Radiation-induced dechlorination of carbon tetrachloride in cyclohexane and n-hexane mixtures. III. The kinetics of liquid-phase reactions of trichloromethyl radicals

✍ Scribed by M. G. Katz; G. Baruch; L. A. Rajbenbach

• Publisher: John Wiley and Sons
• Year: 1978
• Tongue: English
• Weight: 276 KB
• Volume: 10
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550100811

✦ Synopsis

The kinetics of gamma-radiation-induced free-radical chain reactions in solutions of carbon tetrachloride in mixtures of varying composition of cyclohexane and n-hexane was investigated in the temperature range of 296"-413"K. Trichloromethyl radicals were produced by the reaction of radiolytically generated alkyl radicals with the solute. The kinetics of the following reactions were studied:

The following rate expression was obtained:

CCl3 t n-C6H14 -CC13H + sec-C~H13 log k4/k5 = 0.32 f 0.04 -(0.14 f 0.07)/8

The error limits are the standard deviation from the least mean-square Arrhenius plots. The present results, combined with previously measured activation parameters for hydrogen-atom abstraction from c-CgH12 and n-C6H14 by CC13 radicals relative to CC13 combination, afford experimental evidence that the decay of trichloromethyl species in alkane solutions is a diffusion-limited process. The thesis that activation energies of reactions (4) and (5) in the liquid phase are equal to their respective values in the gas phase is confirmed.