Signal enhancement in adsorptive stripping voltammetry of Pt by forced convection during the measurement step

Adsorptive stripping voltammetry (‘formazone-method’) is already known as one of the most sensitive methods for platinum analysis with a detection limit in the low picograms range. In this work, it is shown that the detection limit can be lowered even more by one order of magnitude to 0.2 pg (=1 fmol) Pt in 15 mL electrolyte, corresponding to 68 fmol/L, by applying forced convection during the stripping step of the voltammetric measurement. The sensitivity of the method (given in nA/pg Pt) is enhanced by a factor of 3-5 (in differential pulse mode and 15 mL vial), up to a factor of 30 (using square-wave mode and 3 mL vial). The maximum enhancement factor is limited by the maximum stirrer speed, which can be applied without negative effects on the hanging mercury drop electrode.To check for similar enhancement effects in other types of stripping methods, the behaviour of adsorptive stripping voltammetry for Pt is compared to conventional anodic stripping voltammetry (ASV) of lead, and to adsorptive stripping voltammetry of nickel and cobalt using their dimethylglyoxime (DMG) complexes. No enhancement effect is observed in ASV of lead upon stirring, and the nickel-DMG-system exhibits only a smaller enhancement factor of about 1.5. A reasonable explanation of the higher signal enhancement in the catalytic Pt-formazone-system is the mass transport of reaction products, namely hydrogen, away from the working electrode during the catalytic hydrogen evolution cycle.