PROCEEDINGS OF THE SHEVCHENKO SCIENTIFIC SOCIETY

Chemical Sciences

Archive / Volume LXVI 2021

Natalia PANDIAK1, Oksana HERTSYK2, Mykhaylo YATSYSHYN2, Myroslava TASHAK3

1National Forestry University of Ukraine, Generala Chuprynky Str., 103, 79057 Lviv, Ukraine e-mail: pandyakn@ukr.net

2Franko National University of Lviv, Kyryla i Mefodiy Str., 6, 79005 Lviv, Ukraine,

3Lviv Polytechnic National University, St. Bandery Str, 12, 79013 Lviv, Ukraine

DOI: https://doi.org/10.37827/ntsh.chem.2021.66.047

INFLUENCE OF THE NATURE OF THE ELECTRODE ON THE REACTIVITY OF ACETYLENE-CONTAINING PEROXIDE INITIATORS

The parameters of voltammetric reduction of alkyne peroxides in dimethylformamide-aqueous solutions of tetraalkylammonium salts on electrodes of different nature (C, Pt, Cu, Ti, Fe, Al) are determined. The changes in reactivity of alkyne peroxides in electrochemical reduction processes on different metal surfaces are analyzed. It is established that on active metal surfaces this is manifested by the catalytic action of ions of these metals in the reactions of the dissociation of –O–O– bonds. The presence of Fe2+ ions was found to accelerate the dissociation reaction of the –O–O bond of the cyclohexylamine salt of 4-methyl-4-tert-butylperoxy-2-pentynoic acid. The thermal stability of this peroxide in DMF-aqueous medium in the presence of redox system «ascorbic acid-Fe2+», which is used as an activator of thermal dissociation –O–O– bond, was studied.
Based on the identification of waves of electrochemical reduction of 4-methyl-4-tert-butylperoxy-2-pentynoic acid, its sodium and cyclohexylamine salts on the Cu electrode, the fact of interaction of the surface with alkyne peroxides was confirmed. During electrochemical reduction of alkyne peroxides, rapid chemical interaction of peroxide with a copper surface takes place with the formation of chemical redox transformation products, as a result of which Cu1+ ions accumulate in the electrode space and proceed to catalyse the chemical stage of electrochemical reduction of alkyne peroxides by the ECE mechanism.
The reduction of alkyne peroxides on metal electrodes revealed the existence of a correlation between the overvoltage of hydrogen evolution and E1/2, which indicates the course of the processes associated with the protonation of reagents.
The change of activation parameters during the transition from mercury to solid surfaces in the study of temperature dependences of the limiting currents of reduction of alkyne peroxides in the range of 293–343 K is revealed. The diffusion coefficients (D) of peroxides and the number of electrons (n) involved in the electrode reaction are determined.
We have established that the effect of the nature of the electrode surface is determined by two factors: the affinity of organic peroxides to the surface, which determines both adsorption and chemical interaction, and probably the promoting action of the surface in the protonation processes.

Keywords: alkyne peroxides, voltammetric reduction, reactivity, thermal dissociation.

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How to Cite

PANDIAK N., HERTSYK O., YATSYSHYN M., TASHAK M. INFLUENCE OF THE NATURE OF THE ELECTRODE ON THE REACTIVITY OF ACETYLENE-CONTAINING PEROXIDE INITIATORS. Proc. Shevchenko Sci. Soc. Chem. Sci. 2021 Vol. LXVI. P. 47-56.

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