capacity at pH 2 for As(III) and As(V) is 251 mg/g and 249 mg/g, respectively, which is much higher than most of the reported adsorbents. The adsorption equilibrium reached within 20 and 60 min as the initial solution concentration increased from 10 to 100 mg/L, and the data fitted well using the linear and nonlinear pseudo first and second order model. Isotherm data fitted well to the linear and nonlinear Langmuir, Freundlich, and Redlich-Peterson isotherm adsorption model. Desorption results showed that the adsorption capacity can remain up to 70% after 5 times usage. This work provides a simple and an efficient method for removing arsenic from aqueous solution. Copyright © 2017 Elsevier Ltd. All rights reserved.

Corncob as an effective, eco-friendly, and economic biosorbent for removing the azo dye Direct Yellow 27 from aqueous solutions

PubMed Central

Berber-Villamar, Nayda Karina; Netzahuatl-Muñoz, Alma Rosa; Morales-Barrera, Liliana; Chávez-Camarillo, Griselda Ma.; Flores-Ortiz, César Mateo

2018-01-01

The corncob is an agricultural waste generated in huge quantities during corn processing. In this paper, we tested the capacity of corncob particles for water purification by removing the azo dye Direct Yellow 27 (DY27) via biosorption. The biosorption process was investigated in terms of the kinetics, equilibria, and thermodynamics. Batch biosorption studies showed that the biosorption performance has strong inverse correlations to the solution pH and the corncob particle size, and it increases quickly with increasing contact time and initial dye concentration. The pseudo-second-order kinetic model provides the best fit to the experimental data, whereas the Redlich-Peterson isotherm model is most suitable for describing the observed equilibrium biosorption. The biosorption process is exothermic, spontaneous, and physisorption in character. Fourier transform infrared (FTIR) spectroscopy and confocal scanning laser microscopy (CSLM) studies suggest that lignocellulose and proteins play key roles in the biosorption of DY27 from aqueous solutions by corncob. Furthermore, after biosorption onto the corncob, the dye can be effectively desorbed using 0.1 M NaOH solution. Therefore, the corncob can be used as a promising biosorbent to remediate DY27-contaminated water and wastewater. PMID:29698442

Cadmium-109 Radioisotope Adsorption onto Polypyrrole Coated Sawdust of Dryobalanops aromatic: Kinetics and Adsorption Isotherms Modelling

PubMed Central

Olatunji, Michael Adekunle; Khandaker, Mayeen Uddin; Amin, Yusoff Mohd; Mahmud, Habibun Nabi Muhammad Ekramul

2016-01-01

A radiotracer study was conducted to investigate the removal characteristics of cadmium (109Cd) from aqueous solution by polypyrrole/ sawdust composite. Several factors such as solution pH, sorbent dosage, initial concentration, contact time, temperature and interfering metal ions were found to have influence on the adsorption process. The kinetics of adsorption was relatively fast, reaching equilibrium within 3 hours. A lowering of the solution pH reduced the removal efficiency from 99.3 to ~ 46.7% and an ambient temperature of 25°C was found to be optimum for maximum adsorption. The presence of sodium and potassium ions inhibited 109Cd removal from its aqueous solution. The experimental data for 109Cd adsorption showed a very good agreement with the Langmuir isotherm and a pseudo-first order kinetic model. The surface condition of the adsorbent before and after cadmium loading was investigated using BET, FESEM and FTIR. Considering the low cost of the precursor’s materials and the toxicity of 109Cd radioactive metal, polypyrrole synthesized on the sawdust of Dryobalanops aromatic could be used as an efficient adsorbent for the removal of 109Cd radioisotope from radionuclide-containing effluents. PMID:27706232

Solubility Model for Ferrous Iron Hydroxide, Hibbingite, Siderite, and Chukanovite in High Saline Solutions of Sodium Chloride, Sodium Sulfate, and Sodium Carbonate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Sungtae; Marrs, Cassandra; Nemer, Martin

Here, a solubility model is presented for ferrous iron hydroxide (Fe(OH) 2(s)), hibbingite (Fe 2Cl(OH) 3(s)), siderite (FeCO 3(s)), and chukanovite (Fe 2CO 3(OH) 2(s)). The Pitzer activity coefficient equation was utilized in developing the model to account for the excess free energies of aqueous species in the background solutions of high ionic strength. Solubility limiting minerals were analyzed before and after experiments using X-ray diffraction. Formation of Fe(OH) 2(s) was observed in the experiments that were initiated with Fe 2Cl(OH) 3(s) in Na 2SO 4 solution. Coexistence of siderite and chukanovite was observed in the experiments in Na 2COmore » 3 + NaCl solutions. Two equilibrium constants that had been reported by us for the dissolution of Fe(OH) 2(s) and Fe 2Cl(OH) 3(s) (Nemer et al.) were rederived in this paper, using newer thermodynamic data selected from the literature to maintain internal consistency of the series of our data analyses in preparation, including this paper. Three additional equilibrium constants for the following reactions were determined in this paper: dissolution of siderite and chukanovite and dissociation of the aqueous species Fe(CO 3) 2 –2. Five Pitzer interaction parameters were derived in this paper: β (0), β (1), and C φ parameters for the species pair Fe +2/SO 4 –2; β (0) and β (1) parameters for the species pair Na+/Fe(CO3)2–2. Our model predicts that, among the four inorganic ferrous iron minerals, siderite is the stable mineral in two WIPP-related brines (WIPP: Waste Isolation Pilot Plant), i.e., GWB and ERDA6 (Brush and Domski), and the electrochemical equilibrium between elemental iron and siderite provides a low oxygen fugacity (10 –91.2 atm) that can keep the actinides at their lowest oxidation states. (Nemer et al., Brush and Domski; references numbered 1 and 2 in the main text).« less

Solubility Model for Ferrous Iron Hydroxide, Hibbingite, Siderite, and Chukanovite in High Saline Solutions of Sodium Chloride, Sodium Sulfate, and Sodium Carbonate

DOE PAGES

Kim, Sungtae; Marrs, Cassandra; Nemer, Martin; ...

2017-11-20

Here, a solubility model is presented for ferrous iron hydroxide (Fe(OH) 2(s)), hibbingite (Fe 2Cl(OH) 3(s)), siderite (FeCO 3(s)), and chukanovite (Fe 2CO 3(OH) 2(s)). The Pitzer activity coefficient equation was utilized in developing the model to account for the excess free energies of aqueous species in the background solutions of high ionic strength. Solubility limiting minerals were analyzed before and after experiments using X-ray diffraction. Formation of Fe(OH) 2(s) was observed in the experiments that were initiated with Fe 2Cl(OH) 3(s) in Na 2SO 4 solution. Coexistence of siderite and chukanovite was observed in the experiments in Na 2COmore » 3 + NaCl solutions. Two equilibrium constants that had been reported by us for the dissolution of Fe(OH) 2(s) and Fe 2Cl(OH) 3(s) (Nemer et al.) were rederived in this paper, using newer thermodynamic data selected from the literature to maintain internal consistency of the series of our data analyses in preparation, including this paper. Three additional equilibrium constants for the following reactions were determined in this paper: dissolution of siderite and chukanovite and dissociation of the aqueous species Fe(CO 3) 2 –2. Five Pitzer interaction parameters were derived in this paper: β (0), β (1), and C φ parameters for the species pair Fe +2/SO 4 –2; β (0) and β (1) parameters for the species pair Na+/Fe(CO3)2–2. Our model predicts that, among the four inorganic ferrous iron minerals, siderite is the stable mineral in two WIPP-related brines (WIPP: Waste Isolation Pilot Plant), i.e., GWB and ERDA6 (Brush and Domski), and the electrochemical equilibrium between elemental iron and siderite provides a low oxygen fugacity (10 –91.2 atm) that can keep the actinides at their lowest oxidation states. (Nemer et al., Brush and Domski; references numbered 1 and 2 in the main text).« less

Absorption and emission behaviour of trans- p-coumaric acid in aqueous solutions and some organic solvents

NASA Astrophysics Data System (ADS)

Putschögl, M.; Zirak, P.; Penzkofer, A.

2008-01-01

The absorption and fluorescence behaviour of trans- p-coumaric acid ( trans-4-hydroxycinnamic acid) is investigated in buffered aqueous solution over a wide range from pH 1 to pH 12, in un-buffered water, and in some organic solvents. Absorption cross-section spectra, fluorescence quantum distributions, fluorescence quantum yields, and degrees of fluorescence polarisation are measured. p-Coumaric acid exists in different ionic forms in aqueous solution depending on the pH. There is an equilibrium between the neutral form ( p-CAH 2) and the single anionic form ( p-CAH -) at low pH (p Kna ≈ 4.9), and between the single anionic and the double anionic form ( p-CA 2-) at high pH (p Kaa ≈ 9.35). In the organic solvents studied trans- p-coumaric acid is dissolved in its neutral form. The fluorescence quantum yield of trans- p-coumaric acid in aqueous solution is ϕF ≈ 1.4 × 10 -4 for the neutral and the single anionic form, while it is ϕF ≈ 1.3 × 10 -3 for the double anionic form. For trans- p-coumaric acid in organic solvents fluorescence quantum yields in the range from 4.8 × 10 -5 (acetonitrile) to 1.5 × 10 -4 (glycerol) were measured. The fluorescence spectra are 7700-10,000 cm -1 Stokes shifted in aqueous solution, and 5400-8200 cm -1 Stokes shifted in the studied organic solvents. Decay paths responsible for the low fluorescence quantum yields are discussed (photo-isomerisation and internal conversion for p-CA 2-, solvent-assisted intra-molecular charge-transfer or ππ ∗ to nπ ∗ transfer and internal conversion for p-CAH 2 and p-CAH -). The solvent dependence of the first ππ ∗ electronic transition frequency and of the fluorescence Stokes shift of p-CAH 2 is discussed in terms of polar solute-solvent interaction effects. Thereby the ground-state and excite-state molecular dipole moments are extracted.

Up-scaling mineral-aqueous interfacial processes that govern isotope and trace element partitioning during calcite growth

NASA Astrophysics Data System (ADS)

Lammers, L. N.

2014-12-01

The dependence of the isotopic and trace element composition of calcium carbonate minerals on growth conditions including temperature, pH, and salinity is widely used to infer paleoclimate conditions. These inferences rely heavily on phenomenological observations of biogenic and inorganic precipitation both in and ex situ, where only limited variability in solution conditions can be explored. Ionic fluxes between the mineral surface and aqueous growth solution govern the net uptake of both stoichiometric and trace species during calcification, so developing a mechanistic understanding of the reactions governing these fluxes is critical to refine existing proxies and to develop new ones. The micro-scale mechanisms of calcite precipitation from aqueous solution have been extensively studied, and net ionic uptake post-nucleation is known to occur primarily at monomolecular kink sites along step edges at the mineral surface. In this talk, I will present a theoretical framework that uses the quasi-elementary ion attachment and detachment reactions governing ion uptake at kink sites to simultaneously model bulk mineral growth kinetics and tracer partitioning during calcite precipitation. Several distinct processes occur during ion uptake at kink sites that can influence the distribution of trace species, directly impacting the composition of various carbonate paleoproxies including δ44Ca, δ18O, Sr/Ca and Mg/Ca. The distribution of these trace species will be shown to depend on (1) the relative rates of ion desolvation during attachment to kink sites, (2) the relative rates of bond breaking during detachment from kink sites, and (3) the equilibrium partitioning of trace aqueous species. This model accounts for the impact of solution conditions on net ion fluxes and surface speciation, which in turn controls the population of kink sites available for direct ion exchange with the aqueous phase. The impacts of solution variables including pH, temperature and salinity can be treated independently, which unlike traditional partitioning studies allows the impacts of these parameters to be deconvolved. The type of theoretical framework discussed here can be readily extended to explicitly account for each of the major solution composition variables that are implicated in paleoproxy composition.

Total reflection infrared spectroscopy of water-ice and frozen aqueous NaCl solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Walker, Rachel L.; Searles, Keith; Willard, Jesse A.

2013-12-28

Liquid-like and liquid water at and near the surface of water-ice and frozen aqueous sodium chloride films were observed using attenuated total reflection infrared spectroscopy (ATR-IR). The concentration of NaCl ranged from 0.0001 to 0.01 M and the temperature varied from the melting point of water down to 256 K. The amount of liquid brine at the interface of the frozen films with the germanium ATR crystal increased with salt concentration and temperature. Experimental spectra are compared to reflection spectra calculated for a simplified morphology of a uniform liquid layer between the germanium crystal and the frozen film. This morphologymore » allows for the amount of liquid observed in an experimental spectrum to be converted to the thickness of a homogenous layer with an equivalent amount of liquid. These equivalent thickness ranges from a nanometer for water-ice at 260 K to 170 nm for 0.01 M NaCl close to the melting point. The amounts of brine observed are over an order of magnitude less than the total liquid predicted by equilibrium thermodynamic models, implying that the vast majority of the liquid fraction of frozen solutions may be found in internal inclusions, grain boundaries, and the like. Thus, the amount of liquid and the solutes dissolved in them that are available to react with atmospheric gases on the surfaces of snow and ice are not well described by thermodynamic equilibrium models which assume the liquid phase is located entirely at the surface.« less

Synthesis and application of a new carboxylated cellulose derivative. Part III: Removal of auramine-O and safranin-T from mono- and bi-component spiked aqueous solutions.

PubMed

Teodoro, Filipe Simões; Elias, Megg Madonyk Cota; Ferreira, Gabriel Max Dias; Adarme, Oscar Fernando Herrera; Savedra, Ranylson Marcello Leal; Siqueira, Melissa Fabíola; da Silva, Luis Henrique Mendes; Gil, Laurent Frédéric; Gurgel, Leandro Vinícius Alves

2018-02-15

In the third part of this series of studies, the adsorption of the basic textile dyes auramine-O (AO) and safranin-T (ST) on a carboxylated cellulose derivative (CTA) were evaluated in mono- and bi-component spiked aqueous solutions. Adsorption studies were developed as a function of solution pH, contact time, and initial dye concentration. Adsorption kinetic data were modeled by monocomponent kinetic models of pseudo-first- (PFO), pseudo-second-order (PSO), intraparticle diffusion, and Boyd, while the competitive kinetic model of Corsel was used to model bicomponent kinetic data. Monocomponent adsorption equilibrium data were modeled by the Langmuir, Sips, Fowler-Guggenhein, Hill de-Boer, and Konda models, while the IAST and RAST models were used to model bicomponent equilibrium data. Monocomponent maximum adsorption capacities for AO and ST at pH 4.5 were 2.841 and 3.691 mmol g -1 , and at pH 7.0 were 5.443 and 4.074 mmol g -1 , respectively. Bicomponent maximum adsorption capacities for AO and ST at pH 7.0 were 1.230 and 3.728 mmol g -1 . Adsorption enthalpy changes (Δ ads H) were obtained using isothermal titration calorimetry. The values of Δ ads H ranged from -18.83 to -5.60 kJ mol -1 , suggesting that physisorption controlled the adsorption process. Desorption and re-adsorption of CTA was also evaluated. Copyright © 2017 Elsevier Inc. All rights reserved.

Regular oscillatory behavior of aqueous solutions of CuII salts related to effects on equilibrium dynamics of ortho/para hydrogen spin isomers of water.

PubMed

Morré, D J; Orczyk, J; Hignite, H; Kim, C

2008-02-01

Cell surface and growth-related NADH oxidases with protein disulfide-thiol interchange activity, ECTO-NOX, exhibit copper-dependent, clock-related, temperature-independent and entrainable patterns of regular oscillations in the rate of oxidation of NAD(P)H as do aqueous solutions of copper salts. Because of time scale similarities, a basis for the oscillatory patterns in nuclear spin orientations of the hydrogen atoms of the copper-associated water was sought. Extended X-ray absorption fine structure (EXAFS) measurements at 9302 eV on pure water were periodic with a ca. 3.5 min peak to peak separation. Decomposition fits revealed 5 unequally spaced maxima similar to those observed previously for Cu(II)Cl(2) to generate a period length of about 18 min. With D(2)O, the period length was proportionately increased by 30% to 24 min. The redox potential of water and of D(2)O also oscillated with 18 and 24 min period lengths, respectively. Measurements in the middle infrared spectral region above a water sample surface revealed apparent oscillations in the two alternative orientations of the nuclear spins (ortho and para) of the hydrogen atoms of the water or D(2)O with 5 unequally spaced maxima and respective period lengths of 18 and 24 min. Thus, the time keeping oscillations of ECTO-NOX proteins appear to reflect the equilibrium dynamics of ortho-para hydrogen atom spin ratios of water where the presence of metal cations such as Cu(II) in solution determine period length.

Gas-phase water-mediated equilibrium between methylglyoxal and its geminal diol

PubMed Central

Axson, Jessica L.; Takahashi, Kaito; De Haan, David O.; Vaida, Veronica

2010-01-01

In aqueous solution, aldehydes, and to a lesser extent ketones, hydrate to form geminal diols. We investigate the hydration of methylglyoxal (MG) in the gas phase, a process not previously considered to occur in water-restricted environments. In this study, we spectroscopically identified methylglyoxal diol (MGD) and obtained the gas-phase partial pressures of MG and MGD. These results, in conjunction with the relative humidity, were used to obtain the equilibrium constant, KP, for the water-mediated hydration of MG in the gas phase. The Gibbs free energy for this process, ΔG°, obtained as a result, suggests a larger than expected gas-phase diol concentration. This may have significant implications for understanding the role of organics in atmospheric chemistry. PMID:20142510

Chemical Sensors Based on IR Spectroscopy and Surface-Modified Waveguides

NASA Technical Reports Server (NTRS)

Lopez, Gabriel P.; Niemczyk, Thomas

1999-01-01

Sol-gel processing techniques have been used to apply thin porous films to the surfaces of planar infrared (IR) waveguides to produce widely useful chemical sensors. The thin- film coating serves to diminish the concentration of water and increase the concentration of the analyte in the region probed by the evanescent IR wave. These porous films are composed of silica, and therefore, conventional silica surface modification techniques can be used to give the surface a specific functional character. The sol-gel film was surface-modified to make the film highly hydrophobic. These sensors were shown to be capable of detecting non-polar organic analytes, such as benzonitrile, in aqueous solution with detection limits in the ppb range. Further, these porous sol-gel structures allow the analytes to diffuse into and out of the films rapidly, thus reaching equilibrium in less than ten seconds. These sensors are unique because of the fact that their operation is based on the measurement of an IR absorption spectrum. Thus, these sensors are able to identify the analytes as well as measure concentration with high sensitivity. These developments have been documented in previous reports and publications. Recently, we have also targeted detection of the polar organic molecules acetone and isopropanol in aqueous solution. Polar organics are widely used in industrial and chemical processes, hence it is of interest to monitor their presence in effluents or decontamination process flows. Although large improvements in detection limits were expected with non-polar organic molecules in aqueous solutions using very hydrophobic porous sol-gel films on silicon attenuated total reflectance (Si ATR) waveguides, it was not as clear what the detection enhancements might be for polar organic molecules. This report describes the use of modified sol-gel-coated Si ATR sensors for trace detection and quantitation of small polar organic molecules in aqueous solutions. The detection of both acetone and isopropanol molecules in aqueous solution has been previously reported for chalcogenide fiber optic sensors. The sol-gel film was produced using a mixture of ethyltriethoxysilane and tetraethoxysilane and the surface modification was carried out using trimethylchlorosilane. We have demonstrated that this film concentrates the target polar analytes from aqueous solution in the region probed by the evanescent wave to improve detection limits by as much as a factor of 450.

One-Dimensional Transport with Equilibrium Chemistry (OTEQ) - A Reactive Transport Model for Streams and Rivers

USGS Publications Warehouse

Runkel, Robert L.

2010-01-01

OTEQ is a mathematical simulation model used to characterize the fate and transport of waterborne solutes in streams and rivers. The model is formed by coupling a solute transport model with a chemical equilibrium submodel. The solute transport model is based on OTIS, a model that considers the physical processes of advection, dispersion, lateral inflow, and transient storage. The equilibrium submodel is based on MINTEQ, a model that considers the speciation and complexation of aqueous species, acid-base reactions, precipitation/dissolution, and sorption. Within OTEQ, reactions in the water column may result in the formation of solid phases (precipitates and sorbed species) that are subject to downstream transport and settling processes. Solid phases on the streambed may also interact with the water column through dissolution and sorption/desorption reactions. Consideration of both mobile (waterborne) and immobile (streambed) solid phases requires a unique set of governing differential equations and solution techniques that are developed herein. The partial differential equations describing physical transport and the algebraic equations describing chemical equilibria are coupled using the sequential iteration approach. The model's ability to simulate pH, precipitation/dissolution, and pH-dependent sorption provides a means of evaluating the complex interactions between instream chemistry and hydrologic transport at the field scale. This report details the development and application of OTEQ. Sections of the report describe model theory, input/output specifications, model applications, and installation instructions. OTEQ may be obtained over the Internet at http://water.usgs.gov/software/OTEQ.

Radiation synthesis of biocompatible hydrogels of dextran methacrylate

NASA Astrophysics Data System (ADS)

Szafulera, Kamila; Wach, Radosław A.; Olejnik, Alicja K.; Rosiak, Janusz M.; Ulański, Piotr

2018-01-01

The aim of this work was to synthesize biocompatible dextran-based hydrogels through crosslinking initiated by ionizing radiation. A series of derivatives of dextran has been synthesized by coupling of methacrylated glycidyl to the structure of this polysaccharide, yielding dextran methacrylate (Dex-MA) of the degree of methacrylate substitution (DS) up to 1.13 as characterised by FTIR and NMR spectroscopy. Chemically crosslinked hydrogels were formed by electron-beam irradiation of Dex-MA in aqueous solution in the absence of low-molecular-weight additives such as catalysts, monomers or crosslinking agents. Crosslinking of Dex-MA in aqueous solutions of 20 g/l and above was an efficient process, the gels were formed at doses as low as 0.5 kGy (experiments conducted up to 100 kGy) and were characterised by high content of insoluble fraction (70-100%). Due to high crosslinking density the equilibrium degree of swelling of fabricated gels was controlled principally by the initial concentration of Dex-MA solution subjected to irradiation, and it was in the range of 20 to over 100 g of water absorbed by gram of gel. Cytocompatibility of hydrogels was examined using XTT assay through evaluation of the cell viability being in indirect contact with hydrogels. The results indicated that hydrogels of Dex-MA of the average DS below 1 were not cytotoxic. Altogether, our data demonstrate that irradiation of methacrylated dextran in aqueous solution is an efficient method of fabrication of biocompatible hydrogels, which applications in regeneration medicine are anticipated.

Development of a Low-Cost Spectrophotometric Sensor for ClO2 Gas

NASA Astrophysics Data System (ADS)

Conry, Jessica; Scott, Dane; Apblett, Allen; Materer, Nicholas

2006-04-01

ClO2 is of interest because of it's capability to kill biological hazards such as E. coli and mold. However, ClO2 is a toxic, reactive gas that must be generated at the point-of-use. Gas storage is not possible due to the possibility of an explosion. The need to detect the amount of ClO2 at the point-of-use necessitates a low cost sensor. A low-cost spectrophotometric sensor based on a broad-band light source, a photodiode detector and a band-pass filter is proposed. To verify the design, precise determinations of the gas-phase cross-section and characterization of the optical components are necessary. Known concentrations of ClO2(g) are prepared using the equilibrium relationship between an aqueous solution and the gas phase. The aqueous solutions are obtained by generating the gas via a chemical reaction and passing it through water. The concentrations of the aqueous solutions are then determined by chemical titration and UV-visible absorption measurements. For the solutions, a maximum absorption is observed at 359 nm, and the cross section at this wavelength is determined to be 4.79x10-18cm^2, in agreement with previous observations. Using a broad-band source, the absorption of ClO2 gas is successfully analyzed and concentrations are determined as low as 100 ppm. A more recent prototype based on an UV LED can measure down to concentrations as low as one ppm.

The separation of uranium ions by natural and modified diatomite from aqueous solution.

PubMed

Sprynskyy, Myroslav; Kovalchuk, Iryna; Buszewski, Bogusław

2010-09-15

In this work the natural and the surfactant modified diatomite has been tested for ability to remove uranium ions from aqueous solutions. Such controlling factors of the adsorption process as initial uranium concentration, pH, contact time and ionic strength have been investigated. Effect of ionic strength of solution has been examined using the solutions of NaCl, Na(2)CO(3) and K(2)SO(4). The pseudo-first order and the pseudo-second order models have been used to analyze the adsorption kinetic results, whereas the Langmuir and the Freundlich isotherms have been used to the equilibrium adsorption data. The effects of the adsorbent modification as well as uranium adsorption on the diatomite surface have been studied using X-ray powder diffraction, scanning electron microscopy and FTIR spectroscopy. The maximum adsorption capacities of the natural and the modified diatomite towards uranium were 25.63 micromol/g and 667.40 micromol/g, respectively. The desorptive solutions of HCl, NaOH, Na(2)CO(3), K(2)SO(4), CaCO(3), humic acid, cool and hot water have been tested to recover uranium from the adsorbent. The highest values of uranium desorption (86%) have been reached using 0.1M HCl. Copyright 2010 Elsevier B.V. All rights reserved.

Kinetic and equilibrium characterization of uranium(VI) adsorption onto carboxylate-functionalized poly(hydroxyethylmethacrylate)-grafted lignocellulosics.

PubMed

Anirudhan, T S; Divya, L; Suchithra, P S

2009-01-01

This study investigated the feasibility of using a new adsorbent prepared from coconut coir pith, CP (a coir industry-based lignocellulosic residue), for the removal of uranium [U(VI)] from aqueous solutions. The adsorbent (PGCP-COOH) having a carboxylate functional group at the chain end was synthesized by grafting poly(hydroxyethylmethacrylate) onto CP using potassium peroxydisulphate-sodium thiosulphite as a redox initiator and in the presence of N,N'-methylenebisacrylamide as a crosslinking agent. IR spectroscopy results confirm the graft copolymer formation and carboxylate functionalization. XRD studies confirm the decrease of crystallinity in PGCP-COOH compared to CP, and it favors the protrusion of the functional group into the aqueous medium. The thermal stability of the samples was studied using thermogravimetry (TG). Surface charge density of the samples as a function of pH was determined using potentiometric titration. The ability of PGCP-COOH to remove U(VI) from aqueous solutions was assessed using a batch adsorption technique. The maximum adsorption capacity was observed at the pH range 4.0-6.0. Maximum removal of 99.2% was observed for an initial concentration of 25mg/L at pH 6.0 and an adsorbent dose of 2g/L. Equilibrium was achieved in approximately 3h. The experimental kinetic data were analyzed using a first-order kinetic model. The temperature dependence indicates an endothermic process. U(VI) adsorption was found to decrease with an increase in ionic strength due to the formation of outer-sphere surface complexes on PGCP-COOH. Equilibrium data were best modeled by the Langmuir isotherm. The thermodynamic parameters such as DeltaG(0), DeltaH(0) and DeltaS(0) were derived to predict the nature of adsorption. Adsorption experiments were also conducted using a commercial cation exchanger, Ceralite IRC-50, with carboxylate functionality for comparison. Utility of the adsorbent was tested by removing U(VI) from simulated nuclear industry wastewater. Adsorbed U(VI) ions were desorbed effectively (about 96.2+/-3.3%) by 0.1M HCl. The adsorbent was suitable for repeated use (more than four cycles) without any noticeable loss of capacity.

Remediation of groundwater contaminated with the lead-phenol binary system by granular dead anaerobic sludge-permeable reactive barrier.

PubMed

Faisal, Ayad A H; Abd Ali, Ziad T

2017-10-01

Computer solutions (COMSOL) Multiphysics 3.5a software was used for simulating the one-dimensional equilibrium transport of the lead-phenol binary system including the sorption process through saturated sandy soil as the aquifer and granular dead anaerobic sludge (GDAS) as the permeable reactive barrier. Fourier-transform infrared spectroscopy analysis proved that the carboxylic and alcohol groups are responsible for the bio-sorption of lead onto GDAS, while phosphines, aromatic and alkane are the functional groups responsible for the bio-sorption of phenol. Batch tests have been performed to characterize the equilibrium sorption properties of the GDAS and sandy soil in lead and/or phenol containing aqueous solutions. Numerical and experimental results proved that the barrier plays a potential role in the restriction of the contaminant plume migration and there is a linear relationship between longevity and thickness of the barrier. A good agreement between these results was recognized with root mean squared error not exceeding 0.04.

Adsorption of Ni(II) onto Chemically Modified Spent Grated Coconut (Cocos Nucifera)

NASA Astrophysics Data System (ADS)

Hamzah, F. I.; Khalid, K.; Hanafiah, M. A. K. M.

2017-06-01

A new adsorbent of plant waste origin from coconut processing food factory was explored for removing Ni(II) from aqueous solutions. Several parameters such as pH, dosage, concentration and contact time were studied to obtain optimum conditions for treatment of Ni(II) contaminated wastewater. Spent grated coconut (Cocos nucifera) treated with sulfuric acid (SSGC) showed good adsorption capacity for Ni(II) ion. The amount adsorbed was affected by solution pH with the highest value achieved at pH 5. Other optimum conditions found were; dosage of 0.02 g, and 60 min of equilibrium time. Ni(II) adsorption obeyed the pseudo-second order kinetic model which suggested that chemisorption mechanism occurred in the adsorption process. The equilibrium data presented a better fitting to the Langmuir isotherm model, an indication that monolayer adsorption occurred onto a homogeneous surface. The maximum adsorption capacity, qmax was 97.09 mg g-1, thus SSGC can be classified as good and comparable with other plant waste adsorbents.

Interactions of lysozyme in concentrated electrolyte solutions from dynamic light-scattering measurements.

PubMed Central

Kuehner, D E; Heyer, C; Rämsch, C; Fornefeld, U M; Blanch, H W; Prausnitz, J M

1997-01-01

The diffusion of hen egg-white lysozyme has been studied by dynamic light scattering in aqueous solutions of ammonium sulfate as a function of protein concentration to 30 g/liter. Experiments were conducted under the following conditions: pH 4-7 and ionic strength 0.05-5.0 M. Diffusivity data for ionic strengths up to 0.5 M were interpreted in the context of a two-body interaction model for monomers. From this analysis, two potential-of-mean-force parameters, the effective monomer charge, and the Hamaker constant were obtained. At higher ionic strength, the data were analyzed using a model that describes the diffusion coefficient of a polydisperse system of interacting protein aggregates in terms of an isodesmic, indefinite aggregation equilibrium constant. Data analysis incorporated multicomponent virial and hydrodynamic effects. The resulting equilibrium constants indicate that lysozyme does not aggregate significantly as ionic strength increases, even at salt concentrations near the point of salting-out precipitation. PMID:9414232

Adsorption studies of methylene blue and gentian violet on sugarcane bagasse modified with EDTA dianhydride (EDTAD) in aqueous solutions: kinetic and equilibrium aspects.

PubMed

Gusmão, Karla Aparecida Guimarães; Gurgel, Leandro Vinícius Alves; Melo, Tânia Márcia Sacramento; Gil, Laurent Frédéric

2013-03-30

In this study the adsorption of cationic dyes by modified sugarcane bagasse with EDTA dianhydride (EB) was examined using methylene blue (MB) and gentian violet (GV) as model compounds in aqueous single solutions. The synthesized adsorbent (EB) was characterized by FTIR, elemental analysis, and BET. The capacity of EB to adsorb dyes was evaluated at different contact times, pH values, and initial dye concentrations. According to the obtained results, the adsorption processes could be described by a pseudo-second-order kinetic model. The adsorption isotherms were well fitted by the Langmuir model. Maximum adsorption capacities for MB and GV on EB were found to be 202.43 and 327.83 mg/g, respectively. The free energy change during adsorption of MB and GV was found to be -22.50 and -24.21 kJ/mol, respectively, suggesting that chemisorption is the main mechanism controlling the adsorption process. Copyright © 2013 Elsevier Ltd. All rights reserved.

Iron oxide impregnated Morus alba L. fruit peel for biosorption of Co(II): biosorption properties and mechanism.

PubMed

Koduru, Janardhan Reddy; Chang, Yoon-Young; Yang, Jae-Kyu; Kim, Im-Soon

2013-01-01

Biosorption is an ecofriendly wastewater treatment technique with high efficiency and low operating cost involving simple process for the removal of heavy metal ions from aqueous solution. In the present investigation, Morus alba L. fruit peel powder (MAFP) and iron oxide impregnated Morus alba L. fruit peel powder (IO-MAFP) were prepared and used for treating Co(II) contaminated aqueous solutions. Further the materials were characterized by using FTIR and SEM-EDX analysis. From FT-IR analysis it was found that hydroxyl, methoxy, and carbonyl groups are responsible for Co(II) biosorption. The kinetic data obtained for both biosorbents was well fitted with pseudo-second-order kinetic model. The equilibrium data was in tune with the Langmuir and Freundlich isotherm models. The thermodynamic studies were also carried and it was observed that sorption process was endothermic at 298-328 K. These studies demonstrated that both biosorbents were promising, efficient, economic, and biodegradable sorbents.

Stabilized micelles of amphoteric polyurethane formed by thermoresponsive micellization in HCl aqueous solution.

PubMed

Qiao, Yong; Zhang, Shifeng; Lin, Ouya; Deng, Liandong; Dong, Anjie

2008-04-01

The thermoresponsive micellization behavior of amphoteric polyurethane (APU) was studied in HCl aqueous solution (pH 2.0) through light scattering, transmission electron microscopy, and fluorescent measurement. When APU concentration is high enough, nonreversible assembly of macromolecules can be observed with temperature decreasing from 25 to 4 degrees C. However, micelles reaching equilibrium at 4 degrees C can self-assemble reversibly in the temperature range of 4-55 degrees C. According to our research, we found it is the temperature sensitivity of the poly(propylene oxide) (PPO) segments that leads to the reassembly of APU at lower temperature. We proposed that core-shell-corona micelles ultimately form with hydrophobic core, PPO shell, and hydrophilic corona when temperature increases from 4 to 25 degrees C. This structure is very stable and does not change at higher temperatures (25-55 degrees C). That provides a new way to obtain stable micelles with small size and narrow size distribution at higher concentration of APU.

Decolorisation of Basic Textile Dye from Aqueous Solutions using a Biosorbent derived from Thespesia populnea used Biomass

NASA Astrophysics Data System (ADS)

Gunturu, Bhargavi; Rao Palukuri, Nageswara; Sahadevan, Renganathan

2018-03-01

In the present study, the efficiency of a biosorbent derived from seeds of Thespesia populnea was investigated towards the removal of basic textile dye Methylene Blue from an aqueous solution. Adsorption studies were carried out in batch system. Influence of experimental parameters such as adsorbent dosage (0.1g/L-0.3g/L), PH (2-10) and initial dye concentration (50-130mg/L) on adsorption of dye onto biosorbent was investigated. Maximum uptake of dye was observed with 0.1g/L adsorbent dosage at PH 8.0. Equilibrium uptake of methylene blue dye by the adsorbent was analyzed by Langmuir and Freundlich isotherm models. The data fitted best with Freundlich model, suggesting that adsorption of the dye was by multilayer model on the surface of the adsorbent. Experimental results obtained support that the biosorbent used in the present study can be a suitable low cost alternate for the removal of basic textile dyes.

Pecan nutshell as biosorbent to remove Cu(II), Mn(II) and Pb(II) from aqueous solutions.

PubMed

Vaghetti, Julio C P; Lima, Eder C; Royer, Betina; da Cunha, Bruna M; Cardoso, Natali F; Brasil, Jorge L; Dias, Silvio L P

2009-02-15

In the present study we reported for the first time the feasibility of pecan nutshell (PNS, Carya illinoensis) as an alternative biosorbent to remove Cu(II), Mn(II) and Pb(II) metallic ions from aqueous solutions. The ability of PNS to remove the metallic ions was investigated by using batch biosorption procedure. The effects such as, pH, biosorbent dosage on the adsorption capacities of PNS were studied. Four kinetic models were tested, being the adsorption kinetics better fitted to fractionary-order kinetic model. Besides that, the kinetic data were also fitted to intra-particle diffusion model, presenting three linear regions, indicating that the kinetics of adsorption should follow multiple sorption rates. The equilibrium data were fitted to Langmuir, Freundlich, Sips and Redlich-Peterson isotherm models. Taking into account a statistical error function, the data were best fitted to Sips isotherm model. The maximum biosorption capacities of PNS were 1.35, 1.78 and 0.946mmolg(-1) for Cu(II), Mn(II) and Pb(II), respectively.

Ethylbenzene Removal by Carbon Nanotubes from Aqueous Solution

PubMed Central

Bina, Bijan; Pourzamani, Hamidreza; Rashidi, Alimorad; Amin, Mohammad Mehdi

2012-01-01

The removal of ethylbenzene (E) from aqueous solution by multiwalled, single-walled, and hybrid carbon nanotubes (MWCNTs, SWCNTs, and HCNTs) was evaluated for a nanomaterial dose of 1 g/L, concentration of 10–100 mg/L, and pH 7. The equilibrium amount removed by SWCNTs (E: 9.98 mg/g) was higher than by MWCNTs and HCNTs. Ethylbenzene has a higher adsorption tendency on CNTs, so that more than 98% of it adsorbed in first 14 min, which is related to the low water solubility and the high molecular weight. The SWCNTs performed better for ethylbenzene sorption than the HCNTs and MWCNTs. Isotherms study indicates that the BET isotherm expression provides the best fit for ethylbenzene sorption by SWCNTs. Carbon nanotubes, specially SWCNTs, are efficient and rapid adsorbents for ethylbenzene which possess good potential applications to maintain high-quality water. Therefore, it could be used for cleaning up environmental pollution to prevent ethylbenzene borne diseases. PMID:22187576

Iron Oxide Impregnated Morus alba L. Fruit Peel for Biosorption of Co(II): Biosorption Properties and Mechanism

PubMed Central

Koduru, Janardhan Reddy; Chang, Yoon-Young; Yang, Jae-Kyu; Kim, Im-Soon

2013-01-01

Biosorption is an ecofriendly wastewater treatment technique with high efficiency and low operating cost involving simple process for the removal of heavy metal ions from aqueous solution. In the present investigation, Morus alba L. fruit peel powder (MAFP) and iron oxide impregnated Morus alba L. fruit peel powder (IO-MAFP) were prepared and used for treating Co(II) contaminated aqueous solutions. Further the materials were characterized by using FTIR and SEM-EDX analysis. From FT-IR analysis it was found that hydroxyl, methoxy, and carbonyl groups are responsible for Co(II) biosorption. The kinetic data obtained for both biosorbents was well fitted with pseudo-second-order kinetic model. The equilibrium data was in tune with the Langmuir and Freundlich isotherm models. The thermodynamic studies were also carried and it was observed that sorption process was endothermic at 298–328 K. These studies demonstrated that both biosorbents were promising, efficient, economic, and biodegradable sorbents. PMID:24324384

Electrophoretic Study of the SnO2/Aqueous Solution Interface up to 260 degrees C.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rodriguez-Santiago, V; Fedkin, Mark V.; Wesolowski, David J

2009-01-01

An electrophoresis cell developed in our laboratory was utilized to determine the zeta potential at the SnO{sub 2} (cassiterite)/aqueous solution (10{sup -3} mol kg{sup -1} NaCl) interface over the temperature range from 25 to 260 C. Experimental techniques and methods for the calculation of zeta potential at elevated temperature are described. From the obtained zeta potential data as a function of pH, the isoelectric points (IEPs) of SnO{sub 2} were obtained for the first time. From these IEP values, the standard thermodynamic functions were calculated for the protonation-deprotonation equilibrium at the SnO{sub 2} surface, using the 1-pK surface complexation model.more » It was found that the IEP values for SnO{sub 2} decrease with increasing temperature, and this behavior is compared to the predicted values by the multisite complexation (MUSIC) model and other semitheoretical treatments, and were found to be in excellent agreement.« less

In situ Raman study of dissolved CaCO3 minerals under subduction zone conditions

NASA Astrophysics Data System (ADS)

Facq, S.; Daniel, I.; Sverjensky, D. A.

