Charge Transfer Complex Role in the Formation of Chlorobenzene in the γ-Irradiated Carbon Tetrachloride - Benzene System

The formation of carbon tetrachloride-benzene charge transfer complex was confirmed by UV and NMR spectrometric studies. A change in UV spectrum of benzene is observed upon addition of carbon tetrachloride. The appearance of new bands supports the formation of charge transfer complex. NMR study shows that benzene proton chemical shift depends on the CCI4-C6H6 molar ratio. This observation is another criterion for the formation of benzene - carbon tetrachloride charge transfer complex. Job's Continuous Variation method indicates that a 2:1 CCI4-C6H6 charge transfer complex(2:1 CTC) could be formed. The association constants (K2:1) of this 2:1 CTC was found to be 0.0197 M-2 .The maximum concentration of 2:1 CTC was found at about 33% benzene mole percent. The maximum yield of chlorobenzene was obtained, also, upon radiolysis of CCI4-C6H6 samples at 2:1 molar ratio (33% benzene mole percent). Therefore, it could be concluded that 2:1 CTC participates in thc formation of chlorobenzene upon radiolysis of benzene - carbon tetrachloride system.This conclusion was supported by the dependence of the chlorobenzene yield of γ-irradiated 2: 1 carbon tetrachloride - benzene system on irradiation time according to third order kinetic equation with a very good linearity (R2 = 0.9977). Accordingly, the rate constant for the chlorobenzene formation under this condition, was found to be ∼ 5.5 x 10-7 L2 .moI-2.h-1. We propose a radiation chemical mechanism in which the 2: 1 CTC plays a role in the formation of chlorobenzene