Citation: HU Ren-Zhi, XIE Pin-Hua, ZHANG Qun, SI Fu-Qi, CHEN Yang. Temperature Dependence of C2(a3Пu) Radical Reactions with Sulfur Bearing Molecules[J]. Acta Physico-Chimica Sinica, ;2014, 30(5): 797-802. doi: 10.3866/PKU.WHXB201403072
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The bimolecular rate constants for the gas- phase reactions of C2(a3Пu) with sulfur-bearing molecules (H2S, SO2, CS2) were measured over the temperature range 298-673 K, by means of pulsed laser photolysis/laser-induced fluorescence technique. The rate constants (cm3·molecule-1·s-1) can be fitted by the normal Arrhenius expressions: k(H2S)=(1.61±0.06)×10-12exp[-(180.91±15.73)/T], k(SO2)=(1.26±0.10)×10-15 exp[(2230.68±27.77)/T], k(CS2)=(1.17±0.02)×10-10 exp[(253.31±7.69)/T], where all error estimates are ±2σ and represent the precision of the fit. The observed bimolecular rate constants and positive temperature dependence of k(H2S) show that the reaction of C2(a3Пu) with H2S in the range 298-673 K proceeds via a hydrogen-abstraction mechanism. The bimolecular rate constants for the reaction of C2(a3Пu) with SO2 show a strong negative temperature dependence. The high rate constants for the C2(a3Пu)+CS2 reaction and negative temperature dependence support an addition mechanism.
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