Abstract
We present a method to monitor continuously the electrical conductivity of the solutions in both compartments of a diaphragm cell in which diffusion is occurring. This allows a much smaller initial concentration difference to be applied across the diaphragm rather than the usual larger initial concentration difference. Together with an improved filling procedure and a more reproducible stirring device, these improvements lead to the determination of differential diffusion coefficients with accuracies comparable to those of the precise optical interferometric methods. This is shown for aqueous solutions of NaCl, KC1, Na2SO4, and MgSO4 at 25 °C. By using aqueous solutions of HC1, the H+-exchange properties of the diaphragm and its influence on the measurements become detectable.
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