The photolysis of ethyl sulfide vapor at 2537 r\ has been investigated as a function of substrate and CF4 pressure, time, and temperature. Reaction products with quantum yields in parentheses are ethyl disulfide (0.178), ethane (0.138). butane (0.086), ethanethiol (0.096), 4-methyl-3-thiahexane (0.034) and 4-methyl-3.5-dithiaheptane.Ethyl and ethylthiyl radicals are formed in the primary process and the product yields indicate a net primary decomposition quantum yield of 0.48. A reaction mechanism involving subsequent reactions of the primary fragments is proposed and explains the observed products and the observed variation in rates. Excited radicals and hot radical combination products play a minor role in this system, in contrast to the behavior of lower molecular weight sulfides. Secondary photolysis of the disulfide produced and consumption of ethanethiol are important factors in determining the time dependence of reaction rates in this system. La photolyse de la vapeur de sulfure d'ethyle a 2537 r\ a ete etudiee en fonction de la nature du substrat et de la pression de CF4 ainsi que du temps et de la temperature. Les produits de la reaction, dont les rendements quantiques sont donnes entre parentheses. sont les suivants, disulfure d'ethyle (0.178) ethane (0.138). butane (0.086) ethanethiol (0.096), methyl-4 thia-3 hexane (0.034), et methyl-4 dithia-3,5 heptane.Les radicaux ethyle et ethylthiyle sont formes dans la premiere phase et les rendements de produits indiquent fort nettement un rendement quantique de la decomposition primaire egal a 0.48. Un mecanisme reactionnel impliquant des reactions subsequentes des fragments primaires est propose: celui-ci permet d'ailleurs d'expliquer la formation des produits observes ainsi que les fluctuations observees dans les vitesses deformation. Les radicaux excites et les produits de combinaison de radicaux chauds jouent, en realite. un r61e negligeable dans ce systeme. ce qui va a I'encontre du compoi-tement des sulfures ayant des poids moleculaires plus bas. La photolyse secondaire du compose disulfure obtenue ainsi que la consommation d'ethanethiol sont des facteurs importants pour determiner dans ce systtme la dependance existagt entre le temps et les vitesses de la reaction.[Traduit par le journal]
CONRAD S. SMITEI and ARTHUR R. KNIGHT. Can. J. Chem. 54, 1290 (1976. The triplet mercury photosensitized decomposition of ethyl sulfide vapour has been studied at 25 "C. The reaction products include C2H4 (90 = 0.075), C2H6 (90 = 0.013), C4HI0 (90 = 0.011), C,H5SH ( @ = 0.068), 4-methyl-3-thiahexane ( @ = 0.01 l), and C2H5SSC,H5 (90 = 0.175). The overall decomposition q~~a n t u m yield is 0.38 at high sulfide pressures. The initial decomposition gives principally ethyl radicals and ethylthiyl radicals; a second step which yields ethylene and ethanethiol may account for up to 20' ;;; of the primary process. Comparison of the direct and sensitized decompositions indicates that both likely originate in the triplet manifold of ethyl sulfide.Primary decomposition quantum yields have been accurately redetermined for the direct. [Traduit par le journal]
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