Chemical reaction CO+OH • → CO2+H• autocatalyzed by carbon dioxide: Quantum chemical study of the potential energy surfaces
Abstract
The supercritical carbon dioxide medium, used to increase efficiency in oxy combustion fossil energy technology, may drastically alter both rates and mechanisms of chemical reactions. Here we investigate potential energy surface of the second most important combustion reaction with quantum chemistry methods. Two types of effects are reported: formation of the covalent intermediates and formation of van der Waals complexes by spectator CO2 molecule. While spectator molecule alter the activation barrier only slightly, the covalent bonding opens a new reaction pathway. The mechanism includes sequential covalent binding of CO2 to OH radical and CO molecule, hydrogen transfer from oxygen to carbon atoms, and CH bond dissociation. This reduces the activation barrier by 11 kcal/mol at the rate-determining step and is expected to accelerate the reaction rate. The finding of predicted catalytic effect is expected to play an important role not only in combustion but also in a broad array of chemical processes taking place in supercritical CO2 medium. Furthermore, tt may open a new venue for controlling reaction rates for chemical manufacturing.
- Authors:
-
- Univ. of Central Florida, Orlando, FL (United States); National Research Nuclear Univ. MEPhl, Moscow (Russia)
- Univ. of Central Florida, Orlando, FL (United States)
- Mechanical and Aerospace Engineering 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 Energy Efficiency and Renewable Energy (EERE), Energy Efficiency Office. Federal Energy Management Program Office; USDOE Office of Fossil Energy (FE)
- OSTI Identifier:
- 1329521
- 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: 30; Journal ID: ISSN 1089-5639
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS
Citation Formats
Masunov, Artem E., Wait, Elizabeth, and Vasu, Subith S. Chemical reaction CO+OH • → CO2+H• autocatalyzed by carbon dioxide: Quantum chemical study of the potential energy surfaces. United States: N. p., 2016.
Web. doi:10.1021/acs.jpca.6b03242.
Masunov, Artem E., Wait, Elizabeth, & Vasu, Subith S. Chemical reaction CO+OH • → CO2+H• autocatalyzed by carbon dioxide: Quantum chemical study of the potential energy surfaces. United States. https://doi.org/10.1021/acs.jpca.6b03242
Masunov, Artem E., Wait, Elizabeth, and Vasu, Subith S. Tue .
"Chemical reaction CO+OH • → CO2+H• autocatalyzed by carbon dioxide: Quantum chemical study of the potential energy surfaces". United States. https://doi.org/10.1021/acs.jpca.6b03242. https://www.osti.gov/servlets/purl/1329521.
@article{osti_1329521,
title = {Chemical reaction CO+OH • → CO2+H• autocatalyzed by carbon dioxide: Quantum chemical study of the potential energy surfaces},
author = {Masunov, Artem E. and Wait, Elizabeth and Vasu, Subith S.},
abstractNote = {The supercritical carbon dioxide medium, used to increase efficiency in oxy combustion fossil energy technology, may drastically alter both rates and mechanisms of chemical reactions. Here we investigate potential energy surface of the second most important combustion reaction with quantum chemistry methods. Two types of effects are reported: formation of the covalent intermediates and formation of van der Waals complexes by spectator CO2 molecule. While spectator molecule alter the activation barrier only slightly, the covalent bonding opens a new reaction pathway. The mechanism includes sequential covalent binding of CO2 to OH radical and CO molecule, hydrogen transfer from oxygen to carbon atoms, and CH bond dissociation. This reduces the activation barrier by 11 kcal/mol at the rate-determining step and is expected to accelerate the reaction rate. The finding of predicted catalytic effect is expected to play an important role not only in combustion but also in a broad array of chemical processes taking place in supercritical CO2 medium. Furthermore, tt may open a new venue for controlling reaction rates for chemical manufacturing.},
doi = {10.1021/acs.jpca.6b03242},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 30,
volume = 120,
place = {United States},
year = {Tue Jun 28 00:00:00 EDT 2016},
month = {Tue Jun 28 00:00:00 EDT 2016}
}
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