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 training, constitution, and houses. -- Moh, G. High-temperature steel sulfide chemistry
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Additional resources for Aspects of Molybdenum and Related Chemistry
The crystal structure of these materials is typified by the salt (NH4)s [(MoO3)s(PO4)(HPO4)] 9 3 H20126). Finally, excess alkali causes complete degradation to simple molybdates. The overall degradation requires 20 to 28 moles of NaOH for each mole of 12-acid, the exact number depending upon the valence of the central atom and the chemistry of its simple acid. The 12heteropolytungstates of p+S decompose into the 11-series and 10-1/2 series 4), the latter series converts into the 11-series at low pH values.
Meaningful thermal stability studies on heteropoly compounds must be accompanied by solubility studies of the heated materials to ascertain actual decomposition. In addition, the length of heating must also be specified since such decomposition may be rate dependent in view of the fact that both 12-molybdophosphoric and 12-molybdosilicic acids decompose slowly with time even at room temperature s). A detailed study of the thermal behavior of 12-molybdophosphoric and 12-molybdosilicic acids and several of their metal salts has been carried out s) by the method outlined.
For example, reduction in the 9-m olybdophosphate(V) anion proceeds in definite steps corresponding to the addition of 2, 4, or 6 electrons 23' ls8). In general, 12-heteropoly anions of Si+4 and p+S are more readily reduced than those of Ge +4. Furthermore, heteropolymolybdates are more readily reduced than corresponding heteropolytungstates. For example, in the phosphorus acids, the oxidizing power decreases in the order: 1. 2. 3. 4. 5. Dimeric 9-molybdophosphoric(V) acid (strongest oxidant) 12-Molybdophosphoric(V) acid Dimeric ot-9-tungstophosphoric(V) acid Dimeric/3-9-tungstophosphoric(V) acid 12-Tunstophosphoric(V) acid (weakest oxidant) Ferrous salts, sulfites, urea, uric acid, hydroquinones, or other mild reducing agents are effective.
Aspects of Molybdenum and Related Chemistry by Boschke F.L.