Thermodynamics of adsorption of acetone on active carbon supported metal adsorbents

Adsorption of acetone on active carbon and active carbon supported metals (Ni, Cu, Zn and Cd) have been studied as a function of temperature. Thermodynamic parameters such as G ⁰, H ⁰, and S ⁰ are calculated from virial and Langmuir isotherm expressions. It is observed that active carbon supported metals have more adsorption affinity for acetone as compared to active carbon. Results show that the increase in adsorption affinity for active carbon supported metals is not due to configurational factors affecting the entropy of adsorption, but because of enhanced enthalpy of adsorption. XRD spectra show that active carbon supported metals adsorbents are amorphous and metal residues are present on the surface of active carbon in its reduced form. From adsorption data, isosteric heats and molar entropies of adsorption were calculated as a function of coverages and temperature. The values of isosteric heats of adsorption were found to be higher for active carbon supported metals, which may be due to the chemisorption of adsorbate molecules with metal sites present on the surface of active carbon. The extent of coordination of adsorbate molecules with metal sites is discussed on the basis of the acidic character of metal.     

Flotation and adsorption investigations of the systemn-dodecanoic acid/mercury at different pH values

The systemn-dodecanoic acid/mercury in 0,1 N KCl solutions has been investigated within pH range 4,0–10,5 in order to characterize the adsorption of surfactant and to determine its influence on the flotation of mercury. Flotation tests have been carried out in a model mercury flotation apparatus developed by Pomianowski and Para. Some characteristic parameters of adsorption (attraction constant of Frumkin isotherm, adsorption coefficient at maximum adsorption potential, free standard adsorption enthalpy and area per molecule) have been determined by a. c. polarographic capacity-potential and capacity-time curves. Flotation recovery as well as attraction constant, adsorption coefficient and surface excess reach maximum at pH5,1. It is explained by the assumption of an ion-molecule associate formation.Publ.-No. 810 from Research Institute of Mineral Processing, Academy of Sciences of the German Democratic Republic, Freiberg     

On the Jovanovic model of adsorption

Summary The effect of the hydrostatic pressure exerted by bulk phases on adsorbed phases depends on the mobility of adsorbed phase and on the topographical distribution of adsorption energy. It is shown in this paper that the Langmuir's equation applies also to adsorption of fully mobile hard discs, on heterogeneous surfaces having fully random topographical distribution of adsorption energy. The effects of the hydrostatic pressure are discussed also in the case of heterogeneous surfaces exhibiting patchwise topographical distribution of adsorption energy.

Symbols

Roman Letters a parameter in the Jovanovic isotherm - A fraction of total surface covered - A ₁ fraction covered of sites having a given adsorption energy - A _j fraction of surface covered as evaluated from the Jovanovic adsorption isotherm - b,b _t parameters in various versions of the Langmuir isotherm - B number of adsorption sites on an adsorbent surface - H enthalpy of adsorption - F free energy of adsorption - k Boltzmann's constant - K, K _j ,K _L parameters in various versions of adsorption isotherms - m mass of the adsorbate molecule - N number of adsorbed molecules - N ₀ monolayer capacity in mobile adsorption - N ₁ local adsorption isotherm - N _t overall adsorption isotherm - p pressure of gas phase adsorbate - q canonical molecular partition function for mobile admolecules - q _st isosteric heat of adsorption - R gas constant - S surface area of adsorbent - S ₁ surface area of sites having a given adsorption energy - S ^* minimum change in the external variable S - T absolute tempetature - T _t frozen temperature Greek Letters Greek Letters parameter of the adsorption isotherm - isothermal-isobaric partition function - adsorption energy - area occupied by one adsorbate molecule - area of box of uniform adsorption energy - chemical potential - v frequency of vibrations of admolecules - range of variation of - () distribution of adsorption energy With 2 figures and 1 table     

New thermodynamically consistent competitive adsorption isotherm in RPLC

A new equation of competitive isotherms was derived in the framework of the ideal adsorbed solution (IAS) that predicts multisolute adsorption isotherms from single-solute isotherms. The IAS theory makes this new isotherm thermodynamically consistent, whatever the saturation capacities of these single-component isotherms. On a Kromasil-C(18) column, with methanol-water (80/20 v/v) as the mobile phase, the best single-solute adsorption isotherm of both toluene and ethylbenzene is the liquid-solid extended multilayer BET isotherm. Despite a significant difference between the monolayer capacities of toluene (370 g/l) and ethylbenzene (170 g/l), the experimental adsorption data fit very well to single-component isotherms exhibiting the same capacities (200 g/l). The new competitive model was used for the modeling of the elution band profiles of mixtures of the two compounds. Excellent agreement between experimental and calculated profiles was observed, suggesting that the behavior of the toluene-ethylbenzene adsorbed phase on the stationary phase is close to ideal. For example, the concentrations measured for the intermediate plateau obtained in frontal analysis differ by less than 2% from those predicted by the IAS model.     

