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

Abstract

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.