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The reaction of sulfoxides with peroxy acids in various organic media was studied. The reaction mechanism involves the rapid formation of a sulfoxide-–peroxy acid intermediate which decomposes in the second stage to form carboxylic acid and the corresponding sulfone. The second stage is the rate-limiting step. The reaction medium significantly affects the rate of oxidation. The calculated activation parameters of the oxidation process indicate a compensation effect in the investigated reaction. Correlations between the main physicochemical parameters of solvents and the effective rate constants (k) of dimethyl sulfoxide oxidation with peroxy acids were found. Depending on the reaction conditions, the main factors affecting the k values are specific and nonspecific solvation of the reactants and structural factors. [ABSTRACT FROM AUTHOR]

The kinetics of thermal decomposition of didecanoyl diperoxyadipate in different organic solvents have been studied. The primary homolytic dissociation of the peroxide bond (O-O) is accompanied by secondary induced chain decomposition processes. The reaction medium affects both the rate of primary homolytic decomposition and secondary decomposition processes. Correlation equations have been proposed for the rate constants of the reactions under study and physicochemical parameters of the solvents. [ABSTRACT FROM AUTHOR]

Thermal decomposition of peroxydecanoic acid has been investigated in various organic solvents. The reaction medium significantly affects the rate of peroxydecanoic acid thermal decomposition. It has been shown that primary homolytic decomposition of peroxy group is followed by induced radical chain decomposition reactions. The solvent nature influences both primary homolytic decomposition and secondary induced reactions. The correlation equations relating kinetic parameters of peroxydecanoic acid thermolysis and basic solvent properties have been derived. [ABSTRACT FROM AUTHOR]

The swelling of the polymers into solutions represents by itself the complicated process depending on their different properties. That is why the swelling degree can not be determined via any one physical-chemical property of the solvent. The adequate relationship between the swelling degree and the properties of solvents can be obtained only under condition of taking into account the all acting factors by means of the linear multi-parametric equations. [ABSTRACT FROM AUTHOR]

Data on the distribution of 8-hydroxyquinoline, its methyl-substituted derivatives, and their salts with copper between organic and aqueous phases can be generalized using linear multiparametric equations that take into account the capacity of solvents for specific and nonspecific solvation. [ABSTRACT FROM AUTHOR]

Correlation analysis of the kinetics of thermal decarboxylation of dicarboxylic acids in various media has shown that adequate description requires taking into account the basicity, polarity, and molar volume of the solvent. The rate of the process increases with increase in these parameters, the effect of the basicity of the medium being the determining one, apparently, because of formation of the bond with the carboxylic carbon atom, facilitating the elimination of CO2. [ABSTRACT FROM AUTHOR]

The rate constants for the Beckmann rearrangement of cyclohexanone oxime p-toluenesulfonate in 11 solvents are satisfactorily described by a three-parameter linear correlation including polarizability, electrophilicity, and molar volume of the solvent. The first two factors favor the reaction, whereas increase of the solvent molar volume makes the reaction slower, presumably due to steric hindrances to solvation. [ABSTRACT FROM AUTHOR]

Electrophilic solvation that operates to weaken the oxygen-oxygen bond is shown to a factor relating to the effect of the media on the decomposition rate of peracid esters. However, an adequate correlation between reaction rate and solvent properties can only be obtained by means of multiparameter linear equations including various characteristics simultaneously. [ABSTRACT FROM AUTHOR]

The selectivity in the reaction of tert-butyl hypochlorite with 2,3-dimethylbutane in various solvents may be described by a three-parameter correlation equation taking into account the ability of solvents to nonspecific solvation and their cohesion energy density. [ABSTRACT FROM AUTHOR]

The dependences of the isomer ratio in photochemical chlorination of 2,3-dimethylbutane and of the selectivity in photochemical bromination of a mixture of cyclopropylbenzene and toluene may be described by linear multiparameter equations. In the first case, the determining factors are the nonspecific solvation power and molar volume of the solvent, and in the second, the molar volume and cohesion energy density. [ABSTRACT FROM AUTHOR]

The solvent effect on the rate of reaction of organic reductants with trichloromethylperoxy radicals can be adequaetly described by multiparameter linear equations. The major factor affecting the reaction rate is the solvent cohesion, enhancing the cage effect. [ABSTRACT FROM AUTHOR]

The suggested in publications dependence of the Diels-Alder reaction parameters on the viscosity of the environment is discussed. The preferred description is shown to base on the principle of the linearity of the free energies. In the majority of cases a crucial factor is the capability of solvents of electrophilic solvation. [ABSTRACT FROM AUTHOR]

The change in the second-order rate constants in the reaction of terephthalyl chloride with ethylene glycol obeys the Michaelis-Menten equation, suggesting that in the first stage a donor-acceptor complex is formed. [ABSTRACT FROM AUTHOR]

An initial rate of the isoprene polymerization under the influence of the hydrogen peroxide depends on the properties of solvents. First of all, the electrophylic solvation of the hydrogen peroxide has an influence on the studied process; the non-specific interaction into a system has a lesser impact. [ABSTRACT FROM AUTHOR]