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Determination of V4+:V5+ Ratios in the [V10O28] n – Decavanadate Polyanion

2019; Mineralogical Association of Canada; Volume: 57; Issue: 2 Linguagem: Inglês

10.3749/canmin.1800065

1499-1276

Mark A. Cooper, F. C. Hawthorne, Anthony R. Kampf, John M. Hughes,

Polyoxometalates: Synthesis and Applications

Research Article| March 01, 2019 Determination of V4+:V5+ Ratios in the [V10O28]n– Decavanadate Polyanion Mark A. Cooper; Mark A. Cooper Department of Geological Sciences, University of Manitoba, Winnipeg, Manitoba, R3T 2N2, Canada Search for other works by this author on: GSW Google Scholar Frank C. Hawthorne; Frank C. Hawthorne § Department of Geological Sciences, University of Manitoba, Winnipeg, Manitoba, R3T 2N2, Canada §Corresponding author e-mail address: frank.hawthorne@umanitoba.ca Search for other works by this author on: GSW Google Scholar Anthony R. Kampf; Anthony R. Kampf Mineral Sciences Department, Natural History Museum of Los Angeles County, 900 Exposition Boulevard, Los Angeles, California 90007, USA Search for other works by this author on: GSW Google Scholar John M. Hughes John M. Hughes Department of Geology, University of Vermont, Burlington, Vermont 05405, U.S.A. Search for other works by this author on: GSW Google Scholar Author and Article Information Mark A. Cooper Department of Geological Sciences, University of Manitoba, Winnipeg, Manitoba, R3T 2N2, Canada Frank C. Hawthorne § Department of Geological Sciences, University of Manitoba, Winnipeg, Manitoba, R3T 2N2, Canada Anthony R. Kampf Mineral Sciences Department, Natural History Museum of Los Angeles County, 900 Exposition Boulevard, Los Angeles, California 90007, USA John M. Hughes Department of Geology, University of Vermont, Burlington, Vermont 05405, U.S.A. §Corresponding author e-mail address: frank.hawthorne@umanitoba.ca Publisher: Mineralogical Association of Canada First Online: 26 Mar 2019 Online Issn: 1499-1276 Print Issn: 0008-4476 © 2019 Mineralogical Association of Canada The Canadian Mineralogist (2019) 57 (2): 235–244. https://doi.org/10.3749/canmin.1800065 Article history First Online: 26 Mar 2019 Cite View This Citation Add to Citation Manager Share Icon Share Facebook Twitter LinkedIn MailTo Tools Icon Tools Get Permissions Search Site Citation Mark A. Cooper, Frank C. Hawthorne, Anthony R. Kampf, John M. Hughes; Determination of V4+:V5+ Ratios in the [V10O28]n– Decavanadate Polyanion. The Canadian Mineralogist 2019;; 57 (2): 235–244. doi: https://doi.org/10.3749/canmin.1800065 Download citation file: Ris (Zotero) Refmanager EasyBib Bookends Mendeley Papers EndNote RefWorks BibTex toolbar search Search Dropdown Menu toolbar search search input Search input auto suggest filter your search All ContentBy SocietyThe Canadian Mineralogist Search Advanced Search Abstract The decavanadate anion, [V10O28]6−, is a common constituent of vanadate minerals, and both protonated, [HxV10O28](6−x)−, and mixed-valent, [(V4+xV5+10−x)O28](6+x)−, derivatives also occur. In addition, other highly charged cations (e.g., As5+) may replace some V5+ ions. The V5+–O bond-valence equation of Brown & Altermatt (1985) gives the best calculated valences for V in decavanadates containing only V5+. The V4+–O bond-valence equation of Gagné & Hawthorne (2015) provides the best calculated valences for V4+ in non-decavanadate structures containing only V4+ in [1+4+1] coordination (i.e., one vanadyl bond, four equatorial bonds, and one longer bond trans to the vanadyl bond). Combined application of these two equations to the V–O bond lengths in decavanadates, based on V4+/V5+ estimates, provides the most reliable valence assessment. Based on the high level of agreement between valences calculated in this manner and V4+/V5+ estimates from the V5+–O bond-valence equation of Brown & Altermatt (1985), VC, the following equation gives the best estimate of the formal aggregate valence of V in decavanadate minerals: VP = 1.538(VC) – 2.692. This provides more accurate Lewis basicities for the decavanadate polyanion in analyzing its interaction with the interstitial complex. It should also help in establishing the strengths of donor-hydrogen and hydrogenacceptor bonding in decavanadate systems relevant to catalysis and bacterial-growth inhibition. You do not have access to this content, please speak to your institutional administrator if you feel you should have access.