Abstract
The redox properties of the tri-heteropolytungstosilicates of transition elements KnSiZ(H2O)W11O39 (Z Mn2+, Fe3+, Co2+, Ni2+, Zn2+, Cd2+). In solution have been studied with polarography and cyclic voltammetry as well as with ultraviolet spectroscopy and X-ray photoelectron spectroscopy. The order of the polarographic half-wave potentials (E1/2) of these heteropolyanions is as follows: ZNi2+>Co2+>Zn2+>Fe2+>Mn2+. We have found that the E1/2 of heteropolyanions could be correlated linearly with both the electronegativities X of the transition elements and the logarithm of the rate constants (log ke) of reaction of transition metal ions with hydrated electrons. The reduction mechanism and effects of transition elements on the redox properties of the heteropolyanions have been discussed.
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