Isopolymolybdates and Isopolytungstates

doi:10.1016/S0065-2792(08)60073-4

Advances in Inorganic Chemistry and Radiochemistry

Volume 19, 1976, Pages 239-315

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The chemistry of isopolymolybdates and isopolytungstates has been an area of intense activity for several decades. Yet, even today one cannot claim that all the important processes occurring on acidification of a molybdate or tungstate solution have been elucidated. Numerous contradictory reports appearing in the literature right up to the present have repeatedly done more to confuse than to clarify the subject. Thus, it is hardly surprising that not a single textbook correctly describes the situation in acidified molybdate and tungstate solutions. The number of proposals for polyions occurring in such solutions is legion. With little exaggeration it may be said that there is no conceivable species that has not been proposed at some time or other. Much of the effort involved in this field consists in scrutinizing the experimental conditions, the evaluation of measurements, and the interpretations given in past and present publications. The large number of methods already used in these studies presents a further difficulty.

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Citation Excerpt :
The resulting isopolyanions, [MnOm]k−, are composed of distorted {MO6} polyhedra that share edges and corners and may be linked with two to five polyhedra each. With increase in acidity, the isopolyanions undergo progressive loss of their oxygen and structural conversions, until the composition close to (MO3)n is reached at pH ∼1 and polymeric hydrated trioxides (MO3·H2O)∞, the so-called molybdic and tungstic acids, which are practically insoluble in water, finally precipitate [59–63]. However, according to some 31P, 183W and 17O NMR and Raman spectroscopy data, the complex identified as [PW11O39]7− exists at pH > 4, while at pH ∼2–4 up to ten other PW complexes could be observed by 31P NMR in solutions of H3PW12O40 [39,42–45,47,48].
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Isopolymolybdates and Isopolytungstates

Publisher Summary

Chim. Anal.

Acta Chem. Scand.

Z. Noturforsch. B

J. Amer. Chem. Soc.

Z. Anorg. Allg. Chem.

Nova Ada Regiae Soc. Sci. Upsal.

Progr. Inorg. Chem.

“The Early Transition Metals.”

Inorg. Chem.

Inorg. Chem.

Z. Naturforsch. B

Angew. Chem.

Angew. Chem., Int. Ed. Engl.

Ark. Kemi

“Polyanions et Polycations.”

“Ions mineraux condenses,”

Z. Naturforsch. B

Chimia

Z. Anorg. Chem.

Ark. Kemi

Z. Strukt. Chim.

Chem. Commun.

J. Chem. Soc. A

Z. Naturforsch. B

Angew. Chem.

Angew. Chem., Int. Ed. Engl.

Z. Naturforsch. B

Z. Naturforsch. B

C. R. Acad. Sci., Ser. C

Angew. Chem.

Angew. Chem., Int. Ed. Engl.

J. Chem. Soc. (London)

J. Inorg. Nucl. Chem.

C. R. Acad. Sci., Ser. C

Ann. Chim. [II]

Bull. Soc. Chim. Fr.

C. R. Acad. Set.

C. R. Acad. Set.

Acta Chem. Scand., Ser. A

J. Chem. Phys.

Z. Naturforach. B

Kolloid-Z.

Z. Anorg. Allg. Chem.

Z. Anorg. Allg. Chem.

J. Inorg. Nucl. Chem.

An. R. Soc. Esp. Fis. Quim., Ser. B