The effects of supporting electrolytes and of pressure on the electrode reactions of the aqueous CoW12O405-/6- couple at 25 degreesC are reported, together with limited data on PW12O403-/(4-) and PW12O404-/5-. The half-wave potentials E-1/2 for the CoW12 couple become moderately more positive with increasing electrolyte concentration and cationic charge, and also in the sequences Li+ approximate to Na+ < NH4+ less than or equal to H+ < K+ < Rb+ < Cs+ and Na+ < Mg2+ < Ca2+ < Eu3+. The mean diffusion coefficients for CoW12 with the 1:1 electrolytes are independent of electrolyte concentration and rise only slightly from Li+ to Cs+, averaging (2.4 +/- 0.3) x 10(-6) cm(2) s(-1). Neither the volumes of activation for diffusion DeltaV(diff)(double dagger) (average -0.9 +/- 1.1 cm(3) mol(-1)) nor the electrochemical cell reaction volumes DeltaV(Ag/AgCl) (average -22 +/- 2 cm(3) mol(-1)) for the CoW12 couple show significant dependence on electrolyte identity or concentration. For the PW123-/4- and PW124-/5- couples, DeltaV(Ag/AgCl) = -14 and -26 cm(3) mol(-1), respectively, suggesting a dependence on Delta(Z(2)) (z = ionic charge number) as predicted by the Born-Drude-Nernst theory of electrostriction of solvent, but comparison with DeltaV(Ag/AgCl) for CoW12 and other anion-anion couples shows that the Born-Drude-Nernst approach fails in this context. For aqueous electrode reactions of CoW12, as for other anionic couples such as cyanometalates, the standard rate constants k(el) show specific cation catalysis (Na+ < K+ < Rb+ < Cs+), and DeltaV(el)(double dagger) is invariably positive, in the presence of supporting electrolytes. For the heavier group 1 cations, DeltaV(el)(double dagger) is particularly large (10-15 cm(3) mol(-1)), consistent with a partial dehydration of the cation to facilitate catalysis of the electron-transfer process. The positive values of DeltaV(el)(double dagger) for the CoW12 Couple cannot be attributed to rate control by solvent dynamics, which would lead to DeltaV(el)(double dagger) less than or equal to DeltaV(diff)(double dagger), i.e., to negative or zero DeltaV(el)(double dagger) values. These results stand in sharp contrast to those for aqueous cationic couples, for which k(el) shows relatively little influence of the nature of the counterion and DeltaV(el)(double dagger) is always negative.