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Adsorption Equilibrium (adsorption + equilibrium)
Selected AbstractsTrue and Apparent Temperature Dependence of Protein Adsorption Equilibrium in Reversed-Phase HPLCBIOTECHNOLOGY PROGRESS, Issue 6 2002Szabelski The adsorption behavior of bovine insulin on a C8 -bonded silica stationary phase was investigated at different column pressures and temperatures in isocratic reversed-phase HPLC. Changes in the molar volume of insulin (, Vm) upon adsorption were derived from the pressure dependence of the isothermal retention factor ( k,). The values of , Vm were found to be practically independent of the temperature between 25 and 50 °C at ,96 mL/mol and to increase with increasing temperature, up to ,108 mL/mol reached at 50 °C. This trend was confirmed by two separate series of measurements of the thermal dependence of ln( k,). In the first series the average column pressure was kept constant. The second series involved measurements of ln( k,) under constant mobile-phase flow rate, the average column pressure varying with the temperature. In both cases, a parabolic shape relationship was observed between ln( k,) and the temperature, but the values obtained for ln k, were higher in the first than in the second case. The relative difference in ln( k,), caused by the change in pressure drop induced by the temperature, is equivalent to a systematic error in the estimate of the Gibbs free energy of 12%. Thus, a substantial error is made in the estimates of the enthalpy and entropy of adsorption when neglecting the pressure effects associated with the change in the molar volume of insulin. This work proves that the average column pressure must be kept constant during thermodynamic measurements of protein adsorption constants, especially in RPLC and HIC. Our results show also that there is a critical temperature, Tc , 53 °C, at which ln( k,) is maximum and the insulin adsorption process changes from an exothermic to an endothermic one. This temperature determines also the transition point in the molecular mechanism of insulin adsorption that involves successive unfolding of the protein chain. [source] Adsorption equilibrium of amino acids and antibiotics on non-ionic polymeric sorbentsJOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 4 2004Jae Wook Lee Abstract Adsorption equilibria of two amino acids (phenylalanine and tryptophan) and two antibiotics (penicillin G and cephalosporin C) from aqueous solutions onto non-ionic polymeric sorbents (XAD-4 and XAD-16) were investigated under various experimental conditions such as pH, temperature and organic solvents. The assumption that amino acids adsorbed on polymeric sorbents were desorbed by competitive adsorption with organic solvent as a desorbate was verified using binary adsorption data for amino acids (phenylalanine and tryptophan) and organic solvents (isopropyl alcohol and methanol) on XAD-4 and XAD-16. The experimental data were predicted by using multicomponent adsorption models of an Extended-Langmuir (EL) equation and an ideal adsorbed solution theory (IAST) based on the Langmuir equation as a single-component isotherm. Copyright © 2004 Society of Chemical Industry [source] Creating metal-spiked bed sediments: A case study from Orewa estuary, New Zealand,ENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 10 2008Xueqiang Lu Abstract Spiking sediments to achieve target concentrations of heavy metal pollutants is a key step in sediment toxicity tests. It is difficult, however, to ensure that metals in an artificially spiked sediment will behave naturally. A method has been developed in the present study to create Cu-, Pb-, and Zn-spiked sediments in which naturally occurring adsorption onto sediment surfaces is the dominant process binding the metals and in which precipitation of readily redissolved minerals and other metal-bearing phases (artifacts of the spiking procedure) are avoided. Uncontaminated bed sediment from an intertidal mudflat in the Orewa estuary, New Zealand, was characterized in terms of existing metal content, optimal adsorption pH, and adsorption capacity. Competitive adsorption between Cu and Pb as well as complexation by seawater anions only slightly affected metal adsorption from seawater. Surface complexation modeling indicated that iron oxide surfaces in the sediment likely were dominating metal adsorption processes. Spiking experiments were designed using these established adsorption characteristics but with significantly higher (>100-fold) concentrations of sediments and dissolved metals and a liquid to solid (L:S) ratio of approximately 5.5. An equilibration time of at least 36 h was required to achieve a reproducible target metal concentration, which could be reliably predicted from the L:S ratio and the initial metal concentration in the spiking solution. Adsorption equilibrium remained the process governing metal binding to the sediment, and no indication was observed that the adsorption capacity of the sediment had been exceeded or