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Time‐resolved vibrational chemiluminescence: Rate constants for the reactions of F atoms with H 2 O and HCN, and for the relaxation of HF (v = 1) by H 2 O and HCN
Author(s) -
Frost Robert J.,
Green David S.,
Osborn Martin K.,
Smith Ian W. M.
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.550180808
Subject(s) - chemistry , reaction rate constant , chemiluminescence , relaxation (psychology) , photodissociation , excimer , excimer laser , vibrational energy relaxation , rate equation , analytical chemistry (journal) , laser , atomic physics , kinetics , photochemistry , molecule , optics , psychology , social psychology , physics , organic chemistry , quantum mechanics , chromatography
Rate constants have been determined at (298 ± 4) K for the reactions:and the relaxation processes:Time‐resolved HF(1,0) emission was observed following the photolysis of F 2 with pulses from an excimer laser operating on XeCl (λ = 308 nm). Analysis of the emission traces gave first‐order constants for reaction and relaxation, and their dependence on [H 2 O] and [HCN] yielded:\documentclass{article}\pagestyle{empty}\begin{document}$$ k_{1{\rm a}} = (1.3 \pm 0.1) \times 10^{ - 11} {\rm cm}^{\rm 3} {\rm molecule}^{{\rm - 1}} s^{ - 1} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ k_{1{\rm b}} = (1.3 \pm 0.1) \times 10^{ - 10} {\rm cm}^{\rm 3} {\rm molecule}^{{\rm - 1}} s^{ - 1} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ k_{2{\rm a}} = (3.7 \pm 0.4) \times 10^{ - 13} {\rm cm}^{\rm 3} {\rm molecule}^{{\rm - 1}} s^{ - 1} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ k_{2{\rm b}} = (3.4 \pm 0.2) \times 10^{ - 12} {\rm cm}^{\rm 3} {\rm molecule}^{{\rm - 1}} s^{ - 1} $$\end{document}