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Sample records for adsorption equilibrium time

  1. Time evolution analysis of a 2D solid gas equilibrium: a model system for molecular adsorption and diffusion

    NASA Astrophysics Data System (ADS)

    Berner, S.; Brunner, M.; Ramoino, L.; Suzuki, H.; Güntherodt, H.-J.; Jung, T. A.

    2001-11-01

    The adsorption of sub-phthalocyanine molecules on Ag(1 1 1) has been studied by means of scanning tunneling microscopy (STM). The molecules are observed in different two-dimensional (2D) phases of adsorption which coexist in thermodynamic equilibrium. In the condensed phase the molecules form well-ordered islands with a honeycomb pattern. In the gas phase single molecules can be discriminated in single scan lines by characteristic tip excursions which occur randomly. The energy barrier for surface diffusion as well as the condensation energy to form 2D islands is estimated and discussed.

  2. Arsenic Adsorption Equilibrium Concentration and Adsorption Rate of Activated Carbon Coated with Ferric-Aluminum Hydroxides

    NASA Astrophysics Data System (ADS)

    Zhang, M.; Sugita, H.; Oguma, T.; Hara, J.; Takahashi, S.

    2015-12-01

    In some areas of developing countries, ground or well water contaminated with arsenic has been reluctantly used as drinking water. It is highly desirable that effective and inexpensive arsenic removal agents should be developed and provided to reduce the potential health risk. Previous studies demonstrated that activated carbon coated with ferric-aluminum hydroxides (Fe-Al-C) has high adsorptive potential for removal of arsenic. In this study, a series of experiments using Fe-Al-C were carried to discuss adsorption equilibrium time, adsorption equilibrium concentration and adsorption rate of arsenic for Fe-Al-C. Fe-Al-C used in this study was provided by Astec Co., Ltd. Powder reagent of disodium hydrogen arsenate heptahydrate was dissolved into ion-exchanged water. The solution was then further diluted with ion-exchanged water to be 1 and 10 mg/L as arsenic concentration. The pH of the solution was adjusted to be around 7 by adding HCl and/or NaOH. The solution was used as artificial arsenic contaminated water in two types of experiments (arsenic adsorption equilibrium and arsenic adsorption rate tests). The results of the arsenic equilibrium tests were showed that a time period of about 3 days to reach apparent adsorption equilibrium for arsenic. The apparent adsorption equilibrium concentration and adsorbed amount of arsenic on Fe-Al-C adsorbent could be estimated by application of various adsorption isotherms, but the distribution coefficient of arsenic between solid and liquid varies with experimental conditions such as initial concentration of arsenic and addition concentration of adsorbent. An adsorption rate equation that takes into account the reduction in the number of effective adsorption sites on the adsorbent caused by the arsenic adsorption reaction was derived based on the data obtained from the arsenic adsorption rate tests.

  3. Kinetics and equilibrium adsorption studies of dimethylamine (DMA) onto ion-exchange resin.

    PubMed

    Hu, Qinhai; Meng, Yuanyuan; Sun, Tongxi; Mahmood, Qaisar; Wu, Donglei; Zhu, Jianhang; Lu, George

    2011-01-30

    The fine grained resin ZGSPC106 was used to adsorb dimethylamine (DMA) from aqueous solution in the present research. Batch experiments were performed to examine the effects of initial pH of solution and agitation time on the adsorption process. The thermodynamics and kinetics of adsorption were also analyzed. The maximum adsorption was found at natural pH of DMA solution and equilibrium could be attained within 12 min. The equilibrium adsorption data were conformed satisfactorily to the Langmuir equation. The evaluation based on Langmuir isotherm gave the maximal static saturated adsorption capacity of 138.89 mg/g at 293K. Various thermodynamic parameters such as free energy (ΔG°), enthalpy (ΔH°) and entropy (ΔS°) showed that the adsorption was spontaneous, endothermic and feasible. DMA adsorption on ZGSPC106 fitted well to the pseudo-second-order kinetic model. Furthermore, the adsorption mechanism was discussed by Fourier transform infrared spectroscopy (FT-IR) analysis.

  4. 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.

  5. Adsorption of cadmium from aqueous solution onto untreated coffee grounds: equilibrium, kinetics and thermodynamics.

    PubMed

    Azouaou, N; Sadaoui, Z; Djaafri, A; Mokaddem, H

    2010-12-15

    Adsorption can be used as a cost effective and efficient technique for the removal of toxic heavy metals from wastewater. Waste materials with no further treatment such as coffee grounds from cafeterias may act as adsorbents for the removal of cadmium. Batch kinetic and equilibrium experiments were conducted to study the effects of contact time, adsorbent dose, initial pH, particle size, initial concentration of cadmium and temperature. Three adsorption isotherm models namely, Langmuir, Freundlich and Dubinin-Radushkevich were used to analyse the equilibrium data. The Langmuir isotherm which provided the best correlation for Cd(2+) adsorption onto coffee grounds, shows that the adsorption was favourable and the adsorption capacity found was equal to 15.65 mg g(-1). Thermodynamic parameters were evaluated and the adsorption was exothermic. The equilibrium was achieved less than 120 min. The adsorption kinetic data was fitted with first and second order kinetic models. Finally it was concluded that the cadmium adsorption kinetic onto coffee grounds was well fitted by second order kinetic model rather than first order model. The results suggest that coffee grounds have high possibility to be used as effective and economical adsorbent for Cd(2+) removal.

  6. Equilibrium, kinetic and thermodynamic studies on the adsorption of phenol onto graphene

    SciTech Connect

    Li, Yanhui; Du, Qiuju; Liu, Tonghao; Sun, Jiankun; Jiao, Yuqin; Xia, Yanzhi; Xia, Linhua; Wang, Zonghua; Zhang, Wei; Wang, Kunlin; Zhu, Hongwei; Wu, Dehai

    2012-08-15

    Graphical abstract: The effect of temperature on phenol adsorbed by graphene shows that the equilibrium adsorption capacity of phenol increases with the increase in temperature from 285 to 333 K. Increasing adsorption capacities with temperature indicates that the adsorption of phenol is controlled by an endothermic reaction. Highlights: ► The graphene has high phenol adsorption capacity. ► The graphene has a high specific surface area of 305 m{sup 2}/g. ► The adsorption capacity is high at acidic pH range. ► The graphene has rapid phenol adsorption rate. ► Phenol adsorption is a spontaneous and endothermic process. -- Abstract: Graphene, a new member of carbon family, has been prepared, characterized and used as adsorbent to remove phenol from aqueous solution. The effect parameters including pH, dosage, contact time, and temperature on the adsorption properties of phenol onto graphene were investigated. The results showed that the maximum adsorption capacity can reach 28.26 mg/g at the conditions of initial phenol concentration of 50 mg/L, pH 6.3 and 285 K. Adsorption data were well described by both Freundlich and Langmuir models. The kinetic study illustrated that the adsorption of phenol onto graphene fit the pseudo second-order model. The thermodynamic parameters indicated that the adsorption of phenol onto graphene was endothermic and spontaneous.

  7. Adsorption characteristics of siloxanes in landfill gas by the adsorption equilibrium test

    SciTech Connect

    Nam, Sangchul; Namkoong, Wan; Kang, Jeong-Hee; Park, Jin-Kyu; Lee, Namhoon

    2013-10-15

    Highlights: • Equilibrium test was attempted to evaluate adsorption characteristics of siloxane. • L2 had higher removal efficiency in carbon compared to noncarbon adsorbents. • Total adsorption capacity of siloxane was 300 mg/g by coal activated carbon. • Adsorption characteristics rely on size of siloxane molecule and adsorbent pore. • Conversion of siloxane was caused by adsorption of noncarbon adsorbents. - Abstract: Due to the increase in energy cost by constantly high oil prices and the obligation to reduce greenhouse effect gases, landfill gas is frequently used as an alternative energy source for producing heat and electricity. Most of landfill gas utility facilities, however, are experiencing problems controlling siloxanes from landfill gas as their catalytic oxidizers are becoming fouled by silicon dioxide dust. To evaluate adsorption characteristics of siloxanes, an adsorption equilibrium test was conducted and parameters in the Freundlich and Langmuir isotherms were analyzed. Coconut activated carbon (CA1), coal activated carbon (CA2), impregnated activated carbon (CA3), silicagel (NCA1), and activated alumina (NCA2) were used for the adsorption of the mixed siloxane which contained hexamethyldisiloxane (L2), octamethylcyclotetrasiloxane (D4), and decamethylcyclopentasiloxane (D5). L2 had higher removal efficiency in noncarbon adsorbents compared to carbon adsorbents. The application of Langmuir and Freundlich adsorption isotherm demonstrated that coconut based CA1 and CA3 provided higher adsorption capacity on L2. And CA2 and NCA1 provided higher adsorption capacity on D4 and D5. Based on the experimental results, L2, D4, and D5 were converted by adsorption and desorption in noncarbon adsorbents. Adsorption affinity of siloxane is considered to be affect by the pore size distribution of the adsorbents and by the molecular size of each siloxane.

  8. Adsorption equilibrium and dynamics of gasoline vapors onto polymeric adsorbents.

    PubMed

    Jia, Lijuan; Yu, Weihua; Long, Chao; Li, Aimin

    2014-03-01

    The emission of gasoline vapors is becoming a significant environmental problem especially for the population-dense area and also results in a significant economic loss. In this study, adsorption equilibrium and dynamics of gasoline vapors onto macroporous and hypercrosslinked polymeric resins at 308 K were investigated and compared with commercial activated carbon (NucharWV-A 1100). The results showed that the equilibrium and breakthrough adsorption capacities of virgin macroporous and hypercrosslinked polymeric resins were lower than virgin-activated carbon. Compared with origin adsorbents, however, the breakthrough adsorption capacities of the regenerated activated carbon for gasoline vapors decreased by 58.5 % and 61.3 % when the initial concentration of gasoline vapors were 700 and 1,400 mg/L, while those of macroporous and hypercrosslinked resins decreased by 17.4 % and 17.5 %, and 46.5 % and 45.5 %, respectively. Due to the specific bimodal property in the region of micropore (0.5-2.0 nm) and meso-macropore (30-70 nm), the regenerated hypercrosslinked polymeric resin exhibited the comparable breakthrough adsorption capacities with the regenerated activated carbon at the initial concentration of 700 mg/L, and even higher when the initial concentration of gasoline vapors was 1,400 mg/L. In addition, 90 % of relative humidity had ignorable effect on the adsorption of gasoline vapors on hypercrosslinked polymeric resin. Taken together, it is expected that hypercrosslinked polymeric adsorbent would be a promising adsorbent for the removal of gasoline vapors from gas streams.

  9. Adsorption laboratory experiment for undergraduate chemical engineering: Introducing kinetic, equilibrium and thermodynamic concepts

    NASA Astrophysics Data System (ADS)

    Muryanto, S.; Djatmiko Hadi, S.

    2016-11-01

    Adsorption laboratory experiment for undergraduate chemical engineering program is discussed. The experiment demonstrated adsorption of copper ions commonly found in wastewater using bio-sorbent, i.e. agricultural wastes. The adsorption was performed in a batch mode under various parameters: adsorption time (up to 120 min), initial pH (2 to 6), adsorbent dose (2.0 to 12.0 g L-1), adsorbent size (50 to 170 mesh), initial Cu2+ concentration (25 to 100 ppm) and temperatures (room temp to 40°C). The equilibrium and kinetic data of the experiments were calculated using the two commonly used isotherms: Langmuir and Lagergren pseudo-first-order kinetics. The maximum adsorption capacity for Cu2+ was found as 94.34 mg g-1. Thermodynamically, the adsorption process was spontaneous and endothermic. The calculated activation energy for the adsorption was observed as high as 127.94 kJ mol-1. Pedagogically, the experiment was assumed to be important in increasing student understanding of kinetic, equilibrium and thermodynamic concepts.

  10. Equilibrium and heat of adsorption for organic vapors and activated carbons

    SciTech Connect

    David Ramirez; Shaoying Qi; Mark J. Rood; K. James Hay

    2005-08-01

    Determination of the adsorption properties of novel activated carbons is important to develop new air quality control technologies that can solve air quality problems in a more environmentally sustainable manner. Equilibrium adsorption capacities and heats of adsorption are important parameters for process analysis and design. Experimental adsorption isotherms were thus obtained for relevant organic vapors with activated carbon fiber cloth (ACFC) and coal-derived activated carbon adsorbents (CDAC). The Dubinin-Astakhov (DA) equation was used to describe the adsorption isotherms. The DA parameters were analytically and experimentally shown to be temperature independent. The resulting DA equations were used with the Clausius-Clapeyron equation to analytically determine the isosteric heat of adsorption ({Delta}H{sub s}) of the adsorbate-adsorbent systems studied here. ACFC showed higher adsorption capacities for organic vapors than CDAC. {Delta}H{sub s} values for the adsorbates were independent of the temperature for the conditions evaluated. {Delta}H{sub s} values for acetone and benzene obtained in this study are comparable with values reported in the literature. This is the first time that {Delta}H{sub s} values for organic vapors and these adsorbents are evaluated with an expression based on the Polanyi adsorption potential and the Clausius-Clapeyron equation. 28 refs., 5 figs., 5 tabs., 3 appends.

  11. Adsorption of dyes using peat: equilibrium and kinetic studies.

    PubMed

    Sepúlveda, L; Fernández, K; Contreras, E; Palma, C

    2004-09-01

    In recent years, adsorption has been accepted as one of the most appropriate processes for decolorization of wastewaters. This paper presents experimental results on application of peat for removal of structurally diverse dyes (azo, oxazine, triphenylmethane, thiazine and others) with emphasis on relevant factors such as the adsorbate-adsorbent chemical properties and chemical interaction as well as adsorption conditions. The equilibrium experimental results were fitted to Langmuir and Freundlich isotherms to obtain the characteristic parameters of each model. According to the evaluation using the Langmuir equation, the maximum sorption capacity of basic dyes at 22 degrees C was 667 (mg g(-1)) for Basic Blue 24, 526 (mg g(-1)) for Basic Green 4 and 714 (mg g(-1)) for Basic Violet 4. On the other hand for Acid Black 1 it was only 25 (mg g(-1)). Batch kinetics studies were undertaken and the data evaluated in compliance with chemical sorption mechanisms. For all of the systems studied the pseudo-second order model provided the best correlation of the kinetic experimental data. A film-pore double resistance diffusion model for mass transfer has also been used in this study to determine the effective diffusivity, Deff, for the adsorption of basic dyes in to peat.

  12. Adsorption kinetic and equilibrium study for removal of mercuric chloride by CuCl2-impregnated activated carbon sorbent.

    PubMed

    Li, Xin; Liu, Zhouyang; Lee, Joo-Youp

    2013-05-15

    The intrinsic adsorption kinetics of mercuric chloride (HgCl2) was studied for raw, 4% and 10% CuCl2-impregnated activated carbon (CuCl2-AC) sorbents in a fixed-bed system. An HgCl2 adsorption kinetic model was developed for the AC sorbents by taking into account the adsorption kinetics, equilibrium, and internal and external mass transfer. The adsorption kinetic constants determined from the comparisons between the simulation and experimental results were 0.2, 0.3, and 0.5m(3)/(gs) for DARCO-HG, 4%(wt), and 10%(wt) CuCl2-AC sorbents, respectively, at 140 °C. CuCl2 loading was found to slightly increase the adsorption kinetic constant or at least not to decrease it. The HgCl2 equilibrium adsorption data based on the Langmuir isotherm show that high CuCl2 loading can result in high binding energy of the HgCl2 adsorption onto the carbon surface. The adsorption equilibrium constant was found to increase by ~10 times when CuCl2 loading varied from 0 to 10%(wt), which led to a decrease in the desorption kinetic constant (k2) by ~10 times and subsequently the desorption rate by ~50 times. Intraparticle pore diffusion considered in the model showed good accuracy, allowing for the determination of intrinsic HgCl2 adsorption kinetics.

  13. Adsorptive removal of acrylonitrile by commercial grade activated carbon: kinetics, equilibrium and thermodynamics.

    PubMed

    Kumar, Arvind; Prasad, B; Mishra, I M

    2008-04-01

    The potential of activated carbons--powdered (PAC) and granular (GAC), for the adsorption of acrylonitrile (AN) at different initial AN concentrations (50time, and the change in pH with addition of adsorbents on adsorption was studied. The Langmuir, Freundlich, Tempkin, and Redlich-Peterson (R-P) isotherm equations were used to test their fit with the experimental data, and the model parameters were determined for different temperatures. The Langmuir and R-P models were found to be the best to describe the equilibrium isotherm data of AN adsorption on PAC and GAC, respectively. Error analysis also confirmed the efficacy of the R-P isotherm to best fit the experimental data. The pseudo-second order kinetic model best represents the kinetics of the adsorption of AN onto PAC and GAC. Maximum adsorption capacity of PAC and GAC at optimum conditions of AN removal (adsorbent dose approximately 20 g/l of solution, and equilibrium time approximately 5 h) was found to be 51.72 and 46.63 mg/g, respectively.

  14. Adsorption of cellulase Aspergillus niger on a commercial activated carbon: kinetics and equilibrium studies.

    PubMed

    Daoud, Fatima Boukraa-Oulad; Kaddour, Samia; Sadoun, Tahar

    2010-01-01

    The adsorption kinetics of cellulase Aspergillus niger on a commercial activated carbon has been performed using a batch-adsorption technique. The effect of various experimental parameters such as initial enzyme concentration, contact time and temperature were investigated. The pseudo-first-order and pseudo-second-order kinetic models were used to describe the kinetic data which shows that the adsorption of the enzyme followed the pseudo-second-order rate expression and the rate constants were evaluated. The Langmuir and Freundlich adsorption isotherm models were applied to describe the equilibrium isotherms, and the isotherm constants were determined. It was found that Langmuir model was more suitable for our data. The activation energy of adsorption was also evaluated for the adsorption of enzyme onto activated carbon. It was found 11.37 kJ mol(-1). Thermodynamic parameters Delta G(0), Delta H(0) and DeltaS(0) were calculated, indicating that this process can be spontaneous and endothermic. The adsorption enthalpy and entropy were found 11.12 kJ mol(-1) and 0.084 kJ mol(-1)K(-1), respectively. At 30 degrees C and at pH 4.8, 1g activated carbon adsorbed about 1565 mg of cellulase, with a retention of 70% of the native enzyme activity up to five cycles of repeated batch enzyme reactions.

  15. Adsorption of crystal violet onto functionalised multi-walled carbon nanotubes: Equilibrium and kinetic studies.

    PubMed

    Sabna, V; Thampi, Santosh G; Chandrakaran, S

    2016-12-01

    Synthetic dyes present in effluent from textile, paper and paint industries contain crystal violet (CV), a known carcinogenic agent. This study investigates the modification of multiwalled carbon nanotubes by acid reflux method and equilibrium and kinetic behaviour of adsorption of CV onto functionalized multi-walled carbon nanotubes (fMWNTs) in batch system. High stability of the fMWNTs suspension in water indicates the hydrophilicity of fMWNTs induced due to the formation of functional groups that make hydrogen bonds with water molecules. fMWNTs were characterized by Fourier Transform Infra Red (FTIR) spectroscopy and the functional groups present on the fMWNTs were confirmed. Characteristic variation was observed in the FTIR spectra of fMWNTs after adsorption of crystal violet onto it. Adsorption characteristics were evaluated as a function of system variables such as contact time, dosage of fMWNTs and initial concentration and pH of the crystal violet solution. Adsorption capacity of fMWNTs and percentage removal of the dye increased with increase in contact time, adsorbent dosage and pH but declined with increase in initial concentration of the dye. fMWNTs showed higher adsorption capacity compared to that of pristine MWNTs. Data showed good fit with the Langmuir and Freundlich isotherm models and the pseudo-second order kinetic model; the maximum adsorption capacity was 90.52mg/g. Kinetic parameters such as rate constants, equilibrium adsorption capacities and regression coefficients were estimated. Results indicate that fMWNTs are an effective adsorbent for the removal of crystal violet from aqueous solution.

  16. 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

  17. Adsorption equilibrium, kinetics and thermodynamics of dichloroacetic acid from aqueous solution using mesoporous carbon.

    PubMed

    Ding, Ying; Zhu, Jianzhong; Cao, Yang; Chen, Shenglu

    2014-08-01

    The presence of disinfection by-products, such as trihalomethanes and haloacetic acids in water, is believed to be harmful to human health. In this work, mesoporous carbon was synthesized with the evaporation-induced self-assembly method and employed to evaluate the effects of initial concentration, contact time, pH and temperature on the removal of dichloroacetic acid in batch experiments. Adsorption equilibrium was established in 480 min and the maximum adsorption (350mg/g) of dichloroacetic acid on the mesoporous carbon was observed to occur at 308 K and pH 3.0. Freundlich and Langmuir isotherms were used to analyse the equilibrium data at different temperatures; kinetic data were fitted to the pseudo-first-order and pseudo-second-order models and found that the adsorption capacity, mass transfer coefficient and diffusivity of dichloroacetic acid were directly affected by the physical and chemical parameters. In addition, the various thermodynamic parameters, such as Gibbs free energy (Delta G), enthalpy (Delta H = 54.35 kJmol-1) and entropy (Delta S = 258.36 Jmol-1 K-1) were calculated to analyse the adsorption process. The experimental results indicated that the mesoporous carbon was an excellent adsorbent for dichloroacetic acid removal from aqueous solutions.

  18. Equilibrium and kinetic studies of adsorption of phosphate onto ZnCl2 activated coir pith carbon.

    PubMed

    Namasivayam, C; Sangeetha, D

    2004-12-15

    Phosphate removal from aqueous solution was investigated using ZnCl(2)-activated carbon developed from coir pith, an agricultural solid waste. Studies were conducted to delineate the effect of contact time, adsorbent dose, phosphate concentration, pH, and temperature. The adsorption equilibrium data followed both Langmuir and Freundlich isotherms. Langmuir adsorption capacity was found to be 5.1 mg/g. Adsorption followed second-order kinetics. The removal was maximum in the pH range 3-10. pH effect and desorption studies showed that adsorption occurred by both ion exchange and chemisorption mechanisms. Adsorption was found to be spontaneous and endothermic. Effect of foreign ions on adsorption shows that perchlorate, sulfate, and selenite decreased the percent removal of phosphate.

  19. Kinetics and equilibrium adsorption study of p-nitrophenol onto activated carbon derived from walnut peel.

    PubMed

    Liu, Xiaohong; Wang, Fang; Bai, Song

    2015-01-01

    An original activated carbon prepared from walnut peel, which was activated by zinc chloride, was modified with ammonium hydroxide or sodium hydroxide in order to contrast the adsorption property of the three different activated carbons. The experiment used a static adsorption test for p-nitrophenol. The effects of parameters such as initial concentration, contact time and pH value on amount adsorbed and removal are discussed in depth. The thermodynamic data of adsorption were analyzed by Freundlich and Langmuir models. The kinetic data of adsorption were measured by the pseudo-first-order kinetics and the pseudo-second-order kinetics models. The results indicated that the alkalized carbon samples derived from walnut peel had a better performance than the original activated carbon treated with zinc chloride. It was found that adsorption equilibrium time was 6 h. The maximum removal rate of activated carbon treated with zinc chloride for p-nitrophenol was 87.3% at pH 3,whereas the maximum removal rate of the two modified activated carbon materials was found to be 90.8% (alkalized with ammonium hydroxide) and 92.0% (alkalized with sodium hydroxide) at the same pH. The adsorption data of the zinc chloride activated carbon were fitted to the Langmuir isotherm model. The two alkalized activated carbon samples were fitted well to the Freundlich model. The pseudo-second-order dynamics equation provided better explanation of the adsorption dynamics data of the three activated carbons than the pseudo-first-order dynamics equation.

  20. Equilibrium isotherms, kinetics and thermodynamics studies of phenolic compounds adsorption on palm-tree fruit stones.

    PubMed

    Ahmed, Muthanna J; Theydan, Samar K

    2012-10-01

    Adsorption capacity of an agricultural waste, palm-tree fruit stones (date stones), for phenolic compounds such as phenol (Ph) and p-nitro phenol (PNPh) at different temperatures was investigated. The characteristics of such waste biomass were determined and found to have a surface area and iodine number of 495.71 m2/g and 475.88 mg/g, respectively. The effects of pH (2-12), adsorbent dose (0.6-0.8 g/L) and contact time (0-150 min) on the adsorptive removal process were studied. Maximum removal percentages of 89.95% and 92.11% were achieved for Ph and PNPh, respectively. Experimental equilibrium data for adsorption of both components were analyzed by the Langmuir, Freundlich and Tempkin isotherm models. The results show that the best fit was achieved with the Langmuir isotherm equation with maximum adsorption capacities of 132.37 and 161.44 mg/g for Ph and PNPh, respectively. The kinetic data were fitted to pseudo-first order, pseudo-second order and intraparticle diffusion models, and was found to follow closely the pseudo-second order model for both components. The calculated thermodynamic parameters, namely ΔG, ΔH, and ΔS showed that adsorption of Ph and PNPh was spontaneous and endothermic under examined conditions.

  1. Lead removal from aqueous solution by natural and pretreated clinoptilolite: adsorption equilibrium and kinetics.

    PubMed

    Günay, Ahmet; Arslankaya, Ertan; Tosun, Ismail

    2007-07-19

    Adsorption of Pb(II) ions from aqueous solution onto clinoptilolite has been investigated to evaluate the effects of contact time, initial concentration and pretreatment of clinoptilolite on the removal of Pb(II). Experimental data obtained from batch equilibrium tests have been analyzed by four two-parameter (Freundlich, Langmuir, Temkin and Dubinin-Radushkevich), four three-parameter (Redlich-Peterson, Sips, Toth and Khan) isotherm models, and kinetic models including the pseudo-first order, the pseudo-second order and Elovich equations using nonlinear regression technique. Of the two-parameter isotherms, Temkin isotherm was the best to describe the experimental data. Three-parameter isotherms have higher regression coefficients (>0.99) and lower relative errors (<5%) than two-parameter isotherms. The best fitting isotherm was the Sips followed by Toth and Redlich-Peterson isotherm equations. Maximum experimental adsorption capacity was found to be 80.933 and 122.400 mg/g for raw and pretreated clinoptilolite, respectively, for the initial concentration of 400 mg/L. Kinetic parameters; rate constants, equilibrium adsorption capacities and related coefficients for each kinetic model were evaluated according to relative errors and correlation coefficients. Results of the kinetic studies show that best fitted kinetic models are obtained to be in the order: the pseudo-first order, the pseudo-second order and Elovich equations. Using the thermodynamic equilibrium coefficients, Gibbs free energy of the Pb(II)-clinoptilolite system was evaluated. The negative value of change in Gibbs free energy (DeltaG degrees ) indicates that adsorption of Pb(II) on clinoptilolite is spontaneous.

  2. IgG adsorption on a new protein A adsorbent based on macroporous hydrophilic polymers. I. Adsorption equilibrium and kinetics.

    PubMed

    Perez-Almodovar, Ernie X; Carta, Giorgio

    2009-11-20

    Experimental determination and modeling of IgG binding on a new protein A adsorbent based on a macroporous resin were performed. The new adsorbent consists of polymeric beads based on hydrophilic acrylamido and vinyl monomers with a pore structure optimized to allow favorable interactions of IgG with recombinant protein A coupled to the resin. The particles have average diameter of 57 microm and a narrow particle size distribution. The IgG adsorption equilibrium capacity is 46 mg/cm(3) and the effective pore diffusivity determined from pulse response experiments for non-binding conditions is 8.0 x 10(-8) cm(2)/s. The IgG adsorption kinetics can be described with the same effective diffusivity by taking into account a heterogeneous binding mechanism with fast binding sites, for which adsorption is completely diffusion controlled, and slow binding sites for which adsorption is controlled by the binding kinetics. As a result of this mechanism, the breakthrough curve exhibits a tailing behavior, which appears to be associated with the slow binding sites. A detailed rate model taking into account intraparticle diffusion and binding kinetics is developed and is found capable of predicting both batch adsorption and breakthrough behavior over an ample range of experimental conditions. The corresponding effective diffusivity is independent of protein concentration in solution over the range 0.2-2 mg/cm(3) and of protein binding as a result of the large pore size of the support matrix. Overall, the small particle size and low diffusional hindrance allow capture of IgG with short residence times while attaining substantial dynamic binding capacities.

  3. Adsorption Properties of Tetracycline onto Graphene Oxide: Equilibrium, Kinetic and Thermodynamic Studies

    PubMed Central

    Ghadim, Ehsan Ezzatpour; Manouchehri, Firouzeh; Soleimani, Gholamreza; Hosseini, Hadi; Kimiagar, Salimeh; Nafisi, Shohreh

    2013-01-01

    Graphene oxide (GO) nanoparticle is a high potential effective absorbent. Tetracycline (TC) is a broad-spectrum antibiotic produced, indicated for use against many bacterial infections. In the present research, a systematic study of the adsorption and release process of tetracycline on GO was performed by varying pH, sorption time and temperature. The results of our studies showed that tetracycline strongly loads on the GO surface via π–π interaction and cation–π bonding. Investigation of TC adsorption kinetics showed that the equilibrium was reached within 15 min following the pseudo-second-order model with observed rate constants of k2 = 0.2742–0.5362 g/mg min (at different temperatures). The sorption data has interpreted by the Langmuir model with the maximum adsorption of 323 mg/g (298 K). The mean energy of adsorption was determined 1.83 kJ/mol (298 K) based on the Dubinin–Radushkevich (D–R) adsorption isotherm. Moreover, the thermodynamic parameters such as ΔH°, ΔS° and ΔG° values for the adsorption were estimated which indicated the endothermic and spontaneous nature of the sorption process. The electrochemistry approved an ideal reaction for the adsorption under electrodic process. Simulation of GO and TC was done by LAMMPS. Force studies in z direction showed that tetracycline comes close to GO sheet by C8 direction. Then it goes far and turns and again comes close from amine group to the GO sheet. PMID:24302989

  4. Adsorption and abiotic oxidation of arsenic by aged biofilter media: equilibrium and kinetics.

    PubMed

    Sahabi, Danladi Mahuta; Takeda, Minoru; Suzuki, Ichiro; Koizumi, Jun-ichi

    2009-09-15

    Removal of arsenic from groundwater by biological adsorptive filtration depends largely on its interaction with biogenic iron and manganese oxides surfaces. In the present study we investigated the arsenic adsorption and abiotic oxidation capacities of an aged biofilter medium (BM2) collected from a long time established groundwater treatment plant for removal of iron and manganese by biological filtration. Batch oxidation/adsorption kinetic experiments indicated that BM2 can easily oxidize As(III) to As(V) with the rate of oxidation less affected by pH-variations from 4 to 8.5. The adsorption capacity of the biofilter medium for the produced or added As(V), however, depends strongly on the pH of the solution. The kinetics results have shown that As(III) sorption followed pseudo-second order kinetics, whereas the sorption of As(V) was best described by the intra-particle diffusion model, indicating that adsorptions of As(III) and As(V) onto BM2 were governed by different mechanisms. Adsorption isotherms at 25 degrees C were measured for a range of arsenite and arsenate initial concentrations of 0.67-20 micromol/L and the pH range from 4 to 9. Adsorption maxima were highest at pH 4 and decrease steadily as the pH increases. The equilibrium data for both As(III) and As(V) fitted very well to the Freundlich and Sips isotherm equations and, in most cases, the two isotherms overlapped with the same correlation coefficients, indicating sorption to be multilayer on the heterogeneous surface of BM2. The implication of the data for arsenic removal from water by biological filtration has been discussed.

  5. Equilibrium and kinetics of water adsorption in carbon molecular sieve: theory and experiment.

    PubMed

    Rutherford, S W; Coons, J E

    2004-09-28

    Measurements of water adsorption equilibrium and kinetics in Takeda carbon molecular sieve (CMS) were undertaken in an effort to characterize fundamental mechanisms of adsorption and transport. Adsorption equilibrium revealed a type III isotherm that was characterized by cooperative multimolecular sorption theory. Water adsorption was found to be reversible and did not display hysteresis upon desorption over the conditions studied. Adsorption kinetics measurements revealed that a Fickian diffusion mechanism governed the uptake of water and that the rate of adsorption decreased with increasing relative pressure. Previous investigations have attributed the observed decreasing trend in the rate of adsorption to blocking of micropores. Here, it is proposed that the decrease is attributed to the thermodynamic correction to Fick's law which is formulated on the basis of the chemical potential as the driving force for transport. The thermodynamically corrected formulation accounted for observations of transport of water and other molecules in CMS.

  6. Equilibrium and kinetic adsorption study of the adsorptive removal of Cr(VI) using modified wheat residue.

    PubMed

    Chen, Suhong; Yue, Qinyan; Gao, Baoyu; Xu, Xing

    2010-09-01

    A new adsorbent modified from wheat residue was synthesized after reaction with epichlorohydrin and triethylamine by using the modifying agents of diethylenetriamine in the presence of organic medium of N,N-dimethylformamide. The performance of the modified wheat straw (MWS) was characterized by Fourier transform infrared spectroscopy and point of zero charge analysis. The adsorption was investigated in a batch adsorption system, including both equilibrium adsorption isotherms and kinetics. Results showed that MWR had great anion-adsorbing capacity, due to the existence of a large number of introduced amino groups, and the value of pH(PZC) was around 5.0. Equilibrium data were analyzed using the Langmuir, Freundlich, and Temkin isotherm models and were found to be best represented by the Freundlich isotherm model. Evaluation of the adsorption process identified its endothermic nature. The maximum adsorption capacity of MWS for the removal of Cr(VI) was 322.58mg/g at 328K, indicating that MWS has high chromium removal efficiency, compared to other adsorbents reported. The kinetics of adsorption followed the pseudo-second-order kinetic equation. The mechanism of adsorption was investigated using the intraparticle diffusion model. Thermodynamic parameters (free energy change, enthalpy change, and entropy change) revealed that the adsorption of Cr(VI) onto MWS was endothermic and spontaneous; additionally, the adsorption can be characterized as an ion-exchange process. The results suggest that MWS is an inexpensive and efficient adsorbent for removing Cr(VI) ions from aqueous solution.

  7. Equilibrium and kinetic analysis of phosphorus adsorption from aqueous solution using waste alum sludge.

    PubMed

    Babatunde, A O; Zhao, Y Q

    2010-12-15

    Excess phosphorus (P) in wastewaters promotes eutrophication in receiving waterways. A cost-effective method such as use of novel low-cost adsorbents for its adsorptive removal would significantly reduce such impacts. Using batch experiments, the intrinsic dynamics of P adsorption by waste alum sludge (an inevitable by-product of drinking water treatment plants) was examined. Different models of adsorption were used to describe equilibrium and kinetic data, calculate rate constants and determine the adsorption capacity. Results indicate that the intraparticle rate constant increased from 0.0075 mg g(-1)min(-1) at 5 mg L(-1) to 0.1795 mg g(-1)min(-1) at 60 mg L(-1) indicating that more phosphate is adsorbed per g min at higher P concentration. Further analyses indicate involvement of film and particle diffusion mechanisms as rate controlling steps at lower and higher concentrations, respectively. Mass transfer coefficient obtained ranged from 1.7 × 10(-6) to 1.8 × 10(-8) indicating a rapid transportation of phosphate molecules onto the alum sludge. These results further demonstrates that alum sludge-hitherto thought of as undesirable waste, can be used as novel adsorbent for P removal from wastewater through various applications, thus offsetting a portion of the disposal costs while at the same time improving water quality in sensitive watersheds.

  8. Adsorption of methylene blue onto bamboo-based activated carbon: kinetics and equilibrium studies.

    PubMed

    Hameed, B H; Din, A T M; Ahmad, A L

    2007-03-22

    Bamboo, an abundant and inexpensive natural resource in Malaysia was used to prepare activated carbon by physiochemical activation with potassium hydroxide (KOH) and carbon dioxide (CO(2)) as the activating agents at 850 degrees C for 2h. The adsorption equilibrium and kinetics of methylene blue dye on such carbon were then examined at 30 degrees C. Adsorption isotherm of the methylene blue (MB) on the activated carbon was determined and correlated with common isotherm equations. The equilibrium data for methylene blue adsorption well fitted to the Langmuir equation, with maximum monolayer adsorption capacity of 454.2mg/g. Two simplified kinetic models including pseudo-first-order and pseudo-second-order equation were selected to follow the adsorption processes. The adsorption of methylene blue could be best described by the pseudo-second-order equation. The kinetic parameters of this best-fit model were calculated and discussed.

  9. Equilibrium CO2 adsorption on zeolite 13X prepared from natural clays

    NASA Astrophysics Data System (ADS)

    Garshasbi, Vahid; Jahangiri, Mansour; Anbia, Mansoor

    2017-01-01

    Zeolite 13X was successfully synthesized by hydrothermal treatment using natural clays extracted from Iranian resources. The preliminary natural materials and the final zeolite 13X samples were characterized by X-ray Diffraction (XRD), Fourier-Transfer Infrared (FTIR) spectroscopy, Scanning Electron Microscopy (SEM) and N2 adsorption-desorption isotherm. The effects of various factors such as NaOH addition amount and aging time on the crystalline products were studied during the synthesis process. The optimum conditions related to the synthesis of zeolite 13X were set. Accordingly, NaOH concentration was equal to 4 M. It was further crystallized at 65 °C for 72 h after its homogenization by agitation at room temperature for 120 h. In this study, the zeolite 13X prepared from natural kaolin (13X-K) showed a high BET surface area of 591 m2/g with higher micropore volume (0.250 cm3/g) than other materials. Adsorption equilibrium isotherms of CO2 were investigated using a static, volumetric method. In addition, pressures for the pure component data extended up to 20 bar. The adsorption equilibrium data of CO2 was fitted to Langmuir, Freundlich, Lamgmuir-Freundlich, Toth and BET isotherm models. It was found that the Langmuir-Freundlich model was more suitable than other models for CO2 description. The results showed that the synthetic zeolite has higher equilibrium selectivity for CO2. Also, the CO2 uptake by zeolite 13X-K was equal to 6.9 mmol/g.

  10. Development of adsorbent from Teflon waste by radiation induced grafting: equilibrium and kinetic adsorption of dyes.

    PubMed

    Goel, N K; Kumar, Virendra; Pahan, S; Bhardwaj, Y K; Sabharwal, S

    2011-10-15

    Mutual radiation grafting technique was employed to graft polyacrylic acid (PAA) onto Polytetrafluoroethylene (Teflon) scrap using high energy gamma radiation. Polyacrylic acid-g-Teflon (PAA-g-Teflon) adsorbent was characterized by grafting extent measurement, FTIR spectroscopy, SEM and wet ability & surface energy analysis. The PAA-g-Teflon adsorbent was studied for dye adsorption from aqueous solution of basic dyes, namely, Basic red 29 (BR29) and Basic yellow 11 (BY11). The equilibrium adsorption data were analyzed by Langmuir and Freundlich adsorption isotherm models, whereas, adsorption kinetics was analyzed using pseudo-first order, pseudo-second order and intra-particle diffusion kinetic models. Equilibrium adsorption of BR29 was better explained by Langmuir adsorption model, while that of BY11 by Freundlich adsorption model. The adsorption capacity for BY11 was more than for BR29. Separation factor (R(L)) was found to be in the range 0 < R(L) < 1, indicating favorable adsorption of dyes. Higher coefficient of determination (r(2) > 0.99) and better agreement between the q(e,cal) and q(e,exp) values suggested that pseudo-second order kinetic model better represents the kinetic adsorption data. The non-linearity obtained for intra-particle diffusion plot indicated, more than one process is involved in the adsorption of basic dyes. The desorption studies showed that ~95% of the adsorbed dye could be eluted in suitable eluent.

  11. Evaluation of a predictive model for air/surface adsorption equilibrium constants and enthalpies.

    PubMed

    Arp, Hans Peter H; Goss, Kai-Uwe; Schwarzenbach, René P

    2006-01-01

    A model used to predict equilibrium adsorption to surfaces using a poly-parameter linear free-energy relationship as well as an empirical model used to predict enthalpies of adsorption of volatile compounds were evaluated with new experimental data to cover semivolatile compounds and a larger variability of compound classes. Equilibrium adsorption constants on a quartz surface ranging over seven orders of magnitude were measured for 142 compounds, and enthalpies of adsorption on a quartz surface from -33.7 to -99.8 kJ/mol were measured for 76 compounds. Agreement between experimental and predicted data was within a factor of two (82.1%) or three (100.0%) for the equilibrium adsorption constants and within 20% for the enthalpy of adsorption values. Thus, the scatter in the validation data sets reported here were practically the same as that for the calibration data sets used to derive the models. The few outliers that we identified in the prediction of equilibrium adsorption constants likely are caused by either shortcomings of the reported sorbate parameters or the occurrence of chemical speciation in the water layer on the surface of the quartz.

  12. Dye adsorption onto mesoporous materials: pH influence, kinetics and equilibrium in buffered and saline media.

    PubMed

    Gómez, J M; Galán, J; Rodríguez, A; Walker, G M

    2014-12-15

    Mesoporous materials were used as adsorbents for dye removal in different media: non-ionic, buffered and saline. The mesoporous materials used were commercial (silica gel) as well as as-synthesised materials (SBA-15 and a novel mesoporous carbon). Dye adsorption onto all the materials was very fast and the equilibrium was reached before 1 h. The pH has a significant influence on the adsorption capacity for the siliceous materials since the electrostatic interactions are the driving forces. However, the influence of the pH on the adsorption capacity of the carbonaceous material was lower, since the van der Waals interactions are the driving forces. The ionic strength has a great impact on the siliceous materials adsorption capacity, being their adsorption capacity in a buffered medium six times higher than the corresponding to a non-ionic medium. Nevertheless, ionic strength does not influence on the dye adsorption on the mesoporous carbon. Overall, the as-synthesised carbon material presents a clear potential to treat dye effluents, showing high adsorption capacity (q(e) ≈ 200 mg/g) in all the pH range studied (from 3 to 11); even at low concentrations (C(e) ≈ 10 mg/L) and at short contact times (t(e) < 30 min).

  13. Thermodynamic modeling of solute adsorption equilibrium from near-critical carbon dioxide.

    PubMed

    Yang, Xiaoning

    2004-05-15

    Modeling of adsorption equilibrium for supercritical fluid mixtures, with as few parameters as possible, is important in applications of the technology of supercritical fluid adsorption. In this paper, a correlative model has been developed to represent the adsorption equilibria of solutes from the near-critical CO(2) fluid. A two-dimensional van der Waals equation of state and the three-dimensional P - R equation of state were used to describe the adsorbed and bulk phases, respectively. This model contains five parameters for adsorption equilibrium isotherms at finite concentrations and two parameters for adsorption equilibrium constants at infinite dilution. All the parameters are independent of temperature and pressure. By applying the model to the experimental data from the literature, it was shown that this model is capable of describing the adsorption behavior of solutes from supercritical carbon dioxide over relatively wide temperature and pressure ranges. In addition, the adsorption behavior of supercritical fluid mixtures was investigated at finite and infinite dilution conditions.

  14. Equilibrium studies of copper ion adsorption onto palm kernel fibre.

    PubMed

    Ofomaja, Augustine E

    2010-07-01

    The equilibrium sorption of copper ions from aqueous solution using a new adsorbent, palm kernel fibre, has been studied. Palm kernel fibre is obtained in large amounts as a waste product of palm oil production. Batch equilibrium studies were carried out and system variables such as solution pH, sorbent dose, and sorption temperature were varied. The equilibrium sorption data was then analyzed using the Langmuir, Freundlich, Dubinin-Radushkevich (D-R) and Temkin isotherms. The fit of these isotherm models to the equilibrium sorption data was determined, using the linear coefficient of determination, r(2), and the non-linear Chi-square, chi(2) error analysis. The results revealed that sorption was pH dependent and increased with increasing solution pH above the pH(PZC) of the palm kernel fibre with an optimum dose of 10g/dm(3). The equilibrium data were found to fit the Langmuir isotherm model best, with a monolayer capacity of 3.17 x 10(-4)mol/g at 339K. The sorption equilibrium constant, K(a), increased with increasing temperature, indicating that bond strength between sorbate and sorbent increased with temperature and sorption was endothermic. This was confirmed by the increase in the values of the Temkin isotherm constant, B(1), with increasing temperature. The Dubinin-Radushkevich (D-R) isotherm parameter, free energy, E, was in the range of 15.7-16.7kJ/mol suggesting that the sorption mechanism was ion exchange. Desorption studies showed that a high percentage of the copper was desorbed from the adsorbent using acid solutions (HCl, HNO(3) and CH(3)COOH) and the desorption percentage increased with acid concentration. The thermodynamics of the copper ions/palm kernel fibre system indicate that the process is spontaneous and endothermic.

  15. Equilibrium, kinetic and thermodynamic study of cesium adsorption onto nanocrystalline mordenite from high-salt solution.

    PubMed

    Lee, Keun-Young; Park, Minsung; Kim, Jimin; Oh, Maengkyo; Lee, Eil-Hee; Kim, Kwang-Wook; Chung, Dong-Yong; Moon, Jei-Kwon

    2016-05-01

    In this study, the equilibrium, kinetics and thermodynamics of cesium adsorption by nanocrystalline mordenite were investigated under cesium contamination with high-salt solution, simulating the case of an operation and decommissioning of nuclear facilities or an accident during the processes. The adsorption rate constants were determined using a pseudo second-order kinetic model. The kinetic results strongly demonstrated that the cesium adsorption rate of nano mordenite is extremely fast, even in a high-salt solution, and much faster than that of micro mordenite. In the equilibrium study, the Langmuir isotherm model fit the cesium adsorption data of nano mordenite better than the Freundlich model, which suggests that cesium adsorption onto nano mordenite is a monolayer homogeneous adsorption process. The obtained thermodynamic parameters indicated that the adsorption involved a very stable chemical reaction. In particular, the combination of rapid particle dispersion and rapid cesium adsorption of the nano mordenite in the solution resulted in a rapid and effective process for cesium removal without stirring, which may offer great advantages for low energy consumption and simple operation.

  16. Batch removal of malachite green from aqueous solutions by adsorption on oil palm trunk fibre: equilibrium isotherms and kinetic studies.

    PubMed

    Hameed, B H; El-Khaiary, M I

    2008-06-15

    Oil palm trunk fibre (OPTF)--an agricultural solid waste--was used as low-cost adsorbent to remove malachite green (MG) from aqueous solutions. The operating variables studied were contact time, initial dye concentration, and solution pH. Equilibrium adsorption data were analyzed by three isotherms, namely the Freundlich isotherm, the Langmuir isotherm, and the multilayer adsorption isotherm. The best fit to the data was obtained with the multilayer adsorption. The monolayer adsorption capacity of OPTF was found to be 149.35 mg/g at 30 degrees C. Adsorption kinetic data were modeled using the Lagergren pseudo-first-order, Ho's pseudo-second-order and Elovich models. It was found that the Lagergren's model could be used for the prediction of the system's kinetics. The overall rate of dye uptake was found to be controlled by external mass transfer at the beginning of adsorption, then for initial MG concentrations of 25, 50, 100, 150, and 300 mg/L the rate-control changed to intraparticle diffusion at a later stage, but for initial MG concentrations 200 and 250 mg/L no evidence was found of intraparticle diffusion at any period of adsorption. It was found that with increasing the initial concentration of MG, the pore-diffusion coefficient increased while the film-diffusion coefficient decreased.

  17. Equilibrium, kinetic and thermodynamic studies on the adsorption of 2-nitroaniline onto activated carbon prepared from cotton stalk fibre.

    PubMed

    Li, Kunquan; Zheng, Zheng; Huang, Xingfa; Zhao, Guohua; Feng, Jingwei; Zhang, Jibiao

    2009-07-15

    Activated carbon prepared from cotton stalk fibre has been utilized as an adsorbent for the removal of 2-nitroaniline from aqueous solutions. The influence of adsorbent mass, contact time and temperature on the adsorption was investigated by conducting a series of batch adsorption experiments. The equilibrium data at different temperatures were fitted with the Langmuir, Freundlich, Tempkin, Redlich-Peterson and Langmuir-Freundlich models. The Langmuir-Freundlich isotherm was found to best describe the experimental data. The adsorption amount increased with increasing temperature. The maximum adsorption capacity of 2-nitroaniline was found to be 383 mg/g for initial 2-nitroaniline concentration of 200mg/L at 45 degrees C. The kinetic rates were modeled by using the Lagergren-first-order, pseudo-second-order and Elovich models. The pseudo-second-order model was found to explain the adsorption kinetics most effectively. It was also found that the pore diffusion played an important role in the adsorption, and intraparticle diffusion was the rate-limiting step at the first 30 min for the temperatures of 25, 35 and 45 degrees C. FTIR and (13)C NMR study revealed that the amino and isocyanate groups present on the surface of the adsorbent were involved in chemical interaction with 2-nitroaniline. The negative change in free energy (Delta G degrees) and positive change in enthalpy (Delta H degrees) indicated that the adsorption was a spontaneous and endothermic process.

  18. Adsorption and desorption of arsenate on sandy sediments from contaminated and uncontaminated saturated zones: Kinetic and equilibrium modeling.

    PubMed

    Hafeznezami, Saeedreza; Zimmer-Faust, Amity G; Dunne, Aislinn; Tran, Tiffany; Yang, Chao; Lam, Jacquelyn R; Reynolds, Matthew D; Davis, James A; Jay, Jennifer A

    2016-08-01

    Application of empirical models to adsorption of contaminants on natural heterogeneous sorbents is often challenging due to the uncertainty associated with fitting experimental data and determining adjustable parameters. Sediment samples from contaminated and uncontaminated portions of a study site in Maine, USA were collected and investigated for adsorption of arsenate [As(V)]. Two kinetic models were used to describe the results of single solute batch adsorption experiments. Piecewise linear regression of data linearized to fit pseudo-first order kinetic model resulted in two distinct rates and a cutoff time point of 14-19 h delineating the biphasic behavior of solute adsorption. During the initial rapid adsorption stage, an average of 60-80% of the total adsorption took place. Pseudo-second order kinetic models provided the best fit to the experimental data (R(2) > 0.99) and were capable of describing the adsorption over the entire range of experiments. Both Langmuir and Freundlich isotherms provided reasonable fits to the adsorption data at equilibrium. Langmuir-derived maximum adsorption capacity (St) of the studied sediments ranged between 29 and 97 mg/kg increasing from contaminated to uncontaminated sites. Solid phase As content of the sediments ranged from 3.8 to 10 mg/kg and the As/Fe ratios were highest in the amorphous phase. High-pH desorption experiments resulted in a greater percentage of solid phase As released into solution from experimentally-loaded sediments than from the unaltered samples suggesting that As(V) adsorption takes place on different reversible and irreversible surface sites.

  19. Competitive adsorption of metal cations onto two gram positive bacteria: testing the chemical equilibrium model

    NASA Astrophysics Data System (ADS)

    Fowle, David A.; Fein, Jeremy B.

    1999-10-01

    In order to test the ability of a surface complexation approach to account for metal-bacteria interactions in near surface fluid-rock systems, we have conducted experiments that measure the extent of adsorption in mixed metal, mixed bacteria systems. This study tests the surface complexation approach by comparing estimated extents of adsorption based on surface complexation modeling to those we observed in the experimental systems. The batch adsorption experiments involved Ca, Cd, Cu, and Pb adsorption onto the surfaces of 2 g positive bacteria: Bacillus subtilis and Bacillus licheniformis. Three types of experiments were performed: 1. Single metal (Ca, Cu, Pb) adsorption onto a mixture of B. licheniformis and B. subtilis; 2. mixed metal (Cd, Cu, and Pb; Ca and Cd) adsorption onto either B. subtilis or B. licheniformis; and 3. mixed or single metal adsorption onto B. subtilis and B. licheniformis. %Independent of the experimental results, and based on the site specific stability constants for Ca, Cd, Cu, and Pb interactions with the carboxyl and phosphate sites on B. licheniformis and B. subtilis determined by Fein et al. (1997), by Daughney et al. (1998) and in this study, we estimate the extent of adsorption that is expected in the above experimental systems. Competitive cation adsorption experiments in both single and double bacteria systems exhibit little adsorption at pH values less than 4. With increasing pH above 4.0, the extent of Ca, Cu, Pb and Cd adsorption also increases due to the increased deprotonation of bacterial surface functional groups. In all cases studied, the estimated adsorption behavior is in excellent agreement with the observations, with only slight differences that were within the uncertainties of the estimation and experimental procedures. Therefore, the results indicate that the use of chemical equilibrium modeling of aqueous metal adsorption onto bacterial surfaces yields accurate predictions of the distribution of metals in complex

  20. Equilibrium and kinetic adsorption study of a cationic dye by a natural adsorbent--silkworm pupa.

    PubMed

    Noroozi, B; Sorial, G A; Bahrami, H; Arami, M

    2007-01-02

    In this work the use of silkworm pupa, which is the waste of silk spinning industries has been investigated as an adsorbent for the removal of C.I. Basic Blue 41. The amino acid nature of the pupa provided a reasonable capability for dye removal. Equilibrium adsorption isotherms and kinetics were investigated. The adsorption equilibrium data were analyzed by using various adsorption isotherm models and the results have shown that adsorption behavior of the dye could be described reasonably well by either Langmuir or Freundlich models. The characteristic parameters for each isotherm have been determined. The monolayer adsorption capacity was determined to be 555 mg/g. Kinetic studies indicated that the adsorption follows pseudo-second-order kinetics with a rate constant of 0.0434 and 0.0572 g/min mg for initial dye concentration of 200 mg/l at 20 and 40 degrees C, respectively. Kinetic studies showed that film diffusion and intra-particle diffusion were simultaneously operating during the adsorption process. The rate constant for intra-particle diffusion was estimated to be 1.985 mg/g min(0.5).

  1. Equilibrium and column adsorption studies of 2,4-dinitroanisole (DNAN) on surface modified granular activated carbons.

    PubMed

    Boddu, V M; Abburi, K; Fredricksen, A J; Maloney, S W; Damavarapu, R

    2009-02-01

    2,4-Dinitroanisole (DNAN) is used as a component extensively in the development of insensitive munitions. This may result in release of DNAN into the environment. Here, the results are reported of a study on the removal characteristics of DNAN through adsorption on granular activated carbon (GAC), chitosan coated granular activated carbon (CGAC), acid treated granular activated carbon (AGAC) and alkali treated granular activated carbon (BGAC) under equilibrium and column flow conditions. The effect of pH, contact time, concentration of DNAN, and presence of electrolytes on the uptake of DNAN by the adsorbents was investigated. The equilibrium data were fitted to different types of adsorption isotherms. The data were further analysed on the basis of Lagergren first-order, pseudo second-order and intraparticle diffusion kinetic models. Breakthrough curves were obtained based on column flow results. All the adsorbents were capable of removing about 99% of DNAN from aqueous media, except CGAC which adsorbed about 87% of DNAN.

  2. Methylene blue adsorption onto swede rape straw (Brassica napus L.) modified by tartaric acid: equilibrium, kinetic and adsorption mechanisms.

    PubMed

    Feng, Yanfang; Zhou, Hui; Liu, Guohua; Qiao, Jun; Wang, Jinhua; Lu, Haiying; Yang, Linzhang; Wu, Yonghong

    2012-12-01

    The aim of this study was to develop a promising and competitive bioadsorbent with the abundant of source, low price and environmentally friendly characters to remove cationic dye from wastewater. The swede rape straw (Brassica napus L.) modified by tartaric acid (SRSTA) was prepared, characterized and used to remove methylene blue (MB) from aqueous solution at varied operational conditions (including MB initial concentrations, adsorbent dose, etc.). Results demonstrated that the equilibrium data was well fitted by Langmuir isotherm model. The maximum MB adsorption capacity of SRSTA was 246.4 mg g(-1), which was comparable to the results of some previous studied activated carbons. The higher dye adsorption capacity could be attributed to the presence of more functional groups such as carboxyl group on the surface of SRSTA. The adsorption mechanism was also discussed. The results indicate that SRSTA is a promising and valuable absorbent to remove methylene blue from wastewater.

  3. Rapid adsorption of copper(II) and lead(II) by rice straw/Fe₃O₄ nanocomposite: optimization, equilibrium isotherms, and adsorption kinetics study.

    PubMed

    Khandanlou, Roshanak; Ahmad, Mansor B; Fard Masoumi, Hamid Reza; Shameli, Kamyar; Basri, Mahiran; Kalantari, Katayoon

    2015-01-01

    Rice straw/magnetic nanocomposites (RS/Fe3O4-NCs) were prepared via co-precipitation method for removal of Pb(II) and Cu(II) from aqueous solutions. Response surface methodology (RSM) was utilized to find the optimum conditions for removal of ions. The effects of three independent variables including initial ion concentration, removal time, and adsorbent dosage were investigated on the maximum adsorption of Pb (II) and Cu (II). The optimum conditions for the adsorption of Pb(II) and Cu(II) were obtained (100 and 60 mg/L) of initial ion concentration, (41.96 and 59.35 s) of removal time and 0.13 g of adsorbent for both ions, respectively. The maximum removal efficiencies of Pb(II) and Cu(II) were obtained 96.25% and 75.54%, respectively. In the equilibrium isotherm study, the adsorption data fitted well with the Langmuir isotherm model. The adsorption kinetics was best depicted by the pseudo-second order model. Desorption experiments showed adsorbent can be reused successfully for three adsorption-desorption cycles.

  4. Rapid Adsorption of Copper(II) and Lead(II) by Rice Straw/Fe3O4 Nanocomposite: Optimization, Equilibrium Isotherms, and Adsorption Kinetics Study

    PubMed Central

    Khandanlou, Roshanak; Ahmad, Mansor B.; Fard Masoumi, Hamid Reza; Shameli, Kamyar; Basri, Mahiran; Kalantari, Katayoon

    2015-01-01

    Rice straw/magnetic nanocomposites (RS/Fe3O4-NCs) were prepared via co-precipitation method for removal of Pb(II) and Cu(II) from aqueous solutions. Response surface methodology (RSM) was utilized to find the optimum conditions for removal of ions. The effects of three independent variables including initial ion concentration, removal time, and adsorbent dosage were investigated on the maximum adsorption of Pb (II) and Cu (II). The optimum conditions for the adsorption of Pb(II) and Cu(II) were obtained (100 and 60 mg/L) of initial ion concentration, (41.96 and 59.35 s) of removal time and 0.13 g of adsorbent for both ions, respectively. The maximum removal efficiencies of Pb(II) and Cu(II) were obtained 96.25% and 75.54%, respectively. In the equilibrium isotherm study, the adsorption data fitted well with the Langmuir isotherm model. The adsorption kinetics was best depicted by the pseudo-second order model. Desorption experiments showed adsorbent can be reused successfully for three adsorption-desorption cycles. PMID:25815470

  5. Equilibrium model for biodegradation and adsorption of mixtures in GAC columns

    SciTech Connect

    Erlanson, B.C.; Dvorak, B.I.; Speitel, G.E. Jr.; Lawler, D.F.

    1997-05-01

    Microbial activity in granular activated carbon (GAC) columns has received much attention over the last 15 years because biodegradation of one or more chemicals might increase the GAC service life, thereby decreasing costs. An equilibrium model for simultaneous biodegradation and adsorption was developed and verified with existing data. For simplicity the model was restricted to only two components: one biodegradable and one not. The results from modeling over 300 hypothetical situations identified conditions where biodegradation significantly extends the service life of granular activated carbon (GAC) columns. When the nonbiodegradable chemical controls the service life, the only significant gains in service life occurred when the biodegradable and nonbiodegradable chemical had similar adsorbabilities. When the biodegradable chemical controls the service life, the service life was 1.2--7 times that with adsorption alone, depending on the relative adsorbability of the two chemicals. The increase in service life can be maximized by ensuring that biodegradation begins as soon as possible after start-up. The model provides a good screening tool for initial assessments of process feasibility, preliminary economic analyses, and planning of detailed experimental and computer modeling studies. Examples are presented using benzene and TCE to illustrate how the general trends presented apply to specific cases.

  6. Adsorption equilibrium and kinetics for SO2, NO, CO2 on zeolites FAU and LTA.

    PubMed

    Yi, Honghong; Deng, Hua; Tang, Xiaolong; Yu, Qiongfen; Zhou, Xuan; Liu, Haiyan

    2012-02-15

    In order to develop a single-step process for removing SO(2), NO, CO(2) in flue gas simultaneously by co-adsorption method. Pure component adsorption equilibrium and kinetics of SO(2), NO, and CO(2) on zeolite NaY, NaX, CaA were obtained respectively. Equilibrium data were analyzed by equilibrium model and Henry's law constant. The results suggest that Adsorption affinity follows the trend SO(2)>CO(2)>NO for the same adsorbent. Zeolite with stronger polar surface is a more promising adsorbent candidate. Kinetics behavior was investigated using the breakthrough curve method. The overall mass transfer coefficient and diffusivity factor were determined by a linear driving force model. The results are indicative of micropore diffusion controlling mechanism. NaY zeolite has the minimum resistance of mass transfer duo to the wide pore distribution and large pore amount. CaA zeolite exhibits the highest spatial hindered effect. Finally, co-adsorption effect of SO(2), NO, and CO(2) were investigated by multi-components breakthrough method. SO(2) and NO may form new adsorbed species, however, CO(2) presents a fast breakthrough. Chemical adsorption causes SO(2) transforms to SO(4)(2-), however, element N and C are not detected in adsorbed zeolites.

  7. Removal of phenol from aqueous solutions by adsorption onto organomodified Tirebolu bentonite: equilibrium, kinetic and thermodynamic study.

    PubMed

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

    2009-12-15

    A natural bentonite modified with a cationic surfactant, cetyl trimethylammonium bromide (CTAB), was used as an adsorbent for removal of phenol from aqueous solutions. The natural and modified bentonites (organobentonite) were characterized with some instrumental techniques (FTIR, XRD and SEM). Adsorption studies were performed in a batch system, and the effects of various experimental parameters such as solution pH, contact time, initial phenol concentration, organobentonite concentration, and temperature, etc. were evaluated upon the phenol adsorption onto organobentonite. Maximum phenol removal was observed at pH 9.0. Equilibrium was attained after contact of 1h only. The adsorption isotherms were described by Langmuir and Freundlich isotherm models, and both model fitted well. The monolayer adsorption capacity of organobentonite was found to be 333 mg g(-1). Desorption of phenol from the loaded adsorbent was achieved by using 20% acetone solution. The kinetic studies indicated that the adsorption process was best described by the pseudo-second-order kinetics (R(2) > 0.99). Thermodynamic parameters including the Gibbs free energy (DeltaG degrees), enthalpy (DeltaH degrees), and entropy (DeltaS degrees) were also calculated. These parameters indicated that adsorption of phenol onto organobentonite was feasible, spontaneous and exothermic in the temperature range of 0-40 degrees C.

  8. Adsorption of direct dye on palm ash: kinetic and equilibrium modeling.

    PubMed

    Ahmad, A A; Hameed, B H; Aziz, N

    2007-03-06

    Palm ash, an agriculture waste residue from palm-oil industry in Malaysia, was investigated as a replacement for the current expensive methods of removing direct blue 71 dye from an aqueous solution. The experimental data were analyzed by the Langmuir and Freundlich models of adsorption. Equilibrium data fitted well with Freundlich model in the range of 50-600mg/L. The equilibrium adsorption capacity of the palm ash was determined with the Langmuir equation and found to be 400.01mg dye per gram adsorbent at 30 degrees C. The rates of adsorption were found to conform to the pseudo-second-order kinetics with good correlation. The results indicate that the palm ash could be employed as a low-cost alternative to commercial activated carbon.

  9. Adsorption of reactive dyes from aqueous solutions by fly ash: kinetic and equilibrium studies.

    PubMed

    Dizge, N; Aydiner, C; Demirbas, E; Kobya, M; Kara, S

    2008-02-11

    Adsorption kinetic and equilibrium studies of three reactive dyes namely, Remazol Brillant Blue (RB), Remazol Red 133 (RR) and Rifacion Yellow HED (RY) from aqueous solutions at various initial dye concentration (100-500 mg/l), pH (2-8), particle size (45-112.5 microm) and temperature (293-323 K) on fly ash (FA) were studied in a batch mode operation. The adsorbent was characterized with using several methods such as SEM, XRD and FTIR. Adsorption of RB reactive dye was found to be pH dependent but both RR and RY reactive dyes were not. The result showed that the amount adsorbed of the reactive dyes increased with increasing initial dye concentration and contact time. Batch kinetic data from experimental investigations on the removal of reactive dyes from aqueous solutions using FA have been well described by external mass transfer and intraparticle diffusion models. It was found that external mass transfer and intraparticle diffusion had rate limiting affects on the removal process. This was attributed to the relatively simple macropore structure of FA particles. The adsorption data fitted well with Langmuir and Freundlich isotherm models. The optimum conditions for removal of the reactive dyes were 100mg/l initial dye concentration, 0.6g/100ml adsorbent dose, temperature of 293 K, 45 microm particle size, pH 6 and agitation speed of 250 rpm, respectively. The values of Langmuir and Freundlich constants were found to increase with increasing temperature in the range 135-180 and 15-34 mg/g for RB, 47-86 and 1.9-3.7 mg/g for RR and 37-61 and 3.0-3.6 mg/g for RY reactive dyes, respectively. Different thermodynamic parameters viz., changes in standard free energy, enthalpy and entropy were evaluated and it was found that the reaction was spontaneous and endothermic in nature.

  10. Binary adsorption equilibrium of carbon dioxide and water vapor on activated alumina.

    PubMed

    Li, Gang; Xiao, Penny; Webley, Paul

    2009-09-15

    Adsorption equilibria of a CO2/H2O binary mixture on activated alumina F-200 were measured at several temperatures and over a wide range of concentrations from 4% to around 90% of the saturated water vapor pressure. In comparison with the single-component data, the loading of CO2 was not reduced in the presence of H2O, whereas at low relative humidity the adsorption of H2O was depressed. The binary system was described by a competitive/cooperative adsorption model where the readily adsorbed water layers acted as secondary sites for further CO2 adsorption via hydrogen bonding or hydration reaction. The combination of kinetic models, namely, a Langmuir isotherm for characterizing pure CO2 adsorption and a BET isotherm for H2O, was extended to derive a binary adsorption equilibrium model for the CO2/H2O mixture. Models based on the ideal adsorbed solution theory of Myers and Prausnitz failed to characterize the data over the whole composition range, and a large deviation of binary CO2/H2O equilibrium from ideal solution behavior was observed. The extended Langmuir-BET (LBET) isotherm, analogous to the extended Langmuir equation, drastically underestimated the CO2 loading. By incorporating the interactions between CO2 and H2O molecules on the adsorbent surface and taking into account the effect of nonideality, the realistic interactive LBET (R-LBET) model was found to be in very good agreement with the experimental data. The derived binary isosteric heat of adsorption showed that the heat was reduced by competitive adsorption but promoted by cooperative adsorption.

  11. Equilibrium and dynamic study on hexavalent chromium adsorption onto activated carbon.

    PubMed

    Di Natale, F; Erto, A; Lancia, A; Musmarra, D

    2015-01-08

    In this work, the results of equilibrium and dynamic adsorption tests of hexavalent chromium, Cr (VI), on activated carbon are presented. Adsorption isotherms were determined at different levels of pH and temperature. Dynamic tests were carried out in terms of breakthrough curves of lab-scale fixed bed column at different pH, inlet concentration and flow rate. Both the adsorption isotherms and the breakthrough curves showed non-linear and unconventional trends. The experimental results revealed that chromium speciation played a key role in the adsorption process, also for the occurrence of Cr(VI)-to-Cr(III) reduction reactions. Equilibrium tests were interpreted in light of a multi-component Langmuir model supported by ion speciation analysis. For the interpretation of the adsorption dynamic tests, a mass transfer model was proposed. Dynamic tests at pH 11 were well described considering the external mass transfer as the rate controlling step. Differently, for dynamic tests at pH 6 the same model provided a satisfying description of the experimental breakthrough curves only until a sorbent coverage around 1.6mgg(-1). Above this level, a marked reduction of the breakthrough curve slope was observed in response to a transition to an inter-particle adsorption mechanism.

  12. Equilibrium and kinetic aspects of sodium cromoglycate adsorption on chitosan: mass uptake and surface charging considerations.

    PubMed

    de Lima, C R M; Pereira, M R; Fonseca, J L C

    2013-09-01

    Chitosan has more and more been suggested as a material for use as adsorbent in the treatment of effluents as well as in the synthesis of drug-loaded nanoparticles for controlled release. In both cases, a good understanding of the process of adsorption, both kinetically and in terms of equilibrium, has an importance of its own. In this manuscript we study the interaction between sodium cromoglycate, a drug used in asthma treatment, and chitosan. Equilibrium experiments showed that Sips (or Freundlich-Langmuir) isotherm described well the resultant data and adsorption possibly occurred as in multilayers. A model based on ordinary reaction-rate theory, compounded of two processes, each one with a correlated velocity constant, described the kinetics of sorption. Kinetic and equilibrium data suggested the possibility of surface rearrangement, favored by the increase of temperature.

  13. 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

  14. Kinetics and equilibrium adsorption study of lead(II) onto activated carbon prepared from coconut shell.

    PubMed

    Sekar, M; Sakthi, V; Rengaraj, S

    2004-11-15

    Removal of lead from aqueous solutions by adsorption onto coconut-shell carbon was investigated. Batch adsorption experiments were performed to find out the effective lead removal at different metal ion concentrations. Adsorption of Pb2+ ion was strongly affected by pH. The coconut-shell carbon (CSC) exhibited the highest lead adsorption capacity at pH 4.5. Isotherms for the adsorption of lead on CSC were developed and the equilibrium data fitted well to the Langmuir, Freundlich, and Tempkin isotherm models. At pH 4.5, the maximum lead adsorption capacity of CSC estimated with the Langmuir model was 26.50 mg g(-1) adsorbent. Energy of activation (Ea) and thermodynamic parameters such as DeltaG, DeltaH, and DeltaS were evaluated by applying the Arrhenius and van't Hoff equations. The thermodynamics of Pb(II) on CSC indicates the spontaneous and endothermic nature of adsorption. Quantitative desorption of Pb(II) from CSC was found to be 75% which facilitates the sorption of metal by ion exchange.

  15. Adsorption behaviour of direct yellow 50 onto cotton fiber: equilibrium, kinetic and thermodynamic profile.

    PubMed

    Ismail, L F M; Sallam, H B; Abo Farha, S A; Gamal, A M; Mahmoud, G E A

    2014-10-15

    This study investigated the adsorption of direct yellow 50 onto cotton fiber from aqueous solution by using parameters, such as pH, temperature, contact time, initial dye concentration and the effect of sodium sulphate, tetrasodium edate and trisodium citrate. The extent of dye adsorption increased with increasing contact time, temperature and solution concentration. The experimental data were analyzed by the Langmuir and Freundlich models of adsorption. It was found that the Langmuir equation fit better than the Freundlich equation. The results show that the presence of SE and SC significantly enhance the dye adsorption onto cotton fiber. In addition, the adsorption data obtained at different temperatures of DY50 onto cotton fiber were applied to pseudo first-order, pseudo second-order and intraparticle diffusion models. The rates of adsorption were found to conform to pseudo second-order kinetics with good correlation. Also, free energy of adsorption (ΔG(#)), enthalpy (ΔH(#)), and entropy (ΔS(#)) changes were determined to predict the nature of adsorption. The positive value of the enthalpy change indicated that the adsorption is endothermic process. The activation energy, Ea, is ranged between 1.9 and 3.9kJmol(-1) indicated that the adsorption process is a physisorption. This low value of Ea generally indicates diffusion controlled process.

  16. Adsorption behaviour of direct yellow 50 onto cotton fiber: Equilibrium, kinetic and thermodynamic profile

    NASA Astrophysics Data System (ADS)

    Ismail, L. F. M.; Sallam, H. B.; Abo Farha, S. A.; Gamal, A. M.; Mahmoud, G. E. A.

