Fluorine

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Not to be confused with fluorene, fluorane, or fluoride.
Fluorine, 9F
Small sample of pale yellow liquid fluorine condensed in liquid nitrogen
Liquid fluorine at cryogenic temperatures
General properties
Name, symbol fluorine, F
Pronunciation /fl rin/, /fl rn/, /flrin/
floor-een, floor-in, flohr-een
Allotropes alpha, beta
Appearance gas: very pale yellow
liquid: bright yellow
solid: alpha is opaque, beta is transparent
Fluorine in the periodic table
Hydrogen (diatomic nonmetal)
Helium (noble gas)
Lithium (alkali metal)
Beryllium (alkaline earth metal)
Boron (metalloid)
Carbon (polyatomic nonmetal)
Nitrogen (diatomic nonmetal)
Oxygen (diatomic nonmetal)
Fluorine (diatomic nonmetal)
Neon (noble gas)
Sodium (alkali metal)
Magnesium (alkaline earth metal)
Aluminium (post-transition metal)
Silicon (metalloid)
Phosphorus (polyatomic nonmetal)
Sulfur (polyatomic nonmetal)
Chlorine (diatomic nonmetal)
Argon (noble gas)
Potassium (alkali metal)
Calcium (alkaline earth metal)
Scandium (transition metal)
Titanium (transition metal)
Vanadium (transition metal)
Chromium (transition metal)
Manganese (transition metal)
Iron (transition metal)
Cobalt (transition metal)
Nickel (transition metal)
Copper (transition metal)
Zinc (transition metal)
Gallium (post-transition metal)
Germanium (metalloid)
Arsenic (metalloid)
Selenium (polyatomic nonmetal)
Bromine (diatomic nonmetal)
Krypton (noble gas)
Rubidium (alkali metal)
Strontium (alkaline earth metal)
Yttrium (transition metal)
Zirconium (transition metal)
Niobium (transition metal)
Molybdenum (transition metal)
Technetium (transition metal)
Ruthenium (transition metal)
Rhodium (transition metal)
Palladium (transition metal)
Silver (transition metal)
Cadmium (transition metal)
Indium (post-transition metal)
Tin (post-transition metal)
Antimony (metalloid)
Tellurium (metalloid)
Iodine (diatomic nonmetal)
Xenon (noble gas)
Caesium (alkali metal)
Barium (alkaline earth metal)
Lanthanum (lanthanide)
Cerium (lanthanide)
Praseodymium (lanthanide)
Neodymium (lanthanide)
Promethium (lanthanide)
Samarium (lanthanide)
Europium (lanthanide)
Gadolinium (lanthanide)
Terbium (lanthanide)
Dysprosium (lanthanide)
Holmium (lanthanide)
Erbium (lanthanide)
Thulium (lanthanide)
Ytterbium (lanthanide)
Lutetium (lanthanide)
Hafnium (transition metal)
Tantalum (transition metal)
Tungsten (transition metal)
Rhenium (transition metal)
Osmium (transition metal)
Iridium (transition metal)
Platinum (transition metal)
Gold (transition metal)
Mercury (transition metal)
Thallium (post-transition metal)
Lead (post-transition metal)
Bismuth (post-transition metal)
Polonium (post-transition metal)
Astatine (metalloid)
Radon (noble gas)
Francium (alkali metal)
Radium (alkaline earth metal)
Actinium (actinide)
Thorium (actinide)
Protactinium (actinide)
Uranium (actinide)
Neptunium (actinide)
Plutonium (actinide)
Americium (actinide)
Curium (actinide)
Berkelium (actinide)
Californium (actinide)
Einsteinium (actinide)
Fermium (actinide)
Mendelevium (actinide)
Nobelium (actinide)
Lawrencium (actinide)
Rutherfordium (transition metal)
Dubnium (transition metal)
Seaborgium (transition metal)
Bohrium (transition metal)
Hassium (transition metal)
Meitnerium (unknown chemical properties)
Darmstadtium (unknown chemical properties)
Roentgenium (unknown chemical properties)
Copernicium (transition metal)
Nihonium (unknown chemical properties)
Flerovium (post-transition metal)
Moscovium (unknown chemical properties)
Livermorium (unknown chemical properties)
Tennessine (unknown chemical properties)
Oganesson (unknown chemical properties)

Cl
oxygen fluorine neon
Atomic number (Z) 9
Group, block group 17 (halogens), p-block
Period period 2
Element category diatomic nonmetal
Standard atomic weight ( ) (Ar) 18.998403163(6)[1]
Electron configuration [He] 2s2 2p5[2]
Electrons per shell
2, 7
Physical properties
Phase gas
Melting point 53.48 K (219.67 C, 363.41 F)[3]
Boiling point 85.03 K (188.11 C, 306.60 F)[3]
Density at stp (0 C and 101.325 kPa) 1.696 g/L[4]
when liquid, at b.p. 1.505 g/cm3[5]
Triple point 53.48 K, 90 kPa[3]
Critical point 144.41 K, 5.1724 MPa[3]
Heat of vaporization 6.51 kJ/mol[4]
Molar heat capacity Cp: 31 J/(molK)[5] (at 21.1 C)
Cv: 23 J/(molK)[5] (at 21.1 C)
Vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 38 44 50 58 69 85
Atomic properties
Oxidation states 1 (oxidizes oxygen)
Electronegativity Pauling scale: 3.98[2]
Ionization energies 1st: 1681 kJ/mol
2nd: 3374 kJ/mol
3rd: 6147 kJ/mol
(more)[6]
Covalent radius 64 pm[7]
Van der Waals radius 135 pm[8]
Miscellanea
Crystal structure cubic Cubic crystal structure for fluorine
Thermal conductivity 0.02591 W/(mK)[9]
Magnetic ordering diamagnetic (1.2104)[10][11]
CAS Number 7782
41
4[2]
History
Naming after the mineral fluorite, itself named after Latin fluo (to flow, in s
melting)
Discovery Andr
Marie Ampre (1810)
First isolation Henri Moissan[2] (June 26, 1886)
Named by Humphry Davy
Most stable isotopes of fluorine[12]
iso NA half
life DM DE (MeV) DP
18F trace 109.77 min + (96.9%) 0.634 18O
(3.1%) 1.656 18O
19F 100% is stal with 10 nutrons
viw talk dit | rfrncs | in Wikidata
Fluorin is a chmical lmnt with symol F and atomic numr 9. It is th ligh
tst halogn and xists as a highly toxic pal yllow diatomic gas at standard c
onditions. As th most lctrongativ lmnt, it is xtrmly ractiv: almost
all othr lmnts, including som nol gass, form compounds with fluorin.