that additional metal-bearing phases had been formed. [source] Adsorption equilibrium of amino acids and antibiotics on non-ionic polymeric sorbentsJOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 4 2004Jae Wook Lee Abstract Adsorption equilibria of two amino acids (phenylalanine and tryptophan) and two antibiotics (penicillin G and cephalosporin C) from aqueous solutions onto non-ionic polymeric sorbents (XAD-4 and XAD-16) were investigated under various experimental conditions such as pH, temperature and organic solvents. The assumption that amino acids adsorbed on polymeric sorbents were desorbed by competitive adsorption with organic solvent as a desorbate was verified using binary adsorption data for amino acids (phenylalanine and tryptophan) and organic solvents (isopropyl alcohol and methanol) on XAD-4 and XAD-16. The experimental data were predicted by using multicomponent adsorption models of an Extended-Langmuir (EL) equation and an ideal adsorbed solution theory (IAST) based on the Langmuir equation as a single-component isotherm. Copyright © 2004 Society of Chemical Industry [source] Kinetics and mechanism of Cr(VI) adsorption onto tea-leaves wasteASIA-PACIFIC JOURNAL OF CHEMICAL ENGINEERING, Issue 4 2008Md. Salatul Islam Mozumder Abstract Adsorption equilibrium and kinetic experiments have been conducted in batch mode to evaluate Cr(VI)-tea-leaves waste system. The equilibrium data followed the Langmuir adsorption isotherm and the adsorption was viewed as a physicochemical reversible process. A unified approach model was used to describe the adsorption system from both equilibrium and kinetic viewpoints. The model satisfactorily described both kinetic and equilibrium data. The adsorption and desorption rate constants were evaluated from the model fittings and were not dependent on initial concentration and adsorbent doses. pHzpc of the adsorbent was evaluated as 4.2 ± 0.1, and below that pH the adsorbent surface is positively charged. Adsorption of Cr(VI) was found highly pH-dependent, and the removal efficiency dropped sharply from 95 to 10% when pH of the system changed from 2 to 5. The surface functional groups of tea-leaves waste (before and after adsorption) were analyzed by Fourier transform infrared (FTIR) and the amine groups were found to take part in the adsorption of Cr(VI). The experimental result inferred that electrostatic attraction between the surface and the species is one of the major adsorption mechanisms for binding metal ions to the tea-leaves waste. Copyright © 2008 Curtin University of Technology and John Wiley & Sons, Ltd. [source] Separation of mono- and dibranched hydrocarbons on silicaliteAICHE JOURNAL, Issue 9 2002E. Jolimaitre Breakthrough curves for mixtures of C5 and C6 hydrocarbons with different degrees of branching were obtained experimentally on a silicalite molecular sieve by fixed-bed experiments. The kinetic separation of di- from monobranched hydrocarbons was feasible on this type of zeolite: dimethyl molecules enter silicalite crystals very slowly, whereas monomethyl molecules are quickly adsorbed. Experimental results were compared to a theoretical isothermal model, considering the variation of diffusivity with concentration according to the Maxwell,Stefan theory. The parameters of the model (adsorption equilibria and diffusivities) were determined from single-component breakthrough curves. Experimental curves were generally well represented by the model, but the variation of diffusivity with concentration, as predicted by the Maxwell,Stefan theory, did not significantly improve the model prediction of experimental breakthrough curves by using a mean value of diffusivity. [source] Vacancy solution theory for binary adsorption equilibria in heterogeneous carbonAICHE JOURNAL, Issue 9 2002L. P. Ding A heterogeneous modified vacancy solution model of adsorption developed is evaluated. The new model considers the adsorption process through a mass-action law and is thermodynamically consistent, while maintaining the simplicity in calculation of multicomponent adsorption equilibria, as in the original vacancy solution theory. It incorporates the adsorbent heterogeneity through a pore-width-related potential energy, represented by Steele's 10,4,3 potential expression. The experimental data of various hydrocarbons, CO2 and SO2 on four different activated carbons,Ajax, Norit, Nuxit, and BPL,at multiple temperatures over a wide range of pressures were studied by the heterogeneous modified VST model to obtain the isotherm parameters and micropore-size distribution of carbons. The model successfully correlates the single-component adsorption equilibrium data for all compounds studied on various carbons. The fitting results for the vacancy occupancy parameter are consistent with the pressure change on different carbons, and the effect of pore heterogeneity is important in adsorption at elevated pressure. It predicts binary adsorption equilibria better than the IAST scheme, reflecting the significance of molecular size