The pressure dependence of diffusion coefficients of naphthalene in supercritical C02 and naphthalene-¿8 in supercritical ethylene has been measured by using the NMR fixed field gradient spin-echo Bessel function analysis technique. The pressure dependence of the reorientational motion of naphthalene-if8 in C02 and ethylene has been studied by measuring the deuteron spin-lattice relaxation time, 7), as a function of pressure at several isotherms. The temperatures were chosen to cover two regions of the naphthalene-supercritical solvent phase diagram. The experimental data allowed the molecular level test of the applicability of the Stokes-Einstein and Debye equations in the binary systems studied. The expression D(ij/7')0,75 = constant represents the experimental diffusion data well, and the modified Debye equation describes the reorientational motion of naphthalene in supercritical C02 and ethylene solvents.

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Natural abundance carbon-13 spin-lattice relaxation times and 13G-'H nuclear Overhauser enhancement (NOE) times of 2-ethyl hexylbenzoate (EHB) and 2-ethyl hexylcyclohexanecarboxylate (EHC) have been measured along isotherms of-20,0,20,4.0, and 80 "C at pressures of l-5000 bars using high-pressure, high-resolution NMR techniques. The ability to use pressure as an experimental variable has allowed us to study a wide range of molecular motions from extreme narrowing into the slow motional regime. In addition, the high-resolution capability even at high pressure permits the measurement of 13C and NOE for each individual carbon in the molecules studied. Relaxation in both molecules is successfully analyzed in terms of a model assuming a Cole-Davidson distribution of correlation times. The comparison of parameters used in the model demonstrates the increased flexibility of the EHC ring over the EHB ring and also shows how the presence of the flexible ring contributes to the increased overall mobility of the EHC molecule. The analysis of molecular reorientations in terms of activation volumes also indicates that EHB motion is highly restricted at low temperature.

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