Theoretical investigation on the reaction kinetics of NO2 with CH3OH and HCHO under combustion conditions |
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| Institution: | 1. Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui, 230026, PR China;2. National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui, 230029, PR China;1. Center for Combustion Energy and Department of Energy and Power Engineering, Tsinghua University, Beijing 100084, PR China;2. Key Laboratory for Thermal Science and Power Engineering of MOE and International Joint Laboratory on Low Carbon Clean Energy Innovation, Tsinghua University, Beijing 100084, PR China;3. Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230029, PR China;4. National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui 230029, PR China;1. Center for Combustion Energy and Department of Energy and Power Engineering, Tsinghua University, Beijing 100084, China;2. Key Laboratory for Thermal Science and Power Engineering of MOE, International Joint Laboratory on Low Carbon Clean Energy Innovation, Tsinghua University, Beijing 100084, China;3. Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230029, China;4. National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui 230029, China;1. Key Laboratory for Power Machinery and Engineering of MOE, School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai, 200240, PR China;2. Clean Combustion Research Center, King Abdullah University of Science and Technology, Thuwal, 23955, Kingdom of Saudi Arabia |
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| Abstract: | Methanol (CH3OH) and formaldehyde (HCHO) reacting with nitrogen dioxide (NO2) contribute to the largest uncertainty for the CH3OH/NOx low temperature combustion mechanism. CH3OH and NO2 only undergo H-abstraction reactions, while HCHO + NO2 involves multiple reaction channels, among which H-abstraction dominates. In the present work, a high level quantum chemical method, CCSD(T)/aug-cc-pVQZ//M06–2X-D3/6-311++G(d,p), was employed to investigate the reaction pathways. The reaction kinetics were explored by RRKM/master equation simulations with multidimensional small-curvature tunneling (SCT) corrections and hindered rotor approximations. The H-abstraction reactions with barriers higher than 20 kcal/mol indicate a nonnegligible quantum tunneling effect even under combustion conditions. Our computations predict the tunneling factors to be 3–4 for the studied reactions at 500 K. A significant tunneling effect is also expected for H-abstraction of large alcohols and aldehydes by NO2. The computed total rate coefficients show good agreement with previous experimental measurements over narrow ranges of temperature and pressure, ensuring the accuracy of the reported branching ratios covering a wide T, P range for the two reactions. The results of CH3OH + NO2 reveal the dominant role of HONOcis + CH2OH. It's also uncovered the dominance of HONOcis + CHO pathway in HCHO + NO2 under the studied conditions. The detailed reaction kinetics information reported in this work is useful for building rate rules for the mechanisms of other nitrogen-containing alcohol-based fuels. |
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