Among th lmnts, fluorin ranks 24th in univrsal aundanc and 13th in trr
strial aundanc. Fluorit, th primary minral sourc of fluorin which gav th
 lmnt its nam, was first dscrid in 1529; as it was addd to mtal ors t
o lowr thir mlting points for smlting, th Latin vr fluo maning "flow" ga
v th minral its nam. Proposd as an lmnt in 1810, fluorin provd difficu
lt and dangrous to sparat from its compounds, and svral arly xprimntrs
did or sustaind injuris from thir attmpts. Only in 1886 did Frnch chmist
Hnri Moissan isolat lmntal fluorin using low-tmpratur lctrolysis, a
procss still mployd for modrn production. Industrial production of fluorin
gas for uranium nrichmnt, its largst application, gan during th Manhattan
Projct in World War II.
Owing to th xpns of rfining pur fluorin, most commrcial applications us
fluorin compounds, with aout half of mind fluorit usd in stlmaking. Th
rst of th fluorit is convrtd into corrosiv hydrogn fluorid n rout to v
arious organic fluorids, or into cryolit which plays a ky rol in aluminium r
fining. Organic fluorids hav vry high chmical and thrmal staility; thir
major uss ar as rfrigrants, lctrical insulation and cookwar, th last as
PTFE (Tflon). Pharmacuticals such as atorvastatin and fluoxtin also contain
fluorin, and th fluorid ion inhiits dntal cavitis, and so finds us in too
thpast and watr fluoridation. Gloal fluorochmical sals amount to mor than
US$15 illion a yar.
Fluorocaron gass ar gnrally grnhous gass with gloal-warming potntials
100 to 20,000 tims that of caron dioxid. Organofluorin compounds prsist in
th nvironmnt du to th strngth of th caronfluorin ond. Fluorin has no
known mtaolic rol in mammals; a fw plants synthsiz organofluorin poisons
that dtr hrivors.
Contnts [hid]
1 Charactristics
1.1 Elctron configuration
1.2 Ractivity
1.3 Phass
1.4 Isotops
2 Occurrnc
2.1 Univrs
2.2 Earth
3 History
3.1 Early discovris
3.2 Isolation
3.3 Latr uss
4 Compounds
4.1 Mtals
4.2 Hydrogn
4.3 Othr ractiv nonmtals
4.4 Nol gass
4.5 Organic compounds
5 Production
5.1 Industrial
5.2 Chmical
6 Industrial applications
6.1 Inorganic fluorids
6.2 Organic fluorids
7 Mdicinal applications
7.1 Dntal car
7.2 Pharmacuticals
7.3 PET scanning
7.4 Oxygn carrirs
8 Biological rol
9 Toxicity
9.1 Hydrofluoric acid
9.2 Fluorid ion
10 Environmntal concrns
10.1 Atmosphr
10.2 Bioprsistnc
11 S also
12 Nots
13 Sourcs
13.1 Citations
13.2 Indxd rfrncs
Charactristics
Elctron configuration
Two concntric rings showing valnc and non-valnc lctron shlls
Simplifid structur of th fluorin atom
Fluorin atoms hav nin lctrons, on fwr than non, and lctron configurat
ion 1s22s22p5: two lctrons in a filld innr shll and svn in an outr shll
rquiring on mor to  filld. Th outr lctrons ar inffctiv at nuclar
shilding, and xprinc a high ffctiv nuclar charg of 9 2 = 7; this affe
cts the atom's physical properties.[2]
Fluorine's first ionization energy is third
highest among all elements, behind h
elium and neon,[13] which complicates the removal of electrons from neutral fluo
rine atoms. It also has a high electron affinity, second only to chlorine,[14] a
nd tends to capture an electron to become isoelectronic with the noble gas neon;
[2] it has the highest electronegativity of any element.[15] Fluorine atoms have
a small covalent radius of around 60 picometers, similar to those of its period
neighbors oxygen and neon.[16][17][note 1]
Reactivity
Main article: Chemical characteristics of fluorine
The bond energy of difluorine is much lower than that of either Cl
2 or Br
2 and similar to the easily cleaved peroxide bond; this, along with high electro
negativity, accounts for fluorine's easy dissociation, high reactivity, and stro
ng bonds to non
fluorine atoms.[18][19] Conversely, bonds to other atoms are ver
y strong because of fluorine's high electronegativity. Unreactive substances lik
e powdered steel, glass fragments, and asbestos fibers react quickly with cold f
luorine gas; wood and water spontaneously combust under a fluorine jet.[4][20]
External video
Bright flames during fluorine reactions
Fluorine reacting with caesium
Reactions of elemental fluorine with metals require varying conditions. Alkali m
etals cause explosions and alkaline earth metals display vigorous activity in bu
lk; to prevent passivation from the formation of metal fluoride layers, most oth
er metals such as aluminium and iron must be powdered,[18] and noble metals requ
ire pure fluorine gas at 300450 C (575850 F).[21] Some solid nonmetals (sulfur, phos
phorus) react vigorously in liquid air temperature fluorine.[22] Hydrogen sulfid
e[22] and sulfur dioxide[23] combine readily with fluorine, the latter sometimes
explosively; sulfuric acid exhibits much less activity, requiring elevated temp
eratures.[24]
Hydrogen, like some of the alkali metals, reacts explosively with fluorine.[25]
Carbon, as lamp black, reacts at room temperature to yield fluoromethane. Graphi
te combines with fluorine above 400 C (750 F) to produce non
stoichiometric carbon
monofluoride; higher temperatures generate gaseous fluorocarbons, sometimes wit
h explosions.[26] Carbon dioxide and carbon monoxide react at or just above room
temperature,[27] whereas paraffins and other organic chemicals generate strong
reactions:[28] even fully substituted haloalkanes such as carbon tetrachloride,
normally incombustible, may explode.[29] Although nitrogen trifluoride is stable
, nitrogen requires an electric discharge at elevated temperatures for reaction
with fluorine to occur, due to the very strong triple bond in elemental nitrogen
;[30] ammonia may react explosively.[31][32] Oxygen does not combine with fluori
ne under ambient conditions, but can be made to react using electric discharge a
t low temperatures and pressures; the products tend to disintegrate into their c
onstituent elements when heated.[33][34][35] Heavier halogens[36] react readily
with fluorine as does the noble gas radon;[37] of the other noble gases, only xe
non and krypton react, and only under special conditions.[38]
Phases
Main article: Phases of fluorine
Cube with spherical shapes on the corners and center and spinning molecules in p
lanes in faces
Crystal structure of -fluorin. Sphrs indicat F
2 molculs that may assum any angl. Othr molculs ar constraind to plans
.
