Studies on the Physical Adsorption Equilibria of Gases on Porous Solids over a Wide Temperature Range Spanning the Critical Region—Adsorption on Microporous Activated Carbon

Adsorption equilibria of nitrogen and methane on microporous ( < 2 nm) activated carbon were measured for a wide temperature range (103‐298 K) spanning the critical region. Information relating to Henry constants, the isosteric heat of adsorption, and the amount of limiting adsorption were evaluated. All isotherms show type‐I features for both sub‐ and supercritical temperatures. A new isotherm equation and a consideration for the importance of the effect of the adsorbed phase volume allow this kind of isotherms to be modeled satisfactorily. The model parameter of the saturated amount of absolute adsorption (n⁰_t) equals the limiting adsorption amount (n^itm), leaving the physical meaning of the latter clarified, and the exponent parameter (q) proves to be an appropriate index of surface heterogeneity.     

Adsorption of 1-tetradecene/dodecane mixtures on different types of zeolites

The influence of heterogeneity parameters on the shape of excess adsorption isotherms has been discussed. These isotherms have been calculated according to the equations corresponding to different energy distributions. Next, the isotherm equations have been applied to examine the experimental excess isotherms for 1-tetradecene/dodecane mixture adsorption on different types ofX-zeolites at 293 K, 313 K and 333 K. The zeolite samples have been prepared from NaX-zeolite by exchanging the sodium ions for ions of alkalines and calcium group. Analysis of the above adsorption data by means of different isotherm equations showed that the parameters of aDubinin-Radushkevich-type equation change correctly with temperature and the contents of alkalines in the zeolite samples.     

Heterogeneous microporous structures and adsorption properties of carbon adsorbents

A theoretical basis for calculating parameters of the pore structure of active carbons is considered. Active carbons are classified into four types according to their dispersion and mesopore surface areas. The parameters of micro- and mesopores of active carbons produced in different countries have been determined from benzene vapor adsorption isotherms at 293 K. The differences in parameters of the Dubinin—Stoeckly equation found from adsorption isotherms of different compounds are noted.For part 11, seeIzv. Akad. Nauk SSSR, Ser. Khim., 1990, 2691 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1990,39, 2438 (Engl. Transl.)].Deceased July 13, 1993.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1373–1376, August, 1993.     

Adsorption of Some Surfactants onto Polyvinyl Alcohol as Hydrophobic Polymer Surface

The adsorption of different types of nonionic and anionic surfactants from aqueous solutions onto polyvinyl alcohol has been studied at different temperatures using surface tension measurements. The nonionic surfactants show Langmuirian L-shape isotherms whereas the adsorption isotherms of the anionic surfactants exhibit segmoidal shape. The experimental adsorption isotherms could be fitted to the Langmuir equation and the values of Γ_max and A_min have been calculated. The effect of temperature on the adsorption process as well as on both efficiency and effectiveness of adsorption has been studied.     

Evaluation of defect induced surface heterogeneity in Metal-Organic Framework materials with alkali dopants employing adsorption isotherm modelling

In this article, an assessment of surface structural heterogeneity in porous metal organic framework (MOF) structure has been demonstrated by employing the methane and carbon-dioxide adsorption isotherms data. The virgin MIL-101-(Cr) MOF was synthesized by the hydrothermal method and defects were induced in the MOF structure by doping with various alkali (K, Na, Li) cations. The synthesized MOFs were characterized by XRD, SEM, EDX and BET measurement techniques. In order to understand the defect induced surface heterogeneity by alkali cation dopants, the surface energy distributions for CH₄ and CO₂ adsorptions on MOFs were measured by Dubinin – Astakhov model equation. The surface heterogeneity is mainly controlled by the limiting uptakes of adsorbates, the polarizability of adsorbates and the adsorbate-adsorbent interaction energy.     

Adsorption characteristics of malachite green dye onto novel kappa-carrageenan-g-polyacrylic acid/TiO2–NH2 hydrogel nanocomposite

Batch adsorption experiments were carried out for the removal of malachite green (MG) cationic dye from aqueous solution using novel hydrogel nanocomposite that was prepared by graft copolymerization of acrylic acid (AA) onto kappa-carrageenan (κC) biopolymer in the presence of a crosslinking agent, a free radical initiator and aminosilica-functionalized TiO₂ nanoparticles (κC-g-PAA/TiO₂–NH₂). The factors influencing adsorption capacity of the adsorbents such as initial pH value (pH₀) of the dye solutions, TiO₂–NH₂ content (wt%), initial concentration of the dye, amount of adsorbents, and temperature were investigated. The adsorption capacity of hydrogel nanocomposite for MG was compared with hydrogel. The adsorption behaviors of both adsorbents showed that the adsorption kinetics and isotherms were in good agreement with a pseudo-second-order equation and the Langmuir equation. The high adsorption capacity (q _m= 666–833 (mg/g)) and the favorable heterogeneity factor (n = 1.2–1.5) calculated from isotherm equations show the efficiency of the novel adsorbents.     

A New Organophosphorus Insecticides Removal Process Using Fly ASH

Abstract

Fly ash and soil mixtures with a range of fly ash content from 1 to 100% were used to study adsorption and desorption of four organophosphorus insecticides, ethyl parathion, methyl parathion, fenitrothion and fenthion, in batch experiments. The object of the study was to develop a treatment process using fly ash as sorbent material to isolate/immobilize organic contaminants from aqueous solutions. The adsorption isotherms fit the Freundlich equation x/m=K_dC^1/n. The K_d values increase with the increase of the fly ash content. The isotherms seem to fit the S type, in mixtures of soil with a fly ash content from 0 to 10%, which implies that adsorption becomes easier as the concentration in the liquid phase increases. In mixtures of soil with a fly ash content from 25 to 50% the isotherms become L type and correspond to a decrease of site availability as the solution concentration increases. Finally in mixtures of soil with a fly ash content over 50%, C type adsorption was observed which correspond to a constant partition of the insecticides between the bulk solution and the adsorbent. Mass balance estimations show that the mean percent amounts of insecticides for a range of concentration 0.5–15 mg/l, removed by adsorption in the soil sample are 81.56 % for ethyl parathion, 48.97 % for methyl parathion, 67.06 % for fenitrothion and 86.65 % for fenthion. The adsorption increases as the fly ash content increased and reach the 100% in the “pure” fly ash. The adsorbed amounts of insecticides in mixtures of soils with >50% fly ash content, are up to 99%. In contrast, the amounts of desorption in water decrease as the fly ash content increase.

The results of this research demonstrate that the fly ash shows a significant capacity for adsorption of organophosphorus compounds from aqueous solution and can be used for pesticide removal process.     

Consequence of assuming gamma-type distribution for characterizing structural heterogeneity of microporous solids

Extensive model studies were carried out for the gamma-type distribution, which was used to characterize structural heterogeneity of microporous solids. This distribution lead to a simple equation, which gave a good representation of many adsorption isotherms measured on microporous activated carbons. Assuming physically realistic values of the adsorption parameters, the gamma-type distribution curves were calculated together with curves of the adsorption isotherm, micropore distribution, adsorption potential distribution, enthalpy and entropy of adsorption.

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Die Konsequenz der Annahme einer Gamma-Typ-Verteilung bei der Charakterisierung der strukturellen Heterogenität von mikroporösen Feststoffen

Zusammenfassung Es wurden für die Gamma-Typ-Verteilung, die zur Charakterisierung der strukturellen Heterogenität von mikroporösen Feststoffen genutzt wurde, ausgedchnte Modellrechnungen durchgeführt. Diese Verteilung führte zu einer einfachen Gleichung, die eine gute Darstellung vieler Adsorptionsisothermen an mikroporös-aktiviertem Kohlenstoff erlaubt. Unter der Annahme von physikalisch realistischen Werten für die Adsorptionsparameter wurden die Gamma-Typ-Verteilungskurven zusammen mit Kurven für die Adsorptionsisothermen, der Mikroporenverteilung, der Adsorptionspotentialverteilung und der Enthalphie und Entropie der Adsorption berechnet.

     

Adsorption and Desorption of Water on Tin Dioxide

Adsorption isotherms were obtained for water on SnO₂ samples subjected to heat treatment at various temperatures. The monolayer capacity and adsorption constants were determined by Langmuir equation. The enthalpy and entropy of adsorption were determined using the isobar equation.     

