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Fluorine

Chan Chun Wing Jason


5th December, 2010

Table of Contents
Introduction: .................................................................................................................. 3 Its Physical Properties: .................................................................................................. 3 Its Chemical Properties:................................................................................................ 3 Its Natural Occurrence: ................................................................................................ 3 Its Isotopes: .................................................................................................................... 4 Its some types of reactions: ......................................................................................... 4 Reaction of fluorine with air ...................................................................................... 5 Reaction of fluorine with water ................................................................................ 5 Reaction of fluorine with the halogens ................................................................... 5 Reaction of fluorine with acids ................................................................................. 6 Reaction of fluorine with bases ................................................................................ 6 Its Compounds: ............................................................................................................. 6 Fluorides ...................................................................................................................... 6 Hydrofluoric acid ....................................................................................................... 6 Noble gas compounds ............................................................................................. 7 Organofluorine Compounds .................................................................................... 7 Its Uses: ........................................................................................................................... 7 Industrial use of fluorine-containing compounds ................................................... 7 Dental uses ................................................................................................................. 8 Pharmaceuticals and agrichemicals ...................................................................... 8 Its Industrial Production: ............................................................................................... 9

Introduction:
Fluorine is an nonmetallic chemical element, chemical symbol F, atomic number 9. The lightest halogen, it is the most reactive element, forming compounds with all others except the lighter noble gases like argon, neon and helium. Its only valence is 1, in F2 (the diatomic molecule) and fluorides. A toxic, pale yellow gas with a pungent odour, it can be produced only by electrolysis under special conditions. Its chief source is fluorite; it also occurs in cryolite, fluorapatite, seawater, bones, and teeth. Hydrogen fluoride (HF) is a raw material for many other fluorides. Its water solution, hydrofluoric acid, is used to clean metals and to polish, etch, or frost glass. Other fluorides are useful catalysts and raw materials. Sodium fluoride (NaF) is added to water and tin fluoride (SnF2) to dental-care products to reduce dental caries (see fluoridation of water). Fluorocarbons are hydrocarbons in which some hydrogen atoms have been replaced by fluorine atoms; examples include Freons and Teflon.

Its Physical Properties:


Property Atomic weight Boiling point, C Freezing point, C Critical temperature, C Critical pressure, atm* Density of liquid at b.p., g/ml Density of gas at 0C + 1 atm*, g/liter Dissociation energy, kcal/mol Heat of vaporization, cal/mol Heat of fusion, cal/mol Transition temperature (solid), C
*1 atm = 101.325 kilopascals.

Value 18.998403 188.13 219.61 129.2 55 1.505 1.696 36.8 1510 121.98 227.61

Its Chemical Properties:


Fluorine as a freely reacting oxidant gives the strongest oxidants known.

Its Natural Occurrence:


At an estimated 0.065% of the Earth's crust, fluorine is roughly as plentiful as carbon, nitrogen, or chlorine, and much more plentiful than copper or lead, though much less abundant than iron, aluminum, or magnesium. Compounds whose molecules contain atoms of fluorine are widely distributed in nature. Many minerals contain small amounts of the element, and it is found in both sedimentary and igneous rocks.

Its Isotopes:
Although fluorine (F) has multiple isotopes, only one of these isotopes is stable; as such, it is considered a monoisotopic element. Standard atomic mass: 18.9984032(5) u The nuclide 18F is the radionuclide of fluorine with the longest half-life, about 110 minutes, which is almost 2 hours, and commercially is an important source of positrons- finding its major use in positron emission tomography scanning. representative isotopic composition (mole fraction)

nuclide symbol
14 15

Z(p)

N(n)

isotopic mass (u)

half-life

nuclear spin

F F 16 F 17 F 18 F
18m 19

F 20 F 21 F 22 F 23 F 24 F 25 F 26 F 27 F 28 F 29 F 30 F 31 F

excitation energy 9 5 14.03506(43)# 9 6 15.01801(14) 9 7 16.011466(9) 9 8 17.00209524(27) 9 9 18.0009380(6) 1121.36(15) keV 9 10 18.99840322(7) 9 11 19.99998132(8) 9 12 20.9999490(19) 9 13 22.002999(13) 9 14 23.00357(9) 9 15 24.00812(8) 9 16 25.01210(11) 9 17 26.01962(18) 9 18 27.02676(40) 9 19 28.03567(55)# 9 20 29.04326(62)# 9 21 30.05250(64)# 9 22 31.06043(64)#

