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Citation: TIAN Yan, HE Tian-Jing, CHEN Dong-Ming, LIU Fan-Chen. Reaction Mechanism and Kinetics for the Reaction of ·OH+CH₃CN[J]. Acta Physico-Chimica Sinica, ;2008, 24(04): 587-594. doi: 10.3866/PKU.WHXB20080408 shu

Reaction Mechanism and Kinetics for the Reaction of ·OH+CH₃CN

1.
Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, P. R. China; School of Science, Anhui Agricultural University, Hefei 230036, P. R. China

Received Date: 22 November 2007
Available Online: 7 March 2008

The complex potential energy surface for the reaction of·OH radical with CH3CN, including 2 intermediate complexes, 9 transition states, was theoretically probed at the CBS-QB3 level. The geometries and relative energies for various stationary points were determined. Based on the calculated CBS-QB3 potential energy surface, the possible reaction mechanism of·OH+CH3CN was proposed. The calculated results demonstrated that the formation of P1 (·CH2CN+H2O) was the dominant reaction channel. The rate constant (k1, cm3·molecule-1·s-1) of P1 was calculated by TS theory. Over the temperature range 250-3000 K, we predicted that the expression of k1 was k1(250-3000 K)=2.06×10^-20T^3.045exp(-780.00/T). By comparing with the obtained experimental values it was shown that the values of k1 were in od agreement with the experimental results over the temperature range 250-320 K. The calculated results indicated the formation of P1 (CH3CN+·OH) only needed a barrier of 14.2 kJ·mol-1. While the products ·CH2CN+H2O retrograded to the reactants CH3CN+·OH, an energy barrier of 111.2 kJ·mol-1 was required. These results suggested that the backward direction for the pathway of formation product P1 would be difficult in the ground electronic state.
- ·OH radical; CH3CN; Reaction mechanism; CBS-QB3
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Reaction Mechanism and Kinetics for the Reaction of ·OH+CH3CN

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Reaction Mechanism and Kinetics for the Reaction of ·OH+CH₃CN