ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Shepp's rotating sector theory for determining radical recombination rate constants, kb, has been modified to take account of radical production by a concurrent thermal reaction. A theoretical sector curve expression has been derived which gives the average radical concentration under intermittent illumination as a function of α, the ratio of first-to second-order radical removal rates, n, the ratio of thermal initiation to photoinitiation, and β, the ratio of the flash time to the half time of second-order radical removal. Analysis of the sector curves generated by the modified theory shows that n has a greater effect on kb than α and that the rotating sector method should be applied only to those photochemical systems in which termination by first-order processes is less than 34% (α = 0.52) and thermal initiation is less than 2% (n = 0.02).
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550050317
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