Non-Arrhenius temperature dependence of the rate constant for the H + H2S reaction

Masabumi Yoshimura; Mitsuo Koshi; Hiroyuki Matsui; Kenshu Kamiya; Hideaki Umeyama

doi:10.1016/0009-2614(92)85124-S

Non-Arrhenius temperature dependence of the rate constant for the H + H₂S reaction

Masabumi Yoshimura^*, Mitsuo Koshi, Hiroyuki Matsui, Kenshu Kamiya, Hideaki Umeyama

^*Corresponding author for this work

Department of Applied Chemistry

Research output: Contribution to journal › Article

29 Scopus citations

Abstract

The rate constants for the H(²S) + H₂S reaction were measured behind reflected shock waves (T = 1053-2237 K) and at 293 K, in which H(²S) atoms were generated by the ArF-laser photolysis of H₂S. The resulting rate constant, k = (1.96 ± 0.7) × 10^-17 T^2.1±0.3 exp[- (352 ± 84) / T] cm³ molecule^-1 s^-1, showed a strong non-Arrhenius dependence on the temperature. This dependence is explained by a conventional transition-state theory combined with a quantum-mechanical calculation of the transition state at the PMP4(SDTQ)6-311G**//MP2/6-31G** level.

Original language	English
Pages (from-to)	199-204
Number of pages	6
Journal	Chemical Physics Letters
Volume	189
Issue number	3
DOIs	https://doi.org/10.1016/0009-2614(92)85124-S
State	Published - 7 Feb 1992

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Yoshimura, M., Koshi, M., Matsui, H., Kamiya, K., & Umeyama, H. (1992). Non-Arrhenius temperature dependence of the rate constant for the H + H₂S reaction. Chemical Physics Letters, 189(3), 199-204. https://doi.org/10.1016/0009-2614(92)85124-S

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abstract = "The rate constants for the H(2S) + H2S reaction were measured behind reflected shock waves (T = 1053-2237 K) and at 293 K, in which H(2S) atoms were generated by the ArF-laser photolysis of H2S. The resulting rate constant, k = (1.96 ± 0.7) × 10-17 T2.1±0.3 exp[- (352 ± 84) / T] cm3 molecule-1 s-1, showed a strong non-Arrhenius dependence on the temperature. This dependence is explained by a conventional transition-state theory combined with a quantum-mechanical calculation of the transition state at the PMP4(SDTQ)6-311G**//MP2/6-31G** level.",

author = "Masabumi Yoshimura and Mitsuo Koshi and Hiroyuki Matsui and Kenshu Kamiya and Hideaki Umeyama",

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AU - Yoshimura, Masabumi

AU - Koshi, Mitsuo

AU - Matsui, Hiroyuki

AU - Kamiya, Kenshu

AU - Umeyama, Hideaki

PY - 1992/2/7

Y1 - 1992/2/7

N2 - The rate constants for the H(2S) + H2S reaction were measured behind reflected shock waves (T = 1053-2237 K) and at 293 K, in which H(2S) atoms were generated by the ArF-laser photolysis of H2S. The resulting rate constant, k = (1.96 ± 0.7) × 10-17 T2.1±0.3 exp[- (352 ± 84) / T] cm3 molecule-1 s-1, showed a strong non-Arrhenius dependence on the temperature. This dependence is explained by a conventional transition-state theory combined with a quantum-mechanical calculation of the transition state at the PMP4(SDTQ)6-311G**//MP2/6-31G** level.

AB - The rate constants for the H(2S) + H2S reaction were measured behind reflected shock waves (T = 1053-2237 K) and at 293 K, in which H(2S) atoms were generated by the ArF-laser photolysis of H2S. The resulting rate constant, k = (1.96 ± 0.7) × 10-17 T2.1±0.3 exp[- (352 ± 84) / T] cm3 molecule-1 s-1, showed a strong non-Arrhenius dependence on the temperature. This dependence is explained by a conventional transition-state theory combined with a quantum-mechanical calculation of the transition state at the PMP4(SDTQ)6-311G**//MP2/6-31G** level.

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