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Sample records for adsorption equilibrium constants

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. Philicities, Fugalities, and Equilibrium Constants.

    PubMed

    Mayr, Herbert; Ofial, Armin R

    2016-05-17

    The mechanistic model of Organic Chemistry is based on relationships between rate and equilibrium constants. Thus, strong bases are generally considered to be good nucleophiles and poor nucleofuges. Exceptions to this rule have long been known, and the ability of iodide ions to catalyze nucleophilic substitutions, because they are good nucleophiles as well as good nucleofuges, is just a prominent example for exceptions from the general rule. In a reaction series, the Leffler-Hammond parameter α = δΔG(⧧)/δΔG° describes the fraction of the change in the Gibbs energy of reaction, which is reflected in the change of the Gibbs energy of activation. It has long been considered as a measure for the position of the transition state; thus, an α value close to 0 was associated with an early transition state, while an α value close to 1 was considered to be indicative of a late transition state. Bordwell's observation in 1969 that substituent variation in phenylnitromethanes has a larger effect on the rates of deprotonation than on the corresponding equilibrium constants (nitroalkane anomaly) triggered the breakdown of this interpretation. In the past, most systematic investigations of the relationships between rates and equilibria of organic reactions have dealt with proton transfer reactions, because only for few other reaction series complementary kinetic and thermodynamic data have been available. In this Account we report on a more general investigation of the relationships between Lewis basicities, nucleophilicities, and nucleofugalities as well as between Lewis acidities, electrophilicities, and electrofugalities. Definitions of these terms are summarized, and it is suggested to replace the hybrid terms "kinetic basicity" and "kinetic acidity" by "protophilicity" and "protofugality", respectively; in this way, the terms "acidity" and "basicity" are exclusively assigned to thermodynamic properties, while "philicity" and "fugality" refer to kinetics

  7. Equilibrium Constants You Can Smell.

    ERIC Educational Resources Information Center

    Anderson, Michael; Buckley, Amy

    1996-01-01

    Presents a simple experiment involving the sense of smell that students can accomplish during a lecture. Illustrates the important concepts of equilibrium along with the acid/base properties of various ions. (JRH)

  8. 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.

  9. [Dichotomizing method applied to calculating equilibrium constant of dimerization system].

    PubMed

    Cheng, Guo-zhong; Ye, Zhi-xiang

    2002-06-01

    The arbitrary trivariate algebraic equations are formed based on the combination principle. The univariata algebraic equation of equilibrium constant kappa for dimerization system is obtained through a series of algebraic transformation, and it depends on the properties of monotonic functions whether the equation is solvable or not. If the equation is solvable, equilibrium constant of dimerization system is obtained by dichotomy and its final equilibrium constant of dimerization system is determined according to the principle of error of fitting. The equilibrium constants of trisulfophthalocyanine and biosulfophthalocyanine obtained with this method are 47,973.4 and 30,271.8 respectively. The results are much better than those reported previously.

  10. Water dimer equilibrium constant of saturated vapor

    NASA Astrophysics Data System (ADS)

    Malomuzh, N. P.; Mahlaichuk, V. N.; Khrapatyi, S. V.

    2014-08-01

    The value and temperature dependence of the dimerization constant for saturated water vapor are determined. A general expression that links the second virial coefficient and the dimerization constant is obtained. It is shown that the attraction between water monomers and dimers is fundamental, especially at T > 350 K. The range of application for the obtained results is determined.

  11. Calculation of individual isotope equilibrium constants for geochemical reactions

    USGS Publications Warehouse

    Thorstenson, D.C.; Parkhurst, D.L.

    2004-01-01

    Theory is derived from the work of Urey (Urey H. C. [1947] The thermodynamic properties of isotopic substances. J. Chem. Soc. 562-581) to calculate equilibrium constants commonly used in geochemical equilibrium and reaction-transport models for reactions of individual isotopic species. Urey showed that equilibrium constants of isotope exchange reactions for molecules that contain two or more atoms of the same element in equivalent positions are related to isotope fractionation factors by ?? = (Kex)1/n, where n is the number of atoms exchanged. This relation is extended to include species containing multiple isotopes, for example 13C16O18O and 1H2H18O. The equilibrium constants of the isotope exchange reactions can be expressed as ratios of individual isotope equilibrium constants for geochemical reactions. Knowledge of the equilibrium constant for the dominant isotopic species can then be used to calculate the individual isotope equilibrium constants. Individual isotope equilibrium constants are calculated for the reaction CO2g = CO2aq for all species that can be formed from 12C, 13C, 16O, and 18O; for the reaction between 12C18 O2aq and 1H218Ol; and among the various 1H, 2H, 16O, and 18O species of H2O. This is a subset of a larger number of equilibrium constants calculated elsewhere (Thorstenson D. C. and Parkhurst D. L. [2002] Calculation of individual isotope equilibrium constants for implementation in geochemical models. Water-Resources Investigation Report 02-4172. U.S. Geological Survey). Activity coefficients, activity-concentration conventions for the isotopic variants of H2O in the solvent 1H216Ol, and salt effects on isotope fractionation have been included in the derivations. The effects of nonideality are small because of the chemical similarity of different isotopic species of the same molecule or ion. The temperature dependence of the individual isotope equilibrium constants can be calculated from the temperature dependence of the fractionation

  12. Direct measurement of equilibrium constants for high-affinity hemoglobins.

    PubMed

    Kundu, Suman; Premer, Scott A; Hoy, Julie A; Trent, James T; Hargrove, Mark S

    2003-06-01

    The biological functions of heme proteins are linked to their rate and affinity constants for ligand binding. Kinetic experiments are commonly used to measure equilibrium constants for traditional hemoglobins comprised of pentacoordinate ligand binding sites and simple bimolecular reaction schemes. However, kinetic methods do not always yield reliable equilibrium constants with more complex hemoglobins for which reaction mechanisms are not clearly understood. Furthermore, even where reaction mechanisms are clearly understood, it is very difficult to directly measure equilibrium constants for oxygen and carbon monoxide binding to high-affinity (K(D) < 1 micro M) hemoglobins. This work presents a method for direct measurement of equilibrium constants for high-affinity hemoglobins that utilizes a competition for ligands between the "target" protein and an array of "scavenger" hemoglobins with known affinities. This method is described for oxygen and carbon monoxide binding to two hexacoordinate hemoglobins: rice nonsymbiotic hemoglobin and Synechocystis hemoglobin. Our results demonstrate that although these proteins have different mechanisms for ligand binding, their affinities for oxygen and carbon monoxide are similar. Their large affinity constants for oxygen, 285 and approximately 100 micro M(-1) respectively, indicate that they are not capable of facilitating oxygen transport.

  13. 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.

  14. Constant Entropy Properties for an Approximate Model of Equilibrium Air

    NASA Technical Reports Server (NTRS)

    Hansen, C. Frederick; Hodge, Marion E.

    1961-01-01

    Approximate analytic solutions for properties of equilibrium air up to 15,000 K have been programmed for machine computation. Temperature, compressibility, enthalpy, specific heats, and speed of sound are tabulated as constant entropy functions of temperature. The reciprocal of acoustic impedance and its integral with respect to pressure are also given for the purpose of evaluating the Riemann constants for one-dimensional, isentropic flow.

  15. Microcomputer Calculation of Equilibrium Constants from Molecular Parameters of Gases.

    ERIC Educational Resources Information Center

    Venugopalan, Mundiyath

    1989-01-01

    Lists a BASIC program which computes the equilibrium constant as a function of temperature. Suggests use by undergraduates taking a one-year calculus-based physical chemistry course. Notes the program provides for up to four species, typically two reactants and two products. (MVL)

  16. 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.

  17. A Straightforward Method to Determine Equilibrium Constants from Spectrophotometric Data

    NASA Astrophysics Data System (ADS)

    Keszei, E.; Takács, M. G.; Vizkeleti, B.

    2000-07-01

    Spectrophotometry provides reliable information on the equilibrium concentration in chemically reacting mixtures. However, the widely used traditional linearized models to determine the equilibrium constant from spectrophotometric data do not provide optimal information and unnecessarily complicate data evaluation for students. In this paper we show an easy and straightforward inference method, which makes use only of Beer's Law and an elementary mathematical treatment of the problem. Though the resulting parameter estimation is nonlinear with respect to the equilibrium constant, the commercial availability of many nonlinear parameter estimation software packages eliminates the need for the student to bother with either mathematical or numerical details. Adding a suitable spectral shape function to the model describing equilibrium further facilitates the use of the proposed method and makes it an easy task to determine the components' spectra from equilibrium measurements. Three practical examples are treated in detail in the online version. They illustrate how the method works at different complexity levels and are easy to install in undergraduate physical chemistry labs.

  18. 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).

  19. 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.

  20. 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.

  1. Equilibrium morphologies and effective spring constants of capillary bridges.

    PubMed

    Kusumaatmaja, Halim; Lipowsky, Reinhard

    2010-12-21

    We theoretically study the behavior of a liquid bridge formed between a pair of rigid and parallel plates. The plates are smooth, they may either be homogeneous or decorated by circular patches of more hydrophilic domains, and they are generally not identical. We calculate the mechanical equilibrium distance of the liquid bridge as a function of liquid volume, contact angle, and radius of the chemical domain. We show that a liquid bridge can be an equilibrium configuration as long as the sum of the contact angles at the two walls is larger than 180°. When comparisons are possible, our results agree well with recent analytical and molecular dynamics simulation results. We also derive the effective spring constant of the liquid bridge as it is perturbed from its equilibrium distance. The spring constant diverges when the sum of the contact angles is 180° and is finite otherwise. The value of the spring constant decreases with increasing contact angle and volume, and the rate at which it decreases depends strongly on the properties of the two plates.

  2. Computational calculation of equilibrium constants: addition to carbonyl compounds.

    PubMed

    Gómez-Bombarelli, Rafael; González-Pérez, Marina; Pérez-Prior, María Teresa; Calle, Emilio; Casado, Julio

    2009-10-22

    Hydration reactions are relevant for understanding many organic mechanisms. Since the experimental determination of hydration and hemiacetalization equilibrium constants is fairly complex, computational calculations now offer a useful alternative to experimental measurements. In this work, carbonyl hydration and hemiacetalization constants were calculated from the free energy differences between compounds in solution, using absolute and relative approaches. The following conclusions can be drawn: (i) The use of a relative approach in the calculation of hydration and hemiacetalization constants allows compensation of systematic errors in the solvation energies. (ii) On average, the methodology proposed here can predict hydration constants within +/- 0.5 log K(hyd) units for aldehydes. (iii) Hydration constants can be calculated for ketones and carboxylic acid derivatives within less than +/- 1.0 log K(hyd), on average, at the CBS-Q level of theory. (iv) The proposed methodology can predict hemiacetal formation constants accurately at the MP2 6-31++G(d,p) level using a common reference. If group references are used, the results obtained using the much cheaper DFT-B3LYP 6-31++G(d,p) level are almost as accurate. (v) In general, the best results are obtained if a common reference for all compounds is used. The use of group references improves the results at the lower levels of theory, but at higher levels, this becomes unnecessary.

  3. Extracting equilibrium constants from kinetically limited reacting systems.

    PubMed

    Correia, John J; Stafford, Walter F

    2009-01-01

    It has been known for some time that slow kinetics will distort the shape of a reversible reaction boundary. Here we present a tutorial on direct boundary fitting of sedimentation velocity data for a monomer-dimer system that exhibits kinetic effects. Previous analysis of a monomer-dimer system suggested that rapid reaction behavior will persist until the relaxation time of the system exceeds 100 s (reviewed in Kegeles and Cann, 1978). Utilizing a kinetic integrator feature in Sedanal (Stafford and Sherwood, 2004), we can now fit for the k(off) values and measure the uncertainty at the 95% confidence interval. For the monomer-dimer system the range of well determined k(off) values is limited to 0.005 to 10(-5) s(-1) corresponding to relaxation times (at a loading concentration of the Kd) of approximately 70 to approximately 33,000 s. For shorter relaxation times the system is fast and only the equilibrium constant K but not k(off) can be uniquely determined. For longer relaxation times the system is irreversibly slow, and assuming the system was at initial equilibrium before the start of the run, only the equilibrium constant K but not k(off) can be uniquely determined.

  4. 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

  5. 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.

  6. 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.

  7. 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.

  8. Conjugate Acid-Base Pairs, Free Energy, and the Equilibrium Constant

    ERIC Educational Resources Information Center

    Beach, Darrell H.

    1969-01-01

    Describes a method of calculating the equilibrium constant from free energy data. Values of the equilibrium constants of six Bronsted-Lowry reactions calculated by the author's method and by a conventional textbook method are compared. (LC)

  9. 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.

  10. 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.

  11. Equilibrium constants and protonation site for N-methylbenzenesulfonamides

    PubMed Central

    Rosa da Costa, Ana M; García-Río, Luis; Pessêgo, Márcia

    2011-01-01

    Summary The protonation equilibria of four substituted N-methylbenzenesulfonamides, X-MBS: X = 4-MeO (3a), 4-Me (3b), 4-Cl (3c) and 4-NO2 (3d), in aqueous sulfuric acid were studied at 25 °C by UV–vis spectroscopy. As expected, the values for the acidity constants are highly dependent on the electron-donor character of the substituent (the pK BH+ values are −3.5 ± 0.2, −4.2 ± 0.2, −5.2 ± 0.3 and −6.0 ± 0.3 for 3a, 3b, 3c and 3d, respectively). The solvation parameter m* is always higher than 0.5 and points to a decrease in the importance of solvation on the cation stabilization as the electron-donor character of the substituent increases. Hammett plots of the equilibrium constants showed a better correlation with the σ+ substituent parameter than with σ, which indicates that the initial protonation site is the oxygen atom of the sulfonyl group. PMID:22238552

  12. Equilibrium constants and protonation site for N-methylbenzenesulfonamides.

    PubMed

    Moreira, José A; Rosa da Costa, Ana M; García-Río, Luis; Pessêgo, Márcia

    2011-01-01

    The protonation equilibria of four substituted N-methylbenzenesulfonamides, X-MBS: X = 4-MeO (3a), 4-Me (3b), 4-Cl (3c) and 4-NO(2) (3d), in aqueous sulfuric acid were studied at 25 °C by UV-vis spectroscopy. As expected, the values for the acidity constants are highly dependent on the electron-donor character of the substituent (the pK(BH+) values are -3.5 ± 0.2, -4.2 ± 0.2, -5.2 ± 0.3 and -6.0 ± 0.3 for 3a, 3b, 3c and 3d, respectively). The solvation parameter m* is always higher than 0.5 and points to a decrease in the importance of solvation on the cation stabilization as the electron-donor character of the substituent increases. Hammett plots of the equilibrium constants showed a better correlation with the σ(+) substituent parameter than with σ, which indicates that the initial protonation site is the oxygen atom of the sulfonyl group.

  13. Interpretation of the temperature dependence of equilibrium and rate constants.

    PubMed

    Winzor, Donald J; Jackson, Craig M

    2006-01-01

    The objective of this review is to draw attention to potential pitfalls in attempts to glean mechanistic information from the magnitudes of standard enthalpies and entropies derived from the temperature dependence of equilibrium and rate constants for protein interactions. Problems arise because the minimalist model that suffices to describe the energy differences between initial and final states usually comprises a set of linked equilibria, each of which is characterized by its own energetics. For example, because the overall standard enthalpy is a composite of those individual values, a positive magnitude for DeltaH(o) can still arise despite all reactions within the subset being characterized by negative enthalpy changes: designation of the reaction as being entropy driven is thus equivocal. An experimenter must always bear in mind the fact that any mechanistic interpretation of the magnitudes of thermodynamic parameters refers to the reaction model rather than the experimental system. For the same reason there is little point in subjecting the temperature dependence of rate constants for protein interactions to transition-state analysis. If comparisons with reported values of standard enthalpy and entropy of activation are needed, they are readily calculated from the empirical Arrhenius parameters.

  14. Using nonequilibrium capillary electrophoresis of equilibrium mixtures (NECEEM) for simultaneous determination of concentration and equilibrium constant.

    PubMed

    Kanoatov, Mirzo; Galievsky, Victor A; Krylova, Svetlana M; Cherney, Leonid T; Jankowski, Hanna K; Krylov, Sergey N

    2015-03-03

    Nonequilibrium capillary electrophoresis of equilibrium mixtures (NECEEM) is a versatile tool for studying affinity binding. Here we describe a NECEEM-based approach for simultaneous determination of both the equilibrium constant, K(d), and the unknown concentration of a binder that we call a target, T. In essence, NECEEM is used to measure the unbound equilibrium fraction, R, for the binder with a known concentration that we call a ligand, L. The first set of experiments is performed at varying concentrations of T, prepared by serial dilution of the stock solution, but at a constant concentration of L, which is as low as its reliable quantitation allows. The value of R is plotted as a function of the dilution coefficient, and dilution corresponding to R = 0.5 is determined. This dilution of T is used in the second set of experiments in which the concentration of T is fixed but the concentration of L is varied. The experimental dependence of R on the concentration of L is fitted with a function describing their theoretical dependence. Both K(d) and the concentration of T are used as fitting parameters, and their sought values are determined as the ones that generate the best fit. We have fully validated this approach in silico by using computer-simulated NECEEM electropherograms and then applied it to experimental determination of the unknown concentration of MutS protein and K(d) of its interactions with a DNA aptamer. The general approach described here is applicable not only to NECEEM but also to any other method that can determine a fraction of unbound molecules at equilibrium.

  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. [Characteristics of DNA adsorption and desorption in variable and constant charge soil colloids].

    PubMed

    Wang, Dai-Zhang; Wang, Shen-Yang; Jiang, Xin; Heng, Li-Sha; Tan, Jin-Fang; Liu, Shi-Liang; Cao, Yong-Xian

    2009-09-15

    The characteristics of adsorption and desorption of DNA by Red soil colloid, Latosol colloid, Chao colloid and Cinnamon colloid at different pH values were studied using a batch method. It showed that there was an increase of solution pH after adsorption of DNA by the four soil colloids in both NaCl and KCl electrolyte systems. The increasing ranges of pH values were in order of Red soil colloid > Latosol colloid > Chao colloid > Cinnamon colloid, and NaCl electrolyte system > KCl electrolyte system. The amounts of DNA adsorption on soil colloids decreased with the increase of pH value. The maximum amounts of DNA adsorption in different colloids were about 13.1-14.8 microg x mg(-1) when pH values were 2-4. The decreasing ranges of the amounts of DNA adsorption were about 5.5 microg x mg(-1) in NaCl electrolyte system and 2.1 Mg x mg(-1) in KCl electrolyte system in Red soil colloid and Latosol colloid after the rising of equilibrium solution pH from 4.2 to 8.6, whereas the remarked decreasing ranges of the adsorption amounts of DNA were about 8.3-12.2 microg x mg(-1) on Chao colloid and Cinnamon colloid in two electrolyte systems. The decreasing ranges of DNA adsorption were in order of the constant charge (Chao soil and Cinnamon) colloids > the variable charge (Red soil and Latosol) colloids. The differences of desorption on the variable and the constant charge colloids are very significant while the DNA adsorbed was desorbed with NaOAc solution and NaH2 PO4 solution. The desorption percent desorption of DNA as NaH2PO4 desorbent was 23.5%-40.2% larger on the variable charge colloids than 8.8%-21.6% on the constant charge of colloids at the three different solution pH values of 3, 5 and 7, while that as NaOAc desorbent was 72.3%-85.9% larger on the constant charge colloids than 10%-24.5% on the variable charge colloids. These results implied that the ligand exchange played a more important role in DNA adsorption on the variable charge colloids, and electrostatic

  17. Effects of Adsorption Constant Uncertainty on Contaminant Plume Migration: One and Two Dimensional Numerical Studies

    NASA Astrophysics Data System (ADS)

    Eliassi, M.

    2002-12-01

    In this study, we use one- and two-dimensional (1D and 2D) reactive-transport models to numerically examine variations in predictions due to uncertainty in the adsorption constants. The study specifically focuses on the hydrogeology and mineralogy of the Naturita uranium mill tailings site in Colorado. This work demonstrates the importance of selecting the appropriate adsorption constants when using reactive-transport models to evaluate risk and pollution attenuation at contaminated sites. In our model, uranium is removed from mill tailings leachate through adsorption onto smectite, an abundant clay mineral at the Naturita site. Uranium adsorbs to specific surface sites on both the basal planes and edges of the smectite. Because uranium adsorbs predominantly to the aluminum edge surface sites [>(e)AlOH], we chose to examine uncertainty only in the equilibrium constants associated with these sites. Using the Latin Hypercube Sampling method, one-hundred pairs of adsorption constant (log K) values are selected for the surface species >(e)AlO- and >(e)AlOUO2+, from normal distributions of each log K. Following a grid convergence study, 1D simulation results can be identified by two distinct groups of uranium breakthrough curves. In the first group, the breakthrough curves exhibit a classical sigmoidal shape whereas in the second group the breakthrough curves display higher uranium concentrations in solution over greater distances and times. These two groups are clearly separated by two different ranges of log K >(e)AlO- values or two different ranges for the smectite point of zero charge. Preliminary 2D simulations, in both homogeneous and randomly heterogeneous aquifers demonstrate that plume geometry and migration in longitudinal and transverse directions are also influenced by the choice of adsorption constants.

  18. 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.

  19. 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.

  20. 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.

  1. Calculation of individual isotope equilibrium constants for implementation in geochemical models

    USGS Publications Warehouse

    Thorstenson, Donald C.; Parkhurst, David L.

    2002-01-01

    Theory is derived from the work of Urey to calculate equilibrium constants commonly used in geochemical equilibrium and reaction-transport models for reactions of individual isotopic species. Urey showed that equilibrium constants of isotope exchange reactions for molecules that contain two or more atoms of the same element in equivalent positions are related to isotope fractionation factors by , where is n the number of atoms exchanged. This relation is extended to include species containing multiple isotopes, for example and , and to include the effects of nonideality. The equilibrium constants of the isotope exchange reactions provide a basis for calculating the individual isotope equilibrium constants for the geochemical modeling reactions. The temperature dependence of the individual isotope equilibrium constants can be calculated from the temperature dependence of the fractionation factors. Equilibrium constants are calculated for all species that can be formed from and selected species containing , in the molecules and the ion pairs with where the subscripts g, aq, l, and s refer to gas, aqueous, liquid, and solid, respectively. These equilibrium constants are used in the geochemical model PHREEQC to produce an equilibrium and reaction-transport model that includes these isotopic species. Methods are presented for calculation of the individual isotope equilibrium constants for the asymmetric bicarbonate ion. An example calculates the equilibrium of multiple isotopes among multiple species and phases.

  2. Simultaneous determination of equilibrium constants and enthalpy changes by titration calorimetry: Methods, instruments, and uncertainties.

    PubMed

    Hansen, Lee D; Fellingham, Gilbert W; Russell, Donald J

    2011-02-15

    Calorimetric methods have been used to determine equilibrium constants since 1937, but no comprehensive review of the various calorimeters and methods has been done previously. This article reports methods for quantitative comparison of the capabilities of calorimeters for simultaneous determination of equilibrium constants and enthalpy changes, for determining optimal experimental conditions, and for assessing the effects of systematic and random errors on the accuracy and precision of equilibrium constants and enthalpy changes determined by this method.

  3. 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.

  4. 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

  5. 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).

  6. Measurement of both the equilibrium constant and rate constant for electronic energy transfer by control of the limiting kinetic regimes.

    PubMed

    Vagnini, Michael T; Rutledge, W Caleb; Wagenknecht, Paul S

    2010-02-01

    Electronic energy transfer can fall into two limiting cases. When the rate of the energy transfer back reaction is much faster than relaxation of the acceptor excited state, equilibrium between the donor and acceptor excited states is achieved and only the equilibrium constant for the energy transfer can be measured. When the rate of the back reaction is much slower than relaxation of the acceptor, the energy transfer is irreversible and only the forward rate constant can be measured. Herein, we demonstrate that with trans-[Cr(d(4)-cyclam)(CN)(2)](+) as the donor and either trans-[Cr([15]ane-ane-N(4))(CN)(2)](+) or trans-[Cr(cyclam)(CN)(2)](+) as the acceptor, both limits can be obtained by control of the donor concentration. The equilibrium constant and rate constant for the case in which trans-[Cr([15]ane-ane-N(4))(CN)(2)](+) is the acceptor are 0.66 and 1.7 x 10(7) M(-1) s(-1), respectively. The equilibrium constant is in good agreement with the value of 0.60 determined using the excited state energy gap between the donor and acceptor species. For the thermoneutral case in which trans-[Cr(cyclam)(CN)(2)](+) is the acceptor, an experimental equilibrium constant of 0.99 was reported previously, and the rate constant has now been measured as 4.0 x 10(7) M(-1) s(-1).

  7. A Unified Kinetics and Equilibrium Experiment: Rate Law, Activation Energy, and Equilibrium Constant for the Dissociation of Ferroin

    ERIC Educational Resources Information Center

    Sattar, Simeen

    2011-01-01

    Tris(1,10-phenanthroline)iron(II) is the basis of a suite of four experiments spanning 5 weeks. Students determine the rate law, activation energy, and equilibrium constant for the dissociation of the complex ion in acid solution and base dissociation constant for phenanthroline. The focus on one chemical system simplifies a daunting set of…

  8. The Rigorous Evaluation of Spectrophotometric Data to Obtain an Equilibrium Constant.

    ERIC Educational Resources Information Center

    Long, John R.; Drago, Russell S.

    1982-01-01

    Most students do not know how to determine the equilibrium constant and estimate the error in it from spectrophotometric data that contain experimental errors. This "dry-lab" experiment describes a method that may be used to determine the "best-fit" value of the 1:1 equilibrium constant to spectrophotometric data. (Author/JN)

  9. 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.

  10. Calculation of cooperativity and equilibrium constants of ligands binding to G-quadruplex DNA in solution.

    PubMed

    Kudrev, A G

    2013-11-15

    Equilibrium model of a ligand binding with DNA oligomer has been considered as a process of small molecule adsorption onto a lattice of multiple binding sites. An experimental example has been used to verify the assertion that during saturation of the macromolecule by a ligand should expect effect of cooperativity due to changes in DNA conformation or the mutual influence between bound ligands. Such phenomenon cannot be entirely described by the classical stepwise complex formation model. To evaluate a ligand binding affinity and cooperativity of ligand-oligomer complex formation the statistical approach has been proposed. This new computational approach used to re-examine previously studded ligand binding towards DNA quadruplexes targets with multiple binding sites. The intrinsic equilibrium constants K1-3 of the mesotetrakis-(N-methyl-4-pyridyl)-porphyrin (TMPyP4) binding with the [d(T4G4)]4 and with the [AG3(T2AG3)3] quadruplexes and the correction for the mutual influence between bound ligands (cooperativity parameters ω) was determined from the Job plots based upon the nonlinear least-squares fitting procedure. The re-examination of experimental curves reveals that the equilibrium is affected by the positive cooperative (ω>1) binding of the TMPyP4 ligand with tetramolecular [d(T4G4)]4. However for an intramolecular antiparallel-parallel hybrid structure [AG3(T2AG3)3] the weak anti-cooperativity of TMPyP4 accommodation (ω<1) onto two from three nonidentical sites was detected.

  11. 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.

  12. 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.

  13. Galvanic Cells and the Determination of Equilibrium Constants

    ERIC Educational Resources Information Center

    Brosmer, Jonathan L.; Peters, Dennis G.

    2012-01-01

    Readily assembled mini-galvanic cells can be employed to compare their observed voltages with those predicted from the Nernst equation and to determine solubility products for silver halides and overall formation constants for metal-ammonia complexes. Results obtained by students in both an honors-level first-year course in general chemistry and…

  14. 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

  15. Weak Acid Ionization Constants and the Determination of Weak Acid-Weak Base Reaction Equilibrium Constants in the General Chemistry Laboratory

    ERIC Educational Resources Information Center

    Nyasulu, Frazier; McMills, Lauren; Barlag, Rebecca

    2013-01-01

    A laboratory to determine the equilibrium constants of weak acid negative weak base reactions is described. The equilibrium constants of component reactions when multiplied together equal the numerical value of the equilibrium constant of the summative reaction. The component reactions are weak acid ionization reactions, weak base hydrolysis…

  16. Profiles of equilibrium constants for self-association of aromatic molecules.

    PubMed

    Beshnova, Daria A; Lantushenko, Anastasia O; Davies, David B; Evstigneev, Maxim P

    2009-04-28

    Analysis of the noncovalent, noncooperative self-association of identical aromatic molecules assumes that the equilibrium self-association constants are either independent of the number of molecules (the EK-model) or change progressively with increasing aggregation (the AK-model). The dependence of the self-association constant on the number of molecules in the aggregate (i.e., the profile of the equilibrium constant) was empirically derived in the AK-model but, in order to provide some physical understanding of the profile, it is proposed that the sources for attenuation of the equilibrium constant are the loss of translational and rotational degrees of freedom, the ordering of molecules in the aggregates and the electrostatic contribution (for charged units). Expressions are derived for the profiles of the equilibrium constants for both neutral and charged molecules. Although the EK-model has been widely used in the analysis of experimental data, it is shown in this work that the derived equilibrium constant, K(EK), depends on the concentration range used and hence, on the experimental method employed. The relationship has also been demonstrated between the equilibrium constant K(EK) and the real dimerization constant, K(D), which shows that the value of K(EK) is always lower than K(D).

  17. 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.

  18. Investigation of equilibria in solution. Determination of equilibrium constants with the HYPERQUAD suite of programs.

    PubMed

    Gans, P; Sabatini, A; Vacca, A

    1996-10-01

    A new suite of 10 programs concerned with equilibrium constants and solution equilibria is described. The suite includes data preparation programs, pretreatment programs, equilibrium constant refinement and post-run analysis. Data preparation is facilitated by a customized data editor. The pretreatment programs include manual trial and error data fitting, speciation diagrams, end-point determination, absorbance error determination, spectral baseline corrections, factor analysis and determination of molar absorbance spectra. Equilibrium constants can be determined from potentiometric data and/or spectrophotometric data. A new data structure is also described in which information on the model and on experimental measurements are kept in separate files.

  19. 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.

  20. 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.

  1. Determining equilibrium constants for dimerization reactions from molecular dynamics simulations.

    PubMed

    De Jong, Djurre H; Schäfer, Lars V; De Vries, Alex H; Marrink, Siewert J; Berendsen, Herman J C; Grubmüller, Helmut

    2011-07-15

    With today's available computer power, free energy calculations from equilibrium molecular dynamics simulations "via counting" become feasible for an increasing number of reactions. An example is the dimerization reaction of transmembrane alpha-helices. If an extended simulation of the two helices covers sufficiently many dimerization and dissociation events, their binding free energy is readily derived from the fraction of time during which the two helices are observed in dimeric form. Exactly how the correct value for the free energy is to be calculated, however, is unclear, and indeed several different and contradictory approaches have been used. In particular, results obtained via Boltzmann statistics differ from those determined via the law of mass action. Here, we develop a theory that resolves this discrepancy. We show that for simulation systems containing two molecules, the dimerization free energy is given by a formula of the form ΔG ∝ ln(P(1) /P(0) ). Our theory is also applicable to high concentrations that typically have to be used in molecular dynamics simulations to keep the simulation system small, where the textbook dilute approximations fail. It also covers simulations with an arbitrary number of monomers and dimers and provides rigorous error estimates. Comparison with test simulations of a simple Lennard Jones system with various particle numbers as well as with reference free energy values obtained from radial distribution functions show full agreement for both binding free energies and dimerization statistics.

  2. The Equilibrium Constant for Bromothymol Blue: A General Chemistry Laboratory Experiment Using Spectroscopy

    ERIC Educational Resources Information Center

    Klotz, Elsbeth; Doyle, Robert; Gross, Erin; Mattson, Bruce

    2011-01-01

    A simple, inexpensive, and environmentally friendly undergraduate laboratory experiment is described in which students use visible spectroscopy to determine a numerical value for an equilibrium constant, K[subscript c]. The experiment correlates well with the lecture topic of equilibrium even though the subject of the study is an acid-base…

  3. 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

  4. Understanding atom transfer radical polymerization: effect of ligand and initiator structures on the equilibrium constants.

    PubMed

    Tang, Wei; Kwak, Yungwan; Braunecker, Wade; Tsarevsky, Nicolay V; Coote, Michelle L; Matyjaszewski, Krzysztof

    2008-08-13

    Equilibrium constants in Cu-based atom transfer radical polymerization (ATRP) were determined for a wide range of ligands and initiators in acetonitrile at 22 degrees C. The ATRP equilibrium constants obtained vary over 7 orders of magnitude and strongly depend on the ligand and initiator structures. The activities of the Cu(I)/ligand complexes are highest for tetradentate ligands, lower for tridentate ligands, and lowest for bidentate ligands. Complexes with tripodal and bridged ligands (Me6TREN and bridged cyclam) tend to be more active than those with the corresponding linear ligands. The equilibrium constants are largest for tertiary alkyl halides and smallest for primary alkyl halides. The activities of alkyl bromides are several times larger than those of the analogous alkyl chlorides. The equilibrium constants are largest for the nitrile derivatives, followed by those for the benzyl derivatives and the corresponding esters. Other equilibrium constants that are not readily measurable were extrapolated from the values for the reference ligands and initiators. Excellent correlations of the equilibrium constants with the Cu(II/I) redox potentials and the carbon-halogen bond dissociation energies were observed.

  5. Determination of rate constants and equilibrium constants for solution-phase drug-protein interactions by ultrafast affinity extraction.

    PubMed

    Zheng, Xiwei; Li, Zhao; Podariu, Maria I; Hage, David S

    2014-07-01

    A method was created on the basis of ultrafast affinity extraction to determine both the dissociation rate constants and equilibrium constants for drug-protein interactions in solution. Human serum albumin (HSA), an important binding agent for many drugs in blood, was used as both a model soluble protein and as an immobilized binding agent in affinity microcolumns for the analysis of free drug fractions. Several drugs were examined that are known to bind to HSA. Various conditions to optimize in the use of ultrafast affinity extraction for equilibrium and kinetic studies were considered, and several approaches for these measurements were examined. The dissociation rate constants obtained for soluble HSA with each drug gave good agreement with previous rate constants reported for the same drugs or other solutes with comparable affinities for HSA. The equilibrium constants that were determined also showed good agreement with the literature. The results demonstrated that ultrafast affinity extraction could be used as a rapid approach to provide information on both the kinetics and thermodynamics of a drug-protein interaction in solution. This approach could be extended to other systems and should be valuable for high-throughput drug screening or biointeraction studies.

  6. Determination of Rate Constants and Equilibrium Constants for Solution-Phase Drug–Protein Interactions by Ultrafast Affinity Extraction

    PubMed Central

    2015-01-01

    A method was created on the basis of ultrafast affinity extraction to determine both the dissociation rate constants and equilibrium constants for drug–protein interactions in solution. Human serum albumin (HSA), an important binding agent for many drugs in blood, was used as both a model soluble protein and as an immobilized binding agent in affinity microcolumns for the analysis of free drug fractions. Several drugs were examined that are known to bind to HSA. Various conditions to optimize in the use of ultrafast affinity extraction for equilibrium and kinetic studies were considered, and several approaches for these measurements were examined. The dissociation rate constants obtained for soluble HSA with each drug gave good agreement with previous rate constants reported for the same drugs or other solutes with comparable affinities for HSA. The equilibrium constants that were determined also showed good agreement with the literature. The results demonstrated that ultrafast affinity extraction could be used as a rapid approach to provide information on both the kinetics and thermodynamics of a drug–protein interaction in solution. This approach could be extended to other systems and should be valuable for high-throughput drug screening or biointeraction studies. PMID:24911267

  7. 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.

  8. 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.

  9. A Simple Method to Calculate the Temperature Dependence of the Gibbs Energy and Chemical Equilibrium Constants

    ERIC Educational Resources Information Center

    Vargas, Francisco M.

    2014-01-01

    The temperature dependence of the Gibbs energy and important quantities such as Henry's law constants, activity coefficients, and chemical equilibrium constants is usually calculated by using the Gibbs-Helmholtz equation. Although, this is a well-known approach and traditionally covered as part of any physical chemistry course, the required…

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. Classical calculation of the equilibrium constants for true bound dimers using complete potential energy surface.

    PubMed

    Buryak, Ilya; Vigasin, Andrey A

    2015-12-21

    The present paper aims at deriving classical expressions which permit calculation of the equilibrium constant for weakly interacting molecular pairs using a complete multidimensional potential energy surface. The latter is often available nowadays as a result of the more and more sophisticated and accurate ab initio calculations. The water dimer formation is considered as an example. It is shown that even in case of a rather strongly bound dimer the suggested expression permits obtaining quite reliable estimate for the equilibrium constant. The reliability of our obtained water dimer equilibrium constant is briefly discussed by comparison with the available data based on experimental observations, quantum calculations, and the use of RRHO approximation, provided the latter is restricted to formation of true bound states only.

  15. Classical calculation of the equilibrium constants for true bound dimers using complete potential energy surface

    SciTech Connect

    Buryak, Ilya; Vigasin, Andrey A.

    2015-12-21

    The present paper aims at deriving classical expressions which permit calculation of the equilibrium constant for weakly interacting molecular pairs using a complete multidimensional potential energy surface. The latter is often available nowadays as a result of the more and more sophisticated and accurate ab initio calculations. The water dimer formation is considered as an example. It is shown that even in case of a rather strongly bound dimer the suggested expression permits obtaining quite reliable estimate for the equilibrium constant. The reliability of our obtained water dimer equilibrium constant is briefly discussed by comparison with the available data based on experimental observations, quantum calculations, and the use of RRHO approximation, provided the latter is restricted to formation of true bound states only.

  16. Estimation of the initial equilibrium constants in the formation of tetragonal lysozyme nuclei

    NASA Technical Reports Server (NTRS)

    Pusey, Marc L.

    1991-01-01

    Results are presented from a study of the equilibria, kinetic rates, and the aggregation pathway which leads from a lysozyme monomer crystal to a tetragonal crystal, using dialyzed and recrystallized commercial hen eggwhite lysozyme. Relative light scattering intensity measurements were used to estimate the initial equilibrium constants for undersaturated lysozyme solutions in the tetragonal regime. The K1 value was estimated to be (1-3) x 10 exp 4 L/mol. Estimates of subsequent equilibrium constants depend on the crystal aggregation model chosen or determined. Experimental data suggest that tetragonal lysozyme crystal grows by addition of aggregates preformed in the bulk solution, rather than by monomer addition.

  17. Modeling selenium (IV and VI) adsorption envelopes in selected tropical soils using the constant capacitance model

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The adsorption of selenium (Se) on soil is important due to the relevance of Se to environmental and health issues. The adsorption of Se(IV) and Se(VI) was evaluated on soil samples from São Paulo state, Brazil, as a function of varying pH, and the experimental data were fitted to the constant capac...

  18. Determination of Equilibrium Constants of Metal Complexes from Spectrophotometric Measurements. An Undergraduate Laboratory Experiment

    NASA Astrophysics Data System (ADS)

    Ibañez, Gabriela A.; Olivieri, Alejandro C.; Escandar*, Graciela M.

    1999-09-01

    We describe an undergraduate laboratory practice involving the determination of complex equilibrium constants by spectrophotometric techniques. The results are obtained through model fitting using a computer program. As an example of these determinations, salicylic acid was selected and evaluated in the presence of copper(II) ion. The experimental conditions, general procedures, and computational strategem are discussed.

  19. Calculation of equilibrium constants by matrix method for complexes of gold(III).

    PubMed

    Kudrev, A G

    2008-04-15

    A new matrix approach is proposed to calculate the equilibrium constants of ligands substitution in a metal ion inner coordination sphere with fixed binding sites positions. The proposed method allows to reduce the number of independent variables, necessary for the titration curves fitting without deterioration in the description accuracy. The square planar complexes [MY(4-n)X(n)] n=0-4 formation in solution model includes three independent variables K , omega(cis) and omega(trans) (K -equilibrium constant of replacement of first ligand, omega(cis), omega(trans)-parameters of mutual influence) as an alternative to four stepwise equilibrium constants and two microconstants. In the present investigation experimental spectrophotometric data published in the literature for system {Au(3+)-Cl(-)-Br(-)} were analysed. With the help of the proposed method the equilibrium constants of chloride by bromide ion substitution in internal coordination sphere of Au(III) are calculated K =50; omega(cis)=1.3; omega(trans)=0.7.

  20. Does the Addition of Inert Gases at Constant Volume and Temperature Affect Chemical Equilibrium?

    ERIC Educational Resources Information Center

    Paiva, Joao C. M.; Goncalves, Jorge; Fonseca, Susana

    2008-01-01

    In this article we examine three approaches, leading to different conclusions, for answering the question "Does the addition of inert gases at constant volume and temperature modify the state of equilibrium?" In the first approach, the answer is yes as a result of a common students' alternative conception; the second approach, valid only for ideal…

  1. Revealing equilibrium and rate constants of weak and fast noncovalent interactions.

    PubMed

    Mironov, Gleb G; Okhonin, Victor; Gorelsky, Serge I; Berezovski, Maxim V

    2011-03-15

    Rate and equilibrium constants of weak noncovalent molecular interactions are extremely difficult to measure. Here, we introduced a homogeneous approach called equilibrium capillary electrophoresis of equilibrium mixtures (ECEEM) to determine k(on), k(off), and K(d) of weak (K(d) > 1 μM) and fast kinetics (relaxation time, τ < 0.1 s) in quasi-equilibrium for multiple unlabeled ligands simultaneously in one microreactor. Conceptually, an equilibrium mixture (EM) of a ligand (L), target (T), and a complex (C) is prepared. The mixture is introduced into the beginning of a capillary reactor with aspect ratio >1000 filled with T. Afterward, differential mobility of L, T, and C along the reactor is induced by an electric field. The combination of differential mobility of reactants and their interactions leads to a change of the EM peak shape. This change is a function of rate constants, so the rate and equilibrium constants can be directly determined from the analysis of the EM peak shape (width and symmetry) and propagation pattern along the reactor. We proved experimentally the use of ECEEM for multiplex determination of kinetic parameters describing weak (3 mM > K(d) > 80 μM) and fast (0.25 s ≥ τ ≥ 0.9 ms) noncovalent interactions between four small molecule drugs (ibuprofen, S-flurbiprofen, salicylic acid and phenylbutazone) and α- and β-cyclodextrins. The affinity of the drugs was significantly higher for β-cyclodextrin than α-cyclodextrin and mostly determined by the rate constant of complex formation.

