Experimental and theoretical study on the reaction of CCl2+H2O

被引：0

作者：

Liu, YZ ^{[1
]}

Hu, CJ ^{[1
]}

Pei, LS ^{[1
]}

Chen, CX ^{[1
]}

Ma, XX ^{[1
]}

机构：

[1] Univ Sci & Technol China, Open Lab Bond Select Chem, Dept Chem Phys, Hefei 230026, Peoples R China

来源：

ACTA PHYSICO-CHIMICA SINICA | 2003年 / 19卷 / 06期

关键词：

CCl2; radical; rate constant; Ab initio theoretical calculation; RRKM (Rice-Ramsperger-Kassel-Marcus) theory;

D O I：

10.3866/PKU.WHXB20030601

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Absolute rate constant for the reaction of CCl2 radical with H2O is obtained as (5.45 +/- 0.95) x 10(-14) cm(3) (.) molecule(-1) (.) s(-1) by LP-LIEF technique. The CCl2 is first produced by 213 run laser photolysis of CCl4. The mechanism for the reaction CCl2 + H2O has been studied using a high-level ab initio G2MP2 method. It is found that there are two reaction mechanisms: insertion and addition-elimination. The three primary product channels, HCl + HClCO, HCl + trans-ClCOH and HCl + cis-ClCOH, are studied in detail. Moreover, the branch ratios are calculated using RRKM-TST and convention transition state theories. The calculations show that at lower temperatures the major product channel is HCl + HCClO via the insretion of C atom of CCl2 into OH bond of H2O, whereas the formation of HCl + trans-ClCOH dominates at higher temperatures.

引用

页码：481 / 486

页数：6