Temperature and Phase Effection the Photolysis of Ethyl Iodide

BY RAY H. LUEBBE, JR., AND JOHN E. WILLARD. RECEIVED JULY 28, 1958. The photolysis of ethyl iodide by 2537 A. light has been studied in the liquid at ...
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JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (Registered in U. S. Patent Office)

(0Copyright, 1959, by the American Chemical Society) NUMBER 4

MARCH 2, 1959

VOLUME81

PHYSICAL AND INORGANIC CHEMISTRY [CONTRIBUTION FROM THE

DEPARTMENT OF CHEMISTRY

O F THE UNIVERSITY O F WISCONSIN]

Temperature and Phase Effects on the Photolysis of Ethyl Iodide B Y RAYH. LUEBBE,JR.,

AND JOHN

E. W I L L A R D

RECEIVED JULY 28, 1958 The photolysis of ethyl iodide by 2537 A. light has been studied in the liquid a t 25' and -70' and in the glass a t - 180". The quantum yields for elementary processes in the reaction mechanism have been deduced to be as follows: (a) for the thermal ethyl radicals which escape caging or diffusive recombination with the parent partner, 0.32 a t 25O, 0.08 a t -70" and (by extrapolation) 5 X lod4 a t - 180"; (b) for production of iodine by processes independent of caging effects (probably C2H6 CzHjI + CzHg C2H4 I ) ca. 0.038; (c) for production of H I by C2H61+ C2H. HI, or other hot process, 0.17 a t 25', 0.18 a t -70" and 0.22 a t -180'. The results are in agreement with earlier work by Bunbury, Williams and Hamill on the photolysis of ethyl iodide in showing a competition between H I and 1 2 for thermal ethyl radicals but indicate that about 18% (rather than