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Kinetics of the gas phase reaction of OH radicals with pyrrole and thiophene
Author(s) -
Wallington Timothy J.
Publication year - 1986
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.550180407
Subject(s) - chemistry , thiophene , arrhenius equation , radical , reaction rate constant , diluent , pyrrole , flash photolysis , torr , atmospheric temperature range , photochemistry , analytical chemistry (journal) , photodissociation , kinetics , activation energy , organic chemistry , thermodynamics , physics , quantum mechanics
Abstract Absolute rate constants for the gas phase reaction of OH radicals with pyrrole ( k 1 ) and thiophene ( k 2 ) have been measured over the temperature ranges 298–440 and 274–382 K, respectively, using the flash photolysis‐resonance fluorescence technique. The rate constants obtained were independent of the total pressure of argon diluent over the range 25–100 torr andwere fit by the Arrhenius expressions\documentclass{article}\pagestyle{empty}\begin{document}$$ k_1 = (2.7 \pm _{0.6} ^{0.8}) \times 10^{ - 11} \exp [(403 \pm 93)/T]{\rm cm}^{\rm 3} {\rm molecule}^{{\rm - 1}} {\rm s}^{{\rm - 1}} $$\end{document}and\documentclass{article}\pagestyle{empty}\begin{document}$$ k_2 = (1.2_{ - 0.6} ^{ + 1.0}) \times 10^{ - 12} \exp [(584 \pm 217)/]{\rm cm}^{\rm 3} {\rm molecule}^{{\rm - 1}} {\rm s}^{{\rm - 1}} $$\end{document}with rate constants at 298 ± 2 K of k 1 = (1.03 ± 0.06) × 10 −10 cm 3 molecule −1 s −1 and k 2 = (8.9 ± 0.7) × 10 −12 cm 3 molecule −1 s −1 . [These errors represent two standard deviations (systematic errors could constitute an additional ca. 10% uncertainty)]. These results are discussed with respect to the previous literature data and the atmospheric lifetimes of pyrrole and thiophene.