KINETICS OF THE RECOMBINATION REACTION SH+O-2+AR - IMPLICATIONS FOR THE FORMATION AND LOSS OF HSOO AND SOO IN THE ATMOSPHERE

被引：27

作者：

GOUMRI, A ^{[1
]}

ROCHA, JDR ^{[1
]}

MARSHALL, P ^{[1
]}

机构：

[1] UNIV N TEXAS,DEPT CHEM,DENTON,TX 76203

来源：

JOURNAL OF PHYSICAL CHEMISTRY | 1995年 / 99卷 / 27期

关键词：

D O I：

10.1021/j100027a025

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：

Unimolecular pathways for the dissociation of thiylperoxyl have been investigated computationally. Gaussian-2 (G2) theory was employed to calculate the thermochemistry, and the kinetics of SH + O-2 --> HSOO are analyzed by RRKM theory. Under atmospheric conditions the rate constant is close to the low-pressure limit of k(0) approximate to 9.2 x 10(-34)(T/298 K)(-1.69) molecule(-2) cm(6) s(-1) for T = 200-400 K. By comparison to other tropospheric oxidation reactions of thiyl radicals, addition to oxygen yields the shortest lifetime, although the low G2 S-0 bond dissociation enthalpy implies a small equilibrium constant and means that HSOO formation is likely to be important only below 298 K. Singlet and triplet SOO have been characterized, and Delta H-f,H-298((SOO)-S-1) is predicted to be 185.5 kT mol(-1) The results are discussed in the context of atmospheric chemistry.

引用

页码：10834 / 10836

页数：3

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