Gas-Chromatographic Studies of the Interaction between Water and Methanol Molecules and the Surface of Carbon Materials

The gas-chromatographic method is used to study the interaction of water and methanol molecules with active hydrophilic centres existing at the surface of thermally exfoliated graphite and graphitized thermal carbon black. The concentration of carboxyl and phenol hydroxyl groups at the surface of these sorbents is determined, and heats of adsorption of the studied molecules are shown to be and 28−25 kJ/mol, respectively. It is also shown that adsorption of water at the hydrophilic centres at lowest relative pressure values takes place with formation of clusters consisting of n = 2 water molecules.     

Quantum-Chemical Investigation of the Interaction of Water and Methanol Molecules with Surface Carboxyl Groups on Graphite

A quantum-chemical investigation made of the adsorption of water and methanol at hydrophilic centers (carboxyl groups) on the partly oxidized surface of graphite was undertaken. The enthalpy of adsorption of water and methanol at such centers was determined. It was shown that water is adsorbed at the surface carboxyl groups in the form of dimers, while methanol is adsorbed in the form of single molecules. It was confirmed that the formation of clusters of water molecules in the vicinity of the hydrophilic center is a characteristic feature of the adsorption of water on the surface of graphite and other adsorbents.     

<Emphasis Type="Italic">Ab initio</Emphasis> calculation of the hydration of organic cations and their associates with amines on the surface of kaolinite

It was shown, by ab initio calculations of the characteristics of hydrophilic centers formed on the surfaces of organosubstituted kaolinites with equivalent and superequivalent modifications, that superequivalent modifications of the mineral surface with octadecylammonium chloride, i.e. blocking the hydrophilic centers of the ionic-adsorbed cationic surface-active substance with the molecular adsorbed amine, led to the redistribution of the electron density close to these centers, in particular to the decrease in the effective charge at the hydrophilic centers. The calculated structures and energetics of nanostructures formed by the adsorption of water molecules at such hydrophilic centers showed that such redistribution decreases the energy of their interaction with water, which resulted from theoretical decrease in the energetic effects of hydration of the centers effectively agreed with the experimental values of the heats of adsorption. It was shown that for such adsorbtion systems the energetics were suitable for the formation in the region of the adsorption centers of cyclic structures of water.     

Adsorption of water vapor on modified methacrylate polymeric sorbents

Adsorption of water vapor on methacrylate copolymers and terpolymers was studied. An increase in the content of the cross-linking agent gives rise to increase in the limiting adsorption of water vapor at the saturation pressure (a _s) and to decrease in the concentration of primary adsorption centers. Modification of the initial copolymer containing 60 % of 2,3-epoxypropyl methacrylate (EPMA) monomer and 40 % of cross-linking agent, ethylene dimethacrylate, with diethylenetriamine (DETA) results in an increase in thea _s value, while modification with C₁₂ and C₁₈ alkyl, benzyl, and phenyl groups gives rise to decrease in thea _s values for the copolymeric sorbents. The concentration of primary adsorption centers (a _m) increases considerably on modification of the copolymer with DETA and C₁₂ groups and decreases markedly on modification with benzyl and phenyl groups. For terpolymers, containing EPMA and styrene, an increase in the styrene/EPMA ratio reduces thea _s anda _m values. The copolymer modified with DETA groups possesses the most hydrophilic properties, while the copolymer modified with benzyl group exhibits the most hydrophobic properties. The mechanism of adsorption of water molecules on the polymers is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2163–2167, November, 1995.The work was financially supported by the Russian Foundation for Basic Research (Project No. 94-03-09550).     

