The kinetics and mechanism of the chlorine dioxide iodide ion reaction

被引：42

作者：

Fabian, I ^{[1
]}

Gordon, G ^{[1
]}

机构：

[1] MIAMI UNIV,DEPT CHEM,OXFORD,OH 45056

来源：

INORGANIC CHEMISTRY | 1997年 / 36卷 / 12期

关键词：

D O I：

10.1021/ic961279g

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The oxidation of iodide ion by chlorine dioxide has been studied by stopped-flow techniques at I = 1.0 M (NaClO4). The following two-term rate law was confirmed for the reaction: -d[ClO2]/dt = k(I)[CLO2][I-] + k(II)[ClO2][I-](2). The rate constants at 298 K and the activation parameters are k(I) = (1.87 +/- 0.02) x 10(3) M-1 s(-1), Delta H-I(double dagger) = 35.4 +/- 0.7 kJ/mol, Delta S-1(double dagger) = -63.5 +/- 2.3 J/(mol K), k(II) = (1.25 +/- 0.04) x 10(4) M-2 s(-1), Delta H-II(double dagger) = 36.7 +/- 1.3 kJ/mol, Delta S-II(double dagger) = -43.2 +/- 4.6 J/(mol K). Both the second- and third-order paths are interpreted in terms of an outersphere electron-transfer mechanism. The calculations based on the Marcus theory yield k(I) = 1358 M-1 s(-1) for the second-order path.

引用

页码：2494 / 2497

页数：4

共 26 条

[1] LINEAR FREE-ENERGY RELATIONS IN REDOX REACTIONS - OXIDATION OF IODIDE-ION BY POLY(PYRIDINE)-IRON(III) COMPLEXES AND HEXACHLOROIRIDATE(IV) ION [J].