At room tmpratur, fluorin is a gas of diatomic molculs,[4] pal yllow wh
n pur (somtims dscrid as yllow-grn).[39] It has a charactristic pungn
t odor dtctal at 20 pp.[40] Fluorin condnss into a right yllow liquid
at 188 C (306 F), a transition temperature similar to those of oxygen and nitrogen.[
41]
Fluorine has two solid forms, - nd -fluorine. The ltter crystllizes t 220 C (364 F
) and is transparent and soft, with the same disordered cubic structure of fresh
ly crystallized solid oxygen,[41][note 2] unlike the orthorhombic systems of oth
er solid halogens.[45][46] Further cooling to 228 C (378 F) induces a phase transiti
on into opaque and hard -fluorine, which hs  monoclinic structure with dense, 
ngled lyers of molecules. The trnsition from - to -fluorine is more exothermic t
hn the condenstion of fluorine, nd cn e violent.[45][46][note 3]
Isotopes
Min rticle: Isotopes of fluorine
Only one isotope of fluorine occurs nturlly in undnce, the stle isotope 1
9
F.[47] It hs  high mgnetogyric rtio[note 4] nd exceptionl sensitivity to m
gnetic fields; ecuse it is lso the only stle isotope, it is used in mgnet
ic resonnce imging.[49] Seventeen rdioisotopes with mss numers from 14 to 3
1 hve een synthesized, of which 18
F is the most stle with  hlf-life of 109.77 minutes. Other rdioisotopes hv
e hlf-lives less thn 70 seconds; most decy in less thn hlf  second.[50] Th
e isotopes 17
F nd 18
F undergo + decy, lighter isotopes decy y electron cpture, nd those hevier
thn 19
F undergo decay or neutron emission.[50] One metastable isomer of fluorine is kno
wn, 18m
F, with a half
life of 234 nanoseconds.[51]
Occurrence
Main article: Origin and occurrence of fluorine
Universe
Solar System abundances[52]
Atomic
number Element Relative
amount
6 Carbon 4,800
7 Nitrogen 1,500
8 Oxygen 8,800
9 Fluorine 1
10 Neon 1,400
11 Sodium 24
12 Magnesium 430
Among the lighter elements, fluorine's abundance value of 400 ppb (parts per bil
lion) 24th among elements in the universe is exceptional: other elements from ca
rbon to magnesium are twenty or more times as common.[53] This is because stella
r nucleosynthesis processes bypass fluorine, and any fluorine atoms otherwise cr
eated have high nuclear cross sections, allowing further fusion with hydrogen or
helium to generate oxygen or neon respectively.[53][54]
Beyond this transient existence, three explanations have been proposed for the p
resence of fluorine:[53][55]
during type II supernovae, bombardment of neon atoms by neutrinos could transmut
e them to fluorine;
the solar wind of WolfRayet stars could blow fluorine away from any hydrogen or h
elium atoms; or
fluorine is borne out on convection currents arising from fusion in asymptotic g
iant branch stars.
Earth
See also: List of countries by fluorite production
Fluorine is the thirteenth most common element in Earth's crust at 600700 ppm (pa
rts per million) by mass.[56] Elemental fluorine in Earth's atmosphere would eas
ily react with atmospheric water vapor, precluding its natural occurrence;[57][5
8] it is found only in combined mineral forms, of which fluorite, fluorapatite a
nd cryolite are the most industrially significant.[56][59] Fluorite or fluorspar
(CaF
2), colorful and abundant worldwide, is fluorine's main source; China and Mexico
are the major suppliers. The U.S. led extraction in the early 20th century but
ceased mining in 1995.[59][60][61][62][63] Although fluorapatite (Ca5(PO4)3F) co
ntains most of the world's fluorine, its low mass fraction of 3.5% means that mo
st of it is used as a phosphate. In the U.S. small quantities of fluorine compou
nds are obtained via fluorosilicic acid, a phosphate industry byproduct.[59] Cry
olite (Na
3AlF
6), once used directly in aluminium production, is the rarest and most concentra
ted of these three minerals. The main commercial mine on Greenland's west coast
closed in 1987, and most cryolite is now synthesized.[59]
Major fluorine
containing minerals
Pink globular mass with crystal facets Long prism
like crystal, without luster,
at an angle coming out of aggregate
like rock A parallelogram
shaped outline w
ith space
filling diatomic molecules (joined circles) arranged in two layers
Fluorite Fluorapatite Cryolite
Other minerals such as topaz contain fluorine. Fluorides, unlike other halides,
are insoluble and do not occur in commercially favorable concentrations in salin
e waters.[59] Trace quantities of organofluorines of uncertain origin have been
detected in volcanic eruptions and geothermal springs.[64] The existence of gase
ous fluorine in crystals, suggested by the smell of crushed antozonite, is conte
ntious;[65][66] a 2012 study reported the presence of 0.04% F
2 by weight in antozonite, attributing these inclusions to radiation from the pr
esence of tiny amounts of uranium.[66]
History
Main article: History of fluorine
Early discoveries
Woodcut image showing man at open hearth with tongs and machine bellows to the s
ide in background, man at water
operated hammer with quenching sluice nearby in
foreground
Steelmaking illustration from De re metallica
In 1529, Georgius Agricola described fluorite as an additive used to lower the m
elting point of metals during smelting.[67][68][note 5] He penned the Latin word
fluors (fluo, flow) for fluorite rocks. The name later evolved into fluorspar (s
till commonly used) and then fluorite.[60][72][73] The composition of fluorite w
as later determined to be calcium difluoride.[74]
Hydrofluoric acid was used in glass etching from 1720 onwards.[note 6] Andreas S
igismund Marggraf first characterized it in 1764 when he heated fluorite with su
lfuric acid, and the resulting solution corroded its glass container.[76][77] Sw
edish chemist Carl Wilhelm Scheele repeated the experiment in 1771, and named th
e acidic product fluss
spats
syran (fluorspar acid).[77][78] In 1810, the French
physicist Andr
Marie Ampre suggested that hydrogen and an element analogous to ch
lorine constituted hydrofluoric acid.[79] Sir Humphry Davy proposed that this th
en
unknown substance be named fluorine from fluoric acid and the
ine suffix of
other halogens. This word, with modifications, is used in most European language
s; Greek, Russian, and some others (following Ampre's suggestion) use the name ft
or or derivatives, from the Greek (phths, destuctve) .[80][81] The New Latn na
e luum gave the element ts cuent symbl F; Fl was used n ealy papes.[82
][nte 7]
Islatn
Intal studes n lune wee s dangeus that seveal 19th-centuy expeme
ntes wee deemed "lune matys" ate mstunes wth hydluc acd.[n
te 8] Islatn  elemental lune was hndeed by the exteme csveness
 bth elemental lune tsel and hydgen lude, as well as the lack 
a smple and sutable electlyte.[74][83] Edmnd Fmy pstulated that electly
ss  pue hydluc acd t geneate lune was easble and devsed a me
thd t pduce anhydus samples m acded ptassum blude; nstead,
he dscveed that the esultng (dy) hydgen lude dd nt cnduct elect
cty.[74][83][84] Fmy's me student Hen Mssan peseveed, and ate much
tal and e und that a mxtue  ptassum blude and dy hydgen l
ude was a cnduct, enablng electlyss. T pevent apd csn  the
platnum n hs electchemcal cells, he cled the eactn t extemely lw
tempeatues n a specal bath and ged cells m a me esstant mxtue 
platnum and dum, and used lute stppes.[83][85] In 1886, ate 74 yea
s  et by many chemsts, Mssan slated elemental lune.[84][86]

In 1906, tw mnths bee hs death, Mssan eceved the Nbel Pze n Chems
ty,[87] wth the llwng ctatn:[83]
[I]n ecgntn  the geat sevces endeed by hm n hs nvestgatn and
slatn  the element lune ... The whle wld has admed the geat expe
mental skll wth whch yu have studed that savage beast amng the elements.
