Effect of a single water molecule on the formations of H2O2 + ClO from HO2 + HOCl reaction under tropospheric conditions |
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| Authors: | Tian-lei Zhang Peng Zhang Zi-long Jia Kai Zhang Xin-yi Miao Zhu-qing Wang |
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| Affiliation: | 1. Shaanxi Province Key Laboratory of Catalytic Fundamental and Application, School of Chemical and Environment Science, Shaanxi University of Technology, Hanzhong, Chinatianlei@snut.edu.cn;3. Shaanxi Province Key Laboratory of Catalytic Fundamental and Application, School of Chemical and Environment Science, Shaanxi University of Technology, Hanzhong, China;4. Shandong Provincial Key Laboratory of Ocean Environment Monitoring Technology, Institute of Oceanographic Instrumentation, Shandong Academy of Sciences, Qingdao, China |
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| Abstract: | ABSTRACTIn this work, four different channels, represented by H2O???HO2 + HOCl, HO2???H2O + HOCl, H2O???HOCl + HO2 and HOCl???H2O + HO2 have been analysed for water-catalysed formations of H2O2 + ClO to gain insight into the potential impact of the reaction in the atmosphere. The results at the CCSD(T)/aug-cc-pVTZ//MP2/6-311+G(2df,2p) level show that the H2O???HO2 + HOCl reaction is kinetically the most favourable channel among the four channels. Compared to the channel of H2O2 + ClO formations without water vapour, the effective rate constant of H2O???HO2 + HOCl reaction is estimated to be faster than the naked reaction by 2–3 orders of magnitude, indicating that the single water molecule in the H2O???HO2 + HOCl channel exhibits a positive catalytic effect on enhancing the rate of H2O2 + ClO formations. Meanwhile, it is interesting that the transfer process between H2O???HOCl + HO2 and H2O???HO2 + HOCl has an activation energy of 0.6 kcal?mol?1 and can occur easily under tropospheric conditions. |
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| Keywords: | HO2 HOCl water-catalysed reaction mechanism rate constant |
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