Pulse radiolysis studies on pure carbon tetrachloride, pure chloroform, and their solutions containing polystyrene and benzene, and on polystyrene in cyclohexane solutions were carried out by using the pico- and nanosecond pulse radiolysis system. First direct observation of geminate processes in non polar liquid systems such as pure carbon tetrachloride and pure chloroform were made. In the radiolysis of pure carbon tetrachloride, it was observed that a transient species at 480 nm in formed by the geminate ion recombination process. In the case of chloroform, two absorption bands were observed at 330 nm and around 550 nm. The 550 nm band has not been clearly identified, but it can be considered that the absorption may be cationic species and the decay is related to the geminate recombination process. Pulse radiolysis of the polystyrene solution in cyclohexane showed the excimer absorption with lifetime of 20 ns. In the pulse radiolysis of polystyrene and benzene solutions in both carbon tetrachloride and chloroform, the charge transfer complex between polystyrene (or benzene) and Cl was observed in both solutions. In the pulse radiolysis of benzene in their solutions, the charge transfer complex between benzene and Cl was observed in both solutions. The lifetime of the charge transfer complexes between polystyrene and Cl is shorter than that of the charge transfer complexes between benzene and Cl, in both solutions. This implies that the disappearance of these species is due to proton transfer process.
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