Interaction of Chloride Anion and Chlorine Atom with Indium and Gallium Surfaces: A Quantum-chemical Study

The adsorption of the chloride ion and chlorine atom on clusters simulating the surface of the (111) and (001) faces of the crystal lattice of indium and liquid gallium are calculated using the Hartree–Fock–Roothaan and density functional (B3LYP) quantum-chemical methods. The energy of adsorption of chloride ions from a gas phase at these faces increases in the following series: bridgehollow < on-top positions and equals to 179 kJ mol^–1 for In(111) and 183 kJ mol^–1 for gallium in the on-top position. Both metals exhibit similarity in the formation of bonds between their surface atoms and the adsorbate. The adsorbate charge does not depend on the adsorbed form (chloride ion or chlorine atom) and equals 0.5e. Parameter of a virial adsorption isotherm is estimated with allowance for coulombic interactions near the metal/electrolyte interface.     

Investigation of energetic heterogeneity of carbon black surfaces during adsorption of chromatographically low concentrations of n-pentane

Energetic heterogeneity of different types of industrial carbons was studied by gas-adsorption chromatography in regions of low surface coverages. The main thermodynamic characteristics of n-pentane adsorption on the carbon black surfaces were experimentally determined under the conditions close to the zero coverage of the surface (Henry region). These characteristics include the Henry constants, differential molar heats of adsorption, changes in the entropy of adsorption, and differences in molar heat capacities of the adsorbate in the adsorbed state and its vapors at a constant pressure. The specific features of the geometric structure and ratio of surface regions different in the adsorption energy make it possible to establish the presence of the Henry region in the adsorption isotherm. The gas-chromatographic criteria, which can be used to estimate the degree of energetic heterogeneity of the adsorbent surface, were considered.     

Mechanism of coadsorption of two organic substances on electrodes at strong attractive interaction between their molecules in the adsorption layer

Based on the model of three parallel capacitors, the differential capacitance and the surface concentration of two organic compounds coadsorbed on an electrode are calculated as a function of the potential. It is shown that for the strong attractive interaction of two different adsorbed molecules that occupy equal areas on the surface and for different combinations of the other adsorption parameters is well described by the model of two parallel capacitors with a simple Frumkin isotherm. However, in this case, the effective attraction constant in this isotherm should depend on the electrode potential. The obtained results show that the good agreement of experimental data with the calculations based on the model of two parallel capacitors is insufficient for assuming that the orientation of adsorbed molecules of a given organic compound is potential-independent. On the other hand, if the adsorbate molecule in two different orientations occupies different areas on the electrode surface, then the model of two parallel capacitors does not allow one to describe the dependence of the total surface concentration on the electrode potential even under the conditions where this model adequately describes the differential capacitance curves.     

Percus-Yevick theory of adsorption

We study adsorption of hard sphere particles on to a plane surface with a delta function adsorption potential. The calculation takes account of exclusion via the Percus-Yevick approximation. At low and intermediate bulk adsorbate densities, both type II and type III BET adsorption isotherms can be found for the surface excess density and for the monolayer surface density. The surface excess isotherm agrees with an expansion of the exact surface excess isotherm to second order in the density. We mention some biochemical ramifications of the results.     

Effects of gas adsorption isotherm and liquid contact angle on capillary force for sphere-on-flat and cone-on-flat geometries

This paper explains the origin of the vapor pressure dependence of the asperity capillary force in vapor environments. A molecular adsorbate layer is readily formed on solid surface in ambient conditions unless the surface energy of the solid is low enough and unfavorable for vapor adsorption. Then, the capillary meniscus formed around the solid asperity contact should be in equilibrium with the adsorbate layer, not with the bare solid surface. A theoretical model incorporating the vapor adsorption isotherm into the solution of the Young-Laplace equation is developed. Two contact geometries--sphere-on-flat and cone-on-flat--are modeled. The calculation results show that the experimentally-observed strong vapor pressure dependence can be explained only when the adsorption isotherm of the vapor on the solid surface is taken into account. The large relative partial pressure dependence mainly comes from the change in the meniscus size due to the presence of the adsorbate layer.     

New approach to precise determination of the capacity of an adsorption monolayer

An analytical expression that determines the capacity of adsorption monolayer from the experimental isotherm of polymolecular adsorption and the tabular data on a surface tension and a molar volume of adsorbate is derived.     

