Capillary condensation of a binary mixture in slit-like pores

We investigate the capillary condensation of two model fluid mixtures in slit-like pores, which exhibit different demixing properties in the bulk phase. The interactions between adsorbate particles are modeled by using Lennard-Jones (12,6) potentials and the adsorbing potentials are of the Lennard-Jones (9,3) type. The calculations are performed for different pore widths and at different concentrations of the bulk gas, by means of density functional theory. We evaluate the capillary phase diagrams and discuss their dependence on the parameters of the model. Our calculations indicate that a binary mixture confined to a slit-like pore may exhibit rich phase behavior.     

Modelling adsorbent heterogeneity for adsorption from binary liquid mixtures

It is demonstrated that the detailed structure of the surface energy or selectivity distribution function is not critical to obtaining adequate analytical expressions for surface excess isotherms for adsorption from binary liquid mixtures on heterogeneous adsorbents. The gamma and the uniform selectivity distribution functions, which are very different in form, were successfully used in conjunction with the monolayer-pore filling model for adsorption on a homogeneous site to describe adsorption of various binary liquid mixtures on silica gel. Both models described the salient features of the surface characteristics of the silica gel.     

Equilibrium adsorption of binary mixtures of gases by zeolites and the state of the adsorption phase

A method for analyzing the state of the adsorption phase was developed on the basis of statistical thermodynamics for the case of equilibrium adsorption of binary gaseous mixtures. The procedure for treating experimental data to determine the Helmholtz energy and other thermodynamic functions of a mixture of molecules occluded within zeolite cavities was proposed. A measure of ideal behavior of a mixture of a small number of molecules in the micropore was formulated; in the asymptotic limit such a behavior leads to the Raoult law and to assumption of the validity of the Raoult law when moving along the line of constant value of the Gibbs integral in the ideal adsorption solution theory. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1927–1932, October, 1998.     

On the formation of multilayers in adsorption from binary liquid mixtures

Summary A new excess isotherm is derived for multilayer adsorption from binary liquid mixtures on solid surfaces. This is done by applying the Myers and Sircar's theoretical procedure, and assuming that the adsorption of single components is described by the BET isotherm equation, as modified by Brunauer, Skalny and Bodor. The derived excess equation is next generalized for the case of patchwise heterogeneous solid surfaces. The illustrative calculations presented here include both model investigations and an investigation of two real adsorption systems. It is drawn as a general conclusion that the heterogeneity effects in adsorption from solutions play a greater role than previously supposed.

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Zusammenfassung Eine neue Excessisotherme wurde für vielschichtige Adsorption aus Zweikomponentlösungen an festen Oberflächen abgeleitet. Das wurde mit Anwendung der theoretischen Methode von Myers und Sircar durchgeführt, wobei angenommen wurde, daß die Adsorption der einzelnen Komponenten durch die BET-Gleichung in der Modifizierung von Brunauer, Skalny und Bodor ausgedrückt wird. Die abgeleitete Excessgleichung wurde dann für heterogene feste Oberflächen generalisiert. Die Berechnungen berücksichtigen beide Untersuchungsmodelle und die Untersuchungen der zwei realen Adsorptionssysteme. Es wurde festgestellt, daß der Einfluß der Heterogenität in Adsorption von Lösungen eine größere Rolle spielt, als es vorher angenommen wurde.

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With 9 figures and 1 table     

Reversible adsorption of spherical particles from binary mixtures: long-time behaviour

Formation of monolayers of spherical particles in processes with reversible adsorption from mixtures of large and small particles was simulated in computer experiments. Computer program was based on an algorithm that took into account random sequential adsorption, desorption and lateral diffusion of adsorbed particles (RSA–DLD model). Computer experiments were performed for systems with rate constants of particle adsorption at least 10³ times higher than rate constants of desorption. In processes with very fast adsorption and slow desorption, formation of monolayer can be divided into two stages. During the first stage, the total surface coverage (the coverage with particles of both types) increases very fast and becomes very close to that at equilibrium. During the second stage, the total coverage changes very slowly and the system approaches equilibrium mainly by the replacement of large particles with the small ones. A simple kinetic model for evolution of the monolayer composition during the second stage has been proposed. Kinetic equations related to this model allow the determination of large particles’ desorption rate constants on the basis of changes in the surface concentrations of adsorbed large and small microspheres. The validity of the model has been tested comparing large particles’ desorption rate constants values that had been used for simulations with values of the corresponding rate constants determined using analytical equations, with a view to analysing the simulation results. To cite this article: S. Slomkowski et al., C. R. Chimie 6 (2003).     