410(60)E-24 s [1.0(2) MeV] 11(6)E-21 s [40(20) keV] 64.49(16) s 109.771(20) min 162(7) ns Stable 11.163(8) s 4.158(20) s 4.23(4) s 2.23(14) s 400(50) ms 50(6) ms 9.6(8) ms 4.9(2) ms <40 ns 2.6(3) ms <260 ns 1# ms [>260 ns]

2-# (1/2+) 05/2+ 1+ 5+ 1/2+ 1.0000 2+ 5/2+ 4+,(3+) (3/2,5/2)+ (1,2,3)+ (5/2+)# 1+ 5/2+# 5/2+# 5/2+#

Values marked # are not purely derived from experimental data, but at least partly from systematic trends. Spins with weak assignment arguments are enclosed in parentheses.Uncertainties are given in concise form in parentheses after the corresponding last digits. Uncertainty values denote one standard deviation, except isotopic composition and standard atomic mass from IUPAC which use expanded uncertainties.

Its some types of reactions:


Fluorine reacts with considerable violence with most hydrogen-containing compounds, such as water, ammonia, and all organic chemical substances whether liquids, solids, or gases. The reaction of fluorine with water is very complex, yielding mainly hydrogen fluoride and oxygen with less amounts of hydrogen peroxide, oxygen difluoride, and ozone. Fluorine displaces other nonmetallic elements from their compounds, even those nearest fluorine in chemical activity. It displaces chlorine from sodium 4

chloride, and oxygen from silica, glass, and some ceramic materials. In the absence of hydrofluoric acid, however, fluorine does not significantly etch quartz or glass even after several hours at temperatures as high as 390F (200C). Fluorine is a very toxic and reactive element. Many of its compounds, especially inorganic, are also toxic and can cause severe and deep burns. Care must be taken to prevent liquids or vapors from coming in contact with the skin or eyes.

Reaction of fluorine with air


Fluorine, F2 is not particularly reactive towards with oxygen, O2, or nitrogen, N2. It reacts with moisture in air to form oxygen, O2. 2F2(g) + 2H2O(g) O2(g) + 4HF(g)

Reaction of fluorine with water


Fluorine reacts with water to produce oxygen, O2, and ozone, O3. 2F2(g) + 2H2O(l) O2(g) + 4HF(aq) 3F2(g) + 3H2O(l) O3(g) + 6HF(aq)

Reaction of fluorine with the halogens


Fluorine, F2, reacts with chlorine, Cl2, at 225C to form the interhalogen species ClF. The trifluoride chlorine(III) fluoride is also formed and the reaction does not go to completion. Cl2(g) + F2(g) 2ClF(g) Cl2(g) + 3F2(g) 2ClF3(g) Under more forcing conditions, excess fluorine reacts with chlorine, Cl2, at 350C and 225 atmospheres pressure to form the interhalogen species ClF5. Cl2(g) + 5F2(g) 2ClF5(g) Fluorine, F2, reacts with bromine, Br2, in the gas phase to form the interhalogen species BrF. The product is difficult to obtain pure since BrF disproportionates at toom temperature to form bromine, Br2, and BrF3 and BrF5. Br2(g) + F2(g) 2BrF(g) 3BrF(g) Br2(l) + BrF3(l) 5BrF(g) 2Br2(l) + BrF5(l) Under more forcing conditions, excess fluorine reacts with bromine, Br2, at 150C to form the interhalogen species BrF5.

Br2(l) + 5F2(g) 2BrF5(l) Fluorine, F2, reacts with iodine, I2, at about -45C in CCl3F solvent to form the interhalogen species IF. The product is dificult to obtain pure since IF disproportionates at toom temperature to form iodine, I2, and IF5. I2(g) + F2(g) 2IF(g) 5IF(g) 2I2(s) + IF5(l)

Reaction of fluorine with acids


With dilute acids, fluorine's reaction is probaly dominated by that with water, which produces oxygen, O2, and ozone, O3. 2F2(g) + 2H2O(l) O2(g) + 4HF(aq) 3F2(g) + 3H2O(l) O3(g) + 6HF(aq)

Reaction of fluorine with bases


Fluorine, F2 reacts with dilute aqueous hydroxide solutions to form oxygen(II) fluoride. 2F2(g) + 2OH-(aq) OF2(g) + 2F-(aq) + H2O(l)

Its Compounds:
Fluorine forms a variety of very different compounds, owing to its small atomic size and covalent behavior. Elemental fluorine is a dangerously powerful oxidant, reflecting the extreme electronegativity of fluorine. Hydrofluoric acid is extremely dangerous, whereas, in synthetic drugs incorporating an aromatic ring (e.g., flumazenil), fluorine is used to help prevent toxication or to delay metabolism.

