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SOLUTE-SOLVENT INTERACTIONS IN THE RADIOLYSIS OF ALKYL HALIDE-PENTANE SOLUTIONS

Journal Article · · Journal of the American Chemical Society (U.S.)
DOI:https://doi.org/10.1021/ja00883a003· OSTI ID:4761022

BS>The G values for production of methyl, ethyl, propyl, and pentyl radicals by the radiolysis of 0.25 mole% solutions of iodine in pentane are reduced by the presence of methyl iodide, ethyl iodide, or normal propyl bromide at concentrations in the range of 1%, except for the radical representing the hydrocarbon fragment of the alkyl halide. The latter is produced with high yield. The total G (radicals) is increased from 8.2to about 11.8 by the halide additives. The presence of normal propyl chloride does not produce these effects. Studies of the fate of C/sup 13/H/sub 3/ radicals produced in the radiolysis of C/sup 14/ H/sub 3/I solutions in pentane and of the fate of I/sup 131/ from similar C/sub 2/ H/sub 5/I/sup 131/ solutions were used t o examine further the solute- solvent interactions during radiolysis. The evidence indicates that the reaction RI + e/ sup -/ yields R + I/sup -/ must play a significant role in such systems and supponts the conclusion that neutralization of RH/sup +/ ions by negative ions is less apt to lead to radical production than neutralization by electrons. Electron capture and any other indirect processes which may lead to C/sup 14/H/ sub 3/ production during radiolysis of solution of C/sup 14/H/sub 3/I in pentane increase in yield with increasing concentration below about 0.8 mole% and remain constant at higher concentrations, indicating that all available electrons and other radical producing species react with the halide at this concentration. Iodine production occurs during the radiolysis of ethyl iodide pentane solutions in which only 10% of the energy is absorbed by the ethyl iodide. Tns reflects solute-solvent interactions since G (radicals) in the radiolysis of pentane is 8.2 while G(1/2I/sub 2/) in the radiolysis of C/sub 2/H/sub 5/I is 4. (auth)

Research Organization:
Univ. of Wisconsin, Madison
Sponsoring Organization:
USDOE
NSA Number:
NSA-17-012333
OSTI ID:
4761022
Report Number(s):
TID-16276; 0002-7863
Journal Information:
Journal of the American Chemical Society (U.S.), Journal Name: Journal of the American Chemical Society (U.S.) Vol. Vol: 84; ISSN JACSA
Country of Publication:
Country unknown/Code not available
Language:
English

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