Evaluation of activation volumes for the conversion of peroxynitrous to nitric acid

被引：8

作者：

Kissner, R

Thomas, C

Hamsa, MSA

van Eldik, R ^{[1
]}

Koppenol, WH

机构：

[1] Swiss Fed Inst Technol, Inst Inorgan Chem, CH-8093 Zurich, Switzerland

[2] Univ Erlangen Nurnberg, Inst Inorgan Chem, D-91058 Erlangen, Germany

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2003年 / 107卷 / 51期

关键词：

D O I：

10.1021/jp0362988

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：

Peroxynitrous acid, an inorganic toxin of biological importance, acts both as an oxidizing and a nitrating agent during its conversion to nitric acid. In discussions of the mechanism of this conversion, activation volumes have been invoked to distinguish between possible mechanisms, viz., homolysis of the O-O bond versus rotation via the N-O bond of peroxynitrous acid. A reinvestigation of the activation volume for the conversion of peroxynitrous acid to nitric acid by high-pressure stopped-flow spectrophotometry yielded an average value of 6.9 +/- 0.9 cm(3) mol(-1) at 25 degreesC. Activation volumes currently cited in the literature for this process range from 6 to 10 cm(3) mol(-1) in the temperature range 18-25 degreesC. Such moderately positive values do not support a definite conclusion regarding the mechanism of the conversion.

引用

页码：11261 / 11263

页数：3

共 22 条

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