Molecular Dynamics of Combustion Reactions in Supercritical Carbon Dioxide. 6. Computational Kinetics of Reactions between Hydrogen Atom and Oxygen Molecule H + O 2 ⇌ HO + O and H + O 2 ⇌ HO 2 .

Autor: Wang CH; NanoScience Technology Center , University of Central Florida , 12424 Research Parkway , Orlando , Florida 32826 , United States., Masunov AE; NanoScience Technology Center , University of Central Florida , 12424 Research Parkway , Orlando , Florida 32826 , United States.; School of Modeling, Simulation, and Training , University of Central Florida , 3100 Technology Parkway , Orlando , Florida 32816 , United States.; Department of Chemistry , University of Central Florida , 4111 Libra Drive , Orlando , Florida 32816 , United States.; South Ural State University , Lenin pr. 76 , Chelyabinsk 454080 , Russia.; National Research Nuclear University MEPhI , Kashirskoye shosse 31 , Moscow 115409 , Russia., Allison TC; Southwest Research Institute , San Antonio , Texas 78238 , United States., Chang S; KEPCO Research Institute , Daejeon 34050 , Korea., Lim C; Hanwha Power Systems , Seongnam , Gyeonggi 13488 , Korea., Jin Y; Hanwha Power Systems , Seongnam , Gyeonggi 13488 , Korea., Vasu SS; Center for Advanced Turbomachinery and Energy Research (CATER), Mechanical and Aerospace Engineering , University of Central Florida , Orlando , Florida 32816 , United States.
Jazyk: angličtina
Zdroj: The journal of physical chemistry. A [J Phys Chem A] 2019 Dec 19; Vol. 123 (50), pp. 10772-10781. Date of Electronic Publication: 2019 Dec 10.
DOI: 10.1021/acs.jpca.9b08789
Abstrakt: Reactions of the hydrogen atom and the oxygen molecule are among the most important ones in the hydrogen and hydrocarbon oxidation mechanisms, including combustion in a supercritical CO 2 (sCO 2 ) environment, known as oxy-combustion or the Allam cycle. Development of these energy technologies requires understanding of chemical kinetics of H + O 2 ⇌ HO + O and H + O 2 ⇌ HO 2 in high pressures and concentrations of CO 2 . Here, we combine quantum treatment of the reaction system by the transition state theory with classical molecular dynamics simulation and the multistate empirical valence bonding method to treat environmental effects. Potential of mean force in the sCO 2 solvent at various temperatures 1000-2000 K and pressures 100-400 atm was obtained. The reaction rate for H + O 2 ⇌ HO + O was found to be pressure-independent and described by the extended Arrhenius equation 4.23 × 10 -7 T -0.73 exp(-21 855.2 cal/mol/RT) cm 3 /molecule/s, while the reaction rate H + O 2 ⇌ HO 2 is pressure-dependent and can be expressed as 5.22 × 10 -2 T -2.86 exp(-7247.4 cal/mol/RT) cm 3 /molecule/s at 300 atm.
Databáze: MEDLINE
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