2012-12-01

The fate and the characteristics of the Earth's deep carbon reservoirs are still not well understood [1]. The connection between the surficial and the deep-Earth carbon cycles occurs at subduction zones where carbon is transported into the mantle and where hydrous silicates and carbonate minerals break down releasing H2O and C-species in fluids associated with mantle metasomatism and the generation of arc volcanism [2]. In order to obtain mass balance between recycling and burial in the deep mantle, the study of the dissolution of CaCO3 minerals in equilibrium with aqueous fluids under mantle conditions is crucial. We report a novel integrated experimental and theoretical study of the equilibration of CaCO3 minerals with aqueous solutions (pure water or NaCl solutions) at high pressures and temperatures (0.5 to 8 GPa and 250 to 500 °C). The fluid speciation was studied using in situ Raman spectroscopy coupled to an externally heated membrane type DAC equipped with 500 μm pure synthetic diamond anvils. In a typical experiment, the aqueous fluid and a calcite crystal [3] were loaded in a rhenium gasket. The pressure was determined from the calibrated shift of the carbonate υ1 symmetric stretching mode of aragonite and the temperature measured with a K-type thermocouple. Raman spectra were recorded using a Labram HR800 Raman spectrometer (Horiba Jobin-Yvon) coupled to a Spectra Physics Ar+ laser. At equilibrium with an aragonite crystal, the Raman data show that bicarbonate is the most abundant species in low-pressure fluids (below 4 GPa) whereas carbonate becomes progressively dominant at higher pressure. After correction from their Raman cross-sections [4], the relative amounts of dissolved carbonate and bicarbonate were estimated from the areas of the Raman bands of the carbonate and bicarbonate ions (υ1 and υ5 symmetric stretching modes, respectively). The presence of sodium chloride influences the speciation by extending the pressure field where the bicarbonate species is dominant in the fluid. The Raman data were also used to constrain a theoretical thermodynamic model of the fluid speciation in equilibrium with CaCO3. Building on published calcite solubility data from 400 - 700 °C and 2 - 16 kb [3, 5], revised thermodynamic properties of aqueous CO2 and HCO3-, data for the aqueous CaHCO3+ complex from 4 to 90 °C [6], and estimated dielectric constants of water, enabled an equation of state characterization of the standard Gibbs free energy of CaHCO3+ at the conditions of the Raman study. At 300 - 400 °C, the Raman speciation results were used to constrain equilibrium constants involving the carbonate ion. The results indicate that CO2 is a minor species in fluids in equilibrium with aragonite at 300 - 500 °C and P > 1.0 GPa. Instead, the CaHCO3+ species becomes important at high pressures until carbonate ion becomes the dominant C-species. [1] Marty, B. and Tolstikhin, I.N., Chemical Geology 145, 233 (1998) [2] Schmidt, M.W. and Poli, S., Earth and Planetary Science Letters 163, 163 (1998) [3] Caciagli, N.C. and Manning, C.E., Contributions to Mineralogy and Petrology 146, 275 (2003) [4] Frantz, J., Chemical Geology 152, 211 (1998) [5] Fein, J.B. and Walther, J.V., Contributions to Mineralogy and Petrology 103, 317 (1989) [6] Plummer, L.N. and Busenberg, E., Geochimica et Cosmochimica Acta 46, 1011 (1982)

Removal of methylene blue from aqueous solution by Artist's Bracket fungi: kinetic and equilibrium studies.

PubMed

Naghipour, Daryush; Taghavi, Kamran; Moslemzadeh, Mehrdad

2016-01-01

In this study, adsorption of methylene blue (MB) dye onto Artist's Bracket (AB) fungi was investigated in aqueous solution. Fourier transform infrared and scanning electron microscopy were used to investigate surface characteristic of AB fungi. Influence of operational parameters such as pH, contact time, biosorbent dosage, dye concentration, inorganic salts and temperature was studied on dye removal efficiency. With the increase of pH from 3 to 9, removal efficiency increased from 74.0% to 90.4%. Also, it reduced from 99.8% to 81.8% with increasing initial MB concentration from 25 mg L(-1) to 100 mg L(-1), whereas it increased from 54.7% to 98.7% and from 98.5% to 99.9% with increasing biosorbent dosage from 0.5 g L(-1) to 2 g L(-1) and with increasing temperature from 25 °C to 50 °C, respectively. Isotherm studies have shown adsorption of MB dye over the AB fungi had a better coefficient of determination (R(2)) of 0.98 for Langmuir isotherm. In addition, the maximum monolayer adsorption capacity (qm) was 100 mg g(-1). Also, the MB dye adsorption process followed pseudo-second-order kinetic. In general, AB fungi particles can be favorable for removal of MB dye from dye aqueous solution with natural pH and high temperature.

Biosorption of malachite green from aqueous solutions by Pleurotus ostreatus using Taguchi method

PubMed Central

2014-01-01

Dyes released into the environment have been posing a serious threat to natural ecosystems and aquatic life due to presence of heat, light, chemical and other exposures stable. In this study, the Pleurotus ostreatus (a macro-fungus) was used as a new biosorbent to study the biosorption of hazardous malachite green (MG) from aqueous solutions. The effective disposal of P. ostreatus is a meaningful work for environmental protection and maximum utilization of agricultural residues. The operational parameters such as biosorbent dose, pH, and ionic strength were investigated in a series of batch studies at 25°C. Freundlich isotherm model was described well for the biosorption equilibrium data. The biosorption process followed the pseudo-second-order kinetic model. Taguchi method was used to simplify the experimental number for determining the significance of factors and the optimum levels of experimental factors for MG biosorption. Biosorbent dose and initial MG concentration had significant influences on the percent removal and biosorption capacity. The highest percent removal reached 89.58% and the largest biosorption capacity reached 32.33 mg/g. The Fourier transform infrared spectroscopy (FTIR) showed that the functional groups such as, carboxyl, hydroxyl, amino and phosphonate groups on the biosorbent surface could be the potential adsorption sites for MG biosorption. P. ostreatus can be considered as an alternative biosorbent for the removal of dyes from aqueous solutions. PMID:24620852

Tandem Lewis/Brønsted homogeneous acid catalysis: conversion of glucose to 5-hydoxymethylfurfural in an aqueous chromium(iii) chloride and hydrochloric acid solution

DOE PAGES

Swift, T. Dallas; Nguyen, Hannah; Anderko, Andrzej; ...

2015-07-25

Here, a kinetic model for the tandem conversion of glucose to 5-hydroxymethylfurfural (HMF) through fructose in aqueous CrCl 3–HCl solution was developed by analyzing experimental data. We show that the coupling of Lewis and Brønsted acids in a single pot overcomes equilibrium limitations of the glucose–fructose isomerization leading to high glucose conversions and identify conditions that maximize HMF yield. Adjusting the HCl/CrCl 3 concentration has a more pronounced effect on HMF yield at constant glucose conversion than that of temperature or CrCl 3 concentration. This is attributed to the interactions between HCl and CrCl 3 speciation in solution that leadsmore » to HMF yield being maximized at moderate HCl concentrations for each CrCl 3 concentration. This volcano-like behavior is accompanied with a change in the rate-limiting step from fructose dehydration to glucose isomerization as the concentration of the Brønsted acid increases. The maximum HMF yield in a single aqueous phase is only modest and appears independent of catalysts’ concentrations as long as they are appropriately balanced. However, it can be further maximized in a biphasic system. Our findings are consistent with recent studies in other tandem reactions catalyzed by different catalysts.« less

Methanol Uptake By Low Temperature Aqueous Sulfuric Acid Solutions

NASA Technical Reports Server (NTRS)

Iraci, Laura T.; Essin, Andrew M.; Golden, David M.; Hipskind, R. Stephen (Technical Monitor)

2001-01-01

To evaluate the role of upper tropospheric and lower stratospheric aerosols in the global budget of methanol, the solubility and reactivity of CH3OH in aqueous sulfuric acid solutions are under investigation. Using standard uptake techniques in a Knudsen cell reactor, we have measured the effective Henry's law coefficient, H(*), for methanol dissolution into 45 to 70 percent by weight H2SO4. We find that methanol solubility ranges from 10(exp 5) to 10(exp 8) M/atm and increases with decreasing temperature and with increasing sulfuric acid content. These solubility measurements include uptake due to physical solvation and all rapid equilibria which are established in solution. Our data indicate that simple uptake by aqueous sulfuric acid particles will not be a significant sink for methanol in the UT/LS. These results differ from those recently reported in the literature, and an explanation of this disparity will be presented. In addition to solvation, reaction between primary alcohols and sulfuric acid does occur, leading to the production of alkyl sulfates. Literature values for the rate of this reaction suggest that formation of CH3OSO3H may proceed in the atmosphere but is not significant under our experimental conditions. Results obtained using a complementary equilibrium measurement technique confirm this directly. In addition, the extent of methanol sequestration via formation of mono- and dimethylsulfate will be evaluated under several atmospheric conditions.

Liquid Phase adsorption kinetics and equilibrium of toluene by novel modified-diatomite.

PubMed

Sheshdeh, Reza Khalighi; Abbasizadeh, Saeed; Nikou, Mohammad Reza Khosravi; Badii, Khashayar; Sharafi, Mohammad Sadegh

2014-01-01

The adsorption equilibria of toluene from aqueous solutions on natural and modified diatomite were examined at different operation parameters such as pH, contact time, initial toluene concentration was evaluated and optimum experimental conditions were identified. The surface area and morphology of the nanoparticles were characterized by SEM, BET, XRD, FTIR and EDX analysis. It was found that in order to obtain the highest possible removal of toluene, the experiments can be carried out at pH 6, temperature 25°C, an agitation speed of 200 rpm, an initial toluene concentration of 150 mg/L, a centrifugal rate of 4000 rpm, adsorbent dosage = 0.1 g and a process time of 90 min. The results of this work show that the maximum percentage removal of toluene from aqueous solution in the optimum conditions for NONMD was 96.91% (145.36 mg/g). Furthermore, under same conditions, the maximum adsorption of natural diatomite was 71.45% (107.18 mg/g). Both adsorption kinetic and isotherm experiments were carried out. The experimental data showed that the adsorption follows the Langmuir model and Freundlich model on natural and modified diatomite respectively. The kinetics results were found to conform well to pseudo-second order kinetics model with good correlation. Thus, this study demonstrated that the modified diatomite could be used as potential adsorbent for removal of toluene from aqueous solution.

Facile functionalized of SBA-15 via a biomimetic coating and its application in efficient removal of uranium ions from aqueous solution.

PubMed

Gao, Jun-Kai; Hou, Li-An; Zhang, Guang-Hui; Gu, Ping

2015-04-09

A novel dopamine-functionalized mesoporous silica (DMS), synthesized by grafting dopamine onto a mesoporous molecular sieve (SBA-15), was developed as a sorbent to extract U(VI) from aqueous solution. The method used to modify SBA-15 was simple, facile and cost-effective. The DMS was characterized by SEM, TEM, XRD and BET, showing that the material had an ordered mesoporous structure and a large surface area. The effect of contact time, pH, ionic strength, temperature, and solid-liquid ratio on the sorption process was investigated. It was demonstrated that the adsorption of U(VI) by DMS was fast and that it can be described by the pseudo-second order-equation where the equilibrium time was 20 min. Additionally, the adsorption isotherm data were fitted well by the Langmuir model with the maximum adsorption capacity of DMS of 196 mg/g at pH 6.0. Furthermore, the influence of the K(+) and Na(+) concentrations and solid-to-liquid ratio on the sorption was very weak, and the values of the thermodynamic parameters revealed that the sorption process was exothermic and spontaneous. All the results suggested that the DMS could be used as an excellent adsorbent to remove U(VI) from aqueous solution. Copyright © 2014 Elsevier B.V. All rights reserved.

Tandem Lewis/Brønsted homogeneous acid catalysis: conversion of glucose to 5-hydoxymethylfurfural in an aqueous chromium(iii) chloride and hydrochloric acid solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Swift, T. Dallas; Nguyen, Hannah; Anderko, Andrzej

Here, a kinetic model for the tandem conversion of glucose to 5-hydroxymethylfurfural (HMF) through fructose in aqueous CrCl 3–HCl solution was developed by analyzing experimental data. We show that the coupling of Lewis and Brønsted acids in a single pot overcomes equilibrium limitations of the glucose–fructose isomerization leading to high glucose conversions and identify conditions that maximize HMF yield. Adjusting the HCl/CrCl 3 concentration has a more pronounced effect on HMF yield at constant glucose conversion than that of temperature or CrCl 3 concentration. This is attributed to the interactions between HCl and CrCl 3 speciation in solution that leadsmore » to HMF yield being maximized at moderate HCl concentrations for each CrCl 3 concentration. This volcano-like behavior is accompanied with a change in the rate-limiting step from fructose dehydration to glucose isomerization as the concentration of the Brønsted acid increases. The maximum HMF yield in a single aqueous phase is only modest and appears independent of catalysts’ concentrations as long as they are appropriately balanced. However, it can be further maximized in a biphasic system. Our findings are consistent with recent studies in other tandem reactions catalyzed by different catalysts.« less

Preparation of crosslinked chitosan magnetic membrane for cations sorption from aqueous solution.

PubMed

Khan, Adnan; Begum, Samina; Ali, Nauman; Khan, Sabir; Hussain, Sajjad; Sotomayor, Maria Del Pilar Taboada

2017-05-01

A chitosan magnetic membrane was prepared in order to confer magnetic properties to the membrane, which could be used for the removal of cations from aqueous solution. The crosslinked magnetic membrane was compared with pristine chitosan membrane in term of stability, morphology and cation adsorption capacity. The fabricated magnetic materials are thermally stable as shown by thermogravimetric curves. The membrane containing nickel magnetic particles (CHNiF-G) shows high thermal stability compared to the other membranes. The Fourier transform infrared spectroscopy showed successful preparation of chitosan magnetic membrane. Scanning electron microscopy micrographs showed the rough surface of the membrane with increased porosity. The prepared chitosan membranes were applied to cations of copper, nickel and lead in dilute aqueous solution. The chitosan membrane showed the following adsorption order for metallic cations: Cu 2+ > Ni 2+ > Pb 2+ , while CHNiF-G showed higher capacity, 3.51 mmol g -1 for copper, reflecting the improvement in adsorption capacity, since the amount of copper on pristine chitosan gave 1.40 mmol g -1 . The time required for adsorption to reach to the equilibrium was 6 h for the selected cations using different chitosan membranes. The kinetic study showed that adsorption followed pseudo-second order kinetics. The most commonly used isotherm models, Freundlich, Langmuir and Temkin, were applied to experimental data using linear regression technique. However, The Temkin model fits better to experimental data.

Biosorption of malachite green from aqueous solutions by Pleurotus ostreatus using Taguchi method.

PubMed

Chen, Zhengsuo; Deng, Hongbo; Chen, Can; Yang, Ying; Xu, Heng

2014-03-12

Dyes released into the environment have been posing a serious threat to natural ecosystems and aquatic life due to presence of heat, light, chemical and other exposures stable. In this study, the Pleurotus ostreatus (a macro-fungus) was used as a new biosorbent to study the biosorption of hazardous malachite green (MG) from aqueous solutions. The effective disposal of P. ostreatus is a meaningful work for environmental protection and maximum utilization of agricultural residues.The operational parameters such as biosorbent dose, pH, and ionic strength were investigated in a series of batch studies at 25°C. Freundlich isotherm model was described well for the biosorption equilibrium data. The biosorption process followed the pseudo-second-order kinetic model. Taguchi method was used to simplify the experimental number for determining the significance of factors and the optimum levels of experimental factors for MG biosorption. Biosorbent dose and initial MG concentration had significant influences on the percent removal and biosorption capacity. The highest percent removal reached 89.58% and the largest biosorption capacity reached 32.33 mg/g. The Fourier transform infrared spectroscopy (FTIR) showed that the functional groups such as, carboxyl, hydroxyl, amino and phosphonate groups on the biosorbent surface could be the potential adsorption sites for MG biosorption. P. ostreatus can be considered as an alternative biosorbent for the removal of dyes from aqueous solutions.

Core-based intrinsic fiber-optic absorption sensor for the detection of volatile organic compounds

NASA Astrophysics Data System (ADS)

Klunder, Gregory L.; Russo, Richard E.

1995-03-01

A core-based intrinsic fiber-optic absorption sensor has been developed and tested for the detection of volatile organic compounds. The distal ends of transmitting and receiving fibers are connected by a small cylindrical section of an optically clear silicone rubber. The silicone rubber acts both as a light pipe and as a selective membrane into which the analyte molecules can diffuse. The sensor has been used to detect volatile organics (trichloroethylene, 1,1-dichloroethylene, and benzene) in both aqueous solutions and in the vapor phase or headspace. Absorption spectra obtained in the near-infrared (near-IR) provide qualitative and quantitative information about the analyte. Water, which has strong broad-band absorption in the near-IR, is excluded from the spectra because of the hydrophobic properties of the silicone rubber. The rate-limiting step is shown to be the diffusion through the Nernstian boundary layer surrounding the sensor and not the diffusion through the silicone polymer. The rate of analyte diffusion into the sensor, as measured by the t(sub 90) values (the time required for the sensor to reach 90% of the equilibrium value), is 30 min for measurements in aqueous solutions and approximately 3 min for measurements made in the headspace. The limit of detection obtained with this sensor is approximately 1.1 ppm for trichloroethylene in an aqueous solution.

Dynamics of Magnesite Formation at Low-Temperature and High pCO2 in Aqueous Solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qafoku, Odeta; Dixon, David A.; Rosso, Kevin M.

2015-09-17

Like many metal carbonate minerals, despite conditions of supersaturation, precipitation of magnesite from aqueous solution is kinetically hindered at low temperatures, for reasons that remain poorly understood. The present study examines precipitation products from reaction of Mg(OH)2 in aqueous solutions saturated with supercritical CO2 at high pressures (90 atm and 110 atm) and low temperatures (35 °C and 50 °C). Traditional bulk characterization (X-ray diffraction) of the initial solid formed indicated the presence of hydrated magnesium carbonates (hydromagnesite and nesquehonite), thermodynamically metastable phases that were found to slowly react during ageing to the more stable anhydrous form, magnesite, at temperaturesmore » as low as 35 °C (135-140 days) and at a faster rate at 50 °C (56 days). Undetected by bulk measurements, detailed examination of the precipitates by scanning electron microscopy (SEM) showed that magnesite is present as a minor component at relatively early reaction times (7 days) at 50 °C. In addition to magnesite dominating the solid phases over time, we find that mangesite nucleation and growth occurs more quickly with increasing partial pressure of CO2, and in electrolyte solutions with high bicarbonate content. Furthermore, formation of magnesite was found to be enhanced in sulfate-rich solutions, compared to chloride-rich solutions. We speculate that much of this behavior is possibly due to sulfate serving as sink of protons generated during carbonation reactions. These results support the importance of integrating magnesite as an equilibrium phase in reactive transport calculations of the effects of carbon dioxide sequestration on subsurface formations at long time scales.« less

Stability of sugar solutions: a novel study of the epimerization kinetics of lactose in water.

PubMed

Jawad, Rim; Drake, Alex F; Elleman, Carole; Martin, Gary P; Warren, Frederick J; Perston, Benjamin B; Ellis, Peter R; Hassoun, Mireille A; Royall, Paul G

2014-07-07

This article reports on the stereochemical aspects of the chemical stability of lactose solutions stored between 25 and 60 °C. The lactose used for the preparation of the aqueous solutions was α-lactose monohydrate with an anomer purity of 96% α and 4% β based on the supplied certificate of analysis (using a GC analytical protocol), which was further confirmed here by nuclear magnetic resonance (NMR) analysis. Aliquots of lactose solutions were collected at different time points after the solutions were prepared and freeze-dried to remove water and halt epimerization for subsequent analysis by NMR. Epimerization was also monitored by polarimetry and infrared spectroscopy using a specially adapted Fourier transform infrared attenuated total reflectance (FTIR-ATR) method. Hydrolysis was analyzed by ion chromatography. The three different analytical approaches unambiguously showed that the epimerization of lactose in aqueous solution follows first order reversible kinetics between 25 to 60 °C. The overall rate constant was 4.4 × 10(-4) s(-1) ± 0.9 (± standard deviation (SD)) at 25 °C. The forward rate constant was 1.6 times greater than the reverse rate constant, leading to an equilibrium constant of 1.6 ± 0.1 (±SD) at 25 °C. The rate of epimerization for lactose increased with temperature and an Arrhenius plot yielded an activation energy of +52.3 kJ/mol supporting the hypothesis that the mechanism of lactose epimerization involves the formation of extremely short-lived intermediate structures. The main mechanism affecting lactose stability is epimerization, as no permanent hydrolysis or chemical degradation was observed. When preparing aqueous solutions of lactose, immediate storage in an ice bath at 0 °C will allow approximately 3 min (180 s) of analysis time before the anomeric ratio alters significantly (greater than 1%) from the solid state composition of the starting material. In contrast a controlled anomeric composition (~38% α and ~62% β) will be achieved if an aqueous solution is left to equilibrate for over 4 h at 25 °C, while increasing the temperature up to 60 °C rapidly reduces the required equilibration time.

Prediction of equilibrium parameters of adsorption of lead (II) ions onto diatomite

NASA Astrophysics Data System (ADS)

Salman, Taylan; Ardalı, Yüksel; Gamze Turan, N.

2013-04-01

Heavy metals from industrial wastewaters are one of the most important environmental issues to be solved today. Due to their toxicity and nonbiodegradable nature, heavy metals cause environmental and public health problems. Various techniques have been developed to remove heavy metals from aqueous solutions. These include chemical precipitation, reverse osmosis, ion Exchange and adsorption. Among them, adsorption is considered to be a particularly competitive and effective process for the removal of heavy metals from aqueous solutions. There is growing interest in using low cost, commercially available materials for the adsorption of heavy metals. Diatomite is a siliceous sedimentary rock having an amorphous form of silica (SiO2. nH2O) containing a small amount of microcrystalline material. It has unique combination of physical and chemical properties such as high porosity, high permeability, small particle size, large surface area, and low thermal conductivity. In addition, it is available in Turkey and in various locations around the world. Therefore, diatomite has been successfully used as adsorbent for the removal of heavy metals. The aim of the study is to investigate the adsorption properties of diatomite. The equilibrium adsorption data were applied to the Langmuir, Freundlich and Dubinin-Radushkevic (D-R) isotherm models. Adsorption experiments were performed under batch process, using Pb (II) initial concentration, pH of solution and contact time as variables. The results demonstrated that the adsorption of Pb (II) was strongly dependent on pH of solution. The effect of pH on adsorption of Pb(II) on diatomite was conducted by varying pH from 2 to 12 at 20 oC. In the pH range of 2.0-4.0, the adsorption percentage increases slightly as the pH increasing. At pH>4, the adsorption percentage decreases with increasing pH because hydrolysis product and the precipitation begin to play an important role in the sorption of Pb (II). At pH4, the maximum adsorption capacity of diatomite was found as 26.158 mg/g. The adsorption isotherms of Pb (II) on diatomite can be described well by the Freundlich model. The high adsorption capacity of diatomite makes it suitable low-cost material in the removal of Pb (II) from aqueous solutions.

Aqueous fluid composition in CI chondritic materials: Chemical equilibrium assessments in closed systems

NASA Astrophysics Data System (ADS)

Zolotov, Mikhail Yu.

2012-08-01

Solids of nearly solar composition have interacted with aqueous fluids on carbonaceous asteroids, icy moons, and trans-neptunian objects. These processes altered mineralogy of accreted materials together with compositions of aqueous and gaseous phases. We evaluated chemistry of aqueous solutions coexisted with CI-type chondritic solids through calculations of chemical equilibria in closed water-rock-gas systems at different compositions of initial fluids, water/rock mass ratios (0.1-1000), temperatures (<350 °C), and pressures (<2 kbars). The calculations show that fluid compositions are mainly affected by solubilities of solids, the speciation of chlorine in initial water-rock mixtures, and the occurrence of Na-bearing secondary minerals such as saponite. The major species in modeled alkaline solutions are Na+, Cl-, CO32-,HCO3-, K+, OH-, H2, and CO2. Aqueous species of Mg, Fe, Ca, Mn, Al, Ni, Cr, S, and P are not abundant in these fluids owing to low solubility of corresponding solids. Typical NaCl type alkaline fluids coexist with saponite-bearing mineralogy that usually present in aqueously altered chondrites. A common occurrence of these fluids is consistent with the composition of grains emitted from Enceladus. Na-rich fluids with abundant CO32-,HCO3-, and OH- anions coexist with secondary mineralogy depleted in Na. The Na2CO3 and NaHCO3 type fluids could form via accretion of cometary ices. NaOH type fluids form in reduced environments and may locally occur on parent bodies of CR carbonaceous chondrites. Supposed melting of accreted HCl-bearing ices leads to early acidic fluids enriched in Mg, Fe and other metals, consistent with signs of low-pH alteration in chondrites. Neutralization of these solutions leads to alkaline Na-rich fluids. Sulfate species have negligible concentrations in closed systems, which remain reduced, especially at elevated pressures created by forming H2 gas. Hydrogen, CO2, and H2O dominate in the gaseous phase, though the abundance of methane cannot be fairly estimated.

Effect of stirring on the safety of flammable liquid mixtures.

PubMed

Liaw, Horng-Jang; Gerbaud, Vincent; Chen, Chan-Cheng; Shu, Chi-Min

2010-05-15

Flash point is the most important variable employed to characterize fire and explosion hazard of liquids. The models developed for predicting the flash point of partially miscible mixtures in the literature to date are all based on the assumption of liquid-liquid equilibrium. In real-world environments, however, the liquid-liquid equilibrium assumption does not always hold, such as the collection or accumulation of waste solvents without stirring, where complete stirring for a period of time is usually used to ensure the liquid phases being in equilibrium. This study investigated the effect of stirring on the flash-point behavior of binary partially miscible mixtures. Two series of partially miscible binary mixtures were employed to elucidate the effect of stirring. The first series was aqueous-organic mixtures, including water+1-butanol, water+2-butanol, water+isobutanol, water+1-pentanol, and water+octane; the second series was the mixtures of two flammable solvents, which included methanol+decane, methanol+2,2,4-trimethylpentane, and methanol+octane. Results reveal that for binary aqueous-organic solutions the flash-point values of unstirred mixtures were located between those of the completely stirred mixtures and those of the flammable component. Therefore, risk assessment could be done based on the flammable component flash-point value. However, for the assurance of safety, it is suggested to completely stir those mixtures before handling to reduce the risk. Copyright (c) 2010 Elsevier B.V. All rights reserved.

Solvent kinetic isotope effects of human placental alkaline phosphatase in reverse micelles.

PubMed Central

Huang, T M; Hung, H C; Chang, T C; Chang, G G

1998-01-01

Human placental alkaline phosphatase was embedded in a reverse micellar system prepared by dissolving the surfactant sodium bis(2-ethylhexyl) sulphosuccinate (Aerosol-OT) in 2,2, 4-trimethylpentane. This microemulsion system provides a convenient instrumental tool to study the possible kinetic properties of the membranous enzyme in an immobilized form. The pL (pH/p2H) dependence of hydrolysis of 4-nitrophenyl phosphate has been examined over a pL range of 8.5-12.5 in both aqueous and reverse micellar systems. Profiles of log V versus pL were Ha-bell shaped in the acidic region but reached a plateau in the basic region in which two pKa values of 9.01-9.71 and 9.86-10.48, respectively, were observed in reverse micelles. However, only one pKa value of 9.78-10.27 in aqueous solution was detected. Profiles of log V/K versus pL were bell-shaped in the acidic region. However, they were wave-shaped in the basic region in which a residue of pKa 9.10-9.44 in aqueous solution and 8.07-8.78 in reverse micelles must be dehydronated for the reaction to reach an optimum. The V/K value shifted to a lower value upon dehydronation of a pKa value of 9.80-10.62 in aqueous solution and 11.23-12.17 in reverse micelles. Solvent kinetic isotope effects were measured at three pL values. At pL 9.5, the observed isotope effect was a product of equilibrium isotope effect and a kinetic isotope effect; at pL 10.4, the log V/K value was identical in water and deuterium. The deuterium kinetic isotope effect on V/K was 1.14 in an aqueous solution and 1.16 in reverse micelles. At pL 11.0 at which the log V values reached a plateau in either solvent system, the deuterium kinetic isotope effect on V was 2.08 in an aqueous solution and 0.62 in reverse micelles. Results from a proton inventory experiment suggested that a hydron transfer step is involved in the transition state of the catalytic reaction. The isotopic fractionation factor (pi) for deuterium for the transition state (piT) increased when the pH of the solution was raised. At pL 11.0, the piT was 1.07 in reverse micelles, which corresponds to the inverse-isotope effect of the reaction in this solvent system. Normal viscosity effects on kcat and kcat/Km were observed in aqueous solution, corresponding to a diffusional controlled physical step as the rate-limiting step. We propose that the rate-limiting step of the hydrolytic reaction changes from phosphate releasing in aqueous solution to a covalent phosphorylation or dephosphorylation step in reverse micelles. PMID:9461520

Solvent kinetic isotope effects of human placental alkaline phosphatase in reverse micelles.

PubMed

Huang, T M; Hung, H C; Chang, T C; Chang, G G

1998-02-15

Human placental alkaline phosphatase was embedded in a reverse micellar system prepared by dissolving the surfactant sodium bis(2-ethylhexyl) sulphosuccinate (Aerosol-OT) in 2,2, 4-trimethylpentane. This microemulsion system provides a convenient instrumental tool to study the possible kinetic properties of the membranous enzyme in an immobilized form. The pL (pH/p2H) dependence of hydrolysis of 4-nitrophenyl phosphate has been examined over a pL range of 8.5-12.5 in both aqueous and reverse micellar systems. Profiles of log V versus pL were Ha-bell shaped in the acidic region but reached a plateau in the basic region in which two pKa values of 9.01-9.71 and 9.86-10.48, respectively, were observed in reverse micelles. However, only one pKa value of 9.78-10.27 in aqueous solution was detected. Profiles of log V/K versus pL were bell-shaped in the acidic region. However, they were wave-shaped in the basic region in which a residue of pKa 9.10-9.44 in aqueous solution and 8.07-8.78 in reverse micelles must be dehydronated for the reaction to reach an optimum. The V/K value shifted to a lower value upon dehydronation of a pKa value of 9.80-10.62 in aqueous solution and 11.23-12.17 in reverse micelles. Solvent kinetic isotope effects were measured at three pL values. At pL 9.5, the observed isotope effect was a product of equilibrium isotope effect and a kinetic isotope effect; at pL 10.4, the log V/K value was identical in water and deuterium. The deuterium kinetic isotope effect on V/K was 1.14 in an aqueous solution and 1.16 in reverse micelles. At pL 11.0 at which the log V values reached a plateau in either solvent system, the deuterium kinetic isotope effect on V was 2.08 in an aqueous solution and 0.62 in reverse micelles. Results from a proton inventory experiment suggested that a hydron transfer step is involved in the transition state of the catalytic reaction. The isotopic fractionation factor (pi) for deuterium for the transition state (piT) increased when the pH of the solution was raised. At pL 11.0, the piT was 1.07 in reverse micelles, which corresponds to the inverse-isotope effect of the reaction in this solvent system. Normal viscosity effects on kcat and kcat/Km were observed in aqueous solution, corresponding to a diffusional controlled physical step as the rate-limiting step. We propose that the rate-limiting step of the hydrolytic reaction changes from phosphate releasing in aqueous solution to a covalent phosphorylation or dephosphorylation step in reverse micelles.

Glass-liquid phase separation in highly supersaturated aqueous solutions of telaprevir.

PubMed

Mosquera-Giraldo, Laura I; Taylor, Lynne S

2015-02-02

Amorphous solid dispersions are of great current interest because they can improve the delivery of poorly water-soluble compounds. It has been recently noted that the highly supersaturated solutions generated by dissolution of some ASDs can undergo a phase transition to a colloidal, disordered, drug-rich phase when the concentration exceeds the "amorphous solubility" of the drug. The purpose of this study was to investigate the phase behavior of supersaturated solutions of telaprevir, which is formulated as an amorphous solid dispersion in the commercial product. Different analytical techniques including proton nuclear magnetic resonance spectroscopy (NMR), ultraviolet spectroscopy (UV), fluorescence spectroscopy and flux measurements were used to evaluate the properties of aqueous supersaturated solutions of telaprevir. It was found that highly supersaturated solutions of telaprevir underwent glass-liquid phase separation (GLPS) when the concentration exceeded 90 μg/mL, forming a water-saturated colloidal, amorphous drug-rich phase with a glass transition temperature of 52 °C. From flux measurements, it was observed that the "free" drug concentration reached a maximum at the concentration where GLPS occurred, and did not increase further as the concentration was increased. This phase behavior, which results in a precipitate and a metastable equilibrium between a supersaturated solution and a drug-rich phase, is obviously important in the context of evaluating amorphous solid dispersion formulations and their crystallization routes.

Derivation of Pitzer Interaction Parameters for an Aqueous Species Pair of Sodium and Iron(II)-Citrate Complex

NASA Astrophysics Data System (ADS)

Jang, J. H.; Nemer, M.

2015-12-01

The U.S. DOE Waste Isolation Pilot Plant (WIPP) is a deep underground repository for the permanent disposal of transuranic (TRU) radioactive waste. The WIPP is located in the Permian Delaware Basin near Carlsbad, New Mexico, U.S.A. The TRU waste includes, but is not limited to, iron-based alloys and the complexing agent, citric acid. Iron is also present from the steel used in the waste containers. The objective of this analysis is to derive the Pitzer activity coefficients for the pair of Na+ and FeCit- complex to expand current WIPP thermodynamic database. An aqueous model for the dissolution of Fe(OH)2(s) in a Na3Cit solution was fitted to the experimentally measured solubility data. The aqueous model consists of several chemical reactions and related Pitzer interaction parameters. Specifically, Pitzer interaction parameters for the Na+ and FeCit- pair (β(0), β(1), and Cφ) plus the stability constant for species of FeCit- were fitted to the experimental data. Anoxic gloveboxes were used to keep the oxygen level low (<1 ppm) throughout the experiments due to redox sensitivity. EQ3NR, a computer program for geochemical aqueous speciation-solubility calculations, packaged in EQ3/6 v.8.0a, calculates the aqueous speciation and saturation index using an aqueous model addressed in EQ3/6's database. The saturation index indicates how far the system is from equilibrium with respect to the solid of interest. Thus, the smaller the sum of squared saturation indices that the aqueous model calculates for the given number of experiments, the more closely the model attributes equilibrium to each individual experiment with respect to the solid of interest. The calculation of aqueous speciation and saturation indices was repeated by adjusting stability constant of FeCit-, β(0), β(1), and Cφ in the database until the values are found that make the sum of squared saturation indices the smallest for the given number of experiments. Results will be presented at the time of conference.

Computational methods for reactive transport modeling: An extended law of mass-action, xLMA, method for multiphase equilibrium calculations

NASA Astrophysics Data System (ADS)

Leal, Allan M. M.; Kulik, Dmitrii A.; Kosakowski, Georg; Saar, Martin O.

2016-10-01

We present an extended law of mass-action (xLMA) method for multiphase equilibrium calculations and apply it in the context of reactive transport modeling. This extended LMA formulation differs from its conventional counterpart in that (i) it is directly derived from the Gibbs energy minimization (GEM) problem (i.e., the fundamental problem that describes the state of equilibrium of a chemical system under constant temperature and pressure); and (ii) it extends the conventional mass-action equations with Lagrange multipliers from the Gibbs energy minimization problem, which can be interpreted as stability indices of the chemical species. Accounting for these multipliers enables the method to determine all stable phases without presuming their types (e.g., aqueous, gaseous) or their presence in the equilibrium state. Therefore, the here proposed xLMA method inherits traits of Gibbs energy minimization algorithms that allow it to naturally detect the phases present in equilibrium, which can be single-component phases (e.g., pure solids or liquids) or non-ideal multi-component phases (e.g., aqueous, melts, gaseous, solid solutions, adsorption, or ion exchange). Moreover, our xLMA method requires no technique that tentatively adds or removes reactions based on phase stability indices (e.g., saturation indices for minerals), since the extended mass-action equations are valid even when their corresponding reactions involve unstable species. We successfully apply the proposed method to a reactive transport modeling problem in which we use PHREEQC and GEMS as alternative backends for the calculation of thermodynamic properties such as equilibrium constants of reactions, standard chemical potentials of species, and activity coefficients. Our tests show that our algorithm is efficient and robust for demanding applications, such as reactive transport modeling, where it converges within 1-3 iterations in most cases. The proposed xLMA method is implemented in Reaktoro, a unified open-source framework for modeling chemically reactive systems.

Investigation of Liquid Surface Rheology of Surfactant Solutions by Droplet Shape Oscillations: Experiments

PubMed

Tian; Holt; Apfel

1997-03-01

The experimental results of droplet shape oscillations are reported and applied to the analysis of surface rheological properties of surfactant solutions. An acoustic levitation technique is used to suspend the test drop in air and excite it into quadrupole shape oscillations. The equilibrium surface tension, Gibbs elasticity, and surface dilatational viscosity are determined from the measurements of droplet static shape under different levitation sound pressure, oscillation frequency, and free damping constant. Aqueous solutions of sodium dodecyl sulfate, dodecyltrimethylammonium bromide, and n-octyl beta-d-glucopyranoside are tested with this system. The concentrations of the solutions are below the critical micelle concentration. For these solutions it is found that the surface Gibbs elasticity approaches a maximum at a moderate concentration, and its value is less than that directly calculated from the state equation of a static liquid surface. The surface dilatational viscosity is found to be in a range around 0.1 cps.

Separation of charge-regulated polyelectrolytes by pH-assisted diffusiophoresis.