[nte 9]

1887 dawng  Mssan's appaatus

Nbel Pze pht  Mssan
Late uses
An ampule  uanum hexalude  hex
The Fgdae dvsn  Geneal Mts (GM) expemented wth chlluca
bn egeants n the late 1920s, and Knetc Chemcals was med as a jnt
ventue between GM and DuPnt n 1930 hpng t maket Fen-12 (CCl
2F
2) as ne such egeant. It eplaced eale and me txc cmpunds, ncea
sed demand  ktchen egeats, and became ptable; by 1949 DuPnt had
bught ut Knetc and maketed seveal the Fen cmpunds.[77][88][89][90] P
lytetaluethylene (Teln) was seendptusly dscveed n 1938 by Ry J.
Plunkett whle wkng n egeants at Knetc, and ts supelatve chemcal
and themal esstance lent t t acceleated cmmecalzatn and mass pduc
tn by 1941.[77][88][89]
Lage-scale pductn  elemental lune began dung Wld Wa II. Gemany
used hgh-tempeatue electlyss t make tns  the planned ncenday chl
ne tlude[91] and the Manhattan Pject used huge uanttes t pduce ua
num hexalude  uanum enchment. Snce UF
6 s as csve as lune, gaseus dusn plants e ued specal matea
ls: nckel  membanes, luplymes  seals, and l ud lucabns as
clants and lubcants. Ths bugenng nuclea ndusty late dve pst-wa 
luchemcal develpment.[92]
Cmpunds
Man atcle: Cmpunds  lune
Flune has a ch chemsty, encmpassng ganc and nganc dmans. It c
mbnes wth metals, nnmetals, metallds, and mst nble gases,[93] and usually
assumes an xdatn state  1.[note 10] Fluorine's high electron affinity resu
lts in a preference for ionic bonding; when it forms covalent bonds, these are p
olar, and almost always single.[97][98][note 11]
Metals
See also: Fluoride volatility
Alkali metals form ionic and highly soluble monofluorides; these have the cubic
arrangement of sodium chloride and analogous chlorides.[99][100] Alkaline earth
difluorides possess strong ionic bonds but are insoluble in water,[82] with the
exception of beryllium difluoride, which also exhibits some covalent character a
nd has a quartz
like structure.[101] Rare earth elements and many other metals f
orm mostly ionic trifluorides.[102][103][104]
Covalent bonding first comes to prominence in the tetrafluorides: those of zirco
nium, hafnium[105][106] and several actinides[107] are ionic with high melting p
oints,[108][note 12] while those of titanium,[111] vanadium,[112] and niobium ar
e polymeric,[113] melting or decomposing at no more than 350 C (660 F).[114] Penta
fluorides continue this trend with their linear polymers and oligomeric complexe
s.[115][116][117] Thirteen metal hexafluorides are known,[note 13] all octahedra
l, and are mostly volatile solids but for liquid MoF
6 and ReF
6, and gaseous WF
6.[118][119][120] Rhenium heptafluoride, the only characterized metal heptafluor
ide, is a low
melting molecular solid with pentagonal bipyramidal molecular geom
etry.[121] Metal fluorides with more fluorine atoms are particularly reactive.[1
22]
Structural progression of metal fluorides
Checkerboard
like lattice of small blue and large yellow balls, going in three d
imensions so that each ball has 6 nearest neighbors of opposite type Straight
 chain of alternating balls, violet and yellow, with violet ones also linked to
four more yellow perpendicularly to the chain and each other Ball and stick d
rawing showing central violet ball with a yellow one directly above and below an
d then an equatorial belt of 5 surrounding yellow balls
Sodium fluoride, ionic Bismuth pentafluoride, polymeric Rhenium heptaflu
oride, molecular
Hydrogen
Main articles: Hydrogen fluoride and hydrofluoric acid
Graph showing water and hydrogen fluoride breaking the trend of lower boiling po
ints for lighter molecules
Boiling points of hydrogen halides and chalcogenides, showing the unusually high
values for hydrogen fluoride and water
Hydrogen and fluorine combine to yield hydrogen fluoride, in which discrete mole
cules form clusters by hydrogen bonding, resembling water more than hydrogen chl
oride.[123][124][125] It boils at a much higher temperature than heavier hydroge
n halides and unlike them is fully miscible with water.[126] Hydrogen fluoride r
eadily hydrates on contact with water to form aqueous hydrogen fluoride, also kn
own as hydrofluoric acid. Unlike the other hydrohalic acids, which are strong, h
ydrofluoric acid is a weak acid at low concentrations.[127][note 14] However, it
can attack glass, something the other acids cannot do.[129]
Other reactive nonmetals
Metalloids are included in this section
Chlorine trifluoride, whose corrosive potential ignites asbestos, concrete, sand
and other fire retardants[130]
Binary fluorides of metalloids and p
block nonmetals are generally covalent and
volatile, with varying reactivities. Period 3 and heavier nonmetals can form hyp
ervalent fluorides.[131]
Boron trifluoride is planar and possesses an incomplete octet. It functions as a
Lewis acid and combines with Lewis bases like ammonia to form adducts.[132] Car
bon tetrafluoride is tetrahedral and inert;[note 15] its group analogues, silico
n and germanium tetrafluoride, are also tetrahedral[133] but behave as Lewis aci
ds.[134][135] The pnictogens form trifluorides that increase in reactivity and b
asicity with higher molecular weight, although nitrogen trifluoride resists hydr
olysis and is not basic.[136] The pentafluorides of phosphorus, arsenic, and ant
imony are more reactive than their respective trifluorides, with antimony pentaf
luoride the strongest neutral Lewis acid known.[115][137][138]
Chalcogens have diverse fluorides: unstable difluorides have been reported for o
xygen (the only known compound with oxygen in an oxidation state of +2), sulfur,
and selenium; tetrafluorides and hexafluorides exist for sulfur, selenium, and
tellurium. The latter are stabilized by more fluorine atoms and lighter central
atoms, so sulfur hexafluoride is especially inert.[139][140] Chlorine, bromine,
and iodine can each form mono
, tri
, and pentafluorides, but only iodine heptaf
luoride has been characterized among possible interhalogen heptafluorides.[141]
Many of them are powerful sources of fluorine atoms, and industrial applications
using chlorine trifluoride require precautions similar to those using fluorine.
