Fluorid-Ion

The -t-4 stale is stabilized in aqueous solution by fluoride ions. Cm02 and Cmp4 are formed by strong oxidation or the action of fluorine. 

Phosphorus pentafluoride PF will readily accept an electron pair from a fluoride ion F to form the stable hexafluorophosphate(V) anion PF C. This ion is isoelectronic with SF. and neither SF nor PF show any notable tendency to accept further electron pairs, though there is some evidence for the existence of an SF ion. 

The melting and boiling points of the aluminium halides, in contrast to the boron compounds, are irregular. It might reasonably be expected that aluminium, being a more metallic element than boron, would form an ionic fluoride and indeed the fact that it remains solid until 1564 K. when it sublimes, would tend to confirm this, although it should not be concluded that the fluoride is, therefore, wholly ionic. The crystal structure is such that each aluminium has a coordination number of six, being surrounded by six fluoride ions. 

The very low bond dissociation enthalpy of fluorine is an important factor contributing to the greater reactivity of fluorine. (This low energy may be due to repulsion between non-bonding electrons on the two adjacent fluorine atoms.) The higher hydration and lattice enthalpies of the fluoride ion are due to the smaller size of this ion. 

The small fluoride ion shows a great tendency to act as a ligand and form complex ions, for example [AIF ] , [PF ], [FeFg] in... 

The bond dissociation energy of the hydrogen-fluorine bond in HF is so great that the above equilibrium lies to the left and hydrogen fluoride is a weak acid in dilute aqueous solution. In more concentrated solution, however, a second equilibrium reaction becomes important with the fluoride ion forming the complex ion HFJ. The relevant equilibria are ... 

Most fluorine-containing compounds can be reduced to the fluoride ion, F , which can be detected by the tests given below. 

Since the acetylenic proton is acidic, it often needs to be protected as a trialkylsilyl derivative. It is conveniently deprotected with fluoride ion. 

Elemental fluorine and the fluoride ion are highly toxic. The free element has a characteristic pungent odor, detectable in concentrations as low as 20 ppb, which is below the safe working level. The recommended maximum allowable concentration for a daily 8-hour time-weighted exposure is 1 ppm. 

Tantalum is a gray, heavy, and very hard metal. When pure, it is ductile and can be drawn into fine wire, which is used as a filament for evaporating metals such as aluminum. Tantalum is almost completely immune to chemical attack at temperatures below ISOoC, and is attacked only by hydrofluoric acid, acidic solutions containing the fluoride ion, and free sulfur trioxide. Alkalis attack it only slowly. At high temperatures, tantalum becomes much more reactive. The element has a melting point exceeded only by tungsten and rhenium. Tantalum is used to make a variety... 

One of the unshared pairs of the hydroxide oxygen is used to form a covalent bond to the positively polar ized proton of hydrogen fluoride The covalent bond betwen H and F in hydrogen fluoride breaks with the pair of electrons in this bond becoming an unshared pair of fluoride ion... 

In media such as water and alcohols fluoride ion is strongly solvated by hydro gen bonding and is neither very basic nor very nucleophilic On the other hand the poorly solvated or naked fluoride 10ns that are present when potassium fluoride dis solves m benzene m the presence of a crown ether are better able to express their anionic reactivity Thus alkyl halides react with potassium fluoride m benzene containing 18 crown 6 thereby providing a method for the preparation of otherwise difficultly acces sible alkyl fluorides... 

The fluoride ion is capable of reacting with glass to form SiF4. 

The titration of AF+ with E in a water-acetonitrile mixture is followed potentiometrically using a fluoride ion-selective electrode. The cumulative formation constant for AlEs is determined from the titration curve. 

The extensive hydrolysis of protactinium in its V oxidation state makes the chemical investigation of protactinium extremely difficult. Ions of protactinium(V) must be held in solution as complexes, eg, with fluoride ion, to prevent hydrolysis. 

Because of the corrosive effects and discomfort associated with inhalation of fluorine, chronic toxicity does not occur. Although the metaboHc fate of fluorine is not clear, it does not seem that much is converted to fluoride ion in the body (107). Therefore comparisons to effects of fluoride ion poisoning, known as fluorosis, are probably incorrect. 

The fluoride ion is the least polarizable anion. It is small, having a diameter of 0.136 nm, 0.045 nm smaller than the chloride ion. The isoelectronic E and ions are the only anions of comparable size to many cations. These anions are about the same size as K" and Ba " and smaller than Rb" and Cs". The small size of E allows for high coordination numbers and leads to different crystal forms and solubiUties, and higher bond energies than are evidenced by the other haUdes. Bonds between fluorine and other elements are strong whereas the fluorine—fluorine bond is much weaker, 158.8 kj/mol (37.95 kcal/mol), than the chlorine—chlorine bond which is 242.58 kJ/mol (57.98 kcal/mol). This bond weakness relative to the second-row elements is also seen ia 0-0 and N—N single bonds and results from electronic repulsion. 