PubMed

Hsu, Jyh-Ping; Hsu, Yen-Rei; Shang-Hung, Hsieh; Tseng, Shiojenn

2017-03-29

The potential of separating colloidal particles through simultaneous application of a salt gradient and a pH gradient, or pH-assisted diffusiophoresis, is evaluated by considering the case of spherical polyelectrolytes (PEs) having different equilibrium dissociation constants in an aqueous solution with KCl as the background salt. The simulation results gathered reveal that the dependence of the particle velocity on pH is more sensitive than that in pH-assisted electrophoresis, where an electric field and a pH gradient are applied simultaneously. This implies that the separation efficiency of pH-assisted diffusiophoresis can be better than that of pH-assisted electrophoresis. In particular, two types of PE having different equilibrium dissociation constants can be separated effectively by applying the former by enhancing/reducing their diffusiophoretic velocities.

Adsorption Properties of Low-Cost Biomaterial Derived from Prunus amygdalus L. for Dye Removal from Water

PubMed Central

Deniz, Fatih

2013-01-01

The capability of Prunus amygdalus L. (almond) shell for dye removal from aqueous solutions was investigated and methyl orange was used as a model compound. The effects of operational parameters including pH, ionic strength, adsorbent concentration and mesh size, dye concentration, contact time, and temperature on the removal of dye were evaluated. The adsorption kinetics conformed to the pseudo-second-order kinetic model. The equilibrium data pointed out excellent fit to the Langmuir isotherm model with maximum monolayer adsorption capacity of 41.34 mg g−1 at 293 K. Thermodynamic analysis proved a spontaneous, favorable, and exothermic process. It can be concluded that almond shell might be a potential low-cost adsorbent for methyl orange removal from aqueous media. PMID:23935442

Uptake of Small Organic Compounds by Sulfuric Acid Aerosols: Dissolution and Reaction

NASA Technical Reports Server (NTRS)

Iraci, L. T.; Michelsen, R. R.; Ashbourn, S. F. M.; Staton, S. J. R.

2003-01-01

To assess the role of oxygenated volatile organic compounds in the upper troposphere and lower stratosphere, the interactions of a series of small organic compounds with low-temperature aqueous sulfuric acid will be evaluated. The total amount of organic material which may be taken up from the gas phase by dissolution, surface layer formation, and reaction during the particle lifetime will be quantified. Our current results for acetaldehyde uptake on 40 - 80 wt% sulfuric acid solutions will be compared to those of methanol, formaldehyde, and acetone to investigate the relationships between chemical functionality and heterogeneous activity. Where possible, equilibrium uptake will be ascribed to component pathways (hydration, protonation, etc.) to facilitate evaluation of other species not yet studied in low temperature aqueous sulfuric acid.

Inclusion complex formation of ionic liquids with 4-sulfonatocalixarenes studied by competitive binding of berberine alkaloid fluorescent probe

NASA Astrophysics Data System (ADS)

Miskolczy, Zsombor; Biczók, László

2009-07-01

A clinically important natural isoquinoline alkaloid, berberine, was used as a fluorescent probe to study the encapsulation of 1-alkyl-3-methylimidazolium (C nMIm +) type ionic liquids in 4-sulfonato-substituted calix[4]arene (SCX4) and calix[6]arene (SCX6) at pH 2. Addition of ionic liquids to the aqueous solution of berberine-SCXn inclusion complexes brought about considerable fluorescence intensity diminution due to the extrusion of berberine from the macrocycle into the aqueous phase by the competitive inclusion of C nMIm + cation. The lengthening of the aliphatic side chain of the imidazolium moiety diminished the equilibrium constant of complexation with SCX4, but enhanced the stability of SCX6 complexes. Larger binding strength was found for SCX4.

Adsorption of Benzoic Acid in Aqueous Solution by Bagasse Fly Ash

NASA Astrophysics Data System (ADS)

Suresh, S.

2012-09-01

This paper reports the studies on the benzoic acid (BA) onto bagasse fly ash (BFA) was studied in aqueous solution in a batch system. Physico-chemical properties including surface area, surface texture of the GAC before and after BA adsorption onto BFA were analysed using X-ray diffractometer (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). The optimum initial pH for the adsorption of BA was found to be 5.56. The adsorbent dose was 10 g/l for BFA and the equilibrium time 8 h of reaction. Pseudo first and second order models were used to find the adsorption kinetics. It was found that intraparticle diffusion played important role in the adsorption mechanisms of BA and the adsorption kinetics followed pseudo-second order kinetic model rather than the pseudo first order kinetic model. Isotherm data were generated for BA solution having initial concentrations of BA in the range of 10-200 mg/l for the BFA dosage of 10 g/l at temperatures of 288, 303, and 318 K. The adsorption of BA onto BFA was favorably influenced by an increase in temperature. Equilibrium data were well represented by the Redlich-Peterson isotherm model. Values of the change in entropy ( ΔS 0), heat of adsorption ( ΔH 0) for adsorption of BA on BFA was found to be 120.10 and 19.61 kJ/mol respectively. The adsorption of BA onto BFA was an endothermic reaction. Desorption of BA from BFA was studied by various solvents method. Acetic acid was found to be a better eluant for desorption of BA with a maximum desorption efficiency of 55.2 %. Owing to its heating value, spent BFA can be used as a co-fuel for the production of heat in boiler furnaces.

Quaternized Cellulose Hydrogels as Sorbent Materials and Pickering Emulsion Stabilizing Agents

PubMed Central

Udoetok, Inimfon A.; Wilson, Lee D.; Headley, John V.

2016-01-01

Quaternized (QC) and cross-linked/quaternized (CQC) cellulose hydrogels were prepared by cross-linking native cellulose with epichlorohydrin (ECH), with subsequent grafting of glycidyl trimethyl ammonium chloride (GTMAC). Materials characterization via carbon, hydrogen and nitrogen (CHN) analysis, thermogravimetric analysis (TGA), and Fourier transform infrared (FTIR)/13C solid state NMR spectroscopy provided supportive evidence of the hydrogel synthesis. Enhanced thermal stability of the hydrogels was observed relative to native cellulose. Colloidal stability of octanol and water mixtures revealed that QC induces greater stabilization over CQC, as evidenced by the formation of a hexane–water Pickering emulsion system. Equilibrium sorption studies with naphthenates from oil sands process water (OSPW) and 2-naphthoxy acetic acid (NAA) in aqueous solution revealed that CQC possess higher affinity relative to QC with the naphthenates. According to the Langmuir isotherm model, the sorption capacity of CQC for OSPW naphthenates was 33.0 mg/g and NAA was 69.5 mg/g. CQC displays similar affinity for the various OSPW naphthenate component species in aqueous solution. Kinetic uptake of NAA at variable temperature, pH and adsorbent dosage showed that increased temperature favoured the uptake process at 303 K, where Qm = 76.7 mg/g. Solution conditions at pH 3 or 9 had a minor effect on the sorption process, while equilibrium was achieved in a shorter time at lower dosage (ca. three-fold lower) of hydrogel (100 mg vs. 30 mg). The estimated activation parameters are based on temperature dependent rate constants, k1, which reveal contributions from enthalpy-driven electrostatic interactions. The kinetic results indicate an ion-based associative sorption mechanism. This study contributes to a greater understanding of the adsorption and physicochemical properties of cellulose-based hydrogels. PMID:28773767

Synthesis of fast response crosslinked PVA-g-NIPAAm nanohydrogels by very low radiation dose in dilute aqueous solution

NASA Astrophysics Data System (ADS)

Fathi, Marziyeh; Reza Farajollahi, Ali; Akbar Entezami, Ali

2013-05-01

Nanohydrogels of poly(vinyl alcohol)-g-N-isopropylacrylamide (PVA-g-NIPAAm) are synthesized by PVA and NIPAAm dilute aqueous solution using much less radiation dose of 1-20 Gy via intramolecular crosslinking at ambient temperature. The radiation synthesis of nanohydrogels is performed in the presence of tetrakis (hydroxymethyl) phosphonium chloride (THPC) due to its rapid oxygen scavenging abilities and hydrogen peroxide (H2O2) as a source of hydroxyl radicals. The effect of radiation dose, feed composition ratio of PVA and H2O2 is investigated on swelling properties such as temperature and pH dependence of equilibrium swelling ratio as well as deswelling kinetics. Experimental data exhibit high equilibrium swelling ratio and fast response time for the synthesized nanohydrogels. The average molecular weight between crosslinks (Mc) and crosslinking density (ρx) of the obtained nanohydrogels are calculated from swelling data as a function of radiation dose, H2O2 and PVA amount. Fourier transform infrared spectroscopy (FT-IR), elemental analysis of nitrogen content and thermogravimetric analysis (TGA) are used to confirm the grafting reaction. Lower critical solution temperature (LCST) is measured around 33 °C by differential scanning calorimetry (DSC) for PVA-g-NIPAAm nanohydrogels. Dynamic light scattering (DLS) data demonstrate that the increase of radiation dose leads to the decreasing in dimension of nanohydrogels. Also, rheological studies are confirmed an improvement in the mechanical properties of the nanohydrogels with increasing the radiation dose. A cytotoxicity study exhibits a good biocompatibility for the obtained nanohydrogels. The prepared nanohydrogels show fast swelling/deswelling behavior, high swelling ratio, dual sensitivity and good cytocompatibility, which may find potential applications as biomaterial.

Insulin Particle Formation in Supersaturated Aqueous Solutions of Poly(Ethylene Glycol)

PubMed Central

Bromberg, Lev; Rashba-Step, Julia; Scott, Terrence

2005-01-01

Protein microspheres are of particular utility in the field of drug delivery. A novel, completely aqueous, process of microsphere fabrication has been devised based on controlled phase separation of protein from water-soluble polymers such as polyethylene glycols. The fabrication process results in the formation of spherical microparticles with narrow particle size distributions. Cooling of preheated human insulin-poly(ethylene glycol)-water solutions results in the facile formation of insulin particles. To map out the supersaturation conditions conducive to particle nucleation and growth, we determined the temperature- and concentration-dependent boundaries of an equilibrium liquid-solid phase separation. The kinetics of formation of microspheres were followed by dynamic and continuous-angle static light scattering techniques. The presence of PEG at a pH that was close to the protein's isoelectric point resulted in rapid nucleation and growth. The time elapsed from the moment of creation of a supersaturated solution and the detection of a solid phase in the system (the induction period, tind) ranged from tens to several hundreds of seconds. The dependence of tind on supersaturation could be described within the framework of classical nucleation theory, with the time needed for the formation of a critical nucleus (size <10 nm) being much longer than the time of the onset of particle growth. The growth was limited by cluster diffusion kinetics. The interfacial energies of the insulin particles were determined to be 3.2–3.4 and 2.2 mJ/m2 at equilibrium temperatures of 25 and 37°C, respectively. The insulin particles formed as a result of the process were monodisperse and uniformly spherical, in clear distinction to previously reported processes of microcrystalline insulin particle formation. PMID:16254391

Equilibrium isotope effects on noncovalent interactions in a supramolecular host-guest system.

PubMed

Mugridge, Jeffrey S; Bergman, Robert G; Raymond, Kenneth N

2012-02-01

The self-assembled supramolecular complex [Ga(4)L(6)](12-) (1; L = 1,5-bis[2,3-dihydroxybenzamido]naphthalene) can act as a molecular host in aqueous solution and bind cationic guest molecules to its highly charged exterior surface or within its hydrophobic interior cavity. The distinct internal cavity of host 1 modifies the physical properties and reactivity of bound guest molecules and can be used to catalyze a variety of chemical transformations. Noncovalent host-guest interactions in large part control guest binding, molecular recognition and the chemical reactivity of bound guests. Herein we examine equilibrium isotope effects (EIEs) on both exterior and interior guest binding to host 1 and use these effects to probe the details of noncovalent host-guest interactions. For both interior and exterior binding of a benzylphosphonium guest in aqueous solution, protiated guests are found to bind more strongly to host 1 (K(H)/K(D) > 1) and the preferred association of protiated guests is driven by enthalpy and opposed by entropy. Deuteration of guest methyl and benzyl C-H bonds results in a larger EIE than deuteration of guest aromatic C-H bonds. The observed EIEs can be well explained by considering changes in guest vibrational force constants and zero-point energies. DFT calculations further confirm the origins of these EIEs and suggest that changes in low-frequency guest C-H/D vibrational motions (bends, wags, etc.) are primarily responsible for the observed EIEs. © 2011 American Chemical Society

Adsorption of Direct Blue 53 dye from aqueous solutions by multi-walled carbon nanotubes and activated carbon.

PubMed

Prola, Lizie D T; Machado, Fernando M; Bergmann, Carlos P; de Souza, Felipe E; Gally, Caline R; Lima, Eder C; Adebayo, Matthew A; Dias, Silvio L P; Calvete, Tatiana

2013-11-30

Multi-walled carbon nanotubes (MWCNT) and powder activated carbon (PAC) were used as adsorbents for adsorption of Direct Blue 53 dye (DB-53) from aqueous solutions. The adsorbents were characterised using Raman spectroscopy, N2 adsorption/desorption isotherms, and scanning and transmission electron microscopy. The effects of initial pH, contact time and temperature on adsorption capacity of the adsorbents were investigated. At pH 2.0, optimum adsorption of the dye was achieved by both adsorbents. Equilibrium contact times of 3 and 4 h were achieved by MWCNT and PAC adsorbents, respectively. The general order kinetic model provided the best fit of the experimental data compared to pseudo-first order and pseudo-second order kinetic adsorption models. For DB-53 dye, the equilibrium data (298-323 K) were best fitted to the Sips isotherm model. The maximum sorption capacity for adsorption of the dye occurred at 323 K, with the values of 409.4 and 135.2 mg g(-1) for MWCNT and PAC, respectively. Studies of adsorption/desorption were conducted and the results showed that DB-53 loaded MWCNT could be regenerated (97.85%) using a mixture 50% acetone + 50% of 3 mol L(-1) NaOH. Simulated dye house effluents were used to evaluate the application of the adsorbents for effluent treatment (removal of 99.87% and 97.00% for MWCNT and PAC, respectively, were recorded). Copyright © 2013 Elsevier Ltd. All rights reserved.

Application of four novel fungal strains to remove arsenic from contaminated water in batch and column modes.

PubMed

Jaiswal, Virendra; Saxena, Sangeeta; Kaur, Ispreet; Dubey, Priya; Nand, Sampurna; Naseem, Mariya; Singh, Suman B; Srivastava, Pankaj Kumar; Barik, Saroj Kanta

2018-08-15

Immobilized biomass of novel indigenous fungal strains FNBR_3, FNBR_6, FNBR_13, and FNBR_19 were evaluated for arsenic (As) removal from aqueous solution. Alginate beads containing 0.1 g biomass were used in a batch experiment (200 mg l -1 As; pH 6). Biosorption equilibrium established in first 2 h with As adsorption (mg g -1 ) as 70, 68, 113 and 90 by FNBR_3, FNBR_6, FNBR_13 and FNBR_19, respectively. The equilibrium was fitted to the Langmuir model (r 2  = 0. 90-0.97). The absorption kinetic followed the pseudo second order. Changes in the surface of fungal cells and intracellular As-uptake by fungal biomass were also confirmed by scanning electron microscopy combined with X-ray energy dispersive spectrometer. The presence of different functional groups on fungal cells capable of As-binding was investigated by FTIR. The As-removal by immobilized fungal beads tested in the packed columns also. The As-adsorption by biomass (qe as mg g -1 ) were recorded as 59.5 (FNBR_3 and FNBR_6), 74.8 (FNBR_13), and 66.3 (FNBR_19) in the column and validated by Thomas model. This is the first report concerning the arsenic removal by immobilized biomass of these novel fungal strains from aqueous solution both in batch and column studies with a prospect of their further industrial application. Copyright © 2018 Elsevier B.V. All rights reserved.

Equilibrium, kinetics and mechanism of Au3+, Pd2+ and Ag+ ions adsorption from aqueous solutions by graphene oxide functionalized persimmon tannin.

PubMed

Wang, Zhongmin; Li, Xiaojuan; Liang, Haijun; Ning, Jingliang; Zhou, Zhide; Li, Guiyin

2017-10-01

In this study, a novel bio-adsorbent (PT-GO) was prepared by functionalization persimmon tannin (PT) with graphene oxide (GO) and the effective adsorption behaviors of Au 3+ , Pd 2+ and Ag + ions from aqueous solution was investigated. The PT-GO was characterized by Fourier transform infrared spectrometer (FTIR), scanning electronic microscope (SEM), thermogravimetric analysis (TGA) and Zeta potential. Many influence factors such as pH value, bio-adsorbent dosage, initial concentration of metal ions and contact time were optimized. The maximum adsorption capacity for Au 3+ , Pd 2+ and Ag + was 1325.09mg/g, 797.66mg/g and 421.01mg/g, respectively. The equilibrium isotherm for the adsorption of Au 3+ and Ag + on PT-GO were found to obey the Langmuir model, while the Freundlich model fitted better for Pd 2+ . The adsorption process of Au 3+ , Pd 2+ presented relatively fast adsorption kinetics with pseudo-second-order equation as the best fitting model, while the pseudo-first-order kinetic model was suitable for describing the adsorption of Ag + . Combination of ion exchange, electrostatic interaction and physical adsorption was the mechanism for adsorption of Au 3+ , Pd 2+ and Ag + onto PT-GO bio-adsorbent. Therefore, the PT-GO bio-adsorbent would be an ideal adsorbent for removal of precious metal ions and broaden the potential applications of persimmon tannin in environmental research. Copyright © 2017 Elsevier B.V. All rights reserved.

Chitosan-bound pyridinedicarboxylate Ni(II) and Fe(III) complex biopolymer films as waste water decyanidation agents.

PubMed

Adewuyi, Sheriff; Jacob, Julianah Modupe; Olaleye, Oluwatoyin Omolola; Abdulraheem, Taofiq Olanrewaju; Tayo, Jubril Ayopo; Oladoyinbo, Fatai Oladipupo

2016-10-20

Chitosan is a biopolymer with immense structural advantage for chemical and mechanical modifications to generate novel properties, functions and applications. This work depicts new pyridinedicarboxylicacid (PDC) crosslinked chitosan-metal ion films as veritable material for cyanide ion removal from aqueous solution. The PDC-crosslinked chitosan-metal films (PDC-Chit-Ni(II) and PDC-Chit-Fe(III)) were formed by complexing PDC-crosslinked chitosan film with anhydrous nickel(II) and iron(III) chloride salts respectively. The PDC-Chit and its metal films were characterized employing various analytical and spectroscopic techniques. The FT-IR, UV-vis and the XRD results confirm the presence of the metal ions in the metal coordinated PDC-crosslinked chitosan film. The surface morphological difference of PDC-Chit-Ni(II) film before and after decyanidation was explored with scanning electron microscopy. Furthermore, the quantitative amount of nickel(II) and iron(III) present in the complex were determined using Atomic Absorption Spectrophotometer as 32.3 and 37.2μg/g respectively which portends the biopolymer film as a good complexing agent. Removal of cyanide from aqueous solution with PDC-Chit, PDC-Chit-Ni(II) and PDC-Chit-Fe(III) films was studied with batch equilibrium experiments. At equilibrium, decyanidation capacity (DC) followed the order PDC-Chit-Ni (II)≈PDC-Chit-Fe(III)>PDC-Chit. PDC-Chit-Ni(II) film gave 100% CN(-) removal within 40min decyanidation owing to favorable coordination geometry. Copyright © 2016 Elsevier Ltd. All rights reserved.

Convective diffusion in protein crystal growth

NASA Technical Reports Server (NTRS)

Baird, J. K.; Meehan, E. J., Jr.; Xidis, A. L.; Howard, S. B.

1986-01-01

A protein crystal modeled as a flat plate suspended in the parent solution, with the normal to the largest face perpendicular to gravity and the protein concentration in the solution adjacent to the plate taken to be the equilibrium solubility, is studied. The Navier-Stokes equation and the equation for convective diffusion in the boundary layer next to the plate are solved to calculate the flow velocity and the protein mass flux. The local rate of growth of the plate is shown to vary significantly with depth due to the convection. For an aqueous solution of lysozyme at a concentration of 40 mg/ml, the boundary layer at the top of a 1-mm-high crystal has a thickness of 80 microns at 1 g, and 2570 microns at 10 to the -6th g.

Induced-Charge Enhancement of the Diffusion Potential in Membranes with Polarizable Nanopores

NASA Astrophysics Data System (ADS)

Ryzhkov, I. I.; Lebedev, D. V.; Solodovnichenko, V. S.; Shiverskiy, A. V.; Simunin, M. M.

2017-12-01

When a charged membrane separates two salt solutions of different concentrations, a potential difference appears due to interfacial Donnan equilibrium and the diffusion junction. Here, we report a new mechanism for the generation of a membrane potential in polarizable conductive membranes via an induced surface charge. It results from an electric field generated by the diffusion of ions with different mobilities. For uncharged membranes, this effect strongly enhances the diffusion potential and makes it highly sensitive to the ion mobilities ratio, electrolyte concentration, and pore size. Theoretical predictions on the basis of the space-charge model extended to polarizable nanopores fully agree with experimental measurements in KCl and NaCl aqueous solutions.

Urea enhances the photodynamic efficiency of methylene blue.

PubMed

Nuñez, Silvia C; Yoshimura, Tania M; Ribeiro, Martha S; Junqueira, Helena C; Maciel, Cleiton; Coutinho-Neto, Maurício D; Baptista, Maurício S

2015-09-01

Methylene blue (MB) is a well-known photosensitizer used mostly for antimicrobial photodynamic therapy (APDT). MB tends to aggregate, interfering negatively with its singlet oxygen generation, because MB aggregates lean towards electron transfer reactions, instead of energy transfer with oxygen. In order to avoid MB aggregation we tested the effect of urea, which destabilizes solute-solute interactions. The antimicrobial efficiency of MB (30 μM) either in water or in 2M aqueous urea solution was tested against a fungus (Candida albicans). Samples were kept in the dark and irradiation was performed with a light emitting diode (λ = 645 nm). Without urea, 9 min of irradiation was needed to achieve complete microbial eradication. In urea solution, complete eradication was obtained with 6 min illumination (light energy of 14.4 J). The higher efficiency of MB/urea solution was correlated with a smaller concentration of dimers, even in the presence of the microorganisms. Monomer to dimer concentration ratios were extracted from the absorption spectra of MB solutions measured as a function of MB concentration at different temperatures and at different concentrations of sodium chloride and urea. Dimerization equilibrium decreased by 3 and 6 times in 1 and 2M urea, respectively, and increased by a factor of 6 in 1M sodium chloride. The destabilization of aggregates by urea seems to be applied to other photosensitizers, since urea also destabilized aggregation of Meso-tetra(4-n-methyl-pyridyl)porphyrin, which is a positively charged porphyrin. We showed that urea destabilizes MB aggregates mainly by causing a decrease in the enthalpic gain of dimerization, which was exactly the opposite of the effect of sodium chloride. In order to understand this phenomenon at the molecular level, we computed the free energy for the dimer association process (ΔG(dimer)) in aqueous solution as well as its enthalpic component in aqueous and in aqueous/urea solutions by molecular dynamics simulations. In 2M-urea solution the atomistic picture revealed a preferential solvation of MB by urea compared with MB dimers while changes in ΔH(dimer) values demonstrated a clear shift favoring MB monomers. Therefore, MB monomers are more stable in urea solutions, which have significantly better photophysics and higher antimicrobial activity. This information can be of use for dental and medical professionals that are using MB based APDT protocols. Copyright © 2015 Elsevier B.V. All rights reserved.

Chitosan scaffold as an alternative adsorbent for the removal of hazardous food dyes from aqueous solutions.

PubMed

Esquerdo, V M; Cadaval, T R S; Dotto, G L; Pinto, L A A

2014-06-15

The dye adsorption with chitosan is considered an eco-friendly alternative technology in relation to the existing water treatment technologies. However, the application of chitosan for dyes removal is limited, due to its low surface area and porosity. Then we prepared a chitosan scaffold with a megaporous structure as an alternative adsorbent to remove food dyes from solutions. The chitosan scaffold was characterized by infrared spectroscopy, scanning electron microscopy and structural characteristics. The potential of chitosan scaffold to remove five food dyes from solutions was investigated by equilibrium isotherms and thermodynamic study. The scaffold-dyes interactions were elucidated, and desorption studies were carried out. The chitosan scaffold presented pore sizes from 50 to 200 μm, porosity of 92.2±1.2% and specific surface area of 1135±2 m(2) g(-1). The two-step Langmuir model was suitable to represent the equilibrium data. The adsorption was spontaneous, favorable, exothermic and enthalpy-controlled process. Electrostatic interactions occurred between chitosan scaffold and dyes. Desorption was possible with NaOH solution (0.10 mol L(-1)). The chitosan megaporous scaffold showed good structural characteristics and high adsorption capacities (788-3316 mg g(-1)). Copyright © 2014 Elsevier Inc. All rights reserved.

Poly(methacrylic acid)-grafted chitosan microspheres via surface-initiated ATRP for enhanced removal of Cd(II) ions from aqueous solution.

PubMed

Huang, Liqiang; Yuan, Shaojun; Lv, Li; Tan, Guangqun; Liang, Bin; Pehkonen, S O

2013-09-01

Cross-linked chitosan (CCS) microspheres tethered with pH-sensitive poly(methacrylic acid) (PMAA) brushes were developed for the efficient removal of Cd(II) ions from aqueous solutions. Functional PMAA brushes containing dense and active carboxyl groups (COOH) were grafted onto the CCS microsphere surface via surface-initiated atom transfer radical polymerization (ATRP). Batch adsorption results showed that solution pH values had a major impact on cadmium adsorption by the PMAA-grafted CCS microspheres with the optimal removal observed above pH 5. The CCS-g-PMAA microsphere was found to achieve the adsorption equilibrium of Cd(II) within 1 h, much faster than about 7 h on the CCS microsphere. At pH 5 and with an initial concentration 0.089-2.49 mmol dm(-3), the maximum adsorption capacity of Cd(II), derived from the Langmuir fitting on the PMAA-grafted microspheres was around 1.3 mmol g(-1). Desorption and adsorption cycle experimental results revealed that the PMAA-grafted CCS microspheres loaded with Cd(II) can be effectively regenerated in a dilute HNO3 solution, and the adsorption capacity remained almost unchanged upon five cycle reuse. Copyright © 2013 Elsevier Inc. All rights reserved.

Distillation Separation of Hydrofluoric Acid and Nitric Acid from Acid Waste Using the Salt Effect on Vapor-Liquid Equilibrium

NASA Astrophysics Data System (ADS)

Yamamoto, Hideki; Sumoge, Iwao

2011-03-01

This study presents the distillation separation of hydrofluoric acid with use of the salt effect on the vapor-liquid equilibrium for acid aqueous solutions and acid mixtures. The vapor-liquid equilibrium of hydrofluoric acid + salt systems (fluorite, potassium nitrate, cesium nitrate) was measured using an apparatus made of perfluoro alkylvinylether. Cesium nitrate showed a salting-out effect on the vapor-liquid equilibrium of the hydrofluoric acid-water system. Fluorite and potassium nitrate showed a salting-in effect on the hydrofluoric acid-water system. Separation of hydrofluoric acid from an acid mixture containing nitric acid and hydrofluoric acid was tested by the simple distillation treatment using the salt effect of cesium nitrate (45 mass%). An acid mixture of nitric acid (5.0 mol · dm-3) and hydrofluoric acid (5.0 mol · dm-3) was prepared as a sample solution for distillation tests. The concentration of nitric acid in the first distillate decreased from 5.0 mol · dm-3 to 1.13 mol · dm-3, and the concentration of hydrofluoric acid increased to 5.41 mol · dm-3. This first distillate was further distilled without the addition of salt. The concentrations of hydrofluoric acid and nitric acid in the second distillate were 7.21 mol · dm-3 and 0.46 mol · dm-3, respectively. It was thus found that the salt effect on vapor-liquid equilibrium of acid mixtures was effective for the recycling of acids from acid mixture wastes.

The influence of ionic strength on carbonate-based spectroscopic barometry for aqueous fluids: an in-situ Raman study on Na2CO3-NaCl solutions

PubMed Central

Wu, Jia; Wang, Shixia; Zheng, Haifei

2016-01-01

The Raman wavenumber of the symmetric stretching vibration of carbonate ion (ν1-CO32−) was measured in three aqueous solutions containing 2.0 mol·L−1 Na2CO3 and 0.20, 0.42, or 0.92 mol·L−1 NaCl, respectively, from 122 to 1538 MPa at 22 °C using a moissanite anvil cell. The ν1 Raman signal linearly shifted to higher wavenumbers with increasing pressure. Most importantly, the slope of ν1-CO32− Raman frequency shift (∂ν1/∂P)I was independent of NaCl concentration. Moreover, elevated ionic strength was found to shift the apparent outline of the carbonate peak toward low wavenumbers, possibly by increasing the proportion of the contact ion pair NaCO3−. Further investigations revealed no cross-interaction between the pressure effect and the ionic strength effect on the Raman spectra, possibly because the distribution of different ion-pair species in the carbonate equilibrium was largely pressure-independent. These results suggested that the ionic strength should be incorporated as an additional constraint for measuring the internal pressure of various solution-based systems. Combining the ν1-CO32− Raman frequency slope with the pressure herein with the values for the temperature or the ionic strength dependencies determined from previous studies, we developed an empirical equation that can be used to estimate the pressure of carbonate-bearing aqueous solutions. PMID:27982064

Interaction of Triapine and related thiosemicarbazones with iron(III)/(II) and gallium(III): a comparative solution equilibrium study†

PubMed Central

Enyedy, Éva A.; Primik, Michael F.; Kowol, Christian R.; Arion, Vladimir B.; Kiss, Tamás; Keppler, Bernhard K.

2012-01-01

Stoichiometry and stability of GaIII, FeIII, FeII complexes of Triapine and five related α-N heterocyclic thiosemicarbazones with potential antitumor activity have been determined by pH-potentiometry, UV-vis spectrophotometry, 1H NMR spectroscopy, and spectrofluorimetry in aqueous solution (with 30% DMSO), together with the characterization of the proton dissociation processes. Additionally, the redox properties of the iron complexes were studied by cyclic voltammetry at various pH values. Formation of high stability bis-ligand complexes was found in all cases, which are predominant at physiological pH with FeIII/FeII, whilst only at the acidic pH range with GaIII. The results show that among the thiosemicarbazones with various substituents the N-terminal dimethylation does not exert a measurable effect on the redox potential, but has the highest impact on the stability of the complexes as well as the cytotoxicity, especially in the absence of a pyridine-NH2 group in the molecule. In addition the fluorescence properties of the ligands in aqueous solution and their changes caused by GaIII were studied. PMID:21523301

Measurement of diffusion coefficients important in modeling the absorption rate of carbon dioxide into aqueous N-methyldiethanolamine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rowley, R.L.; Adams, M.E.; Marshall, T.L.

1997-03-01

Natural gas processors use amine treating processes to remove the acid gases H{sub 2}S and CO{sub 2} from gas streams. Absorption rates of gaseous CO{sub 2} into aqueous N-methyldiethanolamine (MDEA) solutions were measured in a quiescent, inverted-tube diffusiometer by monitoring the rate of pressure drop. The absorption rate was found to be insensitive to the diffusion coefficient of CO{sub 2} in solution but very sensitive to the diffusion rate of bicarbonate and protonated MDEA ions. Evidence also suggested that chemical reaction equilibrium is rapid relative to diffusion. A numerical model was developed on the basis of these observations. The modelmore » was used to regress diffusion coefficients of bicarbonate and protonated amine, which must be equivalent by electroneutrality arguments, from measured absorption rates. Complete modeling of the absorption process also required data for the diffusion coefficient of MDEA in water. These were measured using a Taylor dispersion apparatus. CO{sub 2} absorption rates and diffusion coefficients of bicarbonate and protonated MDEA were obtained at 298.2 K and 318.2 K in solutions containing 20, 35, and 50 mass % MDEA in water.« less

Removal of Remazol turquoise Blue G-133 from aqueous solution using modified waste newspaper fiber.

PubMed

Zhang, Xiaoyu; Tan, Jia; Wei, Xinhao; Wang, Lijuan

2013-02-15

Waste newspaper fiber (WNF) was separated and modified via grafting quaternary ammonium salt to obtain an adsorbent, which removes Remazol turquoise Blue G-133 (RTB G-133) from aqueous solutions. SEM and IR were used to analyze the morphology and chemical groups of the modified waste newspaper fiber (MWNF). Batch adsorption studies were conducted with varying adsorbent dosages, solution pH, and contact time. Adsorption isotherms and models were fitted. The SEM photographs show the surface of MWNF is smoother in comparison with that of WNF. The IR analysis indicates that the quaternary ammonium salt was successfully grafted onto the cellulose skeleton in WNF and the chemical interaction played an important role in adsorption. Results show that the equilibrium adsorption capacity can be reached within 360 min, and that the maximum adsorption capacity was 260 mg g(-1). The adsorption of RTB G-133 on MWNF was a spontaneous endothermic process and well fitted pseudo-second-order kinetic model and Langmuir adsorption isotherm model. The results show that MWNF is promising for dye wastewater treatment. Crown Copyright © 2012. Published by Elsevier Ltd. All rights reserved.

Photo-catalytic decolourisation of toxic dye with N-doped titania: a case study with Acid Blue 25.

PubMed

Chakrabortty, Dhruba; Gupta, Susmita Sen

2013-05-01

Dyes are one of the hazardous water pollutants. Toxic Acid Blue 25, an anthraquinonic dye, has been decolourised by photo-catalysing it with nitrogen doped titania in aqueous medium. The photo catalyst was prepared from 15% TiCl3 and 25% aqueous NH3 solution as precursor. XRD and TEM revealed the formation of well crystalline anatase phase having particle size in the nano-range. BET surface area of the sample was higher than that of pure anatase TiO2. DRS showed higher absorption of radiation in visible range compared to pure anatase TiO2. XPS revealed the presence of nitrogen in N-Ti-O environment. The experimental parameters, namely, photocatalyst dose, initial dye concentration as well as solution pH influence the decolourisation process. At pH 3.0, the N-TiO2 could decolourise almost 100% Acid Blue 25 within one hour. The influence of N-TiO2 dose, initial concentration of Acid Blue 25 and solution pH on adsorption-desorption equilibrium is also studied. The adsorption process follows Lagergren first order kinetics while the modified Langmuir-Hinselwood model is suitably fitted for photocatalytic decolourisation of Acid Blue 25.

Adsorption of Pb(II) ions onto biomass from Trifolium resupinatum: equilibrium and kinetic studies

NASA Astrophysics Data System (ADS)

Athar, Makshoof; Farooq, Umar; Aslam, Muhammad; Salman, M.

2013-09-01

The present study provides information about the binding of Pb(II) ions on an eco-friendly and easily available biodegradable biomass Trifolium resupinatum. The powdered biomass was characterized by FTIR, potentiometric titration and surface area analyses. The FTIR spectrum showed the presence of hydroxyl, carbonyl and amino functional groups and Pb(II) ions bound with the oxygen- and nitrogen-containing sites (hydroxyl and amino groups). The acidic groups were also confirmed by titrations. Effects of various environmental parameters (time, pH and concentration) have been studied. The biosorption process achieved equilibrium in a very short period of time (25 min). Non-linear approach for Langmuir and Freundlich models was used to study equilibrium process and root mean-square error was used as an indicator to decide the fitness of the mathematical model. The biosorption process was found to follow pseudo-second-order kinetics and was very fast. Thus, the biomass can be cost-effectively used for the binding of Pb(II) ions from aqueous solutions.

Thermoresponsiveness of hybrid micelles from poly(ethylene glycol)-block-poly(4-vinylpyridium) cations and SO4(2-) anions in aqueous solutions.

PubMed

Wu, Kai; Shi, Linqi; Zhang, Wangqing; An, Yingli; Zhang, Xu; Li, Zhanyong; Zhu, X X

2006-02-14

The SO4(2-)-induced micellization of poly(ethylene glycol)-block-poly(4-vinylpyridium) (PEG110-b-P(4-VPH+)35) and the thermoresponsiveness of these hybrid micelles are studied by dynamic and static light scattering. When the concentration of H2SO4 is high enough, PEG110-b-P(4-VPH+)35 forms stable hybrid micelles with an ionic core of P(4-VPH+)35/SO4(2-) and a PEG corona at 25 degrees C. The formation of the hybrid micelles is reversible. A thermodynamic equilibrium exists between the hybrid micelles and PEG110-b-P(4-VPH+)35 unimers. The shifts of the equilibrium are mainly attributed to the variation of the electrostatic energy and entropic energy of the system. Therefore, the temperature can determine the states of the equilibrium, which means that the dissociation or the formation of the hybrid micelles can be triggered by just varying the temperature.

Rate Dependency During Relaxation of Superelastic Orthodontic NiTi Alloys After Hydrogen Charging

NASA Astrophysics Data System (ADS)

Elkhal Letaief, Wissem; Hassine, Tarek; Gamaoun, Fehmi

2016-03-01

The relaxation behavior under tensile loading of a superelastic NiTi alloy was investigated after hydrogen charging with respect to aging from one to 77 days in air at room temperature. The specimens were immersed for 3 h in a 0.9 % NaCl aqueous solution and then relaxed with an imposed strain of 4.8 %—which results in half of the martensite transformation—for different strain rates of 10-4, 10-3, and 5 × 10-3 s-1. For the non-charged specimens, the relaxed stress at the beginning exhibited a temporary dependence on the strain rates and then reached the same equilibrium stress after 2.5 h. After hydrogen charging, this equilibrium stress did not vary for the as-charged specimen. Nevertheless, the greater the aging period is the greater the equilibrium stress is. This behavior can be attributed to the diffusion of hydrogen into the entire specimen, which hinders the relaxation mechanism of the martensite bands.

Equilibrium and Kinetic Studies of Cd2+ Biosorption by the Brown Algae Sargassum fusiforme

PubMed Central

Zou, Hui-Xi; Li, Nan; Wang, Li-Hua; Yu, Ping; Yan, Xiu-Feng

2014-01-01

A fundamental investigation of the biosorption of Cd2+ from aqueous solution by the edible seaweed Sargassum fusiforme was performed under batch conditions. The influences of experimental parameters, such as the initial pH, sorption time, temperature, and initial Cd2+ concentration, on Cd2+ uptake by S. fusiforme were evaluated. The results indicated that the biosorption of Cd2+ depended on the initial Cd2+ concentration, as well as the pH. The uptake of Cd2+ could be described by the Langmuir isotherm model, and both the Langmuir biosorption equilibrium constant and the maximum biosorption capacity of the monolayer decreased with increasing temperature, thereby confirming the exothermic character of the sorption process. The biosorption kinetics follows the pseudo-second-order kinetic model, and intraparticle diffusion is the sole rate-limiting step for the entire biosorption period. These fundamental equilibrium and kinetic results can support further studies to the removal of cadmium from S. fusiforme harvested from cadmium-polluted waters. PMID:24736449

The peculiarities of spectral manifestations of high-voltage electric discharge in different phase states of ion systems.