Comparison of the adsorption equilibrium of a few low-molecular mass compounds on a monolithic and a packed column in reversed-phase liquid chromatography

Adsorption isotherm data were acquired by frontal analysis for several low-molecular mass compounds (3-phenyl 1-propanol, 4-tert.-butylphenol, butylbenzene, and butyl benzoate) on a classical packed column and a monolithic column using methanol-water RP-HPLC conditions. These columns have similar characteristics (C18-bonded silica, close specific surface areas and bonding densities). In each case, the isotherm model best accounting for the data was the same on both columns. The solute polarity determines the class of this model. For the two -OH compounds it was a Langmuirian adsorption isotherm. The hydrocarbon data were best modeled by an anti-Langmuir convex-downward isotherm model. The adsorption data for the aromatic ester exhibited a nearly linear behavior, depending on the methanol concentration of the mobile phase. A slightly convex downward isotherm was obtained at high methanol concentrations while the best fitting was obtained with a liquid-solid extended multilayer B.E.T. isotherm model at low concentrations. The validation of these models is discussed in detail. In all cases, similar values of the adsorption-desorption constants were found, underlining the closeness of the adsorption energies on both columns. By contrast, the adsorption capacity of the monolithic column was found to be approximately 1.4 greater than that of the packed column in spite of the close values of the surface areas of the silica in both columns.     

Adsorption Isotherm Accounting for the Electrode Elasticity: Special Solutions

The single-phase adsorption on a solid electrode out of a dilute solution is investigated. As a continuation of the previous paper, on the basis of the complete electrocapillarity equation, an adsorption isotherm equation is derived and supplemented by equations of compatibility of the physical quantities. The equations contain a new parameter, , which is a derivative of the dimensionless surface adsorbate concentration by the relative variation of the electrode surface area. Their solution is obtained in relation to the dimensionless charge density of the electrode surface q for the case of = (). As a result of employing a linear model for q by , the problem of determination of the unknown model functions is reduced to common differential equations that use the capacitance or estance curves as the boundary conditions. In the first case, we suggest to calculate the unknown integration parameter by the method of mathematical optimization, employing coulometric data.     

气体临界温度以上吸附平衡的预测研究

Experimental adsorption isotherms of CH4 and N2 higher than critical temperatures on K02 activated carbon were measured with the volumetric method The pressure and temperature ranges were 0～12 MPa and 273～333 K respectively. A model, which took into account the adsorbate properties above critical temperatures and the adsorbent surface heterogeneity by pore size distribution, was proposed in this paper to predict the equilibrium data only using one adsorption isotherm. The gamma distribution was adopted to express the pore size distribution of the activated carbon, and the adsorption potential was calculated bythe 10-4-3 equation for slit shape micro pores. The relationships between the adsorbate density, the saturated adsorption amount and the equilibrium temperature have been discussed in detail. Through this method, the experimental adsorption data of CH4 and N2 were compared with the prediction equilibria. The study illustrates that the predicting method could present the adsorption equilibria accurately in the whole research range. And the mean relative deviations of the prediction of CH4 and N2 are only about 1.9% and 2.9%. This proves that the analyses of the adsorbate properties are reasonable. Inaddition, the model was applied to calculating the equilibrium data of various supercritical adsorption systems published in literatures. Despite different adsorbents and equilibriaconditions, the investigation results demonstrate that the suggested model performs well in predicting the gases adsorption equilibrium data with all mean relatived eviations less than 6.8%. Therefore, the model could be utilized to calculate the gases adsorption equilibrium data above critical temperatures in a wide range.     

Adsorption of n-Butanol on Polycrystalline Silver–Gold Alloys

The adsorption kinetics for n-butanol (c _L = 0.033–1.2 M) on polycrystalline electrodes of silver, gold, and their homogeneous alloys (X _Au = 0.15–0.80) formally obeys the Roginskii–Zel'dovich equation. The steady-state coverage of their surface by the alcohol, _L ^st, is described by the Temkin isotherm. The ratio between the slopes of the _L vs. logt and _L ^st, vs. logc _L dependences perceptibly alters with X _Au. The experimental data are discussed in terms of a quasi-equilibrium competing co-adsorption of water and alcohol at an energetically-nonuniform surface accompanied by a relatively slow redistribution of adsorbate molecules between adsorption centers of different nature. It is shown that quantitative characteristics of the n-butanol adsorption on Ag–Au alloys cannot be calculated in the approximation of additivity of properties on the basis of relevant parameters of adsorption on Ag and Au.     

