Fluorine

Proposed as an element in 1810, fluorine proved difficult and dangerous to separate from its compounds, and several early experimenters died or sustained injuries from their attempts.

Industrial production of fluorine gas for uranium enrichment, its largest application, began during the Manhattan Project in World War II.

Fluorine has no known metabolic role in mammals; a few plants and marine sponges synthesize organofluorine poisons (most often monofluoroacetates) that help deter predation.

[34][35] Oxygen does not combine with fluorine under ambient conditions, but can be made to react using electric discharge at low temperatures and pressures; the products tend to disintegrate into their constituent elements when heated.

[note 6] Andreas Sigismund Marggraf first characterized it in 1764 when he heated fluorite with sulfuric acid, and the resulting solution corroded its glass container.

[82] He also proposed in a letter to Sir Humphry Davy dated August 26, 1812 that this then-unknown substance may be named fluorine from fluoric acid and the -ine suffix of other halogens.

[77][87][88] Frémy's former student Henri Moissan persevered, and after much trial and error found that a mixture of potassium bifluoride and dry hydrogen fluoride was a conductor, enabling electrolysis.

[88][90] In 1906, two months before his death, Moissan received the Nobel Prize in Chemistry,[91] with the following citation:[87] [I]n recognition of the great services rendered by him in his investigation and isolation of the element fluorine ...

[80][92][93][94] Polytetrafluoroethylene (Teflon) was serendipitously discovered in 1938 by Roy J. Plunkett while working on refrigerants at Kinetic, and its superlative chemical and thermal resistance lent it to accelerated commercialization and mass production by 1941.

Since UF6 is as corrosive as fluorine, gaseous diffusion plants required special materials: nickel for membranes, fluoropolymers for seals, and liquid fluorocarbons as coolants and lubricants.

These compounds share many properties with perfluorocarbons such as stability and hydrophobicity,[162] while the functional group augments their reactivity, enabling them to adhere to surfaces or act as surfactants.

[164] Polytetrafluoroethylene (PTFE), the simplest fluoropolymer and perfluoro analogue of polyethylene with structural unit –CF2–, demonstrates this change as expected, but its very high melting point makes it difficult to mold.

[170] About 20% of manufactured HF is a byproduct of fertilizer production, which produces hexafluorosilicic acid (H2SiF6), which can be degraded to release HF thermally and by hydrolysis: Moissan's method is used to produce industrial quantities of fluorine, via the electrolysis of a potassium bifluoride/hydrogen fluoride mixture: hydrogen ions are reduced at a steel container cathode and fluoride ions are oxidized at a carbon block anode, under 8–12 volts, to generate hydrogen and fluorine gas respectively.

[176] While preparing for a 1986 conference to celebrate the centennial of Moissan's achievement, Karl O. Christe reasoned that chemical fluorine generation should be feasible since some metal fluoride anions have no stable neutral counterparts; their acidification potentially triggers oxidation instead.

He devised a method which evolves fluorine at high yield and atmospheric pressure:[177] Christe later commented that the reactants "had been known for more than 100 years and even Moissan could have come up with this scheme.

[185] Fluorine is monoisotopic, so any mass differences between UF6 molecules are due to the presence of 235U or 238U, enabling uranium enrichment via gaseous diffusion or gas centrifuge.

[5][65] About 6,000 metric tons per year go into producing the inert dielectric SF6 for high-voltage transformers and circuit breakers, eliminating the need for hazardous polychlorinated biphenyls associated with oil-filled devices.

[186] Several fluorine compounds are used in electronics: rhenium and tungsten hexafluoride in chemical vapor deposition, tetrafluoromethane in plasma etching[187][188][189] and nitrogen trifluoride in cleaning equipment.

[65] As with other iron alloys, around 3 kg (6.6 lb) metspar is added to each metric ton of steel; the fluoride ions lower its melting point and viscosity.

[92][196] Halogenated refrigerants, termed Freons in informal contexts,[note 16] are identified by R-numbers that denote the amount of fluorine, chlorine, carbon, and hydrogen present.

[227] Tricyclics and other pre-1980s antidepressants had several side effects due to their non-selective interference with neurotransmitters other than the serotonin target; the fluorinated fluoxetine was selective and one of the first to avoid this problem.

Many current antidepressants receive this same treatment, including the selective serotonin reuptake inhibitors: citalopram, its enantiomer escitalopram, and fluvoxamine and paroxetine.

[237][238] Fluorine-18 is often found in radioactive tracers for positron emission tomography, as its half-life of almost two hours is long enough to allow for its transport from production facilities to imaging centers.