[142][143]
Noble gases
Main article: Noble gas compound
Black
and
white photo showing transparent crystals in a dish
These xenon tetrafluoride crystals were photographed in 1962. The compound's syn
thesis, as with xenon hexafluoroplatinate, surprised many chemists.[144]
Noble gases, having complete electron shells, defied reaction with other element
s until 1962 when Neil Bartlett reported synthesis of xenon hexafluoroplatinate;
[145] xenon difluoride, tetrafluoride, hexafluoride, and multiple oxyfluorides h
ave been isolated since then.[146] Among other noble gases, krypton forms a difl
uoride,[147] and radon and fluorine generate a solid suspected to be radon diflu
oride.[148][149] Binary fluorides of lighter noble gases are exceptionally unsta
ble: argon and hydrogen fluoride combine under extreme conditions to give argon
fluorohydride.[38] Helium and neon have no long
lived fluorides,[150] and no neo
n fluoride has ever been observed;[151] helium fluorohydride has been detected f
or milliseconds at high pressures and low temperatures.[150]
Organic compounds
Main article: Organofluorine chemistry
Beaker with two layers of liquid, goldfish and crab in top, coin sunk in the bot
tom
Immiscible layers of colored water (top) and much denser perfluoroheptane (botto
m) 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.[152]
The carbonfluorine bond is organic chemistry's strongest,[153] and gives stabilit
y to organofluorines.[154] It is almost non
existent in nature, but is used in a
rtificial compounds. Research in this area is usually driven by commercial appli
cations;[155] the compounds involved are diverse and reflect the complexity inhe
rent in organic chemistry.[88]
Discrete molecules
Main articles: Fluorocarbon and Perfluorinated compound
The substitution of hydrogen atoms in an alkane by progressively more fluorine a
toms gradually alters several properties: melting and boiling points are lowered
, density increases, solubility in hydrocarbons decreases and overall stability
increases. Perfluorocarbons,[note 16] in which all hydrogen atoms are substitute
d, are insoluble in most organic solvents, reacting at ambient conditions only w
ith sodium in liquid ammonia.[156]
The term perfluorinated compound is used for what would otherwise be a perfluoro
carbon if not for the presence of a functional group,[157][note 17] often a carb
oxylic acid. These compounds share many properties with perfluorocarbons such as
stability and hydrophobicity,[159] while the functional group augments their re
activity, enabling them to adhere to surfaces or act as surfactants;[160] Fluoro
surfactants, in particular, can lower the surface tension of water more than the
ir hydrocarbon
based analogues. Fluorotelomers, which have some unfluorinated ca
rbon atoms near the functional group, are also regarded as perfluorinated.[159]
Polymers
Polymers exhibit the same stability increases afforded by fluorine substitution
(for hydrogen) in discrete molecules; their melting points generally increase to
o.[161] Polytetrafluoroethylene (PTFE), the simplest fluoropolymer and perfluoro
analogue of polyethylene with structural unit CF
2, demonstrates this change as expected, but its very high melting point makes it
difficult to mold.[162] Various PTFE derivatives are less temperature
tolerant
but easier to mold: fluorinated ethylene propylene replaces some fluorine atoms
with trifluoromethyl groups, perfluoroalkoxy alkanes do the same with trifluorom
ethoxy groups,[162] and Nafion contains perfluoroether side chains capped with s
ulfonic acid groups.[163][164] Other fluoropolymers retain some hydrogen atoms;
polyvinylidene fluoride has half the fluorine atoms of PTFE and polyvinyl fluori
de has a quarter, but both behave much like perfluorinated polymers.[165]
Production
Industrial
A machine room
Industrial fluorine cells at Preston
Moissan's method is used to produce industrial quantities of fluorine, via the e
lectrolysis of a potassium fluoride/hydrogen fluoride mixture: hydrogen and fluo
ride ions are reduced and oxidized at a steel container cathode and a carbon blo
ck anode, under 812 volts, to generate hydrogen and fluorine gas respectively.[61
][166] Temperatures are elevated, KF2HF melting at 70 C (158 F) and being electroly
zed at 70130 C (158266 F). KF, which acts as catalyst, is essential since pure HF ca
nnot be electrolyzed.[77][167][168] Fluorine can be stored in steel cylinders th
at have passivated interiors, at temperatures below 200 C (392 F); otherwise nicke
l can be used.[77][169] Regulator valves and pipework are made of nickel, the la
tter possibly using Monel instead.[170] Frequent passivation, along with the str
ict exclusion of water and greases, must be undertaken. In the laboratory, glass
ware may carry fluorine gas under low pressure and anhydrous conditions;[170] so
me sources instead recommend nickel
Monel
PTFE systems.[171]
Chemical
While preparing for a 1986 conference to celebrate the centennial of Moissan's a
chievement, 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:[172]
2 KMnO4 + 2 KF + 10 HF + 3 H2O2 2 K2MnF6 + 8 H2O + 3 O2
2 K2MnF6 + 4 SbF5 4 KSbF6 + 2 MnF3 + F2
Potassium hexafluoromanganate(IV), K2MnF6, has been known since 1899.[173][174]
Christe later commented that the reactants "had been known for more than 100 yea
rs and even Moissan could have come up with this scheme."[175] As late as 2008,
some references still asserted that fluorine was too reactive for any chemical i
solation.[176]
Industrial applications
Main article: Fluorochemical industry
Fluorite mining, which supplies most global fluorine, peaked in 1989 when 5.6 mi
llion metric tons of ore were extracted. Chlorofluorocarbon restrictions lowered
this to 3.6 million tons in 1994; production has since been increasing. Around
4.5 million tons of ore and revenue of US$550 million were generated in 2003; la
ter reports estimated 2011 global fluorochemical sales at $15 billion and predic
ted 201618 production figures of 3.5 to 5.9 million tons, and revenue of at least
$20 billion.[77][177][178][179][180] Froth flotation separates mined fluorite i
nto two main metallurgical grades of equal proportion: 6085% pure metspar is almo
st all used in iron smelting whereas 97%+ pure acidspar is mainly converted to t
he key industrial intermediate hydrogen fluoride.[61][77][181]

Clickable diagram of the fluorochemical industry according to mass flows.