  2. 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.

  3. 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.

  4. Equilibrium theory analysis of liquid chromatography with non-constant velocity.

    PubMed

    Ortner, Franziska; Joss, Lisa; Mazzotti, Marco

    2014-12-19

    In liquid chromatography, adsorption and desorption lead to velocity variations within the column if the adsorbing compounds make up a high volumetric ratio of the mobile phase and if there is a substantial difference in the adsorption capacities. An equilibrium theory model for binary systems accounting for these velocity changes is derived and solved analytically for competitive Langmuir isotherms. Characteristic properties of concentration and velocity profiles predicted by the derived model are illustrated by two exemplary systems. Applicability of the model equations for the estimation of isotherm parameters from experimental data is investigated, and accurate results are obtained for systems with one adsorbing and one inert compound, as well as for systems with two adsorbing compounds.

  5. Model-independent link between the macroscopic and microscopic descriptions of multidentate macromolecular binding: relationship between stepwise, intrinsic, and microscopic equilibrium constants.

    PubMed

    Lluís Garcés, Josep; Rey-Castro, Carlos; David, Calin; Madurga, Sergio; Mas, Francesc; Pastor, Isabel; Puy, Jaume

    2009-11-19

    The binding of ions or other small molecules to macromolecules and surfaces can be macroscopically characterized by means of the stepwise (or stoichiometric) equilibrium constants, which can be obtained experimentally from coverage versus concentration data. The present work presents a novel, simple, and direct interpretation of the stepwise constants in terms of the microscopic, site-specific, stability constants. This formalism can be applied to the most general case, including the heterogeneity of the sites, interactions among them, multicomponent adsorption, and so forth, and, in particular, to chelate complexation. We show that the stepwise equilibrium constants can be expressed as a product of two factors, (i) the average number of free potential sites (per bound ion) of the microscopic species to be complexed (stoichiometric factor) and (ii) the average of the microscopic stability constants of their free potential sites. The latter factor generalizes the concept of the intrinsic equilibrium constant to systems with chelate complexation and reduces to the standard definition for monodentate binding. However, in the case of heterogeneous multidentate complexation, the stoichiometric factor cannot be known a priori, so that the finding of the intrinsic constants is not trivial. One option is to approximate the stoichiometric factor by the value that would correspond to identical active centers. We investigate the accuracy of this assumption by comparing the resulting approximate intrinsic constants to those obtained by Monte Carlo simulation of several binding models. For the cases investigated, it is found that the assumption is quite accurate when no correlated structures (typical of short-range interactions) are formed along the chain. For adsorption of particles attached to a large number of active centers, the formalism presented here leads to the Widom particle insertion method.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. On the Henry constant and isosteric heat at zero loading in gas phase adsorption.

    PubMed

    Do, D D; Nicholson, D; Do, H D

    2008-08-01

    The Henry constant and the isosteric heat of adsorption at zero loading are commonly used as indicators of the strength of the affinity of an adsorbate for a solid adsorbent. It is assumed that (i) they are observable in practice, (ii) the Van Hoff's plot of the logarithm of the Henry constant versus the inverse of temperature is always linear and the slope is equal to the heat of adsorption, and (iii) the isosteric heat of adsorption at zero loading is either constant or weakly dependent on temperature. We show in this paper that none of these three points is necessarily correct, first because these variables might not be observable since they are outside the range of measurability; second that the linearity of the Van Hoff plot breaks down at very high temperature, and third that the isosteric heat versus loading is a strong function of temperature. We demonstrate these points using Monte Carlo integration and Monte Carlo simulation of adsorption of various gases on a graphite surface. Another issue concerning the Henry constant is related to the way the adsorption excess is defined. The most commonly used equation is the one that assumes that the void volume is the volume extended all the way to a boundary passing through the centres of the outermost solid atoms. With this definition the Henry constant can become negative at high temperatures. Although adsorption at these temperatures may not be practical because of the very low value of the Henry constant, it is more useful to define the Henry constant in such a way that it is always positive at all temperatures. Here we propose the use of the accessible volume; the volume probed by the adsorbate when it is in nonpositive regions of the potential, to calculate the Henry constant.

  11. Quantum-statistical equilibrium and the ``law'' of constant Fermi potential

    NASA Astrophysics Data System (ADS)

    Le Coz, Yannick L.

    2003-02-01

    We apply the general quantum-statistical density-matrix formalism to an independent-electron gas within a space-dependent external electric potential, under equilibrium conditions. This problem is analogous to an ideal semiconductor homojunction diode. We solve the resulting equilibrium density-matrix equation using a perturbation theory. Next, we derive a first-order quantum correction to the classical Maxwell-Boltzmann density-potential formula. The correction appears as an added curvature term in external potential. It represents expected quantum-mechanical scattering against a spatially varying potential. Our results indicate that the commonly encountered thermodynamic or statistical-mechanical "law" of constant, equilibrium Fermi potential—with Fermi potential a parameter in the Maxwell-Boltzmann density-potential formula—is not fundamentally exact. In a general space-dependent potential, this "law," we prove, is simply a classical approximation.

  12. Equilibrium constant for carbamate formation from monoethanolamine and its relationship with temperature

    SciTech Connect

    Aroua, M.K.; Benamor, A.; Haji-Sulaiman, M.Z.

    1999-09-01

    Removal of acid gases such as CO{sub 2} and H{sub 2}S using aqueous solutions of alkanolamines is an industrially important process. The equilibrium constant for the formation of carbamate from monoethanolamine was evaluated at various temperatures of 298, 308, 318, and 328 K and ionic strengths up to 1.7 M. From the plot of log{sub 10} K versus I{sup 0.5}, the variation of the thermodynamical constant with temperature follows the relationship log{sub 10} K{sub 1} = {minus}0.934 + (0.671 {times} 10{sup 3})K/T.

  13. Estimating equilibrium constants for aggregation from the product distribution of a dynamic combinatorial library.

    PubMed

    Hunt, Rosemary A R; Ludlow, R Frederick; Otto, Sijbren

    2009-11-19

    Multicomponent chemical systems that exhibit a network of covalent and intermolecular interactions may produce interesting and often unexpected chemical or physical behavior. The formation of aggregates is a well-recognized example and presents a particular analytical challenge. We now report the development of a numerical fitting method capable of estimating equilibrium constants for the formation of aggregates from the product distribution of a dynamic combinatorial library containing self-recognizing library members.

  14. Determination of equilibrium association constants of ligand-DNA complexes by electrospray mass spectrometry.

    PubMed

    Gabelica, Valérie

    2010-01-01

    Electrospray mass spectrometry can be used to detect ligand-DNA noncovalent complexes formed in solution. This chapter describes how to determine equilibrium association constants of the complexes. Particular attention is devoted to describing how to tune an electrospray mass spectrometer using a 12-mer oligodeoxynucleotides duplex in order to perform these experiments. This protocol can then be applied to any nucleic acid structure that can be ionized with electrospray mass spectrometry.

  15. Magnesium dependence of the measured equilibrium constants of aminoacyl-tRNA synthetases.

    PubMed

    Airas, R Kalervo

    2007-12-01

    The apparent equilibrium constants (K') for six reactions catalyzed by aminoacyl-tRNA synthetases from Escherichia coli were measured, the equations for the magnesium dependence of the equilibrium constants were derived, and best-fit analyses between the measured and calculated values were used. The K' values at 1 mM Mg(2+) ranged from 0.49 to 1.13. The apparent equilibrium constants increased with increasing Mg(2+) concentrations. The values were 2-3 times higher at 20 mM Mg(2+) than at 1 mM Mg(2+), and the dependence was similar in the class I and class II synthetases. The main reason for the Mg(2+) dependence is the existence of PP(i) as two magnesium complexes, but only one of them is the real product. AMP exists either as free AMP or as MgAMP, and therefore also has some effect on the measured equilibrium constant. However, these dependences alone cannot explain the measured results. The measured dependence of the K' on the Mg(2+) concentration is weaker than that caused by PP(i) and AMP. Different bindings of the Mg(2+) ions to the substrate tRNA and product aminoacyl-tRNA can explain this observation. The best-fit analysis suggests that tRNA reacts as a magnesium complex in the forward aminoacylation direction but this given Mg(2+) ion is not bound to aminoacyl-tRNA at the start of the reverse reaction. Thus Mg(2+) ions seem to have an active catalytic role, not only in the activation of the amino acid, but in the posttransfer steps of the aminoacyl-tRNA synthetase reaction, too.

  16. 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.

  17. 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 (50adsorption 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.

  18. Henry constant and isosteric heat at zero-loading for gas adsorption in carbon nanotubes.

    PubMed

    Do, D D; Do, H D; Wongkoblap, A; Nicholson, D

    2008-12-28

    The Henry constant and the isosteric heat of adsorption at zero loading in a carbon nanotube bundle are studied with Monte Carlo integration for the adsorption of gases over a range of temperatures. The spacing between nanotubes in a bundle is determined from the minimization of potential energy of interaction between these tubes. We study different tube configurations with bundles of 2, 3, 4 and 7 tubes. Depending on the configuration it is found that the spacing is of between 0.31 to 0.333 nm, and this falls within the range reported in the literature. The Henry constant has been carefully defined so that it will not become negative at high temperatures. This is done with the aid of accessible volume, rather than the usual absolute void volume. We show that linearity of the van't Hoff plot for the Henry constant is not strictly followed. Furthermore the slope of this plot is not equal to the isosteric heat of adsorption at zero loading, which is found to be a strong function of temperature. From the results we find that the Henry constant and the heat of adsorption depend on the tube configuration. In general the adsorption in the cusp interstices is strongest followed by that inside the tube and finally on the outer surface. However for very small tubes adsorption occurs inside the tube first. For molecules with orientation, the behaviour is even more interesting and the shape of the isosteric heat versus temperature depends on the degree of orientation, tube configuration and the domain of adsorption (interstices, inside the tube and on the outer surface).

  19. 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

  20. Calculation of equilibrium binding constants and cooperativity of Cu(II) mixed solvated complexes formation.

    PubMed

    Kudrev, A G

    2012-11-15

    A new extension of matrix approach is proposed to calculate the equilibrium constants of coordinated solvent substitution in a metal ion first salvation shell in the mixed solvent system. The proposed method allows reducing the number of independent variables, necessary to calculate the fractions of species in solution. The equilibrium model of MeCN substitution with DMF and DMSO in the presence of Cu(II) ion for the assessment of structure of intermediate species is presented and verified. The distribution diagrams of Cu(II) species in mixed organic solvents have been analyzed using the modified matrix method. The intrinsic equilibrium constants K of the first solvent molecule replacement in the Cu(II) coordination shell and the correction for the mutual influence between the solvent molecules as ligands in the successive complex formation (cooperativity parameter w) in acetonitrile solution have been calculated from the fitting procedure. It is shown that anticooperative substitution of MeCN by donor ligands in the first coordination shell of the Cu(II) ion is always governed by the change of coordination number during the stepwise process.

  1. 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.

  2. Equilibrium constants in reactions of 2-aminoethanol and ammonia with isophthalaldehyde and terephthalaldehyde.

    PubMed

    Kulla, E; Zuman, P

    2007-12-20

    Equilibria established in reactions between isophthalaldehyde (IPA) and terephthalaldehyde (TPA) on one side and 2-aminoethanol and NH3 on the other side were followed in solutions, where these amines acted both as reagents and as buffers. The equilibrium between TPA and 2-aminoethanol was followed spectrophotometrically; all others, of reactions of TPA with NH3 and of IPA with both NH3 and H2N-CH2CH2-OH, were followed by using polarography. Separate limiting reduction currents of the dialdehyde and its imine enable simultaneous determination of the starting material and the product. The equilibria are shifted more in favor of the imine in reactions of TPA than those of IPA. Equilibrium constants for reactions of both TPA and IPA with 2-aminoethanol are 3 orders of magnitude higher than those observed for the reactions of dialdehydes with NH3, even when the pKa values of these two reagents differ only slightly.

  3. Measuring Equilibrium Binding Constants for the WT1-DNA Interaction Using a Filter Binding Assay.

    PubMed

    Romaniuk, Paul J

    2016-01-01

    Equilibrium binding of WT1 to specific sites in DNA and potentially RNA molecules is central in mediating the regulatory roles of this protein. In order to understand the functional effects of mutations in the nucleic acid-binding domain of WT1 proteins and/or mutations in the DNA- or RNA-binding sites, it is necessary to measure the equilibrium constant for formation of the protein-nucleic acid complex. This chapter describes the use of a filter binding assay to make accurate measurements of the binding of the WT1 zinc finger domain to the consensus WT1-binding site in DNA. The method described is readily adapted to the measurement of the effects of mutations in either the WT1 zinc finger domain or the putative binding sites within a promoter element or cellular RNA.

  4. Equilibrium and dynamic osmotic behaviour of aqueous solutions with varied concentration at constant and variable volume.

    PubMed

    Minkov, Ivan L; Manev, Emil D; Sazdanova, Svetla V; Kolikov, Kiril H

    2013-01-01

    Osmosis is essential for the living organisms. In biological systems the process usually occurs in confined volumes and may express specific features. The osmotic pressure in aqueous solutions was studied here experimentally as a function of solute concentration (0.05-0.5 M) in two different regimes: of constant and variable solution volume. Sucrose, a biologically active substance, was chosen as a reference solute for the complex tests. A custom made osmotic cell was used. A novel operative experimental approach, employing limited variation of the solution volume, was developed and applied for the purpose. The established equilibrium values of the osmotic pressure are in agreement with the theoretical expectations and do not exhibit any evident differences for both regimes. In contrast, the obtained kinetic dependences reveal striking divergence in the rates of the process at constant and varied solution volume for the respective solute concentrations. The rise of pressure is much faster at constant solution volume, while the solvent influx is many times greater in the regime of variable volume. The results obtained suggest a feasible mechanism for the way in which the living cells rapidly achieve osmotic equilibrium upon changes in the environment.

  5. Does the ligand-biopolymer equilibrium binding constant depend on the number of bound ligands?

    PubMed

    Beshnova, Daria A; Lantushenko, Anastasia O; Evstigneev, Maxim P

    2010-11-01

    Conventional methods, such as Scatchard or McGhee-von Hippel analyses, used to treat ligand-biopolymer interactions, indirectly make the assumption that the microscopic binding constant is independent of the number of ligands, i, already bound to the biopolymer. Recent results on the aggregation of aromatic molecules (Beshnova et al., J Chem Phys 2009, 130, 165105) indicated that the equilibrium constant of self-association depends intrinsically on the number of molecules in an aggregate due to loss of translational and rotational degrees of freedom on formation of the complex. The influence of these factors on the equilibrium binding constant for ligand-biopolymer complexation was analyzed in this work. It was shown that under the conditions of binding of "small" molecules, these factors can effectively be ignored and, hence, do not provide any hidden systematic error in such widely-used approaches, such as the Scatchard or McGhee-von Hippel methods for analyzing ligand-biopolymer complexation. © 2010 Wiley Periodicals, Inc. Biopolymers 93: 932-935, 2010.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. Anomalously slow cyanide binding to Glycera dibranchiata monomer methemoglobin component II: Implication for the equilibrium constant

    SciTech Connect

    Mintorovitch, J.; Satterlee, J.D. )

    1988-10-18

    In comparison to sperm whale metmyoglobin, metleghemoglobin {alpha}, methemoglobins, and heme peroxidases, the purified Glycera dibranchiata monomer methemoglobin component II exhibits anomalously slow cyanide ligation kinetics. For the component II monomer methemoglobin this reaction has been studied under pseudo-first-order conditions at pH 6.0, 7.0, 8.0, and 9.0, employing 100-250-fold mole excesses of potassium cyanide at each pH. The analysis shows that the concentration-independent bimolecular rate constant is small in comparison to those of the other heme proteins. Furthermore, the results show that the dissociation rate is extremely slow. Separation of the bimolecular rate constant into contributions from k{sub CN{sup {minus}}} (the rate constant for CN{sup {minus}} binding) and from k{sub HCN} (the rate constant for HCN binding) shows that the former is approximately 90 times greater. These results indicate that cyanide ligation reactions are not instantaneous for this protein, which is important for those attempting to study the ligand-binding equilibria. From the results presented here the authors estimate that the actual equilibrium dissociation constant (K{sub D}) for cyanide binding to this G. dibranchiata monomer methemoglobin has a numerical upper limit that is at least 2 orders of magnitude smaller than the value reported before the kinetic results were known.

  11. Chemical modeling of boron adsorption by humic materials using the constant capacitance model

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The constant capacitance surface complexation model was used to describe B adsorption behavior on reference Aldrich humic acid, humic acids from various soil environments, and dissolved organic matter extracted from sewage effluents. The reactive surface functional groups on the humic materials wer...

  12. Intrinsic surface reaction equilibrium constants of structurally charged amphoteric hydrotalcite-like compounds.

    PubMed

    Hou, Wan-Guo; Song, Shu E

    2004-01-15

    The relative equations among intrinsic surface reaction equilibrium constants (K in 1-pK model, K(a1)(int) and K(a2)(int) in 2-pK model, and *K(Na)(int) and *K(Cl)(int) in inert electrolyte chemical binding model), points of zero charge (PZC), and structural charge density (sigma(st)) for amphoteric solids with structural charge were established to investigate the effects of sigma(st) on intrinsic equilibrium constants and PZC. The intrinsic equilibrium constants of HTlc with general formulas [(Zn,Mg)(1-x)Al(x)(OH)(2)](Cl,OH)(x) and [Mg(1-x)(Fe,Al)(x)(OH)(2)](Cl,OH)(x) were evaluated. The following main conclusions were obtained. For amphoteric solids with structural charge, a point of zero net charge (PZNC) independent of electrolyte concentration (c) exists. A common intersection point (CIP) should appear among the acid-base titration curves at different c, and the pH at the CIP is pH(PZNC). The pK, pK(a1)(int), and pK(a2)(int) may be expressed as a function of pH(PZNC) and sigma(st), and these intrinsic equilibrium constants can be directly calculated from pH(PZNC) and sigma(st). The inert electrolyte chemical binding does not exist for amphoteric surfaces with structural charge. PZNC is not equal to the point of zero net proton charge (PZNPC) when sigma(st) not equal 0. pH(PZNC) > pH(PZNPC) when sigma(st)>0; pH(PZNC) < pH(PZNPC) when sigma(st)<0; and pH(PZNC) = pH(PZNPC) only when sigma(st)=0. With increasing c, the difference between pH(PZNC) and pH(PZNPC) decreases; i.e., pH(PZNPC) moves forward to pH(PZNC) with increasing c. For the HTlc samples studied, with increasing x, the pH(PZNC) and the pK(a1)(int) and pK(a2)(int) decrease, and the pK increases. These results can be explained on the basis of the affinity of metal cations for H(+) or OH(-) and the electrostatic interaction between the charging surface and H(+) or OH(-).

  13. Equilibrium constant for the reversible reaction ClO + O2 - ClO-O2

    NASA Technical Reports Server (NTRS)

    Demore, W. B.

    1990-01-01

    It is shown here that the equilibrium constant for the reversible reaction ClO + O2 - ClO-O2 at stratospheric temperatures must be at least three orders of magnitude less than the current NASA upper limit. The new upper limit greatly diminishes the possible role of ClO-O2 in the chlorine-photosensitized decomposition of O3. Nevertheless, it does not preclude the possibility that it is a significant reservoir of ClO, as well as a possible reactant, at low temperatures characteristic of polar vortices.

  14. Quantum-mechanical calculation of equilibrium geometry and force constants of complex polycyclic molecules

    SciTech Connect

    Shatokhin, S.A.; Gribov, L.A.; Perelygin, I.S.

    1986-09-01

    Equilibrium molecular geometries have been calculated for cyclopropane, cyclobutane, cubane, and certain propellanes, using an algorithm for automatic construction of a system of independent optimization coordinates in the approximation of the semiempirical MINDO/3 method. In the vicinity of the energy minimum that was found, for all of these molecules, parameters of the potential function have been determined, assigned in a system of dependent natural coordinates. Calculations procedures are set forth, along with the principles used in selecting the significant potential constants with the presence of interrelationships among the internal geometric characteristics of the molecules.

  15. 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.

  16. Surface-dependent chemical equilibrium constants and capacitances for bare and 3-cyanopropyldimethylchlorosilane coated silica nanochannels.

    PubMed

    Andersen, Mathias Bækbo; Frey, Jared; Pennathur, Sumita; Bruus, Henrik

    2011-01-01

    We present a combined theoretical and experimental analysis of the solid-liquid interface of fused-silica nanofabricated channels with and without a hydrophilic 3-cyanopropyldimethylchlorosilane (cyanosilane) coating. We develop a model that relaxes the assumption that the surface parameters C(1), C(2), and pK(+) are constant and independent of surface composition. Our theoretical model consists of three parts: (i) a chemical equilibrium model of the bare or coated wall, (ii) a chemical equilibrium model of the buffered bulk electrolyte, and (iii) a self-consistent Gouy-Chapman-Stern triple-layer model of the electrochemical double layer coupling these two equilibrium models. To validate our model, we used both pH-sensitive dye-based capillary filling experiments as well as electro-osmotic current-monitoring measurements. Using our model we predict the dependence of ζ potential, surface charge density, and capillary filling length ratio on ionic strength for different surface compositions, which can be difficult to achieve otherwise.

  17. 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.

  18. 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.

  19. Determination of equilibrium constants for the reaction between acetone and HO2 using infrared kinetic spectroscopy.

    PubMed

    Grieman, Fred J; Noell, Aaron C; Davis-Van Atta, Casey; Okumura, Mitchio; Sander, Stanley P

    2011-09-29

    The reaction between the hydroperoxy radical, HO(2), and acetone may play an important role in acetone removal and the budget of HO(x) radicals in the upper troposphere. We measured the equilibrium constants of this reaction over the temperature range of 215-272 K at an overall pressure of 100 Torr using a flow tube apparatus and laser flash photolysis to produce HO(2). The HO(2) concentration was monitored as a function of time by near-IR diode laser wavelength modulation spectroscopy. The resulting [HO(2)] decay curves in the presence of acetone are characterized by an immediate decrease in initial [HO(2)] followed by subsequent decay. These curves are interpreted as a rapid (<100 μs) equilibrium reaction between acetone and the HO(2) radical that occurs on time scales faster than the time resolution of the apparatus, followed by subsequent reactions. This separation of time scales between the initial equilibrium and ensuing reactions enabled the determination of the equilibrium constant with values ranging from 4.0 × 10(-16) to 7.7 × 10(-18) cm(3) molecule(-1) for T = 215-272 K. Thermodynamic parameters for the reaction determined from a second-law fit of our van't Hoff plot were Δ(r)H°(245) = -35.4 ± 2.0 kJ mol(-1) and Δ(r)S°(245) = -88.2 ± 8.5 J mol(-1) K(-1). Recent ab initio calculations predict that the reaction proceeds through a prereactive hydrogen-bonded molecular complex (HO(2)-acetone) with subsequent isomerization to a hydroxy-peroxy radical, 2-hydroxyisopropylperoxy (2-HIPP). The calculations differ greatly in the energetics of the complex and the peroxy radical, as well as the transition state for isomerization, leading to significant differences in their predictions of the extent of this reaction at tropospheric temperatures. The current results are consistent with equilibrium formation of the hydrogen-bonded molecular complex on a short time scale (100 μs). Formation of the hydrogen-bonded complex will have a negligible impact on the

  20. 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.

  1. Water dimers in the atmosphere III: equilibrium constant from a flexible potential.

    PubMed

    Scribano, Yohann; Goldman, Nir; Saykally, R J; Leforestier, Claude

    2006-04-27

    We present new results for the water dimer equilibrium constant K(p)(T) in the range 190-390 K, using a flexible potential energy surface fitted to spectroscopical data. The increased numerical complexity due to explicit consideration of the monomer vibrations is handled via an adiabatic (6 + 6)d decoupling between intra- and intermolecular modes. The convergence of the canonical partition function of the dimer is ensured by computing all energy levels up to dissociation for total angular momentum values J = 0-5 and using an extrapolation scheme to higher values. The newly calculated values for K(p)(T) are in very good agreement with available experimental data at room temperature. At higher temperatures, an analysis of the convergence of the partition function reveals that quasi-bound states are likely to contribute to the equilibrium constant. Additional thermodynamical quantities (deltaG, deltaH, deltaS, and C(p)) have also been determined and fit to quadratic expressions a + bT + cT2.

  2. Revealing model dependencies in "Assessing the RAFT equilibrium constant via model systems: an EPR study".

    PubMed

    Junkers, Thomas; Barner-Kowollik, Christopher; Coote, Michelle L

    2011-12-01

    In a recent article (W. Meiser, M. Buback, Assessing the RAFT Equilibrium Constant via Model Systems: An EPR Study, Macromol. Rapid Commun. 2011, 18, 1490-1494), it is claimed that evidence is found that unequivocally proves that quantum mechanical calculations assessing the equilibrium constant and fragmentation rate coefficients in dithiobenzoate-mediated reversible addition fragmentation transfer (RAFT) systems are beset with a considerable uncertainty. In the present work, we show that these claims made by Meiser and Buback are beset with a model dependency, as a critical key parameter in their data analysis - the addition rate coefficient of the radicals attacking the C=S double bond in the dithiobenzoate - induces a model insensitivity into the data analysis. Contrary to the claims made by Meiser and Buback, their experimental results can be brought into agreement with the quantum chemical calculations if a lower addition rate coefficient of cyanoisopropyl radicals (CIP) to the CIP dithiobenzoate (CPDB) is assumed. To resolve the model dependency, the addition rate coefficient of CIP radicals to CPDB needs to be determined as a matter of priority.

  3. Charging of silver bromide aqueous interface: evaluation of interfacial equilibrium constants from surface potential data.

    PubMed

    Preočanin, Tajana; Supljika, Filip; Kallay, Nikola

    2010-06-01

    A single crystal silver bromide electrode (SCr-AgBr) was used to measure the inner surface potential (Ψ(0)) at the silver bromide aqueous electrolyte interface as a function of the activities of Br(-) and Ag(+). Absolute values of the surface potential were calculated from electrode potentials of SCr-AgBr using the value of point of zero charge (pBr(pzc)=6.9 [H.A. Hoyen, R.M. Cole, J. Colloid Interface Sci. 41 (1972) 93.]) as the value of point of zero potential. Measurements were performed in potassium nitrate aqueous solutions. The Ψ(0)(pBr) function was linear and slightly dependent on the ionic strength. The reduction values of the slope with respect to the Nernst equation, expressed by the α coefficient, were 0.880,0.935, and 0.950 at ionic strengths of 10(-4), 10(-3), and 10(-2) mol dm(-3), respectively. The results were successfully interpreted by employing the surface complexation model, developed originally for metal oxides and adapted for silver halides. The thermodynamic ("intrinsic") equilibrium constants for binding of bromide (K(n)(∘)) and silver (K(p)(∘)) ions on the corresponding sites at the silver bromide surface were evaluated as lgK(n)(∘)=3.98; lgK(p)(∘)=2.48. Symmetrical counterion surface association was assumed and equilibrium constants were obtained as lgK(NO(3)(-))(∘)=lgK(K(+))(∘)=4.30.

  4. Species-Specific Thiol-Disulfide Equilibrium Constant: A Tool To Characterize Redox Transitions of Biological Importance.

    PubMed

    Mirzahosseini, Arash; Somlyay, Máté; Noszál, Béla

    2015-08-13

    Microscopic redox equilibrium constants, a new species-specific type of physicochemical parameters, were introduced and determined to quantify thiol-disulfide equilibria of biological significance. The thiol-disulfide redox equilibria of glutathione with cysteamine, cysteine, and homocysteine were approached from both sides, and the equilibrium mixtures were analyzed by quantitative NMR methods to characterize the highly composite, co-dependent acid-base and redox equilibria. The directly obtained, pH-dependent, conditional constants were then decomposed by a new evaluation method, resulting in pH-independent, microscopic redox equilibrium constants for the first time. The 80 different, microscopic redox equilibrium constant values show close correlation with the respective thiolate basicities and provide sound means for the development of potent agents against oxidative stress.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  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. 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.

  11. "Assessing the RAFT equilibrium constant via model systems: an EPR study"--response to a comment.

    PubMed

    Meiser, Wibke; Buback, Michael

    2012-08-14

    We have presented an EPR-based approach for deducing the RAFT equilibrium constant, K(eq), of a dithiobenzoate-mediated system [Meiser, W. and Buback M. Macromol. Rapid Commun. 2011, 32, 1490]. Our value is by four orders of magnitude below K(eq) from ab initio calculations for the identical monomer-free system. Junkers et al. [Macromol. Rapid Commun. 2011, 32, 1891] claim that our EPR approach would be model dependent and our data could be equally well fitted by assuming slow addition of radicals to the RAFT agent and slow fragmentation of the so-obtained intermediate radical as well as high cross-termination rate. By identification of all side products, our EPR-based method is shown to be model independent and to provide reliable K(eq) values, which demonstrate the validity of the intermediate radical termination model.

  12. Assessing the RAFT equilibrium constant via model systems: an EPR study.

    PubMed

    Meiser, Wibke; Buback, Michael

    2011-09-15

    Reversible addition-fragmentation chain transfer (RAFT) equilibrium constants, K(eq), for the model system cyano-iso-propyl dithiobenzoate (CPDB) - cyano-iso-propyl radical (CIP) have been deduced via electron paramagnetic resonance (EPR) spectroscopy. The CIP species is produced by thermal decomposition of azobis-iso-butyronitrile (AIBN). In solution of toluene at 70 °C, K(eq) has been determined to be (9 ± 1) L · mol(-1). Measurement of K(eq) = k(ad)/k(β) between 60 and 100 °C yields ΔE(a) = (-28 ± 4) kJ · mol(-1) as the difference in the activation energies of k(ad) and k(β). The data measured on the model system are indicative of fast fragmentation of the intermediate radical produced by addition of CIP to CPDB.

  13. Rough-to-smooth transition of an equilibrium neutral constant stress layer

    NASA Technical Reports Server (NTRS)

    Logan, E., Jr.; Fichtl, G. H.

    1975-01-01

    Purpose of research on rough-to-smooth transition of an equilibrium neutral constant stress layer is to develop a model for low-level atmospheric flow over terrains of abruptly changing roughness, such as those occurring near the windward end of a landing strip, and to use the model to derive functions which define the extent of the region affected by the roughness change and allow adequate prediction of wind and shear stress profiles at all points within the region. A model consisting of two bounding logarithmic layers and an intermediate velocity defect layer is assumed, and dimensionless velocity and stress distribution functions which meet all boundary and matching conditions are hypothesized. The functions are used in an asymptotic form of the equation of motion to derive a relation which governs the growth of the internal boundary layer. The growth relation is used to predict variation of surface shear stress.

  14. 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.

  15. Determination of the equilibrium constant of C60 fullerene binding with drug molecules.

    PubMed

    Mosunov, Andrei A; Pashkova, Irina S; Sidorova, Maria; Pronozin, Artem; Lantushenko, Anastasia O; Prylutskyy, Yuriy I; Parkinson, John A; Evstigneev, Maxim P

    2017-03-01

    We report a new analytical method that allows the determination of the magnitude of the equilibrium constant of complexation, Kh, of small molecules to C60 fullerene in aqueous solution. The developed method is based on the up-scaled model of C60 fullerene-ligand complexation and contains the full set of equations needed to fit titration datasets arising from different experimental methods (UV-Vis spectroscopy, (1)H NMR spectroscopy, diffusion ordered NMR spectroscopy, DLS). The up-scaled model takes into consideration the specificity of C60 fullerene aggregation in aqueous solution and allows the highly dispersed nature of C60 fullerene cluster distribution to be accounted for. It also takes into consideration the complexity of fullerene-ligand dynamic equilibrium in solution, formed by various types of self- and hetero-complexes. These features make the suggested method superior to standard Langmuir-type analysis, the approach used to date for obtaining quantitative information on ligand binding with different nanoparticles.

  16. The universal statistical distributions of the affinity, equilibrium constants, kinetics and specificity in biomolecular recognition.

    PubMed

    Zheng, Xiliang; Wang, Jin

    2015-04-01

    We uncovered the universal statistical laws for the biomolecular recognition/binding process. We quantified the statistical energy landscapes for binding, from which we can characterize the distributions of the binding free energy (affinity), the equilibrium constants, the kinetics and the specificity by exploring the different ligands binding with a particular receptor. The results of the analytical studies are confirmed by the microscopic flexible docking simulations. The distribution of binding affinity is Gaussian around the mean and becomes exponential near the tail. The equilibrium constants of the binding follow a log-normal distribution around the mean and a power law distribution in the tail. The intrinsic specificity for biomolecular recognition measures the degree of discrimination of native versus non-native binding and the optimization of which becomes the maximization of the ratio of the free energy gap between the native state and the average of non-native states versus the roughness measured by the variance of the free energy landscape around its mean. The intrinsic specificity obeys a Gaussian distribution near the mean and an exponential distribution near the tail. Furthermore, the kinetics of binding follows a log-normal distribution near the mean and a power law distribution at the tail. Our study provides new insights into the statistical nature of thermodynamics, kinetics and function from different ligands binding with a specific receptor or equivalently specific ligand binding with different receptors. The elucidation of distributions of the kinetics and free energy has guiding roles in studying biomolecular recognition and function through small-molecule evolution and chemical genetics.

  17. Evaluation of interfacial equilibrium constants from surface potential data: silver chloride aqueous interface.

    PubMed

    Preocanin, Tajana; Supljika, Filip; Kallay, Nikola

    2009-09-15

    A single crystal silver chloride electrode (SCr-AgCl) was used to measure the inner surface potential (Psi(0)) at the silver chloride aqueous electrolyte interface as a function of activity of Cl(-) ions as determined by the Ag/AgCl electrode. Absolute values of the surface potential were calculated from electrode potentials of SCr-AgCl using the value of point of zero charge (pCl(pzc)=5.2) as the value of point of zero potential. Measurements were performed in potassium nitrate aqueous solutions, as well as in the presence of Li, Na, Cs, Mg, and La nitrates. The Psi(0) (pCl) function was found to be linear within the experimental error and practically the same for all the examined electrolytes and almost independent of ionic strength. The reduction of the slope with respect to the Nernst equation, expressed by the alpha coefficient, was (0.88+/-0.01) at I(c)=10(-1) mol dm(-3), (0.87+/-0.01) at I(c)=10(-2) mol dm(-3), and (0.84+/-0.01) at I(c)=10(-3) mol dm(-3). The results were successfully interpreted by employing the surface complexation model developed originally for metal oxides and adapted for silver chloride. The standard ("intrinsic") equilibrium constants for the binding of chloride (K(o)(n)) and silver ions (K(o)(p)) on the corresponding sites at the silver chloride surface were evaluated as lg K(o)(n)=2.67+/-0.05; lg K(o)(p)=2.07+/-0.05. Counterion surface association equilibrium constants were also obtained as lg K(o)(NO3(-))=lg K(o)(K+)=274+/-0.05.

  18. Determining the association constant and adsorption properties of ion pairs in water by fitting surface tension data.

    PubMed

    Pradines, Vincent; Lavabre, Dominique; Micheau, Jean-Claude; Pimienta, Véronique

    2005-11-22

    Association constants and adsorption parameters of tetraalkylammoniumdodecyl sulfate (TAADS) ion pairs in water were determined. We have analyzed water/air surface tension measurements obtained for mixtures of sodium dodecyl sulfate (SDS) and tetraalkylammonium bromide of increasing chain lengths (TMAB, TEAB, TPAB, and TBAB). To reproduce the experimental isotherms, we coupled the association equilibrium of the ion pairs to the equations proposed by Fainerman and co-workers to model the adsorption of binary mixtures of surfactants (SDS and TAADS) with different molar areas at a nonideal surface layer. The parameters found showed that the model is not convenient to describe the effect of the addition of TMAB but a clear coherency was obtained for the three longer compounds. Ranging from TEADS to TBADS increasing hydrophobic interactions give rise to a higher associability but to a lower surface activity. Self-interactions coefficients extracted by the fitting procedure confirmed the importance of attractive interactions between the ion pairs. The calculated surface coverage showed that in every case the compound mainly adsorbed at the interface was the ion pair. For TBADS strong attractive interactions result in a phase transition at very low concentration.

  19. 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

  20. 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.

  1. Lipase-catalyzed transesterification in organic media: solvent effects on equilibrium and individual rate constants.

    PubMed

    García-Alles, L F; Gotor, V

    1998-09-20

    The kinetics of the immobilized lipase B from Candida antarctica have been studied in organic solvents. This enzyme has been shown to be slightly affected by the water content of the organic media, and it does not seem to be subject to mass transfer limitations. On the other hand, some evidence indicates that the catalytic mechanism of reactions catalyzed by this lipase proceeds through the acyl-enzyme intermediate. Moreover, despite the fact that the immobilization support dramatically enhances the catalytic power of the enzyme, it does not interfere with the intrinsic solvent effect. Consequently, this enzyme preparation becomes optimum for studying the role played by the organic solvent in catalysis. To this end, we have measured the acylation and deacylation individual rate constants, and the binding equilibrium constant for the ester, in several organic environments. Data obtained show that the major effect of the organic solvent is on substrate binding, and that the catalytic steps are almost unaffected by the solvent, indicating the desolvation of the transition state. However, the strong decrease in binding for hydrophilic solvents such as THF and dioxane, compared to the rest of solvents, cannot be easily explained by means of thermodynamic arguments (desolvation of the ester substrate). For this reason, data have been considered as an indication of the existence of an unknown step in the catalytic pathway occurring prior to formation of the acyl-enzyme intermediate.

  2. Equilibrium constants from spectrophotometric data: dimer formation in gaseous Br2.

    PubMed

    Tellinghuisen, Joel

    2008-07-03

    The equilibrium constant for the dimerization reaction, 2Br 2(g) right arrow over left arrow Br 4(g), is estimated using the classic spectrophotometric method with precise data and a multiwavelength fitting approach. The analysis is very sensitive to small errors in the data, requiring that parameters for the baseline absorption be included at each wavelength. To that end spectra for 18 Br 2 pressures in the range 6-119 Torr are augmented by six baseline scans to facilitate estimation of three baseline constants and two molar absorptivities at each wavelength, yielding K c = 2.5 +/- 0.4 L/mol at 22 degrees C. This value is more than double the only previous estimate, which was based on analysis of PVT data. With adoption of a literature estimate of Delta H degrees = -9.5 kJ/mol, the new K implies Delta S degrees = -51 J mol (-1) K (-1) (ideal gas, 1 bar reference). The spectra for monomer absorption (peak 227 nm) and dimer absorption (205 nm) are obtained with unprecedented precision.

  3. Discovering a Change in Equilibrium Constant with Change in Ionic Strength: An Empirical Laboratory Experiment for General Chemistry

    NASA Astrophysics Data System (ADS)

    Stolzberg, Richard J.

    1999-05-01

    Students are challenged to investigate the hypothesis that an equilibrium constant, Kc, measured as a product and quotient of molar concentrations, is constant at constant temperature. Spectrophotometric measurements of absorbance of a solution of Fe3+(aq) and SCN-(aq) treated with different amounts of KNO3 are made to determine Kc for the formation of FeSCN2+(aq). Students observe a regular decrease in the value of Kc as the concentration of added KNO3 is increased.

  4. 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.

  5. 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.

  6. 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.

  7. SARS CoV main proteinase: The monomer-dimer equilibrium dissociation constant.

    PubMed

    Graziano, Vito; McGrath, William J; Yang, Lin; Mangel, Walter F

    2006-12-12

    The SARS coronavirus main proteinase (SARS CoV main proteinase) is required for the replication of the severe acute respiratory syndrome coronavirus (SARS CoV), the virus that causes SARS. One function of the enzyme is to process viral polyproteins. The active form of the SARS CoV main proteinase is a homodimer. In the literature, estimates of the monomer-dimer equilibrium dissociation constant, KD, have varied more than 65,0000-fold, from <1 nM to more than 200 microM. Because of these discrepancies and because compounds that interfere with activation of the enzyme by dimerization may be potential antiviral agents, we investigated the monomer-dimer equilibrium by three different techniques: small-angle X-ray scattering, chemical cross-linking, and enzyme kinetics. Analysis of small-angle X-ray scattering data from a series of measurements at different SARS CoV main proteinase concentrations yielded KD values of 5.8 +/- 0.8 microM (obtained from the entire scattering curve), 6.5 +/- 2.2 microM (obtained from the radii of gyration), and 6.8 +/- 1.5 microM (obtained from the forward scattering). The KD from chemical cross-linking was 12.7 +/- 1.1 microM, and from enzyme kinetics, it was 5.2 +/- 0.4 microM. While each of these three techniques can present different, potential limitations, they all yielded similar KD values.

  8. Non-Condon equilibrium Fermi's golden rule electronic transition rate constants via the linearized semiclassical method.