    2014-10-01

    This study investigated the adsorption of direct yellow 50 onto cotton fiber from aqueous solution by using parameters, such as pH, temperature, contact time, initial dye concentration and the effect of sodium sulphate, tetrasodium edate and trisodium citrate. The extent of dye adsorption increased with increasing contact time, temperature and solution concentration. The experimental data were analyzed by the Langmuir and Freundlich models of adsorption. It was found that the Langmuir equation fit better than the Freundlich equation. The results show that the presence of SE and SC significantly enhance the dye adsorption onto cotton fiber. In addition, the adsorption data obtained at different temperatures of DY50 onto cotton fiber were applied to pseudo first-order, pseudo second-order and intraparticle diffusion models. The rates of adsorption were found to conform to pseudo second-order kinetics with good correlation. Also, free energy of adsorption (ΔG#), enthalpy (ΔH#), and entropy (ΔS#) changes were determined to predict the nature of adsorption. The positive value of the enthalpy change indicated that the adsorption is endothermic process. The activation energy, Ea, is ranged between 1.9 and 3.9 kJ mol-1 indicated that the adsorption process is a physisorption. This low value of Ea generally indicates diffusion controlled process.

  17. Adsorption equilibrium and kinetics of monomer-dimer monoclonal antibody mixtures on a cation exchange resin.

    PubMed

    Reck, Jason M; Pabst, Timothy M; Hunter, Alan K; Wang, Xiangyang; Carta, Giorgio

    2015-07-10

    Adsorption equilibrium and kinetics are determined for a monoclonal antibody (mAb) monomer and dimer species, individually and in mixtures, on a macroporous cation exchange resin both under the dilute limit of salt gradient elution chromatography and at high protein loads and low salt based on batch adsorption equilibrium and confocal laser scanning microscopy (CLSM) experiments. In the dilute limit and weak binding conditions, the dimer/monomer selectivity in 10mM phosphate at pH 7 varies between 8.7 and 2.3 decreasing with salt concentration in the range of 170-230mM NaCl. At high protein loads and strong binding conditions (0-60mM NaCl), the selectivity in the same buffer is near unity with no NaCl added, but increases gradually with salt concentration reaching high values between 2 and 15 with 60mM added NaCl. For these conditions, the two-component adsorption kinetics is controlled by pore diffusion and is predicted approximately by a dual shrinking core model using parameters based on single component equilibrium and kinetics measurements.

  18. Equilibrium and kinetic modeling of adsorptive sulfur removal from gasoline by synthesized Ce-Y zeolite

    NASA Astrophysics Data System (ADS)

    Montazerolghaem, Maryam; Rahimi, Amir; Seyedeyn-Azad, Fakhry

    2010-11-01

    In this research, the adsorption of a model sulfur compound, thiophene, from a simulated gasoline onto Ce-Y zeolite in pellet and powder forms was investigated. For this purpose, zeolite Na-Y was synthesized, and Ce-Y zeolite was prepared via solid-state ion-exchanged (SSIE) method. Adsorptive desulfurization of model gasoline was conducted in a batch reactor at ambient conditions to evaluate the equilibrium and kinetics of thiophene adsorption onto Ce-Y zeolite. The equilibrium data were fitted to Langmuire and Toth models. Pseudo-n-order and modified n-order models, LDF-base model, and intra-particle diffusion model were evaluated to fit the kinetic of the adsorption process and to determine the mechanism of it. The corresponding parameters and/or correlation coefficients of each model were reported. The LDF-base model was used also to fit the mass transfer coefficient for both powder and pellet forms of the adsorbent. The best fit estimates for the mass transfer coefficient were obtained 4 × 10-11 m/s and k = 3.1 × 10-12[exp( - t/τ) + 1/(t + 10-4)], for powder and pellet form adsorbents, respectively.

  19. 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.

  20. Equilibrium and kinetic studies of C.I. Basic Blue 41 adsorption onto N, F-codoped flower-like TiO2 microspheres

    NASA Astrophysics Data System (ADS)

    Jiang, Yinhua; Luo, Yingying; Zhang, Fumei; Guo, Leiqun; Ni, Liang

    2013-05-01

    Three-dimensional (3D) N, F-codoped flower-like TiO2 microspheres were successfully synthesized by a hydrothermal method combined with calcination process. The as-prepared samples were characterized by XRD, FE-SEM and EDS. The adsorption abilities of prepared samples were investigated for the removal of C.I. Basic Blue 41(CB41) from aqueous solution. The FE-SEM and adsorption results showed that doping amount of NH4F affected the morphologies of samples and sample NFT-1 with the structure of 3D flower-like microsphere had the highest adsorption amount of CB41. The effects of varying parameters such as pH, contact time, initial dye concentration and temperature on the CB41 adsorption onto NFT-1 were further examined. Equilibrium data correlated with Langmuir, Freundlich and Temkin isotherms. The Langmuir isotherm showed the best fit to the equilibrium data. The kinetic experimental data were analyzed by three kinetic models including the pseudo-first-order model, the pseudo-second-order model and the intraparticle diffusion model to access the adsorption mechanism and the potential rate-controlling step. The pseudo-second-order kinetic model described best for the adsorption of CB41 on NFT-1 and the intraparticle diffusion was not the only rate-controlling step. The thermodynamics parameters as positive values of ΔH° and negative values of ΔG° showed that the adsorption process was endothermic and spontaneous in nature.

  1. Characteristics of equilibrium, kinetics studies for adsorption of Hg(II), Cu(II), and Ni(II) ions by thiourea-modified magnetic chitosan microspheres.

    PubMed

    Zhou, Limin; Wang, Yiping; Liu, Zhirong; Huang, Qunwu

    2009-01-30

    Magnetic chitosan microspheres were prepared and chemically modified with thiourea (TMCS) for adsorption of metal ions. TMCS obtained were investigated by means of X-ray diffraction (XRD), IR, magnetic properties and thermogravimetric analysis (TGA). The adsorption properties of TMCS toward Hg(2+), Cu(2+), and Ni(2+) ions were evaluated. Various factors affecting the uptake behavior such as contact time, temperature, pH and initial concentration of the metal ions were investigated. The kinetics was evaluated utilizing the pseudo-first-order, pseudo-second-order, and the intra-particle diffusion models. The equilibrium data were analyzed using the Langmuir, Freundlich, and Tempkin isotherm models. The adsorption kinetics followed the mechanism of the pseudo-second-order equation for all systems studied, evidencing chemical sorption as the rate-limiting step of adsorption mechanism and not involving a mass transfer in solution. The best interpretation for the equilibrium data was given by Langmuir isotherm, and the maximum adsorption capacities were 625.2, 66.7, and 15.3mg/g for Hg(2+), Cu(2+), and Ni(2+) ions, respectively. TMCS displayed higher adsorption capacity for Hg(2+) in all pH ranges studied. The adsorption capacity of the metal ions decreased with increasing temperature. The metal ion-loaded TMCS with were regenerated with an efficiency of greater than 88% using 0.01-0.1M ethylendiamine tetraacetic acid (EDTA).

  2. Kinetics and equilibrium of adsorption of dissolved organic matter fractions from secondary effluent by fly ash.

    PubMed

    Wei, Liangliang; Wang, Kun; Zhao, Qingliang; Xie, Chunmei; Qiu, Wei; Jia, Ting

    2011-01-01

    Fly ash was used as a low-cost adsorbent for removing dissolved organic matter (DOM) in secondary effluent. Batch experiments were conducted under various adsorbent dosages, pH, contact time, temperatures and DOM fractional characteristics. Under the optimum conditions of fly ash dosage of 15 g/L, temperature of 303 K and contact time of 180 min, a removal of 22.5% of the dissolved organic carbon (DOC), 23.7% of UV-254, 25.9% of the trihalomethanes precursors in secondary effluent was obtained. The adsorption of DOM fractions onto fly ash all followed the pseudo second-order kinetic model, and the hydrophilic fraction adsorption by fly ash also fitted the intraparticle diffusion model quite well. Freundlich and Langmuir models were applicable to the fly ash adsorption and their constants were evaluated. The maximum adsorption capacities of the adsorptions revealed that fly ash was more effective in adsorbing hydrophilic fraction than the acidic fractions. Structure changes of the DOM fractions after fly ash adsorption were also characterized via spectrum analyzing. Those mechanisms presented critical step toward improved efficiencies of fly ash adsorption via further surface-modification.

  3. Adsorption of geosmin and 2-methylisoborneol onto powdered activated carbon at non-equilibrium conditions: influence of NOM and process modelling.

    PubMed

    Zoschke, Kristin; Engel, Christina; Börnick, Hilmar; Worch, Eckhard

    2011-10-01

    The adsorption of the taste and odour (T&O) compounds geosmin and 2-methylisoborneol (2-MIB) onto powdered activated carbon (PAC) has been studied under conditions which are typical for a drinking water treatment plant that uses reservoir water for drinking water production. The reservoir water as well as the pre-treated water (after flocculation) contains NOM that competes with the trace compounds for the adsorption sites on the carbon surface. Although the DOC concentrations in the reservoir water and in the pre-treated water were different, no differences in the competitive adsorption could be seen. By using two special characterisation methods for NOM (adsorption analysis, LC/OCD) it could be proved that flocculation removes only NOM fractions which are irrelevant for competitive adsorption. Different model approaches were applied to describe the competitive adsorption of the T&O compounds and NOM, the tracer model, the equivalent background compound model, and the simplified equivalent background compound model. All these models are equilibrium models but in practice the contact time in flow-through reactors is typically shorter than the time needed to establish the adsorption equilibrium. In this paper it is demonstrated that the established model approaches can be used to describe competitive adsorption of T&O compounds and NOM also under non-equilibrium conditions. The results of the model applications showed that in particular the simplified equivalent background compound model is a useful tool to determine the PAC dosage required to reduce the T&O compounds below the threshold concentration.

  4. Equilibrium and kinetic modeling of adsorption of reactive dye on cross-linked chitosan beads.

    PubMed

    Chiou, Ming Shen; Li, Hsing Ya

    2002-07-22

    The adsorption of reactive dye (Reactive Red 189) from aqueous solutions on cross-linked chitosan beads was studied in a batch system. The equilibrium isotherms at different particle sizes (2.3-2.5, 2.5-2.7 and 3.5-3.8mm) and the kinetics of adsorption with respect to the initial dye concentration (4320, 5760 and 7286 g/m(3)), temperature (30, 40 and 50 degrees C), pH (1.0, 3.0, 6.0 and 9.0), and cross-linking ratio (cross-linking agent/chitosan weight ratio: 0.2, 0.5, 0.7 and 1.0) were investigated. Langmuir and Freundlich adsorption models were applied to describe the experimental isotherms and isotherm constants. Equilibrium data fitted very well to the Langmuir model in the entire saturation concentration range (0-1800 g/m(3)). The maximum monolayer adsorption capacities obtained from the Langmuir model are very large, which are 1936, 1686 and 1642 g/kg for small, mediumand large particle sizes, respectively, at pH 3.0, 30 degrees C, and the cross-linking ratio of 0.2. The pseudo first- and second-order kinetic models were used to describe the kinetic data, and the rate constants were evaluated. The experimental data fitted well to the second-order kinetic model, which indicates that the chemical sorption is the rate-limiting step, instead of mass transfer. The initial dye concentration and the solution pH both significantly affect the adsorption capacity, but the temperature and the cross-linking ratio are relatively minor factors. An increase in initial dye concentration results in the increase of adsorption capacity, which also increases with decreasing pH. The activation energy is 43.0 kJ/mol for the adsorption of the dye on the cross-linked chitosan beads at pH 3.0 and initial dye concentration 3768 g/m(3).

  5. Equilibrium and kinetics study on hexavalent chromium adsorption onto diethylene triamine grafted glycidyl methacrylate based copolymers.

    PubMed

    Maksin, Danijela D; Nastasović, Aleksandra B; Milutinović-Nikolić, Aleksandra D; Suručić, Ljiljana T; Sandić, Zvjezdana P; Hercigonja, Radmila V; Onjia, Antonije E

    2012-03-30

    Two porous and one non-porous crosslinked poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) [abbreviated PGME] were prepared by suspension copolymerization and functionalized with diethylene triamine [abbreviated PGME-deta]. Samples were characterized by elemental analysis, mercury porosimetry, scanning electron microscopy with energy-dispersive X-ray spectroscopy, and transmission electron microscopy. Kinetics of Cr(VI) sorption by PGME-deta were investigated in batch static experiments, in the temperature range 25-70°C. Sorption was rapid, with the uptake capacity higher than 80% after 30 min. Sorption behavior and rate-controlling mechanisms were analyzed using five kinetic models (pseudo-first order, pseudo-second order, Elovich, intraparticle diffusion and Bangham model). Kinetic studies showed that Cr(VI) adsorption adhered to the pseudo-second-order model, with definite influence of pore diffusion. Equilibrium data was tested with Langmuir, Freundlich and Tempkin adsorption isotherm models. Langmuir model was the most suitable indicating homogeneous distribution of active sites on PGME-deta and monolayer sorption. The maximum adsorption capacity from the Langmuir model, Q(max), at pH 1.8 and 25°C was 143 mg g(-1) for PGME2-deta (sample with the highest amino group concentration) while at 70°C Q(max) reached the high value of 198 mg g(-1). Thermodynamic parameters revealed spontaneous and endothermic nature of Cr(VI) adsorption onto PGME-deta.

  6. Dye removal from textile industrial effluents by adsorption on exfoliated graphite nanoplatelets: kinetic and equilibrium studies.

    PubMed

    Carvallho, Marilda N; da Silva, Karolyne S; Sales, Deivson C S; Freire, Eleonora M P L; Sobrinho, Maurício A M; Ghislandi, Marcos G

    2016-01-01

    The concept of physical adsorption was applied for the removal of direct and reactive blue textile dyes from industrial effluents. Commercial graphite nanoplatelets were used as substrate, and the quality of the material was characterized by atomic force and transmission electron microscopies. Dye/graphite nanoplatelets water solutions were prepared varying their pH and initial dye concentration. Exceptionally high values (beyond 100 mg/L) for adsorptive capacity of graphite nanoplatelets could be achieved without complicated chemical modifications, and equilibrium and kinetic experiments were performed. Our findings were compared with the state of the art, and compared with theoretical models. Agreement between them was satisfactory, and allowed us to propose novel considerations describing the interactions of the dyes and the graphene planar structure. The work highlights the important role of these interactions, which can govern the mobility of the dye molecules and the amount of layers that can be stacked on the graphite nanoplatelets surface.

  7. Kinetics and equilibrium studies of malachite green adsorption on rice straw-derived char.

    PubMed

    Hameed, B H; El-Khaiary, M I

    2008-05-01

    In this work, the potential feasibility of rice straw-derived char (RSC) for removal of C.I. Basic Green 4 (malachite green (MG)), a cationic dye from aqueous solution was investigated. The isotherm parameters were estimated by non-linear regression analysis. The equilibrium process was described well by the Langmuir isotherm model. The maximum RSC sorption capacity was found to be 148.74 mg/L at 30 degrees C. The kinetics of MG sorption on RSC followed the Lagergren's pseudo-first-order model and the overall rate of dye uptake was found to 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 results indicated that RSC was an attractive adsorbent for removing basic dye from aqueous solutions.

  8. Adsorption kinetics and equilibrium study of nitrogen species onto radiata pine (Pinus radiata) sawdust.

    PubMed

    Harmayani, Kadek D; Faisal Anwar, A H M

    Nitrogen species (NH3-N, NO3-N, and NO2-N) are found as one of the major dissolved constituents in wastewater or stormwater runoff. In this research, laboratory experiments were conducted to remove these pollutants from the water environment using radiata pine (Pinus radiata) sawdust. A series of batch tests was conducted by varying initial concentration, dosage, particle size, pH, and contact time to check the removal performance. Test results confirmed the effectiveness of radiata pine sawdust for removing these contaminants from the aqueous phase (100% removal of NO3-N, and NO2-N; 55% removal of NH3-N). The adsorbent dosage and initial concentration showed a significantly greater effect on the removal process over pH or particle sizes. The optimum dosage for contaminant removal on a laboratory scale was found to be 12 g. Next, the adsorption kinetics were studied using intraparticle diffusion, liquid-film diffusion, and a pseudo-first order and pseudo-second order model. The adsorption of all species followed a pseudo-second order model but NO2-N adsorption followed both models. In addition, the kinetics of NO2-N adsorption showed two-step adsorption following intraparticle diffusion and liquid-film diffusion. The isotherm study showed that NO3-N and NO2-N adsorption fitted slightly better with the Freundlich model but that NH3-N adsorption followed both Freundlich and Langmuir models.

  9. A model for predicting contaminant removal by adsorption within the International Space Station water processor: 1. Multicomponent equilibrium modeling.

    PubMed

    Bulloch, J L; Hand, D W; Crittenden, J C

    1998-01-01

    A thermodynamic model is developed to predict adsorption equilibrium in the International Space Station water processor's multifiltration beds. The model predicts multicomponent adsorption equilibrium behavior using single-component isotherm parameters and fictitious components representing the background matrix. The fictitious components are determined by fitting total organic carbon and tracer isotherms with the ideal adsorbed solution theory. Multicomponent isotherms using a wastewater with high surfactant and organic compound concentrations are used to validate the equilibrium description on a coconut-shell-based granular activated carbon (GAC), coal-based GAC, and a polymeric adsorbent.

  10. A comparative study of the adsorption equilibrium of progesterone by a carbon black and a commercial activated carbon

    NASA Astrophysics Data System (ADS)

    Valenzuela-Calahorro, Cristóbal; Navarrete-Guijosa, Antonio; Stitou, Mostafa; Cuerda-Correa, Eduardo M.

    2007-04-01

    In this paper the adsorption process of a natural steroid hormone (progesterone) by a carbon black and a commercial activated carbon has been studied. The corresponding equilibrium isotherms have been analyzed according to a previously proposed model which establishes a kinetic law satisfactorily fitting the C versus t isotherms. The analysis of the experimental data points out the existence of two well-defined sections in the equilibrium isotherms. A general equation including these two processes has been proposed, the global adsorption process being fitted to such equation. From the values of the kinetic equilibrium constant so obtained, values of standard average adsorption enthalpy ( ΔH°) and entropy ( ΔS°) have been calculated. Finally, information related to variations of differential adsorption enthalpy ( ΔH) and entropy ( ΔS) with the surface coverage fraction ( θ) was obtained by using the corresponding Clausius-Clapeyron equations.

  11. Thermodynamic parameters for adsorption equilibrium of heavy metals and dyes from wastewaters: Research updated.

    PubMed

    Chang, Yingju; Lai, Juin-Yih; Lee, Duu-Jong

    2016-12-01

    The standard Gibbs free energy, enthalpy and entropy change data for adsorption equilibrium reported in biosorption literature during January 2013-May2016 were listed. Since the studied biosorption systems are all near-equilibrium processes, the enthalpy and entropy change data evaluated by fitting temperature-dependent free energy data using van Hoff's equation reveal a compensation artifact. Additional confusion is introduced with arbitrarily chosen adsorbate concentration unit in bulk solution that added free energy change of mixing into the reported free energy and enthalpy change data. Different standard states may be chosen for properly describing biosorption processes; however, this makes the general comparison between data from different systems inappropriate. No conclusion should be drawn based on unjustified thermodynamic parameters reported in biosorption studies.

  12. Kinetics and equilibrium studies of adsorption of chromium(VI) ion from industrial wastewater using Chrysophyllum albidum (Sapotaceae) seed shells.

    PubMed

    Amuda, O S; Adelowo, F E; Ologunde, M O

    2009-02-01

    A new biosorbent has been prepared by coating Chrysophyllum albidum (Sapotaceae) seed shells with chitosan and/or oxidizing agents such as sulfuric acid. This study investigated the technical feasibility of activated and modified activated C. albidum seed shells carbons for the adsorption of chromium(VI) from aqueous solution. The sorption process with respect to its equilibria and kinetics as well as the effects of pH, contact time, adsorbent mass, adsorbate concentration and particle size on adsorption was also studied. The most effective pH range was found to be between 4.5 and 5 for the sorption of the metal ion. The pseudo-first-order rate equation by Lagergren and pseudo-second-order rate equation were tested on the kinetic data, the adsorption process followed pseudo-second-order rate kinetics, also, isotherm data was analyzed for possible agreement with the Langmuir and Freundlich adsorption isotherms, the Freundlich and Langmuir models for dynamics of metal ion uptake proposed in this work fitted the experimental data reasonably well. However, equilibrium sorption data were better represented by Langmuir model than Freundlich. The adsorption capacity calculated from Langmuir isotherm was 84.31, 76.23 and 59.63mgCr(VI)/g at initial pH of 3.0 at 30 degrees C for the particle size of 1.00-1.25mm with the use of 12.5, 16.5 and 2.1g/L of CACASC, CCASC and ACASC adsorbent mass, respectively. This readily available adsorbent is efficient in the uptake of Cr(VI) ion in aqueous solution, thus, it could be an excellent alternative for the removal of heavy metals and organic matter from water and wastewater.

  13. Adsorption equilibrium of organic vapors on single-walled carbon nanotubes

    USGS Publications Warehouse

    Agnihotri, S.; Rood, M.J.; Rostam-Abadi, M.

    2005-01-01

    Gravimetric techniques were employed to determine the adsorption capacities of commercially available purified electric arc and HiPco single-walled carbon nanotubes (SWNTs) for organic compounds (toluene, methyl ethyl ketone (MEK), hexane and cyclohexane) at relative pressures, p/p0, ranging from 1 ?? 10-4 to 0.95 and at isothermal conditions of 25, 37 and 50 ??C. The isotherms displayed both type I and type II characteristics. Adsorption isotherm modeling showed that SWNTs are heterogeneous adsorbents, and the Freundlich equation best describes the interaction between organic molecules and SWNTs. The heats of adsorption were 1-4 times the heats of vaporization, which is typical for physical adsorption of organic vapors on porous carbons. ?? 2005 Elsevier Ltd. All rights reserved.

  14. Dynamic behaviour of Cd2+ adsorption in equilibrium batch studies by CaCO3(-)-rich Corbicula fluminea shell.

    PubMed

    Ismail, Farhah Amalya; Aris, Ahmad Zaharin; Latif, Puziah Abdul

    2014-01-01

    This work presents the structural and adsorption properties of the CaCO3(-)-rich Corbicula fluminea shell as a natural and economic adsorbent to remove Cd ions from aqueous solutions under batch studies. Experiments were conducted with different contact times, various initial concentrations, initial solution pH and serial biosorbent dosage to examine the dynamic characterization of the adsorption and its influence on Cd uptake capacity. The characterization of the C. fluminea shell using SEM/EDX revealed that the adsorbent surface is mostly impregnated by small particles of potentially calcium salts. The dominant Cd adsorption mechanism is strongly pH and concentration dependent. A maximum Cd removal efficiency of 96.20% was obtained at pH 7 while the optimum adsorbent dosage was observed as 5 g/L. The Langmuir isotherm was discovered to be more suitable to represent the experimental equilibrium isotherm results with higher correlation coefficients (R(2) > 0.98) than Freundlich (R(2) < 0.97).The correlation coefficient values (p < 0.01) indicated the superiority of the Langmuir isotherm over the Freundlich isotherm.

  15. Kinetics and equilibrium adsorption of nano-TiO 2 particles on synthetic biofilm

    NASA Astrophysics Data System (ADS)

    Sahle-Demessie, Endalkachew; Tadesse, Haregewine

    2011-07-01

    Understanding the environmental behavior of nanoparticles includes their interaction with biofilms, which is a covering on the surface of a living or nonliving substrate composed of microorganisms. This study focuses on nano-TiO2 sorption mechanism by synthetic biofilm that was prepared as superporous spherical beads from agarose, using batch stirred flasks kept at room temperature. The pH plays an important part in these phenomena, by its influence on the nanoparticles and biofilm chemistry, where the biofilm nanoTiO2 uptake at neutral pH was enhanced over acidic conditions. Hydroxylation of TiO2 nanoparticles, dependent on pH and the salinity of the solution, influences the stability of colloids, the sorption kinetics via the nature of limiting phases: diffusion through the boundary layer or intrabiofilm mass transfer and the sorption mechanism. The sorption follows pseudo first-order adsorption kinetics with estimated average rate constants of 2.2 (min- 1). Equilibrium isotherms were evaluated using Langmuir and Freundlich isotherms to obtain the maximum uptake at different solution pH and the free energy of the adsorption. The adsorption is apparently irreversible because biofilm limits diffusion of particles out of the pores and the complexation active binding sites on the surface hydrated biofilm to the hydrophilic TiO2 nanoparticles.

  16. Adsorption equilibrium and kinetics of CO2, CH4, N2O, and NH3 on ordered mesoporous carbon.

    PubMed

    Saha, Dipendu; Deng, Shuguang

    2010-05-15

    Ordered mesoporous carbon was synthesized by a self-assembly technique and characterized with TEM, Raman spectroscopy, and nitrogen adsorption/desorption for its physical and pore textural properties. The high BET specific surface area (798 m(2)/g), uniform mesopore-size distribution with a median pore size of 62.6 Å, and large pore volume (0.87 cm(3)/g) make the ordered mesoporous carbon an ideal adsorbent for gas separation and purification applications. Adsorption equilibrium and kinetics of carbon dioxide, methane, nitrous oxide, and ammonia on the ordered mesoporous carbon were measured at 298 K and gas pressures up to 800 Torr. The adsorption equilibrium capacities on the ordered mesoporous carbon at 298 K and 800 Torr for ammonia, carbon dioxide, nitrous oxide, and methane were found to be 6.39, 2.39, 1.5, and 0.53 mmol/g, respectively. Higher adsorption uptakes of methane (3.26 mmol/g at 100 bar) and carbon dioxide (2.21 mmol/g at 13 bar) were also observed at 298 K and elevated pressures. Langmuir, Freundlich, and Toth adsorption equilibrium models were used to correlate all the adsorption isotherms, and a simplified gas diffusion model was applied to analyze the adsorption kinetics data collected at 298 K and four different gas pressures up to 800 Torr.

  17. Effect of pyrolysis temperatures and times on the adsorption of cadmium onto orange peel derived biochar.

    PubMed

    Tran, Hai Nguyen; You, Sheng-Jie; Chao, Huan-Ping

    2016-02-01

    The mechanism and capacity of adsorption of cadmium (Cd) on orange peel (OP)-derived biochar at various pyrolysis temperatures (400, 500, 600, 700 and 800°C) and heating times (2 and 6 h) were investigated. Biochar was characterized using proximate analysis, point of zero charge (PZC) analysis, Fourier transform infrared spectroscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy and X-ray diffraction. Equilibrium and kinetic experiments of Cd adsorption on biochar were performed. The results indicated that the pH value at PZC of biochar approached 9.5. Equilibrium can be reached rapidly (within 1 min) in kinetic experiments and a removal rate of 80.6-96.9% can be generated. The results fitted the pseudo-second-order model closely. The adsorption capacity was estimated using the Langmuir model. The adsorption capacity of Cd on biochar was independent of the pyrolysis temperature and heating time (p>0.01). The maximum adsorption capacity of Cd was 114.69 (mg g(-1)). The adsorption of Cd on biochar was regarded as chemisorption. The primary adsorption mechanisms were regarded as Cπ-cation interactions and surface precipitation. Cadmium can react with calcite to form the precipitation of (Ca,Cd)CO3 on the surface of biochar. The OP-derived biochar can be considered a favourable alternative and a new green adsorbent for removing Cd(2+) ions from an aqueous solution.

  18. Simultaneous adsorption of methyl red and methylene blue onto biochar and an equilibrium modeling at high concentration.

    PubMed

    Ding, Guanyu; Wang, Buyun; Chen, Lingyu; Zhao, Shuangjiao

    2016-11-01

    Methyl red, methylene blue and biochar were used to investigate simultaneous adsorption of dyes onto low-cost adsorbent at different concentrations combinations. Langmuir mixed model could describe the adsorption well at low concentrations. However, it could not describe the adsorption anymore when concentrations of methyl red and methylene blue were higher than 255 and 300 mg L(-1) respectively with 0.5 g L(-1) biochar loading. A new model on the interaction among adsorbed adsorbates at equilibrium was developed. It could describe the adsorption at high concentrations well. According to the experimental results, interaction among dyes molecules would replace the competition onto adsorbent to be the main factor influencing adsorption when amount of adsorbed adsorbates were higher than those required to form a monolayer on all the adsorbing sites of adsorbent. The model was further verified by adsorption with other solute such as glucose or NaCl in solution.

  19. Adsorptive performance of un-calcined sodium exchanged and acid modified montmorillonite for Ni2+ removal: equilibrium, kinetics, thermodynamics and regeneration studies.

    PubMed

    Ijagbemi, Christianah Olakitan; Baek, Mi-Hwa; Kim, Dong-Su

    2010-02-15

    The efficacy of un-calcined sodium exchanged (Na-MMT) and acid modified montmorillonite (A-MMT) has been investigated for adsorptive removal of Ni(2+) from aqueous solution. Physico-chemical parameters such as pH, initial Ni(2+) concentration, and equilibrium contact time were studied in a series of batch adsorption experiments. The equilibrium time of contact for both adsorbents was about 230 min. The Redlich-Peterson model best described the equilibrium sorption of Ni(2+) onto Na-MMT and the Dubinin-Radushkevich model was the best model in predicting the equilibrium sorption of Ni(2+) onto A-MMT. The kinetics of Ni(2+) uptake by Na-MMT and A-MMT followed the pseudo second-order chemisorption mechanism. Sorptions of Ni(2+) onto Na-MMT and A-MMT were spontaneous and endothermic. Regeneration was tried for several cycles with a view to recover the adsorbed Ni(2+) and also to restore Na-MMT and A-MMT to their original states. The un-calcined Na-MMT and A-MMT have adsorptive potentials for removal of Ni(2+) from aqueous bodies.

  20. SO2 gas adsorption by modified kaolin clays: influence of previous heating and time acid treatments.

    PubMed

    Volzone, Cristina; Ortiga, Jose

    2011-10-01

    Modified kaolin clays were used as adsorbents for SO(2) gas adsorptions. The clays were heated up to 900 °C previous to acid treatments with 0.5 N sulfuric acid solutions at boiling temperature during different times up to 1440 min. Equilibrium adsorption at 25 °C and 0.1 MPa was carried out by using a volumetric apparatus. The samples were characterized by chemical analysis, X-ray diffraction and infrared analysis. The heating of the clays followed by acid treatment improved the adsorption capacity of the kaolin clays. The presence of amorphous silica and hydroxyl in the final products improved SO(2) adsorption capacity. Better properties for SO(2) adsorption were found in kaolin rich in not well ordered kaolinite clay mineral.

  1. Adsorption of selected emerging contaminants onto PAC and GAC: Equilibrium isotherms, kinetics, and effect of the water matrix.

    PubMed

    Real, Francisco J; Benitez, F Javier; Acero, Juan L; Casas, Francisco

    2017-03-30

    The removal of three emerging contaminants (ECs) (amitriptyline hydrochloride (AH), methyl salicylate (MS) and 2-phenoxyethanol (PE)) dissolved in several water matrices by means of their adsorption onto powdered activated carbon (PAC) and granular activated carbon (GAC) has been investigated. When dissolved in ultrapure water, adsorption of the ECs followed the trend of AH > MS > PE, with a positive effect of the adsorbent dose. According to the analysis of the adsorption isotherms and adsorption kinetics, PAC showed strongly higher adsorption efficiency in both capacity and velocity of the adsorption, in agreement with its higher mesoporosity. Equilibrium isotherm data were fitted by Langmuir and Freundlich models. Pseudo-second order kinetics modeled very successfully the adsorption process. Finally, the effect of the presence of dissolved organic matter (DOM) in the water matrices (ultrapure water, surface water and two effluents from wastewater treatment plants) on the adsorption of the selected ECs onto PAC was established, as well as its performance on the removal of water quality parameters. Results show a negative effect of the DOM content on the adsorption efficiency. Over 50% of organic matter was removed with high PAC doses, revealing that adsorption onto PAC is an effective technology to remove both micro-pollutants and DOM from water matrices.

  2. Equilibrium, kinetic and thermodynamic studies of mercury adsorption on almond shell.

    PubMed

    Khaloo, Shokooh Sadat; Matin, Amir Hossein; Sharifi, Sahar; Fadaeinia, Masoumeh; Kazempour, Narges; Mirzadeh, Shaghayegh

    2012-01-01

    The application of almond shell as a low cost natural adsorbent to remove Hg(2+) from aqueous solution was investigated. Batch experiments were carried out to evaluate the adsorption capacity of the material. The chemical and physical parameters such as pH, sorbent amount, initial ion concentration, and contact time were optimized for the maximum uptake of mercury onto the solid surface. Adsorption isotherms were expressed by Langmuir and Freundlich adsorption models, and the experimental data were found to fit the Langmuir model rather than the Freundlich. The maximum adsorption capacity obtained from the Langmuir isotherm was 135.13 mg/g. A kinetic study was carried out with pseudo-first-order and pseudo-second-order reaction equations and it was found that the Hg(2+) uptake process followed the pseudo-second-order rate expression. The thermodynamic values, ΔG(0), ΔH(0) and ΔS(0), indicated that adsorption was an endothermic and spontaneous process. The potential of this material for mercury elimination was demonstrated by efficient Hg(2+) removal from a synthetic effluent.

  3. Kinetic, equilibrium isotherm and thermodynamic studies of Cr(VI) adsorption onto low-cost adsorbent developed from peanut shell activated with phosphoric acid.

    PubMed

    ALOthman, Zeid A; Naushad, Mu; Ali, Rahmat

    2013-05-01

    A particular agricultural waste, peanut shell, has been used as precursor for activated carbon production by chemical activation with H₃PO₄. Unoxidized activated carbon was prepared in nitrogen atmosphere which was then heated in air at a desired temperature to get oxidized activated carbon. The prepared carbons were characterized for surface area, surface morphology, and pore volume and utilized for the removal of Cr(VI) from aqueous solution. Batch mode experiments were conducted to study the effects of pH, contact time, particle size, adsorbent dose, initial concentration of adsorbate, and temperature on the adsorption of Cr(VI). Cr(VI) adsorption was significantly dependent on solution pH, and the optimum adsorption was observed at pH 2. Pseudo-first-order, pseudo-second-order, and intraparticle diffusion models were used to analyze the kinetic data obtained at different initial Cr(VI) concentrations. The adsorption kinetic data were described very well by the pseudo-second-order model. Equilibrium isotherm data were analyzed by the Langmuir, Freundlich, and Temkin models. The results showed that the Langmuir adsorption isotherm model fitted the data better in the temperature range studied. The adsorption capacity which was found to increase with temperature showed the endothermic nature of Cr(VI) adsorption. The thermodynamic parameters, such as Gibb's Free energy change (ΔG°), standard enthalpy change (ΔH°), and standard entropy change (ΔS°) were evaluated.

  4. The adsorption of basic dye (Astrazon Blue FGRL) from aqueous solutions onto sepiolite, fly ash and apricot shell activated carbon: kinetic and equilibrium studies.

    PubMed

    Karagozoglu, B; Tasdemir, M; Demirbas, E; Kobya, M

    2007-08-17

    In this study, sepiolite, fly ash and apricot stone activated carbon (ASAC) were used as adsorbents for the investigation of the adsorption kinetics, isotherms and thermodynamic parameters of the basic dye (Astrazon Blue FGRL) from aqueous solutions at various concentrations (100-300 mg/L), adsorbent doses (3-12 g/L) and temperatures (303-323 K). The result showed that the adsorption capacity of the dye increased with increasing initial dye concentration, adsorbent dose and temperature. Three kinetic models, the pseudo-first-order, second-order, intraparticle diffusion, were used to predict the adsorption rate constants. The kinetics of adsorption of the basic dye followed pseudo-second-order kinetics. Equations were developed using the pseudo-second-order model which predicts the amount of the basic dye adsorbed at any contact time, initial dye concentration and adsorbent dose within the given range accurately. The adsorption equilibrium data obeyed Langmuir isotherm. The adsorption capacities (Q0) calculated from the Langmuir isotherm were 181.5 mg/g for ASAC, 155.5 mg/g for sepiolite and 128.2 mg/g for fly ash at 303 K. Thermodynamical parameters were also evaluated for the dye-adsorbent systems and revealed that the adsorption process was endothermic in nature.

  5. Mechanism of highly efficient adsorption of 2-chlorophenol onto ultrasonic graphene materials: Comparison and equilibrium.

    PubMed

    Soltani, Tayyebeh; Lee, Byeong-Kyu

    2016-11-01

    The deficiencies of the recently reported improved Hummers method for the synthesis of graphene oxide (GO), such as high reaction temperature (60°C) and long reaction time (10h), were successfully solved using a low-intensity ultrasonic bath for 30min at 40°C. Furthermore, compared to its conventional synthesis counterpart, a facile and fast, one-step ultrasonic method that excluded hydrazine hydrate was developed to synthesize reduced GO (rGO) from graphite (10min, 50°C) in the presence of hydrazine hydrate (rGO-C, 12h, 90°C). The adsorption characteristics of 2-chlorophenol (2-CP) from an aqueous solution were investigated using rGOs and GOs prepared by ultrasonic (rGO-Us/GO-Us) and conventional (rGO-C/GO-C) methods. Whereas 2-CP was completely removed with rGO-Us after 50min, only 40% of 2-CP was eliminated with rGO-C. The maximum adsorption capacity of 2-CP calculated by the Langmuir model onto rGO-Us (208.67mg/g) was much higher than that onto GO-Us (134.49mg/g). In addition, the ultrasonic graphene adsorption capacities were much higher than the corresponding values of rGO-C (49.9mg/g) and GO-C (32.06mg/g). The enhanced adsorption for rGO-Us and GO-Us is attributed to their greater surface areas, excellent oxygenated groups for GO-Us and superior π-electron-rich matrix for rGO-Us, compared to other adsorbents. The adsorption of 2-CP on the rGO materials increased with increasing solution pH to a maximum around its pKa (pKa=8.85), while the adsorption for the GO materials increased with decreasing solution pH. The adsorption mechanism proceeded via hydrogen bonding in neutral and acidic media, but via π-π electron donor-accepter (EDA) interactions between 2-CP and graphene materials in basic medium. The FTIR spectrum of GO-Us after adsorption indicates that the position and intensity of many peaks of GO-Us were affected due to the adsorption of different 2-CP groups at different pHs.

  6. 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.

  7. Equilibrium, kinetic and thermodynamic studies on the adsorption of the toxins of Bacillus thuringiensis subsp. kurstaki by clay minerals

    NASA Astrophysics Data System (ADS)

    Fu, Qingling; Deng, Yali; Li, Huishu; Liu, Jie; Hu, Hongqing; Chen, Shouwen; Sa, Tongmin

    2009-02-01

    The persistence of Bacillus thuringiensis ( Bt) toxins in soil is further enhanced through association with soil particles. Such persistence may improve the effectiveness of controlling target pests, but impose a hazard to non-target organisms in soil ecosystems. In this study, the equilibrium adsorption of the Bt toxin by four clay minerals (montmorillonite, kaolinite, goethite, and silicon dioxide) was investigated, and the kinetic and thermodynamic parameters were calculated. The results showed that Bt toxin could be adsorbed easily by minerals, and the adsorption was much easier at low temperature than at high temperature at the initial concentration varying from 0 to 1000 mg L -1. The adsorption fitted well to both Langmuir and Freundlich isotherm models, but the Freundlich equation was more suitable. The pseudo-second-order (PSO) was the best application model to describe the adsorption kinetic. The adsorption process appeared to be controlled by chemical process, and the intra-particle diffusion was not the only rate-controlling step. The negative standard free energy ( ΔGmθr) values of the adsorption indicated that the adsorption of the Bt toxin by the minerals was spontaneous, and the changes of the standard enthalpy ( ΔHmθr) showed that the adsorption of the Bt toxin by montmorillonite was endothermic while the adsorption by the other three minerals was exothermic.

  8. Equilibrium and kinetic models on the adsorption of Reactive Black 5 from aqueous solution using Eichhornia crassipes/chitosan composite.

    PubMed

    El-Zawahry, Manal M; Abdelghaffar, Fatma; Abdelghaffar, Rehab A; Hassabo, Ahmed G

    2016-01-20

    New natural biopolymer composite was prepared using extracted cellulose from an environmentally problematic water hyacinth Eichhornia crassipes (EC). The extracted cellulose was functionalized by chitosan and TiO2 nanoparticles to form EC/Chitosan (EC/Cs) composite network. Surface characterization of EC/Cs natural biopolymer composite was examined by spectrum analysis FT-IR, specific surface area, micropore volume, pore width and SEM. Furthermore, the sorption experiments were carried out as a function of pH, various initial dye concentration and contact time. Experiment results showed that the EC/Cs composite have high ability to remove C.I. Reactive Black 5 from its dye-bath effluent. The equilibrium sorption evaluation of RB5 conformed and fitted well to Langmuir adsorption isotherm models and the maximum sorption capacity was 0.606 mg/g. The kinetic adsorption models followed pseudo-second order model and the dye intra-particle diffusion may suggesting a chemical reaction mechanism. Further, it was obvious from the investigation that this composite could be applied as a promising low cost adsorbent for anionic dye removal from aqueous solutions.

  9. Quantifying differences in the impact of variable chemistry on equilibrium uranium(VI) adsorption properties of aquifer sediments

    USGS Publications Warehouse

    Stoliker, Deborah L.; Kent, Douglas B.; Zachara, John M.

    2011-01-01

    Uranium adsorption-desorption on sediment samples collected from the Hanford 300-Area, Richland, WA varied extensively over a range of field-relevant chemical conditions, complicating assessment of possible differences in equilibrium adsorption properties. Adsorption equilibrium was achieved in 500-1000 h although dissolved uranium concentrations increased over thousands of hours owing to changes in aqueous chemical composition driven by sediment-water reactions. A nonelectrostatic surface complexation reaction, >SOH + UO22+ + 2CO32- = >SOUO2(CO3HCO3)2-, provided the best fit to experimental data for each sediment sample resulting in a range of conditional equilibrium constants (logKc) from 21.49 to 21.76. Potential differences in uranium adsorption properties could be assessed in plots based on the generalized mass-action expressions yielding linear trends displaced vertically by differences in logKc values. Using this approach, logKc values for seven sediment samples were not significantly different. However, a significant difference in adsorption properties between one sediment sample and the fines (Kc uncertainty were improved by capturing all data points within experimental errors. The mass-action expression plots demonstrate that applying models outside the range of conditions used in model calibration greatly increases potential errors.

  10. A procedure to find thermodynamic equilibrium constants for CO2 and CH4 adsorption on activated carbon.

    PubMed

    Trinh, T T; van Erp, T S; Bedeaux, D; Kjelstrup, S; Grande, C A

    2015-03-28

    Thermodynamic equilibrium for adsorption means that the chemical potential of gas and adsorbed phase are equal. A precise knowledge of the chemical potential is, however, often lacking, because the activity coefficient of the adsorbate is not known. Adsorption isotherms are therefore commonly fitted to ideal models such as the Langmuir, Sips or Henry models. We propose here a new procedure to find the activity coefficient and the equilibrium constant for adsorption which uses the thermodynamic factor. Instead of fitting the data to a model, we calculate the thermodynamic factor and use this to find first the activity coefficient. We show, using published molecular simulation data, how this procedure gives the thermodynamic equilibrium constant and enthalpies of adsorption for CO2(g) on graphite. We also use published experimental data to find similar thermodynamic properties of CO2(g) and of CH4(g) adsorbed on activated carbon. The procedure gives a higher accuracy in the determination of enthalpies of adsorption than ideal models do.

  11. Quantifying differences in the impact of variable chemistry on equilibrium uranium(VI) adsorption properties of aquifer sediments

    SciTech Connect

    Stoliker, Deborah L.; Kent, Douglas B.; Zachara, John M.

    2011-09-16

    Uranium adsorption-desorption on sediment samples collected from the Hanford 300-Area, Richland, WA varied extensively over a range of field-relevant chemical conditions, complicating assessment of possible differences in equilibrium adsorption properties. Adsorption equilibrium was achieved in 500-1000 hours although dissolved uranium concentrations increased over thousands of hours owing to changes in aqueous chemical composition driven by sediment-water reactions. A non-electrostatic surface complexation reaction, >SOH + UO22+ + 2CO32- = >SOUO2(CO3HCO3)2-, provided the best fit to experimental data for each sediment sample resulting in a range of conditional equilibrium constants (logKc) from 21.49 to 21.76. Potential differences in uranium adsorption properties could be assessed in plots based on the generalized mass-action expressions yielding linear trends displaced vertically by differences in logKc values. Using this approach, logKc values for seven sediment samples were not significantly different. However, a significant difference in adsorption properties between one sediment sample and the fines (<0.063 mm) of another could be demonstrated despite the fines requiring a different reaction stoichiometry. Estimates of logKc uncertainty were improved by capturing all data points within experimental errors. The mass-action expression plots demonstrate that applying models outside the range of conditions used in model calibration greatly increases potential errors.

  12. Equilibrium adsorption of caffeic, chlorogenic and rosmarinic acids on cationic cross-linked starch with quaternary ammonium groups.

    PubMed

    Simanaviciute, Deimante; Klimaviciute, Rima; Rutkaite, Ramune

    2017-02-01

    In the present study, the equilibrium adsorption of caffeic acid (CA) and its derivatives, namely, chlorogenic (CGA) and rosmarinic (RA) acids on cationic cross-linked starch (CCS) with degree of substitution of quaternary ammonium groups of 0.42 have been investigated in relation to the structure and acidity of phenolic acids. The Langmuir, Freundlich and Dubinin-Radushkevich adsorption models have been used to describe the equilibrium adsorption of CA, CGA and RA from their initial solutions and solutions having the equimolar amount of NaOH at different temperatures. In the case of adsorption from the initial solutions of acids the values of adsorption parameters were closely related to the dissociation constants of investigated acids. According to the increasing effectiveness of adsorption, phenolic acids could be arranged in the following order: CA

  13. Adsorption of methylene blue onto jute fiber carbon: kinetics and equilibrium studies.

    PubMed

    Senthilkumaar, S; Varadarajan, P R; Porkodi, K; Subbhuraam, C V

    2005-04-01

    Jute fiber obtained from the stem of a plant was used to prepare activated carbon using phosphoric acid. Feasibility of employing this jute fiber activated carbon (JFC) for the removal of Methylene blue (MB) from aqueous solution was investigated. The adsorption of MB on JFC has found to dependent on contact time, MB concentration and pH. Experimental result follows Langmuir isotherm model and the capacity was found to be 225.64 mg/g. The optimum pH for the MB removal was found to be 5-10. The kinetic data obtained at different concentrations have been analyzed using a pseudo-first-order, pseudo-second-order equation, intraparticle diffusion and Elovich equation. Among the kinetic models studied, the intraparticle diffusion was the best applicable model to describe the adsorption of MB onto JFC.

  14. Time-resolved measurements of equilibrium profiles in MST

    NASA Astrophysics Data System (ADS)

    Deng, B. H.; Brower, D. L.; Ding, W. X.; Yates, T. F.; Anderson, J. K.; Caspary, K.; McCollam, K. J.; Prager, S. C.; Reusch, J. A.; Sarff, J. S.; Craig, D.

    2007-11-01

    Based on the high-speed, three-wave, far-infrared polarimeter-interferometer measurement of Bpol profiles and external coil measurements of Btave and Btw, a new method is developed to derive Btor and other equilibrium profiles (J// and q) with high time resolution. Using Faraday's law, the inductive electric field (E//) profile is also deduced from the temporal derivatives of the time-resolved magnetic field profiles. The derived B(0) values have excellent agreement with direct measurements using a Motional Stark Effect (MSE) diagnostic. Evolution of equilibrium profiles during single sawtooth events in MST, both the slow linear ramp and crash phases, are presented. Profile scaling with plasma current Ip and reversal parameter F is also explored. MHD stability is tested from the spatial gradients of the J// and q profiles, and correlation with fluctuation mode amplitude is investigated. Future improvements to equilibrium reconstruction are expected by measuring Btor(r,t) directly via Cotton-Mouton interferometry.

  15. Interaction of Pseudomonas putida with kaolinite and montmorillonite: a combination study by equilibrium adsorption, ITC, SEM and FTIR.

    PubMed

    Rong, Xingmin; Huang, Qiaoyun; He, Xiaomin; Chen, Hao; Cai, Peng; Liang, Wei

    2008-06-15

    Equilibrium adsorption along with isothermal titration calorimetry (ITC), Fourier transform infrared spectra (FTIR) and scanning electron microscopy (SEM) techniques were employed to investigate the adsorption of Pseudomonas putida on kaolinite and montmorillonite. A higher affinity as well as larger amounts of adsorption of P. putida was found on kaolinite. The majority of sorbed bacterial cells (88.7%) could be released by water from montmorillonite, while only a small proportion (9.3%) of bacteria desorbed from kaolinite surface. More bacterial cells were observed to form aggregates with kaolinite, while fewer cells were within the larger bacteria-montmorillonite particles. The sorption of bacteria on kaolinite was enthalpically more favorable than that on montmorillonite. Based on our findings, it is proposed that the non-electrostatic forces other than electrostatic force play a more important role in bacterial adsorption by kaolinite and montmorillonite. Adsorption of bacteria on clay minerals resulted in obvious shifts of infrared absorption bands of water molecules, showing the importance of hydrogen bonding in bacteria-clay mineral adsorption. The enthalpies of -4.1+/-2.1 x 10(-8) and -2.5+/-1.4 x 10(-8)mJ cell(-1) for the adsorption of bacteria on kaolinite and montmorillonite, respectively, at 25 degrees C and pH 7.0 were firstly reported in this paper. The enthalpy of bacteria-mineral adsorption was higher than that reported previously for bacteria-biomolecule interaction but lower than that of bacterial coaggregation. The bacteria-mineral adsorption enthalpies increased at higher temperature, suggesting that the enthalpy-entropy compensation mechanism could be involved in the adsorption of P. putida on clay minerals. Data obtained in this study would provide valuable information for a better understanding of the mechanisms of mineral-microorganism interactions in soil and associated environments.

  16. Equilibrium and kinetics study on the adsorption of perfluorooctanoic acid from aqueous solution onto powdered activated carbon.

    PubMed

    Qu, Yan; Zhang, Chaojie; Li, Fei; Bo, Xiaowen; Liu, Guangfu; Zhou, Qi

    2009-09-30

    Powdered activated carbon (PAC) was applied to remove perfluorooctanoic acid (PFOA) from the aqueous PFOA solution in this study. Contact time, adsorbent dose and temperature were analyzed as the effect factors in the adsorption reaction. The contact time of maximum PFOA uptake was around 1h while the sorption removal efficiency increased with the PAC concentrations. And the process of adsorption increased from 303 K to 313 K and then decreased from 313 K to 323 K. Among four applied models, the experimental isotherm data were discovered to follow Langmuir isotherm model more closely. Thermodynamically, adsorption was endothermic because enthalpy, entropy and Gibbs constants were 198.5 kJ/mol, 0.709 kJ/mol/K and negative, respectively, which also indicated that the adsorption process was spontaneous and feasible. From kinetic analysis, the adsorption was suggested to be pseudo-second-order model. The adsorption of PFOA on the PAC was mainly controlled by particle diffusion.

  17. Equilibrium and Disequilibrium Dynamics in Cobweb Models with Time Delays

    NASA Astrophysics Data System (ADS)

    Gori, Luca; Guerrini, Luca; Sodini, Mauro

    2015-06-01

    This paper aims to study price dynamics in two different continuous time cobweb models with delays close to [Hommes, 1994]. In both cases, the stationary equilibrium may be not representative of the long-term dynamics of the model, since it is possible to observe endogenous and persistent fluctuations (supercritical Hopf bifurcations) even if a deterministic context without external shocks is considered. In the model in which markets are in equilibrium every time, we show that the existence of time delays in the expectations formation mechanism may cause chaotic dynamics similar to those obtained in [Hommes, 1994] in a discrete time context. From a mathematical point of view, we apply the Poincaré-Lindstedt perturbation method to study the local dynamic properties of the models. In addition, several numerical experiments are used to investigate global properties of the systems.

  18. Adsorption behavior of levulinic acid onto microporous hyper-cross-linked polymers in aqueous solution: Equilibrium, thermodynamic, kinetic simulation and fixed-bed column studies.

    PubMed

    Lin, Xiaoqing; Huang, Qianlin; Qi, Gaoxiang; Xiong, Lian; Huang, Chao; Chen, Xuefang; Li, Hailong; Chen, Xinde

    2017-03-01

    The recovery of levulinic acid (LA) from aqueous solution and actual biomass hydrolysate by a microporous hyper-cross-linked polymer, SY-01, was investigated for the first time under batch and fixed-bed column conditions. The results showed that the optimum pH should be in the acidic range (pH < 3.0) without adjusting the pH. In the single-component system equilibrium study, the Langmuir isotherm model fits the LA adsorption onto SY-01 resin better than the Freundlich isotherm model, indicating that LA adsorption onto SY-01 resin under the concentration range studied is a monolayer homogeneous adsorption process. The maximum adsorption capacity of LA onto SY-01 resin decreased with increasing temperature, ranging from 103.74 to 95.70 mg/g. The obtained thermodynamic parameters suggested that the adsorption of LA on SY-01 was spontaneous (ΔG(0)<-3.788 kJ/mol), and exothermic (ΔH(0) = -11.764 kJ/mol). For kinetic study, the adsorption of LA onto SY-01 resin at various operating conditions follows the pore diffusion model and the intraparticle diffusion is the rate-limiting step for the adsorption of LA onto SY-01 resin. The effective pore diffusivity was dependent upon temperature, but independent of initial LA concentration, and were 3.306 × 10(-10), 5.274 × 10(-10) and 7.707 × 10(-10) m(2)/s at 298, 318 and 338 K, respectively. In desorption process, the recovery efficiency of LA from SY-01 resin was 99.39%, and LA concentration in the eluent was raised 2.97-fold. In conclusion, our results show that the SY-01 resin has potential application in product recovery of LA from biomass hydrolysate.

  19. Adsorption of Zn2+ ions onto NaA and NaX zeolites: kinetic, equilibrium and thermodynamic studies.

    PubMed

    Nibou, D; Mekatel, H; Amokrane, S; Barkat, M; Trari, M

    2010-01-15

    The adsorption of Zn(2+) onto NaA and NaX zeolites was investigated. The samples were synthesized according to a hydrothermal crystallization using aluminium isopropoxide (Al[OCH(CH(3))(2)](3)) as a new alumina source. The effects of pH, initial concentration, solid/liquid ratio and temperature were studied in batch experiments. The Freundlich and the Langmuir models were applied and the adsorption equilibrium followed Langmuir adsorption isotherm. The uptake distribution coefficient (K(d)) indicated that the Zn(2+) removal was the highest at minimum concentration. Thermodynamic parameters were calculated. The negative values of standard enthalpy of adsorption revealed the exothermic nature of the adsorption process whereas the negative activation entropies reflected that no significant change occurs in the internal structure of the zeolites solid matrix during the sorption of Zn(2+). The negative values of Gibbs free energy were indicative of the spontaneity of the adsorption process. Analysis of the kinetic and rate data revealed that the pseudo second-order sorption mechanism is predominant and the intra particle diffusion was the determining step for the sorption of zinc ions. The obtained optimal parameters have been applied to wastewater from the industrial zone (Algeria) in order to remove the contained zinc effluents.

  20. The effect of water temperature on the adsorption equilibrium of dissolved organic matter and atrazine on granular activated carbon

    SciTech Connect

    Bernd Schreiber; Viktor Schmalz; Thomas Brinkmann; Eckhard Worch

    2007-09-15

    The influence of water temperature on the adsorption of natural dissolved organic matter (DOM) on activated carbon has not been investigated intensively yet. In this study, batch experiments with granular activated carbon (GAC) F300, from bituminous coal, have been carried out at three temperatures (5, 20, 35{sup o} C) using a humic acid model water and different types of surface water (lake, river, canal). Furthermore, the adsorption of an anthropogenic contaminant, atrazine, was quantified in the absence and presence of DOM. The results indicate a significant influence of water temperature on the adsorption equilibrium of DOM and atrazine. Contrary to expectations, DOM and atrazine adsorption in surface water tends to be increased with increasing water temperature, whereas the extent of this effect is dependent on the type and concentration of DOM. Furthermore, the temperature effect on atrazine adsorption is controlled by competition of DOM and atrazine on adsorption sites. Some assumptions are proposed and discussed for explaining the temperature effects observed in the batch studies. 39 refs., 4 figs., 2 tabs.

  1. Adsorption of cesium from aqueous solution using agricultural residue--walnut shell: equilibrium, kinetic and thermodynamic modeling studies.

    PubMed

    Ding, Dahu; Zhao, Yingxin; Yang, Shengjiong; Shi, Wansheng; Zhang, Zhenya; Lei, Zhongfang; Yang, Yingnan

    2013-05-01

    A novel biosorbent derived from agricultural residue - walnut shell (WS) is reported to remove cesium from aqueous solution. Nickel hexacyanoferrate (NiHCF) was incorporated into this biosorbent, serving as a high selectivity trap agent for cesium. Field emission scanning electron microscope (FE-SEM) and thermogravimetric and differential thermal analysis (TG-DTA) were utilized for the evaluation of the developed biosorbent. Determination of kinetic parameters for adsorption was carried out using pseudo first-order, pseudo second-order kinetic models and intra-particle diffusion models. Adsorption equilibrium was examined using Langmuir, Freundlich and Dubinin-Radushkevich adsorption isotherms. A satisfactory correlation coefficient and relatively low chi-square analysis parameter χ(2) between the experimental and predicted values of the Freundlich isotherm demonstrate that cesium adsorption by NiHCF-WS is a multilayer chemical adsorption. Thermodynamic studies were conducted under different reaction temperatures and results indicate that cesium adsorption by NiHCF-WS is an endothermic (ΔH° > 0) and spontaneous (ΔG° < 0) process.

  2. Arsenic (III) adsorption on iron acetate coated activated alumina: thermodynamic, kinetics and equilibrium approach

    PubMed Central

    2013-01-01

    The adsorption potential of iron acetate coated activated alumina (IACAA) for removal of arsenic [As (III)] as arsenite by batch sorption technique is described. IACAA was characterized by XRD, FTIR, EDAX and SEM instruments. Percentage adsorption on IACAA was determined as a function of pH, contact time and adsorbent dose. The study revealed that the removal of As (III) was best achieved at pH =7.4. The initial As (III) concentration (0.45 mg/L) came down to less than 0.01 mg/L at contact time 90 min with adsorbent dose of 1 g/100 mL. The sorption was reasonably explained with Langmuir and Freundlich isotherms. The thermodynamic parameters such as ΔG 0 , ΔH 0 , ΔS 0 and E a were calculated in order to understand the nature of sorption process. The sorption process was found to be controlled by pseudo-second order and intraparticle diffusion models. PMID:24359995

  3. Adsorption of Rhodamine B on two novel polar-modified post-cross-linked resins: Equilibrium and kinetics.

    PubMed

    Jiang, Xiangfu; Huang, Jianhan

    2016-04-01

    We employed two polar monomers, triallyl isocyanurate (TAIC) and butyl acrylate (BA), to copolymerize with divinylbenzene (DVB), and synthesized two starting copolymers labeled PDT and PDB. Then, the Friedel-Crafts alkylation reaction was performed for the two starting copolymers, and the residual pendent vinyl groups were consumed, and hence we obtained two novel polar-modified post-cross-linked resins PDTpc and PDBpc. The surface polarity greatly improved due to introduction of the polar monomers, and the Brunauer-Emmett-Teller (BET) surface area and pore volume significantly increased after the Friedel-Crafts alkylation reaction. Compared with the starting copolymers, the non-polar post-cross-linked resin PDVBpc and some other adsorbents in the references, PDTpc and PDBpc possessed a much enhanced adsorption to Rhodamine B, and the equilibrium capacity reached 578.2mg/g and 328.7mg/g, respectively, at an equilibrium concentration of 100mg/L, and the Freundlich model characterized the equilibrium data very well. The adsorption was a fast process and the kinetic data obeyed the micropore diffusion model. These results confirmed that PDTpc and PDBpc had the potential superiority in adsorptive removal of Rhodamine B from aqueous solution.

  4. Real Time Computation of Kinetic Constraints to Support Equilibrium Reconstruction

    NASA Astrophysics Data System (ADS)

    Eggert, W. J.; Kolemen, E.; Eldon, D.

    2016-10-01

    A new method for quickly and automatically applying kinetic constraints to EFIT equilibrium reconstructions using readily available data is presented. The ultimate goal is to produce kinetic equilibrium reconstructions in real time and use them to constrain the DCON stability code as part of a disruption avoidance scheme. A first effort presented here replaces CPU-time expensive modules, such as the fast ion pressure profile calculation, with a simplified model. We show with a DIII-D database analysis that we can achieve reasonable predictions for selected applications by modeling the fast ion pressure profile and determining the fit parameters as functions of easily measured quantities including neutron rate and electron temperature on axis. Secondly, we present a strategy for treating Thomson scattering and Charge Exchange Recombination data to automatically form constraints for a kinetic equilibrium reconstruction, a process that historically was performed by hand. Work supported by US DOE DE-AC02-09CH11466 and DE-FC02-04ER54698.

  5. Adsorption behavior of activated carbon derived from pyrolusite-modified sewage sludge: equilibrium modeling, kinetic and thermodynamic studies.

    PubMed

    Chen, Yao; Jiang, Wenju; Jiang, Li; Ji, Xiujuan

    2011-01-01

    Activated carbon was developed from sewage sludge using pyrolusite as an additive. It was demonstrated that the removal efficiency of two synthetic dyes (Tracid orange GS and Direct fast turquoise blue GL) by the produced adsorbent was up to 97.6%. The activated carbon with pyrolusite addition had 38.2% higher surface area, 43.8% larger micropore and 54.4% larger mesopore production than ordinary sludge-based activated carbons. Equilibrium adsorption isotherms and kinetics were also investigated based on dyes adsorption tests. The experimental data were analyzed by the Langmuir and Freundlich models of adsorption, and the results fitted well to the Langmuir isotherm. The kinetic data have been analyzed using pseudo-first-order, pseudo-second-order and intraparticle diffusion equation. The experimental data fitted very well with pseudo-second-order kinetic model. Activation energies for the adsorption processes ranged between 8.7 and 19.1 kJ mol 1. Thermodynamic parameters such as standard free energy (deltaG0), standard enthalpy (deltaH0) and standard entropy (deltaS0) were evaluated. The adsorption of these two dyes on the activated carbon was found to be a spontaneous and endothermic process in nature.

  6. Adsorption behavior of direct red 80 and congo red onto activated carbon/surfactant: process optimization, kinetics and equilibrium.

    PubMed

    Cheng, Zhengjun; Zhang, Lei; Guo, Xiao; Jiang, Xiaohui; Li, Tian

    2015-02-25

    Adsorptions of congo red and direct red 80 onto activated carbon/surfactant from aqueous solution were optimized. The Box-Behnken design (BBD) has been employed to analyze the effects of concentration of surfactant, temperature, pH, and initial concentration of the dye in the adsorption capacity. Their corresponding experimental data could be evaluated excellently by second order polynomial regression models and the two models were also examined based on the analysis of variance and t test statistics, respectively. The optimum conditions were obtained as follows: Cs=34.10 μM, T=50°C, pH=3.5, and CCR=160 mg/L for the congo red system, and Cs=34.10 μM, T=50°C, pH=6.1, and CDR80=110 mg/L for the direct red 80 system. And in these conditions, the measured experimental maximum adsorption capacities for the congo red and direct red 80 removals were 769.48 mg/g and 519.90 mg/g, which were consistent with their corresponding predicted values, with small relative errors of -2.81% and -0.67%, respectively. The adsorption equilibrium and kinetics for the two dye adsorptions onto AC/DDAC were also investigated. The experimental data were fitted by four isotherm models, and Langmuir model presented the best fit. The kinetic studies indicated that the kinetic data followed the pseudo-second-order model.

  7. Adsorption/desorption of Cd(II), Cu(II) and Pb(II) using chemically modified orange peel: Equilibrium and kinetic studies

    NASA Astrophysics Data System (ADS)

    Lasheen, Mohamed R.; Ammar, Nabila S.; Ibrahim, Hanan S.

    2012-02-01

    Waste materials from industries such as food processing may act as cost effective and efficient biosorbents to remove toxic contaminants from wastewater. This study aimed to establish an optimized condition and closed loop application of processed orange peel for metals removal. A comparative study of the adsorption capacity of the chemically modified orange peel was performed against environmentally problematic metal ions, namely, Cd 2+, Cu 2+ and Pb 2+, from aqueous solutions. Chemically modified orange peel (MOP) showed a significantly higher metal uptake capacity compared to original orange peel (OP). Fourier Transform Infrared (FTIR) Spectra of peel showed that the carboxylic group peak shifted from 1637 to 1644 cm -1 after Pb (II) ions binding, indicated the involvement of carboxyl groups in Pb(II) ions binding. The metals uptake by MOP was rapid and the equilibrium time was 30 min at constant temperature and pH. Sorption kinetics followed a second-order model. The mechanism of metal sorption by MOP gave good fits for Freundlich and Langmuir models. Desorption of metals and regeneration of the biosorbent was attained simultaneously by acid elution. Even after four cycles of adsorption-elution, the adsorption capacity was regained completely and adsorption efficiency of metal was maintained at around 90%.

  8. Characterizing particle-scale equilibrium adsorption and kinetics of uranium(VI) desorption from U-contaminated sediments

    SciTech Connect

    Stoliker, Deborah L.; Liu, Chongxuan; Kent, Douglas B.; Zachara, John M.

    2013-02-12

    Rates of contaminant U(VI) release from individual size fractions of a composite sediment from the seasonally saturated lower vadose zone of the Hanford 300-Area were examined in flow-through batch reactors to maintain quasi-constant chemical conditions. Variability in equilibrium adsorption among the various size fractions was determined in static batch reactors and analyzed using the surface complexation modeling approach. The estimated stoichiometric coefficients of U(VI) surface complexation reactions with respect to pH and carbonate concentrations varied with size fractions. This source of variability significantly increased the uncertainty in U(VI) conditional equilibrium constants over that estimated from experimental errors alone. A minimum difference between conditional equilibrium constants was established in order to evaluate statistically significant differences between sediment adsorption properties. A set of equilibrium and kinetic expressions for cation exchange, calcite dissolution, aerobic respiration, and silica dissolution were incorporated in a reaction-rate model to describe the temporal evolution of solute concentrations observed during the flow-through batch experiments. Parameters in the reaction-rate model, calibrated using experimental data for select size fractions, predicted the changes in solute concentrations for the bulk, <2 mm, sediment sample. Kinetic U(VI) desorption was well described using a multi-rate surface complexation model with an assumed lognormal distribution for the rate constants. The estimated mean and standard deviation were the same for all < 2mm size fractions, but differed in the 2-8mm size fraction. Micropore volumes in the varied size fractions were also similar as assessed using t-plots to analyze N2 desorption data. These findings provide further support for the link between microporosity and particle-scale mass transfer rates controlling kinetic U(VI) adsorption/desorption and for the utility of N2 desorption

  9. Measurement and modelling of adsorption equilibrium, adsorption kinetics and breakthrough curve of toluene at very low concentrations on to activated carbon.

    PubMed

    Réguer, Anne; Sochard, Sabine; Hort, Cécile; Platel, Vincent

    2011-01-01

    Indoor air pollution, characterized by many pollutants at very low concentrations, is nowadays known as a worrying problem for human health. Among physical treatments, adsorption is a widely used process, since porous materials offer high capacity for volatile organic chemicals. However, there are few studies in the literature that deal with adsorption as an indoor air pollution treatment. The aim of this study was to investigate the adsorption of toluene on to activated carbon at characteristic indoor air concentrations. Firstly, global kinetic parameters were determined by fitting Thomas's model to experimental data obtained with batch experiments. Then, these kinetic parameters led to the determination of Henry's coefficient, which was checked with experimental data of the adsorption isotherm. Secondly, we simulated a breakthrough curve made at an inlet concentration 10 times higher than the indoor air level. Even if the kinetic parameters in this experiment are different from those in batch experiments, it can be emphasized that the Henry coefficient stays the same.

  10. Non-equilibrium Thermodynamic Dissolution Theory for Multi-Component Solid/Liquid Surfaces Involving Surface Adsorption and Radiolysis Kinetics

    SciTech Connect

    Stout, R B

    2001-04-01

    A theoretical expression is developed for the dissolution rate response for multi-component radioactive materials that have surface adsorption kinetics and radiolysis kinetics when wetted by a multi-component aqueous solution. An application for this type of dissolution response is the performance evaluation of multi-component spent nuclear fuels (SNFs) for long term interim storage and for geological disposition. Typically, SNF compositions depend on initial composition, uranium oxide and metal alloys being most common, and on reactor burnup which results in a wide range of fission product and actinide concentrations that decay by alpha, beta, and gamma radiation. These compositional/burnup ranges of SNFs, whether placed in interim storage or emplaced in a geologic repository, will potentially be wetted by multi-component aqueous solutions, and these solutions may be further altered by radiolytic aqueous species due to three radiation fields. The solid states of the SNFs are not thermodynamically stable when wetted and will dissolve, with or without radiolysis. The following development of a dissolution theory is based on a non-equilibrium thermodynamic analysis of energy reactions and energy transport across a solid-liquid phase change discontinuity that propagates at a quasi-steady, dissolution velocity. The integral form of the energy balance equation is used for this spatial surface discontinuity analysis. The integral formulation contains internal energy functional of classical thermodynamics for both the SNFs' solid state and surface adsorption species, and the adjacent liquid state, which includes radiolytic chemical species. The steady-state concentrations of radiolytic chemical species are expressed by an approximate analysis of the decay radiation transport equation. For purposes of illustration a modified Temkin adsorption isotherm was assumed for the surface adsorption kinetics on an arbitrary, finite area of the solid-liquid dissolution interface. For

  11. Development, Construction, and Operation of a Multisample Volumetric Apparatus for the Study of Gas Adsorption Equilibrium

    ERIC Educational Resources Information Center

    Ribeiro, Rui P. P. L.; Silva, Ricardo J. S.; Esteves, Isabel A. A. C.; Mota, Jose´ P. B.

    2015-01-01

    The construction of a simple volumetric adsorption apparatus is highlighted. The setup is inexpensive and provides a clear demonstration of gas phase adsorption concepts. The topic is suitable for undergraduate chemistry and chemical engineering students. Moreover, this unit can also provide quantitative data that can be used by young researchers…

  12. Equilibrium models and kinetic for the adsorption of methylene blue on Co-hectorites.

    PubMed

    Ma, Jun; Jia, Yong-Zhong; Jing, Yan; Sun, Jin-He; Yao, Ying; Wang, Xiao-Hua

    2010-03-15

    The adsorption of methylene blue (MB) onto the surface of cobalt doping hectorite (Co-hectorite) was systematically studied. The physical properties of Co-hectorites were investigated, where characterizations were carried out by X-ray diffraction (XRD) and Electron Diffraction Spectrum (EDS) techniques, and morphology was examined by nitrogen adsorption. The sample with a Co content 5% (m/m) had a higher specific surface area than other Co-hectorites. The pore diameters were distributed between 2.5 and 5.0 nm. The adsorption results revealed that Co-hectorite surfaces possessed effective interactions with MB and bases, and greatest adsorption capacity achieved with Co content 5%, where the best-fit isotherm model was the Langmuir adsorption model. Kinetic studies were fitted to the pseudo-second-order kinetic model. The intraparticle diffusion was not the rate-limiting step for the whole reaction.

  13. 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 (qm) of active carbon (AC) in the ACAA-Ca adsorbent material (e.g., qm=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.

  14. Adsorption of Zinc(II) on diatomite and manganese-oxide-modified diatomite: a kinetic and equilibrium study.

    PubMed

    Caliskan, Necla; Kul, Ali Riza; Alkan, Salih; Sogut, Eda Gokirmak; Alacabey, Ihsan

    2011-10-15

    The removal of Zn(II) ions from aqueous solution was studied using natural and MnO(2) modified diatomite samples at different temperatures. The linear Langmuir, Freundlich and Dubinin-Radushkevich (D-R) adsorption equations were applied to describe the equilibrium isotherms. From the D-R model, the mean adsorption energy was calculated as >8 kJ mol(-1), indicating that the adsorption of Zn(II) onto diatomite and Mn-diatomite was physically carried out. In addition, the pseudo-first-order, pseudo-second-order and intraparticle diffusion models were used to determine the kinetic data. The experimental data were well fitted by the pseudo-second-order kinetic model. Thermodynamic parameters such as the enthalpy (ΔH(0)), Gibbs' free energy (ΔG(0)) and entropy (ΔS(0)) were calculated for natural and MnO(2) modified diatomite. These values showed that the adsorption of Zn(II) ions onto diatomite samples was controlled by a physical mechanism and occurred spontaneously.

