Resolving Some Paradoxes in the Thermal Decomposition Mechanism of Acetaldehyde

The Journal of Physical Chemistry. a
R SivaramakrishnanStephen J Klippenstein

Abstract

The mechanism for the thermal decomposition of acetaldehyde has been revisited with an analysis of literature kinetics experiments using theoretical kinetics. The present modeling study was motivated by recent observations, with very sensitive diagnostics, of some unexpected products in high temperature microtubular reactor experiments on the thermal decomposition of CH3CHO and its deuterated analogs, CH3CDO, CD3CHO, and CD3CDO. The observations of these products prompted the authors of these studies to suggest that the enol tautomer, CH2CHOH (vinyl alcohol), is a primary intermediate in the thermal decomposition of acetaldehyde. The present modeling efforts on acetaldehyde decomposition incorporate a master equation reanalysis of the CH3CHO potential energy surface (PES). The lowest-energy process on this PES is an isomerization of CH3CHO to CH2CHOH. However, the subsequent product channels for CH2CHOH are substantially higher in energy, and the only unimolecular process that can be thermally accessed is a reisomerization to CH3CHO. The incorporation of these new theoretical kinetics predictions into models for selected literature experiments on CH3CHO thermal decomposition confirms our earlier experiment and theory-based conc...Continue Reading

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Citations

Oct 7, 2016·Faraday Discussions·Alexander M MebelStephen J Klippenstein
May 28, 2020·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·N Fabian KleimeierRalf I Kaiser
Jun 30, 2019·Physical Chemistry Chemical Physics : PCCP·Chuande ZhaoKun Yu
Feb 23, 2021·Journal of the American Chemical Society·Daniel P ZaleskiKirill Prozument
Jun 14, 2018·The Journal of Physical Chemistry. a·Vahid Saheb, Meymanat Zokaie
Aug 22, 2017·The Journal of Physical Chemistry. a·Vahid SahebS Mohammad Ali Hosseini
Jul 1, 2017·The Journal of Physical Chemistry. a·David E CouchWilliam K Peters
Nov 30, 2018·The Journal of Physical Chemistry. a·Rubik AsatryanEli Ruckenstein

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