PubMed

Gafurov, M M; Aliev, A R; Ataev, M B; Rabadanov, K Sh

2013-10-01

The effects of high-voltage pulsed discharge (HVPD activation) on vibrational spectra of ion salt systems have been studied. The peculiarities of spectral display of HVPD in ion melts and aqueous solutions of electrolytes, in ion-conducting phases of crystalline and glassy salt systems have been investigated. After HVPD a salt system is in non-equilibrium activated state. In the activated state of a salt system, the relaxation time of the vibrational excited states of molecular ions is shorter than in the equilibrium state if the vibrational relaxation rate increases with temperature in the system. For those systems for which the relaxation rate decreases at elevated temperatures, the relaxation time of the vibrational excited states of molecular ions is longer than in the equilibrium state. HVPD activation of a salt system can change the configuration of the electron shell of molecular ions. Therefore, the lifetime values of activated state of salt systems are abnormally large. Copyright © 2013 Elsevier B.V. All rights reserved.

Toxic metals biosorption by Jatropha curcas deoiled cake: equilibrium and kinetic studies.

PubMed

Rawat, Anand P; Rawat, Monica; Rai, J P N

2013-08-01

The equilibrium sorption of Cr(VI) and Cu(II) from aqueous solution using Jatropha curcas deoiled cake, has been studied with respect to adsorbent dosage, contact time, pH, and initial metal concentration in batch mode experiments. Removal of Cu(II) by deoiled cake was greater than that of Cr(VI). The adsorbent chemical characteristics, studied by Fourier transform-infrared analysis, suggested that the presence of Cr(VI) and Cu(II) in the biomass influenced the bands corresponding to hydroxyl and carboxyl groups. Desorption studies revealed that maximum metals recovery was achieved by HNO3 followed by CH3COOH and HCl. The Freundlich isotherm model showed good fit to the equilibrium adsorption data. The adsorption kinetics followed the pseudo-second-order model, which provided the best correlation for the biosorption process, and suggested that J. curcas deoiled cake can be used as an efficient biosorbent over other commonly used sorbents for decontamination of Cr(VI)- and Cu(II)-containing wastewater.

Recovery of acetic acid from dilute aqueous solutions using catalytic dehydrative esterification with ethanol.

PubMed

Yagyu, Daisuke; Ohishi, Tetsuo; Igarashi, Takeshi; Okumura, Yoshikuni; Nakajo, Tetsuo; Mori, Yuichiro; Kobayashi, Shū

2013-03-01

We have developed a direct esterification of aqueous acetic acid with ethanol (molar ratio=1:1) catalyzed by polystyrene-supported or homogeneous sulfonic acids toward the recovery of acetic acid from wastewater in chemical plants. The equilibrium yield was significantly increased by the addition of toluene, which had a high ability to extract ethyl acetate from the aqueous phase. It was shown that low-loading and alkylated polystyrene-supported sulfonic acid efficiently accelerated the reaction. These results suggest that the construction of hydrophobic reaction environments in water was critical in improving the chemical yield. Addition of inorganic salts was also effective for the reaction under not only biphasic conditions (toluene-water) but also toluene-free conditions, because the mutual solubility of ethyl acetate and water was suppressed by the salting-out effect. Among the tested salts, CaCl(2) was found to be the most suitable for this reaction system. Copyright © 2012 Elsevier Ltd. All rights reserved.

Preferential solvation and solvation shell composition of free base and protonated 5, 10, 15, 20-tetrakis(4-sulfonatophenyl)porphyrin in aqueous organic mixed solvents

NASA Astrophysics Data System (ADS)

Farajtabar, Ali; Jaberi, Fatemeh; Gharib, Farrokh

2011-12-01

The solvatochromic properties of the free base and the protonated 5, 10, 15, 20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS) were studied in pure water, methanol, ethanol (protic solvents), dimethylsulfoxide, DMSO, (non-protic solvent), and their corresponding aqueous-organic binary mixed solvents. The correlation of the empirical solvent polarity scale ( ET) values of TPPS with composition of the solvents was analyzed by the solvent exchange model of Bosch and Roses to clarify the preferential solvation of the probe dyes in the binary mixed solvents. The solvation shell composition and the synergistic effects in preferential solvation of the solute dyes were investigated in terms of both solvent-solvent and solute-solvent interactions and also, the local mole fraction of each solvent composition was calculated in cybotactic region of the probe. The effective mole fraction variation may provide significant physico-chemical insights in the microscopic and molecular level of interactions between TPPS species and the solvent components and therefore, can be used to interpret the solvent effect on kinetics and thermodynamics of TPPS. The obtained results from the preferential solvation and solvent-solvent interactions have been successfully applied to explain the variation of equilibrium behavior of protonation of TPPS occurring in aqueous organic mixed solvents of methanol, ethanol and DMSO.

Evaluation of adsorption properties of sulphurised activated carbon for the effective and economically viable removal of Zn(II) from aqueous solutions.

PubMed

Anoop Krishnan, K; Sreejalekshmi, K G; Vimexen, V; Dev, Vinu V

2016-02-01

The prospective application of sulphurised activated carbon (SAC) as an ecofriendly and cost-effective adsorbent for Zinc(II) removal from aqueous phase is evaluated, with an emphasis on kinetic and isotherm aspects. SAC was prepared from sugarcane bagasse pith obtained from local juice shops in Sree Bhadrakali Devi Temple located at Ooruttukala, Neyyattinkara, Trivandrum, India during annual festive seasons. Activated carbon modified with sulphur containing ligands was opted as the adsorbent to leverage on the affinity of Zn(II) for sulphur. We report batch-adsorption experiments for parameter optimisations aiming at maximum removal of Zn(II) from liquid-phase using SAC. Adsorption of Zn(II) onto SAC was maximum at pH 6.5. For initial concentrations of 25 and 100mgL(-1), maximum of 12.3mgg(-1) (98.2%) and 23.7mgg(-1) (94.8%) of Zn(II) was adsorbed onto SAC at pH 6.5. Kinetic and equilibrium data were best described by pseudo-second-order and Langmuir models, respectively. A maximum adsorption capacity of 147mgg(-1) was obtained for the adsorption of Zn(II) onto SAC from aqueous solutions. The reusability of the spent adsorbent was also determined. Copyright © 2015 Elsevier Inc. All rights reserved.

Sodium Sulfate Separation from Aqueous Alkaline Solutions via Crystalline Urea-Functionalized Capsules: Thermodynamics and Kinetics of Crystallization

DOE PAGES

Custelcean, Radu; Sloop, Frederick V.; Rajbanshi, Arbin; ...

2014-12-04

We measured the thermodynamics and kinetics of crystallization of sodium sulfate with a tripodal tris-urea receptor (L1) from aqueous alkaline solutions in the 15 55 C temperature range, with the goal of identifying the optimal conditions for efficient and quick sulfate removal from nuclear wastes. The use of radiolabeled Na 2 35SO 4 provided a practical way to monitor the sulfate concentration in solution by liquid scintillation counting. Our results are consistent with a two-step crystallization mechanism, involving relatively quick dissolution of crystalline L1 followed by the rate-limiting crystallization of the Na 2SO 4(L1) 2(H 2O) 4 capsules. We foundmore » that temperature exerted relatively little influence over the equilibrium sulfate concentration, which ranged between 0.004 and 0.011 M. Moreover, this corresponds to 77 91% removal of sulfate from a solution containing 0.0475 M initial sulfate concentration, as found in a typical Hanford waste tank. The apparent pseudo-first-order rate constant for sulfate removal increased 20-fold from 15 to 55 C, corresponding to an activation energy of 14.1 kcal/mol. At the highest measured temperature of 55 C, 63% and 75% of sulfate was removed from solution within 8 h and 24 h, respectively.« less

Reply to the comment by Wu et al. (2016) on "Behavior of Re and Os during contact between an aqueous solution and oil: Consequences for the application of the Re-Os geochronometer to petroleum" [Geochim. Cosmochim. Acta 158 (2015) 1-21

NASA Astrophysics Data System (ADS)

Reisberg, Laurie; Michels, Raymond; Mahdaoui, Fatima

2016-08-01

We reply here to the questions raised by Wu et al. concerning the results published by Mahdaoui et al. (2015). This paper describes experiments in which aqueous solutions containing ReO4- and OsCl62- were brought in contact with natural oils at various ranges of concentration, time and temperature. The main observation is that the transfer of Re and Os to oils is very efficient under all experimental conditions. Wu et al. argue that thermodynamic equilibrium was not achieved in these experiments as apparent partition coefficients are inconsistent. They conclude that the experiments were flawed by possible leaking of reactors and that the conclusions by Mahdaoui et al. (2015) were not justified. In the following reply we explain that Mahdaoui et al. (2015) never claimed that thermodynamic equilibrium was achieved. Any calculations or considerations in this context are therefore meaningless. We recall the objectives of our publication, which were to experimentally test the behavior of ReO4- and OsCl6- (two plausible chemical forms of Re and Os in deep aquifers of petroleum systems) in aqueous solution-oil systems. To our knowledge these are the first experiments of their kind. The parameters that could influence the precision and reproducibility of our results were discussed in detail in Mahdaoui et al. (2015). The essential point is that all 60 of the experiments provide evidence of substantial transfer of Re and Os from water to oil. In contrast to what was mistakenly understood by Wu et al., the paper does not challenge the use of Re-Os to date geological events affecting petroleum. Instead, by providing a mechanism that might allow Os isotopic homogenization on a basin-wide scale, a critical step missing from most current models, it offers a possible explanation of how Re-Os geochronology in oils could potentially work. More generally, our study suggests that transfer of Re and Os from waters to oil may be an important phenomenon that should not be overlooked.

The radiation resistance and cobalt biosorption activity of yeast strains isolated from the Lanyu low-level radioactive waste repository in Taiwan.

PubMed

Li, Chia-Chin; Chung, Hsiao-Ping; Wen, Hsiao-Wei; Chang, Ching-Tu; Wang, Ya-Ting; Chou, Fong-In

2015-08-01

The ubiquitous nature of microbes has made them the pioneers in radionuclides adsorption and transport. In this study, the radiation resistance and nuclide biosorption capacity of microbes isolated from the Lanyu low-level radioactive waste (LLRW) repository in Taiwan was assessed, the evaluation of the possibility of using the isolated strain as biosorbents for (60)Co and Co (II) from contaminated aqueous solution and the potential impact on radionuclides release. The microbial content of solidified waste and broken fragments of containers at the Lanyu LLRW repository reached 10(5) CFU/g. Two yeast strains, Candida guilliermondii (CT1) and Rhodotorula calyptogenae (RT1) were isolated. The radiation dose necessary to reduce the microbial count by one log cycle of CT1 and RT1 was 2.1 and 0.8 kGy, respectively. Both CT1 and RT1 can grow under a radiation field with dose rate of 6.8 Gy/h, about 100 times higher than that on the surface of the LLRW container in Lanyu repository. CT1 and RT1 had the maximum (60)Co biosorption efficiency of 99.7 ± 0.1% and 98.3 ± 0.2%, respectively in (60)Co aqueous solution (700 Bq/mL), and the (60)Co could stably retained for more than 30 days in CT 1. Nearly all of the Co was absorbed and reached equilibrium within 1 h by CT1 and RT1 in the 10 μg/g Co (II) aqueous solution. Biosorption efficiency test showed almost all of the Co (II) was adsorbed by CT1 in 20 μg/g Co (II) aqueous solution, the efficiency of biosorption by RT1 in 10 μg/g of Co (II) was lower. The maximum Co (II) sorption capacity of CT1 and RT1 was 5324.0 ± 349.0 μg/g (dry wt) and 3737.6 ± 86.5 μg/g (dry wt), respectively, in the 20 μg/g Co (II) aqueous solution. Experimental results show that microbial activity was high in the Lanyu LLRW repository in Taiwan. Two isolated yeast strains, CT1 and RT1 have high potential for use as biosorbents for (60)Co and Co (II) from contaminated aqueous solution, on the other hand, but may have the impact on radionuclides release from LLRW repository. Copyright © 2015 Elsevier Ltd. All rights reserved.

Application of a new bifunctionalized chitosan derivative with zwitterionic characteristics for the adsorption of Cu(2+), Co(2+), Ni(2+), and oxyanions of Cr(6+) from aqueous solutions: Kinetic and equilibrium aspects.

PubMed

de Almeida, Francine Tatiane Rezende; Ferreira, Bruno Christiano Silva; Moreira, Ana Luísa da Silva Lage; de Freitas, Rossimiriam Pereira; Gil, Laurent Frédéric; Gurgel, Leandro Vinícius Alves

2016-03-15

This study describes the synthesis of a new chitosan derivative (C2) with zwitterionic characteristics and its use for the removal of cationic species Cu(2+), Co(2+), and Ni(2+) and anionic species of Cr(6+) in a single aqueous solution. The new adsorbent was synthesized by quaternization of the amine group of chitosan and esterification of hydroxyl groups with EDTA dianhydride. These combined reactions gave both cationic and anionic characteristics to C2 with the release of quaternary ammonium groups and carboxylic groups. The capacity of C2 to adsorb Cu(2+), Co(2+), Ni(2+), and oxyanions of Cr(6+) was evaluated in a batch process with different contact times, pH values, and initial concentrations. Adsorption isotherms were best fitted to the Langmuir and Sips models. The maximum adsorption capacities (Q(max)) of C2 for adsorption of Cu(2+), Co(2+), Ni(2+), and Cr(6+) were 0.698, 1.125, 0.725, and 1.910 mmol/g, respectively. The Δ(ads)G° values were in the range from -20 to -28 kJ/mol. These values suggest a mixed mechanism controlling adsorption. Desorption studies using an aqueous solution consisting of 0.1 mol/L HNO3 were carried out. The reusability of the recovered C2 adsorbent after desorption was also evaluated. Copyright © 2015 Elsevier Inc. All rights reserved.

Poly(hydroxyethyl methacrylate-co-methacryloylglutamic acid) nanospheres for adsorption of Cd2+ ions from aqueous solutions

NASA Astrophysics Data System (ADS)

Esen, Cem; Şenay, Raziye Hilal; Feyzioğlu, Esra; Akgöl, Sinan

2014-02-01

Poly(2-hydroxyethyl methacrylate-co- N-methacryloyl-( l)-glutamic acid) p(HEMA-MAGA) nanospheres have been synthesized, characterized, and used for the adsorption of Cd2+ ions from aqueous solutions. Nanospheres were prepared by surfactant free emulsion polymerization. The p(HEMA-MAGA) nanospheres were characterized by SEM, FTIR, zeta size, and elemental analysis. The specific surface area of nanospheres was found to be 1,779 m2/g. According to zeta size analysis results, average size of nanospheres is 147.3 nm with poly-dispersity index of 0.200. The goal of this study was to evaluate the adsorption performance of p(HEMA-MAGA) nanospheres for Cd2+ ions from aqueous solutions by a series of batch experiments. The Cd2+ concentration was determined by inductively coupled plasma-optical emission spectrometer. Equilibrium sorption experiments indicated a Cd2+ uptake capacity of 44.2 mg g-1 at pH 4.0 at 25 °C. The adsorption of Cd2+ ions increased with increasing pH and reached a plateau value at around pH 4.0. The data were successfully modeled with a Langmuir equation. A series of kinetics experiments was then carried out and a pseudo-second order equation was used to fit the experimental data. Desorption experiments which were carried out with nitric acid showed that the p(HEMA-MAGA) nanospheres could be reused without significant losses of their initial properties in consecutive adsorption and elution operations.

Nano-TiO2, ultrasound and sequential nano-TiO2/ultrasonic degradation of N-acetyl-para-aminophenol from aqueous solution.

PubMed

Ayanda, Olushola S; Nelana, Simphiwe M; Petrik, Leslie F; Naidoo, Eliazer B

2017-10-01

The application of nano-TiO 2 as adsorbent combined with ultrasound for the degradation of N-acetyl-para-aminophenol (AAP) from aqueous solution was investigated. The nano-TiO 2 was characterized by means of powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR). Experimental results revealed that the adsorption of AAP by nano-TiO 2 fitted the pseudo-second-order kinetic model, the equilibrium could be explained by the Freundlich isotherm and the treatment process is exothermic. The optimum removal efficiency of AAP (128.89 mg/g (77.33%)) was achieved at pH 4 when 0.03 g of nano-TiO 2 was mixed with 50 mL of 100 mg/L AAP aqueous solution at ambient temperature, 60 min contact time, and a stirring speed of 120 rpm. Ultrasound at 20 kHz and pH 3 was favorable and it resulted in 52.61% and 57.43% removal efficiency with and without the addition of nano-TiO 2 , respectively. The degradation of AAP by ultrasound followed by nano-TiO 2 treatment resulted in approximately 99.50% removal efficiency. This study showed that a sequential ultrasound and nano-TiO 2 treatment process could be employed for the removal of AAP or other emerging water and wastewater contaminants.

Synthesis and crystal structure of Cd-based metal-organic framework for removal of methyl-orange from aqueous solution

NASA Astrophysics Data System (ADS)

Tella, Adedibu C.; Olawale, Margaret D.; Neuburger, Markus; Obaleye, Joshua A.

2017-11-01

A novel [Cd(INA)2(H2O)]. ISB (1) (INA = isonicotinate; ISB = isobutanol) was synthesized through the reaction between the isonicotinic acid ligand and cadmium (II) salt and characterized by elemental analysis, FTIR and UV-Visible spectroscopies, SEM and Single crystal X-ray diffraction. The crystal is orthorhombic, space group Pbca, a = 12.24(10) Å, b = 15.4646(13) Å, c = 18.8445(17) Å, V = 3569(3) Å3, Z = 8. The pentagonal bipyramid (seven coordinate) around the cadmium (II) ion is of the form CdN2O5 coordinating to four oxygen atoms from carboxylates, one oxygen atom from water molecule and two nitrogen atoms of pyridine. The structure of compound is stabilized by two hydrogen bonds namely intermolecular (O-H-O) and intramolecular type C-H-O accounting for polymeric nature of the metal-organic frameworks. 1 was studied for adsorptive removal of methyl orange (MO) from aqueous solution. Equilibrium isotherm study reveals that Langmuir model gave a better fitting result than the Freundlich model. The pseudo-second order model could be used to interpret adsorption kinetics. The maximum adsorption capacity calculated by Langmuir was 166 mg/g at 300 K. These results indicate the adsorption of MO on 1 is partly due to electrostatic interaction between methyl orange and the adsorbent. 1 could be used as adsorbent to remove methyl orange from aqueous solution.

Phosphorus sorption capacity of biochars varies with biochar type and salinity level.

PubMed

Dugdug, Abdelhafid Ahmed; Chang, Scott X; Ok, Yong Sik; Rajapaksha, Anushka Upamali; Anyia, Anthony

2018-02-10

Biochar is recognized as an effective material for recovering excess nutrients, including phosphorus (P), from aqueous solutions. Practically, that benefits the environment through reducing P losses from biochar-amended soils; however, how salinity influences P sorption by biochar is poorly understood and there has been no direct comparison on P sorption capacity between biochars derived from different feedstock types under non-saline and saline conditions. In this study, biochars derived from wheat straw, hardwood, and willow wood were used to compare P sorption at three levels of electrical conductivity (EC) (0, 4, and 8 dS m -1 ) to represent a wide range of salinity conditions. Phosphorus sorption by wheat straw and hardwood biochars increased as aqueous solution P concentration increased, with willow wood biochar exhibiting an opposite trend for P sorption. However, the pattern for P sorption became the same as the other biochars after the willow wood biochar was de-ashed with 1 M HCl and 0.05 M HF. Willow wood biochar had the highest P sorption (1.93 mg g -1 ) followed by hardwood (1.20 mg g -1 ) and wheat straw biochars (1.06 mg g -1 ) in a 25 mg L -1 P solution. Although the pH in the equilibrium solution was higher with willow wood biochar (~ 9.5) than with the other two biochars (~ 6.5), solution pH had no or minor effects on P sorption by willow wood biochar. The high sorption rate of P by willow wood biochar could be attributed to the higher concentrations of salt and other elements (i.e., Ca and Mg) in the biochar in comparison to that in wheat straw and hardwood biochars; the EC values were 2.27, 0.53, and 0.27 dS m -1 for willow wood, wheat straw, and hardwood biochars, respectively. A portion of P desorbed from the willow wood biochar; and that desorption increased with the decreasing P concentration in the aqueous solution. Salinity in the aqueous solution influenced P sorption by hardwood and willow wood but not by wheat straw biochar. We conclude that the P sorption capacity of the studied biochars is dependent on the concentration of the soluble element in the biochar, which is dependent on the biochar type, as well as the salinity level in the aqueous solution.

On particle track detectors

NASA Technical Reports Server (NTRS)

Benton, E. V.; Gruhn, T. A.; Andrus, C. H.

1973-01-01

Aqueous sodium hydroxide is widely used to develop charged particle tracks in polycarbonate film, particularly Lexan. The chemical nature of the etching process for this system has been determined. A method employing ultra-violet absorbance was developed for monitoring the concentration of the etch products in solution. Using this method it was possible to study the formation of the etching solution saturated in etch products. It was found that the system super-saturates to a significant extent before precipitation occurs. It was also learned that the system approaches its equilibrium state rather slowly. It is felt that both these phenomena may be due to the presence of surfactant in the solution. In light of these findings, suggestions are given regarding the preparation and maintenance of the saturated etch solution. Two additional research projects, involving automated techniques for particle track analysis and particle identification using AgCl crystals, are briefly summarized.

Method for Reduction of Silver Biocide Plating on Metal Surfaces

NASA Technical Reports Server (NTRS)

Steele, John; Nalette, Timothy; Beringer, Durwood

2013-01-01

Silver ions in aqueous solutions (0.05 to 1 ppm) are used for microbial control in water systems. The silver ions remain in solution when stored in plastic containers, but the concentration rapidly decreases to non-biocidal levels when stored in metal containers. The silver deposits onto the surface and is reduced to non-biocidal silver metal when it contacts less noble metal surfaces, including stainless steel, titanium, and nickel-based alloys. Five methods of treatment of contact metal surfaces to deter silver deposition and reduction are proposed: (1) High-temperature oxidation of the metal surface; (2) High-concentration silver solution pre-treatment; (3) Silver plating; (4) Teflon coat by vapor deposition (titanium only); and (5) A combination of methods (1) and (2), which proved to be the best method for the nickel-based alloy application. The mechanism associated with surface treatments (1), (2), and (5) is thought to be the development of a less active oxide layer that deters ionic silver deposition. Mechanism (3) is an attempt to develop an equilibrium ionic silver concentration via dissolution of metallic silver. Mechanism (4) provides a non-reactive barrier to deter ionic silver plating. Development testing has shown that ionic silver in aqueous solution was maintained at essentially the same level of addition (0.4 ppm) for up to 15 months with method (5) (a combination of methods (1) and (2)), before the test was discontinued for nickel-based alloys. Method (1) resulted in the maintenance of a biocidal level (approximately 0.05 ppm) for up to 10 months before that test was discontinued for nickel-based alloys. Methods (1) and (2) used separately were able to maintain ionic silver in aqueous solution at essentially the same level of addition (0.4 ppm) for up to 10 months before the test was discontinued for stainless steel alloys. Method (3) was only utilized for titanium alloys, and was successful at maintaining ionic silver in aqueous solution at essentially the same level of addition (0.4 ppm) for up to 10 months before the test was discontinued for simple flat geometries, but not for geometries that are difficult to Teflon coat.

Studies on Thorium Adsorption Characteristics upon Activated Titanium Hydroxide Prepared from Rosetta Ilmenite Concentrate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gado, M, E-mail: parq28@yahoo.com; Zaki, S

2016-01-01

The titanium hydroxide prepared from Rosetta ilmenite concentrate has been applied for Th (IV) adsorption from its acid aqueous solutions. The prepared hydroxide is first characterized by both Fourier transform infrared (FT-IR) spectrum and thermogravimetric analysis. The relevant factors affecting the adsorption process have been studied. The obtained equilibrium data fits well with the Langmuir isotherm rather than Freundlich isotherm, while the adsorption kinetic data follow the pseudo-second order model. The different thermodynamic parameters have also been calculated and indicate that the adsorption process is spontaneous.

Probing the electrolyte infiltration behaviour of activated carbon supercapacitor electrodes by in situ neutron scattering using aqueous NaCl as electrolyte

DOE PAGES

Liu, Yiqun; Li, Chen; Liu, Cong; ...

2018-04-24

In situ contrast-matched neutron scattering was used to probe the electrolyte infiltration behavior of activated supercapacitor carbon electrodes using an aquoeus 1 M NaCl solution. It was found that only about 20% of the pore volume was infiltrated at chemical equilibrium. The partial infiltration can be attributed to the co-existence of hydrophilic and hydrophilic pores. As a result, the study suggests that for the achievement of optimal capacitance, supercapacitor electrodes should be evacuated before electrolyte infiltration.

Probing the electrolyte infiltration behaviour of activated carbon supercapacitor electrodes by in situ neutron scattering using aqueous NaCl as electrolyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Yiqun; Li, Chen; Liu, Cong

In situ contrast-matched neutron scattering was used to probe the electrolyte infiltration behavior of activated supercapacitor carbon electrodes using an aquoeus 1 M NaCl solution. It was found that only about 20% of the pore volume was infiltrated at chemical equilibrium. The partial infiltration can be attributed to the co-existence of hydrophilic and hydrophilic pores. As a result, the study suggests that for the achievement of optimal capacitance, supercapacitor electrodes should be evacuated before electrolyte infiltration.

Development of a Scaled Quantum Mechanical Force Field for Peptides in Aqueous Solution

DTIC Science & Technology

1996-03-01

differ. Raman and IR techniques are complimentary which helps in assignment of observed vibrational modes. As described in beginning organic ...1588 I NH, .i.sor(98) 2076 2100 24 CH3 55(95) 2125 2207 82 CH3 as’ (56), CH3 as’ (43) 2235 2253 18 CH3 as’(55), CH3 as’(41) 2888 COff .(100) 3155 NH...Application of self- consistent-field ab initio calculations to organic molecules I. Equilibrium struc- ture and force constants of hydrocarbons

Enolization of acetone in superheated water detected via radical formation.

PubMed

Ghandi, Khashayar; Addison-Jones, Brenda; Brodovitch, Jean-Claude; McCollum, Brett M; McKenzie, Iain; Percival, Paul W

2003-08-13

Muoniated free radicals have been detected in muon-irradiated aqueous solutions of acetone at high temperatures and pressures. At temperatures below 250 degrees C, the radical product is consistent with muonium addition to the keto form of acetone. However, at higher temperatures, a different radical was detected, which is attributed to muonium addition to the enol form. Muon hyperfine coupling constants have been determined for both radicals over a wide range of temperatures, significantly extending the range of conditions under which these radicals and the keto-enol equilibrium have been studied.

The adsorption properties of short chain alcohols and Triton X-100 mixtures at the water-air interface.

PubMed

Zdziennicka, Anna

2009-07-15

The adsorption behaviour at the water-air interface of aqueous solutions of Triton X-100 and methanol (ethanol) mixtures at constant Triton X-100 (TX-100) concentration equal to 10(-7), 10(-6), 10(-5), 10(-4), 6x10(-4) and 10(-3)M, respectively, in a wide range of alcohol concentration was investigated by surface tension measurements of solutions. The obtained values of the surface tension of aqueous solutions of "pure" methanol and ethanol and their mixtures with TX-100, as well as the values of propanol solutions and their mixtures with TX-100 as a function of alcohol concentration taken from the literature were compared with those calculated from the Szyszkowski, Connors and Fainerman and Miller equations. On the basis of this comparison it was stated that these equations can be useful for description of the solution surface tension in the wide range of alcohol concentration, but only at the concentrations of Triton X-100 corresponding to its unsaturated layer in the absence of alcohol. It was also stated that the Connors equation is more adequate for concentrated aqueous organic solutions. The measured values of the surface tension were used in the Gibbs equation to determine the surface excess concentration of Triton X-100 and alcohol. Next, on the basis of Gibbs adsorption isotherms those of Guggenheim and Adam and real adsorption isotherms were established. From the obtained adsorption isotherms it results that alcohol influences the shape of TX-100 isotherms in the whole range of alcohol and TX-100 concentration, but TX-100 influences the alcohol isotherms only at TX-100 concentration at which the saturated monolayer at the solution-air interface is formed in the absence of alcohol. This conclusion was confirmed by analysis of the composition of the surface layer in comparison to the composition of the bulk phase in the equilibrium state.

Particle-scale measurement of PAH aqueous equilibrium partitioning in impacted sediments.

PubMed

Ghosh, Upal; Hawthorne, Steven B

2010-02-15

This research investigated the particle-scale processes that control aqueous equilibrium partitioning of PAHs in manufactured gas plant (MGP) site sediments. Dominant particle types in impacted sediments (sand, wood, coal/coke, and pitch) were physically separated under a microscope for equilibrium assessments. Solid-phase microextraction (SPME) combined with selected ion monitoring GC/MS and perdeuterated PAH internal standards were used to determine freely dissolved PAH concentrations in small (0.1-1 mL) water samples at concentrations as low as microg/L (for lower molecular weight PAHs) to ng/L (for higher molecular weight PAHs). For every particle class the initial release of PAHs into the aqueous phase was rapid, and an apparent equilibrium was reached in a matter of days. The average ratio of aqueous total PAH concentration for pitch vs coal/coke particles for eight sediment samples was 20. Thus, sediments that had aged in the field for many decades were not at equilibrium and were still going through a slow process of contaminant mass transfer between the different particle types. A possible consequence of this slow aging process is further lowering of the activity of the chemical as mass transfer is achieved to new sorption sites with time. This study also found that the presence of black carbon even at the level of (1)/(3) of sediment organic carbon does not necessarily imply a BC-dominated sorption behavior, rather source pitch particles if present may dominate PAH partitioning. To our knowledge this is the first report of equilibrium partitioning assessment conducted at the sediment particle scale.

Rate of strontium sorption and the effects of variable aqueous concentrations of sodium and potassium on strontium distribution coefficients of a surficial sediment at the Idaho National Engineering Laboratory, Idaho

USGS Publications Warehouse

Bunde, R.L.; Rosentreter, J.J.; Liszewski, M.J.

1998-01-01

The rate of strontium sorption and the effects of variable aqueous concentrations of sodium and potassium on strontium sorption were measured as part of an investigation to determine strontium chemical transport properties of a surficial sediment at the Idaho National Engineering Laboratory (INEL), Idaho. Batch experimental techniques were used to determine the rate of strontium sorption and strontium distribution coefficients (K(d)s) between aqueous and solid phases. Rate experiments indicate that strontium in solution reached an apparent equilibrium with the sediment in 26 h. K(d)s were derived using the linear isotherm model at initial sodium concentrations from 100 to 5,000 mg/l and initial potassium concentrations from 2 to 150 mg/l. K(d)s ranged from 56 ?? 2 to 62 ?? 3 ml/g at initial aqueous concentrations of sodium and potassium equal to or less than 300 and 150 mg/l, respectively. K(d)s hinged from 4.7 ?? 0.2 to 19 ?? 1 ml/g with initial aqueous concentrations of sodium between 1,000 and 5,000 mg/l. These data indicate that sodium concentrations greater than 300 mg/l in wastewater increase the availability of strontium for transport beneath waste disposal ponds at the INEL by decreasing strontium sorption on the surficial sediment. Wastewater concentrations of sodium and potassium less than 300 and 150 mg/l, respectively, have little effect on the availability of strontium for transport.The rate of strontium sorption and the effects of variable aqueous concentrations of sodium and potassium on strontium sorption were measured as part of an investigation to determine strontium chemical transport properties of a surficial sediment at the Idaho National Engineering Laboratory (INEL), Idaho. Batch experimental techniques were used to determine the rate of strontium sorption and strontium distribution coefficients (Kds) between aqueous and solid phases. Rate experiments indicate that strontium in solution reached an apparent equilibrium with the sediment in 26 h. Kds were derived using the linear isotherm model at initial sodium concentrations from 100 to 5,000 mg/l and initial potassium concentrations from 2 to 150 mg/l. Kds ranged from 56??2 to 62??3 ml/g at initial aqueous concentrations of sodium and potassium equal to or less than 300 and 150 mg/l, respectively. Kds ranged from 4.7??0.2 to 19??1 ml/g with initial aqueous concentrations of sodium between 1,000 and 5,000 mg/l. These data indicate that sodium concentrations greater than 300 mg/l in wastewater increase the availability of strontium for transport beneath waste disposal ponds at the INEL by decreasing strontium sorption on the surficial sediment. Wastewater concentrations of sodium and potassium less than 300 and 150 mg/l, respectively, have little effect on the availability of strontium for transport.

Lysozyme pattern formation in evaporating droplets

NASA Astrophysics Data System (ADS)

Gorr, Heather Meloy

Liquid droplets containing suspended particles deposited on a solid, flat surface generally form ring-like structures due to the redistribution of solute during evaporation (the "coffee ring effect"). The forms of the deposited patterns depend on complex interactions between solute(s), solvent, and substrate in a rapidly changing, far from equilibrium system. Solute self-organization during evaporation of colloidal sessile droplets has attracted the attention of researchers over the past few decades due to a variety of technological applications. Recently, pattern formation during evaporation of various biofluids has been studied due to potential applications in medical screening and diagnosis. Due to the complexity of 'real' biological fluids and other multicomponent systems, a comprehensive understanding of pattern formation during droplet evaporation of these fluids is lacking. In this PhD dissertation, the morphology of the patterns remaining after evaporation of droplets of a simplified model biological fluid (aqueous lysozyme solutions + NaCl) are examined by atomic force microscopy (AFM) and optical microscopy. Lysozyme is a globular protein found in high concentration, for example, in human tears and saliva. The drop diameters, D, studied range from the micro- to the macro- scale (1 microm -- 2 mm). In this work, the effect of evaporation conditions, solution chemistry, and heat transfer within the droplet on pattern formation is examined. In micro-scale deposits of aqueous lysozyme solutions (1 microm < D < 50 microm), the protein motion and the resulting dried residue morphology are highly influenced by the decreased evaporation time of the drop. The effect of electrolytes on pattern formation is also investigated by adding varying concentrations NaCl to the lysozyme solutions. Finally, a novel pattern recognition program is described and implemented which classifies deposit images by their solution chemistries. The results presented in this PhD dissertation provide insight into the evaporative behavior and pattern formation in droplets of simplified model biological fluids (aqueous lysozyme + NaCl). The patterns that form depend sensitively on the evaporation conditions, characteristic time and length scales, and the physiochemical properties of the solutions. The patterns are unique, dependent on solution chemistry, and may therefore act as a "fingerprint" in identifying fluid properties.

Phase Equilibrium Investigation on 2-Phenylethanol in Binary and Ternary Systems: Influence of High Pressure on Density and Solid-Liquid Phase Equilibrium.

PubMed

Domańska, Urszula; Królikowski, Marek; Wlazło, Michał; Więckowski, Mikołaj

2018-05-30

Ionic liquids (ILs) are important new solvents proposed for applications in different separation processes. Herein, an idea of possible use of high pressure in a general strategy of production of 2-phenylethanol (PEA) is discussed. In this work, we present the influence of pressure on the density in binary systems of {1-hexyl-1-methylpyrrolidynium bis{(trifluoromethyl)sulfonyl}imide, [HMPYR][NTf 2 ], or 1-dodecyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}imide, [DoMIM][NTf 2 ] + PEA} in a wide range of temperatures (298.15-348.15 K) and pressures (0.1-40 MPa). The densities at ambient and high pressures are measured to present the physicochemical properties of the ILs used in the process of separation of PEA from aqueous phase. The Tait equation was used for the correlation of density of one-component and two-component systems as a function of mole fraction, temperature, and pressure. The influence of pressure is not significant. These systems exhibit mainly negative molar excess volumes, V E . The solid-liquid phase equilibrium (SLE) of [DoMIM][NTf 2 ] in PEA at atmospheric pressure was measured and compared to the SLE high-pressure results. Additionally, the ternary liquid-liquid phase equilibrium (LLE) at ambient pressure in the {[DoMIM][NTf 2 ] (1) + PEA (2) + water (3)} at temperature T = 308.15 K was investigated. The solubility of water in the [DoMIM][NTf 2 ] is quite high in comparison with that measured by us earlier for ILs ( x 3 = 0.403) at T = 308.15 K, which results in not very successful average selectivity of extraction of PEA from the aqueous phase. The [DoMIM][NTf 2 ] has shown strong interaction with PEA without the immiscibility region. The ternary system revealed Treybal's type phase equilibrium in which two partially miscible binaries ([DoMIM][NTf 2 ] + water) and (PEA + water) exist. From the results of LLE in the ternary system, the selectivity and the solute distribution ratio of separation of water/PEA were calculated and compared to the results obtained for the ILs measured earlier by us. The popular NRTL model was used to correlate the experimental tie-lines in ternary LLE. These results may help in a new technological project of "in situ" extraction of PEA from aqueous phase during the biosynthesis.

Chemical interactions of aluminum with aqueous silica at 25 degrees Celsius

USGS Publications Warehouse

Hem, John David; Roberson, C.E.; Lind, Carol J.; Polxer, W.L.

1973-01-01

Solutions containing from 10 -5 to 10 -2 moles per liter of aluminum and dissolved silica in various ratios were aged at pH levels between 4 and 10 at 25?C. A colloidal amorphous product having the composition of halloysite was produced in most solutions. It had a consistent and reversible equilibrium solubility equivalent to a standard free energy of formation of -8974 ? 1.0 kcal per mole for the formula A12Si2O5(OH)4. Some aging times were longer than 4 years, but most solutions gave consistent solubilities after only a few months of aging. Where silica concentrations were below about 10 -4 molar, microcrystalline gibbsite was formed below pH 6.0 and crystalline bayerite above pH 7.0, but only after much longer aging than was required for crystallization in silica-free solutions. Electron micrographs and diffraction patterns of the synthesized material indicate some crystallinity in the aluminosilicate, but no X-ray diffraction patterns could be obtained even in the material aged 4 years. Solubility relationships for solutions containing fluoride as well as silica and aluminum are explainable by using cryolite stabilities determined in previous work. Aluminum contents of 51 samples of water analyzed for other purposes are in reasonable agreement with the assumption of equilibrium with amorphous clay mineral species similar to the material synthesized in this work. Solubility calculations are summarized graphically for solutions of ionic strength of 0.01 and 0.10.

Metal-organic complexes in geochemical processes: temperature dependence of the standard thermodynamic properties of aqueous complexes between metal cations and dicarboxylate ligands

NASA Astrophysics Data System (ADS)

Prapaipong, Panjai; Shock, Everett L.; Koretsky, Carla M.

