INVESTIGATION INTO THE PRACTICALITIES OF MAKING QUANTITATIVE ELECTROANALYTICAL MEASUREMENTS IN FROZEN ELECTROLYTES

Chronoamperometry and measurements of potential differences in frozen electrolytes were used to determine the suitability of these media for quantitative electroanalytical methods. The Tee samples that we prepa red appeared to consist of volumes of pristine ice crystals, more or l ess devoid of solute, interlaced by channels of dislocated ice crystal s in which the bulk of the solute was located. At conventional electro des, chronoamperometric currents were reasonably representative of the bulk electrolyte concentration: microelectrodes gave an enhanced resp onse due; to preferential formation of dislocated ice crystals. Cyclic voltammetry was used to investigate hexacyanoferrate, ascorbic acid a nd formaldelhyde electrochemistry;in frozen electrolytes. Electrode re actions of the chemical-electrochemical and electrochemical-chemical ( EC) type were examined. The results for the EC mechanism and the strai ght reversible system support the view of the ice structure discussed above.