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THE POTENTIALS AT THE JUNCTIONS OF SALT SOLUTIONS

A concentration-cell consisting of two identical reversible electrodes in contact with two differently concentrated solutions of the same salt gives an electromotive force which is the algebraic sum of three potentials-those at the two electrodes and that at the junction of the solutions. Since for most theoretical purposes the potential at the electrodes alone is desired, many attempts have been made to evaluate the potential at the liquid junction. The effect of interposing strong salt solutions on the electromotive force of the cell has also been studied with the view of eliminating the effect of the liquid junction. It has been usual to test the correctness of the value assigned to the potential at the junction, or the efficacy of the artifice employed in eliminating it, by seeing whether the resulting electromotive force E at the electrodes can be calculated by the equation E = (RT/F)ln(C/IC2) where C1 and C2 are the concentrations of the ions in the two solutions as calculated from conductance measurements, and R, T, and F are the gas-constant, the absolute temperature, and the faraday respectively. Recent work1 has indicated, however, that the voltages calculated by this formula are too high. It therefore seems desirable to investigate the subject of the liquid junction connecting two solutions of the same salt with a view of finding an expression, involving the fewest possible assumptions, for its electromotice force. If the cell Ag, AgCl (solid) + KC1 (O.ln), AgCl (solid) + KC1 (O.Oln), Ag operates reversibly until one faraday passes through it, one equivalent of chloride-ion enters the dilute solution and the same amount of chloride-ion is electrolyzed out of the more concentrated solution. The current is carried across the liquid junction by the movement of nc equivalents of potassium-ion in the direction of the current and by the migration of (1 nc) equivalents of chloride-ion in the reverse direction, nc being the transference-number of the cation. The total effect of the passage of the faraday of electricity is the transference of nc equivalents of salt, or 2nc equivalents of ion, from the 0.1 normal KC1 solution to the 0.01 normal KC1 solution. The accompanying electrical work is the product E F where E is the total E. M. F. of the cell and F is the value of the faraday. Now the electrical work and consequently the electromotive force at the liquid junction will be determined by the 526