The reaction of cyclohexyl radicals with carbon tetrachloride

✍ Scribed by Jim Currie; Howard Sidebottom; John Tedder

• Publisher: John Wiley and Sons
• Year: 1974
• Tongue: English
• Weight: 523 KB
• Volume: 6
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550060404

✦ Synopsis

Abstract

The photolysis of azocyclohexane, carbon tetrachloride, and cyclohexane at 360 nm has been investigated over a wide temperature range. At moderate temperatures a chain reaction ensues from which the following approximate rate constants could be determined assuming 2CCl~3~. → C~2~Cl~6~, k~5~ = 10^9.7^ (303–673K):

equation image

The really striking feature of the results is that they show that termination in bicyclohexyl [reaction (7)] is extremely slow:

equation image

The root‐mean‐square rule for estimating the cross‐combination rate

equation image

is also followed.

The photolysis of carbon tetrachloride and cyclohexane at 250 nm has also been investigated. The reaction is complicated by the occurrence of two concurrent photolytic processes, the main one yielding trichloromethyl radicals and chlorine atoms, and the subsidiary one yielding dichlorocarbene and molecular chlorine. Nonetheless the results from this reaction can be interpreted in the medium temperature range 360–430K, where long chains are present, in terms of the rate constants derived from the azocyclohexane system.