Experimental Tests of Free-Volume Tracer Diffusion in Water and Other Solvents

Using forced Rayleigh scattering, the tracer diffusion of methyl red through water and eight other solvents at different temperatures is investigated and the results are compared to the Cohen-Turnbull theory of free-volume diffusion. In seven solvents the effective non-Arrhenius activation energy measured experimentally agrees with the Cohen-Turnbull energy. In water, however, the diffusion can be described mathematically by the free volume model but there is a disagreement of more than an order of magnitude between these energies. We propose that the unique zero point free volume forced onto water by the strong hydrogen bonding requires a different mechanism for tracer motion