    PubMed

    Sun, Xiang; Geva, Eitan

    2016-06-28

    In this paper, we test the accuracy of the linearized semiclassical (LSC) expression for the equilibrium Fermi's golden rule rate constant for electronic transitions in the presence of non-Condon effects. We do so by performing a comparison with the exact quantum-mechanical result for a model where the donor and acceptor potential energy surfaces are parabolic and identical except for shifts in the equilibrium energy and geometry, and the coupling between them is linear in the nuclear coordinates. Since non-Condon effects may or may not give rise to conical intersections, both possibilities are examined by considering: (1) A modified Garg-Onuchic-Ambegaokar model for charge transfer in the condensed phase, where the donor-acceptor coupling is linear in the primary mode coordinate, and for which non-Condon effects do not give rise to a conical intersection; (2) the linear vibronic coupling model for electronic transitions in gas phase molecules, where non-Condon effects give rise to conical intersections. We also present a comprehensive comparison between the linearized semiclassical expression and a progression of more approximate expressions. The comparison is performed over a wide range of frictions and temperatures for model (1) and over a wide range of temperatures for model (2). The linearized semiclassical method is found to reproduce the exact quantum-mechanical result remarkably well for both models over the entire range of parameters under consideration. In contrast, more approximate expressions are observed to deviate considerably from the exact result in some regions of parameter space.

  9. SARS CoV Main Proteinase: The Monomer-Dimer Equilibrium Dissociation Constant

    SciTech Connect

    Graziano,V.; McGrath, W.; Yang, L.; Mangel, W.

    2006-01-01

    The SARS coronavirus main proteinase (SARS CoV main proteinase) is required for the replication of the severe acute respiratory syndrome coronavirus (SARS CoV), the virus that causes SARS. One function of the enzyme is to process viral polyproteins. The active form of the SARS CoV main proteinase is a homodimer. In the literature, estimates of the monomer-dimer equilibrium dissociation constant, K{sub D}, have varied more than 650000-fold, from <1 nM to more than 200 {mu}M. Because of these discrepancies and because compounds that interfere with activation of the enzyme by dimerization may be potential antiviral agents, we investigated the monomer-dimer equilibrium by three different techniques: small-angle X-ray scattering, chemical cross-linking, and enzyme kinetics. Analysis of small-angle X-ray scattering data from a series of measurements at different SARS CoV main proteinase concentrations yielded K{sub D} values of 5.8 {+-} 0.8 {mu}M (obtained from the entire scattering curve), 6.5 {+-} 2.2 {mu}M (obtained from the radii of gyration), and 6.8 {+-} 1.5 {mu}M (obtained from the forward scattering). The K{sub D} from chemical cross-linking was 12.7 {+-} 1.1 {mu}M, and from enzyme kinetics, it was 5.2 {+-} 0.4 {mu}M. While each of these three techniques can present different, potential limitations, they all yielded similar K{sub D} values.

  10. Non-Condon equilibrium Fermi's golden rule electronic transition rate constants via the linearized semiclassical method

    NASA Astrophysics Data System (ADS)

    Sun, Xiang; Geva, Eitan

    2016-06-01

    In this paper, we test the accuracy of the linearized semiclassical (LSC) expression for the equilibrium Fermi's golden rule rate constant for electronic transitions in the presence of non-Condon effects. We do so by performing a comparison with the exact quantum-mechanical result for a model where the donor and acceptor potential energy surfaces are parabolic and identical except for shifts in the equilibrium energy and geometry, and the coupling between them is linear in the nuclear coordinates. Since non-Condon effects may or may not give rise to conical intersections, both possibilities are examined by considering: (1) A modified Garg-Onuchic-Ambegaokar model for charge transfer in the condensed phase, where the donor-acceptor coupling is linear in the primary mode coordinate, and for which non-Condon effects do not give rise to a conical intersection; (2) the linear vibronic coupling model for electronic transitions in gas phase molecules, where non-Condon effects give rise to conical intersections. We also present a comprehensive comparison between the linearized semiclassical expression and a progression of more approximate expressions. The comparison is performed over a wide range of frictions and temperatures for model (1) and over a wide range of temperatures for model (2). The linearized semiclassical method is found to reproduce the exact quantum-mechanical result remarkably well for both models over the entire range of parameters under consideration. In contrast, more approximate expressions are observed to deviate considerably from the exact result in some regions of parameter space.

  11. SPECIES - EVALUATING THERMODYNAMIC PROPERTIES, TRANSPORT PROPERTIES & EQUILIBRIUM CONSTANTS OF AN 11-SPECIES AIR MODEL

    NASA Technical Reports Server (NTRS)

    Thompson, R. A.

    1994-01-01

    Accurate numerical prediction of high-temperature, chemically reacting flowfields requires a knowledge of the physical properties and reaction kinetics for the species involved in the reacting gas mixture. Assuming an 11-species air model at temperatures below 30,000 degrees Kelvin, SPECIES (Computer Codes for the Evaluation of Thermodynamic Properties, Transport Properties, and Equilibrium Constants of an 11-Species Air Model) computes values for the species thermodynamic and transport properties, diffusion coefficients and collision cross sections for any combination of the eleven species, and reaction rates for the twenty reactions normally occurring. The species represented in the model are diatomic nitrogen, diatomic oxygen, atomic nitrogen, atomic oxygen, nitric oxide, ionized nitric oxide, the free electron, ionized atomic nitrogen, ionized atomic oxygen, ionized diatomic nitrogen, and ionized diatomic oxygen. Sixteen subroutines compute the following properties for both a single species, interaction pair, or reaction, and an array of all species, pairs, or reactions: species specific heat and static enthalpy, species viscosity, species frozen thermal conductivity, diffusion coefficient, collision cross section (OMEGA 1,1), collision cross section (OMEGA 2,2), collision cross section ratio, and equilibrium constant. The program uses least squares polynomial curve-fits of the most accurate data believed available to provide the requested values more quickly than is possible with table look-up methods. The subroutines for computing transport coefficients and collision cross sections use additional code to correct for any electron pressure when working with ionic species. SPECIES was developed on a SUN 3/280 computer running the SunOS 3.5 operating system. It is written in standard FORTRAN 77 for use on any machine, and requires roughly 92K memory. The standard distribution medium for SPECIES is a 5.25 inch 360K MS-DOS format diskette. The contents of the

  12. On the difference of equilibrium constants of DNA hybridization in bulk solution and at the solid-solution interface.

    PubMed

    Oliviero, Giulio; Federici, Stefania; Colombi, Paolo; Bergese, Paolo

    2011-01-01

    The origin of the difference between the equilibrium (affinity) constants of ligand-receptor binding in bulk solution and at a solid-solution interface is discussed in terms of Gibbsian interfacial thermodynamics. It results that the difference is determined by the surface work that the ligand-receptor interaction spends to accommodate surface binding, and in turn that the value of the surface equilibrium constant (strongly) depends on the surface that confines the event. This framework consistently describes a wide set of experimental observations of DNA surface hybridization, correctly predicting that within the surface work window for DNA hybridization, that ranges from -90 to 75 kJ mol(-1), the ratio between surface and bulk equilibrium constants ranges from 10(-16) to 10(13), spanning 29 orders of magnitude.

  13. 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.

  14. A Computational Investigation of the Equilibrium Constants for the Fluorescent and Chemiluminescent States of Coelenteramide.

    PubMed

    Min, Chun-Gang; Pinto da Silva, Luís; Esteves da Silva, Joaquim C G; Yang, Xi-Kun; Huang, Shao-Jun; Ren, Ai-Min; Zhu, Yan-Qin

    2017-01-04

    In spite of recent advances in understanding the mechanism of coelenterate bioluminescence, there is no consensus about which coelenteramide specie and/or state are the light emitter. In this study, a systematic investigation of the geometries and spectra of all possible light emitters has been performed at the TD ωB97XD/6-31+G(d) level of theory, including various fluorescent and chemiluminescent states in vacuum, in a hydrophobic environment and in aqueous solution. To deduce the most probable form of the fluorescent and chemiluminescent coelenteramide emitter, the equilibrium constants for the fluorescent and chemiluminescent states connecting the various species have been calculated. ωB97XD gives a qualitatively good description of fluorescent and chemiluminescent structures. Coelenteramide is formed in a "dark" chemiluminescent state and must evolve to a bright fluorescent state. Moreover, the photoacidity of the phenol group is significantly higher in the fluorescent state than in the chemiluminescent state, which allows the formation of phenolate coelenteramide and clarifies its role as the bioluminescent emitter.

  15. A theoretical study on the electronic structures and equilibrium constants evaluation of Deferasirox iron complexes.

    PubMed

    Salehi, Samie; Saljooghi, Amir Shokooh; Izadyar, Mohammad

    2016-10-01

    Elemental iron is essential for cellular growth and homeostasis but it is potentially toxic to the cells and tissues. Excess iron can contribute in tumor initiation and tumor growth. Obviously, in iron overload issues using an iron chelator in order to reduce iron concentration seems to be vital. This study presents the density functional theory calculations of the electronic structure and equilibrium constant for iron-deferasirox (Fe-DFX) complexes in the gas phase, water and DMSO. A comprehensive study was performed to investigate the Deferasirox-iron complexes in chelation therapy. Calculation was performed in CAMB3LYP/6-31G(d,p) to get the optimized structures for iron complexes in high and low spin states. Natural bond orbital and quantum theory of atoms in molecules analyses was carried out with B3LYP/6-311G(d,p) to understand the nature of complex bond character and electronic transition in complexes. Electrostatic potential effects on the complexes were evaluated using the CHelpG calculations. The results indicated that higher affinity for Fe(III) is not strictly a function of bond length but also the degree of Fe-X (X=O,N) covalent bonding. Based on the quantum reactivity parameters which have been investigated here, it is possible reasonable design of the new chelators to improve the chelator abilities.

  16. 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.

  17. 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.

  18. 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.

  19. Using Electrophoretic Mobility Shift Assays to Measure Equilibrium Dissociation Constants: GAL4-p53 Binding DNA as a Model System

    ERIC Educational Resources Information Center

    Heffler, Michael A.; Walters, Ryan D.; Kugel, Jennifer F.

    2012-01-01

    An undergraduate biochemistry laboratory experiment is described that will teach students the practical and theoretical considerations for measuring the equilibrium dissociation constant (K[subscript D]) for a protein/DNA interaction using electrophoretic mobility shift assays (EMSAs). An EMSA monitors the migration of DNA through a native gel;…

  20. Rate and Equilibrium Constants for an Enzyme Conformational Change during Catalysis by Orotidine 5'-Monophosphate Decarboxylase.

    PubMed

    Goryanova, Bogdana; Goldman, Lawrence M; Ming, Shonoi; Amyes, Tina L; Gerlt, John A; Richard, John P

    2015-07-28

    complex between FOMP and the open enzyme, that the tyrosyl phenol group stabilizes the closed form of ScOMPDC by hydrogen bonding to the substrate phosphodianion, and that the phenyl group of Y217 and F217 facilitates formation of the transition state for the rate-limiting conformational change. An analysis of kinetic data for mutant enzyme-catalyzed decarboxylation of OMP and FOMP provides estimates for the rate and equilibrium constants for the conformational change that traps FOMP at the enzyme active site.

  1. The 'Densitometric Image Analysis Software' and its application to determine stepwise equilibrium constants from electrophoretic mobility shift assays.

    PubMed

    van Oeffelen, Liesbeth; Peeters, Eveline; Nguyen Le Minh, Phu; Charlier, Daniël

    2014-01-01

    Current software applications for densitometric analysis, such as ImageJ, QuantityOne (BioRad) and the Intelligent or Advanced Quantifier (Bio Image) do not allow to take the non-linearity of autoradiographic films into account during calibration. As a consequence, quantification of autoradiographs is often regarded as problematic, and phosphorimaging is the preferred alternative. However, the non-linear behaviour of autoradiographs can be described mathematically, so it can be accounted for. Therefore, the 'Densitometric Image Analysis Software' has been developed, which allows to quantify electrophoretic bands in autoradiographs, as well as in gels and phosphorimages, while providing optimized band selection support to the user. Moreover, the program can determine protein-DNA binding constants from Electrophoretic Mobility Shift Assays (EMSAs). For this purpose, the software calculates a chosen stepwise equilibrium constant for each migration lane within the EMSA, and estimates the errors due to non-uniformity of the background noise, smear caused by complex dissociation or denaturation of double-stranded DNA, and technical errors such as pipetting inaccuracies. Thereby, the program helps the user to optimize experimental parameters and to choose the best lanes for estimating an average equilibrium constant. This process can reduce the inaccuracy of equilibrium constants from the usual factor of 2 to about 20%, which is particularly useful when determining position weight matrices and cooperative binding constants to predict genomic binding sites. The MATLAB source code, platform-dependent software and installation instructions are available via the website http://micr.vub.ac.be.

  2. Determination of rate and equilibrium constants for the reactions between electron transfer mediators and proteins by linear sweep voltammetry.

    PubMed

    Parker, V D; Roddick, A; Seefeldt, L C; Wang, H; Zheng, G

    1997-07-01

    Redox proteins undergo measurable charge transfer at electrodes only under special circumstances, while they readily take part in electron transfer reactions with mediators in solution. Advantage was taken of the latter fact to develop a new method to study the kinetics and equilibria of protein-mediator electron transfer reactions. It was shown that rate and equilibrium constants for the electron exchange between electron transfer mediator and the protein can be obtained from the analysis of the perturbation of the linear sweep voltammetry (LSV) response of the mediator due to the presence of the protein. The experiments were carried out under conditions where the protein does not interact with the electrode. Theoretical data obtained by digital simulation are presented to show the conditions under which rate and equilibrium constants are accessible by the LSV technique. The electron transfer reactions between ferri- and ferrocytochrome c and N,N,N',N'-tetramethylphenylenediamine and the corresponding radical cation in phosphate-buffered saline (0.04 M phosphate, pH 7.4, 0.1 M NaCl) buffer were selected to demonstrate the technique. These studies resulted in an equilibrium constant equal to 1.0 and forward and reverse rate constants equal to 1.6 x 10(4) M-1 s-1. The data available from this method include forward and reverse rate constants for electron transfer and the formal potential for the protein redox couple.

  3. 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%.

  4. 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.

  5. 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.

  6. 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.

  7. 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).

  8. 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.

  9. Equilibrium Fermi's Golden Rule Charge Transfer Rate Constants in the Condensed Phase: The Linearized Semiclassical Method vs Classical Marcus Theory.

    PubMed

    Sun, Xiang; Geva, Eitan

    2016-05-19

    In this article, we present a comprehensive comparison between the linearized semiclassical expression for the equilibrium Fermi's golden rule rate constant and the progression of more approximate expressions that lead to the classical Marcus expression. We do so within the context of the canonical Marcus model, where the donor and acceptor potential energy surface are parabolic and identical except for a shift in both the free energies and equilibrium geometries, and within the Condon region. The comparison is performed for two different spectral densities and over a wide range of frictions and temperatures, thereby providing a clear test for the validity, or lack thereof, of the more approximate expressions. We also comment on the computational cost and scaling associated with numerically calculating the linearized semiclassical expression for the rate constant and its dependence on the spectral density, temperature, and friction.

  10. Rate and equilibrium constants for the addition of N-heterocyclic carbenes into benzaldehydes: a remarkable 2-substituent effect.

    PubMed

    Collett, Christopher J; Massey, Richard S; Taylor, James E; Maguire, Oliver R; O'Donoghue, AnnMarie C; Smith, Andrew D

    2015-06-01

    Rate and equilibrium constants for the reaction between N-aryl triazolium N-heterocyclic carbene (NHC) precatalysts and substituted benzaldehyde derivatives to form 3-(hydroxybenzyl)azolium adducts under both catalytic and stoichiometric conditions have been measured. Kinetic analysis and reaction profile fitting of both the forward and reverse reactions, plus onwards reaction to the Breslow intermediate, demonstrate the remarkable effect of the benzaldehyde 2-substituent in these reactions and provide insight into the chemoselectivity of cross-benzoin reactions.

  11. Rate and Equilibrium Constants for the Addition of N-Heterocyclic Carbenes into Benzaldehydes: A Remarkable 2-Substituent Effect.

    PubMed

    Collett, Christopher J; Massey, Richard S; Taylor, James E; Maguire, Oliver R; O'Donoghue, AnnMarie C; Smith, Andrew D

    2015-06-01

    Rate and equilibrium constants for the reaction between N-aryl triazolium N-heterocyclic carbene (NHC) precatalysts and substituted benzaldehyde derivatives to form 3-(hydroxybenzyl)azolium adducts under both catalytic and stoichiometric conditions have been measured. Kinetic analysis and reaction profile fitting of both the forward and reverse reactions, plus onwards reaction to the Breslow intermediate, demonstrate the remarkable effect of the benzaldehyde 2-substituent in these reactions and provide insight into the chemoselectivity of cross-benzoin reactions.

  12. 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.

  13. Tautomeric ratio and prototropic equilibrium constants of tenoxicam, a 1H and 13C NMR theoretical and experimental study.

    PubMed

    Franco-Pérez, Marco; Moya-Hernández, Rosario; Rojas-Hernández, Alberto; Gutiérrez, Atilano; Gómez-Balderas, Rodolfo

    2011-11-24

    The determination of the micro-equilibrium prototropic constants is often a tough task when the tautomeric ratio favors one of the species or when the chemical exchange is not slow enough to allow the quantitative detection of the tautomeric species. There are just few experimental methods available to reveal the constants of the tautomeric micro-equilibriums; its applicability depends on the nature of the tautomeric system. A combination of experimental and quantum chemistry calculated (1)H and (13)C NMR chemical shifts is presented here to estimate the population of the species participating in the tautomeric equilibriums of the tenoxicam, an important anti-inflammatory drug. A multivariate fitting of a fraction-mol-weighted contribution model, for the NMR chemical shifts of the species in solution, was used to find the populations of the tautomers of tenoxicam. To consider and evaluate the effect of the solvent polarity on the tautomers' populations, experimental determinations were carried out in DMSO-d(6), in an equimolar DMSO-H(2)O mixture of deuterated solvents and in D(2)O. Additionally, by employing HYPNMR, it has been possible to refine the acid-base macroscopic constants of tenoxicam.

  14. Potentiometric determination of equilibrium constants of bases and perchlorates of protonated bases in glacial acetic acid using Superquad.

    PubMed

    Alvarez-Romero, Giaan A; Rojas-Hernández, Alberto; Vázquez, Guillermo A; Ramírez-Silva, Ma Teresa

    2003-03-01

    The traditional method of calculating equilibrium constants in glacial acetic acid medium was developed by Kolthoff and Bruckenstein in 1957; thenceforth, and even presently, few alternatives have been made available to undertake such studies. This paper presents the results obtained with the use of the program Superquad to assess the equilibrium constants of various bases and their protonated perchlorate salts in glacial acetic media. A model of formation equilibria is proposed and fed into the program, considering the species present during an acid-base titration. The calculations of the equilibrium constants using Superquad for pyridine and diethylamine are statistically in agreement with those reported in the literature, (for pyridine: pK(B)=5.98+/-0.02, pK( PyHClO4)=5.47+/-0.02 and for diethylamine pK(B)=5.52+/-0.04, pK( DietHClO4)=4.52+/-0.07). With the use of Superquad, the values found for the aniline were pK(B)=6.95+/-0.06 and pK( AnilHClO4)=4.89+/-0.06.

  15. 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.

  16. 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

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  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. A METHOD FOR THE MEASUREMENT OF SITE-SPECIFIC TAUTOMERIC AND ZWITTERIONIC MICROSPECIES EQUILIBRIUM CONSTANTS

    EPA Science Inventory

    We describe a method for the individual measurement of simultaneously occurring, unimolecular, site-specific "microequilibrium" constants as in, for example, prototropic tautomerism and zwitterionic equilibria. Our method represents an elaboration of that of Nygren et al. (Anal. ...

  3. METHOD FOR THE MEASUREMENT OF SITE-SPECIFIC TAUTOMERIC AND ZWITTERIONIC MICROSPECIES EQUILIBRIUM CONSTANTS

    EPA Science Inventory

    We describe a method for the individual measurement of simultaneously occurring, unimolecular, site-specific “microequilibrium” constants as in, for example, prototropic tautomerism and zwitterionic equilibria. Our method represents an elaboration of that of Nygren et al. (Anal. ...

  4. 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.

  5. Experimental determination of equilibrium constant for the complexing reaction of nitric oxide with hexamminecobalt(II) in aqueous solution.

    PubMed

    Mao, Yan-Peng; Chen, Hua; Long, Xiang-Li; Xiao, Wen-de; Li, Wei; Yuan, Wei-Kang

    2009-02-15

    Ammonia solution can be used to scrub NO from the flue gases by adding soluble cobalt(II) salts into the aqueous ammonia solutions. The hexamminecobalt(II), Co(NH3)6(2+), formed by ammonia binding with Co2+ is the active constituent of eliminating NO from the flue gas streams. The hexamminecobalt(II) can combine with NO to form a complex. For the development of this process, the data of the equilibrium constants for the coordination between NO and Co(NH3)6(2+)over a range of temperature is very important. Therefore, a series of experiments were performed in a bubble column to investigate the chemical equilibrium. The equilibrium constant was determined in the temperature range of 30.0-80.0 degrees C under atmospheric pressure at pH 9.14. All experimental data fit the following equation well: [see text] where the enthalpy and entropy are DeltaH degrees = - (44.559 +/- 2.329)kJ mol(-1) and DeltaS degrees = - (109.50 +/- 7.126) J K(-1)mol(-1), respectively.

  6. Photoluminescence-based correlation of semiconductor electric field thickness with adsorbate Hammett substituent constants. Adsorption of aniline derivatives onto cadmium selenide

    SciTech Connect

    Murphy, C.J.; Leung, L.K.; Kowach, G.R.; Ellis, A.B. ); Lisensky, G.C. )

    1990-11-07

    Adsorption of ring-substituted aniline derivatives, presumably through the amino group, onto the (0001) face of single-crystal n-CdSe or n-CdS (CdS(e)) profoundly affects the semiconductor's photoluminescence (PL) by effecting charge transfer between surface states and the bulk semiconductor. The variations in PL intensity of etched samples are well fit by a dead-layer model, allowing estimation of the adduct-induced changes in depletion width. The magnitude of these changes can be molecularly tuned over nearly 1,000 {angstrom} for moderately doped samples by the control of electron density at the coordination site, a parameter characterized by the Hammett substituent constant {sigma}. In contrast, the affinity of the aniline derivatives for the CdS(e) surface, as estimated from the fit of concentration-dependent PL changes to the Langmuir adsorption isotherm model, is relatively insensitive to aniline substituent; equilibrium constants are {approximately}10{sup 2} M{sup {minus}1}.

  7. 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.

  8. 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.

  9. Spectrophotometric determination of reaction stoichiometry and equilibrium constants of metallochromic indicators. II. The Ca2+-arsenazo III complexes.

    PubMed

    Dorogi, P L; Neumann, E

    1981-04-01

    The analytical method described in the preceding article was applied to spectrophotometric Ca2+-titrations of the metallochromic indicator arsenazo III (Ar). At various reactant concentrations it was determined that Ar forms 1:1,1:2 and 2 : 1 complexes with calcium. The equilibrium constants and extinction coefficients at 602 nm were determined. Corrected to zero ionic strength at 293 K and pH 7.0, the reactions Ca + Ar = CaAr, CaAr + Ar = CaAr2 and CaAr + Ca = Ca2Ar are associated with dissociation equilibrium constants k(11) = 1.6 x 10(-6)M, K12 = 3.2 x 10(-4)M and K21 = 5.8 x 10(-3)M. respectively. The extinction coefficient of unbound indicator is (602) = 9.6 (+/-0.3) x 10(3) cm(-1) M(-1). Arscnazo III complexes with monovalent ions like Na+ and K+ : at zero ionic strength, the dissociation constant of the Na+-Ar complex is about 0.1 M.

  10. Kinetic and equilibrium constants of phytic acid and ferric and ferrous phytate derived from nuclear magnetic resonance spectroscopy.

    PubMed

    Heighton, Lynne; Schmidt, Walter F; Siefert, Ronald L

    2008-10-22

    Inositol phosphates are metabolically derived organic phosphates (P) that increasingly appear to be an important sink and source of P in the environment. Salts of myo-inositol hexakisdihydrogen phosphate (IHP) or more commonly phytate are the most common inositol phosphates in the environment. IHP resists acidic dephosphorylation and enzymatic dephosphorylation as ferric or ferrous IHP. Mobility of IHP iron complexes is potentially pH and redox responsive, making the time scale and environmental fate and transport of the P associated with the IHP of interest to the mass balance of phosphorus. Ferric and ferrous complexes of IHP were investigated by proton nuclear magnetic resonance spectroscopy ( (1)H NMR) and enzymatic dephosphorylation. Ferrous IHP was found to form quickly and persist for a longer period then ferric IHP. Dissociation constants derived from (1)H NMR experiments of chemically exchanging systems at equilibrium were 1.11 and 1.19 and formation constants were 0.90 and 0.84 for ferric and ferrous IHP, respectively. The recovery of P from enzymatic dephosphorylation of ferric and ferrous IHP was consistent with the magnitude of the kinetic and equilibrium rate constants.

  11. A Virtual Mixture Approach to the Study of Multistate Equilibrium: Application to Constant pH Simulation in Explicit Water.

    PubMed

    Wu, Xiongwu; Brooks, Bernard R

    2015-10-01

    Chemical and thermodynamic equilibrium of multiple states is a fundamental phenomenon in biology systems and has been the focus of many experimental and computational studies. This work presents a simulation method to directly study the equilibrium of multiple states. This method constructs a virtual mixture of multiple states (VMMS) to sample the conformational space of all chemical states simultaneously. The VMMS system consists of multiple subsystems, one for each state. The subsystem contains a solute and a solvent environment. The solute molecules in all subsystems share the same conformation but have their own solvent environments. Transition between states is implicated by the change of their molar fractions. Simulation of a VMMS system allows efficient calculation of relative free energies of all states, which in turn determine their equilibrium molar fractions. For systems with a large number of state transition sites, an implicit site approximation is introduced to minimize the cost of simulation. A direct application of the VMMS method is for constant pH simulation to study protonation equilibrium. Applying the VMMS method to a heptapeptide of 3 ionizable residues, we calculated the pKas of those residues both with all explicit states and with implicit sites and obtained consistent results. For mouse epidermal growth factor of 9 ionizable groups, our VMMS simulations with implicit sites produced pKas of all 9 ionizable groups and the results agree qualitatively with NMR measurement. This example demonstrates the VMMS method can be applied to systems of a large number of ionizable groups and the computational cost scales linearly with the number of ionizable groups. For one of the most challenging systems in constant pH calculation, SNase Δ+PHS/V66K, our VMMS simulation shows that it is the state-dependent water penetration that causes the large deviation in lysine66's pKa.

  12. Dynamics of equilibrium folding and unfolding transitions of titin immunoglobulin domain under constant forces.

    PubMed

    Chen, Hu; Yuan, Guohua; Winardhi, Ricksen S; Yao, Mingxi; Popa, Ionel; Fernandez, Julio M; Yan, Jie

    2015-03-18

    The mechanical stability of force-bearing proteins is crucial for their functions. However, slow transition rates of complex protein domains have made it challenging to investigate their equilibrium force-dependent structural transitions. Using ultra stable magnetic tweezers, we report the first equilibrium single-molecule force manipulation study of the classic titin I27 immunoglobulin domain. We found that individual I27 in a tandem repeat unfold/fold independently. We obtained the force-dependent free energy difference between unfolded and folded I27 and determined the critical force (∼5.4 pN) at which unfolding and folding have equal probability. We also determined the force-dependent free energy landscape of unfolding/folding transitions based on measurement of the free energy cost of unfolding. In addition to providing insights into the force-dependent structural transitions of titin I27, our results suggest that the conformations of titin immunoglobulin domains can be significantly altered during low force, long duration muscle stretching.

  13. 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.

  14. 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

  15. 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.

  16. Toward Improving Atmospheric Models and Ozone Projections: Laboratory UV Absorption Cross Sections and Equilibrium Constant of ClOOCl

    NASA Astrophysics Data System (ADS)

    Wilmouth, D. M.; Klobas, J. E.; Anderson, J. G.

    2015-12-01

    Thirty years have now passed since the discovery of the Antarctic ozone hole, and despite comprehensive international agreements being in place to phase out CFCs and halons, polar ozone losses generally remain severe. The relevant halogen compounds have very long atmospheric lifetimes, which ensures that seasonal polar ozone depletion will likely continue for decades to come. Changes in the climate system can further impact stratospheric ozone abundance through changes in the temperature and water vapor structure of the atmosphere and through the potential initiation of solar radiation management efforts. In many ways, the rate at which climate is changing must now be considered fast relative to the slow removal of halogens from the atmosphere. Photochemical models of Earth's atmosphere play a critical role in understanding and projecting ozone levels, but in order for these models to be accurate, they must be built on a foundation of accurate laboratory data. ClOOCl is the centerpiece of the catalytic cycle that accounts for more than 50% of the chlorine-catalyzed ozone loss in the Arctic and Antarctic stratosphere every spring, and so uncertainties in the ultraviolet cross sections of ClOOCl are particularly important. Additionally, the equilibrium constant of the dimerization reaction of ClO merits further study, as there are important discrepancies between in situ measurements and lab-based models, and the JPL-11 recommended equilibrium constant includes high error bars at atmospherically relevant temperatures (~75% at 200 K). Here we analyze available data for the ClOOCl ultraviolet cross sections and equilibrium constant and present new laboratory spectroscopic results.

  17. Thermodynamics at the nanoscale: phase diagrams of nickel-carbon nanoclusters and equilibrium constants for phase transitions.

    PubMed

    Engelmann, Yannick; Bogaerts, Annemie; Neyts, Erik C

    2014-10-21

    Using reactive molecular dynamics simulations, the melting behavior of nickel-carbon nanoclusters is examined. The phase diagrams of icosahedral and Wulff polyhedron clusters are determined using both the Lindemann index and the potential energy. Formulae are derived for calculating the equilibrium constants and the solid and liquid fractions during a phase transition, allowing more rational determination of the melting temperature with respect to the arbitrary Lindemann value. These results give more insight into the properties of nickel-carbon nanoclusters in general and can specifically be very useful for a better understanding of the synthesis of carbon nanotubes using the catalytic chemical vapor deposition method.

  18. Computer codes for the evaluation of thermodynamic properties, transport properties, and equilibrium constants of an 11-species air model

    NASA Technical Reports Server (NTRS)

    Thompson, Richard A.; Lee, Kam-Pui; Gupta, Roop N.

    1990-01-01

    The computer codes developed provide data to 30000 K for the thermodynamic and transport properties of individual species and reaction rates for the prominent reactions occurring in an 11-species nonequilibrium air model. These properties and the reaction-rate data are computed through the use of curve-fit relations which are functions of temperature (and number density for the equilibrium constant). The curve fits were made using the most accurate data believed available. A detailed review and discussion of the sources and accuracy of the curve-fitted data used herein are given in NASA RP 1232.

  19. 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

  20. 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…

  1. The polysiloxane cyclization equilibrium constant: a theoretical focus on small and intermediate size rings.

    PubMed

    Madeleine-Perdrillat, Claire; Delor-Jestin, Florence; de Sainte Claire, Pascal

    2014-01-09

    The nonlinear dependence of polysiloxane cyclization constants (log(K(x))) with ring size (log(x)) is explained by a thermodynamic model that treats specific torsional modes of the macromolecular chains with a classical coupled hindered rotor model. Several parameters such as the dependence of the internal rotation kinetic energy matrix with geometry, the effect of potential energy hindrance, anharmonicity, and the couplings between internal rotors were investigated. This behavior arises from the competing effects of local molecular entropy that is mainly driven by the intrinsic transformation of vibrations in small cycles into hindered rotations in larger cycles and configurational entropy.

  2. 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.

  3. 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.

  4. Folding equilibrium constants of telomere G-quadruplexes in free state or associated with proteins determined by isothermal differential hybridization.

    PubMed

    Wang, Quan; Ma, Li; Hao, Yu-Hua; Tan, Zheng

    2010-11-15

    Guanine rich (G-rich) nucleic acids form G-quadruplex structures that are implicated in many biological processes, pharmaceutical applications, and molecular machinery. The folding equilibrium constant (K(F)) of the G-quadruplex not only determines its stability and competition against duplex formation in genomic DNA but also defines its recognition by proteins and drugs and technical specifications. The K(F) is most conveniently derived from thermal melting analysis that has so far yielded extremely diversified results for the human telomere G-quadruplex. Melting analysis cannot be used for nucleic acids associated with proteins, thus has difficulty to study how protein association affects the folding equilibrium of G-quadruplex structure. In this work, we established an isothermal differential hybridization (IDH) method that is able to determine the K(F) of G-quadruplex, either alone or associated with proteins. Using this method, we studied the folding equilibrium of the core sequence G(3)(T(2)AG(3))(3) from vertebrate telomere in K(+) and Na(+) solutions and how it is affected by proteins associated at its adjacent regions. Our results show that the K(F) obtained for the free G-quadruplex is within 1 order of magnitude of most of those obtained by melting analysis and protein binding beside a G-quadruplex can dramatically destabilize the G-quadruplex.

  5. 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.

  6. Complexation of phosphine ligands with peracetylated beta-cyclodextrin in supercritical carbon dioxide: spectroscopic determination of equilibrium constants.

    PubMed

    Galia, Alessandro; Navarre, Edward C; Scialdone, Onofrio; Ferreira, Michel; Filardo, Giuseppe; Tilloy, Sebastien; Monflier, Eric

    2007-03-15

    The interaction between peracetylated beta-cyclodextrin and several triphenyl phosphine derivatives was studied in supercritical carbon dioxide (scCO2) by UV-visible spectroscopy. The equilibrium constant for a 1:1 complexation reaction was obtained from titration spectra and calculated using two established mathematical models. The values of the equilibrium constants are 1-3 orders of magnitude smaller than those obtained in aqueous solution with analogous phosphines. This is likely due to the absence in scCO2 of the hydrophobic effect, which is replaced by a corresponding, but weaker, CO2-phobic effect. The largest value of Kf was found for complexes of diphenyl(4-adamantylphenyl)phosphine, which is rationalized on the basis of the excellent fit of the phosphine in the cyclodextrin cavity, leading to enhanced host-guest van der Waals interactions. This study can be considered the first step toward the comprehension of the complexation thermodynamics of modified cyclodextrins soluble in scCO2.

  7. The Use of Pseudo-equilibrium Constant Affords Improved QSAR Models of Human Plasma Protein Binding

    PubMed Central

    Zhu, Xiangwei; Sedykh, Alexander; Zhu, Hao; Liu, Shushen; Tropsha, Alexander

    2015-01-01

    Purpose To develop accurate in silico predictors of Plasma Protein Binding (PPB). Methods Experimental PPB data were compiled for over 1,200 compounds. Two endpoints have been considered: (1) fraction bound (%PPB); and (2) the logarithm of a pseudo binding constant (lnKa) derived from %PPB. The latter metric was employed because it reflects the PPB thermodynamics and the distribution of the transformed data is closer to normal. Quantitative Structure-Activity Relationship (QSAR) models were built with Dragon descriptors and three statistical methods. Results Five-fold external validation procedure resulted in models with the prediction accuracy (R2) of 0.67±0.04 and 0.66±0.04, respectively, and the mean absolute error (MAE) of 15.3±0.2% and 13.6±0.2%, respectively. Models were validated with two external datasets: 173 compounds from DrugBank, and 236 chemicals from the US EPA ToxCast project. Models built with lnKa were significantly more accurate (MAE of 6.2–10.7%) than those built with %PPB (MAE of 11.9–17.6%) for highly bound compounds both for the training and the external sets. Conclusion The pseudo binding constant (lnKa) is more appropriate for characterizing PPB binding than conventional %PPB. Validated QSAR models developed herein can be applied as reliable tools in early drug development and in chemical risk assessment. PMID:23568522

  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. Computational Approaches to the Chemical Equilibrium Constant in Protein-ligand Binding.

    PubMed

    Montalvo-Acosta, Joel José; Cecchini, Marco

    2016-12-01

    The physiological role played by protein-ligand recognition has motivated the development of several computational approaches to the ligand binding affinity. Some of them, termed rigorous, have a strong theoretical foundation but involve too much computation to be generally useful. Some others alleviate the computational burden by introducing strong approximations and/or empirical calibrations, which also limit their general use. Most importantly, there is no straightforward correlation between the predictive power and the level of approximation introduced. Here, we present a general framework for the quantitative interpretation of protein-ligand binding based on statistical mechanics. Within this framework, we re-derive self-consistently the fundamental equations of some popular approaches to the binding constant and pinpoint the inherent approximations. Our analysis represents a first step towards the development of variants with optimum accuracy/efficiency ratio for each stage of the drug discovery pipeline.

  10. 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.

  11. 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.

  12. A Computer Simulation Method for the Calculation of Equilibrium Constants for the Formation of Physical Clusters of Molecules: Application to Small Water Clusters.

    DTIC Science & Technology

    1981-08-01

    areas of chemical physics. First, the values of K 2and K 3are related to the second and third virial coefficients of the substance. Second , the theory of...equilibrium constants for dimer and trimer formation are simply related to the second and third virial coefficients . Here we discuss our choice of the Rn and...containment sphere at low temperatures. The equilibrium constant for dimer formation can be related to the second virial coefficient for the gas under

  13. Equilibrium star formation in a constant Q disc: model optimization and initial tests

    NASA Astrophysics Data System (ADS)

    Zheng, Zheng; Meurer, Gerhardt R.; Heckman, Timothy M.; Thilker, David A.; Zwaan, Martin A.

    2013-10-01

    We develop a model for the distribution of the interstellar medium (ISM) and star formation in galaxies based on recent studies that indicate that galactic discs stabilize to a constant stability parameter, which we combine with prescriptions of how the phases of the ISM are determined and for the star formation law (SFL). The model predicts the gas surface mass density and star formation intensity of a galaxy given its rotation curve, stellar surface mass density and the gas velocity dispersion. This model is tested on radial profiles of neutral and molecular ISM surface mass density and star formation intensity of 12 galaxies selected from the H I Nearby Galaxy Survey sample. Our tests focus on intermediate radii (0.3 to 1 times the optical radius) because there are insufficient data to test the outer discs and the fits are less accurate in detail in the centre. Nevertheless, the model produces reasonable agreement with the ISM mass and star formation rate integrated over the central region in all but one case. To optimize the model, we evaluate four recipes for the stability parameter, three recipes for apportioning the ISM into molecular and neutral components, and eight versions of the SFL. We find no clear-cut best prescription for the two-fluid (gas and stars) stability parameter Q2f and therefore for simplicity, we use the Wang and Silk approximation (QWS). We found that an empirical scaling between the molecular-to-neutral ISM ratio (Rmol) and the stellar surface mass density proposed by Leroy et al. works marginally better than the other two prescriptions for this ratio in predicting the ISM profiles, and noticeably better in predicting the star formation intensity from the ISM profiles produced by our model with the SFLs we tested. Thus, in the context of our modelled ISM profiles, the linear molecular SFL and the two-component SFL work better than the other prescriptions we tested. We incorporate these relations into our `constant Q disc' model.

  14. 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.

  15. Determination of equilibrium dissociation constants for recombinant antibodies by high-throughput affinity electrophoresis.

    PubMed

    Pan, Yuchen; Sackmann, Eric K; Wypisniak, Karolina; Hornsby, Michael; Datwani, Sammy S; Herr, Amy E

    2016-12-23

    High-quality immunoreagents enhance the performance and reproducibility of immunoassays and, in turn, the quality of both biological and clinical measurements. High quality recombinant immunoreagents are generated using antibody-phage display. One metric of antibody quality - the binding affinity - is quantified through the dissociation constant (KD) of each recombinant antibody and the target antigen. To characterize the KD of recombinant antibodies and target antigen, we introduce affinity electrophoretic mobility shift assays (EMSAs) in a high-throughput format suitable for small volume samples. A microfluidic card comprised of free-standing polyacrylamide gel (fsPAG) separation lanes supports 384 concurrent EMSAs in 30 s using a single power source. Sample is dispensed onto the microfluidic EMSA card by acoustic droplet ejection (ADE), which reduces EMSA variability compared to sample dispensing using manual or pin tools. The KD for each of a six-member fragment antigen-binding fragment library is reported using ~25-fold less sample mass and ~5-fold less time than conventional heterogeneous assays. Given the form factor and performance of this micro- and mesofluidic workflow, we have developed a sample-sparing, high-throughput, solution-phase alternative for biomolecular affinity characterization.

  16. Determination of equilibrium dissociation constants for recombinant antibodies by high-throughput affinity electrophoresis

    PubMed Central

    Pan, Yuchen; Sackmann, Eric K.; Wypisniak, Karolina; Hornsby, Michael; Datwani, Sammy S.; Herr, Amy E.