Microcalorimetric Study of Water Adsorption on Initial and Polyfluoroalkylated Silicas

Water adsorption on initial and modified Silochrom samples was studied by the adsorption calorimetry. Integral heats of immersional wetting by water were measured simultaneously. It was shown that hydroxyl groups both free and sterically screened by a modifier remain on the modified Silochrom surface. Concentrations of these groups and OH groups chemically interacted with the modifier were estimated. The heat of reaction of water molecules with a free surface OH groups of modified sorbents was determined (≈60 kJ/mol). It was found that the modifying layers of the sorbents are getting loose under the effect of adsorbed water, and water molecules gain access to the sterically screened OH groups; the heat of water interaction with these groups is 54–55 kJ/mol. The energy is consumed for getting the modifying layers loose and the rupture of point contacts between Aerosil particles of the secondary structure of both initial and modified Silochrom that significantly affects the heat of immersion, the differential heat of adsorption, the form of the heat release curve, and the dependence of the differential heat on the adsorption value.     

Hydrophilic Sites on Silica Surface Modified in Gaseous and Liquid Phases

The methods of chromatography, adsorption, and potentiometic titration were used to determine the amount and energetics of the residual hydrophilic sites on the wide-porous silica surfaces modified in gaseous and liquid phases. The concentration of the residual hydrophilic sites on the silica surfaces modified by both methods was shown virtually to be the same. However, the activity of the hydrophilic sites on the sample modified in gaseous phase was significantly higher than that on the sample modified by liquid-phase method. Based on the comparison of the calculated isosteric heats of adsorption of water vapors on the studied modified sorbents with calorimetric heats, which are characteristic for the interaction of water molecules with vicinal and single hydroxyl groups of silica gel, the nature of the residual hydrophilic sites on the silica surfaces modified by these two methods was discussed.     

The surface energy of hydrophilic and hydrophobic adsorbents

Water vapor adsorption and heats of water wetting are studied for hydrophilic quartz, hydrophobic-hydrophilic talc, and hydrophobized Silochrom samples. Water contact angles on the materials under examination are found. The surface thermodynamic parameters of the sorbents are calculated from the data obtained. It is shown that boundary water layers on hydrophilic quartz surface are ordered to a higher extent, while those on hydrophobic basal surfaces of talc particles and hydrophobic surfaces of modified Silochrom samples are ordered to a lower extent relative to liquid water. An empirical equation relating the surface pressure of water films adsorbed on hydrophilic high-energy surfaces with the surface free energy of the latter is proposed. The values of surface free energy are estimated from this equation for a number of important hydrophilic adsorbents.     

The critical size of clusters of water molecules on a carbon surface

The experimental adsorption isotherms of water and nitrogen vapors on graphitized carbonaceous adsorbents with large pore size prepared from ultradispersive technical carbon black have been compared with those on the surface of non-porous graphitized carbon black. The saturation value of water vapor adsorption has been shown to be proportional to the concentration of primary adsorption centers. At low concentrations of these centers the saturation value corresponds to the formation of fractions of a dense monolayer on the surface. The maximum size of clusters of water molecules on a carbonaceous adsorbent surface has been estimated.Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 54–56, January, 1993.     

Preparation of amino-zirconia bonded phases and their evaluation in hydrophilic interaction chromatography of carbohydrates with pulsed amperometric detection

A series of non-porous, microspherical zirconia-based stationary phases with surface bound amine functionality have been introduced and evaluated in hydrophilic interaction chromatography (HILIC) of underivatized, neutral carbohydrates and anion exchange chromatography of nucleotides using pulsed amperometric detection and ultraviolet detection, respectively. Three aminopropyl alkoxysilane compounds were used in the surface modification of the non-porous zirconia support, namely 3-aminopropyltrimethoxysilane (monoamine), N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (diamine), and trimethoxysilylpropyldiethylenetriamine (triamine). Due to the relatively low specific surface area of the non-porous zirconia support used in this study (ca. 7.3 m²/g), zirconia with surface coating of the triamine type yielded the best results as far as the separations of chitooligosaccharides and maltooligosaccharides are concerned. Since a non-porous zirconia could be readily modified with amine functionality via Zr? O? Si bonds, it is expected that all the three aminopropyl alkoxysilane compounds would yield satisfactory results with porous zirconia microparticles because of their much higher specific surface areas. Although the non-porous zirconia exhibited some limitations, the present study has demonstrated that microspherical zirconia particles are suitable supports for the production of polar sorbents for HILIC of carbohydrates. Another surface modification, which involved the activation of the zirconia surface with aldehyde groups followed by reductive amination with tetraethylenepentamine, was also evaluated. Although this chemistry would in principle yield sorbents with higher concentration in amine groups, the conversion of the majority of the primary amine groups of the tetraethyle-nepetamine molecules to secondary amine functions in the course of the reductive amination reaction have provided a stationary phase that did not afford satisfactory resolution for carbohydrates. However, this same stationary phase behaved as a weak anion exchanger and allowed the high resolution separation of nucleoside-5′-mono-, -di-, and triphosphates. Overall, the results obtained with zirconia-based hydrophilic sorbents paralleled those obtained on amino-silica bonded phases.     

