Molecular Dynamics Study of Combustion Reactions in Supercritical Environment. Part 3: Boxed MD Study of CH3 + HO2 → CH3O + OH Reaction Kinetics

Panteleev, Sergey V.; Masunov, Artëm E.; Vasu, Subith S.

doi:10.1021/acs.jpca.7b12233

Title: Molecular Dynamics Study of Combustion Reactions in Supercritical Environment. Part 3: Boxed MD Study of CH₃ + HO₂ → CH₃O + OH Reaction Kinetics

Full Record
Other Related Research

Abstract

The kinetics of reaction CH₃ + HO₂ → CH₃O + OH in supercritical carbon dioxide media at pressures from 0.3 to 1000 atm in the temperature range (600–1600) K was studied using boxed molecular dynamics simulations at QM/MM theory level with periodical boundary conditions. The mechanism of this process includes two consecutive steps: formation and decomposition of CH₃OOH intermediate. We calculated the activation free energies and rate constants of each step, then used Bodenstein’s quasistationary concentrations approximation to estimate the rate constants of the reaction. On the basis of the temperature dependence of the rate constants, parameters in the extended Arrhenius equation were determined. Furthermore, we found that reaction rate of each step, as well as overall reaction, increases with increasing CO₂ pressure in the system. The most capable zone for the process is T = 1000–1200 K, and the CO₂ pressure is about 100 atm.

Authors:

^[1];

^[2];

^[3]

Univ. of Central Florida, Orlando, FL (United States); N. I. Lobachevsky State Univ. of Nizhny Novgorod (Russia)
Univ. of Central Florida, Orlando, FL (United States); South Ural State Univ., Chelyabinsk (Russia); National Research Nuclear Univ. MEPhI, Moscow (Russia)
Univ. of Central Florida, Orlando, FL (United States)

Publication Date:: Mon Mar 05 00:00:00 EST 2018

Research Org.:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Org.:: USDOE Office of Fossil Energy (FE)

OSTI Identifier:: 1480274

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: 122; Journal Issue: 13; 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


                    Panteleev, Sergey V., Masunov, Artëm E., and Vasu, Subith S. Molecular Dynamics Study of Combustion Reactions in Supercritical Environment. Part 3: Boxed MD Study of CH3 + HO2 → CH3O + OH Reaction Kinetics.  United States: N. p., 2018. 
Web.  doi:10.1021/acs.jpca.7b12233.

Copy to clipboard


                    Panteleev, Sergey V., Masunov, Artëm E., & Vasu, Subith S. Molecular Dynamics Study of Combustion Reactions in Supercritical Environment. Part 3: Boxed MD Study of CH3 + HO2 → CH3O + OH Reaction Kinetics.  United States.  https://doi.org/10.1021/acs.jpca.7b12233

Copy to clipboard


                    Panteleev, Sergey V., Masunov, Artëm E., and Vasu, Subith S. Mon .  
"Molecular Dynamics Study of Combustion Reactions in Supercritical Environment. Part 3: Boxed MD Study of CH3 + HO2 → CH3O + OH Reaction Kinetics".  United States.  https://doi.org/10.1021/acs.jpca.7b12233.  https://www.osti.gov/servlets/purl/1480274.

Copy to clipboard


                    
@article{osti_1480274,

  title        = {Molecular Dynamics Study of Combustion Reactions in Supercritical Environment. Part 3: Boxed MD Study of CH3 + HO2 → CH3O + OH Reaction Kinetics},

  author       = {Panteleev, Sergey V. and Masunov, Artëm E. and Vasu, Subith S.},

  abstractNote = {The kinetics of reaction CH3 + HO2 → CH3O + OH in supercritical carbon dioxide media at pressures from 0.3 to 1000 atm in the temperature range (600–1600) K was studied using boxed molecular dynamics simulations at QM/MM theory level with periodical boundary conditions. The mechanism of this process includes two consecutive steps: formation and decomposition of CH3OOH intermediate. We calculated the activation free energies and rate constants of each step, then used Bodenstein’s quasistationary concentrations approximation to estimate the rate constants of the reaction. On the basis of the temperature dependence of the rate constants, parameters in the extended Arrhenius equation were determined. Furthermore, we found that reaction rate of each step, as well as overall reaction, increases with increasing CO2 pressure in the system. The most capable zone for the process is T = 1000–1200 K, and the CO2 pressure is about 100 atm.},

  doi          = {10.1021/acs.jpca.7b12233},

  journal      = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},

  number       = 13,

  volume       = 122,

  place        = {United States},

  year         = {Mon Mar 05 00:00:00 EST 2018},

  month        = {Mon Mar 05 00:00:00 EST 2018}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1021/acs.jpca.7b12233

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 4 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Similar Records in DOE PAGES and OSTI.GOV collections:

Molecular Dynamics Study of Combustion Reactions in a Supercritical Environment. Part 2: Boxed MD Study of CO + OH → CO₂ + H Reaction Kinetics

Journal Article Panteleev, Sergey V. ; Masunov, Artëm E. ; Vasu, Subith S. - Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

