理论研究H_2S与羟基和Cl在没有水分子和有水分子条件下的反应机理  

Theoretical Study on Reaction Mechanism of H_2S with Hydroxide Radical and Cl in the Absence and Presence of Water Molecule

作　　者：毛文雪[1] 隆正文[1] 

机构地区：[1]贵州大学理学院,贵州贵阳550025

出　　处：《贵州大学学报（自然科学版）》2011年第6期22-25,共4页Journal of Guizhou University:Natural Sciences

基　　金：国家自然科学基金(41165007)

摘　　要：本文用量子化学计算方法研究没有水分子和有水分子条件下对Cl+H2S和OH+H2S这两个反应产生的影响。在wb97xd/aug-cc-pvtz水平下的计算结果表明,单个水分子加到反应中会使Cl+H2S和OH+H2S这两个反应的能垒分别减小3.0 kal/mol和2.2 kal/mol.同时两个反应的速率常数在水分子影响下也分别增加了2.5×10-9cm3molecule-1s-1和减小了5.18×10-12cm3molecule-1s-1,计算结果和文献理论值符合得很好。说明水分子对Cl+H2S反应体系有催化的效果,对OH+H2S反应体系没有催化的效果,反而具有减缓反应。The quantum chemical calculations were applied to study the two reactions of C1 ＋ HES and OH ＋ HESwithout water and with a single water molecule. The computed results predict that the activated barriers for two reactions of C1 ＋ H2S and OH ＋ H2S are reduced by 4.3 kal/mol and 3.6 kal/mol respectively. In addition, the calculated results show that the rate constant are increased by 2.5 × 10^-9cm^3 molecule^-1s^-1 and increased 5.18 ×10^-12cm^3 molecule^-1s^-1, respectively. The calculation results agree well with theoretical value of literature. Thus, the calculations show that the single water would play a catalytic role in the reaction of Cl ＋ H2S , but produce negative influence to the reaction of OH ＋ H2 S.

关 键 词：水分子 H2S CL 羟基 

分 类 号：O643.12[理学—物理化学]