Minaret
like electrical devices with wires around them, thicker at the bottom
SF
6 transformers at a Russian railway
See also: Industrial gas
At least 17,000 metric tons of fluorine are produced each year. It costs only $58
per kilogram as uranium or sulfur hexafluoride, but handling challenges multipl
y its price as an element, and most processes that use the latter in large amoun
ts employ in situ generation under vertical integration.[182]
The largest application of fluorine gas, consuming up to 7,000 metric tons annua
lly, is in the preparation of UF
6 for the nuclear fuel cycle. Fluorine is used to fluorinate uranium tetrafluori
de, itself formed from uranium dioxide and hydrofluoric acid.[182] Fluorine is m
onoisotopic, so any mass differences between UF
6 molecules are due to the presence of 235
U or 238
U, enabling uranium enrichment via gaseous diffusion or gas centrifuge.[4][61] A
bout 6,000 metric tons per year go into producing the inert dielectric SF
6 for high
voltage transformers and circuit breakers, eliminating the need for h
azardous polychlorinated biphenyls associated with oil
filled devices.[183] Seve
ral fluorine compounds are used in electronics: rhenium and tungsten hexafluorid
e in chemical vapor deposition, tetrafluoromethane in plasma etching[184][185][1
86] and nitrogen trifluoride in cleaning equipment.[61] Fluorine is also used in
the synthesis of organic fluorides, but its reactivity often necessitates conve
rsion first to the gentler ClF
3, BrF
3, or IF
5, which together allow calibrated fluorination. Fluorinated pharmaceuticals use
sulfur tetrafluoride instead.[61]
Inorganic fluorides
Aluminium extraction depends critically on cryolite
As with other iron alloys, around 3 kg (6.5 lb) metspar is added to each metric
ton of steel; the fluoride ions lower its melting point and viscosity.[61][187]
Alongside its role as an additive in materials like enamels and welding rod coat
s, most acidspar is reacted with sulfuric acid to form hydrofluoric acid, which
is used in steel pickling, glass etching and alkane cracking.[61] One
third of H
F goes into synthesizing cryolite and aluminium trifluoride, both fluxes in the
HallHroult process for aluminium extraction; replenishment is necessitated by thei
r occasional reactions with the smelting apparatus. Each metric ton of aluminium
requires about 23 kg (51 lb) of flux.[61][188] Fluorosilicates consume the seco
nd largest portion, with sodium fluorosilicate used in water fluoridation and la
undry effluent treatment, and as an intermediate en route to cryolite and silico
n tetrafluoride.[189] Other important inorganic fluorides include those of cobal
t, nickel, and ammonium.[61][100][190]
Organic fluorides
Organofluorides consume over 20% of mined fluorite and over 40% of hydrofluoric
acid, with refrigerant gases dominating and fluoropolymers increasing their mark
et share.[61][191] Surfactants are a minor application but generate over $1 bill
ion in annual revenue.[192] Due to the danger from direct hydrocarbonfluorine rea
ctions above 150 C (240 F), industrial fluorocarbon production is indirect, mostly t
hrough halogen exchange reactions such as Swarts fluorination, in which chloroca
rbon chlorines are substituted for fluorines by hydrogen fluoride under catalyst
s. Electrochemical fluorination subjects hydrocarbons to electrolysis in hydroge
n fluoride, and the Fowler process treats them with solid fluorine carriers like
cobalt trifluoride.[88][193]
Refrigerant gases
See also: Refrigerant
Halogenated refrigerants, termed Freons in informal contexts,[note 18] are ident
ified by R
numbers that denote the amount of fluorine, chlorine, carbon, and hyd
rogen present.[61][194] Chlorofluorocarbons (CFCs) like R
11, R
12, and R
114 on
ce dominated organofluorines, peaking in production in the 1980s. Used for air c
onditioning systems, propellants and solvents, their production was below one
te
nth of this peak by the early 2000s, after widespread international prohibition.
[61] Hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs) were designe
d as replacements; their synthesis consumes more than 90% of the fluorine in the
organic industry. Important HCFCs include R
22, chlorodifluoromethane, and R
14
1b. The main HFC is R
134a[61] with a new type of molecule HFO
1234yf, a Hydrofl
uoroolefin (HFO) coming to prominence owing to its global warming potential of l
ess than 1% that of HFC
134a.[195]
Polymers
Shiny spherical drop of water on blue cloth
Fluorosurfactant
treated fabrics are often hydrophobic
Main article: Fluoropolymer
About 180,000 metric tons of fluoropolymers were produced in 2006 and 2007, gene
rating over $3.5 billion revenue per year.[196] The global market was estimated
at just under $6 billion in 2011 and was predicted to grow by 6.5% per year up t
o 2016.[197] Fluoropolymers can only be formed by polymerizing free radicals.[16
1]
Polytetrafluoroethylene (PTFE), sometimes called by its DuPont name Teflon,[198]
represents 6080% by mass of the world's fluoropolymer production.[196] The large
st application is in electrical insulation since PTFE is an excellent dielectric
. It is also used in the chemical industry where corrosion resistance is needed,
in coating pipes, tubing, and gaskets. Another major use is in PFTE
coated fibe
rglass cloth for stadium roofs. The major consumer application is for non
stick
cookware.[198] Jerked PTFE film becomes expanded PTFE (ePTFE), a fine
pored memb
rane sometimes referred to by the brand name Gore
Tex and used for rainwear, pro
tective apparel, and filters; ePTFE fibers may be made into seals and dust filte
rs.[198] Other fluoropolymers, including fluorinated ethylene propylene, mimic P
TFE's properties and can substitute for it; they are more moldable, but also mor
e costly and have lower thermal stability. Films from two different fluoropolyme
rs replace glass in solar cells.[198][199]
The chemically resistant (but expensive) fluorinated ionomers are used as electr
ochemical cell membranes, of which the first and most prominent example is Nafio
n. Developed in the 1960s, it was initially deployed as fuel cell material in sp
acecraft and then replaced mercury
based chloralkali process cells. Recently, th
e fuel cell application has reemerged with efforts to install proton exchange me
mbrane fuel cells into automobiles.[200][201][202] Fluoroelastomers such as Vito
n are crosslinked fluoropolymer mixtures mainly used in O
rings;[198] perfluorob
utane (C4F10) is used as a fire
extinguishing agent.[203]
Surfactants
Main articles: Fluorinated surfactant and Durable water repellent
Fluorosurfactants are small organofluorine molecules used for repelling water an
d stains. Although expensive (comparable to pharmaceuticals at $2002000 per kilog
ram), they yielded over $1 billion in annual revenues by 2006; Scotchgard alone
generated over $300 million in 2000.[192][204][205] Fluorosurfactants are a mino
rity in the overall surfactant market, most of which is taken up by much cheaper
hydrocarbon
based products. Applications in paints are burdened by compounding
costs; this use was valued at only $100 million in 2006.[192]
Agrichemicals