Fluorides
Fluorides are compounds that combine fluorine with some positively charged counterpart. They often consist of crystalline ionic salts. Fluorine compounds with metals are among the most stable of salts.

Hydrofluoric acid
Hydrogen fluoride is a weak acid when dissolved in water, but is still very corrosive and attacks glass. Consequently, fluorides of alkali metals produce basic solutions. For example, a 1 M solution of NaF in water has a pH of 8.59 compared to a 1 M solution of NaOH, a strong base, which has a pH of 14.00. The fluoride ion is basic, therefore hydrofluoric acid is a weak acid in water solution. However, water is not an inert solvent in this case: When less basic solvents such as anhydrous acetic acid are used, hydrofluoric acid is the strongest of the hydrohalogenic acids. Also, owing to the basicity of the fluoride ion, soluble fluorides give basic water solutions. The fluoride ion is a Lewis base, and has a high affinity to certain elements such as calcium and silicon. For example, deprotection of silicon protecting groups is achieved with a fluoride. The fluoride ion is poisonous.

Noble gas compounds


The reactivity of fluorine toward the noble gas xenon was first reported by Neil Bartlett in 1962. Fluorides of krypton and radon have also been prepared. Argon fluorohydride has been observed at cryogenic temperatures.

Organofluorine Compounds
The carbon-fluoride bond is covalent and very stable. The use of a fluorocarbon polymer, poly(tetrafluoroethene) or Teflon, is an example: It is thermostable and waterproof enough to be used in frying pans. Organofluorines may be safely used in applications such as drugs, without the risk of release of toxic fluoride. In synthetic drugs, toxication can be prevented. For example, an aromatic ring is useful but presents a safety problem: enzymes in the body metabolize some of them into poisonous epoxides. When the para position is substituted with fluorine, the aromatic ring is protected and epoxide is no longer produced. The substitution of fluorine for hydrogen in organic compounds offers a very large number of compounds. These compounds often feature single C-F units, but -CF3 and -OCF3 group provide further variation, and more recently the -SF5 group.

Its Uses:
Fluorine-containing compounds are used to increase the fluidity of melts and slags in the glass and ceramic industries. Fluorspar (calcium fluoride) is introduced into the blast furnace to reduce the viscosity of the slag in the metallurgy of iron. Cryolite, Na2AlF6, is used to form the electrolyte in the metallurgy of aluminum. Aluminum oxide is dissolved in this electrolyte, and the metal is reduced electrically from the melt. The use of halocarbons containing fluorine as refrigerants was patented in 1930, and these volatile and stable compounds found a market in aerosol propellants as well as in refrigeration and air-conditioning systems. However, use of fluorocarbons as propellants has declined sharply because of concern over their possible damage to the ozone layer of the atmosphere. A use for fluorine that became prominent during World War II is in the enrichment of the fissionable isotope 235U; the most important process employed uranium hexafluoride. This stable, volatile compound was by far the most suitable material for isotope separation by gaseous diffusion. While consumers are mostly unaware of the fluorine compounds used in industry, some compounds have become familiar to the general public through minor but important uses, such as additives to toothpaste and nonsticking fluoropolymer surfaces on frying pans and razor blades (for example Teflon).

Industrial use of fluorine-containing compounds


Atomic fluorine and molecular fluorine are used for plasma etching in semiconductor manufacturing, flat panel display production and MEMS (microelectromechanical systems) fabrication. Xenon difluoride is also used for this last purpose. Hydrofluoric acid (chemical formula HF) is used to etch glass in light bulbs and other products. Tetrafluoroethylene and perfluorooctanoic acid (PFOA) are directly used in the production of low friction plastics such as Teflon (or polytetrafluoroethylene). 7