[250] Both the WHO and the Institute of Medicine of the US National Academies publish recommended daily allowance (RDA) and upper tolerated intake of fluorine, which varies with age and gender.

[273] One-fifth of the lethal dose can cause adverse health effects,[274] and chronic excess consumption may lead to skeletal fluorosis, which affects millions in Asia and Africa, and, in children, to reduced intelligence.

[274][275] Ingested fluoride forms hydrofluoric acid in the stomach which is easily absorbed by the intestines, where it crosses cell membranes, binds with calcium and interferes with various enzymes, before urinary excretion.

[279] One regional study examined a year of pre-teen fluoride poisoning reports totaling 87 cases, including one death from ingesting insecticide.

The high stability which suited them to their original applications also meant that they were not decomposing until they reached higher altitudes, where liberated chlorine and bromine atoms attacked ozone molecules.

[291][292][293] PFAAs have been found in trace quantities worldwide from polar bears to humans, with PFOS and PFOA known to reside in breast milk and the blood of newborn babies.

[291][292][295] High doses of PFOS and PFOA cause cancer and death in newborn rodents but human studies have not established an effect at current exposure levels.

Color lines in a spectral range
Fluorine 3D molecule
Cube with spherical shapes on the corners and center and spinning molecules in planes in faces
Crystal structure of β-fluorine. Spheres indicate F
2
molecules that may assume any angle. Other molecules are constrained to planes.
Animation showing the crystal structure of beta-fluorine. Molecules on the faces of the unit cell have rotations constrained to a plane.
Woodcut image showing man at open hearth with tongs and machine bellows to the side in background, man at water-operated hammer with quenching sluice nearby in foreground
Steelmaking illustration from De re metallica
1887 drawing of Moissan's apparatus
Graph showing water and hydrogen fluoride breaking the trend of lower boiling points for lighter molecules
Boiling points of hydrogen halides and chalcogenides, showing the unusually high values for hydrogen fluoride and water
Chlorine trifluoride , whose corrosive potential ignites asbestos, concrete, sand and other fire retardants [ 133 ]
Black-and-white photo showing transparent crystals in a dish
These xenon tetrafluoride crystals were photographed in 1962. The compound's synthesis, as with xenon hexafluoroplatinate, surprised many chemists. [ 147 ]
Beaker with two layers of liquid, goldfish and crab in top, coin sunk in the bottom
Immiscible layers of colored water (top) and much denser perfluoroheptane (bottom) in a beaker; a goldfish and crab cannot penetrate the boundary; quarters rest at the bottom.
Skeletal chemical formula
Chemical structure of Nafion , a fluoropolymer used in fuel cells and many other applications [ 155 ]
A machine room
Industrial fluorine cells at Preston
Fluorite Fluorapatite Hydrogen fluoride Metal smelting Glass production Fluorocarbons Sodium hexafluoroaluminate Pickling (metal) Fluorosilicic acid Alkane cracking Hydrofluorocarbon Hydrochlorofluorocarbons Chlorofluorocarbon Teflon Water fluoridation Uranium enrichment Sulfur hexafluoride Tungsten hexafluoride Phosphogypsum
Clickable diagram of the fluorochemical industry according to mass flows
Minaret-like electrical devices with wires around them, thicker at the bottom
SF
6
current transformers at a Russian railway
Aluminium extraction depends critically on cryolite
Shiny spherical drop of water on blue cloth
Fluorosurfactant-treated fabrics are often hydrophobic .
Man holding plastic tray with brown material in it and sticking a small stick into a boy's open mouth
Topical fluoride treatment in Panama
Capsules with "Prozac" and "DISTA" visible
Fluoxetine capsules
Rotating transparent image of a human figure with targeted organs highlighted
A full-body 18
F
PET scan with glucose tagged with radioactive fluorine-18. The normal brain and kidneys take up enough glucose to be imaged. A malignant tumor is seen in the upper abdomen. Radioactive fluorine is seen in urine in the bladder.
NFPA 704 four-colored diamond Health 4: Very short exposure could cause death or major residual injury. E.g. VX gas Flammability 0: Will not burn. E.g. water Instability 4: Readily capable of detonation or explosive decomposition at normal temperatures and pressures. E.g. nitroglycerin Special hazard W+OX: Reacts with water in an unusual or dangerous manner AND is oxidizer
left and right hands, two views, burned index fingers
Hydrofluoric acid burns may not be evident for a day, after which calcium treatments are less effective. [ 262 ]
Animation showing colored representation of ozone distribution by year above North America in 6 steps. It starts with a lot of ozone but by 2060 is all gone.
NASA projection of stratospheric ozone over North America without the Montreal Protocol [ 281 ]