    2016-01-01

    High-quality immunoreagents enhance the performance and reproducibility of immunoassays and, in turn, the quality of both biological and clinical measurements. High quality recombinant immunoreagents are generated using antibody-phage display. One metric of antibody quality – the binding affinity – is quantified through the dissociation constant (KD) of each recombinant antibody and the target antigen. To characterize the KD of recombinant antibodies and target antigen, we introduce affinity electrophoretic mobility shift assays (EMSAs) in a high-throughput format suitable for small volume samples. A microfluidic card comprised of free-standing polyacrylamide gel (fsPAG) separation lanes supports 384 concurrent EMSAs in 30 s using a single power source. Sample is dispensed onto the microfluidic EMSA card by acoustic droplet ejection (ADE), which reduces EMSA variability compared to sample dispensing using manual or pin tools. The KD for each of a six-member fragment antigen-binding fragment library is reported using ~25-fold less sample mass and ~5-fold less time than conventional heterogeneous assays. Given the form factor and performance of this micro- and mesofluidic workflow, we have developed a sample-sparing, high-throughput, solution-phase alternative for biomolecular affinity characterization. PMID:28008969

  17. Theory for rates, equilibrium constants, and Brønsted slopes in F1-ATPase single molecule imaging experiments.

    PubMed

    Volkán-Kacsó, Sándor; Marcus, Rudolph A

    2015-11-17

    A theoretical model of elastically coupled reactions is proposed for single molecule imaging and rotor manipulation experiments on F1-ATPase. Stalling experiments are considered in which rates of individual ligand binding, ligand release, and chemical reaction steps have an exponential dependence on rotor angle. These data are treated in terms of the effect of thermodynamic driving forces on reaction rates, and lead to equations relating rate constants and free energies to the stalling angle. These relations, in turn, are modeled using a formalism originally developed to treat electron and other transfer reactions. During stalling the free energy profile of the enzymatic steps is altered by a work term due to elastic structural twisting. Using biochemical and single molecule data, the dependence of the rate constant and equilibrium constant on the stall angle, as well as the Børnsted slope are predicted and compared with experiment. Reasonable agreement is found with stalling experiments for ATP and GTP binding. The model can be applied to other torque-generating steps of reversible ligand binding, such as ADP and Pi release, when sufficient data become available.

  18. Determination of the equilibrium formation constants of two U(VI)-peroxide complexes at alkaline pH.

    PubMed

    Meca, S; Martínez-Torrents, A; Martí, V; Giménez, J; Casas, I; de Pablo, J

    2011-08-21

    The formation of uranyl-peroxide complexes was studied at alkaline media by using UV-Visible spectrophotometry and the STAR code. Two different complexes were found at a H(2)O(2)/U(VI) ratio lower than 2. A graphical method was used in order to obtain the formation constants of such complexes and the STAR program was used to refine the formation constants values because of its capacity to treat multiwavelength absorbance data and refining equilibrium constants. The values obtained for the two complexes identified were: UO(2)(2+) + H(2)O(2) + 4OH(-) <−> UO(2)(O(2))(OH)(2)(2-) + 2H(2)O: log β°(1,1,4) = 28.1 ± 0.1 (1). UO(2)(2+) + 2H(2)O(2) + 6OH(-) <−> UO(2)(O(2))(2)(OH)(2)(4-) + 4H(2)O: log β°(1,2,6) = 36.8 ± 0.2 (2). At hydrogen peroxide concentrations higher than 10(-5) mol dm(-3), and in the absence of carbonate, the UO(2)(O(2))(2)(OH)(2)(4-) complex is predominant in solution, indicating the significant peroxide affinity of peroxide ions for uranium and the strong complexes of uranium(VI) with peroxide.

  19. Equilibrium constant of the gamma-sultone and extraction constant of sodium and potassium ions from water into benzene in presence of 18-crown-6 and bromocresol green.

    PubMed

    Kolthoff, Izaak M; Chantooni, Miran K; Jyo, Akinori

    2002-07-03

    An extraction procedure for the spectrophotometric determination of sodium or potassium involving a 1:1:1 metal ion: crown ether: sulfonephthalein dye monoanion ion associate has been described in the literature. In a recent paper from this laboratory the total dye content of the organic phase resulting from partitioning bromocresol green (HBCG) alone between water and benzene was determined from back extraction into an aqueous phosphate buffer. In benzene, bromocresol green is present to a large extent as a colorless lactone form, or gamma-sultone. The sultone equilibrium constant, K(dist) (sultone)=[sultone](o)/[BCG(-)](w)gamma(BCG(-))(w)a(H(+)) was found to be 373+/-42 mol(-1) dm(3). In the present study, sodium was extracted from water into benzene with 18-crown-6 and BCG(-), yielding K(dist) (sultone)=232 mol(-1) dm(3) and the conventional extraction constant, K(ex), of (5.49+/-0.49)x10(3) mol(-2) dm(6). Corresponding values from potassium extraction data are 256 mol(-1) dm(3) and (4.80+/-0.51)x10(6) mol(-2) dm(6), respectively. In the absence of ethanol, the calibration plot of sodium closely followed Beer's law, but that of potassium curved downward, approaching linearity in 15% ethanol. High 18-crown-6, low bromocresol green concentrations are analytically favorable for the extraction of potassium from the 15% aqueous ethanol mixture. All plots from the back-extractions (a measure of the total dye content in the benzene phase) were linear. Ethanol markedly reduced the reagent blank, when C(MCl)=0, as a result of the sultone being partitioned less favorably into benzene.

  20. 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.

  1. 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.

  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. Determination of Equilibrium Constant and Relative Brightness in Fluorescence Correlation Spectroscopy by Considering Third-Order Correlations.

    PubMed

    Wu, Zhenqin; Bi, Huimin; Pan, Sichen; Meng, Lingyi; Zhao, Xin Sheng

    2016-11-17

    Fluorescence correlation spectroscopy (FCS) is a powerful tool to investigate molecular diffusion and relaxations, which may be utilized to study many problems such as molecular size and aggregation, chemical reaction, molecular transportation and motion, and various kinds of physical and chemical relaxations. This article focuses on a problem related to using the relaxation term to study a reaction. If two species with different fluorescence photon emission efficiencies are connected by a reaction, the kinetic and equilibrium properties will be manifested in the relaxation term of the FCS curve. However, the conventional FCS alone cannot simultaneously determine the equilibrium constant (K) and the relative fluorescence brightness (Q), both of which are indispensable in the extraction of thermodynamic and kinetic information from the experimental data. To circumvent the problem, an assumption of Q = 0 is often made for the weak fluorescent species, which may lead to numerous errors when the actual situation is not the case. We propose to combine the third-order FCS with the conventional second-order FCS to determine K and Q without invoking other resources. The strategy and formalism are verified by computer simulations and demonstrated in a classical example of the hairpin DNA-folding process.

  4. Optimization of Electrospray Ionization by Statistical Design of Experiments and Response Surface Methodology: Protein-Ligand Equilibrium Dissociation Constant Determinations.

    PubMed

    Pedro, Liliana; Van Voorhis, Wesley C; Quinn, Ronald J

    2016-09-01

    Electrospray ionization mass spectrometry (ESI-MS) binding studies between proteins and ligands under native conditions require that instrumental ESI source conditions are optimized if relative solution-phase equilibrium concentrations between the protein-ligand complex and free protein are to be retained. Instrumental ESI source conditions that simultaneously maximize the relative ionization efficiency of the protein-ligand complex over free protein and minimize the protein-ligand complex dissociation during the ESI process and the transfer from atmospheric pressure to vacuum are generally specific for each protein-ligand system and should be established when an accurate equilibrium dissociation constant (KD) is to be determined via titration. In this paper, a straightforward and systematic approach for ESI source optimization is presented. The method uses statistical design of experiments (DOE) in conjunction with response surface methodology (RSM) and is demonstrated for the complexes between Plasmodium vivax guanylate kinase (PvGK) and two ligands: 5'-guanosine monophosphate (GMP) and 5'-guanosine diphosphate (GDP). It was verified that even though the ligands are structurally similar, the most appropriate ESI conditions for KD determination by titration are different for each. Graphical Abstract ᅟ.

  5. Equilibrium constant for the reaction ClO + ClO ↔ ClOOCl between 250 and 206 K.

    PubMed

    Hume, Kelly L; Bayes, Kyle D; Sander, Stanley P

    2015-05-14

    The chlorine peroxide molecule, ClOOCl, is an important participant in the chlorine-catalyzed destruction of ozone in the stratosphere. Very few laboratory measurements have been made for the partitioning between monomer ClO and dimer ClOOCl at temperatures lower than 250 K. This paper reports absorption spectra for both ClO and ClOOCl when they are in equilibrium at 1 atm and temperatures down to 206 K. The very low ClO concentrations involved requires measuring and calibrating a differential cross section, ΔσClO, for the 10-0 band of ClO. A third law fit of the new results gives Keq = [(2.01 ± 0.17) 10–27 cm3 molecule–1] e(8554∓21)K/T, where the error limits reflect the uncertainty in the entropy change. The resulting equilibrium constants are slightly lower than currently recommended. The slope of the van’t Hoff plot yields a value for the enthalpy of formation of ClOOCl at 298 K, ΔHfo, of 129.8 ± 0.6 kJ mol–1. Uncertainties in the absolute ultraviolet cross sections of ClOOCl and ClO appear to be the limiting factors in these measurements. The new Keq parameters are consistent with the measurements of Santee et al.42 in the stratosphere.

  6. Optimization of Electrospray Ionization by Statistical Design of Experiments and Response Surface Methodology: Protein-Ligand Equilibrium Dissociation Constant Determinations

    NASA Astrophysics Data System (ADS)

    Pedro, Liliana; Van Voorhis, Wesley C.; Quinn, Ronald J.

    2016-09-01

    Electrospray ionization mass spectrometry (ESI-MS) binding studies between proteins and ligands under native conditions require that instrumental ESI source conditions are optimized if relative solution-phase equilibrium concentrations between the protein-ligand complex and free protein are to be retained. Instrumental ESI source conditions that simultaneously maximize the relative ionization efficiency of the protein-ligand complex over free protein and minimize the protein-ligand complex dissociation during the ESI process and the transfer from atmospheric pressure to vacuum are generally specific for each protein-ligand system and should be established when an accurate equilibrium dissociation constant (KD) is to be determined via titration. In this paper, a straightforward and systematic approach for ESI source optimization is presented. The method uses statistical design of experiments (DOE) in conjunction with response surface methodology (RSM) and is demonstrated for the complexes between Plasmodium vivax guanylate kinase ( PvGK) and two ligands: 5'-guanosine monophosphate (GMP) and 5'-guanosine diphosphate (GDP). It was verified that even though the ligands are structurally similar, the most appropriate ESI conditions for KD determination by titration are different for each.

  7. Fundamental and overtone vibrational spectroscopy, enthalpy of hydrogen bond formation and equilibrium constant determination of the methanol-dimethylamine complex.

    PubMed

    Du, Lin; Mackeprang, Kasper; Kjaergaard, Henrik G

    2013-07-07

    We have measured gas phase vibrational spectra of the bimolecular complex formed between methanol (MeOH) and dimethylamine (DMA) up to about 9800 cm(-1). In addition to the strong fundamental OH-stretching transition we have also detected the weak second overtone NH-stretching transition. The spectra of the complex are obtained by spectral subtraction of the monomer spectra from spectra recorded for the mixture. For comparison, we also measured the fundamental OH-stretching transition in the bimolecular complex between MeOH and trimethylamine (TMA). The enthalpies of hydrogen bond formation (ΔH) for the MeOH-DMA and MeOH-TMA complexes have been determined by measurements of the fundamental OH-stretching transition in the temperature range from 298 to 358 K. The enthalpy of formation is found to be -35.8 ± 3.9 and -38.2 ± 3.3 kJ mol(-1) for MeOH-DMA and MeOH-TMA, respectively, in the 298 to 358 K region. The equilibrium constant (Kp) for the formation of the MeOH-DMA complex has been determined from the measured and calculated transition intensities of the OH-stretching fundamental transition and the NH-stretching second overtone transition. The transition intensities were calculated using an anharmonic oscillator local mode model with dipole moment and potential energy curves calculated using explicitly correlated coupled cluster methods. The equilibrium constant for formation of the MeOH-DMA complex was determined to be 0.2 ± 0.1 atm(-1), corresponding to a ΔG value of about 4.0 kJ mol(-1).

  8. 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.

  9. 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.

  10. 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.

  11. 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

  12. Effect-compartment equilibrium rate constant (keo) for propofol during induction of anesthesia with a target-controlled infusion device.

    PubMed

    Lim, Thiam Aun; Wong, Wai Hong; Lim, Kin Yuee

    2006-01-01

    The effect-compartment concentration (C(e)) of a drug at a specific pharmacodynamic endpoint should be independent of the rate of drug injection. We used this assumption to derive an effect-compartment equilibrium rate constant (k(eo)) for propofol during induction of anesthesia, using a target controlled infusion device (Diprifusor). Eighteen unpremedicated patients were induced with a target blood propofol concentration of 5 microg x ml(-1) (group 1), while another 18 were induced with a target concentration of 6 microg x ml(-1) (group 2). The time at loss of the eyelash reflex was recorded. Computer simulation was used to derive the rate constant (k(eo)) that resulted in the mean C(e) at loss of the eyelash reflex in group 1 being equal to that in group 2. Using this population technique, we found the k(eo) to be 0.57 min(-1). The mean (SD) effect compartment concentration at loss of the eyelash reflex was 2.39 (0.70) microg x ml(-1). This means that to achieve a desired C(e) within 3 min of induction, the initial target blood concentration should be set at 1.67 times that of the desired C(e) for 1 min, after which it should revert to the desired concentration.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. Effect of Temperature on Acidity and Hydration Equilibrium Constants of Delphinidin-3-O- and Cyanidin-3-O-sambubioside Calculated from Uni- and Multiwavelength Spectroscopic Data.

    PubMed

    Vidot, Kévin; Achir, Nawel; Mertz, Christian; Sinela, André; Rawat, Nadirah; Prades, Alexia; Dangles, Olivier; Fulcrand, Hélène; Dornier, Manuel

    2016-05-25

    Delphinidin-3-O-sambubioside and cyanidin-3-O-sambubioside are the main anthocyanins of Hibiscus sabdariffa calyces, traditionally used to make a bright red beverage by decoction in water. At natural pH, these anthocyanins are mainly in their flavylium form (red) in equilibrium with the quinonoid base (purple) and the hemiketal (colorless). For the first time, their acidity and hydration equilibrium constants were obtained from a pH-jump method followed by UV-vis spectroscopy as a function of temperature from 4 to 37 °C. Equilibrium constant determination was also performed by multivariate curve resolution (MCR). Acidity and hydration constants of cyanidin-3-O-sambubioside at 25 °C were 4.12 × 10(-5) and 7.74 × 10(-4), respectively, and were significantly higher for delphinidin-3-O-sambubioside (4.95 × 10(-5) and 1.21 × 10(-3), respectively). MCR enabled the obtaining of concentration and spectrum of each form but led to overestimated values for the equilibrium constants. However, both methods showed that formations of the quinonoid base and hemiketal were endothermic reactions. Equilibrium constants of anthocyanins in the hibiscus extract showed comparable values as for the isolated anthocyanins.

  18. Colorimetric Determination of the Iron(III)-Thiocyanate Reaction Equilibrium Constant with Calibration and Equilibrium Solutions Prepared in a Cuvette by Sequential Additions of One Reagent to the Other

    ERIC Educational Resources Information Center

    Nyasulu, Frazier; Barlag, Rebecca

    2011-01-01

    The well-known colorimetric determination of the equilibrium constant of the iron(III-thiocyanate complex is simplified by preparing solutions in a cuvette. For the calibration plot, 0.10 mL increments of 0.00100 M KSCN are added to 4.00 mL of 0.200 M Fe(NO[subscript 3])[subscript 3], and for the equilibrium solutions, 0.50 mL increments of…

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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

  4. (SO2)-S-34-O-16: High-resolution analysis of the (030),(101), (111), (002) and (201) vibrational states; determination of equilibrium rotational constants for sulfur dioxide and anharmonic vibrational constants

    SciTech Connect

    Lafferty, Walter; Flaud, Jean-marie; Ngom, El Hadji A.; Sams, Robert L.

    2009-01-02

    High resolution Fourier transform spectra of a sample of sulfur dioxide, enriched in 34S (95.3%). were completely analyzed leading to a large set of assigned lines. The experimental levels derived from this set of transitions were fit to within their experimental uncertainties using Watson-type Hamiltonians. Precise band centers, rotational and centrifugal distortion constants were determined. The following band centers in cm-1 were obtained: ν0(3ν2)=1538.720198(11), ν0(ν1+ν3)=2475.828004(29), ν0(ν1+ν2+ν3)=2982.118600(20), ν0(2ν3)=2679.800919(35), and ν0(2ν1+ν3)=3598.773915(38). The rotational constants obtained in this work have been fit together with the rotational constants of lower lying vibrational states [ W.J. Lafferty, J.-M. Flaud, R.L. Sams and EL Hadjiabib, in press] to obtain equilibrium constants as well as vibration-rotation constants. These equilibrium constants have been fit together with those of 32S16O2 [J.-M. Flaud and W.J. Lafferty, J. Mol. Spectrosc. 16 (1993) 396-402] leading to an improved equilibrium structure. Finally the observed band centers have been fit to obtain anharmonic rotational constants.

  5. 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

  6. Improved accuracy of low affinity protein-ligand equilibrium dissociation constants directly determined by electrospray ionization mass spectrometry.

    PubMed

    Jaquillard, Lucie; Saab, Fabienne; Schoentgen, Françoise; Cadene, Martine

    2012-05-01

    There is continued interest in the determination by ESI-MS of equilibrium dissociation constants (K(D)) that accurately reflect the affinity of a protein-ligand complex in solution. Issues in the measurement of K(D) are compounded in the case of low affinity complexes. Here we present a K(D) measurement method and corresponding mathematical model dealing with both gas-phase dissociation (GPD) and aggregation. To this end, a rational mathematical correction of GPD (f(sat)) is combined with the development of an experimental protocol to deal with gas-phase aggregation. A guide to apply the method to noncovalent protein-ligand systems according to their kinetic behavior is provided. The approach is validated by comparing the K(D) values determined by this method with in-solution K(D) literature values. The influence of the type of molecular interactions and instrumental setup on f(sat) is examined as a first step towards a fine dissection of factors affecting GPD. The method can be reliably applied to a wide array of low affinity systems without the need for a reference ligand or protein.

  7. Using electrophoretic mobility shift assays to measure equilibrium dissociation constants: GAL4-p53 binding DNA as a model system.

    PubMed

    Heffler, Michael A; Walters, Ryan D; Kugel, Jennifer F

    2012-01-01

    An undergraduate biochemistry laboratory experiment is described that will teach students the practical and theoretical considerations for measuring the equilibrium dissociation constant (K(D) ) for a protein/DNA interaction using electrophoretic mobility shift assays (EMSAs). An EMSA monitors the migration of DNA through a native gel; the DNA migrates more slowly when bound to a protein. To determine a K(D) the amount of unbound and protein-bound DNA in the gel is measured as the protein concentration increases. By performing this experiment, students will be introduced to making affinity measurements and gain experience in performing quantitative EMSAs. The experiment describes measuring the K(D) for the interaction between the chimeric protein GAL4-p53 and its DNA recognition site; however, the techniques are adaptable to other DNA binding proteins. In addition, the basic experiment described can be easily expanded to include additional inquiry-driven experimentation. © 2012 by The International Union of Biochemistry and Molecular Biology.

  8. 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.

  9. 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.

  10. 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).

  11. 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.

  12. 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

  13. 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.

  14. 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.

  15. 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.

  16. Why Does the Human Body Maintain a Constant 37-Degree Temperature?: Thermodynamic Switch Controls Chemical Equilibrium in Biological Systems

    NASA Astrophysics Data System (ADS)

    Chun, Paul W.

    2005-01-01

    Applying the Planck-Benzinger methodology to biological systems, we have established that the negative Gibbs free energy minimum at a well-defined stable temperature, langTSrang, where the bound unavailable energy TΔS° = 0, has its origin in the sequence-specific hydrophobic interactions. Each such system we have examined confirms the existence of a thermodynamic molecular switch wherein a change of sign in [ΔCp°]reaction leads to a true negative minimum in the Gibbs free energy change of reaction, and hence a maximum in the related equilibrium constant, Keq. At this temperature, langTSrang, where ΔH°(TS)(-) = ΔG°(TS)(-)min, the maximum work can be accomplished in transpiration, digestion, reproduction or locomotion. In the human body, this temperature is 37°C. The langTSrang values may vary from one living organism to another, but the fact that the value of TΔS°(T) = 0 will not. There is a lower cutoff point, langThrang, where enthalpy is unfavorable but entropy is favorable, i.e. ΔH°(Th)(+) = TΔS°(Th)(+), and an upper limit, langTmrang, above which enthalpy is favorable but entropy is unfavorable, i.e. ΔH°(Tm)(-) = TΔS°(Tm)(-). Only between these two temperature limits, where ΔG°(T) = 0, is the net chemical driving force favorable for such biological processes as protein folding, protein-protein, protein-nucleic acid or protein-membrane interactions, and protein self-assembly. All interacting biological systems examined using the Planck-Benzinger methodology have shown such a thermodynamic switch at the molecular level, suggesting that its existence may be universal.

  17. Determination of equilibrium and rate constants for complex formation by fluorescence correlation spectroscopy supplemented by dynamic light scattering and Taylor dispersion analysis.

    PubMed

    Zhang, Xuzhu; Poniewierski, Andrzej; Jelińska, Aldona; Zagożdżon, Anna; Wisniewska, Agnieszka; Hou, Sen; Hołyst, Robert

    2016-10-04

    The equilibrium and rate constants of molecular complex formation are of great interest both in the field of chemistry and biology. Here, we use fluorescence correlation spectroscopy (FCS), supplemented by dynamic light scattering (DLS) and Taylor dispersion analysis (TDA), to study the complex formation in model systems of dye-micelle interactions. In our case, dyes rhodamine 110 and ATTO-488 interact with three differently charged surfactant micelles: octaethylene glycol monododecyl ether C12E8 (neutral), cetyltrimethylammonium chloride CTAC (positive) and sodium dodecyl sulfate SDS (negative). To determine the rate constants for the dye-micelle complex formation we fit the experimental data obtained by FCS with a new form of the autocorrelation function, derived in the accompanying paper. Our results show that the association rate constants for the model systems are roughly two orders of magnitude smaller than those in the case of the diffusion-controlled limit. Because the complex stability is determined by the dissociation rate constant, a two-step reaction mechanism, including the diffusion-controlled and reaction-controlled rates, is used to explain the dye-micelle interaction. In the limit of fast reaction, we apply FCS to determine the equilibrium constant from the effective diffusion coefficient of the fluorescent components. Depending on the value of the equilibrium constant, we distinguish three types of interaction in the studied systems: weak, intermediate and strong. The values of the equilibrium constant obtained from the FCS and TDA experiments are very close to each other, which supports the theoretical model used to interpret the FCS data.

  18. Understanding Chemical Equilibrium Using Entropy Analysis: The Relationship between [delta]S[subscript tot](sys[superscript o]) and the Equilibrium Constant

    ERIC Educational Resources Information Center

    Bindel, Thomas H.

    2010-01-01

    Entropy analyses as a function of the extent of reaction are presented for a number of physicochemical processes, including vaporization of a liquid, dimerization of nitrogen dioxide, and the autoionization of water. Graphs of the total entropy change versus the extent of reaction give a visual representation of chemical equilibrium and the second…

  19. A simple method for estimating equilibrium constants for serum testosterone binding resulting in an optimal free testosterone index for use in elderly men.

    PubMed

    Ross, H Alec; Meuleman, Eric J; Sweep, Fred C G J

    2005-01-01

    An algorithm was developed to evaluate equilibrium constants for testosterone (Te) and sex hormone-binding globulin (SHBG) or albumin from serum free testosterone (FTe) measurements performed in a panel of 30 healthy elderly men by means of a near-reference method, i.e., symmetric dialysis (affinity constants: SHBG-Te, 1.13 x 10(9) L/mol; albumin-Te, 4.4 x 10(4) L/mol). Using these estimates, a free testosterone index (FTeI) was calculated from total Te and SHBG concentrations in a further 35 elderly men. This FTeI perfectly matches with actually measured free testosterone concentrations by symmetric dialysis in this second group, with a mean ratio index/measurement of 0.998+/-0.016 (SEM). The efficacy of the algorithm, which represents a simple alternative to previous cumbersome methods for estimation of equilibrium constants, is thereby demonstrated.

  20. 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.

  1. 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.

  2. 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

  3. The binding of cytochrome c peroxidase and ferricytochrome c. A spectrophotometric determination of the equilibrium association constant as a function of ionic strength.

    PubMed

    Erman, J E; Vitello, L B

    1980-07-10

    Complex formation between cytochrome c peroxidase and ferricytochrome c perturbs the optical absorption spectrum in the Soret band by about 2%. This perturbation can be utilized as a measure of the complex formed in solution and permits the determination of the stoichiometry and the equilibrium association constant for this reaction. At pH 6, in cacodylate/KNO3 buffers, only a 1:1 complex between cytochrome c peroxidase and ferricytochrome c is detected. The equilibrium association constant for the complex has been determined as a function of ionic strength and varies between (6.0 +/- 3.6) x 10(6) M-1 and (2.2 +/- 1.9) x 10(6) M-1 over the ionic strength range 0.01 M to 0.20 M.

  4. Determination of equilibrium constants and computational interaction energies for adducts of [Rh2(RCO2)(4-n)(PC)n] (n = 0-2) with Lewis bases.

    PubMed

    Hirva, Pipsa; Esteban, Julio; Lloret, Julio; Lahuerta, Pascual; Pérez-Prieto, Julia

    2007-04-02

    Properties of dirhodium catalysts with cyclometalated aryl phosphine ligands have been studied. We report here the study of the acid-base reaction of Rh2(RCO2)2(PC)2(H2O)2 catalysts (PC = cyclometalated aryl phosphine) with different Lewis bases. The determination of the equilibrium constants of these reactions can be used to study to which extent the properties of the axial coordination site of the catalyst, considered the active site, are affected by modification of the metalated phosphines, the carboxylate ligands, or the incoming axial ligand. The trends in the computational density functional theory interaction energies show good agreement with the major trends in the equilibrium constants, thus enabling a further study of the influence of the modification of the ligand core.

  5. Association-dissociation of the flavoprotein hog kidney D-amino acid oxidase. Determination of the monomer-dimer equilibrium constant and the energetics of subunit association.

    PubMed

    Horiike, K; Shiga, K; Nishina, Y; Isomoto, A; Yamano, T

    1977-11-01

    The enzyme concentration dependence of spectrophotometric titrations of hog kidney D-amino acid oxidase [EC 1.4.3.3] with p-aminobenzoate was studied. The monomer-dimer equilibrium constant of the oxidized holoenzyme at 25 degrees C was estimated to be 7 X 10(5)M-1 at pH 7.5 and 4X 10(6)M-1 at pH 8.3. The energetics of subunit association are discussed.

  6. 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.

  7. Analysis of responsive characteristics of ionic-strength-sensitive hydrogel with consideration of effect of equilibrium constant by a chemo-electro-mechanical model.

    PubMed

    Li, Hua; Lai, Fukun; Luo, Rongmo

    2009-11-17

    A multiphysics model is presented in this paper for analysis of the influence of various equilibrium constants on the smart hydrogel responsive to the ionic strength of environmental solution, and termed the multieffect-coupling ionic-strength stimulus (MECis) model. The model is characterized by a set of partial differential governing equations by consideration of the mass and momentum conservations of the system and coupled chemical, electrical, and mechanical multienergy domains. The Nernst-Planck equations are derived by the mass conservation of the ionic species in both the interstitial fluid of the hydrogel and the surrounding solution. The binding reaction between the fixed charge groups of the hydrogel and the mobile ions in the solution is described by the fixed charge equation, which is based on the Langmuir monolayer theory. As an important effect for the binding reaction, the equilibrium constant is incorporated into the fixed charge equation. The kinetics of the hydrogel swelling/deswelling is illustrated by the mechanical equation, based on the law of momentum conservation for the solid polymeric networks matrix within the hydrogel. The MECis model is examined by comparison of the numerical simulations and experiments from open literature. The analysis of the influence of different equilibrium constants on the responsive characteristics of the ionic-strength-sensitive hydrogel is carried out with detailed discussion.

  8. Distinguishing between keto-enol and acid-base forms of firefly oxyluciferin through calculation of excited-state equilibrium constants.

    PubMed

    Falklöf, Olle; Durbeej, Bo

    2014-11-15

    Although recent years have seen much progress in the elucidation of the mechanisms underlying the bioluminescence of fireflies, there is to date no consensus on the precise contributions to the light emission from the different possible forms of the chemiexcited oxyluciferin (OxyLH2) cofactor. Here, this problem is investigated by the calculation of excited-state equilibrium constants in aqueous solution for keto-enol and acid-base reactions connecting six neutral, monoanionic and dianionic forms of OxyLH2. Particularly, rather than relying on the standard Förster equation and the associated assumption that entropic effects are negligible, these equilibrium constants are for the first time calculated in terms of excited-state free energies of a Born-Haber cycle. Performing quantum chemical calculations with density functional theory methods and using a hybrid cluster-continuum approach to describe solvent effects, a suitable protocol for the modeling is first defined from benchmark calculations on phenol. Applying this protocol to the various OxyLH2 species and verifying that available experimental data (absorption shifts and ground-state equilibrium constants) are accurately reproduced, it is then found that the phenolate-keto-OxyLH(-) monoanion is intrinsically the preferred form of OxyLH2 in the excited state, which suggests a potential key role for this species in the bioluminescence of fireflies.

  9. 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.

  10. Solvent extraction of silver picrate by 3m-crown-m ethers (m = 5, 6) and its mono-benzo-derivative from water into benzene or chloroform: elucidation of an extraction equilibrium using component equilibrium constants.

    PubMed

    Kudo, Yoshihiro; Usami, Jun; Katsuta, Shoichi; Takeda, Yasuyuki

    2004-03-10

    Ion-pair formation constant (K(AgPic) in mol(-1)dm(3)) of silver picrate (AgPic), those (K(AgLPic)) of its ion-pair complexes (AgLPic) with crown ethers (L) and complex formation constants (K(AgL)) of Ag(+) with L (15-crown-5 ether (15C5) and benzo-15C5) in water (w) were determined potentiometrically at 25 degrees C. Compounds used as L were 18-crown-6 ether (18C6), its benzo-derivative (B18C6) and the two 15C5 derivatives. Extraction constants (K(ex) in mol(-1)dm(3)) of AgPic with L (15C5, 18C6, B18C6) from acidic w-phases into either C(6)H(6) or CHCl(3) were recalculated from K(AgPic), K(AgL), K(AgLPic) and data opened in previous papers. Thus obtained K(ex) was divided into five component equilibrium constants containing K(AgL) and K(AgLPic) anew. Then, contributions of the component constants, K(AgL), K(AgLPic) and distribution constants of AgLPic between the w- and C(6)H(6)-phases, to K(ex) were discussed and compared with corresponding extraction systems of NaPic and KPic with18C6.

  11. Label-Free Kinetics: Exploiting Functional Hemi-Equilibrium to Derive Rate Constants for Muscarinic Receptor Antagonists.

    PubMed

    Riddy, Darren M; Valant, Celine; Rueda, Patricia; Charman, William N; Sexton, Patrick M; Summers, Roger J; Christopoulos, Arthur; Langmead, Christopher J

    2015-10-01

    Drug receptor kinetics is as a key component in drug discovery, development, and efficacy; however, determining kinetic parameters has historically required direct radiolabeling or competition with a labeled tracer. Here we present a simple approach to determining the kinetics of competitive antagonists of G protein-coupled receptors by exploiting the phenomenon of hemi-equilibrium, the state of partial re-equilibration of agonist, antagonist, and receptor in some functional assays. Using functional [Ca(2+)]i-flux and extracellular kinases 1 and 2 phosphorylation assays that have short incubation times and therefore are prone to hemi-equilibrium "behaviors," we investigated a wide range of structurally and physicochemically distinct muscarinic acetylcholine receptor antagonists. Using a combined operational and hemi-equilibrium model of antagonism to both simulate and analyze data, we derived estimates of association and dissociation rates for the test set of antagonists, identifying both rapidly dissociating (4-DAMP, himbacine) and slowly dissociating (tiotropium, glycopyrrolate) ligands. The results demonstrate the importance of assay incubation time and the degree of receptor reserve in applying the analytical model. There was an excellent correlation between estimates of antagonist pK(B), k(on), and k(off) from functional assays and those determined by competition kinetics using whole-cell [(3)H]N-methylscopolamine binding, validating this approach as a rapid and simple method to functionally profile receptor kinetics of competitive antagonists in the absence of a labeled tracer.

  12. 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.

  13. 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.

  14. 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).

  15. Beyond transition state theory: accurate description of nuclear quantum effects on the rate and equilibrium constants of chemical reactions using Feynman path integrals.

    PubMed

    Vanícek, Jirí

    2011-01-01

    Nuclear tunneling and other nuclear quantum effects have been shown to play a significant role in molecules as large as enzymes even at physiological temperatures. I discuss how these quantum phenomena can be accounted for rigorously using Feynman path integrals in calculations of the equilibrium and kinetic isotope effects as well as of the temperature dependence of the rate constant. Because these calculations are extremely computationally demanding, special attention is devoted to increasing the computational efficiency by orders of magnitude by employing efficient path integral estimators.

  16. The equilibrium constant for N2O5 = NO2 + NO3 - Absolute determination by direct measurement from 243 to 397 K

    NASA Technical Reports Server (NTRS)

    Cantrell, C. A.; Davidson, J. A.; Mcdaniel, A. H.; Shetter, R. E.; Calvert, J. G.

    1988-01-01

    Direct determinations of the equilibrium constant for the reaction N2O5 = NO2 + NO3 were carried out by measuring NO2, NO3, and N2O5 using long-path visible and infrared absorption spectroscopy as a function of temperature from 243 to 397 K. The first-order decay rate constant of N2O5 was experimentally measured as a function of temperature. These results are in turn used to derive a value for the rate coefficient for the NO-forming channel in the reaction of NO3 with NO2. The implications of the results for atmospheric chemistry, the thermodynamics of NO3, and for laboratory kinetics studies are discussed.

  17. 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.

  18. 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.

  19. 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).

  20. Laser flash photolysis generation and kinetic studies of porphyrin-manganese-oxo intermediates. Rate constants for oxidations effected by porphyrin-Mn(V)-oxo species and apparent disproportionation equilibrium constants for porphyrin-Mn(IV)-oxo species.

    PubMed

    Zhang, Rui; Horner, John H; Newcomb, Martin

    2005-05-11

    Porphyrin-manganese(V)-oxo and porphyrin-manganese(IV)-oxo species were produced in organic solvents by laser flash photolysis (LFP) of the corresponding porphyrin-manganese(III) perchlorate and chlorate complexes, respectively, permitting direct kinetic studies. The porphyrin systems studied were 5,10,15,20-tetraphenylporphyrin (TPP), 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (TPFPP), and 5,10,15,20-tetrakis(4-methylpyridinium)porphyrin (TMPyP). The order of reactivity for (porphyrin)Mn(V)(O) derivatives in self-decay reactions in acetonitrile and in oxidations of substrates was (TPFPP) > (TMPyP) > (TPP). Representative rate constants for reaction of (TPFPP)Mn(V)(O) in acetonitrile are k = 6.1 x 10(5) M(-1) s(-1) for cis-stilbene and k = 1.4 x 10(5) M(-1) s(-1) for diphenylmethane, and the kinetic isotope effect in oxidation of ethylbenzene and ethylbenzene-d(10) is k(H)/k(D) = 2.3. Competitive oxidation reactions conducted under catalytic conditions display approximately the same relative rate constants as were found in the LFP studies of (porphyrin)Mn(V)(O) derivatives. The apparent rate constants for reactions of (porphyrin)Mn(IV)(O) species show inverted reactivity order with (TPFPP) < (TMPyP) < (TPP) in reactions with cis-stilbene, triphenylamine, and triphenylphosphine. The inverted reactivity results because (porphyrin)Mn(IV)(O) disproportionates to (porphyrin)Mn(III)X and (porphyrin)Mn(V)(O), which is the primary oxidant, and the equilibrium constants for disproportionation of (porphyrin)Mn(IV)(O) are in the order (TPFPP) < (TMPyP) < (TPP). The fast comproportionation reaction of (TPFPP)Mn(V)(O) with (TPFPP)Mn(III)Cl to give (TPFPP)Mn(IV)(O) (k = 5 x 10(8) M(-1) s(-1)) and disproportionation reaction of (TPP)Mn(IV)(O) to give (TPP)Mn(V)(O) and (TPP)Mn(III)X (k approximately 2.5 x 10(9) M(-1) s(-1)) were observed. The relative populations of (porphyrin)Mn(V)(O) and (porphyrin)Mn(IV)(O) were determined from the ratios of observed rate constants for

  1. Fourier Transform Microwave Spectrum of Propene-3-d1 (CH2=CHCH2D), Quadrupole Coupling Constants of Deuterium and a Semiexperimental Equilibrium Structure of Propene.

    PubMed

    Demaison, Jean; Craig, Norman C; Gurusinghe, Ranil Malaka; Tubergen, Michael John; Rudolph, Heinz Dieter; Coudert, Laurent H; Szalay, Peter G; Császár, Attila G

    2017-04-03

    The ground state rotational spectrum of propene-3-d1, CH2=CHCH2D, was measured by Fourier transform microwave spectroscopy. Transitions were assigned for the two conformers, one with the D atom in the symmetry plane (S) and the other with the D atom out of plane (A). The energy difference between the two conformers was calculated to be 6.5 cm-1, the S conformer having lower energy. The quadrupole hyperfine structure due to deuterium was resolved and analyzed for the two conformers. The experimental quadrupole coupling and the centrifugal distortion constants compared favorably to their ab initio counterparts. Ground state rotational constants for the S conformer are 40582.157(9), 9067.024(1), and 7766.0165(12) MHz. Ground state rotational constants for the A conformer are 43403.75(3), 8658.961(2), and 7718.247(2) MHz. For the A conformer, a small tunneling splitting (19 MHz) due to internal rotation was observed and analyzed. Using the new rotational constants of this work as well as those previously determined for the 13C species and for some deuterium-substituted species from the literature, a new semiexperimental equilibrium structure was determined and its high accuracy was confirmed. The difficulty in obtaining accurate coordinates for the out-of-plane hydrogen atom is discussed.

  2. 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

  3. 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.

  4. 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.

  5. 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.

  6. Refining thermodynamic constants for mercury(II)-sulfides in equilibrium with metacinnabar at sub-micromolar aqueous sulfide concentrations.

    PubMed

    Drott, A; Björn, E; Bouchet, S; Skyllberg, U

    2013-05-07

    An important issue in mercury (Hg) biogeochemistry is to explore the influence of aqueous Hg(II) forms on bacterial uptake, and subsequent methyl mercury formation, under iron(III) and sulfate reducing conditions. The success of this is dependent on relevant information on the thermodynamic stability of Hg-sulfides. In the present study, we determined the solubility of a commercially available HgS(s) phase, which was shown by X-ray diffraction to be a mixture of 83% metacinnabar and 17% cinnabar. At aqueous sulfide concentrations between 0.060 and 84 μM, well below levels in previous studies, we report a solubility product (log Ksp ± SE) of -36.8 ± 0.1 (HgS(s) + H(+) = Hg(2+) + HS(-), I = 0, T = 25 °C, pH 6-10, n = 20) for metacinnabar. This value is 0.7 log units higher than previous estimates. Complementing our data with data from Paquette and Helz (1997), we took advantage of a large data set (n = 65) covering a wide range of aqueous sulfide (0.06 μM-140 mM) and pH (1-11). On the basis of this, we report refined formation constants (±SE) for the three aqueous Hg(II)-sulfide species proposed by Schwarzenbach and Widmer (1963): Hg(2+) + 2HS(-) = Hg(SH)2(0); log K = 39.1 ± 0.1, Hg(2+) + 2HS(-) = HgS2H(-) + H(+); log K = 32.5 ± 0.1, Hg(2+) + 2HS(-) = HgS2(2-) + 2H(+); log K = 23.2 ± 0.1. Our refined log K values differ from previous estimates by 0.2-0.6 log units. Furthermore, at the low sulfide concentrations in our study we could rule out the value of -10.0 for the reaction HgS(s) + H2O = HgOHSH(aq) as reported by Dyrssén and Wedborg (1991). By establishing a solubility product for the most environmentally relevant HgS(s) phase, metacinnabar, and extending the range of aqueous sulfide concentrations to sub-micromolar levels, relevant for soils, sediments, and waters, this study decreases the uncertainty in stability constants for Hg-sulfides, thereby improving the basis for understanding the bioavailability and mobility of Hg(II) in the environment.

  7. Equilibrium and rate constants, and reaction mechanism of the HF dissociation in the HF(H2O)7 cluster by ab initio rare event simulations.

    PubMed

    Elena, Alin Marin; Meloni, Simone; Ciccotti, Giovanni

    2013-12-12

    We perform restrained hybrid Monte Carlo (MC) simulations to compute the equilibrium constant of the dissociation reaction of HF in HF(H2O)7. We find that the HF is a stronger acid in the cluster than in the bulk, and its acidity is higher at lower T. The latter phenomenon has a vibrational entropic origin, resulting from a counterintuitive balance of intra- and intermolecular terms. We find also a temperature dependence of the reactions mechanism. At low T (≤225 K) the dissociation reaction follows a concerted path, with the H atoms belonging to the relevant hydrogen bond chain moving synchronously. At higher T (300 K), the first two hydrogen atoms move together, forming an intermediate metastable state having the structure of an eigen ion (H9O4(+)), and then the third hydrogen migrates completing the reaction. We also compute the dissociation rate constant, kRP. At very low T (≤75 K) kRP depends strongly on the temperature, whereas it gets almost constant at higher T’s. With respect to the bulk, the HF dissociation in the HF(H2O)7 is about 1 order of magnitude faster. This is due to a lower free energy barrier for the dissociation in the cluster.

  8. A new nuclear magnetic resonance algorithm to determine equilibrium constants of the species in the B(III)-H2O system.