nonideality. [source] Metal ion-imprinted polymer microspheres derived from copper methacrylate for selective separation of heavy metal ionsJOURNAL OF APPLIED POLYMER SCIENCE, Issue 1 2008Anh Hoang Dam Abstract Microbeads of metal ion-imprinted polymers (MIIPs) were prepared by a novel precipitation polymerization technique, in which copper methacrylate monomer and ethylene glycol dimethacrylate crosslinker were copolymerized in a rotary evaporator. The prepared microbeads had mono- or narrow size dispersity, and their sizes increased from 1 to 4 ,m with decreasing solvent amount or increasing initiator concentration. The absorption capacity and selectivity of the imprinted polymer for copper ion were determined in the presence of various competitive metal ions. As results, adsorption equilibrium was quickly achieved in about 10 min with high absorbability (about 90%). The effects of pH, initial metallic ion concentration, and MIIP bead size on the absorption capacity were investigated. The Cu(II)-imprinted polymers exhibited extremely high selectivity, which was much higher than that of corresponding blank polymers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008 [source] A new approach to describe high-pressure adsorption isotherms in subcritical and supercritical conditionsAICHE JOURNAL, Issue 7 2009Ch. Chilev Abstract In this article, we present a new approach to describe adsorption equilibrium of pure gases in a wide range of pressure. This approach is based on a simple statistical mechanics treatment combining the potential theory and lattice fluid models. The obtained equation for the calculation of the excess adsorption can predict the curve progression of isotherms defined by the IUPAC I classification, and for those at supercritical conditions. Notwithstanding that the basic idea of the developed equation is to adapt to the adsorption equilibrium in supercritical conditions at high pressure, the model correlates very well experimental data at low pressure in subcritical conditions. It is applicable to a wide range of pressures and fits satisfactorily the experimental data in a broad range of pressures and temperatures. In particular, the model predicts the maximum of excess adsorption and its minimum. A comparison between this approach and two others is given. © 2009 American Institute of Chemical Engineers AIChE J, 2009 [source] Recovery of transition metal complex by reverse flow adsorptionAICHE JOURNAL, Issue 1 2008Jeroen Dunnewijk Abstract Reverse flow adsorption (RFA) is a technique with a definite potential to prevent the leaching of a homogenous catalyst. In this work, we model an RFA-process for a continuous ideally stirred tank reactor with an adsorption bed upstream and another one downstream from the reactor. The model parameters concerning adsorption equilibrium and kinetics are taken from previous experimental studies on CoCl2 adsorption on polymer-bound trifenylfosfine. We use this model to study the concentration profiles of CoCl2 in the adsorption beds during consecutive adsorption,desorption cycles. The model calculations show that the concentration profile eventually reaches a fixed position after a number of adsorption,desorption cycles, even though internal mass transfer was a limiting factor. Hence, the transition metal is kept within the system boundaries, which is an essential requirement for the application of RFA. © 2007 American Institute of Chemical Engineers AIChE J, 2008 [source] Modeling and design of vapor-phase biofiltration for chlorinated volatile organic compoundsAICHE JOURNAL, Issue 9 2002Walter Den A mathematical model was developed for biofilter design and performance prediction with reference to the purification of contaminated gas streams. The model incorporated important aspects such as mass transfer, biodegradation, and adsorption processes. A systematic modeling protocol incorporated the development of a scale-up strategy based on dimensional analysis and similitude. Trichloroethylene (TCE) was employed as the model contaminant for biofiltration testing and model verification. The biokinetic and adsorption parameters for the contaminant were determined independently from a series of minibiofilter and miniadsorber column experiments, specifically designed to simulate the actual biofilter operational regimes in a miniature scale. Bench-scale biofilter experiments employing granular activated carbon columns indicated the good predictive capability of the model for the removal of TCE. Dynamic simulation studies were performed to assess the transient- and steady-state behavior of the model under various operating conditions. Model sensitivity was studied to evaluate the influence of adsorption equilibrium, transport and biological parameters on the biofilter dynamics. The results demonstrated that the biofilter performance was greatly influenced by the Monod coefficients and the biofilm thickness. [source] Novel Coagulation Method for Direct Coagulation Casting of Aqueous Alumina Slurries Prepared Using a