ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The reactions of ground-state oxygen atoms with carbonothioicdichloride, carbonothioicdifluoride, and tetrafluoro-1,3-dithietane have been studied in a crossed molecular jet reactor in order to determine the initial reaction products and in a fast-flow reactor in order to determine their overall rate constants at temperatures between 250 and 500 K. These rate constants arek(O + C2CS) =(3.09 ± 0.54) × 10-11 exp(+115 ± 106 cal/mol/RT),k(O + F2CS) = (1.22 ± 0.19) × 10-11 exp(-747 ± 95 cal/mol/RT), andk(O + F4C2S2) = (2.36 ± 0.52) × 10-11 exp(-1700 ± 128 cal/mol/RT) cm3/molec·sec. The detected reaction products and their rate constants indicate that the primary reaction mechanism is the electrophilic addition of the oxygen atom to the sulfur atom contained in the reactant molecule to form an energy-rich adduct which then decomposes by C-S bond cleavage.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550110502
