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Title: A theoretical analysis of the reaction between ethyl and molecular oxygen

Abstract

Using a combination of electronic-structure theory, variational transition-state theory, and solutions to the time-dependent master equation, the authors have studied the kinetics of the title reaction theoretically over wide ranges of temperature and pressure. The agreement between theory and experiment is quite good. By comparing the theoretical and experimental results describing the kinetic behavior, they have been able to deduce a value for the C{sub 2}H{sub 5}-O{sub 2} bond energy of {approximately}34 kcal/mole and a value for the exit-channel transition-state energy of {minus}4.3 kcal/mole (measured from reactants). These numbers compare favorably with the electronic-structure theory predictions of 33.9 kcal/mole and {minus}3.0 kcal/mole, respectively. The master-equation solutions show three distinct temperature regimes for the reaction, discussed extensively in the paper. Above T {approx} 700 K, the reaction can be written as an elementary step, C{sub 2}H{sub 5} + O{sub 2} {leftrightarrow} C{sub 2}H{sub 4} + HO{sub 2}, with the rate coefficient, k(T) = 3.19 x 10{sup {minus}17} T{sup 1.02} exp(2035/RT) cm{sup 3}/molec.-sec., independent of pressure even though the intermediate collision complex may suffer a large number of collisions.

Authors:
; ;
Publication Date:
Research Org.:
Sandia National Labs., Albuquerque, NM (US); Sandia National Labs., Livermore, CA (US)
Sponsoring Org.:
US Department of Energy (US)
OSTI Identifier:
751238
Report Number(s):
SAND2000-8491C
TRN: AH200019%%48
DOE Contract Number:  
AC04-94AL85000
Resource Type:
Conference
Resource Relation:
Conference: 28th Annual Combustion Symposium, Edinburgh, Scotland (GB), 07/30/2000--08/04/2000; Other Information: PBD: 13 Dec 2000
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COMBUSTION KINETICS; ETHANE; OXIDATION; BINDING ENERGY; CHEMICAL BONDS; ENERGY-LEVEL TRANSITIONS

Citation Formats

James A. Miller, Stephen J. Klippenstein, and Stuart H. Robertson. A theoretical analysis of the reaction between ethyl and molecular oxygen. United States: N. p., 2000. Web.
James A. Miller, Stephen J. Klippenstein, & Stuart H. Robertson. A theoretical analysis of the reaction between ethyl and molecular oxygen. United States.
James A. Miller, Stephen J. Klippenstein, and Stuart H. Robertson. Wed . "A theoretical analysis of the reaction between ethyl and molecular oxygen". United States. doi:. https://www.osti.gov/servlets/purl/751238.
@article{osti_751238,
title = {A theoretical analysis of the reaction between ethyl and molecular oxygen},
author = {James A. Miller and Stephen J. Klippenstein and Stuart H. Robertson},
abstractNote = {Using a combination of electronic-structure theory, variational transition-state theory, and solutions to the time-dependent master equation, the authors have studied the kinetics of the title reaction theoretically over wide ranges of temperature and pressure. The agreement between theory and experiment is quite good. By comparing the theoretical and experimental results describing the kinetic behavior, they have been able to deduce a value for the C{sub 2}H{sub 5}-O{sub 2} bond energy of {approximately}34 kcal/mole and a value for the exit-channel transition-state energy of {minus}4.3 kcal/mole (measured from reactants). These numbers compare favorably with the electronic-structure theory predictions of 33.9 kcal/mole and {minus}3.0 kcal/mole, respectively. The master-equation solutions show three distinct temperature regimes for the reaction, discussed extensively in the paper. Above T {approx} 700 K, the reaction can be written as an elementary step, C{sub 2}H{sub 5} + O{sub 2} {leftrightarrow} C{sub 2}H{sub 4} + HO{sub 2}, with the rate coefficient, k(T) = 3.19 x 10{sup {minus}17} T{sup 1.02} exp(2035/RT) cm{sup 3}/molec.-sec., independent of pressure even though the intermediate collision complex may suffer a large number of collisions.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Wed Dec 13 00:00:00 EST 2000},
month = {Wed Dec 13 00:00:00 EST 2000}
}

Conference:
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