Collection of Czechoslovak Chemical Communications - digital archive 

Abstract

Oxidation of butyraldehyde to butyric acid catalysed by ferrocene in 10 solvents has been described by kinetic equations for autocatalysis. Rate constants of these equations were correlated with the properties of solvents. The oxidation rate was found to be independent of viscosity and fluidity of the reaction medium, electrophilicity expressed by E_Tfunction and the donor ability of solvents. Only in nonpolar solvents the oxidation rate depended on (n_D)^-2_s. The rate of the title oxidation reaction was dependent on the polarity of reaction medium which was characterized by dipole moment and by functions of dielectric constants and increased with increasing solvent polarity. A similar dependence was also obtained with the use of solubility parameter and cohesion pressure of solvents. The rate of the oxidation increase with increasing solubility of oxygen in solvents. These dependences were used to discuss some steps of the mechanism of this oxidation.