| 姚秋月,文明杰,鲁有松,李明静,张田雷.化学通报,2017,80(10):963-970. |
| 水分子催化HCl NO3反应机理及动力学性质的理论研究 |
| Theoretical Study On the Mechanism and Kinetics for Water-Catalyzed the HCl NO3 reaction |
| 投稿时间：2017-01-18 修订日期：2017-03-31 |
| DOI： |
| 中文关键词: HCl NO3 水催化 反应机理 速率常数 有效速率常数 |
| 英文关键词:NO3 HCl Water-catalyzed Reaction mechanism Rate constant Effective rate constant |
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| 中文摘要: |
| 本文采用CCSD(T)/aug-cc-pVTZ//B3LYP/6-311 G(2d,p)方法对HCl NO3反应机理及速率常数进行了研究,并在此基础上考虑了单个水分子对该反应的影响。研究结果表明,HCl NO3反应经历了生成产物为Cl HNO3的通道,克服了13.67 kcal.mol-1的能垒。当加入一分子水时,所得的产物并没有发生改变,但势能面却比裸反应复杂得多,经历了NO3???H2O HCl、H2O???HCl NO3和HCl???H2O NO3三条反应通道。水分子在通道NO3???H2O HCl中对Cl HNO3产物的生成起正催化作用,而在H2O???HCl NO3和HCl???H2O NO3通道中则起负催化作用。在240～425 K范围内通道HCl???H2O NO3的有效速率常数k"RW3为2.98×10-27～2.66×10-16 cm3.molecules-1.s-1,比相同温度下其它两个水参与通道NO3???H2O HCl、H2O???HCl NO3对应的速率常数大了6～8个数量级,说明通道HCl???H2O NO3为水分子参与反应的优势通道。此外,该通道比相同温度下裸反应的速率常数kR1提高了0.33×104～1.07×107倍,且在298 K时,k’RW3/k’total已达到95.9%,说明此时在实际大气环境中水分子对NO3 HCl反应有明显的影响。 |
| 英文摘要: |
| In this article, the mechanism and rate constant for the reaction of HCl NO3 without and with a water molecule were studied at CCSD(T)/aug-cc-pVTZ//B3LYP/6-311 G(2d,p) level of theory. The results show that there is only one channel for the NO3 HCl naked reaction, labeled as HNO3 Cl formation channel. When one water molecule is added, the product of the reaction does not change, but the potential energy surface of the reaction becomes quite complex, yielding three different channels of NO3???H2O HCl, H2O???HCl NO3 and HCl???H2O NO3. The single water molecule in NO3???H2O HCl Channel has a positive influence on reducing the reaction barrier of HNO3 Cl formation, whereas it shows a negative effect in H2O???HCl NO3 and HCl???H2O NO3 Channels. The rate constant for the NO3 HCl reaction is computed to be 2.24×10-31~1.34×10-24 cm3×molecule-1×s-1 within the temperature range of 240~425 K, which is good agreement with the available experimental values. The rate constant of HCl???H2O NO3 Channel is predicted to be faster by 0.33×104～1.07×107 times than that of the NO3 HCl naked reaction. Besides, its effective rate constant k’RW3/k’total is up to 95.9% at 298 K, that is, the single water molecule has a obvious effect on the atmospheric reaction of NO3 HCl. |
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