Poly(Acrylate) DispersantJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 2 2008Kuttan Prabhakaran Coagulation of concentrated aqueous alumina slurries prepared using an ammonium poly(acrylate) dispersant by MgO has been studied for direct coagulation casting (DCC). A small amount of MgO (0.2 wt% of alumina) increased the viscosity of the concentrated alumina slurry with time and finally transformed it into a stiff gel. The mechanism of coagulation is proposed such that the time-delayed in situ generation of Mg2+ ions from the sparingly soluble MgO forms Mg,poly(acrylate) with the unadsorbed ammonium poly(acrylate) molecules in solution that shift the poly(acrylate) adsorption equilibrium toward the left by depleting the poly(acrylate) molecules adsorbed on the alumina particle surface. This leads to insufficient dispersant coverage on the particle surface and coagulation of the slurry. DCC using MgO is possible only if the slurry is prepared at a dispersant concentration higher than that required for optimum dispersion as the slurries prepared at the optimum dispersant concentration underwent premature coagulation. The gelation time could be tailored within 20 min to a few hours by maintaining the temperature in the range of 70°,30°C. The wet coagulated bodies prepared from 50 vol% alumina slurry showed a compressive strength of nearly 0.05 MPa. [source] Accessibility of simple gases in disordered carbons: theory and simulationASIA-PACIFIC JOURNAL OF CHEMICAL ENGINEERING, Issue 5 2009T. X. Nguyen Abstract We present a review of our recent studies on the accessibility of simple gases (Ar, N2, CH4 and CO2) in disordered microporous carbons using transition state theory (TST) and molecular simulation techniques. A realistic carbon model rather than the slit-pore approximation is utilised, providing more accurate understanding of complex adsorption equilibrium and dynamics behaviour at the molecular level in porous carbons, especially kinetic restriction of adsorbate molecules through highly constricted pore mouths of coals and molecular sieve carbons (MSC). This kinetic restriction leads to a molecular sieving effect which plays a vital role in gas separation using the MSCs. In particular, the realistic carbon model of a saccharose char used in a recent study was obtained by hybrid reverse Monte Carlo simulation. The time of adsorption or desorption of the single gas molecule between two neighbouring pores through a highly constricted window of the realistic saccharose char model was determined using TST. Finally, the validation of TST calculated results of adsorption and desorption times against experimental measurements as well as molecular dynamics simulation is also presented in this article. Copyright © 2009 Curtin University of Technology and John Wiley & Sons, Ltd. [source] Studies of lysozyme binding to histamine as a ligand for hydrophobic charge induction chromatographyBIOTECHNOLOGY PROGRESS, Issue 1 2010Qing-Hong Shi Abstract Histamine was immobilized on Sepharose CL-6B (Sepharose) for use as a ligand of hydrophobic charge induction chromatography (HCIC) of proteins. Lysozyme adsorption onto Histamine-Sepharose (HA-S) was studied by adsorption equilibrium and calorimetry to uncover the thermodynamic mechanism of the protein binding. In both the experiments, the influence of salt (ammonium sulfate and sodium sulfate) was examined. Adsorption isotherms showed that HA-S exhibited a high salt tolerance in lysozyme adsorption. This property was well explained by the combined contributions of hydrophobic interaction and aromatic stacking. The isotherms were well fitted to the Langmuir equation, and the equilibrium parameters for lysozyme adsorption were obtained. In addition, thermodynamic parameters (,Hads, ,Sads, and ,Gads) for the adsorption were obtained by isothermal titration calorimetry by titrating lysozyme solutions into the adsorbent suspension. Furthermore, free histamine was titrated into lysozyme solution in the same salt-buffers. Compared with the binding of lysozyme to free histamine, lysozyme adsorption onto HA-S was characterized by a less favorable ,Gads and an unfavorable ,Sads because histamine was covalently attached to Sepharose via a three-carbon-chain spacer. Consequently, the immobilized histamine could only associate with the residues on the protein surface rather than those in the hydrophobic pocket, causing a less favorable orientation between histamine and lysozyme. Further comparison of thermodynamic parameters indicated that the unfavorable ,Sads was offset by a favorable ,Hads, thus exhibiting typical enthalpy-entropy compensation. Moreover, thermodynamic analyses indicated the importance of the dehydration of lysozyme molecule and HA-S during the adsorption and a substantial conformational change of the protein during adsorption. The results have provided clear insights into the adsorption mechanisms of lysozyme onto the new HCIC material. © 2009 American Institute of Chemical Engineers Biotechnol. Prog., 2010 [source] | ||||||||||||||||