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
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
收藏
页码:2494 / 2497
页数:4
相关论文
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].
ADEDINSEWO, CO ;
ADEGITE, A .
INORGANIC CHEMISTRY, 1979, 18 (12) :3597-3601
[2]  
[Anonymous], 1987, DISINFECTANT RESIDUA
[3]   ELECTRON-TRANSFER BETWEEN AZIDE AND CHLORINE DIOXIDE - THE EFFECT OF SOLVENT BARRIER NONADDITIVITY [J].
AWAD, HH ;
STANBURY, DM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (09) :3636-3642
[4]   PULSE RADIOLYSIS OF AQUEOUS THIOCYANATE AND IODIDE SOLUTIONS [J].
BAXENDALE, JH ;
BEVAN, PLT ;
STOTT, DA .
TRANSACTIONS OF THE FARADAY SOCIETY, 1968, 64 (549P) :2389-+
[5]   ENERGETICS OF FORMATION OF L2- AND (CNS)2- IN AQUEOUS SOLUTION [J].
BAXENDALE, JH ;
BEVAN, PLT .
JOURNAL OF THE CHEMICAL SOCIETY A -INORGANIC PHYSICAL THEORETICAL, 1969, (15) :2240-+
[6]  
Bray W. C., 1906, Z PHYS CHEM, V54, P575
[7]   KINETIC STUDY OF REDUCTION OF NEPTUNIUM(VI) AND PLUTONIUM(VI) BY IODIDE-ION IN AQUEOUS PERCHLORATE MEDIA [J].
COOPER, J ;
REENTS, WD ;
WOODS, M ;
SJOBLOM, R ;
SULLIVAN, JC .
INORGANIC CHEMISTRY, 1977, 16 (05) :1030-1032
[8]   COMPLEX-FORMATION REACTIONS OF THE CHLORITE ION [J].
FABIAN, I ;
GORDON, G .
INORGANIC CHEMISTRY, 1991, 30 (19) :3785-3787
[9]   KINETIC STUDY OF REACTION BETWEEN CHLORINE DIOXIDE AND POTASSIUM IODIDE IN AQUEOUS SOLUTION [J].
FUKUTOMI, H ;
GORDON, G .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1967, 89 (06) :1362-&