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Absolute rate constants for the reactions of O( 3 P) atoms with DCl and DBr
Author(s) -
Brown Raymond D. H.,
Smith Ian W. M.
Publication year - 1978
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.550100102
Subject(s) - chemistry , reaction rate constant , arrhenius equation , chemiluminescence , molecule , relaxation (psychology) , drift tube , work (physics) , molecular oxygen , oxygen , analytical chemistry (journal) , atomic physics , kinetics , thermodynamics , organic chemistry , activation energy , psychology , social psychology , physics , quantum mechanics , ion
Earlier work on the reactions of O( 3 P) atoms with HCl and HBr has been extended by measuring rate constants forA flow‐tube method was used with chemiluminescent monitoring of the removal of atomic oxygen. Rate constants were measured at temperatures between 340 and 489 K for (2a) and 295 and 419 K for (2b); they can be matched by the Arrhenius expressions:\documentclass{article}\pagestyle{empty}\begin{document}$$ k_{2a} = 3.7(\pm 0.9) \times 10^{- 12} \exp \left({\frac{{- (7.0 \pm 0.5kcal/mole)}}{{RT}}} \right) $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ k_{2b} = 5.8(\pm 0.5) \times 10^{- 12} \exp \left({\frac{{- (3.5 \pm 0.2kcal/mole)}}{{RT}}} \right) $$\end{document}where the units are cm 3 molecule −1 sec −1 and the errors correspond to a single standard deviation. The results of a quasiclassical trajectory study of collisions of O( 3 P) with HCl ( v = 0,1, and 2) and DCl ( v = 0,1, and 2) are also reported. These strengthen the conclusion that, although the rates of reactions (1a) and (2a) are selectively enhanced by vibrationally exciting HCl or DCl, molecules with 0 < v ⩽ 2 are mainly removed in collisions with O( 3 P) atoms by nonreactive relaxation.