Free Radical Motion in Super Critical Fluids Probed by EPR Spectroscopy

EPR spectra of the nitroxide radical 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) are reported in super critical and in liquid n -hexane and ethanol for 25−200 bar and 295−600 K. At low radical concentration (<10 -5 M) the line width is controlled by the spin-rotation interaction and is quantitatively predicted by liquid-phase theory for solvent densities ρ greater than the critical density ρ c . Deviations at lower densities are assigned to clustering effects and the crossover to gas-phase behavior. Rate constants for Heisenberg spin exchange ([TEMPO] > 10 -3 M) up to 580 K are also reported. They again follow liquid-phase theory for ρ > ρ c . Deviations at low densities may be explained by a gas-phase behavior without clustering effects.