Niobium Preparation

Eighteen isotopes of niobium are known. The metal can be isolated from tantalum, and prepared in several ways. 

Other Metals. AH the sodium metal produced comes from electrolysis of sodium chloride melts in Downs ceUs. The ceU consists of a cylindrical steel cathode separated from the graphite anode by a perforated steel diaphragm. Lithium is also produced by electrolysis of the chloride in a process similar to that used for sodium. The other alkaH and alkaHne-earth metals can be electrowon from molten chlorides, but thermochemical reduction is preferred commercially. The rare earths can also be electrowon but only the mixture known as mischmetal is prepared in tonnage quantity by electrochemical means. In addition, beryIHum and boron are produced by electrolysis on a commercial scale in the order of a few hundred t/yr. Processes have been developed for electrowinning titanium, tantalum, and niobium from molten salts. These metals, however, are obtained as a powdery deposit which is not easily separated from the electrolyte so that further purification is required. 

Niobium Halides and Oxyhalides. AH possible haUdes of pentavalent niobium are known and preparations of lower valent haUdes generally start with the pentahaUde. Ease of reduction decreases from iodide to fluoride. 

Niobium Penta.fIuoride, Niobium pentafluoride is prepared best by direct fluorination of the metal with either fluorine or anhydrous hydrofluoric acid at 250—300°C. The volatile NbF is condensed in a pyrex or quartz cold trap, from which it can be vacuum-sublimed at 120°C to yield colorless monoclinic crystals. It is very hygroscopic and reacts vigorously with water to give a clear solution of hydrofluoric acid and H2NbOF ... 

Niobium Pent chloride. Niobium pentachloride can be prepared in a variety of ways but most easily by direct chlorination of niobium metal. The reaction takes place at 300—350°C. Chlorination of a niobium pentoxide—carbon mixture also yields the pentachloride however, generally the latter is contaminated with niobium oxide trichloride. The pentachloride is a lemon-yeUow crystalline soHd that melts to a red-orange Hquid and hydrolyzes readily to hydrochloric acid and niobic acid. It is soluble in concentrated hydrochloric and sulfuric acids, sulfur monochloride, and many organic solvents. 

Niobium Oxide Trichloride. Niobium oxide trichloride, NbOCl, also can be prepared in a variety of ways, ie, oxidation of the... 

Niobium Pentabromide. Niobium pentabromide is most conveniently prepared by reaction of bromine with niobium metal at ca 500°C. It is a fairly volatile yellow-red compound that is hygroscopic and readily hydrolyzes. It is soluble in water, alcohol, and ethyl bromide. 

Niobium Oxide Tribromide. Niobium oxide tribromide, NbOBr, is a yeUowbrown soHd which is readily hydrolyzed by moist air. It is prepared by reaction of bromine with a mixture of niobium pentoxide and carbon at 550°C. It decomposes in vacuum to the pentabromide and pentoxide at 320°C. 

Niobic Acid. Niobic acid, Nb20 XH2O, includes all hydrated forms of niobium pentoxide, where the degree of hydration depends on the method of preparation, age, etc. It is a white insoluble precipitate formed by acid hydrolysis of niobates that are prepared by alkaH pyrosulfate, carbonate, or hydroxide fusion base hydrolysis of niobium fluoride solutions or aqueous hydrolysis of chlorides or bromides. When it is formed in the presence of tannin, a volurninous red complex forms. Freshly precipitated niobic acid usually is coUoidal and is peptized by water washing, thus it is difficult to free from traces of electrolyte. Its properties vary with age and reactivity is noticeably diminished on standing for even a few days. It is soluble in concentrated hydrochloric and sulfuric acids but is reprecipitated on dilution and boiling and can be complexed when it is freshly made with oxaHc or tartaric acid. It is soluble in hydrofluoric acid of any concentration. 

Lithium niobate [12031 -63-9] Nb20 or LiNbO, is prepared by the soHd-state reaction of lithium carbonate with niobium pentoxide. After... 

Sihca is reduced to siUcon at 1300—1400°C by hydrogen, carbon, and a variety of metallic elements. Gaseous siUcon monoxide is also formed. At pressures of >40 MPa (400 atm), in the presence of aluminum and aluminum haUdes, siUca can be converted to silane in high yields by reaction with hydrogen (15). SiUcon itself is not hydrogenated under these conditions. The formation of siUcon by reduction of siUca with carbon is important in the technical preparation of the element and its alloys and in the preparation of siUcon carbide in the electric furnace. Reduction with lithium and sodium occurs at 200—250°C, with the formation of metal oxide and siUcate. At 800—900°C, siUca is reduced by calcium, magnesium, and aluminum. Other metals reported to reduce siUca to the element include manganese, iron, niobium, uranium, lanthanum, cerium, and neodymium (16). 

