Aspects of Molybdenum and Related Chemistry by Boschke F.L.

By Boschke F.L.

Content material: Tsigdinos, G. A. Heteropoly compounds of molybdenum and tungsten. -- Tsigdinos, G. A. Inorganic sulfur compounds of molybdenum and tungsten -- their guidance, constitution, and homes. -- Moh, G. High-temperature steel sulfide chemistry

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Guanidinium, cesium, silver, and thallium salts of different basicities have sometimes been reported but these are almost certainly mixtures. Hydration The crystalline free acids and salts are all highly hydrated. Corresponding compounds of the phosphorus and arsenic series differ in the amounts of water of crystallization. For example, each of the free acids is reported in two forms: H6[P2MolaO62 ] 9 33 H20 - Orange H6[P2MolsO62] " 37 H20 - Bright Orange H6[As2Mo18062] 925 H 2 0 - Orange-red H6[As2Mo18062]" 35 H 2 0 - Yellow The higher hydrates of both acids are unstable at ordinary temperatures.

Cyclic voltammogramof 2 x 10- 4 M (NH4)6[P2Mo180621 in 1 M H2SO4 at 25 C from cyclic voltammetry and shown in Fig. 01 to 10 Hz. The general shape of the voltammogram indicates some reversibility of the first three waves at the sweep rates studied. 22, - 0 . 0 1 , and - 0 . 1 5 V Is, lss). Although the polarograms of H4[PMol iVO4o] and Hs [PMoloV204o] in water solution show that these acids are considerably decomposed, the data in water dioxane solutions I s, I ss) show that dioxane stabilizes the anion structures toward hydrolysis.

The 9-molybdophosphates may also be converted to 12-molybdophosphates by treatment with acid. In turn, the reverse reaction may be brought about by treatment with base or additional phosphoric acid. The analogous tungstates exhibit similar behavior. Some heteropoly acids are easily decomposed in acid solution as has been shown by spectroscopic studies 153). The order of increasing stability is 12-molybdophosphate, 12-molybdogermanate, 12-molybdosilicate, and 9-molybdophosphate 153). anions 7, 23, 27, 28).

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