1999-10-01

By combining results from regression and correlation methods, standard state thermodynamic properties for aqueous complexes between metal cations and divalent organic acid ligands (oxalate, malonate, succinate, glutarate, and adipate) are evaluated and applied to geochemical processes. Regression of experimental standard-state equilibrium constants with the revised Helgeson-Kirkham-Flowers (HKF) equation of state yields standard partial molal entropies (S¯°) of aqueous metal-organic complexes, which allow determination of thermodynamic properties of the complexes at elevated temperatures. In cases where S¯° is not available from either regression or calorimetric measurement, the values of S¯° can be estimated from a linear correlation between standard partial molal entropies of association (ΔS¯°r) and standard partial molal entropies of aqueous cations (S¯°M). The correlation is independent of cation charge, which makes it possible to predict S¯° for complexes between divalent organic acids and numerous metal cations. Similarly, correlations between standard Gibbs free energies of association of metal-organic complexes (ΔḠ°r) and Gibbs free energies of formation (ΔḠ°f) for divalent metal cations allow estimates of standard-state equilibrium constants where experimental data are not available. These correlations are found to be a function of ligand structure and cation charge. Predicted equilibrium constants for dicarboxylate complexes of numerous cations were included with those for inorganic and other organic complexes to study the effects of dicarboxylate complexes on the speciation of metals and organic acids in oil-field brines. Relatively low concentrations of oxalic and malonic acids affect the speciation of cations more than similar concentrations of succinic, glutaric, and adipic acids. However, the extent to which metal-dicarboxylate complexes contribute to the speciation of dissolved metals depends on the type of dicarboxylic acid ligand; relative concentration of inorganic, mono-, and dicarboxylate ligands; and the type of metal cation. As an example, in the same solution, dicarboxylic acids have a greater influence on the speciation of Fe+2 and Mg+2 than on the speciation of Zn+2 and Mn+2.

Determining Oxygen Isotopic Fractionation between the ferrous sulfate, melanterite, and aqueous sulfate

NASA Astrophysics Data System (ADS)

Shulaker, D. Z.; Kohl, I.; Coleman, M. L.

2011-12-01

Studying regions on Earth that are analogous to Mars serve as case studies for studying astrobiology and planetary surface rock formation processes. Rio Tinto, Spain is very rich in iron sulfates, and has an environment that is possibly very similar to the former environment on Mars. Certain bacteria play significant roles in accelerating pyrite oxidation rates, the products of which contribute to the formation of ferrous sulfates, such as melanterite. During mineral crystallization in an aqueous solution, there are systematic isotopic differences between dissolved species and solid phases. Quantifying this fractionation enables isotopic analysis to be used to trace the original isotopic signature of the dissolved species. Isotope fractionation has been determined for minerals such as gypsum and epsomite, and from these results and theoretical predictions, it is expected that melanterite, a mineral potentially found on Mars, would be more enriched in oxygen-18 relative to the aqueous solution from which it crystallized.Thus, determining the oxygen-18 isotopic fractionation between melanterite and dissolved sulfate has many potential benefits for understanding surface processes on Mars and its past environment. To investigate the oxygen isotope fractionation for melanterite, acidic aqueous solutions saturated with dissolved hydrated ferrous sulfate were evaporated at 25 deg C and 40 deg C and under different conditions to induce different evaporation rates. During evaporation, the aqueous solution and crystallized melanterite were sampled at different stages. Oxygen-18 isotopic compositions were then measured. However, the fractionations observed in the experiments were opposite from predictions. At 25 deg C without enhanced evaporation, the dissolved sulfate was +5.5 per mil relative to the solid, while at 40 deg C it was +4.3 per mil. With enhanced evaporation, fractionation was +2.1 per mil, while at 40 deg C it was +3.6 per mil. In addition, at 40 deg C, evaporation rates and fractionation were larger than at 25 deg C. Because no Rayleigh fractionation was observed, this system was not in equilibrium, and was most likely dominated by kinetics. Because of the unexpected results, further research will be conducted on the oxygen isotope fractionation of melanterite.

Competitive adsorption of furfural and phenolic compounds onto activated carbon in fixed bed column.

PubMed

Sulaymon, Abbas H; Ahmed, Kawther W

2008-01-15

For a multicomponent competitive adsorption of furfural and phenolic compounds, a mathematical model was builtto describe the mass transfer kinetics in a fixed bed column with activated carbon. The effects of competitive adsorption equilibrium constant, axial dispersion, external mass transfer, and intraparticle diffusion resistance on the breakthrough curve were studied for weakly adsorbed compound (furfural) and strongly adsorbed compounds (parachlorophenol and phenol). Experiments were carried out to remove the furfural and phenolic compound from aqueous solution. The equilibrium data and intraparticle diffusion coefficients obtained from separate experiments in a batch adsorber, by fitting the experimental data with theoretical model. The results show that the mathematical model includes external mass transfer and pore diffusion using nonlinear isotherms and provides a good description of the adsorption process for furfural and phenolic compounds in a fixed bed adsorber.

Adsorption of Reactive Red M-2BE dye from water solutions by multi-walled carbon nanotubes and activated carbon.

PubMed

Machado, Fernando M; Bergmann, Carlos P; Fernandes, Thais H M; Lima, Eder C; Royer, Betina; Calvete, Tatiana; Fagan, Solange B

2011-09-15

Multi-walled carbon nanotubes and powdered activated carbon were used as adsorbents for the successful removal of Reactive Red M-2BE textile dye from aqueous solutions. The adsorbents were characterised by infrared spectroscopy, N(2) adsorption/desorption isotherms and scanning electron microscopy. The effects of pH, shaking time and temperature on adsorption capacity were studied. In the acidic pH region (pH 2.0), the adsorption of the dye was favourable using both adsorbents. The contact time to obtain equilibrium at 298K was fixed at 1h for both adsorbents. The activation energy of the adsorption process was evaluated from 298 to 323K for both adsorbents. The Avrami fractional-order kinetic model provided the best fit to the experimental data compared with pseudo-first-order or pseudo-second-order kinetic adsorption models. For Reactive Red M-2BE dye, the equilibrium data were best fitted to the Liu isotherm model. Simulated dyehouse effluents were used to check the applicability of the proposed adsorbents for effluent treatment. Copyright © 2011 Elsevier B.V. All rights reserved.

Kinetic and isotherm analyses for thorium (IV) adsorptive removal from aqueous solutions by modified magnetite nanoparticle using response surface methodology (RSM)

NASA Astrophysics Data System (ADS)

Karimi, Mohammad; Milani, Saeid Alamdar; Abolgashemi, Hossein

2016-10-01

In this study, the ability and the adsorption capacity of magnetite/aminopropyltriethoxysilane/glutaraldehyde (Fe3O4/APTES/GA) adsorbent were evaluated for the adsorption of thorium (IV) ions from aqueous solutions. The influence of the several variables such as pH (1-5), Th (IV) initial concentration (50-300 mg L-1) and adsorbent concentration (1-5 g L-1) on the Th (IV) adsorption were investigated by response surface methodology (RSM). The results showed that the highest absorption capacity (q) was 107.23 mg g-1 with respect to pH = 4.5, initial concentration of 250 mg L-1 and adsorbent concentration of 1 g L-1 for 90 min. Modeling equilibrium sorption data with the Langmuir, Freundlich and Dubinin-Radushkevich models pointed out that the results were in good agreement with Langmuir model. The experimental kinetic data were well fitted to pseudo-second-order equation with R2 = 0.9739. Also thermodynamic parameters (ΔGo, ΔHo, ΔSo) declared that the Th (IV) adsorption was endothermic and spontaneous.

Data of furfural adsorption on nano zero valent iron (NZVI) synthesized from Nettle extract.

PubMed

Fazlzadeh, Mehdi; Ansarizadeh, Mohammad; Leili, Mostafa

2018-02-01

Among various water and wastewater treatment methods, adsorption techniques are widely used to remove certain classes of pollutants due to its unique features. Thus, the aim of this data article is to synthesize zero valent iron nanoparticles (NZVI) from Nettle leaf extract by green synthesis method as an environmentally friendly technique, and to evaluate it's efficiency in the removal of furfural from aqueous solutions. The data of possible adsorption mechanism and isotherm of furfural on the synthesized adsorbent are depicted in this data article. The data acquired showed that the adsorption trend follows the pseudo-second order kinetic model and that the Langmuir isotherm was suitable for correlation of equilibrium data with the maximum adsorption capacity of 454.4 mg/g. The information of initial furfural concentration, pH, adsorbent dosage and contact time effects on the removal efficiency are presented. Considering the findings data, the developed nanoparticle from Nettle leaf extract, as a low cost adsorbent, could be considered as promising adsorbent for furfural and probably similar organic pollutants removal from aqueous solutions.

In-situ preparation of NaA zeolite/chitosan porous hybrid beads for removal of ammonium from aqueous solution.

PubMed

Yang, Kai; Zhang, Xiang; Chao, Cong; Zhang, Bing; Liu, Jindun

2014-07-17

Inorganic/organic hybrid materials play important roles in removal of contaminants from wastewater. Herein, we used the natural materials of halloysite and chitosan to prepare a new adsorbent of NaA zeolite/chitosan porous hybrid beads by in-situ hydrothermal synthesis method. SEM indicated that the porous hybrid beads were composed of 6-8 μm sized cubic NaA zeolite particles congregated together with chitosan. The adsorption behavior of NH4(+) from aqueous solution onto hybrid beads was investigated at different conditions. The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms. A maximum adsorption capacity of 47.62 mg/g at 298 K was achieved according to Langmuir model. The regenerated or reused experiments indicated that the adsorption capacity of the hybrid beads could maintain in 90% above after 10 successive adsorption-desorption cycles. The high adsorption and reusable ability implied potential application of the hybrid beads for removing NH4(+) pollutants from wastewater. Copyright © 2014 Elsevier Ltd. All rights reserved.

Adsorption isotherms and kinetics studies of malachite green on chitin hydrogels.

PubMed

Tang, Hu; Zhou, Weijie; Zhang, Lina

2012-03-30

A chitin hydrogel with concentration 3 wt% (CG3) was successfully prepared from chitin solution dissolved in 8 wt% NaOH/4 wt% urea aqueous system at low temperature by crosslinking with 5 wt% epichlorohydrin. The experimental results revealed that CG3 exhibited high efficiency to remove dye (malachite green) from aqueous solution, as a result of their microporous structure, large surface area and affinity on the dye. The equilibrium process was described well by the Langmuir isotherm model, showing a monolayer adsorption. From kinetic experiments, the adsorption process followed the pseudo-second-order kinetic model, indicating that the overall rate of dye uptake could be controlled by external mass transfer at the beginning of adsorption, while intraparticle diffusion controlled the overall rate of adsorption at a later stage. The activation energy calculated from Arrhenius equation and the result of SEM and FTIR indicated that the adsorption of malachite green on the CG3 was physical process. This work provided an attractive adsorbent for removing of the hazardous materials from wastewater. Crown Copyright © 2012. Published by Elsevier B.V. All rights reserved.

Biosorption of Pb(II) from aqueous solution by Solanum melongena leaf powder as a low-cost biosorbent prepared from agricultural waste.

PubMed

Yuvaraja, Gutha; Krishnaiah, Nettem; Subbaiah, Munagapati Venkata; Krishnaiah, Abburi

2014-02-01

Solanum melongena leaves are relatively galore and used as inexpensive material. This paper presents the characterization and evaluation of potential of S. melongena leaf powder (SMLP) for removal of Pb(II) from aqueous solution as a function of pH, biomass dosage, initial metal ion concentration, contact time and temperature. Experimental data were analyzed in terms of three kinetic models such as the pseudo-first-order, pseudo-second-order and intraparticle diffusion models and the results showed that the biosorption processes of Pb(II) followed well pseudo-second-order kinetics. Langmuir and Freundlich isotherm models were applied to describe the biosorption process. Langmuir isotherm described the equilibrium data very well, with a maximum monolayer sorption capacity of 71.42 mg/g for Pb(II) ions at 323 K. The biosorption process was spontaneous and endothermic in nature with negative ΔG° (-8.746, -8.509 and -7.983 kJ/mol) and positive value for ΔH° (3.698 kJ/mol). Copyright © 2013 Elsevier B.V. All rights reserved.

Complex Behavior of Aqueous α-Cyclodextrin Solutions. Interfacial Morphologies Resulting from Bulk Aggregation.

PubMed

Hernandez-Pascacio, Jorge; Piñeiro, Ángel; Ruso, Juan M; Hassan, Natalia; Campbell, Richard A; Campos-Terán, José; Costas, Miguel

2016-07-05

The spontaneous aggregation of α-cyclodextrin (α-CD) molecules in the bulk aqueous solution and the interactions of the resulting aggregates at the liquid/air interface have been studied at 283 K using a battery of techniques: transmission electron microscopy, dynamic light scattering, dynamic surface tensiometry, Brewster angle microscopy, neutron reflectometry, and ellipsometry. We show that α-CD molecules spontaneously form aggregates in the bulk that grow in size with time. These aggregates adsorb to the liquid/air interface with their size in the bulk determining the adsorption rate. The material that reaches the interface coalesces laterally to form two-dimensional domains on the micrometer scale with a layer thickness on the nanometer scale. These processes are affected by the ages of both the bulk and the interface. The interfacial layer formed is not in fast dynamic equilibrium with the subphase as the resulting morphology is locked in a kinetically trapped state. These results reveal a surprising complexity of the parallel physical processes taking place in the bulk and at the interface of what might have seemed initially like a simple system.

Kinetics of absorption of CO{sub 2} in concentrated aqueous methyldiethanolamine solutions in the range 296 K to 343 K

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pani, F.; Gaunand, A.; Cadours, R.

1997-03-01

The kinetics of CO{sub 2} absorption by aqueous solutions of methyl diethanol amine (MDEA) were measured in the temperature range (296--343) K and MDEA concentration range (830--4,380) mol/m{sup 3} (10--50 mass %). A thermoregulated constant interfacial area Lewis-type cell was operated by recording the pressure drop during batch absorption. The kinetic results are in agreement with a fast regime of absorption according to film theory. MDEA depletion at the interface has a significant effect on the kinetics at the CO{sub 2} pressures (100 to 200 kPa) studied in this work, especially at low temperatures and low MDEA concentrations. Considering onlymore » the reaction between CO{sub 2} and MDEA, the CO{sub 2} absorption appears as a first-order reaction with respect to MDEA. The activation energy found for the reaction between CO{sub 2} and MDEA is 45 kJ/mol, but this value depends significantly (by about 10% in the worst case) on the vapor-liquid equilibrium data used.« less

Congo red adsorption from aqueous solutions by using chitosan hydrogel beads impregnated with nonionic or anionic surfactant.

PubMed

Chatterjee, Sudipta; Lee, Dae S; Lee, Min W; Woo, Seung H

2009-09-01

The adsorption performance of CS beads impregnated with triton X-100 (TX-100) as a nonionic surfactant and sodium dodecyl sulfate (SDS) as an anionic surfactant was investigated for the removal of anionic dye (congo red) from aqueous solution. While the adsorption capacity of CS/TX-100 beads was enhanced at all concentrations of TX-100 (0.005-0.1%), the increase in the concentration of SDS above 0.01% in the CS/SDS beads gradually reduced the adsorption capacity of the beads. Equilibrium adsorption isotherm data indicated a good fit to the Sips isotherm model and a heterogeneous adsorption process. The Sips maximum adsorption capacity in dry weight of the CS/TX-100 beads was 378.79 mg/g and 318.47 mg/g for the CS/SDS beads, higher than the 223.25mg/g of the CS beads. Modification of CS beads by impregnation with nonionic surfactant, or even anionic surfactant, at low concentrations is a possible way to enhance adsorption of anionic dye.

Benzene carboxylic acid derivatized graphene oxide nanosheets on natural zeolites as effective adsorbents for cationic dye removal.

PubMed

Yu, Yang; Murthy, Bandaru N; Shapter, Joseph G; Constantopoulos, Kristina T; Voelcker, Nicolas H; Ellis, Amanda V

2013-09-15

Graphene oxide (GO) nanosheets were grafted to acid-treated natural clinoptilolite-rich zeolite powders followed by a coupling reaction with a diazonium salt (4-carboxybenzenediazoniumtetrafluoroborate) to the GO surface. Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and thermogravimetric analysis (TGA) revealed successful grafting of GO nanosheets onto the zeolite surface. The application of the adsorbents for the adsorption of rhodamine B from aqueous solutions was then demonstrated. After reaching adsorption equilibrium the maximum adsorption capacities were shown to be 50.25, 55.56 and 67.56 mg g(-1) for pristine natural zeolite, GO grafted zeolite (GO-zeolite) and benzene carboxylic acid derivatized GO-zeolite powders, respectively. The adsorption behavior was fitted to a Langmuir isotherm and shown to follow a pseudo-second-order reaction model. Further, a relationship between surface functional groups, pH and adsorption efficiency was established. Results indicate that benzene carboxylic acid derivatized GO-zeolite powders are environmentally favorable adsorbents for the removal of cationic dyes from aqueous solutions. Copyright © 2013 Elsevier B.V. All rights reserved.

Kinetics, isothermal and thermodynamics studies of electrocoagulation removal of basic dye rhodamine B from aqueous solution using steel electrodes

NASA Astrophysics Data System (ADS)

Adeogun, Abideen Idowu; Balakrishnan, Ramesh Babu

2017-07-01

Electrocoagulation was used for the removal of basic dye rhodamine B from aqueous solution, and the process was carried out in a batch electrochemical cell with steel electrodes in monopolar connection. The effects of some important parameters such as current density, pH, temperature and initial dye concentration, on the process, were investigated. Equilibrium was attained after 10 min at 30 °C. Pseudo-first-order, pseudo-second-order, Elovich and Avrami kinetic models were used to test the experimental data in order to elucidate the kinetic adsorption process; pseudo-first-order and Avrami models best fitted the data. Experimental data were analysed using six model equations: Langmuir, Freudlinch, Redlich-Peterson, Temkin, Dubinin-Radushkevich and Sips isotherms and it was found that the data fitted well with Sips isotherm model. The study showed that the process depends on current density, temperature, pH and initial dye concentration. The calculated thermodynamics parameters (Δ G°, Δ H° and Δ S°) indicated that the process is spontaneous and endothermic in nature.

Contact ion pair formation between hard acids and soft bases in aqueous solutions observed with 2DIR spectroscopy.

PubMed

Sun, Zheng; Zhang, Wenkai; Ji, Minbiao; Hartsock, Robert; Gaffney, Kelly J

2013-12-12

The interaction of charged species in aqueous solution has important implications for chemical, biological, and environmental processes. We have used 2DIR spectroscopy to study the equilibrium dynamics of thiocyanate chemical exchange between free ion (NCS(-)) and contact ion pair configurations (MNCS(+)), where M(2+) = Mg(2+) or Ca(2+). Detailed studies of the influence of anion concentration and anion speciation show that the chemical exchange observed with the 2DIR measurements results from NCS(-) exchanging with other anion species in the first solvation shell surrounding Mg(2+) or Ca(2+). The presence of chemical exchange in the 2DIR spectra provides an indirect, but robust, determinant of contact ion pair formation. We observe preferential contact ion pair formation between soft Lewis base anions and hard Lewis acid cations. This observation cannot be easily reconciled with Pearson's acid-base concept or Collins' Law of Matching Water Affinities. The anions that form contact ion pairs also correspond to the ions with an affinity for water and protein surfaces, so similar physical and chemical properties may control these distinct phenomena.

Competitive adsorption of Pb2+ and Zn2+ ions from aqueous solutions by modified coal fly ash

NASA Astrophysics Data System (ADS)

Astuti, Widi; Martiani, Wulan; Any Ismawati Khair, N.

2017-03-01

Coal fly ash (CFA), which is a solid waste generated in large amounts worldwide, is mainly composed of some oxides having high crystallinity, including quartz (SiO2) and mullite (3Al2O3 2SiO2), and unburned carbon as a mesopore material that enables it to act as a dual site adsorbent. To decrease the crystallinity, CFA was modified by sodium hydroxide treatment. The modified fly ash (MFA) contains lower amount of Si and Al and has a higher specific surface area than the untreated fly ash (CFA). The objective of this study is to investigate the competitive adsorption of Pb2+ and Zn2+ from aqueous solutions by CFA and MFA. The effect of pH, contact time and initial concentration was investigated. Effective pH for Pb2+ and Zn2+ removal was 4. A greater percentage of Pb2+ and Zn2+ was removed with a decrease in the initial concentration of Pb2+ and Zn2+. Quasi-equilibrium reached in 240 min.

Adsorption of dimethyl trisulfide from aqueous solution on a low-cost adsorbent: thermally activated pinecone

NASA Astrophysics Data System (ADS)

Shang, Jingge; He, Wei; Fan, Chengxin

2015-01-01

Thermally activated pinecone (TAP) was used for the adsorption of dimethyl trisulfide (DMTS) from aqueous solutions, which was proved to be the main odorous in algae-caused black bloom. The effects of adsorbent dosage, adsorbate concentration and contact time on DMTS biosorption were studied. The TAP produced at 600°C exhibited a relatively high surface area (519.69 m2/g) and excellent adsorption capacity. The results show that the adsorption of DMTS was initially fast and that the equilibrium time was 6 h. Higher initial DMTS concentrations led to lower removal percentages but higher adsorption capacity. The removal percentage of DMTS increased and the adsorption capacity of TAP decreased with an increase in adsorbent dosage. The adsorption process conforms well to a pseudo-second-order kinetics model. The adsorption of DMTS is more appropriately described by the Freundlich isotherm ( R 2 =0.996 1) than by the Langmuir isotherm ( R 2 =0.916 9). The results demonstrate that TAP could be an attractive low-cost adsorbent for removing DMTS from water.

An experimental study of the solubility and speciation of tantalum in fluoride-bearing aqueous solutions at elevated temperature

DOE PAGES

Timofeev, Alexander; Migdisov, Art. A.; Williams-Jones, A. E.

2016-10-27

Here, the solubility of Ta 2O 5 (solid) and the speciation of tantalum in HF-bearing aqueous solutions have been determined at temperatures of 100-250 °C and vapour-saturated water pressure. Tantalum is transported as the species Ta(OH) 5 0 at low HF concentration and pH ~1-3. At higher HF concentration, tantalum mobility is controlled by the species TaF 3(OH) 3- and TaF 5; the presence of TaF 5 0 is only evident at ≤150 °C. Equilibrium constants range from -17.4 ± 0.45 to -16.4 ± 0.12 for the formation of Ta(OH) 5 from crystalline Ta 2O 5 and from -8.24 ±more » 0.64 to -8.55 ± 0.68 for the formation of TaF 3(OH) 3- at 100 and 250 °C, respectively. For TaF 5 0, they were determined to be 0.13 at 100 °C and -0.35 at 150 °C.« less

The effects of the macrotetralide actin antibiotics on the equilibrium extraction of alkali metal salts into organic solvents.

PubMed

Eisenman, G; Ciani, S; Szabo, G

1969-12-01

In order to clarify the mechanism by which neutral molecules such as the macrotetralide actin antibiotics make phospholipid bilayer membranes selectively permeable to cations, we have studied, both theoretically and experimentally, the extraction by these antibiotics of cations from aqueous solutions into organic solvents. The experiments involve merely shaking an organic solvent phase containing the antibiotic with aqueous solutions containing various cationic salts of a lipid-soluble colored anion. The intensity of color of the organic phase is then measured spectrophotometrically to indicate how much salt has been extracted. From such measurements of the equilibrium extraction of picrate and dinitrophenolate salts of Li, Na, K, Rb, Cs, and NH4 into n-hexane, dichloromethane, and hexane-dichloromethane mixtures, we have verified that the chemical reactions are as simple as previously postulated, at least for nonactin, monactin, dinactin, and trinactin. The equilibrium constant for the extraction of each cation by a given macrotetralide actin antibiotic was also found to be measurable with sufficient precision for meaningful differences among the members of this series of antibiotics to be detected. It is noteworthy that the ratios of selectivities among the various cations were discovered to be characteristic of a given antibiotic and to be completely independent of the solvent used. This finding and others reported here indicate that the size and shape of the complex formed between the macrotetralide and a given cation is the same, regardless of the species of cation bound. For such "isosteric" complexes, notable simplifications of the theory become possible which enable us to predict not only the electrical properties of a membrane made of the same solvent and having the thinness of the phospholipid bilayer but also, and more importantly, the electrical properties of the phospholipid bilayer membrane itself. These predictions will be compared with experimental data for phospholipid bilayer membranes in the accompanying paper.

Synthesis and characterization of oleic acid surface modified magnetic iron oxide nanoparticles by using biocompatible w/o microemulsion for heavy metal removal

NASA Astrophysics Data System (ADS)

Rose, Laili Che; Suhaimi, Hamdan; Mamat, Mazidah; Lik, Thang Zhe

2017-09-01

Oleic acid modified magnetic iron oxide nanoparticles (OA-MIONs) was prepared for removal of Cu2+ ion from aqueous solution. OA-MIONs was prepared by W/O microemulsion template which composed of mixed non-ionic surfactants and 1-hexanol as emulsifier. The effect of weight ratio of the constituent of microemulsion template on the physical and chemical properties of OA-MIONs was studied by characterization using Fourier transform infrared (FT-IR), scanning electron microscopy (SEM) and X-ray powder diffraction (XRD) analysis. FT-IR spectra showed that all templates shared similar chemical structure with slight difference in the peak intensity. Scanning electron micrograph illustrated that the OA-MIONs synthesized via template with the lowest weight ratio of emulsifier to heptane had a more regular spherical shape and was well-distributed. XRD had confirmed that the identity of synthesized OA-MIONs was Fe3O4. Based on the characterization result, the template with lowest weight ratio of emulsifier to heptane was chosen for the heavy metal adsorption study. The adsorption capacity OA-MIONs as a function of pH, contact time and adsorbent dosage were studied. The adsorption process reached equilibrium for 90 minutes and successfully adsorbed 43% of Cu2+ ion from aqueous solution. The adsorption behavior was well described by Langmuir isotherm. The maximum adsorption capacity was determined and found to be 555.56 mg/g. The value of Langmuir equilibrium parameter, RL was found between 0 and 1, suggested that a favorable monolayer adsorption process had taken out.

Removing uranium (VI) from aqueous solution with insoluble humic acid derived from leonardite.

PubMed

Meng, Fande; Yuan, Guodong; Larson, Steven L; Ballard, John H; Waggoner, Charles A; Arslan, Zikri; Han, Fengxiang X

2017-12-01

The occurrence of uranium (U) and depleted uranium (DU)-contaminated wastes from anthropogenic activities is an important environmental problem. Insoluble humic acid derived from leonardite (L-HA) was investigated as a potential adsorbent for immobilizing U in the environment. The effect of initial pH, contact time, U concentration, and temperature on U(VI) adsorption onto L-HA was assessed. The U(VI) adsorption was pH-dependent and achieved equilibrium in 2 h. It could be well described with pseudo-second-order model, indicating that U(VI) adsorption onto L-HA involved chemisorption. The U(VI) adsorption mass increased with increasing temperature with maximum adsorption capacities of 91, 112 and 120 mg g -1 at 298, 308 and 318 K, respectively. The adsorption reaction was spontaneous and endothermic. We explored the processes of U(VI) desorption from the L-HA-U complex through batch desorption experiments in 1 mM NaNO 3 and in artificial seawater. The desorption process could be well described by pseudo-first-order model and reached equilibrium in 3 h. L-HA possessed a high propensity to adsorb U(VI). Once adsorbed, the release of U(VI) from L-HA-U complex was minimal in both 1 mM NaNO 3 and artificial seawater (0.06% and 0.40%, respectively). Being abundant, inexpensive, and safe, L-HA has good potential for use as a U adsorbent from aqueous solution or immobilizing U in soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

User's guide to PHREEQC (Version 2) : a computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations

USGS Publications Warehouse

Parkhurst, David L.; Appelo, C.A.J.

1999-01-01

PHREEQC version 2 is a computer program written in the C programming language that is designed to perform a wide variety of low-temperature aqueous geochemical calculations. PHREEQC is based on an ion-association aqueous model and has capabilities for (1) speciation and saturation-index calculations; (2) batch-reaction and one-dimensional (1D) transport calculations involving reversible reactions, which include aqueous, mineral, gas, solid-solution, surface-complexation, and ion-exchange equilibria, and irreversible reactions, which include specified mole transfers of reactants, kinetically controlled reactions, mixing of solutions, and temperature changes; and (3) inverse modeling, which finds sets of mineral and gas mole transfers that account for differences in composition between waters, within specified compositional uncertainty limits.New features in PHREEQC version 2 relative to version 1 include capabilities to simulate dispersion (or diffusion) and stagnant zones in 1D-transport calculations, to model kinetic reactions with user-defined rate expressions, to model the formation or dissolution of ideal, multicomponent or nonideal, binary solid solutions, to model fixed-volume gas phases in addition to fixed-pressure gas phases, to allow the number of surface or exchange sites to vary with the dissolution or precipitation of minerals or kinetic reactants, to include isotope mole balances in inverse modeling calculations, to automatically use multiple sets of convergence parameters, to print user-defined quantities to the primary output file and (or) to a file suitable for importation into a spreadsheet, and to define solution compositions in a format more compatible with spreadsheet programs. This report presents the equations that are the basis for chemical equilibrium, kinetic, transport, and inverse-modeling calculations in PHREEQC; describes the input for the program; and presents examples that demonstrate most of the program's capabilities.

Synthesis, characterization and application of Lagerstroemia speciosa embedded magnetic nanoparticle for Cr(VI) adsorption from aqueous solution.

PubMed

Srivastava, Shalini; Agrawal, Shashi Bhushan; Mondal, Monoj Kumar

2017-05-01

Lagerstroemia speciosa bark (LB) embedded magnetic nanoparticles were prepared by co-precipitation of Fe 2+ and Fe 3+ salt solution with ammonia and LB for Cr(VI) removal from aqueous solution. The native LB, magnetic nanoparticle (MNP), L. speciosa embedded magnetic nanoparticle (MNPLB) and Cr(VI) adsorbed MNPLB particles were characterized by SEM-EDX, TEM, BET-surface area, FT-IR, XRD and TGA methods. TEM analysis confirmed nearly spherical shape of MNP with an average diameter of 8.76nm and the surface modification did not result in the phase change of MNP as established by XRD analysis, while led to the formation of secondary particles of MNPLB with diameter of 18.54nm. Characterization results revealed covalent binding between the hydroxyl group of MNP and carboxyl group of LB particles and further confirmed its physico-chemical nature favorable for Cr(VI) adsorption. The Cr(VI) adsorption on to MNPLB particle as an adsorbent was tested under different contact time, initial Cr(VI) concentration, adsorbent dose, initial pH, temperature and agitation speed. The results of the equilibrium and kinetics of adsorption were well described by Langmuir isotherm and pseudo-second-order model, respectively. The thermodynamic parameters suggest spontaneous and endothermic nature of Cr(VI) adsorption onto MNPLB. The maximum adsorption capacity for MNPLB was calculated to be 434.78mg/g and these particles even after Cr(VI) adsorption were collected effortlessly from the aqueous solution by a magnet. The desorption of Cr(VI)-adsorbed MNPLB was found to be more than 93.72% with spent MNPLB depicting eleven successive adsorption-desorption cycles. Copyright © 2016. Published by Elsevier B.V.

pH-Dependent Liquid-Liquid Phase Separation of Highly Supersaturated Solutions of Weakly Basic Drugs.

PubMed

Indulkar, Anura S; Box, Karl J; Taylor, Robert; Ruiz, Rebeca; Taylor, Lynne S

2015-07-06

Supersaturated solutions of poorly aqueous soluble drugs can be formed both in vivo and in vitro. For example, increases in pH during gastrointestinal transit can decrease the aqueous solubility of weakly basic drugs resulting in supersaturation, in particular when exiting the acidic stomach environment. Recently, it has been observed that highly supersaturated solutions of drugs with low aqueous solubility can undergo liquid-liquid phase separation (LLPS) prior to crystallization, forming a turbid solution such that the concentration of the drug in the continuous solution phase corresponds to the amorphous solubility while the colloidal phase is composed of a disordered drug-rich phase. Although it is well established that the equilibrium solubility of crystalline weakly basic drugs follows the Henderson-Hasselbalch relationship, the impact of pH on the LLPS phenomenon or the amorphous solubility has not been explored. In this work, the LLPS concentration of three weakly basic compounds-clotrimazole, nicardipine, and atazanavir-was determined as a function of pH using three different methods and was compared to the predicted amorphous solubility, which was calculated from the pH-dependent crystalline solubility and by estimating the free energy difference between the amorphous and crystalline forms. It was observed that, similar to crystalline solubility, the experimental amorphous solubility at any pH follows the Henderson-Hasselbalch relation and can be predicted if the amorphous solubility of the free base is known. Excellent agreement between the LLPS concentration and the predicted amorphous solubility was observed. Dissolution studies of amorphous drugs showed that the solution concentration can reach the corresponding LLPS concentration at that pH. Solid-state analysis of the precipitated material confirmed the amorphous nature. This work provides insight into the pH-dependent precipitation behavior of poorly water-soluble compounds and provides a fundamental basis with which to understand the performance of supersaturating dosage forms.

Isotherm-Based Thermodynamic Models for Solute Activities of Organic Acids with Consideration of Partial Dissociation.

PubMed

Nandy, Lucy; Ohm, Peter B; Dutcher, Cari S

2016-06-23

Organic acids make up a significant fraction of the organic mass in atmospheric aerosol particles. The calculation of gas-liquid-solid equilibrium partitioning of the organic acid is therefore critical for accurate determination of atmospheric aerosol physicochemical properties and processes such as new particle formation and activation to cloud condensation nuclei. Previously, an adsorption isotherm-based statistical thermodynamic model was developed for capturing solute concentration-activity relationships for multicomponent aqueous solutions over the entire concentration range (Dutcher et al. J. Phys. Chem. C/A 2011, 2012, 2013), with model parameters for energies of adsorption successfully related to dipole-dipole electrostatic forces in solute-solvent and solvent-solvent interactions for both electrolytes and organics (Ohm et al. J. Phys. Chem. A 2015). However, careful attention is needed for weakly dissociating semivolatile organic acids. Dicarboxylic acids, such as malonic acid and glutaric acid are treated here as a mixture of nondissociated organic solute (HA) and dissociated solute (H(+) + A(-)). It was found that the apparent dissociation was greater than that predicted by known dissociation constants alone, emphasizing the effect of dissociation on osmotic and activity coefficient predictions. To avoid additional parametrization from the mixture approach, an expression was used to relate the Debye-Hückel hard-core collision diameter to the adjustable solute-solvent intermolecular distance. An improved reference state treatment for electrolyte-organic aqueous mixtures, such as that observed here with partial dissociation, has also been proposed. This work results in predictive correlations for estimation of organic acid and water activities for which there is little or no activity data.

Selective biosorption of lanthanide (La, Eu, Yb) ions by Pseudomonas aeruginosa

DOE Office of Scientific and Technical Information (OSTI.GOV)

Texier, A.C.; Andres, Y.; Cloirec, P. le

1999-02-01

The ability of Pseudomonas aeruginosa to adsorb selectively La{sup 3+}, Eu{sup 3+}, and Yb{sup 3+} from aqueous solution was investigated. The lanthanide biosorption equilibrium obeyed the Brunauer-Emmett-Teller isotherm model, indicating multilayer adsorption. Determined levels of maximum adsorption capacities were 397 {micro}mol/g for lanthanum, 290 {micro}mol/g for europium and 326 {micro}mol/g for ytterbium. The results indicated that there were about 100 preferential sites for lanthanum per g of dry biomass. Experiments with mixed-cation solutions showed that the sequence of preferential biosorption was Eu{sup 3+} = Yb{sup 3+} > La{sup 3+}. Biomass dried at 37 and 70 C showed the same selectivemore » behavior as wet biomass. Inert microbial biomass dried at 37 C appeared to be the most efficient form for experimental use. The uptake of lanthanide by P. aeruginosa cells was not affected by the presence of sodium, potassium, calcium, chloride, sulfate and nitrate ions. Aluminum was a strong inhibitor of lanthanide ions biosorption. 87% of the total Al{sup 3+} was removed from the 3 mM solution, whereas only 8%, 20% and 3% of the total La{sup 3+}, Eu{sup 3+}, and Yb{sup 3+}, respectively, were sorbed from 3 mM solutions. The results suggested that cells of Pseudomonas aeruginosa may find promising applications for removal and separation of lanthanide ions from aqueous effluents.« less

User's guide to PHREEQC, a computer program for speciation, reaction-path, advective-transport, and inverse geochemical calculations

USGS Publications Warehouse

Parkhurst, D.L.

1995-01-01

PHREEQC is a computer program written in the C pwgranuning language that is designed to perform a wide variety of aqueous geochemical calculations. PHREEQC is based on an ion-association aqueous model and has capabilities for (1) speciation and saturation-index calculations, (2) reaction-path and advective-transport calculations involving specified irreversible reactions, mixing of solutions, mineral and gas equilibria surface-complex-ation reactions, and ion-exchange reactions, and (3) inverse modeling, which finds sets of mineral and gas mole transfers that account for composition differences between waters, within specified compositional uncertainties. PHREEQC is derived from the Fortran program PHREEQE, but it has been completely rewritten in C with the addition many new capabilities. New features include the capabilities to use redox couples to distribute redox elements among their valence states in speciation calculations; to model ion-exchange and surface-compiexation reactions; to model reactions with a fixed-pressure, multicomponent gas phase (that is, a gas bubble); to calculate the mass of water in the aqueous phase during reaction and transport calculations; to keep track of the moles of minerals present in the solid phases and determine antomaticaHy the thermodynamically stable phase assemblage; to simulate advective transport in combination with PHREEQC's reaction-modeling capability; and to make inverse modeling calculations that allow for uncertainties in the analytical data. The user interface is improved through the use of a simplified approach to redox reactions, which includes explicit mole-balance equations for hydrogen and oxygen; the use of a revised input that is modular and completely free format; and the use of mineral names and standard chemical symbolism rather than index numbers. The use of (2 eliminates nearly all limitations on army sizes, including numbers of elements, aqueous species, solutions, phases, and lengths of character strings. A new equation solver that optimizes a set of equalities subject to both equality and inequality constraints is used to determine the thermodynamically stable set of phases in equilibrium with a solution. A more complete Newton-Raphson formulation, master-species switching, and scaling of the algebraic equations reduce the number of failures of the nunmrical method in PHREEQC relative to PHREEQE. This report presents the equations that are the basis for chemical equilibrium and inverse-modeling calculations in PHREEQC, describes the input for the program, and presents twelve examples that demonstrate most of the program's capabilities.

Model for capping of membrane receptors based on boundary surface effects

PubMed Central

Gershon, N. D.

