Determination of soluble chromium in simulated PWR coolant by differential-pulse adsorptive stripping voltammetry

An analytical method has been developed for the determination of dissolved chromium at concentrations less than 2 mug/l. in PWR coolant by differential-pulse adsorptive stripping voltammetry at a hanging mercury drop electrode. Concentrations above 2 mug/l. can be determined by appropriate dilution of the sample. The method is based on measurement of the current associated with reduction of a chromium(III)-DTPA (diethylenetriaminepenta-acetic acid) complex adsorbed at the surface of the mercury drop. The effects of boric acid, pH, DTPA concentration, accumulation potential and time were investigated together with the oxidation state of the chromium. No interference was observed from other transition metal ions expected to be present in PWR coolant. No alternative chemical technique of similar sensitivity was available for comparison with the results obtained in solutions containing <1 mug/l. chromium. Recoveries from simulated coolant solutions were greater than 95% and the relative standard deviations for single determinations were in the range 12-25%. The statistical limit of detection at the 95% confidence level was 0.023 mug/l. This method of analysis should prove valuable in corrosion studies and is uniquely capable of following the changes in soluble chromium concentration in PWR coolant that follow operational changes in the reactor.