About 30% of agrichemicals contain fluorine,[206] most of them herbicides and fu
ngicides with a few crop regulators. Fluorine substitution, usually of a single
atom or at most a trifluoromethyl group, is a robust modification with effects a
nalogous to fluorinated pharmaceuticals: increased biological stay time, membran
e crossing, and altering of molecular recognition.[207] Trifluralin is a promine
nt example, with large
scale use in the U.S. as a weedkiller,[207][208] but it i
s a suspected carcinogen and has been banned in many European countries.[209] So
dium monofluoroacetate (1080) is a mammalian poison in which two acetic acid hyd
rogens are replaced with fluorine and sodium; it disrupts cell metabolism by rep
lacing acetate in the citric acid cycle. First synthesized in the late 19th cent
ury, it was recognized as an insecticide in the early 20th, and was later deploy
ed in its current use. New Zealand, the largest consumer of 1080, uses it to pro
tect kiwis from the invasive Australian common brushtail possum.[210] Europe and
the U.S. have banned 1080.[211][212][note 19]
Medicinal applications
Dental care
Man holding plastic tray with brown material in it and sticking a small stick in
to a boy's open mouth
Topical fluoride treatment in Panama
Main articles: Fluoride therapy, Water fluoridation, and Water fluoridation cont
roversy
Population studies from the mid
20th century onwards show topical fluoride reduc
es dental caries. This was first attributed to the conversion of tooth enamel hy
droxyapatite into the more durable fluorapatite, but studies on pre
fluoridated
teeth refuted this hypothesis, and current theories involve fluoride aiding enam
el growth in small caries.[213] After studies of children in areas where fluorid
e was naturally present in drinking water, controlled public water supply fluori
dation to fight tooth decay[214] began in the 1940s and is now applied to water
supplying 6 percent of the global population, including two
thirds of Americans.
[215][216] Reviews of the scholarly literature in 2000 and 2007 associated water
fluoridation with a significant reduction of tooth decay in children.[217] Desp
ite such endorsements and evidence of no adverse effects other than mostly benig
n dental fluorosis,[218] opposition still exists on ethical and safety grounds.[
216][219] The benefits of fluoridation have lessened, possibly due to other fluo
ride sources, but are still measurable in low
income groups.[220] Sodium monoflu
orophosphate and sometimes sodium or tin(II) fluoride are often found in fluorid
e toothpastes, first introduced in the U.S. in 1955 and now ubiquitous in develo
ped countries, alongside fluoridated mouthwashes, gels, foams, and varnishes.[22
0][221]
Pharmaceuticals
Capsules with "Prozac" and "DISTA" visible
Fluoxetine capsules
Twenty percent of modern pharmaceuticals contain fluorine.[222] One of these, th
e cholesterol
reducer atorvastatin (Lipitor), made more revenue than any other d
rug until it became generic in 2011.[223] The combination asthma prescription Se
retide, a top
ten revenue drug in the mid
2000s, contains two active ingredients
, one of which fluticasone is fluorinated.[224] Many drugs are fluorinated to de
lay inactivation and lengthen dosage periods because the carbonfluorine bond is v
ery stable.[225] Fluorination also increases lipophilicity because the bond is m
ore hydrophobic than the carbonhydrogen bond, and this often helps in cell membra
ne penetration and hence bioavailability.[224]
Tricyclics and other pre
1980s antidepressants had several side effects due to t
heir non
selective interference with neurotransmitters other than the serotonin
target; the fluorinated fluoxetine was selective and one of the first to avoid t
his problem. Many current antidepressants receive this same treatment, including
the selective serotonin reuptake inhibitors: citalopram, its isomer escitalopra
m, and fluvoxamine and paroxetine.[226][227] Quinolones are artificial broad
spe
ctrum antibiotics that are often fluorinated to enhance their effects. These inc
lude ciprofloxacin and levofloxacin.[228][229][230][231] Fluorine also finds use
in steroids:[232] fludrocortisone is a blood pressure
raising mineralocorticoid
, and triamcinolone and dexamethasone are strong glucocorticoids.[233] The major
ity of inhaled anesthetics are heavily fluorinated; the prototype halothane is m
uch more inert and potent than its contemporaries. Later compounds such as the f
luorinated ethers sevoflurane and desflurane are better than halothane and are a
lmost insoluble in blood, allowing faster waking times.[234][235]
PET scanning
Main article: Positron emission tomography
Rotating transparent image of a human figure with targeted organs highlighted
A full
body 18
F PET scan
Fluorine
18 is often found in radioactive tracers for positron emission tomograp
hy, as its half
life of almost two hours is long enough to allow for its transpo
rt from production facilities to imaging centers.[236] The most common tracer is
fluorodeoxyglucose[236] which, after intravenous injection, is taken up by gluc
ose
requiring tissues such as the brain and most malignant tumors;[237] computer

assisted tomography can then be used for detailed imaging.[238]
Oxygen carriers
See also: Blood substitute and Liquid breathing
Liquid fluorocarbons can hold large volumes of oxygen or carbon dioxide, more so
than blood, and have attracted attention for their possible uses in artificial
blood and in liquid breathing.[239] Because fluorocarbons do not normally mix wi
th water, they must be mixed into emulsions (small droplets of perfluorocarbon s
uspended in water) to be used as blood.[240][241] One such product, Oxycyte, has
been through initial clinical trials.[242] These substances can aid endurance a
thletes and are banned from sports; one cyclist's near death in 1998 prompted an
investigation into their abuse.[243][244] Applications of pure perfluorocarbon
liquid breathing (which uses pure perfluorocarbon liquid, not a water emulsion)
include assisting burn victims and premature babies with deficient lungs. Partia
l and complete lung filling have been considered, though only the former has had
any significant tests in humans.[245] An Alliance Pharmaceuticals effort reache
d clinical trials but was abandoned because the results were not better than nor
mal therapies.[246]
Biological role
Main article: Biological aspects of fluorine
The gifblaar is one of the few organofluorine
synthesizing organisms
Fluorine is not essential for humans or other mammals; small amounts may be bene
ficial for bone strength, but this has not been definitively established. As the
re are many environmental sources of trace fluorine, the possibility of a fluori
ne deficiency could apply only to artificial diets.[247][248] Natural organofluo
rines have been found in microorganisms and plants[64] but not animals.[249] The
most common is fluoroacetate, which is used as a defense against herbivores by
at least 40 plants in Africa, Australia and Brazil.[211] Other examples include
terminally fluorinated fatty acids, fluoroacetone, and 2
fluorocitrate.[249] An
enzyme that binds fluorine to carbon adenosyl