2D-SAFT-VR approach to study of the adsorption isotherms for binary mixtures

In this article we present results of approximating molecular modeling of the gas mixtures methane-nitrogen, methane-carbon dioxide, and nitrogen-carbon dioxide adsorbed on activated carbon at a temperature of 318.2 K, based on the Statistical Associating Fluid Theory for potentials of Variable Range. Unlike the previous work (Castro et al.) showing the results in rescaled units, in this work the results obtained are shown in real units as obtained in the experiments.     

Capillary condensation of short-chain molecules

A density-functional study of capillary condensation of fluids of short-chain molecules confined to slitlike pores is presented. The molecules are modeled as freely jointed tangent spherical segments with a hard core and with short-range attractive interaction between all the segments. We investigate how the critical parameters of capillary condensation of the fluid change when the pore width decreases and eventually becomes smaller than the nominal linear dimension of the single-chain molecule. We find that the dependence of critical parameters for a fluid of dimers and of tetramers on pore width is similar to that of the monomer fluid. On the other hand, for a fluid of chains consisting of a larger number of segments we observe an inversion effect. Namely, the critical temperature of capillary condensation decreases with increasing pore width for a certain interval of values of the pore width. This anomalous behavior is also influenced by the interaction between molecules and pore walls. We attribute this behavior to the effect of conformational changes of molecules upon confinement.     

Thermodynamics of adsorption of binary aqueous organic liquid mixtures on a RPLC adsorbent

The surface excess adsorption isotherms of organic solvents commonly used in RPLC with water as co-eluent or organic modifiers (methanol, ethanol, 2-propanol, acetonitrile and tetrahydrofuran) were measured on a porous silica surface derivatized with chlorotrimethylsilane (C1-silica with 3.92 micromol C1 groups per m2 of SiO2), using the dynamic minor disturbance method. The 5 microm diameter particles were packed in a 150 mm x 4.6 mm column. The isotherm data were derived from signals resulting from small perturbations of the equilibrium between the aqueous-organic solutions and the adsorbent surface. The partial molar surface area of the adsorbed components were assumed to be the same as those of the pure components. The difference sigma-sigmai* between the surface tensions of the adsorbed mixtures and that of the pure liquids was measured as a function of the organic modifier molar fraction. A simple and unique convention for the position of the Gibbs dividing surface was proposed to delimit the Gibbs's adsorbed phase and the bulk liquid phase. The activity coefficients of the organic modifiers and of water and their thermodynamic equilibrium constants between the two phases were measured. The strong non-ideal behavior of the adsorbed phase is mostly accounted for by the surface heterogeneity. Some regions of the surface (bonded -Si(CH3)3 moieties) preferentially adsorb the organic compound while the regions close to unreacted silanols preferentially adsorb water.     

Computer simulations of adsorption and diffusion for binary mixtures of methane and hydrogen in titanosilicates

Equilibrium molecular dynamics (MD) simulations of equimolar mixtures of hydrogen and methane were performed in three different titanosilicates: naturally occurring zorite and two synthetic titanosilicates, ETS-4 and ETS-10. In addition, single-component MD simulations and adsorption isotherms generated using grand canonical Monte Carlo simulations were performed to support the mixture simulations. The goal of this study was to determine the best membrane material to carry out hydrogen/methane separations. ETS-10 has a three-dimensional pore network. ETS-4 and zorite have two-dimensional pore networks. The simulations carried out in this study show that the increased porosity of ETS-10 results in self-diffusion coefficients for both hydrogen and methane that are higher in ETS-10 than in either ETS-4 or zorite. Methane only showed appreciable displacement in ETS-10. The ability of the methane molecules to move in all three directions in ETS-10 was demonstrated by the high degree of isotropy shown in the values of the x, y, and z components of the self-diffusion coefficient for methane in ETS-10. From our simulations we conclude that ETS-10 would be better suited for fast industrial separations of hydrogen and methane. However, the separation would not result in a pure hydrogen stream. In contrast, ETS-4 and zorite would act as true molecular sieves for separations of hydrogen and methane, as the methane would not move through membranes made of these materials. This was indicated by the near-zero self-diffusion coefficient of methane in ETS-4 and zorite.     

Thermodynamic investigation of the adsorption of amides on graphite from their liquids and binary mixtures

We report a thermodynamic investigation of the adsorption of saturated and unsaturated (cis- and trans-) alkyl amides onto the surface of graphite from their pure liquids and from binary mixtures. We identify the formation of solid monolayers of the amides at temperatures when the bulk materials are liquid. The extent of this presolidification is much more extensive than other related materials, indicating that these amide layers are significantly more stable. The monolayer stability is found to be greatest for saturated amides. In addition, the stability of unsaturated amides is extremely sensitive to the location of the double bonds in the alkyl chain of the molecules, and trans isomers are found to be more stable than cis. We also address the preferential adsorption and mixing behavior of amide mixtures and amides mixed with other species coadsorbed onto graphite from binary solution. The results indicate that the amide molecules appear to be adsorbed with their principal axis parallel to the graphite surface and that amides are found to be strongly preferentially adsorbed with respect to alkanes. Interestingly the amides appear to mix rather better than might have been expected. There is also evidence of a number of other transitions in the adsorbates.     