1978-01-01

Crosslinking of membrane surface receptors may lead to their segregation into patches and then into a single large aggregate at one pole of the cell. This process is called capping. Here, a novel explanation of such a process is presented in which the membrane is viewed as a supersaturated solution of receptors in the lipid bilayer and the adjacent two aqueous layers. Without a crosslinking agent, a patch of receptors that is less than a certain size cannot stay in equilibrium with the solution and thus should dissolve. Patches greater than a certain size are stable and can, in principle, grow by the precipitation of the remaining dissolved receptors from the supersaturated solution. The task of the crosslinking molecules is to form such stable patches. These considerations are based on a qualitative thermodynamic calculation that takes into account the existence of a boundary tension in a patch (in analogy to the surface tension of a droplet). Thermodynamically, these systems should cap spontaneously after the patches have reached a certain size. But, in practice, such a process can be very slow. A suspension of patches may stay practically stable. The ways in which a cell may abolish this metastable equilibrium and thus achieve capping are considered and possible effects of capping inhibitors are discussed. PMID:274724

Ammonium removal from aqueous solutions by using natural Chinese (Chende) zeolite as adsorbent.

PubMed

Huang, Haiming; Xiao, Xianming; Yan, Bo; Yang, Liping

2010-03-15

This paper presents a study of the removal of ammonium ion from aqueous solutions using natural Chinese (Chende) zeolite. A series of experiments was conducted to examine the effects of solution pH, particle size, contact time, adsorbent dosage, and the presence of other cation- and anion species on ammonium removal. The findings indicated that these parameters named had a significant effect on the removal of ammonium by the zeolite. The effect of other cations on the removal of ammonium followed the order of preference Na(+)>K(+)>Ca(2+)>Mg(2+) at identical mass concentrations, and the effect of the presence of individual anions followed the order of preference carbonate>chloride>sulfate>phosphate at identical mass concentrations of ammonium ions. Kinetic analysis showed that the adsorption of ammonium on zeolite at different ranges of particle size well followed the pseudo-second-order model and followed the intra-particle diffusion model only during the initial 60 min of the adsorption process. Equilibrium isotherm data was fitted to the linear Langmuir- and Freundlich models with the latter model providing the better description of the process (R(2)=0.991-0.997) compared to the former (R(2)=0.902-0.989). (c) 2009 Elsevier B.V. All rights reserved.

Simultaneous adsorption of Cd²⁺ and BPA on amphoteric surfactant activated montmorillonite.

PubMed

Liu, Chongmin; Wu, Pingxiao; Zhu, Yajie; Tran, Lytuong

2016-02-01

The study mainly investigated the simultaneous adsorption of bisphenol A (BPA) and Cd(2+) from aqueous solution on octadecane-betaine modified montmorillonite (BS-Mt). The characteristics of the obtained materials were analyzed by X-ray diffraction (XRD), Fourier-transform infrared (FTIR), Specific surface area (BET) and Scanning electron microscopy/Energy disperse spectroscopy (SEM/EDS), confirming that BS-18 was successfully introduced into Mt. Also, factors including initial solution pH, initial Cd(2+)/BPA concentration, contact time and adsorbent dosage on the adsorption processes were shown to be crucial for Cd(2+) adsorption, whereas had negligible effects on BPA adsorption. In this study, we found that pseudo-second-order model fitted well with the adsorption kinetic studies for both Cd(2+) and BPA with an equilibrium time of 24 h. The Cd(2+) and BPA adsorption isotherm could be well described by Freundlich model and Langmuir model, respectively. On the basis of kinetic models, the maximum adsorption capacity of Cd(2+) in aqueous solution was slightly enhanced after modification, indicating that Cd(2+) adsorption on BS-Mt was mainly attributed to direct electrostatic attraction and the chelate reaction, while the dramatic enhancement of maximum adsorption capacity for BPA was due to the hydrophobic interaction. Copyright © 2015 Elsevier Ltd. All rights reserved.

Removal of inorganic mercury from aquatic environments by multi-walled carbon nanotubes.

PubMed

Yaghmaeian, Kamyar; Khosravi Mashizi, Reza; Nasseri, Simin; Mahvi, Amir Hossein; Alimohammadi, Mahmood; Nazmara, Shahrokh

2015-01-01

Mercury is considered as a toxic heavy metal in aquatic environments due to accumulation in bodies of living organisms. Exposure to mercury may lead to different toxic effects in humans including damages to kidneys and nervous system. Multi-walled carbon nanotubes (MWCNTs) were selected as sorbent to remove mercury from aqueous solution using batch technique. ICP instrument was used to determine the amount of mercury in solution. Moreover, pH, contact time and initial concentration of mercury were studied to determine the influence of these parameters on the adsorption conditions. Results indicate that the adsorption strongly depended on pH and the best pH for adsorption is about 7. The rate of adsorption process initially was rapid but it was gradually reduced with increasing of contact time and reached the equilibrium after 120 min. In addition, more than 85 % of initial concentration of 0.1 mg/l was removed at 0.5 g/l concentration of sorbent and contact time of 120 min. Meanwhile, the adsorption process followed the pseudo second-order model and the adsorption isotherms could be described by both the Freundlich and the Langmuir models. This study showed that MWCNTs can effectively remove inorganic mercury from aqueous solutions as adsorbent.

Sorption behavior of nano-TiO2 for the removal of selenium ions from aqueous solution.

PubMed

Zhang, Lei; Liu, Na; Yang, Lijun; Lin, Qing

2009-10-30

Titanium dioxide nanoparticles were employed for the sorption of selenium ions from aqueous solution. The process was studied in detail by varying the sorption time, pH, and temperature. The sorption was found to be fast, and to reach equilibrium basically within 5.0 min. The sorption has been optimized with respect to the pH, maximum sorption has been achieved from solution of pH 2-6. Sorbed Se(IV) and Se(VI) were desorbed with 2.0 mL 0.1 mol L(-1) NaOH. The kinetics and thermodynamics of the sorption of Se(IV) onto nano-TiO2 have been studied. The kinetic experimental data properly correlate with the second-order kinetic model (k(2)=0.69 g mg(-1) min(-1), 293 K). The overall rate process appears to be influenced by both boundary layer diffusion and intraparticle diffusion. The sorption data could be well interpreted by the Langmuir sorption isotherm. The mean energy of adsorption (14.46 kJ mol(-1)) was calculated from the Dubinin-Radushkevich (D-R) adsorption isotherm at room temperature. The thermodynamic parameters for the sorption were also determined, and the DeltaH(0) and DeltaG(0) values indicate exothermic behavior.

Metal ion removal from aqueous solution using physic seed hull.

PubMed

Mohammad, Masita; Maitra, Saikat; Ahmad, Naveed; Bustam, Azmi; Sen, T K; Dutta, Binay K

2010-07-15

The potential of physic seed hull (PSH), Jantropha curcas L. as an adsorbent for the removal of Cd(2+) and Zn(2+) metal ions from aqueous solution has been investigated. It has been found that the amount of adsorption for both Cd(2+) and Zn(2+) increased with the increase in initial metal ions concentration, contact time, temperature, adsorbent dosage and the solution pH (in acidic range), but decreased with the increase in the particle size of the adsorbent. The adsorption process for both metal ions on PSH consists of three stages-a rapid initial adsorption followed by a period of slower uptake of metal ions and virtually no uptake at the final stage. The kinetics of metal ions adsorption on PSH followed a pseudo-second-order model. The adsorption equilibrium data were fitted in the three adsorption isotherms-Freundlich, Langmuir and Dubinin-Radushkevich isotherms. The data best fit in the Langmuir isotherm indication monolayer chemisorption of the metal ions. The adsorption capacity of PSH for both Zn(2+) and Cd(2+) was found to be comparable with other available adsorbents. About 36-47% of the adsorbed metal could be leached out of the loaded PSH using 0.1M HCl as the eluting medium. 2010 Elsevier B.V. All rights reserved.

Development of a new adsorbent from agro-industrial waste and its potential use in endocrine disruptor compound removal.

PubMed

Rovani, Suzimara; Censi, Monique T; Pedrotti, Sidnei L; Lima, Eder C; Cataluña, Renato; Fernandes, Andreia N

2014-04-30

A new activated carbon (AC) material was prepared by pyrolysis of a mixture of coffee grounds, eucalyptus sawdust, calcium hydroxide and soybean oil at 800°C. This material was used as adsorbent for the removal of the endocrine disruptor compounds 17β-estradiol (E2) and 17α-ethinylestradiol (EE2) from aqueous solutions. The carbon material was characterized by scanning electron microscopy (SEM), infrared spectroscopy (FTIR), N2 adsorption/desorption curves and point of zero charge (pHPZC). Variables including the initial pH of the adsorbate solutions, adsorbent masses and contact time were optimized. The optimum range of initial pH for removal of endocrine disruptor compounds (EDC) was 2.0-11.0. The kinetics of adsorption were investigated using general order, pseudo first-order and pseudo-second order kinetic models. The Sips isotherm model gave the best fits of the equilibrium data (298K). The maximum amounts of E2 and EE2 removed at 298K were 7.584 (E2) and 7.883mgg(-1) (EE2) using the AC as adsorbent. The carbon adsorbent was employed in SPE (solid phase extraction) of E2 and EE2 from aqueous solutions. Copyright © 2014 Elsevier B.V. All rights reserved.

Biosorption of copper by marine algae Gelidium and algal composite material in a packed bed column.

PubMed

Vilar, Vítor J P; Botelho, Cidália M S; Loureiro, José M; Boaventura, Rui A R

2008-09-01

Marine algae Gelidium and algal composite material were investigated for the continuous removal of Cu(II) from aqueous solution in a packed bed column. The biosorption behaviour was studied during one sorption-desorption cycle of Cu(II) in the flow through column fed with 50 and 25 mg l(-1) of Cu(II) in aqueous solution, at pH 5.3, leading to a maximum uptake capacity of approximately 13 and 3 mg g(-1), respectively, for algae Gelidium and composite material. The breakthrough time decreases as the inlet copper concentration increases, for the same flow rate. The pH of the effluent decreases over the breakthrough time of copper ions, which indicates that ion exchange is one of the mechanisms involved in the biosorption process. Temperature has little influence on the metal uptake capacity and the increase of the ionic strength reduces the sorption capacity, decreasing the breakthrough time. Desorption using 0.1M HNO(3) solution was 100% effective. After two consecutive sorption-desorption cycles no changes in the uptake capacity of the composite material were observed. A mass transfer model including film and intraparticle resistances, and the equilibrium relationship, for adsorption and desorption, was successfully applied for the simulation of the biosorption column performance.

A spectrophotometric study of the formation and deprotonation of thioarsenite species in aqueous solution at 22 °C

NASA Astrophysics Data System (ADS)

Zakaznova-Herzog, Valentina P.; Seward, Terry M.

2012-04-01

The ionization constants of thioarsenous acid have been determined at 22 °C by measuring the ultraviolet and visible spectra of thioarsenite species in dilute, aqueous sulfide solutions having S/As = 4.18, As = 1.1 × 10-4 mol/dm3 and pH ≈ 6-10.4. No oxidized species such as arsenate, thioarsenate or polysulfides were detected in the experimental solutions. The equilibrium constants for the thioarsenous acid ionization reactions were obtained from a principal component analysis treatment of the spectra and are as follows: H3AsS3=H+H2AsS3- for which pKa1=3.77 (±0.15) H2-AsS32-=H+H2AsS3- for which pKa2=6.53 (±0.08) HAsS32-=H+AsS33- for which pKa3=9.29 (±0.08) The pKa’s for the oxythioarsenous ionization reactions have also been estimated by analogy with those for the end member arsenous and thioarsenous acids. The data emphasize the important role of the simple arsenic(III) thioanions in defining the transport and redox chemistry of arsenic in sulfide-containing natural waters.

MONITORING THE SPECIATION OF AQUEOUS FREE CHLORINE FROM PH 1-12 WITH RAMAN SPECTROSCOPY TO DETERMINE THE IDENTITY OF THE POTENT LOW-PH OXIDANT

EPA Science Inventory

The speciation of aqueous free chlorine above pH 5 is a well-understood equilibrium of H2O + HOCl (equilibrium) OCl- + H3O+ with a pKa of 7.5. However, the identity of another very potent oxidant present at low pH (below 5) has been attributed by some researchers to Cl2 (aq), a...

Aqueous electrolytes for redox flow battery systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Tianbiao; Li, Bin; Wei, Xiaoliang

An aqueous redox flow battery system includes an aqueous catholyte and an aqueous anolyte. The aqueous catholyte may comprise (i) an optionally substituted thiourea or a nitroxyl radical compound and (ii) a catholyte aqueous supporting solution. The aqueous anolyte may comprise (i) metal cations or a viologen compound and (ii) an anolyte aqueous supporting solution. The catholyte aqueous supporting solution and the anolyte aqueous supporting solution independently may comprise (i) a proton source, (ii) a halide source, or (iii) a proton source and a halide source.

Ultrasonic-assisted synthesis of novel nanocomposite of poly(vinyl alcohol) and amino-modified MCM-41: A green adsorbent for Cd(II) removal.

PubMed

Soltani, Roozbeh; Dinari, Mohammad; Mohammadnezhad, Gholamhossein

2018-01-01

Amino-modified MCM-41/poly(vinyl alcohol) nanocomposite (M-MCM-41/PVOH NC) was developed for the adsorption of Cd(II) from aqueous media. M-MCM-41/PVOH NC was prepared through ultrasonic-assisted and simple blending procedure with economical and environmentally friendly polymer. The as-prepared adsorbent was characterized by FT-IR, TEM, FE-SEM and TGA. The contact time, solution pH and initial concentration of Cd(II) were found to affect the adsorption of Cd(II) from aqueous media. Kinetic studies were carried out and pseudo-first-order (PFO), pseudo-second-order (PSO), Elovich, and intra-particle diffusion (IPD) reaction kinetic models were examined. The kinetic results revealed that the adsorption of Cd(II) onto M-MCM-41/PVOH NC followed PSO kinetic model and is a chemical adsorption. The equilibrium adsorption data were evaluated by different isotherms viz. Langmuir, Freundlich, and Dubinin Radushkevich (D-R) equations. The equilibrium data fitted better with the Langmuir isotherm and the maximum adsorption capacity of M-MCM-41/PVOH NC at 298K was calculated to be 46.73mgg -1 for Cd(II) on a typical saturated monomolecular layer with a fixed number of localized adsorption sites. Copyright © 2017 Elsevier B.V. All rights reserved.

Defluoridation using biomimetically synthesized nano zirconium chitosan composite: kinetic and equilibrium studies.

PubMed

Prasad, Kumar Suranjit; Amin, Yesha; Selvaraj, Kaliaperumal

2014-07-15

The present study reports a novel approach for synthesis of Zr nanoparticles using aqueous extract of Aloe vera. Resulting nanoparticles were embedded into chitosan biopolymer and termed as CNZr composite. The composite was subjected to detailed adsorption studies for removal of fluoride from aqueous solution. The synthesized Zr nanoparticles showed UV-vis absorption peak at 420nm. TEM result showed the formation of polydispersed, nanoparticles ranging from 18nm to 42nm. SAED and XRD analysis suggested an fcc (face centered cubic) Zr crystallites. EDAX analysis suggested that Zr was an integral component of synthesized nanoparticles. FT-IR study indicated that functional group like NH, CO, CN and CC were involved in particle formation. The adsorption of fluoride on to CNZr composite worked well at pH 7.0, where ∼99% of fluoride was found to be adsorbed on adsorbent. Langmuir isotherm model best fitted the equilibrium data since it presented higher R(2) value than Freundlich model. In comparison to pseudo-first order kinetic model, the pseudo-second order model could explain adsorption kinetic behavior of F(-) onto CNZr composite satisfactorily with a good correlation coefficient. The present study revealed that CNZr composite may work as an effective tool for removal of fluoride from contaminated water. Copyright © 2014 Elsevier B.V. All rights reserved.

Pb(II) adsorption by a novel activated carbon - alginate composite material. A kinetic and equilibrium study.

PubMed

Cataldo, Salvatore; Gianguzza, Antonio; Milea, Demetrio; Muratore, Nicola; Pettignano, Alberto

2016-11-01

The adsorption capacity of an activated carbon - calcium alginate composite material (ACAA-Ca) has been tested with the aim of developing a new and more efficient adsorbent material to remove Pb(II) ion from aqueous solution. The study was carried out at pH=5, in NaCl medium and in the ionic strength range 0.1-0.75molL -1 . Differential Pulse Anodic Stripping Voltammetry (DP-ASV) technique was used to check the amount of Pb(II) ion removed during kinetic and equilibrium experiments. Different kinetic (pseudo first order, pseudo second order and Vermuelen) and equilibrium (Langmuir and Freundlich) models were used to fit experimental data, and were statistically compared. Calcium alginate (AA-Ca) improves the adsorption capacity (q m ) of active carbon (AC) in the ACAA-Ca adsorbent material (e.g., q m =15.7 and 10.5mgg -1 at I=0.25molL -1 , for ACAA-Ca and AC, respectively). SEM-EDX and thermogravimetric (TGA) measurements were carried out in order to characterize the composite material. The results of the speciation study on the Pb(II) solution and of the characterization of the ACAA-Ca and of the pristine AA-Ca and AC were evaluated in order to explain the specific contribution of AC and AA-Ca to the adsorption of the metal ion. Copyright © 2016 Elsevier B.V. All rights reserved.

Colloidal Particle Adsorption at Water-Water Interfaces with Ultralow Interfacial Tension

NASA Astrophysics Data System (ADS)

Keal, Louis; Colosqui, Carlos E.; Tromp, R. Hans; Monteux, Cécile

2018-05-01

Using fluorescence confocal microscopy we study the adsorption of single latex microparticles at a water-water interface between demixing aqueous solutions of polymers, generally known as a water-in-water emulsion. Similar microparticles at the interface between molecular liquids have exhibited an extremely slow relaxation preventing the observation of expected equilibrium states. This phenomenon has been attributed to "long-lived" metastable states caused by significant energy barriers Δ F ˜γ Ad≫kBT induced by high interfacial tension (γ ˜10-2 N /m ) and nanoscale surface defects with characteristic areas Ad≃10 - 30 nm2 . For the studied water-water interface with ultralow surface tension (γ ˜10-4 N /m ) we are able to characterize the entire adsorption process and observe equilibrium states prescribed by a single equilibrium contact angle independent of the particle size. Notably, we observe crossovers from fast initial dynamics to slower kinetic regimes analytically predicted for large surface defects (Ad≃500 nm2). Moreover, particle trajectories reveal a position-independent damping coefficient that is unexpected given the large viscosity contrast between phases. These observations are attributed to the remarkably diffuse nature of the water-water interface and the adsorption and entanglement of polymer chains in the semidilute solutions. This work offers some first insights on the adsorption dynamics or kinetics of microparticles at water-water interfaces in biocolloidal systems.

Physical phenomena and the microgravity response

NASA Technical Reports Server (NTRS)

Todd, Paul

1989-01-01

The living biological cell is not a sack of Newtonian fluid containing systems of chemical reactions at equilibrium. It is a kinetically driven system, not a thermodynamically driven system. While the cell as a whole might be considered isothermal, at the scale of individual macromolecular events there is heat generated, and presumably sharp thermal gradients exist at the submicron level. Basic physical phenomena to be considered when exploring the cell's response to inertial acceleration include particle sedimentation, solutal convection, motility electrokinetics, cytoskeletal work, and hydrostatic pressure. Protein crystal growth experiments, for example, illustrate the profound effects of convection currents on macromolecular assembly. Reaction kinetics in the cell vary all the way from diffusion-limited to life-time limited. Transport processes vary from free diffusion, to facilitated and active transmembrane transport, to contractile-protein-driven motility, to crystalline immobilization. At least four physical states of matter exist in the cell: aqueous, non-aqueous, immiscible-aqueous, and solid. Levels of order vary from crystalline to free solution. The relative volumes of these states profoundly influence the cell's response to inertial acceleration. Such subcellular phenomena as stretch-receptor activation, microtubule re-assembly, synaptic junction formation, chemotactic receptor activation, and statolith sedimentation were studied recently with respect to both their basic mechanisms and their responsiveness to inertial acceleration. From such studies a widespread role of cytoskeletal organization is becoming apparent.

IUPAC-NIST Solubility Data Series. 100. Rare Earth Metal Fluorides in Water and Aqueous Systems. Part 3. Heavy Lanthanides (Gd–Lu)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mioduski, Tomasz; Gumiński, Cezary, E-mail: cegie@chem.uw.edu.pl; Zeng, Dewen, E-mail: dewen-zeng@hotmail.com

This is the third part of the volume devoted to solubility data for the rare earth metal (REM) fluorides in water and in aqueous ternary and multicomponent systems. It covers experimental results of trivalent fluorides of Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu (so-called heavy lanthanides), since no quantitative data on solubilities of TbF{sub 4} and YbF{sub 2} (the most stable compounds at these valencies) are available. The related literature has been covered through the end of 2014. Compilations of all available papers with the solubility data are introduced for each REM fluoride with a corresponding critical evaluation.more » Every such assessment contains a collection of all solubility results in aqueous solution, a selection of suggested solubility data, a solubility equation, and a brief discussion of the multicomponent systems. Only simple fluorides (no complexes or double salts) are treated as the input substances in this report. General features of the systems, such as nature of the equilibrium solid phases, solubility as a function of temperature, influence of ionic strength, solution pH, mixed solvent medium on the solubility, quality of the solubility results, and the solubility as a function of REM atomic number, have already been presented in Part 1 of the volume.« less

Uptake of Hypobromous Acid (HOBr) by Aqueous Sulfuric Acid Solutions: Low-Temperature Solubility and Reaction

NASA Technical Reports Server (NTRS)

Iraci, Laura T.; Michelsen, Rebecca R.; Ashbourn, Samatha F. M.; Rammer, Thomas A.; Golden, David M.

2005-01-01

Hypobromous acid (HOBr) is a key species linking inorganic bromine to the chlorine and odd hydrogen chemical families. We have measured the solubility of HOBr in 45 - 70 wt% sulfuric acid solutions representative of upper tropospheric and lower stratospheric aerosol composition. Over the temperature range 201 - 252 K, HOBr is quite soluble in sulfuric acid, with an effective Henry's law coefficient, H* = 10(exp 4) - 10(exp 7) mol/L/atm. H* is inversely dependent on temperature, with Delta H = -46.2 kJ/mol and Delta S = -106.2 J/mol/K for 55 - 70 wt% H2SO4 solutions. Our study includes temperatures which overlap both previous measurements of HOBr solubility. For uptake into aqueous 45 wt% H2SO4, the solubility can be described by log H* = 3665/T - 10.63. For 55 - 70 wt% H2SO4, log H* = 2412/T - 5.55. At temperatures colder than approx. 213 K, the solubility of HOBr in 45 wt% H2SO4 is noticeably larger than in 70 wt% H2SO4. The solubility of HOBr is comparable to that of HBr, indicating that upper tropospheric and lower stratospheric aerosols should contain equilibrium concentrations of HOBr which equal or exceed those of HBr. Our measurements indicate chemical reaction of HOBr upon uptake into aqueous sulfuric acid in the presence of other brominated gases followed by evolution of gaseous products including Br2O and Br2, particularly at 70 wt% H2SO4.

Tannin-immobilized mesoporous silica bead (BT-SiO2) as an effective adsorbent of Cr(III) in aqueous solutions.

PubMed

Huang, Xin; Liao, Xuepin; Shi, Bi

2010-01-15

This study describes a new approach for the preparation of tannin-immobilized adsorbent by using mesoporous silica bead as the supporting matrix. Bayberry tannin-immobilized mesoporous silica bead (BT-SiO2) was characterized by powder X-ray diffraction to verify the crystallinity, field-emission scanning electron microscopy to observe the surface morphology, and surface area and porosity analyzer to measure the mesoporous porous structure. Subsequently, the adsorption experiments to Cr(III) were applied to evaluate the adsorption performances of BT-SiO2. It was found that the adsorption of Cr(III) onto BT-SiO2 was pH-dependent, and the maximum adsorption capacity was obtained in the pH range of 5.0-5.5. The adsorption capacity was 1.30 mmol g(-1) at 303 K and pH 5.5 when the initial concentration of Cr(III) was 2.0 mmol L(-1). Based on proton nuclear magnetic resonance (HNMR) analyses, the adsorption mechanism of Cr(III) on BT-SiO2 was proved to be a chelating interaction. The adsorption kinetic data can be well described using pseudo-first-order model and the equilibrium data can be well fitted by the Langmuir isothermal model. Importantly, no bayberry tannin was leached out during the adsorption process and BT-SiO2 can simultaneously remove coexisting metal ions from aqueous solutions. In conclusion, this study provides a new strategy for the preparation of tannin-immobilized adsorbents that are highly effective in removal of heavy metals from aqueous solutions.

Effects of pressure on aqueous chemical equilibria at subzero temperatures with applications to Europa

USGS Publications Warehouse

Marion, G.M.; Kargel, J.S.; Catling, D.C.; Jakubowski, S.D.

2005-01-01

Pressure plays a critical role in controlling aqueous geochemical processes in deep oceans and deep ice. The putative ocean of Europa could have pressures of 1200 bars or higher on the seafloor, a pressure not dissimilar to the deepest ocean basin on Earth (the Mariana Trench at 1100 bars of pressure). At such high pressures, chemical thermodynamic relations need to explicitly consider pressure. A number of papers have addressed the role of pressure on equilibrium constants, activity coefficients, and the activity of water. None of these models deal, however, with processes at subzero temperatures, which may be important in cold environments on Earth and other planetary bodies. The objectives of this work were to (1) incorporate a pressure dependence into an existing geochemical model parameterized for subzero temperatures (FREZCHEM), (2) validate the model, and (3) simulate pressure-dependent processes on Europa. As part of objective 1, we examined two models for quantifying the volumetric properties of liquid water at subzero temperatures: one model is based on the measured properties of supercooled water, and the other model is based on the properties of liquid water in equilibrium with ice. The relative effect of pressure on solution properties falls in the order: equilibrium constants(K) > activity coefficients (??) > activity of water (aw). The errors (%) in our model associated with these properties, however, fall in the order: ?? > K > aw. The transposition between K and ?? is due to a more accurate model for estimating K than for estimating ??. Only activity coefficients are likely to be significantly in error. However, even in this case, the errors are likely to be only in the range of 2 to 5% up to 1000 bars of pressure. Evidence based on the pressure/temperature melting of ice and salt solution densities argue in favor of the equilibrium water model, which depends on extrapolations, for characterizing the properties of liquid water in electrolyte solutions at subzero temperatures, rather than the supercooled water model. Model-derived estimates of mixed salt solution densities and chemical equilibria as a function of pressure are in reasonably good agreement with experimental measurements. To demonstrate the usefulness of this low-temperature, high-pressure model, we examined two hypothetical cases for Europa. Case 1 dealt with the ice cover of Europa, where we asked the question: How far above the putative ocean in the ice layer could we expect to find thermodynamically stable brine pockets that could serve as habitats for life? For a hypothetical nonconvecting 20 km icy shell, this potential life zone only extends 2.8 km into the icy shell before the eutectic is reached. For the case of a nonconvecting icy shell, the cold surface of Europa precludes stable aqueous phases (habitats for life) anywhere near the surface. Case 2 compared chemical equilibria at 1 bar (based on previous work) with a more realistic 1460 bars of pressure at the base of a 100 km Europan ocean. A pressure of 1460 bars, compared to 1 bar, caused a 12 K decrease in the temperature at which ice first formed and a 11 K increase in the temperature at which MgSO4. 12H2O first formed. Remarkably, there was only a 1.2 K decrease in the eutectic temperatures between 1 and 1460 bars of pressure. Chemical systems and their response to pressure depend, ultimately, on the volumetric properties of individual constituents, which makes every system response highly individualistic. Copyright ?? 2005 Elsevier Ltd.

Recovery of Pyruvic Acid using Tri-n-butylamine Dissolved in Non-Toxic Diluent (Rice Bran Oil)

NASA Astrophysics Data System (ADS)

Pal, Dharm; Keshav, Amit

2016-04-01

An attempt has been made to investigate the effectiveness of the vegetable oil based biocompatible solvent for the separation of pyruvic acid from fermentation broth, by using rice bran oil as natural, non-toxic diluent. Reactive extraction of pyruvic acid (0.1-0.5 k mol/m3) from aqueous solutions has been studied using tri-n-butylamine (TBA; 10-70 %) as an extractant dissolved in non toxic rice bran oil at T = 30 ± 1 °C. Results were presented in terms of distribution coefficient (Kd), extraction efficiency (E %), loading ratio (Z), and complexation constant (\\varphi_{α β }). Extraction equilibrium was interpreted using mass action modeling approach. Based on the extent of loading (Z < 0.5) only (1:1), pyruvic acid: TBA complex was proposed. Equilibrium complexation constant was evaluated to 1.22 m3/k mol. Results obtained are useful in understanding the extraction mechanism.

Methylene blue adsorption on graphene oxide/calcium alginate composites.

PubMed

Li, Yanhui; Du, Qiuju; Liu, Tonghao; Sun, Jiankun; Wang, Yonghao; Wu, Shaoling; Wang, Zonghua; Xia, Yanzhi; Xia, Linhua

2013-06-05

Graphene oxide has been used as an adsorbent in wastewater treatment. However, the dispersibility in aqueous solution and the biotoxicity to human cells of graphene oxide limits its practical application in environmental protection. In this research, a novel environmental friendly adsorbent, calcium alginate immobilized graphene oxide composites was prepared. The effects of pH, contact time, temperature and dosage on the adsorption properties of methylene blue onto calcium alginate immobilized graphene oxide composites were investigated. The equilibrium adsorption data were described by the Langmuir and Freundlich isotherms. The maximum adsorption capacity obtained from Langmuir isotherm equation was 181.81 mg/g. The pseudo-first order, pseudo-second order, and intraparticle diffusion equation were used to evaluate the kinetic data. Thermodynamic analysis of equilibriums indicated that the adsorption reaction of methylene blue onto calcium alginate immobilized graphene oxide composites was exothermic and spontaneous in nature. Copyright © 2013 Elsevier Ltd. All rights reserved.

Solubility of methanol in low-temperature aqueous sulfuric acid and implications for atmospheric particle composition

NASA Technical Reports Server (NTRS)

Iraci, Laura T.; Essin, Andrew M.; Golden, David M.; Hipskind, R. Stephen (Technical Monitor)

2001-01-01

Using traditional Knudsen cell techniques, we find well-behaved Henry's law uptake of methanol in aqueous 45 - 70 wt% H2SO4 solutions at temperatures between 197 and 231 K. Solubility of methanol increases with decreasing temperature and increasing acidity, with an effective Henry's law coefficient ranging from 10(exp 5) - 10(exp 8) M/atm. Equilibrium uptake of methanol into sulfuric acid aerosol particles in the upper troposphere and lower stratosphere will not appreciably alter gas-phase concentrations of methanol. The observed room temperature reaction between methanol and sulfuric acid is too slow to provide a sink for gaseous methanol at the temperatures of the upper troposphere and lower stratosphere. It is also too slow to produce sufficient quantities of soluble reaction products to explain the large amount of unidentified organic material seen in particles of the upper troposphere.

Solubility of carbon dioxide in aqueous mixtures of alkanolamines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dawodu, O.F.; Meisen, A.

1994-07-01

The solubility of CO[sub 2] in water + N-methyldiethanolamine + monoethanolamine (MDEA + MEA) and water + N-methyldiethanolamine + diethanolamine (MDEA + DEA) are reported at two compositions of 3.4 M MDEA + 0.8 M MEA or DEA and 2.1 M MDEA + 2.1 M MEA or DEA at temperatures from 70 to 180 C and CO[sub 2] partial pressures from 100 to 3,850 kPa. The solubility of CO[sub 2] in the blends decreased with an increase in temperature but increased with an increase in CO[sub 2] partial pressure. At low partial pressures of CO[sub 2] and the same totalmore » amine concentration, the equilibrium CO[sub 2] loadings were in the order MDEA + MEA > MDEA + DEA > MDEA. However, at high CO[sub 2] partial pressures, the equilibrium CO[sub 2] loadings in the MDEA solutions were higher than those of the MDEA + MEA and MDEA + DEA blends of equal molar strengths due to the stoichiometric loading limitations of MEA and DEA. The nonadditivity of the equilibrium loadings for single amine systems highlights the need for independent measurements on amine blends.« less

Response surface methodology for cadmium biosorption on Pseudomonas aeruginosa.

PubMed

Ahmady-Asbchin, Salman

2016-01-01

In this research the effects of various physicochemical factors on Cd(2+) biosorption such as initial metal concentration, pH and contact exposure time were studied. This study has shown a Cd(2+) biosorption, equilibrium time of about 5 min for Pseudomonas aeruginosa and the adsorption equilibrium data were well described by Langmuir equation. The maximum capacity for biosorption has been extrapolated to 0.56 mmol.g(-1) for P. aeruginosa. The thermodynamic properties ΔG(0), ΔH(0), and ΔS(0) of Cd(2+) for biosorption were analyzed by the equilibrium constant value obtained from experimented data at different temperatures. The results show that biosorption of Cd(2+) by P. aeruginosa are endothermic and spontaneous with ΔH value of 36.35 J.mol(-1). By response surface methodology, the quadratic model has adequately described the experimental data based on the adjusted determination coefficient (R(2) = 0.98). The optimum conditions for maximum uptake onto the biosorbent were established at 0.5 g.l(-1) biosorbent concentration, pH 6 for the aqueous solution, and a temperature of 30 °C.

Physical and chemical interactions at the interface between atmospheric pressure plasmas and aqueous solutions

NASA Astrophysics Data System (ADS)

Lindsay, Alexander; Byrns, Brandon; Knappe, Detlef; Graves, David; Shannon, Steven

2014-10-01

Transport and reactions of charged species, neutrals, and photons at the interface between plasmas and liquids must be better quantified. The work presented here combines theoretical and experimental investigations of conditions in the gas and liquid phases in proximity to the interface for various discharges. OES is used to determine rotational and vibrational temperatures of OH, NO, and N2+; the relationship between these temperatures that characterize the distribution of internal energy states and gas and electron kinetic temperatures is considered. The deviation of OH rotational states from equilibrium under high humidity conditions is also presented. In contradiction with findings of other groups, high energy rotational states appear to become underpopulated with increasing humidity. In the aqueous phase, concentrations of longer-lived species such as nitrate, nitrite, hydrogen peroxide, and ozone are determined using ion chromatography and colorimetric methods. Spin-traps and electron paramagnetic resonance (EPR) are investigated for characterization of short-lived aqueous radicals like OH, O2-, NO, and ONOO-. Finally, experimental results are compared to a numerical model which couples transport and reactions within and between the bulk gas and liquid phases.

Diode laser differential absorption spectrometry for measurements of some parameters of condensed media.

PubMed

Liger, V V; Bolshov, M A; Kuritsyn, Yu A; Krivtsun, V M; Zybin, A V; Niemax, K

2007-04-01

A method of diode laser differential absorption spectrometry (DLDAS) is proposed. The method is based on the detection of absorption spectra variations caused by the changes of a parameter of a condensed media (temperature, composition of the components of a mixture, pH, etc.). Some simple theoretical background of the proposed technique is presented. The potentialities of the method are demonstrated in the experiments on remote contactless measurement of the temperature of aqueous solutions and measurement of the deviations of the composition of a mixture of dyes from the equilibrium state.

Experimental investigation of the phase equilibria in the carbon dioxide-propane-3 M MDEA system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jou, F.Y.; Mather, A.E.; Otto, F.D.

1995-07-01

The treating of liquefied petroleum gas (LPG) to remove carbon dioxide and hydrogen sulfide using aqueous alkanolamine solutions is an important aspect of gas processing. One of the amines used in the natural gas industry is methyldiethanolamine (MDEA). Measurements of the phase equilibria in the carbon dioxide-propane-3 M MDEA system have been made at 25 and 40 C at pressures up to 15.5 MPa. Vapor-liquid, liquid-liquid, and vapor-liquid-liquid equilibria were determined. The vapor-liquid equilibrium data were compared with the model of Deshmukh and Mather.

Kinetic, isotherm and thermodynamic studies of amaranth dye biosorption from aqueous solution onto water hyacinth leaves.

PubMed

Guerrero-Coronilla, Imelda; Morales-Barrera, Liliana; Cristiani-Urbina, Eliseo

2015-04-01

The present study explored the kinetics, equilibrium and thermodynamics of amaranth (acid red 27) anionic dye (AD) biosorption to water hyacinth leaves (LEC). The effect of LEC particle size, contact time, solution pH, initial AD concentration and temperature on AD biosorption was studied in batch experiments. AD biosorption increased with rising contact time and initial AD concentration, and with decreasing LEC particle size and solution pH. Pseudo-second-order chemical reaction kinetics provided the best correlation for the experimental data. Isotherm studies showed that the biosorption of AD onto LEC closely follows the Langmuir isotherm, with a maximum biosorption capacity of about 70 mg g(-1). The thermodynamic parameters confirm that AD biosorption by LEC is non-spontaneous and endothermic in nature. Results indicate that LEC is a strong biosorbent capable of effective detoxification of AD-laden wastewaters. Copyright © 2015 Elsevier Ltd. All rights reserved.

Solid-solution aqueous-solution equilibria: thermodynamic theory and representation

USGS Publications Warehouse

Glynn, P.D.; Reardon, E.J.

1990-01-01

Thorstenson and Plummer's (1977) "stoichiometric saturation' model is reviewed, and a general relation between stoichiometric saturation Kss constants and excess free energies of mixing is derived for a binary solid-solution B1-xCxA: GE = RT[ln Kss - xln(xKCA) - (l-x)ln((l-x)KBA)]. This equation allows a suitable excess free energy function, such as Guggenheim's (1937) sub-regular function, to be fitted from experimentally determined Kss constants. Solid-phase free energies and component activity-coefficients can then be determined from one or two fitted parameters and from the endmember solubility products KBA and KCA. A general form of Lippmann's (1977,1980) "solutus equation is derived from an examination of Lippmann's (1977,1980) "total solubility product' model. Lippmann's ??II or "total solubility product' variable is used to represent graphically not only thermodynamic equilibrium states and primary saturation states but also stoichiometric saturation and pure phase saturation states. -from Authors

Adsorption of Pb(II) ions from aqueous environment using eco-friendly chitosan schiff's base@Fe3O4 (CSB@Fe3O4) as an adsorbent; kinetics, isotherm and thermodynamic studies.

PubMed

Weijiang, Zhang; Yace, Zhang; Yuvaraja, Gutha; Jiao, Xu

2017-12-01

Chitosan and its derivatives can be used to modify magnetic materials to promote the adsorption properties of the magnetic materials for the removal of meal ions. In this study a novel CSB@Fe 3 O 4 was prepared, characterized by XRD, FTIR, SEM, TEM, and VSM analysis and utilized as an adsorbent material for the removal of Pb(II) ions from aqueous solution. Batch studies were performed to evaluate the influences of various experimental parameters like pH, adsorbent dosage, contact time, initial concentration, and the effect of temperature. Optimum conditions for Pb(II) removal were found to be pH 5, adsorbent dosage 0.5g and equilibrium time of 105min. The pseudo-first-order, pseudo-second-order and intraparticle diffusion models were used to analyze kinetic data. The data fit well with the second-order kinetic model. The equilibrium data were analyzed using the Langmuir, and Freundlich isotherm models. The best interpretation for the equilibrium data was given by Langmuir isotherm, and the maximum adsorption capacity was found to be 83.33mg/g for CSB@Fe 3 O 4 . The calculated thermodynamic parameters ΔG°(-9.728, -9.034 and -7.883kJ/mol for 303, 313, and 323K), ΔH° (20.39kJ/mol) and ΔS° (0.0947J/molK) showed that the adsorption of Pb(II) ions were feasible, spontaneous and endothermic in nature. Copyright © 2017 Elsevier B.V. All rights reserved.

