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8547239 
Journal Article 
Effect of high pressure on the distribution of isomers in the radical chain chlorination of several saturated hydrocarbons by chlorine 
Zhulin, VM; Rubinshtein, BI 
1976 
1 
Bulletin of the Academy of Sciences of the USSR. Division of Chemical Science
ISSN: 0568-5230 
Kluwer Academic Publishers-Plenum Publishers 
25 
2 
333-336 
English 
1. In the radical chain chlorination of n-pentane and n-hexane by chlorine at 40°, the ratio between the sec-alkyl chloride and n-alkyl chloride isomers increases with increasing pressure. The difference between the activation volumes for the splitting off of hydrogen atoms by the Cl radical from the secondary and primary carbon atoms is -0.7 cm3/mole. 2. The ratio of sec-hexyl chloride to n-hexyl chloride increases with increasing pressure more strongly, the higher is the concentration of the complexing solvent (tert-butylbenzene). 3. The polar (induction) effect displayed in the chlorination of 1-chlorobutane, while altering the values of the determined rate constants for the splitting off of the hydrogen atoms, does not appear to have an appreciable effect on the activation volumes of the respective reactions. © 1976 Plenum Publishing Corporation.