VISUAL RANGE SPECTRA OF AQUEOUS HETEROANION SOLUTIONS

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1963

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Ohio State University

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“Changes of $V_{v}$ - spectra with increasing $O^{-II}$ coordination were used to trace the mechanisms for formation of $[VWo_{2}O_{10}]^{-3}, [VMo_{2}O_{10}]^{-3}$ and $[VMoWO_{3}]^{-3}$ ions for tetr4acoordinate structure, $[OV(OZO_{3})_{2}]^{-3}$. Then, the reactions of these ions with $[X^{v}O_{m}]^{v-2m}(X^{v} = P\stackrel{\overline{v}}{-})$ As $\stackrel{\overline{v}}{-}, Si\stackrel{\overline{IV}}{-},Ge\stackrel{\overline{IV}}{-}$ or $B\stackrel{\overline{III}}{-})$) ions in competitions with $[W_{3}O_{10}]^{-2}$ and $[Mo_{3}O_{10}]^{2-}$ activated complexes to form ions of $[X^{v}(YZ_{2}O_{10})_{4}]^{v-4a}$ structure were followed, under reducing conditions productive of $W_{\bar{X}}$ or $Mo_{\bar{V}}$ as well as under non-reducing conditions. Transformations to hexacoordinate units $\{OY[O_{2}Z(O_{0,5})_{4}]_{2}O\}-a$-n were observed, as expected from isotypies of the acids $H_{4n-v} Y_{4} Z_{s} O_{40}\cdot n H_{2}O$ with $H_{2}PW_{12}O_{40}\cdot 29H_{2}O$. Spectrophotometry of anolytes and catholytes in electrolysis of the acids and ammonium salts gave concordant results, and characterization of anode and cathode deposits yielded data useful in describing the electronic bands of heteropoly blue berthollide semiconductors.”

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Author Institution: Department of Engineering Physics, Applied Physics Group, Battelle Memorial Institute

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