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Kinetic investigation of the reaction of ethylperoxy radicals with ethanol
Author(s) -
Kuzhanthaivelan S.,
Rajakumar B.
Publication year - 2021
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.21441
Subject(s) - chemistry , radical , transition state theory , conformational isomerism , atmospheric temperature range , kinetic energy , activation energy , thermodynamics , reaction rate constant , reactivity (psychology) , kinetics , transition state , computational chemistry , molecule , organic chemistry , catalysis , physics , medicine , alternative medicine , pathology , quantum mechanics
The thermodynamic and kinetic investigation for the reaction of ethylperoxy radical (CH 3 CH 2 OO • ) with ethanol (CH 3 CH 2 OH) was studied computationally with variational transition state theory. The geometry optimization calculations showed that both the reactants have two conformers. The energetics and thermodynamic properties were calculated using the G4 composite method. The results showed that the abstraction of H atom from the ─CH 2 ─ site is most feasible, when compared to the other pathways, since it has the lowest energy barrier. The rate coefficient calculations for the title reaction were carried out using the multistructural canonical variational transition state theory with small curvature tunneling corrections in the temperature range of 400‐1500 K. The results showed a similar trend to that of the energetics in which the abstraction of the H atom from the ─CH 2 ─ site has a larger rate coefficient, when compared to other reaction pathways. The reactivity trend towards the H atom abstraction by ethylperoxy radicals varies as ─CH 2 > ─CH 3 > ─OH. The contributions from the ground‐state conformers of both the reactants were included into the total kinetics using the Boltzmann probability distribution. The obtained temperature‐dependent expression for the studied reaction is k total = 1.51 × 10 −32 T 6.3 exp(−3691/ T ) cm 3 molecule −1 s −1 .