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dc.contributor.authorGrajales Gonzalez, Edwing
dc.contributor.authorMonge Palacios, Manuel
dc.contributor.authorSarathy, Mani
dc.date.accessioned2018-04-16T07:49:42Z
dc.date.available2018-04-16T07:49:42Z
dc.date.issued2018-03-21
dc.identifier.citationGrajales-González E, Monge-Palacios M, Sarathy SM (2018) Theoretical Kinetic Study of the Unimolecular Keto–Enol Tautomerism Propen-2-ol ↔ Acetone. Pressure Effects and Implications in the Pyrolysis of tert- and 2-Butanol. The Journal of Physical Chemistry A 122: 3547–3555. Available: http://dx.doi.org/10.1021/acs.jpca.8b00836.
dc.identifier.issn1089-5639
dc.identifier.issn1520-5215
dc.identifier.pmid29558796
dc.identifier.doi10.1021/acs.jpca.8b00836
dc.identifier.urihttp://hdl.handle.net/10754/627478
dc.description.abstractThe need for renewable and cleaner sources of energy has made biofuels an interesting alternative to fossil fuels, especially in the case of butanol isomers, with its favorable blend properties and low hygroscopicity. Although C4 alcohols are prospective fuels, some key reactions governing their pyrolysis and combustion have not been adequately studied, leading to incomplete kinetic models. Enols are important intermediates in the combustion of C4 alcohols, as well as in atmospheric processes. Butanol reactions kinetics is poorly understood. Specifically, the unimolecular tautomerism of propen-2-ol ↔ acetone, which is included in butanol combustion kinetic models, is assigned rate parameters based on the tautomerism vinyl alcohol ↔ acetaldehyde as an analogy. In an attempt to update current kinetic models for tert- and 2-butanol, a theoretical kinetic study of the titled reaction was carried out by means of CCSD(T,FULL)/aug-cc-pVTZ//CCSD(T)/6-31+G(d,p) ab initio calculations, with multistructural torsional anharmonicity and variational transition state theory considerations in a wide temperature and pressure range (200-3000 K; 0.1-108 kPa). Results differ from vinyl alcohol ↔ acetaldehyde analogue reaction, which shows lower rate constant values. It was observed that decreasing pressure leads to a decrease in rate constants, describing the expected falloff behavior. Tunneling turned out to be important, especially at low temperatures. Accordingly, pyrolysis simulations in a batch reactor for tert- and 2-butanol with computed rate constants showed important differences in comparison with previous results, such as larger acetone yield and quicker propen-2-ol consumption.
dc.description.sponsorshipThis work was supported by King Abdullah University of Science and Technology (KAUST), Office of Sponsored Research (OSR), under Award No. OSR-2016-CRG5-3022. We appreciate the resources of the Supercomputing Laboratory at KAUST.
dc.publisherAmerican Chemical Society (ACS)
dc.relation.urlhttps://pubs.acs.org/doi/10.1021/acs.jpca.8b00836
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry A, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.jpca.8b00836.
dc.titleTheoretical Kinetic Study of the Unimolecular Keto–Enol Tautomerism Propen-2-ol ↔ Acetone. Pressure Effects and Implications in the Pyrolysis of tert- and 2-Butanol
dc.typeArticle
dc.contributor.departmentChemical and Biological Engineering Program
dc.contributor.departmentClean Combustion Research Center
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Division
dc.identifier.journalThe Journal of Physical Chemistry A
dc.eprint.versionPost-print
kaust.personGrajales Gonzalez, Edwing
kaust.personMonge Palacios, Manuel
kaust.personSarathy, Mani
kaust.grant.numberOSR-2016-CRG5-3022
dc.date.published-online2018-03-21
dc.date.published-print2018-04-12


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