Shannon, R, Tomlin, AS orcid.org/0000-0001-6621-9492, Robertson, S et al. (3 more authors) (2015) Global Uncertainty Propagation and Sensitivity Analysis in the CH₃OCH₂ + O₂ System: Combining Experiment and Theory To Constrain Key Rate Coefficients in DME Combustion. The Journal of Physical Chemistry A, 119 (28). pp. 7430-7438. ISSN 1089-5639
Abstract
Statistical rate theory calculations, in particular formulations of the chemical master equation, are widely used to calculate rate coefficients of interest in combustion environments as a function of temperature and pressure. However, despite the increasing accuracy of electronic structure calculations, small uncertainties in the input parameters for these master equation models can lead to relatively large uncertainties in the calculated rate coefficients. Master equation input parameters may be constrained further by using experimental data and the relationship between experiment and theory warrants further investigation. In this work, the CH₃OCH₂ + O₂ system, of relevance to the combustion of dimethyl ether (DME), is used as an example and the input parameters for master equation calculations on this system are refined through fitting to experimental data. Complementing these fitting calculations, global sensitivity analysis is used to explore which input parameters are constrained by which experimental conditions, and which parameters need to be further constrained to accurately predict key elementary rate coefficients. Finally, uncertainties in the calculated rate coefficients are obtained using both correlated and uncorrelated distributions of input parameters.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2015, American Chemical Society. This document is the Accepted Manuscript version of a Published Work that will appear in final form in Journal of Physical Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/acs.jpca.5b00620. Uploaded in accordance with the publisher's self-archiving policy. |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemical & Process Engineering (Leeds) The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemistry (Leeds) > Physical Chemistry (Leeds) |
Depositing User: | Symplectic Publications |
Date Deposited: | 07 May 2015 13:32 |
Last Modified: | 19 May 2021 21:47 |
Published Version: | http://dx.doi.org/10.1021/acs.jpca.5b00620 |
Status: | Published |
Publisher: | American Chemical Society |
Identification Number: | 10.1021/acs.jpca.5b00620 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:84293 |