  15. Equilibrium adsorption studies of some aromatic pollutants from dilute aqueous solutions on activated carbon at different temperatures

    SciTech Connect

    Khan, A.R.; Ataullah, R.; Al-Haddad, A.

    1997-10-01

    Aqueous solutions of phenol, p-chlorophenol, and p-nitrophenol have been used to determine the adsorption isotherm for single solute systems on activated carbon at different temperatures. The experimental program has been conducted to investigate the influence of concentration and temperature. All the reported equilibrium isotherm equations have been tried on present and published experimental data. A generalized isotherm equation which was proposed by Khan et al. and tested for bi-solute adsorption data has been modified for single-solute system. The temperature dependency has also been incorporated into a generalized equation. It has been noticed that the Radke and Prausnitz and generalized isotherm equations could represent the entire data with a minimum average percentage error. The influence of different adsorbents, sorbate concentrations, and pH of aqueous solutions has also been discussed in detail. The temperature dependency has been investigated using both the Dubinin-Astakov and the modified generalized equation. The generalized equation describes the experimental and published data adequately and provides a single value of differential molar heat of adsorption, {Delta}H{sub ads}, for a single solute adsorption system. The Dubinin-Astakov isotherm equation has shown an increasing trend of {Delta}H{sub ads} as the loading of adsorbent has increased.

  16. Continuous equilibrium scores: factoring in the time before a fall.

    PubMed

    Wood, Scott J; Reschke, Millard F; Owen Black, F

    2012-07-01

    The equilibrium (EQ) score commonly used in computerized dynamic posturography is normalized between 0 and 100, with falls assigned a score of 0. The resulting mixed discrete-continuous distribution limits certain statistical analyses and treats all trials with falls equally. We propose a simple modification of the formula in which peak-to-peak sway data from trials with falls is scaled according the percent of the trial completed to derive a continuous equilibrium (cEQ) score. The cEQ scores for trials without falls remain unchanged from the original methodology. The cEQ factors in the time before a fall and results in a continuous variable retaining the central tendencies of the original EQ distribution. A random set of 5315 Sensory Organization Test trials were pooled that included 81 falls. A comparison of the original and cEQ distributions and their rank ordering demonstrated that trials with falls continue to constitute the lower range of scores with the cEQ methodology. The area under the receiver operating characteristic curve (0.997) demonstrates that the cEQ retained near-perfect discrimination between trials with and without falls. We conclude that the cEQ score provides the ability to discriminate between ballistic falls from falls that occur later in the trial. This approach of incorporating time and sway magnitude can be easily extended to enhance other balance tests that include fall data or incomplete trials.

  17. Adsorption energies of mercury-containing species on CaO and temperature effects on equilibrium constants predicted by density functional theory calculations.

    PubMed

    Kim, Bo Gyeong; Li, Xinxin; Blowers, Paul

    2009-03-03

    The adsorption of Hg, HgCl, and HgCl2 on the CaO surface was investigated theoretically so the fundamental interactions between Hg species and this potential sorbent can be explored. Surface models of a 4 x 4 x 2 cluster, a 5 x 5 x 2 cluster, and a periodic structure using density functional theory calculations with LDA/PWC and GGA/BLYP functionals, as employed in the present work, offer a useful description for the thermodynamic properties of adsorption on metal oxides. The effect of temperature on the equilibrium constant for the adsorption of mercury-containing species on the CaO (0 0 1) surface was investigated with GGA/BLYP calculations in the temperature range of 250-600 K. Results show that, at low coverage of elemental mercury, adsorption on the surface is physisorption while the two forms of oxidized mercury adsorption undergo stronger adsorption. The adsorption energies decrease with increasing coverage for elemental mercury on the surfaces. The chlorine atom enhances the adsorption capacity and adsorbs mercury to the CaO surface more strongly. The adsorption energy is changed as the oxidation state varies, and the equilibrium constant decreases as the temperature increases, in good agreement with data for exothermic adsorption systems.

  18. 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.

  19. Equilibrium isotherms, kinetics, and thermodynamics studies for congo red adsorption using calcium alginate beads impregnated with nano-goethite.

    PubMed

    Munagapati, Venkata Subbaiah; Kim, Dong-Su

    2017-03-24

    The present study is concerned with the batch adsorption of congo red (CR) from an aqueous solution using calcium alginate beads impregnated with nano-goethite (CABI nano-goethite) as an adsorbent. The optimum conditions for CR removal were determined by studying operational variables viz. pH, adsorbent dose, contact time, initial dye ion concentration and temperature. The CABI nano-goethite was characterized by Fourier transform infrared spectroscopy (FTIR), X- ray diffraction (XRD) and Scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) analysis. The CR sorption data onto CABI nano-goethite were described using Langmuir, Freundlich, Dubinin-Radushkevich and Temkin isotherm models. The results show that the best fit was achieved with the Langmuir isotherm model. The maximum adsorption capacity (181.1mg/g) of CR was occurred at pH 3.0. Kinetic studies showed that the adsorption followed a pseudo-second-order model. Desorption experiments were carried out to explore the feasibility of regenerating the adsorbent and the adsorbed CR from CABI nano-goethite. The best desorbing agent was 0.1M NaOH with an efficiency of 94% recovery. The thermodynamic parameters ΔG°, ΔH°, and ΔS° for the CR adsorption were determined by using adsorption capacities at five different temperatures (293, 303, 313, 323 and 303K). Results show that the adsorption process was endothermic and favoured at high temperature.

  20. Adsorption of methylene blue onto activated carbon produced from tea (Camellia sinensis L.) seed shells: kinetics, equilibrium, and thermodynamics studies.

    PubMed

    Gao, Jun-Jie; Qin, Ye-Bo; Zhou, Tao; Cao, Dong-Dong; Xu, Ping; Hochstetter, Danielle; Wang, Yue-Fei

    2013-07-01

    Tea (Camellia sinensis L.) seed shells, the main byproduct of the manufacture of tea seed oil, were used as precursors for the preparation of tea activated carbon (TAC) in the present study. A high yield (44.1%) of TAC was obtained from tea seed shells via a one-step chemical method using ZnCl2 as an agent. The Brunauer-Emmett-Teller (BET) surface area and the total pore volumes of the obtained TAC were found to be 1530.67 mg(2)/g and 0.7826 cm(3)/g, respectively. The equilibrium adsorption results were complied with Langmuir isotherm model and its maximum monolayer adsorption capacity was 324.7 mg/g for methylene blue. Adsorption kinetics studies indicated that the pseudo-second-order model yielded the best fit for the kinetic data. An intraparticle diffusion model suggested that the intraparticle diffusion was not the only rate-controlling step. Thermodynamics studies revealed the spontaneous and exothermic nature of the sorption process. These results indicate that tea seed shells could be utilized as a renewable resource to develop activated carbon which is a potential adsorbent for methylene blue.

  1. Adsorption of Pb(II) ions from aqueous solution by native and activated bentonite: kinetic, equilibrium and thermodynamic study.

    PubMed

    Kul, Ali Riza; Koyuncu, Hülya

    2010-07-15

    In this study, the adsorption kinetics, equilibrium and thermodynamics of Pb(II) ions on native (NB) and acid activated (AAB) bentonites were examined. The specific surface areas, pore size and pore-size distributions of the samples were fully characterized. The adsorption efficiency of Pb(II) onto the NB and AAB was increased with increasing temperature. The kinetics of adsorption of Pb(II) ions was discussed using three kinetic models, the pseudo-first-order, the pseudo-second-order and the intra-particle diffusion model. The experimental data fitted very well the pseudo-second-order kinetic model. The initial sorption rate and the activation energy were also calculated. The activation energy of the sorption was calculated as 16.51 and 13.66 kJ mol(-1) for NB and AAB, respectively. Experimental results were also analysed by the Langmuir, Freundlich and Dubinin-Redushkevich (D-R) isotherm equations at different temperatures. R(L) separation factor for Langmuir and the n value for Freundlich isotherm show that Pb(II) ions are favorably adsorbed by NB and AAB. Thermodynamic quantities such as Gibbs free energy (DeltaG), the enthalpy (DeltaH) and the entropy change of sorption (DeltaS) were determined as about -5.06, 10.29 and 0.017 kJ mol(-1) K(-1), respectively for AAB. It was shown that the sorption processes were an endothermic reactions, controlled by physical mechanisms and spontaneously.

  2. Adsorption of methylene blue onto activated carbon produced from tea (Camellia sinensis L.) seed shells: kinetics, equilibrium, and thermodynamics studies*

    PubMed Central

    Gao, Jun-jie; Qin, Ye-bo; Zhou, Tao; Cao, Dong-dong; Xu, Ping; Hochstetter, Danielle; Wang, Yue-fei

    2013-01-01

    Tea (Camellia sinensis L.) seed shells, the main byproduct of the manufacture of tea seed oil, were used as precursors for the preparation of tea activated carbon (TAC) in the present study. A high yield (44.1%) of TAC was obtained from tea seed shells via a one-step chemical method using ZnCl2 as an agent. The Brunauer-Emmett-Teller (BET) surface area and the total pore volumes of the obtained TAC were found to be 1 530.67 mg2/g and 0.782 6 cm3/g, respectively. The equilibrium adsorption results were complied with Langmuir isotherm model and its maximum monolayer adsorption capacity was 324.7 mg/g for methylene blue. Adsorption kinetics studies indicated that the pseudo-second-order model yielded the best fit for the kinetic data. An intraparticle diffusion model suggested that the intraparticle diffusion was not the only rate-controlling step. Thermodynamics studies revealed the spontaneous and exothermic nature of the sorption process. These results indicate that tea seed shells could be utilized as a renewable resource to develop activated carbon which is a potential adsorbent for methylene blue. PMID:23825151

  3. Equilibrium model constraints on baryon cycling across cosmic time

    NASA Astrophysics Data System (ADS)

    Mitra, Sourav; Davé, Romeel; Finlator, Kristian

    2015-09-01

    Galaxies strongly self-regulate their growth via energetic feedback from stars, supernovae, and black holes, but these processes are among the least understood aspects of galaxy formation theory. We present an analytic galaxy evolution model that directly constrains such feedback processes from observed galaxy scaling relations. The equilibrium model, which is broadly valid for star-forming central galaxies that dominate cosmic star formation, is based on the ansatz that galaxies live in a slowly evolving equilibrium between inflows, outflows, and star formation. Using a Bayesian Monte Carlo Markov chain approach, we constrain our model to match observed galaxy scaling relations between stellar mass and halo mass, star formation rate, and metallicity from 0 < z < 2. A good fit (χ2 ≈ 1.6) is achieved with eight free parameters. We further show that constraining our model to any two of the three data sets also produces a fit to the third that is within reasonable systematic uncertainties. The resulting best-fitting parameters that describe baryon cycling suggest galactic outflow scalings intermediate between energy and momentum-driven winds, a weak dependence of wind recycling time on mass, and a quenching mass scale that evolves modestly upwards with redshift. This model further predicts a stellar mass-star formation rate relation that is in good agreement with observations to z ˜ 6. Our results suggest that this simple analytic framework captures the basic physical processes required to model the mean evolution of stars and metals in galaxies, despite not incorporating many canonical ingredients of galaxy formation models such as merging or disc formation.

  4. Adsorption of heavy metal cations by Na-clinoptilolite: equilibrium and selectivity studies.

    PubMed

    Mihaly-Cozmuta, L; Mihaly-Cozmuta, A; Peter, A; Nicula, C; Tutu, H; Silipas, Dan; Indrea, Emil

    2014-05-01

    This paper summarizes the conclusions of experiments conducted on the adsorption of Cd(2+), Co(2+), Cu(2+), Mn(2+), Ni(2+), Pb(2+) and Zn(2+) onto zeolite. The focus of the experiments was to establish the influence of the initial pH of the contact solution as well as the selectivity of zeolite on the efficiency of the adsorption process. To this end, experimental adsorption isotherms were established for the pH values ranging from 1 to 4 by using the Na-form of clinoptilolite (particle size range 0.5-1 mm) as an adsorbent. Langmuir, Freundlich and Dubinin-Raduschkevich isotherm models were used to validate the experimental data and the Gibbs free energy was calculated based on the distribution coefficient. From the Langmuir model, correlations between the maximum adsorption capacity and selected physical-chemical parameters of the cations studied were established. The results of the experiments suggest that the selectivity of zeolite is strongly influenced by the pH of the contact solution, dehydration energy of cations, diffusion coefficient and the pH at which the precipitation of hydroxides occurs.

  5. Three model space experiments on chemical reactions. [Gibbs adsorption, equilibrium shift and electrodeposition

    NASA Technical Reports Server (NTRS)

    Grodzka, P.; Facemire, B.

    1977-01-01

    Three investigations conducted aboard Skylab IV and Apollo-Soyuz involved phenomena that are of interest to the biochemistry community. The formaldehyde clock reaction and the equilibrium shift reaction experiments conducted aboard Apollo Soyuz demonstrate the effect of low-g foams or air/liquid dispersions on reaction rate and chemical equilibrium. The electrodeposition reaction experiment conducted aboard Skylab IV demonstrate the effect of a low-g environment on an electrochemical displacement reaction. The implications of the three space experiments for various applications are considered.

  6. Adsorption kinetics and equilibrium studies for removal of acid azo dyes by aniline formaldehyde condensate

    NASA Astrophysics Data System (ADS)

    Terangpi, Praisy; Chakraborty, Saswati

    2016-12-01

    Adsorption of two acid dyes named Acid orange 8 (AO8) and Acid violet 7 (AV7) by amine based polymer aniline formaldehyde condensate (AFC) was studied. Adsorption of both dyes was favored at acidic pH. Electrostatic attraction between protonated amine group (NH3 +) of AFC and anionic sulfonate group (SO3 -) of dye molecule along with hydrogen bond formation and interaction between aromatic group of dye and AFC were responsible mechanisms for dye uptake. Isotherm of AO8 was Type I and followed Langmuir isotherm model. AV7 isotherm on AFC was of Type III and followed Freundlich model. Kinetics study showed that external mass transfer was the rate limiting step followed by intraparticle diffusion. Maximum adsorption capacities of AO8 and AV7 were observed as 164 and 68 mg/g. AO8 dye being smaller in molecular size was adsorbed more due to higher diffusion rate and higher dye: AFC ratio, which enhanced the interaction between dye and polymer.

  7. Adsorption equilibrium and thermodynamics of CO2 and CH4 on carbon molecular sieves

    NASA Astrophysics Data System (ADS)

    Song, Xue; Wang, Li'ao; Ma, Xu; Zeng, Yunmin

    2017-02-01

    Carbon molecular sieves (CMS) are widely used in the separation of dioxide carbon and methane. In this research, three commercial CMS were utilized to analyze the pore structure and chemical properties. The adsorption isotherms of CO2 and CH4 were studied at 298 K, 308 K and 318 K over the pressure range of 0-1 MPa by an Intelligent Gravimetric analysis (IGA-100B, UK). Langmuir model was adopted to fit the experimental data. The working capacity and selectivity were employed to evaluate the adsorbents. The adsorption thermodynamics were discussed. The adsorbed amounts of both CO2 and CH4 are found to be highly related with the BET specific surface area and the volume of micropores, and also are interrelated with the total pore volume and micropore surface area. The standard enthalpy change (ΔHΘ), standard Gibbs free energy (ΔGΘ) and standard entropy change (ΔSΘ) at zero surface loading are negative, manifesting the adsorption process is exothermic and spontaneous, and the system tends to be ordered. With the increasing surface coverage, the absolute values of Gibbs free energy (ΔG) decrease whereas the absolute values of enthalpy change (ΔH) and entropy change(ΔS) increase. This indicates that as the adsorbed amount increases, the degree of the spontaneity reduces, the intermolecular forces among the adsorbate molecules increase, the orderliness of the system improves and the adsorbed amount approaches the maximum adsorbed capacity.

  8. Optical luminescence studies of diffusion times at the potassium ethyl xanthate adsorption layer on the surface of sphalerite minerals

    NASA Astrophysics Data System (ADS)

    Todoran, R.; Todoran, D.; Anitas, E. M.; Szakács, Zs

    2016-08-01

    We propose reflectance measurements as a method for the evaluation of the kinetics of adsorption processes, to compute the diffusion times of the adsorption products at the thin layers formed at the sphalerite natural mineral-potassium ethyl xanthate solution interface. The method is based on the intensity measurement of the reflected monochromatic radiation obtained from the mineral-xanthate thin layer as a function of time. These determinations were made at the thin layer formed between the sphalerite or activated sphalerite natural minerals with potassium ethyl xanthate, for different solutions concentrations and pH values at constant temperature. Diffusion times of desorbed molecular species into the liquid bring important information about the global kinetics of the ions in this phase during adsorption processes at interfaces. Analysing the time dependence of this parameter one concluded on the diffusion properties of the xanthate molecule in the solution depending on its concentration and pH, knowing that at the initial time these molecules had a uniform spread. This method enabled us to determine that, in time interval of approximately 35 minutes to achieve dynamic equilibrium in the formation of the interface layer, one had three different kinetic behaviours of our systems. In the first 5-8 min one had highly adsorbent character, the state of equilibrium is followed by low adsorbent properties. Gaining information on the adsorption kinetics in the case of xanthate on mineral surface leads to the optimization of the industrial froth flotation process.

  9. Experimental studies on equilibrium adsorption isosteres and determination of the thermodynamic quantities of polar media on alumina Al2O3

    NASA Astrophysics Data System (ADS)

    Yonova, Albena

    2017-03-01

    The present work is a revieif of theoretical and experimental study on the adsorption performance of the adsorbent Alumina (Al2O3) used in the adsorption system. An experimental investigation on the equilibrium adsorption isosteres at low pressure (< 1 atm) of working pairs Al2O3/H2O and Al2O3/C2H6O2 is carried out. The isovolume measurement method is adopted in the test setup to directly measure the saturated vapor pressures of working pairs at vapor-liquid equilibrium (dG=0 and dμi=0). Quantity adsorbed is determined from pressure, volume and temperature using gas law. The isosteric heat of adsorption is calculated from the slope of the plot of lnP versus 1/T different amounts of adsorbate onto adsorbent as follows: 0,01 vol% Al2O3/H2O; 0,03 vol% Al2O3/H2O; 0,1 vol% Al2O3/H2O; 0,01 vol% Al2O3/C2H6O2; 0,03 vol% Al2O3/C2H6O2; 0,1 vol% Al2O3/C2H6O2. This study shows that adsorption working pair Al2O3 C2H6O2 has better adsorption performances than those of the A2O3/H2O. Surface acidity! is a most important property! far both adsorption and catalysis and therefore is examined structure of active sites of alumina surface. Thermodynamic parameters such as isosteric heat of adsorption, isosteric enthalpy and entropy of adsorption are critical design variables in estimating the performance and predicting the mechanism of an adsorption process and are also one of the basic requirements for the characterization and optimization of an adsorption process

  10. Equilibrium and Heat of Adsorption for Organic Vapors and Activated Carbons

    DTIC Science & Technology

    2005-05-01

    Technol. 2005, 39, 5864-5871 5864 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 39, NO. 15, 2005 10.1021/es048144r CCC: $30.25  2005 American Chemical...0.654 VOL. 39, NO. 15, 2005 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 5865 have due to the drag force on the sample pan. In addition, the N2 flow prevented...results are provided as lines. 5866 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 39, NO. 15, 2005 Increasing the adsorption temperature from 20 to 60 °C

  11. Characterizing particle-scale equilibrium adsorption and kinetics of uranium(VI) desorption from U-contaminated sediments

    USGS Publications Warehouse

    Stoliker, Deborah L.; Liu, Chongxuan; Kent, Douglas B.; Zachara, John M.

    2013-01-01

    Rates of U(VI) release from individual dry-sieved size fractions of a field-aggregated, field-contaminated composite sediment from the seasonally saturated lower vadose zone of the Hanford 300-Area were examined in flow-through reactors to maintain quasi-constant chemical conditions. The principal source of variability in equilibrium U(VI) adsorption properties of the various size fractions was the impact of variable chemistry on adsorption. This source of variability was represented using surface complexation models (SCMs) with different stoichiometric coefficients with respect to hydrogen ion and carbonate concentrations for the different size fractions. A reactive transport model incorporating equilibrium expressions for cation exchange and calcite dissolution, along with rate expressions for aerobic respiration and silica dissolution, described the temporal evolution of solute concentrations observed during the flow-through reactor experiments. Kinetic U(VI) desorption was well described using a multirate SCM with an assumed lognormal distribution for the mass-transfer rate coefficients. The estimated mean and standard deviation of the rate coefficients were the same for all <2 mm size fractions but differed for the 2–8 mm size fraction. Micropore volumes, assessed using t-plots to analyze N2 desorption data, were also the same for all dry-sieved <2 mm size fractions, indicating a link between micropore volumes and mass-transfer rate properties. Pore volumes for dry-sieved size fractions exceeded values for the corresponding wet-sieved fractions. We hypothesize that repeated field wetting and drying cycles lead to the formation of aggregates and/or coatings containing (micro)pore networks which provided an additional mass-transfer resistance over that associated with individual particles. The 2–8 mm fraction exhibited a larger average and standard deviation in the distribution of mass-transfer rate coefficients, possibly caused by the abundance of

  12. Removal of Bisphenol A aqueous solution using surfactant-modified natural zeolite: Taguchi's experimental design, adsorption kinetic, equilibrium and thermodynamic study.

    PubMed

    Genç, Nevim; Kılıçoğlu, Ödül; Narci, Ali Oğuzhan

    2017-02-01

    In this study, surfactant-modified natural zeolite was used to remove Bisphenol A (BPA) from aqueous solutions. Kinetics, equilibrium and thermodynamics of BPA adsorption on the adsorbent surfaces were investigated. The experimental data were described with the Temkin isotherm and the pseudo-second- order kinetic model. Taguchi's robust design approach was used to optimize adsorption of BPA. Experimentation was planned as per Taguchi's L27 orthogonal array. Tests were conducted with different adsorbate amount, pH, time, initial concentration of BPA, temperature and agitation speed. The optimum levels of control factors for maximum total organic carbon removal were defined (adsorbate amount at 0.25 g, pH at 7, time at 30 min, initial concentration of BPA at 50 mg/L, temperature at 30°C and agitation speed at 200 rpm). The ANOVA analysis shown that the most effective control factor is adsorbent dosage; its contribution is 56.4%. Contribution of pH and mixing rate are 7.5% and 7.6%, respectively. A confirmation experiment was conducted to verify the feasibility and effectiveness of the optimal combination. The observed value of S/N (ηobs = 39) ratio is compared with that of the predicted value (ηopt = 48). The prediction error, that is, ηopt - ηobs = 9, is within CI value.

  13. Equilibrium modeling and kinetic studies on the adsorption of basic dye by a low-cost adsorbent: coconut (Cocos nucifera) bunch waste.

    PubMed

    Hameed, B H; Mahmoud, D K; Ahmad, A L

    2008-10-01

    In this paper, the ability of coconut bunch waste (CBW), an agricultural waste available in large quantity in Malaysia, to remove basic dye (methylene blue) from aqueous solution by adsorption was studied. Batch mode experiments were conducted at 30 degrees C to study the effects of pH and initial concentration of methylene blue (MB). Equilibrium adsorption isotherms and kinetics were investigated. The experimental data were analyzed by the Langmuir, Freundlich and Temkin models of adsorption. The adsorption isotherm data were fitted well to Langmuir isotherm and the monolayer adsorption capacity was found to be 70.92 mg/g at 30 degrees C. The kinetic data obtained at different concentrations have been analyzed using a pseudo-first-order, pseudo-second-order equation and intraparticle diffusion equation. The experimental data fitted very well the pseudo-second-order kinetic model.

  14. Impact of the molecular structure and adsorption mode of D-π-A dye sensitizers with a pyridyl group in dye-sensitized solar cells on the adsorption equilibrium constant for dye-adsorption on TiO2 surface.

    PubMed

    Ooyama, Yousuke; Yamaguchi, Naoya; Ohshita, Joji; Harima, Yutaka

    2016-12-07

    D-π-A dyes NI-4 bearing a pyridyl group, YNI-1 bearing two pyridyl groups and YNI-2 bearing two thienylpyridyl groups as the anchoring group on the TiO2 surface have been developed as dye sensitizers for dye-sensitized solar cells (DSSCs), where NI-4 and YNI-2 can adsorb onto the TiO2 electrode through the formation of the coordinate bond between the pyridyl group of the dye and the Lewis acid site (exposed Ti(n+) cations) on the TiO2 surface, but YNI-1 is predominantly adsorbed on the TiO2 electrode through the formation of the hydrogen bond between the pyridyl group of the dye and the Brønsted acid sites (surface-bound hydroxyl groups, Ti-OH) on the TiO2 surface. The difference in the dye-adsorption mode among the three dyes on the TiO2 surface has been investigated from the adsorption equilibrium constant (Kad) based on the Langmuir adsorption isotherms. It was found that the Kad values of YNI-1 and YNI-2 are higher than that of NI-4, and more interestingly, the Kad value of YNI-2 is higher than that of YNI-1. This work demonstrates that that for the D-π-A dye sensitizers with the pyridyl group as the anchoring group to the TiO2 surface the number of pyridyl groups and the dye-adsorption mode on the TiO2 electrode as well as the molecular structure of the dye sensitizer affect the Kad value for the adsorption of the dye to the TiO2 electrode, that is, resulting in a difference in the Kad value among the D-π-A dye sensitizers NI-4, YNI-1 and YNI-2.

  15. Application of a micromembrane chromatography module to the examination of protein adsorption equilibrium.

    PubMed

    Káňavová, Natália; Kosior, Anna; Antošová, Monika; Faber, René; Polakovič, Milan

    2012-11-01

    A micromembrane chromatography module based on a 96-well plate design and enabling fast and simple separation of small amounts of proteins was used for the determination of binding capacities of lysozyme, bovine serum albumin, ovalbumin, bovine γ-globulin, and human immunoglobulin G on a hydrophobic membrane Sartobind® Phenyl. Dependence of the binding capacity of the proteins on the ammonium sulfate concentration was examined in the salt concentration range of 0.5-2.0 mol L(-1). An exponential increase of the binding capacity was observed for all proteins. Simple Langmuir one-component isotherm was found suitable for the characterization of the effect of protein concentration in all cases. A combined effect of protein and salt concentrations was expressed via the Langmuir exponential isotherm and fitted the adsorption data for three of the investigated proteins well.

  16. On the 2D-transition, hysteresis and thermodynamic equilibrium of Kr adsorption on a graphite surface.

    PubMed

    Diao, Rui; Fan, Chunyan; Do, D D; Nicholson, D

    2015-12-15

    The adsorption and desorption of Kr on graphite at temperatures in the range 60-88K, was systematically investigated using a combination of several simulation techniques including: Grand Canonical Monte Carlo (GCMC), Canonical kinetic-Monte Carlo (C-kMC) and the Mid-Density Scheme (MDS). Particular emphasis was placed on the gas-solid, gas-liquid and liquid-solid 2D phase transitions. For temperatures below the bulk triple point, the transition from a 2D-liquid-like monolayer to a 2D-solid-like state is manifested as a sub-step in the isotherm. A further increase in the chemical potential leads to another rearrangement of the 2D-solid-like state from a disordered structure to an ordered structure that is signalled by (1) another sub-step in the monolayer region and (2) a spike in the plot of the isosteric heat versus density at loadings close to the dense monolayer coverage concentration. Whenever a 2D transition occurs in a grand canonical isotherm it is always associated with a hysteresis, a feature that is not widely recognised in the literature. We studied in details this hysteresis with the analysis of the canonical isotherm, obtained with C-kMC, which exhibits a van der Waals (vdW) type loop with a vertical segment in the middle. We complemented the hysteresis loop and the vdW curve with the analysis of the equilibrium transition obtained with the MDS, and found that the equilibrium transition coincides exactly with the vertical segment of the C-kMC isotherm, indicating the co-existence of two phases at equilibrium. We also analysed adsorption at higher layers and found that the 2D-coexistence is also observed, provided that the temperature is well below the triple point. Finally the 2D-critical temperatures were obtained for the first three layers and they are in good agreement with the experimental data in the literature.

  17. Kinetic and equilibrium studies for the adsorption process of cadmium(II) and copper(II) onto Pseudomonas aeruginosa using square wave anodic stripping voltammetry method.

    PubMed

    Kong, Bo; Tang, Biyu; Liu, Xiaoying; Zeng, Xiandong; Duan, Haiyan; Luo, Shenglian; Wei, Wanzhi

    2009-08-15

    A novel method for the simultaneous determination of cadmium(II) and copper(II) during the adsorption process onto Pseudomonas aeruginosa was developed. The concentration of the free metal ions was successfully detected by square wave anodic stripping voltammetry (SWASV) on the mercaptoethane sulfonate (MES) modified gold electrode, while the P. aeruginosa was efficiently avoided approaching to the electrode surface by the MES monolayer. And the anodic stripping peaks of Cd(2+) and Cu(2+) appear at -0.13 and 0.34V respectively, at the concentration range of 5-50 microM, the peak currents of SWASV present linear relationships with the concentrations of cadmium and copper respectively. As the determination of Cd(2+) and Cu(2+) was in real time and without pretreatment, the kinetic characteristics of the adsorption process were studied and all the corresponding regression parameters were obtained by fitting the electrochemical experimental data to the pseudo-second-order kinetic model. Moreover, Langmuir and Freundlich models well described the biosorption isotherms. And there were some differences in the amount of metal ion adsorbed at equilibrium (q(e)) and other kinetics parameters when the two ions coexisted were compared with the unaccompanied condition, which were also discussed in this paper. The proposed electrode system provides excellent platform for the simultaneous determination of trace metals in complex biosorption process.

  18. Removal of direct blue-106 dye from aqueous solution using new activated carbons developed from pomegranate peel: adsorption equilibrium and kinetics.

    PubMed

    Amin, Nevine Kamal

    2009-06-15

    The use of cheap, high efficiency and ecofriendly adsorbent has been studied as an alternative source of activated carbon for the removal of dyes from wastewater. This study investigates the use of activated carbons prepared from pomegranate peel for the removal of direct blue dye from aqueous solution. A series of experiments were conducted in a batch system to assess the effect of the system variables, i.e. initial pH, temperature, initial dye concentration adsorbent dosage and contact time. The results showed that the adsorption of direct blue dye was maximal at pH 2, as the amount of adsorbent increased, the percentage of dye removal increased accordingly but it decreased with the increase in initial dye concentration and solution temperature. The adsorption kinetics was found to follow pseudo-second-order rate kinetic model, with a good correlation (R(2)>0.99) and intra-particle diffusion as one of the rate determining steps. Langmuir, Freundlich, Temkin, Dubinin-RadushKevich (D-R) and Harkins-Jura isotherms were used to analyze the equilibrium data at different temperatures. In addition, various thermodynamic parameters, such as standard Gibbs free energy (DeltaG degrees ), standard enthalpy (DeltaH degrees ), standard entropy (DeltaS degrees ), and the activation energy (E(a)) have been calculated. The adsorption process of direct blue dye onto different activated carbons prepared from pomegranate peel was found to be spontaneous and exothermic process. The findings of this investigation suggest that the physical sorption plays a role in controlling the sorption rate.

  19. Lysozyme adsorption in pH-responsive hydrogel thin-films: the non-trivial role of acid-base equilibrium.

    PubMed

    Narambuena, Claudio F; Longo, Gabriel S; Szleifer, Igal

    2015-09-07

    We develop and apply a molecular theory to study the adsorption of lysozyme on weak polyacid hydrogel films. The theory explicitly accounts for the conformation of the network, the structure of the proteins, the size and shape of all the molecular species, their interactions as well as the chemical equilibrium of each titratable unit of both the protein and the polymer network. The driving forces for adsorption are the electrostatic attractions between the negatively charged network and the positively charged protein. The adsorption is a non-monotonic function of the solution pH, with a maximum in the region between pH 8 and 9 depending on the salt concentration of the solution. The non-monotonic adsorption is the result of increasing negative charge of the network with pH, while the positive charge of the protein decreases. At low pH the network is roughly electroneutral, while at sufficiently high pH the protein is negatively charged. Upon adsorption, the acid-base equilibrium of the different amino acids of the protein shifts in a nontrivial fashion that depends critically on the particular kind of residue and solution composition. Thus, the proteins regulate their charge and enhance adsorption under a wide range of conditions. In particular, adsorption is predicted above the protein isoelectric point where both the solution lysozyme and the polymer network are negatively charged. This behavior occurs because the pH in the interior of the gel is significantly lower than that in the bulk solution and it is also regulated by the adsorption of the protein in order to optimize protein-gel interactions. Under high pH conditions we predict that the protein changes its charge from negative in the solution to positive within the gel. The change occurs within a few nanometers at the interface of the hydrogel film. Our predictions show the non-trivial interplay between acid-base equilibrium, physical interactions and molecular organization under nanoconfined conditions

  20. RESORCINOL-FORMALDEHYDE ADSORPTION OF CESIUM (Cs+) FROM HANFORD WASTE SOLUTIONS-PART I: BATCH EQUILIBRIUM STUDY

    SciTech Connect

    HASSAN, NEGUIBM

    2004-03-30

    Batch equilibrium measurements were conducted with a granular Resorcinol-Formaldehyde (RF) resin to determine the distribution coefficients (Kds) for cesium. In the tests, Hanford Site actual waste sample containing radioactive cesium and a pretreated waste sample that was spiked with non-radioactive cesium were used. Initial concentrations of non-radioactive cesium in the waste sample were varied to generate an equilibrium isotherm for cesium. Two additional tests were conducted using a liquid to solid phase ratio of 10 and a contact time of 120 hours. The measured distribution coefficient (Kd) for radioactive cesium (137Cs) was 948 mL/g; the Kd for non-radioactive cesium (133Cs) was 1039 mL/g. The Kd for non-radioactive cesium decreased from 1039 to 691 mL/g as the initial cesium concentration increased. Very little change of the Kd was observed at initial cesium concentrations above 64 mg/mL. The maximum sorption capacity for cesium on granular RF resin was 1.17 mmole/g dry resin. T his value was calculated from the fit of the equilibrium isotherm data to the Dubinin-Radushkevich equation. Previously, a total capacity of 2.84 mmole/g was calculated by Bibler and Wallace for air-dried RF resin.

  1. 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.

  2. A novel polar-modified post-cross-linked resin and its enhanced adsorption to salicylic acid: Equilibrium, kinetics and breakthrough studies.

    PubMed

    Wang, Xiaomei; Li, Guoqiang; Guo, Deping; Zhang, Yaling; Huang, Jianhan

    2016-05-15

    Improving the surface polarity is of significance for the post-cross-linked resins to enhance their adsorption to polar aromatic compounds. In the present study, we prepared a novel polar-modified post-cross-linked PDEpc_D by the Friedel-Crafts alkylation reaction and the amination reaction, the Brunauer-Emmett-Teller (BET) surface area and pore volume increased significantly after the Friedel-Crafts alkylation reaction and the surface polarity improved greatly after the amination reaction. Batch adsorption showed that PDEpc_D possessed a much enhanced adsorption to salicylic acid as compared the precursors PDE and PDEpc as well as the non-polar post-cross-linked PDVBpc. The equilibrium data was characterized by the Freundlich model, π-π stacking, hydrogen bonding and static interaction were the possible driving forces. The adsorption was a fast process and the kinetic data obeyed the micropore diffusion model. Column adsorption-desorption experiments suggested that PDEpc_D was a potential candidate for adsorptive removal of salicylic acid from aqueous solution.

  3. Process development for removal and recovery of cadmium from wastewater by a low-cost adsorbent: Adsorption rates and equilibrium studies

    SciTech Connect

    Periasamy, K.; Namasivayam, C. . Dept. of Environmental Sciences)

    1994-02-01

    Activated carbon prepared from peanut hulls (PHC), an agricultural waste by-product, has been used for the adsorption of Cd(II) from synthetic wastewater. The adsorption data fit better with the Freundlich adsorption isotherm. The applicability of the Lagergren kinetic model has also been investigated. An almost quantitative removal of 20 mg/L Cd(II) by 0.7 g of PHC/L of aqueous solution was observed in the pH range 3.5--9.5. A comparative study with a commercial granular activated carbon (CAC) showed that the adsorption capacity (K[sub f]) of PHC was 31 times larger than that of CAC.

  4. Role of the solvent in the adsorption-desorption equilibrium of cinchona alkaloids between solution and a platinum surface: correlations among solvent polarity, cinchona solubility, and catalytic performance.

    PubMed

    Ma, Zhen; Zaera, Francisco

    2005-01-13

    The role that the nature of the solvent plays in defining the extent of cinchona alkaloid adsorption-desorption equilibrium on platinum surfaces has been studied both by testing their solubility in 54 different solvents and by probing the stability of adsorbed cinchona in the presence of those solvents. The solubilities vary by as much as 5-6 orders of magnitude, display volcano-type correlations with solvent polarity and dielectric constant, and follow a cinchonine < cinchonidine < quinine, quinidine sequence. The adsorption-desorption equilibrium shifts toward the solution with increasing dissolving power of the solvent. The relevance of these results to the behavior of cinchona as chiral modifiers in hydrogenation catalysis is discussed.

  5. Kinetics, equilibrium and thermodynamics of adsorption of 2-biphenylamine and dibenzylamine from aqueous solutions by Fe3O4/bentonite nanocomposite

    NASA Astrophysics Data System (ADS)

    Vasheghani F., B.; Rajabi, F. H.; Omidi, M. H.; Shabanian, S.

    2015-05-01

    Magnetic Fe3O4/bentonite nanocomposite is synthesized by chemical co-precipitation method. Experimental data are modelled by Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich isotherms. Freundlich and Langmuir isotherm model fitted the equilibrium data for the dibenzylamine (DBA) and 2-biphenylamine (BPA) respectively, compared to the other isotherm models. The calculated thermodynamic parameters, Δ G°, Δ H°, and Δ S° showed that the DBA and BPA adsorption on bentonite nanocomposite is spontaneous and endothermic under examined conditions. Experimental data were also modeled using the adsorption kinetic models. The results show that the adsorption processes of DBA and BPA followed well the pseudo-second-order kinetics. Results indicated that Fe3O4/bentonite nanocomposite could be an alternative for more costly adsorbents used for organic toxicants removal.

  6. Contact time optimization of two-stage batch adsorber design using second-order kinetic model for the adsorption of phosphate onto alunite.

    PubMed

    Ozacar, Mahmut

    2006-09-01

    The adsorption of phosphate onto alunite in a batch adsorber has been studied. Four kinetic models including pseudo first- and second-order equation, intraparticle diffusion equation and the Elovich equation were selected to follow the adsorption process. Kinetic parameters, rate constants, equilibrium adsorption capacities and related correlation coefficients, for each kinetic model were calculated and discussed. It was shown that the adsorption of phosphate onto alunite could be described by the pseudo second-order equation. Adsorption of phosphate onto alunite followed the Langmuir isotherm. A model has been used for the design of a two-stage batch adsorber based on pseudo second-order adsorption kinetics. The model has been optimized with respect to operating time in order to minimize total operating time to achieve a specified amount of phosphate removal using a fixed mass of adsorbent. The results of two-stage batch adsorber design studies showed that the required times for specified amounts of phosphate removal significantly decreased. It is particularly suitable for low-cost adsorbents/adsorption systems when minimising operating time is a major operational and design criterion, such as, for highly congested industrial sites in which significant volume of effluent need to be treated in the minimum amount of time.

  7. Dynamic and equilibrium performance of sensors based on short peptide ligands for affinity adsorption of human IgG using surface plasmon resonance.

    PubMed

    Islam, Nafisa; Shen, Fei; Gurgel, Patrick V; Rojas, Orlando J; Carbonell, Ruben G

    2014-08-15

    This paper characterizes the potential of novel hexameric peptide ligands for on-line IgG detection in bioprocesses. Surface Plasmon Resonance (SPR) was used to study the binding of human IgG to the hexameric peptide ligand HWRGWV, which was covalently grafted to alkanethiol self-assembled monolayers (SAM) on gold surfaces. Peptide coupling on SAMs was verified, followed by covalent grafting of peptides with a removable Fmoc or acetylated N-termini via their C-termini to produce active peptide SPR sensors that were tested for IgG binding. The dynamics and extent of peptide-IgG binding were compared with results from a conventional system using protein A attached on a gold surface via disulfide monolayers. IgG binding to protein A on disulfide monolayers yielded equilibrium dissociation constants of 1.4×10(-7)M. The corresponding dissociation constant value for the acetylated version of the peptide (Ac-HWRGWV) supported on alkanethiol SAM was 5.8×10(-7)M and that for HWRGWV on the alkanethiol SAM (after de-protection of Fmoc-HWRGWVA) was 1.2×10(-6)M. Maximum IgG binding capacities, Qm of 6.7, 3.8, and 4.1mgm(-2) were determined for the protein A and the two forms of HWRGWV-based biosensors, respectively. Real-time data for the kinetics of adsorption were used to determine the apparent rate constants for adsorption and desorption. The results were analyzed to understand the mechanism of IgG binding to the protein and peptide ligands. It was found that the peptide-IgG binding was reaction controlled, however the protein A-IgG binding mechanism was partially mass transfer (diffusion) controlled. The adsorption rate constants, ka, for the protein A ligand increased with decreasing concentration of analyte and the peptide ligand ka values was constant at different IgG concentrations and flow rates.

  8. From Non-equilibrium to Equilibrium: Micellar Kinetics seen by Time-resolved Small-angle Scattering

    NASA Astrophysics Data System (ADS)

    Lund, Reidar

    The kinetic pathways of self-assembled nanostructures are not fully understood. Time-resolved small-angle X-ray/neutron scattering (TR-SAXS/SANS) is powerful technique1 that allows kinetics processes such as nucleation processes2,3 and morphological transitions4,5 to be followed with structural resolution over time scales starting from milliseconds. Neutrons offer the additional advantage of facile contrast variation through H/D substitution schemes, which also allow equilibrium processes such as molecular exchange and diffusion to be studied1 , 6 , 7. Here we will highlight the current capabilities of TR-SAS and show results on the kinetics of polymeric micelles. We will address how the understanding of kinetic pathways can be used control the nanostructure.

  9. Uptake of gaseous formaldehyde by soil surfaces: a combination of adsorption/desorption equilibrium and chemical reactions

    NASA Astrophysics Data System (ADS)

    Li, Guo; Su, Hang; Li, Xin; Kuhn, Uwe; Meusel, Hannah; Hoffmann, Thorsten; Ammann, Markus; Pöschl, Ulrich; Shao, Min; Cheng, Yafang

    2016-08-01

    Gaseous formaldehyde (HCHO) is an important precursor of OH radicals and a key intermediate molecule in the oxidation of atmospheric volatile organic compounds (VOCs). Budget analyses reveal large discrepancies between modeled and observed HCHO concentrations in the atmosphere. Here, we investigate the interactions of gaseous HCHO with soil surfaces through coated-wall flow tube experiments applying atmospherically relevant HCHO concentrations of ˜ 10 to 40 ppbv. For the determination of uptake coefficients (γ), we provide a Matlab code to account for the diffusion correction under laminar flow conditions. Under dry conditions (relative humidity = 0 %), an initial γ of (1.1 ± 0.05) × 10-4 is determined, which gradually drops to (5.5 ± 0.4) × 10-5 after 8 h experiments. Experiments under wet conditions show a smaller γ that drops faster over time until reaching a plateau. The drop of γ with increasing relative humidity as well as the drop over time can be explained by the adsorption theory in which high surface coverage leads to a reduced uptake rate. The fact that γ stabilizes at a non-zero plateau suggests the involvement of irreversible chemical reactions. Further back-flushing experiments show that two-thirds of the adsorbed HCHO can be re-emitted into the gas phase while the residual is retained by the soil. This partial reversibility confirms that HCHO uptake by soil is a complex process involving both adsorption/desorption and chemical reactions which must be considered in trace gas exchange (emission or deposition) at the atmosphere-soil interface. Our results suggest that soil and soil-derived airborne particles can either act as a source or a sink for HCHO, depending on ambient conditions and HCHO concentrations.

  10. Enhanced adsorptive removal of Safranine T from aqueous solutions by waste sea buckthorn branch powder modified with dopamine: Kinetics, equilibrium, and thermodynamics

    NASA Astrophysics Data System (ADS)

    Xu, Xiaohui; Bai, Bo; Wang, Honglun; Suo, Yourui

    2015-12-01

    Polydopamine coated sea buckthorn branch powder (PDA@SBP) was facilely synthesized via a one-pot bio-inspired dip-coating approach. The as-synthesized PDA@SBP was characterized using Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM). The adsorption progresses of Safranine T on the surface of PDA@SBP adsorbent were systematically investigated. More specifically, the effects of solution pH, contact time, initial concentration and temperature were evaluated, respectively. The experimental results showed the adsorption capacity of PDA@SBP at 293.15 K could reach up to 54.0 mg/g; the adsorption increased by 201.7% compared to that of native SBP (17.9 mg/g). Besides, kinetics studies showed that pseudo-second-order kinetic model adequately described the adsorption behavior. The adsorption experimental data could be fitted well a Freundlich isotherm model. Thermodynamic analyses showed that the ST adsorption was a physisorption endothermic process. Regeneration of the spent PDA@SBP adsorbent was conducted with 0.1 M HCl without significant reduction in adsorption capacity. On the basis of these investigations, it is believed that the PDA@SBP adsorbent could have potential applications in sewage disposal areas because of their considerable adsorption capacities, brilliant regeneration capability, and cost-effective and eco-friendly preparation and use.

  11. Polar modified post-cross-linked resin and its adsorption toward salicylic acid from aqueous solution: Equilibrium, kinetics and breakthrough studies.

    PubMed

    Fu, Zhenyu; He, Chunlian; Huang, Jianhan; Liu, You-Nian

    2015-08-01

    A novel polar modified post-cross-linked resin PDMPA was synthesized, characterized and evaluated for adsorption of salicylic acid from aqueous solution. PDMPA was prepared by a suspension polymerization of methyl acrylate (MA) and divinylbenzene (DVB), a Friedel-Crafts reaction and an amination reaction. After characterization of the chemical and pore structure of PDMPA, the adsorption behaviors of salicylic acid on PDMPA were determined in comparison with the precursor resins. The equilibrium adsorption capacity of salicylic acid on PDMPA was much larger than the precursor resins and the equilibrium data were correlated by both of the Langmuir and Freundlich models. The pseudo-second-order rate equation fitted the kinetic data better than the pseudo-first-order rate equation, and the micropore diffusion model could characterize the kinetic data very well. The dynamic experimental results showed that the breakthrough point and saturated point of salicylic acid on PDMPA were 40.3 and 92.4BV (1BV=10mL) at a feed concentration of 995.8mg/L and a flow rate of 1.4mL/min, and the resin column could be regenerated by 16.0BV of a mixture desorption solvent containing 0.01mol/L of NaOH (w/v) and 50% of ethanol (v/v).

  12. On the time needed to reach an equilibrium structure of the radiation belts

    DOE PAGES

    Ripoll, J. -F.; Loran, V.; Cunningham, Gregory Scott; ...

    2016-08-01

    In this paper, we complement the notion of equilibrium states of the radiation belts with a discussion on the dynamics and time needed to reach equilibrium. We solve for the equilibrium states obtained using 1D radial diffusion with recently developed hiss and chorus lifetimes at constant values of Kp = 1, 3 and 6. We find that the equilibrium states at moderately low Kp, when plotted vs L-shell (L) and energy (E), display the same interesting S-shape for the inner edge of the outer belt as recently observed by the Van Allen Probes. The S-shape is also produced as themore » radiation belts dynamically evolve toward the equilibrium state when initialized to simulate the buildup after a massive dropout or to simulate loss due to outward diffusion from a saturated state. Physically, this shape, intimately linked with the slot structure, is due to the dependence of electron loss rate (originating from wave-particle interactions) on both energy and L-shell. Equilibrium electron flux profiles are governed by the Biot number (τDiffusion/τloss), with large Biot number corresponding to low fluxes and low Biot number to large fluxes. The time it takes for the flux at a specific (L, E) to reach the value associated with the equilibrium state, starting from these different initial states, is governed by the initial state of the belts, the property of the dynamics (diffusion coefficients), and the size of the domain of computation. Its structure shows a rather complex scissor form in the (L, E) plane. The equilibrium value (phase space density or flux) is practically reachable only for selected regions in (L, E) and geomagnetic activity. Convergence to equilibrium requires hundreds of days in the inner belt for E > 300 keV and moderate Kp (≤3). It takes less time to reach equilibrium during disturbed geomagnetic conditions (Kp ≥ 3), when the system evolves faster. Restricting our interest to the slot region, below L = 4, we find that only small regions in (L, E) space

  13. On the time needed to reach an equilibrium structure of the radiation belts

    SciTech Connect

    Ripoll, J. -F.; Loran, V.; Cunningham, Gregory Scott; Reeves, Geoffrey D.; Shprits, Y. Y.

    2016-08-01

    In this paper, we complement the notion of equilibrium states of the radiation belts with a discussion on the dynamics and time needed to reach equilibrium. We solve for the equilibrium states obtained using 1D radial diffusion with recently developed hiss and chorus lifetimes at constant values of Kp = 1, 3 and 6. We find that the equilibrium states at moderately low Kp, when plotted vs L-shell (L) and energy (E), display the same interesting S-shape for the inner edge of the outer belt as recently observed by the Van Allen Probes. The S-shape is also produced as the radiation belts dynamically evolve toward the equilibrium state when initialized to simulate the buildup after a massive dropout or to simulate loss due to outward diffusion from a saturated state. Physically, this shape, intimately linked with the slot structure, is due to the dependence of electron loss rate (originating from wave-particle interactions) on both energy and L-shell. Equilibrium electron flux profiles are governed by the Biot number (τDiffusionloss), with large Biot number corresponding to low fluxes and low Biot number to large fluxes. The time it takes for the flux at a specific (L, E) to reach the value associated with the equilibrium state, starting from these different initial states, is governed by the initial state of the belts, the property of the dynamics (diffusion coefficients), and the size of the domain of computation. Its structure shows a rather complex scissor form in the (L, E) plane. The equilibrium value (phase space density or flux) is practically reachable only for selected regions in (L, E) and geomagnetic activity. Convergence to equilibrium requires hundreds of days in the inner belt for E > 300 keV and moderate Kp (≤3). It takes less time to reach equilibrium during disturbed geomagnetic conditions (Kp ≥ 3), when the system evolves faster. Restricting our interest to the slot region, below L = 4, we find that only small regions in

  14. Rheology modulated non-equilibrium fluctuations in time-dependent diffusion processes

    NASA Astrophysics Data System (ADS)

    Maity, Debonil; Bandopadhyay, Aditya; Chakraborty, Suman

    2016-11-01

    The effect of non-Newtonian rheology, manifested through a viscoelastic linearized Maxwell model, on the time-dependent non-equilibrium concentration fluctuations due to free diffusion as well as thermal diffusion of a species is analyzed theoretically. Contrary to the belief that non-equilibrium Rayleigh line is not influenced by viscoelastic effects, through rigorous calculations, we put forward the fact that viscoelastic effects do influence the non-equilibrium Rayleigh line, while the effects are absent for the equilibrium scenario. The non-equilibrium process is quantified through the concentration fluctuation auto-correlation function, also known as the structure factor. The analysis reveals that the effect of rheology is prominent for both the cases of free diffusion and thermal diffusion at long times, where the influence of rheology dictates not only the location of the peaks in concentration dynamic structure factors, but also the magnitudes; such peaks in dynamic structure factors are absent in the case of Newtonian fluid. At smaller times, for the case of free diffusion, presence of time-dependent peak(s) are observed, which are weakly dependent on the influence of rheology, a phenomenon which is absent in the case of thermal diffusion. Different regimes of the frequency dependent overall dynamic structure factor, depending on the interplay of the fluid relaxation time and momentum diffusivity, are evaluated. The static structure factor is not affected to a great extent for the case of free-diffusion and is unaffected for the case of thermal diffusion.

  15. Spontaneous Time Symmetry Breaking in System with Mixed Strategy Nash Equilibrium: Evidences in Experimental Economics Data

    NASA Astrophysics Data System (ADS)

    Wang, Zhijian; Xu, Bin; Zhejiang Collaboration

    2011-03-01

    In social science, laboratory experiment with human subjects' interaction is a standard test-bed for studying social processes in micro level. Usually, as in physics, the processes near equilibrium are suggested as stochastic processes with time-reversal symmetry (TRS). To the best of our knowledge, near equilibrium, the breaking time symmetry, as well as the existence of robust time anti-symmetry processes, has not been reported clearly in experimental economics till now. By employing Markov transition method to analysis the data from human subject 2x2 Games with wide parameters and mixed Nash equilibrium, we study the time symmetry of the social interaction process near Nash equilibrium. We find that, the time symmetry is broken, and there exists a robust time anti-symmetry processes. We also report the weight of the time anti-symmetry processes in the total processes of each the games. Evidences in laboratory marketing experiments, at the same time, are provided as one-dimension cases. In these cases, time anti-symmetry cycles can also be captured. The proposition of time anti-symmetry processes is small, but the cycles are distinguishable.

  16. Bisphenol-A modified hyper-cross-linked polystyrene resin for salicylic acid removal from aqueous solution: adsorption equilibrium, kinetics and breakthrough studies.

    PubMed

    Hu, Huanxiao; Wang, Xiaomei; Li, Shengyong; Huang, Jianhan; Deng, Shuguang

    2012-04-15

    In this study, a series of bisphenol-A modified hyper-cross-linked polystyrene resins labeled as HJ-L00, HJ-L02, HJ-L04, HJ-L06 and HJ-L08 were synthesized, characterized and evaluated for adsorptive removal of salicylic acid from aqueous solutions. The structural characterization results indicated that the resins possessed predominant micropores/mesopores, moderate specific surface area and a few bisphenol-A groups on the surface. All the bisphenol-A modified hyper-cross-linked resins were effective for removing salicylic acid from aqueous solutions, and sample HJ-L02 had the largest adsorption capacity. The adsorption equilibrium data were correlated by the Freundlich isotherm model, and a positive adsorption enthalpy was obtained. The kinetic data were analyzed with two diffusion models and indicated that the intra-particle diffusion was the sole rate-controlling step in the first stage. The dynamic experimental results showed that the breakthrough point of the HJ-L02 adsorbent was at 90.2 BV (bed volume, 1 BV=10 mL) for a feed concentration of 500.0mg/L of salicylic acid, and 14.0 BV of 1% of sodium hydroxide could completely regenerate the HJ-L02 adsorbent column.

  17. Equilibrium and kinetic studies on acid dye Acid Red 88 adsorption by magnetic ZnFe2O4 spinel ferrite nanoparticles.

    PubMed

    Konicki, Wojciech; Sibera, Daniel; Mijowska, Ewa; Lendzion-Bieluń, Zofia; Narkiewicz, Urszula

    2013-05-15

    A magnetic ZnFe2O4 (MNZnFe) was synthesized by microwave assisted hydrothermal method and was used as an adsorbent for the removal of acid dye Acid Red 88 (AR88) from aqueous solution. The effects of various parameters such as initial AR88 concentration (10-56 mg L(-1)), pH solution (3.2-10.7), and temperature (20-60°C) were investigated. Prepared magnetic ZnFe2O4 was characterized by XRD, SEM, HRTEM, ICP-AES, BET, FTIR, and measurements of the magnetic susceptibility. The experimental data were analyzed by the Langmuir and Freundlich models of adsorption. Equilibrium data fitted well with the Langmuir model. Pseudo-first-order and pseudo-second-order kinetic models and intraparticle diffusion model were used to examine the adsorption kinetic data. The adsorption kinetics was found to follow the pseudo-second-order kinetic model. Thermodynamics parameters, ΔG°, ΔH° and ΔS°, indicate that the adsorption of AR88 onto MNZnFe was spontaneous and exothermic in nature.

  18. Large Time Out-of-Equilibrium Dynamics of a Manifold in a Random Potential

    NASA Astrophysics Data System (ADS)

    Cugliandolo, Leticia F.; Kurchan, Jorge; Le Doussal, Pierre

    1996-03-01

    We study the out-of-equilibrium dynamics of an elastic manifold in a random potential using mean-field theory. We find two asymptotic time regimes: (i) stationary dynamics; (ii) slow aging dynamics with violation of equilibrium theorems. We obtain an analytical solution valid for all large times with universal scalings of two-time quantities with space. A nonanalytic scaling function crosses over to ultrametricity when the correlations become long range. We propose procedures to test numerically or experimentally the extent to which this scenario holds for a given system.

  19. Modeling of phase equilibrium and vapor adsorption on carbon black based on a combination of a lattice theory and equation of state.

    PubMed

    Ustinov, E A; Do, D D

    2002-09-15

    A thermodynamic approach is developed in this paper to describe the behavior of a subcritical fluid in the neighborhood of vapor-liquid interface and close to a graphite surface. The fluid is modeled as a system of parallel molecular layers. The Helmholtz free energy of the fluid is expressed as the sum of the intrinsic Helmholtz free energies of separate layers and the potential energy of their mutual interactions calculated by the 10-4 potential. This Helmholtz free energy is described by an equation of state (such as the Bender or Peng-Robinson equation), which allows us a convenient means to obtain the intrinsic Helmholtz free energy of each molecular layer as a function of its two-dimensional density. All molecular layers of the bulk fluid are in mechanical equilibrium corresponding to the minimum of the total potential energy. In the case of adsorption the external potential exerted by the graphite layers is added to the free energy. The state of the interface zone between the liquid and the vapor phases or the state of the adsorbed phase is determined by the minimum of the grand potential. In the case of phase equilibrium the approach leads to the distribution of density and pressure over the transition zone. The interrelation between the collision diameter and the potential well depth was determined by the surface tension. It was shown that the distance between neighboring molecular layers substantially changes in the vapor-liquid transition zone and in the adsorbed phase with loading. The approach is considered in this paper for the case of adsorption of argon and nitrogen on carbon black. In both cases an excellent agreement with the experimental data was achieved without additional assumptions and fitting parameters, except for the fluid-solid potential well depth. The approach has far-reaching consequences and can be readily extended to the model of adsorption in slit pores of carbonaceous materials and to the analysis of multicomponent adsorption

  20. Real time equilibrium reconstruction for control of the discharge in the DIII-D tokamak

    SciTech Connect

    Ferron, J.R.; Walker, M.L.; Lao, L.L.; Penaflor, B.G.; St. John, H.E.; Humphreys, D.A.; Leuer, J.A.

    1997-07-01

    Optimum performance of a tokamak discharge requires accurate feedback control of many of the discharge parameters. For this to be possible, the values of these parameters must be accurately measured. The values of many discharge parameters, such as shape and safety factor profile, are not directly measured but can be evaluated from the available diagnostic data: magnetic field and flux measurements, for example. The most complete evaluation comes from a least squares fit of the diagnostic data to the Grad-Shafranov model that describes the force balance of the tokamak equilibrium, while allowing for a distributed current source. This full reconstruction of the equilibrium has normally been performed offline using a computation-intensive fitting code such as EFIT. This paper provides an introduction to a practical method for performing an equilibrium reconstruction in real time for arbitrary time-varying discharge shapes and current profiles. A detailed description of the algorithm is given in Ref. 2. An approximate solution to the Grad-Shafranov equilibrium relation is found which best fits the diagnostic measurements so that an equilibrium solution consistent with force balance, expressed in terms of the spatial distributions of the toroidal current density and poloidal flux, is available in real time for accurate evaluation of the discharge parameters. The algorithm is very close to that of EFIT and is executed on a time scale fast enough for control of the DIII-D tokamak.

  1. Enhancing adsorption capacity of toxic malachite green dye through chemically modified breadnut peel: equilibrium, thermodynamics, kinetics and regeneration studies.

    PubMed

    Chieng, Hei Ing; Lim, Linda B L; Priyantha, Namal

    2015-01-01

    Breadnut skin, in both its unmodified (KS) and base-modified (BM-KS) forms, was investigated for its potential use as a low-cost adsorbent for the removal of toxic dye, malachite green (MG). Characterization of the adsorbents was carried out using scanning electron microscope, X-ray fluorescence and Fourier transform infra-red spectroscopy. Batch adsorption experiments, carried out under optimized conditions, for the adsorption of MG were fitted using five isotherm models (Langmuir, Freundlich, Dubinin-Radushkevich, Temkin and Sips) and six error functions to determine the best-fit model. The adsorption capacity was greatly enhanced when breadnut skin was chemically modified with NaOH, leading to an adsorption capacity of 353.0 mg g(-1), that was far superior to most reported adsorbents for the removal of MG. Thermodynamics studies indicated that the adsorption of MG was spontaneous on KS and BM-KS, and the reactions were endothermic and exothermic, respectively. Kinetics studies showed that both followed the pseudo-second order. Regeneration experiments on BM-KS indicated that its adsorption capacity was still maintained at>90% even after five cycles. It can be concluded that NaOH-modified breadfruit skin has great potential to be utilized in real-life application as a low-cost adsorbent for the removal of MG in wastewater treatment.

  2. Equilibrium and kinetic modeling of iron adsorption and the effect by chloride, sulfate, and hydroxyl: evaluation of PVC-U drinking pipes.

    PubMed

    Wang, Jia -Ying; Li, Shu-Ping; Xin, Kun-Lun; Tao, Tao

    2016-12-01

    The update of pipeline was quick over the last few years and the plastic pipes were widely used in the drinking water distribution systems (DWDSs), especially in the small-diameter pipes. In this study, the iron adsorptive characteristics and the affecting factors in unplasticized poly(vinyl chloride) (PVC-U) pipe were investigated. Results showed that the average amount of iron in the 10-year-old PVC-U pipe's interior surface was 2.80 wt% which was almost 187 times larger than that in a new one. Goethite (α-FeOOH) and magnetite (Fe3O4) were the major iron compounds in the scales which covered on the old pipes' interior surface and showed loose and porous images under a scanning electron microscope. Moreover, the influence of the iron concentration on the adsorption amount and rate was discussed. The adsorption amount was significantly influenced by iron concentration, but similar adsorption rate was discovered. Notably, iron was quantitatively adsorbed by PVC-U pipe during the experimental period in accordance with the pseudo second order kinetic model. Meanwhile, regression model and response surface methodology were used to analyze the regular of iron adsorption in different concentrations of chloride (Cl(-)), sulfate (SO4(2-)), and hydroxyl (OH(-)). It can be concluded that Cl(-) and OH(-) showed the strong ability of iron adsorption which were larger than SO4(2-).

  3. MS for investigation of time-dependent protein adsorption on surfaces in complex biological samples

    PubMed Central

    Undin, Torgny; Lind, Sara Bergström; Dahlin, Andreas P

    2015-01-01

    Aim: This study aims at developing a nondestructive way for investigating protein adsorption on surfaces such as biomaterials using mass spectrometry. Methods: Ventricular cerebrospinal fluid in contact with poly carbonate membranes were used as adsorption templates and on-surface enzymatic digestion was applied to desorb proteins and cleave them into peptides. Mass spectrometric analysis provided both protein identification and determination of protein specific adsorption behavior. Results: In general, the adsorption increased with incubation time but also protein-specific time-resolved adsorption patterns from the complex protein solution were discovered. Conclusion: The method developed is a promising tool for the characterization of biofouling, which sometimes causes rejection and encapsulation of implants and can be used as complement to other surface analytical techniques. PMID:28031905

  4. A time-accurate implicit method for chemical non-equilibrium flows at all speeds

    NASA Technical Reports Server (NTRS)

    Shuen, Jian-Shun

    1992-01-01

    A new time accurate coupled solution procedure for solving the chemical non-equilibrium Navier-Stokes equations over a wide range of Mach numbers is described. The scheme is shown to be very efficient and robust for flows with velocities ranging from M less than or equal to 10(exp -10) to supersonic speeds.

  5. Phosphate Adsorption using Modified Iron Oxide-based Sorbents in Lake Water: Kinetics, Equilibrium, and Column Tests

    EPA Science Inventory

    Adsorption behavior of Bayoxide ® E33 (E33) and three E33-modified sorbents for the removal of phosphate from lake water was investigated in this study. E33-modified sorbents were synthesized by coating with manganese (E33/Mn) and silver (E33/AgI and E33/AgII) nanoparticles. Adso...

  6. Evolution of equilibrium Pickering emulsions--a matter of time scales.

    PubMed

    Kraft, Daniela J; Luigjes, Bob; de Folter, Julius W J; Philipse, Albert P; Kegel, Willem K

    2010-09-30

    A new class of equilibrium solid-stabilized oil-in-water emulsions harbors a competition of two processes on disparate time scales that affect the equilibrium droplet size in opposing ways. The aim of this work is to elucidate the molecular origins of these two time scales and demonstrate their effects on the evolution of the emulsion droplet size. First, spontaneous emulsification into particle-covered droplets occurs through in situ generation of surface-active molecules by hydrolysis of molecules of the oil phase. We show that surface tensions of the oil-water interfaces in the absence of stabilizing colloidal particles are connected to the concentration of these surface-active molecules, and hence also to the equilibrium droplet size in the presence of colloids. As a consequence, the hydrolysis process sets the time scale of formation of these solid-stabilized emulsions. A second time scale is governing the ultimate fate of the solid-stabilized equilibrium emulsions: by condensation of the in situ generated amphiphilic molecules onto the colloidal particles, their wetting properties change, leading to a gradual transfer from the aqueous to the oil phase via growth of the emulsion droplets. This migration is observed macroscopically by a color change of the water and oil phases, as well as by electron microscopy after polymerization of the oil phase in a phase separated sample. Surprisingly, the relative oil volume sets the time scale of particle transfer. Phase separation into an aqueous phase and an oil phase containing colloidal particles is influenced by sedimentation of the emulsion droplets. The two processes of formation of surface-active molecules through hydrolysis and condensation thereof on the colloidal surface have an opposite influence on the droplet size. By their interplay, a dynamic equilibrium is created where the droplet size always adjusts to the thermodynamically stable state.

  7. Mixing times towards demographic equilibrium in insect populations with temperature variable age structures.

    PubMed

    Damos, Petros

    2015-08-01

    In this study, we use entropy related mixing rate modules to measure the effects of temperature on insect population stability and demographic breakdown. The uncertainty in the age of the mother of a randomly chosen newborn, and how it is moved after a finite act of time steps, is modeled using a stochastic transformation of the Leslie matrix. Age classes are represented as a cycle graph and its transitions towards the stable age distribution are brought forth as an exact Markov chain. The dynamics of divergence, from a non equilibrium state towards equilibrium, are evaluated using the Kolmogorov-Sinai entropy. Moreover, Kullback-Leibler distance is applied as information-theoretic measure to estimate exact mixing times of age transitions probabilities towards equilibrium. Using empirically data, we show that on the initial conditions and simulated projection's trough time, that population entropy can effectively be applied to detect demographic variability towards equilibrium under different temperature conditions. Changes in entropy are correlated with the fluctuations of the insect population decay rates (i.e. demographic stability towards equilibrium). Moreover, shorter mixing times are directly linked to lower entropy rates and vice versa. This may be linked to the properties of the insect model system, which in contrast to warm blooded animals has the ability to greatly change its metabolic and demographic rates. Moreover, population entropy and the related distance measures that are applied, provide a means to measure these rates. The current results and model projections provide clear biological evidence why dynamic population entropy may be useful to measure population stability.

  8. Time-Resolved Photoemission of Correlated Electrons Driven Out of Equilibrium

    SciTech Connect

    Moritz, B.; Devereaux, T.P.; Freericks, J.K.; /Georgetown U.

    2010-02-15

    We describe the temporal evolution of the time-resolved photoemission response of the spinless Falicov-Kimball model driven out of equilibrium by strong, applied fields. The model is one of the few possessing a metal-insulator transition and admitting an exact solution in the time domain. The nonequilibrium dynamics, evaluated using an extension of dynamical mean-field theory, show how the driven system differs from two common viewpoints - a quasi-equilibrium system at an elevated, effective temperature (the 'hot' electron model) or a rapid interaction quench ('melting' of the Mott gap) - due to the rearrangement of electronic states and redistribution of spectral weight. The results demonstrate the inherent trade-off between energy and time resolution accompanying the finite width probe-pulses, characteristic of those employed in pump-probe, time-domain experiments, which can be used to focus attention on different aspects of the dynamics near the transition.

  9. 2,4-D adsorption to biochars: effect of preparation conditions on equilibrium adsorption capacity and comparison with commercial activated carbon literature data.

    PubMed

    Kearns, J P; Wellborn, L S; Summers, R S; Knappe, D R U

    2014-10-01

    Batch isotherm experiments were conducted with chars to study adsorption of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D). Chars generated from corncobs, bamboo and wood chips in a laboratory pyrolyzer at 400-700 °C were compared with traditional kiln charcoals collected from villages in S/SE Asia and with activated carbons (ACs). 2,4-D uptake by laboratory chars obtained from bamboo and wood chips after 14 h of pyrolysis at 700 °C, from wood chips after 96 h of pyrolysis at 600 °C, and one of the field-collected chars (basudha) was comparable to ACs. H:C and O:C ratios declined with pyrolysis temperature and duration while surface area increased to >500 m(2)/g. Increasing pyrolysis intensity by increasing temperature and/or duration of heating was found to positively influence adsorption capacity yield (mg(2,4-D/g(feedstock))) over the range of conditions studied. Economic analysis showed that high temperature chars can be a cost-effective alternative to ACs for water treatment applications.

  10. Time-dependent non-equilibrium dielectric response in QM/continuum approaches

    SciTech Connect

    Ding, Feizhi; Lingerfelt, David B.; Li, Xiaosong E-mail: li@chem.washington.edu; Mennucci, Benedetta E-mail: li@chem.washington.edu

    2015-01-21

    The Polarizable Continuum Models (PCMs) are some of the most inexpensive yet successful methods for including the effects of solvation in quantum-mechanical calculations of molecular systems. However, when applied to the electronic excitation process, these methods are restricted to dichotomously assuming either that the solvent has completely equilibrated with the excited solute charge density (infinite-time limit), or that it retains the configuration that was in equilibrium with the solute prior to excitation (zero-time limit). This renders the traditional PCMs inappropriate for resolving time-dependent solvent effects on non-equilibrium solute electron dynamics like those implicated in the instants following photoexcitation of a solvated molecular species. To extend the existing methods to this non-equilibrium regime, we herein derive and apply a new formalism for a general time-dependent continuum embedding method designed to be propagated alongside the solute’s electronic degrees of freedom in the time domain. Given the frequency-dependent dielectric constant of the solvent, an equation of motion for the dielectric polarization is derived within the PCM framework and numerically integrated simultaneously with the time-dependent Hartree fock/density functional theory equations. Results for small molecular systems show the anticipated dipole quenching and electronic state dephasing/relaxation resulting from out-of-phase charge fluctuations in the dielectric and embedded quantum system.

  11. Removal of azo dye by a highly graphitized and heteroatom doped carbon derived from fish waste: Adsorption equilibrium and kinetics.

    PubMed

    Liu, Zhengang; Zhang, Fang; Liu, Tingting; Peng, Nana; Gai, Chao

    2016-11-01

    A highly graphitized and heteroatom doped porous carbon was prepared from fish waste in the present study. The morphology and chemical composition of the resultant porous carbon were characterized by SEM-EDS, TEM, BET, XRD and Raman measurement. The prepared porous carbon was employed as an adsorbent for acid orange 7, a typical azo dye, removal from aqueous solution. The results showed that the porous carbon had ultrahigh surface area of 2146 m(2)/g, a high degree of graphitization structure and naturally doped with nitrogen and phosphorous. The maximum adsorption capacity of acid orange 7 reached 285.71 mg/g due to unique property of the prepared porous carbon. In addition, acid orange 7 adsorption onto the porous carbon well followed pseudo-second-order kinetics model and acid orange 7 diffusion in micropores was the potential rate controlling step.

  12. Adsorption equilibrium and transport kinetics for a range of probe gases in Takeda 3A carbon molecular sieve.

    PubMed

    Rutherford, S W; Coons, J E

    2005-04-15

    Measurements of adsorption equilibria and transport kinetics for argon, oxygen and nitrogen at 20, 50, and 80 degrees C on commercially derived Takeda carbon molecular sieve (CMS) employed for air separation have been undertaken in an effort to elucidate fundamental mechanisms of transport. Results indicate that micropore diffusion which is modeled by a Fickian diffusion process, governs the transport of oxygen molecules and the pore mouth barrier controls argon and nitrogen transport which is characterized by a linear driving force (LDF) model. For the three temperatures studied, the pressure dependence of the diffusivity and the LDF rate constant appear to be well characterized by a formulation based on the chemical potential as the driving force for transport. Isosteric heat of adsorption at zero loading and activation energy measurements are compared with predictions made from a previously proposed molecular model for characterizing CMS.

