Reaction of Br(-) with WF6: Competition between Charge Transfer and Association; Influence of Temperature, Pressure, and Vibrational Energy
Abstract
The rate coefficient for the reaction of Br(-) with WF sub 6 was found to be (6 plus or minus 2) x 10 to the minus 10th cm cubed s to the minus 1st, independent of temperature and pressure over the ranges 243 to 433 K and 0. 2 to 1.2 Torr. The reaction proceeds by two channels: association to form WF sub 6 Br(-) and charge transfer to form WF sub 6(-). The association fraction was found to depend strongly on temperature and pressure, varying from more than 90% association at low temperatures and high pressures to less than 10% association at high temperatures and low pressures. The reaction as studied here is in the falloff regime of association reactions. A steep temperature dependence is observed in the association fraction at high temperatures. This steep temperature dependence is a consequence of WF sub 6 having many low frequency vibrational levels. Vibrational energy is here found to promote charge transfer more efficiently than does kinetic energy.
Document Details
- Document Type
- Technical Report
- Publication Date
- Jan 01, 1991
- Accession Number
- ADA248043
Entities
People
- Albert A Viggiano
- John F. Paulson
Organizations
- Phillips Laboratory