PROCEEDINGS OF THE SHEVCHENKO SCIENTIFIC SOCIETY

Chemical Sciences

Archive / Volume LXVI 2021

Volodymyr DUTKA1, Galyna MIDYANA2, Yuriy DUTKA2, Olena PAL’CHIKOVA2

1Ivan Franko National University of Lviv, Kyryla i Mefodiy Str., 6, 79005 Lviv, Ukraine, e-mail: vdutka@ukr.net

2Department of the Physical Chemistry of Fossil Fuels, L.M. Litvinenko Institute of Physical Organic and Coal Chemistry of UNAS, Naukova St. 3a, 79060 Lviv, Ukraine

DOI: https://doi.org/10.37827/ntsh.chem.2021.66.034

OXIDATION OF NITROGEN-CONTAINING COMPOUNDS BY PEROXY ACIDS IN VARIOUS ORGANIC SOLVENTS

The rate of oxidation reaction of pyridine, acridine, qinoline, 8-oxyqinoline by peroxy acids in benzene and acetone was studied. The rate of oxidation pyridine by peroxydecanoic acid in 12 organic solvents was studied. It has been found the effective rate constants (k) and the activation energy (Ea) of studied process. Between the parameters of the transition state ΔН≠ and ΔЅ≠ is some linear relationship, indicating on the presence of the counteraction effect in our series of experiments. The rate of oxidation and activation energy inflation of solvation peroxy acid and pyridine was calculated. The reaction medium affects the rate of oxidation. 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 rate constants and the basic physicochemical parameters of solvents at 313 K has the form
k = –418.6833 – (580.4603 ± 82.7014)f(n) – (453.2688 ± 47.6337)f(ε) –
– (0.4139 ± 0.0289)B + (14.9936 ± 1.5711)ET + (0.2934 ± 0.0326)δ2 +
+ (1.3132 ± 0.1877)VM
N = 10; R = 0.9908; S = 2.2035; F = 3.3849.
Correlation equations for effective rate constants for other temperatures are similar. The correlation equation for effective energies (Ea) of activation and the basic physicochemical parameters of solvents has the form:
Еак = 89.3888 + (252.1450 ± 21.9776)f(n) + (110.0989 ± 19.2279)f(ε) +
+ (0.1011 ± 0.0090)δ2 + (0.2540 ± 0.0206)VM
N = 10; R = 0.9862; S = 1.7897; F = 3.3801.
The molar volume, Hildebrand's function, f(n) and f(ε) of solvent have effect on the energy of activation process. The proposed correlation equations relate the parameters of the transition state of the oxidation process and the physic-chemical parameters of solvents.

Keywords: acrydine, oxidation reaction, peroxy acids, activation energy, correlation equation

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How to Cite

Dutka V., Midyana G., Dutka Yu., Pal’chikova O. OXIDATION OF THE ACRYDINE BY PEROXYDECANIC ACID IN VARIOUS ORGANIC SOLVENTS. Proc. Shevchenko Sci. Soc. Chem. Sci. 2021 Vol. LXVI. P. 34-46.

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