  13. Universal time fluctuations in near-critical out-of-equilibrium quantum dynamics.

    PubMed

    Campos Venuti, Lorenzo; Zanardi, Paolo

    2014-02-01

    Out-of-equilibrium quantum systems display complex temporal patterns. Such time fluctuations are generically exponentially small in the system volume and therefore can be safely ignored in most of the cases. However, if one consider small quench experiments, time fluctuations can be greatly enhanced. We show that time fluctuations may become stronger than other forms of equilibrium quantum fluctuations if the quench is performed close to a critical point. For sufficiently relevant operators the full distribution function of dynamically evolving observable expectation values becomes a universal function uniquely characterized by the critical exponents and the boundary conditions. At regular points of the phase diagram and for nonsufficiently relevant operators the distribution becomes Gaussian. Our predictions are confirmed by an explicit calculation on the quantum Ising model.

  14. Modeling, kinetic, and equilibrium characterization of paraquat adsorption onto polyurethane foam using the ion-pairing technique.

    PubMed

    Vinhal, Jonas O; Lage, Mateus R; Carneiro, José Walkimar M; Lima, Claudio F; Cassella, Ricardo J

    2015-06-01

    We studied the adsorption of paraquat onto polyurethane foam (PUF) when it was in a medium containing sodium dodecylsulfate (SDS). The adsorption efficiency was dependent on the concentration of SDS in solution, because the formation of an ion-associate between the cationic paraquat and the dodecylsulfate anion was found to be a fundamental step in the process. A computational study was carried out to identify the possible structure of the ion-associate in aqueous medium. The obtained data demonstrated that the structure is probably formed from four units of dodecylsulfate bonded to one paraquat moiety. The results showed that 94% of the paraquat present in 45 mL of a solution containing 3.90 × 10(-5) mol L(-1) could be retained by 300 mg of PUF, resulting in the removal of 2.20 mg of paraquat. The experimental data were reasonably adjusted to the Freundlich isotherm and to the pseudo-second-order kinetic model. Also, the application of Morris-Weber and Reichenberg models indicated that both film-diffusion and intraparticle-diffusion processes were active during the control of the adsorption kinetics.

  15. Equilibrium distributions of simple biochemical reaction systems for time-scale separation in stochastic reaction networks

    PubMed Central

    Mélykúti, Bence; Hespanha, João P.; Khammash, Mustafa

    2014-01-01

    Many biochemical reaction networks are inherently multiscale in time and in the counts of participating molecular species. A standard technique to treat different time scales in the stochastic kinetics framework is averaging or quasi-steady-state analysis: it is assumed that the fast dynamics reaches its equilibrium (stationary) distribution on a time scale where the slowly varying molecular counts are unlikely to have changed. We derive analytic equilibrium distributions for various simple biochemical systems, such as enzymatic reactions and gene regulation models. These can be directly inserted into simulations of the slow time-scale dynamics. They also provide insight into the stimulus–response of these systems. An important model for which we derive the analytic equilibrium distribution is the binding of dimer transcription factors (TFs) that first have to form from monomers. This gene regulation mechanism is compared to the cases of the binding of simple monomer TFs to one gene or to multiple copies of a gene, and to the cases of the cooperative binding of two or multiple TFs to a gene. The results apply equally to ligands binding to enzyme molecules. PMID:24920118

  16. Adsorption of methylene blue dye onto activated carbons based on agricultural by-products: equilibrium and kinetic studies.

    PubMed

    Ioannou, Z; Simitzis, J

    2013-01-01

    Mixtures of novolac resin and olive stone biomass (20/80 and 40/60 w/w) were cured, pyrolyzed up to 1,000 °C and activated with CO2 under a continuous flow operation (named N20B-cCa and N40B-cCa respectively). Commercial activated charcoal was similarly re-activated with CO2 and used for comparison reasons (AC-a). The characterization of these materials was performed by Fourier transform Infrared (FTIR) analysis and their specific surface area was determined according to DIN 66132. The materials were tested for their adsorption abilities at different temperatures (298, 333 K) and initial dye concentrations (0.01-0.35 g/L) using 1 L of methylene blue (MB) solution in 10 g of activated carbon. MB adsorption kinetic was also studied. The FTIR spectra of all activated carbons show absorption peaks which correspond to -OH, -CH, -C-O-C- groups and to aromatic ring. The presence of the absorption peak at about 1,400 cm(-1) for N20B-cCa, N40B-cCa indicates more acidic groups on them compared to the commercial AC-a. The specific surface area of N20B-cCa, N40B-cCa and AC-a has values equal to 352, 342 and 760 m(2)/g respectively. From the applied kinetic models, pseudo-second-order equation could best describe MB adsorption. Consequently, such adsorbents can be used as filters to adsorb dyes from wastewaters.

  17. Real-Time NMR Studies of Oxyamine Ligations of Reducing Carbohydrates under Equilibrium Conditions.

    PubMed

    Baudendistel, Oliver R; Wieland, Daniel E; Schmidt, Magnus S; Wittmann, Valentin

    2016-11-21

    Ligation reactions at the anomeric center of carbohydrates have gained increasing importance in the field of glycobiology. Oxyamines are frequently used in labeling, immobilization, and bioconjugation of reducing carbohydrates. Herein, we present a systematic investigation of these ligation reactions under aqueous conditions. A series of four unprotected monosaccharides (glucose, N-acetylglucosamine, mannose, and 2-deoxyglucose) and one disaccharide (N,N'-diacetylchitobiose) was reacted with three primary and one secondary oxyamine. We monitored the concentrations of the starting materials and products by (1) H NMR spectroscopy and determined reaction times and equilibrium yields. Our experiments show that the outcome of the ligation reaction is not only dependent on the sugar and oxyamine used but also strongly on the reaction conditions. In the case of glucose, lowering the pH from 6 to 3 led to steadily increasing reaction rates, whereas the yields were decreasing at the same time. Variation of the temperature did not only influence the product ratio in equilibrium but can also have a strong impact on the equilibrium yield. In the case of reactions of a primary oxyamine, increased temperatures led to a higher proportion of acyclic products. Reaction of the secondary oxyamine with glucose unexpectedly led to lower yields at higher temperatures.

  18. Evolution to the equilibrium in a dissipative and time dependent billiard

    NASA Astrophysics Data System (ADS)

    Galia, Marcus Vinícius Camillo; Oliveira, Diego F. M.; Leonel, Edson D.

    2017-01-01

    We study the convergence towards the equilibrium for a dissipative and stochastic time-dependent oval billiard. The dynamics of the system is described by using a generic four dimensional nonlinear map for the variables: the angular position of the particle, the angle formed by the trajectory of the particle with the tangent line at the position of the collision, the absolute velocity of the particle, and the instant of the hit with the boundary. The dynamics of the stationary state as well as the dynamical evolution towards the equilibrium is made by using an ensemble of non interacting particles. Finally, we make a connection with the thermodynamic by using the energy equipartition theorem.

  19. Chemical noise produced by equilibrium adsorption/desorption of surface pyridine at Au-Ag-Au bimetallic atom-scale junctions studied by fluctuation spectroscopy.

    PubMed

    Hwang, Tai-Wei; Branagan, Sean P; Bohn, Paul W

    2013-03-20

    The chemical noise contained in conductance fluctuations resulting from adsorption and desorption of pyridine at Au-Ag-Au bimetallic atom-scale junctions (ASJs) exhibiting ballistic electron transport is studied using fluctuation spectroscopy. ASJs are fabricated by electrochemical Ag deposition in a Au nanogap to produce a high-conductance Ag quantum wire, followed by electromigration-induced thinning in pyridine solution to create stable ASJs. The conductance behavior of the resulting ASJs is analyzed by sequential autocorrelation and Fourier transform of the current-time data to yield the power spectral density (PSD). In these experiments the PSDs from Ag ASJs in pyridine exhibit two main frequency regions: 1/f noise originating from resistance fluctuations of the junction itself at low frequencies, and a Lorentzian noise component arising from molecular adsorption/desorption fluctuations at higher frequencies. The characteristic cutoff frequency of the Lorentzian noise component determines the relaxation time of molecular fluctuations, which, in turn, is sensitive to the kinetics of the adsorption/desorption process. The kinetics are found to depend on concentration and on the adsorption binding energy. The junction size (<5G0), on the other hand, does not affect the kinetics, as the cutoff frequency remains unchanged. Concentration-dependent adsorption free energies are interpreted as arising from a distribution of binding energies, N(E(b)), on the Ag ASJ. Other observations, such as long lifetime ASJs and two-level fluctuations in conductance, provide additional evidence for the integral role of the adsorbate in determining ASJ reorganization dynamics.

  20. Adsorptive removal of 2-chlorophenol by low-cost coir pith carbon.

    PubMed

    Namasivayam, C; Kavitha, D

    2003-03-17

    Adsorption of 2-chlorophenol (2-CP) by coir pith carbon was carried out by varying the parameters such as agitation time, 2-CP concentration, adsorbent dose, pH and temperature. Adsorption equilibrium reached at 40, 60, 80 and 100 min for 2-CP concentration of 10, 20, 30 and 40 mg/l, respectively. Adsorption followed second-order kinetics. The adsorption equilibrium data obeyed Freundlich isotherm. Acidic pH was favorable for the adsorption of 2-CP. Desorption studies showed that chemisorption plays a major role in the adsorption process.

  1. Equilibrium, FTIR, scanning electron microscopy and small wide angle X-ray scattering studies of chromates adsorption on modified bentonite

    NASA Astrophysics Data System (ADS)

    Majdan, Marek; Maryuk, Oksana; Pikus, Stanisław; Olszewska, Elzbieta; Kwiatkowski, Ryszard; Skrzypek, Henryk

    2005-04-01

    The study presents a discussion about the adsorption mechanism of chromate anions on bentonite modified by hexadecyltrimethylammonium bromide (HDTMA-Br). The formation of alkylammonium chromates: HDTMAHCrO 4, (HDTMA) 2Cr 2O 7 and to the lesser extent (HDTMA) 2CrO 4 at the water-bentonite interface is examined based on the Scanning Electron Microscopy and surface tension measurements. The histograms of HDTMA/Cr(VI) molar ratio on the bentonite surface, found from Scanning Electron Microscopy (SEM) measurements, show that for the majority of points of bentonite surface the value of this ratio is in 1-2 range. FTIR spectra of modified bentonite samples show the change from gauche to trans conformation in the surfactant arrangement in the clay interlayer accompanying its concentration increase. In turn Small Wide Angle X-Ray Scattering (SWAXS) patterns evidently suggest incorporation of chromate anions into the interlamellar space of bentonite structure.

  2. Equilibrium and Response Properties of the Integrate-and-Fire Neuron in Discrete Time

    PubMed Central

    Helias, Moritz; Deger, Moritz; Diesmann, Markus; Rotter, Stefan

    2009-01-01

    The integrate-and-fire neuron with exponential postsynaptic potentials is a frequently employed model to study neural networks. Simulations in discrete time still have highest performance at moderate numerical errors, which makes them first choice for long-term simulations of plastic networks. Here we extend the population density approach to investigate how the equilibrium and response properties of the leaky integrate-and-fire neuron are affected by time discretization. We present a novel analytical treatment of the boundary condition at threshold, taking both discretization of time and finite synaptic weights into account. We uncover an increased membrane potential density just below threshold as the decisive property that explains the deviations found between simulations and the classical diffusion approximation. Temporal discretization and finite synaptic weights both contribute to this effect. Our treatment improves the standard formula to calculate the neuron's equilibrium firing rate. Direct solution of the Markov process describing the evolution of the membrane potential density confirms our analysis and yields a method to calculate the firing rate exactly. Knowing the shape of the membrane potential distribution near threshold enables us to devise the transient response properties of the neuron model to synaptic input. We find a pronounced non-linear fast response component that has not been described by the prevailing continuous time theory for Gaussian white noise input. PMID:20130755

  3. Variable-Field Analytical Ultracentrifugation: I. Time-Optimized Sedimentation Equilibrium

    PubMed Central

    Ma, Jia; Metrick, Michael; Ghirlando, Rodolfo; Zhao, Huaying; Schuck, Peter

    2015-01-01

    Sedimentation equilibrium (SE) analytical ultracentrifugation (AUC) is a gold standard for the rigorous determination of macromolecular buoyant molar masses and the thermodynamic study of reversible interactions in solution. A significant experimental drawback is the long time required to attain SE, which is usually on the order of days. We have developed a method for time-optimized SE (toSE) with defined time-varying centrifugal fields that allow SE to be attained in a significantly (up to 10-fold) shorter time than is usually required. To achieve this, numerical Lamm equation solutions for sedimentation in time-varying fields are computed based on initial estimates of macromolecular transport properties. A parameterized rotor-speed schedule is optimized with the goal of achieving a minimal time to equilibrium while limiting transient sample preconcentration at the base of the solution column. The resulting rotor-speed schedule may include multiple over- and underspeeding phases, balancing the formation of gradients from strong sedimentation fluxes with periods of high diffusional transport. The computation is carried out in a new software program called TOSE, which also facilitates convenient experimental implementation. Further, we extend AUC data analysis to sedimentation processes in such time-varying centrifugal fields. Due to the initially high centrifugal fields in toSE and the resulting strong migration, it is possible to extract sedimentation coefficient distributions from the early data. This can provide better estimates of the size of macromolecular complexes and report on sample homogeneity early on, which may be used to further refine the prediction of the rotor-speed schedule. In this manner, the toSE experiment can be adapted in real time to the system under study, maximizing both the information content and the time efficiency of SE experiments. PMID:26287634

  4. Deducting the temperature dependence of the structural relaxation time in equilibrium far below the nominal Tg by aging the decoupled conductivity relaxation to equilibrium.

    PubMed

    Wojnarowska, Z; Ngai, K L; Paluch, M

    2014-05-07

    Using broadband dielectric spectroscopy we investigate the changes in the conductivity relaxation times τσ observed during the physical aging of the protic ionic conductor carvedilol dihydrogen phosphate (CP). Due to the large decoupling of ion diffusion from host molecule reorientation, the ion conductivity relaxation time τσ(Tage,tage) can be directly measured at temperatures Tage below Tg for exceedingly long aging times tage till τσ(Tage,tage) has reached the equilibrium value τσ(eq)(Tage). The dependence of τσ(Tage,tage) on tage is well described by the stretched exponential function, τσ(Tage, tage) = Aexp[-((tage)/(τage(Tage)))(β)] + τσ(eq)(Tage), where β is a constant and τage(Tage) can be taken as the structural α-relaxation time of the equilibrium liquid at T = Tage. The value of τσ(eq)(Tage) obtained after 63 days long annealing of CP, deviates from the Vogel-Fulcher-Tammann-Hesse (VFTHσ) dependence of τσ(T) determined from data taken above Tg and extrapolated down to Tage. Concurrently, τage(Tage) also deviates from the Vogel-Fulcher-Tammann-Hesse (VFTHα) dependence. The results help to answer the longstanding question of whether the VFTH dependence of τσ(T) as well as the structural α-relaxation time τα(T) holds or not in the equilibrium liquid state far below Tg.

  5. Deducting the temperature dependence of the structural relaxation time in equilibrium far below the nominal Tg by aging the decoupled conductivity relaxation to equilibrium

    NASA Astrophysics Data System (ADS)

    Wojnarowska, Z.; Ngai, K. L.; Paluch, M.

    2014-05-01

    Using broadband dielectric spectroscopy we investigate the changes in the conductivity relaxation times τσ observed during the physical aging of the protic ionic conductor carvedilol dihydrogen phosphate (CP). Due to the large decoupling of ion diffusion from host molecule reorientation, the ion conductivity relaxation time τσ(Tage,tage) can be directly measured at temperatures Tage below Tg for exceedingly long aging times tage till τσ(Tage,tage) has reached the equilibrium value τ _σ ^{eq} ( {T_{age} } ). The dependence of τσ(Tage,tage) on tage is well described by the stretched exponential function, τ _σ ( {T_{age},t_{age} } ) = Aexp[ { - ( {{t_{age} }/{τ _{age ( {T_{age} } )}}} )^β } ] + τ _σ ^{eq} ( {T_{age} } ), where β is a constant and τage(Tage) can be taken as the structural α-relaxation time of the equilibrium liquid at T = Tage. The value of τ _σ ^{eq} ( {T_{age} } ) obtained after 63 days long annealing of CP, deviates from the Vogel-Fulcher-Tammann-Hesse (VFTHσ) dependence of τσ(T) determined from data taken above Tg and extrapolated down to Tage. Concurrently, τage(Tage) also deviates from the Vogel-Fulcher-Tammann-Hesse (VFTHα) dependence. The results help to answer the longstanding question of whether the VFTH dependence of τσ(T) as well as the structural α-relaxation time τα(T) holds or not in the equilibrium liquid state far below Tg.

  6. Approximate but accurate quantum dynamics from the Mori formalism. II. Equilibrium time correlation functions.

    PubMed

    Montoya-Castillo, Andrés; Reichman, David R

    2017-02-28

    The ability to efficiently and accurately calculate equilibrium time correlation functions of many-body condensed phase quantum systems is one of the outstanding problems in theoretical chemistry. The Nakajima-Zwanzig-Mori formalism coupled to the self-consistent solution of the memory kernel has recently proven to be highly successful for the computation of nonequilibrium dynamical averages. Here, we extend this formalism to treat symmetrized equilibrium time correlation functions for the spin-boson model. Following the first paper in this series [A. Montoya-Castillo and D. R. Reichman, J. Chem. Phys. 144, 184104 (2016)], we use a Dyson-type expansion of the projected propagator to obtain a self-consistent solution for the memory kernel that requires only the calculation of normally evolved auxiliary kernels. We employ the approximate mean-field Ehrenfest method to demonstrate the feasibility of this approach. Via comparison with numerically exact results for the correlation function Czz(t)=Re⟨σz(0)σz(t)⟩, we show that the current scheme affords remarkable boosts in accuracy and efficiency over bare Ehrenfest dynamics. We further explore the sensitivity of the resulting dynamics to the choice of kernel closures and the accuracy of the initial canonical density operator.

  7. Effect of adsorption time on the adhesion strength between salivary pellicle and human tooth enamel.

    PubMed

    Zhang, Y F; Zheng, J; Zheng, L; Zhou, Z R

    2015-02-01

    Salivary pellicle is a biofilm that is formed by the selective adsorption of salivary proteins. Almost all the functions of the salivary pellicle (lubricating properties, anti-caries properties, etc.) are closely associated with its adhesion strength to tooth surface. The objective of this study was to investigate the effect of adsorption time on the adhesion strength between salivary pellicle and human tooth enamel, aiming to understand what act as the determinant of the interfacial adhesion. In this study, human tooth enamel samples were immersed in human whole saliva in vitro to obtain a salivary pellicle on the surface of enamel. Immersion treatments lasting up to 1, 3, 10 and 60 min were conducted, respectively. Nano-scratch tests were conducted on the surface of enamel after different adsorption times. The wettability of enamel surface was measured through water contact angle. Results showed that the shear energy between salivary pellicle and enamel surface increased exponentially with the adsorption time. The adhesion force between salivary pellicle and bare enamel surface was more than twice that between salivary pellicle and salivary pellicle. It was found that both the wettability and zeta potential of enamel increased obviously after 1 min saliva-adsorption treatment, and then they almost kept stable as the adsorption time further increased. In summary, the adhesion strength between initial salivary pellicle and enamel surface was much higher than that between initial salivary pellicle and outer salivary pellicle. It seemed that electrostatic interaction contributed to the adhesion between the initial salivary pellicle and enamel surface, but not to the adhesion between the initial and outer salivary pellicle. The results would be helpful to extend the understanding of the adhesion mechanism of salivary pellicle and then to develop new artificial saliva and dental restorative materials.

  8. Fluctuations around equilibrium laws in ergodic continuous-time random walks.

    PubMed

    Schulz, Johannes H P; Barkai, Eli

    2015-06-01

    We study occupation time statistics in ergodic continuous-time random walks. Under thermal detailed balance conditions, the average occupation time is given by the Boltzmann-Gibbs canonical law. But close to the nonergodic phase, the finite-time fluctuations around this mean are large and nontrivial. They exhibit dual time scaling and distribution laws: the infinite density of large fluctuations complements the Lévy-stable density of bulk fluctuations. Neither of the two should be interpreted as a stand-alone limiting law, as each has its own deficiency: the infinite density has an infinite norm (despite particle conservation), while the stable distribution has an infinite variance (although occupation times are bounded). These unphysical divergences are remedied by consistent use and interpretation of both formulas. Interestingly, while the system's canonical equilibrium laws naturally determine the mean occupation time of the ergodic motion, they also control the infinite and Lévy-stable densities of fluctuations. The duality of stable and infinite densities is in fact ubiquitous for these dynamics, as it concerns the time averages of general physical observables.

  9. Complex time dependent wave packet technique for thermal equilibrium systems - Electronic spectra

    NASA Technical Reports Server (NTRS)

    Reimers, J. R.; Wilson, K. R.; Heller, E. J.

    1983-01-01

    A time dependent wave packet method is presented for the rapid calculation of the properties of systems in thermal equilibrium and is applied, as an illustration, to electronic spectra. The thawed Gaussian approximation to quantum wave packet dynamics combined with evaluation of the density matrix operator by imaginary time propagation is shown to give exact electronic spectra for harmonic potentials and excellent results for both a Morse potential and for the band contours of the three transitions of the visible electronic absorption spectrum of the iodine molecule. The method, in principle, can be extended to many atoms (e.g., condensed phases) and to other properties (e.g., infrared and Raman spectra and thermodynamic variables).

  10. Plasma Shape Control on the National Spherical Torus Experiment (NSTX) using Real-time Equilibrium Reconstruction

    SciTech Connect

    D.A. Gates; J.R. Ferron; M. Bell; T. Gibney; R. Johnson; R.J. Marsala; D. Mastrovito; J.E. Menard; D. Mueller; B. Penaflor; S.A. Sabbagh; T. Stevenson

    2005-04-15

    Plasma shape control using real-time equilibrium reconstruction has been implemented on the National Spherical Torus Experiment (NSTX). The rtEFIT code originally developed for use on DIII-D was adapted for use on NSTX. The real-time equilibria provide calculations of the flux at points on the plasma boundary, which is used as input to a shape control algorithm known as isoflux control. The flux at the desired boundary location is compared to a reference flux value, and this flux error is used as the basic feedback quantity for the poloidal-field coils on NSTX. The hardware that comprises the control system is described, as well as the software infrastructure. Examples of precise boundary control are also presented.

  11. Real-time extraction of plasma equilibrium parameters in KSTAR tokamak using statistical methods

    NASA Astrophysics Data System (ADS)

    Na, Yong-Su; Jeon, Young-Mu; Hong, S. H.; Hwang, Y. S.

    2001-02-01

    To improve inherent shortcomings of statistical methods and apply them to the extraction of plasma equilibrium parameters in a fast timescale for real-time plasma control, new concepts of statistical methods such as principal component analysis-based neural network (NN), functional parametrization (FP)-based NN and double network are introduced by modifying NN and FP. These new methods are benchmarked and compared with the conventional techniques of NN and FP in a simple single-filament system. As a result of their applications to identification of plasma equilibrium parameters in the Korea Superconducting Tokamak Advanced Research tokamak, particularly, the double network concept among them has successfully achieved the improvement of drawbacks in the conventional methods. It is shown that more reliable results from the double network method can be obtained by combining several different statistical treatments as a primary network. Even in the case of nonoptimized methods united as a primary network, quite acceptable results can be achieved in the double network method.

  12. Near real time vapor detection and enhancement using aerosol adsorption

    DOEpatents

    Novick, Vincent J.; Johnson, Stanley A.

    1999-01-01

    A vapor sample detection method where the vapor sample contains vapor and ambient air and surrounding natural background particles. The vapor sample detection method includes the steps of generating a supply of aerosol that have a particular effective median particle size, mixing the aerosol with the vapor sample forming aerosol and adsorbed vapor suspended in an air stream, impacting the suspended aerosol and adsorbed vapor upon a reflecting element, alternatively directing infrared light to the impacted aerosol and adsorbed vapor, detecting and analyzing the alternatively directed infrared light in essentially real time using a spectrometer and a microcomputer and identifying the vapor sample.

  13. Near real time vapor detection and enhancement using aerosol adsorption

    DOEpatents

    Novick, V.J.; Johnson, S.A.

    1999-08-03

    A vapor sample detection method is described where the vapor sample contains vapor and ambient air and surrounding natural background particles. The vapor sample detection method includes the steps of generating a supply of aerosol that have a particular effective median particle size, mixing the aerosol with the vapor sample forming aerosol and adsorbed vapor suspended in an air stream, impacting the suspended aerosol and adsorbed vapor upon a reflecting element, alternatively directing infrared light to the impacted aerosol and adsorbed vapor, detecting and analyzing the alternatively directed infrared light in essentially real time using a spectrometer and a microcomputer and identifying the vapor sample. 13 figs.

  14. Time-Depending Parametric Variational Approach for an Economic General Equilibrium Problem of Pure Exchange with Application

    NASA Astrophysics Data System (ADS)

    Scaramuzzino, F.

    2009-09-01

    This paper considers a qualitative analysis of the solution of a pure exchange general economic equilibrium problem according to two independent parameters. Some recently results obtained by the author in the static and the dynamic case have been collected. Such results have been applied in a particular parametric case: it has been focused the attention on a numerical application for which the existence of the solution of time-depending parametric variational inequality that describes the equilibrium conditions has been proved by means of the direct method. By using MatLab computation after a linear interpolation, the curves of equilibrium have been visualized.

  15. Equilibrium distributions and relaxation times in gaslike economic models: an analytical derivation.

    PubMed

    Calbet, Xavier; López, José-Luis; López-Ruiz, Ricardo

    2011-03-01

    A step-by-step procedure to derive analytically the exact dynamical evolution equations of the probability density functions (PDFs) of well-known kinetic wealth exchange economic models is shown. This technique gives a dynamical insight into the evolution of the PDF, for example, allowing the calculation of its relaxation times. Their equilibrium PDFs can also be calculated by finding its stationary solutions. This gives as a result an integro-differential equation, which can be solved analytically in some cases and numerically in others. This should provide some guidance into the type of PDFs that can be derived from particular economic agent exchange rules or, for that matter, any other kinetic model of gases with particular collision physics.

  16. Indicial response approach derived from Navier-Stokes equations. Part 1: Time-invariant equilibrium state

    NASA Technical Reports Server (NTRS)

    Truong, K. V.; Tobak, M.

    1990-01-01

    The indicial response approach is recast in a form appropriate to the study of vortex induced oscillations phenomena. An appropriate form is demonstrated for the indicial response of the velocity field which may be derived directly from the Navier-Stokes equations. On the basis of the Navier-Stokes equations, it is demonstrated how a form of the velocity response to an arbitrary motion may be determined. To establish its connection with the previous work, the new approach is applied first to the simple situation wherein the indicial response has a time invariant equilibrium state. Results for the aerodynamic response to an arbitrary motion are shown to confirm to the form obtained previously.

  17. A time-accurate algorithm for chemical non-equilibrium viscous flows at all speeds

    NASA Technical Reports Server (NTRS)

    Shuen, J.-S.; Chen, K.-H.; Choi, Y.

    1992-01-01

    A time-accurate, coupled solution procedure is described for the chemical nonequilibrium Navier-Stokes equations over a wide range of Mach numbers. This method employs the strong conservation form of the governing equations, but uses primitive variables as unknowns. Real gas properties and equilibrium chemistry are considered. Numerical tests include steady convergent-divergent nozzle flows with air dissociation/recombination chemistry, dump combustor flows with n-pentane-air chemistry, nonreacting flow in a model double annular combustor, and nonreacting unsteady driven cavity flows. Numerical results for both the steady and unsteady flows demonstrate the efficiency and robustness of the present algorithm for Mach numbers ranging from the incompressible limit to supersonic speeds.

  18. Generalized Rayleigh-Taylor instability in the presence of time-dependent equilibrium

    NASA Astrophysics Data System (ADS)

    Basu, B.

    1997-08-01

    Plasma instability under the combined influence of the gravity and an eastward electric field, commonly referred to as the generalized Rayleigh-Taylor instability, is considered for a time-dependent equilibrium situation. In the nighttime equatorial ionosphere the time-dependent equilibrium situation arises because of the vertically upward EB0 drift of the plasma in conjunction with the altitude-dependent recombination process and the collisional diffusion process. After determining the time-dependent equilibrium density and, in particular, the inverse density gradient scale length L-1, which determines the growth rate of the instability, the stability of small-amplitude perturbations is analyzed. The general solution of the problem, where the effects of all of the above-mentioned processes are included simultaneously, requires numerical analysis. In this paper the effects are studied in limiting situations for which useful analytic solutions can be obtained. The effect of diffusion on L-1 is studied by neglecting both the upward plasma drift and the altitude variation of the recombination frequency νR, and it is verified that the effect is negligible for typical values of the ionospheric parameters. The effects of the other two processes on L-1 are studied by neglecting diffusion. The effect of the altitude variation of νR on the linear growth of the perturbations is studied by adopting the so-called local approximation. It is found that the value of L-1 and hence the value of the growth rate are enhanced by the altitude variation of νR. The enhancements rapidly increase with time to large values at lower altitudes and to significant values at higher altitudes when compared with the values for the spatially uniform νR case. Consequently, the time evolution of the instability and, more importantly, the level of fluctuations at saturation will be significantly affected by the enhancements. The nonlocal aspect of the instability in

  19. Non-equilibrium effects of core-cooling and time-dependent internal heating on mantle flush events

    NASA Astrophysics Data System (ADS)

    Yuen, D. A.; Balachandar, S.; Steinbach, V. C.; Honda, S.; Reuteler, D. M.; Smedsmo, J. J.; Lauer, G. S.

    We have examined the non-equilibrium effects of core-cooling and time-dependent internal-heating on the thermal evolution of the Earth's mantle and on mantle flush events caused by the two major phase transitions. Both two- and three-dimensional models have been employed. The mantle viscosity responds to the secular cooling through changes in the averaged temperature field. A viscosity which decreases algebraically with the average temperature has been considered. The time-dependent internal-heating is prescribed to decrease exponentially with a single decay time. We have studied the thermal histories with initial Rayleigh numbers between 2 x 107 and 108 . Flush events, driven by the non-equilibrium forcings, are much more dramatic than those produced by the equilibrium boundary conditions and constant internal heating. Multiple flush events are found under non-equilibrium conditions in which there is very little internal heating or very fast decay rates of internal-heating. Otherwise, the flush events take place in a relatively continuous fashion. Prior to massive flush events small-scale percolative structures appear in the 3D temperature fields. Time-dependent signatures, such as the surface heat flux, also exhibits high frequency oscillatory patterns prior to massive flush events. These two observations suggest that the flush event may be a self-organized critical phenomenon. The Nusselt number as a function of the time-varying Ra does not follow the Nusselt vs. Rayleigh number power-law relationship based on equilibrium (constant temperature) boundary conditions. Instead Nu(t) may vary non-monotonically with time because of the mantle flush events. Convective processes in the mantle operate quite differently under non-equilibrium conditions from its behaviour under the usual equilibrium situations.

  20. Application of activated carbon derived from 'waste' bamboo culms for the adsorption of azo disperse dye: kinetic, equilibrium and thermodynamic studies.

    PubMed

    Wang, Lianggui

    2012-07-15

    The utilization of activated carbon derived from 'waste' bamboo culms (BAC) for the removal of Disperse Red 167 (DR167), an azo disperse dye, was investigated. Studies of the properties of the adsorbent, the effect of contact time, the initial pH of the solution, the initial concentration of the dye solution and temperature indicated that a low initial pH or concentration of dye solution favors the adsorption process; temperature exerts a greater effect on the removal of azo disperse red 167 dye from aqueous solution. Kinetic and isotherm data were fitted to five non-linear kinetic and nine non-linear isotherm equations. In addition, the fits were evaluated in terms of the non-linear coefficient, Chi-square test, Marquardt's percent standard deviation error function and small-sample-corrected Akaike Information Criterion (AICc) methodology. The results showed that the AICc analysis was the best statistical tool for analyzing the data, the intra-particle diffusion and the pseudo-first-order models played important roles in the controlling rate step, and the Temkin equation best described the BAC isotherm data. Furthermore, the thermodynamic analysis indicated that the adsorption was a spontaneous, endothermic, entropy-increasing and physical process. Two types of commercial activated carbon, Filtrasorb 400 and Filtrasorb (F400 and F300), were used as contrast adsorbents. The contrast experiments revealed that BAC exhibits similar properties to F400 and F300. The utilization of bamboo wastes as carbon precursors is feasible.

  1. Tubulin equilibrium unfolding followed by time-resolved fluorescence and fluorescence correlation spectroscopy

    PubMed Central

    Sánchez, Susana A.; Brunet, Juan E.; Jameson, David M.; Lagos, Rosalba; Monasterio, Octavio

    2004-01-01

    The pathway for the in vitro equilibrium unfolding of the tubulin heterodimer by guanidinium chloride (GdmCl) has been studied using several spectroscopic techniques, specifically circular dichroism (CD), two-photon Fluorescence Correlation Spectroscopy (FCS), and time-resolved fluorescence, including lifetime and dynamic polarization. The results show that tubulin unfolding is characterized by distinct processes that occur in different GdmCl concentration ranges. From 0 to 0.5 M GdmCl, a slight alteration of the tubulin heterodimer occurs, as evidenced by a small, but reproducible increase in the rotational correlation time of the protein and a sharp decrease in the secondary structure monitored by CD. In the range 0.5–1.5 M GdmCl, significant decreases in the steady-state anisotropy and average lifetime of the intrinsic tryptophan fluorescence occur, as well as a decrease in the rotational correlation time, from 48 to 26 nsec. In the same GdmCl range, the number of protein molecules (labeled with Alexa 488), as determined by two-photon FCS measurements, increases by a factor of two, indicating dissociation of the tubulin dimer into monomers. From 1.5 to 4 M GdmCl, these monomers unfold, as evidenced by the continual decrease in the tryptophan steady-state anisotropy, average lifetime, and rotational correlation time, concomitant with secondary structural changes. These results help to elucidate the unfolding pathway of the tubulin heterodimer and demonstrate the value of FCS measurements in studies on oligomeric protein systems. PMID:14691224

  2. Performance, kinetics, and equilibrium of methylene blue adsorption on biochar derived from eucalyptus saw dust modified with citric, tartaric, and acetic acids.

    PubMed

    Sun, Lei; Chen, Dongmei; Wan, Shungang; Yu, Zebin

    2015-12-01

    Biochar derived from eucalyptus saw dust modified with citric, tartaric, and acetic acids at low temperatures was utilized as adsorbent to remove methylene blue (MB) from aqueous solutions. Fourier transform infrared spectroscopy analysis showed that the carboxyl group was introduced on the biochar surface. Adsorption experiment data indicated that eucalyptus saw dust modified with citric acid showed higher MB adsorption efficiency than that modified with tartaric and acetic acids. Pseudo-second-order kinetics was the most suitable model for describing MB adsorption on biochar compared with pseudo-first-order, Elovich, and intraparticle diffusion models. The calculated values of ΔG(0) and ΔH(0) indicated the spontaneous and endothermic nature of the adsorption process. MB adsorption on biochar followed the Langmuir isotherm. The maximum adsorption capacities for eucalyptus saw dust modified with citric, tartaric, and acetic acids were 178.57, 99.01, and 29.94 mg g(-1), respectively, at 35°C.

  3. Time-resolved chromatographic analysis and mechanisms in adsorption and catalysis.

    PubMed

    Roubani-Kalantzopoulou, Fani

    2009-03-06

    The main object of this review is the study of fundamentals of adsorption and heterogeneous catalysis, a benefit for the understanding of adsorptive and catalytic properties. This work aims to define and record, with the utmost accuracy, the phenomena and the possible reactions. A new methodology for the study of the adsorption is presented, which is a version of the well-known inverse gas chromatography. This reversed-flow inverse gas chromatography (RF-IGC) is technically very simple, and it is combined with a mathematical analysis that gives the possibility for the estimation of various physicochemical parameters related to adsorbent or catalyst characterization, under conditions compatible with the operation of real adsorbents and catalysts. On this base, this methodology has been successfully applied to the study of the impact of air pollutants, volatile organic and/or inorganic, on many solids such as marbles, ceramics, oxide-pigments of works of art, building materials, authentic statues of the Greek Archaeological Museums. Moreover, this methodology proved to be a powerful tool for studying the topography of active sites of heterogeneous surfaces in the nano-scale domain. Thus, some very important local quantities for the surface chemistry have been determined experimentally for many solids including thin films. These physicochemical local quantities (among which adsorption energy and entropy, surface diffusion coefficient, probability density function) have been determined from the experimental pairs of height of extra chromatographic peaks and time by a nonlinear least-squares method, through personal computer programs written in GW BASIC and lately in FORTRAN. Through the time-resolved analysis the surface characterization of the examined materials took place. In addition, the kinetic constants responsible for adsorption/desorption and surface chemical reactions have also been calculated. Thus, important answers have been provided to the following

  4. Adsorption studies of methylene blue dye on tunisian activated lignin

    NASA Astrophysics Data System (ADS)

    Kriaa, A.; Hamdi, N.; Srasra, E.

    2011-02-01

    Activated carbon prepared from natural lignin, providing from a geological deposit, was used as the adsorbent for the removal of methylene blue (MB) dye from aqueous solutions. Batch adsorption studies were conducted to evaluate various experimental parameters like pH and contact time for the removal of this dye. Effective pH for MB removal was 11. Kinetic study showed that the adsorption of dye was gradual process. Quasi equilibrium reached in 4 h. Pseudo-first-order, pseudo-second-order were used to fit the experimental data. Pseudo-second-order rate equation was able to provide realistic description of adsorption kinetics. The experimental isotherms data were also modelled by the Langmuir and Freundlich equation of adsorption. Equilibrium data fitted well with the Langmuir model with maximum monolayer adsorption capacity of 147 mg/g. Activated lignin was shown to be a promising material for adsorption of MB from aqueous solutions.

  5. Adsorption of 1,1,1,2-tetrafluoroethane by various adsorbents

    SciTech Connect

    Lin, S.H.; Lin, R.C.

    1999-11-01

    Experiments have been conducted to investigate gas-phase adsorption characteristics of 1,1,1,2-tetrafluoroethane (HFC-134a) by activated carbon fiber, extruded activated carbon, granular activated carbon, activated alumina, and molecular sieve. HGC-134a is currently regarded as an excellent replacement for chlorofluorocarbon-12, a refrigerating and cooling agent extensively used previously in all automobiles and many cooling systems. Performances of HFC-134a adsorption were characterized by the equilibrium adsorption capacity, time to reach equilibrium, and desorption efficiency of exhausted adsorbent. A simple thermal treatment process with proper operating temperature and treatment duration was found to be effective for the regeneration of exhausted absorbents. Adsorption isotherms of the empirical Freundlich and Hossens types were observed to adequately represent the equilibrium adsorption data. A mass transfer model based on the pseudo steady state squared driving force was adopted to describe the mass transfer process of HFC-134a adsorption.

  6. A time-asymptotic one equation non-equilibrium model for reactive transport in a two phase porous medium

    NASA Astrophysics Data System (ADS)

    Yohan, D.; Gerald, D.; Magali, G.; Michel, Q.

    2008-12-01

    The general problem of transport and reaction in multiphase porous media has been a subject of extensive studies during the last decades. For example, biologically mediated porous media have seen a long history of research from the environmental engineering point of view. Biofilms (aggregate of microorganisms coated in a polymer matrix generated by bacteria) have been particularly examined within the context of bioremediation in the subsurface zone. Five types of models may be used to describe these kinds of physical system: 1) one-equation local mass equilibrium models when the assumption of local mass equilibrium is valid 2) two equations models when the assumption of local mass equilibrium is not valid 3) one equation non-equilibrium models 4) mixed models coupling equations solved at two different scales 5) one equation time-asymptotic models. In this presentation, we use the method of volume averaging with closure to extend the time- asymptotic model at the Darcy scale to the reactive case. Closure problems are solved for simple unit cells, and the macro-scale model is validated against pore-scale simulations.

  7. Adsorption equilibrium, kinetics and thermodynamics of α-amylase on poly(DVB-VIM)-Cu(+2) magnetic metal-chelate affinity sorbent.

    PubMed

    Osman, Bilgen; Kara, Ali; Demirbel, Emel; Kök, Senay; Beşirli, Necati

    2012-09-01

    Designing an immobilised metal ion affinity process on large-scale demands that a thorough understanding be developed regarding the adsorption behaviour of proteins on metal-loaded gels and the characteristic adsorption parameters to be evaluated. In view of this requirement, interaction of α-amylase as a model protein with newly synthesised magnetic-poly(divinylbenzene-1-vinylimidazole) [m-poly(DVB-VIM)] microbeads (average diameter, 53-212 μm) was investigated. The m-poly(DVB-VIM) microbeads were prepared by copolymerising of divinylbenzene (DVB) with 1-vinylimidazole (VIM). The m-poly(DVB-VIM) microbeads were characterised by N(2) adsorption/desorption isotherms, electron spin resonance, elemental analysis, scanning electron microscope and swelling studies. Cu(2+) ions were chelated on the m-poly(DVB-VIM) beads and used in adsorption of α-amylase in a batch system. The maximum α-amylase adsorption capacity of the m-poly(DVB-VIM)-Cu(2+) beads was determined as 10.84 mg/g at pH 6.0, 25 °C. The adsorption data were analyzed using three isotherm models, which are the Langmuir, Freundlich and Dubinin-Radushkevich isotherm models. The pseudo-first-order, pseudo-second-order, modified Ritchie's-second-order and intraparticle diffusion models were used to test dynamic experimental data. The study of temperature effect was quantified by calculating various thermodynamic parameters such as Gibbs free energy, enthalpy and entropy changes.

  8. Temperature dependence of the structural relaxation time in equilibrium below the nominal T(g): results from freestanding polymer films.

    PubMed

    Ngai, K L; Capaccioli, Simone; Paluch, Marian; Prevosto, Daniele

    2014-05-22

    When the thickness is reduced to nanometer scale, freestanding high molecular weight polymer thin films undergo large reduction of degree of cooperativity and coupling parameter n in the Coupling Model (CM). The finite-size effect together with the surfaces with high mobility make the α-relaxation time of the polymer in nanoconfinement, τ(α)(nano)(T), much shorter than τ(α)(bulk)(T) in the bulk. The consequence is avoidance of vitrification at and below the bulk glass transition temperature, T(g)(bulk), on cooling, and the freestanding polymer thin film remains at thermodynamic equilibrium at temperatures below T(g)(bulk). Molecular dynamics simulations have shown that the specific volume of the freestanding film is the same as the bulk glass-former at equilibrium at the same temperatures. Extreme nanoconfinement renders total or almost total removal of cooperativity of the α-relaxation, and τ(α)(nano)(T) becomes the same or almost the same as the JG β-relaxation time τ(β)(bulk)(T) of the bulk glass-former at equilibrium and at temperatures below T(g)(bulk). Taking advantage of being able to obtain τ(β)(bulk)(T) at equilibrium density below T(g)(bulk) by extreme nanoconfinement of the freestanding films, and using the CM relation between τ(α)(bulk)(T) and τ(β)(bulk)(T), we conclude that the Vogel-Fulcher-Tammann-Hesse (VFTH) dependence of τ(α)(bulk)(T) cannot hold for glass-formers in equilibrium at temperatures significantly below T(g)(bulk). In addition, τ(α)(bulk)(T) does not diverge at the Vogel temperature, T₀, as suggested by the VFTH-dependence and predicted by some theories of glass transition. Instead, τ(α)(bulk)(T) of the glass-former at equilibrium has a much weaker temperature dependence than the VFTH-dependence at temperature below T(g)(bulk) and even below T₀. This conclusion from our analysis is consistent with the temperature dependence of τ(α)(bulk)(T) found experimentally in polymers aged long enough time to attain the

  9. Time dependent wettability of graphite upon ambient exposure: The role of water adsorption

    NASA Astrophysics Data System (ADS)

    Amadei, Carlo A.; Lai, Chia-Yun; Heskes, Daan; Chiesa, Matteo

    2014-08-01

    We report the temporal evolution of the wettability of highly ordered pyrolytic graphite (HOPG) exposed to environmental conditions. Macroscopic wettability is investigated by static and dynamic contact angles (SCA and DCA) obtaining values comparable to the ones presented in the literature. SCA increases from ˜68° to ˜90° during the first hour of exposure after cleaving, whereas DCA is characterized by longer-scale (24 h) time evolution. We interpret these results in light of Fourier transform infrared spectroscopy, which indicates that the evolution of the HOPG wettability is due to adsorption of molecules from the surrounding atmosphere. This hypothesis is further confirmed by nanoscopic observations obtained by atomic force microscope (AFM)-based force spectroscopy, which monitor the evolution of surface properties with a spatial resolution superior to macroscopic experiments. Moreover, we observe that the results of macro- and nanoscale measurements evolve in similar fashion with time and we propose a quantitative correlation between SCA and AFM measurements. Our results suggest that the cause of the transition in the wettability of HOPG is due to the adsorption of hydrocarbon contaminations and water molecules from the environment. This is corroborated by annealing the HOPG is vacuum conditions at 150°, allowing the desorption of molecules on the surface, and thus re-establishing the initial macro and nano surface properties. Our findings can be used in the interpretation of the wettability of more complicated systems derived from HOPG (i.e., graphene).

  10. Equilibrium adsorption isotherm studies of Cu (II) and Co (II) in high concentration aqueous solutions on Ag-TiO2-modified kaolinite ceramic adsorbents

    NASA Astrophysics Data System (ADS)

    Ajenifuja, E.; Ajao, J. A.; Ajayi, E. O. B.

    2016-03-01

    Photocatalytic ceramic adsorbents were prepared from locally sourced kaolinite clay minerals for the removal of copper and cobalt ions from high concentration aqueous solutions. The minerals were treated with mild acid before modification using silver nanoparticles sources and titanium-oxide nanoparticles. Batch adsorption experiment was carried out on the targeted ions and the results were analyzed by Langmuir and Freundlich equation at different concentrations (100-1000 mg/l). As-received raw materials do not exhibit any adsorption capacity. However, the adsorption isotherms for modified kaolinite clay ceramic adsorbents could be fitted well by the Langmuir model for Cu2+ and Co2+ with correlation coefficient (R) of up to 0.99705. The highest and lowest monolayer coverage (q max) were 93.023 and 30.497 mg/g for Cu2+ and Co2+, respectively. The separation factor (R L ) was less than one (<1), indicating that the adsorption of metal ions on modified ceramic adsorbent is favorable. The highest adsorbent adsorption capacity (K f ) and intensity (n) constants obtained from Freundlich model are 14.401 (Cu2+ on KLN-T) and 6.057 (Co2+ on KLN-T).

  11. Adsorption of ammonium on biochar prepared from giant reed.

    PubMed

    Hou, Jie; Huang, Lei; Yang, Zhimin; Zhao, Yaqi; Deng, Chaoren; Chen, Yucheng; Li, Xin

    2016-10-01

    Giant reed was used as precursor for making biochar in order for the adsorption of NH4 (+)-N from aqueous solution. And the adsorption of the product to NH4 (+)-N was examined. The surface features of biochar were investigated by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy/energy dispersive spectrometer (SEM-EDS), and X-ray diffraction (XRD). XRD patterns showed several peaks and correspond to the high amount of crystalline material. The crystals contain KCl, K2O, CaO, MgO, and SiO and possess high surface area which enhances adsorption. The influence of different parameters such as initial concentration, adsorption time, pH, and ionic strength has been carried out. The adsorption could reach equilibrium through 24 h reaction and had the best adsorption amount at the solution pH values from 7 to 9. The cation has great influence on the adsorption of NH4 (+)-N, whereas the anion exerted a weaker effect. The adsorption followed pseudo-first-order and pseudo-second-order models. And the intraparticle diffusion and desorption studies further elucidated that the mechanism of adsorption on the product was ion exchange. The product equilibrium data was well described by the Langmuir and Freundlich model. The maximum adsorption capacities were 1.490 mg/g. Biochar derived from giant reed at 500 °C was suggested as a promising adsorbent for the removal of NH4 (+)-N from slightly polluted wastewater.

  12. Equilibrium, kinetic and sorber design studies on the adsorption of Aniline blue dye by sodium tetraborate-modified Kaolinite clay adsorbent.

    PubMed

    Unuabonah, Emmanuel I; Adebowale, Kayode O; Dawodu, Folasegun A

    2008-09-15

    Raw Kaolinite clay obtained Ubulu-Ukwu, Delta State of Nigeria and its sodium tetraborate (NTB)-modified analogue was used to adsorb Aniline blue dye. Fourier transformed infrared spectra of NTB-modified Kaolinite suggests that modification was effective on the surface of the Kaolinite clay with the strong presence of inner -OH functional group. The modification of Kaolinite clay raised its adsorption capacity from 1666 to 2000 mg/kg. Modeling adsorption data obtained from both unmodified and NTB-modified Kaolinite clay reveals that the adsorption of Aniline blue dye on unmodified Kaolinite clay is on heterogeneous adsorption sites because it followed strongly the Freundlich isotherm equation model while adsorption data from NTB-modified Kaolinite clay followed strongly the Langmuir isotherm equation model which suggest that Aniline blue dye was adsorb homogeneous adsorption sites on the NTB-modified adsorbent surface. There was an observed increase in the amount of Aniline blue adsorbed as initial dye concentration was increased from 10 to 30 mg/L. It was observed that kinetic data obtained generally gave better robust fit to the second-order kinetic model (SOM). The initial sorption rate was found to increased with increasing initial dye concentration (from 10 to 20 mg/L) for data obtained from 909 to 1111 mg kg(-1)min(-1) for unmodified and 3325-5000 mg kg(-1) min(-1) for NTB-modified adsorbents. Thereafter there was a decrease in initial sorption rate with further increase in dye concentration. The linearity of the plots of the pseudo-second-order model with very high-correlation coefficients indicates that chemisorption is involved in the adsorption process. From the design of a single-batch adsorber it is predicted that the NTB-modified Kaolinite clay adsorbent will require 50% less of the adsorbent to treat certain volumes of wastewater containing 30 mg/L of Aniline blue dye when it is compared with the unmodified adsorbent. This will be cost effective in

  13. [Thermodynamics adsorption and its influencing factors of chlorpyrifos and triazophos on the bentonite and humus].

    PubMed

    Zhu, Li-Jun; Zhang, Wei; Zhang, Jin-Chi; Zai, De-Xin; Zhao, Rong

    2010-11-01

    The adsorption of chlorpyrifos and triazophos on bentonite and humus was investigated by using the equilibrium oscillometry. The adsorption capacity of chlorpyrifos and triazophos on humus was great higher than bentonite at the same concentration. Equilibrium data of Langmuir, Freundlich isotherms showed significant relationship to the adsorption of chlorpyrifos and triazophos on humus (chlorpyrifos: R2 0.996 4, 0.996 3; triazophos: R2 0.998 9, 0.992 4). Langmuir isotherm was the best for chlorpyrifos and triazophos on bentonite (chlorpyrifos: R2 = 0.995 7, triazophos: R2 = 0.998 9). The pH value, adsorption equilibrium time and temperature were the main factors affecting adsorption of chlorpyrifos and triazophos on bentonite and humus. The adsorption equilibrium time on mixed adsorbent was 12h for chlorpyrifos and 6h for triazophos respectively. The mass ratio of humus and bentonite was 12% and 14% respectively, the adsorption of chlorpyrifos and triazophos was the stronglest and tended to saturation. At different temperatures by calculating the thermodynamic parameters deltaG, deltaH and deltaS, confirmed that the adsorption reaction was a spontaneous exothermic process theoretically. The adsorption was the best when the pH value was 6.0 and the temperature was 15 degrees C.

  14. Adsorption behavior of some radionuclides on the Chinese weathered coal.

    PubMed

    Wu, Jianfeng; Xu, Qichu; Bai, Tao

    2007-08-01

    The equilibrium and kinetic properties of Am(III), Eu(III) and Cs(I) ions adsorption by three weathered coals (WCs) from China, have been investigated in batch stirred-tank experiments. The effects of contact time, solution acidity and initial sorbate concentration on the adsorption of Am(III), Eu(III) and Cs(I) by Yuxian(YX) Tongchuan (TC) and Pingxiang (PX) WC were evaluated. The radionuclide ions are able to form complex compounds with carboxylic and phenolic groups of WCs and they are also bounded with phenolic groups even at high acidity reaction solution (>0.1 mol/L). Mechanisms including ion exchange, complexation and adsorption to the coal surface are possible in the sorption process. The acidity of the solution played an important role in the adsorption. Even acidity as high as 0.1 mol/L, 60% of Am(III) or Eu(III), 40% of Cs(I) were found to be sorbed on the YX WC, which had the best adsorption capacity for Am(III) and Eu(III). Our batch adsorption studies showed the equilibrium adsorption data fit the linear Langmuir and Freundlich adsorption isotherm. The maximum equilibrium uptake of Eu(III) were 0.412, 3.701, 5.446 mmol/g for JXWC, TCWC and YXWC, respectively.

  15. Characteristics of selective fluoride adsorption by biocarbon-Mg/Al layered double hydroxides composites from protein solutions: kinetics and equilibrium isotherms study.

    PubMed

    Ma, Wei; Lv, Tengfei; Song, Xiaoyan; Cheng, Zihong; Duan, Shibo; Xin, Gang; Liu, Fujun; Pan, Decong

    2014-03-15

    In the study, two novel applied biocarbon-Mg/Al layered double hydroxides composites (CPLDH and CPLDH-Ca) were successfully prepared and characterized by TEM, ICP-AES, XFS, EDS, FTIR, XRD, BET and pHpzc. The fluoride removal efficiency (RF) and protein recovery ratio (RP) of the adsorbents were studied in protein systems of lysozyme (LSZ) and bovine serum albumin (BSA). The results showed that the CPLDH-Ca presented remarkable performance for selective fluoride removal from protein solution. It reached the maximum RF of 92.1% and 94.8% at the CPLDH-Ca dose of 2.0g/L in LSZ and BSA system, respectively. The RP in both systems of LSZ and BSA were more than 90%. Additionally, the RP of CPLDH-Ca increased with the increase of ionic strengths, and it almost can be 100% with more than 93% RF. Fluoride adsorption by the CPLDH-Ca with different initial fluoride concentrations was found to obey the mixed surface reaction and diffusion controlled adsorption kinetic model, and the overall reaction rate is probably controlled by intra-particle diffusion, boundary layer diffusion and reaction process. The adsorption isotherms of fluoride in BSA system fit the Langmuir-Freundlich model well. The BSA has synergistic effect on fluoride adsorption and the degree increased with the increase of the initial BSA concentration.

  16. Removal of mercury(II) ions in aqueous solution using the peel biomass of Pachira aquatica Aubl: kinetics and adsorption equilibrium studies.

    PubMed

    Santana, Andrea J; dos Santos, Walter N L; Silva, Laiana O B; das Virgens, Cesário F

    2016-05-01

    Mercury is a highly toxic substance that is a health hazard to humans. This study aims to investigate powders obtained from the peel of the fruit of Pachira aquatica Aubl, in its in natura and/or acidified form, as an adsorbent for the removal of mercury ions in aqueous solution. The materials were characterized by Fourier transform infrared spectroscopy and thermogravimetric analysis. The infrared spectra showed bands corresponding to the axial deformation of carbonyls from carboxylic acids, the most important functional group responsible for fixing the metal species to the adsorbent material. The thermograms displayed mass losses related to the decomposition of three major components, i.e., hemicellulose, cellulose, and lignin. The adsorption process was evaluated using cold-vapor atomic fluorescence spectrometry (CV AFS) and cold-vapor atomic absorption spectrometry (CV AAS). Three isotherm models were employed. The adsorption isotherm model, Langmuir-Freundlich, best represented the adsorption process, and the maximum adsorption capacity was predicted to be 0.71 and 0.58 mg g(-1) at 25 °C in nature and acidified, respectively. Adsorption efficiencies were further tested on real aqueous wastewater samples, and removal of Hg(II) was recorded as 69.6 % for biomass acidified and 76.3 % for biomass in nature. Results obtained from sorption experiments on real aqueous wastewater samples revealed that recovery of the target metal ions was very satisfactory. The pseudo-second-order model showed the best correlation to the experimental data. The current findings showed that the investigated materials are potential adsorbents for mercury(II) ion removal in aqueous solution, with acidified P. aquatica Aubl being the most efficient adsorbent.

  17. Direct evaluation of the position dependent diffusion coefficient and persistence time from the equilibrium density profile in anisotropic fluids.

    PubMed

    Olivares-Rivas, Wilmer; Colmenares, Pedro J; López, Floralba

    2013-08-21

    We derive expressions for the transverse diffusion coefficient D(z) and the average persistence time τ(z; L) within a layer of width L, for particles of a non-homogeneous fluid enclosed in a planar nanopore. The method allows the direct evaluation of these position-dependent dynamical quantities from the equilibrium local particle density profile. We use results for the density and persistence time profiles from the virtual layer molecular dynamics method to numerically assess the significance of the Smoluchowski approximation.

  18. The dynamics of single protein molecules is non-equilibrium and self-similar over thirteen decades in time

    SciTech Connect

    Hu, Xiaohu; Hong, Liang; Smith, Micholas Dean; Neusius, Thomas; Cheng, Xiaolin; Smith, Jeremy C.

    2015-11-23

    Here, internal motions of proteins are essential to their function. The time dependence of protein structural fluctuations is highly complex, manifesting subdiffusive, non-exponential behavior with effective relaxation times existing over many decades in time, from ps up to ~102s (refs 1-4). Here, using molecular dynamics simulations, we show that, on timescales from 10–12 to 10–5s, motions in single proteins are self-similar, non-equilibrium and exhibit ageing. The characteristic relaxation time for a distance fluctuation, such as inter-domain motion, is observation-time-dependent, increasing in a simple, power-law fashion, arising from the fractal nature of the topology and geometry of the energy landscape explored. Diffusion over the energy landscape follows a non-ergodic continuous time random walk. Comparison with single-molecule experiments suggests that the non-equilibrium self-similar dynamical behavior persists up to timescales approaching the in vivo lifespan of individual protein molecules.

  19. The dynamics of single protein molecules is non-equilibrium and self-similar over thirteen decades in time

    DOE PAGES

    Hu, Xiaohu; Hong, Liang; Smith, Micholas Dean; ...

    2015-11-23

    Here, internal motions of proteins are essential to their function. The time dependence of protein structural fluctuations is highly complex, manifesting subdiffusive, non-exponential behavior with effective relaxation times existing over many decades in time, from ps up to ~102s (refs 1-4). Here, using molecular dynamics simulations, we show that, on timescales from 10–12 to 10–5s, motions in single proteins are self-similar, non-equilibrium and exhibit ageing. The characteristic relaxation time for a distance fluctuation, such as inter-domain motion, is observation-time-dependent, increasing in a simple, power-law fashion, arising from the fractal nature of the topology and geometry of the energy landscape explored.more » Diffusion over the energy landscape follows a non-ergodic continuous time random walk. Comparison with single-molecule experiments suggests that the non-equilibrium self-similar dynamical behavior persists up to timescales approaching the in vivo lifespan of individual protein molecules.« less

  20. [Adsorption behavior of exogenous thorium on soil contaminated by rare earth industries].

    PubMed

    Guo, Peng-ran; Jia, Xiao-yu; Duan, Tai-cheng; Qiu, Rong-liang; Chen, Hang-ting

    2009-10-15

    The adsorption behavior of exogenous thorium on soil was studied to evaluate the contaminated risk on soil. The adsorption capacity, equilibrium time, distribution coefficient and desorption ability were investigated by the experiments of static adsorption. The strong adsorption ability of exogenous thorium on soil samples was observed by high adsorption ratio (> 92%) and low desorption ratio (< 5%) in equilibrium, and the biggest distribution coefficient was over 10(4). The adsorption capacity and equilibrium time were related to soil properties. According to the results of adsorption, Freundlich equation (r > or = 0.9167) and Elovich equation (R2 > or = 0.8980) were primely fit for describing the thermodynamics and kinetics of the adsorption of exogenous thorium on soil samples, respectively, which indicated that the adsorption was belonged to the nonlinear adsorption, and was affected by the diffusion of thorium on soil surface and in mineral interbed. Sequential extraction procedure was employed to evaluate the bound fractions of exogenous thorium adsorbed on soil samples. Based on the extracted results of thorium fractions, exogenous thorium was presented in the labile nonresidual fractions (over 58%) at the low initial concentration (10(-7) - 10(-6) mol x L(-1)), and nonresidual fractions enhanced with the increase of the initial amount, meanwhile more exogenous throium was transferred to the stable residual fractions.

  1. Bromate adsorption using Fe-pillared bentonite.

    PubMed

    He, Shilong; Zhang, Dandan; Gu, Li; Zhang, Shenghua; Yu, Xin

    2012-01-01

    Bromate is an emerging hazardous substance in drinking water. In this study, the removal ofbromate by Fe-pillared bentonite was investigated using various experimental parameters: contact time, initial concentration (Co), temperature, initial pH and competing anions. The adsorption ofbromate followed the pseudo-second-order kinetic better than it followed other kinetic models, and the pseudo-second-order kinetic study showed that equilibrium could be achieved within 60 min. Equilibrium isotherms were analyzed by Freundlich, Langmuir, Redlich-Peterson and Toth isotherm models. The Toth and Redlich-Peterson models better represented the bromate adsorption. Results also indicated that, other than the competing anions and solution pH, temperature was a key parameter affecting adsorption. It was ultimately concluded that Fe-pillared bentonite was effective at removing bromate from water.

  2. Biochars prepared from anaerobic digestion residue, palm bark, and eucalyptus for adsorption of cationic methylene blue dye: characterization, equilibrium, and kinetic studies.

    PubMed

    Sun, Lei; Wan, Shungang; Luo, Wensui

    2013-07-01

    Biochars prepared from anaerobic digestion residue (BC-R), palm bark (BC-PB) and eucalyptus (BC-E) were used as sorbents for removal of cationic methylene blue dye (MB). The FE-SEM images indicated that the biochars have a well-developed pore structure, and the Brunauer-Emmett-Teller surface areas of BC-R, BC-PB, and BC-E were 7.60, 2.46, and 10.35 m(2)g(-1), respectively. The efficiencies of MB removal in the samples with initial concentrations of 5 mg L(-1) at pH 7.0 and 40°C by BC-R, BC-PB, and BC-E after 2h were 99.5%, 99.3%, and 86.1%, respectively. Pseudo-second-order kinetics was the most suitable model for describing the adsorption of MB onto the biochars. The experimental data were best described by the Langmuir isotherm model, with a maximum monolayer adsorption capacity of 9.50 mg g(-1) at 40°C for BC-R. The biochars produced from the three types of solid waste showed considerable potential for adsorption.

  3. Calculating the mean time to capture for tethered ligands and its effect on the chemical equilibrium of bound ligand pairs.

    PubMed

    Shen, Lu; Decker, Caitlin G; Maynard, Heather D; Levine, Alex J

    2016-09-01

    We present here the calculation of the mean time to capture of a tethered ligand to the receptor. This calculation is then used to determine the shift in the partitioning between (1) free, (2) singly bound, and (3) doubly bound ligands in chemical equilibrium as a function of the length of the tether. These calculations are used in the research article Fibroblast Growth Factor 2 Dimer with Superagonist in vitro Activity Improves Granulation Tissue Formation During Wound Healing (Decker et al., in press [1]) to explain quantitatively how changes in polymeric linker length in the ligand dimers modifies the efficacy of these molecules relative to that of free ligands.

  4. Periodic protein adsorption at the gold/biotin aqueous solution interface: evidence of kinetics with time delay

    PubMed Central

    Neff, H.; Laborde, H. M.; Lima, A. M. N.

    2016-01-01

    An oscillatory molecular adsorption pattern of the protein neutravidin from aqueous solution onto gold, in presence of a pre-deposited self assembled mono-molecular biotin film, is reported. Real time surface Plasmon resonance sensing was utilized for evaluation of the adsorption kinetics. Two different fractions were identified: in the initial phase, protein molecules attach irreversibly onto the Biotin ligands beneath towards the jamming limit, forming a neutravidin-biotin fraction. Afterwards, the growth rate exhibits distinct, albeit damped adsorption-desorption oscillations over an extended time span, assigned to a quasi reversibly bound fraction. These findings agree with, and firstly confirm a previously published model, proposing macro-molecular adsorption with time delay. The non-linear dynamic model is applicable to and also resembles non-damped oscillatory binding features of the hetero-catalytic oxidation of carbon monoxide molecules on platinum in the gas phase. An associated surface residence time can be linked to the dynamics and time scale required for self-organization. PMID:27808155

  5. Periodic protein adsorption at the gold/biotin aqueous solution interface: evidence of kinetics with time delay

    NASA Astrophysics Data System (ADS)

    Neff, H.; Laborde, H. M.; Lima, A. M. N.

    2016-11-01

    An oscillatory molecular adsorption pattern of the protein neutravidin from aqueous solution onto gold, in presence of a pre-deposited self assembled mono-molecular biotin film, is reported. Real time surface Plasmon resonance sensing was utilized for evaluation of the adsorption kinetics. Two different fractions were identified: in the initial phase, protein molecules attach irreversibly onto the Biotin ligands beneath towards the jamming limit, forming a neutravidin-biotin fraction. Afterwards, the growth rate exhibits distinct, albeit damped adsorption-desorption oscillations over an extended time span, assigned to a quasi reversibly bound fraction. These findings agree with, and firstly confirm a previously published model, proposing macro-molecular adsorption with time delay. The non-linear dynamic model is applicable to and also resembles non-damped oscillatory binding features of the hetero-catalytic oxidation of carbon monoxide molecules on platinum in the gas phase. An associated surface residence time can be linked to the dynamics and time scale required for self-organization.

  6. Determination of equilibrium electron temperature and times using an electron swarm model with BOLSIG+ calculated collision frequencies and rate coefficients

    NASA Astrophysics Data System (ADS)

    Pusateri, Elise N.; Morris, Heidi E.; Nelson, Eric M.; Ji, Wei

    2015-08-01

    Electromagnetic pulse (EMP) events produce low-energy conduction electrons from Compton electron or photoelectron ionizations with air. It is important to understand how conduction electrons interact with air in order to accurately predict EMP evolution and propagation. An electron swarm model can be used to monitor the time evolution of conduction electrons in an environment characterized by electric field and pressure. Here a swarm model is developed that is based on the coupled ordinary differential equations (ODEs) described by Higgins et al. (1973), hereinafter HLO. The ODEs characterize the swarm electric field, electron temperature, electron number density, and drift velocity. Important swarm parameters, the momentum transfer collision frequency, energy transfer collision frequency, and ionization rate, are calculated and compared to the previously reported fitted functions given in HLO. These swarm parameters are found using BOLSIG+, a two term Boltzmann solver developed by Hagelaar and Pitchford (2005), which utilizes updated cross sections from the LXcat website created by Pancheshnyi et al. (2012). We validate the swarm model by comparing to experimental effective ionization coefficient data in Dutton (1975) and drift velocity data in Ruiz-Vargas et al. (2010). In addition, we report on electron equilibrium temperatures and times for a uniform electric field of 1 StatV/cm for atmospheric heights from 0 to 40 km. It is shown that the equilibrium temperature and time are sensitive to the modifications in the collision frequencies and ionization rate based on the updated electron interaction cross sections.

  7. Determination of equilibrium electron temperature and times using an electron swarm model with BOLSIG+ calculated collision frequencies and rate coefficients

    DOE PAGES

    Pusateri, Elise N.; Morris, Heidi E.; Nelson, Eric M.; ...

    2015-08-04

    Electromagnetic pulse (EMP) events produce low-energy conduction electrons from Compton electron or photoelectron ionizations with air. It is important to understand how conduction electrons interact with air in order to accurately predict EMP evolution and propagation. An electron swarm model can be used to monitor the time evolution of conduction electrons in an environment characterized by electric field and pressure. Here a swarm model is developed that is based on the coupled ordinary differential equations (ODEs) described by Higgins et al. (1973), hereinafter HLO. The ODEs characterize the swarm electric field, electron temperature, electron number density, and drift velocity. Importantmore » swarm parameters, the momentum transfer collision frequency, energy transfer collision frequency, and ionization rate, are calculated and compared to the previously reported fitted functions given in HLO. These swarm parameters are found using BOLSIG+, a two term Boltzmann solver developed by Hagelaar and Pitchford (2005), which utilizes updated cross sections from the LXcat website created by Pancheshnyi et al. (2012). We validate the swarm model by comparing to experimental effective ionization coefficient data in Dutton (1975) and drift velocity data in Ruiz-Vargas et al. (2010). In addition, we report on electron equilibrium temperatures and times for a uniform electric field of 1 StatV/cm for atmospheric heights from 0 to 40 km. We show that the equilibrium temperature and time are sensitive to the modifications in the collision frequencies and ionization rate based on the updated electron interaction cross sections.« less

  8. Determination of equilibrium electron temperature and times using an electron swarm model with BOLSIG+ calculated collision frequencies and rate coefficients

    SciTech Connect

    Pusateri, Elise N.; Morris, Heidi E.; Nelson, Eric M.; Ji, Wei

    2015-08-04

    Electromagnetic pulse (EMP) events produce low-energy conduction electrons from Compton electron or photoelectron ionizations with air. It is important to understand how conduction electrons interact with air in order to accurately predict EMP evolution and propagation. An electron swarm model can be used to monitor the time evolution of conduction electrons in an environment characterized by electric field and pressure. Here a swarm model is developed that is based on the coupled ordinary differential equations (ODEs) described by Higgins et al. (1973), hereinafter HLO. The ODEs characterize the swarm electric field, electron temperature, electron number density, and drift velocity. Important swarm parameters, the momentum transfer collision frequency, energy transfer collision frequency, and ionization rate, are calculated and compared to the previously reported fitted functions given in HLO. These swarm parameters are found using BOLSIG+, a two term Boltzmann solver developed by Hagelaar and Pitchford (2005), which utilizes updated cross sections from the LXcat website created by Pancheshnyi et al. (2012). We validate the swarm model by comparing to experimental effective ionization coefficient data in Dutton (1975) and drift velocity data in Ruiz-Vargas et al. (2010). In addition, we report on electron equilibrium temperatures and times for a uniform electric field of 1 StatV/cm for atmospheric heights from 0 to 40 km. We show that the equilibrium temperature and time are sensitive to the modifications in the collision frequencies and ionization rate based on the updated electron interaction cross sections.

  9. Applications and limits of theoretical adsorption models for predicting the adsorption properties of adsorbents.

    PubMed

    Park, Hyun Ju; Nguyen, Duc Canh; Na, Choon-Ki; Kim, Chung-il

    2015-01-01

    The objective of this study is to evaluate the applicability of adsorption models for predicting the properties of adsorbents. The kinetics of the adsorption of NO3- ions on a PP-g-AA-Am non-woven fabric have been investigated under equilibrium conditions in both batch and fixed bed column processes. The adsorption equilibrium experiments in the batch process were carried out under different adsorbate concentration and adsorbent dosage conditions and the results were analyzed using adsorption isotherm models, energy models, and kinetic models. The results of the analysis indicate that the adsorption occurring at a fixed adsorbate concentration with a varying adsorbent dosage occur more easily compared to those under a fixed adsorbent dosage with a varying adsorbate concentration. In the second part of the study, the experimental data obtained using fixed bed columns were fit to Bed Depth Service Time, Bohart-Adams, Clark, and Wolborska models, to predict the breakthrough curves and determine the column kinetic parameters. The adsorption properties of the NO3- ions on the PP-g-AA-Am non-woven fabric were differently described by different models for both the batch and fixed bed column process. Therefore, it appears reasonable to assume that the adsorption properties were dominated by multiple mechanisms, depending on the experimental conditions.

  10. Photocatalytic TMO-NMs adsorbent: Temperature-Time dependent Safranine degradation, sorption study validated under optimized effective equilibrium models parameter with standardized statistical analysis

    NASA Astrophysics Data System (ADS)

    Wahab, Rizwan; Khan, Farheen; Kaushik, Nagendra Kumar; Musarrat, Javed; Al-Khedhairy, Abdulaziz A.

