Determination of plutonium by secondary coulometric titration with internally generated iron(II)

The method for plutonium determination based on secondary controlled-potential coulometry, as described by SHULTS, is applied for analysis in the range of 0.1–5 mg plutonium. The method involves the oxidation of plutonium to Pu(VI) with perchloric acid followed by its reduction by an internally generated ferrous mediator. This is a two step procedure, involving the reduction of Pu(VI) and Fe(III) to a mixture of Pu(III) and Fe(II), followed by the oxidation of Pu(III) and Fe(II) to Pu(IV) and Fe(III), respectively. The net results is the reduction of Pu(VI) to Pu(IV), measured as the difference between the currents consumed during the reduction and oxidation steps. The original method of SHULTS involves 10–25 mg plutonium for each determination. Since the present method is intended for the analysis of smaller amounts of plutonium, the oxidation procedure described in the original version had to be modified. The method is found to work satisfactorily with a precision better than 0.1% at 5 mg level and 1.2% for 0.1 mg plutonium.