TEMPERATURE-DEPENDENCE OF SELF-DIFFUSION IN COMPRESSED MONOHYDRIC ALCOHOLS

The p,T-dependence of the self-diffusion coefficient D for methanol, methan(2H)ol and ethanol has been studied between 150 and 450 K at pressures up to 250 MPa. The experiments were performed in strengthened high-pressure glass cells by the application of the nuclear magnetic resonance (NMR) spin-echo technique with pulsed magnetic-field gradients. Upon cooling, molecular mobility is strongly reduced, leading to a pronounced non-Arrhenius temperature dependence of D. Applying the rough hard-sphere model (Chandler) to our data, a dramatic decrease of the A-parameter with falling temperature is observed. This behavior indicates that attractive intermolecular interactions dominate translational mobility. The best description of the data is given by the empirical Vogel-Tammann-Fulcher (VTF) equation, with ideal glass transition temperatures T0, that are in excellent agreement with those obtained from calorimetric studies. The isotope effect for self-diffusion in methanol and methan(2H)ol increases from ∼5% at high temperatures to about 40% in the supercooled region. This drastic increase is assumed to originate from a difference in hydrogen bond strength of the isotopes, as has already been found for light and heavy water. © 1990 American Institute of Physics.