HSS和HOO反应机理的研究

Studies on the reaction mechanism of HSS and HOO

作者：曹佳(延安大学化学与化工学院)；李琦(延安大学化学与化工学院)；王智香(延安大学化学与化工学院)；高楼军(延安大学化学与化工学院)；付峰(延安大学化学与化工学院)

Author：CAO Jia(College of Chemistry & Chemical engineering, Yanan University)；LI Qi(College of Chemistry & Chemical engineering, Yanan University)；WANG Zhi-Xiang(College of Chemistry & Chemical engineering, Yanan University)；GAO Lou-Jun(College of Chemistry & Chemical engineering, Yanan University)；FU Feng(College of Chemistry & Chemical engineering, Yanan University)

收稿日期：2014-05-20 年卷（期）页码：2015,52(4):855-859

期刊名称：四川大学学报: 自然科学版

Journal Name：Journal of Sichuan University (Natural Science Edition)

关键字：HOO；HSS；反应机理；速率常数

Key words：HSS; HOO; Reaction mechanism; Rate constant

基金项目：陕西省教育厅专项科研计划项目(2013JK0667)；延安大学青年项目资助(YDQ2013-16)；延安大学化学与化工学院自然科学专项基金资助(YDHG2014-Z04)；陕西省大学生创新创业训练计划项目（1449）

中文摘要

本文采用G2M(CC5)//B3PW91/6-311+G(3df,2p)方法研究了HSS和HOO反应机理. 结果表明，HSS与HOO反应主要存在4条通道，分别生成产物P1(H2O+SSO), P2(H2O2+1S2), P3(H2S2+1O2)和P4(H2+SSOO)，主通道为生成P1(H2O+SSO)的通道，其表观活化能为-12431 kJ?mol-1. 根据传统过渡态理论结合隧道效应校正，计算了各个通道在298~1000 K温度范围内的表观速率常数k，发现产物P1(H2O+SSO)主产物，总速率常数呈现负温度系数效应. 此外，理论预测了稳定物种的生成焓(ΔfHe298K)，计算结果与实验较为接近.

英文摘要

The mechanism for the reaction of HSS with HOO is investigated by using G2M(CC5)//B3PW91/6-311+G(3df,2p). Four possible reaction channels〓for the formation of P1(H2O+SSO), P2(H2O2+1S2), P3(H2S2+1O2) and P4(H2+SSOO) are found in the reaction of HOO and HSS. The result indicates that the main channel is the formation of P1(H2O+SSO) with the apparent activation energy of -12431 kJ?mol-1. Rate constants of all the channels over the temperature range of 298~1000 K are evaluated using the transition state theory. Formation enthalpies (ΔfHe298K) of all the minima are predicted, which are in good agreement with the available experimental values.

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论文摘要

HSS和HOO反应机理的研究

Studies on the reaction mechanism of HSS and HOO