    PubMed

    Botello, J C; Morales-Domínguez, E; Domínguez, J M; Gutiérrez, A; Rojas-Hernández, A; Ramírez, M T

    2003-05-01

    Several efforts have been attempted to study species formation by Nuclear Magnetic Resonance (NMR) in systems with several chemical equilibria present. The majority of these are qualitative and only a few have tried to relate component fractions of a distribution diagram with experimental area fractions determined from NMR spectra to obtain equilibrium constants values. In this work we present a new focus that attempts to relate the species concentration fractions in the system with area fractions beneath NMR peaks to achieve this task. 11B-NMR data of B(III)-H2O systems have been processed with the aid of formation constant values (-log *beta) obtained by potentiometry which are 9.17+/-0.01 for B(OH)3, 9.79+/-0.08 for B2O(OH)5-, 19.90+/-0.09 for B3O3(OH)4- and 38.50+/-0.04 for B5O6(OH)4-, form B(III)-H2O systems with 0.075 M< or = [B(III)]total< or = 0.700 M, in agreement with previous reports and NMR behavior. The treatment of NMR data developed in this work gives a new methodology to obtain formation constants and suggests the possibility to establish a generalization of Beer's law to NMR spectroscopy.

  9. Comparative study of the dynamic gravimetric and pulse chromatographic methods for the determination of Henry constants of adsorption for VOC zeolite systems

    NASA Astrophysics Data System (ADS)

    Nokerman, J.; Canet, X.; Mougin, P.; Limborg-Noetinger, S.; Frère, M.

    2005-09-01

    In this paper, we propose a comparative study between a gravimetric apparatus operating under dynamic conditions and a pulse chromatographic device developed for the determination of Henry constants of adsorption for VOC-zeolite systems. In both cases, we provide a description of the experimental set-up and procedure, as well as a complete report on the treatment of the rough experimental data. The experimental errors are also discussed. The comparison work is based on the study of the adsorption of toluene on a NaY zeolite (Si/Al 2.43) for temperatures ranging from 503 to 623 K. The maximal discrepancy found between the experimental Henry constants was 15.0%. The pulse chromatographic method is only dedicated to high-temperature measurements. For low-temperature experiments, the rough data cannot be treated in an efficient way, and it is not possible to obtain reliable Henry constant values. The dynamic gravimetric method is not temperature limited. It is however time-consuming, especially when low-temperature measurements (not presented in this paper) are concerned. Both methods are complementary if the determination of Henry constants is required in a wide temperature range.

  10. Modulation of the adsorption properties at air-water interfaces of complexes of egg white ovalbumin with pectin by the dielectric constant.

    PubMed

    Kudryashova, Elena V; de Jongh, Harmen H J

    2008-02-15

    The possibility of modulating the mesoscopic properties of food colloidal systems by the dielectric constant is studied by determining the impact of small amounts of ethanol (10%) on the adsorption of egg white ovalbumin onto the air-water interface in the absence and presence of pectin. The adsorption kinetics was monitored using tensiometry. The addition of ethanol resulted in considerably slower adsorption of the protein onto the interface, and this effect was enhanced when the protein was in complex with the pectin. Time-resolved fluorescence measurements demonstrated that in the case of noncomplexed ovalbumin the addition of ethanol resulted in a more condensed protein surface layer where ovalbumin adopted a preferred orientation at the interface. In contrast, the effect of ethanol on the ovalbumin-pectin complex suggested a pronounced multipoint electrostatic interaction between protein and polyelectrolyte and the formation of a more rigid spatial arrangement within the complex, thereby leading to suppressed protein-protein interactions. From this work it is concluded that by the enhanced binding affinity between ovalbumin and pectin a strong effect on the adsorption properties of the protein can be accomplished. This work does therefore illustrate how solvent quality can be exploited effectively to enhance or suppress protein functional behavior in complex applications containing air-water interfaces.

  11. 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...

  12. Reversible hydrogen transfer reactions in thiyl radicals from cysteine and related molecules: absolute kinetics and equilibrium constants determined by pulse radiolysis.

    PubMed

    Nauser, Thomas; Koppenol, Willem H; Schöneich, Christian

    2012-05-10

    The mercapto group of cysteine (Cys) is a predominant target for oxidative modification, where one-electron oxidation leads to the formation of Cys thiyl radicals, CysS(•). These Cys thiyl radicals enter 1,2- and 1,3-hydrogen transfer reactions, for which rate constants are reported in this paper. The products of these 1,2- and 1,3-hydrogen transfer reactions are carbon-centered radicals at position C(3) (α-mercaptoalkyl radicals) and C(2) ((•)C(α) radicals) of Cys, respectively. Both processes can be monitored separately in Cys analogues such as cysteamine (CyaSH) and penicillamine (PenSH). At acidic pH, thiyl radicals from CyaSH permit only the 1,2-hydrogen transfer according to equilibrium 12, (+)H(3)NCH(2)CH(2)S(• )⇌ (+)H(3)NCH(2)(•)CH-SH, where rate constants for forward and reverse reaction are k(12) ≈ 10(5) s(-1) and k(-12) ≈ 1.5 × 10(5)s(-1), respectively. In contrast, only the 1,3-hydrogen transfer is possible for thiyl radicals from PenSH according to equilibrium 14, ((+)H(3)N/CO(2)H)C(α)-C(CH(3))(2)-S(•) ⇌ ((+)H(3)N/CO(2)H)(•)C(α)-C(CH(3))(2)-SH, where rate constants for the forward and the reverse reaction are k(14) = 8 × 10(4) s(-1) and k(-14) = 1.4 × 10(6) s(-1). The (•)C(α) radicals from PenSH and Cys have the additional opportunity for β-elimination of HS(•)/S(•-), which proceeds with k(39) ≈ (3 ± 1) × 10(4) s(-1) from (•)C(α) radicals from PenSH and k(-34) ≈ 5 × 10(3) s(-1) from (•)C(α) radicals from Cys. The rate constants quantified for the 1,2- and 1,3-hydrogen transfer reactions can be used as a basis to calculate similar processes for Cys thiyl radicals in proteins, where hydrogen transfer reactions, followed by the addition of oxygen, may lead to the irreversible modification of target proteins.

  13. Three rotor potential energy scans, conformational equilibrium constants and vibrational analysis of 3-fluoro-1-propanol CH(2)FCH(2)CH(2)OH.

    PubMed

    Badawi, Hassan M; Förner, Wolfgang; Ali, Shaikh A

    2008-01-01

    The conformational stability and the three rotor internal rotations in 3-fluoro-1-propanol were investigated by the DFT-B3LYP/6-311+G** and the ab initio MP2/6-311+G** levels of theory. The calculated potential energy curves of the molecule at both levels of theory were consistent with complex conformational equilibria of about 12 minima, all of which were predicted to have real frequencies at both the B3LYP and the MP2 levels. The lowest energy minimum in the potential curves of 3-fluoro-1-propanol was predicted to correspond to the Gauche-gauche-trans (Ggt) conformer in excellent agreement with microwave and electron diffraction results. The equilibrium constants for the conformational interconversion of the molecule were calculated and found to correspond to an equilibrium mixture of about 33% Ggt, 14% Ggg1 and 13% Gg1g and about 43% Ggt, 12% Ggg1 and 10% Gg1g distribution by the B3LYP/6-311+G** and the MP2/6-311+G** calculations, respectively, at 298.15K. The vibrational frequencies of each molecule in its three stable forms were computed at B3LYP level and complete vibrational assignments were made based on normal coordinate calculations and comparison with experimental data of the molecule.

  14. Basis for the equilibrium constant in the interconversion of l-lysine and l-beta-lysine by lysine 2,3-aminomutase.

    PubMed

    Chen, Dawei; Tanem, Justinn; Frey, Perry A

    2007-02-01

    l-beta-lysine and beta-glutamate are produced by the actions of lysine 2,3-aminomutase and glutamate 2,3-aminomutase, respectively. The pK(a) values have been titrimetrically measured and are for l-beta-lysine: pK(1)=3.25 (carboxyl), pK(2)=9.30 (beta-aminium), and pK(3)=10.5 (epsilon-aminium). For beta-glutamate the values are pK(1)=3.13 (carboxyl), pK(2)=3.73 (carboxyl), and pK(3)=10.1 (beta-aminium). The equilibrium constants for reactions of 2,3-aminomutases favor the beta-isomers. The pH and temperature dependencies of K(eq) have been measured for the reaction of lysine 2,3-aminomutase to determine the basis for preferential formation of beta-lysine. The value of K(eq) (8.5 at 37 degrees C) is independent of pH between pH 6 and pH 11; ruling out differences in pK-values as the basis for the equilibrium constant. The K(eq)-value is temperature-dependent and ranges from 10.9 at 4 degrees C to 6.8 at 65 degrees C. The linear van't Hoff plot shows the reaction to be enthalpy-driven, with DeltaH degrees =-1.4 kcal mol(-1) and DeltaS degrees =-0.25 cal deg(-1) mol(-1). Exothermicity is attributed to the greater strength of the bond C(beta)-N(beta) in l-beta-lysine than C(alpha)-N(alpha) in l-lysine, and this should hold for other amino acids.

  15. Rate and equilibrium constant of the reaction of 1-methylvinoxy radicals with O2: CH3COCH2 + O2<--> CH3COCH2O2.

    PubMed

    Hassouna, Melynda; Delbos, Eric; Devolder, Pascal; Viskolcz, Bela; Fittschen, Christa

    2006-06-01

    The reaction of 1-methylvinoxy radicals, CH3COCH2, with molecular oxygen has been investigated by experimental and theoretical methods as a function of temperature (291-520 K) and pressure (0.042-10 bar He). Experiments have been performed by laser photolysis coupled to a detection of 1-methylvinoxy radicals by laser-induced fluorescence LIF. The potential energy surface calculations were performed using ab inito molecular orbital theory at the G3MP2B3 and CBSQB3 level of theory based on the density function theory optimized geometries. Derived molecular properties of the characteristic points of the potential energy surface were used to describe the mechanism and kinetics of the reaction under investigation. At 295 K, no pressure dependence of the rate constant for the association reaction has been observed: k(1,298K) = (1.18 +/- 0.04) x 10(-12) cm3 s(-1). Biexponential decays have been observed in the temperature range 459-520 K and have been interpreted as an equilibrium reaction. The temperature-dependent equilibrium constants have been extracted from these decays and a standard reaction enthalpy of deltaH(r,298K) = -105.0 +/- 2.0 kJ mol(-1) and entropy of deltaS(r,298K) = -143.0 +/- 4.0 J mol(-1) K(-1) were derived, in excellent agreement with the theoretical results. Consistent heats of formation for the vinoxy and the 1-methylvinoxy radical as well as their O2 adducts are recommended based on our complementary experimental and theoretical study deltaH(f,298K) = 13.0 +/- 2.0, -32. 9+/- 2.0, -85.9 +/- 4.0, and -142.1 +/- 4.0 kJ mol(-1) for CH2CHO, CH3COCH2 radicals, and their adducts, respectively.

  16. ATP sulfurylase-dependent assays for inorganic pyrophosphate: applications to determining the equilibrium constant and reverse direction kinetics of the pyrophosphatase reaction, magnesium binding to orthophosphate, and unknown concentrations of pyrophosphate.

    PubMed

    Daley, L A; Renosto, F; Segel, I H

    1986-09-01

    A continuous, coupled, spectrophotometric assay is described in which the enzyme ATP sulfurylase is employed to measure the concentration of inorganic pyrophosphate (PPi) at equilibrium with known concentrations of inorganic orthophosphate (Pi) in the presence of excess inorganic pyrophosphatase (PPitase). In agreement with previous reports, the apparent equilibrium constant (Keq,app) of the PPi hydrolysis reaction was shown to decrease as the concentration of Mg2+ is increased. At pH 7.3, 30 degrees C, in the presence of 150 mM NaCl and 1 mM free Mg2+, Keq,app (calculated as [Pi]t2/[PPi]t) was 1950. Measurements of Keq,app at different total concentrations of Mg2+ and Pi permitted the determination of K0, the dissociation constant of the Mg-Pi complex. In 0.05 M Tris-Cl, pH 8.0, at 30 degrees C, K0 was 3.6 mM. In the presence of excess ATP sulfurylase, yeast PPitase catalyzed PPi formation from Pi with a specific activity (Vmax) of 9 units X mg protein-1 at pH 8.0, 30 degrees C, and 1 mM free Mg2+. Half-maximum reverse reaction velocity was observed at a total Pi concentration of 18 mM. (Under the same conditions, Vmax of the PPi hydrolysis reaction was 530 units X mg protein-1.) A radiochemical end point ("reaction-to-completion") assay for measuring unknown concentrations of PPi was devised. In the presence of excess 35S-adenosine-5'-phosphosulfate ([35S]APS) as the cosubstrate, 35SO2-4 formation was stoichiometric with added PPi. (The 35SO2-4 and [35S]APS are separated by adsorption of the latter onto charcoal.) The sensitivity of the assay can be adjusted by varying the specific radioactivity of the [35S]APS. In the absence of interfering substances, as little as 2 pmol of PPi per 1.0 ml assay volume can be measured. The sensitivity of the assay is reduced in the presence of ATP plus perchlorate (which synergistically inhibit the enzyme). However, if the bulk of the ATP is removed from perchloric acid extracts of tissues with glucose and hexokinase, initial

  17. 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.

  18. Equilibrium binding constants for Tl+ with gramicidins A, B and C in a lysophosphatidylcholine environment determined by 205Tl nuclear magnetic resonance spectroscopy.

    PubMed Central

    Hinton, J F; Koeppe, R E; Shungu, D; Whaley, W L; Paczkowski, J A; Millett, F S

    1986-01-01

    Nuclear Magnetic Resonance (NMR) 205Tl spectroscopy has been used to monitor the binding of Tl+ to gramicidins A, B, and C packaged in aqueous dispersions of lysophosphatidylcholine. For 5 mM gramicidin dimer in the presence of 100 mM lysophosphatidylcholine, only approximately 50% or less of the gramicidin appears to be accessible to Tl+. Analysis of the 205Tl chemical shift as a function of Tl+ concentration over the 0.65-50 mM range indicates that only one Tl+ ion can be bound by gramicidin A, B, or C under these experimental conditions. In this system, the Tl+ equilibrium binding constant is 582 +/- 20 M-1 for gramicidin 1949 +/- 100 M-1 for gramicidin B, and 390 +/- 20 M-1 for gramicidin C. Gramicidin B not only binds Tl+ more strongly but it is also in a different conformational state than that of A and C, as shown by Circular Dichroism spectroscopy. The 205Tl NMR technique can now be extended to determinations of binding constants of other cations to gramicidin by competition studies using a 205Tl probe. PMID:2420383

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. Oligomer formation of the bacterial second messenger c-di-GMP: reaction rates and equilibrium constants indicate a monomeric state at physiological concentrations.

    PubMed

    Gentner, Martin; Allan, Martin G; Zaehringer, Franziska; Schirmer, Tilman; Grzesiek, Stephan

    2012-01-18

    Cyclic diguanosine-monophosphate (c-di-GMP) is a bacterial signaling molecule that triggers a switch from motile to sessile bacterial lifestyles. This mechanism is of considerable pharmaceutical interest, since it is related to bacterial virulence, biofilm formation, and persistence of infection. Previously, c-di-GMP has been reported to display a rich polymorphism of various oligomeric forms at millimolar concentrations, which differ in base stacking and G-quartet interactions. Here, we have analyzed the equilibrium and exchange kinetics between these various forms by NMR spectroscopy. We find that the association of the monomer into a dimeric form is in fast exchange (equilibrium constant of about 1 mM. At concentrations above 100 μM, higher oligomers are formed in the presence of cations. These are presumably tetramers and octamers, with octamers dominating above about 0.5 mM. Thus, at the low micromolar concentrations of the cellular environment and in the absence of additional compounds that stabilize oligomers, c-di-GMP should be predominantly monomeric. This finding has important implications for the understanding of c-di-GMP recognition by protein receptors. In contrast to the monomer/dimer exchange, formation and dissociation of higher oligomers occurs on a time scale of several hours to days. The time course can be described quantitatively by a simple kinetic model where tetramers are intermediates of octamer formation. The extremely slow oligomer dissociation may generate severe artifacts in biological experiments when c-di-GMP is diluted from concentrated stock solution. We present a simple method to quantify c-di-GMP monomers and oligomers from UV spectra and a procedure to dissolve the unwanted oligomers by an annealing step.

  4. Constraining the chlorine monoxide (ClO)/chlorine peroxide (ClOOCl) equilibrium constant from Aura Microwave Limb Sounder measurements of nighttime ClO.

    PubMed

    Santee, Michelle L; Sander, Stanley P; Livesey, Nathaniel J; Froidevaux, Lucien

    2010-04-13

    The primary ozone loss process in the cold polar lower stratosphere hinges on chlorine monoxide (ClO) and one of its dimers, chlorine peroxide (ClOOCl). Recently, analyses of atmospheric observations have suggested that the equilibrium constant, K(eq), governing the balance between ClOOCl formation and thermal decomposition in darkness is lower than that in the current evaluation of kinetics data. Measurements of ClO at night, when ClOOCl is unaffected by photolysis, provide a useful means of testing quantitative understanding of the ClO/ClOOCl relationship. Here we analyze nighttime ClO measurements from the National Aeronautics and Space Administration Aura Microwave Limb Sounder (MLS) to infer an expression for K(eq). Although the observed temperature dependence of the nighttime ClO is in line with the theoretical ClO/ClOOCl equilibrium relationship, none of the previously published expressions for K(eq) consistently produces ClO abundances that match the MLS observations well under all conditions. Employing a standard expression for K(eq), A x exp(B/T), we constrain the parameter A to currently recommended values and estimate B using a nonlinear weighted least squares analysis of nighttime MLS ClO data. ClO measurements at multiple pressure levels throughout the periods of peak chlorine activation in three Arctic and four Antarctic winters are used to estimate B. Our derived B leads to values of K(eq) that are approximately 1.4 times smaller at stratospherically relevant temperatures than currently recommended, consistent with earlier studies. Our results are in better agreement with the newly updated (2009) kinetics evaluation than with the previous (2006) recommendation.

  5. Equivalence of Mg2+ and Na+ ions in salt dependence of the equilibrium binding and dissociation rate constants of Escherichia coli RNA polymerase open complex.

    PubMed

    Loziński, Tomasz; Bolewska, Krystyna; Wierzchowski, Kazimierz L

    2009-06-01

    Conflicting experimental data on the influence of Mg(2+) ions on the salt dependence of formation/dissociation of open transcription complex (RPo) of Escherichia coli RNA polymerase led us to carry systematic measurements of the dissociation rate constant (k(d)) and thermodynamic stability of complexes at lambdaP(R) and Pa promoters in a broad range of [NaCl] and [MgCl(2)] at 25, 31 and 37 degrees C, using fluorescence detected abortive transcription assay. Values of k(d) determined in MgCl(2) in the presence of heparin, as a commonly used anionic competitor, were shown to depend on heparin concentration whereas in NaCl this effect was not observed. Kinetics of dissociation was therefore determined in the course of salt-induced down-shift of the binding equilibrium. Salt derivatives of k(d)'s (n(d)) appeared to be similar in NaCl (approximately 8.5) and MgCl(2) (approximately 10) for both complexes. Isotherms of fractional occupancy of promoters by RNAP as a function of ln [salt] were shown to conform to a sigmoid Boltzman function parameterized to include binding constant of RPo and a net change (n(obs)) in the number of electrolyte ions associated with complex components upon its formation/dissociation. The fitted values of n(obs) appeared also similar in NaCl and in MgCl(2): approximately 18 for RPo/lambdaP(R) and approximately 20 for RPo/Pa, respectively. Overall unfavorable vant'Hoff enthalpy (DeltaH(obs)) of RPo proved to be much higher in MgCl(2) than in NaCl by ca. 20 kcal/mol for both complexes, rendering them profoundly less stable in the former salt. In both salts, DeltaH(obs) was higher by approximately 30 kcal/mol for RPo/Pa relative to RPo/lambdaP(R). Similarity of n(obs) and n(d) values for the two salts indicates thermodynamic equivalence of Mg(2+) and Na(+) in [salt]-controlled binding equilibrium of RPo. This finding remains in disagreement with earlier data and suggests that salt effects on open complex stability should be sought in global

  6. 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.

  7. 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.

  8. 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.

  9. Chemical Principles Revisited: Chemical Equilibrium.

    ERIC Educational Resources Information Center

    Mickey, Charles D.

    1980-01-01

    Describes: (1) Law of Mass Action; (2) equilibrium constant and ideal behavior; (3) general form of the equilibrium constant; (4) forward and reverse reactions; (5) factors influencing equilibrium; (6) Le Chatelier's principle; (7) effects of temperature, changing concentration, and pressure on equilibrium; and (8) catalysts and equilibrium. (JN)

  10. Application of surface complexation models to anion adsorption by natural materials

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Various chemical models of ion adsorption will be presented and discussed. Chemical models, such as surface complexation models, provide a molecular description of anion adsorption reactions using an equilibrium approach. Two such models, the constant capacitance model and the triple layer model w...

  11. 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.

  12. Determination of equilibrium constant of amino carbamate adduct formation in sisomicin by a high pH based high performance liquid chromatography.

    PubMed

    Wlasichuk, Kenneth B; Tan, Li; Guo, Yushen; Hildebrandt, Darin J; Zhang, Hao; Karr, Dane E; Schmidt, Donald E

    2015-01-01

    Amino carbamate adduct formation from the amino group of an aminoglycoside and carbon dioxide has been postulated as a mechanism for reducing nephrotoxicity in the aminoglycoside class compounds. In this study, sisomicin was used as a model compound for amino carbamate analysis. A high pH based reversed-phase high performance liquid chromatography (RP-HPLC) method is used to separate the amino carbamate from sisomicin. The carbamate is stable as the breakdown is inhibited at high pH and any reactive carbon dioxide is removed as the carbonate. The amino carbamate was quantified and the molar fraction of amine as the carbamate of sisomicin was obtained from the HPLC peak areas. The equilibrium constant of carbamate formation, Kc, was determined to be 3.3 × 10(-6) and it was used to predict the fraction of carbamate over the pH range in a typical biological systems. Based on these results, the fraction of amino carbamate at physiological pH values is less than 13%, and the postulated mechanism for nephrotoxicity protection is not valid. The same methodology is applicable for other aminoglycosides.

  13. Evaluating the Equilibrium Association Constant between ArtinM Lectin and Myeloid Leukemia Cells by Impedimetric and Piezoelectric Label Free Approaches.

    PubMed

    Carvalho, Fernanda C; Martins, Denise C; Santos, Adriano; Roque-Barreira, Maria-Cristina; Bueno, Paulo R

    2014-12-01

    Label-free methods for evaluating lectin-cell binding have been developed to determine the lectin-carbohydrate interactions in the context of cell-surface oligosaccharides. In the present study, mass loading and electrochemical transducer signals were compared to characterize the interaction between lectin and cellular membranes by measuring the equilibrium association constant, Ka , between ArtinM lectin and the carbohydrate sites of NB4 leukemia cells. By functionalizing sensor interfaces with ArtinM, it was possible to determine Ka over a range of leukemia cell concentrations to construct analytical curves from impedimetric and/or mass-associated frequency shifts with analytical signals following a Langmuir pattern. Using the Langmuir isotherm-binding model, the Ka obtained were (8.9 ± 1.0) × 10(-5) mL/cell and (1.05 ± 0.09) × 10(-6) mL/cell with the electrochemical impedance spectroscopy (EIS) and quartz crystal microbalance (QCM) methods, respectively. The observed differences were attributed to the intrinsic characteristic sensitivity of each method in following Langmuir isotherm premises.

  14. HDM-PAMPA to predict gastrointestinal absorption, binding percentage, equilibrium and kinetics constants with human serum albumin and using 2 end-point measurements.

    PubMed

    Bujard, Alban; Petit, Charlotte; Carrupt, Pierre-Alain; Rudaz, Serge; Schappler, Julie

    2017-01-15

    The parallel artificial membrane permeability assay (PAMPA) is a high-throughput screening (HTS) technique developed to predict passive permeability through numerous different biological membranes, such as the gastrointestinal tract (GIT), the blood brain barrier (BBB), and the dermal layer. PAMPA is based on an artificial membrane, such as hexadecane (HDM), which separates two compartments (i.e., a donor and an acceptor compartment). In the present study, an HDM-PAMPA method was developed with human serum albumin (HSA) under iso-pH and gradient-pH conditions to predict the percentage of binding, dissociation/association constants (Kd and Ka, respectively) and dissociation/association kinetic rates (koff and kon, respectively) between a given drug and HSA. Thanks to the kinetic properties of PAMPA, a two end-point assay was implemented to obtain all three properties. The assay was used to measure basic, acidic, and amphoteric compounds. The protein was free in solution, allowing a direct comparison between this assay and equilibrium dialysis (ED). The developed PAMPA enabled screening of up to 96 compounds in a single run, generating valuable information on absorption and distribution in a high-throughput and high-repeatable manner.

  15. Determination of the microscopic equilibrium dissociation constants for risedronate and its analogues reveals two distinct roles for the nitrogen atom in nitrogen-containing bisphosphonate drugs.

    PubMed

    Hounslow, Andrea M; Carran, John; Brown, Richard J; Rejman, Dominik; Blackburn, G Michael; Watts, Donald J

    2008-07-24

    Microscopic equilibrium dissociation constants, k as, were determined for four nitrogen-containing bisphosphonates (N-BP): risedronate and its analogues 2-(2-aminophenyl)-1-hydroxyethylidene-1,1-bisphosphonate, NE 11807, and NE 97220. The proportion of each and of analogues 2-(3'-( N-ethyl)pyridinium)-ethylidenebisphosphonate and 2-(3-piperinidyl)-1-hydroxyethylidene-1,1-bisphosphonate, having a positively charged nitrogen and three negative charges on the bisphosphonate group ("carbocation analogue") at pH 7.5, was calculated. When set in order of increasing potency at inhibiting farnesyl diphosphate (FDP) synthase (their intracellular target), the N-BPs are also ranked in order of decreasing mole fraction of carbocation analogue. However, only a weak correlation exists between potency for inhibiting FDP synthase and potency for inhibiting Dictyostelium discoideum growth. It is concluded that, although high potency for inhibiting FDP synthase is favored when the nitrogen atom in a N-BP is uncharged, N-BPs having a positively charged nitrogen can still be potent inhibitors of Dictyostelium growth owing to favorable interaction with a second, unidentified target.

  16. 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.

  17. 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.

  18. 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.

  19. Bovine β-lactoglobulin is dimeric under imitative physiological conditions: dissociation equilibrium and rate constants over the pH range of 2.5-7.5.

    PubMed

    Mercadante, Davide; Melton, Laurence D; Norris, Gillian E; Loo, Trevor S; Williams, Martin A K; Dobson, Renwick C J; Jameson, Geoffrey B

    2012-07-18

    The oligomerization of β-lactoglobulin (βLg) has been studied extensively, but with somewhat contradictory results. Using analytical ultracentrifugation in both sedimentation equilibrium and sedimentation velocity modes, we studied the oligomerization of βLg variants A and B over a pH range of 2.5-7.5 in 100 mM NaCl at 25°C. For the first time, to our knowledge, we were able to estimate rate constants (k(off)) for βLg dimer dissociation. At pH 2.5 k(off) is low (0.008 and 0.009 s(-1)), but at higher pH (6.5 and 7.5) k(off) is considerably greater (>0.1 s(-1)). We analyzed the sedimentation velocity data using the van Holde-Weischet method, and the results were consistent with a monomer-dimer reversible self-association at pH 2.5, 3.5, 6.5, and 7.5. Dimer dissociation constants K(D)(2-1) fell close to or within the protein concentration range of ∼5 to ∼45 μM, and at ∼45 μM the dimer predominated. No species larger than the dimer could be detected. The K(D)(2-1) increased as |pH-pI| increased, indicating that the hydrophobic effect is the major factor stabilizing the dimer, and suggesting that, especially at low pH, electrostatic repulsion destabilizes the dimer. Therefore, through Poisson-Boltzmann calculations, we determined the electrostatic dimerization energy and the ionic charge distribution as a function of ionic strength at pH above (pH 7.5) and below (pH 2.5) the isoelectric point (pI∼5.3). We propose a mechanism for dimer stabilization whereby the added ionic species screen and neutralize charges in the vicinity of the dimer interface. The electrostatic forces of the ion cloud surrounding βLg play a key role in the thermodynamics and kinetics of dimer association/dissociation.

  20. 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.

  1. Solvatochromism in binary mixtures: first report on a solvation free energy relationship between solvent exchange equilibrium constants and the properties of the medium.

    PubMed

    Silva, Priscilla L; Trassi, Marco A S; Martins, Clarissa T; El Seoud, Omar A

    2009-07-16

    We have employed UV-vis spectroscopy in order to investigate details of the solvation of six solvatochromicindicators, hereafter designated as "probes", namely, 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1-yl) phenolate(RB); 4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePM; 1-methylquinolinium-8-olate, QB;2-bromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePMBr, 2,6-dichloro-4-(2,4,6-triphenylpyridinium-1-yl) phenolate (WB); and 2,6-dibromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate,MePMBr2, respectively. These can be divided into three pairs, each includes two probes of similar p kappa(a) in water and different lipophilicity. Solvation has been studied in binary mixtures, BMs, of water, W, with 12protic organic solvents, S, including mono- and bifunctional alcohols (2-alkoxyethanoles, unsaturated and chlorinated alcohols). Each medium was treated as a mixture of S, W, and a complex solvent, S-W, formed by hydrogen bonding. Values of lambda max (of the probe intramolecular charge transfer) were converted into empirical polarity scales, ET(probe) in kcal/mol, whose values were correlated with the effective mole fraction of waterin the medium, chi W(effective). This correlation furnished three equilibrium constants for the exchange of solvents int he probe solvation shell; phi W/S (W substitutes S); phi S-W/W (S-W substitutes W), and phi S-W/S (S-W substitutes S), respectively. The values of these constants depend on the physicochemical properties of the probe and the medium. We tested, for the first time, the applicability of a new solvation free energy relationship: phi =constant + a alpha(BM) + b beta(BM) + s(pi* (BM) + d delta) + p log P (BM), where a, b, s, and p are regression coefficients; RBM,alpha (BM), beta(BM) and pi (BM) are solvatochromic parameters of the BM, delta is a correction term for pi*, and log P is an empirical scale of lipophilicity. Correlations were carried out with two-, three-, and four-medium descriptors

  2. 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.

  3. Transient state kinetics of enzyme IICBGlc, a glucose transporter of the phosphoenolpyruvate phosphotransferase system of Escherichia coli: equilibrium and second order rate constants for the glucose binding and phosphotransfer reactions.

    PubMed

    Meadow, Norman D; Savtchenko, Regina S; Nezami, Azin; Roseman, Saul

    2005-12-23

    During translocation across the cytoplasmic membrane of Escherichia coli, glucose is phosphorylated by phospho-IIA(Glc) and Enzyme IICB(Glc), the last two proteins in the phosphotransfer sequence of the phosphoenolpyruvate:glucose phosphotransferase system. Transient state (rapid quench) methods were used to determine the second order rate constants that describe the phosphotransfer reactions (phospho-IIA(Glc) to IICB(Glc) to Glc) and also the second order rate constants for the transfer from phospho-IIA(Glc) to molecularly cloned IIB(Glc), the soluble, cytoplasmic domain of IICB(Glc). The rate constants for the forward and reverse phosphotransfer reactions between IIA(Glc) and IICB(Glc) were 3.9 x 10(6) and 0.31 x 10(6) m(-1) s(-1), respectively, and the rate constant for the physiologically irreversible reaction between [P]IICB(Glc) and Glc was 3.2 x 10(6) m(-1) s(-1). From the rate constants, the equilibrium constants for the transfer of the phospho-group from His90 of [P]IIA(Glc) to the phosphorylation site Cys of IIB(Glc) or IICB(Glc) were found to be 3.5 and 12, respectively. These equilibrium constants signify that the thiophospho-group in these proteins has a high phosphotransfer potential, similar to that of the phosphohistidinyl phosphotransferase system proteins. In these studies, preparations of IICB(Glc) were invariably found to contain endogenous, firmly bound Glc (estimated K'(D) approximately 10(-7) m). The bound Glc was kinetically competent and was rapidly phosphorylated, indicating that IICB(Glc) has a random order, Bi Bi, substituted enzyme mechanism. The equilibrium constant for the binding of Glc was deduced from differences in the statistical goodness of fit of the phosphotransfer data to the kinetic model.

  4. Effect of grain size on uranium(VI) surface complexation kinetics and adsorption additivity.

    PubMed

    Shang, Jianying; Liu, Chongxuan; Wang, Zheming; Zachara, John M

    2011-07-15

    The contribution of variable grain sizes to uranium adsorption/desorption was studied using a sediment from the US DOE Hanford site. The sediment was wet sieved into four size fractions: coarse sand (1-2 mm), medium sand (0.2-1 mm), fine sand (0.053-0.2 mm), and clay/silt fraction (<0.053 mm). For each size fraction and their composite (sediment), batch and flow-cell experiments were performed to determine uranium adsorption isotherms and kinetic uranium adsorption and subsequent desorption. The results showed that uranium adsorption isotherms and adsorption/desorption kinetics were size specific, reflecting the effects of size-specific adsorption site concentration and kinetic rate constants. The larger-size fraction had a larger mass percentage in the sediment but with a smaller adsorption site concentration and generally a slower uranium adsorption/desorption rate. The same equilibrium surface complexation reaction and reaction constant could describe uranium adsorption isotherms for all size fractions and the composite after accounting for the effect of adsorption site concentration. Mass-weighted, linear additivity was observed for both uranium adsorption isotherms and adsorption/desorption kinetics in the composite. One important implication of this study is that grain-size distribution may be used to estimate uranium adsorption site and adsorption/desorption kinetic rates in heterogeneous sediments from a common location.

  5. Three applications of path integrals: equilibrium and kinetic isotope effects, and the temperature dependence of the rate constant of the [1,5] sigmatropic hydrogen shift in (Z)-1,3-pentadiene.

    PubMed

    Zimmermann, Tomáš; Vaníček, Jiří

    2010-11-01

    Recent experiments have confirmed the importance of nuclear quantum effects even in large biomolecules at physiological temperature. Here we describe how the path integral formalism can be used to describe rigorously the nuclear quantum effects on equilibrium and kinetic properties of molecules. Specifically, we explain how path integrals can be employed to evaluate the equilibrium (EIE) and kinetic (KIE) isotope effects, and the temperature dependence of the rate constant. The methodology is applied to the [1,5] sigmatropic hydrogen shift in pentadiene. Both the KIE and the temperature dependence of the rate constant confirm the importance of tunneling and other nuclear quantum effects as well as of the anharmonicity of the potential energy surface. Moreover, previous results on the KIE were improved by using a combination of a high level electronic structure calculation within the harmonic approximation with a path integral anharmonicity correction using a lower level method.

  6. Dynamics and thermodynamics of toxic metals adsorption onto soil-extracted humic acid.

    PubMed

    Shaker, Medhat A; albishri, Hassan M

    2014-09-01

    Humic acids, HA represent a large portion of natural organic matter in soils, sediments and waters. They are environmentally important materials due to their extensive ubiquity and strong complexation ability, which can influence heavy metal removal and transportation in waters. The thermodynamics and kinetics of the adsorption of Cd(II) and Cr(VI) onto solid soil-derived HA have been investigated at optimum conditions of pH (5.5±0.1), metal concentration (10-100mmolL(-1)) and different temperatures (293-323K). The suitability of adsorption models such as Freundlich and Langmuir to equilibrium data was investigated. The adsorption was well described by Langmuir isotherm model in multi-detectable steps. Adsorption sites, i (i=A, B, C) with different capacities, νi are characterized. The stoichiometric site capacity is independent of temperature and equilibrium constant, Ki. Adsorption sites A and B are selectively occupied by Cr(VI) cations while sites A and C are selectively occupied by Cd(II) cations. The thermodynamic parameters of adsorption systems are correlated for each adsorption step. The adsorption is endothermic, spontaneous and favorable. Different kinetic models are applied and the adsorption of these heavy metals onto HA follows pseudo-second-order kinetics and equilibrium is achieved within 24h. The adsorption reaction is controlled by diffusion processes and the type of the adsorption is physical.

  7. Analysis of fast and slow acid dissociation equilibria of 3',3″,5',5″-tetrabromophenolphthalein and determination of its equilibrium constants by capillary zone electrophoresis.

    PubMed

    Takayanagi, Toshio

    2013-01-01

    Acid dissociation constants of 3',3″,5',5″-tetrabrompohenolphthalein (TBPP) were determined in an aqueous solution by capillary zone electrophoresis at an ionic strength of 0.01 mol/L. Two steps of the fast acid-dissociation equilibria including precipitable species of H2TBPP were analyzed at a weakly acidic pH region by using the change in effective electrophoretic mobility of TBPP with the pH of the separation buffer. On the other hand, an acid-dissociation reaction of TBPP at an alkaline pH region was reversible, but very slow to reach its equilibrium; the two TBPP species concerned with the equilibrium were detected as distinct signals in the electropherograms. After reaching its equilibrium, the acid-dissociation constant was determined with the signal height corresponding to its dianion form. Thus, three steps of the acid dissociation constants of TBPP were determined in an aqueous solution as pKa1 = 5.29 ± 0.06, pKa2 = 6.35 ± 0.02, and pKa3 = 11.03 ± 0.04.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. Experimental adsorption isotherms based on inverse gas chromatography.

    PubMed

    Kalogirou, E; Bassiotis, I; Artemiadi, Th; Margariti, S; Siokos, V; Roubani-Kalantzopoulou, F

    2002-09-06

    A new chromatographic perturbation method is used for studying the adsorption-desorption equilibrium in various gas-solid heterogeneous systems. It is the reversed-flow method giving accurate and precise values of many physicochemical constants including the basic and necessary adsorption isotherm values. For four inorganic oxides, namely, Cr2O3, Fe2O3, TiO2 and PbO, and two aromatic hydrocarbons (benzene, toluene) these adsorption isotherms have been determined through a non-linear model.

  13. 2, 4 dichlorophenol (2, 4-DCP) sorption from aqueous solution using granular activated carbon and polymeric adsorbents and studies on effect of temperature on activated carbon adsorption.

    PubMed

    Ghatbandhe, A S; Yenkie, M K N

    2008-04-01

    Adsorption equilibrium, kinetics and thermodynamics of 2,4-dichlorophenol (2,4-DCP), one of the most commonly used chlorophenol, onto bituminous coal based Filtrasorb-400 grade granular activated carbon, were studied in aqueous solution in a batch system with respect to temperature. Uptake capacity of activated carbon found to increase with temperature. Langmuir isotherm models were applied to experimental equilibrium data of 2, 4-DCP adsorption and competitive studies with respect to XAD resin were carried out. Equilibrium data fitted very well to the Langmuir equilibrium model. Adsorbent monolayer capacity 'Q0, Langmuir constant 'b' and adsorption rate constant 'k(a)' were evaluated at different temperatures for activated carbon adsorption. This data was then used to calculate the energy of activation of adsorption and also the thermodynamic parameters, namely the free energy of adsorption, deltaG0, enthalpy of adsorption, deltaH0 and the entropy of adsorption deltaS0. The obtained results showed that the monolayer capacity increases with the increase in temperatures. The obtained values of thermodynamic parameters showed that adsorption of 2,4 DCP is an endothermic process. Synthetic resin was not found efficient to adsorb 2,4 DCP compared to activated carbon. The order of adsorption efficiencies of three resins used in the study found as XAD7HP > XAD4 > XAD1180.

  14. 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.

  15. Petroleum resins adsorption onto quartz sand: near infrared (NIR) spectroscopy study.

    PubMed

    Balabin, Roman M; Syunyaev, Rustem Z

    2008-02-15

    In this paper we have tried to evaluate adsorption parameters of petroleum resins. Near infrared (NIR) spectroscopy is applied for resins bulk concentration evaluation during adsorption process. NIR experimental scheme and parameters are provided. NIR spectra range of 9000-13,000 cm(-1) is chosen. Quartz sand (0.2-0.8 mm fraction) is used as adsorbent; benzene is used as solvent. Different approaches of "NIR spectra-resins concentration" calibration model building are discussed. Partial least squares (PLS) regression method is used. Langmuir model is chosen for experimental data fitting. Combined usage of kinetic and isothermic data gives us ability to evaluate the maximal adsorbed mass density, the equilibrium constant of adsorption, and the rate constants of adsorption (and desorption). The rate constants of resins adsorption and desorption are found to be concentration independent.

  16. Measurements of VOC adsorption/desorption characteristics of typical interior building materials

    SciTech Connect

    An, Y.; Zhang, J.S.; Shaw, C.Y.

    2000-07-01

    The adsorption/desorption of volatile organic compounds (VOCs) on interior building material surfaces (i.e., the sink effect) can affect the VOC concentrations in a building, and thus need to be accounted for an indoor air quality (IAQ) prediction model. In this study, the VOC adsorption/desorption characteristics (sink effect) were measured for four typical interior building materials including carpet, vinyl floor tile, painted drywall, and ceiling tile. The VOCs tested were ethylbenzene, cyclohexanone, 1,4-dichlorobenzene, benzaldehyde, and dodecane. These five VOCs were selected because they are representative of hydrocarbons, aromatics, ketones, aldehydes, and chlorine substituted compounds. The first order reversible adsorption/desorption model was based on the Langmuir isotherm was used to analyze the data and to determine the equilibrium constant of each VOC-material combination. It was found that the adsorption/desorption equilibrium constant, which is a measure of the sink capacity, increased linearly with the inverse of the VOC vapor pressure. For each compound, the adsorption/desorption equilibrium constant, and the adsorption rate constant differed significantly among the four materials tested. A detailed characterization of the material structure in the micro-scale would improve the understanding and modeling of the sink effect in the future. The results of this study can be used to estimate the impact of sink effect on the VOC concentrations in buildings.