Development of an alkaline/surfactant/polymer compositional reservoir simulator

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhuyan, D.

1989-01-01

The mathematical formulation of a generalized three-dimensional compositional reservoir simulator for high-pH chemical flooding processes is presented in this work. The model assumes local thermodynamic equilibrium with respect to both reaction chemistry and phase behavior and calculates equilibrium electrolyte and phase compositions as a function of time and position. The reaction chemistry considers aqueous electrolytic chemistry, precipitation/dissolution of minerals, ion exchange reactions on matrix surface, reaction of acidic components of crude oil with the bases in the aqueous solution and cation exchange reactions with the micelles. The simulator combines this detailed reaction chemistry associated with these processes with the extensivemore » physical and flow property modeling schemes of an existing chemical flood simulator (UTCHEM) to model the multiphase, multidimensional displacement processes. The formulation of the chemical equilibrium model is quite general and is adaptable to simulate a variety of chemical descriptions. In addition to its use in the simulation of high-pH chemical flooding processes, the model will find application in the simulation of other reactive flow problems like the ground water contamination, reinjection of produced water, chemical waste disposal, etc. in one, two or three dimensions and under multiphase flow conditions. In this work, the model is used to simulate several hypothetical cases of high-pH chemical floods, which include cases from a simple alkaline preflush of a micellar/polymer flood to surfactant enhanced alkaline-polymer flooding and the results are analyzed. Finally, a few published alkaline, alkaline-polymer and surfactant-alkaline-polymer corefloods are simulated and compared with the experimental results.« less

Molecular Dynamics Simulation of Surface Tension of NaCl Aqueous Solution at 298.15K: from Diluted to Highly Supersaturated Concentrations

NASA Astrophysics Data System (ADS)

Wang, Xiaoxiang; Chen, Chuchu; Poeschl, Ulirch; Su, Hang; Cheng, Yafang

2017-04-01

Sodium chloride (NaCl) is one of the key components of atmospheric aerosol particles. Concentration-depend surface tension of aqueous NaCl solution is essential to determine the equilibrium between droplet NaCl solution and water vapor, which is important in regards to aerosol-cloud interaction and aerosol climate effects. Although supersaturated NaCl droplets can be widely found under atmospheric conditions, the experimental determined concentration dependency of surface tension is limited up to the saturated concentration range due to technical difficulties, i.e., heterogeneous nucleation since nearly all surface tension measurement techniques requires contact of the sensor and solution surface. In this study, the surface tension of NaCl aqueous solution with solute mass fraction from 0 to 1 was calculated using molecular dynamics (MD) simulation. The surface tension increases monotonically and near linearly when mass fraction of NaCl (xNaCl) is lower than 0.265 (saturation point), which follows theoretical predictions (e.g., E-AIM, SP parameterization, and PK parameterization). Once entering into the supersaturated concentration range, the calculated surface tension starts to deviate from the near-linear extrapolation and adopts a slightly higher increasing rate until xNaCl of 0.35. We found that these two increasing phases (xNaCl 0.35) is mainly driven by the increase of excessive surface enthalpy when the solution becomes concentrated. After that, the surface tension remains almost unchanged until xNaCl of 0.52. This phenomenon is supported by the results from experiment based Differential Koehler Analyses. The stable surface tension in this concentration range is attributed to a simultaneous change of surface excess enthalpy and entropy at similar degree. When the NaCl solution is getting more concentrated than xNaCl of 0.52, the simulated surface tension regains an even faster growing momentum and shows the tendency of ultimately approaching the surface tension of molten NaCl at 298.15 K ( 148.4 mN/m by MD simulation). Energetic analyses imply that this fast increase is primarily still an excessive surface enthalpy-driven process, although concurrent fluctuation of excessive surface entropy is also expected but in a much smaller scale. Our results unfold the global landscape of concentration dependence of aqueous NaCl solution and its driven forces: a water surface tension dominated regime (xNaCl from 0 to 0.35), a transition regime (xNaCl from 0.35 to 0.52) and a molten NaCl surface tension dominated regime (xNaCl beyond 0.52).

Purification of biomaterials by phase partitioning

NASA Technical Reports Server (NTRS)

Harris, J. M.

1984-01-01

A technique which is particularly suited to microgravity environments and which is potentially more powerful than electrophoresis is phase partitioning. Phase partitioning is purification by partitioning between the two immiscible aqueous layers formed by solution of the polymers poly(ethylene glycol) and dextran in water. This technique proved to be very useful for separations in one-g but is limited for cells because the cells are more dense than the phase solutions thus tend to sediment to the bottom of the container before reaching equilibrium with the preferred phase. There are three phases to work in this area: synthesis of new polymers for affinity phase partitioning; development of automated apparatus for ground-based separations; and design of apparatus for performing simple phase partitioning space experiments, including examination of mechanisms for separating phases in the absence of gravity.

Complexation of C60 fullerene with aromatic drugs.

PubMed

Evstigneev, Maxim P; Buchelnikov, Anatoly S; Voronin, Dmitry P; Rubin, Yuriy V; Belous, Leonid F; Prylutskyy, Yuriy I; Ritter, Uwe

2013-02-25

The contributions of various physical factors to the energetics of complexation of aromatic drug molecules with C(60) fullerene are investigated in terms of the calculated magnitudes of equilibrium complexation constants and the components of the net Gibbs free energy. Models of complexation are developed taking into account the polydisperse nature of fullerene solutions in terms of the continuous or discrete (fractal) aggregation of C(60) molecules. Analysis of the energetics has shown that stabilization of the ligand-fullerene complexes in aqueous solution is mainly determined by intermolecular van der Waals interactions and, to lesser extent, by hydrophobic interactions. The results provide a physicochemical basis for a potentially new biotechnological application of fullerenes as modulators of biological activity of aromatic drugs. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Removal of anionic dye Congo red from aqueous solution by raw pine and acid-treated pine cone powder as adsorbent: equilibrium, thermodynamic, kinetics, mechanism and process design.

PubMed

Dawood, Sara; Sen, Tushar Kanti

2012-04-15

Pine cone a natural, low-cost agricultural by-product in Australia has been studied for its potential application as an adsorbent in its raw and hydrochloric acid modified form. Surface study of pine cone and treated pine cone was investigated using Fourier transform infrared (FTIR) and scanning electron microscopy (SEM). The modification process leads to increases in the specific surface area and decreases mean particle sizes of acid-treated pine cone when compared to raw pine cone biomass. Batch adsorption experiments were performed to remove anionic dye Congo red from aqueous solution. It was found that the extent of Congo red adsorption by both raw pine cone biomass and acid-treated biomass increased with initial dye concentration, contact time, temperature but decreased with increasing solution pH and amount of adsorbent of the system. Overall, kinetic studies showed that the dye adsorption process followed pseudo-second-order kinetics based on pseudo-first-order and intra-particle diffusion models. The different kinetic parameters including rate constant, half-adsorption time, and diffusion coefficient were determined at different physico-chemical conditions. Equilibrium data were best represented by Freundlich isotherm model among Langmuir and Freundlich adsorption isotherm models. It was observed that the adsorption was pH dependent and the maximum adsorption of 32.65 mg/g occurred at pH of 3.55 for an initial dye concentration of 20 ppm by raw pine cone, whereas for acid-treated pine cone the maximum adsorption of 40.19 mg/g for the same experimental conditions. Freundlich constant 'n' also indicated favourable adsorption. Thermodynamic parameters such as ∆G(0), ∆H(0), and ∆S(0) were calculated. A single-stage batch absorber design for the Congo red adsorption onto pine cone biomass also presented based on the Freundlich isotherm model equation. Copyright © 2012 Elsevier Ltd. All rights reserved.

Determination of the solubility of inorganic salts by headspace gas chromatography.

PubMed

Chai, X S; Zhu, J Y

2003-05-09

This work reports a novel method for determination of salt solubility using headspace gas chromatography. A very small amount of volatile compound (such as methanol) is added in the studied solution. Due to the molecular interaction in the solution, the vapor-liquid equilibrium (VLE) partitioning coefficient of the volatile species will change with different salt contents in the solution. Therefore, the concentration of volatile species in the vapor phase is proportional to the salt concentration in the liquid phase, which can be easily determined by headspace gas chromatography. Until the salt concentration in the solution is saturated, the concentration of volatile compound in the vapor phase will continue to increase further and a breakpoint will appear on the VLE curve. The solubility of the salts can be determined by the identification of the breakpoint. It was found that the measured solubility of sodium carbonate and sodium sulfate in aqueous solutions is slightly higher (about 6-7%) than those reported in the literature method. The present method can be easily applied to industrial solution systems.

Thermodynamic Modeling of Organic-Inorganic Aerosols with the Group-Contribution Model AIOMFAC

NASA Astrophysics Data System (ADS)

Zuend, A.; Marcolli, C.; Luo, B. P.; Peter, T.

2009-04-01

Liquid aerosol particles are - from a physicochemical viewpoint - mixtures of inorganic salts, acids, water and a large variety of organic compounds (Rogge et al., 1993; Zhang et al., 2007). Molecular interactions between these aerosol components lead to deviations from ideal thermodynamic behavior. Strong non-ideality between organics and dissolved ions may influence the aerosol phases at equilibrium by means of liquid-liquid phase separations into a mainly polar (aqueous) and a less polar (organic) phase. A number of activity models exists to successfully describe the thermodynamic equilibrium of aqueous electrolyte solutions. However, the large number of different, often multi-functional, organic compounds in mixed organic-inorganic particles is a challenging problem for the development of thermodynamic models. The group-contribution concept as introduced in the UNIFAC model by Fredenslund et al. (1975), is a practical method to handle this difficulty and to add a certain predictability for unknown organic substances. We present the group-contribution model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients), which explicitly accounts for molecular interactions between solution constituents, both organic and inorganic, to calculate activities, chemical potentials and the total Gibbs energy of mixed systems (Zuend et al., 2008). This model enables the computation of vapor-liquid (VLE), liquid-liquid (LLE) and solid-liquid (SLE) equilibria within one framework. Focusing on atmospheric applications we considered eight different cations, five anions and a wide range of alcohols/polyols as organic compounds. With AIOMFAC, the activities of the components within an aqueous electrolyte solution are very well represented up to high ionic strength. We show that the semi-empirical middle-range parametrization of direct organic-inorganic interactions in alcohol-water-salt solutions enables accurate computations of vapor-liquid and liquid-liquid equilibria. References Fredenslund, A., Jones, R. L., and Prausnitz, J. M.: Group-Contribution Estimation of Activity Coefficients in Nonideal Liquid Mixtures, AIChE J., 21, 1086-1099, 1975. Rogge, W. F., Mazurek, M. A., Hildemann, L. M., Cass, G. R., and Simoneit, B. R. T.: Quantification of Urban Organic Aerosols at a Molecular Level: Identification, Abundance and Seasonal Variation, Atmos. Environ., 27, 1309-1330, 1993. Zhang, Q. et al.: Ubiquity and dominance of oxygenated species in organic aerosols in anthropogenically influenced Northern Hemisphere midlatitudes, Geophys. Res. Lett., 34, L13 801, 2007. Zuend, A., Marcolli, C., Luo, B. P., and Peter, T.: A thermodynamic model of mixed organic-inorganic aerosols to predict activity coefficients, Atmos. Chem. Phys., 8, 4559-4593, 2008.

Characterization, dissolution and solubility of the hydroxypyromorphite-hydroxyapatite solid solution [(PbxCa1-x)5(PO4)3OH] at 25 °C and pH 2-9.

PubMed

Zhu, Yinian; Huang, Bin; Zhu, Zongqiang; Liu, Huili; Huang, Yanhua; Zhao, Xin; Liang, Meina

2016-01-01

The interaction between Ca-HAP and Pb(2+) solution can result in the formation of a hydroxyapatite-hydroxypyromorphite solid solution [(PbxCa1-x)5(PO4)3(OH)], which can greatly affect the transport and distribution of toxic Pb in water, rock and soil. Therefore, it's necessary to know the physicochemical properties of (PbxCa1-x)5(PO4)3(OH), predominantly its thermodynamic solubility and stability in aqueous solution. Nevertheless, no experiment on the dissolution and related thermodynamic data has been reported. Dissolution of the hydroxypyromorphite-hydroxyapatite solid solution [(PbxCa1-x)5(PO4)3(OH)] in aqueous solution at 25 °C was experimentally studied. The aqueous concentrations were greatly affected by the Pb/(Pb + Ca) molar ratios (XPb) of the solids. For the solids with high XPb [(Pb0.89Ca0.11)5(PO4)3OH], the aqueous Pb(2+) concentrations increased rapidly with time and reached a peak value after 240-720 h dissolution, and then decreased gradually and reached a stable state after 5040 h dissolution. For the solids with low XPb (0.00-0.80), the aqueous Pb(2+) concentrations increased quickly with time and reached a peak value after 1-12 h dissolution, and then decreased gradually and attained a stable state after 720-2160 h dissolution. The dissolution process of the solids with high XPb (0.89-1.00) was different from that of the solids with low XPb (0.00-0.80). The average K sp values were estimated to be 10(-80.77±0.20) (10(-80.57)-10(-80.96)) for hydroxypyromorphite [Pb5(PO4)3OH] and 10(-58.38±0.07) (10(-58.31)-10(-58.46)) for calcium hydroxyapatite [Ca5(PO4)3OH]. The Gibbs free energies of formation (ΔG f (o) ) were determined to be -3796.71 and -6314.63 kJ/mol, respectively. The solubility decreased with the increasing Pb/(Pb + Ca) molar ratios (XPb) of (PbxCa1‒x)5(PO4)3(OH). For the dissolution at 25 °C with an initial pH of 2.00, the experimental data plotted on the Lippmann diagram showed that the solid solution (PbxCa1-x)5(PO4)3(OH) dissolved stoichiometrically at the early stage of dissolution and moved gradually up to the Lippmann solutus curve and the saturation curve for Pb5(PO4)3OH, and then the data points moved along the Lippmann solutus curve from right to left. The Pb-rich (PbxCa1-x)5(PO4)3(OH) was in equilibrium with the Ca-rich aqueous solution. Graphical abstractLippmann diagrams for dissolution of the hydroxypyromorphite-hydroxyapatite solid solution [(PbxCa1-x)5(PO4)3OH] at 25 ˚C and an initial pH of 2.00.

Hydration and conformational equilibria of simple hydrophobic and amphiphilic solutes.

PubMed Central

Ashbaugh, H S; Kaler, E W; Paulaitis, M E

1998-01-01

We consider whether the continuum model of hydration optimized to reproduce vacuum-to-water transfer free energies simultaneously describes the hydration free energy contributions to conformational equilibria of the same solutes in water. To this end, transfer and conformational free energies of idealized hydrophobic and amphiphilic solutes in water are calculated from explicit water simulations and compared to continuum model predictions. As benchmark hydrophobic solutes, we examine the hydration of linear alkanes from methane through hexane. Amphiphilic solutes were created by adding a charge of +/-1e to a terminal methyl group of butane. We find that phenomenological continuum parameters fit to transfer free energies are significantly different from those fit to conformational free energies of our model solutes. This difference is attributed to continuum model parameters that depend on solute conformation in water, and leads to effective values for the free energy/surface area coefficient and Born radii that best describe conformational equilibrium. In light of these results, we believe that continuum models of hydration optimized to fit transfer free energies do not accurately capture the balance between hydrophobic and electrostatic contributions that determines the solute conformational state in aqueous solution. PMID:9675177

SOLVENT EXTRACTION PROCESS

DOEpatents

Jonke, A.A.

1957-10-01

In improved solvent extraction process is described for the extraction of metal values from highly dilute aqueous solutions. The process comprises contacting an aqueous solution with an organic substantially water-immiscible solvent, whereby metal values are taken up by a solvent extract phase; scrubbing the solvent extract phase with an aqueous scrubbing solution; separating an aqueous solution from the scrubbed solvent extract phase; and contacting the scrubbed solvent phase with an aqueous medium whereby the extracted metal values are removed from the solvent phase and taken up by said medium to form a strip solution containing said metal values, the aqueous scrubbing solution being a mixture of strip solution and an aqueous solution which contains mineral acids anions and is free of the metal values. The process is particularly effective for purifying uranium, where one starts with impure aqueous uranyl nitrate, extracts with tributyl phosphate dissolved in carbon tetrachloride, scrubs with aqueous nitric acid and employs water to strip the uranium from the scrubbed organic phase.

Compatibility of amino acids in ice Ih and high-pressure phases: implications for the origin of life

NASA Astrophysics Data System (ADS)

Hao, J.; Giovenco, E.; Pedreira-Segade, U.; Montagnac, G.; Daniel, I.

2017-12-01

Icy environments may have been common on the early Earth due to the faint young sun. Previous studies have proposed that the formation of large icy bodies in the early ocean could concentrate the building blocks of life in eutectic fluids and therefore facilitate the polymerization of monomers. This hypothesis is based on the untested assumption that organic molecules are virtually incompatible in ice Ih. In this study, we conducted freezing experiments to explore the partitioning behavior of selected amino acids (glycine, L-alanine, L-proline, and L-phenylalanine) between ice Ih and aqueous solutions analogous to seawater. We let ice crystals grow slowly from a few seeds in equilibrium with the solution and used Raman spectroscopy to analyze in situ the relative concentrations of amino acids in the ice and aqueous solution. During freezing, there was no precipitation of amino acid crystals, indicating that the concentrations in solution never reached their solubility limit, even when the droplet was mostly frozen. Analyses of the Raman spectra of ice and eutectic solution showed that considerable amounts of amino acids existed in the ice phase with partition coefficients ranging between 0.2 and 0.5. This study also explored the partitioning of amino acids between other phases of ice (ice VI and ice VII) and solutions at high pressures and observed similar results. These observations implied little incompatibility of amino acids in ice during the freezing of the solutions, rendering the hypothesis of a cold origin of life unwarranted. However, incorporation into ice could significantly improve the efficiency of extraterrestrial transport of small organics. Therefore, this study supports the hypothesis of extraterrestrial delivery of organic molecules in the icy comets and asteroids to the primitive Earth as suggested by an increasing number of independent observations.

Production of activated carbon from biodiesel solid residues: An alternative for hazardous metal sorption from aqueous solution.

PubMed

Ribeiro, Rita F L; Soares, Vitor C; Costa, Letícia M; Nascentes, Clésia C

2015-10-01

In this study, the potential for the sorption of Pb(2+) and Cd(2+) from aqueous solutions using HNO3-treated activated carbon (TAC) obtained from radish press cake (Raphanus sativus L.), a solid residue from biodiesel production, was investigated. Activated carbon (AC) was obtained by physical activation with CO2(g). Chemical modification with HNO3 was employed to increase the sorption capability of the AC. The sorption of Pb(2+) and Cd(2+) was studied in monometallic systems in equilibrium with different metal-ion concentrations (10-400 mg L(-1)). The experimental sorption equilibrium data were fit to the Langmuir and Freundlich isotherm models. The maximum sorption capacity (qmax) obtained for AC from the Langmuir isotherm was 45.5 mg g(-1) for Cd(2+) and 250 mg g(-1) for Pb(2+). Moreover, TAC presented qmax of 166.7 mg g(-1) (1.48 mmol g(-1)) for Cd(2+) and 500.0 mg g(-1) (2.41 mmol g(-1)) for Pb(2+)showing the effect of chemical modification. Sorption-desorption studies showed that the interaction between metals and TAC is reversible and this sorbent can be reused for several consecutive cycles. Furthermore, the sorption of Cd(2+) and Pb(2+) by TAC was not affected by the presence of competing ions. The experimental data obtained in this study indicated that this solid residue is viable for the production of sorbents that remove metals, such as cadmium and lead, from wastewaters and thereby contribute to the sustainable development of the production of biodiesel. Copyright © 2015 Elsevier Ltd. All rights reserved.

Synthesis and characterization of low-cost activated carbon prepared from Malawian baobab fruit shells by H3PO4 activation for removal of Cu(II) ions: equilibrium and kinetics studies

NASA Astrophysics Data System (ADS)

Vunain, Ephraim; Kenneth, Davie; Biswick, Timothy

2017-12-01

In this study, low-cost activated carbon (AC) prepared from baobab fruit shells by chemical activation using phosphoric acid was evaluated for the removal of Cu(II) ions from aqueous solution. The prepared activated carbon samples were characterized using N2-adsorption-desorption isotherms, SEM, FTIR, EDX and XRD analysis. The sample activated at 700 °C was chosen as our optimized sample because its physicochemical properties and BET results were similar to those of a commercial sample. The N2-adsorption-desorption results of the optimized sample revealed a BET surface area of 1089 m2/g, micropore volume of 0.3764 cm3/g, total pore volume of 0.4330 cm3/g and pore size of 1.45 nm. Operational parameters such as pH, initial copper concentration, contact time, adsorbent dosage and temperature were studied in a batch mode. Equilibrium data were obtained by testing the adsorption data using three different isotherm models: Langmuir, Freundlich and Dubinin-Radushkevish (D-R) models. It was found that the adsorption of copper correlated well with the Langmuir isotherm model with a maximum monolayer adsorption capacity of 3.0833 mg/g. The kinetics of the adsorption process was tested through pseudo-first-order and pseudo-second-order models. The pseudo-second-order kinetic model provided the best correlation for the experimental data studied. The adsorption followed chemisorption process. The study provided an effective use of baobab fruit shells as a valuable source of adsorbents for the removal of copper ions from aqueous solution. This study could add economic value to baobab fruit shells in Malawi, reduce disposal problems, and offer an economic source of AC to the AC users.

Comparison of adsorption equilibrium models and error functions for the study of sulfate removal by calcium hydroxyapatite microfibrillated cellulose composite.

PubMed

Hokkanen, Sanna; Bhatnagar, Amit; Koistinen, Ari; Kangas, Teija; Lassi, Ulla; Sillanpää, Mika

2018-04-01

In the present study, the adsorption of sulfates of sodium sulfate (Na 2 SO 4 ) and sodium lauryl sulfate (SLS) by calcium hydroxyapatite-modified microfibrillated cellulose was studied in the aqueous solution. The adsorbent was characterized using elemental analysis, Fourier transform infrared, scanning electron microscope and elemental analysis in order to gain the information on its structure and physico-chemical properties. The adsorption studies were conducted in batch mode. The effects of solution pH, contact time, the initial concentration of sulfate and the effect of competing anions were studied on the performance of synthesized adsorbent for sulfate removal. Adsorption kinetics indicated very fast adsorption rate for sulfate of both sources (Na 2 SO 4 and SLS) and the adsorption process was well described by the pseudo-second-order kinetic model. Experimental maximum adsorption capacities were found to be 34.53 mg g -1 for sulfates of SLS and 7.35 mg g -1 for sulfates of Na 2 SO 4. The equilibrium data were described by the Langmuir, Sips, Freundlich, Toth and Redlich-Peterson isotherm models using five different error functions.

Biosorption of Fe(II) and Mn(II) Ions from Aqueous Solution by Rice Husk Ash

PubMed Central

Zhao, Jiaying; Jiang, Zhao; Shan, Dexin; Lu, Yan

2014-01-01

Rice husk ash (RHA), an agricultural waste, was used as biosorbent for the removal of Iron(II) and Manganese(II) ions from aqueous solutions. The structural and morphological characteristics of RHA and its elemental compositions before and after adsorption of Fe(II) and Mn(II) were determined by scanning electron microscopic (SEM) and X-ray fluorescence (XRF) analyses. Batch experiments were carried out to determine the influence of initial pH, contact time, adsorbent dosage, and initial concentration on the removal of Fe(II) and Mn(II) ions. Langmuir, Freundlich, and Dubinin-Radushkevich (D-R) models were applied to describe the biosorption isotherm of the metal ions by RHA. The correlation coefficient (R 2) of Langmuir and Freundlich isotherm models equals 0.995 and 0.901 for Fe(II), 0.9862 and 0.8924 for Mn(II), respectively, so the Langmuir model fitted the equilibrium data better than the Freundlich isotherm model. The mean free energy values evaluated from the D-R model indicated that the biosorption of Fe(II) and Mn(II) onto RHA was physical in nature. Experimental data also showed that the biosorption processes of both metal ions complied with the pseudo-second-order kinetics. PMID:24982918

Fast microwave-assisted green synthesis of xanthan gum grafted acrylic acid for enhanced methylene blue dye removal from aqueous solution.

PubMed

Makhado, Edwin; Pandey, Sadanand; Nomngongo, Philiswa N; Ramontja, James

2017-11-15

In the present project, graft polymerization was employed to synthesis a novel adsorbent using acrylic acid (AA) and xanthan gum (XG) for cationic methylene dye (MB + ) removal from aqueous solution. The XG was rapidly grafted with acrylic acid (CH 2 =CHCOOH) under microwave heating. Fourier-transform infrared spectroscopy (FTIR), Proton Nuclear magnetic resonance spectroscopy ( 1 H NMR), scanning electron microscopy (SEM), X-ray diffraction (XRD) and Thermal gravimetric analysis (TGA) techniques were used to verify the adsorbent formed under optimized reaction conditions. Optimum reaction conditions [AA (0.4M), APS (0.05M), XG (2gL -1 ), MW power (100%), MW time (80s)] offer maximum %G and %GE of 484 and 78.3, respectively. The removal ratio of adsorbent to MB + reached to 92.8% at 100mgL -1 . Equilibrium and kinetic adsorptions of dyes were better explained by the Langmuir isotherm and pseudo second-order kinetic model respectively. The results demonstrate xanthan gum grafted polyacrylic acid (mw XG-g-PAA) absorbent had the universality for removal of dyes through the chemical adsorption mechanism. Copyright © 2017 Elsevier Ltd. All rights reserved.

Removal of Hg(II) from aqueous solution by resin loaded magnetic β-cyclodextrin bead and graphene oxide sheet: Synthesis, adsorption mechanism and separation properties.

PubMed

Cui, Limei; Wang, Yaoguang; Gao, Liang; Hu, Lihua; Wei, Qin; Du, Bin

2015-10-15

Resin loaded magnetic β-cyclodextrin bead and graphene oxide sheet (MCD-GO-R) was synthesized successfully and found to be an excellent adsorbent for Hg(II) removal. The as-prepared adsorbent was characterized by SEM, FTIR, BET, magnetization curve and zeta potential analysis respectively. Good magnetic performance made MCD-GO-R simply recover from aqueous solution at low magnetic field within 30s. And also, the rich functional groups and outstanding dispersity play an important role in the adsorption process. The maximum adsorption capacity was 88.43 mg g(-1) at 323 K and pH 7.1. The as-prepared adsorbent could perform well in a wide pH range from 4.0 to 10.0. Static adsorption experimental data showed good correlation with pseudo-second-order model and Freundlich isotherm models. It was found that the contaminant adsorption was accomplished mainly via chelation or ion exchange and come to equilibrium in only 30 min. All experimental results, especially the excellent reproducibility and resistance to ion interference, suggest that MCD-GO-R has promising applications in water treatment. Copyright © 2015 Elsevier Inc. All rights reserved.

One-step synthesized calcium phosphate-based material for the removal of alizarin S dye from aqueous solutions: isothermal, kinetics, and thermodynamics studies

NASA Astrophysics Data System (ADS)

Adeogun, Abideen Idowu; Babu, Ramesh Balakrishnan

2015-07-01

Calcium phosphate hydroxyapatite (Ca-Hap) synthesized from CaCO3 and H3PO5, it was characterized by scanning electron microscopy, Fourier transform infrared, and X-ray diffraction. The Ca-Hap was used for the removal of Alizarin Red S dye from its aqueous solution. The kinetics, equilibrium, and thermodynamic of the adsorption of the dye onto the Ca-Hap were investigated. The effects of contact time, initial dye concentration, pH as well as temperature on adsorption capacity of Ca-Hap were studied. Experimental data were analyzed using six model equations: Langmuir, Freudlinch, Redlich-Peterson, Temkin, Dubinin-Radushkevich, and Sips isotherms and it was found that the data fitted well with Sips and Dubinin-Radushkevich isotherm models. Pseudo-first-order, pseudo-second-order, Elovic, and Avrami kinetic models were used to test the experimental data in order to elucidate the kinetic adsorption process and it was found that pseudo-second-order model best fit the data. The calculated thermodynamics parameters (∆G°, ∆H° and ∆S°) indicated that the process is spontaneous and endothermic in nature.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Takeshita, Kenji

A mathematical model to predict the extraction behavior of metal ion between a polymer gel and an aqueous solution was proposed. It consists of the Flory-Huggins formula for evaluating thermodynamically the physico-chemical properties of polymer gel, the modified Stokes-Einstein equation to evaluate the mass transfer rate of metal ion into polymer gel and the equation to evaluate the extraction equilibrium. The extraction of lanthanide elements, Nd(III), Sm(III) and Gd(III), from an aqueous solution containing nitrate ion was carried out by the use of SDB (styrene-divinylbenzene copolymer) gel swollen with a bidentate organophosphorus compound, CMP (dihexyl-N,N-diethylcarbamoylmethylpohosphonate). The binary extraction and themore » effect of the crosslinking degree of SDB gel on the extraction rate were examined. These experimental results were in agreement with the predictions calculated by the proposed model. It was confirmed that the extraction behavior of lanthanide ions into the SDB gel was predicted accurately, when the physico-chemical properties of SDB gel, such as the affinity between SDB and CMP ({chi}) and the crosslinking degree ({nu}{sub e}), and a coefficient defined in the modified Stokes-Einstein equation (K{sub 0}) were known. This model is available as a tool to design an extraction chromatographic process using polymer gel.« less

Adsorption isotherms and kinetics of activated carbons produced from coals of different ranks.

PubMed

Purevsuren, B; Lin, Chin-Jung; Davaajav, Y; Ariunaa, A; Batbileg, S; Avid, B; Jargalmaa, S; Huang, Yu; Liou, Sofia Ya-Hsuan

2015-01-01

Activated carbons (ACs) from six coals, ranging from low-rank lignite brown coal to high-rank stone coal, were utilized as adsorbents to remove basic methylene blue (MB) from an aqueous solution. The surface properties of the obtained ACs were characterized via thermal analysis, N2 isothermal sorption, scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and Boehm titration. As coal rank decreased, an increase in the heterogeneity of the pore structures and abundance of oxygen-containing functional groups increased MB coverage on its surface. The equilibrium data fitted well with the Langmuir model, and adsorption capacity of MB ranged from 51.8 to 344.8 mg g⁻¹. Good correlation coefficients were obtained using the intra-particle diffusion model, indicating that the adsorption of MB onto ACs is diffusion controlled. The values of the effective diffusion coefficient ranged from 0.61 × 10⁻¹⁰ to 7.1 × 10⁻¹⁰ m² s⁻¹, indicating that ACs from lower-rank coals have higher effective diffusivities. Among all the ACs obtained from selected coals, the AC from low-rank lignite brown coal was the most effective in removing MB from an aqueous solution.

Approaching behavior of a pair of spherical bubbles in quiescent liquids

NASA Astrophysics Data System (ADS)

Sanada, Toshiyuki; Kusuno, Hiroaki

2015-11-01

Some unique motions related bubble-bubble interaction, such as equilibrium distance, wake induced lift force, have been proposed by theoretical analysis or numerical simulations. These motions are different from the solid spheres like DKT model (Drafting, Kissing and Tumbling). However, there is a lack of the experimental verification. In this study, we experimentally investigated the motion of a pair of bubbles initially positioned in-line configuration in ultrapure water or an aqueous surfactant solution. The bubble motion were observed by two high speed video cameras. The bubbles Reynolds number was ranged from 50 to 300 and bubbles hold the spherical shape in this range. In ultrapure water, initially the trailing bubble deviated from the vertical line on the leading bubble owing to the wake of the leading bubble. And then, the slight difference of the bubble radius changed the relative motion. When the trailing bubble slightly larger than the leading bubble, the trailing bubble approached to the leading bubble due to it's buoyancy difference. The bubbles attracted and collided only when the bubbles rising approximately side by side configuration. In addition, we will also discuss the motion of bubbles rising in an aqueous surfactant solution.

Kinetics of removal of carbon dioxide by aqueous solutions of N,N-diethylethanolamine and piperazine.

PubMed

Konduru, Prashanti B; Vaidya, Prakash D; Kenig, Eugeny Y

2010-03-15

N,N-Diethylethanolamine (DEEA) is a very promising absorbent for CO(2) removal from gaseous streams, as it can be prepared from renewable resources. Aqueous mixtures of DEEA and piperazine (PZ) are attractive for the enhancement of CO(2) capture, due to the high CO(2) loading capacity of DEEA and high reactivity of PZ. In the present work, for the first time, the equilibrium and kinetic characteristics of the CO(2) reaction with such mixtures were considered. Kinetic data were obtained experimentally, by using a stirred cell reactor. These data were interpreted using a homogeneous activation mechanism, by which the investigated reaction was considered as a reaction between CO(2) and DEEA in parallel with the reaction of CO(2) with PZ. It is found that, in the studied range of temperatures, 298-308 K, and overall amine concentrations, 2.1-2.5 kmol/m(3), this reaction system belongs to the fast pseudo-first-order reaction regime systems. The second-order rate constant for the CO0 reaction with PZ was determined from the absorption rate measurements in the activated DEEA solutions, and its value at 303 K was found to be 24,450 m(3)/(kmol s).

Potentiality of Neopestalotiopsis clavispora ASU1 in biosorption of cadmium and zinc.

PubMed

Hassan, Sedky H A; Koutb, Mostafa; Nafady, Nivien Allam; Hassan, Elhagag Ahmed

2018-07-01

In this study, a fungal isolate was isolated from avocado fruit collected from a market in Makkah city, Saudi Arabia, and identified as Neopestalotiopsis clavispora ASU1. The biomass of Neopestalotiopsis clavispora ASU1 was used as a natural bio-sorbent for removal of Cd(II) and Zn(II) from aqueous solutions. Characterization of fungal biomass was performed using Fourier transform infrared spectroscopy, X-ray Diffractometer, and BET surface area. Different factors on Cd(II) and Zn(II) biosorption were studied to evaluate the maximum conditions for metals biosorption. The (q max ) for Cd(II) and Zn (II) by N. clavispora ASU1 calculated from the Langmuir adsorption isotherm was 185.3 ± 0.25 and 153.8 ± 0.21 mg/g, respectively. Based on r 2 , the equilibrium biosorption isotherms fitted well with Langmuir model than Freundlich isotherm. The adsorption kinetics was studied, and the biosorption followed to the pseudo-second-order model. Thus, the current study indicated that the biomass of N. clavispora ASU1 is an effective adsorbent for the removal of heavy metals from aqueous solutions. Copyright © 2018 Elsevier Ltd. All rights reserved.

Spontaneous and Flow-Driven Interfacial Phase Change: Dynamics of Microemulsion Formation at the Pore Scale.

PubMed

Tagavifar, Mohsen; Xu, Ke; Jang, Sung Hyun; Balhoff, Matthew T; Pope, Gary A

2017-11-14

The dynamic behavior of microemulsion-forming water-oil-amphiphiles mixtures is investigated in a 2.5D micromodel. The equilibrium phase behavior of such mixtures is well-understood in terms of macroscopic phase transitions. However, what is less understood and where experimental data are lacking is the coupling between the phase change and the bulk flow. Herein, we study the flow of an aqueous surfactant solution-oil mixture in porous media and analyze the dependence of phase formation and spatial phase configurations on the bulk flow rate. We find that a microemulsion forms instantaneously as a boundary layer at the initial surface of contact between the surfactant solution and oil. The boundary layer is temporally continuous because of the imposed convection. In addition to the imposed flow, we observe spontaneous pulsed Marangoni flows that drag the microemulsion and surfactant solution into the oil stream, forming large (macro)emulsion droplets. The formation of the microemulsion phase at the interface distinguishes the situation from that of the more common Marangoni flow with only two phases present. Additionally, an emulsion forms via liquid-liquid nucleation or the Ouzo effect (i.e., spontaneous emulsification) at low flow rates and via mechanical mixing at high flow rates. With regard to multiphase flow, contrary to the common belief that the microemulsion is the wetting liquid, we observe that the minor oil phase wets the solid surface. We show that a layered flow pattern is formed because of the out-of-equilibrium phase behavior at high volumetric flow rates (order of 2 m/day) where advection is much faster than the diffusive interfacial mass transfer and transverse mixing, which promote equilibrium behavior. At lower flow rates (order of 30 cm/day), however, the dynamic and equilibrium phase behaviors are well-correlated. These results clearly show that the phase change influences the macroscale flow behavior.

Insights into Supramolecular Sites Responsible for Complete Separation of Biomass-Derived Phenolics and Glucose in Metal-Organic Framework NU-1000.

PubMed

Yabushita, Mizuho; Li, Peng; Durkin, Kathleen A; Kobayashi, Hirokazu; Fukuoka, Atsushi; Farha, Omar K; Katz, Alexander

2017-05-02

The molecular origins of adsorption of lignin-derived phenolics to metal-organic framework NU-1000 are investigated from aqueous solution as well as in competitive mode with glucose present in the same aqueous mixture. A comparison of adsorption equilibrium constants (K ads ) for phenolics functionalized with either carboxylic acid or aldehyde substituents demonstrated only a slight increase (less than a factor of 6) for the former according to both experiments and calculations. This small difference in K ads between aldehyde and carboxylic-acid substituted adsorbates is consistent with the pyrene unit of NU-1000 as the adsorption site, rather than the zirconia nodes, while at saturation coverage, the adsorption capacity suggests multiple guests per pyrene. Experimental standard free energies of adsorption directly correlated with the molecular size and electronic structure calculations confirmed this direct relationship, with the pyrene units as adsorption site. The underlying origins of this relationship are grounded in noncovalent π-π interactions as being responsible for adsorption, the same interactions present in the condensed phase of the phenolics, which to a large extent govern their heat of vaporization. Thus, NU-1000 acts as a preformed aromatic cavity for driving aromatic guest adsorption from aqueous solution and does so specifically without causing detectable glucose adsorption from aqueous solution, thereby achieving complete glucose-phenolics separations. The reusability of NU-1000 during an adsorption/desorption cycle was good, even with some of the phenolic compounds with greatest affinity not easiliy removed with water and ethanol washes at room temperature. A competitive adsorption experiment gave an upper bound for K ads for glucose of at most 0.18 M -1 , which can be compared with K ads for the phenolics investigated here, which fell in the range of 443-42 639 M -1 . The actual value of K ads for glucose may be much closer to zero given the lack of observed glucose uptake with NU-1000 as adsorbent.

