Fluorine/fluoride solubility

Siher I) fluoride, AgF, is prepared by evaporation of a solution of excess Ag20 in HF after filtration or by heating anhydrous AgBF. The anhydrous salt is yellow hydrates are known, It is very soluble in water and in many organic solvents. Used as a mild fluorinating agent. On treatment of a solution with Ag a sub-fluoride, Ag2F, is formed. 

The presence of fluorine as a soluble fluoride in drinking water to the extent of 2 ppm may cause mottled enamel in teeth, when used by children acquiring permanent teeth in smaller amounts, however, fluorides are added to water supplies to prevent dental cavities. 

In the geochemistry of fluorine, the close match in the ionic radii of fluoride (0.136 nm), hydroxide (0.140 nm), and oxide ion (0.140 nm) allows a sequential replacement of oxygen by fluorine in a wide variety of minerals. This accounts for the wide dissemination of the element in nature. The ready formation of volatile silicon tetrafluoride, the pyrohydrolysis of fluorides to hydrogen fluoride, and the low solubility of calcium fluoride and of calcium fluorophosphates, have provided a geochemical cycle in which fluorine may be stripped from solution by limestone and by apatite to form the deposits of fluorspar and of phosphate rock (fluoroapatite [1306-01 -0]) approximately CaF2 3Ca2(P0 2 which ate the world s main resources of fluorine (1). 

Although stable at ambieat temperature, calcium fluoride is slowly hydrolyzed by moist air at about 1200°C, presumably to CaO and HF. Calcium fluoride is not attacked by alkahes or by reactive fluorine compounds, but is decomposed by hot, high boiling acids, as ia the reactioa with coaceatrated sulfuric acid which is the process used to produce hydrogea fluoride. Calcium fluoride is slightly soluble ia cold dilute acids, and somewhat more soluble ia solutioas of alumiaum hahdes. 

Hydrofluoric acid, at relatively high concentrations and at elevated temperatures, dissolves columbite-tantalite concentrates at a reasonable rate. The dissolution process is based on the fluorination of tantalum, niobium and other metal oxides and their conversion into soluble complex fluoride acids yielding complex fluoride ions. 

In both cases, the fluorination of the complex oxides of tantalum and niobium leads to the formation of the water-soluble compounds (NH4)2TaF7 and (NH4)3NbOF6, the insoluble lithium fluoride and die gaseous components H20, NH3 and HF. 

Another way of applying the selective extraction method directly on the initial solution is to produce a solution of low acidity. This can be achieved by using the hydrofluoride method for fluorination and decomposition of raw material. As was discussed in Paragraph 8.2.2, the raw material is fluorinated by molten ammonium hydrofluoride yielding soluble complex fluorides of ammonium and tantalum or niobium. The cake obtained following fluorination is dissolved in water, leading to a solution of low initial acidity that is related for the most part to the partial hydrolysis of complex fluoride compounds. The acidity of the solution is first adjusted to ensure selective tantalum extraction. In the second step, the acidity of the raffinate is increased to provide the necessary conditions for niobium extraction. 

Because the fluoride ion is so small, the lattice enthalpies of its ionic compounds tend to be high (see Table 6.6). As a result, fluorides are less soluble than other halides. This difference in solubility is one of the reasons why the oceans are salty with chlorides rather than fluorides, even though fluorine is more abundant than chlorine in the Earth s crust. Chlorides are more readily dissolved and washed out to sea. There are some exceptions to this trend in solubilities, including AgF, which is soluble the other silver halides are insoluble. The exception arises because the covalent character of the silver halides increases from AgCl to Agl as the anion becomes larger and more polarizable. Silver fluoride, which contains the small and almost unpolarizable fluoride ion, is freely soluble in water because it is predominantly ionic. 

The halogens show smooth trends in chemical properties down the group fluorine has some anomalous properties, such as its strength as an oxidizing agent and the lower solubilities of most fluorides. 

Sodium beryllium fluoride (Na2BeF4) is water-soluble and sodium aluminum fluoride (Na,AlF6) is water-insoluble. A part of the silicon volatilizes off as silicon tetrafluoride (SiF4), while the other part remains in the residue as silicon dioxide (Si02). Fluorination of silicon is unnecessary and it would be economical to recover all of it as silica. This is accomplished by using soda ash, i.e., sodium carbonate (Na2C03) in the reaction mixture ... 

Inorganic salts that contain halogens are usually soluble. They commonly occur as simple, single, negatively charged anions in soil. There are two common exceptions to this generalization. First, fluorine is commonly found bonded to phosphate in insoluble minerals called apatites, which are calcium phosphate fluorides. 

Fluorine is an essential element involved in several enzymatic reactions in various organs, it is present as a trace element in bone mineral, dentine and tooth enamel and is considered as one of the most efficient elements for the prophylaxis and treatment of dental caries. In addition to their direct effect on cell biology, fluoride ions can also modify the physico-chemical properties of materials (solubility, structure and microstructure, surface properties), resulting in indirect biological effects. The biological and physico-chemical roles of fluoride ions are the main reasons for their incorporation in biomaterials, with a pre-eminence for the biological role and often both in conjunction. This chapter focuses on fluoridated bioceramics and related materials, including cements. The specific role of fluorinated polymers and molecules will not be reviewed here. 

Mesophase pitch, consisting of a mixture of various aromatic hydrocarbons, reacts with fluorine between 50-130°C to give pitch fluorides [56] with the composition CFj 3 to CF159. These materials have a higher fluorine content than graphite fluoride (see Section 2.7), have very low surface energy and are soluble in some fluorinated solvents. 

Where the organic substrate is sufficiently volatile, and not very soluble in hydrogen fluoride, the process can be highly efficient for many fluorinations, with current efficiencies between 80-100%. 

Thus, although the CAVE process has definite value in its ability to fluorinate smoothly certain organic compounds which are not particularly amenable to other methods of fluorination, for example, by the ECF Simons process, its general application is obviously severely limited by the combined requirements that substrates be only slightly soluble in hydrogen fluoride and sufficiently volatile at the temperature of the cell ( 100 °C) to permit diffusion though the porous carbon matrix of the anode. 

Thus, a stable derivative of phosphorus triamide, P(NH2)3, could not be obtained. Such expectations were encouraged by recent work of Kodama and Parry (12), who succeeded in ammonolyzing phosphorus trifluoride-borane, F3P.BH3, with formation of a stable phosphorus triamide-borane, (H2N)3P.BH3. Ammonolysis of boron- or phosphorus-fluorine rather than -chlorine bonds is advantageous, since ammonium fluoride is insoluble in liquid ammonia and can easily be separated, while ammonium chloride is readily soluble. 

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