ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The photolysis of C2H5I in a glassy salt matrix (5M, 7.5M, 10M) of aqueous LiCl at 77 K with light of λ = 254 nm has been conducted, product analysis being by ESR and UV spectroscopy. The electrolytic medium causes the ionization of product HI, and I- concentrations can be continuously determined. During photolysis [I-] is less than the amount of C2H5I decomposed. But after photolysis thaw-freeze cycling is accompanied by progressive growth in [I-] until the yield matches the C2H5I loss, the quantum yields being 0.26, 0.20, and 0.17 for the three LiCl solutions, respectively. The quantum yield of unionized HI is unchanged, however, at around 0.36, the overall change being due to a fall in the extent to which the HI is ionized in the direct photolysis (ø = 0.22, 0.16, and 0.11). It is proposed that this is a consequence of the density increase of matrix packing as the LiCl concentration is increased so that fewer HI are in contact with the aqueous medium and cage recombination is favored.The results establish that the primary reaction is essentially exclusive: and that substantial aggregates of C2H5I exist within which HI are caged and cannot be ionized. The direct reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm C}_{\rm 2}{\rm H}_{\rm 5}{\rm I}+ h\nu \to {\rm C}_{\rm 2}{\rm H}_5^. + {\rm I}^. $$\end{document} occurs only to a trivial extent, ø; = 10-4, C2H5 arising virtually totally via \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm C}_{\rm 2}{\rm H}_{\rm 4}+ {\rm H}^. \to {\rm C}_{\rm 2}{\rm H}_5^. $$\end{document}
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550130604
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