Kinetics and mechanisms for reactions of OH with methanol and ethanol have been investigated at the CCSD(T)/6-311 + G(3df, 2p)//MP2/6-31l + G(3df,2p) level of theory. The total and individual rate constants, and product branching ratios for the reactions have been computed in the temperature range 200-3000 K with variational transition state theory by including the effects of multiple reflections above the wells of their pre-reaction complexes, quantum-mechanical tunneling and hindered internal rotations. The predicted results can be represented by the expressions k1 =4 .65 × 10-20 × T2.68 exp(414/T) and k2 = 9.11 × 10 -20 × T2.58 exp(748/T) cm3 molecule -1 s-1 for the CH3OH and C2H 5OH reactions, respectively. These results are in reasonable agreements with available experimental data except that of OH + C 2H5OH in the high temperature range. The former reaction produces 96-89% of the H2O + CH2OH products, whereas the latter process produces 98-70% of H2O + CH3CHOH and 2-21% of the H2O + CH2CH2OH products in the temperature range computed (200-3000 K).
|Number of pages||8|
|Journal||Proceedings of the Combustion Institute|
|State||Published - 1 Jan 2007|
|Event||31st International Symposium on Combustion - Heidelberg, Germany|
Duration: 5 Aug 2006 → 11 Aug 2006
- Theoretical study