Theoretical study on the dimerization of Si(OH) 4 in aqueous solution and its dependence on temperature and dielectric constant

NASA Astrophysics Data System (ADS)

Tossell, J. A.

2005-01-01

Energetics for the condensation dimerization reaction of monosilicic acid: 2Si(⇒SiOH+HO have been calculated quantum mechanically, in gas-phase and aqueous solution, over a range of temperatures and dielectric constants. The calculated gas phase energy, E g, for this reaction is -6.6 kcal/mol at the very accurate composite G2 level, but the vibrational, rotational and translational contributions to the free energy in the gas-phase, ΔG VRT, sum to + 2.5 kcal/mol and the hydration free energy contribution calculated with a polarizable continuum model, ΔΔG COSMO, for a dielectric constant of 78.5, is about + 6.2 kcal/mol. Thus, the free energy change for the reaction in aqueous solution at ambient conditions is about + 2.1 kcal/mol and the equilibrium constant is ˜10 -1.5, in reasonable agreement with experiment. As T increases, ΔG VRT increases slowly. As the dielectric constant decreases (for example, under high T and P conditions in the supercritical region), ΔΔG COSMO decreases substantially. Thus, at elevated T and P, if the effective dielectric constant of the aqueous fluid is 10 or less, the reaction becomes much more favorable, consistent with recent experimental observations. The PΔV contribution to the enthalpy is also considered, but cannot be accurately determined. We have also calculated 29Si-NMR shieldings and Raman frequencies for Si(OH) 4, Si 2O 7H 6 and some other oligomeric silicates. We correctly reproduce the separation of monomer and dimer peaks observed in the 29Si-NMR spectrra at ambient T and P. The Raman spectral data are somewhat ambiguous, and the new peaks seen at high T and P could arise either from the dimer or from a 3-ring trimer, which is calculated to be highly stabilized entropically at high T.

A resolution approach of racemic phenylalanine with aqueous two-phase systems of chiral tropine ionic liquids.

PubMed

Wu, Haoran; Yao, Shun; Qian, Guofei; Yao, Tian; Song, Hang

2015-10-30

Aqueous two-phase systems (ATPS) based on tropine type chiral ionic liquids and inorganic salt solution were designed and prepared for the enantiomeric separation of racemic phenylalanine. The phase behavior of IL-based ATPS was comprehensive investigated, and phase equilibrium data were correlated by Merchuk equation. Various factors were also systematically investigated for their influence on separation efficiency. Under the appropriate conditions (0.13g/g [C8Tropine]pro, 35mg/g Cu(Ac)2, 20mg/g d,l-phenylalanine, 0.51g/g H2O and 0.30g/g K2HPO4), the enantiomeric excess value of phenylalanine in solid phase (mainly containing l-enantiomer) was 65%. Finally, the interaction mechanism was studied via 1D and 2D NMR. The results indicate that d-enantiomer of phenylalanine interacts more strongly with chiral ILs and Cu(2+) based on the chiral ion-pairs space coordination mechanism, which makes it tend to remain in the top IL-rich phase. By contrast, l-enantiomer is transferred into the solid phase. Above chiral ionic liquids aqueous two-phase systems have demonstrated obvious resolution to racemic phenylalanine and could be promising alterative resolution approach for racemic amino acids in aqueous circumstance. Copyright © 2015. Published by Elsevier B.V.

How to explain Si isotopes of chert?

NASA Astrophysics Data System (ADS)

Liu, Y.

2016-12-01

The variations of d30Si values in diagenetic chert and chert- associated BIFs over time can be used to reconstruct the environmental conditions of the early Earth, and become a hot topic in the Si isotope society. However, there are several different views of explaining the variation of d30Si values over time. Moreover, there are disputes in explaining the distribution of Si isotope in several main reservoirs in surface systems. Those disagreements are caused by lacking key Si isotope fractionation factors associated with the formation processes of chert and its altered products. There are many unexplained observations about Si isotope distributions in Earth's surface systems (Opfergelt and Delmelle, 2012). For example, the deduced Si isotope equilibrium fractionation factors by Rayleigh model at ambient temperature between clay and the solution D30Siclay-solution = -1.5 ‰ and -2.05 ‰ (Hughes et al., 2013) obviously disagree with common sense, which dictates that stiffer chemical bonds will enrich heavier isotopes, i.e., the precipitated minerals will preferentially incorporate heavy isotopes relative to aqueous H4SiO4 due to their shorter Si-O bonds. Another similar case is the fractionation between quartz and solution. Most field observations suggested that solution will be enriched with heavier Si isotope compared to quartz, conflicting to the fact that quartz is the one with much shorter Si-O bonds than aqueous H4SiO4 (ca. 1.610Å vs. 1.639Å). Here we provide equilibrium and kinetic Si isotope fractionation factors associated with the formation of amorphous quartz and other secondary minerals in polymerization, co-precipitation and adsorption processes. The adsorption processes of silica gel to Fe-hydroxides have been carefully examined. The Si isotope fractionations due to the formation of mono-dentate to quadru-dentate adsorbed Fe-Si complexes have been calculated. These data can explain well the experimental observations (e.g., Zheng et al., 2016) and provide further insights into such processes. With the knowledge of Si isotope fractionations of those processes, we can quantitatively evaluate the net Si isotope fractionation during the chert formation processes and can link the Si isotope composition of chert to that of seawater from now to early Archean.

Competitive adsorption of phenolic compounds from aqueous solution using sludge-based activated carbon.

PubMed

Mohamed, E F; Andriantsiferana, C; Wilhelm, A M; Delmas, H

2011-01-01

Preparation of activated carbon from sewage sludge is a promising approach to produce cheap and efficient adsorbent for pollutants removal as well as to dispose of sewage sludge. The first objective of this study was to investigate the physical and chemical properties (BET surface area, ash and elemental content, surface functional groups by Boehm titration and weight loss by thermogravimetric analysis) of the sludge-based activated carbon (SBAC) so as to give a basic understanding of its structure and to compare to those of two commercial activated carbons, PICA S23 and F22. The second and main objective was to evaluate the performance of SBAC for single and competitive adsorption of four substituted phenols (p-nitrophenol, p-chlorophenol, p-hydroxy benzoic acid and phenol) from their aqueous solutions. The results indicated that, despite moderate micropore and mesopore surface areas, SBAC had remarkable adsorption capacity for phenols, though less than PICA carbons. Uptake of the phenolic compound was found to be dependent on both the porosity and surface chemistry of the carbons. Furthermore, the electronegativity and the hydrophobicity of the adsorbate have significant influence on the adsorption capacity. The Langmuir and Freundlich models were used for the mathematical description of the adsorption equilibrium for single-solute isotherms. Moreover, the Langmuir-Freundlich model gave satisfactory results for describing multicomponent system isotherms. The capacity of the studied activated carbons to adsorb phenols from a multi-solute system was in the following order: p-nitrophenol > p-chlorophenol > PHBA > phenol.

PROCESS OF REMOVING PLUTONIUM VALUES FROM SOLUTION WITH GROUP IVB METAL PHOSPHO-SILICATE COMPOSITIONS

DOEpatents

Russell, E.R.; Adamson, A.W.; Schubert, J.; Boyd, G.E.

1957-10-29

A process for separating plutonium values from aqueous solutions which contain the plutonium in minute concentrations is described. These values can be removed from an aqueous solution by taking an aqueous solution containing a salt of zirconium, titanium, hafnium or thorium, adding an aqueous solution of silicate and phosphoric acid anions to the metal salt solution, and separating, washing and drying the precipitate which forms when the two solutions are mixed. The aqueous plutonium containing solution is then acidified and passed over the above described precipi-tate causing the plutonium values to be adsorbed by the precipitate.

Removal of mercury from its aqueous solution using charcoal-immobilized papain (CIP).

PubMed

Dutta, Susmita; Bhattacharyya, Aparupa; De, Parameswar; Ray, Parthasarathi; Basu, Srabanti

2009-12-30

In the present work mercury has been eradicated from its aqueous solution using papain, immobilized on activated charcoal by physical adsorption method. Operating parameters for adsorption of papain on activated charcoal like pH, amount of activated charcoal, initial concentration of papain in solution have been varied in a suitable manner for standardization of operating conditions for obtaining the best immobilized papain sample based on their specific enzymatic activity. The immobilized papain sample obtained at initial papain concentration 40.0 g/L, activated charcoal amount 0.5 g and pH 7 shows the best specific enzymatic activity. This sample has been designated as charcoal-immobilized papain (CIP) and used for further studies of mercury removal. Adsorption equilibrium data fit most satisfactorily with the Langmuir isotherm model for adsorption of papain on activated charcoal. Physicochemical characterization of CIP has been done. The removal of mercury from its simulated solution of mercuric chloride using CIP has been studied in a lab-scale batch contactor. The operating parameters viz., the initial concentration of mercury in solution, amount of CIP and pH have been varied in a prescribed manner. Maximum removal achieved in the batch study was about 99.4% at pH 7, when initial metal concentration and weight of CIP were 20.0mg/L and 0.03 g respectively. Finally, the study of desorption of mercury has been performed at different pH values for assessment of recovery process of mercury. The results thus obtained have been found to be satisfactory.

Effects of pulsed ultrasound on the adsorption of n-alkyl anionic surfactants at the gas/solution interface of cavitation bubbles.

PubMed

Yang, Limei; Sostaric, Joe Z; Rathman, James F; Kuppusamy, Periannan; Weavers, Linda K

2007-02-15

Sonolysis of argon-saturated aqueous solutions of the nonvolatile surfactants sodium dodecyl sulfate (SDS) and sodium 1-pentanesulfonate (SPSo) was investigated at three ultrasonic frequencies under both continuous wave (CW) and pulsed ultrasound. Secondary carbon-centered radicals were detected by spin trapping using 3,5-dibromo-4-nitrosobenzenesulfonic acid (DBNBS) and electron paramagnetic resonance (EPR) spectroscopy. Following sonolysis, -*CH- radicals were observed for both surfactants under both sonication modes. Under CW at 354 kHz, the maximum plateau -*CH- radical yield was higher for SPSo than for SDS, indicating that SDS, which is more surface active under equilibrium conditions, accumulates at the gas/solution interface of cavitation bubbles to a lesser degree, compared with the less surface active surfactant, SPSo. However, after sonolysis (354 kHz) under pulsed ultrasound with a pulse length of 100 ms and an interval of 500 ms, the -*CH- radical yield at the plateau concentrations was higher for SDS than for SPSo due to increased amounts of SDS accumulation on the bubble surfaces. In contrast to the findings following sonolysis at 354 kHz, sonolysis of aqueous surfactant solutions at 620 kHz and 803 kHz showed a higher -*CH- radical yield for SDS compared with SPSo under CW but lower -*CH- radical yield with increasing pulsing interval, indicating a frequency dependence on accumulation. Results indicate that pulsing the ultrasonic wave has a significant effect on the relative adsorption ability of n-alkyl surfactants at the gas/solution surface of cavitation bubbles.

Effects of the microbial siderophore DFO-B on Pb and Cd speciation in aqueous solution.

PubMed

Mishra, Bhoopesh; Haack, Elizabeth A; Maurice, Patricia A; Bunker, Bruce A

2009-01-01

This study investigates the complexation environments of aqueous Pb and Cd in the presence of the trihydroxamate microbial siderophore, desferrioxamine-B (DFO-B) as a function of pH. Complexation of aqueous Pb and Cd with DFO-B was predicted using equilibrium speciation calculation. Synchrotron-based X-ray absorption fine structure (XAFS) spectroscopy at Pb L(III) edge and Cd K edge was used to characterize Pb and Cd-DFO-B complexes at pH values predicted to best represent each of the metal-siderophore complexes. Pb was not found to be complexed measurably by DFO-B at pH 3.0, but was complexed by all three hydroxamate groups to form a totally "caged" hexadentate structure at pH 7.5-9.0. At the intermediate pH value (pH 4.8), a mixture of Pb-DFOB complexes involving binding of the metal through one and two hydroxamate groups was observed. Cd, on the other hand, remained as hydrated Cd2+ at pH 5.0, occurred as a mixture of Cd-DFOB and inorganic species at pH 8.0, and was bound by three hydroxamate groups from DFO-B at pH 9.0. Overall, the solution species observed with EXAFS were consistent with those predicted thermodynamically. However, Pb speciation at higher pH values differed from that predicted and suggests that published constants underestimate the binding constant for complexation of Pb with all three hydroxamate groups of the DFO-B ligand. This molecular-level understanding of metal-siderophore solution coordination provides physical evidence for complexes of Pb and Cd with DFO-B, and is an important first step toward understanding processes at the microbial- and/or mineral-water interface in the presence of siderophores.

Poorly crystalline hydroxyapatite: A novel adsorbent for enhanced fulvic acid removal from aqueous solution

NASA Astrophysics Data System (ADS)

Wei, Wei; Yang, Lei; Zhong, Wenhui; Cui, Jing; Wei, Zhenggui

2015-03-01

In this study, poorly crystalline hydroxyapatite (HAP) was developed as an efficient adsorbent for the removal of fulvic acid (FA) from aqueous solution. Surface functionality, crystallinity, and morphology of the synthetic adsorbent were studied by Fourier-transformation infrared (FT-IR) spectroscopy, powder X-ray diffraction (XRD) and transmission electron microscopy (TEM). The effects of various parameters such as crystallinity of adsorbent, contact time, adsorbent dosage, pH, initial adsorbate concentration, temperature, ionic strength and the presence of alkaline earth metal ions on FA adsorption were investigated. Results indicated that the nanosized HAP calcined at lower temperature was poorly crystalline (Xc = 0.23) and had better adsorption capacity for FA than those (Xc = 0.52, 0.86) calcined at higher temperature. FA removal was increased with increases of adsorbent dosage, temperature, ionic strength and the presence of alkali earth metal ions, but decreased as the pH increased. Kinetic studies showed that pseudo-second-order kinetic model better described the adsorption process. Equilibrium data were best described by Sips models, and the estimated maximum adsorption capacity of poorly crystalline HAP was 90.20 mg/g at 318 K, displaying higher efficiency for FA removal than previously reported adsorbents. FT-IR results revealed that FA adsorption over the adsorbent could be attributed to the surface complexation between the oxygen atom of functional groups of FA and calcium ions of HAP. Regeneration studies indicated that HAP could be recyclable for a long term. Findings of the present work highlight the potential for using poorly crystalline HAP nanoparticles as an effective and recyclable adsorbent for FA removal from aqueous solution.

Chemically modified Moringa oleifera seed husks as low cost adsorbent for removal of copper from aqueous solution

NASA Astrophysics Data System (ADS)

Ghafar, Faridah; Mohtar, Aminullah; Sapawe, Norzahir; Hadi, Norulakmal Nor; Salleh, Marmy Roshaidah Mohd

2017-12-01

Moringa oleifera husks (MOH) are an agricultural byproduct that may have potential as adsorbent for removal of heavy metal ions in wastewater such as copper (Cu2+). The release of Cu2+ to the environment by the mining and electroplating industries cause a major problem because it is toxic and can cause liver and kidney problems. Hence, it is important to remove copper before the wastewater can be discharged to the environment. In order to increase the adsorption capacity, the MOH was chemically modified using citric acid. The raw and modified MOH were analyzed using Fourier Transform Infra-Red (FTIR) for identification of functional groups present at the adsorbent surface. The adsorption study was carried out using the batch technique in water bath shaker investigating different parameters; adsorbent dosage (30 - 70 g/L), initial concentration of copper (30 - 150 mg/L), contact time (2 - 90 min), temperature (27 - 60 °C) at constant agitation of 100 rpm. The concentrations of copper in aqueous solution before and after the adsorption process was analyzed using Atomic Absorption Spectrum (AAS). The highest percentage removal of copper was found at 10g/L of adsorbent dosage with 30 mg/L of initial concentration and temperature 30 °C. It was also observed that the adsorption of copper by MOH was approaching to equilibrium at 60 min of reaction time. From the FTIR analysis, it was found that the MOH contains hydroxyl, carboxyl and amine groups. The high adsorption capacity of modified MOH to remove copper from aqueous solution makes it preferable and attractive alternative to commercial adsorbent.

Self-assembled three-dimensional reduced graphene oxide-based hydrogel for highly efficient and facile removal of pharmaceutical compounds from aqueous solution.

PubMed

Umbreen, Nadia; Sohni, Saima; Ahmad, Imtiaz; Khattak, Nimat Ullah; Gul, Kashif

2018-05-14

Herein, self-assembled three-dimensional reduced graphene oxide (RGO)-based hydrogels were synthesized and characterized in detail. A thorough investigation on the uptake of three widely used pharmaceutical drugs, viz. Naproxen (NPX), Ibuprofen (IBP) and Diclofenac (DFC) was carried out from aqueous solutions. To ensure the sustainability of developed hydrogel assembly, practically important parameters such as desorption, recyclability and applicability to real samples were also evaluated. Using the developed 3D hydrogels as adsorptive platforms, excellent decontamination for the above mentioned persistent pharmaceutical drugs was achieved in acidic pH with a removal efficiency in the range of 70-80%. These hydrogels showed fast adsorption kinetics and experimental findings were fitted to different kinetic models, such as pseudo-first order, pseudo-second order, intra-particle and the Elovich models in an attempt to better understand the adsorption kinetics. Furthermore, equilibrium adsorption data was fitted to the Langmuir and Freundlich models, where relatively higher R 2 values obtained in case of former one suggested that monolayer adsorption played an important part in drug uptake. Thermodynamic aspects were also studied and negative ΔG 0 values obtained indicated the spontaneous nature of adsorption process. The study was also extended to check practical utility of as-prepared hydrogels by spiking real aqueous samples with drug solution, where high % recoveries obtained for NPX, IBP and DFC were of particular importance with regard to prospective application in wastewater treatment systems. We advocate RGO-based hydrogels as environmentally benign, readily recoverable/recyclable material with excellent adsorption capacity for application in wastewater purification. Copyright © 2018 Elsevier Inc. All rights reserved.

Adsorption of methyl orange from aqueous solution by aminated pumpkin seed powder: Kinetics, isotherms, and thermodynamic studies.

PubMed

Subbaiah, Munagapati Venkata; Kim, Dong-Su

2016-06-01

Present research discussed the utilization of aminated pumpkin seed powder (APSP) as an adsorbent for methyl orange (MO) removal from aqueous solution. Batch sorption experiments were carried to evaluate the influence of pH, initial dye concentration, contact time, and temperature. The APSP was characterized by using Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscopy (SEM). The experimental equilibrium adsorption data were fitted using two two-parameter models (Langmuir and Freundlich) and two three-parameter models (Sips and Toth). Langmuir and Sips isotherms provided the best model for MO adsorption data. The maximum monolayer sorption capacity was found to be 200.3mg/g based on the Langmuir isotherm model. The pseudo-first-order and pseudo-second-order model equations were used to analyze the kinetic data of the adsorption process and the data was fitted well with the pseudo-second-order kinetic model (R(2)>0.97). The calculated thermodynamic parameters such as ΔG(0), ΔH(0) and ΔS(0) from experimental data showed that the sorption of MO onto APSP was feasible, spontaneous and endothermic in the temperature range 298-318 K. The FTIR results revealed that amine and carboxyl functional groups present on the surface of APSP. The SEM results show that APSP has an irregular and porous surface which is adequate morphology for dye adsorption. Desorption experiments were carried to explore the feasibility of adsorbent regeneration and the adsorbed MO from APSP was desorbed using 0.1M NaOH with an efficiency of 93.5%. Findings of the present study indicated that APSP can be successfully used for removal of MO from aqueous solution. Copyright © 2016 Elsevier Inc. All rights reserved.

Mg2+ ion effect on conformational equilibrium of poly A . 2 poly U and poly A poly U in aqueous solutions.

PubMed

Sorokin, Victor A; Valeev, Vladimir A; Gladchenko, Galina O; Degtiar, Marina V; Karachevtsev, Victor A; Blagoi, Yuri P

2003-01-15

Differential UV spectroscopy and thermal denaturation were used to study the Mg(2+) ion effect on the conformational equilibrium in poly A.2 poly U (A2U) and poly A . poly U (AU) solutions at low (0.01 M Na(+)) and high (0.1 M Na(+)) ionic strengths. Four complete phase diagrams were obtained for Mg(2+)-polynucleotide complexes in ranges of temperatures 20-96 degrees C and concentrations (10(-5)-10(-2)) M Mg(2+). Three of them have a 'critical' point at which the type of the conformational transition changes. The value of the 'critical' concentration ([Mg(t)(2+)](cr)=(4.5+/-1.0) x 10(-5) M) is nearly independent of the initial conformation of polynucleotides (AU, A2U) and of Na(+) contents in the solution. Such a value is observed for Ni(2+) ions too. The phase diagram of the (A2U+Mg(2+)) complex with 0.01 M Na(+) has no 'critical' point: temperatures of (3-->2) and (2-->1) transitions increase in the whole Mg(2+) range. In (AU+Mg(2+)) phase diagram at 0.01 M Na(+) the temperature interval in which triple helices are formed and destroyed is several times larger than at 0.1 M Na(+). Using the ligand theory, a qualitative thermodynamic analysis of the phase diagrams was performed.

Antidiabetic Bis-Maltolato-OxoVanadium(IV): Conversion of inactive trans- to bioactive cis-BMOV for possible binding to target PTP-1B

PubMed Central

Scior, Thomas; Mack, Hans-Georg; García, José Antonio Guevara; Koch, Wolfhard

2008-01-01

The postulated transition of Bis-Maltolato-OxoVanadium(IV) (BMOV) from its inactive trans- into its cis-aquo-BMOV isomeric form in solution was simulated by means of computational molecular modeling. The rotational barrier was calculated with DFT – B3LYP under a stepwise optimization protocol with STO-3G, 3-21G, 3-21G*, and 6-31G ab initio basis sets. Our computed results are consistent with reports on the putative molecular mechanism of BMOV triggering the insulin-like cellular response (insulin mimetic) as a potent inhibitor of the protein tyrosine phosphatase-1B (PTP-1B). Initially, trans-BMOV is present in its solid dosage form but in aqueous solution, and during oral administration, it is readily converted into a mixture of “open-type” and “closed-type” complexes of cis-aquo-BMOV under equilibrium conditions. However, in the same measure as the “closed-type” complex binds to the cytosolic PTP-1B, it disappears from solution, and the equilibrium shifts towards the “closed-type” species. In full accordance, the computed binding mode of cis-BMOV is energetically favored over sterically hindered trans-BMOV. In view of our earlier report on prodrug hypothesis of vanadium organic compounds the present results suggest that cis-BMOV is the bioactive species. PMID:19920909

Hydrodynamics of the VanA-type VanS histidine kinase: an extended solution conformation and first evidence for interactions with vancomycin

PubMed Central

Phillips-Jones, Mary K.; Channell, Guy; Kelsall, Claire J.; Hughes, Charlotte S.; Ashcroft, Alison E.; Patching, Simon G.; Dinu, Vlad; Gillis, Richard B.; Adams, Gary G.; Harding, Stephen E.

2017-01-01

VanA-type resistance to glycopeptide antibiotics in clinical enterococci is regulated by the VanSARA two-component signal transduction system. The nature of the molecular ligand that is recognised by the VanSA sensory component has not hitherto been identified. Here we employ purified, intact and active VanSA membrane protein (henceforth referred to as VanS) in analytical ultracentrifugation experiments to study VanS oligomeric state and conformation in the absence and presence of vancomycin. A combination of sedimentation velocity and sedimentation equilibrium in the analytical ultracentrifuge (SEDFIT, SEDFIT-MSTAR and MULTISIG analysis) showed that VanS in the absence of the ligand is almost entirely monomeric (molar mass M = 45.7 kDa) in dilute aqueous solution with a trace amount of high molar mass material (M ~ 200 kDa). The sedimentation coefficient s suggests the monomer adopts an extended conformation in aqueous solution with an equivalent aspect ratio of ~(12 ± 2). In the presence of vancomycin over a 33% increase in the sedimentation coefficient is observed with the appearance of additional higher s components, demonstrating an interaction, an observation consistent with our circular dichroism measurements. The two possible causes of this increase in s – either a ligand induced dimerization and/or compaction of the monomer are considered. PMID:28397853

Thermodynamic model for solution behavior and solid-liquid equilibrium in Na-Al(III)-Fe(III)-Cr(III)-Cl-H2O system at 25°C

NASA Astrophysics Data System (ADS)

André, Laurent; Christov, Christomir; Lassin, Arnault; Azaroual, Mohamed

2018-03-01

The knowledge of the thermodynamic behavior of multicomponent aqueous electrolyte systems is of main interest in geo-, and environmental-sciences. The main objective of this study is the development of a high accuracy thermodynamic model for solution behavior, and highly soluble M(III)Cl3(s) (M= Al, Fe, Cr) minerals solubility in Na-Al(III)-Cr(III)-Fe(III)-Cl-H2O system at 25°C. Comprehensive thermodynamic models that accurately predict aluminium, chromium and iron aqueous chemistry and M(III) mineral solubilities as a function of pH, solution composition and concentration are critical for understanding many important geochemical and environmental processes involving these metals (e.g., mineral dissolution/alteration, rock formation, changes in rock permeability and fluid flow, soil formation, mass transport, toxic M(III) remediation). Such a model would also have many industrial applications (e.g., aluminium, chromium and iron production, and their corrosion, solve scaling problems in geothermal energy and oil production). Comparisons of solubility and activity calculations with the experimental data in binary and ternary systems indicate that model predictions are within the uncertainty of the data. Limitations of the model due to data insufficiencies are discussed. The solubility modeling approach, implemented to the Pitzer specific interaction equations is employed. The resulting parameterization was developed for the geochemical Pitzer formalism based PHREEQC database.

Highly efficient fluoride adsorption from aqueous solution by nepheline prepared from kaolinite through alkali-hydrothermal process.

PubMed

Wang, Hao; Feng, Qiming; Liu, Kun; Li, Zishun; Tang, Xuekun; Li, Guangze

2017-07-01

A direct alkali-hydrothermal induced transformation process was adopted to prepare nepheline from raw kaolinite (shortened form RK in this paper) and NaOH solution in this paper. Structure and morphology characterizations of the synthetic product showed that the nepheline possessed high degree of crystallinity and uniform surface morphology. Specific surface area of nepheline is 18 m 2 /g, with a point of zero charge at around pH 5.0-5.5. The fluoride (F - ions) adsorption by the synthetic nepheline (shortened form SN in this paper) from aqueous solution was also investigated under different experimental conditions. The adsorption process well matched the Langmuir isotherm model with an amazing maximum adsorption capacity of 183 mg/g at 323 K. The thermodynamic parameters (ΔG 0 , ΔH 0 , and ΔS 0 ) for adsorption on SN were also determined from the temperature dependence. The adsorption capacities of fluoride on SN increased with increasing of temperature and initial concentration. Initial pH value also had influence on adsorption process. Adsorption of fluoride was rapidly increased in 5-60 min and thereafter increased slowly to reach the equilibrium in about 90-180 min under all conditions. The adsorption followed a pseudo-second order rate law. Copyright © 2017 Elsevier Ltd. All rights reserved.

Transport behaviors of anionic azo dyes at interface between surfactant-modified flax shives and aqueous solution: Synchrotron infrared and adsorption studies

NASA Astrophysics Data System (ADS)

Wang, Wenxia; Huang, Guohe; An, Chunjiang; Xin, Xiaying; Zhang, Yan; Liu, Xia

2017-05-01

From the viewpoint of sustainability, biomass adsorbent has a high potential in pollution control and there is an emerging interest to investigate the behaviors of pollutants at the interface between biomass adsorbent and solution. This study investigated the performance of cetyltrimethylammonium bromide surfactant-modified flax shives (MFS) for removal of anionic azo dyes from aqueous solution. The equilibrium and kinetic analysis for the adsorption of Acid Orange 7 (AO-7), Acid Red 18 (AR-18) and Acid Black 1 (AB-1) on MFS were conducted. The surface of MFS was characterized by synchrotron infrared and SEM analysis. The absorbed amount of three anionic azo dyes varied with the change of adsorbent dosage, pH and ionic strength. The adsorption isotherm data well fit to the Langmuir model. The adsorption process followed the pseudo-second-order kinetics and the liquid film diffusion models. Thermodynamic studies indicated that the adsorption of three anionic azo dyes was spontaneous. The adsorption of AR-18 and AB-1 onto MFS was endothermic while the adsorption of AO-7 was exothermic. The results can help better understand the behaviors of organic pollutants at biomass adsorbent-water interface. They also present the potential of using MFS as a suitable adsorbent for the removal of anionic azo dyes from wastewater.

Arsenic(V) removal from aqueous solutions using an anion exchanger derived from coconut coir pith and its recovery.

PubMed

Anirudhan, T S; Unnithan, Maya R

2007-01-01

The performance of a new anion exchanger (AE) prepared from coconut coir pith (CP), for the removal of arsenic(V) [As(V)] from aqueous solutions was evaluated in this study. The adsorbent (CP-AE) carrying dimethylaminohydroxypropyl weak base functional group was synthesized by the reaction of CP with epichlorohydrin and dimethylamine followed by treatment of hydrochloric acid. IR spectroscopy results confirm the presence of -NH(+)(CH(3))(2)Cl(-) group in the adsorbent. XRD studies confirm the decrease of crystallinity in CP-AE compared to CP, and it favours the protrusion of the functional group into the aqueous medium. Batch experiments were conducted to examine the efficiency of the adsorbent on As(V) removal. Maximum removal of 99.2% was obtained for an initial concentration of 1 mgl(-1) As(V) at pH 7.0 and an adsorbent dose of 2 gl(-1). The kinetics of sorption of As(V) onto CP-AE was described using the pseudo-second-order model. The equilibrium isotherms were determined for different temperatures and the results were analysed using the Langmuir equation. The temperature dependence indicates an exothermic process. Utility of the adsorbent was tested by removing As(V) from simulated groundwater. Regeneration studies were performed using 0.1N HCl. Batch adsorption-desorption studies illustrate that CP-AE could be used to remove As(V) from ground water and other industrial effluents.

The geochemical evolution of aqueous sodium in the Black Creek Aquifer, Horry and Georgetown counties, South Carolina

USGS Publications Warehouse

Zack, Allen L.; Roberts, Ivan

1988-01-01

The Black Creek aquifer contains dilute seawater near the North Carolina State line, probably the result of incomplete flushing of ancient seawater. Data do not indicate that the dilute seawater has migrated toward areas of fresh ground-water withdrawals. The concentration of chloride in ground-water samples ranges from 5 to 720 milligrams per liter and that of sodium from 160 to 690 milligrams per liter. Ion-exchange reactions (sodium for calcium and fluoride for hydroxyl) occur with the calcium carbonate dissolution reaction which produces calcium, bicarbonate, and hydroxyl ions. The reaction sequence and stoichiometry result in an aqueous solution in which the sum of bicarbonate and chloride equivalents per liter is equal to the equivalents per liter of sodium. Calcium ions are exchanged for sodium ions derived from sodium-rich clays upgradient of the dilute seawater. The cation-exchange reaction equilibrates at a sodium concentration of 280 milligrams per liter. Amounts of sodium greater than 280 milligrams per liter are contributed from dilute seawater. The cation-exchange reaction approaches an equilibrium which represents a mass-action limit in terms of the ratio of sodium to calcium in solution versus the ratio of exchangeable sodium to calcium on clay surfaces. Where the limit of calcium carbonate solubility is approached and dissolution ceases, some precipitation of calcite probably takes place. The dissolution of calcite exposes fossil shark teeth which release fluoride ions to the ground water through anion exchange with aqueous hydroxyl ions.

Time-resolved and steady-state fluorescence studies of excited-state proton-transfer reactions of proflavine

NASA Astrophysics Data System (ADS)

De Silvestri, S.; Laporta, P.

1984-01-01

Time-resolved and steady-state fluorescence studies of proflavine in aqueous solution are presented. The observation of a monoexponential fluorescence decay with a time constant decreasing with increasing pH and the presence of an anomalous red-shift in the fluorescence spectrum as a function of pH indicate the existence of a complex proton-transfer mechanism in the excited state. A reaction scheme is proposed and the corresponding proton-transfer rates are evaluated. An excited-state pK value of 12.85 is obtained for the equilibrium between the cationic form of proflavine and the same form dissociated at an amino group.

Photophysics of aggregated 9-methylthiacarbocyanine bound to polyanions

NASA Astrophysics Data System (ADS)

Chibisov, Alexander K.; Görner, Helmut

2002-05-01

The photophysical properties of 3,3 '-diethyl-9-methylthiacarbocyanine (DTC) were studied in the presence of polystyrene sulfonate (PSS), polyacrylic acid (PAA) and polymethacrylic acid (PMA). The absorption spectra reflect a monomer/dimer equilibrium in neat aqueous solution and a shift towards bound H-aggregates, bound dimers and bound monomers on increasing the ratio of polyanion residue to dye concentrations ( r). These equilibria also determine the photodeactivation modes of DTC. The fluorescence intensity is reduced, when dimers and aggregates are present and strongly enhanced for low dye loading ( r=10 4). In contrast, the quantum yield of intersystem crossing is enhanced for bound dimers ( r=10 3).

Biosorption Behavior of Ciprofloxacin onto Enteromorpha prolifera: Isotherm and Kinetic Studies.

PubMed

Wu, Shaoling; Li, Yanhui; Zhao, Xindong; Du, Qiuju; Wang, Zonghua; Xia, Yanzhi; Xia, Linhua

2015-01-01

The studies aimed at the feasibility of using Enteromorpha prolifera for the removal of ciprofloxacin from aqueous solutions. Batch experiments were carried out for the biosorption of ciprofloxacin onto Enteromorpha prolifera. The factors affecting the biosorption process such as the initial concentration, dosage, pH and the contact time were studied. Enteromorpha prolifera exhibited a maximum biosorption capacity of 21.7 mg/g. The pseudo-second-order kinetic model described the ciprofloxacin biosorption process with a good fitting. The optimum pH of ciprofloxacin adsorbed by Enteromorpha prolifera was 10. Biosorption equilibrium studies demonstrated that the biosorption followed Freundlich isotherm model, which implied a heterogeneous biosorption phenomenon.

Adsorption of organic compounds onto activated carbons from recycled vegetables biomass.

PubMed

Mameli, Anna; Cincotti, Alberto; Lai, Nicola; Crisafulli, Carmelo; Sciré, Salvatore; Cao, Giacomo

2004-01-01

The removal of organic species from aqueous solution by activated carbons is investigated. The latter ones are prepared from olive husks and almond shells. A wide range of surface area values are obtained varying temperature and duration of both carbonization and activation steps. The adsorption isotherm of phenol, catechol and 2,6-dichlorophenol involving the activated carbons prepared are obtained at 25 degrees C. The corresponding behavior is quantitatively correlated using classical isotherm, whose parameters are estimated by fitting the equilibrium data. A two component isotherm (phenol/2,6-dichlorophenol) is determined in order to test activated carbon behavior during competitive adsorption.

23Na NUCLEAR MAGNETIC RESONANCE RELAXATION STUDIES OF SODIUM ION INTERACTION WITH SOLUBLE RNA*

PubMed Central

James, Thomas L.; Noggle, Joseph H.

1969-01-01

Interactions between 23Na+ and soluble RNA in aqueous solution are studied with the use of 23Na nuclear magnetic resonance. At low concentrations of NaCl, the interactions obey a simple equilibrium model with a formation constant log (Kf)3 = 2.8 ± 0.3. The relaxation rate of the bound sodium is found to be T1B-1 = 222 ± 19 sec-1 compared to that of free sodium T1F-1 = 17.5 sec-1. At high NaCl concentrations, the system deviates from the model, possibly owing to aggregation of the soluble RNA. PMID:5256995

Ion-exchange controls the kinetics of deswelling of polyelectrolyte microgels in solutions of oppositely charged surfactant.

PubMed

Nilsson, Peter; Hansson, Per

2005-12-22

The kinetics of deswelling of sodium polyacrylate microgels (radius 30-140 microm) in aqueous solutions of dodecyltrimethylammonium bromide is investigated by means of micropipet-assisted light microscopy. The purpose of the study is to test a recent model (J. Phys. Chem. B 2003, 107, 9203) proposing that the rate of the volume change is controlled by the transport of surfactant from the solution to the gel core (ion exchange) via the surfactant-rich surface phase appearing in the gel during the volume transition. Equilibrium swelling characteristics of the gel network in surfactant-free solutions and with various amounts of surfactant present are presented and discussed with reference to related systems. A relationship between gel volume and degree of surfactant binding is determined and used in theoretical predictions of the deswelling kinetics. Experimental data for single gel beads observed during deswelling under conditions of forced convection are presented and compared with model calculations. It is demonstrated that the dependences of the kinetics on initial gel size, the surfactant concentration in the solution, and the liquid flow rate are well accounted for by the model. It is concluded that the deswelling rates of the studied gels are strongly influenced by the mass transport of surfactant between gel and solution (stagnant layer diffusion), but only to a minor extent by the transport through the surface phase. The results indicate that, during the volume transition, swelling equilibrium (network relaxation/transport of water) is established on a relatively short time scale and, therefore, can be treated as independent of the ion-exchange kinetics. Theoretical aspects of the kinetics and mechanisms of surfactant transport through the surface phase are discussed.

A water activity based model of heterogeneous ice nucleation kinetics for freezing of water and aqueous solution droplets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Knopf, Daniel A.; Alpert, Peter A.

Immersion freezing of water and aqueous solutions by particles acting as ice nuclei (IN) is a common process of heterogeneous ice nucleation which occurs in many environments, especially in the atmosphere where it results in the glaciation of clouds. Here we experimentally show, using a variety of IN types suspended in various aqueous solutions, that immersion freezing temperatures and kinetics can be described solely by temperature, T, and solution water activity, aw, which is the ratio of the vapour pressure of the solution and the saturation water vapour pressure under the same conditions and, in equilibrium, equivalent to relative humiditymore » (RH). This allows the freezing point and corresponding heterogeneous ice nucleation rate coefficient, Jhet, to be uniquely expressed by T and aw, a result we term the aw based immersion freezing model (ABIFM). This method is independent of the nature of the solute and accounts for several varying parameters, including cooling rate and IN surface area, while providing a holistic description of immersion freezing and allowing prediction of freezing temperatures, Jhet, frozen fractions, ice particle production rates and numbers. Our findings are based on experimental freezing data collected for various IN surface areas, A, and cooling rates, r, of droplets variously containing marine biogenic material, two soil humic acids, four mineral dusts, and one organic monolayer acting as IN. For all investigated IN types we demonstrate that droplet freezing temperatures increase as A increases. Similarly, droplet freezing temperatures increase as the cooling rate decreases. The log 10(J het) values for the various IN types derived exclusively by T and aw, provide a complete description of the heterogeneous ice nucleation kinetics. Thus, the ABIFM can be applied over the entire range of T, RH, total particulate surface area, and cloud activation timescales typical of atmospheric conditions. Finally, we demonstrate that ABIFM can be used to derive frozen fractions of droplets and ice particle production for atmospheric models of cirrus and mixed phase cloud conditions.« less