Reaction kinetics of hydrogen addition reactions to methyl butenoate

Autor:	Xiaoqing You, Yage Gao, Xiaoyu Li
Rok vydání:	2020
Předmět:	chemistry.chemical_classification Addition reaction Double bond Hydrogen General Physics and Astronomy chemistry.chemical_element Hydrogen atom abstraction Dissociation (chemistry) Chemical kinetics Reaction rate constant chemistry Physical chemistry Molecule Physical and Theoretical Chemistry
Zdroj:	Physical Chemistry Chemical Physics. 22:5286-5292
ISSN:	1463-9084 1463-9076
DOI:	10.1039/c9cp06570a
Popis:	To investigate the kinetics of hydrogen addition reactions of unsaturated methyl esters, we selected two representative molecules that are isomers with C[double bond, length as m-dash]C double bonds at different locations, i.e. methyl 2-butenoate and methyl 3-butenoate for study. An appropriate quantum chemical method was determined to compute the potential energy surfaces. The high-pressure limit rate constants were computed by applying multi-structural canonical variational transition state theory including tunneling by the multi-dimensional small-curvature tunneling approximation. The master equation analysis was followed to study the pressure-dependence of the rate constants of H addition and the subsequent dissociation reactions. The results show that it is easier for the H atom to add to the C[double bond, length as m-dash]C than to the C[double bond, length as m-dash]O bond because of the lower barrier heights, and the hydrogen addition reactions are faster for both methyl 2-butenoate and methyl 3-butenoate, except that the hydrogen abstraction is dominant at above 1700 K for methyl 2-butenoate. Using our computed rate constants, the prediction for methyl propanoate mole fraction agreed better with experimental data of methyl 2-butenoate combustion.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::7318166526569f0a5b81252fbb8cb4a8 https://doi.org/10.1039/c9cp06570a Zobrazit plný text záznamu