Oxy-fuel combustion technology holds a great promise in both increasing the efficiency of the energy conversion and reducing environmental impact. Yet, effects of the higher pressures and replacement of the nitrogen with carbon dioxide diluent are not well understood at present. The title reaction is one of the most important processes in combustion. Despite numerous studies, the effects of supercritical carbon dioxide environment did not receive much attention in the past. In this work, we report the results of boxed molecular dynamics simulations of these effects at QM/MM theory level with periodical boundary conditions. The free energy barriers for HOCOmore »« less
Cited by 10
https://doi.org/10.1021/acs.jpca.7b09774

Full Text Available
Molecular dynamics of combustion reactions in supercritical carbon dioxide. Part 4: boxed MD study of formyl radical dissociation and recombination

Journal Article Panteleev, Sergey V. ; Masunov, Artëm E. ; Vasu, Subith S. - Journal of Molecular Modeling

Fossil fuel oxy-combustion is an emergent technology where habitual nitrogen diluent is replaced by high pressure (supercritical) carbon dioxide. The supercritical state of CO2 increases the efficiency of the energy conversion and the absence of nitrogen from the reaction mixture reduces pollution by NOx. However, the effects of a supercritical environment on elementary reactions kinetics are not well understood at present. We used boxed molecular dynamics simulations at the QM/MM theory level to predict the kinetics of dissociation/recombination reaction HCO• + [M] ↔ H• + CO + [M], an important elementary step in many combustion processes. A wide range ofmore »« less
https://doi.org/10.1007/s00894-018-3912-4
Quantum chemical and master equation study of OH + CH ₂ O → H ₂ O + CHO reaction rates in supercritical CO ₂ environment

Journal Article Wait, Elizabeth E. ; Masunov, Artëm E. ; Vasu, Subith S. - International Journal of Chemical Kinetics

Abstract We investigated the reaction rates of OH + CH ₂ O → H ₂ O + CHO at CO ₂ pressures of up to 1000 atm with and without CO ₂ molecule included in a reactive complex. Both mechanisms begin with formation of the hydrogen‐bonded prereactive complexes. Our ab initio calculations indicate a possibility of catalytic effect, predicting an activation barrier that one order of magnitude lower when the CO ₂ molecule is involved. To verify this effect, we use the Rice–Ramsperger–Kassel–Marcus theory and solve unimolecular master equations in the steady‐state approximation. We assume the equilibrium between prereactive complexesmore »« less
Cited by 10
https://doi.org/10.1002/kin.21228
Molecular Dynamics of Combustion Reactions in Supercritical Carbon Dioxide. Part 5: Computational Study of Ethane Dissociation and Recombination Reactions C₂H₆ ⇌ CH₃ + CH₃

Journal Article Wang, Chun-Hung ; Panteleev, Sergey V. ; Masunov, Artëm E. ; ... - Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

Fossil fuel oxy-combustion is an emerging technology where the habitual nitrogen diluent is replaced by high-pressure supercritical CO₂ (sCO₂), which increases the efficiency of energy conversion. In this study, the chemical kinetics of the combustion reaction C₂H₆ ⇌ CH₃ + CH₃ in the sCO₂ environment is predicted at 30–1000 atm and 1000–2000 K. We adopt a multiscale approach, where the reactive complex is treated quantum mechanically in rigid rotor/harmonic oscillator approximation, while environment effects at different densities are taken into account by the potential of mean force, produced with classical molecular dynamics (MD). Here, we used boxed MD, where enhancedmore »« less
Cited by 4
https://doi.org/10.1021/acs.jpca.9b02302

Full Text Available
Temperature dependence for the absolute rate constant for the reaction CH/sub 2/OH + O/sub 2/. -->. HO/sub 2/ + H/sub 2/CO from 215 to 300 K

Journal Article Nesbitt, F L ; Payne, W A ; Stief, L J - J. Phys. Chem.; (United States)

The absolute rate constant for the reaction CH/sub 2/OH + O/sub 2/ ..-->.. HO/sub 2/ + H/sub 2/CO has been determined from 215 to 300 K in a discharge flow system at 1-Torr pressure. The decay of CH/sub 2/OH was monitored in excess O/sub 2/ by collision-free sampling mass spectrometry. The temperature dependence observed is quite different from the usual Arrhenius form. For the 215-250 K interval, an activation energy of 3.4 kcal/mol is obtained. Above 250 K, the rate constant increases at a slower rate; previous high-temperature studies (1000-2000 K) again show a faster increase in the rate constant.more »« less
https://doi.org/10.1021/j100325a008

Similar Records

Title: Molecular Dynamics Study of Combustion Reactions in Supercritical Environment. Part 3: Boxed MD Study of CH3 + HO2 → CH3O + OH Reaction Kinetics

Abstract

Citation Formats

Title: Molecular Dynamics Study of Combustion Reactions in Supercritical Environment. Part 3: Boxed MD Study of CH₃ + HO₂ → CH₃O + OH Reaction Kinetics