Autoprotolysis constants by coulometric titration

A procedure is described for the evaluation of autoprotolysis constants in which a strong acid is titrated with coulometrically generated strong base. A two-compartment cell is used, and the acid may be added as such to the solvent under study, or generated in situ in the cell. When a silver auxiliary electrode can be used, as with solutions containing bromide ion, a single-compartment cell may be used, which seems to give more accurate results because it avoids the errors caused by diffusion of solution through the diaphragm. The results for the constants obtained for ethylene glycol, for methanol and for water are in reasonable agreement with values in the literature.