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Absolute rate constants for F + CH 3 CHO and CH 3 CO + O 2 , relative rate study of CH 3 CO + NO, and the product distribution of the F + CH 3 CHO reaction
Author(s) -
Sehested Jens,
Christensen Lene K.,
Nielsen Ole J.,
Wallington Timothy J.
Publication year - 1998
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/(sici)1097-4601(1998)30:12<913::aid-kin6>3.0.co;2-5
Subject(s) - chemistry , radical , radiolysis , reaction rate constant , decomposition , bond cleavage , product distribution , photochemistry , analytical chemistry (journal) , kinetics , organic chemistry , catalysis , physics , quantum mechanics
Using a pulse‐radiolysis transient UV–VIS absorption system, rate constants for the reactions of F atoms with CH 3 CHO (1) and CH 3 CO radicals with O 2 (2) and NO (3) at 295 K and 1000 mbar total pressure of SF 6 was determined to be k 1 =(1.4±0.2)×10 −10 , k 2 =(4.4±0.7)×10 −12 , and k 3 =(2.4±0.7)×10 −11 cm 3 molecule −1 s −1 . By monitoring the formation of CH 3 C(O)O 2 radicals (λ>250nm) and NO 2 (λ=400.5nm) following radiolysis of SF 6 /CH 3 CHO/O 2 and SF 6 /CH 3 CHO/O 2 /NO mixtures, respectively, it was deduced that reaction of F atoms with CH 3 CHO gives (65±9)% CH 3 CO and (35±9)% HC(O)CH 2 radicals. Finally, the data obtained here suggest that decomposition of HC(O)CH 2 O radicals via CC bond scission occurs at a rate of <4.7×10 5 s −1 . © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 913–921, 1998