Iodine

Iodine is a chemical element with symbol I

and atomic number 53. The heaviest of the
stable halogens, it exists as a lustrous,
black non-metallic solid at standard
conditions that melts to form a deep violet
almost black liquid at 114 degrees Celsius,
and boils to a violet gas at 184 degrees
Celsius. The element was discovered by
the French chemist Bernard Courtois in
1811. It was named two years later by
Joseph Louis Gay-Lussac from this
property, after the Greek ἰώδης "violet-
coloured".
 Iodine,  53I

Iodine

Pronunciation /ˈaɪədaɪn, -dɪn, -diːn/

(EYE-ə-dyn, -din, -deen)

Appearance lustrous metallic gray,

violet as a gas

Standard atomic weight 126.904 47(3)[1]

Ar, std(I)

Iodine in the periodic table

Br
↑
I
↓
At
tellurium ← iodine → xenon

Atomic number (Z) 53

Group group 17 (halogens)

Period period 5
Block p-block

Element category reactive nonmetal

 
Electron configuration [Kr] 4d10 5s2 5p5

Electrons per shell 2, 8, 18, 18, 7

Physical properties

Phase at STP solid

Melting point 386.85 K (113.7 °C,

236.66 °F)

Boiling point 457.4 K (184.3 °C,

363.7 °F)

Density (near r.t.) 4.933 g/cm3

Triple point 386.65 K, 12.1 kPa

Critical point 819 K, 11.7 MPa

Heat of fusion (I2) 15.52 kJ/mol

Heat of vaporisation (I2) 41.57 kJ/mol
Molar heat capacity (I2) 54.44 J/(mol·K)

Vapour pressure (rhombic)
P (Pa) 1 10 100 1 k 10 k 100 k

at T (K) 260 282 309 342 381 457

Atomic properties

Oxidation states −1, +1, +3, +4, +5, +6,

+7 (a strongly acidic
oxide)

Electronegativity Pauling scale: 2.66

Ionisation energies 1st: 1008.4 kJ/mol

2nd: 1845.9 kJ/mol
3rd: 3180 kJ/mol

Atomic radius empirical: 140 pm

Covalent radius 139±3 pm

Van der Waals radius 198 pm

 Spectral lines of iodine

Other properties

Natural occurrence primordial

Crystal structure orthorhombic

Thermal conductivity 0.449 W/(m·K)

Electrical resistivity 1.3×107 Ω·m (at 0 °C)

Magnetic ordering diamagnetic[2]

Magnetic susceptibility −88.7·10−6 cm3/mol

(298 K)[3]

Bulk modulus 7.7 GPa

CAS Number 7553-56-2

History

Discovery and first Bernard Courtois (1811)

isolation
Main isotopes of iodine
Isotope Abundance Half-life (t1/2) Decay mode Product

123I syn 13 h ε, γ 123Te

124 124
I syn 4.176 d ε Te

125 125
I syn 59.40 d ε Te

127I 100% stable

129I trace 1.57×107 y β− 129Xe

131
I syn 8.02070 d β−, γ 131
Xe

135
I syn 6.57 h β− 135
Xe

Iodine occurs in many oxidation states,

including iodide (I−), iodate (IO−3), and the
various periodate anions. It is the least
abundant of the stable halogens, being the
sixty-first most abundant element. It is the
heaviest essential mineral nutrient. Iodine
is essential in the synthesis of thyroid
hormones.[4] Iodine deficiency affects
about two billion people and is the leading
preventable cause of intellectual
disabilities.

The dominant producers of iodine today

are Chile and Japan. Iodine and its
compounds are primarily used in nutrition.
Due to its high atomic number and ease of
attachment to organic compounds, it has
also found favour as a non-toxic
radiocontrast material. Because of the
specificity of its uptake by the human
body, radioactive isotopes of iodine can
also be used to treat thyroid cancer. Iodine
is also used as a catalyst in the industrial
production of acetic acid and some
polymers.

