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Studies on the Kinetics of the CH + H(2) Reaction and Implications for the Reverse Reaction, (3)CH(2) + H

[Image: see text] The reaction of CH radicals with H(2) has been studied by the use of laser flash photolysis, probing CH decays under pseudo-first-order conditions using laser-induced fluorescence (LIF) over the temperature range 298–748 K at pressures of ∼5–100 Torr. Careful data analysis was requ...

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Autores principales: Blitz, Mark A., Onel, Lavinia, Robertson, Struan H., Seakins, Paul W.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10026075/
https://www.ncbi.nlm.nih.gov/pubmed/36857400
http://dx.doi.org/10.1021/acs.jpca.2c08097
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author Blitz, Mark A.
Onel, Lavinia
Robertson, Struan H.
Seakins, Paul W.
author_facet Blitz, Mark A.
Onel, Lavinia
Robertson, Struan H.
Seakins, Paul W.
author_sort Blitz, Mark A.
collection PubMed
description [Image: see text] The reaction of CH radicals with H(2) has been studied by the use of laser flash photolysis, probing CH decays under pseudo-first-order conditions using laser-induced fluorescence (LIF) over the temperature range 298–748 K at pressures of ∼5–100 Torr. Careful data analysis was required to separate the CH LIF signal at ∼428 nm from broad background fluorescence, and this interference increased with temperature. We believe that this interference may have been the source of anomalous pressure behavior reported previously in the literature ( R. A. Brownsword; J. Chem. Phys.1997, 106, 7662−7677). The rate coefficient k(1) shows complex behavior: at low pressures, the main route for the CH(3)* formed from the insertion of CH into H(2) is the formation of (3)CH(2) + H, and as the pressure is increased, CH(3)* is increasingly stabilized to CH(3). The kinetic data on CH + H(2) have been combined with experimental shock tube data on methyl decomposition and literature thermochemistry within a master equation program to precisely determine the rate coefficient of the reverse reaction, (3)CH(2) + H → CH + H(2). The resulting parametrization is k(CH(2)+H)(T) = (1.69 ± 0.11) × 10(–10) × (T/298 K)((0.05±0.010)) cm(3) molecule(–1) s(–1), where the errors are 1σ.
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spelling pubmed-100260752023-03-21 Studies on the Kinetics of the CH + H(2) Reaction and Implications for the Reverse Reaction, (3)CH(2) + H Blitz, Mark A. Onel, Lavinia Robertson, Struan H. Seakins, Paul W. J Phys Chem A [Image: see text] The reaction of CH radicals with H(2) has been studied by the use of laser flash photolysis, probing CH decays under pseudo-first-order conditions using laser-induced fluorescence (LIF) over the temperature range 298–748 K at pressures of ∼5–100 Torr. Careful data analysis was required to separate the CH LIF signal at ∼428 nm from broad background fluorescence, and this interference increased with temperature. We believe that this interference may have been the source of anomalous pressure behavior reported previously in the literature ( R. A. Brownsword; J. Chem. Phys.1997, 106, 7662−7677). The rate coefficient k(1) shows complex behavior: at low pressures, the main route for the CH(3)* formed from the insertion of CH into H(2) is the formation of (3)CH(2) + H, and as the pressure is increased, CH(3)* is increasingly stabilized to CH(3). The kinetic data on CH + H(2) have been combined with experimental shock tube data on methyl decomposition and literature thermochemistry within a master equation program to precisely determine the rate coefficient of the reverse reaction, (3)CH(2) + H → CH + H(2). The resulting parametrization is k(CH(2)+H)(T) = (1.69 ± 0.11) × 10(–10) × (T/298 K)((0.05±0.010)) cm(3) molecule(–1) s(–1), where the errors are 1σ. American Chemical Society 2023-03-01 /pmc/articles/PMC10026075/ /pubmed/36857400 http://dx.doi.org/10.1021/acs.jpca.2c08097 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Blitz, Mark A.
Onel, Lavinia
Robertson, Struan H.
Seakins, Paul W.
Studies on the Kinetics of the CH + H(2) Reaction and Implications for the Reverse Reaction, (3)CH(2) + H
title Studies on the Kinetics of the CH + H(2) Reaction and Implications for the Reverse Reaction, (3)CH(2) + H
title_full Studies on the Kinetics of the CH + H(2) Reaction and Implications for the Reverse Reaction, (3)CH(2) + H
title_fullStr Studies on the Kinetics of the CH + H(2) Reaction and Implications for the Reverse Reaction, (3)CH(2) + H
title_full_unstemmed Studies on the Kinetics of the CH + H(2) Reaction and Implications for the Reverse Reaction, (3)CH(2) + H
title_short Studies on the Kinetics of the CH + H(2) Reaction and Implications for the Reverse Reaction, (3)CH(2) + H
title_sort studies on the kinetics of the ch + h(2) reaction and implications for the reverse reaction, (3)ch(2) + h
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10026075/
https://www.ncbi.nlm.nih.gov/pubmed/36857400
http://dx.doi.org/10.1021/acs.jpca.2c08097
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