Abstract
The chromatographic peak-broadening (Taylor dispersion) method is used to measure the diffusion of trace amounts of dissolved ions in solutions of supporting electrolytes. A small volume of solution containing both the tracer ion and the supporting electrolyte is injected into a laminar stream of the supporting electrolyte confined within a long capillary tube. The dispersion of the injected solute is monitored downstream by differential refractometry using a liquid chromatography detector. Provided a correction is made for the coupled flow of the supporting electrolyte accompanying the tracer ion, the tracer diffusion coefficient can be evaluated from the shape of the eluted solute peak. The proposed method is tested by measuring the tracer diffusion of Ca 2+ ions in aqueous NaCl solutions, for which accurate diaphragm-cell data exist. Tracer diffusion coefficients are also reported for Cd 2+, Co 2+, Cu 2+, Ni 2+ and Zn 2+ ions in 0.1–1.0 M aqueous Na 2SO 4 solutions at 25°C.
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