History
In 1811, iodine was discovered by French
chemist Bernard Courtois,[5][6] who was
born to a manufacturer of saltpetre (an
essential component of gunpowder). At
the time of the Napoleonic Wars, saltpetre
was in great demand in France. Saltpetre
produced from French nitre beds required
sodium carbonate, which could be isolated
from seaweed collected on the coasts of
Normandy and Brittany. To isolate the
sodium carbonate, seaweed was burned
and the ash washed with water. The
remaining waste was destroyed by adding
sulfuric acid. Courtois once added
excessive sulfuric acid and a cloud of
purple vapour rose. He noted that the
vapour crystallised on cold surfaces,
making dark crystals.[7] Courtois
suspected that this material was a new
element but lacked funding to pursue it
further.[8]

Courtois gave samples to his friends,

Charles Bernard Desormes (1777–1838)
and Nicolas Clément (1779–1841), to
continue research. He also gave some of
the substance to chemist Joseph Louis
Gay-Lussac (1778–1850), and to physicist
André-Marie Ampère (1775–1836). On 29
November 1813, Desormes and Clément
made Courtois' discovery public. They
described the substance to a meeting of
the Imperial Institute of France.[9] On 6
December, Gay-Lussac announced that the
new substance was either an element or a
compound of oxygen.[10][11][12] It was Gay-
Lussac who suggested the name "iode",
from the Greek word ἰοειδής[13] (ioeidēs)
for violet (because of the colour of iodine
vapor).[5][10] Ampère had given some of his
sample to English chemist Humphry Davy
(1778–1829), who experimented on the
substance and noted its similarity to
chlorine.[14] Davy sent a letter dated 10
December to the Royal Society of London
stating that he had identified a new
element.[15] Arguments erupted between
Davy and Gay-Lussac over who identified
iodine first, but both scientists
acknowledged Courtois as the first to
isolate the element.[8]

In early periodic tables, iodine is often

given the symbol J, for jod, its name in
German.[16]

Properties
Violet iodine vapour in a round-bottomed flask

Iodine is the fourth halogen, being a

member of group 17 in the periodic table,
below fluorine, chlorine, and bromine; it is
the heaviest stable member of its group.
(The scarce and fugitive fifth halogen, the
radioactive astatine, is not well-studied
due to its expense and inaccessibility in
large quantities, but appears to show
various unusual properties due to
relativistic effects.) Iodine has an electron
configuration of [Kr]4d105s25p5, with the
seven electrons in the fifth and outermost
shell being its valence electrons. Like the
other halogens, it is one electron short of a
full octet and is hence a strong oxidising
agent, reacting with many elements in
order to complete its outer shell, although
in keeping with periodic trends, it is the
weakest oxidising agent among the stable
halogens: it has the lowest
electronegativity among them, just 2.66 on
the Pauling scale (compare fluorine,
chlorine, and bromine at 3.98, 3.16, and
2.96 respectively; astatine continues the
trend with an electronegativity of 2.2).
Elemental iodine hence forms diatomic
molecules with chemical formula I2, where
two iodine atoms share a pair of electrons
in order to each achieve a stable octet for
themselves; at high temperatures, these
diatomic molecules reversibly dissociate a
pair of iodine atoms. Similarly, the iodide
anion, I−, is the strongest reducing agent
among the stable halogens, being the
most easily oxidised back to diatomic
I2.[17] (Astatine goes further, being indeed
unstable as At− and readily oxidised to At0
or At+, although the existence of At2 is not
settled.)[18]

The halogens darken in colour as the

group is descended: fluorine is a very pale
yellow gas, chlorine is greenish-yellow, and
bromine is a reddish-brown volatile liquid.
Iodine conforms to the prevailing trend,
being a shiny black crystalline solid that
melts at 114 °C and boils at 183 °C to form
a violet gas. This trend occurs because the
wavelengths of visible light absorbed by
the halogens increase down the group
(though astatine may not conform to it,
depending on how metallic it turns out to
be).[17] Specifically, the violet colour of
iodine gas results from the electron
transition between the highest occupied
antibonding πg molecular orbital and the
lowest vacant antibonding σu molecular
orbital.[19]
Elemental iodine is slightly soluble in
water, with one gram dissolving in 3450 ml
at 20 °C and 1280 ml at 50 °C; potassium
iodide may be added to increase solubility
via formation of triiodide ions, among
other polyiodides.[19] Nonpolar solvents
such as hexane and carbon tetrachloride
provide a higher solubility.[20] Polar
solutions, such as aqueous solutions, are
brown, reflecting the role of these solvents
as Lewis bases; on the other hand,
nonpolar solutions are violet, the color of
iodine vapour.[19] Charge-transfer
complexes form when iodine is dissolved
in polar solvents, hence changing the
colour. Iodine is violet when dissolved in
carbon tetrachloride and saturated
hydrocarbons but deep brown in alcohols
and amines, solvents that form charge-
transfer adducts.[21]

