Nonthermal rate constants for CH4* + X → CH3 + HX, X = H, O, OH, and O2
Abstract
Quasiclassical trajectories are essential to compute nonthermal rate constants, k*, for abstraction reactions involving highly-excited methane CH4* and the radicals H, O, OH, and O2. Several temperatures and internal energies of methane, Evib, are observed, and significant nonthermal rate enhancements for large Evib are found. Specifically, when CH4* is internally excited close to its dissociation threshold (Evib approximate to D0 = 104 kcal/mol), its reactivity with H, O, and OH is shown to be collision-rate-limited and to approach that of comparably-sized radicals, such as CH3, with k* > 10-10 cm3 molecule-1 s-1. Rate constants this large are more typically associated with barrierless reactions, and at 1000 K, this represents a nonthermal rate enhancement, k*/k, of more than two orders of magnitude relative to thermal rate constants k. We show that large nonthermal rate constants persist even after significant internal cooling, with k*/k > 10 down to Evib approximate to D0/4. The competition among collisional cooling and nonthermal reactivity is studied using a simple model, and nonthermal reactions are shown to account for up to 35%-50% of the fate of the products of H + CH3 = CH4* under conditions of practical relevance to combustion. Lastly, the accuracy of an effectivemore »
- Authors:
-
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1510465
- Alternate Identifier(s):
- OSTI ID: 1502269
- Grant/Contract Number:
- AC02-06CH11357; FWP 59044
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 150; Journal Issue: 11; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Jasper, Ahren W., Sivaramakrishnan, Raghu, and Klippenstein, Stephen J. Nonthermal rate constants for CH4* + X → CH3 + HX, X = H, O, OH, and O2. United States: N. p., 2019.
Web. doi:10.1063/1.5090394.
Jasper, Ahren W., Sivaramakrishnan, Raghu, & Klippenstein, Stephen J. Nonthermal rate constants for CH4* + X → CH3 + HX, X = H, O, OH, and O2. United States. https://doi.org/10.1063/1.5090394
Jasper, Ahren W., Sivaramakrishnan, Raghu, and Klippenstein, Stephen J. Thu .
"Nonthermal rate constants for CH4* + X → CH3 + HX, X = H, O, OH, and O2". United States. https://doi.org/10.1063/1.5090394. https://www.osti.gov/servlets/purl/1510465.
@article{osti_1510465,
title = {Nonthermal rate constants for CH4* + X → CH3 + HX, X = H, O, OH, and O2},
author = {Jasper, Ahren W. and Sivaramakrishnan, Raghu and Klippenstein, Stephen J.},
abstractNote = {Quasiclassical trajectories are essential to compute nonthermal rate constants, k*, for abstraction reactions involving highly-excited methane CH4* and the radicals H, O, OH, and O2. Several temperatures and internal energies of methane, Evib, are observed, and significant nonthermal rate enhancements for large Evib are found. Specifically, when CH4* is internally excited close to its dissociation threshold (Evib approximate to D0 = 104 kcal/mol), its reactivity with H, O, and OH is shown to be collision-rate-limited and to approach that of comparably-sized radicals, such as CH3, with k* > 10-10 cm3 molecule-1 s-1. Rate constants this large are more typically associated with barrierless reactions, and at 1000 K, this represents a nonthermal rate enhancement, k*/k, of more than two orders of magnitude relative to thermal rate constants k. We show that large nonthermal rate constants persist even after significant internal cooling, with k*/k > 10 down to Evib approximate to D0/4. The competition among collisional cooling and nonthermal reactivity is studied using a simple model, and nonthermal reactions are shown to account for up to 35%-50% of the fate of the products of H + CH3 = CH4* under conditions of practical relevance to combustion. Lastly, the accuracy of an effective temperature model for estimating k* from k is quantified.},
doi = {10.1063/1.5090394},
journal = {Journal of Chemical Physics},
number = 11,
volume = 150,
place = {United States},
year = {Thu Mar 21 00:00:00 EDT 2019},
month = {Thu Mar 21 00:00:00 EDT 2019}
}
Web of Science
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