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Rate constants for the reactions of Cl atoms with HCOOH and with HOCO radicals
Author(s) -
Li Qiang,
Osborne Michael C.,
Smith Ian W. M.
Publication year - 2000
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(2000)32:2<85::aid-kin3>3.0.co;2-i
Subject(s) - chemistry , reaction rate constant , flash photolysis , radical , formic acid , photochemistry , molecule , photodissociation , kinetics , organic chemistry , physics , quantum mechanics
Rate constants have been measured at room temperature for the reactions of Cl atoms with formic acid and with the HOCO radical: R1 Cl + HCOOH → HCl + HOCO R2 Cl + HOCO → HCl + CO 2 Cl atoms were generated by flash photolysis of Cl 2 and the progress of reaction was followed by time‐resolved infrared absorption measurements using tunable diode lasers on the CO 2 that was formed either in the pair of reactions ( R1) plus ( R2), or in reaction ( R1) followed by R3 O 2 + HOCO → HO 2 + CO 2 In a separate series of experiments, conditions were chosen so that the kinetics of CO 2 formation were dominated either by the rate of reaction ( R1) or by that of reactions ( R1) and ( R2) combined. The results of our analysis of these experiments yielded: k 1 = (1.8 3 ± 0.12) × 10 −13 cm 3 molecule −1 s −1k 2 = (4.8 ± 1.0) × 10 −11 cm 3 molecule −1 s −1 © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 85–91, 2000