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Determination of V (super 4+) : V (super 5+) ratios in the [V (sub 10) O (sub 28) ] (super n-) decavanadate polyanion

Mark A. Cooper, Frank C. Hawthorne, Anthony R. Kampf and John M. Hughes
Determination of V (super 4+) : V (super 5+) ratios in the [V (sub 10) O (sub 28) ] (super n-) decavanadate polyanion
The Canadian Mineralogist (March 2019) 57 (2): 235-244


The decavanadate anion, [V (sub 10) O (sub 28) ] (super 6-) , is a common constituent of vanadate minerals, and both protonated, [H (sub x) V (sub 10) O (sub 28) ] (super (6-x)-) , and mixed-valent, [(V (super 4+) (sub x) V (super 5+) (sub 10-x) )O (sub 28) ] (super (6+x)-) , derivatives also occur. In addition, other highly charged cations (e.g., As (super 5+) ) may replace some V (super 5+) ions. The V (super 5+) -O bond-valence equation of Brown & Altermatt (1985) gives the best calculated valences for V in decavanadates containing only V (super 5+) . The V (super 4+) -O bond-valence equation of Gagne & Hawthorne (2015) provides the best calculated valences for V (super 4+) in non-decavanadate structures containing only V (super 4+) 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 V (super 4+) /V (super 5+) estimates, provides the most reliable valence assessment. Based on the high level of agreement between valences calculated in this manner and V (super 4+) /V (super 5+) estimates from the V (super 5+) -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.

ISSN: 0008-4476
EISSN: 1499-1276
Coden: CAMIA6
Serial Title: The Canadian Mineralogist
Serial Volume: 57
Serial Issue: 2
Title: Determination of V (super 4+) : V (super 5+) ratios in the [V (sub 10) O (sub 28) ] (super n-) decavanadate polyanion
Affiliation: University of Manitoba, Department of Geological Sciences, Winnipeg, MB, Canada
Pages: 235-244
Published: 201903
Text Language: English
Publisher: Mineralogical Association of Canada, Ottawa, ON, Canada
References: 54
Accession Number: 2019-029446
Categories: General mineralogy
Document Type: Serial
Bibliographic Level: Analytic
Illustration Description: illus. incl. 2 tables
Secondary Affiliation: Natural History Museum of Los Angeles County, USA, United StatesUniversity of Vermont, USA, United States
Country of Publication: Canada
Secondary Affiliation: GeoRef, Copyright 2019, American Geosciences Institute. Abstract, copyright, Mineralogical Association of Canada. Reference includes data from GeoScienceWorld, Alexandria, VA, United States
Update Code: 201916
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