A Theoretical Study of NH2 Radical Reactions with Propane and Its Kinetic Implications in NH3-Propane Blends’ Oxidation

Giri, Binod Raj; Shrestha, Krishna Prasad; Mai, Tam V.-T.; Giri, Sushant; Adil, Mohammad; Naik, R. Thirumaleswara; Mauss, Fabian; Huynh, Lam Kim

doi:10.3390/en16165943

Title: A Theoretical Study of NH₂ Radical Reactions with Propane and Its Kinetic Implications in NH₃-Propane Blends’ Oxidation

Journal Article · 10 August 2023 · Energies

DOI: https://doi.org/10.3390/en16165943 · OSTI ID:2203414

Giri, Binod Raj ^[1];

^[2]; Mai, Tam V.-T. ^[3]; Giri, Sushant ^[1];

^[1]; Naik, R. Thirumaleswara ^[4]; Mauss, Fabian ^[5];

^[6]

King Abdullah University of Science and Technology (KAUST), Thuwal (Saudi Arabia)
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Duy Tan University, Ho Chi Minh City (Vietnam)
King Abdullah University of Science and Technology (KAUST), Thuwal (Saudi Arabia); Indian Institute of Science, Bangalore (India)
Brandenburg University of Technology, Cottbus (Germany)
International University, Ho Chi Minh City (Vietnam); Vietnam National University, Ho Chi Minh City (Vietnam

The reaction of NH₂ radicals with C₃H₈ is crucial for understanding the combustion behavior of NH₃/C₃H₈ blends. In this study, we investigated the temperature dependence of the rate coefficients for the hydrogen abstraction reactions of C₃H₈ by NH₂ radicals using high-level theoretical approaches. The potential energy surface was constructed at the CCSD(T)/cc-pV(T, Q)//M06-2X/aug-cc-pVTZ level of theory, and the rate coefficients were computed using conventional transition state theory, incorporating the corrections for quantum tunneling and hindered internal rotors (HIR). The computed rate coefficients showed a strong curvature in the Arrhenius behavior, capturing the experimental literature data well at low temperatures. However, at T > 1500 K, the theory severely overpredicted the experimental data. The available theoretical studies did not align with the experiment at high temperatures, and the possible reasons for this discrepancy are discussed. At 300 K, the reaction of NH₂ with C₃H₈ predominantly occurs at the secondary C-H site, which accounts for approximately 95% of the total reaction flux. However, the hydrogen abstraction reaction at the primary C-H site becomes the dominant reaction above 1700 K. A composite kinetic model was built, which incorporated the computed rate coefficients for NH₂ + C₃H₈ reactions. The importance of NH₂ + C₃H₈ reactions in predicting the combustion behavior of NH₃/C₃H₈ blends was demonstrated by kinetic modeling.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); Vietnam National University HoChiMinh City (VNU-HCM)

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 2203414

Report Number(s):: LA-UR--23-26601

Journal Information:: Energies, Journal Name: Energies Journal Issue: 16 Vol. 16; ISSN 1996-1073

Publisher:: MDPICopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
energy
reaction kinetics
kinetic modeling
ammonia
propane
NH2

Title: A Theoretical Study of NH2 Radical Reactions with Propane and Its Kinetic Implications in NH3-Propane Blends’ Oxidation

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References (52)

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Title: A Theoretical Study of NH₂ Radical Reactions with Propane and Its Kinetic Implications in NH₃-Propane Blends’ Oxidation