SQUARE-WAVE POLAROGRAPHY (REPRINTED FROM THE ANALYST, VOL 77, PG 685-695, 1952)

A method is described for eliminating the undesirable effect of the double-layer capacity current on the sensitivity of an A.C. polarograph. A square-wave voltage is used in place of the usual sinusoidal polarising voltage, and the amplitude of the A.C. component of the cell current is measured shortly before each sudden change in the applied voltage. Preliminary results suggest that the method is useful for the detection, at concentrations down to 2 x 10(-7) of ions that are reversibly reduced, and that the sensitivity of the method is not greatly influenced by the presence of large concentrations of ions that produce interfering waves on the ordinary polarogram. Brief mention is made of an extension of the method that permits the detection of certain metallic ions at concentrations of 10(-9) M.