Supercritical fluids (SCF) are highly compressed gases which combine properties of gases and liquids in an intriguing manner. A fluid is supercritical when it is above its critical temperature and critical pressure, where there is no discontinuous transition between the gas and liquid phases as a function of density. A supercritical fluid behaves like a gas in that it will expand to fill the confines of a container but forms solutions and has solvent power of a liquid. Supercritical fluids exhibit valuable thermodynamic and transport properties that make them particularly useful for chromatography and for a variety of extraction processes. Recently these fluids have been considered as interesting alternatives to organic solvents for the study of chemical reactions. Some properties show why SCF have solvent power similar to liquids, but better mass transfer characteristics: Density, gas 1; SCF 700; liquid 1000 kg/m3. Viscosity, gas 10-5; SCF 10-4; liquid 10-3 N s/m3. Diffusion coefficient, gas 10-1; SCF 10-4; liquid 10-5 cm2/s. A unique feature of fluids in the supercritical regime is their extreme compressibility. Densities ranging all the way from that of a dilute gas to that of a dense liquid can be achieved through modest changes in applied pressure. Since many properties of a fluid vary directly with its density, SCFs provide a convenient continuously tuneable solvent medium for many chemical processes.
Environmentally benign separation and reactions processes are emerging to utilize the unique properties of SCF. Supercritical CO2 is, next to water, the cheapest and more ecological solvent available to man. So, carbon dioxide is the supercritical fluid of choice because it is natural, non-toxic, and cheap, having often good selectivity and capacity. Supercritical CO2 is used to extract caffeine from green coffee beans to make decaffeinated coffee or to extract flavour compounds for use in the food, pharmaceutical and cosmetic applications. A better use of supercritical CO2 requires an in-depth characterisation of its properties over a wide range of temperatures and pressures, followed by reactivity studies. The supercritical cell built in our laboratory is used with absorption (NIR/VIS/UV), fluorescence, flash photolysis and single photon counting equipment. Our present work focus on photoinduced reactions in supercritical fluids, namely excited-state proton-transfers and photoinduced electron transfers. Some of the species involved in these reactions are also good probes of solvent properties and may contribute to the characterisation of supercritical media. We study the unusual photophysics behaviour of some substances at high pressure. The specific use of photophysic characteristics of molecules for probing the macro and micromolecular behaviour of SCF is also studied.