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Reaction of C2(a 3Πu) with methanol: temperature dependence and deuterium isotope effect
Renzhi Hu1, Qun Zhang, Yang Chen
1Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui 230026, People's Republic of China.
Abstract:
Bimolecular rate constants for the gas-phase reactions of C(2)(a (3)Π(u)) with a variety of methanol isotopomers including CH(3)OH (k(1)), CH(3)OD (k(2)), CD(3)OH (k(3)), and CD(3)OD (k(4)) have been measured over the temperature range of 293-673 K by means of pulsed laser photolysis/laser-induced fluorescence technique. The rate constants, in units of cm(3) molecule(-1) s(-1), can be fitted by the normal Arrhenius expressions: k(1)(T)=(1.32±0.02)×10(-11)×exp[-(366.80±4.44)/T], k(2)(T)=(1.34±0.02)×10(-11) exp[-(376.86±5.09)/T], k(3)(T)=(1.09±0.02)×10(-11) exp[-(640.00±7.23)/T], and k(4)(T)=(1.12±0.01)×10(-11)×exp[-(666.37±4.63)/T], where all error estimates are ±2σ and represent the precision of the fit. The observed deuterium kinetic isotope effects, k(1)/k(2) and k(1)/k(3), along with the positive temperature dependences of k(T), allow us to reach a conclusion that the reaction of C(2)(a (3)Π(u)) with methanol in 293-673 K proceeds via a site-specific hydrogen abstraction mechanism, that is, H-atom abstraction from the methyl site rather than from the hydroxyl site dominating reactivity.
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