Temperature-Dependent Kinetic Study of the Reactions of Hydrogen Atoms with H<sub>2</sub>S and C<sub>2</sub>H<sub>4</sub>S
A discharge-flow reactor combined with modulated molecular beam mass spectrometry technique was employed to determine the rate constants of H-atom reactions with hydrogen sulfide and thiirane. The rate constants for both reactions were determined at a total pressure of 2 Torr from 220 to 950 K under...
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| Format: | Article |
| Language: | English |
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MDPI AG
2023-11-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/23/7883 |
| Summary: | A discharge-flow reactor combined with modulated molecular beam mass spectrometry technique was employed to determine the rate constants of H-atom reactions with hydrogen sulfide and thiirane. The rate constants for both reactions were determined at a total pressure of 2 Torr from 220 to 950 K under pseudo-first-order conditions by monitoring either consumption of H atoms in excess of H<sub>2</sub>S (C<sub>4</sub>H<sub>4</sub>S) or the molecular species in excess of atomic hydrogen. For H + H<sub>2</sub>S reaction, a suggested previously strong curvature of the Arrhenius plot was confirmed: <i>k</i><sub>l</sub> = 8.7 × 10<sup>−13</sup> × (<i>T</i>/298)<sup>2.87</sup> × exp(−125/<i>T</i>) cm<sup>3</sup> molecule<sup>−1</sup> s<sup>−1</sup> with a conservative uncertainty of 15% at all temperatures. Non-Arrhenius behavior was also observed for the reaction of H-atom with C<sub>2</sub>H<sub>4</sub>S, with the experimental rate constant data being best fitted to a sum of two exponential functions: <i>k</i><sub>2</sub> = 1.85 × 10<sup>−10</sup> exp(−1410/<i>T</i>) + 4.17 × 10<sup>−12</sup> exp(−242/<i>T</i>) cm<sup>3</sup> molecule<sup>−1</sup> s<sup>−1</sup> with an independent of temperature uncertainty of 15%. |
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| ISSN: | 1420-3049 |