I2•PPh3 charge-transfer complexes in CH2Cl2. From left

to right: (1) I2 dissolved in dichloromethane – no CT
complex. (2) A few seconds after excess PPh3 was
added – CT complex is forming. (3) One minute later
after excess PPh3 was added, the CT complex
[Ph3PI]+I− has been formed. (4) Immediately after
excess I2 was added, which contains [Ph3PI]+[I3]−.[22]
The melting and boiling points of iodine
are the highest among the halogens,
conforming to the increasing trend down
the group, since iodine has the largest
electron cloud among them that is the
most easily polarised, resulting in its
molecules having the strongest van der
Waals interactions among the halogens.
Similarly, iodine is the least volatile of the
halogens.[17] Because it has the largest
atomic radius among the halogens, iodine
has the lowest first ionisation energy,
lowest electron affinity, lowest
electronegativity and lowest reactivity of
the halogens.[17]
Structure of solid iodine

The interhalogen bond in diiodine is the

weakest of all the halogens. As such, 1%
of a sample of gaseous iodine at
atmospheric pressure is dissociated into
iodine atoms at 575 °C. Temperatures
greater than 750 °C are required for
fluorine, chlorine, and bromine to
dissociate to a similar extent. Most bonds
to iodine are weaker than the analogous
bonds to the lighter halogens.[17] Gaseous
iodine is composed of I2 molecules with
an I–I bond length of 266.6 pm. The I–I
bond is one of the longest single bonds
known. It is even longer (271.5 pm) in solid
orthorhombic crystalline iodine, which has
the same crystal structure as chlorine and
bromine. (The record is held by iodine's
neighbour xenon: the Xe–Xe bond length
is 308.71 pm.)[23] As such, within the
iodine molecule, significant electronic
interactions occur with the two next-
nearest neighbours of each atom, and
these interactions give rise, in bulk iodine,
to a shiny appearance and
semiconducting properties.[17] Iodine is a
two-dimensional semiconductor with a
band gap of 1.3 eV (125 kJ/mol): it is a
semiconductor in the plane of its
crystalline layers and an insulator in the
perpendicular direction.[17]

Isotopes

Of the thirty-seven known isotopes of

iodine, only one occurs in nature, iodine-
127. The others are radioactive and have
half-lives too short to be primordial. As
such, iodine is monoisotopic and its
atomic weight is known to great precision,
as it is a constant of nature.[17]

The longest-lived of the radioactive

isotopes of iodine is iodine-129, which has
a half-life of 15.7 million years, decaying
via beta decay to stable xenon-129.[24]
Some iodine-129 was formed along with
iodine-127 before the formation of the
Solar System, but it has by now completely
decayed away, making it an extinct
radionuclide that is nevertheless still
useful in dating the history of the early
Solar System or very old groundwaters,
due to its mobility in the environment. Its
former presence may be determined from
an excess of its daughter xenon-
129.[25][26][27][28][29] Traces of iodine-129
still exist today, as it is also a cosmogenic
nuclide, formed from cosmic ray spallation
of atmospheric xenon: these traces make
up 10−14 to 10−10 of all terrestrial iodine. It
also occurs from open-air nuclear testing,
and is not hazardous because of its
incredibly long half-life, the longest of all
fission products. At the peak of
thermonuclear testing in the 1960s and
1970s, iodine-129 still made up only about
10−7 of all terrestrial iodine.[30] Excited
states of iodine-127 and iodine-129 are
often used in Mössbauer spectroscopy.[17]

