Pulsed laser kinetic studies of liquids under high pressure

Technical Report · Mon Nov 25 00:00:00 EST 1991

DOI:https://doi.org/10.2172/5873343· OSTI ID:5873343

Eyring, E M

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; USDOE, Washington, DC (United States)
• DOE Contract Number: FG02-84ER13227
• OSTI ID: 5873343
• Report Number(s): DOE/ER/13227-T3; ON: DE92008085
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CHEMICAL REACTION KINETICS
PRESSURE EFFECTS
BIPYRIDINES
CARBONYLS
FLUORESCENCE
MOLYBDENUM COMPLEXES
NEODYMIUM LASERS
PROGRESS REPORT
PULSED IRRADIATION
AZINES
COMPLEXES
DOCUMENT TYPES
HETEROCYCLIC COMPOUNDS
IRRADIATION
KINETICS
LASERS
LUMINESCENCE
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PYRIDINES
REACTION KINETICS
SOLID STATE LASERS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties