Chen DN, Jin HF, Wang ZD, Zhang LD, Qi F (2011) Unimolecular Decomposition of Ethyl Hydroperoxide: Ab Initio/Rice-Ramsperger-Kassel-Marcus Theoretical Prediction of Rate Constants. Journal of Physical Chemistry A 115(5), 602-611. [In English]

Web link: http://dx.doi.org/10.1021/jp1099305

Keywords:

density-functional thermochemistry, evaluated kinetic data, gas-phase, acidity, upper troposphere, peroxy-radicals, rotation barriers, photoelectron-spectroscopy, thermodynamic properties, alkyl, hydroperoxides, c2h5+o-2 reaction

Abstract: Alkyl hydropercuddes are found to be important intermediates in the combustion and oxidation processes of hydrocarbons. However, studies. of ethyl hydroperoxide (CH(3)CH(2)OOH) are limited. In this work, kinetics and mechanisms for unimolecular decomposition of CH(3)CH(2)OOH have been investigated. The potential energy surface of decomposition reactions have first been predicted at the CCSD(T)/6-311+G(3df,2p)//B3LYP/6-311G(d, p) level. The results show that the formation of CH(3)CH(2)O + OH via O-O direct bond dissociation is dominant, the branching ratio of which is over 99% in the whole temperature range from 300 to 1000 K, and its rate constant can be expressed as k1 = 9.26 x 10(52)T(-11.91)exp(-26879/T) s(-1) at 1 atm. The rate constants of the reaction CH(3)CH(2)OOH ->, CH(3)CH(2)O + OH at different temperatures and pressures have been calculated, which can help us to comprehend the reactions of CH(3)CH(2)OOH at experimental conditions.