The most popular device for fluoride analysis is the ion-selective electrode (see Electro analytical techniques). Analysis usiag the electrode is rapid and this is especially useful for dilute solutions and water analysis. Because the electrode responds only to free fluoride ion, care must be taken to convert complexed fluoride ions to free fluoride to obtain the total fluoride value (8). The fluoride electrode also can be used as an end poiat detector ia titration of fluoride usiag lanthanum nitrate [10099-59-9]. Often volumetric analysis by titration with thorium nitrate [13823-29-5] or lanthanum nitrate is the method of choice. The fluoride is preferably steam distilled from perchloric or sulfuric acid to prevent iaterference (9,10). Fusion with a sodium carbonate—sodium hydroxide mixture or sodium maybe required if the samples are covalent or iasoluble. 

Fluorides ia small (1 ppm ia water, 0.1% ia dentifrices) quantities have been shown to provide dramatic reduction ia dental decay. Fluorides also show promise for bone treatment and ia pharmaceuticals (qv) (see also Chemotherapeutics, anticancer Steroids). However, larger quantities of fluorides can lead to dental fluorosis, bone fracture, and even death. The oral LD q for free fluoride ion ia rats appears to be 50 to 100 mg/kg body weight based on LD q values for several fluorides. 

Compounds containing fluorine and chlorine are also donors to BF3. Aqueous fluoroboric acid and the tetrafluoroborates of metals, nonmetals, and organic radicals represent a large class of compounds in which the fluoride ion is coordinating with trifluoroborane. Representative examples of these compounds are given in Table 5. Coordination compounds of boron trifluoride with the chlorides of sodium, aluminum, iron, copper, 2inc, tin, and lead have been indicated (53) they are probably chlorotrifluoroborates. 

Toxicity. Fluoroborates are excreted mostly in the urine (22). Sodium fluoroborate is absorbed almost completely into the human bloodstream and over a 14-d experiment all of the NaBF ingested was found in the urine. Although the fluoride ion is covalently bound to boron, the rate of absorption of the physiologically inert BF from the gastrointestinal tract of rats exceeds that of the physiologically active simple fluorides (23). 

For many years fluorine has been deterrnined by the Willard-Winters method in which finely ground ore, after removal of organic matter, is distilled with 72% perchloric acid in glass apparatus. The distillate, a dilute solution of fluorosiUcic acid, is made alkaline to release fluoride ion, adjusted with monochloroacetic acid at pH 3.4, and titrated with thorium nitrate, using sodium a1i2arine sulfonate as indicator. 

Health and Safety Factors. The low solubiUty of calcium fluoride reduces the potential problem of fluoride-related toxicity. Water saturated with calcium fluoride has a fluoride concentration of 8.1 ppm as compared to the recommended water fluoridation level of 1 ppm fluoride ion. However, because the solubiUty of calcium fluoride ia stomach acid is higher, continued oral ingestion of calcium fluoride could produce symptoms of fluorosis. The adopted TWA limit for fluorides as F is 2.5 mg/m (68,69). 

Because of the small size of the fluoride ion, F participates in coordination stmctures of high rank. Tantalum and niobium form stable hexafluorotantalate and hexafluoroniobate ions and hydrogen fluoride attacks these usually acid-resistant metals. Hydrogen fluoride in water is a weak acid. Two dissociation constants are... 

Analytical Procedures. Oxygen difluoride may be determined conveniently by quantitative appHcation of k, nmr, and mass spectroscopy. Purity may also be assessed by vapor pressure measurements. Wet-chemical analyses can be conducted either by digestion with excess NaOH, followed by measurement of the excess base (2) and the fluoride ion (48,49), or by reaction with acidified KI solution, followed by measurement of the Hberated I2 (4). 

The JnitedSfates Pharmacopeia (76) specifications for sodium monofluorophosphate require a minimum of 12.1% fluoride as PO F (theoretical 13.2%) and a maximum of 1.2% fluoride ion reflecting unreacted sodium fluoride. Analysis for PO F is by difference between total fluoride ia the product less fluoride ion as determined by a specific ion electrode. The oral LD q of sodium monofluorophosphate ia rats is 888 mg/kg. 

Halogen exchange with KF is not successful ia acetic acid (10). Hydrogen bonding of the acid hydrogen with the fluoride ion was postulated to cause acetate substitution for the haUde however, the products of dissolved KF ia acetic acid are potassium acetate and potassium bifluoride (11). Thus KF acts as a base rather than as a fluorinating agent ia acetic acid. 

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