Microwaves and sorption on oxides: a surface temperature investigation

Microwave heating is not the same as conventional heating, and it is believed that this difference, the "microwave effect," may be interpreted to be due to selective, local heating. The temperature at the surface where sorption occurs is "effectively" greater than the measured solid or gas temperature. In these studies, measurements of the amounts of adsorption as functions of the partial pressures of a specific adsorbate in the presence of microwave irradiation were related to the conventional adsorption isotherms. Equating the adsorbate pressure required to achieve a specific coverage (an isostere) in the presence of microwave irradiation to the amount adsorbed for a conventional isotherm allowed for an estimate of the "effective" surface temperature in the presence of microwaves. It was found that the effective surface temperature increased when using adsorbates having a higher permittivity or when increasing the microwave power. The implication of this change in the surface energy for specific species in the presence of microwaves is discussed.     

Revision of adsorption models of xyloglucan on microcrystalline cellulose

Interactions among cellulose, hemicellulose and pectins are important for plant cell wall assembly and properties and also for industrial applications of these polysaccharides. Therefore, binding of pectin and xyloglucan on microcrystalline cellulose was investigated in this experiment by adsorption isotherms, zeta potential and scanning electron microscopy (SEM). Analysis of three isotherm models (Langmuir, Freundlich and Fowler-Guggenheim isotherms) showed that the experimental adsorption isotherm was well described via the Fowler-Guggenheim model, which includes lateral interaction between the adsorbate. The adsorption isotherm and zeta potential measurement showed that at temperature 25 °C only xyloglucan adsorbed on the microcrystalline cellulose. In case of xyloglucan on cellulose, the equilibrium was reached in about 3–4 h, and the kinetics of adsorption were well described by the multiexponential equation. Analysis of the model suggests that two steps can be distinguished: diffusion and reconformation in an adsorbed layer. No adsorption of pectin was observed in this study. SEM study showed that xyloglucan may prevent cellulose from aggregation.     

Adsorptive Removal of Thorium(IV) from Aqueous Solutions Using Synthesized Polyamidoxime Chelating Resin: Equilibrium,Kinetic, and Thermodynamic Studies

In this study, an amidoximated chelating ion exchange resin was prepared by poly-acrylonitrile (PAN) grafted potato starch. The adsorbent characterizations such as specific surface area, pore volume, average pore radius, and Fourier transform infrared (FTIR) spectrum of the resin were measured. The effects of pH, adsorbent dosage, contact time, initial concentration of thorium ion, and temperature on adsorption of thorium ion from aqueous solutions were investigated. Four isotherm models including Langmuir, Freundlich, Dubinin-Radushkevich, and Temkin were applied to analyze the equilibrium isotherm data. The results showed that Langmuir and Temkin models had a good agreement with experimental data. The maximum capacity of the adsorbent using the Langmuir isotherm model was 227.27 mg · g^?1. The kinetic models like pseudo-first-order, pseudo-second-order, Elovich, and intraparticle were examined to describe the adsorption process. The kinetics of the adsorption process was found to follow the pseudo-second-order kinetic model. The thermodynamic parameters (ΔG°, ΔH°, ΔS°) were also calculated using equilibrium constant values at various temperatures (25, 35, 45, 55°C) and the positive value for ΔH° showed an endothermic adsorption process. The study suggests that the prepared adsorbent has promising potential for the removal of thorium from wastewaters.      

Synthesis and characterization of <Emphasis Type="Italic">β</Emphasis>-cyclodextrin–carboxymethyl cellulose–graphene oxide composite materials and its application for removal of basic fuchsin

A novel β-cyclodextrin–carboxymethyl cellulose–graphene oxide composite material (β-CD–CMC–GO) was synthesized, and its application as excellent adsorbents was carried out for removal basic fuchsin (BF) in aqueous solution. The structure and morphology of β-CD–CMC–GO composite material were characterized by using FTIR, SEM, TEM, XRD, TG and DSC methods. The composites could remove basic fuchsin from aqueous solution efficiently. The adsorption experiment was carried out and the optimum experimental conditions were ascertained. The highest adsorption efficiency was obtained 97.3% at 0.015 g/mL dosage of β-CD–CMC–GO, the temperature of 25 °C and time of 2.5 h. Adsorption kinetics, adsorption isotherm and adsorption thermodynamic were used to analyze the adsorption system. The experimental data of adsorption kinetics of system were well followed by pseudo-second-order equation. The adsorption isotherm data were fitted using Langmuir isotherm model and Freundlich isotherm model. The maximum adsorption capacity of basic fuchsin reached 58.65 mg/g. The thermodynamic parameters indicated that the adsorption process was spontaneous and exothermic. The adsorbent has excellent regeneration ability and reproducibility. The proposed method shows that the β-CD–CMC–GO could be applied to removal of basic fuchsin in wastewater with satisfactory result.