Pulsed laser kinetic studies of liquids under high pressure

Technical Report · Mon Jun 21 04:00:00 EDT 1993

DOI:https://doi.org/10.2172/6347274· OSTI ID:6347274

Eyring, E M

Experiments have been developed for measuring the rates of chemical reactions liquids and in supercritical Co[sub 2]. A pulsed (Q-switch) Nd:YAG laser at 355 nm was the pump beam for laser flash photolysis studies of molybdenum and tungsten hexacarbonyls undergoing ligand displacement reactions by bidentate chelating agents such as 2,2[prime]-bipyridine in toluene. Experiments were carried out at 0.1 to 150 MPa. In the case of molybdenum complexes, the reaction mechanism for thermal ring closure is found from activation volumes to change from associative interchange to dissociative interchange as substituents on the 2,2[prime]-bipyridine ligands become bulkier. In a similar study of more rigid, substituted phenanthroline bidentate ligands it was found that substituent bulkiness had little effect on the thermal ring closure mechanism. Similar high pressure flash photolysis experiments with tungsten hexacarbonyl have also been completed. The concentration dependence of the fluorescence and nonradiative decay quantum yields for cresyl violet in several solvent have been reported as well as stability constants for the complexation of lithium ion by four different crown ethers dissolved in a room temperature molten salt.

• Research Organization: Utah Univ., Salt Lake City, UT (United States)
• Sponsoring Organization: DOE; USDOE, Washington, DC (United States)
• DOE Contract Number: FG02-84ER13227
• OSTI ID: 6347274
• Report Number(s): DOE/ER/13227-7; ON: DE93017826
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400500 -- Photochemistry
AZINES
BIPYRIDINES
CARBONYLS
CHELATING AGENTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPLEXES
DECOMPOSITION
DOCUMENT TYPES
ELECTROMAGNETIC RADIATION
HETEROCYCLIC COMPOUNDS
HIGH PRESSURE
KINETICS
LASER RADIATION
LIGANDS
MOLYBDENUM COMPLEXES
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
PROGRESS REPORT
PYRIDINES
RADIATIONS
REACTION KINETICS
TRANSITION ELEMENT COMPLEXES
TUNGSTEN COMPLEXES
VERY HIGH PRESSURE