Ion imprinted adsorbent for the removal of Ni(II) from waste water: preparation,characterization, and adsorption

Abstract

In this paper, a selective nickel ions chelating adsorbents (Ni-CMCS) were prepared based on carboxymethyl chitosan by ion imprinting technique. Scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) were used to investigate their physicochemical properties. Brunauer-Emmett-Teller (BET) analysis showed that the BET surface area of Ni-CMCS had a significant increase after ion imprinting process. The effects of pH value, contact time and initial concentration of Ni(II) were studied. The adsorption kinetics were investigated, which indicated that Ni-CMCS was better fitted with pseudo-second-order kinetic model (R² = 0.9991) with film diffusion process as rate controlling step. The adsorption isotherms study indicated that Langmuir model matched better with the experimental data for Ni-CMCS (R² = 0.9617). Besides, the maximum adsorption capacity calculated from the Langmuir equation was 82.78?mg g^?1. Moreover, the selectivity experiment suggested that Ni-CMCS had good selectivity in the presence of Co(II), Mn(II), or Cd(II). After used four cycles, Ni-CMCS kept great adsorption capacity.     

Assessment of Hydrophobic-Hydrophilic Properties of Microporous Materials from Water Adsorption Isotherms

The characterization of the hydrophobic-hydrophilic properties of different types of microporous materials, namely activated carbons, pillared clays and zeolites, was made by the determination of water adsorption isotherms. The data were analysed by the Dubinin and Astakhov (D-A) equation. The use of the E parameter of the D-A equation as a measure of the hydrophobic-hydrophilic character is proposed. When the information obtained from the E parameter is compared with the information that can be obtained from other parameters used in the literature to characterize the hydrophobicity of materials, it is found that the former is more sensitive and is more directly related with the shape of the adsorption isotherms which, ultimately, is the more direct manifestation of the hydrophobic-hydrophilic properties of a given material.     

Investigation of activated carbon surface heterogeneity by argon and nitrogen low-pressure quasi-equilibrium volumetry

Surface heterogeneity can be assessed by adsorption of different gaseous probes on solid materials. In the present study, four types of activated carbons were analyzed by classical N2 Brunauer-Emmett-Teller (BET) measurements and by low-pressure quasi-equilibrium volumetry (LPQEV) (Villieras, F.; Michot, L. J.; Bardot, F.; Cases, J. M.; Francois, M.; Rudzinski, W. Langmuir 1997, 13, 1104). Three methods of data evaluation were applied: (a) the Frenkel-Halsey-Hill method for estimation of fractal dimensions from BET data, (b) the Horwath-Kawazoe method to calculate the pore size distribution from LPQEV Ar and N2 adsorption isotherms, and (c) the derivative isotherm summation (DIS) method to describe the solid's surface heterogeneity by a concept of local derivative isotherms. Similar Ar and N2 adsorption energy distributions were obtained on all carbons, which indicates the presence of mainly nonpolar surfaces. When adsorption was described by the van der Waals equation, the ratio between the interaction energy of different energetic sites with argon and nitrogen was 0.88. This value corresponded very well with a slope obtained when Ar and N2 positions of local isotherms by the DIS method were compared. This relationship has an important impact because it enables one to constrain the modeling of local isotherms. This study, besides the surface information, showed large possibilities of the DIS method for the surface analysis not only in terms of solid heterogeneity characterization but also in terms of polarity assessment.     

ADSORPTION ISOTHERMS OF SOME COMMERCIAL SURFACTANTS ONTO CLAY. COMPARISONS WITH SYNTHESIS SURFACTANT

Abstract

The adsorption of polyoxyethylene mono soya bean fatty acid [Soy (EO)_20,40 and ₈₀] and polyoxyethylene (80) monolinoleate [Li(EO)₈₀] onto Na-montmorillonite has been determined at 30°C. The adsorption isotherms of all the tested surfactants exhibit an L-shaped following the Langmuirian model. The experimental adsorption data are fitted to Langmuir adsorption equation, the maximum amount adsorbed, Γ_max, and the minimum area occupied per molecule, A_max at the pseudo-plateau have been calculated. Γ_max value increases with the increase in the number of ethylene oxide units following the order, Soy (EO)₂₀ < Soy (EO)₄₀ Soy (EO) ? Li (EO)₈₀. Both Soy (EO)₈₀ and Li (EO)₈₀ nearly show the same adsorption behavior.     