Adsorption of gas mixtures on homogeneous solid surfaces I. Model of double associates for adsorption of binary mixtures

Summary The adsorbate-adsorbate association model (AA model) is used to describe the adsorption of binary gas mixtures on homogeneous adsorbents. The single and double associates are considered only, because most useful equations are obtained. The association parallel and normal to surface is discussed. The model of associates normal to surface explains theGonzalez andHolland adsorption isotherm.

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Zusammenfassung Zur Beschreibung der Adsorption einer binären Gasmischung an homogenen Adsorbentien wurde ein Modell über Adsorbat-Adsorbat-Assoziationen zu Grunde gelegt. Es wurden nur einfache und doppelte Assoziate betrachtet, weil diese Annahmen zu gut anwendbaren Gleichungen führen. Dabei wird die Assoziation sowohl normal als auch senkrecht zur Grenzfläche untersucht. Das Modell der Assoziate normal zur Grenzfläche führt zur Adsorptionsisotherme vonGonzalez undHolland.

     

Capillary condensation as a morphological transition

The process of capillary condensation/evaporation in cylindrical pores is considered within the idea of symmetry breaking. Capillary condensation/evaporation is treated as a morphological transition between the wetting film configurations of different symmetry. We considered two models: (i) the classical Laplace theory of capillarity and (ii) the Derjaguin model which takes into account the surface forces expressed in terms of the disjoining pressure. Following the idea of Everett and Haynes, the problem of condensation/evaporation is considered as a transition from bumps/undulations to lenses. Using the method of phase portraits, we discuss the mathematical mechanisms of this transition hidden in the Laplace and Derjaguin equations. Analyzing the energetic barriers of the bump and lens formation, it is shown that the bump formation is a prerogative of capillary condensation: for the vapor-liquid transition in a pore, the bump plays the same role as the spherical nucleus in a bulk fluid. We show also that the Derjaguin model admits a variety of interfacial configurations responsible for film patterning at specific conditions.     

Capillary condensation of adsorbates in porous materials

Hysteresis in capillary condensation is important for the fundamental study and application of porous materials, and yet experiments on porous materials are sometimes difficult to interpret because of the many interactions and complex solid structures involved in the condensation and evaporation processes. Here we make an overview of the significant progress in understanding capillary condensation and hysteresis phenomena in mesopores that have followed from experiment and simulation applied to highly ordered mesoporous materials such as MCM-41 and SBA-15 over the last few decades.     

New model describing adsorption from liquid binary mixtures of nonelectrolytes with limited and unlimited miscibility of components

Using the thermodynamic idea of complementary systems, and based on fundamental concepts of the theory of volume filling of micropores, we derived a new universal model describing adsorption from solutions with limited and unlimited miscibility of components. The model takes into account the differences in collision diameters of adsorbed molecules as well as the competitive nature of adsorption from solutions. The applicability of this new approach is tested against experimental data.     

Capillary isoelectric focusing--reproducibility and protein adsorption

Capillary isoelectric focusing (CIEF) is an important tool for the quality assurance of biotechnologically maintained drugs and for proteome analysis. The critical performance parameters of this technique are the precisions of isoelectric point (pI) values and peak areas. Compared to capillary zone electrophoresis (CZE), where precise results can be obtained (e.g., 0.5% relative standard deviation (RSD) for peak areas, n = 60), only few data are available for CIEF experiments. So far, reproducible data of pI values (RSD = 0.5%) have been acquired, but peak areas show inferior results (about 3-15% RSD). Nonstable capillary coatings and protein adsorption have been discussed as possible reasons. Recent work of Righetti et al. [25, 27] has proven that the use of coated capillaries can reduce the adsorption of proteins by 50% but cannot prevent it. In our CIEF experiments irregular and poorly reproducible peak patterns have been observed. In a long-time experiment of 106 repeated runs, an overall RSD of 10% was obtained for peak areas, RSD of 2% only in series of about 10 consecutive replicates. Especially at higher concentrations the reproducibility deteriorates. This seems to be the result of a self-amplifying process, induced by adsorbed protein molecules, leading to further agglomerations. CZE control experiments in linear polyacrylamide (LPA)-coated capillaries proved a strong pH dependency of these effects within a small range. Compared to bare fused-silica surfaces, adsorption effects are reduced but not inhibited. An enhancement of reproducibility in CIEF experiments can be achieved only by controlling the interactions of proteins and capillary walls.