Photolysis of carbon tetrachloride in the presence of alkanes

✍ Scribed by Ian Matheson; John Tedder; Howard Sidebottom

• Publisher: John Wiley and Sons
• Year: 1982
• Tongue: English
• Weight: 556 KB
• Volume: 14
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550140908

✦ Synopsis

The photolysis of carbon tetrachloride in the presence of a number of alkanes has been investigated in the gas phase. The products obtained from the photolysis experiments were those expected from a chain reaction in which trichloromethyl radicals abstract hydrogen atoms from the alkane. The data have been used to determine Arrhenius parameters for hydrogen abstraction from the series of alkanes CH4, CzH6, CzH8, and i-C4H1O by trichloromethyl radicals,

mol-s) E4 (kcal/mol) CH4 9.7 f 0.6 17.9 f 1.2 CZH6 9.0 f 0.3 14.2 f 0.6 (CHdzCHz 8.2 f 0.9 10.6 f 1.6 (CH3hCH 7.7 f 0.3 7.7 f 0.5 and also for chlorine atom abstraction from CC14 by the corresponding alkyl radicals,

9.1 0.1 9.4 f 0.5 9.0 f 0.7 9.9 f 0.2 9.9 f 1.1 10.2 f 1.3

The rate data obtained are used to explain why termination reactions involving alkyl radicals become less significant as the alkane becomes more complex.