1980 Volume 53 Issue 8 Pages 2167-2172
The concept of a “moving unit”—a group of molecules which move together for the time much longer than the velocity auto-correlation time, τ—was introduced in order to obtain information about cooperative translational motions of molecules in associated solution. The mutual diffusion coefficient was theoretically expressed in terms of the self diffusion coefficients and the number of moving units. The theoretical results were applied to the study of the mutual diffusion coefficients for methanol–carbon tetrachloride and ethanol–carbon tetrachloride solutions measured by Rayleigh scattering. It was shown that the mean number of alcohol molecules which constitute a moving unit is much smaller than the mean association number of alcohol, especially in the high concentration range of alcohol. This indicates that the hydrogen-bonded polymer of alcohol molecules cannot move without changing the polymer shape within the time τ.
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