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Absolute rate constants for the reactions of O(3P) atoms with DCl and DBr

✍ Scribed by Raymond D. H. Brown; Ian W. M. Smith

Publisher: John Wiley and Sons
Year: 1978
Tongue: English
Weight: 680 KB
Volume: 10
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550100102

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✦ Synopsis

Abstract

Earlier work on the reactions of O(^3^P) atoms with HCl and HBr has been extended by measuring rate constants for
equation image

A 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:

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.

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