    2017-02-01

    In this paper, chemically synthesized copper oxide nanoparticles (CuO-NPs), were employed for two processes: one is photocatalytic degradation and second one adsorption for the sorption of safranine (SA) dye in an aqueous medium at pH = 12.01. The optimized analytes amount (nano-adsorbent = 0.10 g, conc. range of SA dye 56.13 ppm to 154.37 ppm, pH = 12.01, temperature 303 K) reached to equilibrium point in 80 min, which acquired for chemical adsorption-degradation reactions. The degredated SA dye data’s recorded by UV-visible spectroscopy for the occurrence of TMO-NMs of CuO-NPs at anticipated period of interval. The feasible performance of CuO-NPs was admirable, shows good adsorption capacity qm = 53.676 mg g‑1 and most convenient to best fitted results establish by linear regression equation, corresponded for selected kinetic model (pseudo second order (R2 = 0.9981), equilibrium isotherm models (Freundlich, Langmuir, Dubnin-Radushkevich (D-R), Temkin, H-J and Halsey), and thermodynamic parameters (∆H° = 75461.909 J mol‑1, ∆S° = 253.761 J mol‑1, ∆G° = ‑1427.93 J mol‑1, Ea = 185.142 J mol‑1) with error analysis. The statistical study revealed that CuO-NPs was an effective adsorbent certified photocatalytic efficiency (η = 84.88%) for degradation of SA dye, exhibited more feasibility and good affinity toward adsorbate, the sorption capacity increases with increased temperature at equilibrium point.

  11. Photocatalytic TMO-NMs adsorbent: Temperature-Time dependent Safranine degradation, sorption study validated under optimized effective equilibrium models parameter with standardized statistical analysis

    PubMed Central

    Wahab, Rizwan; Khan, Farheen; Kaushik, Nagendra Kumar; Musarrat, Javed; Al-Khedhairy, Abdulaziz A.

    2017-01-01

    In this paper, chemically synthesized copper oxide nanoparticles (CuO-NPs), were employed for two processes: one is photocatalytic degradation and second one adsorption for the sorption of safranine (SA) dye in an aqueous medium at pH = 12.01. The optimized analytes amount (nano-adsorbent = 0.10 g, conc. range of SA dye 56.13 ppm to 154.37 ppm, pH = 12.01, temperature 303 K) reached to equilibrium point in 80 min, which acquired for chemical adsorption-degradation reactions. The degredated SA dye data’s recorded by UV-visible spectroscopy for the occurrence of TMO-NMs of CuO-NPs at anticipated period of interval. The feasible performance of CuO-NPs was admirable, shows good adsorption capacity qm = 53.676 mg g−1 and most convenient to best fitted results establish by linear regression equation, corresponded for selected kinetic model (pseudo second order (R2 = 0.9981), equilibrium isotherm models (Freundlich, Langmuir, Dubnin-Radushkevich (D-R), Temkin, H-J and Halsey), and thermodynamic parameters (∆H° = 75461.909 J mol−1, ∆S° = 253.761 J mol−1, ∆G° = −1427.93 J mol−1, Ea = 185.142 J mol−1) with error analysis. The statistical study revealed that CuO-NPs was an effective adsorbent certified photocatalytic efficiency (η = 84.88%) for degradation of SA dye, exhibited more feasibility and good affinity toward adsorbate, the sorption capacity increases with increased temperature at equilibrium point. PMID:28195174

  12. Removal of Reactofix Navy Blue 2 GFN from aqueous solutions using adsorption techniques.

    PubMed

    Gupta, Vinod Kumar; Jain, Rajeev; Varshney, Shaily; Saini, Vipin Kumar

    2007-03-15

    The wheat husk, an agricultural by-product, has been activated and used as an adsorbent for the adsorption of Reactofix Navy Blue 2 GFN from aqueous solution. In this work, adsorption of Reactofix Navy Blue 2 GFN on wheat husk and charcoal has been studied by using batch studies. The equilibrium adsorption level was determined to be a function of the solution pH, adsorbent dosage, dye concentration and contact time. The equilibrium adsorption capacities of wheat husk and charcoal for dye removal were obtained using Freundlich and Langmuir isotherms. Thermodynamic parameters such as the free energies, enthalpies and entropies of adsorption were also evaluated. Adsorption process is considered suitable for removing color, COD from waste water.

  13. Comparison of adsorption equilibrium models for the study of CL-, NO3- and SO4(2-) removal from aqueous solutions by an anion exchange resin.

    PubMed

    Dron, Julien; Dodi, Alain

    2011-06-15

    The removal of chloride, nitrate and sulfate ions from aqueous solutions by a macroporous resin is studied through the ion exchange systems OH(-)/Cl(-), OH(-)/NO(3)(-), OH(-)/SO(4)(2-), and HCO(3)(-)/Cl(-), Cl(-)/NO(3)(-), Cl(-)/SO(4)(2-). They are investigated by means of Langmuir, Freundlich, Dubinin-Radushkevitch (D-R) and Dubinin-Astakhov (D-A) single-component adsorption isotherms. The sorption parameters and the fitting of the models are determined by nonlinear regression and discussed. The Langmuir model provides a fair estimation of the sorption capacity whatever the system under study, on the contrary to Freundlich and D-R models. The adsorption energies deduced from Dubinin and Langmuir isotherms are in good agreement, and the surface parameter of the D-A isotherm appears consistent. All models agree on the order of affinity OH(-)adsorption isotherms. The nonlinear regression results are also compared with linear regressions. While the parameter values are not affected, the evaluation of the best fitting model is biased by linearization.

  14. Generalized random sequential adsorption

    NASA Astrophysics Data System (ADS)

    Tarjus, G.; Schaaf, P.; Talbot, J.

    1990-12-01

    Adsorption of hard spherical particles onto a flat uniform surface is analyzed by using generalized random sequential adsorption (RSA) models. These models are defined by releasing the condition of immobility present in the usual RSA rules to allow for desorption or surface diffusion. Contrary to the simple RSA case, generalized RSA processes are no longer irreversible and the system formed by the adsorbed particles on the surface may reach an equilibrium state. We show by using a distribution function approach that the kinetics of such processes can be described by means of an exact infinite hierarchy of equations reminiscent of the Kirkwood-Salsburg hierarchy for systems at equilibrium. We illustrate the way in which the systems produced by adsorption/desorption and by adsorption/diffusion evolve between the two limits represented by ``simple RSA'' and ``equilibrium'' by considering approximate solutions in terms of truncated density expansions.

  15. Adsorption of Compounds that Mimic Urban Stormwater Dissolved Organic Nitrogen.

    PubMed

    Mohtadi, Mehrdad; James, Bruce R; Davis, Allen P

    2017-02-01

      Stormwater runoff carrying nitrogen can accelerate eutrophication. Bioretention facilities are among low impact development systems which are commonly used to manage urban stormwater quality and quantity. They are, however, not designed to remove dissolved organic nitrogen (DON) and may become a net DON exporter. Adsorption of seven organic nitrogenous compounds onto several adsorbents was examined. Batch adsorption study revealed that coal activated carbon (AC) exhibited the best performance in adsorption of the selected organic nitrogenous compounds. The highest adsorption capacity of coal AC was 0.4 mg N/g for pyrrole at an equilibrium concentration of 0.02 mg N/L, while adsorption was not detectable for urea at the same equilibrium concentration. The fastest compound to reach equilibrium adsorption capacity onto the coal AC was pyrrole (1 hour). The adsorption capacity of the coal AC for pyrrole and N-acetyl-d-glucosamine and 1-hour contact time is recommended for designing bioretention systems targeting organic nitrogenous compounds.

  16. Predicting protein dynamic binding capacity from batch adsorption tests.

    PubMed

    Carta, Giorgio

    2012-10-01

    The dynamic binding capacity (DBC) and its dependence on residence time influence the design and productivity of adsorption columns used in protein capture applications. This paper offers a very simple approach to predict the DBC of an adsorption column based on a measurement of the equilibrium binding capacity (EBC) and of the time needed to achieve one-half of the EBC in a batch adsorption test. The approach is based on a mass transfer kinetics model that assumes pore diffusion with a rectangular isotherm; however, the same approach is also shown to work for other systems where solute transport inside the particle occurs through other transport mechanisms.

  17. Measurement of surface stay times for physical adsorption of gases. Ph.D. Thesis - Va. Univ.; [using molecular beam time of flight technique

    NASA Technical Reports Server (NTRS)

    Wilmoth, R. G.

    1973-01-01

    A molecular beam time-of-flight technique is studied as a means of determining surface stay times for physical adsorption. The experimental approach consists of pulsing a molecular beam, allowing the pulse to strike an adsorbing surface and detecting the molecular pulse after it has subsequently desorbed. The technique is also found to be useful for general studies of adsorption under nonequilibrium conditions including the study of adsorbate-adsorbate interactions. The shape of the detected pulse is analyzed in detail for a first-order desorption process. For mean stay times, tau, less than the mean molecular transit times involved, the peak of the detected pulse is delayed by an amount approximately equal to tau. For tau much greater than these transit times, the detected pulse should decay as exp(-t/tau). However, for stay times of the order of the transit times, both the molecular speed distributions and the incident pulse duration time must be taken into account.

  18. Spectral analysis of finite-time correlation matrices near equilibrium phase transitions

    NASA Astrophysics Data System (ADS)

    Vinayak; Prosen, T.; Buča, B.; Seligman, T. H.

    2014-10-01

    We study spectral densities for systems on lattices, which, at a phase transition display, power-law spatial correlations. Constructing the spatial correlation matrix we prove that its eigenvalue density shows a power law that can be derived from the spatial correlations. In practice time series are short in the sense that they are either not stationary over long time intervals or not available over long time intervals. Also we usually do not have time series for all variables available. We shall make numerical simulations on a two-dimensional Ising model with the usual Metropolis algorithm as time evolution. Using all spins on a grid with periodic boundary conditions we find a power law, that is, for large grids, compatible with the analytic result. We still find a power law even if we choose a fairly small subset of grid points at random. The exponents of the power laws will be smaller under such circumstances. For very short time series leading to singular correlation matrices we use a recently developed technique to lift the degeneracy at zero in the spectrum and find a significant signature of critical behavior even in this case as compared to high temperature results which tend to those of random matrix models.

  19. Removal of hazardous pharmaceutical dyes by adsorption onto papaya seeds.

    PubMed

    Weber, Caroline Trevisan; Collazzo, Gabriela Carvalho; Mazutti, Marcio Antonio; Foletto, Edson Luiz; Dotto, Guilherme Luiz

    2014-01-01

    Papaya (Carica papaya L.) seeds were used as adsorbent to remove toxic pharmaceutical dyes (tartrazine and amaranth) from aqueous solutions, in order to extend application range. The effects of pH, initial dye concentration, contact time and temperature were investigated. The kinetic data were evaluated by the pseudo first-order, pseudo second-order and Elovich models. The equilibrium was evaluated by the Langmuir, Freundlich and Temkin isotherm models. It was found that adsorption favored a pH of 2.5, temperature of 298 K and equilibrium was attained at 180-200 min. The adsorption kinetics followed the pseudo second-order model, and the equilibrium was well represented by the Langmuir model. The maximum adsorption capacities were 51.0 and 37.4 mg g(-1) for tartrazine and amaranth, respectively. These results revealed that papaya seeds can be used as an alternative adsorbent to remove pharmaceutical dyes from aqueous solutions.

  20. 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.

  1. Summary of Adsorption Capacity and Adsorption Kinetics of Uranium and Other Elements on Amidoxime-based Adsorbents from Time Series Marine Testing at the Pacific Northwest National Laboratory

    SciTech Connect

    Gill, Gary A.; Kuo, Li-Jung; Strivens, Jonathan E.; Wood, Jordana R.; Schlafer, Nicholas J.; Janke, Christopher J.; Das, Sadananda; Mayes, Richard; Saito, Tomonori; Brown, Suree S.; Tsouris, Constantinos; Tsouris, Costas; Wai, Chien M.; Pan, Horng-Bin

    2016-09-29

    The Pacific Northwest National Laboratory (PNNL) has been conducting marine testing of uranium adsorbent materials for the Fuel Resources Program, Department of Energy, Office of Nuclear Energy (DOE-NE) beginning in FY 2012. The marine testing program is being conducted at PNNL’s Marine Sciences Laboratory (MSL), located at Sequim Bay, along the coast of Washington. One of the main efforts of the marine testing program is the determination of adsorption capacity and adsorption kinetics for uranium and selected other elements (e.g. vanadium, iron, copper, nickel, and zinc) for adsorbent materials provided primarily by Oak Ridge National Laboratory (ORNL), but also includes other Fuel Resources Program participants. This report summarizes the major marine testing results that have been obtained to date using time series sampling for 42 to 56 days using either flow-through column or recirculating flume exposures. The major results are highlighted in this report, and the full data sets are appended as a series of Excel spreadsheet files. Over the four year period (2012-2016) that marine testing of amidoxime-based polymeric adsorbents was conducted at PNNL’s Marine Science Laboratory, there has been a steady progression of improvement in the 56-day adsorbent capacity from 3.30 g U/kg adsorbent for the ORNL 38H adsorbent to the current best performing adsorbent prepared by a collaboration between the University of Tennessee and ORNL to produce the adsorbent SB12-8, which has an adsorption capacity of 6.56 g U/kg adsorbent. This nearly doubling of the adsorption capacity in four years is a significant advancement in amidoxime-based adsorbent technology and a significant achievement for the Uranium from Seawater program. The achievements are evident when compared to the several decades of work conducted by the Japanese scientists beginning in the 1980’s (Kim et al., 2013). The best adsorbent capacity reported by the Japanese scientists was 3.2 g U/kg adsorbent for a

  2. Out of equilibrium thermal field theories: Finite time after switching on the interaction and Wigner transforms of projected functions

    NASA Astrophysics Data System (ADS)

    Dadić, I.

    2001-01-01

    We study out of equilibrium thermal field theories with switching on the interaction occurring at finite time using the Wigner transforms of two-point functions. For two-point functions we define the concept of a projected function: it is zero if any of the times refers to the time before switching on the interaction; otherwise it depends only on the relative coordinates. This definition includes bare propagators, one-loop self-energies, etc. For the infinite-average-time limit of the Wigner transforms of projected functions we define the analyticity assumptions: (1) The function of energy is analytic above (below) the real axis. (2) The function goes to zero as the absolute value of energy approaches infinity in the upper (lower) semiplane. Without use of the gradient expansion, we obtain the convolution product of projected functions. We sum the Schwinger-Dyson series in closed form. In the calculation of the Keldysh component (both resummed and single self-energy insertion approximation) contributions appear which are not the Fourier transforms of projected functions, signaling the limitations of the method. In the Feynman diagrams there is no explicit energy conservation at vertices; there is an overall energy-smearing factor taking care of the uncertainty relations. The relation between the theories with the Keldysh time path and with the finite time path enables one to rederive the results, such as the cancellation of pinching, collinear, and infrared singularities, hard thermal loop resummation, etc.

  3. [Adsorption of perfluorooctanesulfonate (PFOS) onto modified activated carbons].

    PubMed

    Tong, Xi-Zhen; Shi, Bao-You; Xie, Yue; Wang, Dong-Sheng

    2012-09-01

    Modified coal and coconut shell based powdered activated carbons (PACs) were prepared by FeCl3 and medium power microwave treatment, respectively. Batch experiments were carried out to evaluate the characteristics of adsorption equilibrium and kinetics of perfluorooctanesulfonate (PFOS) onto original and modified PACs. Based on pore structure and surface functional groups characterization, the adsorption behaviors of modified and original PACs were compared. The competitive adsorption of humic acid (HA) and PFOS on original and modified coconut shell PACs were also investigated. Results showed that both Fe3+ and medium power microwave treatments changed the pore structure and surface functional groups of coal and coconut shell PACs, but the changing effects were different. The adsorption of PFOS on two modified coconut shell-based PACs was significantly improved. While the adsorption of modified coal-based activated carbons declined. The adsorption kinetics of PFOS onto original and modified coconut shell-based activated carbons were the same, and the time of reaching adsorption equilibrium was about 6 hours. In the presence of HA, the adsorption of PFOS by modified PAC was reduced but still higher than that of the original.

  4. Batch studies of adsorption of copper and lead on activated carbon from Eucalyptus camaldulensis dehn. bark.

    PubMed

    Patnukao, Phussadee; Kongsuwan, Apipreeya; Pavasant, Prasert

    2008-01-01

    Powdered activated carbon (PAC) prepared from Eucalyptus camaldulensis Dehn. bark was tested for its adsorption capacity for Cu(II) and Pb(II). The experiment was conducted to investigate the effects of pH, contact time, initial metal concentration, and temperature. The best adsorption of both Cu(II) and Pb(II) occurred at pH 5, where the adsorption reached equilibrium within 45 min for the whole range of initial heavy metal concentrations (0.1-10 mmol/L). The adsorption kinetics was found to follow the pseudo-second order model where equilibrium adsorption capacities and adsorption rate constants increased with initial heavy metal concentrations. The adsorption isotherm followed Langmuir better than Freundlich models within the temperature range (25-60 degrees C). The maximum adsorption capacities (qm) occurred at 60 degrees C, where qm for Cu(II) and Pb(II) were 0.85 and 0.89 mmol/g, respectively. The enthalpies of Cu(II) and Pb(II) adsorption were 43.26 and 58.77 kJ/mol, respectively. The positive enthalpy of adsorption indicated an endothermic nature of the adsorption.

  5. Modulation of proteins adsorption onto the surface of chitosan complexed with anionic copolymers. Real time analysis by surface plasmon resonance.

    PubMed

    Aguilar, María R; Gallardo, Alberto; Lechuga, Laura M; Calle, Ana; San Román, Julio

    2004-07-14

    The interpolyelectrolyte complex formation between chitosan and anionic polyacrylic derivatives, bearing sulfonic moieties, as well as the protein adsorption onto the chitosan/polyacrylic complexes were studied by surface plasmon resonance (SPR) optical biosensor. This unique technique allows a real time monitoring of different surface molecular interactions with very high sensitivity. The acrylic macromolecules are two families of copolymers of 2-acrylamido-2-methylpropane sulfonic acid (AMPS) and, respectively, 2-hydroxyethylmethacrylate (HEMA) and N,N'-dimethylacrylamide (DMAA). The complexation process was evaluated through the SPR measurements resulting from the flowing of polyacrylic aqueous solution over the sensor previously coated with chitosan. The SPR was able to differentiate strong ionic bonds from other weak and reversible interactions. By means of the coated sensors (uncomplexed and the whole series of complexed chitosan), SPR cold be used for a simple "in vitro" protein adsorption analysis, by flowing aqueous solutions of albumin and fibrinogen. While both proteins were adsorbed on the uncomplexed chitosan, the complexed coatings exhibited different and very promising behaviors. In particular, they showed no adsorption or only selective adsorption of albumin.

  6. Protein nanoparticle interaction: A spectrophotometric approach for adsorption kinetics and binding studies

    NASA Astrophysics Data System (ADS)

    Vaishanav, Sandeep K.; Chandraker, Kumudini; Korram, Jyoti; Nagwanshi, Rekha; Ghosh, Kallol K.; Satnami, Manmohan L.

    2016-08-01

    Investigating the protein nanoparticle interaction is crucial to understand how to control the biological interactions of nanoparticles. In this work, Model protein Bovine serum albumin (BSA) was used to evaluate the process of protein adsorption to the gold nanoparticles (GNPs) surface. The binding of a model protein (BSA) to GNPs was investigated through fluorescence quenching measurements. The strong affinities of BSA for GNPs were confirmed by the high value of binding constant (Ks) which was calculated to be 2.2 × 1011 L/mol. In this consequence, we also investigated the adsorption behavior of BSA on GNPs surface via UV-Vis spectroscopy. The effect of various operational parameters such as pH, contact time, initial BSA concentration, and temperature on adsorption of BSA was investigated using batch adsorption experiments. Kinetics of adsorption was found to follow the pseudo-second order rate equation. The suitability of Freundlich and Langmuir adsorption models to the equilibrium data was investigated. The equilibrium adsorption was well described by the Freundlich isotherm model. The maximum adsorption capacity for BSA adsorbed on GNPs was 58.71 mg/g and equilibrium constant was 0.0058 calculated by the Langmuir model at 298 K and pH = 11.0. Thermodynamic parameters showed that the adsorption of BSA onto GNPs was feasible, spontaneous, and exothermic.

  7. 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

    2016-04-01

    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.

  8. A comparative adsorption study: 17β-estradiol onto aerobic granular sludge and activated sludge.

    PubMed

    Zheng, Xiao-ying; He, Yu-jie; Chen, Wei; Wang, Ming-yang; Cao, Su-lan; Ni, Ming; Chen, Yu

    2016-01-01

    Adsorption plays a significant role in removing hydrophobic 17β-estradiol (E2) from wastewater. Batch experiments were conducted to compare the adsorption of E2 onto activated aerobic granular sludge (AGS) and activated sludge (AS), and features evaluated included the adsorption kinetics, thermodynamics, and influence of other environmental factors. By using a non-chemical wet-heat technique, both AGS and AS were treated to inactivated status. Then, after loading E2, the adsorption equilibrium capacity of the AGS was found to be greater than that of the AS at the same initial concentration of E2. Moreover, both the adsorption processes corresponded to a pseudo-second-order kinetic model; the adsorption rate constant of AGS was found to be higher and the half-adsorption time was shorter than that of AS. Next, evaluations of adsorption isotherms and thermodynamics indicated that the adsorption process was mainly a physical process. Lower temperatures facilitated a higher equilibrium adsorption capacity. However, the adsorption binding sites of AGS were distributed more uniformly at higher temperature, in contrast to the distribution found for AS. Finally, acidic conditions and an appropriate ionic strength (0.4 mol/L) were found to be particularly conducive to the adsorption process. Overall, the results showed that AGS has the potential to adsorb E2 with significant efficiency, thereby offering a new and more efficient means of treating E2 and trace oestrogens in wastewater.

  9. Enhanced adsorptive removal of toxic dyes using SiO2 nanofibers

    NASA Astrophysics Data System (ADS)

    Batool, S. S.; Imran, Z.; Hassan, Safia; Rasool, Kamran; Ahmad, Mushtaq; Rafiq, M. A.

    2016-05-01

    Electrospinning method was used to synthesize porous SiO2 nanofibers. The adsorption of Methyl Orange and Safranin O by porous SiO2 nanofibers was carried out by varying the parameters such as pH, contact time, adsorbent dose, dye concentration, and temperature. Equilibrium adsorption data followed Langmuir isotherms. Kinetic adsorption followed second-order rate kinetics model. The maximum adsorption capacity for Methyl Orange and Safranin O was found to be 730.9 mg/g and 960.4 mg/g, respectively. Acidic pH was favorable for the adsorption of Methyl Orange while basic pH was favorable for the adsorptions of Safranin O. Modeling study suggested the major mode of adsorption, while thermodynamic study showed the endothermic reactions. This effort has pronounced impact on environmental applications of SiO2 nanofibers as auspicious adsorbent nanofibers for organic material from aqueous solution.

  10. Adsorption of trihalomethanes from water with carbon nanotubes.

    PubMed

    Lu, Chungsying; Chung, Yao-Lei; Chang, Kuan-Foo

    2005-03-01

    Commercial carbon nanotubes (CNTs) were purified by acid solution and were employed as adsorbents to study adsorption of trihalomethanes (THMs) from water. The properties of CNTs such as purity, structure and nature of the surface were greatly improved after acid treatment which made CNTs become more hydrophilic and suitable for adsorption of low molecular weight and relatively polar THM molecules. The adsorption of THMs onto CNTs fluctuates very little in the pH range 3-7, but decreases with pH value as pH exceeds 7. A comparative study between CNTs and powdered activated carbon (PAC) for adsorption of THMs from water was also conducted. The short time needed to reach equilibrium as well as the high adsorption capacity of CHCl3, which accounts for a significant portion of THMs in the chlorinated drinking water, suggests that CNTs possess highly potential applications for THMs removal from water.

  11. Reuse of Solid Waste in Adsorption of the Textile Dye

    NASA Astrophysics Data System (ADS)

    Meziti, Chafika; Boukerroui, Abdelhamid

    This work presents the study of the reuse of a regenerated spent bleaching earth (RSBE). The RSBE material was tested in the removal of a basic textile dye presents in aqueous solution. The effect of physicochemical parameters such as stirring speed, initial concentration, contact time and temperature have been invested and thermodynamic nature of the adsorption process was determined by calculating the ΔH°, ΔS° and ΔG° values The results obtained show that the adsorption mechanism was described by the Langmuir model and the adsorption capacity, qmax (72.41 to 82.37 mg.g-1), increases with temperature (20-50 °C). The thermodynamic parameters show a presence of a strong affinity between two phases (liquid-solid) and an endothermic equilibrium adsorption process. However, the phenomenon of the adsorption kinetic follows the pseudo second order kinetic model.

  12. [Kinetics of adsorption of Pb2+ onto small river sediment].

    PubMed

    Shi, Gui-Tao; Chen, Zhen-Lou; Bi, Chun-Juan; Sun, Chao; Sun, Yue-Di; Xu, Shi-Yuan

    2009-06-15

    The batch experiments of adsorption of Pb2+ onto small river sediments were conducted. The kinetics of the sorption process was analyzed. The results showed that the equilibrium time of adsorption increased with the increasing of sediment mass in solution, while both adsorbed Pb2+ on per unit of sediment and Pb2+ concentration in the solution after equilibrium decreased. More than 95% of Pb2+ in solution was removed when sediment contents larger than 0.6 g x L(-1). Both pseudo-first-order and pseudo-second-order kinetics were tested and it was found that the latter gave a better explanation of the adsorption process. The equilibrium adsorption capacities calculated from the pseudo-second-order model could represent the true value. There was no significant correlation between initial adsorption rate of Pb2+ and the amount of sediment in solution. However, the pseudo-second-order rate constant increased in the solution with more adsorbent, namely chemical adsorption controlled the process. Elovich equation could explain the mechanism of sorption in the solution with higher contents of sediment; nevertheless, the process of low concentration of adsorbent adsorbing Pb2+ disagreed well with Elovich equation. In terms of adsorption rate in the sorption, intra-particle diffusion dominated in the more sediment solution. On the other hand, multi-linearity was presented for the adsorption rate in less adsorbent solution. The first, sharper portion represented adsorption on the external surface. The second portion indicated Pb2+ diffused gradually into the interior of particles and intra-particle diffusion controlled.

  13. Non-equilibrium Dirac carrier dynamics in graphene investigated with time- and angle-resolved photoemission spectroscopy.

    PubMed

    Gierz, Isabella; Link, Stefan; Starke, Ulrich; Cavalleri, Andrea

    2014-01-01

    We have used time- and angle-resolved photoemission spectroscopy (tr-ARPES) to assess the influence of many-body interactions on the Dirac carrier dynamics in graphene. From the energy-dependence of the measured scattering rates we directly determine the imaginary part of the self-energy, visualizing the existence of a relaxation bottleneck associated with electron-phonon coupling. A comparison with static line widths obtained by high-resolution ARPES indicates that the dynamics of photo-excited carriers in graphene are solely determined by the equilibrium self-energy. Furthermore, the subtle interplay of different many-body interactions in graphene may allow for carrier multiplication, where the absorption of a single photon generates more than one electron-hole pair via impact ionization. We find that, after photo-excitation, the number of carriers in the conduction band along the ΓK-direction keeps increasing for about 40 fs after the pump pulse is gone. A definite proof of carrier multiplication in graphene, however, requires a more systematic study, carefully taking into account the contribution of momentum relaxation on the measured rise time.

  14. Adsorptive removal of methylene blue by CuO-acid modified sepiolite as effective adsorbent and its regeneration with high-temperature gas stream.

    PubMed

    Su, Chengyuan; Wang, Liang; Chen, Menglin; Huang, Zhi; Lin, Xiangfeng

    In this study, the dynamic adsorption of methylene blue dye onto CuO-acid modified sepiolite was investigated. Meanwhile, the equilibrium and kinetic data of the adsorption process were studied to understand the adsorption mechanism. Furthermore, a high-temperature gas stream was applied to regenerate the adsorbent. The results showed that the Langmuir isotherm model was applied to describe the adsorption process. The positive value of enthalpy change indicated that the adsorption process was endothermic in nature. In the dynamic adsorption process, the best adsorption performance was achieved when the ratio of column height to diameter was 2.56 and the treatment capacity was 6 BV/h. The optimal scenario for regeneration experiments was the regeneration temperature of 550-650 °C, the space velocity of 100 min(-1) and the regeneration time of 10 min. The effective adsorption of CuO-acid modified sepiolite was kept for 12 cycles of adsorption and regeneration.

  15. Phosphate mediated adsorption and electron transfer of cytochrome c. A time-resolved SERR spectroelectrochemical study.

    PubMed

    Capdevila, Daiana A; Marmisollé, Waldemar A; Williams, Federico J; Murgida, Daniel H

    2013-04-21

    The study of proteins immobilized on biomimetic or biocompatible electrodes represents an active field of research as it pursues both fundamental and technological interests. In this context, adsorption and redox properties of cytochrome c (Cyt) on different electrode surfaces have been extensively reported, although in some cases with contradictory results. Here we report a SERR spectroelectrochemical study of the adsorption and electron transfer behaviour of the basic protein Cyt on electrodes coated with amino-terminated monolayers. The obtained results show that inorganic phosphate (Pi) and ATP anions are able to mediate high affinity binding of the protein with preservation of the native structure and rendering an average orientation that guarantees efficient pathways for direct electron transfer. These findings aid the design of Cyt-based bioelectronic devices and understanding the modulation by Pi and ATP of physiological functions of Cyt.

  16. Neon and CO2 adsorption on open carbon nanohorns.

    PubMed

    Krungleviciute, Vaiva; Ziegler, Carl A; Banjara, Shree R; Yudasaka, Masako; Iijima, S; Migone, Aldo D

    2013-07-30

    We present the results of a thermodynamics and kinetics study of the adsorption of neon and carbon dioxide on aggregates of chemically opened carbon nanohorns. Both the equilibrium adsorption characteristics, as well as the dependence of the kinetic behavior on sorbent loading, are different for these two adsorbates. For neon the adsorption isotherms display two steps before reaching the saturated vapor pressure, corresponding to adsorption on strong and on weak binding sites; the isosteric heat of adsorption is a decreasing function of sorbent loading (this quantity varies by about a factor of 2 on the range of loadings studied), and the speed of the adsorption kinetics increases with increasing loading. By contrast, for carbon dioxide there are no substeps in the adsorption isotherms; the isosteric heat is a nonmonotonic function of loading, the value of the isosteric heat never differs from the bulk heat of sublimation by more than 15%, and the kinetic behavior is opposite to that of neon, with equilibration times increasing for higher sorbent loadings. We explain the difference in the equilibrium properties observed for neon and carbon dioxide in terms of differences in the relative strengths of adsorbate-adsorbate to adsorbate-sorbent interaction for these species.

  17. Lattice Boltzmann simulation of gas-solid adsorption processes at pore scale level

    NASA Astrophysics Data System (ADS)

    Zhou, L.; Qu, Z. G.; Chen, L.; Tao, W. Q.

    2015-11-01

    A two-dimensional lattice Boltzmann (LB) approach was established to implement kinetic concentration boundary conditions in interfacial mass-transfer processes and to simulate the adsorption process in porous media at pore scale and mesoscopic levels. A general treatment was applied to conduct three types of concentration boundary conditions effectively and accurately. Applicability for adsorption was verified by two benchmark examples, which were representative of the interparticle mass transport and intraparticle mass transport in the adsorption system, respectively. The gas-solid adsorption process in reconstructed porous media at the pore scale level was numerically investigated. Mass-transfer processes of the adsorption reaction were simulated by executing Langmuir adsorption kinetics on surfaces of adsorbent particles. Meanwhile, the homogeneous solid diffusion model (HSDM) was used for mass transport in interior particles. The transient adsorbed amount was obtained in detail, and the impact of flow condition, porosity, and adsorbent particle size on the entire dynamic adsorption performance was investigated. The time needed to approach steady state decreased with increased fluid velocity. Transient adsorption capability and time consumption to equilibrium were nearly independent of porosity, whereas increasing pore size led to a moderating adsorption rate and more time was consumed to approach the saturation adsorption. Benefiting from the advantages of the LB method, both bulk and intraparticle mass transfer performances during adsorption can be obtained using the present pore scale approach. Thus, interparticle mass transfer and intraparticle mass transfer are the two primary segments, and intraparticle diffusion has the dominant role.

  18. Individual and competitive adsorption of phenol and nickel onto multiwalled carbon nanotubes

    PubMed Central

    Abdel-Ghani, Nour T.; El-Chaghaby, Ghadir A.; Helal, Farag S.

    2014-01-01

    Individual and competitive adsorption studies were carried out to investigate the removal of phenol and nickel ions by adsorption onto multiwalled carbon nanotubes (MWCNTs). The carbon nanotubes were characterized by different techniques such as X-ray diffraction, scanning electron microscopy, thermal analysis and Fourier transformation infrared spectroscopy. The different experimental conditions affecting the adsorption process were investigated. Kinetics and equilibrium models were tested for fitting the adsorption experimental data. The characterization experimental results proved that the studied adsorbent possess different surface functional groups as well as typical morphological features. The batch experiments revealed that 300 min of contact time was enough to achieve equilibrium for the adsorption of both phenol and nickel at an initial adsorbate concentration of 25 mg/l, an adsorbent dosage of 5 g/l, and a solution pH of 7. The adsorption of phenol and nickel by MWCNTs followed the pseudo-second order kinetic model and the intraparticle diffusion model was quite good in describing the adsorption mechanism. The Langmuir equilibrium model fitted well the experimental data indicating the homogeneity of the adsorbent surface sites. The maximum Langmuir adsorption capacities were found to be 32.23 and 6.09 mg/g, for phenol and Ni ions, respectively. The removal efficiency of MWCNTs for nickel ions or phenol in real wastewater samples at the optimum conditions reached up to 60% and 70%, respectively. PMID:26257938

  19. Partition Equilibrium

    NASA Astrophysics Data System (ADS)

    Feldman, Michal; Tennenholtz, Moshe

    We introduce partition equilibrium and study its existence in resource selection games (RSG). In partition equilibrium the agents are partitioned into coalitions, and only deviations by the prescribed coalitions are considered. This is in difference to the classical concept of strong equilibrium according to which any subset of the agents may deviate. In resource selection games, each agent selects a resource from a set of resources, and its payoff is an increasing (or non-decreasing) function of the number of agents selecting its resource. While it has been shown that strong equilibrium exists in resource selection games, these games do not possess super-strong equilibrium, in which a fruitful deviation benefits at least one deviator without hurting any other deviator, even in the case of two identical resources with increasing cost functions. Similarly, strong equilibrium does not exist for that restricted two identical resources setting when the game is played repeatedly. We prove that for any given partition there exists a super-strong equilibrium for resource selection games of identical resources with increasing cost functions; we also show similar existence results for a variety of other classes of resource selection games. For the case of repeated games we identify partitions that guarantee the existence of strong equilibrium. Together, our work introduces a natural concept, which turns out to lead to positive and applicable results in one of the basic domains studied in the literature.

  20. Adsorption of a cationic surfactant by a magsorbent based on magnetic alginate beads.

    PubMed

    Obeid, Layaly; El Kolli, Nadia; Dali, Noëlle; Talbot, Delphine; Abramson, Sébastien; Welschbillig, Mathias; Cabuil, Valérie; Bée, Agnès

    2014-10-15

    Adsorption of cetylpyridinium chloride (CPC), a cationic surfactant, by magnetic alginate beads (MagAlgbeads) was investigated. The magnetic adsorbent (called magsorbent) was prepared by encapsulation of magnetic functionalized nanoparticles in an alginate gel. The influence on CPC adsorption of several parameters such as contact time, pH and initial surfactant concentration was studied. The equilibrium isotherm shows that adsorption occurs through both electrostatic interactions with charge neutralization of the carboxylate groups of the beads and hydrophobic interactions inducing the formation of surfactant aggregates in the beads. The dosage of calcium ions released in the solution turns out to be a useful tool for understanding the adsorption mechanisms. Adsorption is accompanied by a shrinking of the beads that corresponds to a 45% reduction of the volume. Adsorption kinetic experiments show that equilibrium time is strongly dependent on the surfactant concentration, which monitors the nature of the interactions. On the other hand, since the pH affects the ionization state of adsorption sites, adsorption depends on the pH solution, maximum adsorption being obtained in a large pH range (3.2-12) in agreement with the pKa value of alginate (pKa=3.4-4.2). Finally, due to the formation of micelle-like surfactants aggregates in the magnetic alginate beads, they could be used as a new efficient magsorbent for hydrophobic pollutants.

  1. Adsorption of carbon dioxide, methane and nitrogen on an ultramicroporous copper metal-organic framework.

    PubMed

    Wu, Xiaofei; Yuan, Bin; Bao, Zongbi; Deng, Shuguang

    2014-09-15

    An ultramicroporous copper metal-organic framework (Cu-MOF), Cu(hfipbb)(H2hfipbb)0.5 [H2hfipbb=4,4'-(hexafluoro-isopropylidene) bis(benzoic acid)] was successfully synthesized by a microwave-assisted method (1) with a shorter reaction time and higher MOFs yield. The obtained Cu-MOF sample was characterized with scanning electron microscopy for crystal structure, powder X-ray diffraction for phase structure, and carbon dioxide adsorption at 273 K for pore textural properties. Single-component adsorption (adsorption equilibrium and kinetics) of CO2, CH4, and N2 on 1 was measured using a Micromeritics ASAP 2020 adsorption porosimeter at 278, 298 and 318 K, and pressures up to 1 bar. Isosteric heats of adsorption, Henry's constants, and diffusion time constants were calculated and carefully analyzed. Adsorption equilibrium selectivity (α), adsorbent selection parameter for pressure swing adsorption processes (S), kinetic selectivity and combined separation selectivity (β) for CO2/CH4, CO2/N2 and CH4/N2 binary mixtures were estimated based on the single-component adsorption data. The relative high values of the adsorption selectivities suggest that Cu-MOF is a promising adsorbent for separating CO2/CH4, CO2/N2 and CH4/N2 gas pairs.

  2. Adsorption character for removal Cu(II) by magnetic Cu(II) ion imprinted composite adsorbent.

    PubMed

    Ren, Yueming; Wei, Xizhu; Zhang, Milin

    2008-10-01

    A novel magnetic Cu(II) ion imprinted composite adsorbent (Cu(II)-MICA) was synthesized, characterized and applied for the selective removal Cu(II) from aqueous solution in the batch system. The adsorption-desorption and selectivity characteristics were investigated. The maximum adsorption occurred at pH 5-6. The equilibrium time was 6.0h, and a pseudo-second-order model could best describe adsorption kinetics. The adsorption equilibrium data fit Langmuir isotherm equation well with a maximum adsorption capacity of 46.25mg/g and Langmuir adsorption equilibrium constant of 0.0956L/mg at 298K. Thermodynamic parameters analysis predicted an exothermic nature of adsorption and a spontaneous and favourable process that could be mainly governed by physisorption mechanism. The relative selectivity coefficients of Cu(II)-MICA for Cu(II)/Zn(II) and Cu(II)/Ni(II) were 2.31, 2.66 times greater than the magnetic non-imprinted composite adsorbent (MNICA). Results suggested that Cu(II)-MICA was a material of efficient, low-cost, convenient separation under magnetic field and could be reused five times with about 14% regeneration loss.

  3. Adsorptive Removal and Adsorption Kinetics of Fluoroquinolone by Nano-Hydroxyapatite.

    PubMed

    Chen, Yajun; Lan, Tao; Duan, Lunchao; Wang, Fenghe; Zhao, Bin; Zhang, Shengtian; Wei, Wei

    2015-01-01

    Various kinds of antibiotics, especially fluoroquinolone antibiotics (FQs) have been widely used for the therapy of infectious diseases in human and livestock. For their poorly absorbed by living organisms, large-scale misuse or abuse of FQs will foster drug resistance among pathogenic bacteria, as well as a variety of environmental problems when they were released in the environment. In this work, the adsorption properties of two FQs, namely norfloxacin (NOR) and ciprofloxacin (CIP), by nano-hydroxyapatite (n-HAP) were studied by batch adsorption experiments. The adsorption curves of FQs by n-HAP were simulated by Langmuir and Freundlich isotherms. The results shown that NOR and CIP can be adsorbed effectively by the adsorbent of n-HAP, and the adsorption capacity of FQs increase with increasing dosage of n-HAP. The optimum dosage of n-HAP for FQs removal was 20 g · L(-1), in which the removal efficiencies is 51.6% and 47.3%, and an adsorption equilibrium time is 20 min. The maximum removal efficiency occurred when pH is 6 for both FQs. The adsorption isotherm of FQs fits well for both Langmuir and Freundlich equations. The adsorption of both FQs by n-HAP follows second-order kinetics.

  4. Adsorptive Removal and Adsorption Kinetics of Fluoroquinolone by Nano-Hydroxyapatite

    PubMed Central

    Chen, Yajun; Lan, Tao; Duan, Lunchao; Wang, Fenghe; Zhao, Bin; Zhang, Shengtian; Wei, Wei

    2015-01-01

    Various kinds of antibiotics, especially fluoroquinolone antibiotics (FQs) have been widely used for the therapy of infectious diseases in human and livestock. For their poorly absorbed by living organisms, large-scale misuse or abuse of FQs will foster drug resistance among pathogenic bacteria, as well as a variety of environmental problems when they were released in the environment. In this work, the adsorption properties of two FQs, namely norfloxacin (NOR) and ciprofloxacin (CIP), by nano-hydroxyapatite (n-HAP) were studied by batch adsorption experiments. The adsorption curves of FQs by n-HAP were simulated by Langmuir and Freundlich isotherms. The results shown that NOR and CIP can be adsorbed effectively by the adsorbent of n-HAP, and the adsorption capacity of FQs increase with increasing dosage of n-HAP. The optimum dosage of n-HAP for FQs removal was 20 g·L-1, in which the removal efficiencies is 51.6% and 47.3%, and an adsorption equilibrium time is 20 min. The maximum removal efficiency occurred when pH is 6 for both FQs. The adsorption isotherm of FQs fits well for both Langmuir and Freundlich equations. The adsorption of both FQs by n-HAP follows second-order kinetics. PMID:26698573

  5. Adsorption of globular proteins on locally planar surfaces. II. Models for the effect of multiple adsorbate conformations on adsorption equilibria and kinetics.

    PubMed Central

    Minton, A P

    1999-01-01

    Equilibrium and kinetic models for nonspecific adsorption of proteins to planar surfaces are presented. These models allow for the possibility of multiple interconvertible surface conformations of adsorbed protein. Steric repulsion resulting in area exclusion by adsorbed molecules is taken into account by treating the adsorbate as a thermodynamically nonideal two-dimensional fluid. In the equilibrium model, the possibility of attractive interactions between adsorbed molecules is taken into account in a limited fashion by permitting one of the adsorbed species to self-associate. Calculated equilibrium adsorption isotherms exhibit apparent high-affinity and low-affinity binding regions, corresponding respectively to adsorption of ligand at low fractional area occupancy in an energetically favorable side-on conformation and conversion at higher fractional area occupancy of the side-on conformation to an entropically favored end-on conformation. Adsorbate self-association may lead to considerable steepening of the adsorption isotherm, compensating to a variable extent for the broadening effect of steric repulsion. Kinetic calculations suggest that in the absence of attractive interactions between adsorbate molecules, the process of adsorption may be highly "stretched" along the time axis, rendering the attainment of adsorption equilibrium in the context of conventional experiments problematic. PMID:9876132

  6. Uranium removal from aqueous solution by coir pith: equilibrium and kinetic studies.

    PubMed

    Parab, Harshala; Joshi, Shreeram; Shenoy, Niyoti; Verma, Rakesh; Lali, Arvind; Sudersanan, M

    2005-07-01

    Basic aspects of uranium adsorption by coir pith have been investigated by batch equilibration. The influence of different experimental parameters such as final solution pH, adsorbent dosage, sorption time, temperature and various concentrations of uranium on uptake were evaluated. Maximum uranium adsorption was observed in the pH range 4.0-6.0. The Freundlich and Langmuir adsorption models were used for the mathematical description of the adsorption equilibrium. The equilibrium data fitted well to both the equilibrium models in the studied concentration range of uranium (200-800 mg/l) and temperatures (305-336 K). The coir pith exhibited the highest uptake capacity for uranium at 317 K, at the final solution pH value of 4.3 and at the initial uranium concentration of 800 mg/l. The kinetics of the adsorption process followed a second-order adsorption. The adsorbent used proved to be suitable for removal of uranium from aqueous solutions. 0.2 N HCl was effective in uranium desorption. The results indicated that the naturally abundant coir pith of otherwise nuisance value exhibited considerable potential for application in removal of uranium from aqueous solution.

  7. Influence of time to achieve substrate distribution equilibrium between brain tissue and blood on quantitation of the blood-brain barrier P-glycoprotein effect.

    PubMed

    Padowski, Jeannie M; Pollack, Gary M

    2011-12-02

    Active efflux transport processes at the blood-brain barrier (BBB), such as P-glycoprotein (P-gp)-mediated efflux, can limit brain uptake of therapeutics. Accurate determination of the consequent impact on brain uptake is assumed to require sampling post-attainment of brain-to-blood distribution equilibrium. Because this approach is not always feasible, understanding the relationship between apparent degree of efflux (e.g., calculated BBB P-gp effect) and the fraction of time remaining until distribution equilibrium is achieved (FTDE) would be advantageous. This study employed simulation strategies to explore this relationship in the simplest relevant system (absence of protein binding, saturable uptake, or metabolism at the BBB). Concentration-time profiles were simulated with a 4-compartment system (blood, peripheral tissues, BBB endothelium and brain parenchyma). A unidirectional endothelium-to-blood rate constant, PS(e), represented P-gp-mediated efflux. A parameter space was selected to simulate an 18-fold P-gp effect, (K(p,brain) at distribution equilibrium in the absence [K(p,brain)=82] vs. presence [K(p,brain)=4.5] of P-gp-mediated flux), as observed for paclitaxel in P-gp-deficient vs. P-gp-competent mice. Hypothetical compounds with different P-gp effects, peripheral compartment distribution kinetics, or times to achieve distribution equilibrium were simulated by perturbing the values of relevant model parameters. P-gp effects calculated prior to attainment of distribution equilibrium may be substantially erroneous. However, reasonably accurate estimates can be obtained relatively early in the net distributional phase (under 20% error at FTDE>0.36 or 0.11 for bolus or infusion administration, respectively). Potential errors associated with non-equilibrium calculations are dependent on both P-gp-mediated and P-gp-independent components of flux across the BBB.

  8. Investigation kinetics mechanisms of adsorption malachite green onto activated carbon.

    PubMed

    Onal, Y; Akmil-Başar, C; Sarici-Ozdemir, C

    2007-07-19

    Lignite was used to prepare activated carbon (T3K618) by chemical activation with KOH. Pore properties of the activated carbon such as BET surface area, pore volume, pore size distribution, and pore diameter were characterized by t-plot based on N2 adsorption isotherm. BET surface area of activated carbon is determined as 1000 m2/g. Adsorption capacity of malachite green (MG) onto T3K618 activated carbon was investigated in a batch system by considering the effects of various parameters like initial concentration (100, 150 and 200 mg/L) and temperature (25, 40 and 50 degrees C). The adsorption process was relatively fast and equilibrium was reached after about 20 min for 100, 150 mg/L at all adsorption temperature. Equilibrium time for 200 mg/L was determined as 20 min and 40 min at 298, 313 and 323 K, respectively. Simple mass and kinetic models were applied to the experimental data to examine the mechanisms of adsorption and potential rate controlling steps such as external mass transfer, intraparticle diffusion. Pseudo second-order model was found to explain the kinetics of MG adsorption most effectively. It was found that both mass transfer and pore diffusion are important in determining the adsorption rates. The intraparticle diffusion rate constant, external mass transfer coefficient, film and pore diffusion coefficient at various temperatures were evaluated. The activation energy (Ea) was determined as 48.56, 63.16, 67.93 kJ/mol for 100, 150, 200 mg/L, respectively. The Langmiur and Freundlich isotherm were used to describe the adsorption equilibrium studies at different temperatures. Langmiur isotherm shows better fit than Freundlich isotherm in the temperature range studied. The thermodynamic parameters, such as DeltaG degrees, DeltaS and DeltaH degrees were calculated. The thermodynamics of dyes-T3K618 system indicates endothermic process.

  9. Off-equilibrium scaling behaviors driven by time-dependent external fields in three-dimensional O(N) vector models.

    PubMed

    Pelissetto, Andrea; Vicari, Ettore

    2016-03-01

    We consider the dynamical off-equilibrium behavior of the three-dimensional O(N) vector model in the presence of a slowly varying time-dependent spatially uniform magnetic field H(t)=h(t)e, where e is an N-dimensional constant unit vector, h(t)=t/t(s), and t(s) is a time scale, at fixed temperature T≤T(c), where T(c) corresponds to the continuous order-disorder transition. The dynamic evolutions start from equilibrium configurations at h(i)<0, correspondingly t(i)<0, and end at time t(f)>0 with h(t(f))>0, or vice versa. We show that the magnetization displays an off-equilibrium scaling behavior close to the transition line H(t)=0. It arises from the interplay among the time t, the time scale t(s), and the finite size L. The scaling behavior can be parametrized in terms of the scaling variables t(s)(κ)/L and t/t(s)(κ(t)), where κ>0 and κ(t)>0 are appropriate universal exponents, which differ at the critical point and for Tequilibrium scaling behaviors at and below T(c). We also discuss hysteresis phenomena in round-trip protocols for the time dependence of the external field. We define a scaling function for the hysteresis loop area of the magnetization that can be used to quantify how far the system is from equilibrium.

  10. Adsorption characteristics of brilliant green dye on kaolin.

    PubMed

    Nandi, B K; Goswami, A; Purkait, M K

    2009-01-15

    Experimental investigations were carried out to adsorb toxic brilliant green dye from aqueous medium using kaolin as an adsorbent. Characterization of kaolin is done by measuring: (i) particle size distribution using particle size analyzer, (ii) BET surface area using BET surface analyzer, and (iii) structural analysis using X-ray diffractometer. The effects of initial dye concentration, contact time, kaolin dose, stirring speed, pH and temperature were studied for the adsorption of brilliant green in batch mode. Adsorption experiments indicate that the extent of adsorption is strongly dependent on pH of solution. Free energy of adsorption (DeltaG0), enthalpy (DeltaH0) and entropy (DeltaS0) changes are calculated to know the nature of adsorption. The calculated values of DeltaG0 at 299K and 323K indicate that the adsorption process is spontaneous. The estimated values of DeltaH0 and DeltaS0 both show the negative sign, which indicate that the adsorption process is exothermic and the dye molecules are organized on the kaolin surface in less randomly fashion than in solution. The adsorption kinetic has been described by first-order, pseudo-second-order and intra-particle-diffusion models. It was observed that the rate of dye adsorption follows pseudo-second-order model for the dye concentration range studied in the present case. Standard adsorption isotherms were used to fit the experimental equilibrium data. It was found that the adsorption of brilliant green on kaolin follows the Langmuir adsorption isotherm.

  11. Adsorption study of Ammonia Nitrogen by watermelon rind

    NASA Astrophysics Data System (ADS)

    Ibrahim, A.; Yusof, L.; Beddu, N. S.; Galasin, N.; Lee, P. Y.; Lee, R. N. S.; Zahrim, A. Y.

    2016-06-01

    The utilization of fruit waste for low-cost adsorbents as a replacement for costly conventional methods of removing ammonia nitrogen from wastewater has been reviewed. The adsorption studies were conducted as a function of contact time and adsorbent dosage and it were carried out on four different adsorbents; fresh watermelon rind and modified watermelon rind with sodium hydroxide (NaOH), potassium hydroxide (KOH) and sulphuric acid (H2SO4). Adsorbents were tested for characterization by using zeta potential test and all samples shows negative values thus makes it favourable for the adsorption process. The batch experimental result showed that adsorption process is rapid and equilibrium was established within 40 minutes of contact time. The ammonia nitrogen removal rate amounted in range of 96% to 99%, and the adsorption capacities were in range of 1.21 to 1.24 mg/g for all four different types of adsorbents used.

  12. Kinetics of Remazol Black B adsorption onto carbon prepared from sugar beet pulp.

    PubMed

    Dursun, Arzu Y; Tepe, Ozlem; Uslu, Gülşad; Dursun, Gülbeyi; Saatci, Yusuf

    2013-04-01

    Dried sugar beet pulp, an agricultural solid waste, was used for the production of carbon. Carbonised beet pulp was tested in the adsorption of Remazol Black B dye, and adsorption studies with real textile wastewater were also performed. Batch kinetic studies showed that an equilibrium time of 180 min was needed for the adsorption. The maximum dye adsorption capacity was obtained as 80.0 mg g(-1) at the temperature of 25 °C at pH = 1.0. The Langmuir and Freundlich adsorption models were used for the mathematical description of the adsorption equilibrium, and it was reported that experimental data fitted very well to the Langmuir model. Mass transfer and kinetic models were applied to the experimental data to examine the mechanisms of adsorption and potential rate-controlling steps. It was found that both external mass transfer and intraparticle diffusion played an important role in the adsorption mechanisms of dye, and adsorption kinetics followed the pseudo-second-order type kinetic model. The thermodynamic analysis indicated that the sorption process was exothermic and spontaneous in nature.

  13. [Study on treatment of methylene blue wastewater by fly ash adsorption-Fenton and thermal regeneration].

    PubMed

    Bai, Yu-Jie; Zhang, Ai-Li; Zhou, Ji-Ti

    2012-07-01

    The physicochemical properties of water-washed fly ash (FA) and acid modified fly ash (M-FA) were investigated. The adsorption of methylene blue by FA and M-FA were studied by batch experiments. Two methods, Fenton-drive oxidation regeneration and thermal regeneration, were used for regeneration of the used FA and M-FA. The result showed that the rate of adsorption process followed the second order kinetics and the adsorption followed Langmuir isotherms. The adsorption equilibrium time was 30 min, and the equilibrium adsorption capacity of FA and M-FA were 4.22 mg x g(-1) and 5.98 mg x g(-1) respectively. The adsorption capability of M-FA was higher than that of FA. In the range of pH 2-12, the adsorption capacity of M-FA increased with the increase of pH, whereas the adsorption capacity of FA decreased slowly until the pH 8 and then increased. Electrostatic adsorption was the major factor on the adsorption capacity. Around 61% and 55% percentage regeneration (PR) were obtained for FA and M-FA respectively when 78.4 mmol x L(-1) H2O2 and 0.72 mmol x L(-1) Fe2+ were used. When the condition of thermal regeneration was 400 degrees C and 2 h, a positive correlation can be found between the PRs of FA and regeneration times, the PRs were 102%, 104% and 107% in three cycles of adsorption-thermal regeneration process. However a negative correlation can be found between the PRs of M-FA and regeneration times, the PRs were 82%, 75% and 74% in three cycles of adsorption-thermal regeneration process. The PR of FA was higher than that of M-FA, and thermal regeneration was superior to Fenton-drive regeneration.

  14. [Influence of reaction time of urea hydrolysis-based co-precipitation on the structure of ZnAl layered double hydroxides and the phosphate adsorption].

    PubMed

    Lu, Ying; Cheng, Xiang; Xing, Bo; Sun, Zhong-en; Sun, De-zhi

    2012-08-01

    A series of ZnAl layered double hydroxides (LDHs) were prepared by urea hydrolysis-based homogeneous co-precipitation for studying their structure and phosphate adsorption capacities. The results show that all the samples exhibited a typical layered structure as the reaction time extended from 12 h to 96 h, whereas Zn/Al molar ratio in the ZnAls decreased from 2.06 to 0.70 and the specific surface area markedly increased to be 7.6-fold higher than that of ZnAl-12. Phosphate adsorption capacity of the ZnAl was in general increased gradually with the reaction time extension, which can be attributed to the surface area rising as well as the increased positive charge of LDHs layer caused by a higher proportion of Al. This reveals that physicochemical adsorption on LDHs surface would have played an important role during the phosphate adsorption. With a reaction time of 24 h, a high amount of exchangeable interlayer anions was observed, giving rise to a highest phosphate uptake of 34.1 mg x g(-1) by the ZnAl-24. It indicates the ion exchange was another major pathway for the phosphate removal. For all the ZnAls with different reaction times, the phosphate adsorption isotherms fit well with Langmuir-type equations; the adsorption kinetics followed pseudo-second-order models.

  15. Adsorption modeling for macroscopic contaminant dispersal analysis

    SciTech Connect

    Axley, J.W.

    1990-05-01

    Two families of macroscopic adsorption models are formulated, based on fundamental principles of adsorption science and technology, that may be used for macroscopic (such as whole-building) contaminant dispersal analysis. The first family of adsorption models - the Equilibrium Adsorption (EA) Models - are based upon the simple requirement of equilibrium between adsorbent and room air. The second family - the Boundary Layer Diffusion Controlled Adsorption (BLDC) Models - add to the equilibrium requirement a boundary layer model for diffusion of the adsorbate from the room air to the adsorbent surface. Two members of each of these families are explicitly discussed, one based on the linear adsorption isotherm model and the other on the Langmuir model. The linear variants of each family are applied to model the adsorption dynamics of formaldehyde in gypsum wall board and compared to measured data.

  16. Adsorption of congo red by chitosan hydrogel beads impregnated with carbon nanotubes.

    PubMed

    Chatterjee, Sudipta; Lee, Min W; Woo, Seung H

    2010-03-01

    The adsorption performance of chitosan (CS) hydrogel beads was investigated after multiwalled carbon nanotubes (MWCNTs) impregnation for the removal of congo red (CR) as an anionic dye. The study of the adsorption capacity of CS/CNT beads as a function of the CNT concentration indicated that 0.01% CNT impregnation was the most useful for enhancing the adsorption capacity. The sulfur (%) in the CS/CNT beads measured by energy dispersive X-ray (EDX) was 2.5 times higher than that of normal CS beads after CR adsorption. Equilibrium adsorption isotherm data of the CS/CNT beads exhibited better fit to the Langmuir isotherm model than to the Freundlich isotherm model, and the heterogeneity factor (n) value of the CS/CNT beads calculated from the Sips isotherm model was close to unity (0.98). The maximum adsorption capacity of CS/CNT beads obtained from the Langmuir model was 450.4 mg g(-1).

  17. Adsorption characteristics and behaviors of graphene oxide for Zn(II) removal from aqueous solution

    NASA Astrophysics Data System (ADS)

    Wang, Hou; Yuan, Xingzhong; Wu, Yan; Huang, Huajun; Zeng, Guangming; Liu, Yan; Wang, Xueli; Lin, Ningbo; Qi, Yu

    2013-08-01

    In this study, graphene oxide (GO) was synthesized via modified Hummers’ method, and characterized by scanning electron microscopy (SEM), atomic force microscope (AFM), X-ray diffraction (XRD), and Fourier transform infrared spectrum (FT-IR), X-ray photoelectron spectroscopy (XPS). The adsorption of Zn(II) on GO as a function of pH, adsorbent dosage, foreign ions, contact time, and temperature was investigated using batch technique. Results showed that the suitable pH for Zn(II) removal was about 7.0, and the optimal dosage was 2 mg. The adsorption of Zn(II) onto GO increased sharply within 20 min and obtained equilibrium gradually. Meanwhile, foreign ion and temperature also affected the adsorption performance of GO. The adsorption process was found to be well described by the pseudo-second-order rate model. Equilibrium studies indicated that the data of Zn(II) adsorption followed the Langmuir model. The maximum adsorption capacity for Zn(II) was up to 246 mg/g with a Langmuir adsorption equilibrium constant of 5.7 L/g at 20 °C. The thermodynamic parameters calculated from temperature-dependent sorption isotherms suggested that Zn(II) sorption on GO was an exothermic and spontaneous process in nature. The possibility of Zn(II) recovery was investigated and the result revealed that the maximum Zn(II) recovery yield was achieved with hydrochloric acid.

  18. Adsorption of methyl tertiary butyl ether on granular zeolites: Batch and column studies.

    PubMed

    Abu-Lail, Laila; Bergendahl, John A; Thompson, Robert W

    2010-06-15

    Methyl tertiary butyl ether (MTBE) has been shown to be readily removed from water with powdered zeolites, but the passage of water through fixed-beds of very small powdered zeolites produces high friction losses not encountered in flow through larger sized granular materials. In this study, equilibrium and kinetic adsorption of MTBE onto granular zeolites, a coconut shell granular activated carbon (CS-1240), and a commercial carbon adsorbent (CCA) sample was evaluated. In addition, the effect of natural organic matter (NOM) on MTBE adsorption was evaluated. Batch adsorption experiments determined that ZSM-5 was the most effective granular zeolite for MTBE adsorption. Further equilibrium and kinetic experiments verified that granular ZSM-5 is superior to CS-1240 and CCA in removing MTBE from water. No competitive adsorption effects between NOM and MTBE were observed for adsorption to granular ZSM-5 or CS-1240, however there was competition between NOM and MTBE for adsorption onto the CCA granules. Fixed-bed adsorption experiments for longer run times were performed using granular ZSM-5. The bed depth service time model (BDST) was used to analyze the breakthrough data.

  19. Adsorption of Methyl Tertiary Butyl Ether on Granular Zeolites: Batch and Column Studies

    PubMed Central

    Abu-Lail, Laila; Bergendahl, John A.; Thompson, Robert W.

    2010-01-01

    Methyl tertiary butyl ether (MTBE) has been shown to be readily removed from water with powdered zeolites, but the passage of water through fixed beds of very small powdered zeolites produces high friction losses not encountered in flow through larger sized granular materials. In this study, equilibrium and kinetic adsorption of MTBE onto granular zeolites, a coconut shell granular activated carbon (CS-1240), and a commercial carbon adsorbent (CCA) sample was evaluated. In addition, the effect of natural organic matter (NOM) on MTBE adsorption was evaluated. Batch adsorption experiments determined that ZSM-5 was the most effective granular zeolite for MTBE adsorption. Further equilibrium and kinetic experiments verified that granular ZSM-5 is superior to CS-1240 and CCA in removing MTBE from water. No competitive-adsorption effects between NOM and MTBE were observed for adsorption to granular ZSM-5 or CS-1240, however there was competition between NOM and MTBE for adsorption onto the CCA granules. Fixed-bed adsorption experiments for longer run times were performed using granular ZSM-5. The bed depth service time model (BDST) was used to analyze the breakthrough data. PMID:20153106

  20. 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.

  1. Adsorption behavior of alpha -cypermethrin on cork and activated carbon.

    PubMed

    Domingues, Valentina F; Priolo, Giuseppe; Alves, Arminda C; Cabral, Miguel F; Delerue-Matos, Cristina

    2007-08-01

    Studies were undertaken to determine the adsorption behavior of alpha -cypermethrin [R)-alpha -cyano-3-phenoxybenzyl(1S)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate, and (S)-alpha-cyano-3-phenoxybenzyl (1R)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate] in solutions on granules of cork and activated carbon (GAC). The adsorption studies were carried out using a batch equilibrium technique. A gas chromatograph with an electron capture detector (GC-ECD) was used to analyze alpha -cypermethrin after solid phase extraction with C18 disks. Physical properties including real density, pore volume, surface area and pore diameter of cork were evaluated by mercury porosimetry. Characterization of cork particles showed variations thereby indicating the highly heterogeneous structure of the material. The average surface area of cork particles was lower than that of GAC. Kinetics adsorption studies allowed the determination of the equilibrium time - 24 hours for both cork (1-2 mm and 3-4 mm) and GAC. For the studied alpha -cypermethrin concentration range, GAC revealed to be a better sorbent. However, adsorption parameters for equilibrium concentrations, obtained through the Langmuir and Freundlich models, showed that granulated cork 1-2 mm have the maximum amount of adsorbed alpha-cypermethrin (q(m)) (303 microg/g); followed by GAC (186 microg/g) and cork 3-4 mm (136 microg/g). The standard deviation (SD) values, demonstrate that Freundlich model better describes the alpha -cypermethrin adsorption phenomena on GAC, while alpha -cypermethrin adsorption on cork (1-2 mm and 3-4 mm) is better described by the Langmuir. In view of the adsorption results obtained in this study it appears that granulated cork may be a better and a cheaper alternative to GAC for removing alpha -cypermethrin from water.

  2. [Modification of natural siderite and enhanced adsorption of arsenic].

    PubMed

    Zhao, Kai; Guo, Hua-Ming; Li, Yuan; Ren, Yan

    2012-02-01

    Groundwater with high arsenic concentration has widely been found in China. More attention has been paid to economic and efficient arsenic removal technology. Natural siderite, which was abundant and relatively cheap, was used as the main raw material for arsenic adsorption by batch methods. Modified conditions of natural siderite, including temperature and time of calcination and adhesive addition, were carried out for arsenic removal. Results showed that the maximum removal efficiency was reached with the calcination temperature of 350 degrees C for 90 minutes and an adhesive dosage of 10 mg x g(-1). With the ratio of solid to liquid of 0.5 g: 50 mL and the initial concentration of 5 mg x L(-1) for either As(III) or As(V) at 25 degrees C, arsenic concentrations at equilibrium time were lower than 10 microg x L(-1). Characteristics of adsorption kinetics and adsorption isotherm on the optimal modified adsorbent were also evaluated. It was found that the arsenic adsorption kinetics fitted pseudo-second order kinetics equation, and the adsorption achieved equilibrium at about 12 h. The adsorption isotherm could be well described by Langmuir and Freundlich models. The maximum adsorption capacity was 1039 microg x g(-1) for As(III) and 1 026 microg x g(-1) for As(V). Furthermore, X-ray diffraction (XRD), scanning electron microscopy (SEM), and BET method were used to investigate main mechanisms of arsenic removal. Results showed that modified adsorbent had higher specific surface area and contained the spherical coating of Fe(II) and Fe(III) on the surface, in comparison with pristine material, which were believed to contribute to the high adsorption capacity of the modified material. The modified natural siderite appears to be a promising adsorbent that is worthy of further studies and practical application for arsenic removal.

  3. Interactions of nanoparticles with proteins: determination of equilibrium constants.

    PubMed

    Treuel, Lennart; Malissek, Marcelina

    2013-01-01

    The behavior of nanoparticles towards proteins is an important aspect across wide areas of nanotoxicology and nanomedicine. In this chapter, we describe a procedure to study the adsorption of proteins onto nanoparticle surfaces. Circular dichroism (CD) spectroscopy is utilized to quantify the amount of free protein in a solution, and the experimental information is evaluated to derive equilibrium constants for the protein adsorption/desorption equilibrium. These equilibrium constants are comparable parameters in describing the interactions between proteins and nanoparticles.

  4. Adsorption of phenanthrene on natural snow.

    PubMed

    Domine, Florent; Cincinelli, Alessandra; Bonnaud, Elodie; Martellini, Tania; Picaud, Sylvain

    2007-09-01

    The snowpack is a reservoir for semivolatile organic compounds (SVOCs) and, in particular, for persistent organic pollutants (POPs), which are sequestered in winter and released to the atmosphere or hydrosphere in the spring. Modeling these processes usually assumes that SVOCs are incorporated into the snowpack by adsorption to snow surfaces, but this has never been proven because the specific surface area (SSA) of snow has never been measured together with snow composition. Here we expose natural snow to phenanthrene vapors (one of the more volatile POPs) and measure for the first time both the SSA and the chemical composition of the snow. The results are consistent with an adsorption equilibrium. The measured Henry's law constant is H(Phen)(T) = 2.88 x 10(22) exp(-10660/7) Pa m2 mol(-1), with Tin Kelvin. The adsorption enthalpy is delta H(ads) = -89 +/- 18 kJ mol(-1). We also perform molecular dynamics calculations of phenanthrene adsorption to ice and obtain AHads = -85 +/- 8 kJ mol(-1), close to the experimental value. Results are applied to the adsorption of phenanthrene to the Arctic and subarctic snowpacks. The subarctic snowpack, with a low snow area index (SAI = 1000), is a negligible reservoir of phenanthrene, butthe colder Arctic snowpack, with SAI = 2500, sequesters most of the phenanthrene present in the (snow + boundary layer) system.

  5. Kinetic and thermodynamic studies of sulforaphane adsorption on macroporous resin.

    PubMed

    Yuanfeng, Wu; Lei, Zhang; Jianwei, Mao; Shiwang, Liu; Jun, Huang; Yuru, You; Lehe, Mei

    2016-08-15

    The adsorption equilibrium, kinetic and thermodynamic of sulforaphane (SF) adsorption onto macroporous resin in aqueous phase were studied. The SP850 resin was screened as the appropriate resin for SF purification. From the equilibrium studies, the Redlich-Peterson model was found to be the best for description of the adsorption behavior of SF onto SP850 resin, followed by the Freundlich model and the Langmuir model. Batch equilibrium experiments demonstrated that, in the examined temperature range, the equilibrium adsorption capacity of SP850 resin decreased with increasing adsorption temperature. Thermodynamics studies indicated that the adsorption of SF was a physical, exothermic, and spontaneous process. The adsorption kinetics revealed that the pseudo-second-order kinetic model was suitable to characterize the kinetics of adsorption of SF onto SP850. Finally, the intra-particle diffusion model demonstrated that SF diffused quickly into macropores, and that diffusion slowed down in the meso- and micropores.

  6. Time of flight-secondary ion mass spectrometry analysis of protein adsorption on a polyvinylidene difluoride surface modified by ion irradiation.

    PubMed

    Okuji, Shigeto; Kitazawa, Hideaki; Takeda, Yoshihiko

    2016-12-01

    We investigated the effects of nanoscopic surface modification of polyvinylidene difluoride (PVDF) and low-density polyethylene (LDPE) by plasma-based ion implantation on protein adsorption with time of flight-secondary ion mass spectrometry (ToF-SIMS) analysis. The chemical composition of the LDPE and PVDF surfaces was changed by ion irradiation. In particular, irradiation substantially decreased the number of CH and CF bonds on the PVDF surface, but only slightly decreased that of CH bonds for LDPE. These decreases may reflect a higher hydrogen recombination rate of the LDPE than the PVDF surface. An increase in oxygen was observed on both the LDPE and PVDF surfaces following ion irradiation, but was saturated after irradiation of 1×10(15)cm(-2) on the PVDF surface. The hydrophilicity of the ion-irradiated LDPE surface was promoted with an increase of the total ion fluence. Ion irradiation also changed the surface properties of PVDF to become more hydrophilic, but the variation did not correlate with the total ion fluence presumably due to the presence of fluorine atoms and the saturation of oxidation. Both bovine serum albumin (BSA) and collagen adsorption were suppressed on the LDPE surface by ion irradiation, which may have resulted from a decrease of the hydrophobic interaction. By contrast, ion irradiation increased protein adsorption on the PVDF surface, and BSA was adsorbed more than collagen, whereas there was no difference in the adsorption between BSA and collagen on the ion-irradiated LDPE surface. Moreover, the adsorption of BSA decreased on the oxygen- and fluorine-rich PVDF surface. These results indicate that the nanoscopic composition changes on the PVDF surface affect the adsorption behavior of BSA. Specifically, ferroelectric property on the PVDF surface was changed by ion irradiation and the nanoscopic change in polarity presumably affected the protein adsorption. Our findings suggest that selective adsorption control of protein can be

  7. 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.

  8. Removal of Pb(II) by adsorption onto Chinese walnut shell activated carbon.

    PubMed

    Yi, Zheng-ji; Yao, Jun; Kuang, Yun-fei; Chen, Hui-lun; Wang, Fei; Yuan, Zhi-min

    2015-01-01

    The excessive discharge of Pb(II) into the environment has increasingly aroused great concern. Adsorption is considered as the most effective method for heavy metal removal. Chinese walnut shell activated carbon (CWSAC) was used as an adsorbent for the removal of Pb(II) from aqueous solution. Batch experiments were conducted by varying contact time, temperature, pH, adsorbent dose and initial Pb(II) concentration. Adsorption equilibrium was established within 150 min. Although temperature effect was insignificant, the Pb(II) adsorption was strongly pH dependent and the maximum removal was observed at pH 5.5. The Pb(II) removal efficiency increased with increasing CWSAC dosage up to 2.0 g/L and reached a maximum of 94.12%. Langmuir and Freundlich adsorption isotherms were employed to fit the adsorption data. The results suggested that the equilibrium data could be well described by the Langmuir isotherm model, with a maximum adsorption capacity of 81.96 mg/g. Adsorption kinetics data were fitted by pseudo-first- and pseudo-second-order models. The result indicated that the pseudo-first-order model best describes the adsorption kinetic data. In summary, CWSAC could be a promising material for the removal of Pb(II) from wastewater.