  17. Metal adsorption on mosses: Toward a universal adsorption model.

    PubMed

    González, A G; Pokrovsky, O S

    2014-02-01

    This study quantifies the adsorption of heavy metals on 4 typical moss species used for environmental monitoring in the moss bag technique. The adsorption of Cu(2+), Cd(2+), Ni(2+), Pb(2+) and Zn(2+) onto Hypnum sp., Sphagnum sp., Pseudoscleropodium purum and Brachytecium rutabulum has been investigated using a batch reactor in a wide range of pH (1.3-11.0) and metal concentrations in solution (1.6μM-3.8mM). A Linear Programming Model (LPM) was applied for the experimental data to derive equilibrium constants and the number of surface binding sites. The surface acid-base titration performed for 4 mosses at a pH range of 3-10 in 0.1M NaNO3 demonstrated that Sphagnum sp. is the most efficient adsorbent as it has the maximal number of proton-binding sites on the surface (0.65mmol g(-1)). The pKa computed for all the moss species suggested the presence of 5 major functional groups: phosphodiester, carboxyl, phosphoryl, amine and polyphenols. The results of pH-edge experiments demonstrated that B. rutabulum exhibits the highest percentage of metal adsorption and has the highest number of available sites for most of the metals studied. However, according to the results of the constant pH "Langmuirian" isotherm, Sphagnum sp. can be considered as the strongest adsorbent, although the relative difference from other mosses is within 20%. The LPM was found to satisfactorily fit the experimental data in the full range of the studied solution parameters. The results of this study demonstrate a rather similar pattern of five metal adsorptions on mosses, both as a function of pH and as a metal concentration, which is further corroborated by similar values of adsorption constants. Therefore, despite the species and geographic differences between the mosses, a universal adsorption edge and constant pH adsorption isotherm can be recommended for 4 studied mosses. The quantitative comparison of metal adsorption with other common natural organic and inorganic materials demonstrates

  18. Determination of Equilibrium Constants of Some Novel Antioxidant Compounds and Study on their Complexes with Some Divalent Metal ions in Ethanol-water Mixed.

    PubMed

    Atabey, Hasan; Findik, Esra; Sari, Hayati; Ceylan, Mustafa

    2012-12-01

    This study aims to investigate the nature and type of complexes formed in solution, between novel antioxidant compounds [P1(4-(1-(3-hydroxy-4-methoxyphenyl)propyl)benzene-1,2-diol) and P2(4-(1-(3-hydroxy-4-methoxyphenyl)propyl)benzene-1,3-diol)] and the ions Cu2+, Ni2+, Zn2+ and Co2+. Potentiometric titration technique was used to follow the formation of complexes during the course of coordination. The stability of the complexes formed was controlled through the determination of stability constants in aqueous ethanol solution at 25 ± 0.1 C° and ionic strength of 0.1 M NaCl. Basicity of the ligand was also assessed by the determination of the dissociation constants of the ligand. All the constants were computed by computer refinement of pH-volume data using the SUPERQUAD program. The species distribution diagram of each type of complex has been obtained after computer calculation process.

  19. Fast and considerable adsorption of methylene blue dye onto graphene oxide.

    PubMed

    Zhang, Wenjie; Zhou, Chunjiao; Zhou, Weichang; Lei, Aihua; Zhang, Qinglin; Wan, Qiang; Zou, Bingsuo

    2011-07-01

    The quite efficient adsorption of methylene blue dye from an aqueous solution by graphene oxide was studied. The favorable electrostatic attraction is the main interaction between methylene blue and graphene oxide. As graphene oxide has the special nanostructural properties and negatively charged surface, the positively charged methylene blue molecules can be easily adsorbed on it. In the aqueous solution of methylene blue at 293 K, the adsorption data could be fitted by the Langmuir equation with a maximum adsorption amount of 1.939 mg/mg and a Langmuir adsorption equilibrium constant of 18.486 mL/mg. The adsorption amount increased with the increase of the solution pH (3-11), was not affected significantly by KCl under the examined condition and the adsorption process was exothermic in nature. The fast and considerable adsorption of graphene oxide could be regarded as a potential adsorbent for cationic dye removal in wastewater treatment process.

  20. 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-).

  1. 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.

  2. 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.

  3. Adsorption of humic acids and trace metals in natural waters

    NASA Technical Reports Server (NTRS)

    Leung, W. H.

    1982-01-01

    Studies concerning the interactions between suspended hydrous iron oxide and dissolved humic acids and trace metals are reported. As a major component of dissolved organic matters and its readiness for adsorption at the solid/water interface, humic acids may play a very important role in the organometallic geochemistry of suspended sediments and in determining the fate and distribution of trace metals, pesticides and anions in natural water systems. Most of the solid phases in natural waters contain oxides and hydroxides. The most simple promising theory to describe the interactions of hydrous iron oxide interface is the surface complex formation model. In this model, the adsorptions of humic acids on hydrous iron oxide may be interpreted as complex formation of the organic bases (humic acid oxyanions) with surface Fe ions. Measurements on adsorptions were made in both fresh water and seawater. Attempts have been made to fit our data to Langmuir adsorption isotherm. Adsorption equilibrium constants were determined.

  4. Comparing the removal of perchlorate when using single-walled carbon nanotubes (SWCNTs) or granular activated carbon: adsorption kinetics and thermodynamics.

    PubMed

    Lou, Jie C; Hsu, Yung S; Hsu, Kai L; Chou, Ming S; Han, Jia Y

    2014-01-01

    This study aims to remove perchlorate using single-walled carbon nanotubes (SWCNTs) or granular activated carbon (GAC). Dynamic and equilibrium adsorption experiments were performed to evaluate the thermodynamic behavior of perchlorate on SWCNTs and GAC. Key parameters affecting the adsorption, such as pH, ionic strength, and temperature were studied. The experimental results showed that the dynamic adsorption experiment achieved equilibrium in approximately eight hours. The adsorption capacity increased as the concentration of perchlorate increased or as the ionic strength decreased. The selected adsorption models were the modified Freundlich, the pseudo-1st-order, and the pseudo-2nd-order equations. The results showed that the modified Freundlich equation best described the kinetic adsorption processes. The maximal adsorption capacities of GAC and SWCNTs were 33.87-28.21 mg/g and 13.64 - 10.03 mg/g, respectively, at a constant temperature between 5°C and 45°C. The thermodynamic parameters, such as the equilibrium constant (K0 ), the standard free energy changes (ΔG°), the standard enthalpy change (ΔH°) and the standard entropy change (ΔS°), were obtained. The results of the isothermal equilibrium adsorption experiment showed that low pH levels, low ionic strength, and low-temperature conditions facilitated the perchlorate adsorption, indicating that GAC and SWCNTs are potential absorbents for water treatment.

  5. 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.

  6. Formation and reactivity of a porphyrin iridium hydride in water: acid dissociation constants and equilibrium thermodynamics relevant to Ir-H, Ir-OH, and Ir-CH2- bond dissociation energetics.

    PubMed

    Bhagan, Salome; Wayland, Bradford B

    2011-11-07

    Aqueous solutions of group nine metal(III) (M = Co, Rh, Ir) complexes of tetra(3,5-disulfonatomesityl)porphyrin [(TMPS)M(III)] form an equilibrium distribution of aquo and hydroxo complexes ([(TMPS)M(III)(D(2)O)(2-n)(OD)(n)]((7+n)-)). Evaluation of acid dissociation constants for coordinated water show that the extent of proton dissociation from water increases regularly on moving down the group from cobalt to iridium, which is consistent with the expected order of increasing metal-ligand bond strengths. Aqueous (D(2)O) solutions of [(TMPS)Ir(III)(D(2)O)(2)](7-) react with dihydrogen to form an iridium hydride complex ([(TMPS)Ir-D(D(2)O)](8-)) with an acid dissociation constant of 1.8(0.5) × 10(-12) (298 K), which is much smaller than the Rh-D derivative (4.3 (0.4) × 10(-8)), reflecting a stronger Ir-D bond. The iridium hydride complex adds with ethene and acetaldehyde to form organometallic derivatives [(TMPS)Ir-CH(2)CH(2)D(D(2)O)](8-) and [(TMPS)Ir-CH(OD)CH(3)(D(2)O)](8-). Only a six-coordinate carbonyl complex [(TMPS)Ir-D(CO)](8-) is observed for reaction of the Ir-D with CO (P(CO) = 0.2-2.0 atm), which contrasts with the (TMPS)Rh-D analog which reacts with CO to produce an equilibrium with a rhodium formyl complex ([(TMPS)Rh-CDO(D(2)O)](8-)). Reactivity studies and equilibrium thermodynamic measurements were used to discuss the relative M-X bond energetics (M = Rh, Ir; X = H, OH, and CH(2)-) and the thermodynamically favorable oxidative addition of water with the (TMPS)Ir(II) derivatives.

  7. Sequential hydration energies of the sulfate ion, from determinations of the equilibrium constants for the gas-phase reactions: SO4(H2O)(n)2- = SO4(H2O)(n-1)2- + H2O.

    PubMed

    Blades, Arthur T; Kebarle, Paul

    2005-09-22

    Sequential hydration energies of SO4(H2O)(n)2- were obtained from determinations of the equilibrium constants of the following reactions: SO4(H2O)(n)2- = SO4(H2O)(n-1)2- + H2O. The SO4(2-) ions were produced by electrospray and the equilibrium constants Kn,n-1 were determined with a reaction chamber attached to a mass spectrometer. Determinations of Kn,n-1 at different temperatures were used to obtain DeltaG0n,n-1, DeltaH0 n,n-1, and DeltaS0n,n-1 for n = 7 to 19. Interference of the charge separation reaction SO4(H2O)(n)2- = HSO4(H2O)(n-k)- + OH(H2O)(k-1)- at higher temperatures prevented determinations for n < 7. The DeltaS0n,n-1 values obtained are unusually low and this indicates very loose, disordered structures for the n > or = 7 hydrates. The DeltaH0n,n-1 values are compared with theoretical values DeltaEn,n-1, obtained by Wang, Nicholas, and Wang. Rate constant determinations of the dissociation reactions n,n - 1, obtained with the BIRD method by Wong and Williams, showed relatively lower rates for n = 6 and 12, which indicate that these hydrates are more stable. No discontinuities of the DeltaG0n,n-1 values indicating an unusually stable n = 12 hydrate were observed in the present work. Rate constants evaluated from the DeltaG0n,n-1 results also fail to indicate a lower rate for n = 12. An analysis of the conditions used in the two types of experiments indicates that the different results reflect the different energy distributions expected at the dissociation threshold. Higher internal energies prevail in the equilibrium measurements and allow the participation of more disordered transition states in the reaction.

  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. 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

  10. Automated method for determination of dissolved organic carbon-water distribution constants of structurally diverse pollutants using pre-equilibrium solid-phase microextraction.

    PubMed

    Ripszam, Matyas; Haglund, Peter

    2015-02-01

    Dissolved organic carbon (DOC) plays a key role in determining the environmental fate of semivolatile organic environmental contaminants. The goal of the present study was to develop a method using commercially available hardware to rapidly characterize the sorption properties of DOC in water samples. The resulting method uses negligible-depletion direct immersion solid-phase microextraction (SPME) and gas chromatography-mass spectrometry. Its performance was evaluated using Nordic reference fulvic acid and 40 priority environmental contaminants that cover a wide range of physicochemical properties. Two SPME fibers had to be used to cope with the span of properties, 1 coated with polydimethylsiloxane and 1 coated with polystyrene divinylbenzene polydimethylsiloxane, for nonpolar and semipolar contaminants, respectively. The measured DOC-water distribution constants showed reasonably good reproducibility (standard deviation ≤ 0.32) and good correlation (R(2)  = 0.80) with log octanol-water partition coefficients for nonpolar persistent organic pollutants. The sample pretreatment is limited to filtration, and the method is easy to adjust to different DOC concentrations. These experiments also utilized the latest SPME automation that largely decreases total cycle time (to 20 min or shorter) and increases sample throughput, which is advantageous in cases when many samples of DOC must be characterized or when the determinations must be performed quickly, for example, to avoid precipitation, aggregation, and other changes of DOC structure and properties. The data generated by this method are valuable as a basis for transport and fate modeling studies.

  11. Effect of Grain Size on Uranium(VI) Surface Complexation Kinetics and Adsorption Additivity

    SciTech Connect

    Shang, Jianying; Liu, Chongxuan; Wang, Zheming; Zachara, John M.

    2011-07-27

    Laboratory experiments were performed to investigate the contribution of variable grain sizes to uranium adsorption/desorption in a sediment collected from the US DOE Hanford site. The sediment was wet-sieved into four size fractions: coarse sand (1-2 mm), medium sand (0.2-1 mm), fine sand (0.05-0.2 mm), and clay/silt fraction (< 0.05mm). For each size fraction and their composite (sediment), batch experiments were performed to determine uranium adsorption isotherms, and stirred flow-cell experiments were conducted to derive kinetic data of uranium adsorption and subsequent desorption. The results showed that uranium adsorption isotherms and adsorption/desorption kinetics were size-specific, reflecting the effects of size-specific adsorption site concentration and kinetic rate constants. The larger-size fraction had a larger mass percentage in the sediment, but with a smaller adsorption site concentration and generally a slower uranium adsorption/desorption rate. The same equilibrium surface complexation reaction and reaction constant could describe uranium adsorption isotherms for all size fractions and the composite after accounting for the effect of adsorption site concentration. Mass-weighted, linear additivity was observed for both uranium adsorption isotherms and adsorption/desorption kinetics in the composite. Our analysis also showed that uranium adsorption site concentration estimated from the adsorption isotherms was 3 orders of magnitude less than a site concentration estimated from sediment surface area and generic site density. One important implication of this study is that grain size distribution may be used to estimate uranium adsorption site, and adsorption/desorption kinetic rates in heterogeneous sediments from a common location.

  12. 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.

  13. 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.

  14. 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.

  15. Chemical Principles Revisited: Using the Equilibrium Concept.

    ERIC Educational Resources Information Center

    Mickey, Charles D., Ed.

    1981-01-01

    Discusses the concept of equilibrium in chemical systems, particularly in relation to predicting the position of equilibrium, predicting spontaneity of a reaction, quantitative applications of the equilibrium constant, heterogeneous equilibrium, determination of the solubility product constant, common-ion effect, and dissolution of precipitates.…

  16. Equilibrium Principles: A Game for Students

    NASA Astrophysics Data System (ADS)

    Edmonson, Lionel J., Jr.; Lewis, Don L.

    1999-04-01

    The laboratory exercise is a game using marked sugar cubes as dice. The game emphasizes the dynamic character of equilibrium. Forward and reverse rate-constant values are used to calculate an equilibrium constant and to predict equilibrium populations. Predicted equilibrium populations are compared with experimental results.

  17. [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.

  18. Electrostatically-driven fast association and perdeuteration allow detection of transferred cross-relaxation for G protein-coupled receptor ligands with equilibrium dissociation constants in the high-to-low nanomolar range.

    PubMed

    Catoire, Laurent J; Damian, Marjorie; Baaden, Marc; Guittet, Eric; Banères, Jean-Louis

    2011-07-01

    The mechanism of signal transduction mediated by G protein-coupled receptors is a subject of intense research in pharmacological and structural biology. Ligand association to the receptor constitutes a critical event in the activation process. Solution-state NMR can be amenable to high-resolution structure determination of agonist molecules in their receptor-bound state by detecting dipolar interactions in a transferred mode, even with equilibrium dissociation constants below the micromolar range. This is possible in the case of an inherent ultra-fast diffusive association of charged ligands onto a highly charged extracellular surface, and by slowing down the (1)H-(1)H cross-relaxation by perdeuterating the receptor. Here, we demonstrate this for two fatty acid molecules in interaction with the leukotriene BLT2 receptor, for which both ligands display a submicromolar affinity.

  19. 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.

  20. Investigating the thermodynamic stability of Bacillus subtilis spore-uranium(VI) adsorption though surface complexation modeling

    NASA Astrophysics Data System (ADS)

    Harrold, Z.; Hertel, M.; Gorman-Lewis, D.

    2012-12-01

    Dissolved uranium speciation, mobility, and remediation are increasingly important topics given continued and potential uranium (U) release from mining operations and nuclear waste. Vegetative bacterial cell surfaces are known to adsorb uranium and may influence uranium speciation in the environment. Previous investigations regarding U(VI) adsorption to bacterial spores, a differentiated and dormant cell type with a tough proteinaceous coat, include U adsorption affinity and XAFS data. We investigated the thermodynamic stability of aerobic, pH dependent uranium adsorption to bacterial spore surfaces using purified Bacillus subtilis spores in solution with 5ppm uranium. Adsorption reversibility and kinetic experiments indicate that uranium does not precipitate over the duration of the experiments and equilibrium is reached within 20 minutes. Uranium-spore adsorption edges exhibited adsorption at all pH measured between 2 and 10. Maximum adsorption was achieved around pH 7 and decreased as pH increased above 7. We used surface complexation modeling (SCM) to quantify uranium adsorption based on balanced chemical equations and derive thermodynamic stability constants for discrete uranium-spore adsorption reactions. Site specific thermodynamic stability constants provide insight on interactions occurring between aqueous uranium species and spore surface ligands. The uranium adsorption data and SCM parameters described herein, also provide a basis for predicting the influence of bacterial spores on uranium speciation in natural systems and investigating their potential as biosorption agents in engineered systems.

  1. Modeling adsorption: Investigating adsorbate and adsorbent properties

    NASA Astrophysics Data System (ADS)

    Webster, Charles Edwin

    1999-12-01

    Surface catalyzed reactions play a major role in current chemical production technology. Currently, 90% of all chemicals are produced by heterogeneously catalyzed reactions. Most of these catalyzed reactions involve adsorption, concentrating the substrate(s) (the adsorbate) on the surface of the solid (the adsorbent). Pore volumes, accessible surface areas, and the thermodynamics of adsorption are essential in the understanding of solid surface characteristics fundamental to catalyst and adsorbent screening and selection. Molecular properties such as molecular volumes and projected molecular areas are needed in order to convert moles adsorbed to surface volumes and areas. Generally, these molecular properties have been estimated from bulk properties, but many assumptions are required. As a result, different literature values are employed for these essential molecular properties. Calculated molar volumes and excluded molecular areas are determined and tabulated for a variety of molecules. Molecular dimensions of molecules are important in the understanding of molecular exclusion as well as size and shape selectivity, diffusion, and adsorbent selection. Molecular dimensions can also be used in the determination of the effective catalytic pore size of a catalyst. Adsorption isotherms, on zeolites, (crystalline mineral oxides) and amorphous solids, can be analyzed with the Multiple Equilibrium Analysis (MEA) description of adsorption. The MEA produces equilibrium constants (Ki), capacities (ni), and thermodynamic parameters (enthalpies, ΔHi, and entropies, ΔSi) of adsorption for each process. Pore volumes and accessible surface areas are calculated from the process capacities. Adsorption isotherms can also be predicted for existing and new adsorbate-adsorbent systems with the MEA. The results show that MEA has the potential of becoming a standard characterization method for microporous solids that will lead to an increased understanding of their behavior in gas

  2. Rapid-Equilibrium Enzyme Kinetics

    ERIC Educational Resources Information Center

    Alberty, Robert A.

    2008-01-01

    Rapid-equilibrium rate equations for enzyme-catalyzed reactions are especially useful because if experimental data can be fit by these simpler rate equations, the Michaelis constants can be interpreted as equilibrium constants. However, for some reactions it is necessary to use the more complicated steady-state rate equations. Thermodynamics is…

  3. 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.

  4. 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.

  5. Adsorption behavior of methylene blue on carbon nanotubes.

    PubMed

    Yao, Yunjin; Xu, Feifei; Chen, Ming; Xu, Zhongxiao; Zhu, Zhiwen

    2010-05-01

    The effect of temperature on the equilibrium adsorption of methylene blue dye from aqueous solution using carbon nanotubes was investigated. The equilibrium adsorption data were analyzed using two widely applied isotherms: Langmuir and Freundlich. The results revealed that Langmuir isotherm fit the experimental results well. Kinetic analyses were conducted using pseudo-first and second-order models and the intraparticle diffusion model. The regression results showed that the adsorption kinetics were more accurately represented by pseudo-second-order model. The activation energy of system (Ea) was calculated as 18.54 kJ/mol. Standard free energy changes (DeltaG(0)), standard enthalpy change (DeltaH(0)), and standard entropy change (DeltaS(0)) were calculated using adsorption equilibrium constants obtained from the Langmuir isotherm at different temperatures. All DeltaG(0) values were negative; the DeltaH(0) values and DeltaS(0) values of CNTs were 7.29 kJ/mol and 64.6 J/mol K, respectively. Results suggested that the methylene blue adsorption on CNTs was a spontaneous and endothermic process.

  6. Adsorption studies of azotetrazolate and 3,6-dihydrazinotetrazine on peat.

    PubMed

    Borkowski, Andrzej; Rydelek, Paweł; Szala, Mateusz

    2013-01-01

    The objective of our studies was the evaluation of the adsorption process of two high-nitrogen compounds-dihydrazinotetrazine (DHTz) and azotetrazolate ion (AZ)-on a chosen peat. The experiments were performed using a static method at three different temperatures (283, 298, and 333 K). The adsorption process of DHTz and AZ on peat was characterized by isotherms according to the Freundlich and Langmuir models. The obtained correlations between adsorption and equilibrium concentration were in good accordance with the Freundlich and Langmuir models, as confirmed by high values of the correlation coefficients (0.97-0.99). Adsorption of AZ on peat was less efficient than that of DHTz, and this inference was experimentally proven. The maximum surface coverages of peat particles with adsorbate according to the Langmuir model were calculated as 0.02 and 0.17 mol kg(-1) (at 298 K) for AZ and DHTz, respectively. The determined adsorption equilibrium constants confirmed greater adsorption of DHTz on the investigated peat. It can be concluded that adsorption of AZ occurred to a much lesser extent compared to that of DHTz, pointing to a potentially greater threat of migration of soluble azotetrazolates in soil. Standard enthalpies of adsorption estimated for AZ and DHTz were -11.1 and -23.7 kJ mol(-1), respectively. Based on these adsorption enthalpy values, it can be stated that both investigated compounds are adsorbed on peat by a physisorption process.

  7. Adsorption characteristics of metal ions on chitosan chemically modified by D-galactose

    SciTech Connect

    Kondo, Kazuo; Sumi, Hisaharu; Matsumoto, Michiaki

    1996-07-01

    The adsorption characteristics of metal ions on chitosan chemically modified by D-galactose were examined. The pH dependency on the distribution ratio was found to be affected by the valency of the metal ion, and the apparent adsorption equilibrium constants of the metal ions were determined. The order of adsorption of the metal ions is Ga > In > Nd > Eu for the trivalent metal ions and Cu > Ni > Co for the divalent metal ions. It is believed that amino and hydroxyl groups in the chitosan act as a chelating ligand.

  8. Robust design of binary countercurrent adsorption separation processes

    SciTech Connect

    Storti, G. ); Mazzotti, M.; Morbidelli, M.; Carra, S. )

    1993-03-01

    The separation of a binary mixture, using a third component having intermediate adsorptivity as desorbent, in a four section countercurrent adsorption separation unit is considered. A procedure for the optimal and robust design of the unit is developed in the frame of Equilibrium Theory, using a model where the adsorption equilibria are described through the constant selectivity stoichiometric model, while mass-transfer resistances and axial mixing are neglected. By requiring that the unit achieves complete separation, it is possible to identify a set of implicity constraints on the operating parameters, that is, the flow rate ratios in the four sections of the unit. From these constraints explicit bounds on the operating parameters are obtained, thus yielding a region in the operating parameters space, which can be drawn a priori in terms of the adsorption equilibrium constants and the feed composition. This result provides a very convenient tool to determine both optimal and robust operating conditions. The latter issue is addressed by first analyzing the various possible sources of disturbances, as well as their effect on the separation performance. Next, the criteria for the robust design of the unit are discussed. Finally, these theoretical findings are compared with a set of experimental results obtained in a six port simulated moving bed adsorption separation unit operated in the vapor phase.

  9. 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.

  10. 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.

  11. Adsorption rate of phenol from aqueous solution onto organobentonite: surface diffusion and kinetic models.

    PubMed

    Ocampo-Perez, Raul; Leyva-Ramos, Roberto; Mendoza-Barron, Jovita; Guerrero-Coronado, Rosa M

    2011-12-01

    The concentration decay curves for the adsorption of phenol on organobentonite were obtained in an agitated tank batch adsorber. The experimental adsorption rate data were interpreted with diffusional models as well as first-order, second-order and Langmuir kinetic models. The surface diffusion model adjusted the data quite well, revealing that the overall rate of adsorption was controlled by surface diffusion. Furthermore, the surface diffusion coefficient increased raising the mass of phenol adsorbed at equilibrium and was independent of the particle diameter in the range 0.042-0.0126 cm. It was demonstrated that the overall rate of adsorption was essentially not affected by the external mass transfer. The second-order and the Langmuir kinetic models fitted the experimental data quite well; however, the kinetic constants of both models varied without any physical meaning while increasing the particle size and the mass of phenol adsorbed at equilibrium.

  12. 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.

  13. An Equilibrium and Kinetic Investigation of Salt-Cycloamylose Complexes

    DTIC Science & Technology

    1976-12-08

    Coneinut on reverse aide It necessary and identify by blo * number) Equilibrium constants inorganic anions Rate constants Ultrasonic relaxation Inclusion...The equilibrium constants and rate constants for the formation of inclusion complexes of cycloheptaamylose with small inorganic anions were measured by...of cyclo- amylose chemistry. Recently, equilibrium constants for cyclohexaamylose, sometimes denoted by a-CD, with various Tnorganic salts were

  14. Generalized adsorption isotherms for molecular and dissociative adsorption of a polar molecular species on two polar surface geometries: Perovskite (100) (Pm-3m) and fluorite (111) (Fm-3m)

    NASA Astrophysics Data System (ADS)

    Danielson, Thomas; Hin, Celine; Savara, Aditya

    2016-08-01

    Lattice based kinetic Monte Carlo simulations have been used to determine a functional form for the second order adsorption isotherms on two commonly investigated crystal surfaces: the (111) fluorite surface and the (100) perovskite surface which has the same geometric symmetry as the NaCl (100) surface. The functional form is generalized to be applicable to all values of the equilibrium constant by a shift along the pressure axis. Functions have been determined for estimating the pressure at which a desired coverage would be achieved and, conversely, for estimating the coverage at a certain pressure. The generalized form has been calculated by investigating the surface adsorbate coverage across a range of thermodynamic equilibrium constants that span the range 10-26 to 1013. The equations have been shown to be general for any value of the adsorption equilibrium constant.

  15. Generalized adsorption isotherms for molecular and dissociative adsorption of a polar molecular species on two polar surface geometries: Perovskite (100) (Pm-3m) and fluorite (111) (Fm-3m)

    DOE PAGES

    Danielson, Thomas; Hin, Celine; Savara, Aditya

    2016-08-10

    Lattice based kinetic Monte Carlo (KMC) simulations have been used to determine a functional form for the second order adsorption isotherms on two commonly investigated crystal surfaces: the (111) fluorite surface and the (100) perovskite surface which has the same geometric symmetry as the NaCl (100) surface. The functional form is generalized to be applicable to all values of the equilibrium constant by a shift along the pressure axis. Functions have been determined for estimating the pressure at which a desired coverage would be achieved and for estimating the coverage at a certain pressure. The generalized form has been calculatedmore » by investigating the surface adsorbate coverage across a range of thermodynamic equilibrium constants that span the range 10-26 to 1013. Finally, the equations have been shown to be general for any value of the adsorption equilibrium constant.« less

  16. Generalized adsorption isotherms for molecular and dissociative adsorption of a polar molecular species on two polar surface geometries: Perovskite (100) (Pm-3m) and fluorite (111) (Fm-3m)

    SciTech Connect

    Danielson, Thomas; Hin, Celine; Savara, Aditya

    2016-08-10

    Lattice based kinetic Monte Carlo (KMC) simulations have been used to determine a functional form for the second order adsorption isotherms on two commonly investigated crystal surfaces: the (111) fluorite surface and the (100) perovskite surface which has the same geometric symmetry as the NaCl (100) surface. The functional form is generalized to be applicable to all values of the equilibrium constant by a shift along the pressure axis. Functions have been determined for estimating the pressure at which a desired coverage would be achieved and for estimating the coverage at a certain pressure. The generalized form has been calculated by investigating the surface adsorbate coverage across a range of thermodynamic equilibrium constants that span the range 10-26 to 1013. Finally, the equations have been shown to be general for any value of the adsorption equilibrium constant.

  17. 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.

  18. 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.

  19. 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.

  20. Predicting heavy metals' adsorption edges and adsorption isotherms on MnO2 with the parameters determined from Langmuir kinetics.

    PubMed

    Hu, Qinghai; Xiao, Zhongjin; Xiong, Xinmei; Zhou, Gongming; Guan, Xiaohong

    2015-01-01

    Although surface complexation models have been widely used to describe the adsorption of heavy metals, few studies have verified the feasibility of modeling the adsorption kinetics, edge, and isotherm data with one pH-independent parameter. A close inspection of the derivation process of Langmuir isotherm revealed that the equilibrium constant derived from the Langmuir kinetic model, KS-kinetic, is theoretically equivalent to the adsorption constant in Langmuir isotherm, KS-Langmuir. The modified Langmuir kinetic model (MLK model) and modified Langmuir isotherm model (MLI model) incorporating pH factor were developed. The MLK model was employed to simulate the adsorption kinetics of Cu(II), Co(II), Cd(II), Zn(II) and Ni(II) on MnO2 at pH3.2 or 3.3 to get the values of KS-kinetic. The adsorption edges of heavy metals could be modeled with the modified metal partitioning model (MMP model), and the values of KS-Langmuir were obtained. The values of KS-kinetic and KS-Langmuir are very close to each other, validating that the constants obtained by these two methods are basically the same. The MMP model with KS-kinetic constants could predict the adsorption edges of heavy metals on MnO2 very well at different adsorbent/adsorbate concentrations. Moreover, the adsorption isotherms of heavy metals on MnO2 at various pH levels could be predicted reasonably well by the MLI model with the KS-kinetic constants.

  1. Utilization of powdered waste sludge (PWS) for removal of textile dyestuffs from wastewater by adsorption.

    PubMed

    Ozmihci, Serpil; Kargi, Fikret

    2006-11-01

    Acid pre-treated powdered waste sludge (PWS) was used for removal of textile dyestuffs from aqueous medium by adsorption as an alternative to the use of powdered activated carbon (PAC). The rate and extent of dysetuff removals were determined for four different dyestuffs at different PWS concentrations varying between 1 and 6 gl(-1). Biosorbed dyestuff concentrations at equilibrium decreased with increasing PWS concentration for all dyestuffs tested. PWS was more effective for adsorption of Remazol red RR and Chrisofonia direct yellow 12 as compared to the other dyestuffs tested. More than 80% percent dyestuff removal was obtained for all dyestuffs at PWS concentrations above 4 gl(-1) after 6h of incubation. Similar to percent dyestuff removal, the rate of adsorption was maximum at a PWS concentration of 4 gl(-1). Kinetics of adsorption of dyestuffs was investigated by using the first- and second-order kinetic models and the kinetic constants were determined. Second-order kinetics was found to fit the experimental data better than the first-order model for all dyestuffs tested. Adsorption isotherms were established for all dyestuffs used and the isotherm constants were determined by using the experimental data. Langmuir and the generalized adsorption isotherms were found to be more suitable than the Freundlich isotherm for correlation of equilibrium adsorption data. Acid pre-treated PWS was proven to be an effective adsorbent for dyestuff removal as compared to the other adsorbents reported in literature studies.

  2. Influence of clay mineral structure and surfactant nature on the adsorption capacity of surfactants by clays.

    PubMed

    Sánchez-Martín, M J; Dorado, M C; del Hoyo, C; Rodríguez-Cruz, M S

    2008-01-15

    Adsorption of three surfactants of different nature, Triton X-100 (TX100) (non-ionic), sodium dodecylsulphate (SDS) (anionic) and octadecyltrimethylammonium bromide (ODTMA) (cationic) by four layered (montmorillonite, illite, muscovite and kaolinite) and two non-layered (sepiolite and palygorskite) clay minerals was studied. The objective was to improve the understanding of surfactant behaviour in soils for the possible use of these compounds in remediation technologies of contaminated soils by toxic organic compounds. Adsorption isotherms were obtained using surfactant concentrations higher and lower than the critical micelle concentration (cmc). These isotherms showed different adsorption stages of the surfactants by the clay minerals, and were classified in different subgroups of the L-, S- or H-types. An increase in the adsorption of SDS and ODTMA by all clay minerals is observed up to the cmc of the surfactant in the equilibrium solution is reached. However, there was further TX100 adsorption when the equilibrium concentration was well above the cmc. Adsorption constants from Langmuir and Freundlich equations (TX100 and ODTMA) or Freundlich equation (SDS) were used to compare adsorption of different surfactants by clay minerals studied. These constants indicated the surfactant adsorption by clay minerals followed this order ODTMA>TX100>SDS. The adsorption of TX100 and ODTMA was higher by montmorillonite and illite, and the adsorption of SDS was found to be higher by kaolinite and sepiolite. Results obtained show the influence of clay mineral structure and surfactant nature on the adsorption capacity of surfactants by clays, and they indicate the interest to consider the soil mineralogical composition when one surfactant have to be selected in order to establish more efficient strategies for the remediation of soils and water contaminated by toxic organic pollutants.

  3. Adsorption kinetics of azinphosmethyl from aqueous solution onto pyrolyzed Horseshoe sea crab shell from the Atlantic Ocean.

    PubMed

    Gulen, J; Aroguz, A Z; Dalgin, D

    2005-07-01

    The adsorption behavior of azinphosmethyl on pyrolyzed Horseshoe Crab (Limulus polyphemus) outer shell, as a residue, from the Atlantic Ocean, collected along the Maine coast, USA, has been studied with regards to its kinetic and equilibrium conditions, taking into account adsorbate concentrations of 2 x 10(-3), 4 x 10(-3), 6 x 10(-3), and 8 x 10(-3), as well as temperatures of 30 degrees C, 40 degrees C, 50 degrees C, and 60 degrees C. The yield of adsorption of azinphosmethyl from aqueous solution ranged from 56.1% to 61% with temperature increasing. Kinetic studies showed that adsorption rate decreased as the initial azinphosmethyl concentration increased. It was found, that the adsorption reaction obeyed first-order kinetics. The overall rate constants were estimated for different temperatures. The activation energy for adsorption was about 1.52 kJmol(-1), which implies that azinphosmethyl mainly adsorbed physically onto Horseshoe Crab outer shell. Langmuir and Freundlich isotherms were applied to the experimental data and isotherm constants were calculated. The thermodynamic parameters DeltaG0, DeltaH0 and DeltaS0 for the adsorption reaction were evaluated based on equilibrium data and in connection with this result the thermodynamic aspects of adsorption reaction were discussed. The adsorption was found to be endothermic in nature. The adsorbent used in this study proved highly efficient for the removal of azinphosmethyl.

  4. Estimation of adsorption energy for water molecules on a multi-walled carbon nanotube thin film by measuring electric resistance

    NASA Astrophysics Data System (ADS)

    Kokabu, Takuya; Inoue, Shuhei; Matsumura, Yukihiko

    2016-11-01

    Gas sensors based on carbon nanotube (CNT) films have attracted attention owing to their low power consumption. For further development of these sensors, we need to understand the surface interaction of the films with gas molecules. In our previous research, we investigated the influence of water molecules on the electrical conductance of multi-walled CNT films and explained this phenomenon using a two-layer adsorption model. This work motivated us to measure the adsorption energy of CNT-H2O. In this study, we focused on the first-layer adsorption and investigated the sheet resistance to water vapor pressure at various temperatures using the transmission line method (TLM). The results were fitted to Langmuir adsorption model and the adsorption equilibrium constant was determined. The temperature dependence of the sheet resistance followed a model of fluctuation induced tunneling (FIT), in which the energy barrier at the CNT junction is regarded as the main factor influencing the electrical conductance of the CNT film. The sheet resistance and equilibrium constant decreased as temperature increased. This result was consistent with the adsorption phenomenon. Finally, the adsorption energy was determined to be 0.22-0.31 eV, which is larger than the previously calculated value. It was also reported that the adsorption energy of the gas molecules in the interstitial site between two carbon nanotubes was larger than that on the CNT surface. These results indicate that the CNT junction plays a key role in the detection of gas molecules.

  5. The Conceptual Change Approach to Teaching Chemical Equilibrium

    ERIC Educational Resources Information Center

    Canpolat, Nurtac; Pinarbasi, Tacettin; Bayrakceken, Samih; Geban, Omer

    2006-01-01

    This study investigates the effect of a conceptual change approach over traditional instruction on students' understanding of chemical equilibrium concepts (e.g. dynamic nature of equilibrium, definition of equilibrium constant, heterogeneous equilibrium, qualitative interpreting of equilibrium constant, changing the reaction conditions). This…

  6. 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.

  7. Temperature dependence of the NO3 absorption cross-section above 298 K and determination of the equilibrium constant for NO3 + NO2 <--> N2O5 at atmospherically relevant conditions.

    PubMed

    Osthoff, Hans D; Pilling, Michael J; Ravishankara, A R; Brown, Steven S

    2007-11-21

    The reaction NO3 + NO2 <--> N2O5 was studied over the 278-323 K temperature range. Concentrations of NO3, N2O5, and NO2 were measured simultaneously in a 3-channel cavity ring-down spectrometer. Equilibrium constants were determined over atmospherically relevant concentration ranges of the three species in both synthetic samples in the laboratory and ambient air samples in the field. A fit to the laboratory data yielded Keq = (5.1 +/- 0.8) x 10(-27) x e((10871 +/- 46)/7) cm3 molecule(-1). The temperature dependence of the NO3 absorption cross-section at 662 nm was investigated over the 298-388 K temperature range. The line width was found to be independent of temperature, in agreement with previous results. New data for the peak cross section (662.2 nm, vacuum wavelength) were combined with previous measurements in the 200 K-298 K region. A least-squares fit to the combined data gave sigma = [(4.582 +/- 0.096) - (0.00796 +/- 0.00031) x T] x 10(-17) cm2 molecule(-1).

  8. Adsorption of Ba2+ by Ca-exchange clinoptilolite tuff and montmorillonite clay.

    PubMed

    Chávez, M L; de Pablo, L; García, T A

    2010-03-15

    The adsorption of barium by Ca-exchanged clinoptilolite and montmorillonite is presented. The kinetics of adsorption of Ba(2+) were evaluated contacting 1g portion of each adsorber with 100mL 0.1N BaCl(2) for 200 h. Adsorption by Ca-clinoptilolite is defined by second-order kinetics of rate constant K(v) 8.232 x 10(-2) g mg(-1)h(-1) and maximum removal of 71.885 mg g(-1). It is a two-stage process initiated by a rapid uptake of Ba(2+) followed by more moderate kinetics. The adsorption isotherms were determined contacting 0.2g of each adsorber with 10 mL 0.1-0.005N BaCl(2)+CaCl(2) solution, Ba(2+)/Ca(2+) ratio 1, for periods of 7 days for the tuff and 2 days for the clay. The equilibrium adsorption is described by the Langmuir model, of equilibrium constant K 0.0151 L mg(-1) and maximum adsorption of 15.29 mg g(-1). The adsorption of Ba(2+) by Ca-exchanged montmorillonite also follows a second-order reaction of rate constant K(v) 3.179 x 10(-2) g mg(-1)h(-1), and calculated separation of 36.74 mg g(-1); the Langmuir isotherm is defined by the constant K 0.034 L mg(-1) and maximum adsorption of 15.29 mg g(-1). X-ray diffraction shows that the exchange of Ba(2+) modifies the d(001) of Ca-montmorillonite from 15.4 to 12.4A.

  9. 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.

  10. 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.

  11. Predicting Adsorption Affinities of Small Molecules on Carbon Nanotubes Using Molecular Dynamics Simulation.

    PubMed

    Comer, Jeffrey; Chen, Ran; Poblete, Horacio; Vergara-Jaque, Ariela; Riviere, Jim E

    2015-12-22

    Computational techniques have the potential to accelerate the design and optimization of nanomaterials for applications such as drug delivery and contaminant removal; however, the success of such techniques requires reliable models of nanomaterial surfaces as well as accurate descriptions of their interactions with relevant solutes. In the present work, we evaluate the ability of selected models of naked and hydroxylated carbon nanotubes to predict adsorption equilibrium constants for about 30 small aromatic compounds with a variety of functional groups. The equilibrium constants determined using molecular dynamics coupled with free-energy calculation techniques are directly compared to those derived from experimental measurements. The calculations are highly predictive of the relative adsorption affinities of the compounds, with excellent correlation (r ≥ 0.9) between calculated and measured values of the logarithm of the adsorption equilibrium constant. Moreover, the agreement in absolute terms is also reasonable, with average errors of less than one decade. We also explore possible effects of surface loading, although we demonstrate that they are negligible for the experimental conditions considered. Given the degree of reliability demonstrated, we move on to employing the in silico techniques in the design of nanomaterials, using the optimization of adsorption affinity for the herbacide atrazine as an example. Our simulations suggest that, compared to other modifications of graphenic carbon, polyvinylpyrrolidone conjugation gives the highest affinity for atrazine-substantially greater than that of graphenic carbon alone-and may be useful as a nanomaterial for delivery or sequestration of atrazine.

  12. 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.

