Pulsed laser kinetic studies of liquids under high pressure. Progress report, November 29, 1990--November 25, 1991
A high pressure apparatus constructed for measuring the rates of reactions in liquids under pressures ranging from 1 atm to 2000 atm has been used to measure the complexation kinetics of molybdenum hexacarbonyl reacting with 2,2-bipyridine, 4,4{prime}-dimethyl-2-2{prime}-bipyridine and 4,4{prime}-diphenyl-2-2{prime} bipyridine in toluene. Pentacarbonyl reaction intermediates are created by a 10 nsec flash of frequency tripled Nd:YAG laser light. Measured activation volumes for chelate ligand ring closure indicate a change in mechanism from associative interchange to dissociative interchange as steric hindrance increases. A similar high pressure kinetics study of molybdenum carbonyl complexation by several substituted phenanthrolines is now well advanced that indicates that with the more rigid phenanthroline ligands steric effects from bulky substituents have less effect on the ring closure mechanism than in the case of the bipyridine ligands. An experimental concentration dependence of the fluorescence quantum yield of cresyl violet has been harmonized with previously published contradictory reports. Fluorescence of cresyl violet in various solvents and in micellar systems has also been systematically explored.
- Research Organization:
- Utah Univ., Salt Lake City, UT (United States)
- Sponsoring Organization:
- USDOE, Washington, DC (United States)
- DOE Contract Number:
- FG02-84ER13227
- OSTI ID:
- 10123820
- Report Number(s):
- DOE/ER/13227-T3; ON: DE92008085
- Resource Relation:
- Other Information: PBD: 25 Nov 1991
- Country of Publication:
- United States
- Language:
- English
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