Abstract
The rate constants for scavenging of the mobile positive ion in trans-decalin have been measured using the time-resolved microwave conductivity (TRMC) pulse radiolysis technique for a series of olefins and cyclopropane. For the olefins the values vary from ⩽2x10 8dm 3/mol/s for ethylene to 1.6x10 11dm 3/mol/s for cyclohexene. Steady-state γ radiolysis of solutions of isobutene in trans-decalin results in the formation of isobutane and C 8 and C 14 products which display different dependences on solute concentration. The results are explained in terms of the formation of a complex between the solvent radical cation and isobutene which can dissociate, within a timescale of approx. 1 ns, to give isobutane or on neutralisation leads to the formation of C 14 condensation products. The C 8 products which are formed above 5 x 10 -2mol/dm 3 are attributed to reaction of the complex with isobutene to form the olefin dimer cation. Cyclopropane is unreactive, i.e. k<10 8dm 3/mol/s, towards the mobile positive ion in trans-decalin.
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Schedule a callMore From: International Journal of Radiation Applications & Instrumentation. Part C, Radiation Physics & Chemistry
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