Mechanistic studies and rate coefficients calculations of hydrogen abstraction from ethanol by methyl peroxy radical and hydroperoxyl radical

Abstract

The reactions of ${\text{XO}}_2^{\bullet }$ (X = CH₃, H) with C₂H₅OH were investigated over the temperature range of 300–1500 K. The geometries of the stationary points were optimised at the MP2/aug-cc-pVTZ level and the energetics were refined at the CCSD(T)/aug-cc-pVTZ and the QCISD(T)/cc-pVTZ levels of theory. Six possible hydrogen abstraction channels were explored and it showed that the channels producing XO₂H and CH₃CHOH were favourable. The stable prereactive complexes were identified and their role was considered in the rate coefficient calculations. The rate coefficients have positive temperature dependence and the tunneling effect is more important at low temperature than at high temperature.

GRAPHICAL ABSTRACT

KEYWORDS:

• Ethanol
• methyl peroxy radical
• hydroperoxyl radical
• rate coefficient

Disclosure statement

No potential conflict of interest was reported by the authors.

Additional information

Funding

This work is supported by the National Natural Science Foundation of China (No. 51576139 and 51876141) and key laboratory of high efficiency and low emission engine technology (No. 2017CX02015), ministry of industry and information technology, Beijing institute of technology.