Precipitation of fluoride

Waste treatment of fluoroborate solutions includes a pretreatment with aluminum sulfate to facditate hydrolysis, and final precipitation of fluoride with lime (18). The aluminum sulfate treatment can be avoided by hydrolyzing the fluoroborates at pH 2 in the presence of calcium chloride at this pH, hydrolysis is most rapid at elevated temperature (19). 

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. 

Despite many advantages fluoridation may also have some drawbacks. One of the most important is increased formation of dental calculi. As fluoridation considerably reduces the solubility of apatites, the supersaturation of saliva with respect to apatite is appreciably increased and may favour the spontaneous precipitation of fluoridated apatites and the formation of dental calculi. This phenomenon would occur especially in the case of fluoridated toothpaste, and most of them... 

Analysis of the oxyfluoride for osmium and fluorine followed alkaline hydrol3rsis in a closed vessel. A sealed longnecked capsule, containing the sample, was broken by turning a stopcock, into the hore of which, the neck of the capsule extended. The capsule was wholly immersed in aqueous alkali. Osmium was determined by reduction to the metal with hydrazine hydrate.Fluorine was estimated by the Willard and Winter distillation followed hy precipitation of fluoride as PbClF. Fluorine was also determined in the filtrate following the osmium precipitation (Found F, 31T Os, 61-9, F,OOs requires F, 31-5 O, 5-4 Os, 63-1%). 

Fig. 2. Reproducibility of the sub-stoichiometric precipitation of fluoride with lanthanum...

TABLE 7.33. Precipitation of Fluoride from Chlorate Liquor... 

Addition of calcium nitrate solution to a fluoride gives a white precipitate of calcium fluoride, CaFj. If the latter is precipitated slowly, it can be filtered off and weighed to estimate the fluoride. Fluoride can also be determined by the addition of sodium chloride and lead nitrate which precipitate lead chlorofluoride, PbClF. This is filtered off and weighed. 

Add a few drops of saturated calcium chloride solution, and allow to stand for several hours. If fluorine is present, a gelatinous precipitate of calcium fluoride will form. 

Solvent extraction—purification of wet-process phosphoric acid is based on preferential extraction of H PO by an organic solvent vs the cationic impurities present in the acid. Because selectivity of acid over anionic impurities is usually not sufficient, precipitation or evaporation steps are included in the purification process for removal. Cmde wet-process acid is typically concentrated and clarified prior to extraction to remove post-precipitated sludge and improve partition of the acid into the solvent. Concentration also partially eliminates fluoride by evaporation of HF and/or SiF. Chemical precipitation of sulfate (as Ba or Ca salts), fluorosiUcates (as Na salt), and arsenic (as sulfides) may also be used as a prepurification step preceding solvent extraction. 

Sodium alumiaate is an effective precipitant for soluble phosphate ia sewage and is especially useful ia wastewater having low alkaliaity (20,21). Sodium alumiaate hydrolyzes ia water to Al(OH)2 and Al" which precipitate soluble phosphate as aluminum phosphate [7784-30-7], AlPO. Sodium alumiaate has also been described as an effective aid for the removal of fluorides from some iadustrial waste waters (22). Combiaations of sodium alumiaate and other chemicals are being used to improve the detackification of paint particles ia water from spray-painting operations (23). 

Nitric acid oxidizes antimony forming a gelantinous precipitate of a hydrated antimony pentoxide (8). With sulfuric acid an indefinite compound of low solubihty, probably an oxysulfate, is formed. Hydrofluoric acid forms fluorides or fluocomplexes with many insoluble antimony compounds. Hydrochloric acid in the absence of air does not readily react with antimony. Antimony also forms complex ions with organic acids. 

Precipitation of cerous fluoride [7758-88-5] fiom aqueous solution by HF addition produces CeF n Y25 from which the anhydrous... 

When a warm solution of and HCl is allowed to cool, orange needles of KCrO Cl precipitate. The fluoride, bromide, and iodide analogues... 

Preparation of aryl fluorides Addition of fluoroboric acid to a solution of a diazonium salt causes the precipitation of an aryl diazonium fluoroborate. When the dry aryl diazonium fluoroborate is heated, an aryl fluoride results. This is the Schiemann reaction it is the most general method for the preparation of aryl fluorides. 

With the exception of the fluorides, the halides are all very water-soluble and deliquescent, Precipitation of the insoluble fluorides can be used as a qualitative test for these elements. The distinctive ability of Sc to form complexes is illustrated by the fact that an excess of F causes the first-precipitated SCF3 to redissolve as... 