Surface energy of hydrophobic adsorbents

The adsorption of water vapor and the heat of wetting of hydrophilic hydromica and hydrophobized samples of kaolinite and Silochrom were studied. The contact angles for the wetting of the investigated materials with water were obtained. The thermodynamic characteristics of the surface of the sorbents and the interfacial region at their boundary with water were calculated from the obtained data. It was shown that the boundary water layers close to the hydrophilic surface of the hydromica are more ordered while those close to the hydrophobic surfaces of the modified samples of kaolinite, Silochrom, and the reference sample (extremely hydrophobic Teflon) are less ordered than liquid water. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 2, pp. 87–91, March–April, 2006.     

Comparative study of CTAB adsorption on bituminous coal and clay mineral

Adsorption of cetyltrimethylammonium bromide (CTAB) onto bituminous coal (BC) and a clay mineral, montmorillonite (MMT), was studied. Simultaneous measurements of the CTAB adsorption and zeta potential determination of the adsorption suspensions were carried out. The adsorption isotherms were found to be of the typical Langmuir type; values of the CTAB adsorption capacities were calculated (a _m = 0.65 mmol g⁻¹ for coal and a _m = 3.24 mmol g⁻¹ for MMT). The shape of the adsorption isotherms was correlated with zeta potential values at the adsorption equilibrium. The adsorption properties of both sorbents were studied by voltammetry on carbon paste electrodes (CPE) modified with coal-CTAB and MMT-CTAB system, respectively. Open circuit sorption with differential pulse voltammetry was performed in order to compare the sorption properties of the systems with the unmodified sorbents. The Cu²⁺ adsorption on BC and MMT decreased to approximately 50 % and 40 %, respectively. The surface adsorption mechanism of CTAB on coal based on hydrophilic interactions was proposed. In the case of montmorillonite, the CTAB intercalation is expected via ion exchange into the inter-layer space forming a double- or triple-layer arrangement.     

Microcalorimetric Study of Methanol Adsorption on Initial Silica and Silica Modified with Polyfluoroalkyl Groups

The adsorption of methanol on initial silica and modified silica samples containing large mesopores is studied by the adsorption–calorimetric method. The grafted tridecylfluoroalkyl groups have a tilted orientation on the silica and physically screen the part of the surface OH groups that have not been involved in the reaction with a modifier. Adsorbed methanol makes the modifying layer looser, thus facilitating the accessibility of methanol molecules to these hydrophilic adsorption sites. Concentrations of OH groups involved in the chemical interaction with molecules of the modifier, OH groups physically screened by its organofluoric radicals, and OH groups located on the surface areas free of the modifier are quantitatively estimated. An additional silanization of the modified silica leads to coverage of silica surface areas that are free of organofluoric modifier with trimethylsilyl radicals. The heat of interaction between the methanol molecules and silica surface hydroxyl groups is determined; it is equal to 60 kJ/mol. The structure of the modifying organofluoric layer and changes in this structure that resulted from additional silanization of the surface and from the methanol adsorption are discussed.     

