C2（a3Пu）自由基与含硫小分子反应的温度效应

doi:10.3866/PKU.WHXB201403072

Abstract

Abstract:

The bimolecular rate constants for the gas- phase reactions of C₂(a³П_u) 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(a³П_u) with H₂S in the range 298-673 K proceeds via a hydrogen-abstraction mechanism. The bimolecular rate constants for the reaction of C₂(a³П_u) with SO₂ show a strong negative temperature dependence. The high rate constants for the C₂(a³П_u)+CS₂ reaction and negative temperature dependence support an addition mechanism.

Key words: C₂(a³П_u) radical, Laser induced fluorescence, Rate constant, Temperature dependence

HU Ren-Zhi, XIE Pin-Hua, ZHANG Qun, SI Fu-Qi, CHEN Yang. Temperature Dependence of C₂(a³П_u) Radical Reactions with Sulfur Bearing Molecules[J]. Acta Phys. -Chim. Sin. 2014, 30(5), 797-802. doi: 10.3866/PKU.WHXB201403072

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Temperature Dependence of C₂(a³П_u) Radical Reactions with Sulfur Bearing Molecules

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Temperature Dependence of C2(a3Пu) Radical Reactions with Sulfur Bearing Molecules

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Temperature Dependence of C₂(a³П_u) Radical Reactions with Sulfur Bearing Molecules