Tracer method membrane transport

Zelsmann and co-workers [88] have reported tracer diffusion coefficients for water in Nafion membranes exposed to water vapor of controlled activity. These were determined by various techniques, including isotopic exchange across the membrane. They reported apparent self-diffiision coefficients of water much lower than those determined by Zawodzinski et al. [64], with a weaker dependence on water content, varying from 0.5 x 10 cm to 3 x 10 cm /s as the relative humidity is varied from 20 to 100%. It is likely that a different measurement method generates these large differences. In the experiments of Zelsmaim et al., water must permeate into and through the membrane from vapor phase on one side to vapor phase on the other. Since the membrane surface in contact with water vapor is extremely hydrophobic (see Table 7), there is apparently a surface barrier to water uptake from the vapor which dominates the overall rate of water transport in this type of experiment. 

A laboratory membrane brine electrolysis cell, designed for automated operation, was constructed ( 1,2). This system enables the measurement of the sodium ion transport number of a membrane under specific sets of conditions using a radiotracer method. In such an experiment, the sodium chloride anolyte solution is doped with 22Na radio-tracer, a timed electrolysis is performed, and the fraction of current carried by sodium ion through the membrane is determined by the amount of radioactivity that has transferred to the sodium hydroxide catholyte solution. The voltage drop across the membrane during electrolysis is simultaneously measured, so that the overall performance of the material can be evaluated. 

A simple classification of the main macroscopic techniques is shown in Table 1, and this provides a useful framework for our review. Macroscopic measurements generally yield transport diffusivities, although variants of the techniques, using isotopically tagged tracers, can be devised to measure self-diffusivities. The large majority of the macroscopic techniques involve transient measurements. Steady-state or quasi-steady-state methods, notably membrane permeation and catalyst effectiveness measurements, have been demonstrated, but their application has been limited to a few systems. 

Of course, there are more bulk properties of interest than the above parameters related to transport of the fast ions and electrons. Metal cation transport is minor, but still a most crucial parameter, because it eventually leads to membrane walkout, demixing, or decomposition in chemical gradients. Methods used for investigating metal cation diffusion comprise reactivity studies, interdiffusion couples, and tracer studies, using analytical SEM, EPMA, SIMS or radioactivity for the diffusion profile analyses. 

The electrical methods for measuring properties of ion transport through membranes are very attractive in comparison with tracer fluxes methods because of their accuracy and rapidity. 

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