Determination of standard isotherms of the sorption of some vapors with cellulose

Standard isotherms of the sorption of water, methanol, and benzene vapors on cellulose using a cellulose standard are determined. The standard, namely, mesoporous cellulose with specific surface of up to 350 m2/g, is obtained by the method of exchanging water in swollen cellulose with organic solvents. A comparison of the experimental sorption isotherm with the standard isotherm makes it possible to determine the specific surface of celluloses accessible a the given sorbate and, in combination with the Brunauer-Emmett-Teller adsorption equation, to characterize their surface properties. The identity of the sorption properties of the initial and dewatered (porous) celluloses relative to active vapors is shown, which evidences the assumed mechanism of swelling as the sorbent's division into morphological structures with the formation of new surface. A comparative analysis of the sorption properties of cellulose and silica, whose nature of active sorption centers is similar (weak acid hydroxyl groups), has been made. The affinity of the standard isotherms and close values of the cross-sectional area of different sorbates on both sorbents testify the similarity in their sorption behavior. Thus, the processes of sorption with rigid and swelling sorbents can be regarded in a unified context. Therefore, the adsorption models developed for rigid sorbents can be applied to cellulose sorbents to analyze their sorption properties.     

Study of Water,Methanol And Isopropanol Adsorption on The Surface of Titanosilicas of Different Structure

The adsorption of water, methyl and i-propyl alcohol vapours has been studied on the surface of titanosilicas produced by various methods, as well as on the surface of pure silicon and titanium oxides. Based on findings of the studies, it was concluded that the presence on the surface of pyrogenic titanosilicas (TAS) of hydrolytically unstable Si-O-Ti bonds is responsible for their increased adsorption activity towards water molecules. A dissociative adsorption of H₂O on titanosiloxane bridges is accompanied by an appearance of additional groups ≡SiOH and ≡TiOH, which, in turn, become sites of adsorption of subsequent water molecules. This revised version was published online in August 2006 with corrections to the Cover Date.     

Water vapor adsorption and microporous structure of carbon adsorbents. 18. Effect of surface chemistry of activated carbons on water vapor adsorption

This investigation has been devoted to a study of the chemical composition of the surfaces of activated carbons. A study has been made of the way in which changes in the surface chemistry of a series of carbons, as a result of heat treatment, affects the nature of their adsorption of water vapor. A differentiation has been made between oxygen-containing groups found on the surface of activated carbons before and after their heat treatment. It has been established that the original adsorption centers, which play a determining role in water vapor adsorption by activated carbons, comprise functional groups like strongly acidic free hydrogen ions, carboxylic and phenolic groups, situated on on the pore surface of the activated carbons. The number of these functional groups on the pore surface of the activated carbons has been correlated with the parametera ₀ (the number of original adsorption centers) in the isotherm equation for water vapor adsorption. The relative pressure corresponding to the formation of an adsorption layer on the surface of the activated carbons has been shown to depend on the number of original adsorption centers, the acidic functional groups.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 35–40, January, 1991.     

State and structure of water in vicinity of hydrophobic surfaces

Criterial values of the specific heat of water wetting, surface pressure, and contact angle classifying surfaces into hydrophilic and hydrophobic are proposed based on the analysis of own and published data. The most characteristic properties of hydrophobic surfaces, i.e., large surface area per water molecule in the conventional adsorption monolayer and the absence of continuous two-layer water film on the adsorbent surface at vapor pressure close to saturation, are discussed using nonporous carbon-based materials as example. The presence of residual hydrophilic groups that act as sites of the clusterization of polar molecules on the surface of graphitized carbon black is confirmed by gas chromatography and the concentration of these sites is calculated. The amount of water molecules in the surface cluster is determined at different stages of adsorption. Procedures for preparing organically modified layered silicates and silica as basic objects of the study of the interaction between water molecules and hydrophobic surfaces are considered. It is proven that the boundary water layer in the vicinity of hydrophobic surface consists of a thin (∼0.5 nm) depletion layer with a density of 0.4 g/cm³ and a considerable amount (25–30%) of water molecules with free OH groups and thicker (∼35 nm) layer, which is characterized by a more ordered network of hydrogen bonds compared to liquid water. Data obtained by X-ray scattering and neutron and reflection methods, and sum-frequency vibrational spectroscopy are compared with the results of calorimetric study of the interaction between water and hydrophobic surface, as well as with the data of molecular-statistical calculations of the state of water molecules in the surface layer.     

