✦ LIBER ✦

Thermochemistry and kinetics of the reaction of methyl mercaptan with iodine

✍ Scribed by Lilian G. S. Shum; Sidney W. Benson

Publisher: John Wiley and Sons
Year: 1983
Tongue: English
Weight: 904 KB
Volume: 15
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550150504

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✦ Synopsis

The gas-phase reaction CH3SH + IZ has been studied spectrophotometrically over the temperature range of 476-604 K. It was found that the reaction undergoes H abstraction by I at 5575 K, leading to the formation of MeSI and followed by a secondary reaction which leads to the formation of MeSSMe:

Taking into consideration the effect of reaction (2), the equilibrium constant Kl(554 K) has been evaluated to be 0.025 f 0.004. This value was combined with the estimated values Sg8 (CHBSI, g) = 73.7 f 1.0 eu and (AC0,1,554) = 0.87 f 0.3 eu to obtain AH~,zss = 4.03 f 0.73 kcal/mol. This yields AHym (CH3S1, g) = 7.16 f 0.73 kcal/mol when combined with known thermochemical values for CHBH, HI, and 12. A kinetic study was vitiated by the concurrent heterogeneous reaction of MeSH and 12 at lower temperatures and the rather complicated chemistry occurring at elevated temperatures. However, attempts at measuring rate constants at 554 K lead to a lower limit of (CHsS., g) t 29.5 f 2 kcaVmol when an estimated value of A = 1010.8*0.z L/mol.s for the reaction I t CH3SH S? CH3S t HI is used. D H L (CH3S-I) is estimated to be 49.3 f 1.7 kcal/mol. The bond strengths of some divalent sulfurs and the reaction mechanisms are discussed. A crude estimate of DHO(H-CH2SH) = 96 f 1 kcal has been obtained from the kinetic data.

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