One was Ekeberg s tantalum and the other he called niobium (Niobe was the daughter of Tantalus). Despite the chronological precedence of the name columbium, lUPAC adopted niobium in 1950, though columbium is still sometimes used in US industry. Impure niobium metal was first isolated by C. W. Blomstrand in 1866 by the reduction of the chloride with hydrogen, but the first pure samples of metallic niobium and tantalum were not prepared until 1907 when W. von Bolton reduced the fluorometallates with sodium. 

Precipitation of fluoride compounds from solutions of hydrofluoric acid, HF, is performed by the addition of certain soluble compounds to solutions containing niobium or tantalum. Initial solutions can be prepared by dissolving metals or oxides of tantalum or niobium in HF solution. Naturally, a higher concentration of HF leads to a higher dissolution rate, but it is recommended to use a commercial 40-48% HF acid. A 70% HF solution is also available, but it is usually heavily contaminated by H2SiF6 and other impurities, and the handling of such solutions is extremely dangerous. 

Tantalum and niobium oxides dissolve very slowly in HF solutions. Thus, it is recommended to use a high concentration of HF or a mixture of HF and H2SO4 at a temperature of about 70-90°C. The best precursors for the preparation of fluoride solutions are hydroxides. Both tantalum hydroxide, Ta205 nH20, and niobium hydroxide, M Os-nHjO, dissolve well, even in diluted HF solutions. 

Using metallic precursors, HF solutions with higher concentrations of tantalum or niobium can be achieved. It is possible to prepare solutions that have maximum concentrations of about 1000 g/1 tantalum oxide and about 600 g/1 niobium oxide (Me205). 

Synthesis of the compounds from such HF solutions is performed by adding soluble fluoride compounds to the tantalum or niobium solution or by recrystallization of prepared fluoride compounds from water or HF solutions of different concentrations. In the first case, the composition of the compounds obtained depends on the ratio between Ta/Nb and the added metal and on the initial concentration of the HF used, whereas in the second case, it depends only on the HF concentration. 

Crystals of Rb7TaF7 were prepared from relatively diluted solutions of HF, while re-crystallization of rubidium heptafluorotantalate, Rb7TaF7, using a 33% HF solution resulted in the precipitation of rubidium hexafluorotantalate, RbTaFe [56]. Under the same conditions, niobium-containing solutions yielded rubidium oxyfluoroniobate, Rb2NbOF5 [29]. 

Table 6 summarizes the main compounds that can be prepared by adding alkali metal fluorides to fluorine solutions that contain niobium or tantalum. 

The compound (NIDsNbaOFig can be prepared by adding ammonium fluoride, NH4F, to a solution containing Nb (3.20 M/l) and F (27.10 M/l). The solubility isotherm (25°) of this compound is presented in Fig. 5. The minimum point on the solubility isotherm approximately corresponds to the stoichiometrical ammonium-niobium ratio of the compound (NfLOsNbsOFig. 

Table 7. Niobium-containing compounds prepared from HF solutions. Reproduced from [61], D. V. Tsikaeva, A. I. Agulyansky, Y. I. Balabanov, V. Y. Kuznetsov, V. T. Kalinnikov, Zh. Neorg. Khim. 34 (1989) 3046, Copyright 1989, with permission of Nauka (Russian Academy of Sciences) publishing.

TaF5 and NbF5 are prepared from their respective oxides by fluorination with fluorine, F2, or with anhydrous hydrogen fluoride, HF [73-75]. Rakov et al. reported the interaction between niobium metal and anhydrous hydrogen fluoride as being the most effective way of preparing NbF5 [76]. 

The stoichiometry of the prepared compounds depends not only on the composition of the initial mixture, but also on the initial oxide s fluorination activity. Unlike tantalum oxide, fluorination of niobium oxide by an ammonium hydrofluoride melt results in the formation of oxyfluoroniobates, but not of fluoroniobates. During the first step of Nb205 fluorination, (NH4)3NbOF6 is formed according to the following interaction [51, 52, 105, 111, 121, 122] ... 

The formation of (NH4)3NbOF6 and its decomposition products define the composition of the niobium fluoride compounds that can be prepared by the hydrofluoride method [123-125]. 

Nickel and copper containing compounds have been prepared in a similar manner. The phases obtained by the simultaneous fluorination of niobium oxide and other bivalent metal oxides were MHNbOF5, M21,Nb03F3 and M4UNb209, where M11 = Co Ni, Cu [129, 131],... 

Raman spectra of fluoride solutions containing niobium were investigated by Keller [171]. Solutions were prepared by dissolving niobium fluoride compounds in solutions of hydrofluoride acid, HF, of different concentrations. 

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