V. DUTKA1, G. MIDYANA2, E. PAL’CHIKOVA3, Yu. DUTKA1
1Ivan Franko National University of Lviv, Kyryla & Mefodiya Str., 6, 79005 Lviv, Ukraine
2Physical-Chemistry of Combustible Minerals Department of Lytvynenko Institute of Physical-Organic
Chemistry and Coal Chemistry
National Academy of Science of Ukraine, Lviv, Ukraine
3Institute of Geology and Geochemistry of Fossil Fuels, National Academy of Science of Ukraine, Lviv,
Ukraine
DOI: https://doi.org/10.37827/ntsh.chem.2018.53.145
SOLVENT EFFECT ON THE RATE OF THERMAL DECOMPOSITION OF ALIPHATIC PEROXY ACIDS
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.
Key words: thermolysis, peroxyacids, solvent effects, correlations equations, activation energy
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How to Cite
Dutka V., Midyana G., Pal’chikova E., Dutka Yu. SOLVENT EFFECT ON THE RATE OF THERMAL DECOMPOSITION OF ALIPHATIC PEROXY ACIDS Proc. Shevchenko Sci. Soc. Chem. Sci. 2018 Vol. LIII. P. 145-154.
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