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A study of the reactions of NO3 radicals with organic sulfides: Reactivity trend at 298 K

โœ Scribed by E. P. Daykin; P. H. Wine

Book ID
102926702
Publisher
John Wiley and Sons
Year
1990
Tongue
English
Weight
722 KB
Volume
22
Category
Article
ISSN
0538-8066

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โœฆ Synopsis

A laser flash photolysis-long path laser absorption technique has been employed to investigate the kinetics of NO3 reactions with CH3SCH3(kl), CDsSCD3(kz), and CzH5SCzHS(k3) in 500 torr air at 298 K. The dependence of k l on total pressure (20-500 torr) and oxygen partial pressure (0-100 torr) has also been investigated, with no dependence observed. Measured rate coefficients in units of cm3 molecule-' s-' are kl = 13 2 3, k p = 3.4 2 0.8, and k3 = 48 2 12, where the quoted uncertainties are %estimates of absolute accuracy. The magnitude of NO3 + sulfide rate coefficients and negative activation energies for k l (reported by other investigators) suggest that reaction does not proceed via a direct hydrogen abstraction mechanism. However, the reactivity trend observed in this study provides evidence that the reaction mechanism does involve breaking a carbon-hydrogen bond.

(W)

NO3 + CH3SCH3 -HN03 + CH3SCH2 AH = -5.2 kcal mol-' * NO2 + CHBS(0)CHB ( U C ) )

adduct + product -36.6 kcal mo1-I

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