The effect of alkali metal (M) chloride or triflate supporting electrolytes (0.1-1.0 mol L-1) on the midpoint potential E-m of the aqueous AlW(12)O(40)(5-/6-)couple in cyclic voltammetry, after correction (E-corr) for liquid junction potentials, can be represented in terms of ionic strength according to the extended Debye-Huckel equation. However, unrealistically short AlW12O405-/6- cation closest-approach distances are required to accommodate the specific effects of M+, and the infinite-dilution potential E-corr(0) values are not quite consistent from one M+ to another. The pressure dependence of E-m is qualitatively consistent with expectations based on the Born-Drude-Nernst theory. The strong accelerating effects of supporting electrolytes on the standard electrode reaction rate constant k(el) at pH 3 as measured by alternating current voltammetry (ACV), and on the homogeneous self-exchange rate constant k(ex) at pH 3-7 as measured by Al-27 line broadening, depend specifically on the identity and concentration of M+ (Li+ < Na+ < K+ < Rb+) rather than on the ionic strength, whereas the effect of the nature of the supporting anion (Cl-or CF3SO3-) is negligible. Extrapolation of k(el) and k(ex) to zero [M+] indicates that the uncatalyzed electron transfer rate is negligibly small relative to the M+ catalyzed rates. The kinetic effects of M+ show no evidence of the saturation expected had they been due primarily to ion pairing with AlW12O405-/6-. The catalytic effect of M+ operates primarily through lowering the enthalpy of activation, which is partially offset by a strongly negative entropy of activation and, for the homogeneous exchange catalyzed by K+ or Rb+, becomes mildly negative; thus, the catalytic effect of M+ is enthalpy-driven but entropy-limited. For the electrode reaction, the volume of activation averages + 4.5 +/- 0.2 cm(3) mol(-1) for all M+ and [M+], in contrast to the negative value predicted theoretically for the uncatalyzed reaction. These results are consistent with a reaction mechanism, previously proposed for other anion-anion electron-transfer reactions, in which anion-anion electron transfer is facilitated by partially dehydrated M+.