Ionic Transference Numbers in Cellophane Membranes

The "apparent" cation transference number within cellophane is determined for HCl, KCl, NH(4)Cl, NaCl, and LiCl. The method consists in measuring the E.M.F. in a concentration chain employing Ag:AgCl electrodes or calomel electrodes and calculating from formulas derived for cases of simple, unconstrained diffusion. The transference numbers and the cation mobilities relative to the chloride ion were found to be higher in the cellophane (relative cation mobilities increased about 40 per cent). The effect of the membrane is discussed. It is emphasized that with the introduction of a membrane as a liquid junction new factors are introduced, which are not considered in the formulas ordinarily used. Such factors may be activity changes due to dimensional or other reasons and particularly electrical effects exhibited by the membrane upon the ionic diffusion. Accordingly the transference number, as determined, may lack well defined physical significance.