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Reduced molybdovanadophosphates
Umeå University, Faculty of Science and Technology, Chemistry.
Umeå University, Faculty of Science and Technology, Chemistry.
Umeå University, Faculty of Science and Technology, Chemistry.
2002 (English)In: European Journal of Inorganic Chemistry, ISSN 1434-1948, no 3, 743-9 p.Article in journal (Refereed) Published
Abstract [en]

The equilibrium speciation in the aqueous H+/MoO42-/ HVO42-/HPO42-/e(-) system, 0.600 M Na(CI) medium at 25 degreesC, was characterised by potentiometric [H+] (glass electrode) and {epsilon(-)} (platinum electrode) titration techniques as fundamental tools, complemented by V-51(V) NMR (131.6 MHz) and V-IV ESR spectroscopy. The study has been focused on solutions with the Keggin ratio, (Mo + V)/P = 12:1 and Mo/V > 5, in the pH range 1.4-4,5, where anions having the formula [(HzMo12-x-yVxVyPO40)-V-V-P-IV]((3+x+2y-z)-) are predominant species. Added numbers of electrons per vanadium(V) (e(-)/V-V) have been kept less than one to exclude reduction of molybdenum(VI). Six reduced molybdovanadophosphate species have been identified. The [(MO11VPO40)-P-IV](5-) species [logbeta = 154.15 +/- 0.03 (3sigma)] and the mixed-valence species [(Mo10VVPO40)-V-V-P-IV](6-) (logbeta = 155.84 +/- 0.02) can both be monoprotonated, These species have pK(a) values of 0.93 and 3.68, respectively. A "fully" reduced Keggin species, [(H2Mo10V2PO40)-P-IV](5-) (logbeta = 171.27 +/- 0.06), and a lacunary [(H4Mo10VPO39)-P-IV](5-) species (logbeta = 142.0 +/- 0.2) were found as well. Except for the molybdovanadophosphate species, the only reduced species formed, in the present investigation, is the vanadyl ion, VO2+. logK(red) (2 H+ + VO2+ + e reversible arrow VO2+ + H2O) was deterinined to 17.15 +/- 0.01 (E-0 = 1014.5 +/- 0.6 mV).

Place, publisher, year, edition, pages
2002. no 3, 743-9 p.
Keyword [en]
polyoxometalates, NMR spectroscopy, redox chemistry, speciation, formation constants
Identifiers
URN: urn:nbn:se:umu:diva-9009OAI: oai:DiVA.org:umu-9009DiVA: diva2:148680
Available from: 2008-02-26 Created: 2008-02-26 Last updated: 2011-01-13Bibliographically approved

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Andersson, IngegärdPettersson, Lage

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