单分子水对H2O2+Cl气相反应影响的理论研究

doi:10.3866/PKU.WHXB201404032

Acta Phys. -Chim. Sin. ›› 2014, Vol. 30 ›› Issue (6): 1061-1070.doi: 10.3866/PKU.WHXB201404032

• THEORETICAL AND COMPUTATIONAL CHEMISTRY • Previous Articles Next Articles

Theoretical Study on the effect of a Single Water Molecule on the H₂O₂+Cl Gas Reaction

XU Qiong¹, ZHANG Tian-Lei¹, Lü Wen-Bin¹, WANG Rui¹, WANG Zhi-Yin¹, WANG Wen-Liang², WANG Zhu-Qing³

1 School of Chemical & Environment Science, Shaanxi University of Technology, Hanzhong 723001, Shaanxi Province, P. R. China;
2 Key Laboratory for Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710062, P. R. China;
3 Shandong Provincial Key Laboratory of Ocean Environment Monitoring Technology, Shandong Academy of Sciences Institute of Oceanographic Instrumentation, Qingdao 266001, Shandong Province, P. R.China

Received:2014-01-20 Revised:2014-03-31 Published:2014-05-26
Contact: XU Qiong, WANG Wen-Liang E-mail:xuq@snut.edu.cn;wlwang@snnu.edu.cn
Supported by:
The project was supported by the National Natural Science Foundation of China (21173139, 21207081), Education Department of Shaanxi Provincial Government Research Project, China (12JK0625), Funds of Research Programs of Shaanxi University of Technology, China (SLGQD13(2)-3, SLGQD13(2)-4), and Natural Science Foundation of Shandong Province, China (ZR2012DQ001).

Abstract

Abstract:

The reaction mechanism and rate constant of the H₂O₂+Cl reaction, with and without a single water molecule, was investigated theoretically at the CCSD(T)/aug-cc-pVTZ//B3LYP/aug-cc-pVTZ level of theory. The calculated results show that there is only one channel for the formation of HO₂+HCl in the naked H₂O₂+Cl reaction with an apparent activation energy of 10.21 kJ·mol^-1. When one water molecule is added, the product of the reaction does not change, but the potential energy surface of the reaction becomes complex, yielding three different channels RW1, RW2, and RW3. The single water molecule in the RW1 and RW2 reaction channels has a negative influence on reducing the reaction barrier for the formation of HO₂+HCl, whereas it has a positive influence in Channel RW3. Additionally, to estimate the importance of these processes in the atmosphere, their rate constants were evaluated using conventional transition state theory with the Wigner tunneling correction. The result shows that the rate constant for the naked H₂O₂+Cl reaction is 1.60×10^-13 cm³ ·molecule^-1 ·s^-1 at 298.2 K, which is in good agreement with experimental values. Although the rate constant of channel RW3 is predicted to be 46.6-131 times larger than that of the naked H₂O₂+Cl reaction, its effective rate constant is smaller by 10-14 orders of magnitude than that of the naked reaction, that is, for the H₂O₂ + Cl reaction the naked reaction almost exclusively occurs under tropospheric conditions.

Key words: H₂O₂, Cl, Water-catalyzed, Reaction mechanism, Rate constant

XU Qiong, ZHANG Tian-Lei, Lü Wen-Bin, WANG Rui, WANG Zhi-Yin, WANG Wen-Liang, WANG Zhu-Qing. Theoretical Study on the effect of a Single Water Molecule on the H₂O₂+Cl Gas Reaction[J]. Acta Phys. -Chim. Sin. 2014, 30(6), 1061-1070. doi: 10.3866/PKU.WHXB201404032

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Theoretical Study on the effect of a Single Water Molecule on the H₂O₂+Cl Gas Reaction

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Theoretical Study on the effect of a Single Water Molecule on the H₂O₂+Cl Gas Reaction