A town adds 2.0 ppm of F ion to fluoridate its water supply (fluoridation of water reduces the incidence of dental caries). If the concentration of Ca2+ in the water is 3.5 X 10-4 M, will a precipitate of CaF2 form when the water is fluoridated ... 

No available data was found on the precipitation from fluoride solutions of niobium and tantalum fluoride compounds containing tri- and tetravalent metals. 

The addition of ammonium fluoride leads to the precipitation of ammonium hydrofluoride, NH4HF2. 

The fact that tantalum and niobium complexes form in fluoride solutions not only supplements fundamental data on the coordination chemistry of fluoride compounds, but also has a broad practical importance. This type of solution is widely used in the technology of tantalum and niobium compounds in raw material digestion, liquid-liquid extraction, precipitation and re-pulping of hydroxides, and in the crystallization and re-crystallization of K-salts and other complex fluoride compounds. 

The process of separating the intermediate products from the purified solutions, in the form of solid complex fluoride salts or hydroxides, is also related to the behavior of tantalum and niobium complexes in solutions of different compositions. The precipitation of complex fluoride compounds must be performed under conditions that prevent hydrolysis, whereas the precipitation of hydroxides is intended to be performed along with hydrolysis in order to reduce contamination of the oxide material by fluorine. 

The optimal temperature range for the fluorination process was found to be about 230-290°C. The resulting cake was leached with water. The prepared solution was separated from the precipitate by regular filtration and the separated insoluble precipitate was identified as lithium fluoride, LiF. The solution contained up to 90 g/1 Ta205. Solution acidity was relatively low, with a typical pH = 3-4, and was suitable for the precipitation of potassium heptafluorotantalate, K2TaF7, tantalum hydroxide or further purification by liquid-liquid extraction after appropriate adjustment of the solution acidity [113]. 

The optimal temperature range for the interaction was found to be 150-230°C. The cake resulting from the fluorination process was also successfully leached with water, dissolving ammonium oxyfluoroniobate, (NH4)3NbOF6. The solution was separated from the precipitate of lithium fluoride. The main parameters of the solution were a niobium concentration of about 75 g/1 Nb205, pH = 3—4. 

The cake is leached with water in order to dissolve tantalum and niobium (and other related compounds) in the form of fluoride salts of ammonium. Ammonium fluoroferrate and fluoromanganate are unstable in aqueous solutions of low acidity. It is assumed that iron and manganese will form precipitates of insoluble fluorides or oxyfluorides that can be separated from the solution by filtration. 

Equations (141) and (142) describe the equilibrium between the hydrolysis of complex fluoride acids (shift to the right) and the fluorination of hydroxides (shift to the left). Near complete precipitation of hydroxides can be achieved by applying an excessive amount of ammonia. Typically, precipitation is performed by adding ammonia solution up to pH = 8-9. However, the precipitate that separates from the mother solution can be contaminated with as much as 20% wt. fluorine [490]. Analysis of niobium hydroxides obtained under different precipitation conditions showed that the most important parameter affecting the fluorine content of the resultant hydroxide is the amount of ammonia added [490]. Sheka et al. [491] found that increasing the pH to 9.6 toward the end of the precipitation process leads to a significant reduction in fluorine content of the niobium hydroxide. 

Potassium heptafluorotantalate, K2TaF7, or as it is called by its commercial name K-salt, is a starting material for tantalum metal production. K-salt is produced by adding potassium fluoride, KF, or potassium chloride, KC1, to a tantalum strip solution that results from a liquid-liquid extraction process. In order to prevent hydrolysis and co-precipitation of potassium oxyfluoro-tantalate, a small excess of HF is added to the solution [24]. Another way to avoid the possible formation and co-precipitation of oxyfluoride phases is to use potassium hydrofluoride, KHF2, as a potassium-containing agent. The yield of the precipitation depends mostly on the concentration of the potassium-containing salt and is independent of the HF concentration [535]. 

Modem refining technology uses tantalum and niobium fluoride compounds, and includes fluorination of raw material, separation and purification of tantalum and niobium by liquid-liquid extraction from such fluoride solutions. Preparation of additional products and by-products is also related to the treatment of fluoride solutions oxide production is based on the hydrolysis of tantalum and niobium fluorides into hydroxides production of potassium fluorotantalate (K - salt) requires the precipitation of fine crystals and finishing avoiding hydrolysis. Tantalum metal production is related to the chemistry of fluoride melts and is performed by sodium reduction of fluoride melts. Thus, the refining technology of tantalum and niobium involves work with tantalum and niobium fluoride compounds in solid, dissolved and molten states. 

DETERMINATION OF FLUORIDE PRECIPITATION AS LEAD CHL0R0FLU0RIDE COUPLED WITH VOLHARD TITRATION... 

---