THE GAS PHASE ASSOCIATION OF LEWIS ACIDS AND BASES. II. N(CH3)3 AND NH(CH3)2 IN COMPETITION FOR BF3,
Abstract
A detailed analysis is presented of the rate laws expected for Lewis acid-base gas phase association reactions at pressures above several mm Hg. It is shown that in a competive system (B2 and B3 competing for A) the ratio of association rate constants, k3/k2, is given by (AB3/AB2)(B2/B3), irrespective of the relative efficiencies for stabilization of the vibrationally excited AB3 and AB2 by internal energy conversion vs energy transfer to the ambient gas. However, if the latter process were to dominate, the measured (k3/k2) would depend on the nature of the ambient gas. An experimental procedure was developed for measuring the relative amounts of salt produced in a competitive system, based on IR analyses of acetonitrile solutions of the mixed salts. This procedure is particularly applicable to systems in which the residual gases are preferentially absorbed in the solids produced. Data on the (CH3)3N - (CH3)2HN BF3 system are presented. The results show that at room temperature the ratio of association rate constants, k3/k2 = 0.89 = 0.17, over the range 3 to 43 mm Hg total pressure. This ratio rose slightly (to 0.95) at about 0.6 mm Hg, the lowest pressure studied. (Author)
Document Details
- Document Type
- Technical Report
- Publication Date
- Jan 01, 1943
- Accession Number
- AD0419893
Entities
People
- Dennis Price
- S. H. Bauer
Organizations
- Cornell University