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Study of the reactions of oxygen atoms with carbonothioicdichloride, carbonothioicdifluoride, and tetrafluoro‐1,3‐dithietane
Author(s) -
Slagle Irene R.,
Gutman David
Publication year - 1979
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550110502
Subject(s) - chemistry , reaction rate constant , adduct , electrophile , oxygen , bond cleavage , sulfur , oxygen atom , electrophilic addition , molecule , medicinal chemistry , kinetics , organic chemistry , catalysis , physics , quantum mechanics
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 are(O + C 2 CS) =(3.09 ± 0.54) × 10 −11 exp(+115 ± 106 cal/mol/ RT ),(O + F 2 CS) = (1.22 ± 0.19) × 10 −11 exp(‐747 ± 95 cal/mol/ RT ), and(O + F 4 C 2 S 2 ) = (2.36 ± 0.52) × 10 −11 exp(‐1700 ± 128 cal/mol/ RT ) cm 3 /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.