The other iodine radioisotopes have much

shorter half-lives, no longer than days.[24]
Some of them have medical applications
involving the thyroid gland, where the
iodine that enters the body is stored and
concentrated. Iodine-123 has a half-life of
thirteen hours and decays by electron
capture to tellurium-123, emitting gamma
radiation; it is used in nuclear medicine
imaging, including single photon emission
computed tomography (SPECT) and X-ray
computed tomography (X-Ray CT)
scans.[31] Iodine-125 has a half-life of fifty-
nine days, decaying by electron capture to
tellurium-125 and emitting low-energy
gamma radiation; the second-longest-lived
iodine radioisotope, it has uses in
biological assays, nuclear medicine
imaging and in radiation therapy as
brachytherapy to treat a number of
conditions, including prostate cancer,
uveal melanomas, and brain tumours.[32]
Finally, iodine-131, with a half-life of eight
days, beta decays to an excited state of
stable xenon-131 that then converts to the
ground state by emitting gamma radiation.
It is a common fission product and thus is
present in high levels in radioactive fallout.
It may then be absorbed through
contaminated food, and will also
accumulate in the thyroid. As it decays, it
may cause damage to the thyroid. The
primary risk from exposure to high levels
of iodine-131 is the chance occurrence of
radiogenic thyroid cancer in later life.
Other risks include the possibility of non-
cancerous growths and thyroiditis.[33]
The usual means of protection against the
negative effects of iodine-131 is by
saturating the thyroid gland with stable
iodine-127 in the form of potassium iodide
tablets, taken daily for optimal
prophylaxis.[34] However, iodine-131 may
also be used for medicinal purposes in
radiation therapy for this very reason,
when tissue destruction is desired after
iodine uptake by the tissue.[35] Iodine-131
is also used as a radioactive
tracer.[36][37][38][39]

Chemistry and compounds

Halogen bond energies (kJ/mol)[19]
X XX HX BX3 AlX3 CX4
F 159 574 645 582 456
Cl 243 428 444 427 327
Br 193 363 368 360 272
I 151 294 272 285 239

Though it is the least reactive of the

halogens, iodine is still one of the more
reactive elements. For example, while
chlorine gas will halogenate carbon
monoxide, nitric oxide, and sulfur dioxide
(to phosgene, nitrosyl chloride, and sulfuryl
chloride respectively), iodine will not do
so. Furthermore, iodination of metals
tends to result in lower oxidation states
than chlorination or bromination; for
example, rhenium metal reacts with
chlorine to form rhenium hexachloride, but
with bromine it forms only rhenium
pentabromide and iodine can achieve only
rhenium tetraiodide.[17] By the same token,
however, since iodine has the lowest
ionisation energy among the halogens and
is the most easily oxidised of them, it has
a more significant cationic chemistry and
its higher oxidation states are rather more
stable than those of bromine and chlorine,
for example in iodine heptafluoride.[19]

Hydrogen iodide

The simplest compound of iodine is

hydrogen iodide, HI. It is a colourless gas
that reacts with oxygen to give water and
iodine. Although it is useful in iodination
reactions in the laboratory, it does not
have large-scale industrial uses, unlike the
other hydrogen halides. Commercially, it is
usually made by reacting iodine with
hydrogen sulfide or hydrazine:[40]

H2O
2 I2 + N2H4 ⟶ 4 HI + N2

At room temperature, it is a colourless gas,

like all of the hydrogen halides except
hydrogen fluoride, since hydrogen cannot
form strong hydrogen bonds to the large
and only mildly electronegative iodine
atom. It melts at −51.0 °C and boils at
−35.1 °C. It is an endothermic compound
that can exothermically dissociate at room
temperature, although the process is very
slow unless a catalyst is present: the
reaction between hydrogen and iodine at
room temperature to give hydrogen iodide
does not proceed to completion. The H–I
bond dissociation energy is likewise the
smallest of the hydrogen halides, at
295 kJ/mol.[41]

Aqueous hydrogen iodide is known as

hydroiodic acid, which is a strong acid.
Hydrogen iodide is exceptionally soluble in
water: one litre of water will dissolve 425
litres of hydrogen iodide, and the saturated
solution has only four water molecules per
molecule of hydrogen iodide.[42]
Commercial so-called "concentrated"
hydroiodic acid usually contains 48–57%
HI by mass; the solution forms an
azeotrope with boiling point 126.7 °C at
56.7 g HI per 100 g solution. Hence
hydroiodic acid cannot be concentrated
past this point by evaporation of water.[41]

