Electrolytic determination of nanomolar concentrations of silver in solution with a piezoelectric quartz crystal

Silver in solution is determined in situ by the frequency change of a piezoelectric quartz crystal on electrodeposition on the electrode of the crystal. The electrolyte solution flows through a cell containing the platinum-plated electrode (cathode) of the quartz crystal, a coiled platinum-wire anode and a silver—silver(I) chloride reference electrode, and is electrolyzed at —0.2 V vs. $\text{Ag}\text{AgCl}$. The frequency change is proportional to the silver concentration in the range 10^-5–5 × 10^-7 M after electrodeposition for 5 min, and in the range 10^-8–10^-9 M by recycling 20 ml of the solution over the electrodes for 3 h.