fluoride synthase was discovered i
n bacteria in 2002.[250]
Toxicity
Main article: Fluorine
related hazards
A diagonal placard with warning poison
A diagonal placard with warning corrosive
A diagonal placard with warning inhalant
A diagonal placard with warning oxidant
U.S. hazard signs for commercially transported fluorine[251]
Elemental fluorine is highly toxic to living organisms. Its effects in humans st
art at concentrations lower than hydrogen cyanide's 50 ppm[252] and are similar
to those of chlorine:[253] significant irritation of the eyes and respiratory sy
stem as well as liver and kidney damage occur above 25 ppm, which is the immedia
tely dangerous to life and health value for fluorine.[254][255] Eyes and noses a
re seriously damaged at 100 ppm,[254] and inhalation of 1,000 ppm fluorine will
cause death in minutes,[256] compared to 270 ppm for hydrogen cyanide.[257]
Hydrofluoric acid
left and right hands, two views, burned index fingers
Hydrofluoric acid burns may not be evident for a day, after which calcium treatm
ents are less effective.[258]
See also: Chemical burn
Hydrofluoric acid is a contact poison with greater hazards than many strong acid
s like sulfuric acid even though it is weak: it remains neutral in aqueous solut
ion and thus penetrates tissue faster, whether through inhalation, ingestion or
the skin, and at least nine U.S. workers died in such accidents from 1984 to 199
4. It reacts with calcium and magnesium in the blood leading to hypocalcemia and
 possible death through cardiac arrhythmia.[259] Insoluble calcium fluoride form
ation triggers strong pain[260] and burns larger than 160 cm2 (25 in2) can cause
serious systemic toxicity.[261]
Exposure may not be evident for eight hours for 50% HF, rising to 24 hours for l
ower concentrations, and a burn may initially be painless as hydrogen fluoride a
ffects nerve function. If skin has been exposed to HF, damage can be reduced by
rinsing it under a jet of water for 1015 minutes and removing contaminated clothi
ng.[262] Calcium gluconate is often applied next, providing calcium ions to bind
with fluoride; skin burns can be treated with 2.5% calcium gluconate gel or spe
cial rinsing solutions.[263][264][265] Hydrofluoric acid absorption requires fur
ther medical treatment; calcium gluconate may be injected or administered intrav
enously. Using calcium chloride a common laboratory reagent in lieu of calcium g
luconate is contraindicated, and may lead to severe complications. Excision or a
mputation of affected parts may be required.[261][266]
Fluoride ion
See also: Fluoride toxicity
Soluble fluorides are moderately toxic: 510 g sodium fluoride, or 3264 mg fluoride
ions per kilogram of body mass, represents a lethal dose for adults.[267] One
f
ifth of the lethal dose can cause adverse health effects,[268] and chronic exces
s consumption may lead to skeletal fluorosis, which affects millions in Asia and
Africa.[268][269] Ingested fluoride forms hydrofluoric acid in the stomach whic
h is easily absorbed by the intestines, where it crosses cell membranes, binds w
ith calcium and interferes with various enzymes, before urinary excretion. Expos
ure limits are determined by urine testing of the body's ability to clear fluori
de ions.[268][270]
Historically, most cases of fluoride poisoning have been caused by accidental in
gestion of insecticides containing inorganic fluorides.[271] Most current calls
to poison control centers for possible fluoride poisoning come from the ingestio
n of fluoride
containing toothpaste.[268] Malfunctioning water fluoridation equi
pment is another cause: one incident in Alaska affected almost 300 people and ki
lled one person.[272] Dangers from toothpaste are aggravated for small children,
and the Centers for Disease Control and Prevention recommends supervising child
ren below six brushing their teeth so that they do not swallow toothpaste.[273]
One regional study examined a year of pre
teen fluoride poisoning reports totali
ng 87 cases, including one death from ingesting insecticide. Most had no symptom
s, but about 30% had stomach pains.[271] A larger study across the U.S. had simi
lar findings: 80% of cases involved children under six, and there were few serio
us cases.[274]
Environmental concerns
Atmosphere
Animation showing colored representation of ozone distribution by year above Nor
th 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 P
rotocol[275]
See also: Ozone depletion and global warming
The Montreal Protocol, signed in 1987, set strict regulations on chlorofluorocar
bons (CFCs) and bromofluorocarbons due to their ozone damaging potential (ODP).
The high stability which suited them to their original applications also meant t
hat they were not decomposing until they reached higher altitudes, where liberat
ed chlorine and bromine atoms attacked ozone molecules.[276] Even with the ban,
and early indications of its efficacy, predictions warned that several generatio
ns would pass before full recovery.[277][278] With one
tenth the ODP of CFCs, hy
drochlorofluorocarbons (HCFCs) are the current replacements,[279] and are themse
lves scheduled for substitution by 20302040 by hydrofluorocarbons (HFCs) with no
chlorine and zero ODP.[280] In 2007 this date was brought forward to 2020 for de
veloped countries;[281] the Environmental Protection Agency had already prohibit
ed one HCFC's production and capped those of two others in 2003.[280] Fluorocarb
on gases are generally greenhouse gases with global
warming potentials (GWPs) of
about 100 to 10,000; sulfur hexafluoride has a value of around 20,000.[282] An
outlier is HFO
1234yf which is a new type of refrigerant called a Hydrofluoroole
fin (HFO) and has attracted global demand due to its GWP of 4 compared to 1,430
for the current refrigerant standard HFC
134a.[195]
Biopersistence
Perfluorooctanesulfonic acid, a key Scotchgard component until 2000[283]
Main article: Biopersistence of fluorinated organics
Organofluorines exhibit biopersistence due to the strength of the carbonfluorine
bond. Perfluoroalkyl acids (PFAAs), which are sparingly water
soluble owing to t
heir acidic functional groups, are noted persistent organic pollutants;[284] per
fluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) are most ofte
n researched.[285][286][287] PFAAs have been found in trace quantities worldwide
from polar bears to humans, with PFOS and PFOA known to reside in breast milk a
nd the blood of newborn babies. A 2013 review showed a slight correlation betwee
n groundwater and soil PFAA levels and human activity; there was no clear patter
n of one chemical dominating, and higher amounts of PFOS were correlated to high
er amounts of PFOA.[285][286][288] In the body, PFAAs bind to proteins such as s
erum albumin; they tend to concentrate within humans in the liver and blood befo
re excretion through the kidneys. Dwell time in the body varies greatly by speci
es, with half
lives of days in rodents, and years in humans.[285][286][289] High
doses of PFOS and PFOA cause cancer and death in newborn rodents but human stud
ies have not established an effect at current exposure levels.[285][286][289]
See also