Fluorine is used indirectly in the production of halons such as freon. Along with some of its compounds, fluorine is used in the production of pure uranium from uranium hexafluoride and in the synthesis of numerous commercial fluorochemicals, including vitally important pharmaceuticals, agrochemical compounds, lubricants, and textiles. Chlorofluorocarbons (CFCs) are used extensively in air conditioning and in refrigeration. CFCs have been banned for these applications because they contribute to ozone destruction and the ozone hole. It is interesting to note that, since it is chlorine and bromine radicals that harm the ozone layer, not fluorine, compounds that do not contain chlorine or bromine but contain only fluorine, carbon, and hydrogen (called hydrofluorocarbons) are not on the United States Environmental Protection Agency list of ozone-depleting substances, and have been widely used as replacements for the chlorine- and bromine-containing fluorocarbons. Hydrofluorocarbons do have a greenhouse effect, but a small one compared with carbon dioxide and methane. Sodium hexafluoroaluminate (cryolite), is used in the electrolysis of aluminium. In much higher concentrations, sodium fluoride has been used as an insecticide, especially against cockroaches. Fluorides have been used in the past to help molten metal flow, hence the name, which derives from Latin verb fluere, meaning to flow. Some researchers including US space scientists in the early 1960s have studied elemental fluorine gas as a possible rocket propellant due to its exceptionally high specific impulse. The experiments failed because fluorine proved difficult to handle, and its combustion products proved extremely toxic and corrosive. Compounds of fluorine such as fluoropolymers, potassium fluoride, and cryolite are utilized in applications such as anti-reflective coatings and dichroic mirrors on account of their unusually low refractive index. Sulfur hexafluoride is used in high voltage switch gear as a dielectric medium.

Dental uses
Inorganic compounds of fluoride, including sodium fluoride (NaF), stannous fluoride (SnF2) and sodium MFP, are used in toothpaste to prevent dental cavities. These or related compounds are also added to some municipal water supplies, a process called water fluoridation, although the practice has remained controversial since its beginnings in 1945.

Pharmaceuticals and agrichemicals


An estimated fifth of pharmaceutical compounds and 30% of agrochemical compounds contain fluorine. Many important agents for general anesthesia such as sevoflurane, desflurane, and isoflurane are hydrofluorocarbon derivatives. The fluorinated antiinflammatories dexamethasone and triamcinolone are among the most potent of the synthetic corticosteroids class of drugs. Fludrocortisone ("Florinef") is one of the most common mineralocorticoids, a class of drugs that mimics the actions of aldosterone.

Fluconazole is a triazole antifungal drug used in the treatment and prevention of superficial and systemic fungal infections. Fluoroquinolones are a family of broad-spectrum antibiotics. SSRI antidepressants, except in a few instances, are fluorinated molecules. These include citalopram, escitalopram, fluoxetine, fluvoxamine, and paroxetine. A notable exception is sertraline. Because of the difficulty of biological systems in dealing with metabolism of fluorinated molecules, fluorinated antibiotics and antidepressants are among the major fluorinated organics found in treated city sewage and wastewater. Compounds containing 18F, a radioactive isotope that emits positrons, are often used in positron emission tomography, because its half-life of 110 minutes is long by the standards of positron-emitters. One such species is fluorodeoxyglucose. The main isotope of fluorine,19F, in the form of inert fluorinated gases or liquids, is used as the imaged nucleus in MRI. Many medicinal drugs have increased lipophilicity from containing fluorine in their chemical structure. This enhancement of lipophilicity increases the drugs bioavailability from increased cell wall penetration.

Its Industrial Production:


Industrial production of fluorine entails the electrolysis of hydrogen fluoride in the presence of potassium fluoride. This method is based on the pioneering studies by Moissan. Fluorine gas forms at the anode, and hydrogen gas at the cathode. Under these conditions, the potassium fluoride (KF) converts to potassium bifluoride (KHF2), which is the actual electrolyte. This potassium bifluoride aids electrolysis by greatly increasing the electrical conductivity of the solution. The hydrogen fluoride (HF) required for the electrolysis is typically obtained from phosphate-containing minerals with significant amounts of calcium fluorides (e.g. calcium fluorite, CaF2). Upon treatment with sulfuric acid (H2SO4), the phosphate-containing minerals release hydrogen fluoride as follows: HF + KF KHF2 2KHF2 2KF + H2 + F2 CaF2 + H2SO4 2HF + CaSO4 In 1986, while preparing for a conference to celebrate the 100th anniversary of the discovery of fluorine, Karl Christe discovered a purely chemical preparation involving the reaction of solutions in anhydrous HF, K2MnF6, and SbF5 at 150 C: 2K2MnF6 + 4SbF5 4KSbF6 + 2MnF3 + F2 Though its not a practical synthesis on the large scale, this report demonstrates that electrolysis is not the sole route to the element.

This fluorine production process, however, can be energy intensive because electrolysis requires a large amount of energy to operate. Also, such processes can have high operating costs because of the constant requirement for mineral extraction. Molecular fluorine, F2, is mainly used for the production of two compounds of commercial interest, uranium hexafluoride and sulfur hexafluoride

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