Impact of Water on the OH + HOCl Reaction

详细信息    查看全文

• 作者：Javier Gonzalez ; Josep M. Anglada ; Robert J. Buszek ; Joseph S. Francisco
• 刊名：Journal of the American Chemical Society
• 出版年：2011
• 出版时间：March 16, 2011
• 年：2011
• 卷：133
• 期：10
• 页码：3345-3353
• 全文大小：929K
• 年卷期：v.133,no.10(March 16, 2011)
• ISSN：1520-5126

文摘

The effect of a single water molecule on the OH + HOCl reaction has been investigated. The naked reaction, the reaction without water, has two elementary reaction paths, depending on how the hydroxyl radical approaches the HOCl molecule. In both cases, the reaction begins with the formation of prereactive hydrogen bond complexes before the abstraction of the hydrogen by the hydroxyl radical. When water is added, the products of the reaction do not change, and the reaction becomes quite complex yielding six different reaction paths. Interestingly, a geometrical rearrangement occurs in the prereactive hydrogen bonded region, which prepares the HOCl moiety to react with the hydroxyl radical. The rate constant for the reaction without water is computed to be 2.2 脳 10^鈭?3 cm³ molecule^鈭? s^鈭? at room temperature, which is in good agreement with experimental values. The reaction between ClOH路路路H₂O and OH is estimated to be slower than the naked reaction by 4鈭? orders of magnitude. Although, the reaction between ClOH and the H₂O路路路HO complex is also predicted to be slower, it is up to 2.2 times faster than the naked reaction at altitudes below 6 km. Another intriguing finding of this work is an interesting three-body interchange reaction that can occur, that is HOCl + HO路路路H₂O 鈫?HOCl路路路H₂O + OH.