  9. Selective and effective adsorption of methyl blue by barium phosphate nano-flake.

    PubMed

    Zhang, Fan; Zhao, Zongshan; Tan, Ruiqin; Guo, Yanqun; Cao, Lujie; Chen, Liang; Li, Jia; Xu, Wei; Yang, Ye; Song, Weijie

    2012-11-15

    We report the synthesis of barium phosphate (BP) nano-flake and its adsorption behavior to methyl blue (MB) in aqueous solution. The as-obtained BP nano-flake revealed pure rhombohedral crystal structure. The adsorption capacity of MB onto BP reached 1500 mg g(-1). The adsorption equilibrium results fitted well with the Freundlich isotherm model. The adsorption process took less than 30 min to reach equilibrium. The adsorption kinetics was elucidated by the pseudo-second-order kinetic equation. It followed 2-stage and 3-stage intra-particle diffusion models for the low and high concentration of dye solutions, respectively. The adsorption of MB using the BP nano-flake was highly selective, compared with the adsorption of other dyes. The interactions between MB and BP were mainly the ionic interaction and hydrogen bonds, which were confirmed by the X-ray photoelectron spectroscopic results and the density functional theory calculations. The BP nano-flake revealed less than 5% decrease in adsorption amount when it was recycled and reused five times. The present work shows that the BP nano-flake is promising for practical applications in MB removal from aqueous solutions.

  10. Phase transitions within the isolated polymer molecule: Coupling of the polymer threading a membrane transition to the helix-random coil, the collapse, the adsorption, and the equilibrium polymerization transitions

    NASA Astrophysics Data System (ADS)

    Di Marzio, Edmund A.; Kasianowicz, John J.

    2003-09-01

    The polymer threading a membrane transition (PTM), which is a first-order thermodynamic phase transition for an isolated linear polymer in the limit of infinite molecular weight, is coupled to the other four phase transitions of the isolated polymer molecule. They are (1) the helix-random coil (HR) phase transition which can be diffuse (polypeptides), second-order (DNA) or first-order (collagen) depending on the number of strands, (2) the collapse (C) transition which is usually second-order but can be first-order for polymeric solvents, (3) adsorption onto a surface (SA) which is second-order, (4) a model of equilibrium polymerization (P) which is first-order. In each case an exact expression for the partition function of the coupled pair is given as a one-dimensional summation over products of the individual partition functions corresponding to sides 1 and 2. Using a procedure analogous to evaluation of the grand canonical ensemble the summation can be performed and the character of the transition elucidated in the limit of infinite molecular weight. Given that the solutions on either side are sufficiently diverse there are 15 possible translocation pair couplings. They are PTM-PTM, HR-HR, C-C, SA-SA, P-P, PTM-HR, PTM-C, PTM-SA, PTM-P, HR-C, HR-SA, HR-P, C-SA, C-P, SA-P. The PTM-P coupling is most interesting because one can create polymer in the PTM side even though the P side is in the depolymerization regime. For HR-HR there are eight possible translocation modes. For example, as we raise the temperature we can have H1→H2→R1→R2 in obvious notation. These exact model solutions provide a thermodynamic base for the study of the kinetics of significant technological problems such as the translocation of DNA through pores imbedded in membranes. They also throw light on the nature of polymer-membrane-pore interactions in living cells and viruses.

  11. Real-time monitoring on the adsorption process of salicylic acid onto chitosan membrane using dielectric spectroscopy: macroscale concentration polarization and dynamics.

    PubMed

    Li, Yuhong; Gao, Weidong; Zhao, Kongshuang; Yang, Gang; Zhu, Zhonghe; Cui, Rongjing

    2013-03-28

    The adsorption process of salicylic acid (SA) onto chitosan membrane is monitored in real time by the dielectric relaxation spectroscopy (DRS) method. A unique dielectric relaxation, which is related to the macroscale concentration polarization layers (CPLs) in the SA solution caused by the adsorption, is observed. By modeling the measured systems composed of the membrane, the CPLs, and the SA solution, the dielectric spectra are analyzed systematically on the basis of the interfacial polarization theory. The parameters about the constituent phases, i.e., the dielectric constant εm and the conductivity κm of the chitosan membrane, the conductivity distribution (κ1 to κ2), and the thickness dCPL of the CPL, are obtained. The time-dependent εm and κm give insight into the microstate of the chitosan membrane during the adsorption. Furthermore, the time evolution of the conductivity gradient of the CPL, Δκ/dCPL, is combined to interpret the adsorption mechanism. It is suggested that the noninvasive dielectric monitoring may be applied to many adsorption and release processes.

  12. Quaternized dimethylaminoethyl methacrylate strong base anion exchange fibers for As(V) adsorption

    NASA Astrophysics Data System (ADS)

    Kavaklı, Cengiz; Akkaş Kavaklı, Pınar; Turan, Burcu Dila; Hamurcu, Aslı; Güven, Olgun

    2014-09-01

    N,N-Dimethylaminoethyl methacrylate (DMAEMA) grafted polyethylene/polypropylene (PE/PP) nonwoven fibers (DMAEMA-g-PE/PP) was prepared by radiation-induced graft polymerization. DMAEMA graft chains on nonwoven fibers were quaternized with dimethyl sulfate solution for the preparation of strong base anion exchange fibers (QDMAEMA-g-PE/PP). Fiber structures were characterized by FTIR, XPS and SEM techniques. The effect of solution pH, contact time, initial As(V) ion concentration and coexisting ions on the As(V) adsorption capacity of the QDMAEMA-g-PE/PP fibers were investigated by performing batch adsorption experiments. The adsorption of As(V) by QDMAEMA-g-PE/PP fibers was found to be independent on solution pH in the range 4.00-10.00. Kinetic experiments show that the As(V) adsorption rate was rapid and As(V) adsorption follows pseudo second-order kinetic model. As(V) adsorption equilibrium data were analyzed using Langmuir and Freundlich adsorption isotherm model equations. Langmuir and Freundlich adsorption isotherm models fitted the experimental data well. The maximum adsorption capacity (qmax) calculated from Langmuir isotherm was found to be 83.33 mg As(V)/g polymer at pH 7.00. The adsorbent was used for three cycles without significant loss of adsorption capacity. The adsorbed As(V) ions were desorbed effectively by a 0.1 M NaOH solution.

  13. AgII doped MIL-101 and its adsorption of iodine with high speed in solution

    NASA Astrophysics Data System (ADS)

    Mao, Ping; Qi, Bingbing; Liu, Ying; Zhao, Lei; Jiao, Yan; Zhang, Yi; Jiang, Zheng; Li, Qiang; Wang, Jinfeng; Chen, Shouwen; Yang, Yi

    2016-05-01

    In order to improve the adsorption speed of iodine from water, MIL-101 with extra-large specific surface area (3054 m2/g) was chosen as a base material, and then, Ag was doped into MIL-101 to enhance its adsorption capacity through an incipient-wetness impregnation method. With the characterization of SEM-EDS, TEM, XRD, XPS, TGA, IR, and BET techniques, the resulting Ag was identified to be stay in the framework of MIL-101 stably in the form of AgII (generally, AgII cation is not stable). However, after the adsorption of I- anions, AgII stay in the cages of MIL-101 in the form of AgI/AgI3. It is important to note that, all adsorbents show high adsorption speed of iodine in solution. The equilibrium adsorption time of the adsorbents were acquired by only a few minutes, which can be attributed to its large BET surface area. An interesting note is that, when the doping amount of Ag is less than 9%, the iodine anions adsorption capacity of Ag@MIL-101 is greater than its theoretical adsorption capacity. It shows that both physical adsorption and chemical adsorption are existed in the adsorption process. This study hopefully leads to a new and highly efficient Ag-based adsorbent for iodide adsorb from solutions.

  14. Adsorption characteristics of cellulase and β-glucosidase on Avicel, pretreated sugarcane bagasse, and lignin.

    PubMed

    Machado, Daniele Longo; Moreira Neto, João; da Cruz Pradella, José Geraldo; Bonomi, Antonio; Rabelo, Sarita Cândida; da Costa, Aline Carvalho

    2015-01-01

    Although adsorption is an essential step in the enzymatic hydrolysis of lignocellulosic materials, literature reports controversial results in relation to the adsorption of the cellulolitic enzymes on different biomasses/pretreatments, which makes difficult the description of this phenomenon in hydrolysis mathematical models. In this work, the adsorption of these enzymes on Avicel and sugarcane bagasse pretreated by the hydrothermal bagasse (HB) and organosolv bagasse (OB) methods was evaluated. The results have shown no significant adsorption of β-glucosidase on Avicel or HB. Increasing solids concentration from 5% (w/v) to 10% (w/v) had no impact on the adsorption of cellulase on the different biomasses if stirring rates were high enough (>100 rpm for Avicel and >150 rpm for HB and OB). Adsorption equilibrium time was low for Avicel (10 Min) when compared with the lignocellulosic materials (120 Min). Adsorption isotherms determined at 4 and 50 °C have shown that for Avicel there was a decrease in the maximum adsorption capacity (Emax) with the temperature increase, whereas for HB increasing temperature increased Emax . Also, Emax increased with the content of lignin in the material. Adsorption studies of cellulase on lignin left after enzymatic digestion of HB show lower but significant adsorption capacity (Emax = 11.92 ± 0.76 mg/g).

  15. Informational Equilibrium.

    DTIC Science & Technology

    1982-09-01

    that for variouis standard types of equilibria* they hold. In particular, if one uses the teaporary equilibrium framework one can use the standard ...T, the integral converges toward f’ia(da) f fU(b~dc)6(a,b,c)T( asdm ) A B C which is fR (da) f d(lib,c) U0 T (cab) A BxC Me converse Is obvious

  16. Removal of phenol and chlorophenols from water by coir pith carbon: equilibrium and rate studies.

    PubMed

    Namasivayam, C; Kavitha, D

    2004-07-01

    Batch mode studies were conducted to study the removal of phenol, 2,4,6-Trichlorophenol (TCP) and Pentachlorophenol (PCP) from aqueous solution on coir pith carbon by adsorption process under varying experimental conditions such as agitation time, adsorbent dose, pH and temperature. Kinetics of adsorption obeyed second order rate equation and the rate constant was found to be in the range 0.0098-0.0672, 0.0949-0.8801 and 0.172-0.305 g/mg/min for phenol, TCP and PCP respectively. Equilibrium adsorption data follow Langmuir isotherm for phenol and PCP and the adsorption capacities were found to be 48.3 mg and 3.7 mg/g, respectively. For TCP, adsorption followed Freundlich isotherm only. Acidic pH was favorable for the adsorption of all the chlorophenols. Studies on pH effect and desorption show that chemisorption seems to play a major rule in the adsorption process. The positive values of H0 24.99, 18.69, and 8.907 kJ/mol for phenol, TCP and PCP respectively, confirm the endothermic nature of adsorption.

  17. Coexistence and local μ-stability of multiple equilibrium points for memristive neural networks with nonmonotonic piecewise linear activation functions and unbounded time-varying delays.

    PubMed

    Nie, Xiaobing; Zheng, Wei Xing; Cao, Jinde

    2016-12-01

    In this paper, the coexistence and dynamical behaviors of multiple equilibrium points are discussed for a class of memristive neural networks (MNNs) with unbounded time-varying delays and nonmonotonic piecewise linear activation functions. By means of the fixed point theorem, nonsmooth analysis theory and rigorous mathematical analysis, it is proven that under some conditions, such n-neuron MNNs can have 5(n) equilibrium points located in ℜ(n), and 3(n) of them are locally μ-stable. As a direct application, some criteria are also obtained on the multiple exponential stability, multiple power stability, multiple log-stability and multiple log-log-stability. All these results reveal that the addressed neural networks with activation functions introduced in this paper can generate greater storage capacity than the ones with Mexican-hat-type activation function. Numerical simulations are presented to substantiate the theoretical results.

  18. Boronate affinity adsorption of RNA: possible role of conformational changes

    NASA Technical Reports Server (NTRS)

    Singh, N.; Willson, R. C.; Fox, G. E. (Principal Investigator)

    1999-01-01

    Batch equilibrium adsorption isotherm determination is used to characterize the adsorption of mixed yeast RNA on agarose-immobilized m-aminophenylboronic acid. It is shown that the affinity-enhancing influence of divalent cations depends strongly on the precise nature of the cation used, with barium being far more effective than the conventionally-used magnesium. This adsorption-promoting influence of barium is suggested to arise primarily from ionic influences on the structure and rigidity of the RNA molecule, as the adsorption of ribose-based small molecules is not similarly affected. The substitution of barium for the standard magnesium counterion does not greatly promote the adsorption of DNA, implying that the effect is specific to RNA and may be useful in boronate-based RNA separations. RNA adsorption isotherms exhibit sharp transitions as functions of temperature, and these transitions occur at different temperatures with Mg2+ and with Ba2+. Adsorption affinity and capacity were found to increase markedly at lower temperatures, suggestive of an enthalpically favored interaction process. The stoichiometric displacement parameter, Z, in Ba2+ buffer is three times the value in Mg2+ buffer, and is close to unity.

  19. Kinetics and isotherms of Neutral Red adsorption on peanut husk.

    PubMed

    Han, Runping; Han, Pan; Cai, Zhaohui; Zhao, Zhenhui; Tang, Mingsheng

    2008-01-01

    Adsorption of Neutral Red (NR) onto peanut husk in aqueous solutions was investigated at 295 K. Experiments were carried out as function of pH, adsorbent dosage, contact time, and initial concentration. The equilibrium adsorption data were analyzed by Langmuir, Freundlich, Temkin, Dubinin-Radushkevich, and Toth isotherm models. The results indicated that the Toth and Langmuir models provided the best correlation of the experimental data. The adsorption capacity of peanut husk for the removal of NR was determined with the Langmuir and found to be 37.5 mg/g at 295 K. The adsorption kinetic data were modeled using the pseudo-first order, pseudo-second order, and intra-particle diffusion kinetic equations. It was seen that the pseudo-first order and pseudo-second order kinetic equations could describe the adsorption kinetics. The intraparticle diffusion model was also used to express the adsorption process at the two-step stage. It was implied that peanut husk may be suitable as adsorbent material for adsorption of NR from aqueous solutions.

  20. Driving force behind adsorption-induced protein unfolding: a time-resolved X-ray reflectivity study on lysozyme adsorbed at an air/water interface.

    PubMed

    Yano, Yohko F; Uruga, Tomoya; Tanida, Hajime; Toyokawa, Hidenori; Terada, Yasuko; Takagaki, Masafumi; Yamada, Hironari

    2009-01-06

    Time-resolved X-ray reflectivity measurements for lysozyme (LSZ) adsorbed at an air/water interface were performed to study the mechanism of adsorption-induced protein unfolding. The time dependence of the density profile at the air/water interface revealed that the molecular conformation changed significantly during adsorption. Taking into account previous work using Fourier transform infrared (FTIR) spectroscopy, we propose that the LSZ molecules initially adsorbed on the air/water interface have a flat unfolded structure, forming antiparallel beta-sheets as a result of hydrophobic interactions with the gas phase. In contrast, as adsorption continues, a second layer forms in which the molecules have a very loose structure having random coils as a result of hydrophilic interactions with the hydrophilic groups that protrude from the first layer.

  1. Adsorption and isotopic fractionation of Xe

    NASA Technical Reports Server (NTRS)

    Bernatowicz, T. J.; Podosek, F. A.

    1986-01-01

    A theoretical description of the mechanisms of isotopic fractionation arising during adsorption of noble gases in a Henry's Law pressure regime is given. Experimental data on the isotopic composition of Xe adsorbed on activated charcoal in the temperature range 220 K to 350 K are presented. Both theoretical considerations and the experimental data indicate that equilibrium adsorption does not significantly alter the isotopic structure of adsorbed structure of adsorbed noble gases. Therefore, if adsorption is responsible for the elemental noble gas pattern in meteorites and the earth, the heavy noble gas isotopic fractionation between them must have been produced prior to and by a different process than equilibrium adsorption.

  2. Removal of Heavy Metals by Adsorption onto Activated Carbon Derived from Pine Cones of Pinus roxburghii.

    PubMed

    Saif, Muhammad Jawwad; Zia, Khalid Mahmood; Fazal-ur-Rehman; Usman, Muhammad; Hussain, Abdullah Ijaz; Chatha, Shahzad Ali Shahid

    2015-04-01

    Activated carbon derived from cones of Pinus roxburghii (Himalayan Pine) was used as an adsorbent for the removal of copper, nickel and chromium ions from waste water. Surface analysis was carried out to determine the specific surface area and pore size distribution of the pine cone derived activated carbon. Optimal parameters, effect of adsorbent quantity, pH, equilibrium time, agitation speed and temperature were studied. Equilibrium data were evaluated by Langmuir and Freundlich isotherm models. Langmuir isotherm afforded the best fit to the equilibrium data with a maximum adsorption capacity of 14.2, 31.4 and 29.6 mg/g for Cu(II), Ni(II) and Cr(VI) respectively. Maximum adsorption of Cu(II), Ni(II) was observed in the pH range 4.0 to 4.5, whereas the best adsorption of Cr(VI) was observed at pH 2.5. It was found that 180 minutes was sufficient to gain adsorption equilibrium. The adsorption process follows a pseudo-second-order kinetic model.

  3. Kinetics of faceting of crystals in growth, etching, and equilibrium

    NASA Astrophysics Data System (ADS)

    Vlachos, D. G.; Schmidt, L. D.; Aris, R.

    1993-03-01

    The faceting of crystals in equilibrium with the gas phase and also during crystal growth and etching conditions is studied using the Monte Carlo method. The dynamics of the transformation of unstable crystallographic orientations into hill and valley structures and the spatial patterns that develop are examined as functions of surface temperature, crystallographic orientation, and strength of interatomic potential for two transport processes: adsorption-desorption and surface diffusion. The results are compared with the continuum theory for facet formation. Thermodynamically unstable orientations break into hill and valley structures, and faceting exhibits three time regimes: disordering, facet nucleation, and coarsening of small facets to large facets. Faceting is accelerated as temperature increases, but thermal roughening can occur at high temperatures. Surface diffusion is the dominant mechanism at short times and small facets but adsorption-desorption becomes important at long times and large facets. Growth and etching promote faceting for conditions close to equilibrium but induce kinetic roughening for conditions far from equilibrium. Simultaneous irreversible growth and etching conditions with fast surface diffusion result in enhanced faceting.

  4. Preparation of activated carbon from corn cob and its adsorption behavior on Cr(VI) removal.

    PubMed

    Tang, Shuxiong; Chen, Yao; Xie, Ruzhen; Jiang, Wenju; Jiang, Yanxin

    2016-01-01

    Operation experiments were conducted to optimize the preparation of activated carbons from corn cob. The Cr(VI) adsorption capacity of the produced activated carbons was also evaluated. The impact of the adsorbent dosage, contact time, initial solution pH and temperature was studied. The results showed that the produced corn cob activated carbon had a good Cr(VI) adsorptive capacity; the theoretical maximum adsorption was 34.48 mg g(-1) at 298 K. The Brunauer-Emmett-Teller and iodine adsorption value of the produced activated carbon could be 924.9 m(2) g(-1) and 1,188 mg g(-1), respectively. Under the initial Cr(VI) concentration of 10 mg L(-1) and the original solution pH of 5.8, an adsorption equilibrium was reached after 4 h, and Cr(VI) removal rate was from 78.9 to 100% with an adsorbent's dosage increased from 0.5 to 0.7 g L(-1). The kinetics and equilibrium data agreed well with the pseudo-second-order kinetics model and the Langmuir isotherm model. The equilibrium adsorption capacity improved with the increment of the temperature.

  5. Adsorption of humic acid from aqueous solutions on crosslinked chitosan-epichlorohydrin beads: kinetics and isotherm studies.

    PubMed

    Wan Ngah, W S; Hanafiah, M A K M; Yong, S S

    2008-08-01

    The adsorption of humic acid on crosslinked chitosan-epichlorohydrin (chitosan-ECH) beads was investigated. Chitosan-ECH beads were characterized by Fourier transform infrared spectroscopy (FTIR), surface area and pore size analyses, and scanning electron microscopy (SEM). Batch adsorption experiments were carried out and optimum humic acid adsorption on chitosan-ECH beads occurred at pH 6.0, agitation rate of 300 rpm and contact time of 50 min. Adsorption equilibrium isotherms were analyzed by Langmuir and Freundlich models. Freundlich model was found to show the best fit for experimental data while the maximum adsorption capacity determined from Langmuir model was 44.84 mg g(-1). The adsorption of humic acid on chitosan-ECH beads was best described with pseudo-first-order kinetic model. For desorption study, more than 60% of humic acid could be desorbed from the adsorbent using 1.0M HCl for 180 min.

  6. 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.

  7. Adsorption characteristics of methylene blue onto agricultural wastes lotus leaf in bath and column modes.

    PubMed

    Han, Xiuli; Wang, Wei; Ma, Xiaojian

    2011-01-01

    The adsorption potential of lotus leaf to remove methylene blue (MB) from aqueous solution was investigated in batch and fixed-bed column experiments. Langmuir, Freundlich, Temkin and Koble-Corrigan isotherm models were employed to discuss the adsorption behavior. The results of analysis indicated that the equilibrium data were perfectly represented by Temkin isotherm and the Langmuir saturation adsorption capacity of lotus leaf was found to be 239.6 mg g(-1) at 303 K. In fixed-bed column experiments, the effects of flow rate, influent concentration and bed height on the breakthrough characteristics of adsorption were discussed. The Thomas and the bed-depth/service time (BDST) models were applied to the column experimental data to determine the characteristic parameters of the column adsorption. The two models were found to be suitable to describe the dynamic behavior of MB adsorbed onto the lotus leaf powder column.

  8. Kinetic model of water vapour adsorption by gluten-free starch

    NASA Astrophysics Data System (ADS)

    Ocieczek, Aneta; Kostek, Robert; Ruszkowska, Millena

    2015-01-01

    This study evaluated the kinetics of water vapour adsorption on the surface of starch molecules derived from wheat. The aim of the study was to determine an equation that would allow estimation of water content in tested material in any timepoint of the adsorption process aimed at settling a balance with the environment. An adsorption isotherm of water vapour on starch granules was drawn. The parameters of the Guggenheim, Anderson, and De Boer equation were determined by characterizing the tested product and adsorption process. The equation of kinetics of water vapour adsorption on the surface of starch was determined based on the Guggenheim, Anderson, and De Boer model describing the state of equilibrium and on the model of a first-order linear inert element describing the changes in water content over time.

  9. A novel reusable nanocomposite: FeOOH/CBC and its adsorptive property for methyl orange

    NASA Astrophysics Data System (ADS)

    Wang, Zhuanpei; Ma, Yongjun; He, Honglei; Pei, Chonghua; He, Ping

    2015-03-01

    Porous network-like FeOOH/ carbonized bacterial cellulose (FeOOH/CBC) nanocomposite was successfully prepared and used as adsorbent of organic dyes. The phases, morphology, structure and adsorptive properties of FeOOH/CBC nanocomposite were characterized by XRD, FI-IR, SEM, TEM, BET and UV-vis. The adsorption equilibrium of as-prepared FeOOH/CBC nanocomposite for methyl orange (MO) was achieved within one hour, with the maximum adsorption capacity for MO reaching 107.68 mg/g at pH 6.0 and 30 °C. As-prepared FeOOH/CBC nanocomposite maintains high adsorption activities after four times of adsorption and desorption, accompanying the removal rate for MO is up to 60% in 10 min.

  10. Removal of tetracycline from wastewater using pumice stone: equilibrium, kinetic and thermodynamic studies.

    PubMed

    Guler, Ulker Asli; Sarioglu, Meltem

    2014-01-01

    In this study, pumice stone was used for the removal of tetracyline (TC) from aqueous solutions. It was characterized by XRD, FT-IR, SEM and BET analyses. Cation exchange capacity of pumice stone was found to be 9.9 meq/100 g. Effect of various parameters such as solution pH (2-11), adsorbent dosage (0.5-10 g/L), contact time (2.5-120 min), initial TC concentration (5-300 mg/L) and temperature (20-50°C) on TC adsorption onto pumice was investigated. Also the adsorption of TC on pumice stone was studied as a function of Na(+) and Cu(2+) cations changing pH from 2 to 11 using batch experiments. The best removal efficiency performance was exhibited at adsorbent dosage 10 g/L, pH 3, contact time 120 min. Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherm models were applied to the equilibrium data. The result has shown that the adsorption was favorable, physicochemical in nature and agrees well with Langmuir and Freundlich models. The maximum Langmuir adsorption capacity was found to be 20.02 mg/g. The adsorption behavior of TC on pumices stone was fitted well in the pseudo-second order kinetics model. Thermodynamic parameters calculated from the adsorption data at different temperature showed that the adsorption reaction was feasible, spontaneous and exothermic.

  11. Optimization of dye adsorption time and film thickness for efficient ZnO dye-sensitized solar cells with high at-rest stability.

    PubMed

    Chang, Wei-Chen; Lee, Chia-Hua; Yu, Wan-Chin; Lin, Chun-Min

    2012-12-28

    Photoelectrodes for dye-sensitized solar cells were fabricated using commercially available zinc oxide (ZnO) nanoparticles and sensitized with the dye N719. This study systematically investigates the effects of two fabrication factors: the ZnO film thickness and the dye adsorption time. Results show that these two fabrication factors must be optimized simultaneously to obtain efficient ZnO/N719-based cells. Different film thicknesses require different dye adsorption times for optimal cell performance. This is because a prolonged dye adsorption time leads to a significant deterioration in cell performance. This is contrary to what is normally observed for titanium dioxide-based cells. The highest overall power conversion efficiency obtained in this study was 5.61%, which was achieved by 26-μm-thick photoelectrodes sensitized in a dye solution for 2 h. In addition, the best-performing cell demonstrated remarkable at-rest stability despite the use of a liquid electrolyte. Approximately 70% of the initial efficiency remained after more than 1 year of room-temperature storage in the dark. To better understand how dye adsorption time affects electron transport properties, this study also investigated cells based on 26-μm-thick films using electrochemical impedance spectroscopy (EIS). The EIS results show good agreement with the measured device performance parameters.

  12. Adsorptive removal of chlorophenols from aqueous solution by low cost adsorbent--Kinetics and isotherm analysis.

    PubMed

    Radhika, M; Palanivelu, K

    2006-11-02

    Adsorptive removal of parachlorophenol (PCP) and 2,4,6-trichlorophenol (TCP) from aqueous solutions by activated carbon prepared from coconut shell was studied and compared with activated carbon of commercial grade (CAC). Various chemical agents in different concentrations were used (KOH, NaOH, CaCO(3), H(3)PO(4) and ZnCl(2)) for the preparation of coconut shell activated carbon. The coconut shell activated carbon (CSAC) prepared using KOH as chemical agent showed high surface area and best adsorption capacity and was chosen for further studies. Batch adsorption studies were conducted to evaluate the effect of various parameters such as pH, adsorbent dose, contact time and initial PCP and TCP concentration. Adsorption equilibrium reached earlier for CSAC than CAC for both PCP and TCP concentrations. Under optimized conditions the prepared activated carbon showed 99.9% and 99.8% removal efficiency for PCP and TCP, respectively, where as the commercially activated carbon had 97.7% and 95.5% removal for PCP and TCP, respectively, for a solution concentration of 50mg/L. Adsorption followed pseudo-second-order kinetics. The equilibrium adsorption data were analysed by Langmuir, Freundlich, Redlich-Peterson and Sips model using non-linear regression technique. Freundlich isotherms best fitted the data for adsorption equilibrium for both the compounds (PCP and TCP). Similarly, acidic pH was favorable for the adsorption of both PCP and TCP. Studies on pH effect and desorption revealed that chemisorption was involved in the adsorption process. The efficiency of the activated carbon prepared was also tested with real pulp and paper mill effluent. The removal efficiency using both the carbons were found highly satisfactory and was about 98.7% and 96.9% as phenol removal and 97.9% and 93.5% as AOX using CSAC and CAC, respectively.

  13. Estimating equilibrium ensemble averages using multiple time slices from driven nonequilibrium processes: theory and application to free energies, moments, and thermodynamic length in single-molecule pulling experiments.

    PubMed

    Minh, David D L; Chodera, John D

    2011-01-14

    Recently discovered identities in statistical mechanics have enabled the calculation of equilibrium ensemble averages from realizations of driven nonequilibrium processes, including single-molecule pulling experiments and analogous computer simulations. Challenges in collecting large data sets motivate the pursuit of efficient statistical estimators that maximize use of available information. Along these lines, Hummer and Szabo developed an estimator that combines data from multiple time slices along a driven nonequilibrium process to compute the potential of mean force. Here, we generalize their approach, pooling information from multiple time slices to estimate arbitrary equilibrium expectations. Our expression may be combined with estimators of path-ensemble averages, including existing optimal estimators that use data collected by unidirectional and bidirectional protocols. We demonstrate the estimator by calculating free energies, moments of the polymer extension, the thermodynamic metric tensor, and the thermodynamic length in a model single-molecule pulling experiment. Compared to estimators that only use individual time slices, our multiple time-slice estimators yield substantially smoother estimates and achieve lower variance for higher-order moments.

  14. Solvothermal synthesis of different phase N-TiO2 and their kinetics, isotherm and thermodynamic studies on the adsorption of methyl orange.

    PubMed

    Fan, Jimin; Zhao, Zhihuan; Liu, Wenhui; Xue, Yongqiang; Yin, Shu

    2016-05-15

    The different crystal forms of nitrogen doped-titanium oxide (N-TiO2) with different particle sizes were produced by precipitation-solvothermal method and their adsorption mechanism were also investigated. The adsorption kinetics showed that rutile N-TiO2 displayed higher adsorption capacity than anatase for methyl orange (MO) and its adsorption behavior followed the pseudo-second-order kinetics. The equilibrium adsorption rate of N-TiO2 for MO was well fitted by the Langmuir isotherm model and the adsorption process was monolayer adsorption. The adsorption capacity decreased with increasing temperature. The average correlation coefficient was beyond 97%. The thermodynamic parameters (ΔaGm(ө), ΔaHm(ө), and ΔaSm(ө)) were calculated. It was found that anatase and rutile N-TiO2 had different adsorption enthalpy and entropy. The smaller the particle size, the greater the surface area and surface energy was, then ΔaGm(ө) decreased and the standard equilibrium constant increased at the same time. The adsorption process onto different crystalline phase N-TiO2 was exothermic and non-spontaneous.

  15. Removal of aluminium from aqueous solutions using PAN-based adsorbents: characterisation, kinetics, equilibrium and thermodynamic studies.

    PubMed

    Aly, Zaynab; Graulet, Adrien; Scales, Nicholas; Hanley, Tracey

    2014-03-01

    Economic adsorbents in bead form were fabricated and utilised for the adsorption of Al(3+) from aqueous solutions. Polyacrylonitrile (PAN) beads, PAN powder and the thermally treated PAN beads (250 °C/48 h/Ar and 600 °C/48 h/Ar-H2) were characterised using different techniques including Fourier transform infrared spectroscopy, X-ray diffraction, specific surface analysis (Brunauer-Emmett-Teller), thermogravimetric analysis as well as scanning electron microscopy. Effects of pH, contact time, kinetics and adsorption isotherms at different temperatures were investigated in batch mode experiments. Aluminium kinetic data best fit the Lagergren pseudo-second-order adsorption model indicating a one-step, surface-only, adsorption process with chemisorption being the rate limiting step. Equilibrium adsorption data followed a Langmuir adsorption model with fairly low monolayer adsorption capacities suitable for freshwater clean-up only. Various constants including thermodynamic constants were evaluated from the experimental results obtained at 20, 40 and 60 °C. Positive values of ΔH° indicated that the adsorption of Al(3+) onto all three adsorbents was endothermic with less energy input required for PAN powder compared to PAN beads and low-temperature thermally treated PAN. Negative ΔG° values indicated that the aluminium adsorption process was spontaneous for all adsorbents examined.

  16. Adsorptive removal of phenol from aqueous solution with zeolitic imidazolate framework-67.

    PubMed

    Pan, Yong; Li, Zhi; Zhang, Zhe; Tong, Xiong-Shi; Li, Hai; Jia, Chong-Zhi; Liu, Bei; Sun, Chang-Yu; Yang, Lan-Ying; Chen, Guang-Jin; Ma, De-Yun

    2016-03-15

    ZIF-67(zinc-methylimidazolate framework-67), one of the zeolitic imidazolate frameworks (ZIFs), was used for the removal of phenol from aqueous solutions via adsorption and shows high adsorption capacity for phenol. The thermodynamic and kinetic adsorption behavior of ZIF-67 for phenol in water with concentration ranging from 50 to 300 ppm were investigated in a batch reactor and a ZIF-67 packed column, respectively. The effects of pH, contact time, zeta potential of the adsorbent and temperature on the adsorption behavior were evaluated, and the results demonstrated that the adsorption is primarily brought about by a specific favorable interaction (electrostatic interaction) between phenol and ZIF-67 surface. The suitability of the Langmuir adsorption model to the equilibrium data was investigated for each phenol-adsorbent system, which the results showed that the equilibrium data for all the phenol-sorbent systems fitted the Langmuir model. Thermodynamic parameters such as Gibbs free energy are calculated from the experimental data at different temperatures. The adsorbent could be perfectly regenerated at 120 °C with little loss in the adsorption ability.

  17. Removal of Cd2+ from aqueous solution by adsorption using Fe-montmorillonite.

    PubMed

    Wu, Pingxiao; Wu, Weimin; Li, Shuzhen; Xing, Ning; Zhu, Nengwu; Li, Ping; Wu, Jinghua; Yang, Chen; Dang, Zhi

    2009-09-30

    Fe-montmorillonite (Fe-Mont.) is obtained by exchanging the original interlayer cations of montmorillonite by poly-hydroxyl ferric. In this paper, Fe-Mont. was synthesized by using Ca-montmorillonite (Ca-Mont.) directly under ultrasonic treatment with the aim to enhance the ability of removal of heavy metal ions from wastewater. The modified materials were characterized by X-ray diffraction (XRD) and Fourier transform infrared (FT-IR). Batch equilibrium experiments of Cd(II) ions (Cd(2+)) adsorption on the Fe-Mont. were performed. Effects of the initial pH of the solution and contact time on the adsorption of Cd(2+) were studied. Four types of adsorption isotherms were applied to describe the adsorption isotherms of Cd(2+) by Fe-Mont. The relationship between adsorbing capacity (q(e)) and equilibrium mass concentration (C(e)) is in accordance with the isothermal adsorption equation of Langmuir. Three kinetic models, including pseudo-first-order, pseudo-second-order and the Elovich equation model, were used to analyze the Cd(2+) adsorption process. The pseudo-second-order chemical reaction kinetics provide the best correlation of the experimental data, therefore the adsorption dynamics follows the laws of pseudo-second-order kinetics.

  18. Adsorption of Hg2+ from aqueous solution onto polyacrylamide/attapulgite.

    PubMed

    Zhao, Yijiang; Chen, Yan; Li, Meisheng; Zhou, Shouyong; Xue, Ailian; Xing, Weihong

    2009-11-15

    Polyacrylamide/attapulgite (PAM/ATP) was prepared by the solution polymerization of acrylamide (AM) onto gamma-methacryloxypropyl trimethoxy silane (KH-570)-modified attapulgite (ATP). PAM/ATP was characterized using Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS). The effects of contact time, adsorbent dosage, and pH of the initial solution on the adsorption capacities for Hg(2+) were investigated. The adsorption process was rapid; 88% of adsorption occurred within 5 min and equilibrium was achieved at around 40 min. The equilibrium data fitted the Langmuir sorption isotherms well, and the maximum adsorption capacity of Hg(2+) onto PAM/ATP was found to be 192.5 mg g(-1). The adsorption kinetics of PAM/ATP fitted a pseudo-second-order kinetic model. Our results suggest that chemisorption processes could be the rate-limiting steps in the process of Hg(2+) adsorption. Hg(2+) adsorbed onto PAM/ATP could be effectively desorbed in hot acetic acid solution, and the adsorption capacity of the regenerated adsorbents could still be maintained at 95% by the sixth cycle.

  19. Characteristic Evaluation of Graphene Oxide for Bisphenol A Adsorption in Aqueous Solution

    PubMed Central

    Phatthanakittiphong, Thatchaphong; Seo, Gyu Tae

    2016-01-01

    This paper investigates the characteristics of graphene oxide (GO) for Bisphenol A (BPA) adsorption in water. Batch experiments on the influence of significant parameters were performed. While an improvement of the adsorption capacity of BPA was obtained by the increment of contact time and the initial BPA concentration, the increment of pH above 8, GO dosage, and temperature showed the reverse results. The thermodynamic study suggested that BPA adsorption on GO was an exothermic and spontaneous process. The kinetics was explained by the pseudo-second-order model which covers all steps of adsorption. The fit of the results with the Langmuir isotherm indicated the monolayer adsorption. At 298 K, the adsorption reached equilibrium within 30 min with the maximum adsorption capacity of 49.26 mg/g. The low BPA adsorption capacity of GO can be interpreted by the occurrence of oxygen-containing functional groups (OCFGs) that are able to form hydrogen bonds with the surrounding OCFGs and water molecules. This effect inhibited the role of π–π interactions that are mainly responsible for the adsorption of BPA. PMID:28335257

  20. Detailed Study of BSA Adsorption on Micro- and Nanocrystalline Diamond/β-SiC Composite Gradient Films by Time-Resolved Fluorescence Microscopy.

    PubMed

    Handschuh-Wang, Stephan; Wang, Tao; Druzhinin, Sergey I; Wesner, Daniel; Jiang, Xin; Schönherr, Holger

    2017-01-24

    The adsorption of bovine serum albumin (BSA) on micro- and nanocrystalline diamond/β-SiC composite films synthesized using the hot filament chemical vapor deposition (HFCVD) technique has been investigated by confocal fluorescence lifetime imaging microscopy. BSA labeled with fluorescein isothiocyanate (FITC) was employed as a probe. The BSA(FITC) conjugate was found to preferentially adsorb on both O-/OH-terminated microcrystalline and nanocrystalline diamond compared to the OH-terminated β-SiC, resulting in an increasing amount of BSA adsorbed to the gradient surfaces with an increasing diamond/β-SiC ratio. The different strength of adsorption (>30 times for diamond with a grain size of 570 nm) coincides with different surface energy parameters and differing conformational changes upon adsorption. Fluorescence data of the adsorbed BSA(FITC) on the gradient film with different diamond coverage show a four-exponential decay with decay times of 3.71, 2.54, 0.66, and 0.13 ns for a grain size of 570 nm. The different decay times are attributed to the fluorescence of thiourea fluorescein residuals of linked FITC distributed in BSA with different dye-dye and dye-surface distances. The longest decay time was found to correlate linearly with the diamond grain size. The fluorescence of BSA(FITC) undergoes external dynamic fluorescence quenching on the diamond surface by H- and/or sp(2)-defects and/or by amorphous carbon or graphite phases. An acceleration of the internal fluorescence concentration quenching in BSA(FITC) because of structural changes of albumin due to adsorption, is concluded to be a secondary contributor. These results suggest that the micro- and nanocrystalline diamond/β-SiC composite gradient films can be utilized to spatially control protein adsorption and diamond crystallite size, which facilitates systematic studies at these interesting (bio)interfaces.

  1. Adsorption of Single and Binary Gases on Polystyrene and Carbon Adsorbents

    NASA Astrophysics Data System (ADS)

    Rothstein, Daniel P.

    Time-dependent transmissions of light organic gases at low concentrations through crosslinked polystyrene and activated carbon adsorbents were measured and analyzed to extract kinetic and equilibrium parameters and to evaluate these parameters in terms of several models of adsorption. Mass -balance in the adsorber bed allows calculation of the equilibrium adsorbed-phase concentration and the model-independent adsorption capacity. Adsorption isotherms are calculated from transmission curves for eight light organic gases adsorbed on polystyrene at several temperatures. The power-law forms of the Freundlich and Chakravarti-Dhar isotherms and the concentration-dependent adsorption capacities indicate heterogeneous adsorption well below monolayer coverage. The effects of heterogeneity increase as non-linearity of the isotherm increases. A mesopore structure is indicated for polystyrene. Characteristic curves are independent of temperature, but the use of an affinity coefficient is not able to demonstrate their independence of adsorbate. Isosteric hearts of adsorption are larger than the heats of vaporization and decrease with increasing surface coverage for three alkanes adsorbed on polystyrene. The transmission curves of several binary mixtures of gases with non-linear isotherms reveal adsorption interference, with adsorption capacities smaller than those from single -component experiments. The pairs with unequal adsorption capacities exhibit displacement, in qualitative agreement with adsorption interference models. The equilibrium adsorption of the binary mixtures cannot be reproduced by single-component isotherm parameters alone, but are described by modified Freundlich isotherms requiring binary experiments. Adsorption in a porous medium is described by a model including four dynamic processes: gas- and solid -phase diffusion, interfacial mass-transfer resistance, and a first-order chemical reaction. A new time-dependent solution to the differential equations of

  2. [Adsorption kinetic and thermodynamic studies of lead onto activated carbons from cotton stalk].

    PubMed

    Li, Kun-quan; Zheng, Zheng; Jiang, Jian-chun; Zhang, Ji-biao

    2010-05-01

    Low-cost high surface area microporous carbons were prepared from cotton stalk and cotton stalk fiber by H3PO4 activation. The adsorption of lead ions on the carbons was investigated by conducting a series of batch adsorption experiments. The influence of solution pH value, contact time and temperature was investigated. The adsorption kinetics, thermodynamic behavior and mechanism were also discussed. The surface area and pore structure of the activated carbons were analyzed by BET equation, BJH method and H-K method according to the data from nitrogen adsorption at 77K. Boehm titration, Fourier transform infrared spectroscopy (FTIR), the point of zero charge (pH(PZC)) measurement and elemental analysis were used to characterize the surface properties. The results show that the carbons from cotton stalk and cotton stalk fiber have high surface area of 1570 and 1731 m2 x g(-1), and high content of oxygen-containing functional groups of 1.43 and 0.83 mmol x g(-1). The adsorption experiments show that the carbons have high adsorption capacity for lead, and the maximum adsorption equilibrium amount was found to be 120 mg x g(-1). The adsorption amount increased with contact time, and almost 80% of the adsorption occurred in the first 5 min. The pseudo-second-order model describes the adsorption kinetics most effectively. The Freundlich isotherm was found to the best explanation for experimental data. The negative change in free energy (delta G0) and positive change in enthalpy (delta H0) indicate that the adsorption is a spontaneous and endothermic process, and the adsorption of lead ions onto the carbons might be involved in an ion-exchange mechanism.

  3. Modeling studies: Adsorption of aniline blue by using Prosopis Juliflora carbon/Ca/alginate polymer composite beads.

    PubMed

    Kumar, M; Tamilarasan, R

    2013-02-15

    The research article describes the experimental and modeling study for the adsorptive removal of aniline blue dye (AB dye) from aqueous matrices using a Prosopis Juliflora modified carbon/Ca/alginate polymer bead as a low cost and eco-friendly adsorbent. The rate of adsorption was investigated under various experimental parameters such as contact time, adsorbent dose, dye concentration, pH and temperature. The kinetics, equilibrium and thermodynamic studies were assessed to find out the efficiency of the adsorption process. The equilibrium uptake capacity of the adsorption process was found with Freundlich and Langmuir adsorption isotherm equations and it was evaluated by dimensionless separation factor (R(L)). The dynamics of adsorption was predicted by pseudo-first order, pseudo-second order Lagergren's equation and intra particle diffusion model. Adsorption feasibility was assessed with thermodynamic parameters such as isosteric heat of adsorption (ΔH°), standard entropy (ΔS°) and Gibbs free energy (ΔG°) using VantHoff plot. The alginate bead was characterized with FTIR spectroscopy and Scanning Electron Microscopy (SEM).

  4. The adsorption of Cd(II) ions on sulphuric acid-treated wheat bran.

    PubMed

    Ozer, A; Pirinççi, H B

    2006-09-21

    The adsorption of Cd(II) ions which is one of the most important toxic metals by using sulphuric acid-treated wheat bran (STWB) was investigated. The effects of solution pH and temperature, contact time and initial Cd(II) concentration on the adsorption yield were studied. The equilibrium time for the adsorption process was determined as 4 h. The adsorbent used in this study gave the highest adsorption capacity at around pH 5.4. At this pH, adsorption capacity for an initial Cd(II) ions concentration of 100 mg/L was found to be 43.1 mg/g at 25 degrees C for contact time of 4 h. The equilibrium data were analysed using Langmuir and Freundlich isotherm models to calculate isotherm constants. The maximum adsorption capacity (qmax) which is a Langmuir constant decreased from 101.0 to 62.5 mg/g with increasing temperature from 25 to 70 degrees C. Langmuir isotherm data were evaluated to determine the thermodynamic parameters for the adsorption process. The enthalpy change (deltaH(o)) for the process was found to be exothermic. The free energy change (deltaG(o)) showed that the process was feasible. The kinetic results indicated that the adsorption process of Cd(II) ions by STWB followed first-order rate expression and adsorption rate constant was calculated as 0.0081 l/min at 25 degrees C. It was observed that the desorption yield of Cd(II) was highly pH dependent.

  5. Adsorption of CO2 by alginate immobilized zeolite beads

    NASA Astrophysics Data System (ADS)

    Suratman, A.; Kunarti, E. S.; Aprilita, N. H.; Pamurtya, I. C.

    2017-03-01

    Immobilized zeolit in alginate beads for adsorption of CO2 was developed. Alginate immobilized zeolit beads was generated by dropping the mixture of Na-alginate and zeolite solution into Ca2+ solution. The adsorption efficacy such as the influence of contact time, mass of zeolite, flowrate of CO2, and mass of adsorbent was evaluated. The adsorption of CO2 onto alginate immobilized zeolit beads was investigated by performing both equilibrium and kinetic batch test. Bead was characterized by FTIR and SEM. Alginate immobilized zeolit beads demonstrated significantly higher sorption efficacy compared to plain alginate beads and zeolite with 0.25 mmol CO2 adsorbed /g adsorbent. Optimum condition was achieved with mass composition of alginate:zeolite (3:1), flowrate 50 mL/min for 20 minutes. The alginate immobilized zeolit beads showed that adsorption of CO2 followed Freundlich isotherm and pseudo second order kinetic model. Adsorption of CO2 onto alginate immobilized zeolite beads is a physisorption with adsorption energy of 6.37 kJ/mol. This results indicates that the alginate immobilized zeolit beads can be used as promising adsorbents for CO2.

  6. Adsorptive decolorization of methylene blue by crosslinked porous starch.

    PubMed

    Guo, Lei; Li, Guiying; Liu, Junshen; Meng, Yanfeng; Tang, Yanfeng

    2013-04-02

    Crosslinked porous starch (CPS) was prepared by two steps. Native starch was crosslinked with epichlorohydrin and then CPS was prepared by hydrolyzing the crosslinked starch with α-amylase. As a biodegradable and safe adsorbent, CPS was used to remove methylene blue (MB) from the aqueous solution based on its characterizations, including surface area, pore volume and scanning electron microscopy (SEM). The results indicate that the adsorption capacity of CPS is much higher than native starch and relatively higher than porous starch. The effects of the initial concentration of MB, the time and temperature on the adsorption capacity were investigated. The pseudo-first-order kinetic model provides a better correlation of the experimental data in comparison with the pseudo-second-order model. The equilibrium adsorption data are well described by the Langmuir isotherm model with a maximum adsorption capacity of 9.46mg g(-1). The adsorption of MB on CPS is endothermic and spontaneous in nature. The thermodynamics data are in good agreement with physical adsorption mechanism.

  7. Polyphenylene sulfide based anion exchange fiber: synthesis, characterization and adsorption of Cr(VI).

    PubMed

    Huang, Jiajia; Zhang, Xin; Bai, Lingling; Yuan, Siguo

    2012-01-01

    A fibrous strong base anion exchanger (QAPPS) was prepared for the first time via chloromethylation and quaternary amination reaction of polyphenylene sulfide fiber (PPS), and its physical-chemical structure and adsorption behavior for Cr(VI) were characterized by FTIR, Energy Dispersive Spectrometry, TG-DTG, elemental analysis and batch adsorptive technique, respectively. The novel fibrous adsorbent could effectively adsorb Cr(VI) over the pH range 1-12, the maximum adsorption capacity was 166.39 mg/g at pH 3.5, and the adsorption behavior could be described well by Langmuir isotherm equation model. The adsorption kinetics was studied using pseudo first-order and pseudo second-order models, and the t1/2 and equilibrium adsorption time were 5 and 20 min respectively when initial Cr(VI) concentration was 100 mg/L. The saturated fibers could be regenerated rapidly by a mixed solution of 0.5 mol/L NaOH and 0.5 mol/L NaCl, and the adsorption capacity was well maintained after six adsorption-desorption cycles.

  8. Microwave-assisted modification on montmorillonite with ester-containing Gemini surfactant and its adsorption behavior for triclosan.

    PubMed

    Liu, Bo; Lu, Junxiang; Xie, Yu; Yang, Bin; Wang, Xiaoying; Sun, Runcang

    2014-03-15

    To obtain effective adsorbent that can remove emerging organic pollutant of triclosan (TCS) in aquatic environment, different ester-containing Gemini surfactant-modified MMT (EMMT) were prepared under microwave irradiation. The whole process was rapid, uniform, easy and energy-efficient. The structures and morphology of EMMT were characterized by XRD, TEM, FT-IR, SEM and TGA. The results revealed that the saturated intercalation amount of this surfactant was 0.8 times to cation exchange capacity (CEC) of MMT, and there was electrostatic interaction between ester-containing Gemini surfactant and MMT. In addition, they bound in the ways of intercalation, intercalation-adsorption or adsorption, which relied on the dosage of the surfactant. The surface of EMMT was hydrophobic, rough and fluffy, which contributed to its strong adsorption capacity. The adsorption equilibrium data of EMMT for TCS were fitted to Langmuir and Freundlich isothermal adsorption model. The result showed that Langmuir isothermal adsorption model could describe the adsorption behavior better, the adsorption behavior of TCS on EMMT was confirmed to a surface monolayer adsorption, and notably the theoretical maximum adsorption capacity was up to 133 mg/g. Therefore, this work lays important foundation on developing effective and safe absorbent materials for the treatment of emerging organic pollutants.

  9. The adsorption of plutonium IV and V on goethite

    NASA Astrophysics Data System (ADS)

    Sanchez, Arthur L.; Murray, James W.; Sibley, Thomas H.

    1985-11-01

    The adsorption of Pu(IV) and Pu(V) on goethite (αFeOOH) from NaNO 3 solution shows distinct differences related to the different hydrolytic character of these two oxidation states. Under similar solution conditions, the adsorption edge of the more strongly hydrolyzable Pu(IV) occurs in the pH range 3 to 5 while that for Pu(V) is at pH 5 to 7. The adsorption edge for Pu(V) shifts with time to lower pH values and this appears to be due to the reduction of Pu(V) to Pu(IV) in the presence of the goethite surface. These results suggest that redox transformations may be an important aspect of Pu adsorption chemistry and the resulting scavenging of Pu from natural waters. Increasing ionic strength (from 0.1 M to 3 M NaCl or NaNO 3 and 0.03 M to 0.3 M Na 2SO 4) did not influence Pu(IV) or Pu(V) adsorption. In the presence of dissolved organic carbon (DOC), Pu(V) reduction to Pu(IV) occurred in solution. Pu(IV) adsorption on goethite decreased by 30% in the presence of 240 ppm natural DOC found in Soap Lake, Washington waters. Increasing concentrations of carbonate ligands decreased Pu(IV) and Pu(V) adsorption on goethite, with an alkalinity of 1000 meq/l totally inhibiting adsorption. The Pu-goethite adsorption system provides the data base for developing a thermodynamic model of Pu interaction with an oxide surface and with dissolved ligands, using the MINEQL computer program. From the model calculations we determined equilibrium constants for the adsorption of Pu(IV) hydrolysis species. The model was then applied to Pu adsorption in carbonate media to see how the presence of CO 3-2 could influence the mobility of Pu. The decrease in adsorption appears to be due to formation of a Pu-CO 3 complex. Model calculations were used to predict what the adsorption curves would look like if Pu-CO 3 complexes formed.

  10. Ag{sup II} doped MIL-101 and its adsorption of iodine with high speed in solution

    SciTech Connect

    Mao, Ping; Qi, Bingbing; Liu, Ying; Zhao, Lei; Jiao, Yan; Zhang, Yi; Jiang, Zheng; Li, Qiang; Wang, Jinfeng; Chen, Shouwen; Yang, Yi

    2016-05-15

    In order to improve the adsorption speed of iodine from water, MIL-101 with extra-large specific surface area (3054 m{sup 2}/g) was chosen as a base material, and then, Ag was doped into MIL-101 to enhance its adsorption capacity through an incipient-wetness impregnation method. With the characterization of SEM-EDS, TEM, XRD, XPS, TGA, IR, and BET techniques, the resulting Ag was identified to be stay in the framework of MIL-101 stably in the form of Ag{sup II} (generally, Ag{sup II} cation is not stable). However, after the adsorption of I{sup −} anions, Ag{sup II} stay in the cages of MIL-101 in the form of AgI/AgI{sub 3}. It is important to note that, all adsorbents show high adsorption speed of iodine in solution. The equilibrium adsorption time of the adsorbents were acquired by only a few minutes, which can be attributed to its large BET surface area. An interesting note is that, when the doping amount of Ag is less than 9%, the iodine anions adsorption capacity of Ag@MIL-101 is greater than its theoretical adsorption capacity. It shows that both physical adsorption and chemical adsorption are existed in the adsorption process. This study hopefully leads to a new and highly efficient Ag-based adsorbent for iodide adsorb from solutions. - Graphical abstract: Ag{sup II} stay in the framework of MIL-101 stably because of F{sup -}, after the adsorption of I{sup -} anions, Ag{sup I}I /Ag{sup I}I{sub 3} stay in the cages of MIL-101. The equilibrium adsorption time of Ag@MIL-101 were acquired by only a few minutes. - Highlights: • Ag{sup II} was doped into MIL-101 by an incipient-wetness impregnation method. • Both physical adsorption and chemical adsorption are verified in the adsorption process. • Ag@MIL-101 exhibits high adsorption speed and adsorption capacity. • Ag@MIL-101 can be effectively applied to the removal of radioactive iodide anions from water in acidic and neutral medium.

  11. Improved curve fits for the thermodynamic properties of equilibrium air suitable for numerical computation using time-dependent or shock-capturing methods, part 1

    NASA Technical Reports Server (NTRS)

    Tannehill, J. C.; Mugge, P. H.

    1974-01-01

    Simplified curve fits for the thermodynamic properties of equilibrium air were devised for use in either the time-dependent or shock-capturing computational methods. For the time-dependent method, curve fits were developed for p = p(e, rho), a = a(e, rho), and T = T(e, rho). For the shock-capturing method, curve fits were developed for h = h(p, rho) and T = T(p, rho). The ranges of validity for these curves fits were for temperatures up to 25,000 K and densities from 10 to the minus 7th power to 10 to the 3d power amagats. These approximate curve fits are considered particularly useful when employed on advanced computers such as the Burroughs ILLIAC 4 or the CDC STAR.

  12. Adsorption Model for Off-Gas Separation

    SciTech Connect

    Veronica J. Rutledge

    2011-03-01

    The absence of industrial scale nuclear fuel reprocessing in the U.S. has precluded the necessary driver for developing the advanced simulation capability now prevalent in so many other countries. Thus, it is essential to model complex series of unit operations to simulate, understand, and predict inherent transient behavior and feedback loops. A capability of accurately simulating the dynamic behavior of advanced fuel cycle separation processes will provide substantial cost savings and many technical benefits. The specific fuel cycle separation process discussed in this report is the off-gas treatment system. The off-gas separation consists of a series of scrubbers and adsorption beds to capture constituents of interest. Dynamic models are being developed to simulate each unit operation involved so each unit operation can be used as a stand-alone model and in series with multiple others. Currently, an adsorption model has been developed in gPROMS software. Inputs include gas stream constituents, sorbent, and column properties, equilibrium and kinetic data, and inlet conditions. It models dispersed plug flow in a packed bed under non-isothermal and non-isobaric conditions for a multiple component gas stream. The simulation outputs component concentrations along the column length as a function of time from which the breakthrough data is obtained. It also outputs temperature along the column length as a function of time and pressure drop along the column length. Experimental data will be input into the adsorption model to develop a model specific for iodine adsorption on silver mordenite as well as model(s) specific for krypton and xenon adsorption. The model will be validated with experimental breakthrough curves. Another future off-gas modeling goal is to develop a model for the unit operation absorption. The off-gas models will be made available via the server or web for evaluation by customers.

  13. Influence of Soil Solution Salinity on Molybdenum Adsorption by Soils

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Molybdenum (Mo) adsorption on five arid-zone soils from California was investigated as a function of equilibrium solution Mo concentration (0-30 mg L-1), solution pH (4-8), and electrical conductivity (EC = 0.3 or 8 dS m-1). Molybdenum adsorption decreased with increasing pH. An adsorption maximum...

  14. Time-dependent solution for axisymmetric flow over a blunt body with ideal gas, CF4, or equilibrium air chemistry

    NASA Technical Reports Server (NTRS)

    Hamilton, H. H., II; Spall, J. R.

    1986-01-01

    A time-asymptotic method has been used to obtain steady-flow solutions for axisymmetric inviscid flow over several blunt bodies including spheres, paraboloids, ellipsoids, and spherically blunted cones. Comparisons with experimental data and results of other computational methods have demonstrated that accurate solutions can be obtained using this approach. The method should prove useful as an analysis tool for comparing with experimental data and for making engineering calculations for blunt reentry vehicles.

  15. Importance of surface diffusivities in pesticide adsorption kinetics onto granular versus powdered activated carbon: experimental determination and modeling.

    PubMed

    Baup, S; Wolbert, D; Laplanche, A

    2002-10-01

    Three pesticides (atrazine, bromoxynil and diuron) and two granular activated carbons are involved in equilibrium and kinetic adsorption experiments. Equilibrium is represented by Freundlich isotherm law and kinetic is described by the Homogeneous Surface Diffusion Model, based on external mass transfer and intraparticle surface diffusion. Equilibrium and long-term experiments are conducted to compare Powdered Activated Carbon and Granular Activated Carbon. These first investigations show that crushing GAC into PAC improves the accessibility of the adsorption sites without increasing the number of these sites. In a second part, kinetics experiments are carried out using a Differential Column Batch Reactor. Thanks to this experimental device, the external mass transfer coefficient k(f) is calculated from empirical correlation and the effect of external mass transfer on adsorption is likely to be minimized. In order to obtain the intraparticle surface diffusion coefficient D. for these pesticides, comparisons between experimental kinetic data and simulations are conducted and the best agreement leads to the Ds coefficient. This procedure appears to be an efficient way to acquire surface diffusion coefficients for the adsorption of pesticides onto GAC. Finally it points out the role of surface diffusivity in the adsorption rate. As a matter of fact, even if the amount of the target-compound that could be potentially adsorbed is really important, its surface diffusion coefficient may be small, so that its adsorption may not have enough contact time to be totally achieved.

  16. 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.

  17. Derivation of the Fano profile from time-dependent density-functional theory for local thermodynamic equilibrium plasmas

    NASA Astrophysics Data System (ADS)

    Kiyokawa, Shuji

    2007-04-01

    We give the derivation of the Fano profile (the resonance energy position, the resonance width Γ , and q value) from the time-dependent nonrelativistic density-functional theory (DFT) and propose a scheme for calculating the photoabsorption cross section of hot dense plasmas. As a consequence of this derivation, we show the line profile is obtained as a superposition of Fano and Lorentz profiles when the competition of two optically allowed bound-bound and bound-free transitions occurs. We also show the results of the photoabsorption cross section by applying our scheme to an Fe plasma (density is 7.85g/cm3 , temperature is 100eV ), where the calculation is carried out without numerical divergence for any photon energy. The calculated results are in good agreement with those of Grimaldi.

  18. Equilibrium and non-equilibrium kinetics of self-assembled surfactant monolayers: a vibrational sum-frequency study of dodecanoate at the fluorite-water interface.

    PubMed

    Schrödle, Simon; Richmond, Geraldine L

    2008-04-16

    The adsorption, desorption, and equilibrium monomer exchange processes of sodium dodecanoate at the fluorite(CaF 2)-water interface have been studied. For the first time, we use in situ vibrational sum-frequency spectroscopy (VSFS) to gain insights into the mechanism and kinetics of monolayer self-assembly at the mineral-water interface. By exploiting the nonlinear optical response of the adsorbate, the temporal correlation of headgroup adsorption and alignment of the surfactant's alkyl chain was monitored. Because of the unique surface-specificity of VSFS, changes in the interfacial water structure were also tracked experimentally. The spectra clearly reveal that the structure of interfacial water molecules is severely disturbed at the start of the adsorption process. With the formation of a well-ordered adsorbate layer, it is partially reestablished; however, the molecular orientation and state of coordination is significantly altered. Even at very low surfactant concentrations, overcharging of the mineral surface (i.e., the adsorption of adsorbates past the point of electrostatic equilibrium) was observed. This points out the importance of effects other than electrostatic interactions and it is proposed that cooperative effects of both water structure and surfactant hemimicelle formation at the interface are key factors. The present study also investigates desorption kinetics of partially and fully established monolayers and a statistical model for data analysis is proposed. Additional experiments were performed in the presence of electrolytes and showed that uni- and divalent anions affect the nonequilibrium kinetics of self-assembled monolayers in strikingly different ways.

  19. Fabrication of novel magnetic nanocomposite with a number of adsorption sites for the removal of dye.

    PubMed

    Li, Leilei; Duan, Huimin; Wang, Xiaojiao; Luo, Chuannan

    2015-01-01

    In this current work, a novel functional ionic liquid-coated Fe3O4@chitosan@graphene oxide was synthesized and tested as adsorbents for methylene blue through batch adsorption tests. The physicochemical properties of the adsorbent were investigated using scanning electron microscopy, x-ray diffraction, and fourier transform infrared spectroscopy. The adsorption capacity of the adsorbent was evaluated as a function of initial dye concentration, pH, contact time and temperature. The adsorption results indicated that the adsorption followed a pseudo-second-order kinetics. The equilibrium adsorption was well-described by the Langmuir isotherm model and the maximum adsorption capacity was to be 262 mg/g. The negative value of ΔH° shows exothermic nature of adsorption process and the negative value of ΔG° indicated that the adsorption reaction is spontaneous. Moreover, the ionic liquid-coated Fe3O4@chitosan@graphene oxide could be repeatedly used by simple treatment without obvious structure and performance degradation. The obtained results suggested that the potential applications of ionic liquid-coated Fe3O4@chitosan@graphene oxide in deep-purification of polluted water.

  20. Adsorption of methylene blue and Congo red from aqueous solution by activated carbon and carbon nanotubes.

    PubMed

    Szlachta, M; Wójtowicz, P

    2013-01-01

    This study was conducted to determine the adsorption removal of dyes by powdered activated carbon (PAC, Norit) and multi-walled carbon nanotubes (MWCNTs, Chinese Academy of Science) from an aqueous solution. Methylene blue (MB) and Congo red (CR) were selected as model compounds. The adsorbents tested have a high surface area (PAC 835 m(2)/g, MWCNTs 358 m(2)/g) and a well-developed porous structure which enabled the effective treatment of dye-contaminated waters and wastewaters. To evaluate the capacity of PAC and MWCNTs to adsorb dyes, a series of batch adsorption experiments was performed. Both adsorbents exhibited a high adsorptive capacity for MB and CR, and equilibrium data fitted well with the Langmuir model, with the maximum adsorption capacity up to 400 mg/g for MB and 500 mg/g for CR. The separation factor, RL, revealed the favorable nature of the adsorption process under experimental conditions. The kinetics of adsorption was studied at various initial dye concentrations and solution temperatures. The pseudo-second-order model was used for determining the adsorption kinetics of MB and CR. The data obtained show that adsorption of both dyes was rapid in the initial stage and followed by slower processing to reach the plateau. The uptake of dyes increased with contact time, irrespective of their initial concentration and solution temperature. However, changes in the solution temperature did not significantly influence dye removal.

  1. Efficient removal and highly selective adsorption of Hg2+ by polydopamine nanospheres with total recycle capacity

    NASA Astrophysics Data System (ADS)

    Zhang, Xiulan; Jia, Xin; Zhang, Guoxiang; Hu, Jiamei; Sheng, Wenbo; Ma, Zhiyuan; Lu, Jianjiang; Liu, Zhiyong

    2014-09-01

    This study reported a new method for efficient removal of Hg2+ from contaminated water using highly selective adsorptive polydopamine (PDA) nanospheres, which were uniform and had a small diameter (150-200 nm). The adsorption isotherms, kinetics, thermodynamics were investigated. Also, the effects of ionic strength, co-existing ions on removing ability of PDA nanospheres for Hg2+ were studied. Adsorption of Hg2+ was very fast and efficient as adsorption equilibrium was completed within 4 h and the maximum adsorption capacities were 1861.72 mg/g, 2037.22 mg/g, and 2076.81 mg/g at 298 K, 313 K, and 328 K respectively, increasing with increasing of temperature. The PDA nanospheres exhibited highly selective adsorption of Hg2+ and had a total desorption capacity of 100% in hydrochloric acid solution, pH 1. The results showed that the structure of PDA nanospheres remained almost unchanged after recycling five times. Furthermore, X-ray photoelectron spectroscopy (XPS) was employed to determine the elements of PDA nanospheres before and after Hg2+ adsorption. Considering their efficient and highly Hg2+ selective adsorption, total recycle capacity, and high stability, PDA nanospheres will be feasible in a number of practical applications.

  2. Adsorption of Ag, Cu and Hg from aqueous solutions using expanded perlite.

    PubMed

    Ghassabzadeh, Hamid; Mohadespour, Ahmad; Torab-Mostaedi, Meisam; Zaheri, Parisa; Maragheh, Mohammad Ghannadi; Taheri, Hossein

    2010-05-15

    The aim of the present work was to investigate the ability of expanded perlite (EP) to remove of silver, copper and mercury ions from aqueous solutions. Batch adsorption experiments were carried out and the effect of pH, adsorbent dosage, contact time and temperature of solution on the removal process has been investigated. The optimum pH for the adsorption was found to be 6.5. Adsorption of these metal ions reached their equilibrium concentration in 120, 240 and 180 min for Ag (I), Cu (II) and Hg (II) ions, respectively. Experimental data were also evaluated in terms of kinetic characteristics of adsorption and it was found that adsorption process for these metal ions followed well pseudo-second-order kinetics. Using Langmuir isotherm model, maximum adsorption capacity of EP was found to be 8.46, 1.95 and 0.35 mg/g for Ag (I), Cu (II) and Hg (II) ions, respectively. Finally, the thermodynamic parameters including, the change of free energy (DeltaG degrees ), enthalpy (DeltaH degrees ) and entropy (DeltaS degrees ) of adsorption were calculated for each metal ion. The results showed that the adsorption of these metal ions on EP was feasible and exothermic at 20-50 degrees C.

  3. Enhanced adsorption of mercury ions on thiol derivatized single wall carbon nanotubes.

    PubMed

    Bandaru, Narasimha Murthy; Reta, Nekane; Dalal, Habibullah; Ellis, Amanda V; Shapter, Joseph; Voelcker, Nicolas H

    2013-10-15

    Thiol-derivatized single walled carbon nanotube (SWCNT-SH) powders were synthesized by reacting acid-cut SWCNTs with cysteamine hydrochloride using carbodiimide coupling. Infrared (IR) spectroscopy, Raman spectroscopy and thermogravimetric analysis confirmed the successful functionalization of the SWCNTs. SWCNT-SH powders exhibited a threefold higher adsorption capacity for Hg(II) ions compared to pristine SWCNTs, and a fourfold higher adsorption capacity compared to activated carbon. The influence of adsorption time, pH, initial metal concentration and adsorbent dose on Hg(II) ion removal was investigated. The maximum adsorption capacity of the SWCNT-SH powders was estimated by using equilibrium isotherms, such as Freundlich and Langmuir, and the maximum adsorption capacity of the SWCNT-SH powder was found to be 131 mg/g. A first-order rate model was employed to describe the kinetic adsorption process of Hg(II) ions onto the SWCNT-SH powders. Desorption studies revealed that Hg(II) ions could be easily removed from the SWCNT-SH powders by altering the pH. Further, the adsorption efficiency of recovered SWCNT-SH powders was retained up to 91%, even after 5 adsorption/desorption cycles.

  4. Kinetic modeling of liquid-phase adsorption of phosphate on dolomite.

    PubMed

    Karaca, S; Gürses, A; Ejder, M; Açikyildiz, M

    2004-09-15

    The adsorption of phosphate from aqueous solution on dolomite was investigated at 20 and 40 degrees C in terms of pseudo-second-order mechanism for chemical adsorption as well as an intraparticle diffusion mechanism process. Adsorption was changed with increased contact time, initial phosphate concentration, temperature, solution pH. A pseudo-second-order model and intraparticle diffusion model have been developed to predict the rate constants of adsorption and equilibrium capacities. The activation energy of adsorption can be evaluated using the pseudo-second-order rate constants. The adsorption of phosphate onto dolomite are an exothermically activated process. A relatively low activation energy and a model highly fitting to intraparticle diffusion suggest that the adsorption of phosphate by dolomite may involve not only physical but also chemisorption. This was likely due to its combined control of chemisorption and intraparticle diffusion. However, for phosphate/dolomite system chemical reaction is important and significant in the rate-controlling step, and for the adsorption of phosphate onto dolomite the pseudo-second-order chemical reaction kinetics provides the best correlation of the experimental data.

  5. [Adsorption of methylene blue from aqueous solution onto magnetic Fe3O4/ graphene oxide nanoparticles].

    PubMed

    Chang, Qing; Jiang, Guo-Dong; Hu, Meng-Xuan; Huang, Jia; Tang, He-Qing

    2014-05-01

    A simple ultrasound-assisted co-precipitation method was developed to prepare magnetic Fe3O4/graphene oxide (Fe3O4/ GO) nanoparticles. The characterization with transmission electron microscope (TEM) indicated that the products possessed small particle size. The hysteresis loop of the dried Fe3O4/GO nanoparticles demonstrated that the sample had typical features of superparamagnetic material. Batch adsorption studies were carried out to investigate the effects of the initial pH of the solution, the dosage of adsorbent, the contact time and temperature on the adsorption of methylene blue. The results indicated that the composites prepared could be used over a broad pH range (pH 6-9). The adsorption process was very fast within the first 25 min and the equilibrium was reached at 180 min. The adsorption equilibrium and kinetics data fitted well with the Langmuir isotherm model and the pseudo-second-order kinetic model. The adsorption process was a spontaneous and endothermic process in nature. The composite exhibited fairly high adsorption capacity (196.5 mg.g-1) of methylene blue at 313 K. In addition, the magnetic composite could be effectively and simply separated by using an external magnetic field, and then regenerated by hydrogen peroxide and recycled for further use. The results indicated that the adsorbent had a potential in the application of the dye wastewater treatment.

  6. Removal of beta-blockers from aqueous media by adsorption onto graphene oxide.

    PubMed

    Kyzas, George Z; Koltsakidou, Anastasia; Nanaki, Stavroula G; Bikiaris, Dimitrios N; Lambropoulou, Dimitra A

    2015-12-15

    The aim of the present study is the evaluation of graphene oxide (GhO) as adsorbent material for the removal of beta-blockers (pharmaceutical compounds) in aqueous solutions. The composition and morphology of prepared materials were characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR). Atenolol (ATL) and propranolol (PRO) were used as model drug molecules and their behavior were investigated in terms of GhO dosage, contact time, temperature and pH. Adsorption mechanisms were proposed and the pH-effect curves after adsorption were discussed. The kinetic behavior of GhO-drugs system was analyzed after fitting to pseudo-first and -second order equations. The adsorption equilibrium data were fitted to Langmuir, Freundlich and Langmuir-Freundlich model calculating the maximum adsorption capacity (67 and 116 mg/g for PRO and ATL (25 °C), respectively). The temperature effect on adsorption was tested carrying out the equilibrium adsorption experiments at three different temperatures (25, 45, 65 °C). Then, the thermodynamic parameters of enthalpy, free energy and entropy were calculated. Finally, the desorption of drugs from GhO was evaluated by using both aqueous eluants (pH2-10) and organic solvents.

  7. Nonlinear transport in an out-of-equilibrium single-site Bose-Hubbard model: Scaling, rectification, and time dynamics

    NASA Astrophysics Data System (ADS)

    Purkayastha, Archak; Dhar, Abhishek; Kulkarni, Manas

    2016-11-01

    Recent experiments in hybrid-quantum systems facilitate the potential realization of one of the most fundamental interacting Hamiltonian-reservoir systems, namely the single-site Bose-Hubbard model coupled to two reservoirs at different temperatures. Using Redfield equations in a Born-Markov approximation, we compute nonequilibrium average particle number, energy, and currents beyond linear response regime, both time dynamics and steady state, and investigate its dependence on various tunable parameters analytically. We find interesting scaling laws in high-temperature regimes that are independent of choice of bath spectral functions. We also demonstrate that the system shows very interesting particle and energy current rectification properties which can be controlled via the relative strength of interaction and temperatures, as well as via the degree of asymmetry in system-bath coupling. Specifically, we find inversion of direction of energy rectification as a function of the relative strength of the interaction strength and the temperatures. We also show that, in the limit of low-temperature and high interaction strength, our results are consistent with the nonequilibrium spin-Boson model. Our results are experimentally relevant not only to hybrid quantum systems but also in other areas such as molecular junctions.

  8. Evaluation of Penicillium digitatum sterilization using non-equilibrium atmospheric pressure plasma by terahertz time-domain spectroscopy

    NASA Astrophysics Data System (ADS)

    Hiraoka, Takehiro; Ebizuka, Noboru; Takeda, Keigo; Ohta, Takayuki; Kondo, Hiroki; Ishikawa, Kenji; Kawase, Kodo; Ito, Masafumi; Sekine, Makoto; Hori, Masaru

    2011-10-01

    Recently, the plasma sterilization has attracted much attention as a new sterilization technique that takes the place of spraying agricultural chemicals. The conventional methods for sterilization evaluation, was demanded to culture the samples for several days after plasma treatment. Then, we focused on Terahertz time-domain spectroscopy (THz-TDS). At the THz region, vibrational modes of biological molecules and fingerprint spectra of biologically-relevant molecules were also observed. In this study, our purpose was measurement of the fingerprint spectrum of the Penicillium digitatum (PD) spore and establishment of sterilization method by THz-TDS. The sample was 40mg/ml PD spore suspensions which dropped on cover glass. The atmospheric pressure plasma generated under the conditions which Ar gas flow was 3slm, and alternating voltage of 6kV was applied. The samples were exposed the plasma from 10mm distance for 10 minutes. We could obtain the fingerprint spectrum of the PD spore from 0.5 to 0.9THz. This result indicated the possibility of in-situ evaluation for PD sterilization using THz-TDS.

  9. 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

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

    PubMed

    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.

  11. Adsorption of Cd(II) and Pb(II) from aqueous solutions on activated alumina.

    PubMed

    Naiya, Tarun Kumar; Bhattacharya, Ashim Kumar; Das, Sudip Kumar

    2009-05-01

    The ability of activated alumina as synthetic adsorbent was investigated for adsorptive removal of Cd(II) and Pb(II) ions from aqueous solutions. Various physico-chemical parameters such as pH, initial metal ion concentration, and adsorbent dosage level and equilibrium contact time were studied. The optimum solution pH for adsorption of Cd(II) and Pb(II) from aqueous solutions was found to be 5. Kinetics data were best described by pseudo-second order model. The effective particle diffusion coefficient of Cd(II) and Pb(II) are of the order of 10(-10) m(2)/s. Values of mass transfer coefficient were estimated as 4.868x10(-6) cm/s and 6.85x10(-6) cm/s for Cd(II) and Pb(II) adsorption respectively. The equilibrium adsorption data for Cd(II) and Pb(II) were better fitted to Langmuir adsorption isotherm model. The thermodynamic studies indicated that the adsorption was spontaneous and exothermic for Cd(II) adsorption and endothermic for Pb(II). The sorption energy calculated from Dubinin-Radushkevich isotherm were 11.85 kJ/mol and 11.8 kJ/mol for the adsorption of Cd(II) and Pb(II) respectively which indicated that both the adsorption processes were chemical in nature. Desorption studies were carried out using dilute mineral acids. Application studies carried out using industrial waste water samples containing Cd(II) and Pb(II) showed the suitability of activated alumina in waste water treatment plant operation.

  12. 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.

  13. Thermodynamic efficiency out of equilibrium

    NASA Astrophysics Data System (ADS)

    Sivak, David; Crooks, Gavin

    2011-03-01

    Molecular-scale machines typically operate far from thermodynamic equilibrium, limiting the applicability of equilibrium statistical mechanics to understand their efficiency. Thermodynamic length analysis relates a non-equilibrium property (dissipation) to equilibrium properties (equilibrium fluctuations and their relaxation time). Herein we demonstrate that the thermodynamic length framework follows directly from the assumptions of linear response theory. Uniting these two frameworks provides thermodynamic length analysis a firmer statistical mechanical grounding, and equips linear response theory with a metric structure to facilitate the prediction and discovery of optimal (minimum dissipation) paths in complicated free energy landscapes. To explore the applicability of this theoretical framework, we examine its accuracy for simple bistable systems, parametrized to model single-molecule force-extension experiments. Through analytic derivation of the equilibrium fluctuations and numerical calculation of the dissipation and relaxation time, we verify that thermodynamic length analysis (though derived in a near-equilibrium limit) provides a strikingly good approximation even far from equilibrium, and thus provides a useful framework for understanding molecular motor efficiency.

  14. Thrombin, kallikrein and complement C5b-9 adsorption on hydrophilic and hydrophobic titanium and glass after short time exposure to whole blood.

    PubMed

    Yahyapour, Noushin; Eriksson, Cecilia; Malmberg, Per; Nygren, Håkan

    2004-07-01

    Hydrophilic and hydrophobic titanium and glass were exposed to capillary whole blood between 5s and 24h. The time-sequence for adsorption of thrombin, kallikrein and complement C5b-9, and their relationship with adherent platelets and polymorphonuclear granulocyte (PMN) activation were investigated. Adsorbed thrombin and kallikrein were measured by cleavage of specific chromogenic substances, S-2238 and S-2303, respectively. Complement C5b-9 and expression of CD11b, CD66b, CD62P and Pan-platelets were measured by immunofluorescence. Thrombin and kallikrein were present on the surfaces during the whole investigated periods. Platelet adhesion and PMN cell adhesion and activation on all surfaces and activation of platelets on hydrophobic surfaces showed a similar pattern to thrombin adsorption. Kallikrein adsorption had a different pattern on each surface. C5b-9 was detected between 32min and 24h of blood exposure and a varying pattern of C5b-9 coverage was observed on each surface. In conclusion, our results indicate that the interaction between material and blood coagulation and kinin-activating proteins regulate the adhesion and activation of blood cells, whereas after longer time the coagulation and kallikrein-kinin system play minor roles and the complement system is decisive for mediating and elongating the inflammatory process.

  15. Langmuir probe measurements in a time-fluctuating-highly ionized non-equilibrium cutting arc: Analysis of the electron retarding part of the time-averaged current-voltage characteristic of the probe

    SciTech Connect

    Prevosto, L.; Mancinelli, B.; Kelly, H.

    2013-12-15

    This work describes the application of Langmuir probe diagnostics to the measurement of the electron temperature in a time-fluctuating-highly ionized, non-equilibrium cutting arc. The electron retarding part of the time-averaged current-voltage characteristic of the probe was analysed, assuming that the standard exponential expression describing the electron current to the probe in collision-free plasmas can be applied under the investigated conditions. A procedure is described which allows the determination of the errors introduced in time-averaged probe data due to small-amplitude plasma fluctuations. It was found that the experimental points can be gathered into two well defined groups allowing defining two quite different averaged electron temperature values. In the low-current region the averaged characteristic was not significantly disturbed by the fluctuations and can reliably be used to obtain the actual value of the averaged electron temperature. In particular, an averaged electron temperature of 0.98 ± 0.07 eV (= 11400 ± 800 K) was found for the central core of the arc (30 A) at 3.5 mm downstream from the nozzle exit. This average included not only a time-average over the time fluctuations but also a spatial-average along the probe collecting length. The fitting of the high-current region of the characteristic using such electron temperature value together with the corrections given by the fluctuation analysis showed a relevant departure of local thermal equilibrium in the arc core.

  16. Langmuir probe measurements in a time-fluctuating-highly ionized non-equilibrium cutting arc: analysis of the electron retarding part of the time-averaged current-voltage characteristic of the probe.

    PubMed

    Prevosto, L; Kelly, H; Mancinelli, B

    2013-12-01

    This work describes the application of Langmuir probe diagnostics to the measurement of the electron temperature in a time-fluctuating-highly ionized, non-equilibrium cutting arc. The electron retarding part of the time-averaged current-voltage characteristic of the probe was analysed, assuming that the standard exponential expression describing the electron current to the probe in collision-free plasmas can be applied under the investigated conditions. A procedure is described which allows the determination of the errors introduced in time-averaged probe data due to small-amplitude plasma fluctuations. It was found that the experimental points can be gathered into two well defined groups allowing defining two quite different averaged electron temperature values. In the low-current region the averaged characteristic was not significantly disturbed by the fluctuations and can reliably be used to obtain the actual value of the averaged electron temperature. In particular, an averaged electron temperature of 0.98 ± 0.07 eV (= 11400 ± 800 K) was found for the central core of the arc (30 A) at 3.5 mm downstream from the nozzle exit. This average included not only a time-average over the time fluctuations but also a spatial-average along the probe collecting length. The fitting of the high-current region of the characteristic using such electron temperature value together with the corrections given by the fluctuation analysis showed a relevant departure of local thermal equilibrium in the arc core.

  17. Direct Observation of Thermal Equilibrium of Excited Triplet States of 9,10-Phenanthrenequinone. A Time-Resolved Resonance Raman Study.

    PubMed

    Kumar, Venkatraman Ravi; Rajkumar, Nagappan; Ariese, Freek; Umapathy, Siva

    2015-10-08

    The photochemistry of aromatic ketones plays a key role in various physicochemical and biological processes, and solvent polarity can be used to tune their triplet state properties. Therefore, a comprehensive analysis of the conformational structure and the solvent polarity induced energy level reordering of the two lowest triplet states of 9,10-phenanthrenequinone (PQ) was carried out using nanosecond-time-resolved absorption (ns-TRA), time-resolved resonance Raman (TR(3)) spectroscopy, and time dependent-density functional theory (TD-DFT) studies. The ns-TRA of PQ in acetonitrile displays two bands in the visible range, and these two bands decay with similar lifetime at least at longer time scales (μs). Interestingly, TR(3) spectra of these two bands indicate that the kinetics are different at shorter time scales (ns), while at longer time scales they followed the kinetics of ns-TRA spectra. Therefore, we report a real-time observation of the thermal equilibrium between the two lowest triplet excited states of PQ, assigned to nπ* and ππ* of which the ππ* triplet state is formed first through intersystem crossing. Despite the fact that these two states are energetically close and have a similar conformational structure supported by TD-DFT studies, the slow internal conversion (∼2 ns) between the T(2)(1(3)nπ*) and T(1)(1(3)ππ*) triplet states indicates a barrier. Insights from the singlet excited states of PQ in protic solvents [ J. Chem. Phys. 2015 , 142 , 24305 ] suggest that the lowest nπ* and ππ* triplet states should undergo hydrogen bond weakening and strengthening, respectively, relative to the ground state, and these mechanisms are substantiated by TD-DFT calculations. We also hypothesize that the different hydrogen bonding mechanisms exhibited by the two lowest singlet and triplet excited states of PQ could influence its ISC mechanism.

  18. The adsorption of chromium (VI) from industrial wastewater by acid and base-activated lignocellulosic residues.

    PubMed

    Alvarez, Patricia; Blanco, Clara; Granda, Marcos

    2007-06-01

    This study deals with the adsorption of Cr(VI) from synthetic and industrial wastewater, produced by a sewage plant. The activated carbons were prepared from a lignocellulosic raw material by thermal treatment at 450 and 650 degrees C in the presence of acid (AlCl(3), HCl, H(3)PO(4) and H(2)SO(4)) and base (NaOH) agents. To optimize the adsorption of Cr(VI), the chemical modifications caused by each activating agent (related to the capability of Cr(VI) removal), and the optimal experimental conditions of the pH, Cr(VI) concentration, adsorbent dose and residence time, were studied. Thus, treatment with H(3)PO(4) gives rise to carbons with a high surface area and high efficiency for Cr(VI) removal at short equilibrium times. In contrast, the generation of active surface sites by means of NaOH requires longer equilibrium times, the adsorption being less effective than in the former case. The adsorption isotherms obey the Langmuir equation only in the first stages of the reaction but fit the Freundlich equations over the whole range studied, so the heat of adsorption can be easily calculated. The results also show that the activated carbons obtained can be recovered by filtration with an efficiency of 30% in the third cycle.

  19. Dynamic sorption of ammonium by sandy soil in fixed bed columns: Evaluation of equilibrium and non-equilibrium transport processes.

    PubMed

    Jellali, S; Diamantopoulos, E; Kallali, H; Bennaceur, S; Anane, M; Jedidi, N

    2010-01-01

    The release of excess nitrogen-containing compounds into groundwater is a major concern in aquifer recharge by the Soil Aquifer Treatment (SAT) process. Ammonium (NH(4)(+)) is one of the most nocive and common nitrogen compounds in wastewaters. In order to assess the risk of wastewater use for aquifer recharge, NH(4)(+)adsorption onto Souhil wadi soil sampled from the SAT pilot plant (Nabeul, Tunisia) was studied using laboratory columns experiments. Several experiments were conducted using aqueous synthetic solutions under different aqueous ammonium concentrations and flow rates. Furthermore, a real wastewater solution was used to test the effect of competitive cations contents on NH(4)(+) adsorption. Afterwards, the Hydrus-1D model was used in inverse mode to simulate the ammonium transport through the Souhil wadi soil. For the synthetic solutions, the adsorbed ammonium amount varied from 1 to 30.7 mg kg(-1) for aqueous ammonium concentrations between 4.9 and 36.4 mg L(-1). The linear isotherm model was found to be the most suitable for describing this adsorption. The flow rate decrease from 45 to 15 mL min(-1) induced an increase in the ammonium adsorption capacity by 49%. Indeed, the lesser the flow rate is, the longer the residence time and the higher the exchange between the aqueous solution and soil matrix. The use of wastewater instead of aqueous synthetic solution decreased about 7 times the Souhil wadi adsorption capacity of ammonium because of its relatively high concentrations of competitive ions such as calcium and magnesium. The use of the Hydrus-1D model showed that the chemical non-equilibrium model was the best to simulate the ammonium transport through the laboratory soil columns.

  20. Multilayer adsorption on fractal surfaces.

    PubMed

    Vajda, Péter; Felinger, Attila

    2014-01-10

    Multilayer adsorption is often observed in liquid chromatography. The most frequently employed model for multilayer adsorption is the BET isotherm equation. In this study we introduce an interpretation of multilayer adsorption measured on liquid chromatographic stationary phases based on the fractal theory. The fractal BET isotherm model was successfully used to determine the apparent fractal dimension of the adsorbent surface. The nonlinear fitting of the fractal BET equation gives us the estimation of the adsorption equilibrium constants and the monolayer saturation capacity of the adsorbent as well. In our experiments, aniline and proline were used as test molecules on reversed phase and normal phase columns, respectively. Our results suggest an apparent fractal dimension 2.88-2.99 in the case of reversed phase adsorbents, in the contrast with a bare silica column with a fractal dimension of 2.54.

  1. Ab initio molecular dynamics study of ethylene adsorption onto Si(001) surface: short-time Fourier transform analysis of structural coordinate autocorrelation function.

    PubMed

    Lee, Yung Ting; Lin, Jyh Shing

    2013-12-05

    The reaction dynamics of ethylene adsorption onto the Si(001) surface have been studied by combining density functional theory-based molecular dynamics simulations with molecular adsorption sampling scheme for investigating all kinds of reaction pathways and corresponding populations. Based on the calculated results, three possible reaction pathways--the indirect adsorption, the direct adsorption, and the repelling reaction--have been found. First, the indirect adsorption, in which the ethylene (C2H(4(ads))) forms the π-bonded C2H(4(ads)) with the buckled-down Si atom to adsorb on the Si(001) surface and then turns into the di-σ-bonded C2H(4(ads)), is the major reaction pathway. The short-time Fourier transform analysis of structural coordinate autocorrelation function is performed to further investigate the evolution of different vibrational modes along this indirect reaction pathway. This analysis illustrates that the Infrared (IR) inactive peak of the C=C stretching mode of the π-bonded C2 H4(ads) shifts to the IR inactive peak of the C-C stretching mode of di-σ-bonded C2H(4(ads)), which is in a good agreement with the IR inactive peak of the C=C stretching mode vanished in the vibrational spectrum at 150 K (Nagao et al., J. Am. Chem. Soc. 2004, 126, 9922). Second, the direct adsorption, in which the di-σ-bonded C2H(4(ads)) is formed directly with the Si intradimer or the Si interdimer on the Si(001) surface, is the less significant reaction pathway. This reaction pathway leads to the C-C stretching mode and the C-H stretching mode of the di-σ-bonded C2H(4(ads)) appeared in the vibrational spectra at 48 and 150 K, respectively (Nagao et al., J. Am. Chem. Soc. 2004, 126, 9922). Finally, the repelling reaction, in which the C2H(4(g)) first interacts with the Si dimer and then is repelled by Si atoms, is the least important reaction pathway. Consequently, neither the π-bonded C2H(4(ads)) nor the di-σ-bonded C2H(4(ads)) is formed on the Si(001) surface.

  2. Adsorption of arsenic ions on Brazilian sepiolite: effect of contact time, pH, concentration, and calorimetric investigation.

    PubMed

    Guerra, Denis L; Batista, Adriano C; da Costa, Paulo C Corrêa; Viana, Rúbia R; Airoldi, Claudio

    2010-06-01

    The original sepiolite clay mineral has been collected from Amazon region, Brazil. The compound 2-aminomethylpyridine (AMP) was anchored onto Amazon sepiolite surface by heterogeneous route. The natural (SPT) and modified (SPT(AMP)) sepiolite samples were characterized by elemental analysis, SEM, N(2) adsorption, and nuclear magnetic nuclei of (29)Si and (13)C. The well-defined peaks obtained in the (13)C NMR spectrum in the 0-160 ppm region confirmed the attachment of organic functional groups as pendant chains bonded into the porous clay. The ability of these materials to remove As(V) from aqueous solution was followed by a series of adsorption isotherms at room temperature and pH 4.0. The maximum number of moles adsorbed was determined to be 7.26×10(-2) and 11.70×10(-2) mmol g(-1) for SPT and SPT(AMP), respectively. In order to evaluate the clay samples as adsorbents in dynamic system, a glass column was fulfilled with clay samples (1.0 g) and it was fed with 2.0×10(-2) mmol dm(-3) As(V) at pH 4.0. The energetic effects caused by metal cations adsorption were determined through calorimetric titrations. Thermodynamics indicated the existence of favorable conditions for such As(V)-nitrogen interactions.

  3. Adsorption of heavy metal ions from aqueous solution by carboxylated cellulose nanocrystals.

    PubMed

    Yu, Xiaolin; Tong, Shengrui; Ge, Maofa; Wu, Lingyan; Zuo, Junchao; Cao, Changyan; Song, Weiguo

    2013-05-01

    A novel nanoadsorbent for the removal of heavy metal ions is reported. Cotton was first hydrolyzed to obtain cellulose nanocrystals (CNCs). CNCs were then chemically modified with succinic anhydride to obtain SCNCs. The sodic nanoadsorbent (NaSCNCs) was further prepared by treatment of SCNCs with saturated NaHCO3 aqueous solution. Batch experiments were carried out with SCNCs and NaSCNCs for the removal of Pb2+ and Cd2+. The effects of contact time, pH, initial adsorption concentration, coexisting ions and the regeneration performance were investigated. Kinetic studies showed that the adsorption equilibrium time of Pb2+ and Cd2+ was reached within 150 min on SCNCs and 5 min on NaSCNCs. The adsorption capacities of Pb2+ and Cd2+ on SCNCs and NaSCNCs increased with increasing pH. The adsorption isotherm was well fitted by the Langmuir model. The maximum adsorption capacities of SCNCs and NaSCNCs for Pb2+ and Cd2+ were 367.6 mg/g, 259.7 mg/g and 465.1 mg/g, 344.8 mg/g, respectively. SCNCs and NaSCNCs showed high selectivity and interference resistance from coexisting ions for the adsorption of Pb2+. NaSCNCs could be efficiently regenerated with a mild saturated NaCl solution with no loss of capacity after two recycles. The adsorption mechanisms of SCNCs and NaSCNCs were discussed.

  4. Adsorption calorimetry during metal vapor deposition on single crystal surfaces: Increased flux, reduced optical radiation, and real-time flux and reflectivity measurements

    NASA Astrophysics Data System (ADS)

    Sellers, Jason R. V.; James, Trevor E.; Hemmingson, Stephanie L.; Farmer, Jason A.; Campbell, Charles T.

    2013-12-01

    Thin films of metals and other materials are often grown by physical vapor deposition. To understand such processes, it is desirable to measure the adsorption energy of the deposited species as the film grows, especially when grown on single crystal substrates where the structure of the adsorbed species, evolving interface, and thin film are more homogeneous and well-defined in structure. Our group previously described in this journal an adsorption calorimeter capable of such measurements on single-crystal surfaces under the clean conditions of ultrahigh vacuum [J. T. Stuckless, N. A. Frei, and C. T. Campbell, Rev. Sci. Instrum. 69, 2427 (1998)]. Here we describe several improvements to that original design that allow for heat measurements with ˜18-fold smaller standard deviation, greater absolute accuracy in energy calibration, and, most importantly, measurements of the adsorption of lower vapor-pressure materials which would have previously been impossible. These improvements are accomplished by: (1) using an electron beam evaporator instead of a Knudsen cell to generate the metal vapor at the source of the pulsed atomic beam, (2) changing the atomic beam design to decrease the relative amount of optical radiation that accompanies evaporation, (3) adding an off-axis quartz crystal microbalance for real-time measurement of the flux of the atomic beam during calorimetry experiments, and (4) adding capabilities for in situ relative diffuse optical reflectivity determinations (necessary for heat signal calibration). These improvements are not limited to adsorption calorimetry during metal deposition, but also could be applied to better study film growth of other elements and even molecular adsorbates.

  5. Adsorption calorimetry during metal vapor deposition on single crystal surfaces: Increased flux, reduced optical radiation, and real-time flux and reflectivity measurements

    SciTech Connect

    Sellers, Jason R. V.; James, Trevor E.; Hemmingson, Stephanie L.; Farmer, Jason A.; Campbell, Charles T.

    2013-12-15

    Thin films of metals and other materials are often grown by physical vapor deposition. To understand such processes, it is desirable to measure the adsorption energy of the deposited species as the film grows, especially when grown on single crystal substrates where the structure of the adsorbed species, evolving interface, and thin film are more homogeneous and well-defined in structure. Our group previously described in this journal an adsorption calorimeter capable of such measurements on single-crystal surfaces under the clean conditions of ultrahigh vacuum [J. T. Stuckless, N. A. Frei, and C. T. Campbell, Rev. Sci. Instrum. 69, 2427 (1998)]. Here we describe several improvements to that original design that allow for heat measurements with ∼18-fold smaller standard deviation, greater absolute accuracy in energy calibration, and, most importantly, measurements of the adsorption of lower vapor-pressure materials which would have previously been impossible. These improvements are accomplished by: (1) using an electron beam evaporator instead of a Knudsen cell to generate the metal vapor at the source of the pulsed atomic beam, (2) changing the atomic beam design to decrease the relative amount of optical radiation that accompanies evaporation, (3) adding an off-axis quartz crystal microbalance for real-time measurement of the flux of the atomic beam during calorimetry experiments, and (4) adding capabilities for in situ relative diffuse optical reflectivity determinations (necessary for heat signal calibration). These improvements are not limited to adsorption calorimetry during metal deposition, but also could be applied to better study film growth of other elements and even molecular adsorbates.

  6. Equilibrium analysis for heavy metal cation removal using cement kiln dust.

    PubMed

    El Zayat, Mohamed; Elagroudy, Sherien; El Haggar, Salah

    2014-01-01

    Ion exchange, reverse osmosis, and chemical precipitation have been investigated extensively for heavy metal uptake. However, they are deemed too expensive to meet stringent effluent characteristics. In this study, cement kiln dust (CKD) was examined for the removal of target heavy metals. Adsorption studies in completely mixed batch reactors were used to generate equilibrium pH adsorption edges. Studies showed the ability of CKD to remove the target heavy metals in a pH range below that of precipitation after an equilibrium reaction time of 24 h. A surface titration experiment indicated negative surface charge of the CKD at pH below 10, meaning that electrostatic attraction of the divalent metals can occur below the pH required for precipitation. However, surface complexation was also important due to the substantive metal removal. Accordingly, a surface complexation model approach that utilizes an electrostatic term in the double-layer description was used to estimate equilibrium constants for the protolysis interactions of the CKD surface as well as equilibria between background ions and the sorbent surface. It was concluded that the removal strength of adsorption is in the order: Pb > Cu > Cd. The experiments were also supported by Fourier transform infrared spectroscopy (FTIR).

  7. Open problems in non-equilibrium physics

    SciTech Connect

    Kusnezov, D.

    1997-09-22

    The report contains viewgraphs on the following: approaches to non-equilibrium statistical mechanics; classical and quantum processes in chaotic environments; classical fields in non-equilibrium situations: real time dynamics at finite temperature; and phase transitions in non-equilibrium conditions.

  8. Adsorptive desulfurization by activated alumina.

    PubMed

    Srivastav, Ankur; Srivastava, Vimal Chandra

    2009-10-30

    This study reports usage of commercial grade activated alumina (aluminum oxide) as adsorbent for the removal of sulfur from model oil (dibenthiophene (DBT) dissolved in n-hexane). Bulk density of alumina was found to be 1177.77 kg/m(3). The BET surface area of alumina was found to decrease from 143.6 to 66.4 m(2)/g after the loading of DBT at optimum conditions. The carbon-oxygen functional groups present on the surface of alumina were found to be effective in the adsorption of DBT onto alumina. Optimum adsorbent dose was found to be 20 g/l. The adsorption of DBT on alumina was found to be gradual process, and quasi-equilibrium reached in 24 h. Langmuir isotherm best represented the equilibrium adsorption data. The heat of adsorption and change in entropy for DBT adsorption onto alumina was found to be 19.5 kJ/mol and 139.2 kJ/mol K, respectively.

  9. Kinetic studies of elemental mercury adsorption in activated carbon fixed bed reactor.

    PubMed

    Skodras, G; Diamantopoulou, Ir; Pantoleontos, G; Sakellaropoulos, G P

    2008-10-01

    Activated carbons are suitable materials for Hg(0) adsorption in fixed bed operation or in injection process. The fixed bed tests provide good indication of activated carbons effectiveness and service lives, which depend on the rates of Hg(0) adsorption. In order to correlate fixed bed properties and operation conditions, with their adsorptive capacity and saturation time, Hg(0) adsorption tests were realized in a bench-scale unit, consisted of F400 activated carbon fixed bed reactor. Hg(0) adsorption tests were conducted at 50 degrees C, under 0.1 and 0.35 ng/cm(3) Hg(0) initial concentrations and with carbon particle sizes ranging between 75-106 and 150-250 microm. Based on the experimental breakthrough data, kinetic studies were performed to investigate the mechanism of adsorption and the rate controlling steps. Kinetic models evaluated include the Fick's intraparticle diffusion equation, the pseudo-first order model, the pseudo-second order model and Elovich kinetic equation. The obtained experimental results revealed that the increase in particle size resulted in significant decrease of breakthrough time and mercury adsorptive capacity, due to the enhanced internal diffusion limitations and smaller external mass transfer coefficients. Additionally, higher initial mercury concentrations resulted in increased breakthrough time and mercury uptake. From the kinetic studies results it was observed that all the examined models describes efficiently Hg(0) breakthrough curves, from breakpoint up to equilibrium time. The most accurate prediction of the experimental data was achieved by second order model, indicating that the chemisorption rate seems to be the controlling step in the procedure. However, the successful attempt to describe mercury uptake with Fick's diffusion model and the first order kinetic model, reveals that the adsorption mechanism studied was complex and followed both surface adsorption and particle diffusion.

  10. Color removal from paper mill effluent through adsorption technology.

    PubMed

    Jain, C K; Kumar, Arvind; Hayssam Izazy, M

    2009-02-01

    The bagasse fly ash, obtained from the local sugar industry, has been used as an inexpensive and effective adsorbent for the removal of color from pulp and paper industry. Effect of various operating variables, viz., contact time, initial concentration, adsorbent dose and particle size on the removal of color has been studied and discussed. It is found that for optimum removal of color, contact time for adsorption equilibrium equals to 60 min., at dosage of 2 g/l of baggase fly ash. The material exhibits good removal capacity (86%) and follows both the Langmuir and the Freundlich models.

  11. Adsorption and desorption properties of trans-resveratrol on cellulose cotton.

    PubMed

    Takagai, Yoshitaka; Kubota, Toshio; Kobayashi, Hidetoshi; Tashiro, Tomoyasu; Takahashi, Atsushi; Igarashi, Shukuro

    2005-02-01

    The adsorption and desorption properties of trans-Resveratrol (Res) on the cellulose cotton were investigated under various conditions, such as the pH, alcohol percentage, temperature and equilibrium times. Moreover, the acidic-dissociation constants were determined to be pKa1 = 8.01, pKa2 = 9.86 and pKa3 = 10.5 by a curve-fitting method. Also, it was found that the adsorption depended on the temperature and salting effect. On the other hand, the desorptions from cellulose were examined using several kinds of water-miscible organic solvents (methanol, ethanol, acetone and THF).

  12. Malachite green adsorption onto natural zeolite and reuse by microwave irradiation.

    PubMed

    Han, Runping; Wang, Yu; Sun, Qing; Wang, Lulu; Song, Jiyun; He, Xiaotian; Dou, Chanchan

    2010-03-15

    Natural zeolite was used for the removal of malachite green (MG) from aqueous solution in batch mode and reused by microwave irradiation. The isotherm data were analyzed by the Langmuir, Freundlich, Redlich-Peterson, and Koble-Corrigan isotherm model. The better fit for the equilibrium process was Koble-Corrigan model. The kinetic studies indicated that the adsorption followed the pseudo-second-order kinetic. Thermodynamic calculations showed that the adsorption was spontaneous and endothermic process. Spent zeolite was treated by microwave irradiation and it was found that yield of regeneration was 85.8% in the case of microwave irradiated time 10 min at 160 W.

  13. Equilibrium fluctuations in the theory of surface processes on microparticles

    NASA Astrophysics Data System (ADS)

    Tovbin, Yu. K.

    2010-11-01

    The question of the role of equilibrium fluctuations in the adsorption theory and kinetics of surface processes occurring on the particles of the nanometer size range is discussed. Differences are put forward that need to be introduced to the fluctuation theory of surface processes on microparticles and that generalize Hill's approach to describing the thermodynamic properties of small systems. We show the importance of allowing for the discrete character of adsorption centers on the surfaces and their heterogeneity when describing adsorption isotherms and the rates of adsorption processes.

  14. Methylene blue adsorption from aqueous solution by activated carbon: effect of acidic and alkaline solution treatments.

    PubMed

    Ijagbemi, Christianah O; Chun, Ji I; Han, Da H; Cho, Hye Y; O, Se J; Kim, Dong S

    2010-01-01

    The removal of Methylene Blue (MB) from aqueous solution using activated carbon (AC) has been investigated. Adsorption experiments were conducted and the maximum adsorption capacity was determined. The effect of experimental parameters such as pH, dye concentration and temperature were studied on the adsorption process. Equilibrium data were mathematically modeled using the Langmuir and Freundlich adsorption models to describe the equilibrium isotherms at different dye concentrations and temperature. Parameters of best-fit model were calculated and discussed. To understand the mechanism of adsorption, kinetic models were employed to follow the adsorption processes; the pseudo-first-order best described the adsorption of MB onto AC. It was found that pH plays a major role in the adsorption process; adsorption capacity was influenced by the physical and surface chemical properties of carbon and the pH of the solution. 99.0% MB removal was achieved at equilibrium.

  15. Equilibrium Electroconvective Instability

    NASA Astrophysics Data System (ADS)

    Rubinstein, I.; Zaltzman, B.

    2015-03-01

    Since its prediction 15 years ago, hydrodynamic instability in concentration polarization at a charge-selective interface has been attributed to nonequilibrium electro-osmosis related to the extended space charge which develops at the limiting current. This attribution had a double basis. On the one hand, it has been recognized that neither equilibrium electro-osmosis nor bulk electroconvection can yield instability for a perfectly charge-selective solid. On the other hand, it has been shown that nonequilibrium electro-osmosis can. The first theoretical studies in which electro-osmotic instability was predicted and analyzed employed the assumption of perfect charge selectivity for the sake of simplicity and so did the subsequent studies of various time-dependent and nonlinear features of electro-osmotic instability. In this Letter, we show that relaxing the assumption of perfect charge selectivity (tantamount to fixing the electrochemical potential of counterions in the solid) allows for the equilibrium electroconvective instability. In addition, we suggest a simple experimental test for determining the true, either equilibrium or nonequilibrium, origin of instability in concentration polarization.

  16. Adsorption of methylene blue onto poly(cyclotriphosphazene-co-4,4'-sulfonyldiphenol) nanotubes: kinetics, isotherm and thermodynamics analysis.

    PubMed

    Chen, Zhonghui; Zhang, Jianan; Fu, Jianwei; Wang, Minghuan; Wang, Xuzhe; Han, Runping; Xu, Qun

    2014-05-30

    Poly(cyclotriphosphazene-co-4,4'-sulfonyldiphenol) (PZS) nanotubes, an excellent adsorbent, were successfully synthesized by an in situ template method and used for the removal of methylene blue (MB) from aqueous solution. The morphology and structures of as-synthesized PZS nanotubes were characterized by scanning electron microscopy, transmission electron microscope, Fourier transform infrared spectroscopy and N2 adsorption/desorption isotherms. The effects of temperature, concentration, pH and contact time on MB adsorption were studied. It was favorable for adsorption under the condition of basic and high temperature. The pseudo-first-order, pseudo-second-order and intraparticle diffusion models were used to fit adsorption data in the kinetic studies. And results showed that the adsorption kinetics were more accurately described by the pseudo-second-order model. The equilibrium isotherms were conducted using Freundlich and Langmuir models. It has been demonstrated that the better agreement was Langmuir isotherm with correlation coefficient of 0.9933, equilibrium absorption capacity of 69.16mg/g and the corresponding contact time of 15min. Thermodynamic analyses showed that MB adsorption onto the PZS nanotubes was endothermic and spontaneous and it was also a physisorption process.

  17. Biosorption studies on waste cotton seed for cationic dyes sequestration: equilibrium and thermodynamics

    NASA Astrophysics Data System (ADS)

    Sivarajasekar, N.; Baskar, R.; Ragu, T.; Sarika, K.; Preethi, N.; Radhika, T.

    2016-01-01

    The immature Gossypium hirsutum seeds—an agricultural waste was converted into a novel adsorbent and its effectiveness for cationic dyes removal was discussed in this study. Characterization revealed that sulfuric acid activated waste Gossypium hirsutum seed (WGSAB) contains surface area 496 m2 g-1. The ability of WGSAB to adsorb basic red 2 (BR2) and basic violet 3 (BV3) from aqueous solutions has been studied. Batch adsorption studies were carried out at different initial dye concentrations (100-300 mg l-1), contact time (1-5 h), pH (2-12) and temperature (293-323 K) to understand the adsorption mechanism. Adsorption data were modeled using Langmuir, Freundlich and Toth adsorption isotherms. Equilibrium data of the adsorption process fitted very well to the Toth model for both dyes. The Langmuir maximum adsorption capacity was 66.69 mg g-1 for BV3 and 50.11 mg g-1 for BR2 at optimum conditions. The near unity value of Toth isotherm constant (BR2: 0.999 and BV3: 1.0) indicates that WGSAB surface is heterogeneous in nature. The maximum adsorption capacity predicted by Toth isotherm of BV3 (66.699 mg g-1) is higher than BR2 (50.310 mg g-1). The kinetic investigation revealed that the BR2 and BV3 were chemisorbed on WGSAB surface following Avrami fractional order kinetics. Further, the fractional order and rate constant values are almost similar for every concentration in both the dyes. The thermodynamic parameters such as ΔH 0, ΔS 0 and ΔG 0 were evaluated. The dye adsorption process was found to be spontaneous and endothermic for the two dyes. Regeneration of WGSAB exhausted by the two dyes could be possible via acetic acid as elutant.

  18. Mesoporous carbon adsorbents from melamine-formaldehyde resin using nanocasting technique for CO2 adsorption.

    PubMed

    Goel, Chitrakshi; Bhunia, Haripada; Bajpai, Pramod K

    2015-06-01

    Mesoporous carbon adsorbents, having high nitrogen content, were synthesized via nanocasting technique with melamine-formaldehyde resin as precursor and mesoporous silica as template. A series of adsorbents were prepared by varying the carbonization temperature from 400 to 700°C. Adsorbents were characterized thoroughly by nitrogen sorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), elemental (CHN) analysis, Fourier transform infrared (FTIR) spectroscopy and Boehm titration. Carbonization temperature controlled the properties of the synthesized adsorbents ranging from surface area to their nitrogen content, which play major role in their application as adsorbents for CO2 capture. The nanostructure of these materials was confirmed by XRD and TEM. Their nitrogen content decreased with an increase in carbonization temperature while other properties like surface area, pore volume, thermal stability and surface basicity increased with the carbonization temperature. These materials were evaluated for CO2 adsorption by fixed-bed column adsorption experiments. Adsorbent synthesized at 700°C was found to have the highest surface area and surface basicity along with maximum CO2 adsorption capacity among the synthesized adsorbents. Breakthrough time and CO2 equilibrium adsorption capacity were investigated from the breakthrough curves and were found to decrease with increase in adsorption temperature. Adsorption process for carbon adsorbent-CO2 system was found to be reversible with stable adsorption capacity over four consecutive adsorption-desorption cycles. From three isotherm models used to analyze the equilibrium data, Temkin isotherm model presented a nearly perfect fit implying the heterogeneous adsorbent surface.

  19. Comparison of equilibrium and non-equilibrium distribution coefficients for the human drug carbamazepine in soil.

    PubMed

    Williams, C F; Watson, J E; Nelson, S D

    2014-01-01

    The distribution coefficient (KD) for the human drug carbamazepine was measured using a non-equilibrium technique. Repacked soil columns were prepared using an Airport silt loam (Typic Natrustalf) with an average organic matter content of 2.45%. Carbamazepine solutions were then leached through the columns at 0.5, 1.0 and 1.5 mL min(-1) representing average linear velocities of 1.8, 3.5 and 5.3 cm h(-1) respectively. Each flow rate was replicated three times and three carbamazepine pulses were applied to each column resulting in a total of 9 columns with 27 total carbamazepine pulses. Breakthrough curves were used to determine KD using the parameter fitting software CXTFIT. Results indicate that as flow rate decreased from 5.3 to 1.8 cm h(-1), KD increased an average of 21%. Additionally, KD determined by column leaching (14.7-22.7 L kg(-1)) was greater than KD determined by a 2h batch equilibrium adsorption (12.6 L kg(-1)). Based on these KD's carbamazepine would be generally characterized as non-mobile in the soil investigated. However, repeated carbamazepine applications resulted in an average 22% decrease in KD between the first and third applications. Decreasing KD is attributed to differences in sorption site kinetics and carbamazepine residence time in contact with the soil. This would indicate that the repeated use of reclaimed wastewater at high application rates for long-term irrigation or groundwater recharge has the potential to lead to greater transport of carbamazepine than KD determined by batch equilibrium would predict.

  20. Retrieval of Kinetic Temperature and Carbon Dioxide Abundance from Non-Local Thermodynamic Equilibrium Limb Emission Measurements made by the SABER Experiment on the TIMED Satellite

    NASA Technical Reports Server (NTRS)

    Mertens, Christopher J.; Mlynczak, Martin G.; Lopez-Puertas, Manuel; Wintersteiner, Peter P.; Picard, Richard H.; Winick, Jeremy R.; Gordley, Larry L.; Russell, James M., III

    2002-01-01

    The Sounding of the Atmosphere using Broadband Emission Radiometry (SABER) experiment was launched onboard the TIMED satellite in December, 2001. SABER is designed to provide measurements of the key radiative and chemical sources and sinks of energy in the mesosphere and lower thermosphere (MLT). SABER measures Earth limb emission in 10 broadband radiometer channels ranging from 1.27 micrometers to 17 micrometers. Measurements are made both day and night over the latitude range from 54 deg. S to 87 deg. N with alternating hemisphere coverage every 60 days. In this paper we concentrate on retrieved profiles of kinetic temperature (T(sub k)) and CO2 volume mixing ratio (vmr), inferred from SABER-observed 15 micrometer and 4.3 micrometer limb emissions, respectively. SABER-measured limb radiances are in non-local thermodynamic equilibrium (non-LTE) in the MLT region. The complexity of non-LTE radiation transfer combined with the large volume of data measured by SABER requires new retrieval approaches and radiative transfer techniques to accurately and efficiently retrieve the data products. In this paper we present the salient features of the coupled non-LTE T(sub k)/CO2 retrieval algorithm, along with preliminary results.

  1. Adsorption of Acid Red 57 from aqueous solutions onto polyacrylonitrile/activated carbon composite.

    PubMed

    El-Bindary, Ashraf A; Diab, Mostafa A; Hussien, Mostafa A; El-Sonbati, Adel Z; Eessa, Ahmed M

    2014-04-24

    The adsorption of Acid Red 57 (AR57) onto Polyacrylonitrile/activated carbon (PAN/AC) composite was investigated in aqueous solution in a batch system with respect to contact time, pH and temperature. Physical characteristics of (PAN/AC) composite such as fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM) were obtained. Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms and the isotherm constants were determined. The activation energy of adsorption was also evaluated for the adsorption of AR57 onto (PAN/AC) composite. The pseudo-first-order and pseudo-second-order kinetic models were used to describe the kinetic data. The dynamic data fitted the pseudo-second-order kinetic model well. The activation energy, change of free energy, enthalpy and entropy of adsorption were also evaluated for the adsorption of AR57 onto (PAN/AC) composite. The thermodynamics of the adsorption indicated spontaneous and exothermic nature of the process. The results indicate that (PAN/AC) composite could be employed as low-cost material for the removal of acid dyes from textile effluents.

  2. Adsorption of Pb(II) from aqueous solution by silica-gel supported hyperbranched polyamidoamine dendrimers.

    PubMed

    Niu, Yuzhong; Qu, Rongjun; Sun, Changmei; Wang, Chunhua; Chen, Hou; Ji, Chunnuan; Zhang, Ying; Shao, Xia; Bu, Fanling

    2013-01-15

    The adsorption properties of silica-gel supported hyperbranched polyamidoamine dendrimers (SiO(2)-G0-SiO(2)-G4.0) have been investigated by batch method. The effect of pH of the solution, contact time, initial Pb(II) ion concentration, temperature and coexisting metal ions have been demonstrated. The results indicated that the optimum pH value was 5. Adsorption kinetics was found to follow the pseudo-second-order model and controlled by film diffusion. The adsorption isotherms were fitted by Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherm models. Langmuir isotherm model was found to be more suitable to describe the equilibrium data, suggesting the uptake of Pb(II) ions by monolayer adsorption. From D-R isotherm model, the calculated mean free energy E demonstrated the adsorption processes occurred by chemical ion-exchange mechanism. FTIR analysis revealed that amine groups were mainly responsible for the adsorption of Pb(II) by amino-terminated adsorbents, while CO of ester groups also participated in the adsorption process of ester-terminated ones. The adsorbents can selectively adsorb Pb(II) from binary ion systems in the presence of Mn(II), Cu(II), Co(II), and Ni(II). Based on the results, it is concluded that SiO(2)-G0-SiO(2)-G4.0 had great potential for the removal of Pb(II) from aqueous solution.

  3. Evaluation of vermicompost as a raw natural adsorbent for adsorption of pesticide methylparathion.

    PubMed

    Mendes, Camila Bitencourt; Lima, Giovana de Fátima; Alves, Vanessa Nunes; Coelho, Nívia Maria Melo; Dragunski, Douglas Cardoso; Tarley, César Ricardo Teixeira

    2012-01-01

    The assessment of vermicompost (VC) as a low-cost and alternative adsorbent for the removal of the pesticide methylparathion (MP) from an aqueous medium has been investigated by batch and column experiments. Parameters related to MP adsorption, i.e. equilibrium time (61.5 min) and adsorption pH (6.8) were optimized by using Doehlert design. The initial and final MP concentrations after adsorption assays were determined by square-wave adsorptive cathodic stripping voltammetry using an electrode composed of a multiwalled carbon nanotube dispersed in mineral oil. Batch adsorption experimental data were fitted to the Langmuir and Freundlich isotherm adsorptions, and a very good fit to the Langmuir linear model, giving a maximum adsorption capacity (MAC) of 0.17 mg g(-1). This result was very similar to that obtained with the column experiments. In order to evaluate the MP desorption from column packed VC, 100.0 ml of nitric acid solution (pH 3.0) has been percolated through material. No leaching of MP was observed, thus confirming the strong interaction between MP and VC. The satisfactory MAC obtained and low cost makes the VC a reliable natural material for the removal of MP from aqueous effluents.

  4. Non-equilibrium supramolecular polymerization.

    PubMed

    Sorrenti, Alessandro; Leira-Iglesias, Jorge; Markvoort, Albert J; de Greef, Tom F A; Hermans, Thomas M

    2017-03-28

    Supramolecular polymerization has been traditionally focused on the thermodynamic equilibrium state, where one-dimensional assemblies reside at the global minimum of the Gibbs free energy. The pathway and rate to reach the equilibrium state are irrelevant, and the resulting assemblies remain unchanged over time. In the past decade, the focus has shifted to kinetically trapped (non-dissipative non-equilibrium) structures that heavily depend on the method of preparation (i.e., pathway complexity), and where the assembly rates are of key importance. Kinetic models have greatly improved our understanding of competing pathways, and shown how to steer supramolecular polymerization in the desired direction (i.e., pathway selection). The most recent innovation in the field relies on energy or mass input that is dissipated to keep the system away from the thermodynamic equilibrium (or from other non-dissipative states). This tutorial review aims to provide the reader with a set of tools to identify different types of self-assembled states that have been explored so far. In particular, we aim to clarify the often unclear use of the term "non-equilibrium self-assembly" by subdividing systems into dissipative, and non-dissipative non-equilibrium states. Examples are given for each of the states, with a focus on non-dissipative non-equilibrium states found in one-dimensional supramolecular polymerization.

  5. The adsorptive capacity of vapor-phase mercury chloride onto powdered activated carbon derived from waste tires.

    PubMed

    Lin, Hsun-Yu; Yuan, Chung-Shin; Wu, Chun-Hsin; Hung, Chung-Hsuang

    2006-11-01

    Injection of powdered activated carbon (PAC) upstream of particulate removal devices (such as electrostatic precipitator and baghouses) has been used effectively to remove hazardous air pollutants, particularly mercury-containing pollutants, emitted from combustors and incinerators. Compared with commercial PACs (CPACs), an alternative PAC derived from waste tires (WPAC) was prepared for this study. The equilibrium adsorptive capacity of mercury chloride (HgCl2) vapor onto the WPAC was further evaluated with a self-designed bench-scale adsorption column system. The adsorption temperatures investigated in the adsorption column were controlled at 25 and 150 degrees C. The superficial velocity and residence time of the flow were 0.01 m/sec and 4 sec, respectively. The adsorption column tests were run under nitrogen gas flow. Experimental results showed that WPAC with higher Brunauer-Emmett-Teller (BET) surface area could adsorb more HgCl2 at room temperature. The equilibrium adsorptive capacity of HgCl2 for WPAC measured in this study was 1.49 x 10(-1) mg HgCl2/g PAC at 25 degrees C with an initial HgCI2 concentration of 25 microg/m3. With the increase of adsorption temperature < or = 150 degrees C, the equilibrium adsorptive capacity of HgCl2 for WPAC was decreased to 1.34 x 10(-1) mg HgCl2/g PAC. Furthermore, WPAC with higher sulfur contents could adsorb even more HgCl2 because of the reactions between sulfur and Hg2+ at 150 degrees C. It was demonstrated that the mechanisms for adsorbing HgCl2 onto WPAC were physical adsorption and chemisorption at 25 and 150 degrees C, respectively. Experimental results also indicated that the apparent overall driving force model appeared to have the good correlation with correlation coefficients (r) > 0.998 for HgCl2 adsorption at 25 and 150 degrees C. Moreover, the equilibrium adsorptive capacity of HgCl2 for virgin WPAC was similar to that for CPAC at 25 degrees C, whereas it was slightly higher for sulfurized WPAC than for

  6. Relevance of equilibrium in multifragmentation

    SciTech Connect

    Furuta, Takuya; Ono, Akira

    2009-01-15

    The relevance of equilibrium in a multifragmentation reaction of very central {sup 40}Ca + {sup 40}Ca collisions at 35 MeV/nucleon is investigated by using simulations of antisymmetrized molecular dynamics (AMD). Two types of ensembles are compared. One is the reaction ensemble of the states at each reaction time t in collision events simulated by AMD, and the other is the equilibrium ensemble prepared by solving the AMD equation of motion for a many-nucleon system confined in a container for a long time. The comparison of the ensembles is performed for the fragment charge distribution and the excitation energies. Our calculations show that there exists an equilibrium ensemble that well reproduces the reaction ensemble at each reaction time t for the investigated period 80{<=}t{<=}300 fm/c. However, there are some other observables that show discrepancies between the reaction and equilibrium ensembles. These may be interpreted as dynamical effects in the reaction. The usual static equilibrium at each instant is not realized since any equilibrium ensemble with the same volume as that of the reaction system cannot reproduce the fragment observables.

  7. A comparative study and evaluation of sulfamethoxazole adsorption onto organo-montmorillonites.

    PubMed

    Lu, Laifu; Gao, Manglai; Gu, Zheng; Yang, Senfeng; Liu, Yuening

    2014-12-01

    Three organo-montmorillonites were prepared using surfactants, and their adsorption behaviors toward sulfamethoxazole (SMX) were investigated. The surfactants used were cetyltrimethyl ammonium bromide (CTMAB), 3-(N,N-dimethylhexadecylammonio) propane sulfonate (HDAPS) and 1,3-bis(hexadecyldimethylammonio)-propane dibromide (BHDAP). The properties of the organo-montmorillonites were characterized by X-ray diffraction, scanning electron microscopy and N2 adsorption-desorption isotherm measurements. Results showed that the interlayer spacing of montmorillonite was increased and the surface area as well as the morphology were changed. Batch adsorption experiments showed that the surfactant loading amount had a great effect on the adsorption of SMX. The adsorption process was pH dependent and the maximum adsorption capacity was obtained at pH3 for HDAPS-Mt, while CTMAB-Mt and BHDAP-Mt showed a high removal efficiency at 3-11. The adsorption capacity increased with the initial SMX concentration and contact time but decreased with increasing solution ionic strength. Kinetic data were best described by the pseudo second-order model. Equilibrium data were best represented by the Langmuir model, and the Freundlich constant (n) indicated a favorable adsorption process. The maximum adsorption capacity of SMX was 235.29 mg/g for CTMAB-Mt, 155.28 mg/g for HDAPS-Mt and 242.72 mg/g for BHDAP-Mt. Thermodynamic parameters were calculated to evaluate the spontaneity and endothermic or exothermic nature. The adsorption mechanism was found to be dominated by electrostatic interaction, while hydrophobic interaction played a secondary role.

  8. Adsorption of B. Subtilis and P. Mendocina Onto Fe-Oxide Coated Quartz and Pure Quartz

    NASA Astrophysics Data System (ADS)

    Ams, D.; Fein, J. B.

    2002-12-01

    Understanding the controls on bacterial adsorption onto mineral surfaces is crucial in order to model a range of processes, such as contaminant transport, mineral dissolution behavior, and bioremediation techniques. At present, little is known concerning the adsorption behavior of bacteria, even onto some of the most common mineral surfaces present in near-surface environments. In this study, we measured the adsorption of a Gram positive bacterial species (B. subtilis) and a Gram negative species (P. mendocina) onto a quartz sand, and onto an Fe-oxide coated quartz sand, both as functions of time, pH and bacteria:mineral mass ratio. The extent of adsorption was determined by measuring the concentration of free bacteria in the mineral-bacteria systems both before, and after, reaction, using a uv-vis spectrophotometric approach. pH and bacteria:mineral ratio exert strong controls on the extent of bacterial adsorption of both species onto Fe-coated quartz. The extent of adsorption of B. subtilis onto the Fe-coated quartz increases with decreasing pH from close to 0% at pH 10 to a plateau of approximately 80% adsorption between pH 6 and 4. Below pH 4, adsorption of B. subtilis decreases to 50% at pH 2. Adsorption of P. mendocina is similar to that observed for B. subtilis, only it is significantly less extensive under otherwise identical conditions. These adsorption behaviors are in marked contrast to that observed for both species onto the uncoated quartz. There is little to no adsorption of either species onto the uncoated quartz sand over most of the pH range studied. We use a thermodynamic approach to model the adsorption behavior of each species onto the Fe-coated quartz sand, determining equilibrium constants for the dominant adsorption reactions. Our results demonstrate that bacterial adsorption within geologic systems can be strongly dependent on mineralogy, fluid composition, and on the bacterial species present. However, our modeling approach enables the

  9. Adsorption of dyestuff from aqueous solutions through oxalic acid-modified swede rape straw: adsorption process and disposal methodology of depleted bioadsorbents.

    PubMed

    Feng, Yanfang; Dionysiou, Dionysios D; Wu, Yonghong; Zhou, Hui; Xue, Lihong; He, Shiying; Yang, Linzhang

    2013-06-01

    Swede rape straw (Brassica napus L.) was modified by oxalic acid under mild conditions producing an efficient dye adsorbent (SRSOA). This low-cost and environmental friendly bioadsorbent was characterized by various techniques and then applied to purify dye-contaminated aqueous solutions. Equilibrium study showed that the Langmuir model demonstrated the best fit to the equilibrium data and the methylene blue (MB) adsorption capacity calculated by this model was 432mgg(-1). The adsorption process and mechanism is also discussed. To properly deal with the dye-loaded bioadsorbents, the disposal methodology is discussed and a biochar based on depleted bioadsorbents was for the first time produced and examined. This method both solved the disposal problem of contaminant-loaded bioadsorbents and produced an useful adsorbent thereafter. The study indicates that SRSOA is a promising substitute for ACs in purifying dye-contaminated wastewater and that producing biochars from contaminant-loaded bioadsorbents maybe a feasible disposal method.

  10. Urine pH, container composition, and exposure time influence adsorptive loss of 11-nor-delta9-tetrahydrocannabinol-9-carboxylic acid.

    PubMed

    Jamerson, Matthew H; McCue, Joseph J; Klette, Kevin L

    2005-10-01

    11-nor-delta9-Tetrahydrocannabinol-9-carboxylic acid (11-nor-delta9-THC-COOH) is the primary cannabinoid present in the urine of individuals who have used marijuana and is the target analyte identified at forensic urinalysis drug testing laboratories. The preparation, storage, transport, and processing of control materials for gas chromatography-mass spectrometric (GC-MS) analysis of human urine specimens is critical to accurate compound identification and quantification. Previous studies have suggested that adsorptive loss of 11-nor-delta9-THC-COOH is influenced by container composition and storage temperature. In this study, urine solutions of 11-nor-delta9-THC-COOH (7.5, 15, 60, and 500 ng/mL) at three physiologically-relevant pHs (4.6, 6.5, and 8.4) were prepared and subjected to storage and processing in containers of different compositions (polypropylene and borosilicate glass). Analyte identification and quantification were achieved using tetramethylammonium hydroxide/iodomethane-based derivatization followed by GC separation and electron-impact MS. These analyses demonstrate that adsorptive loss of 11-nor-delta9-THC-COOH is a phenomenon found in acidic urine solutions and is relatively absent in urine solutions that are near-neutral or basic. Furthermore, the data indicate that the adsorptive loss of 11-nor-delta9-THC-COOH is dependent on solution-container exposure time and is similar between containers of two distinct compositions. These results suggest that for optimal analytical control performance, solution pH and control processing times are critical elements.

  11. Lattice Boltzmann simulation of the gas-solid adsorption process in reconstructed random porous media.

    PubMed

    Zhou, L; Qu, Z G; Ding, T; Miao, J Y

    2016-04-01

    The gas-solid adsorption process in reconstructed random porous media is numerically studied with the lattice Boltzmann (LB) method at the pore scale with consideration of interparticle, interfacial, and intraparticle mass transfer performances. Adsorbent structures are reconstructed in two dimensions by employing the quartet structure generation set approach. To implement boundary conditions accurately, all the porous interfacial nodes are recognized and classified into 14 types using a proposed universal program called the boundary recognition and classification program. The multiple-relaxation-time LB model and single-relaxation-time LB model are adopted to simulate flow and mass transport, respectively. The interparticle, interfacial, and intraparticle mass transfer capacities are evaluated with the permeability factor and interparticle transfer coefficient, Langmuir adsorption kinetics, and the solid diffusion model, respectively. Adsorption processes are performed in two groups of adsorbent media with different porosities and particle sizes. External and internal mass transfer resistances govern the adsorption system. A large porosity leads to an early time for adsorption equilibrium because of the controlling factor of external resistance. External and internal resistances are dominant at small and large particle sizes, respectively. Particle size, under which the total resistance is minimum, ranges from 3 to 7 μm with the preset parameters. Pore-scale simulation clearly explains the effect of both external and internal mass transfer resistances. The present paper provides both theoretical and practical guidance for the design and optimization of adsorption systems.

  12. Timing and conditions of high-pressure metamorphism in the western Grenville Province: Constraints from accessory mineral composition and phase equilibrium modeling

    NASA Astrophysics Data System (ADS)

    Marsh, Jeffrey H.; Culshaw, Nicholas G.

    2014-07-01

    Previous geochronological analyses of high pressure (HP) metamorphic rocks in the western Grenville Province, Ontario, Canada have yielded precise U-Pb zircon ages; however, uncertainty has remained as to whether these ages represent the timing of HP metamorphism or the granulite/amphibolite facies overprint accompanying exhumation to a hot middle orogenic crust. Detailed study of these HP rocks, involving garnet, rutile, and zircon trace element analysis, phase equilibrium modeling, and zircon U-Pb geochronology, has yielded much improved constraints on the timing and conditions of HP metamorphism. Zircon from five of the six HP samples yield anchored discordia upper intercept and 207Pb/206Pb weighted average ages between 1097 and 1085 Ma, and typically have trace element compositions consistent with growth in a garnet-rich, plagioclase-poor eclogite-type assemblage (i.e. no negative Eu anomaly and flat HREE trends). Titanium-in-zircon and Zr-in-rutile thermometry indicates that the range of zircon crystallization temperatures for most samples (643-767 °C) is close to that of rutile inclusions in garnet (668-753 °C) and matrix rutile (690-772 °C). Phase relations in a pseudosection calculated for the sample that best preserves the HP assemblage indicate that: (1) the stability field for the inclusions observed in garnet and kyanite is between 11.5 < P < 14 kbar and 600 < T < 700 °C, and (2) zircon and rutile crystallization temperatures intersect the inferred HP assemblage field (Grt + Cpx + Ky + Rt + Hbl + Qtz) and garnet and kyanite modal isopleths at P > ~ 15 kbar, indicating that the ca. 1090 Ma zircon ages date metamorphism at eclogite facies conditions. Thus, the deep burial of mafic lower crust that resulted in HP metamorphism in the western CGB occurred just prior to the main "Ottawan" phase of continental collision in the western Grenville Province (ca. 1080-1040 Ma).

  13. Equilibrium, kinetic and thermodynamic studies of acid Orange 52 dye biosorption by Paulownia tomentosa Steud. leaf powder as a low-cost natural biosorbent.

    PubMed

    Deniz, Fatih; Saygideger, Saadet D

    2010-07-01

    The biosorption of Acid Orange 52 onto the leaf powder of Paulownia tomentosa Steud. was studied in a batch adsorption system to estimate the equilibrium, kinetic and thermodynamic parameters as a function of solution pH, biosorbent concentration, dye concentration, biosorbent size, temperature and contact time. The Langmuir, Freundlich and Temkin isotherm models were used for modeling the biosorption equilibrium. The experimental equilibrium data could be well interpreted by the Temkin and Langmuir isotherms with maximum adsorption capacity of 10.5 mg g(-1). In order to state the sorption kinetics, the fits of pseudo-first order, pseudo-second order, Elovich and intraparticle diffusion kinetic models were investigated. It was obtained that the biosorption process followed the pseudo-second order rate kinetics. Thermodynamic studies indicated that this system was exothermic process. The results revealed that P. tomentosa leaf powder could be an efficient biosorbent for the treatment of wastewater containing Acid Orange 52.

  14. Accelerating Multiagent Reinforcement Learning by Equilibrium Transfer.

    PubMed

    Hu, Yujing; Gao, Yang; An, Bo

    2015-07-01

    An important approach in multiagent reinforcement learning (MARL) is equilibrium-based MARL, which adopts equilibrium solution concepts in game theory and requires agents to play equilibrium strategies at each state. However, most existing equilibrium-based MARL algorithms cannot scale due to a large number of computationally expensive equilibrium computations (e.g., computing Nash equilibria is PPAD-hard) during learning. For the first time, this paper finds that during the learning process of equilibrium-based MARL, the one-shot games corresponding to each state's successive visits often have the same or similar equilibria (for some states more than 90% of games corresponding to successive visits have similar equilibria). Inspired by this observation, this paper proposes to use equilibrium transfer to accelerate equilibrium-based MARL. The key idea of equilibrium transfer is to reuse previously computed equilibria when each agent has a small incentive to deviate. By introducing transfer loss and transfer condition, a novel framework called equilibrium transfer-based MARL is proposed. We prove that although equilibrium transfer brings transfer loss, equilibrium-based MARL algorithms can still converge to an equilibrium policy under certain assumptions. Experimental results in widely used benchmarks (e.g., grid world game, soccer game, and wall game) show that the proposed framework: 1) not only significantly accelerates equilibrium-based MARL (up to 96.7% reduction in learning time), but also achieves higher average rewards than algorithms without equilibrium transfer and 2) scales significantly better than algorithms without equilibrium transfer when the state/action space grows and the number of agents increases.

  15. Preparation and adsorption properties of nano magnetite chitosan films for heavy metal ions from aqueous solution

    SciTech Connect

    Lasheen, M.R.; El-Sherif, Iman Y.; Tawfik, Magda E.; El-Wakeel, S.T.; El-Shahat, M.F.

    2016-08-15

    Highlights: • Nano magnetite–chitosan films were prepared by casting method. • The efficiency of the prepared films for removing heavy metals was investigated. • The adsorption mechanism was studied using different isotherm and kinetic models. • Films reuse and metals recovery were studied. - Abstract: Nano magnetite chitosan (NMag–CS) film was prepared and characterized with different analytical methods. X-ray diffraction (XRD) patterns confirmed the formation of a pure magnetite structure and NMag–CS nanocomposite. TEM image of the film, revealed the uniform dispersion of magnetite nanoparticles inside chitosan matrix. The adsorption properties of the prepared film for copper, lead, cadmium, chromium and nickel metal ions were evaluated. Different factors affecting the uptake behavior by the composite films such as time, initial pH and film dose were investigated. The adsorption equilibrium attained using 2 g/L of the film after 120 min of reaction. The equilibrium data were analyzed using Langmuir and Freundlich models. The adsorption kinetics followed the mechanism of the pseudo-second-order equation for all metals. The metals regenerated from films with an efficiency greater than 95% using 0.1 M ethylene diamine tetra acetic acid (EDTA) and films were successfully reused for adsorption.

  16. Adsorptive property of Cu(2+)-loaded montmorillonite clays for Escherichia coli K88 in vitro.

    PubMed

    Guo, Tong; Cao, Shoujun; Su, Rui; Li, Zhiqiang; Hu, Ping; Xu, Zirong

    2011-01-01

    The adsorption properties of Cu(2+)-loaded montmorillonite clays (MMT-Cu) for Escherichia coli K88 as a function of time, bacteria concentrations, pH, ionic strength and temperature were investigated. The results showed that the bacteria adsorption onto MMT-Cu surface reached equilibrium after 90 min. The percentages of E. coli K88 adsorbed onto the surfaces of MMT-Cu and montmorillonite clays (MMT) at equilibrium were 88.9% and 56.5%, respectively. Scanning electron microscopy revealed that a lot of E. coli K88 adhered to the surface of MMT-Cu. The zeta potential of MMT-Cu was relatively high as compared to that of MMT. The adsorptive ability of MMT-Cu for E. coli K88 was higher than that of MMT (P < 0.05). Moreover, pH, ionic strength and temperature produced a strong influence on the extent of E. coli K88 adsorption to surface of MMT-Cu and MMT. The mechanism of adsorption of E. coli onto MMT-Cu may involve electrostatic attraction and physiochemical properties of bacterial cell walls and minerals surfaces.

  17. Enhanced fluoride adsorption by nano crystalline γ-alumina: adsorption kinetics, isotherm modeling and thermodynamic studies

    NASA Astrophysics Data System (ADS)

    Chinnakoti, Prathibha; Chunduri, Avinash L. A.; Vankayala, Ranganayakulu K.; Patnaik, Sandeep; Kamisetti, Venkataramaniah

    2016-06-01

    Nano materials in particular nano oxides with enhanced surface area and an excellent catalytic surface serve as potential adsorbents for defluoridation of water. In the present study nano γ-alumina was synthesized through a simple and low cost, surfactant assisted solution combustion method. As synthesized material was characterized by XRD and FESEM for its phase, size and morphological characteristics. Surface properties have been investigated by BET method. Nano γ-alumina was further used for a detailed adsorption study to remove fluoride from water. Batches of experiments were performed at various experimental conditions such as solution pH, adsorbent dose, initial fluoride concentration and contact time to test the defluoridation ability of γ-alumina. Fluoride Adsorption by nano sized γ-alumina was rapid and reached equilibrium within two hours. The adsorption worked well at pH 4.0, where ˜96 % of fluoride was found to be adsorbed on adsorbent. It was possible to reduce fluoride levels to as low as 0.3 mg/L (within the safe limit of WHO: ≤1.5 mg/L) from an initial fluoride levels of 10 mg/L. This could be achieved using a very small quantity, 1 g/L of γ-alumina at pH 4 within 1 h of contact time. Defluoridation capacity of nano γ-alumina was further investigated by fitting the equilibrium data to various isotherm as well as kinetic models. The present study revealed that γ-alumina could be an efficient adsorbent for treating fluoride contaminated water.

  18. The adsorption of hetero- and alicyclic thiophene derivatives from water-acetonitrile solutions on the surface of porous graphitic carbon under high-performance liquid chromatography conditions

    NASA Astrophysics Data System (ADS)

    Saifutdinov, B. R.; Emel'yanova, N. S.; Kurbatova, S. V.; Pimerzin, A. A.

    2012-07-01

    The adsorption of hetero- and alicyclic thiophene derivatives synthesized for the first time from water-acetonitrile solutions with various compositions on the surface of porous graphitic carbon was studied by the high-performance liquid chromatography method. The retention factor and Henry adsorption constant values and equilibrium constants of quasi-chemical reactions of the adsorption and solvation of the heterocyclic compounds studied were calculated using the Lanin-Nikitin equation. The influence of the structure of hetero- and alicyclic thiophene derivative molecules on their adsorption on the surface of porous graphitic carbon and solvation in water-acetonitrile solutions was discussed. The Lanin-Nikitin model was found to be more informative in the interpretation of the adsorption-chromatographic experiment data compared with the Snyder-Soczewinski and Scott-Kucera models.

  19. 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.

  20. Nitrate removal from aqueous solution by adsorption onto various materials.

    PubMed

    Oztürk, Neşe; Bektaş, T Ennil

    2004-08-09

    In this study sepiolite, sepiolite activated by HCl, slag and powdered activated carbon were used as adsorbent with a particle size was between 71 and 80 microm (200-170 mesh). NaNO3 solution (100 mg/l) was used in batch adsorption experiments for nitrate removal. First kinetic studies were carried out and it was determined that slag was not effective for nitrate removal, then contact time, pH and adsorbent dosage effects on nitrate removal by adsorption were investigated using other adsorbents except slag. The equilibrium time was found to be 30, 45, 5 min for sepiolite, powdered activated carbon and activated sepiolite, respectively. The most effective pH value for nitrate removal was 2 for powdered activated carbon. pH value did not affect nitrate removal significantly for other adsorbents. Adsorbent dosages were varied from 5 to 20 g/l solutions. An increase in adsorbent dosage increased the percent removal of nitrate. A series of isotherm studies were undertaken and the data evaluated for compliance with the Langmuir and Freundlich isotherm models. To investigate the adsorption mechanisms, three simplified kinetic models, i.e., first-, second-order and intraparticle diffusion were tested. Adsorption followed second-order rate kinetics. The correlation coefficients for second order kinetic model are greater than 0.996. Experimental data show that sepiolite activated by HCl was effective for nitrate removal.

  1. Preparation and characterization of poly(AA co PVP)/PGS composite and its application for methylene blue adsorption.

    PubMed

    Yang, Cai-xia; Lei, Lei; Zhou, Peng-xin; Zhang, Zhe; Lei, Zi-qiang

    2015-04-01

    Poly (AA co PVP)/PGS (PAPP) composite adsorbent was prepared by radical polymerization from Acrylic acid (AA), Polyvinylpyrrolidone (PVP) and Palygorskite (PGS), using N,N-methylenebisacrylamide (MBA) as cross-linker and potassium persulfate (KPS) as initiator. The PAPP was characterized with Fourier transform infrared (FT-IR), thermogravimetric analysis (TG), scanning electron microscope (SEM) and transmission electron microscopy (TEM). PAPP was used as adsorbent for the removal of methylene blue from aqueous solutions. The influences of pH, adsorption temperature and adsorption time on the adsorption properties of the composite to the dye were also investigated. Meanwhile, the adsorption rate data and adsorption equilibrium date were analyzed based on the pseudo-first-order and pseudo-second-order kinetic model, Langmuir and Freundlich isotherm models, respectively. The results indicating that the kinetic behavior better fit with the pseudo-second-order kinetic model. The maximum equilibrium adsorption capacity (q(m)) is 1815 mg/g at 289 K. The isotherm behavior can be explained by the Langmuir isotherm models. The activation energy was also evaluated for the removal of methylene blue onto PAPP. These results demonstrate that this composite material could be used as a good adsorbent for the removal of cationic dyes from wastewater.

  2. Adsorption study of anionic reactive dye from aqueous solution to Mg-Fe-CO3 layered double hydroxide (LDH)

    NASA Astrophysics Data System (ADS)

    Ahmed, I. M.; Gasser, M. S.

    2012-10-01

    Mg-Fe-Cl Layered double hydroxides (LDHs) have been prepared using a method involving separate nucleation and aging steps with Mg/Fe = 3. The interlayer anions readily replaced by carbonate are characterized by X-ray diffraction (XRD) and FTIR. The effects of different parameters, such as pH, contact time, concentration of dye and temperature on the capacity and adsorption mechanism of Mg-Fe-CO3-LDH in removing an anionic dye (congo red, CR) from aqueous solution were separately investigated. The results show that Mg-Fe-CO3-LDH is particularly efficient in removing CR and the dye removal increases with decreasing pH. The adsorption of CR on Mg-Fe-CO3-LDH reached equilibrium after 15 min where 100 mg/L CR was removed. The equilibrium isotherm indicates that the adsorption of CR onto Mg-Fe-CO3-LDH fits to Langmuir and Freundlich equation as well. The adsorption data obtained from the Langmuir model gave good values of the determination coefficient and the saturated adsorption capacity of Mg-Fe-CO3-LDH for CR was found to be 104.6 mg/g. The regeneration study indicates that the prepared LDH could be used for several cycles. The thermodynamic parameters have been calculated, and the adsorption process was found to be spontaneous, endothermic in nature and follows a pseudo-second-order kinetic model.