  13. Molecular dynamics simulations of uranyl and uranyl carbonate adsorption at aluminosilicate surfaces.

    PubMed

    Kerisit, Sebastien; Liu, Chongxuan

    2014-04-01

    Adsorption at mineral surfaces is a critical factor controlling the mobility of uranium(VI) in aqueous environments. Therefore, molecular dynamics (MD) simulations were performed to investigate uranyl(VI) adsorption onto two neutral aluminosilicate surfaces, namely, the orthoclase (001) surface and the octahedral aluminum sheet of the kaolinite (001) surface. Although uranyl preferentially adsorbs as a bidentate inner-sphere complex on both surfaces, the free energy of adsorption on the orthoclase surface (-15 kcal mol(-1)) is significantly more favorable than that at the kaolinite surface (-3 kcal mol(-1)), which is attributed to differences in surface functional groups and the ability of the orthoclase surface to release a surface potassium ion upon uranyl adsorption. The structures of the adsorbed complexes compare favorably with X-ray absorption spectroscopy results. Simulations of the adsorption of uranyl complexes with up to three carbonate ligands revealed that uranyl complexes coordinated to up to two carbonate ions are stable on the orthoclase surface whereas uranyl carbonate surface complexes are unfavored at the kaolinite surface. Combining the MD-derived equilibrium adsorption constants for orthoclase with aqueous equilibrium constants for uranyl carbonate species indicates the presence of adsorbed uranium complexes with one or two carbonates under alkaline conditions, in support of current uranium(VI) surface complexation models.

  14. Molecular Dynamics Simulations of Uranyl and Uranyl Carbonate Adsorption at Alumino-silicate Surfaces

    SciTech Connect

    Kerisit, Sebastien N.; Liu, Chongxuan

    2014-03-03

    Adsorption at mineral surfaces is a critical factor controlling the mobility of uranium(VI) in aqueous environments. Therefore, molecular dynamics (MD) simulations were performed to investigate uranyl(VI) adsorption onto two neutral alumino-silicate surfaces, namely the orthoclase (001) surface and the octahedral aluminum sheet of the kaolinite (001) surface. Although uranyl preferentially adsorbed as a bi-dentate innersphere complex on both surfaces, the free energy of adsorption at the orthoclase surface (-15 kcal mol-1) was significantly more favorable than that at the kaolinite surface (-3 kcal mol-1), which was attributed to differences in surface functional groups and to the ability of the orthoclase surface to dissolve a surface potassium ion upon uranyl adsorption. The structures of the adsorbed complexes compared favorably with X-ray absorption spectroscopy results. Simulations of the adsorption of uranyl complexes with up to three carbonate ligands revealed that uranyl complexes coordinated to up to 2 carbonate ions are stable on the orthoclase surface whereas uranyl carbonate surface complexes are unfavored at the kaolinite surface. Combining the MD-derived equilibrium adsorption constants for orthoclase with aqueous equilibrium constants for uranyl carbonate species indicates the presence of adsorbed uranium complexes with one or two carbonates in alkaline conditions, in support of current uranium(VI) surface complexation models.

  15. 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.

  16. Grinding kinetics and equilibrium states

    NASA Technical Reports Server (NTRS)

    Opoczky, L.; Farnady, F.

    1984-01-01

    The temporary and permanent equilibrium occurring during the initial stage of cement grinding does not indicate the end of comminution, but rather an increased energy consumption during grinding. The constant dynamic equilibrium occurs after a long grinding period indicating the end of comminution for a given particle size. Grinding equilibrium curves can be constructed to show the stages of comminution and agglomeration for certain particle sizes.

  17. 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.

  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. Laser temperature jump relaxation measurements of adsorption/desorption kinetics at liquid/solid interfaces

    SciTech Connect

    Waite, S.W.; Harris, J.M.; Holzwarth, J.F.

    1995-04-15

    The iodine laser temperature jump method is used to study adsorption/desorption kinetics at a methylated silica/solution interface. A suspension of C1-derivatized fumed silica is used for the kinetic measurements. The colloidal silica does not significantly change the attenuation of near-IR radiation from the iodine laser and allows the surface site concentration to be varied so that adsorption and desorption rates can be determined. The temperature jump relaxation method was used to investigate the effect of electrolyte on adsorption of a charged solute (ANS) on a C1 silica surface. Adsorption equilibrium conditions were optimized to observe a maximum relaxation signal. Without electrolyte, the relaxation signal is biexponential, which is also reflected in a broad chromatographic peak shape and a two-site sorption isotherm. When electrolyte is added, the relaxation signal is primarily single exponential, which agrees with the linear adsorption isotherm. The adsorption rate and equilibrium constant were found to increase significantly with added electrolyte, which showed that adsorption kinetics can influence both band broadening and retention. 28 refs., 7 figs., 4 tab.

  20. Competitive adsorption of furfural and phenolic compounds onto activated carbon in fixed bed column.

    PubMed

    Sulaymon, Abbas H; Ahmed, Kawther W

    2008-01-15

    For a multicomponent competitive adsorption of furfural and phenolic compounds, a mathematical model was builtto describe the mass transfer kinetics in a fixed bed column with activated carbon. The effects of competitive adsorption equilibrium constant, axial dispersion, external mass transfer, and intraparticle diffusion resistance on the breakthrough curve were studied for weakly adsorbed compound (furfural) and strongly adsorbed compounds (parachlorophenol and phenol). Experiments were carried out to remove the furfural and phenolic compound from aqueous solution. The equilibrium data and intraparticle diffusion coefficients obtained from separate experiments in a batch adsorber, by fitting the experimental data with theoretical model. The results show that the mathematical model includes external mass transfer and pore diffusion using nonlinear isotherms and provides a good description of the adsorption process for furfural and phenolic compounds in a fixed bed adsorber.

  1. Implementing an Equilibrium Law Teaching Sequence for Secondary School Students to Learn Chemical Equilibrium

    ERIC Educational Resources Information Center

    Ghirardi, Marco; Marchetti, Fabio; Pettinari, Claudio; Regis, Alberto; Roletto, Ezio

    2015-01-01

    A didactic sequence is proposed for the teaching of chemical equilibrium law. In this approach, we have avoided the kinetic derivation and the thermodynamic justification of the equilibrium constant. The equilibrium constant expression is established empirically by a trial-and-error approach. Additionally, students learn to use the criterion of…

  2. The elimination of siloxanes from the biogas of a wastewater treatment plant by means of an adsorption process.

    PubMed

    Trapote, Arturo; García, Mariano; Prats, Daniel

    2016-12-01

    Siloxanes present in the biogas produced during anaerobic digestion in wastewater treatment plants (WWTPs) can damage the mechanism of cogeneration heat engines and obstruct the process of energy valorization. The objective of this research is to detect the presence of siloxanes in the biogas and evaluate a procedure for their elimination. A breakthrough curve of a synthetic decamethylcyclopentasiloxane on an experimental bed of activated carbon was modeled and the theoretical mathematical model of the adsorption process was adjusted. As a result, the constants of the model were obtained: the mass transfer constant, Henry's equilibrium constant, and the Eddy diffusion. The procedure developed allows the adsorption equilibrium of siloxanes on activated carbon to be predicted, and makes it possible to lay the basis for the design of an appropriate activated carbon module for the elimination of siloxanes in a WWTP.

  3. Correlation of ph dependant equilibrium isotherms of heavy metal biosorption with a modified Freundlich model.

    PubMed

    Liu, X; Goodfellow, M R; Yu, Q; Zheng, C

    2004-12-01

    Equilibrium isotherms of heavy metal biosorption are commonly correlated with adsorption models such as the Freundlich model. On the other hand, the adsorption properties of heavy metal biosorption are strongly influenced by the solution pH of the biosorption system. Therefore, standard adsorption models are limited to the correlation of equilibrium isotherms under constant pH values. In this paper, a modified Freundlich model was developed for the correlation of pH dependent equilibrium isotherms of heavy metal biosorption. The model was based on the mechanism that the functional groups for heavy metal interactions are weakly acidic groups and the uptake capacities of the biomass are affected through the association and dissociation equilibrium between two apparent ionic forms. Both the standard and the modified Freundlich models were tested with isotherm data for Cd2+, Cu2+ and Ni2+ biosorption onto pre-treated biomass of marine alga Durvillaea potatorum under various solution pH values. Regression analyses indicated that the developed model correlated the experimental data well.

  4. Adsorption of Benzoic Compounds onto Stainless Steel Particles

    PubMed

    Suzuki; Shibata; Inoue

    1997-09-15

    Equilibrium experiment was conducted to investigate the factors determining the adsorption of benzoic acid (BA) and its derivatives, m- and p-hydroxy BA, onto SUS316L stainless steel particles of 8-10 &mgr;m diameter and under 100 mesh. Adsorption isotherms of these benzoic compounds were determined in the presence of 0.05 M NaCl at pH 4 and 30°C. The adsorptions of the these compounds were described well by a Langmuirian model for both adsorbents. When the maximum number of the benzoic compound adsorption sites was expressed on the basis of unit surface area (N, mol/m2), the N values were relatively constant, while the greatest value of the affinity (K, ml/&mgr;mol) was obtained for p-hydroxy BA, although its value was in the same range as that of the other two adsorbates. Diffuse-reflectance Fourier transform infrared spectra of the fine adsorbent (8-10 &mgr;m diameter) after equilibration suggest that the adsorption mainly takes place through the carboxyl group of the adsorbate-stainless steel surface interaction for all adsorbates, whereas concomitant interaction occurs in part with participation of the phenolic hydroxyl group for p-OH BA adsorbate, accounting for the difference in adsorption properties. Copyright 1997 Academic Press. Copyright 1997Academic Press

  5. 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.

  6. 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).

  7. Partition and water/oil adsorption of some surfactants.

    PubMed

    Tadmouri, Rawad; Zedde, Chantal; Routaboul, Corinne; Micheau, Jean-Claude; Pimienta, Véronique

    2008-10-02

    Adsorption isotherms have been determined at the water/oil interface for five biphasic systems involving surfactants (non-ionic and ionic) present in both phases at partition equilibrium. The systems studied were polyoxyethylene(23)lauryl ether (Brij35) in water/hexane and four ionic surfactants, hexadecyltrimethylammonium bromide (CTAB), and a series of three tetraalkylammonium dodecylsulfate (TEADS, TPADS, and TBADS) in water/CH 2Cl 2. Interfacial tension measurements performed at the water/air and water/oil interfaces provided all the necessary information for the determination of the adsorption parameters by taking partition into account. These measurements also allowed the comparison of the adsorption properties at both interfaces which showed an increase of the adsorption equilibrium constant and a decrease of the maximum surface concentration at the water/oil interface compared to water/air. The values of the critical aggregation concentration showed, in all cases, that only the surfactant dissolved in the aqueous phase contribute to the decrease of the water/oil interfacial tension. In the case of the four ionic surfactants, the critical aggregation concentration obtained in biphasic conditions were lowered because of the formation of mixed surfactant-CH 2Cl 2 aggregates.

  8. 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.

  9. Experimental determination of the thermodynamic parameters affecting the adsorption behaviour and dispersion effectiveness of PCE superplasticizers

    SciTech Connect

    Plank, J.; Sachsenhauser, B.; Reese, J. de

    2010-05-15

    For adsorption of three different allylether-based PCE superplasticizers on CaCO{sub 3} surface, the thermodynamic parameters DELTAH, DELTAS and DELTAG were determined experimentally. The GIBBS standard free energy of adsorption DELTAG{sub 0ads}, the standard enthalpy of adsorption DELTAH{sub 0ads} and the standard entropy of adsorption DELTAS{sub 0ads} applying to an unoccupied CaCO{sub 3} surface were obtained via a linear regression of ln K (equilibrium constant) versus 1 / T (VAN'T HOFF plot). Additionally, the thermodynamic parameters characteristic for a CaCO{sub 3} surface loaded already with polymer (isosteric conditions) were determined using a modified CLAUSIUS-CLAPEYRON equation. For all PCE molecules, negative DELTAG values were found, indicating that adsorption of these polymers is energetically favourable and a spontaneous process. Adsorption of PCEs possessing short side chains is mainly instigated by electrostatic attraction and a release of enthalpy. Contrary to this, adsorption of PCEs with long side chains occurs because of a huge gain in entropy. The gain in entropy results from the release of counter ions attached to the carboxylate groups of the polymer backbone and of water molecules and ions adsorbed on the CaCO{sub 3} surface. With increased surface loading, however, DELTAG{sub isosteric} decreases and adsorption ceases when DELTAG becomes 0. The presence of Ca{sup 2+} ions in the pore solution strongly impacts PCE adsorption, due to complexation of carboxylate groups and a reduced anionic charge amount of the molecule. In the presence of Ca{sup 2+}, adsorption of allylether-based PCEs is almost exclusively driven by a gain in entropy. Consequently, PCEs should produce a strong entropic effect upon adsorption to be effective cement dispersants. Molecular architecture, anionic charge density and molecular weight as well as the type of anchor groups present in a superplasticizer determine whether enthalpy or entropy is the dominant force for

  10. Entropically favored adsorption of cellulosic molecules onto carbon materials through hydrophobic functionalities.

    PubMed

    Yabushita, Mizuho; Kobayashi, Hirokazu; Hasegawa, Jun-Ya; Hara, Kenji; Fukuoka, Atsushi

    2014-05-01

    Carbon-based materials have attracted interest as high-performance catalysts for the aqueous-phase conversion of cellulose. The adsorption of β-glucans plays a crucial role in the catalytic performance of carbons, although the primary driving force and details of the adsorption process remain unclear. This study demonstrates that adsorption occurs at hydrophobic sites on the carbon surface and that hydrophilic groups are not involved. Analysis of adsorption temperature dependence also reveals that the entropy change associated with adsorption is positive. Our results indicate that adsorption occurs by entropically driven hydrophobic interactions in addition to CH-π hydrogen bonding. These same CH-π hydrogen bonds are also confirmed by DFT calculations. The adsorption of β-glucans on carbons is significantly stronger than the affinity between β-glucans. The adsorption equilibrium constants of β-glucans on carbons increase exponentially with increasing degrees of polymerization, which supports the theory of strong interactions between the carbon and the long β-glucans found in cellulose.

  11. Thermodynamic and kinetic investigations of PO3-4 adsorption on blast furnace slag.

    PubMed

    Oguz, Ensar

    2005-01-01

    The kinetics of adsorption of PO(3-)(4) by blast furnace slag were found to be fast, reaching equilibrium in 20 min and following a pseudo-second-order rate equation. The adsorption behavior of PO(3-)(4) on blast furnace slag has been studied as a function of the solution agitation speed, pH, and temperature. Results have been analyzed by Freundlich, Langmuir, BET, and Dubinin-Radushkevich (D-R) adsorption isotherms. The mean energy of adsorption, 10.31 kJ mol(-1), was calculated from the D-R adsorption isotherm. The rate constants were calculated for 293, 298, 303, and 308 K using a pseudo-second-order rate equation and the activation energy (E(a)) was derived using the Arrhenius equation. Thermodynamic parameters such as DeltaH(0), DeltaS(0), and DeltaG(0) were calculated from the slope and intercept of linear plot of lnK(D) against 1/T. The DeltaH(0) and DeltaG(0) values of PO(3-)(4) adsorption on the blast furnace slag show endothermic heat of adsorption. But there is a negative free energy value, indicating that the process of PO(3-)(4) adsorption is favored at high temperatures.

  12. Phosphorus adsorption on natural sediments with different pH incorporating surface morphology characterization.

    PubMed

    Huang, Lei; Fang, Hongwei; He, Guojian; Chen, Minghong

    2016-09-01

    Sediment samples from University Lake (U.L.) and Anacostia River (A.R.) were collected to study the phosphorus (P) adsorption with pH at 3.65, 4.75, and 5.65. The surface micro-morphology and pore structures of sediment particles were obtained using a scanning electron microscopy and gas adsorption method, respectively. Fourier analysis was then applied to approximate the surface morphology, which was incorporated into the Langmuir isotherm to directly derive the model parameters for P adsorption simulation. Meanwhile, an empirical function of pH was introduced to represent the pH effect on P adsorption. A stronger P adsorption was observed for the A.R. sediment due to the more clay minerals, smaller median diameter, and a greater percentage of large pores, and the increasing pH resulted in a decrease of adsorption equilibrium constant as well as the P adsorption capacity, which was well reproduced by the adsorption isotherms. This study would benefit the mechanism study of the interactions between sediment particles and pollutants, providing references for understanding the pollutants' transport in aqueous systems.

  13. Kinetic study for copper adsorption onto soil minerals in the absence and presence of humic acid.

    PubMed

    Komy, Zanaty R; Shaker, Ali M; Heggy, Said E M; El-Sayed, Mohamed E A

    2014-03-01

    Equilibrium and kinetics of Cu(2+) adsorption onto soil minerals (kaolinite and hematite) in the absence and presence of humic acid have been investigated under various conditions. The influences of ionic strength, pH and solution cations on the rate of the adsorption have been studied. The rate and the amount of adsorbed Cu(2+) onto soil minerals in the absence or the presence of humic acid increased with decreasing ionic strength, increasing pH and in the presence of the background electrolyte K(+) rather than Ca(2+). Humic acid enhanced the rate and the amount of adsorbed Cu(2+) onto soil minerals. The adsorption equilibrium data showed that adsorption behavior of Cu(2+) could be described more reasonably by Langmiur adsorption isotherm than Freundlich isotherm in the absence or presence of humic acid. Pseudo first and pseudo second order models were used to evaluate the kinetic data and the rate constants. The results indicated that the adsorption of Cu(2+) onto hematite and kaolinite in the absence and presence of humic acid is more conforming to pseudo second order kinetics.

  14. 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.

  15. 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.

  16. Nanoparticle-protein interactions: a thermodynamic and kinetic study of the adsorption of bovine serum albumin to gold nanoparticle surfaces.

    PubMed

    Boulos, Stefano P; Davis, Tyler A; Yang, Jie An; Lohse, Samuel E; Alkilany, Alaaldin M; Holland, Lisa A; Murphy, Catherine J

    2013-12-03

    Investigating the adsorption process of proteins on nanoparticle surfaces is essential to understand how to control the biological interactions of functionalized nanoparticles. In this work, a library of spherical and rod-shaped gold nanoparticles (GNPs) was used to evaluate the process of protein adsorption to their surfaces. The binding of a model protein (bovine serum albumin, BSA) to GNPs as a function of particle shape, size, and surface charge was investigated. Two independent comparative analytical methods were used to evaluate the adsorption process: steady-state fluorescence quenching titration and affinity capillary electrophoresis (ACE). Although under favorable electrostatic conditions kinetic analysis showed a faster adsorption of BSA to the surface of cationic GNPs, equilibrium binding constant determinations indicated that BSA has a comparable binding affinity to all of the GNPs tested, regardless of surface charge. BSA was even found to adsorb strongly to GNPs with a pegylated/neutral surface. However, these fluorescence titrations suffer from significant interference from the strong light absorption of the GNPs. The BSA-GNP equilibrium binding constants, as determined by the ACE method, were 10(5) times lower than values determined using spectroscopic titrations. While both analytical methods could be suitable to determine the binding constants for protein adsorption to NP surfaces, both methods have limitations that complicate the determination of protein-GNP binding constants. The optical properties of GNPs interfere with Ka determinations by static fluorescence quenching analysis. ACE, in contrast, suffers from material compatibility issues, as positively charged GNPs adhere to the walls of the capillary during analysis. Researchers seeking to determine equilibrium binding constants for protein-GNP interactions should therefore utilize as many orthogonal techniques as possible to study a protein-GNP system.

  17. 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.

  18. 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.

  19. 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

  20. Are Fundamental Constants Really Constant?

    ERIC Educational Resources Information Center

    Swetman, T. P.

    1972-01-01

    Dirac's classical conclusions, that the values of e2, M and m are constants and the quantity of G decreases with time. Evoked considerable interest among researchers and traces historical development by which further experimental evidence points out that both e and G are constant values. (PS)

  1. 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).

  2. 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.

  3. Adsorption of CO(2), CH(4), N(2)O, and N(2) on MOF-5, MOF-177, and zeolite 5A.

    PubMed

    Saha, Dipendu; Bao, Zongbi; Jia, Feng; Deng, Shuguang

    2010-03-01

    Adsorption equilibrium and kinetics of CO(2), CH(4), N(2)O, and N(2) on two newly discovered adsorbents, metal-organic frameworks MOF-5 and MOF-177 and one traditional adsorbent, zeolite 5A were determined to assess their efficacy for CO(2), CH(4), and N(2)O removal from air and separation of CO(2) from CH(4) in pressure swing adsorption processes. Adsorption equilibrium and kinetics data for CO(2), CH(4), N(2)O, and N(2) on all three adsorbents were measured volumetrically at 298K and gas pressures up to 800 Torr. Adsorption equilibrium capacities of CO(2) and CH(4) on all three adsorbents were determined gravimetrically at 298 K and elevated pressures (14 bar for CO(2) and 100 bar for CH(4)). The Henry's law and Langmuir adsorption equilibrium models were applied to correlate the adsorption isotherms, and a classical micropore diffusion model was used to analyze the adsorption kinetic data. The adsorption equilibrium selectivity was calculated from the ratio of Henry's constants, and the adsorbent selection parameter for pressure swing adsorption processes were determined by combining the equilibrium selectivity and working capacity ratio. Based on the selectivity and adsorbent selection parameter results, zeolite 5A is a better adsorbent for removing CO(2) and N(2)O from air and separation of CO(2) from CH(4), whereas MOF-177 is the adsorbent of choice for removing CH(4) from air. However, both MOF adsorbents have larger adsorption capacities for CO(2) and CH(4) than zeolite 5A at elevated pressures, suggesting MOF-5 and MOF-177 are better adsorbents for CO(2) and CH(4) storage. The CH(4) adsorption capacity of 22 wt.% on MOF-177 at 298K and 100 bar is probably the largest adsorption uptake of CH(4) on any dry adsorbents. The average diffusivity of CO(2), CH(4) and N(2)O in MOF-5 and MOF-177 is in the order of 10(-9) m(2)/s, as compared to 10(-11) m(2)/s for CO(2), CH(4) and N(2)O in zeolite 5A. The effects of gas pressure on diffusivity for different adsorabte

  4. Equilibrium and kinetics analysis of carbon dioxide capture using immobilized amine on a mesoporous silica

    SciTech Connect

    Monazam, E., Shadle, L., Pennline, H., Miller, D., Fauth, D., Hoffman, J., Gray, M.

    2012-01-01

    The equilibrium and conversion-time data on the absorption of carbon dioxide (CO{sub 2}) with amine-based solid sorbent were analyzed over the range of 303–373 K. Data on CO{sub 2} loading on amine based solid sorbent at these temperatures and CO{sub 2} partial pressure between 10 and 760 mm Hg obtained from volumetric adsorption apparatus were fitted to a simple equilibrium model to generate the different parameters (including equilibrium constant) in the model. Using these constants, a correlation was obtained to define equilibrium constant and maximum CO{sub 2} loading as a function of temperature. In this study, a shrinking core model (SCM) was applied to elucidate the relative importance of pore diffusion and surface chemical reaction in controlling the rate of reaction. Application of SCM to the data suggested a surface reaction-controlled mechanism for the temperature of up to 40°C and pore-diffusion mechanism at higher temperature.

  5. Equilibrium and Absorption Kinetics of Carbon Dioxide by solid Supported Amine Sorbent

    SciTech Connect

    Monazam, Esmail R.; Shadle, Lawrence J.; Siriwardane, Ranjani

    2011-11-01

    The equilibrium and conversion-time data on the absorption of carbon dioxide (CO{sub 2}) with amine-based solid sorbent were analyzed over the range of 303–373 K. Data on CO{sub 2} loading on amine based solid sorbent at these temperatures and CO{sub 2} partial pressure between 10 and 760 mm Hg obtained from volumetric adsorption apparatus were fitted to a simple equilibrium model to generate the different parameters (including equilibrium constant) in the model. Using these constants, a correlation was obtained to define equilibrium constant and maximum CO{sub 2} loading as a function of temperature. In this study, a shrinking core model (SCM) was applied to elucidate the relative importance of pore diffusion and surface chemical reaction in controlling the rate of reaction. Application of SCM to the data suggested a surface reaction-controlled mechanism for the temperature of up to 40°C and pore-diffusion mechanism at higher temperature.

  6. 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.

  7. Adsorption and desorption of atrazine and deethylatrazine by low organic carbon geologic materials

    USGS Publications Warehouse

    Roy, W.R.; Krapac, I.G.

    1994-01-01

    The adsorption and desorption of atrazine (2-chloro-4-ethylamino-6- isopropylamino-s-triazine) and a primary metabolite, deethylatrazine (2- amino-4-chloro-6-isopropylamino-s-triazine; DEA), by low organic C (??? 3.3 g kg-1) materials were measured by batch-equilibrium techniques. The adsorbents were samples of glacial outwash sand, till, and stream sediments. The adsorption of both atrazine and DEA conformed to linear isotherms. The adsorption of atrazine by most of the adsorbents yielded apparent K(oc) values that were in excess of those based on surface agricultural soils. Adsorption correlated with only the pH of the sand-water suspensions. The desorption of atrazine was hysteretic under the conditions of the measurement. DEA had a lower affinity for the same adsorbents; the mean ratio of K(d) values of DEA to those of atrazine was 0.37 ?? 0.20. DEA adsorption did not correlate with organic C, surface area, clay content of the adsorbents, or with the pH of the suspensions. DEA adsorption, unlike atrazine, tended to be reversible. There was a linear relationship between the adsorption constants of atrazine and those of DEA.

  8. Adsorption and desorption of atrazine and deethylatrazine by low organic carbon geologic materials

    SciTech Connect

    Roy, W.R.; Krapac, I.G.

    1994-05-01

    The adsorption and desorption of atrazine (2-chloro-4-ethylamino-6- isopropylamino-s-triazine) and a primary metabolite, deethylatrazine (2-amino-4-chloro-6-isopropylamino-s-triazine; DEA), by low organic C ({le} 3.3 g kg{sup -1}) materials were measured by batch-equilibrium techniques. The adsorbents were samples of glacial outwash sand, till, and stream sediments. The adsorption of both atrazine and DEA conformed to linear isotherms. The adsorption of atrazine by most of the absorbents yielded apparent K, values that were in excess of those based on surface agricultural soils. Adsorption correlated with only the pH of the sand-water suspensions. The desorption of atrazine was hysteretic under the conditions of the measurement. DEA had a lower affinity for the same adsorbents; the mean ratio of Kd values of DEA to those of atrazine was 0.37 {+-} 0.20. DEA adsorption did not correlate with organic C, surface area, clay content of the adsorbents, or with the pH of the suspensions. DEA adsorption, unlike atrazine, tended to be reversible. There was a linear relationship between the adsorption constants of atrazine and those of DEA. 40 refs., 8 figs., 3 tabs.

  9. Hexavalent chromium removal performance of anionic functionalized monolithic polymers: column adsorption, regeneration and modelling.

    PubMed

    Barlik, Necla; Keskinler, Bülent; Kocakerim, M Muhtar

    2016-01-01

    Anionic functionalized monolithic macro-porous polymers were used for the removal of hexavalent chromium(VI) anions from aqueous solution in column experiments. At a flux of 1.0 cm min and 30 mg Cr(VI) L(-1) feed concentration, breakthrough capacity and apparent capacity were 0.066 g Cr(VI) g(-1) anionic monolith and 0.144 g Cr(VI) g(-1) anionic monolith, respectively. The degree of column utilization was found to lie in the range 41-46%. Two kinetic models, theoretical and Thomas models, were applied to experimental data to predict the breakthrough curves and to determine the characteristic parameters of the column useful for process design. The simulation of the whole breakthrough curve was effective with the models. At a flux of 1.0 cm min and 30 mg Cr(VI) L(-1) feed concentration, the dispersion coefficient and adsorption equilibrium constant (K) were 3.14 × 10(-7) m s(-1) and 3,840, respectively. Also, Thomas model parameters k1 (rate constant of adsorption) and qm (equilibrium solid-phase concentration of sorbed solute) were 1.08 × 10(-3) L mg(-1) min(-1) and 0.124 g g(-1), respectively. After reaching equilibrium adsorption capacity, the monoliths were regenerated using 1 N HCl and were subsequently re-tested. It was found that the regeneration efficiency reduced from 98% after second usage to 97% after the third usage.

  10. Adsorption of acid dyes from aqueous solution on activated bleaching earth.

    PubMed

    Tsai, W T; Chang, C Y; Ing, C H; Chang, C F

    2004-07-01

    In the present study, activated bleaching earth was used as clay adsorbent for an investigation of the adsorbability and adsorption kinetics of acid dyes (i.e., acid orange 51, acid blue 9, and acid orange 10) with three different molecular sizes from aqueous solution at 25 degrees C in a batch adsorber. The rate of adsorption has been investigated under the most important process parameters (i.e., initial dye concentration). A simple pseudo-second-order model has been tested to predict the adsorption rate constant, equilibrium adsorbate concentration, and equilibrium adsorption capacity by the fittings of the experimental data. The results showed that the adsorbability of the acid acids by activated bleaching earth follows the order: acid orange 51 > acid blue 9 > acid orange 10, parallel to the molecular weights and molecular sizes of the acid dyes. The adsorption removals (below 3%) of acid blue 9 and acid orange 10 onto the clay adsorbent are far lower than that (approximately 24%) of acid orange 51. Further, the adsorption kinetic of acid orange 51 can be well described by the pseudo-second-order reaction model. Based on the isotherm data obtained from the fittings of the adsorption kinetics, the Langmuir model appears to fit the adsorption better than the Freundlich model. The external coefficients of mass transfer of the acid orange 51 molecule across the boundary layer of adsorbent particle have also been estimated at the order of 10(-4)-10(-5) cm s(-1) based on the film-pore model and pseudo-second-order reaction model.

  11. Adsorption of phenol from aqueous solution by using carbonised beet pulp.

    PubMed

    Dursun, Gülbeyi; Ciçek, Handan; Dursun, Arzu Y

    2005-10-17

    The beet pulp, a major low value by-product in sugar industry was used to prepare carbon for phenol adsorption. It was produced by carbonisation in N2 atmosphere at 600 degrees C for 1.5 h. The surface area of beet pulp carbon was measured as 47.5 m2g(-1) by using BET method. The adsorption studies of phenol from aqueous solution on beet pulp carbon (BPC) have been studied in the range of 25-500 mgdm(-3) initial phenol concentrations and at the temperatures of 25, 40 and 60 degrees C. The maximum phenol adsorption capacity was obtained as 89.5 mgg(-1)at the temperature of 60 degrees C at pH=6.0. The Freundlich and Langmuir adsorption models were used for the mathematical description of the adsorption equilibrium and it was reported that experimental data fitted very well to Freundlich model, although they could be modelled by the Langmuir equation. Batch adsorption models, based on the assumption of the pseudo-first order and pseudo-second order mechanism, were applied to examine the kinetics of the adsorption. The results showed that kinetic data were followed more closely the pseudo-second order model than the pseudo-first order. The thermodynamic parameters such as, equilibrium constant (K), Gibbs free energy changes (DeltaG degrees ), standard enthalpy change (DeltaH degrees ) and standard entropy change (DeltaS degrees ) had been determined. The results show that adsorption of phenol on BPC is an endothermic and spontaneous in nature.

  12. 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.

  13. Ligand(s)-to-metal charge transfer as a factor controlling the equilibrium constants of late first-row transition metal complexes: revealing the Irving-Williams thermodynamical series.

    PubMed

    Varadwaj, Pradeep R; Varadwaj, Arpita; Jin, Bih-Yaw

    2015-01-14

    A unified relationship between the experimental formation constants and the ligand(s)-to-metal charge transfer values of versatile ligand complexes of late transition series first-row bivalent metal ions is uncovered. The latter property not only explicates the Irving-Williams series but also rationalizes quantitatively Pearson's concept of hard and soft acids and bases by correlating the gas-phase to aqueous solution-phase chemistry in a broad sense.

  14. 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.

  15. 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.

  16. 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

  17. On the Equilibrium States of Interconnected Bubbles or Balloons.

    ERIC Educational Resources Information Center

    Weinhaus, F.; Barker, W.

    1978-01-01

    Describes the equilibrium states of a system composed of two interconnected, air-filled spherical membranes of different sizes. The equilibrium configurations are determined by the method of minimization of the availability of the system at constant temperature. (GA)

  18. Thermodynamics and Kinetics of Chemical Equilibrium in Solution.

    ERIC Educational Resources Information Center

    Leenson, I. A.

    1986-01-01

    Discusses theory of thermodynamics of the equilibrium in solution and dissociation-dimerization kinetics. Describes experimental procedure including determination of molar absorptivity and equilibrium constant, reaction enthalpy, and kinetics of the dissociation-dimerization reaction. (JM)

  19. Kafirin adsorption on ion-exchange resins: isotherm and kinetic studies.

    PubMed

    Kumar, Prashant; Lau, Pei Wen; Kale, Sandeep; Johnson, Stuart; Pareek, Vishnu; Utikar, Ranjeet; Lali, Arvind

    2014-08-22

    Kafirin is a natural, hydrophobic and celiac safe prolamin protein obtained from sorghum seeds. Today kafirin is found to be useful in designing delayed delivery systems and coatings of pharmaceuticals and nutraceuticals where its purity is important and this can be obtained by adsorptive chromatography. This study is the first scientific insight into the isotherm and kinetic studies of kafirin adsorption on anion- and cation-exchange resins for practical applications in preparative scale chromatography. Adsorption isotherms of kafirin were determined for five anion- and two cation-exchange resins in batch systems. Isotherm parameters such as maximum binding capacity and dissociation constant were determined from Langmuir isotherm, and adsorptive capacity and affinity constant from Freundlich isotherm. Langmuir isotherm was found to fit the adsorption equilibrium data well. Batch uptake kinetics for kafirin adsorption on these resins was also carried out and critical parameters including the diffusion coefficient, film mass transfer coefficient, and Biot number for film-pore diffusion model were calculated. Both the isotherm and the kinetic parameters were considered for selection of appropriate resin for kafirin purification. UNOsphere Q (78.26 mg/ml) and Toyopearl SP-650M (57.4 mg/ml) were found to offer better kafirin binding capacities and interaction strength with excellent uptake kinetics under moderate operating conditions. With these adsorbents, film diffusion resistance was found to be major governing factor for adsorption (Bi<10 and δ<1). Based on designer objective function, UNOsphere Q was found be best adsorbent for binding of kafirin. The data presented is valuable for designing large scale preparative adsorptive chromatographic kafirin purification systems.

  20. The importance of surface adsorption on the washout of semivolatile organic compounds by rain

    NASA Astrophysics Data System (ADS)

    Simcik, Matt F.

    The washout of semivolatile organic compounds (SOCs) by rain is an important removal mechanism from the atmosphere and an important loading mechanism to terrestrial and aquatic systems. In this paper, the rain washout equation is modified to include gas-phase SOC adsorption to the surface of raindrops. The relative influence of gas adsorption is a function of the air-water interface adsorption constant, Kia, Henry's law CONSTANT, H, the fraction of the SOCs associated with particles, φ, and the diameter of the raindrop, dR. Theoretical gas-phase washout ratios were calculated assuming a rainfall intensity of 10 mm/h and spherical raindrops for polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and polychlorinated dibenzo- p-dioxins (PCDDs). Results for PAHs indicate that gas-phase washout including surface adsorption exceed those calculated considering only Henry's law dissolution for low volatility PAHs. This shift in gas-phase partitioning being dominated by dissolution to the bulk water of the rain drop to being dominated by adsorption to the raindrop surface occurs at sub-cooled liquid saturated vapor pressures around 10 -5 Pa, corresponding to PAHs with greater than or equal to five aromatic rings. Similar calculations for PCBs indicate similar gas-phase washout ratios (10 to ˜10 4), and a similar shift from dissolution to adsorption in the range of sub-cooled liquid saturated vapor pressures of 10 -2.7 to 10 -1.4 Pa. Calculations for polychlorinated dibenzo- p-dioxins (PCDDs) indicate that adsorption dominates all gas-phase washout of PCDDs. Kinetic calculations indicate that even the least volatile SOCs reach equilibrium with the rain within hundreds of meters of the bottom of a cloud, depending on rainfall rate. Given the theoretical domination of gas-phase adsorption to the surface of raindrops, traditional rain samplers may underestimate actual washout ratios and ultimately loadings to terrestrial and aquatic surfaces because of

  1. Ab initio prediction of adsorption isotherms for small molecules in metal-organic frameworks: the effect of lateral interactions for methane/CPO-27-Mg.

    PubMed

    Sillar, Kaido; Sauer, Joachim

    2012-11-07

    A hybrid method that combines density functional theory for periodic structures with wave function-based electron correlation methods for finite-size models of adsorption sites is employed to calculate energies for adsorption of CH(4) onto different sites in the metal-organic framework (MOF) CPO-27-Mg (Mg-MOF-74) with chemical accuracy. The adsorption energies for the Mg(2+), linker, second layer sites are -27.8, -18.3, and -15.1 kJ/mol. Adsorbate-adsorbate interactions increase the average CH(4) adsorption energy by about 10% (2.4 kJ/mol). The free rotor-harmonic oscillator-ideal gas model is applied to calculate free energies/equilibrium constants for adsorption on the individual sites. This information is used in a multisite Langmuir model, augmented with a Bragg-Williams model for lateral interactions, to calculate adsorption isotherms. This ab initio approach yields the contributions of the individual sites to the final isotherms and also of the lateral interactions that contribute about 15% to the maximum excess adsorption capacity. Isotherms are calculated for both absolute amounts, for calculation of isosteric heats of adsorption as function of coverage, and excess amounts, for comparison with measured isotherms. Agreement with observed excess isotherms is reached if the experimentally determined limited accessibility of adsorption sites (78%) is taken into account.

  2. Quantification of the effects of organic and carbonate buffers on arsenate and phosphate adsorption on a goethite-based granular porous adsorbent.

    PubMed

    Kanematsu, Masakazu; Young, Thomas M; Fukushi, Keisuke; Sverjensky, Dimitri A; Green, Peter G; Darby, Jeannie L

    2011-01-15

    Interest in the development of oxide-based materials for arsenate removal has led to a variety of experimental methods and conditions for determining arsenate adsorption isotherms, which hinders comparative evaluation of their adsorptive capacities. Here, we systematically investigate the effects of buffer (HEPES or carbonate), adsorbent dose, and solution pH on arsenate and phosphate adsorption isotherms for a previously well characterized goethite-based adsorbent (Bayoxide E33 (E33)). All adsorption isotherms obtained at different adsorbate/adsorbent concentrations were identical when 1 mM of HEPES (96 mg C/L) was used as a buffer. At low aqueous arsenate and phosphate concentration (∼1.3 μM), however, adsorption isotherms obtained using 10 mM of NaHCO(3) buffer, which is a reasonable carbonate concentration in groundwater, are significantly different from those obtained without buffer or with HEPES. The carbonate competitive effects were analyzed using the extended triple layer model (ETLM) with the adsorption equilibrium constant of carbonate calibrated using independent published carbonate adsorption data for pure goethite taking into consideration the different surface properties. The successful ETLM calculations of arsenate adsorption isotherms for E33 under various conditions allowed quantitative comparison of the arsenate adsorption capacity between E33 and other major adsorbents initially tested under varied experimental conditions in the literature.

  3. Surface complexation modeling calculation of Pb(II) adsorption onto the calcined diatomite

    NASA Astrophysics Data System (ADS)

    Ma, Shu-Cui; Zhang, Ji-Lin; Sun, De-Hui; Liu, Gui-Xia

    2015-12-01

    Removal of noxious heavy metal ions (e.g. Pb(II)) by surface adsorption of minerals (e.g. diatomite) is an important means in the environmental aqueous pollution control. Thus, it is very essential to understand the surface adsorptive behavior and mechanism. In this work, the Pb(II) apparent surface complexation reaction equilibrium constants on the calcined diatomite and distributions of Pb(II) surface species were investigated through modeling calculations of Pb(II) based on diffuse double layer model (DLM) with three amphoteric sites. Batch experiments were used to study the adsorption of Pb(II) onto the calcined diatomite as a function of pH (3.0-7.0) and different ionic strengths (0.05 and 0.1 mol L-1 NaCl) under ambient atmosphere. Adsorption of Pb(II) can be well described by Freundlich isotherm models. The apparent surface complexation equilibrium constants (log K) were obtained by fitting the batch experimental data using the PEST 13.0 together with PHREEQC 3.1.2 codes and there is good agreement between measured and predicted data. Distribution of Pb(II) surface species on the diatomite calculated by PHREEQC 3.1.2 program indicates that the impurity cations (e.g. Al3+, Fe3+, etc.) in the diatomite play a leading role in the Pb(II) adsorption and dominant formation of complexes and additional electrostatic interaction are the main adsorption mechanism of Pb(II) on the diatomite under weak acidic conditions.

  4. Adsorption of arsenic(V) into modified lamellar Kenyaite.

    PubMed

    Guerra, Denis Lima; Airoldi, Claudio; Viana, Rúbia Ribeiro

    2009-04-30

    The synthetic Kenyaite sample was used for organofunctionalization process with N-propyldiethylenetrimethoxysilane and bis[3-(triethoxysilyl)propyl]tetrasulfide. The resulted materials were submitted to process of adsorption with arsenic solution at pH 2.0 and 298+/-1K. The adsorption isotherms were adjusted using a modified Langmuir equation with regression non-linear; the net thermal effects obtained from calorimetric titration measurements were adjusted to a modified Langmuir equation. The adsorption process was exothermic (Delta(int)H=-4.08 to -5.94 kJ mol(-1)) accompanied by increase in entropy (Delta(int)S=41.29-62.09 J K(-1)mol(-1)) and Gibbs energy (Delta(int)G=-22.33 to -24.45 kJ mol(-1)). The energetic effect caused by metal cation adsorption was determined through calorimetric titration at the solid-liquid interface and gave a net thermal effect that enabled the calculation of the exothermic values and the equilibrium constant.

