D. V. Batov

Intermolecular forces and the internal pressure of liquids

The problem of the introduction of the term internal pressure from the standpoint of intermolecular forces is solved. It is shown that internal pressure is created by the macrosystem average force field of the structural units of a liquid. Internal pressure is shown to be not an energy characteristic, but a macrosystem average force parameter of the interaction between the structural units of a liquid phase system, although it has the energy density dimension, [J/m3].

Amino acid behavior in aqueous denaturant solutions: temperature dependence of the L-histidine-amide interaction.

We have studied the thermodynamics of the pair interaction between aromatic amino acid-l-histidine and nonelectrolyte denaturing globular proteins-hydrophilic urea (U) and presumably hydrophobic dimethylformamide (DMF) in the temperature range of 288-328 K. Our study does indicate for the first time the anomalous temperature dependence of the enthalpies and entropies of the l-histidine-U and l-histidine-DMF interaction in water, which is consistent with the previously reported results for water-urea (U) and water-U-l-phenylalanine systems. This phenomenon is found to be closely related to the behavior of water, since in all cases, the extrema observed arise in the temperature range of 300-308 K, where the temperature dependence of the heat capacity of pure water passes through the minimum. The amino acid-urea interaction is shown to be accompanied in a wide temperature range by a large negative enthalpy change, which reveals a strong tendency of urea binding with polar and charged groups of proteins.

Preparation, heat capacity, and combustion characteristics of water-surfactant-halogenated hydrocarbon microemulsions suitable for combined fire-extinguishing means

Water-sodium dodecyl sulfate-triethanolamine-1-pentanol-1,1,2,2-tetrafluorodibromoethane (C2F4Br2) microemulsions differing in the H2O/C2F4Br2 ratio and content of surfactants were prepared. The principal possibility of combining halogenated hydrocarbons with water for developing new fire-extinguishing formulations was demonstrated. The emulsions obtained are of the oil-in-water type and are incombustible. The flash point and heat capacity of the systems were determined.

Calorimetric study of the solvation of benzene and its chloro-, nitro-, and aminoderivatives by n-hexane, 1-butanol, and mixed solvent n-hexane-1-butanol

The heats of dissolution of benzene, chlorobenzene, ortho-dichlorobenzene, nitrobenzene, and aniline in n-hexane and 1-butanol and those of benzene, chlorobenzene, nitrobenzene, and aniline in a mixture of n-hexane and 1-butanol were measured by calorimetry at 25°C. The enthalpies of solvation of the compounds were calculated. The correlation between the enthalpies of solvation of the compounds and their molar refraction was studied. The enthalpies of solvation of the compounds and their functional groups by the mixture of n-hexane and 1-butanol were considered.

Enthalpies of dissolution of n-alkanes in a mixture of methanol-formamide

The enthalpies of dissolution of n-hexane, n-octane, and n-decane are determined thermochemically under standard conditions to describe nonspecific solvation in a mixed solvent of methanol-formamide. Experimental data are matched with the values obtained using model calculations. It is found that the differences between the experimental and calculated enthalpies of dissolution in the region with a high content of formamide could be due to the preferable solvation of n-alkanes by methanol.

The Adsorption of Aqueous—Organic Mixture Components on Cellulose

The isotherms of composition changes were obtained for the cellulose—water—dimethylsulfoxide and cellulose—water—acetonitrile systems. The isotherms of sorption of aqueous—organic mixture components on cellulose were calculated. The heat effects of wetting of cellulose with water—dimethylsulfoxide and water — acetonitrile solutions were measured. The special features of sorption of the components on cellulose were shown to be related to the character of cluster formation in the binary systems under consideration.

The thermochemical characteristics of solution of phenol and benzoic acid in water-dimethylsulfoxide and water-acetonitrile mixtures

The solution of phenol and benzoic acid in water-dimethylsulfoxide (DMSO) and water-acetonitrile (AN) mixtures was studied. As distinct from benzoic acid, the thermodynamic characteristics of solution of phenol sharply change at concentrations corresponding to a change in the character of cluster formation in water-DMSO and water-AN mixtures. Differences in the solvation of phenol and benzoic acid are explained by different mechanisms of the interaction of the solutes with clusters existing in binary mixtures.

A model approach to the thermodynamics of microemulsion systems: Estimation of adequacy of the two-phase model of microemulsions

An approach to the thermodynamics of microemulsions based on the use of the two-phase model was suggested. In this model, one phase is the dispersion medium, and the other, the sum of disperse phase nanodrops. Experimental estimation of the adequacy of this approach showed that the model can be used to quantitatively satisfactorily solve microemulsion thermodynamics problems. The degree of two-phase model inadequacy did not exceed 10%.

Enthalpies of transfer of mebicarum from water to aqueous solutions of carbamide and its methyl-substituted derivatives at 298.15 K

The standard molar enthalpies of solution of Mebicarum (MbCA) in aqueous solutions of carbamide (CA), 1,3-dimethylcarbamide (1,3-DMCA), and 1,1,3,3-tetramethylcarbamide (TMCA) of various molalities, as well as the enthalpies of dilution of solutions of these compounds, were measured at 298.15 K. The enthalpy of transfer of MbCA from water to aqueous solutions of 1,3-DMCA exhibits an unusual dependence on the concentration of 1,3-DMCA. An analysis of the McMillan-Mayer enthalpy parameters of pair interactions revealed that the hydration of MbCA should be regarded as a superposition of the hydrophobic and hydrophilic mechanisms, with the latter one being predominant.

Thermal and volumetric properties of methanol–hexamethylphosphortriamide mixtures under standard conditions

Enthalpic and volumetric characteristics of mixing in a methanol (MeOH)–hexamethylphosphortriamide (HMPT, 2) mixture are studied. Based on an analysis of concentration changes in the obtained data and the calculated partial molar characteristics, it is shown that at 0.2 molar fractions > х2 > 0.7 molar fractions, the variation in the composition of the mixture slightly alters the character of intermolecular interactions characteristic of pure components. It is found that MeOH–HMPT mixtures experience most changes in intermolecular interaction and structure within the range of 0.2–0.7 molar fractions of HMPT.