New optical cell design for laser flash photolysis studies in supercritical fluids

A high-pressure optical cell has been designed that achieves an effective separation between the chemical sample and the pressurizing medium and system. This design limits possible sample contamination and catalytic effects under supercritical fluid sample conditions. Laser flash photolysis experiments were carried out on molybdenum hexacarbonyl dissolved in supercritical CO2. The thermal ring closure reaction of the species Mo(CO)5L, where L is 2,2′-bipyridine was found to proceed at rates comparable to those measured previously in liquid benzene or toluene. Much larger activation volumes were found for the reaction in supercritical CO2 than in liquid toluene.