  3. Multilayer adsorption of Cu(II) and Cd(II) over Brazilian Orchid Tree (Pata-de-vaca) and its adsorptive properties

    NASA Astrophysics Data System (ADS)

    Jorgetto, Alexandre de O.; da Silva, Adrielli C. P.; Wondracek, Marcos H. P.; Silva, Rafael I. V.; Velini, Edivaldo D.; Saeki, Margarida J.; Pedrosa, Valber A.; Castro, Gustavo R.

    2015-08-01

    Through very simple and inexpensive processes, pata-de-vaca leaves were turned into a powder and applied as an adsorbent for the uptake of Cu(II) and Cd(II) from water. The material was characterized through SEM, EDX, FTIR and surface area measurement. The material had its point of zero charge determined (5.24), and its adsorption capacity was evaluated as a function of time, pH and metal concentration. The material presented fast adsorption kinetics, reaching adsorption equilibrium in less than 5 min and it had a good correlation with the pseudo-second order kinetic model. Optimum pH for the adsorption of Cu(II) and Cd(II) were found to be in the range from 4 to 5, approximately. In the experiment as a function of the analyte concentration, analogously to gas adsorption, the material presented a type II isotherm, indicating the formation of multilayers for both species. Such behavior was explained with basis in the alternation between cations and anions over the material's surface, and the maximum adsorption capacity, considering the formation of the multilayers were found to be 0.238 mmol L-1 for Cu(II) and 0.113 mmol L-1 for Cd(II).

  4. A fundamental study of the impact of pressure on the adsorption mechanism in reversed-phase liquid chromatography.

    PubMed

    Åsberg, Dennis; Samuelsson, Jörgen; Fornstedt, Torgny

    2016-07-29

    A fundamental investigation of the pressure effect on individual adsorption sites was undertaken based on adsorption energy distribution and adsorption isotherm measurements. For this purpose, we measured adsorption equilibrium data at pressures ranging from 100 to 1000bar at constant flow and over a wide concentration range for three low-molecular-weight solutes, antipyrine, sodium 2-naphthalenesulfonate, and benzyltriethylammonium chloride, on an Eternity C18 stationary phase. The adsorption energy distribution was bimodal for all solutes, remaining clearly so at all pressures. The bi-Langmuir model best described the adsorption in these systems and two types of adsorption sites were identified, one with a low and another with a high energy of interaction. Evidence exists that the low-energy interactions occur at the interface between the mobile and stationary phases and that the high-energy interactions occur nearer the silica surface, deeper in the C18 layer. The contribution of each type of adsorption site to the retention factor was calculated and the change in solute molar volume from the mobile to stationary phase during the adsorption process was estimated for each type of site. The change in solute molar volume was 2-4 times larger at the high-energy site, likely because of the greater loss of solute solvation layer when penetrating deeper into the C18 layer. The association equilibrium constant increased with increasing pressure while the saturation capacity of the low-energy site remained almost unchanged. The observed increase in saturation capacity for the high-energy site did not affect the column loading capacity, which was almost identical at 50- and 950-bar pressure drops over the column.

  5. Estimating the plasma effect-site equilibrium rate constant (Ke₀) of propofol by fitting time of loss and recovery of consciousness.

    PubMed

    Wu, Qi; Sun, Baozhu; Wang, Shuqin; Zhao, Lianying; Qi, Feng

    2013-01-01

    The present paper proposes a new approach for fitting the plasma effect-site equilibrium rate constant (Ke0) of propofol to satisfy the condition that the effect-site concentration (Ce) is equal at the time of loss of consciousness (LOC) and recovery of consciousness (ROC). Forty patients receiving intravenous anesthesia were divided into 4 groups and injected propofol 1.4, 1.6, 1.8, or 2 mg/kg at 1,200 mL/h. Durations from the start of injection to LOC and to ROC were recorded. LOC and ROC were defined as an observer's assessment of alertness and sedation scale change from 3 to 2 and from 2 to 3, respectively. Software utilizing bisection method iteration algorithms was built. Then, Ke0 satisfying the CeLOC=CeROC condition was estimated. The accuracy of the Ke0 estimated by our method was compared with the Diprifusor TCI Pump built-in Ke0 (0.26 min(-1)), and the Orchestra Workstation built-in Ke0 (1.21 min(-1)) in another group of 21 patients who were injected propofol 1.4 to 2 mg/kg. Our results show that the population Ke0 of propofol was 0.53 ± 0.18 min(-1). The regression equation for adjustment by dose (mg/kg) and age was Ke0=1.42-0.30 × dose-0.0074 × age. Only Ke0 adjusted by dose and age achieved the level of accuracy required for clinical applications. We conclude that the Ke0 estimated based on clinical signs and the two-point fitting method significantly improved the ability of CeLOC to predict CeROC. However, only the Ke0 adjusted by dose and age and not a fixed Ke0 value can meet clinical requirements of accuracy.

  6. Metal adsorption by agricultural biosorbents: Adsorption isotherm, kinetic and biosorbents chemical structures.

    PubMed

    Sadeek, Sadeek A; Negm, Nabel A; Hefni, Hassan H H; Wahab, Mostafa M Abdel

    2015-11-01

    Biosorption of Cu(II), Co(II) and Fe(III) ions from aqueous solutions by rice husk, palm leaf and water hyacinth was investigated as a function of initial pH, initial heavy metal ions concentration and treatment time. The adsorption process was examined by two adsorption isotherms: Langmuir and Freundlich isotherms. The experimental data of biosorption process were analyzed using pseudo-first order, pseudo-second order kinetic models. The equilibrium biosorption isotherms showed that the three studied biosorbents possess high affinity and sorption capacity for Cu(II), Co(II) and Fe(III) ions. Rice husk showed more efficiency than palm leaf and water hyacinth. Adsorption of Cu(II) and Co(II) was more efficient in alkaline medium (pH 9) than neutral medium due to the high solubility of metal ion complexes. The metal removal efficiency of each biosorbent was correlated to its chemical structure. DTA studies showed formation of metal complex between the biosorbents and the metal ions. The obtained results showed that the tested biosorbents are efficient and alternate low-cost biosorbent for removal of heavy metal ions from aqueous media.

  7. Thorough removal of inorganic and organic mercury from aqueous solutions by adsorption on Lemna minor powder.

    PubMed

    Li, Shun-Xing; Zheng, Feng-Ying; Yang, Huang; Ni, Jian-Cong

    2011-02-15

    The adsorption ability of duckweed (Lemna minor) powders for removing inorganic and organic mercury (methyl and ethyl mercury) has been studied using cold vapour atomic absorption spectrometry. The optimal adsorption conditions were: (a) the pH value of the solution 7.0 for inorganic and ethyl mercury, 9.0 for methyl mercury, and (b) equilibrium adsorption time 10, 20, and 40 min for inorganic mercury, methyl mercury, and ethyl mercury, respectively. After adsorption by L. minor powder for 40 min, when the initial concentrations of inorganic and organic mercury were under 12.0 μg L(-1) and 50.0 μg L(-1), respectively, the residual concentrations of mercury could meet the criterion of drinking water (1.0 μg L(-1)) and the permitted discharge limit of wastewater (10.0 μg L(-1)) set by China and USEPA, respectively. Thorough removal of both inorganic and organic mercury from aqueous solutions was reported for the first time. The significant adsorption sites were C-O-P and phosphate groups by the surface electrostatic interactions with aqueous inorganic and organic mercury cations, and then the selective adsorption was resulted from the strong chelating interaction between amine groups and mercury on the surface of L. minor cells.

  8. Surface chemistry of ferrihydrite: Part 2. Kinetics of arsenate adsorption and coprecipitation

    USGS Publications Warehouse

    Fuller, C.C.; Dadis, J.A.; Waychunas, G.A.

    1993-01-01

    The kinetics of As(V) adsorption by ferrihydrite was investigated in coprecipitation and postsynthesis adsorption experiments conducted in the pH range 7.5-9.0. In coprecipitation experiments, As(V) was present in solution during the hydrolysis and precipitation of iron. In adsorption experiments, a period of rapid (<5 min) As(V) uptake from solution was followed by continued uptake for at least eight days, as As(V) diffused to adsorption sites on ferrihydrite surfaces within aggregates of colloidal particles. The time dependence of As(V) adsorption is well described by a general model for diffusion into a sphere if a subset of surface sites located near the exterior of aggregates is assumed to attain adsorptive equilibrium rapidly. The kinetics of As(V) desorption after an increase in pH were also consistent with diffusion as a rate-limiting process. Aging of pure ferrihydrite prior to As(V) adsorption caused a decrease in adsorption sites on the precipitate owing to crystallite growth. In coprecipitation experiments, the initial As(V) uptake was significantly greater than in post-synthesis adsorption experiments, and the rate of uptake was not diffusion limited because As(V) was coordinated by surface sites before crystallite growth and coagulation processes could proceed. After the initial adsorption, As(V) was slowly released from coprecipitates for at least one month, as crystallite growth caused desorption of As(V). Adsorption densities as high as 0.7 mole As(V) per mole of Fe were measured in coprecipitates, in comparison to 0.25 mole As(V) per mole of Fe in post-synthesis adsorption experiments. Despite the high Concentration of As(V) in the precipitates, EXAFS spectroscopy (Waychunas et al., 1993) showed that neither ferric arsenate nor any other As-bearing surface precipitate or solid solution was formed. The high adsorption densities are possible because the ferrihydrite particles are extremely small, approaching the size of small dioctahedral chains at

  9. Adsorption of Sb(III) and Sb(V) on Freshly Prepared Ferric Hydroxide (FeOxHy).

    PubMed

    He, Zan; Liu, Ruiping; Liu, Huijuan; Qu, Jiuhui

    2015-02-01

    This study prepared fresh ferric hydroxide (in-situ FeOxHy) by the enhanced hydrolysis of Fe(3+) ions, and investigates its adsorptive behaviors toward Sb(III) and Sb(V) through laboratory and pilot-scale studies. A contact time of 120-min was enough to achieve adsorption equilibrium for Sb(III) and Sb(V) on the in-situ FeOxHy, and the Elovich model was best to describe the adsorption kinetics of Sb(III) and Sb(V). The Freundlich model was better than Langmuir model to describe the adsorption of Sb(III) and Sb(V) on the in-situ FeOxHy, and the maximum adsorption capacity of Sb(III) and Sb(V) was determined to be 12.77 and 10.21 mmol/g the in-situ FeOxHy as Fe, respectively. Adsorption of Sb(V) decreased whereas that of Sb(III) increased with elevated pH over pH 3-10, owing to the different electrical properties of Sb(III) and Sb(V). Adsorption of Sb(III) and Sb(V) was slightly affected by ionic strength, and thus indicated the formation of inner sphere complexes between Sb and the adsorbent. Sulfate and carbonate showed little effect on the adsorption of Sb(III) and Sb(V). Phosphate significantly inhibited the adsorption of Sb(V), whereas slightly effected that of Sb(III) due to its similar chemical structure to Sb(V). Pilot-scale continuous experiment indicated the feasibility of using in-situ FeOxHy to remove Sb(V), and equilibrium adsorption capacity at the equilibrium Sb(V) concentration of 10 μg/L was determined to be 0.11, 0.07, 0.07, 0.11, and 0.12 mg/g the in-situ FeOxHy as Fe at equilibrium pH of 7.5-7.7, 6.9-7.0, 6.3-6.6, 5.9-6.4, and 5.2-5.9, respectively.

  10. Adsorption of Sb(III) and Sb(V) on Freshly Prepared Ferric Hydroxide (FeOxHy)

    PubMed Central

    He, Zan; Liu, Ruiping; Liu, Huijuan; Qu, Jiuhui

    2015-01-01

    Abstract This study prepared fresh ferric hydroxide (in-situ FeOxHy) by the enhanced hydrolysis of Fe3+ ions, and investigates its adsorptive behaviors toward Sb(III) and Sb(V) through laboratory and pilot-scale studies. A contact time of 120-min was enough to achieve adsorption equilibrium for Sb(III) and Sb(V) on the in-situ FeOxHy, and the Elovich model was best to describe the adsorption kinetics of Sb(III) and Sb(V). The Freundlich model was better than Langmuir model to describe the adsorption of Sb(III) and Sb(V) on the in-situ FeOxHy, and the maximum adsorption capacity of Sb(III) and Sb(V) was determined to be 12.77 and 10.21 mmol/g the in-situ FeOxHy as Fe, respectively. Adsorption of Sb(V) decreased whereas that of Sb(III) increased with elevated pH over pH 3–10, owing to the different electrical properties of Sb(III) and Sb(V). Adsorption of Sb(III) and Sb(V) was slightly affected by ionic strength, and thus indicated the formation of inner sphere complexes between Sb and the adsorbent. Sulfate and carbonate showed little effect on the adsorption of Sb(III) and Sb(V). Phosphate significantly inhibited the adsorption of Sb(V), whereas slightly effected that of Sb(III) due to its similar chemical structure to Sb(V). Pilot-scale continuous experiment indicated the feasibility of using in-situ FeOxHy to remove Sb(V), and equilibrium adsorption capacity at the equilibrium Sb(V) concentration of 10 μg/L was determined to be 0.11, 0.07, 0.07, 0.11, and 0.12 mg/g the in-situ FeOxHy as Fe at equilibrium pH of 7.5–7.7, 6.9–7.0, 6.3–6.6, 5.9–6.4, and 5.2–5.9, respectively. PMID:25741175

  11. Cu2+, Cd2+ and Pb2+ adsorption from aqueous solutions by pyrite and synthetic iron sulphide.

    PubMed

    Ozverdi, Arzu; Erdem, Mehmet

    2006-09-01

    In this study, removal of Cu(2+), Cd(2+) and Pb(2+) from aqueous solutions by adsorption onto pyrite and synthetic iron sulphide (SIS) was investigated as a function of pH, contact time, adsorbent dosage, initial metal concentration and temperature. It has been determined that the adsorption of metal ions onto both adsorbents is pH dependent and the adsorption capacities increase with the increasing temperature. The mechanisms governing the metal removal processes were determined as chemical precipitation at low pH (<3) due to H(2)S generation and adsorption at high pH (in the range of 3-6). The metal adsorption yields also increased with the increasing adsorbent dosage and contact time and reached to equilibrium for both adsorbents. The Cu(2+), Cd(2+) and Pb(2+) adsorption capacities of both adsorbents decrease in the order of Pb(2+)>Cu(2+)>Cd(2+). Except for cadmium, little fraction of copper and lead in the solid adsorption residues was desorbed in acidic media.

  12. Batch and fixed-bed adsorption of tartrazine azo-dye onto activated carbon prepared from apricot stones

    NASA Astrophysics Data System (ADS)

    Albroomi, H. I.; Elsayed, M. A.; Baraka, A.; Abdelmaged, M. A.

    2016-02-01

    This work describes the potential of utilizing prepared activated carbon from apricot stones as an efficient adsorbent material for tartrazine (TZ) azo-dye removal in a batch and dynamic adsorption system. The results revealed that activated carbons with well-developed surface area (774 m2/g) and pore volume (1.26 cm3/g) can be manufactured from apricot stones by H3PO4 activation. In batch experiments, effects of the parameters such as initial dye concentration and temperature on the removal of the dye were studied. Equilibrium was achieved in 120 min. Adsorption capacity was found to be dependent on the initial concentration of dye solution, and maximum adsorption was found to be 76 mg/g at 100 mg/L of TZ. The adsorption capacity at equilibrium (q e) increased from 22.6 to 76 mg/g with an increase in the initial dye concentrations from 25 to 100 mg/L. The thermodynamic parameters such as change in free energy (ΔG 0), enthalpy (ΔH 0) and entropy (ΔS 0) were determined and the positive value of (ΔH) 78.1 (K J mol-1) revealed that adsorption efficiency increased with an increase in the process temperature. In fixed-bed column experiments, the effect of selected operating parameters such as bed depth, flow rate and initial dye concentration on the adsorption capacity was evaluated. Increase in bed height of adsorption columns leads to an extension of breakthrough point as well as the exhaustion time of adsorbent. However, the maximum adsorption capacities decrease with increases of flow rate. The breakthrough data fitted well to bed depth service time and Thomas models with high coefficient of determination, R 2 ≥ 94.

  13. Generalized statistical model for multicomponent adsorption equilibria on zeolites

    SciTech Connect

    Rota, R.; Gamba, G.; Paludetto, R.; Carra, S.; Morbidelli, M. )

    1988-05-01

    The statistical thermodynamic approach to multicomponent adsorption equilibria on zeolites has been extended to nonideal systems, through the correction of cross coefficients characterizing the interaction between unlike molecules. Estimation of the model parameters requires experimental binary equilibrium data. Comparisons with the classical model based on adsorbed solution theory are reported for three nonideal ternary systems. The two approaches provide comparable results in the simulation of binary and ternary adsorption equilibrium data at constant temperature and pressure.

  14. [Preparation of surface molecularly imprinted polymers for penicilloic acid, and its adsorption properties].

    PubMed

    Zheng, Penglei; Luo, Zhimin; Chang, Ruimiao; Ge, Yanhui; Du, Wei; Chang, Chun; Fu, Qiang

    2015-09-01

    On account of the specificity and reproducibility for the determination of penicilloic acid in penicillin, this study aims to prepare penicilloic acid imprinted polymers (PEOA-MIPs) by surface polymerization method at the surface of modified silica particles by using penicilloic acid (PEOA) as the template molecule, methacrylic acid (MAA) as the functional monomer, ethylene glycol dimethacrylate ( EGDMA) as the cross linker, and methanol/acetonitrile as the solvents. The synthesis conditions were optimized, and PEOA-MIPs had the best adsorption capacity when the molar ratio of template molecule/functional monomer was 1 :4, cross linking degree was 85% and the solvent ratio of methanol/acetonitrile was 1 :1 (v/v). The adsorption properties were evaluated by adsorption experiments, including the adsorption isotherms, kinetics and selectivity. The adsorption process between PEOA-MIPs and PEOA fitted the Langmuir adsorption isotherm with the maximum adsorption capacity of 122. 78 mg/g and the pseudo-second-order reaction kinetics with fast adsorption kinetics (the equilibrium time of 45 min). The as-synthesized PEOA-MIPs were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), and thermal gravimetric analysis (TGA). The results indicated that the MIPs layer has been successfully grafted on the surface of SiO2 microparticles and the PEOA-MIPs had the excellent thermal stability. The PEOA-MIPs showed the highest selective recognition for PEOA. The PEOA-MIPs possess a high adsorption capacity, rapid mass-transfer rate and high selectivity to PEOA when compared with non-imprinted polymers (PEOA-NIPs). The PEOA-MIPs was expected to be used as the solid phase extraction medium and this study provides the potential applications for fast recognition and analysis of the penicilloic acid in penicillin.

  15. Pressure swing adsorption processes: Intraparticle diffusion/convection models

    SciTech Connect

    Lu, Zuping; Loureiro, J.M.; LeVan, M.D. . Dept. of Chemical Engineering); Rodrigues, A.E. . School of Engineering)

    1993-11-01

    The dynamic behavior of a three-step one-column isothermal PSA process is assessed by simulation; three models are used: equilibrium, intraparticle diffusion, and intraparticle diffusion/convection. Two process performance parameters, product enrichment and recovery of the light component, are used to measure the separation performance. The effects of several operating variables on the process performance are addressed. Higher pressure ratios (P[sub h]/P[sub l]) and higher adsorption capacities increase the process performance. The process performance is practically independent of the step rates, although it can decrease if high feed rates are used together with large feed duration times. The limiting performance of the system is found in the absence of mass-transfer resistances. Intraparticle convection, enhancing mass transfer inside particles, increases the process performance relative to intraparticle diffusion alone; the improvement is limited by the equilibrium situation.

  16. Adsorption and desorption of reversible supramolecular polymers

    NASA Astrophysics Data System (ADS)

    Zweistra, Henk J. A.; Besseling, N. A. M.

    2006-08-01

    We report numerical mean-field results on the quasichemical level of approximation that describe adsorption of reversible supramolecular polymers at a flat interface. Emphasis is laid on the regime of strong adsorption from a dilute solution. There are two differences with respect to macromolecular polymer adsorption: (i) adsorption sets in at relatively high monomer concentrations of the surrounding solution, and (ii) the surface is filled within a much narrower concentration range. Contrary to macromolecular polymers, supramolecular polymers can therefore be desorbed by dilution of the equilibrium solution by solvent within an experimentally accessible concentration window. Based on simple thermodynamic arguments, we provide a quantitative explanation why supramolecular polymers adsorb at relatively high concentrations. Moreover, we discuss the (by comparison) narrow concentration window wherein filling of the surface occurs. This is attributed to the cooperative nature of supramolecular polymer adsorption. The degree of cooperativity is quantified by means of the Hill parameter n .

  17. Adsorption of xenon and krypton on shales

    NASA Technical Reports Server (NTRS)

    Podosek, F. A.; Bernatowicz, T. J.; Kramer, F. E.

    1981-01-01

    A method that uses a mass spectrometer as a manometer is employed in the measurement of Xe and Kr adsorption parameters on shales and related samples, where gas partial pressures were lower than 10 to the -11th atm, corresponding adsorption coverages are only small fractions of a monolayer, and Henry's Law behavior is expected and observed. Results show heats of adsorption in the 2-7 kcal/mol range, and Henry constants at 0-25 C of 1 cu cm STP/g per atmosphere are extrapolated. Although the adsorption properties obtained are variable by sample, the range obtained suggests that shales may be capable of an equilibrium adsorption with modern air high enough to account for a significant fraction of the atmospheric inventory of Xe, and perhaps even of Kr. This effect will nevertheless not account for the factor-of-25 defficiency of atmospheric Xe, in comparison with the planetary gas patterns observed in meteorites.

  18. Monte Carlo simulations of Protein Adsorption

    NASA Astrophysics Data System (ADS)

    Sharma, Sumit; Kumar, Sanat K.; Belfort, Georges

    2008-03-01

    Amyloidogenic diseases, such as, Alzheimer's are caused by adsorption and aggregation of partially unfolded proteins. Adsorption of proteins is a concern in design of biomedical devices, such as dialysis membranes. Protein adsorption is often accompanied by conformational rearrangements in protein molecules. Such conformational rearrangements are thought to affect many properties of adsorbed protein molecules such as their adhesion strength to the surface, biological activity, and aggregation tendency. It has been experimentally shown that many naturally occurring proteins, upon adsorption to hydrophobic surfaces, undergo a helix to sheet or random coil secondary structural rearrangement. However, to better understand the equilibrium structural complexities of this phenomenon, we have performed Monte Carlo (MC) simulations of adsorption of a four helix bundle, modeled as a lattice protein, and studied the adsorption behavior and equilibrium protein conformations at different temperatures and degrees of surface hydrophobicity. To study the free energy and entropic effects on adsorption, Canonical ensemble MC simulations have been combined with Weighted Histogram Analysis Method(WHAM). Conformational transitions of proteins on surfaces will be discussed as a function of surface hydrophobicity and compared to analogous bulk transitions.

  19. Kinetics and thermodynamics of protein adsorption: a generalized molecular theoretical approach.

    PubMed Central

    Fang, F; Szleifer, I

    2001-01-01

    The thermodynamics and kinetics of protein adsorption are studied using a molecular theoretical approach. The cases studied include competitive adsorption from mixtures and the effect of conformational changes upon adsorption. The kinetic theory is based on a generalized diffusion equation in which the driving force for motion is the gradient of chemical potentials of the proteins. The time-dependent chemical potentials, as well as the equilibrium behavior of the system, are obtained using a molecular mean-field theory. The theory provides, within the same theoretical formulation, the diffusion and the kinetic (activated) controlled regimes. By separation of ideal and nonideal contributions to the chemical potential, the equation of motion shows a purely diffusive part and the motion of the particles in the potential of mean force resulting from the intermolecular interactions. The theory enables the calculation of the time-dependent surface coverage of proteins, the dynamic surface tension, and the structure of the adsorbed layer in contact with the approaching proteins. For the case of competitive adsorption from a solution containing a mixture of large and small proteins, a variety of different adsorption patterns are observed depending upon the bulk composition, the strength of the interaction between the particles, and the surface and size of the proteins. It is found that the experimentally observed Vroman sequence is predicted in the case that the bulk solution is at a composition with an excess of the small protein, and that the interaction between the large protein and the surface is much larger than that of the smaller protein. The effect of surface conformational changes of the adsorbed proteins in the time-dependent adsorption is studied in detail. The theory predicts regimes of constant density and dynamic surface tension that are long lived but are only intermediates before the final approach to equilibrium. The implications of the findings to the

  20. Interfaces at equilibrium: A guide to fundamentals.

    PubMed

    Marmur, Abraham

    2016-05-20

    The fundamentals of the thermodynamics of interfaces are reviewed and concisely presented. The discussion starts with a short review of the elements of bulk thermodynamics that are also relevant to interfaces. It continues with the interfacial thermodynamics of two-phase systems, including the definition of interfacial tension and adsorption. Finally, the interfacial thermodynamics of three-phase (wetting) systems is discussed, including the topic of non-wettable surfaces. A clear distinction is made between equilibrium conditions, in terms of minimizing energies (internal, Gibbs or Helmholtz), and equilibrium indicators, in terms of measurable, intrinsic properties (temperature, chemical potential, pressure). It is emphasized that the equilibrium indicators are the same whatever energy is minimized, if the boundary conditions are properly chosen. Also, to avoid a common confusion, a distinction is made between systems of constant volume and systems with drops of constant volume.

  1. Computational Investigation of Conformational Changes in Proteins upon Adsorption

    NASA Astrophysics Data System (ADS)

    Sharma, Sumit; Anand, Gaurav; Belfort, Georges; Kumar, Sanat K.

    2009-03-01

    Amyloidogenic diseases, such as, Alzheimer's, are caused by adsorption and aggregation of partially unfolded proteins. Protein adsorption is often accompanied by conformational rearrangements, which are thought to affect many properties such as their adhesion strength to the surface, biological activity, and aggregation tendency. Experiments have shown that many proteins, upon adsorption to hydrophobic surfaces, undergo a helix to sheet or random coil secondary structural rearrangement. To better understand the equilibrium structural complexities of this phenomenon, we have performed Monte Carlo (MC) simulations and Single Chain Mean Field calculations of adsorption of different proteins, modeled as lattice chains, to study the adsorption behavior and equilibrium protein conformations at different temperatures, protein concentration and surface hydrophobicity. Free energy and entropic effects on adsorption have been studied by determining density of states using Weighted Histogram Analysis Method. Conformational transitions of proteins on surfaces will be discussed as a function of surface hydrophobicity.

  2. 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.

  3. 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.

  4. Preparation, Characterization and Methylene Blue Dye Adsorption Ability of Acid Activated-Natural Zeolite

    NASA Astrophysics Data System (ADS)

    Saputra, O. A.; Prameswari, M. D.; Kinanti, V. T. D.; Mayasari, O. D.; Sutarni, Y. D.; Apriany, K.; Lestari, W. W.

    2017-02-01

    The aim of this research was to prepare an acid-activated natural zeolite (Ac-Zeo) as a low-cost adsorbent material and to investigate their ability on methylene blue dye removal in aqueous solution. The natural zeolite was activated using hydrochloric acid and the final product was characterized using Fourier transform infra-red (FTIR), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The adsorption process was carried out using the batch method. Some parameters like pH condition, contact time and varied dye initial concentration were studied to determine the adsorption ability of Ac-Zeo. In this study, kinetic adsorption was evaluated using pseudo-second order model approach and found that the kinetic adsorption rate constanta (k) and adsorption capacity at equilibrium are 0.1872 mg.g-1.min-1 and 14.94 mg.g-1, respectively. Moreover, Langmuir, Freundlich, and Dubinin–Kaganer–Radushkevich isotherm adsorption models as well as sorption mechanism were studied in this research.

  5. [Adsorption properties of modified graphene for methylene blue removal from wastewater].

    PubMed

    Wu, Yan; Luo, Han-Jin; Wang, Hou; Zhang, Zi-Long; Wang, Can; Wang, Yu-Wei

    2013-11-01

    In this study, cetyltrimethylammonium bromide (CTAB) was chosen to modify graphene, which was applied to remove methylene blue (MB) from aqueous solutions. The characteristics of graphene and modified graphene were characterized by X-ray diffraction (XRD), Fourier transform infrared spectrum (FTIR), thermal gravimetric analyzer (TGA), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The effects of factors including pH, contact time, temperature, and dosage on the adsorption properties of MB onto graphene and modified graphene were investigated. The results revealed that the addition of CTAB in preparation could obviously increase the specific surface area and improve the efficiency of removal. The adsorption processes were rapid within the first 15 min and reached equilibrium in about 120 min. The adsorption kinetics fitted well with the pseudo-second-order model. The optimal reaction temperature was 293 K, the optimal concentration of adsorbent dosage was 2 g x L(-1), and the initial pH value of the solution had little impact on the amount of adsorption. The adsorption capacity of MB on modified graphene inferred from the Langmuir model was 86.43 mg x g(-1) at 293 K, and the adsorption was an exothermic process.

  6. A facile method for improving the covalent crosslinking adsorption process of catalase immobilization.

    PubMed

    Ran, Jingyu; Jia, Shaoyi; Liu, Yong; Zhang, Wei; Wu, Songhai; Pan, Xiaolei

    2010-08-01

    In this paper, we introduced a polydiol (mixture of 1,2-propanediol, 1,3-propanediol, and 2,3-butanediol) to improve the covalent crosslinking adsorption process of immobilized catalase onto chitosan beads. The adsorption behavior was investigated by means of adsorption kinetics and adsorption isotherm. The protein content in crosslinking agent required for approximately 45 min to reach the relative equilibrium, and the protein content in solution of the control group and the pretreated group were 6.63 microg/mL and 6.20 microg/mL, respectively. The maximum catalase adsorption capacity of the control group and the pretreated group were observed as 23.118 microg/g and 25.688 microg/g at pH 7.0, respectively. Temperature profiles showed that 40 degrees C was the ideal temperature for active domain of catalase, and the relative activity of pretreated group was 1.12 times higher than that of the control group. The K(m) value of the control group (67 mM) was higher than that of the pretreated group (54 mM). Thermal stability, operational stability, and the effect of surfactant on catalase adsorption were also explored in this study.

  7. Adsorption of uranium by amidoximated chitosan-grafted polyacrylonitrile, using response surface methodology.

    PubMed

    Xu, Chao; Wang, Jingjing; Yang, Tilong; Chen, Xia; Liu, Xunyue; Ding, Xingcheng

    2015-05-05

    The amidoximated chitosan-grafted polyacrylonitrile (CTS-g-PAO) was prepared for the adsorption of uranium from water. The effects of pH, concentration of uranium and the solid-liquid ratio on the adsorption of uranium by CTS-g-PAO were optimized using Doehlert design of response surface methodology (RSM). The adsorption capacity and removal efficiency achieved 312.06 mg/g and 86.02%, respectively. The adsorption process attained equilibrium only in 120 min. More than 80% of the absorbed uranium could be desorbed by 0.1 mol/l HCl or EDTA-Na, and CTS-g-PAO could be reused at least 3 times. The CTS-g-PAO and U(VI) ions formed a chelate complex due to FTIR spectral analysis. The surface morphology of CTS-g-PAO was also investigated by SEM. The adsorption process was better described by Langmuir isotherm and pseudo second order kinetic model. Results obtained indicated that CTS-g-PAO was very promising in adsorption of uranium from water.

  8. Modification of bentonite with a cationic surfactant: An adsorption study of textile dye Reactive Blue 19.

    PubMed

    Ozcan, Adnan; Omeroğlu, Ciğdem; Erdoğan, Yunus; Ozcan, A Safa

    2007-02-09

    The utilization of modified bentonite with a cationic surfactant (dodecyltrimethylammonium (DTMA) bromide) as an adsorbent was successfully carried out to remove a synthetic textile dye (Reactive Blue 19 (RB19)) by adsorption, from aqueous solutions. Batch studies were carried out to address various experimental parameters such as pH, contact time and temperature. The surface modification of bentonite with a surfactant was examined using the FTIR spectroscopic technique and elemental analysis. Effective pH for the adsorption of RB19 onto DTMA-bentonite was around 1.5. The Langmuir isotherm model was found to be the best to represent the equilibrium with experimental data. The maximum adsorption capacity (q(max)) has been found to be 3.30x10(-4)molg(-1) or 206.58mgg(-1). The thermodynamic study indicated that the adsorption of RB19 onto DTMA-bentonite was favored with the negative Gibbs free energy values. The pseudo-second-order rate equation was able to provide the best description of adsorption kinetics and the intraparticle diffusion model was also applicable up to 40min for the adsorption of RB19 onto DTMA-bentonite.

  9. Adsorption of Procion Red MX 8B using spent tea leaves as adsorbent

    NASA Astrophysics Data System (ADS)

    Heraldy, Eddy; Osa, Riesta Ramdhaniyati; Suryanti, Venty

    2016-02-01

    The adsorption of Procion Red MX 8B using spent tea leaves (STL) as adsorbent, has been studied by batch adsorption technique. The adsorbent was activated by NaOH 4% for 24 hours for delignification process. The adsorbent was characterized using FTIR to indetify the functional groups of cellulose was shown by uptake -OH, C-H and C-O. The optimum conditions of adsorption experiments were achieved when pH was set as 6 with contact time of 75 minutes and capacity of adsorption was 3.28 mg/g. The equilibrium data were fitted to Langmuir and Isotherm Freundlichs. The kinetic models, pseudo first order and pseudo second order were employed to describe the adsorption mechanism. The experimental results showed that the pseudo second order equation was the best model that described the adsorption behavior with the coefficient of correlation (R2) was equal higher than 0.99 The results suggested that STL had high potential to be used as effective adsorbent for Procion Red MX 8B removal.

  10. Study on the adsorption of Cu(II) by folic acid functionalized magnetic graphene oxide

    NASA Astrophysics Data System (ADS)

    Wang, Cuicui; Ge, Heyi; Zhao, Yueying; Liu, Shanshan; Zou, Yu; Zhang, Wenbo

    2017-02-01

    The folic acid functionalized magnetic graphene oxide (FA-mGO) as a new adsorbent has been synthesized in this work for the elimination of Cu(II) from waste water. The as-prepared FA-mGO was tested by SEM, TEM, particle size analyzer, FTIR, XRD, Roman spectrum, TGA and magnetic properties analyzer. Some factors, such as adsorbent dose, pH, contact time, initial concentration of adsorbate and temperature were explored. The results showed that the FA-mGO had the better adsorption performance than mGO. After 40 min, the adsorption equilibrium could be reached. Furthermore, the adsorption property obeyed the pseudo-second order kinetic model and the Temkin isotherms well. The maximum adsorption capacity was 283.29 mg/g for Cu(II) from Pseudo-second-order model at pH=5 and 318 K. The chelation action between FA and Cu(II) along with electrostatic incorporation between GO and Cu(II) determined the favourable adsorption property. Besides, thermodynamic studies results ∆G0<0, ∆H0>0, ∆S0>0 suggested that the adsorption mechanism was an endothermic and spontaneous process essentially. Finally, desorption and reusability studies imply FA-mGO has an excellent reproducibility and is benefit to environmental protection and resource conservation.

  11. [Preparation of HDTMA-modified Zeolite and Its Performance in Nitro-phenol Adsorption from Wastewaters].

    PubMed

    Guo, Jun-yuan; Wang, Bin

    2016-05-15

    In this study, natural zeolite was modified by HDTMA. Effects of the modified conditions, HDTMA-modified zeolite doses, solution pH values, and reaction time on nitro-phenol removal were investigated, and the adsorption kinetics and isotherms were discussed. Compared with natural zeolite, HDTMA-modified zeolite showed better performance in nitro-phenol removal. An adsorption capacity of 2.53 mg · g⁻¹ was achieved when the concentration of HDTMA solution (pH = 10) was 1.2% in preparation of modified zeolite. This adsorption capacity was higher than that obtained by natural zeolite (0.54 mg · g⁻¹). In adsorption tests, when HDTMA- modified zeolite dose was adjusted to 8 g · L⁻¹, the removal efficiency of nitro-phenol reached 93.9% after 90 min reaction, with wastewater pH of 6. Furthermore, the nitro-phenol adsorption process could be well fitted to the pseudo-first-order kinetics model (R² > 0.90), whereas the adsorption isotherm results indicated that Langmuir model provided the best fitting for the equilibrium data at different temperatures, with R² of higher than 0.90.

  12. Liquid phase adsorption behavior of inulin-type fructan onto activated charcoal.

    PubMed

    Li, Kecheng; Liu, Song; Xing, Ronge; Yu, Huahua; Qin, Yukun; Li, Pengcheng

    2015-05-20

    This study describes liquid phase adsorption characteristics of inulin-type fructan onto activated charcoal. Batch mode experiments were conducted to study the effects of pH, contact time, temperature and initial concentration of inulin. Nearly neutral solution (pH 6-8) was favorable to the adsorption and the equilibrium was attained after 40 min with the maximum adsorption Qmax 0.182 g/g (adsorbate/adsorbent) at 298 K. The experimental data analysis indicated that the adsorption process fitted well with the pseudo-second-order kinetic model (R(2) = 1) and Langmuir isotherms model (R(2) > 0.99). Thermodynamic parameters revealed that the adsorption process was spontaneous and exothermic with a physical nature. Inulin desorption could reach 95.9% using 50% ethanol solution and activated charcoal could be reused without significant losses in adsorption capacity. These results are of practical significance for the application of activated charcoal in the production and purification of inulin-type fructan.

  13. Preparation and characterization of chitosan-zirconium(IV) composite for adsorption of vanadium(V).

    PubMed

    Zhang, Lingfan; Liu, Xin; Xia, Wei; Zhang, Wenqing

    2014-03-01

    In this present study, an inorganic-biopolymer composite based on chitosan-zirconium(IV) was prepared and investigated as a biosorbent for the removal of vanadium(V) ions from aqueous solution. The resulting composite before and after adsorbed V(V) were characterized by using FT-IR, XRD, SEM and EDS, respectively. Various relevant parameters affecting the adsorption capacity such as pH, initial concentration, contact time, temperature and co-existing ions were evaluated. The results demonstrated that the optimum pH was found to be 4.0 and the equilibrium was achieved after 4h for V(V) adsorption. The Langmuir isotherm model could be well described the adsorption of V(V), with the maximum adsorption capacity of 208 mg g(-1) at 30 °C. The kinetics data were well fitted to pseudo-second-order equation, indicating that chemical sorption as the rate-limiting step of adsorption mechanism. The calculated thermodynamic parameters such as ΔG°, ΔH° and ΔS° indicated that the adsorption process was feasible, spontaneous and endothermic in nature. Moreover, co-existing ions including nitrate, chloride and sulfate had a certain effect on the uptake of V(V). The V(V) loaded chitosan-zirconium(IV) composite could be regenerated by 0.01 mol L(-1) sodium hydroxide, with efficiency greater than 95%.

  14. Adsorption behavior of poly(dimethyl-diallylammonium chloride) on pulp fiber studied by cryo-time-of-flight secondary ion mass spectrometry and cryo-scanning electron microscopy

    NASA Astrophysics Data System (ADS)

    Masumi, Takashi; Matsushita, Yasuyuki; Aoki, Dan; Takama, Ruka; Saito, Kaori; Kuroda, Katsushi; Fukushima, Kazuhiko

    2014-01-01

    In this study, the adsorption behavior of poly(dimethyl-diallylammonium chloride) (PDADMAC), a retention agent used in papermaking, in a dual polymer system with anionic poly(acrylamide) (A-PAM) was investigated by time-of-flight secondary ion mass spectrometry (TOF-SIMS). Initially, fragment structures and cleavage patterns were identified via TOF-SIMS experiments with deuterium-labeled PDADMAC and the unlabeled analogue. Visualization of PDADMAC on a dry handsheet surface using traditional TOF-SIMS analysis indicated that the electrostatic interaction between coagulated PDADMAC and A-PAM was relatively weak. A novel cryo-TOF-SIMS/SEM system enabled the evaluation of a wet handsheet containing PDADMAC. Analysis of this sample indicated that PDADMAC adsorbs onto the fiber surface and collects preferentially on the tangled fibrils located between fibers.

  15. Kinetic studies of the liquid-phase adsorption of a reactive dye onto activated lignite

    SciTech Connect

    Petrolekas, P.D.; Maggenakis, G.

    2007-02-14

    The kinetics of batch adsorption of a commercial reactive dye onto activated lignite has been investigated at temperatures of 26, 40, and 55{sup o}C, using aqueous solutions with initial dye concentrations in the range of 15-60 mg/L. An empirical single parameter relationship of the adsorbent loading versus the square root of contact time was proposed, which was determined to provide a very good description of the batch adsorption transients up to equilibrium. The data were also examined by means of the Elovich equation. The effect of the temperature and the initial dye concentration on the adsorption kinetics was analyzed, and the results were discussed by considering that intraparticle diffusion is the dominant mechanism.

  16. Study of malachite green adsorption by organically modified clay using a batch method

    NASA Astrophysics Data System (ADS)

    Arellano-Cárdenas, Sofía; López-Cortez, Socorro; Cornejo-Mazón, Maribel; Mares-Gutiérrez, Juan Carlos

    2013-09-01

    The adsorption of toxic dye malachite green from aqueous effluents by organically modified clay was studied in a batch system. The organoclay (OC) used was prepared by the intercalation of cationic surfactant hexadecyltrimethylammonium bromide in a Mexican montmorillonite. The effects of initial dye concentration, temperature, pH, and contact time were investigated. The OC showed a high dye removal (99.6%) from an initial dye concentration of 60 mg L-1 at pH 6 and 25 °C. The adsorption capacity was independent of pH and increased with the temperature. Equilibrium data were well fitted by Langmuir adsorption model. The rate of sorption was adjusted to a pseudo second-order kinetic model.

  17. 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.

  18. Enhanced adsorption of atrazine from aqueous solution by molecularly imprinted TiO2 film

    NASA Astrophysics Data System (ADS)

    Zhang, Chunjing; Yan, Jinlong; Zhang, Chunxiao; Yang, Zhengpeng

    2012-07-01

    TiO2 film imprinted by atrazine molecule at the surface of quartz crystal was prepared using molecular imprinting and surface sol-gel process. The molecularly imprinted TiO2 film was characterized by scanning electron microscopy and cyclic voltammetry, and the atrazine adsorption was investigated by quartz crystal microbalance (QCM) technique. In comparison with non-imprinted TiO2 film, the molecularly imprinted TiO2 film exhibits high selectivity for atrazine, better reversibility and a much higher adsorption capacity for the target molecule, the adsorption equilibrium constant estimated from the in situ frequency measurement is about 6.7 × 104 M-1, which is thirteen times higher than that obtained on non-imprinted TiO2 film.

  19. Preparation of PVA/amino multi-walled carbon nanotubes nanocomposite microspheres for endotoxin adsorption.

    PubMed

    Zong, Wenhui; Chen, Jian; Han, Wenyan; Cheng, Guanghui; Chen, Jie; Wang, Yue; Wang, Weichao; Ou, Lailiang; Yu, Yaoting; Shen, Jie

    2017-03-23

    A novel polyvinyl alcohol-amino multi-walled carbon nanotube (PVA-AMWCNT) nanocomposite microsphere was prepared successfully for the first time and used for endotoxin removal. The resulting AMWCNT modified PVA microsphere was characterized by SEM, Raman spectrum and fluorescence image, which indicated AMWCNT was dispersed into the macropores of PVA microsphere uniformly. The PVA-AMWCNT microspheres showed better adsorption capability and faster adsorption equilibrium for endotoxin in aqueous solution when compared to the PVA microsphere with polymyxin B (PMB) as ligand. More noteworthy, the PVA based microspheres had little nonspecific adsorption in simulated serum. Therefore, PVA-AMWCNT nanocomposite microsphere with an excellent haemocompatibility has a great potential application in clinical blood purification.

  20. 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.

    2016-12-01

    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.

  1. Adsorption of Basic Violet 14 in aqueous solutions using KMnO4-modified activated carbon.

    PubMed

    Shi, Qianqian; Zhang, Jian; Zhang, Chenglu; Nie, Wei; Zhang, Bo; Zhang, Huayong

    2010-03-01

    In this paper, an activated carbon was prepared from Typha orientalis and then treated with KMnO(4) and used for the removal of Basic Violet 14 from aqueous solutions. KMnO(4) treatment influenced the physicochemical properties of the carbon and improved its adsorption capacity. Adsorption experiments were then conducted with KMnO(4)-modified activated carbon to study the effects of carbon dosage (250-1500 mg/L), pH (2-10), ion strength (0-0.5 mol/L), temperature, and contact time on the adsorption of Basic Violet 14 from aqueous solutions. The equilibrium data were analyzed by the Langmuir and Freundlich isotherms and fitted well with the Langmuir model. The pseudo-first-order, pseudo-second-order, and intraparticle diffusion models were used to evaluate the kinetic data and the pseudo-second-order kinetics was the best with good correlation.

  2. Adsorption isotherms, kinetics, thermodynamics and desorption studies of 2,4,6-trichlorophenol on oil palm empty fruit bunch-based activated carbon.

    PubMed

    Tan, I A W; Ahmad, A L; Hameed, B H

    2009-05-30

    The adsorption characteristics of 2,4,6-trichlorophenol (TCP) on activated carbon prepared from oil palm empty fruit bunch (EFB) were evaluated. The effects of TCP initial concentration, agitation time, solution pH and temperature on TCP adsorption were investigated. TCP adsorption uptake was found to increase with increase in initial concentration, agitation time and solution temperature whereas adsorption of TCP was more favourable at acidic pH. The adsorption equilibrium data were best represented by the Freundlich and Redlich-Peterson isotherms. The adsorption kinetics was found to follow the pseudo-second-order kinetic model. The mechanism of the adsorption process was determined from the intraparticle diffusion model. Boyd plot revealed that the adsorption of TCP on the activated carbon was mainly governed by particle diffusion. Thermodynamic parameters such as standard enthalpy (DeltaH degrees ), standard entropy (DeltaS degrees ), standard free energy (DeltaG degrees ) and activation energy were determined. The regeneration efficiency of the spent activated carbon was high, with TCP desorption of 99.6%.

  3. Kinetics and mechanism of adsorption of methylene blue from aqueous solution by nitric-acid treated water-hyacinth.

    PubMed

    El-Khaiary, Mohammad I

    2007-08-17

    Kinetics adsorption experiments were conducted to evaluate the adsorption characteristics of a cationic dye (methylene blue, MB) onto nitric-acid treated water-hyacinth (N-WH). Results showed that N-WH can remove MB effectively from aqueous solution. The loading of MB onto N-WH was found to increase significantly with increasing the initial MB concentration, but the residual concentration of MB in solution also increased. A complete removal of MB from solution was only achieved at the lower range of initial MB concentration (less than 286 mg/L). Temperature had a slight effect on the amount adsorbed at equilibrium. The adsorption rate was fast and more than half of the adsorbed-MB was removed in the first 15 min at room temperature, which makes the process practical for industrial application. The adsorption kinetics at room temperature could be expressed by the pseudo second order model, while at higher temperatures (45-80 degrees C) and low MB concentration (97 mg/L) both Lagergren's model and the pseudo second order model can be used to predict the kinetics of adsorption. The overall rate of dye uptake was found to be controlled by external mass transfer at the beginning of adsorption, then gradually changed to intraparticle diffusion control at a later stage. The initial period where external mass transfer is the rate controlling step was found to increase with increasing initial MB concentration and decrease with increasing temperature. The increase in temperature was also found to increase the rate of adsorption and reduce the time required to reach equilibrium. The initial rate of adsorption, h(o), was calculated, it was found to increase with increasing temperature, while the increase in MB concentration decreased h(o) at the lower concentration range then increased h(o) again at high concentration. The value of the activation coefficient, E, was found to be 8.207 kJ/mol, which indicates a diffusion controlled process.

  4. Shape characteristics of equilibrium and non-equilibrium fractal clusters.

    PubMed

    Mansfield, Marc L; Douglas, Jack F

    2013-07-28

    It is often difficult in practice to discriminate between equilibrium and non-equilibrium nanoparticle or colloidal-particle clusters that form through aggregation in gas or solution phases. Scattering studies often permit the determination of an apparent fractal dimension, but both equilibrium and non-equilibrium clusters in three dimensions frequently have fractal dimensions near 2, so that it is often not possible to discriminate on the basis of this geometrical property. A survey of the anisotropy of a wide variety of polymeric structures (linear and ring random and self-avoiding random walks, percolation clusters, lattice animals, diffusion-limited aggregates, and Eden clusters) based on the principal components of both the radius of gyration and electric polarizability tensor indicates, perhaps counter-intuitively, that self-similar equilibrium clusters tend to be intrinsically anisotropic at all sizes, while non-equilibrium processes such as diffusion-limited aggregation or Eden growth tend to be isotropic in the large-mass limit, providing a potential means of discriminating these clusters experimentally if anisotropy could be determined along with the fractal dimension. Equilibrium polymer structures, such as flexible polymer chains, are normally self-similar due to the existence of only a single relevant length scale, and are thus anisotropic at all length scales, while non-equilibrium polymer structures that grow irreversibly in time eventually become isotropic if there is no difference in the average growth rates in different directions. There is apparently no proof of these general trends and little theoretical insight into what controls the universal anisotropy in equilibrium polymer structures of various kinds. This is an obvious topic of theoretical investigation, as well as a matter of practical interest. To address this general problem, we consider two experimentally accessible ratios, one between the hydrodynamic and gyration radii, the other

  5. Adsorption of Cd(II) and Pb(II) by a novel EGTA-modified chitosan material: kinetics and isotherms.

    PubMed

    Zhao, Feiping; Repo, Eveliina; Yin, Dulin; Sillanpää, Mika E T

    2013-11-01

    In this study, a novel adsorbent was synthesized by functionalizing chitosan with ethylene glycol-bis(2-aminoethylether)-N,N,N',N'-tetraacetic acid (EGTA) ligands. The adsorption capability of EGTA-modified chitosan was investigated by the removal of Cd(II) and Pb(II) from aqueous solutions. The adsorption and regeneration studies were performed by batch techniques. The effects of pH, contact time, and initial metal concentration were studied. Metal uptake by EGTA-chitosan was 0.74 mmol g(-1) for Cd(II) and 0.50 mmol g(-1) for Pb(II). The adsorption mechanism, that the adsorbent formed octahedral chelate structures with bivalent metal ions, was proposed tentatively based on the experimental results of FTIR and the theoretically calculated data of point charges. The kinetics of Cd(II) and Pb(II) on EGTA-chitosan complied with the pseudo-second-order model and the adsorption rate was also influenced by intra-particle diffusion. BiLangmuir isotherm model was well fitted to the experimental data of one-component adsorption suggesting the surface heterogeneity of the novel adsorbent. The extended form of the BiLangmuir model was tested for the modeling of two-component adsorption equilibrium of Cd(II) and Pb(II) on EGTA-chitosan. In the two-component solution, both competitive adsorption and positive synergy of chelation between metal ions occurred and the novel adsorbent showed higher affinity toward Cd(II).

  6. Polydopamine-mediated surface functionalization of electrospun nanofibrous membranes: Preparation, characterization and their adsorption properties towards heavy metal ions

    NASA Astrophysics Data System (ADS)

    Wu, Chunlin; Wang, Heyun; Wei, Zhong; Li, Chuan; Luo, Zhidong

    2015-08-01

    In this paper, a simple and versatile approach for the fabrication of a polyethyleneimine (PEI)-functionalized nanofibrous membrane utilizing polydopamine (PDA) as a mediator is proposed. The morphology and structure of the PDA-coated and PEI-grafted nanofibrous membranes were confirmed using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. Due to a large specific surface area and long fibrous morphology, the synthesized membranes were used as novel adsorbents for copper ion (Cu2+) removal from aqueous solutions. The adsorption of Cu2+ was investigated on the synthesized membranes regarding the membrane dosages, initial solution pH values, initial solution concentrations, contact times and temperatures. In addition, the adsorption equilibrium data of PEI-grafted membranes were well fitted with the Langmuir adsorption isotherm, and a maximum adsorption capacity value of 33.59 mg g-1 was determined (while it was 21.94 mg g-1 for the PDA-coated membranes). The thermodynamic parameters indicated that Cu2+ absorption was a spontaneous and exothermic adsorption process. In addition, XPS peak differentiation imitating analysis permitted the proposal of a copper-amine coordination adsorption mechanism that can be used to explain changes in the adsorption properties compared to PDA coating nanofibrous membranes.

  7. Influence of pH on the adsorption of uranium ions by oxidized activated carbon and chitosan

    SciTech Connect

    Park, G.I.; Park, H.S.; Woo, S.I.

    1999-03-01

    The adsorption characteristics of uranyl ions on surface-oxidized carbon were compared with those of powdered chitosan over a wide pH range. In particular, an extensive analysis was made on solution pH variation during the adsorption process or after adsorption equilibrium. Uranium adsorption on the two adsorbents was revealed to be strongly dependent on the initial pH of the solution. A quantitative comparison of the adsorption capacities of the two adsorbents was made, based on the isotherm data obtained at initial pH 3, 4, and 5. In order to analyze the adsorption kinetics incorporated with pH effects, batch experiments at various initial pH values were carried out, and solution pH profiles with the adsorption time were also evaluated. The breakthrough behavior in a column packed with oxidized carbon was also characterized with respect to the variation of effluent pH. Based on these experimental results, the practical applicability of oxidized carbon for uranium removal from acidic radioactive liquid waste was suggested.

  8. Recovery of oil from oil-in-water emulsion using biopolymers by adsorptive method.

    PubMed

    Elanchezhiyan, S Sd; Sivasurian, N; Meenakshi, Sankaran

    2014-09-01

    In the present study, it is aimed to identify, a low cost sorbent for the recovery of oil from oil-in-water emulsion using biopolymers such as chitin and chitosan. Chitin has the greater adsorption capacity than chitosan due to its hydrophobic nature. The characterizations of chitin and chitosan were done using FTIR, SEM, EDAX, XRD, TGA and DSC techniques. Under batch equilibrium mode, a systematic study was performed to optimize the various equilibrium parameters viz., contact time, pH, dosage, initial concentration of oil, and temperature. The adsorption process reached equilibrium at 40 min of contact time and the percentage removal of oil was found to be higher (90%) in the acidic medium. The Freundlich and Langmuir models were applied to describe the equilibrium isotherms and the isotherm constants were calculated. Thermodynamic parameters such as ΔG°, ΔH° and ΔS° were calculated to find out the nature of the sorption mechanism. The kinetic studies were investigated with reaction-based and diffusion-based models. The suitable mechanism for the removal of oil has been established.

  9. Adsorption of Cu(II) on Oxidized Multi-Walled Carbon Nanotubes in the Presence of Hydroxylated and Carboxylated Fullerenes

    PubMed Central

    Wang, Jing; Li, Zhan; Li, Shicheng; Qi, Wei; Liu, Peng; Liu, Fuqiang; Ye, Yuanlv; Wu, Liansheng; Wang, Lei; Wu, Wangsuo

    2013-01-01

    The adsorption of Cu(II) on oxidized multi-walled carbon nanotubes (oMWCNTs) as a function of contact time, pH, ionic strength, temperature, and hydroxylated fullerene (C60(OH)n) and carboxylated fullerene (C60(C(COOH)2)n) were studied under ambient conditions using batch techniques. The results showed that the adsorption of Cu(II) had rapidly reached equilibrium and the kinetic process was well described by a pseudo-second-order rate model. Cu(II) adsorption on oMWCNTs was dependent on pH but independent of ionic strength. Compared with the Freundlich model, the Langmuir model was more suitable for analyzing the adsorption isotherms. The thermodynamic parameters calculated from temperature-dependent adsorption isotherms suggested that Cu(II) adsorption on oMWCNTs was spontaneous and endothermic. The effect of C60(OH)n on Cu(II) adsorption of oMWCNTs was not significant at low C60(OH)n concentration, whereas a negative effect was observed at higher concentration. The adsorption of Cu(II) on oMWCNTs was enhanced with increasing pH values at pH < 5, but decreased at pH ≥ 5. The presence of C60(C(COOH)2)n inhibited the adsorption of Cu(II) onto oMWCNTs at pH 4–6. The double sorption site model was applied to simulate the adsorption isotherms of Cu(II) in the presence of C60(OH)n and fitted the experimental data well. PMID:24009683

  10. Isotherms for Water Adsorption on Molecular Sieve 3A: Influence of Cation Composition

    SciTech Connect

    Lin, Ronghong; Ladshaw, Austin; Nan, Yue; Liu, Jiuxu; Yiacoumi, Sotira; Tsouris, Costas; DePaoli, David W.; Tavlarides, Lawrence L.

    2015-06-16

    This study is part of our continuing efforts to address engineering issues related to the removal of tritiated water from off-gases produced in used nuclear fuel reprocessing facilities. In the current study, adsorption equilibrium of water on molecular sieve 3A beads was investigated. Adsorption isotherms for water on the UOP molecular sieve 3A were measured by a continuous-flow adsorption system at 298, 313, 333, and 353 K. Experimental data collected were analyzed by the Generalized Statistical Thermodynamic Adsorption (GSTA) isotherm model. The K+/Na+ molar ratio of this particular type of molecular sieve 3A was ~4:6. Our results showed that the GSTA isotherm model worked very well to describe the equilibrium behavior of water adsorption on molecular sieve 3A. The optimum number of parameters for the current experimental data was determined to be a set of four equilibrium parameters. This result suggests that the adsorbent crystals contain four energetically distinct adsorption sites. In addition, it was found that water adsorption on molecular sieve 3A follows a three-stage adsorption process. This three-stage adsorption process confirmed different water adsorption sites in molecular sieve crystals. In addition, the second adsorption stage is significantly affected by the K+/Na+ molar ratio. In this stage, the equilibrium adsorption capacity at a given water vapor pressure increases as the K+/Na+ molar ratio increases.

  11. Isotherms for Water Adsorption on Molecular Sieve 3A: Influence of Cation Composition

    DOE PAGES

    Lin, Ronghong; Ladshaw, Austin; Nan, Yue; ...

    2015-06-16

    This study is part of our continuing efforts to address engineering issues related to the removal of tritiated water from off-gases produced in used nuclear fuel reprocessing facilities. In the current study, adsorption equilibrium of water on molecular sieve 3A beads was investigated. Adsorption isotherms for water on the UOP molecular sieve 3A were measured by a continuous-flow adsorption system at 298, 313, 333, and 353 K. Experimental data collected were analyzed by the Generalized Statistical Thermodynamic Adsorption (GSTA) isotherm model. The K+/Na+ molar ratio of this particular type of molecular sieve 3A was ~4:6. Our results showed that themore » GSTA isotherm model worked very well to describe the equilibrium behavior of water adsorption on molecular sieve 3A. The optimum number of parameters for the current experimental data was determined to be a set of four equilibrium parameters. This result suggests that the adsorbent crystals contain four energetically distinct adsorption sites. In addition, it was found that water adsorption on molecular sieve 3A follows a three-stage adsorption process. This three-stage adsorption process confirmed different water adsorption sites in molecular sieve crystals. In addition, the second adsorption stage is significantly affected by the K+/Na+ molar ratio. In this stage, the equilibrium adsorption capacity at a given water vapor pressure increases as the K+/Na+ molar ratio increases.« less

  12. Kinetic and steric differences in adsorption in two porous metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Lask, Kathleen; Krungleviciute, Vaiva; Bulut, Murat; Migone, Aldo; Lee, J.-Y.; Li, Jing

    2008-03-01

    Kinetic and steric differences are two of the three fundamental mechanisms underlying the use of adsorption in applications to gas mixture separations. We present experimental results on kinetics and equilibrium adsorption measurements of tetrafluoromethane and argon on two metal-organic framework (MOF) materials: RPM1-Co or [Co3(bpdc)3bpy].4DMF.H2O] (bpdc = biphenyldicarboxylate, bpy = 4,4'-bipyridine, DMF = N,N- dimethylformamide) and Cu-BTC or Cu3(BTC)2(H2O)3 (BTC = benzene-1,3,5-tricarboxylate). The adsorbates display significant differences in their kinetics on RPM1-Co (i.e., there are sizable differences in the time required for each gas to reach equilibrium after it is allowed access to the substrate). Our equilibrium measurements show that CF4 is sterically precluded from adsorbing in the small tetrahedral-shaped side pockets present in Cu-BTC. We will compare our experimental results with predictions for how adsorption kinetics depends on the size of the adsorbate and on those of the pores present in the substrate.

  13. Adsorption of oxygen onto zeolites at pressures up to 15 MPa

    NASA Astrophysics Data System (ADS)

    Helvensteijn, Bernardus P.; Wang, Yu; Levan, Douglas; Luna, Bernadette; Kashani, Ali

    2012-06-01

    For NASA applications, high-pressure oxygen is an integral part of portable life support systems (PLSSs) for Extravehicular Activities (EVAs), some fuel cell systems and potential In Situ Resource Utilization (ISRU) systems. New high-pressure oxygen generation systems will be needed on the International Space Station (to enable EVAs after the Shuttle is retired), on a Lunar Lander (to use lower pressure cryogenic tanks as a source of high pressure oxygen for EVAs) and on a planetary habitat (to generate and store high pressure oxygen for extended periods of time). One of the candidate technologies for producing high-pressure oxygen, temperature swing adsorption (TSA) compression, offers many advantages but has a low technology readiness level. Evaluation of technical feasibility and safety issues, and specification of operating parameters of the compressor require the availability of fundamental equilibrium adsorption data. A cryogenic, highpressure volumetric equilibrium adsorption apparatus has been developed at NASA Ames Research Center to facilitate collection of the needed data. The apparatus incorporates cryogenic and vacuum surrounds, and a high-pressure oxygen circuit. In this paper, lowtemperature equilibrium isotherms of oxygen on various sorbent materials are presented. The data presented will aid the development of a space qualified TSA system

  14. Adsorption of toxic carbamate pesticide oxamyl from liquid phase by newly synthesized and characterized graphene quantum dots nanomaterials.

    PubMed

    Agarwal, Shilpi; Sadeghi, Nima; Tyagi, Inderjeet; Gupta, Vinod Kumar; Fakhri, Ali

    2016-09-15

    Graphene quantum dots have been synthesized using the microwave-assisted hydrothermal route. The surface textural and morphological structure of synthesized adsorbent i.e. graphene quantum dots was analyzed using various analytical techniques such as X-ray diffraction, Transmission electron Microscopy, Atomic Force Microscopy and N2 adsorption-desorption instrumental techniques. The application of graphene quantum dots as an adsorbent for the removal of noxious pesticide compound i.e. oxamyl from aqueous solutions was well investigated and elucidated. The impact of several effective parameters such as effect of agitation speed, pH, adsorbent dose, contact time, temperature and initial concentration on sorption efficiency was studied and optimized using batch adsorption experiments. The optimized pH for maximum oxamyl adsorption was found to be 8.0 and for the maximum adsorption rates the adsorbent dose of 0.6g was found to be optimum to carry out the adsorption with in less than 25min of contact time. From the results obtained, it is clear that for all contact times, an increase in oxamyl concentration resulted in increase in the percent oxamyl removal. The adsorption equilibrium and kinetic data were well fitted and found to be in good agreement with the Langmuir isotherm and pseudo-second-order kinetic model.

  15. Removal of Neutral Red from aqueous solution by adsorption on spent cottonseed hull substrate.

    PubMed

    Zhou, Qi; Gong, Wenqi; Xie, Chuanxin; Yang, Dongjiang; Ling, Xiaoqing; Yuan, Xiao; Chen, Shaohua; Liu, Xiaofang

    2011-01-15

    Cottonseed hull, a low-cost widely available agricultural waste in China, after used as substrate for the white rot fungus Pleurotus ostreatus cultivation, was tested for the removal of Neutral Red (NR), a cationic dye, from aqueous solution. A batch adsorption study was carried out with varied solution pH, adsorbent dosage, reaction time and initial NR concentration. The results show that the kinetics of dye removal by the spent cottonseed hull substrate (SCHS) is prompt in the first 5 min and the adsorption equilibrium can be attained after 240 min. The biosorption kinetics and equilibrium follow typical pseudo-second-order and Langmuir adsorption models. Thermodynamic parameters of ΔG°, ΔH° and ΔS° show that the adsorption is a spontaneous and endothermic process. Fourier transform infrared (FTIR) spectroscopy was used for the characterization of possible dye-biosorbent interaction. This study provides a facile method to produce low-cost biosorbent for the purification of dye contaminated water.

  16. Synthesis, characterization and adsorption properties of diethylenetriamine-modified hypercrosslinked resins for efficient removal of salicylic acid from aqueous solution.

    PubMed

    Huang, Jianhan; Jin, Xiaoying; Mao, Jinglin; Yuan, Bin; Deng, Rujie; Deng, Shuguang

    2012-05-30

    We report an effective approach for tailoring the pore textural properties and surface polarity of a hypercrosslinked resin to enhance its adsorption capacity and selectivity for removing salicylic acid from aqueous solution. Four hypercrosslinked resins were synthesized by controlling the reaction time of the self Friedel-Crafts reaction of chloromethylated polystyrene-co-divinylbenzene, and then modified with diethylenetriamine to adjust their surface polarity. The resins were characterized with N(2) adsorption for pore textural properties, Fourier transform infrared spectroscopy (FT-IR) for surface functional groups, chemical analysis for residual chlorine content and weak basic exchange capacity. Adsorption equilibrium, kinetics and breakthrough performance were determined for the removal of salicylic acid from aqueous solution on a selected resin HJ-M01. The equilibrium adsorption capacity of salicylic acid on HJ-M01 is significantly higher than that on its precursor HJ-11 and a few commercial adsorbents including AB-8, XAD-4 and XAD-7. The dynamic adsorption capacity of salicylic acid on HJ-M01 was found to be 456.4 mg/L at a feed concentration of 1000 mg/L and 294 K. The used resin could be fully regenerated with 1% sodium hydroxide solution. The hypercrosslinked resins being developed were promising alternatives to commercial adsorbents for removing salicylic acid and other volatile organic compounds (VOCs) from aqueous solution.

  17. Adsorption of Pb(II) and Cd(II) from aqueous solutions using titanate nanotubes prepared via hydrothermal method.

    PubMed

    Xiong, Lin; Chen, Cheng; Chen, Qing; Ni, Jinren

    2011-05-30

    Titanate nanotubes (TNs) with specific surface areas of 272.31 m(2)g(-1) and pore volumes of 1.264 cm(3)g(-1) were synthesized by alkaline hydrothermal method. The TNs were investigated as adsorbents for the removal of Pb(II) and Cd(II) from aqueous solutions. The FT-IR analysis indicated that Pb(II) and Cd(II) adsorption were mainly ascribed to the hydroxyl groups in the TNs. Batch experiments were conducted by varying contact time, pH and adsorbent dosage. It was shown that the initial uptake of each metal ion was very fast in the first 5 min, and adsorption equilibrium was reached after 180 min. The adsorption of Pb(II) and Cd(II) were found to be maximum at pH in the range of 5.0-6.0. The adsorption kinetics of both metal ions followed the pseudo-second-order model. Equilibrium data were best fitted with the Langmuir isotherm model, and the maximum adsorption capacities of Pb(II) and Cd(II) were determined to be 520.83 and 238.61 mg g(-1), respectively. Moreover, more than 80% of Pb(II) and 85% of Cd(II) adsorbed onto TNs can be desorbed with 0.1M HCl after 3h. Thus, TNs were considered to be effective and promising materials for the removal of both Pb(II) and Cd(II) from wastewater.

  18. Competitive adsorption characteristics of fluoride and phosphate on calcined Mg-Al-CO3 layered double hydroxides.

    PubMed

    Cai, Peng; Zheng, Hong; Wang, Chong; Ma, Hongwen; Hu, Jianchao; Pu, Yubing; Liang, Peng

    2012-04-30

    With synthetic wastewater, competitive adsorption characteristics of fluoride and phosphate on calcined Mg-Al-CO(3) layered double hydroxides (CLDH) were investigated. A series of batch experiments were performed to study the influence of various experimental parameters, such as pH, contact time, and order of addition of the anions on the competitive adsorption of fluoride and phosphate on CLDH. It was found that the optimal pH is around 6 and it took 24 h to attain equilibrium when fluoride and phosphate were simultaneous added. The order of addition of anions influenced the adsorption of fluoride and phosphate on CLDH. The kinetic data were analyzed using the pseudo first-order and pseudo second-order models and they were found to fit very well the pseudo second-order kinetic model. Data of equilibrium experiments were fitted well to Langmuir isotherm and the competitive monolayer adsorption capacities of fluoride and phosphate were found to be obviously lower than those of single anion at 25 °C. The results of X-ray diffraction, Scanning Electron Microscopy with energy-dispersive X-ray analyses, and ATR-FTIR demonstrate that the adsorption mechanism involves the rehydration of mixed metal oxides and concomitant intercalation of fluoride and phosphate ions into the interlayer to reconstruct the initial LDHs structure.

  19. Kinetic, equilibrium and thermodynamic studies for the removal of lead (II) and copper (II) ions from aqueous solutions by nanocrystalline TiO

    NASA Astrophysics Data System (ADS)

    Rashidi, Fatemeh; Sarabi, Reza Sadeghi; Ghasemi, Zinab; Seif, Ahmad

    2010-12-01

    Titanium dioxide nanocrystallites were synthesized as adsorbents through the hydrolysis of titanium tetrachloride as the precursor in hydrochloric acid. The product was analyzed by XRD, BET and SEM-EDX; analysis indicated that the particles were a mixture of 86.8% rutile and 13.2% anatase TiO 2 with spherical shapes. The adsorption of Pb (II) and Cu (II) metal ions from aqueous solution onto nano- TiO 2 were investigated with variations in pH, contact time, initial metal ion concentration and temperature. The kinetics, adsorption isotherm and adsorption thermodynamics of the heavy metals were studied. The kinetics data were analyzed by the pseudo-first order, pseudo-second order and intraparticle diffusion kinetic models; the best correlation coefficients were obtained for the pseudo-second order kinetic model. The adsorption results obtained from equilibrium experiments were analyzed by Freundlich, Langmuir, Temkin and Dubinin-Radushkevich isotherms with the Freundlich isotherm giving the best fitting isotherm to the equilibrium data. The thermodynamic parameters ( ΔG°, ΔH° and ΔS°) were calculated and it was found that the adsorption process is spontaneous and endothermic and is favored at higher temperature.

  20. Direct Detection of a Chemical Equilibrium between a Localized Singlet Diradical and Its σ-Bonded Species by Time-Resolved UV/Vis and IR Spectroscopy.

    PubMed

    Yoshidomi, Shohei; Mishima, Megumi; Seyama, Shin; Abe, Manabu; Fujiwara, Yoshihisa; Ishibashi, Taka-Aki

    2017-03-06

    Localized singlet diradicals are key intermediates in bond homolyses. The singlet diradicals are energetically much less stable than the σ-bonded species. In general, only one-way reactions from diradicals to σ-bonded species are observed. In this study, a thermal equilibrium between a singlet 1,2-diazacyclopentane-3,5-diyl diradical and the corresponding σ-bonded species was directly observed. The singlet diradical was more stable than the σ-bonded species. The solvent effect clarified key features, such as the zwitterionic character of the singlet diradical. The effect of the nitrogen atoms is discussed in detail.

  1. Kinetic and equilibrium measurements of coal drying

    SciTech Connect

    Heller, A.; Elliott, G.R.B.

    1980-01-01

    The retention, attachment, and release of water (sorption, adsorption, and desorption) in Fruitland subbituminous coal are shown to be very complex phenomena. The vapor pressure and thermodynamic activity of water in the coal at about 315 K vary sharply with composition. Removal of 60% of the water initially present reduces the vapor pressure by about 60%. The total moisture content of saturated coal also varies with temperature. A 10 K rise in temperature reduces the sorbed water by about 8%. There is strong hysteresis in the sorption behavior; water which is desorbed by reducing the vapor pressure over a coal sample is not fully replaced by adsorption when the vapor pressure is returned to its original level. These measurements of desorption and adsorption reflect stable and metastable equilibria. Kinetic measurements are reported for approach to a new equilibrium if the vapor pressure over the coal is reduced. The kinetic measurements reflect the shape of the pores while equilibrium vapor pressures reflect how tightly the water is bound in the pores. Both types of measurement show changes in behavior at the same compositions. Implications of these results for UCG are discussed.

  2. 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