Conversions of ethanol in thermolysis of dyes adsorbed on a silica surface

Using thermal desorption measurements with mass spectrometric analysis of the gas phase, we have studied the characteristics of the interaction of ethanol molecules with the silica surface under conditions when some of the adsorption centers are occupied by molecules of a heteroaromatic dye. The characteristics of the thermal conversions of ethanol on the surface are described in terms of ideas concerning the nature of the active centers on a surface of dispersed silicon dioxide. We observed occurrence of the reaction of ethoxylation of the surface with an increase in temperature. The interaction between the ethanol molecules and the dye molecules occurs with formation of a complex in an excited state upon UV irradiation, which stimulates adsorption of the solvent in strongly bound forms with decomposition of the complex in the surface layer.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 28, No. 1, pp. 87–91, January–February, 1992.     

DFT study of the adsorption of microsolvated glycine on a hydrophilic amorphous silica surface

Density functional theory (DFT) periodic ab initio molecular dynamics calculations are used to study the adsorption of gaseous and microsolvated glycine on a hydroxylated, hydrophilic silica surface. The silica model is presented and the interaction of water with surface silanols is studied. The heat of interaction of water is higher with the associated silanols (be they terminal or geminal ones) studied here than with isolated silanols presented in past works. Glycine is stabilized in a parallel mode on the hydroxylated surface. Terminal silanols do not allow the stabilization of the zwitterionic form, whereas geminal silanols do. Molecular dynamics (MD) first-principle calculations show that microsolvated zwitterion glycine directly binds through the carboxylate function to a surface silanol rather than through water molecules. The adsorption mode, whether with or without additional water molecules, is parallel to the surface. The ammonium function does not interact directly with the silanol groups but rather through water molecules. Thus, the carboxylate and ammonium functions exhibit two different reactivities towards silanols. The calculated free energies, taking into account the chemical potentials of water and glycine in the gas phase, suggest the existence of a thermodynamic domain in which the glycine is present in the gas phase as well as strongly adsorbed on specific sites of the surface.     

Interaction between bilirubin and sodium deoxycholate and their adsorption from mixed solutions on the surface of silica sorbents

The interaction between the bile pigment bilirubin and sodium deoxycholate is studied in aqueous buffer solutions at pH 7.4. It is established that bilirubin forms strong complexes with deoxycholate trimers. The complexation constant is determined by spectrophotometry. The adsorption of bilirubin and sodium deoxycholate from their mixed solutions on the surface of a hydrophilic and two hydrophobic silica sorbents is investigated. It is shown that bilirubin is adsorbed on the surface of all these sorbents only in the free state. Sodium deoxycholate is adsorbed in the forms of monomers and trimers. The affinity of all adsorbed particles is higher for hydrophobic silica sorbents. The binding constants of bilirubin, as well as monomers and trimers of deoxycholate, with the surfaces of all examined sorbents are determined.     

Structure of adsorption layers and conformation transformations of ethylhydroxyethylcellulose on surfaces of titanium and iron oxides

Regularities of the adsorption of ethylhydroxyethylcellulose (EHEC) hydrophilic polymer on a surface of inorganic pigments of TiO₂ and Fe₂O₃ were investigated by infrared spectroscopy. It was found that the adsorption interaction between EHEC and a surface of oxides is accompanied by conformation transformations of the adsorbed molecules of EHEC. The means by which macromolecules bind with active centers on a surface of metal oxides and the influence of the oxides’ nature on the EHEC macromolecule conformation transformations determining the structure of the adsorption layer upon adsorption were established.