The effect of heat treatment on the adsorption properties of solids. II. The effect of heat treatment on the character of the adsorption isotherm

In this study the nitrogen adsorption isotherms of heat-treated zinc oxalate, sintered magnesium oxide, and some oxidised pitch resins are considered. It is shown that characterisation of the adsorption isotherm can be via the monolayer capacity, the BET constant C, or plots of the degree of coverage of the surface at various relative vapour pressures. These parameters are critically assessed and shown to be dependent upon the closeness to the manner in which the complete adsorption isotherm is described by the BET equation. In considering the complete adsorption isotherm it is considered best to characterise the adsorption data by quoting the statistical monolayer capacity and the value of C at this point on the adsorption isotherm. The adsorption isotherms are then best compared by plotting as the number of statistical layers against the relative pressure. The further characterisation by plotting the apparent variation in C or the degree of coverage of the surface against the relative pressure has a usefulness if the limitations of the method are noted.     

CO2 adsorption on zeolite X/activated carbon composites

Two series of zeolite X/activated carbon composites with different ratios of zeolite and activated carbon were prepared through a combination process of CO₂ activation of the mixtures of elutrilithe and pitch and subsequent hydrothermal crystallization in alkaline solution. An additional surface modification was achieved in diluted NH₄Cl solution. CO₂ and N₂ uptakes on the composites before and after modification were determined for pressures up to 101?kPa at 273 and 298?K, respectively. Langmuir-Freundlich and Toth adsorption models were used to describe the adsorption isotherms of CO₂ and the corresponding heats of adsorption were estimated with the Clausius-Clapeyron equation. Both before and after modification, all composites exhibited a remarkable preferential adsorption of CO₂ compared to N₂, with the modified composites showing a higher adsorption selectivity to CO₂ over N₂ than the unmodified composites. With an increasing ratio of zeolite in the composites, adsorption capacity and adsorption heat of CO₂ on the composites increased simultaneously. Lower adsorption heat was observed both before and after modification especially at the low-loading region and when there was less energetic heterogeneity on the surface of the modified composites. The results may be attributed to the elimination of strong basic sites on the modified composites, which is favorable for desorption of CO₂ on the adsorbents and application in pressure swing adsorption processes.     

Adsorption of isopropanol on a nickel catalyst

The adsorption isotherms of isopropanol on a Ni catalyst (15 wt % on SiO₂) in the temperature range of 273–303 K are determined. An increase in the isosteric heat of adsorption and entropy of adsorption after treating the catalyst with high frequency plasma in hydrogen and adding 1.5 wt % of Ce is detected, with treatment involving glow discharge plasma in Ar and O₂ having virtually no impact on these values. At a low degree of surface filling, the adsorption isotherms are described by the equation of induced adsorption. It is concluded that adsorbed isopropanol molecules are present in two forms: positively and negatively charged.     

Isotherms of adsorption of aromatic compounds on cellulose from heptane-isopropanol solutions

The isotherms of adsorption of benzene, anisole, benzyl alcohol, and benzaldehyde on the surface of microspherical mesoporous crosslinked cellulose were calculated from the chromatographic peaks of these compounds with consideration given to the longitudinal smearing of the analyte zone under the action of adsorption forces. The solvents were n-heptane-isopropanol mixtures containing various amounts of isopropanol (up to 2 vol %). The adsorption isotherms were described using equations of the displacement adsorption theory. The mechanism of the sorption of aromatic compounds and the physical meaning of the constants entering into the adsorption isotherm equation were discussed.     

Adsorption Properties and Composition of Binary Kolliphor Mixtures at the Water–Air Interface at Different Temperatures

The studies on the adsorption properties and composition of the adsorbed monolayer at the water–air interface of the binary Kolliphor^® ELP (ELP) and Kolliphor^® RH 40 (RH40) mixtures based on the measurements of the surface tension (γ_LV) of their aqueous solution in the temperature range from 293 to 318 K were carried out. The γ_LV isotherms were described by the exponential function of the second order and the Szyszkowski equation as well as predicted by Fainerman and Miller equation. The obtained γ_LV isotherms were analyzed using the exponential function of the second order, the Szyszkowski, Fainerman and Miller as well as independent adsorption equations. The γ_LV isotherms were also used for determination of the Gibbs surface excess concentration of RH40, ELP and their mixture (Γ) at the water–air interface as well as the mixed monolayer composition. Based on Γ and the constant a in the Szyszkowski equation, the standard thermodynamic functions of adsorption were considered. From the consideration dealing with the γ_LV isotherms obtained by us, it results, among others, that these isotherms for the non-ideal solution of macromolecular surfactants mixture can be predicted using the Fainerman and Miller equation. From this consideration, it also results that a simple method proposed by us, based on the isotherms of RH40 and ELP, allows us to predict the composition of their mixed monolayer in the whole concentration range of RH40 and ELP in the bulk phase.