  5. The adsorption of HCl on volcanic ash

    NASA Astrophysics Data System (ADS)

    Gutiérrez, Xochilt; Schiavi, Federica; Keppler, Hans

    2016-03-01

    Understanding the interaction between volcanic gases and ash is important to derive gas compositions from ash leachates and to constrain the environmental impact of eruptions. Volcanic HCl could potentially damage the ozone layer, but it is unclear what fraction of HCl actually reaches the stratosphere. The adsorption of HCl on volcanic ash was therefore studied from -76 to +150 °C to simulate the behavior of HCl in the dilute parts of a volcanic plume. Finely ground synthetic glasses of andesitic, dacitic, and rhyolitic composition as well as a natural obsidian from Vulcano (Italy) served as proxies for fresh natural ash. HCl adsorption is an irreversible process and appears to increase with the total alkali content of the glass. Adsorption kinetics follow a first order law with rate constants of 2.13 ṡ10-6 s-1 to 1.80 ṡ10-4 s-1 in the temperature range investigated. For dacitic composition, the temperature and pressure dependence of adsorption can be described by the equation ln ⁡ c = 1.26 + 0.27 ln ⁡ p - 715.3 / T, where c is the surface concentration of adsorbed HCl in mg/m2, T is temperature in Kelvin, and p is the partial pressure of HCl in mbar. A comparison of this model with a large data set for the composition of volcanic ash suggests that adsorption of HCl from the gas phase at relatively low temperatures can quantitatively account for the majority of the observed Cl concentrations. The model implies that adsorption of HCl on ash increases with temperature, probably because of the increasing number of accessible adsorption sites. This temperature dependence is opposite to that observed for SO2, so that HCl and SO2 are fractionated by the adsorption process and the fractionation factor changes by four orders of magnitude over a temperature range of 250 K. The assumption of equal adsorption of different species is therefore not appropriate for deriving volcanic gas compositions from analyses of adsorbates on ash. However, with the experimental

  6. 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...

  7. Selective Adsorption on Fluorinated Plastic Enables the Optical Detection of Molecular Pollutants in Water

    NASA Astrophysics Data System (ADS)

    Lanfranco, R.; Giavazzi, F.; Salina, M.; Tagliabue, G.; Di Nicolò, E.; Bellini, T.; Buscaglia, M.

    2016-05-01

    Amorphous fluorinated plastic can be produced with a refractive index similar to that of water, a condition that makes it essentially invisible when immersed in aqueous solutions. Because of this property, even a small amount of adsorbed molecules on the plastic-water interface provides a detectable optical signal. We investigate two distinct substrates made of this material, characterized by different interface areas: a prism and a microporous membrane. We demonstrate that both substrates enable the label-free detection of molecular compounds in water even without any surface functionalization. The adsorption of molecules on the planar surface of the prism provides an increase of optical reflectivity, whereas the adsorption on the internal surface of the microporous membrane yields an increase of scattered light. Despite the different mechanisms, we find a similar optical response upon adsorption. We confirm this result by a theoretical model accounting for both reflection and scattering. We investigate the spontaneous adsorption process for different kinds of molecules: surfactants with different charges, a protein (lysozyme), and a constituent of gasoline (hexane). The measured equilibrium and kinetic constants for adsorption differ by orders of magnitudes among the different classes of molecules. By suitable analytical models, accounting for the effects of mass limitation and transport, we find a simple and general scaling of the adsorption parameters with the molecular size.

  8. Adsorption kinetics and isotherm of anionic dyes onto organo-bentonite from single and multisolute systems.

    PubMed

    Shen, Dazhong; Fan, Jianxin; Zhou, Weizhi; Gao, Baoyu; Yue, Qinyan; Kang, Qi

    2009-12-15

    The performances of polydiallydimethylammonium modified bentonite (PDADMA-bentonite) as an adsorbent to remove anionic dyes, namely Acid Scarlet GR (AS-GR), Acid Turquoise Blue 2G (ATB-2G) and Indigo Carmine (IC), were investigated in single, binary and ternary dye systems. In adsorption from single dye solutions with initial concentration of 100 micromol/L, the dosage of PDADMA-bentonite needed to remove 95% dye was 0.42, 0.68 and 0.75 g/L for AS-GR, ATB-2G and IC, respectively. The adsorption isotherms of the three dyes obeyed the Langmuir isotherm model with the equilibrium constants of 0.372, 0.629 and 4.31 L/micromol, the saturation adsorption amount of 176.3, 149.2 and 228.7 micromol/g for ATB-2G, IC and AS-GR, respectively. In adsorption from mixed dye solutions, the isotherm of each individual dye followed an expanded Langmuir isotherm model and the relationship between the total amount of dyes adsorbed and the total equilibrium dye concentration was interpreted well by Langmuir isotherm model. In the region of insufficient dosage of PDADMA-bentonite, the dye with a larger affinity was preferentially removed by adsorption. Desorption was observed in the kinetic curve of the dye with lower affinity on PDADMA-bentonite surface by the competitive adsorption. The kinetics in single dye solution and the total adsorption of dyes in binary and ternary dye systems nicely followed pseudo-second-order kinetic model.

  9. Adsorption of Cu2+ ions using chitosan-modified magnetic Mn ferrite nanoparticles synthesized by microwave-assisted hydrothermal method

    NASA Astrophysics Data System (ADS)

    Meng, Yuying; Chen, Deyang; Sun, Yitao; Jiao, Dongling; Zeng, Dechang; Liu, Zhongwu

    2015-01-01

    Chitosan-modified Mn ferrite nanoparticles were synthesized by a one-step microwave-assisted hydrothermal method. These Mn ferrite magnetic composite nanoparticles were employed to absorb Cu2+ ions in water. XRD verified the spinel structure of the MnFe2O4 nanoparticles. Chitosan modification does not result in any phase change of MnFe2O4. FTIR and zeta potentials curves for all samples suggest that chitosan can be successfully coated on the Mn ferrites. TEM characterization showed that the modified MnFe2O4 nanoparticles have a cubic shape with a mean diameter of ∼100 nm. For adsorption behavior, the effects of experiment parameters such as solution pH value, contact time and initial Cu2+ ions concentration on the adsorption efficiency were systematically investigated. The results showed that increasing solution pH value and extending contact time are favorable for improving adsorption efficiency. Especially, adsorption efficiency can reach up to 100% and 96.7% after 500 min adsorption at pH 6.5 for the solutions with initial Cu2+ ions concentration of 50 mg/L and 100 mg/L. Adsorption data fits well with the Langmuir isotherm models with a maximum adsorption capacity (qm) and a Langmuir adsorption equilibrium constant (K) of 65.1 mg/g and 0.090 L/mg, respectively. The adsorption kinetic agrees well with pseudo second order model with the pseudo second rate constants (K2) of 0.0468 and 0.00189 g/mg/min for solutions with initial Cu2+ ions of 50 and 100 mg/L, respectively.

  10. Predictive model for Pb(II) adsorption on soil minerals (oxides and low-crystalline aluminum silicate) consistent with spectroscopic evidence

    NASA Astrophysics Data System (ADS)

    Usiyama, Tomoki; Fukushi, Keisuke

    2016-10-01

    Mobility of Pb(II) in surface condition is governed by adsorption processes on soil minerals such as iron oxides and low-crystalline aluminum silicates. The adsorption effectiveness and the surface complex structures of Pb(II) vary sensitively with solution conditions such as pH, ionic strength, Pb(II) loading, and electrolyte anion type. This study was undertaken to construct a quantitative model for Pb(II) on soil minerals. It can predict the adsorption effectiveness and surface complex structures under any solution conditions using the extended triple layer model (ETLM). The Pb(II) adsorption data for goethite, hydrous ferric oxide (HFO), quartz, and low-crystalline aluminum silicate (LCAS) were analyzed with ETLM to retrieve the surface complexation reactions and these equilibrium constants. The adsorption data on goethite, HFO and quartz were referred from reports of earlier studies. Those data for LCAS were measured under a wide range of pH, ionic strength and Pb(II) loadings in NaNO3 and NaCl solutions. All adsorption data can be reasonably regressed using ETLM with the assumptions of inner sphere bidentate complexation and inner sphere monodentate ternary complexation with electrolyte anions, which are consistent with previously reported spectroscopic evidence. Predictions of surface speciation under widely various solution conditions using ETLM revealed that the inner sphere bidentate complex is the predominant species at neutral to high pH conditions. The inner sphere monodentate ternary complex becomes important at low pH, high surface Pb(II) coverage, and high electrolyte concentrations, of which the behavior is consistent with the spectroscopic observation. Comparisons of the obtained adsorption constants on goethite, HFO and quartz exhibited good linear relations between the reciprocals of dielectric constants of solids and adsorption constants. Those linear relations support predictions of the adsorption constants of all oxides based on Born

  11. Adsorption behavior and mechanism of chloramphenicols, sulfonamides, and non-antibiotic pharmaceuticals on multi-walled carbon nanotubes.

    PubMed

    Zhao, Heng; Liu, Xue; Cao, Zhen; Zhan, Yi; Shi, Xiaodong; Yang, Yi; Zhou, Junliang; Xu, Jiang

    2016-06-05

    The adsorption behavior of different emerging contaminants (3 chloramphenicols, 7 sulfonamides, and 3 non-antibiotic pharmaceuticals) on five types of multi-walled carbon nanotubes (MWCNTs), and the underlying factors were studied. Adsorption equilibriums were reached within 12h for all compounds, and well fitted by the Freundlich isotherm model. The adsorption affinity of pharmaceuticals was positively related to the specific surface area of MWCNTs. The solution pH was an important parameter of pharmaceutical adsorption on MWCNTs, due to its impacts on the chemical speciation of pharmaceuticals and the surface electrical property of MWCNTs. The adsorption of ionizable pharmaceuticals decreased in varying degrees with the increased ionic strength. MWCNT-10 was found to be the strongest adsorbent in this study, and the Freundlich constant (KF) values were 353-2814mmol(1-n)L(n)/kg, 571-618mmol(1-n)L(n)/kg, and 317-1522mmol(1-n)L(n)/kg for sulfonamides, chloramphenicols, and non-antibiotic pharmaceuticals, respectively. The different adsorption affinity of sulfonamides might contribute to the different hydrophobic of heterocyclic substituents, while chloramphenicols adsorption was affected by the charge distribution in aromatic rings via substituent effects.

  12. Exploring Chemical Equilibrium with Poker Chips: A General Chemistry Laboratory Exercise

    ERIC Educational Resources Information Center

    Bindel, Thomas H.

    2012-01-01

    A hands-on laboratory exercise at the general chemistry level introduces students to chemical equilibrium through a simulation that uses poker chips and rate equations. More specifically, the exercise allows students to explore reaction tables, dynamic chemical equilibrium, equilibrium constant expressions, and the equilibrium constant based on…

  13. Adsorption and desorption kinetics of (60)Co and (137)Cs in fresh water rivers.

    PubMed

    Fiengo Pérez, Fabricio; Sweeck, Lieve; Bauwens, Willy; Van Hees, May; Elskens, Marc

    2015-11-01

    Radionuclides released in water systems--as well as heavy metals and organic toxicants--sorb to both the suspended solid particles and the bed sediments. Sorption is usually represented mathematically by the distribution coefficient. This approach implies equilibrium between phases and instantaneous fixation (release) of the pollutant onto (from) the surface of the soil particle. However, empirical evidence suggests that for some radionuclides the fixation is not achieved instantaneously and that the reversibility of the process can be slow. Here the adsorption/desorption kinetics of (60)Co and (137)Cs in fresh water environments were simulated experimentally and later on modelled mathematically, while the influence of the most relevant factors affecting the sorption were taken into account. The experimental results suggest that for adsorption and the desorption more than 24 h are needed to reach equilibrium, moreover, It was observed that the desorption rate constants for (60)Co and (137)Cs lie within ranges which are of two to three orders of magnitude lower than the adsorption rate constants.

  14. Soil adsorption studies of a rice herbicide, cyhalofop-butyl, in two texturally different soils of India.

    PubMed

    Sondhia, Shobha; Khare, Rishi Raj

    2014-10-01

    The ability of herbicides to be adsorbed by the soil and sediment and their tendency to be desorbed are some of the most important factors affecting soil and water contamination. Therefore, a sorption study was conducted to evaluate the adsorption of cyhalofop-butyl, butyl (2R)-2-[4-(4-cyano-2-fluorophenoxy) phenoxy] propanoate, in the sandy clay loam and clayey soils using a batch equilibrium method. The adsorption of cyhalofop-butyl was found positively related with the clay and organic carbon content. Freundlich constants (Kf) of cyhalofop-butyl in the clayey and sandy clay loam were found to be 13.39 and 2.21, respectively. Sorption coefficients (Koc) and distribution coefficients (Kd) were found to be 265.38 and 2,092.79, and 1.38 and 11.48, for sandy clay loam and clayey soils, respectively. The adsorption isotherm suggested a relatively higher affinity of cyhalofop-butyl to the adsorption sites at low equilibrium concentrations. The low value of the soil organic carbon partition coefficient (Koc) of cyhalofop-butyl in the sandy loam soil suggested its weaker adsorption in soil and thus increased its risk of mobility into water sources; hence, it should be used judiciously to prevent groundwater contamination.

  15. Reversibility of substrate adsorption for the cellulases Cel7A, Cel6A, and Cel7B from Hypocrea jecorina.

    PubMed

    Pellegrini, Vanessa O A; Lei, Nina; Kyasaram, Madhuri; Olsen, Johan P; Badino, Silke F; Windahl, Michael S; Colussi, Francieli; Cruys-Bagger, Nicolaj; Borch, Kim; Westh, Peter

    2014-10-28

    Adsorption of cellulases on the cellulose surface is an integral part of the catalytic mechanism, and a detailed description of the adsorption process is therefore required for a fundamental understanding of this industrially important class of enzymes. However, the mode of adsorption has proven intricate, and several key questions remain open. Perhaps most notably it is not clear whether the adsorbed enzyme is in dynamic equilibrium with the free population or irreversibly associated with no or slow dissociation. To address this, we have systematically investigated adsorption reversibility for two cellobiohydrolases (Cel7A and Cel6A) and one endoglucanase (Cel7B) on four types of pure cellulose substrates. Specifically, we monitored dilution-induced release of adsorbed enzyme in samples that had previously been brought to a steady state (constant concentration of free enzyme). In simple dilution experiments (without centrifugation), the results consistently showed full reversibility. In contrast to this, resuspension of enzyme-substrate pellets separated by centrifugation showed extensive irreversibility. We conclude that these enzymes are in a dynamic equilibrium between free and adsorbed states but suggest that changes in the physical properties of cellulose caused by compaction of the pellet hampers subsequent release of adsorbed enzyme. This latter effect may be pertinent to both previous controversies in the literature on adsorption reversibility and the development of enzyme recycling protocols in the biomass industry.

  16. Adsorption of lanthanum to goethite in the presence of gluconate

    SciTech Connect

    Hull, Laurence C.; Sarah Pepper; Sue Clark

    2005-05-01

    Adsorption of Lanthanum to Goethite in the Presence of Gluconic Acid L. C. HULL,1 S. E. PEPPER2 AND S. B. CLARK2 1Idaho National Engineering and Environmental Laboratory, Idaho Falls, ID (hulllc@inel.gov) 2Washington State University, Pullman, WA (spepper@wsu.edu), (s_clark@wsu.edu) Lanthanide and trivalent-actinide elements in radioactive waste can pose risks to humans and ecological systems for many years. Organic complexing agents, from natural organic matter or the degradation of waste package components, can alter the mobility of these elements. We studied the effect of gluconic acid, as an analogue for cellulose degradation products, on the adsorption of lanthanum, representing lanthanide and trivalent-actinide elments, to goethite, representing natural iron minearals and degradation products of waste packages. Batch pH adsorption edge experiments were conducted with lanthanum alone, and with lanthanum and gluconate at a 1:1 mole ratio. Lanthanum concentrations studied were 0.1, 1, and 10 mM, covering a range from 10% to 1000% of the calculated available adsorption sites on goethite. In the absence of gluconate, lanthanum was primarily present in solution as free lanthanum ion. With gluconate present, free lanthanum concentration in solution decreased with increasing pH as step-wise deprotonation of the gluconate molecule increased the fraction lanthanum complexed with gluconate. Adsorption to the goethite surface was represented with the diffuse double-layer model. The number of adsorption sites and the intrinsic binding constants for the surface complexes were estimated from the pH adsorption edge data using the computer code FITEQL 4.0. Two surface reactions were used to fit the adsorption data in the absence of gluconate. A strong binding site with no proton release and a much higher concentration of weak binding sites with release of two protons per lanthanum adsorbed. The adsorption of lanthanum was not measurably affected by the presence of gluconate

  17. Effect of cation type, alkyl chain length, adsorbate size on adsorption kinetics and isotherms of bromide ionic liquids from aqueous solutions onto microporous fabric and granulated activated carbons.

    PubMed

    Hassan, Safia; Duclaux, Laurent; Lévêque, Jean-Marc; Reinert, Laurence; Farooq, Amjad; Yasin, Tariq

    2014-11-01

    The adsorption from aqueous solution of imidazolium, pyrrolidinium and pyridinium based bromide ionic liquids (ILs) having different alkyl chain lengths was investigated on two types of microporous activated carbons: a fabric and a granulated one, well characterized in terms of surface chemistry by "Boehm" titrations and pH of point of zero charge measurements and of porosity by N2 adsorption at 77 K and CO2 adsorption at 273 K. The influence of cation type, alkyl chain length and adsorbate size on the adsorption properties was analyzed by studying kinetics and isotherms of eight different ILs using conductivity measurements. Equilibrium studies were carried out at different temperatures in the range [25-55 °C]. The incorporation of ILs on the AC porosity was studied by N2 adsorption-desorption measurements at 77 K. The experimental adsorption isotherms data showed a good correlation with the Langmuir model. Thermodynamic studies indicated that the adsorption of ILs onto activated carbons was an exothermic process, and that the removal efficiency increased with increase in alkyl chain length, due to the increase in hydrophobicity of long chain ILs cations determined with the evolution of the calculated octanol-water constant (Kow). The negative values of free energies indicated that adsorption of ILs with long chain lengths having hydrophobic cations was more spontaneous at the investigated temperatures.

  18. Adsorption of drinking water fluoride on a micron-sized magnetic Fe3O4@Fe-Ti composite adsorbent

    NASA Astrophysics Data System (ADS)

    Zhang, Chang; Li, Yingzhen; Wang, Ting-Jie; Jiang, Yanping; Wang, Haifeng

    2016-02-01

    A micron-sized magnetic adsorbent (MMA) for fluoride removal from drinking water was prepared by spray drying and subsequent calcination of a magnetic Fe3O4@Fe-Ti core-shell nanoparticle slurry. The MMA granules had high mechanical strength and stability against water scouring, can be easily separated from the water by a magnet, and had a high selectivity for fluoride versus common co-existing ions and high fluoride removal efficiency in a wide range of initial pH of 3-11. Abundant hydroxyl groups on the MMA surface acted as the active sites for fluoride adsorption, which resulted in a high affinity of the MMA for fluoride. The pH in the adsorption process affected the adsorption significantly. At neutral initial pH, the adsorption isotherm was well fitted with the Langmuir model, and the maximum adsorption capacity reached a high value of 41.8 mg/g. At a constant pH of 3, multilayer adsorption of fluoride occurred due to the abundant positive surface charges on the MMA, and the adsorption isotherm was well fitted with the Freundlich model. The MMA had a fast adsorption rate, and adsorption equilibrium was achieved within 2 min. The adsorption kinetics followed a quasi-second order model. The regeneration of the MMA was easy and fast, and can be completed within 2 min. After 10 recycles, the fluoride removal efficiency of the MMA still remained high. These properties showed that the MMA is a promising adsorbent for fluoride removal.

  19. From surfactant adsorption kinetics to asymmetric nanomembrane mechanics: pendant drop experiments with subphase exchange.

    PubMed

    Ferri, James K; Kotsmar, Csaba; Miller, Reinhard

    2010-12-15

    Adsorption equilibrium is the state in which the chemical potential of each species in the interface and bulk is the same. Dynamic phenomena at fluid-fluid interfaces in the presence of surface active species are often probed by perturbing an interface or adjoining bulk phase from the equilibrium state. Many methods designed for studying kinetics at fluid-fluid interfaces focus on removing the system from equilibrium through dilation or compression of the interface. This modifies the surface excess concentration Γ(i) and allows the species distribution in the bulk C(i) to respond. There are only a few methods available for studying fluid-fluid interfaces which seek to control C(i) and allow the interface to respond with changes to Γ(i). Subphase exchange in pendant drops can be achieved by the injection and withdrawal of liquid into a drop at constant volumetric flow rate R(E) during which the interfacial area and drop volume V(D) are controlled to be approximately constant. This can be accomplished by forming a pendant drop at the tip of two coaxial capillary tubes. Although evolution of the subphase concentration C(i)(t) is dictated by extrinsic factors such as R(E) and V(D), complete subphase exchange can always be attained when a sufficient amount of liquid is used. This provides a means to tailor driving forces for adsorption and desorption in fluid-fluid systems and in some cases, fabricate interfacial materials of well-defined composition templated at these interfaces. The coaxial capillary pendant drop (CCPD) method opens a wide variety of experimental possibilities. Experiments and theoretical frameworks are reviewed for the study of surfactant exchange kinetics, macromolecular adsorption equilibrium and dynamics, as well as the fabrication of a wide range of soft surface materials and the characterization of their mechanics. Future directions for new experiments are also discussed.

  20. Adsorption isotherms, kinetics and thermodynamic studies towards understanding the interaction between cross-linked alginate-guar gum matrix and chymotrypsin.

    PubMed

    Woitovich Valetti, Nadia; Picó, Guillermo

    2016-02-15

    The adsorption kinetics of chymotrypsin, a pancreatic serine protease, onto an alginate-gum guar matrix cross-linked with epichlorohydrin has been performed using a batch-adsorption technique. The effect of various experimental parameters such as pH, salt presence, 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. The Langmuir, Freundlich and Hill adsorption isotherm models were applied to describe the equilibrium isotherms, and the isotherm constants were determined. It was found that Hill model was more suitable for our data because the isotherm data showed a sigmoidal behavior with the free enzyme concentration increasing in equilibrium. At 8°C and at pH 5.0, 1g hydrate matrix adsorbed about 7mg of chymotrypsin. In the desorption process 80% of the biological activity of chymotrypsin was recovered under the condition of 50mM phosphate buffer, pH 7.00-500mM NaCl. When successive cycles of adsorption/washing/desorption were performed, it was observed that the matrix remained functional until the fourth cycle of repeated batch enzyme adsorption. These results are important in terms of diminishing of cost and waste generation.

  1. Recyclable Mg-Al layered double hydroxides for fluoride removal: Kinetic and equilibrium studies.

    PubMed

    Kameda, Tomohito; Oba, Jumpei; Yoshioka, Toshiaki

    2015-12-30

    Mg-Al layered double hydroxides (LDHs) intercalated with NO3(-) (NO3 · Mg-Al LDH) and Cl(-) (Cl · Mg-Al LDH) were found to adsorb fluoride from aqueous solutions. Fluoride is removed by anion exchange in solution with NO3(-) and Cl(-) intercalated in the LDH interlayer. In both cases, the residual F concentration is lower than the effluent standards for F in Japan (8 mg/L). The rate-determining step in the removal of F using NO3 · Mg-Al and Cl · Mg-Al LDH is chemical adsorption involving F(-) anion exchange with intercalated NO3(-) and Cl(-) ions. The removal of F is described by pseudo-second-order reaction kinetics, with Langmuir-type adsorption. The values obtained for the maximum adsorption and the equilibrium adsorption constant are respectively 3.3 mmol g(-1) and 2.8 with NO3 · Mg-Al LDH, and 3.2 mmol g(-1) and 1.5 with Cl · Mg-Al LDH. The F in the F · Mg-Al LDH produced in these reactions was found to exchange with NO3(-) and Cl(-) ions in solution. The regenerated NO3 · Mg-Al and Cl · Mg-Al LDHs thus obtained can be used once more to capture aqueous F. This suggests that NO3 · Mg-Al and Cl · Mg-Al LDHs can be recycled and used repeatedly for F removal.

  2. A Constant Pressure Bomb

    NASA Technical Reports Server (NTRS)

    Stevens, F W

    1924-01-01

    This report describes a new optical method of unusual simplicity and of good accuracy suitable to study the kinetics of gaseous reactions. The device is the complement of the spherical bomb of constant volume, and extends the applicability of the relationship, pv=rt for gaseous equilibrium conditions, to the use of both factors p and v. The method substitutes for the mechanical complications of a manometer placed at some distance from the seat of reaction the possibility of allowing the radiant effects of reaction to record themselves directly upon a sensitive film. It is possible the device may be of use in the study of the photoelectric effects of radiation. The method makes possible a greater precision in the measurement of normal flame velocities than was previously possible. An approximate analysis shows that the increase of pressure and density ahead of the flame is negligible until the velocity of the flame approaches that of sound.

  3. 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.

  4. Removal of mixed pesticides from aqueous solutions using organoclays: evaluation of equilibrium and kinetic model.

    PubMed

    Saha, Ajoy; Ahammed Shabeer Tp; Gajbhiye, V T; Gupta, Suman; Kumar, Rajesh

    2013-07-01

    Removal of mixed pesticides, namely alachlor, metolachlor, chlorpyriphos, fipronil, α-endosulfan, β-endosulfan, p,p'-DDT and two metabolites p,p'-DDE and endosulfan sulphate from aqueous solution by batch adsorption onto three commercial organo-modified montmorillonite clays [modified with octadecylamine (ODA-M), modified with dimethyl- dialkylamine (DMDA-M) and modified with octadecylamine and aminopropyltriethoxysilane (ODAAPS-M)] were investigated. Effect of process variables, mainly contact time and initial concentration of mixed pesticides, on adsorption phenomenon were evaluated. To understand the adsorption kinetic pseudo-first-order and pseudo-second-order models were tested. The pseudo-second-order model provided the best fit for explaining adsorption kinetics, on the basis of high correlation coefficient (r) and normalized percent deviation values. The adsorption equilibrium was explained by the Freundlich isotherm (r = 0.951-0.992). High values (0.17-0.52 mg g⁻¹) of Freundlich constant (K(f)) indicated higher affinity of pesticides towards all three organoclays, as a result of hydrophobic interaction between the adsorbent/adsorbate systems. Pesticides with high octanol-water partition coefficient (K(ow)) and low water solubility showed faster adsorption with higher K(f) values as compared to the pesticides with low K(ow) and high water solubility. The order of organoclays for removal efficiency of mixed pesticide was ODAAPS-M > DMDA-M > ODA-M. These findings may find application to decontaminate or treat mixed pesticide contaminated industrial/agricultural waste waters.

  5. 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

  6. 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.

  7. Kinetic study of aluminum adsorption by aluminosilicate clay minerals

    SciTech Connect

    Walker, W.J.; Cronan, C.S.; Patterson, H.H.

    1988-01-01

    The adsorption kinetics of Al/sup 3 +/ by montmorillonite, kaolinite, and vermiculite were investigated as a function of the initial Al concentration, the surface area of the clay, and H/sup +/ concentration, at 25/sup 0/, 18/sup 0/, and 10/sup 0/C. In order to minimize complicated side reactions the pH range was kept between 3.0 and 4.1. Results showed that the adsorption rate was first order with respect to both the initial Al concentration and the clay surface area. Changes in pH within this narrow range had virtually no effect on adsorption rate. This zero order reaction dependence suggested that the H/sup +/, compared to Al, has a weak affinity for the surface. The rates of adsorption decreased in the order of montmorillonite > kaolinite > vermiculite when compared on the basis of equal surface areas, but changed to kaolinite > montmorillonite > vermiculite when the clays were compared on an equal exchange capacity basis. The calculated apparent activation energies were < 32 kJ mol/sup -1/, indicating that over the temperature range of the study the adsorption process is only marginally temperature sensitive. The mechanism is governed by a simple electrostatic cation exchange involving outer sphere complexes between adsorbed Al and the clay surface. Vermiculite, may have a second reaction step governed by both electrostatic attraction and internal ion diffusion. Equilibrium constants for the formation of an adsorbed Al clay complex were also estimated and are 10/sup 5.34/, 10/sup 5.18/, and 10/sup 4.94/ for kaolinite, montmorillonite, and vermiculite, respectively, suggesting that these clays could play a significant role in controlling soil solutions Al concentrations.

  8. 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.

  9. 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.

  10. The impact of particle size on the adsorption of citrate to hematite.

    PubMed

    Noerpel, Matthew R; Lenhart, John J

    2015-12-15

    We investigated the adsorption of citric acid on the surface of two different sized hematite nanoparticles using batch adsorption experiments, Fourier-transform infrared spectroscopy, surface complexation modeling and computational molecular modeling. Citrate adsorption reached a maximum between pH approximately 2.5 and 5.5 and declined as the pH was increased or decreased from that range. At high surface loading conditions, the dominant adsorbed citrate structure was outer-sphere in nature with a protonation state that varied with pH. At low pH, there was also evidence of an inner-sphere complex consistent with a binuclear, bidentate structure where the hydroxyl group was deprotonated and played an active role in the adsorption. An inner-sphere complex was also detected at low citrate surface loading conditions. Surface-area normalized surface coverages were similar for both sizes of hematite, however, the inner sphere complex appeared to be slightly more prevalent on the smaller hematite. Based on these structures, a triple layer surface complexation model comprised of two outer-sphere complexes and one inner-sphere complex was used to describe the adsorption data for both hematite sizes across a range of solution conditions with a single set of surface area dependent equilibrium constants.

  11. Ice-surface adsorption enhanced colligative effect of antifreeze proteins in ice growth inhibition

    NASA Astrophysics Data System (ADS)

    Mao, Yougang; Ba, Yong

    2006-09-01

    This Communication describes a mechanism to explain antifreeze protein's function to inhibit the growth of ice crystals. We propose that the adsorption of antifreeze protein (AFP) molecules on an ice surface induces a dense AFP-water layer, which can significantly decrease the mole fraction of the interfacial water and, thus, lower the temperature for a seed ice crystal to grow in a super-cooled AFP solution. This mechanism can also explain the nearly unchanged melting point for the ice crystal due to the AFP's ice-surface adsorption. A mathematical model combining the Langmuir theory of adsorption and the colligative effect of thermodynamics has been proposed to find the equilibrium constants of the ice-surface adsorptions, and the interfacial concentrations of AFPs through fitting the theoretical curves to the experimental thermal hysteresis data. This model has been demonstrated by using the experimental data of serial size-mutated beetle Tenebrio molitor (Tm) AFPs. It was found that the AFP's ice-surface adsorptions could increase the interfacial AFP's concentrations by 3 to 4 orders compared with those in the bulk AFP solutions.

  12. Ice-surface adsorption enhanced colligative effect of antifreeze proteins in ice growth inhibition.

    PubMed

    Mao, Yougang; Ba, Yong

    2006-09-07

    This Communication describes a mechanism to explain antifreeze protein's function to inhibit the growth of ice crystals. We propose that the adsorption of antifreeze protein (AFP) molecules on an ice surface induces a dense AFP-water layer, which can significantly decrease the mole fraction of the interfacial water and, thus, lower the temperature for a seed ice crystal to grow in a super-cooled AFP solution. This mechanism can also explain the nearly unchanged melting point for the ice crystal due to the AFP's ice-surface adsorption. A mathematical model combining the Langmuir theory of adsorption and the colligative effect of thermodynamics has been proposed to find the equilibrium constants of the ice-surface adsorptions, and the interfacial concentrations of AFPs through fitting the theoretical curves to the experimental thermal hysteresis data. This model has been demonstrated by using the experimental data of serial size-mutated beetle Tenebrio molitor (Tm) AFPs. It was found that the AFP's ice-surface adsorptions could increase the interfacial AFP's concentrations by 3 to 4 orders compared with those in the bulk AFP solutions.

  13. Adsorption of CaCO3 Particles on Cationic Cellulose Graft Copolymers

    PubMed

    Halab-Kessira; Ricard

    1996-12-25

    The behavior of small inorganic particles at the fiber/water interface has been analyzed from the kinetics and isotherms of adsorption of CaCO3 particles onto cationic fibers. The introduction of cationic moieties onto cellulosic fibers leads to a copolymer that can easily adsorb negatively charged particles. At equilibrium, the adsorption ratio of CaCO3 particles on a cationic copolymer of cellulose and poly(2-acryloxyethyltrimethylammonium chloride) is related closely to the particle size, the temperature, the agitation, and the ionic strength of the suspension. Kinetic models have shown that the weakly charged copolymers present a high-affinity-type kinetics when the CaCO3 particle average diameter is small (20 to 30 μm). For an average particle diameter equal to 72 μm, the kinetics corresponds to an adsorption with a lower affinity. The rate constants are 6.6 x 10(-12), 2.9 x 10(-12), and 1.2 x 10(-12) m3/s for particles with average diameters of 20, 30, and 72 μm, respectively. We have also noted that the adsorption increases with agitation and reaches a plateau after 5 min. The ionic strength influences the electrostatic interactions between the positive sites of the graft and the anion of the adsorbate. Indeed a decreasing adsorption is observed when the ionic strength increases.

  14. Effect of surface acidity and basicity of aluminas on asphaltene adsorption and oxidation.

    PubMed

    Nassar, Nashaat N; Hassan, Azfar; Pereira-Almao, Pedro

    2011-08-01

    This study investigates the effect of surface acidity and basicity of aluminas on asphaltene adsorption followed by air oxidation. Equilibrium batch adsorption experiments were conducted at 25°C with solutions of asphaltenes in toluene at concentrations ranging from 100 to 3000 g/L using three conventional alumina adsorbents with different surface acidity. Data were found to better fit to the Freundlich isotherm model showing a multilayer adsorption. Results showed that asphaltene adsorption is strongly affected by the surface acidity, and the adsorption capacities of asphaltenes onto the three aluminas followed the order acidic>basic and neutral. Asphaltenes adsorbed over aluminas were subjected to oxidation in air up to 600°C in a thermogravimetric analyzer to study the catalytic effect of aluminas with different surface acidity. A correlation was found between Freundlich affinity constant (1/n) and the catalytic activity. Basic alumina that has the lowest 1/n value, depicting strongest interactions, has the highest catalytic activity, followed by neutral and acidic aluminas, respectively.

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

    NASA Astrophysics Data System (ADS)

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

    2009-01-01

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

  16. Adsorption and degradation of model volatile organic compounds by a combined titania-montmorillonite-silica photocatalyst.

    PubMed

    Chen, Jiangyao; Li, Guiying; He, Zhigui; An, Taicheng

    2011-06-15

    A series of adsorptive photocatalysts, combined titania-montmorillonite-silica were synthesized. The resultant photocatalysts consisted of more and more spherically agglomerated TiO(2) particles with increasing of TiO(2) content, and anatase was the only crystalline phase with nano-scale TiO(2) particles. With increasing of the cation exchange capacity to TiO(2) molar ratio, specific surface area and pore volume increased very slightly. In a fluidized bed photocatalytic reactor by choosing toluene, ethyl acetate and ethanethiol as model pollutants, all catalysts had relatively high adsorption capacities and preferred to adsorb higher polarity pollutants. Langmuir isotherm model better described equilibrium data compared to Freundlich model. Competitive adsorptions were observed for the mixed pollutants on the catalysts, leading to decrease adsorption capacity for each pollutant. The combined titania-montmorillonite-silica photocatalyst exhibited excellent photocatalytic removal ability to model pollutants of various components. Almost 100% of degradation efficiency was achieved within 120 min for each pollutant with about 500 ppb initial concentration, though the efficiencies of multi-component compounds slightly decreased. All photocatalytic reactions followed the Langmuir-Hinshelwood model. Degradation rate constants of multi-component systems were lower than those for single systems, following the order of tolueneadsorption capacities for different pollutants of various components.

  17. Kinetic study of brilliant green adsorption from aqueous solution onto white rice husk ash.

    PubMed

    Tavlieva, Mariana P; Genieva, Svetlana D; Georgieva, Velyana G; Vlaev, Lyubomir T

    2013-11-01

    The present research was focused on the study of adsorption kinetics of brilliant green (BG) onto white rice husk ash from aqueous solutions. The research was performed in the temperature interval 290-320 K in 10° steps and in the concentration range of 3-100 mg L(-1). Batch studies were conducted in order to determine the optimal adsorbent dose, and the time required to reach the adsorption equilibrium at each temperature. The effect of the initial concentration of brilliant green was studied (pH not adjusted), as well as the effect of temperature. The maximum adsorption capacity of the WRHA for BG at 320 K was determined to be 85.56 mg g(-1). The adsorption kinetic data were analyzed employing several kinetic models: pseudo-first-order equation, pseudo-second-order equation, Elovichequation, Banghman's equation, Diffusion-chemisorption model, and Boyd kinetic expression. It was established that the adsorption process obeyed the pseudo-second-order kinetic model. Based on the rate constants obtained by this kinetic model using Arrhenius and Eyring equations, the activation parameters were determined, namely the activation energy (50.04 kJ mol(-1)), the change of entropy (-318.31 J mol(-1) K(-1)), enthalpy (-47.50 kJ mol(-1)), and Gibbs free energy (range 44.81-54.36 kJ mol(-1)) for the formation of activated complex from the reagents.

  18. The adsorption of Cr(VI) on sulphuric acid-treated wheat bran.

    PubMed

    Ozer, A; Ozer, D

    2004-06-01

    Wheat bran, a by-product of wheat milling industries, was converted into a cheap and efficient material by treating with sulphuric acid and used for the adsorption of Cr(VI) from aqueous solution. Effects of various parameters such as initial pH of solution, contact time, initial Cr(VI) concentration and temperature were studied. The sulphuric acid-treated wheat bran (STWB) gave the highest adsorption efficiency at pH 1.5. The equilibrium data were fitted better to Langmuir isotherm model compared to Freundlich model at all the temperatures studied. The adsorption capacity increased from 91 to 133 mg gl(-1) with an increase in temperature from 20 degrees C to 50 degrees C. The adsorption process was found to be endothermic and Langmuir isotherm data were evaluated to determine the thermodynamic parameters for the process. Thermodynamic parameters showed that the process was feasible. The results indicated that the chromium removal process by STWB followed first-order rate expression and adsorption rate constants increased with increasing temperature.

  19. The effect of mixed HCl-KCl competitive adsorbate on Pt adsorption and catalytic properties of Pt-Sn/Al2O3 catalysts in propane dehydrogenation

    NASA Astrophysics Data System (ADS)

    Zangeneh, Farnaz Tahriri; Taeb, Abbas; Gholivand, Khodayar; Sahebdelfar, Saeed

    2015-12-01

    The effect of competitive adsorbate concentration and combination on the adsorption of H2PtCl6 onto γ-Al2O3 in the preparation and performance of PtSnK/γ-Al2O3 catalyst for propane dehydrogenation was investigated. The catalysts were prepared by sequential impregnation of Sn and Pt precursors. The effect of competitor concentration on Pt adsorption was studied by using hydrochloric acid (0.1-0.3 M) and the effect of pH was studied by using KCl/HCl mixtures at constant (0.1 M) total chloride ion concentration. The catalysts were characterized by nitrogen adsorption/desorption, XRD, XRF, SEM and CO chemisorption. The catalytic performance tests were carried out in a fixed-bed quartz reactor under kinetic controlled condition for proper catalyst screening. It was found that the corrosive competitor HCl could be partially substituted with KCl without appreciable impact on catalyst performance with the advantage of lower acid attack on the support and reduced leaching of the deposited tin. A model based on initial concentration and uptake of the adsorbates was developed to obtain the adsorption parameters. Values of 890 μmol/g and 600 lit/mol were obtained for adsorption site concentration of the tin-impregnated support and equilibrium constant for Pt adsorption, respectively, for HCl concentration range of 0.1-0.3 M.

  20. Conceptual adsorption models and open issues pertaining to performance assessment

    SciTech Connect

    Serne, R.J.

    1991-10-01

    Recently several articles have been published that question the appropriateness of the distribution coefficient, Rd, concept to quantify radionuclide migration. Several distinct issues are raised by various critics. In this paper I provide some perspective on issues surrounding the modeling of nuclide retardation. The first section defines adsorption terminology and discusses various adsorption processes. The next section describes five commonly used adsorption conceptual models, specifically emphasizing what attributes that affect adsorption are explicitly accommodated in each model. I also review efforts to incorporate each adsorption model into performance assessment transport computer codes. The five adsorption conceptual models are (1) the constant Rd model, (2) the parametric Rd model, (3) isotherm adsorption models, (4) mass-action adsorption models, and (5) surface-complexation with electrostatics models. The final section discusses the adequacy of the distribution ratio concept, the adequacy of transport calculations that rely on constant retardation factors and the status of incorporating sophisticated adsorption models into transport codes.

  1. Adsorption of cobalt ferrite nanoparticles within layer-by-layer films: a kinetic study carried out using quartz crystal microbalance.

    PubMed

    Alcantara, Gustavo B; Paterno, Leonardo G; Afonso, André S; Faria, Ronaldo C; Pereira-da-Silva, Marcelo A; Morais, Paulo C; Soler, Maria A G

    2011-12-28

    The paper reports on the successful use of the quartz crystal microbalance technique to assess accurate kinetics and equilibrium parameters regarding the investigation of in situ adsorption of nanosized cobalt ferrite particles (CoFe(2)O(4)--10.5 nm-diameter) onto two different surfaces. Firstly, a single layer of nanoparticles was deposited onto the surface provided by the gold-coated quartz resonator functionalized with sodium 3-mercapto propanesulfonate (3-MPS). Secondly, the layer-by-layer (LbL) technique was used to build multilayers in which the CoFe(2)O(4) nanoparticle-based layer alternates with the sodium sulfonated polystyrene (PSS) layer. The adsorption experiments were conducted by modulating the number of adsorbed CoFe(2)O(4)/PSS bilayers (n) and/or by changing the CoFe(2)O(4) nanoparticle concentration while suspended as a stable colloidal d