SOLVENT EFFECT ON THE RATE OF THERMAL DECOMPOSITION OF ALIPHATIC PEROXY ACIDS
Journal Title: Праці Наукового товариства ім. Шевченка - Year 2018, Vol 53, Issue
Abstract
The thermal decomposition of aliphatic peroxy acids in various organic solvents was studied. It shown that the primary homolytic dissociation of the peroxide group accompanied by secondary reactions of chain-inducted decomposition. The reaction medium affects the rate of both the primary homolytic dissociation and secondary induced decomposition processes. Correlation equations between the rate constants of the reactions in study and the physicochemical parameters of the solvents were proposed. The correlation equation for effective thermolysis rate constants and the basic physicochemical parameters of solvents at 383 K has the form: k = –70.312 + (0.3230 ± 0.0343)B + (0.7648 ± 0.0786)VM. N = 12; R = 0.9606; S = ±7.3762; F = 0.4880. The basicity, and molar volume of solvent have effect of thermolysis process. The influence of polarization, polarizability and Hilderbrand's function on the thermal decay process is negligible. Correlation equations for effective rate constants for other temperatures are similar. The proposed correlation equations relate the parameters of the transition state of the thermolysis process and the physic-chemical parameters of solvents.
Authors and Affiliations
Volodymyr DUTKA, Galyna MIDYANA, Olena PAL’CHIKOVA, Yu DUTKA
Keywords
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