Abstract
The self-diffusion coefficient D of liquid water was measured at temperatures between +30 and −25°C by means of a novel technique involving tritium as a tracer. At temperatures warmer than 0°C the present results agree well with the results of the most recent measurements of Wang who used 18O as a tracer. At temperatures below 0°C the present measurements for D are the only ones available. Using the present values for D and the most accurate values available in literature for the viscosity η and the dielectric relaxation time τ the quantities Dη/T, Dτ, and τ(η/T)−1 were found to be constants between +30 and −20°C. Based on this result values for D, η, and τ for temperatures between +40 and −40°C were computed. Interpretation of the present data in terms of Eyring's transition state theory of rate processes revealed that for liquid water self-diffusion, dielectric relaxation, and viscous flow involve at temperatures between +40 and −40°C the same activation mechanism with an activation energy that is strongly temperature dependent. It is further shown that the constancy of the quantities Dη/T, Dτ, and τ(η/T)−1 allow computing Eyring's structural parameters λ, λ1, λ2, and λ3.
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