Laser-heating thermal modulation voltammetric determination of phosphate ion using a graphite-reinforced carbon electrode.

Thermal modulation (TM) voltammetry was successfully applied to the determination of phosphate ion in natural water, by using a He-Cd dual laser as a heating source and a graphite-reinforced carbon (GRC) electrode. A heteropoly ion, i.e., 12-molybdophosphate ion ([PMo(VI)(12)O(40)](3-)), was formed through a reaction between a phosphate ion and molybdate ions in an acidic solution, and its electroreduction was examined in a flow electrolytic cell by TM voltammetry. Measured TM voltammograms showed two peaks corresponding to two successive two-electron reductions of the 12-molybdophosphate ion, and the peak intensities were proportional to the concentration of the phosphate ion. Because of the strong adsorption of 12-molybdophosphate ion onto the GRC electrode, a detection limit as low as 0.8 nmol dm(-3) (S/N = 3) was achieved. The determination of phosphate ion in real samples (river water) was carried out by spectrophotometry (the molybdenum-blue method) and TM voltammetry, and the determination values obtained by both methods were in a good agreement with each other. These results prove the possibility of TM voltammetry as an electroanalytical method.