The Gas-Phase Radiolysis of Cycloheptatriene

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The γ radiolysis of cycloheptatriene (CHT) in the gas phase has been investigated as a function of the pressure (2–14 mmHg) and in the presence of various additives (NO, O2, NH3, N2O, and C3H8). The G values obtained at 10.5 mmHg and at a total dose of 1.1×1019 eV are as follows: hydrogen, 0.50; methane, 0.16; acetylene, 1.52; cyclopentadiene, 0.29; benzene, 0.65; toluene, 1.68; dimers, 2.99. The yields of toluene and cyclopentadiene decrease with the pressure and are not appreciably affected by these additives; this suggests a contribution of the excited CHT molecules formed by direct excitation to their formation. The formation of dimers and benzene is affected by a radical scavenger (O2, NO), indicating the importance of the radical processes. The reaction products obtained via a C7H7+ ion, which is well known to be produced by the irradiation of CHT, have not been observed, while in the radiolysis of CHT in the presence of benzene and a radical scavenger, biphenylmethane has been produced, presumably by a reaction of the C7H7+ ion with benzene. Therefore, it was assumed that the C7H7+ ion produced from CHT does not contribute to the dimer formation, but may initiate the ionic polymerization.
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