Solid zirconium carbonates

A single publication reporting thermodynamic data for Zr carbonate solids was found. Aja et al. [95AJA/WOO] studied the dissolution of natural weloganite 

For a number of reasons, this result cannot be verified  

For the reasons listed above, this constant was rejected without reinterpretation. 

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Studies of the Zr0Cl2-Na2C03-H20 system and the equivalent potassium carbonate (356) and ammonium carbonate (339) systems have led the authors to conclude that the solid phase contains a mixture of basic zirconium carbonates and hydroxocarbonates of composition M[Zr(0H)3C03] and ZrOCOs JiHgO and that the solution phase contains anions of compositions [Zr0(C03)2] " and [Zr(0H)4(C03)2] . The [Zr0(C03) ] anion has also been obtained in a barium salt (31). 

DER/FAU] Dervin, J., Faucherre, J., Pruszek, H., Etude en solution et a I etat solide des carbonates complexes de zirconium et d hafnium. Rev. Chim. Miner., 11, (1974), 372-387, in French. Cited on pages 210,211,304. 

Alkaline-Earth Titanates. Some physical properties of representative alkaline-earth titanates ate Hsted in Table 15. The most important apphcations of these titanates are in the manufacture of electronic components (109). The most important member of the class is barium titanate, BaTi03, which owes its significance to its exceptionally high dielectric constant and its piezoelectric and ferroelectric properties. Further, because barium titanate easily forms solid solutions with strontium titanate, lead titanate, zirconium oxide, and tin oxide, the electrical properties can be modified within wide limits. Barium titanate may be made by, eg, cocalcination of barium carbonate and titanium dioxide at ca 1200°C. With the exception of Ba2Ti04, barium orthotitanate, titanates do not contain discrete TiO ions but ate mixed oxides. Ba2Ti04 has the P-K SO stmcture in which distorted tetrahedral TiO ions occur. 

Zirconium. The solid metal is very resistant to corrosion. It reacts, when heated, with carbon, nitrogen, oxygen and the halogens. Finely divided may ignite spontaneously in air. It is attacked by HF and aqua regia. 

Small Quantities. Wear eye protection, laboratory coat, and nitrile rubber gloves. In a fume hood, add the zirconium tetrachloride in small portions to a large volume of stirred water and crushed ice in a beaker. When the reaction is complete, neutralize with sodium carbonate or dilute hydrochloric acid. The liquid portion of the reaction mixture may be washed into the drain, while the solid residue may be treated as normal refuse.8... 

It must also be pointed out that other basic materials have been synthesized which present no surface oxygens and hydroxyls, but other types of active sites whose exact nature remains controversial. These type of solids are, for example, impregnated imides and nitrides on zeolites and alumina, amorphous oxynitrides obtained by treatment with ammonia or aluminium orthophosphate, zirconium phosphate, aluminium vanadate or galloaluminophosphate, and KF supported on alumina/1,3,41 One of the main advantages of these solids with respect to basic oxides is their resistance to carbon dioxide or water. 

The zirconium and hafnium complexes of trifluoroacetyl-acetone are white crystalline solids, insoluble in water but soluble in benzene, cyclohexane, and carbon tetrachloride. The hafnium complex melts at 128 to 129° and the zirconium complex at 130 to 131°. The complexes have been subjected to gas-phase chromatography and may be sublimed at 115° at a pressure of 0.05 mm. The proton magnetic resonance spectra of the compounds dissolved in carbon tetrachloride show single peaks in the methyl and methylene regions. The peaks appear at 2.20 and 6.00 p.p.m. (5) relative to tetramethylsilane (internal reference) for the zirconium complex and at 2.20 and 5.97 p.p.m. for the hafnium complex. 

Anhydrous zirconium oxide chloride, ZrOCl2 [7699-43-6] has been prepared by the reaction of dichlorine oxide with a zirconium tetrachloride suspension in carbon tetrachloride starting at —30° C and slowly rising to room temperature. The white solid is extremely hygroscopic and decomposes to ZrCl and Zr02 at 250°C (200). 

Hydroboration of coordinated alkenes has been achieved with the phosphine-stabilized olefin complexes, (775-C5H5)2Zr(772-CH2=CHR)(PPh2Me) (R = H, 78 Et, 79 Ph, 80), upon addition of the Lewis-acidic borane, HB(C6F5)2 (Equation (5)).37,65 Solid-state characterization indicates a weak interaction between the formally positively charged zirconium center and the carbon adjacent to the borate anion. This interaction is maintained in solution, as an upheld shifted 13C NMR resonance is observed for this carbon, which is in agreement with previous reports of metal-carbon interactions of this type. 

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