G. A. Petukhova

Quantitative characteristics of active sites on the surface of sorbents produced by the modification of kaolinite with chlorosilanes

The amount of hydroxyl and alkyl groups on the surface of sorbents synthesized by chemical modification is determined. The interaction of chlorosilanes and organosilanes with the kaolinite surface is investigated. A correlation between the pH value of a suspension of the obtained sorbent and the amount of active sites on its surface is established.

The synthesis and adsorption properties of polyvinylchloride nanofilms with ligand groups

Polyvinylchloride (PVC) samples with a fairly developed surface were prepared by the spontaneous removal of the solvent (benzyl alcohol) from a polymer gel. The surface of the product was modified to obtain ethanolocyclame and sodium acetocyclame nanofilms. The structure and composition of the nanofilms were studied by IR Fourier spectroscopy. The adsorption of nitrogen vapor at −196°C and benzene and water at 20°C on the nanofilms was investigated. Surface modification was shown to increase the stability of PVC in water and benzene and the specific surface area and volume of nanopores. The conclusion was drawn that nanofilm ligand groups could stoichiometrically interact with water and benzene molecules on PVC with a modified surface.

STATISTICAL INTERPRETATION OF THE DUBININ-RADUSHKEVICH EQUATION

A statistical approach was applied to describe the model of a homogeneous microporous adsorbent and obtain the dependences of the thermodynamic functions on the number of molecules and the temperature for molecular aggregates in discrete micropores over a wide region of fillings that lead to the Dubinin—Radushkevich equation. The energy nonuniformity of the adsorption space is the fundamental property of carbon adsorbents. In the region of small fillings, the statistical approach leads to Henrys law and the finite value of the initial differential energy of adsorption. The value of sorption corresponding to the saturated vapor pressure decreases with increasing temperature, but the decrease is considerably less than for the density of the corresponding liquid.

Adsorption of vapor mixtures of water and organic substance on activated carbons

The isotherms of water adsorption in the presence of an organic substance vapor with a specified concentration are calculated from experimental data on the joint frontal dynamics of adsorption of water vapor and several organic substances (benzene, hexane, cyclohexane, tetrachloromethane, and perfluorotripropylamine) on two samples of activated carbons. The influence of the organic substances on the equilibrium water adsorption decreases with an increase in the molecule size.

Prediction of the micropore structure parameters and adsorption properties of activated carbons

A regularity govering variations of volume and linear size of micropores in carbon adsorbents during their vapor-gas activation was found. A parameter was proposed that characterizes the degree of development of the micropore system in activating carbons and an initial carbonized material. The parameter is defined as the number (or surface area) of micropores in the volume unit of the micropore zones. This parameter allows one to rationalize the choice of carbonized materials for the preparation of activated carbons with specified adsorption properties and to establish the range of activation beyond which the structure of the micropores loses stability. Furthermore, the parameter serves to predict how activation affects micropore structure parameters and adsorption properties of carbons. This in turn indicates the optimal degrees of microporosity of carbons needed to attain required adsorption properties.

A model of the two-stage condensation mechanism of water adsorption on nonporous carbon adsorbents

The mechanism of adsorption of water molecules on nonporous carbon adsorbents has been suggested in terms of two different states of adsorbed water; stretched liquid water and water that occupies an intermediate state between the liquid and vapor. Two stages of adsorption were distinguished: condensation and pre-condensation that assumes the formation of molecular associates. The BET model was used to describe the pre-condensation stage. The equations of the adsorption isotherm for water vapor in the region of condensation process and the expression for the determination of the specific hydrophilic surface of adsorbents were found. Examination of the experimental data on adsorption of water vapor on nongraphitized samples of carbon adsorbents shows that in the region of polymolecular adsorption, all isotherms fall into a common curve determined by the equation of the stretched liquid film and can be calculated regardless of the properties of individual liquid water. The equation for adsorption of water vapor on the hydrophobic surface was obtained.

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.

Adsorption on nonporous and supermicroporous adsorbents

The mean values of the characteristic energy of C6H6 adsorption in large micropores were calculated from the adsorption isotherms of benzene vapor on carbon blacks. The supermicropores are characterized by the significant dispersion of the adsorption potential resulted from the pore-size distribution, which imparts the polymolecular character to adsorption. The effect of enhancement of the characteristic energy of adsorption was analyzed, which was caused by the overlap of the force fields of the opposite pore walls and the reduction of the adsorption film surface with micropore volume filling. The both factors are comparable by magnitude and depend on the micropore sizes.

Thermodynamic investigation of the state of water adsorbed by carbonaceous adsorbents

The state of water adsorbed on active carbons and canal soot was studied using the “chemical potential—entropy—temperature” diagram. In the range of the relative pressures from 0.174 to 1, the state of adsorbed water is similar to the state of a stretched liquid. The molar volume, heat of evaporation, and surface tension of stretched water were calculated at different relative pressures. Near the spinodal, the molar volume of stretched water is 25% higher, and the surface tension is considerably lower compared to water.

The influence of low-temperature oxidation of active carbons by nitric acid on their physicochemical properties

The influence of oxidation by nitric acid on the character of oxygen-containing functional surface groups and porous structure of active carbons is considered. Adsorption properties of the initial and oxidized carbons are studied using adsorption isotherms of vapor of n-hexane and polar substances (water and methanol).