A study of the behavior of the dried collodion membrane toward the bivalent calcium ion showed that:

1. There is almost no potential difference established across a membrane separating two calcium chloride solutions of 0.1 and 0.01 N concentrations.

2. The transfer numbers of chlorine and calcium, as measured in electrical transfer experiments, are both close to 0.5.

3. A sample of membrane in equilibrium with a solution of calcium chloride has an extremely high electrical resistance, greater than is observed with solutions of the chlorides of any of the monovalent cations.

4. The total electrolyte content of a membrane in equilibrium with a solution of calcium chloride was only 20 per cent of that observed when the solution was lithium chloride and 10 per cent of that found when the solution was potassium chloride.

In explaining these various results it is supposed that (1), (2) and (3) are all the result of (4), that is, of the inability of the calcium ion to penetrate any but the largest of the membrane pores. As the total quantity of electrolyte able to penetrate the membrane is very small the electrical conductivity must also be very small. Moreover, the few larger pores that are large enough to transport the hydrated calcium ion are too large to exert any appreciable effect in decreasing the mobility of the anion. Thus the membrane has no effect in modifying the potentials established across concentration chains with CaCl2 and the transfer numbers determined experimentally are what one would expect if no membrane were present.

This content is only available as a PDF.