RATE CONSTANTS FOR THE COMBINATION OF TRICHLOROMETHYL RADICALS AND THE ELECTRON-TRANSFER REACTION BETWEEN HYDROXYMETHYL RADICALS AND CARBON-TETRACHLORIDE IN SOLUTION

被引:42
作者
PAUL, H [1 ]
机构
[1] UNIV NOTRE DAME, RADIAT LAB, NOTRE DAME, IN 46556 USA
关键词
D O I
10.1002/kin.550110504
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
The rate constant for the bimolecular combination of trichloromethyl radicals in methanol is determined as a function of temperature by steady‐state kinetics and electron‐spin resonance with modulated radical initiation. The rate constant is in accord with the Smoluchowski equation and indicates a diffusion‐controlled radical termination. The temperature dependence of the rate constant for the electron‐transfer reaction between hydroxymethyl radicals and carbon tetrachloride in methanol is determined, and is found to disagree with predictions of the Marcus theory. This disagreement is tentatively ascribed to the structure of the transition state. Copyright © 1979 John Wiley & Sons, Inc.
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页码:495 / 509
页数:15
相关论文
共 45 条
[1]  
BAGDASARYAN KS, 1963, KINET KATAL, V4, P844
[2]   ADDITION OF BROMOTRICHLOROMETHANE TO VINYL ACETATE .2. KINETICS OF PHOTOCHEMICAL REACTION [J].
BENGOUGH, WI ;
THOMSON, RAM .
TRANSACTIONS OF THE FARADAY SOCIETY, 1961, 57 (11) :1928-&
[3]   ELECTRON-SPIN RESONANCE MEASUREMENTS OF TERMINATION RATE CONSTANTS FOR TERT-BUTYL RADICALS IN SOLUTION [J].
BENNETT, JE ;
SUMMERS, R .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1977, (11) :1504-1508
[4]   TERMINATION RATE CONSTANTS OF TAU-BUTYL RADICALS, IN SOLUTION - INTERFERENCE BY CIS-AZOISOBUTANE [J].
BENNETT, JE ;
EYRE, JA ;
RIMMER, CP ;
SUMMERS, R .
CHEMICAL PHYSICS LETTERS, 1974, 26 (01) :69-71
[5]  
BENSON SW, 1960, F CHEM KINETICS, P502
[6]   REACTIONS OF ALKOXY RADICALS .4. KINETICS AND ABSOLUTE RATE CONSTANTS FOR SOME T-BUTYL HYPOCHLORITE CHLORINATIONS [J].
CARLSSON, DJ ;
INGOLD, KU .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1967, 89 (19) :4891-&
[7]   ABSOLUTE RATE CONSTANTS FOR COMBINATION OF TRICHLOROMETHYL RADICALS AND FOR THEIR REACTION WITH T-BUTYL HYPOCHLORITE [J].
CARLSSON, DJ ;
HOWARD, JA ;
INGOLD, KU .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1966, 88 (20) :4726-&
[8]  
CARLSSON DJ, 1969, INT J CHEM KINET, V1, P315
[9]   RATE CONSTANTS AND ACTIVATION PARAMETERS FOR OUTER-SPHERE ELECTRON-TRANSFER REACTIONS AND COMPARISONS WITH PREDICTIONS OF MARCUS THEORY [J].
CHOU, M ;
CREUTZ, C ;
SUTIN, N .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1977, 99 (17) :5615-5623
[10]  
CLARK ID, 1969, COMPREHENSIVE CHEM K