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Title: Communication: Thermal unimolecular decomposition of syn-CH3CHOO: A kinetic study

Abstract

The thermal decomposition of syn-ethanal-oxide (syn-CH3CHOO) through vinyl hydrogen peroxide (VHP) leading to hydroxyl radical is characterized using a modification of the HEAT thermochemical protocol. The isomerization step of syn-CH3CHOO to VHP via a 1,4 H-shift, which involves a moderate barrier of 72 kJ/mol, is found to be rate determining. A two-dimensional master equation approach, in combination with semi-classical transition state theory, is employed to calculate the time evolution of various species as well as to obtain phenomenological rate coefficients. This work suggests that, under boundary layer conditions in the atmosphere, thermal unimolecular decomposition is the most important sink of syn-CH3CHOO. Thus, the title reaction should be included into atmospheric modeling. Here, the fate of cold VHP, the intermediate stabilized by collisions with a third body, has also been investigated

Authors:
ORCiD logo [1];  [1];  [2];  [1]
+ Show Author Affiliations
  1. The Univ. of Texas at Austin, Austin, TX (United States)
  2. Harvard-Smithsonian Center for Astrophysics, Cambridge, MA (United States)
Publication Date:
Research Org.:
The Univ. of Texas at Austin, Austin, TX (United States). Dept. of Chemistry
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1465482
Alternate Identifier(s):
OSTI ID: 1328452
Grant/Contract Number:  
FG02-07ER15884
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 13; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Nguyen, Thanh Lam, McCaslin, Laura, McCarthy, Michael C., and Stanton, John F. Communication: Thermal unimolecular decomposition of syn-CH3CHOO: A kinetic study. United States: N. p., 2016. Web. doi:10.1063/1.4964393.
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Nguyen, Thanh Lam, McCaslin, Laura, McCarthy, Michael C., & Stanton, John F. Communication: Thermal unimolecular decomposition of syn-CH3CHOO: A kinetic study. United States. https://doi.org/10.1063/1.4964393
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Nguyen, Thanh Lam, McCaslin, Laura, McCarthy, Michael C., and Stanton, John F. Wed . "Communication: Thermal unimolecular decomposition of syn-CH3CHOO: A kinetic study". United States. https://doi.org/10.1063/1.4964393. https://www.osti.gov/servlets/purl/1465482.
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@article{osti_1465482,
title = {Communication: Thermal unimolecular decomposition of syn-CH3CHOO: A kinetic study},
author = {Nguyen, Thanh Lam and McCaslin, Laura and McCarthy, Michael C. and Stanton, John F.},
abstractNote = {The thermal decomposition of syn-ethanal-oxide (syn-CH3CHOO) through vinyl hydrogen peroxide (VHP) leading to hydroxyl radical is characterized using a modification of the HEAT thermochemical protocol. The isomerization step of syn-CH3CHOO to VHP via a 1,4 H-shift, which involves a moderate barrier of 72 kJ/mol, is found to be rate determining. A two-dimensional master equation approach, in combination with semi-classical transition state theory, is employed to calculate the time evolution of various species as well as to obtain phenomenological rate coefficients. This work suggests that, under boundary layer conditions in the atmosphere, thermal unimolecular decomposition is the most important sink of syn-CH3CHOO. Thus, the title reaction should be included into atmospheric modeling. Here, the fate of cold VHP, the intermediate stabilized by collisions with a third body, has also been investigated},
doi = {10.1063/1.4964393},
journal = {Journal of Chemical Physics},
number = 13,
volume = 145,
place = {United States},
year = {Wed Oct 05 00:00:00 EDT 2016},
month = {Wed Oct 05 00:00:00 EDT 2016}
}
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https://doi.org/10.1063/1.4964393
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