Unlike hydrogen fluoride, anhydrous liquid

hydrogen iodide is difficult to work with as
a solvent, because its boiling point is low,
it has a small liquid range, its dielectric
constant is low and it does not dissociate
appreciably into H2I+ and HI−2 ions – the
latter, in any case, are much less stable
than the bifluoride ions (HF−2) due to the
very weak hydrogen bonding between
hydrogen and iodine, though its salts with
very large and weakly polarising cations
such as Cs+ and NR+4 (R = Me, Et, Bun) may
still be isolated. Anhydrous hydrogen
iodide is a poor solvent, able to dissolve
only small molecular compounds such as
nitrosyl chloride and phenol, or salts with
very low lattice energies such as
tetraalkylammonium halides.[41]

Other binary iodides

Nearly all elements in the periodic table

form binary iodides. The exceptions are
decidedly in the minority and stem in each
case from one of three causes: extreme
inertness and reluctance to participate in
chemical reactions (the noble gases);
extreme nuclear instability hampering
chemical investigation before decay and
transmutation (many of the heaviest
elements beyond bismuth); and having an
electronegativity higher than iodine's
(oxygen, nitrogen, and the first three
halogens), so that the resultant binary
compounds are formally not iodides but
rather oxides, nitrides, or halides of iodine.
(Nonetheless, nitrogen triiodide is named
as an iodide as it is analogous to the other
nitrogen trihalides.)[43]
Given the large size of the iodide anion
and iodine's weak oxidising power, high
oxidation states are difficult to achieve in
binary iodides, the maximum known being
in the pentaiodides of niobium, tantalum,
and protactinium. Iodides can be made by
reaction of an element or its oxide,
hydroxide, or carbonate with hydroiodic
acid, and then dehydrated by mildly high
temperatures combined with either low
pressure or anhydrous hydrogen iodide
gas. These methods work best when the
iodide product is stable to hydrolysis;
otherwise, the possibilities include high-
temperature oxidative iodination of the
element with iodine or hydrogen iodide,
high-temperature iodination of a metal
oxide or other halide by iodine, a volatile
metal halide, carbon tetraiodide, or an
organic iodide. For example,
molybdenum(IV) oxide reacts with
aluminium(III) iodide at 230 °C to give
molybdenum(II) iodide. An example
involving halogen exchange is given below,
involving the reaction of tantalum(V)
chloride with excess aluminium(III) iodide
at 400 °C to give tantalum(V) iodide:[43]

Lower iodides may be produced either

through thermal decomposition or
disproportionation, or by reducing the
higher iodide with hydrogen or a metal, for
example:[43]

Most of the iodides of the pre-transition

metals (groups 1, 2, and 3, along with the
lanthanides and actinides in the +2 and +3
oxidation states) are mostly ionic, while
nonmetals tend to form covalent
molecular iodides, as do metals in high
oxidation states from +3 and above. Ionic
iodides MIn tend to have the lowest
melting and boiling points among the
halides MXn of the same element, because
the electrostatic forces of attraction
between the cations and anions are
weakest for the large iodide anion. In
contrast, covalent iodides tend to instead
have the highest melting and boiling
points among the halides of the same
element, since iodine is the most
polarisable of the halogens and, having the
most electrons among them, can
contribute the most to van der Waals
forces. Naturally, exceptions abound in
intermediate iodides where one trend
gives way to the other. Similarly,
solubilities in water of predominantly ionic
iodides (e.g. potassium and calcium) are
the greatest among ionic halides of that
element, while those of covalent iodides
(e.g. silver) are the lowest of that element.
In particular, silver iodide is very insoluble
in water and its formation is often used as
a qualitative test for iodine.[43]

Iodine halides

The halogens form many binary,

diamagnetic interhalogen compounds with
stoichiometries XY, XY3, XY5, and XY7
(where X is heavier than Y), and iodine is
no exception. Iodine forms all three
possible diatomic interhalogens, a
trifluoride and trichloride, as well as a
pentafluoride and, exceptionally among
the halogens, a heptafluoride. Numerous
cationic and anionic derivatives are also
characterised, such as the wine-red or
bright orange compounds of ICl+2 and the
dark brown or purplish black compounds
of I2Cl+. Apart from these, some
pseudohalides are also known, such as
cyanogen iodide (ICN), iodine thiocyanate
(ISCN), and iodine azide (IN3).[44]
Iodine monochloride

