| Cite this article as: Hao Hao,Zhou Lu,Shi Shao-Xu,Ma Hong-He. Study on Reaction Mechanism and Kinetics of NO and SH Radical [J]. J. At. Mol. Phys.(原子与分子物理学报), 2024, 41: 061003 (in Chinese) |
| Study on Reaction Mechanism and Kinetics of NO and SH Radical |
| Hits 198 Download times 57 Received:December 30, 2022 Revised:February 02, 2023 |
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| Key Words
SH radical NO Reaction mechanism Rate constant Density functional theory Deep peaking shaving |
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| Abstract
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| In order to explore the influence of interaction between nitrogen and sulfur components on the evolution of sulfur components in the operation of coal-fired power generation units during deep peak shaving, the detailed reaction mechanism of NO and SH radical was studied.B3LYP/6-311++G(d,p) method was used to optimize the geometry of all stationary species on the reaction path between SH radical and NO, and IRC verified the correctness of the reaction path. At the CCSD(T)/def2-TZVPP level, the energy of each stationary point on the reaction path was calculated, and the potential energy surfaces of the reaction in the singlet state and triplet state were obtained by frequency correction and zero-point energy correction. The calculation results show that there are eight reaction paths and three possible products, respectively P1(SN+OH),P2(3SO+3NH),P3(3S+HNO). The channel (7) (R→3IM8→3IM9→P1) is the dominant channel of this reaction, and the main product of the reaction is P1. The reaction rate constants of this reaction channel in the range of 298~2000K were calculated according to the traditional transition state theory and the variable transition state theory and combined with tunnel correction, and the three parameters of the reaction rate constant were fitted as kCVT/Eckart=1.203×10-2T4.25exp(-108.29/RT)cm3•molecule-1•s-1 with a positive temperature coefficient effect. The calculated rate constants are in good agreement with literature values and apply to a wider temperature range, and the resulting kinetic parameters and thermodynamic data can be used for the establishment of the sulfur evolution mechanism in combustion. |
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