ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Hydrogen, cycloalkene, and bicycloalkyl were found to be the principal products which account for ≍97% of all products formed in the gas-phase radiolysis of water vapor containing low concentrations of cycloalkanes. From the ratios of cycloalkene-to-bicycloalkyl yields extrapolated to the zero dose, the self- and cross-disproportionation-to-recombination rate constant ratios Δ = kd/kc were determined for the following 12 reactions: Δ(c-C5H9, c-C5H9) = 0.73; Δ(c-C5D9, c-C5D9) = 0.58; Δ(c-C6H11, cC6H11) = 0.59; Δ(c-C6D11, c-C6D11) = 0.46; Δ(c-C5H9, c-C6H11) = 0.28; Δ(c-C5D9, c-C6H11) = 0.28; Δ(c-C5H9, c-C6D11) = 0.24; Δ(c-C5D9, c-C6D11) = 0.24; Δ(c-C6H11, c-C5H9) = 0.33; Δ(c-C6H11, c-C5D9) = 0.25; Δ(c-C6D11, c-C5H9) = 0.35; and Δ(c-C6D11, c-C5D9) = 0.28, where in the case of the cross-disproportionation the symbol Δ(R1,R2) is used to represent kd/kc for the disproportionation in which radical R1 captures a hydrogen (deuterium) atom from radial R2. The geometrical mean rule holds in the cross-combination reactions of cyclopentyl and cyclohexyl radicals. The kinetic isotope effect in the disproportionation reaction was determined as 1.24 ± 0.06.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550141002
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