Iodine monofluoride (IF) is unstable at

room temperature and disproportionates
very readily and irreversibly to iodine and
iodine pentafluoride, and thus cannot be
obtained pure. It can be synthesised from
the reaction of iodine with fluorine gas in
trichlorofluoromethane at −45 °C, with
iodine trifluoride in trichlorofluoromethane
at −78 °C, or with silver(I) fluoride at
0 °C.[44] Iodine monochloride (ICl) and
iodine monobromide (IBr), on the other
hand, are moderately stable. The former, a
volatile red-brown compound, was
discovered independently by Joseph Louis
Gay-Lussac and Humphry Davy in 1813–4
not long after the discoveries of chlorine
and iodine, and it mimics the intermediate
halogen bromine so well that Justus von
Liebig was misled into mistaking bromine
(which he had found) for iodine
monochloride. Iodine monochloride and
iodine monobromide may be prepared
simply by reacting iodine with chlorine or
bromine at room temperature and purified
by fractional crystallisation. Both are quite
reactive and attack even platinum and
gold, though not boron, carbon, cadmium,
lead, zirconium, niobium, molybdenum,
and tungsten. Their reaction with organic
compounds depends on conditions. Iodine
chloride vapour tends to chlorinate phenol
and salicyclic acid, since when iodine
chloride undergoes homolytic
dissociation, chlorine and iodine are
produced and the former is more reactive.
However, iodine chloride in
tetrachloromethane solution results in
iodination being the main reaction, since
now heterolytic fission of the I–Cl bond
occurs and I+ attacks phenol as an
electrophile. However, iodine
monobromide tends to brominate phenol
even in tetrachloromethane solution
because it tends to dissociate into its
elements in solution, and bromine is more
reactive than iodine.[44] When liquid, iodine
monochloride and iodine monobromide
+
dissociate into I2X and IX−2 anions (X = Cl,
Br); thus they are significant conductors of
electricity and can be used as ionising
solvents.[44]

Iodine trifluoride (IF3) is an unstable yellow

solid that decomposes above −28 °C. It is
thus little-known. It is difficult to produce
because fluorine gas would tend to oxidise
iodine all the way to the pentafluoride;
reaction at low temperature with xenon
difluoride is necessary. Iodine trichloride,
which exists in the solid state as the
planar dimer I2Cl6, is a bright yellow solid,
synthesised by reacting iodine with liquid
chlorine at −80 °C; caution is necessary
during purification because it easily
dissociates to iodine monochloride and
chlorine and hence can act as a strong
chlorinating agent. Liquid iodine trichloride
conducts electricity, possibly indicating
dissociation to ICl+2 and ICl−4 ions.[45]

Iodine pentafluoride (IF5), a colourless,

volatile liquid, is the most
thermodynamically stable iodine fluoride,
and can be made by reacting iodine with
fluorine gas at room temperature. It is a
fluorinating agent, but is mild enough to
store in glass apparatus. Again, slight
electrical conductivity is present in the
liquid state because of dissociation to IF+4
and IF−6. The pentagonal bipyramidal iodine
heptafluoride (IF7) is an extremely
powerful fluorinating agent, behind only
chlorine trifluoride, chlorine pentafluoride,
and bromine pentafluoride among the
interhalogens: it reacts with almost all the
elements even at low temperatures,
fluorinates Pyrex glass to form iodine(VII)
oxyfluoride (IOF5), and sets carbon
monoxide on fire.[46]

Iodine oxides and oxoacids

Structure of iodine pentoxide

Iodine oxides are the most stable of all the

halogen oxides, because of the strong I–O
bonds resulting from the large
electronegativity difference between
iodine and oxygen, and they have been
known for the longest time.[21] The stable,
white, hygroscopic iodine pentoxide (I2O5)
has been known since its formation in
1813 by Gay-Lussac and Davy. It is most
easily made by the dehydration of iodic
acid (HIO3), of which it is the anhydride. It
will quickly oxidise carbon monoxide
completely to carbon dioxide at room
temperature, and is thus a useful reagent
in determining carbon monoxide
concentration. It also oxidises nitrogen
oxide, ethylene, and hydrogen sulfide. It
reacts with sulfur trioxide and
peroxydisulfuryl difluoride (S2O6F2) to
form salts of the iodyl cation, [IO2]+, and is
reduced by concentrated sulfuric acids to
iodosyl salts involving [IO]+. It may be
fluorinated by fluorine, bromine trifluoride,
sulfur tetrafluoride, or chloryl fluoride,
resulting iodine pentafluoride, which also
reacts with iodine pentoxide, giving
iodine(V) oxyfluoride, IOF3. A few other
less stable oxides are known, notably I4O9
and I2O4; their structures have not been
determined, but reasonable guesses are
IIII(IVO3)3 and [IO]+[IO3]− respectively.[47]
Standard reduction potentials for aqueous I species[48]
+ −
E°(couple) a(H ) = 1 E°(couple) a(OH ) = 1
(acid) (base)
I2/I− +0.535 I2/I− +0.535
HOI/I− +0.987 IO−/I− +0.48
    IO−3/I− +0.26
HOI/I2 +1.439 IO−/I2 +0.42
IO−3/I2 +1.195    
IO−3/HOI +1.134 IO−3/IO− +0.15
IO−4/IO−3 +1.653    
H5IO6/IO−3 +1.601 H3IO2− −
6 /IO3 +0.65

