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dc.contributor.authorChavarrio Cañas, Javier Eduardo
dc.contributor.authorMonge Palacios, Manuel
dc.contributor.authorZhang, Xiaoyuan
dc.contributor.authorSarathy, Mani
dc.date.accessioned2021-09-13T06:09:48Z
dc.date.available2021-09-13T06:09:48Z
dc.date.issued2021-09-05
dc.date.submitted2021-05-13
dc.identifier.citationChavarrio Cañas, J. E., Monge-Palacios, M., Zhang, X., & Sarathy, S. M. (2021). Probing the gas-phase oxidation of ammonia: Addressing uncertainties with theoretical calculations. Combustion and Flame, 111708. doi:10.1016/j.combustflame.2021.111708
dc.identifier.issn1556-2921
dc.identifier.issn0010-2180
dc.identifier.doi10.1016/j.combustflame.2021.111708
dc.identifier.urihttp://hdl.handle.net/10754/671159
dc.description.abstractThe kinetics of the reactions H2NO + O2(3Σg−) → HNO(X˜1A′) + HO2 and NH2 + HO2 → NH3 + O2(3Σg−), which are, respectively, very sensitive chain-propagation and chain-termination reactions in ammonia kinetic models, have been revisited by means of high-level electronic structure and variational transition state theory calculations with the goal of improving former predictions and the performance of ammonia kinetic models. In addition, the rate constants of the reactions H2NO + O2(3Σg−) → HNO(a˜3A″) + HO2, NH2 + HO2 → H2NO + OH, and NH2 + HO2 → NH3 + O2(1Δg), which take place on excited-state potential energy surfaces and/or yield the electronically excited species HNO(a˜3A″) and O2(1Δg), have been also calculated for the first time in order to assess their importance in ammonia oxidation. We observed that spin contamination and multi-reference character are pronounced in many of the investigated reactions, and these features were handled by performing post-CCSD(T) electronic structure calculations with the W3X-L composite method as well as restricted open shell coupled cluster calculations. Branching ratios were also analyzed, and indicate that the contribution of the electronically excited species HNO(a˜3A″) and O2(1Δg) are of little importance even at very high temperatures; however, we do not preclude an effect of those species at certain conditions that contribute to their yield. The calculated rate constants were implemented in two recent kinetic models to perform jet stirred reactor, rapid compression machine, and flow reactor simulations, concluding that the model predictions are very sensitive to the reactions H2NO + O2(3Σg−) → HNO(X˜1A′) + HO2 and NH2 + HO2 → NH3 + O2(3Σg−).
dc.description.sponsorshipThis work is supported by Saudi Aramco Research and Development Center under research agreement number RGC/3/3837–01–01 and by the King Abdullah University of Science and Technology (KAUST) under grant number OSR-2019-CRG7–4051.
dc.publisherElsevier BV
dc.relation.urlhttps://linkinghub.elsevier.com/retrieve/pii/S001021802100451X
dc.rightsNOTICE: this is the author’s version of a work that was accepted for publication in Combustion and Flame. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Combustion and Flame, [, , (2021-09-05)] DOI: 10.1016/j.combustflame.2021.111708 . © 2021. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.titleProbing the gas-phase oxidation of ammonia: Addressing uncertainties with theoretical calculations
dc.typeArticle
dc.contributor.departmentChemical Engineering Program
dc.contributor.departmentClean Combustion Research Center
dc.contributor.departmentCombustion and Pyrolysis Chemistry (CPC) Group
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.identifier.journalCombustion and Flame
dc.rights.embargodate2023-09-05
dc.eprint.versionPost-print
dc.identifier.pages111708
kaust.personChavarrio Cañas, Javier E.
kaust.personMonge Palacios, Manuel
kaust.personZhang, Xiaoyuan
kaust.personSarathy, Mani
kaust.grant.numberOSR-2019-CRG7–4051.
dc.date.accepted2021-08-18
dc.identifier.eid2-s2.0-85112467408
refterms.dateFOA2021-09-13T08:24:06Z
kaust.acknowledged.supportUnitCRG
kaust.acknowledged.supportUnitOSR
dc.date.published-online2021-09-05
dc.date.published-print2021-09


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