Mechanism and Rate Constants of the CH3+ CH2CO Reaction: A Theoretical Study

Mechanism and Rate Constants of the CH3+ CH2CO Reaction: A Theoretical Study The mechanism of the reaction of ketene with methyl radical has been studied by ab initio CCSD(T)‐F12/cc‐pVQZ‐f12//B2PLYPD3/6‐311G** calculations of the potential energy surface. Temperature‐ and pressure‐dependent reaction rate constants have been computed using the Rice–Ramsperger–Kassel–Marcus (RRKM)–Master Equation and transition state theory methods. Three main channels have been shown to dominate the reaction; the formation of the collisionally stabilized CH3COCH2 radical and the production of the C2H5 + CO and HCCO + CH4 bimolecular products. Relative contributions of the CH3COCH2, C2H5 + CO, and HCCO + CH4 channels strongly depend on the reaction conditions; the formation of thermalized CH3COCH2 is favored at low temperatures and high pressures, HCCO + CH4 is dominant at high temperatures, whereas the yield of C2H5 + CO peaks at intermediate temperatures around 1000 K. The C2H5 + CO channel is favored by a decrease in pressure but remains the second most important reaction pathway after HCCO + CH4 under typical flame conditions. The calculated rate constants at different pressures are proposed for kinetic modeling of ketene reactions in combustion in the form of modified Arrhenius expressions. Only rate constant to form CH3COCH2 depends on pressure, whereas those to produce C2H5 + CO and HCCO + CH4 appeared to be pressure independent. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png International Journal of Chemical Kinetics Wiley

Mechanism and Rate Constants of the CH3+ CH2CO Reaction: A Theoretical Study

Loading next page...
 
/lp/wiley/mechanism-and-rate-constants-of-the-ch3-ch2co-reaction-a-theoretical-uUU2f8eLQL
Publisher
Wiley Subscription Services, Inc., A Wiley Company
Copyright
Copyright © 2018 Wiley Periodicals, Inc., A Wiley Company
ISSN
0538-8066
eISSN
1097-4601
D.O.I.
10.1002/kin.21156
Publisher site
See Article on Publisher Site

Abstract

The mechanism of the reaction of ketene with methyl radical has been studied by ab initio CCSD(T)‐F12/cc‐pVQZ‐f12//B2PLYPD3/6‐311G** calculations of the potential energy surface. Temperature‐ and pressure‐dependent reaction rate constants have been computed using the Rice–Ramsperger–Kassel–Marcus (RRKM)–Master Equation and transition state theory methods. Three main channels have been shown to dominate the reaction; the formation of the collisionally stabilized CH3COCH2 radical and the production of the C2H5 + CO and HCCO + CH4 bimolecular products. Relative contributions of the CH3COCH2, C2H5 + CO, and HCCO + CH4 channels strongly depend on the reaction conditions; the formation of thermalized CH3COCH2 is favored at low temperatures and high pressures, HCCO + CH4 is dominant at high temperatures, whereas the yield of C2H5 + CO peaks at intermediate temperatures around 1000 K. The C2H5 + CO channel is favored by a decrease in pressure but remains the second most important reaction pathway after HCCO + CH4 under typical flame conditions. The calculated rate constants at different pressures are proposed for kinetic modeling of ketene reactions in combustion in the form of modified Arrhenius expressions. Only rate constant to form CH3COCH2 depends on pressure, whereas those to produce C2H5 + CO and HCCO + CH4 appeared to be pressure independent.

Journal

International Journal of Chemical KineticsWiley

Published: Jan 1, 2018

References

You’re reading a free preview. Subscribe to read the entire article.


DeepDyve is your
personal research library

It’s your single place to instantly
discover and read the research
that matters to you.

Enjoy affordable access to
over 18 million articles from more than
15,000 peer-reviewed journals.

All for just $49/month

Explore the DeepDyve Library

Search

Query the DeepDyve database, plus search all of PubMed and Google Scholar seamlessly

Organize

Save any article or search result from DeepDyve, PubMed, and Google Scholar... all in one place.

Access

Get unlimited, online access to over 18 million full-text articles from more than 15,000 scientific journals.

Your journals are on DeepDyve

Read from thousands of the leading scholarly journals from SpringerNature, Elsevier, Wiley-Blackwell, Oxford University Press and more.

All the latest content is available, no embargo periods.

See the journals in your area

DeepDyve

Freelancer

DeepDyve

Pro

Price

FREE

$49/month
$360/year

Save searches from
Google Scholar,
PubMed

Create lists to
organize your research

Export lists, citations

Read DeepDyve articles

Abstract access only

Unlimited access to over
18 million full-text articles

Print

20 pages / month

PDF Discount

20% off