More important are the four oxoacids:

hypoiodous acid (HIO), iodous acid (HIO2),
iodic acid (HIO3), and periodic acid (HIO4
or H5IO6). When iodine dissolves in
aqueous solution, the following reactions
occur:[48]
 I2 + ⇌ HIO + H+ Kac = 2.0 × 10−13
H2O + I− mol2 l−2
I2 + 2 ⇌ IO− + H2O
Kalk = 30 mol−1 l
OH− + I−

Hypoiodous acid is unstable to

disproportionation. The hypoiodite ions
thus formed disproportionate immediately
to give iodide and iodate:[48]

3 IO− ⇌ 2 I− + IO−3 K = 1020

Iodous acid and iodite are even less stable

and exist only as a fleeting intermediate in
the oxidation of iodide to iodate, if at all.[48]
Iodates are by far the most important of
these compounds, which can be made by
oxidising alkali metal iodides with oxygen
at 600 °C and high pressure, or by
oxidising iodine with chlorates. Unlike
chlorates, which disproportionate very
slowly to form chloride and perchlorate,
iodates are stable to disproportionation in
both acidic and alkaline solutions. From
these, salts of most metals can be
obtained. Iodic acid is most easily made
by oxidation of an aqueous iodine
suspension by electrolysis or fuming nitric
acid. Iodate has the weakest oxidising
power of the halates, but reacts the
quickest.[49]
Many periodates are known, including not
only the expected tetrahedral IO−4, but also
square-pyramidal IO3−
5 , octahedral
orthoperiodate IO5−
6 , [IO3(OH)3]2−,

[I2O8(OH2)]4−, and I2O4−

9 . They are usually
made by oxidising alkaline sodium iodate
electrochemically (with lead(IV) oxide as
the anode) or by chlorine gas:[50]

IO−3 + 6 OH− → IO5−

6 + 3 H2O + 2 e−

IO−3 + 6 OH− + Cl2 → IO5−

6 + 2 Cl−+3H O
2

They are thermodymically and kinetically

powerful oxidising agents, quickly
oxidising Mn2+ to MnO−4, and cleaving
glycols, α-diketones, α-ketols, α-
aminoalcohols, and α-diamines.[50]
Orthoperiodate especially stabilises high
oxidation states among metals because of
its very high negative charge of −5.
Orthoperiodic acid, H5IO6, is stable, and
dehydrates at 100 °C in a vacuum to
metaperiodic acid, HIO4. Attempting to go
further does not result in the nonexistent
iodine heptoxide (I2O7), but rather iodine
pentoxide and oxygen. Periodic acid may
be protonated by sulfuric acid to give the
I(OH)+6 cation, isoelectronic to Te(OH)6 and
Sb(OH)−6, and giving salts with bisulfate
and sulfate.[21]

Polyiodine compounds
When iodine dissolves in strong acids,
such as fuming sulfuric acid, a bright blue
paramagnetic solution including I+2 cations
is formed. A solid salt of the diiodine
cation may be obtained by oxidising iodine
with antimony pentafluoride:[21]

SO2
2 I2 + 5 SbF5 ⟶ 2 I2Sb2F11 + SbF3
20°C

The salt I2Sb2F11 is dark blue, and the blue

tantalum analogue I2Ta2F11 is also known.
Whereas the I–I bond length in I2 is
267 pm, that in I+2 is only 256 pm as the
missing electron in the latter has been
removed from an antibonding orbital,
making the bond stronger and hence
shorter. In fluorosulfuric acid solution,
deep-blue I+2 reversibly dimerises below
−60 °C, forming red rectangular
diamagnetic I2+
4 . Other polyiodine cations
are not as well-characterised, including
bent dark-brown or black I+3 and
centrosymmetric C2h green or black I+5,
known in the AsF−6 and AlCl−4 salts among
others.[21][51]

