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Reaction of hydrogen atoms with diethyldisulfide and ethylmethyldisulfide

✍ Scribed by M. M. Ekwenchi; I. Safarik; O. P. Strausz

Publisher
John Wiley and Sons
Year
1981
Tongue
English
Weight
754 KB
Volume
13
Category
Article
ISSN
0538-8066

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✦ Synopsis

H atoms react with CzH5SSC;H5 to give CzH5SH as the sole retrievable product with d~ = 2.32 a t 25Β°C and 2.84 a t 145Β°C. The primary reaction is postulated to be H + CzHsSSCzH5 CzH5SH + CzH5S with k l = (4.73 f 0.64) X exp [-(1710 f 69)/RT] cm3/mol-s relative to the rate constant of the H + CzH4 -CzHs reaction. The high value of the entropy of activation suggests the presence of partial hydrogen bonding in diethyldisulfide which is broken in the transition state. Ethylmethyldisulfide reacts similarly: H + CzH5SSCH3 -C2H5SH + CH3S or CHBSH + CzH5S. The thiyl radicals propagate a chain of radical exchange reactions forming the symmetrical disulfides with exposure-time-dependent quantum yields. The overall kinetics conform to a 16-step mechanism from which the rate constants of the elementary reactions could be established by computer modeling. Thiyl radicals react considerably more slowly with disulfides than H atoms.

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