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Title: On the low-temperature limit of HACA

Abstract

In this work, rates of two mechanisms, hydrogen abstraction C2H2 (carbon) addition (HACA) and C2H2 (carbon) addition hydrogen migration (CAHM), were intercompared with each other at postflame conditions of a laminar premixed flame of ethylene. The analysis showed that HACA is substantially faster than CAHM, in contrast with the conclusions reached in a recent study of Zhang et al. The difference between the two studies is largely due to dissimilar assignments of the thermodynamics of the H abstraction and of the islands of stability pulling the HACA reaction sequence. In support of this conclusion, the kinetics and thermodynamics of the key HACA reaction step were recalculated at a reliable level of quantum and reaction-rate theories. The implication of the present results is that both HACA and CAHM mechanisms can explain formation of aliphatic groups chemisorbed at edges of aromatics; however, a quantitative relationship is yet to be established with the experimental observations.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2]
  1. Univ. of California, Berkeley, CA (United States)
  2. Florida International Univ., Miami, FL (United States); Samara National Research Univ. (Russia)
Publication Date:
Research Org.:
Florida International Univ., Miami, FL (United States)
Sponsoring Org.:
Government of the Russian Federation; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1594773
Grant/Contract Number:  
FG02-04ER15570; 14.Y26.31.0020
Resource Type:
Accepted Manuscript
Journal Name:
Proceedings of the Combustion Institute
Additional Journal Information:
Journal Volume: 37; Journal Issue: 1; Conference: 37.International Symposium on Combustion, Dublin (Ireland), 29 Jul - 3 Aug 2018; Journal ID: ISSN 1540-7489
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; HACA; Reaction mechanisms; Soot; PAH; Growth

Citation Formats

Frenklach, Michael, Singh, Ravi I., and Mebel, Alexander M. On the low-temperature limit of HACA. United States: N. p., 2018. Web. https://doi.org/10.1016/j.proci.2018.05.068.
Frenklach, Michael, Singh, Ravi I., & Mebel, Alexander M. On the low-temperature limit of HACA. United States. https://doi.org/10.1016/j.proci.2018.05.068
Frenklach, Michael, Singh, Ravi I., and Mebel, Alexander M. Fri . "On the low-temperature limit of HACA". United States. https://doi.org/10.1016/j.proci.2018.05.068. https://www.osti.gov/servlets/purl/1594773.
@article{osti_1594773,
title = {On the low-temperature limit of HACA},
author = {Frenklach, Michael and Singh, Ravi I. and Mebel, Alexander M.},
abstractNote = {In this work, rates of two mechanisms, hydrogen abstraction C2H2 (carbon) addition (HACA) and C2H2 (carbon) addition hydrogen migration (CAHM), were intercompared with each other at postflame conditions of a laminar premixed flame of ethylene. The analysis showed that HACA is substantially faster than CAHM, in contrast with the conclusions reached in a recent study of Zhang et al. The difference between the two studies is largely due to dissimilar assignments of the thermodynamics of the H abstraction and of the islands of stability pulling the HACA reaction sequence. In support of this conclusion, the kinetics and thermodynamics of the key HACA reaction step were recalculated at a reliable level of quantum and reaction-rate theories. The implication of the present results is that both HACA and CAHM mechanisms can explain formation of aliphatic groups chemisorbed at edges of aromatics; however, a quantitative relationship is yet to be established with the experimental observations.},
doi = {10.1016/j.proci.2018.05.068},
journal = {Proceedings of the Combustion Institute},
number = 1,
volume = 37,
place = {United States},
year = {2018},
month = {6}
}

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Cited by: 16 works
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