Attempts to carry out potentiometric determination of plutonium (by AgO-oxidation method) following the determination of thorium (by complexometric EDTA titration) gave positively biased irreproducible values of plutonium. In order to understand the factors leading to the erroneous values of plutonium, the effect of varying amounts of AgO and EDTA on redox [Fe(II)/K2Cr2O7] titration in the medium consisting of 1M H2SO4 and 0,4M HNO3 was studied. When AgO (up to 200 mg) was added in the titration medium and destroyed by sulfamic acid prior to the redox titration, the dichromate tittre value (amount of standard K2Cr2O7 solution equivalent to 1 g of Fe(II) solution) showed negative bias. The bias was found to decrease with increase in time interval between AgO destruction and the redox titration. The presence of EDTA (up to 15 mg) gave positive bias in the titre value. Results on the titre values obtained under different conditions of the aqueous medium indicated the possibility of formation of unstable Ag(II)-sulfamic acid compled, which is probably responsible for the irreproducible values of plutonium.