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Title: Potential energy surfaces for the reactions of HO2 radical with CH2O and HO2 in CO2 environment

Abstract

Here, we report on potential energies for the transition state, reactant, and product complexes along the reaction pathways for hydrogen transfer reactions to hydroperoxyl radical from formaldehyde H2CO + HO2 → HCO + H2O2 and another hydroperoxyl radical 2HO2 → H2O2 + O2 in the presence of one carbon dioxide molecule. Both covalently bonded intermediates and weak intermolecular complexes are identified and characterized. We found that reactions that involve covalent intermediates have substantially higher activation barriers and are not likely to play a role in hydrogen transfer kinetics. The van der Waals complexation with carbon dioxide does not affect hydrogen transfer from formaldehyde, but it lowers the barrier for hydroperoxyl self-reaction by nearly 3 kcal/mol. This indicates that CO2 environment is likely to have catalytic effect on HO2 self-reaction, which needs to be included in kinetic combustion mechanisms in supercritical CO2.

Authors:
 [1];  [2];  [3]
+ Show Author Affiliations
  1. Univ. of Central Florida, Orlando, FL (United States); National Research Nuclear Univ. MEPhl, Moscow (Russia)
  2. Univ. of Central Florida, Orlando, FL (United States); Florida State Univ., Tallahassee, FL (United States)
  3. Univ. of Central Florida, Orlando, FL (United States)
Publication Date:
Research Org.:
Univ. of Central Florida, Orlando, FL (United States)
Sponsoring Org.:
USDOE Office of Fossil Energy (FE)
OSTI Identifier:
1329520
Grant/Contract Number:  
FE0025260
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 120; Journal Issue: 39; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
20 FOSSIL-FUELED POWER PLANTS

Citation Formats

Masunov, Artem E., Atlanov, Arseniy A., and Vasu, Subith S. Potential energy surfaces for the reactions of HO2 radical with CH2O and HO2 in CO2 environment. United States: N. p., 2016. Web. doi:10.1021/acs.jpca.6b07257.
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Masunov, Artem E., Atlanov, Arseniy A., & Vasu, Subith S. Potential energy surfaces for the reactions of HO2 radical with CH2O and HO2 in CO2 environment. United States. https://doi.org/10.1021/acs.jpca.6b07257
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Masunov, Artem E., Atlanov, Arseniy A., and Vasu, Subith S. Tue . "Potential energy surfaces for the reactions of HO2 radical with CH2O and HO2 in CO2 environment". United States. https://doi.org/10.1021/acs.jpca.6b07257. https://www.osti.gov/servlets/purl/1329520.
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@article{osti_1329520,
title = {Potential energy surfaces for the reactions of HO2 radical with CH2O and HO2 in CO2 environment},
author = {Masunov, Artem E. and Atlanov, Arseniy A. and Vasu, Subith S.},
abstractNote = {Here, we report on potential energies for the transition state, reactant, and product complexes along the reaction pathways for hydrogen transfer reactions to hydroperoxyl radical from formaldehyde H2CO + HO2 → HCO + H2O2 and another hydroperoxyl radical 2HO2 → H2O2 + O2 in the presence of one carbon dioxide molecule. Both covalently bonded intermediates and weak intermolecular complexes are identified and characterized. We found that reactions that involve covalent intermediates have substantially higher activation barriers and are not likely to play a role in hydrogen transfer kinetics. The van der Waals complexation with carbon dioxide does not affect hydrogen transfer from formaldehyde, but it lowers the barrier for hydroperoxyl self-reaction by nearly 3 kcal/mol. This indicates that CO2 environment is likely to have catalytic effect on HO2 self-reaction, which needs to be included in kinetic combustion mechanisms in supercritical CO2.},
doi = {10.1021/acs.jpca.6b07257},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 39,
volume = 120,
place = {United States},
year = {Tue Aug 23 00:00:00 EDT 2016},
month = {Tue Aug 23 00:00:00 EDT 2016}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1021/acs.jpca.6b07257
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    Works referencing / citing this record:

    Quantum chemical and master equation study of OH + CH 2 O → H 2 O + CHO reaction rates in supercritical CO 2 environment
    journal, November 2018

    • Wait, Elizabeth E.; Masunov, Artëm E.; Vasu, Subith S.
    • International Journal of Chemical Kinetics, Vol. 51, Issue 1
    • DOI: 10.1002/kin.21228

    Theoretical studies of reaction mechanisms for potential reactions of HNCO with HO 2 radicals
    journal, March 2020

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