The only important polyiodide anion in

aqueous solution is linear triiodide, I−3. Its
formation explains why the solubility of
iodine in water may be increased by the
addition of potassium iodide solution:[21]
 I2 + I− ⇌ I−3 (Keq = ~700 at 20 °C)

Many other polyiodides may be found

when solutions containing iodine and
iodide crystallise, such as I−5, I−9, I2−
4 , and I2−
8 ,
whose salts with large, weakly polarising
cations such as Cs+ may be isolated.[21][52]

Organoiodine compounds

Structure of the oxidising agent 2-iodoxybenzoic acid

Organoiodine compounds have been
fundamental in the development of
organic synthesis, such as in the Hofmann
elimination of amines,[53] the Williamson
ether synthesis,[54] the Wurtz coupling
reaction,[55] and in Grignard reagents.[56]

The carbon–iodine bond is a common

functional group that forms part of core
organic chemistry; formally, these
compounds may be thought of as organic
derivatives of the iodide anion. The
simplest organoiodine compounds, alkyl
iodides, may be synthesised by the
reaction of alcohols with phosphorus
triiodide; these may then be used in
nucleophilic substitution reactions, or for
preparing Grignard reagents. The C–I bond
is the weakest of all the carbon–halogen
bonds due to the minuscule difference in
electronegativity between carbon (2.55)
and iodine (2.66). As such, iodide is the
best leaving group among the halogens, to
such an extent that many organoiodine
compounds turn yellow when stored over
time due to decomposition into elemental
iodine; as such, they are commonly used in
organic synthesis, because of the easy
formation and cleavage of the C–I
bond.[57] They are also significantly denser
than the other organohalogen compounds
thanks to the high atomic weight of
iodine.[58] A few organic oxidising agents
like the iodanes contain iodine in a higher
oxidation state than −1, such as 2-
iodoxybenzoic acid, a common reagent for
the oxidation of alcohols to aldehydes,[59]
and iodobenzene dichloride (PhICl2), used
for the selective chlorination of alkenes
and alkynes.[60] One of the more well-
known uses of organoiodine compounds
is the so-called iodoform test, where
iodoform (CHI3) is produced by the
exhaustive iodination of a methyl ketone
(or another compound capable of being
oxidised to a methyl ketone), as follows:[61]
Some drawbacks of using organoiodine
compounds as compared to
organochlorine or organobromine
compounds is the greater expense and
toxicity of the iodine derivatives, since
iodine is expensive and organoiodine
compounds are stronger alkylating
agents.[62] For example, iodoacetamide
and iodoacetic acid denature proteins by
irreversibly alkylating cysteine residues
and preventing the reformation of disulfide
linkages.[63]
Halogen exchange to produce iodoalkanes
by the Finkelstein reaction is slightly
complicated by the fact that iodide is a
better leaving group than chloride or
bromide. The difference is nevertheless
small enough that the reaction can be
driven to completion by exploiting the
differential solubility of halide salts, or by
using a large excess of the halide salt.[61]
In the classic Finkelstein reaction, an alkyl
chloride or an alkyl bromide is converted
to an alkyl iodide by treatment with a
solution of sodium iodide in acetone.
Sodium iodide is soluble in acetone and
sodium chloride and sodium bromide are
not.[64] The reaction is driven toward
products by mass action due to the
precipitation of the insoluble salt.[65][66]

Occurrence and production

Iodine is the least abundant of the stable
halogens, comprising only 0.46 parts per
million of Earth's crustal rocks (compare:
fluorine 544 ppm, chlorine 126 ppm,
bromine 2.5 ppm). Among the eighty-four
elements which occur in significant
quantities (elements 1–42, 44–60, 62–83,
and 90–92), it ranks sixty-first in
abundance.[67] Iodide minerals are rare,
and most deposits that are concentrated
enough for economical extraction are
iodate minerals instead. Examples include
lautarite, Ca(IO3)2, and dietzeite,
7Ca(IO3)2·8CaCrO4.[67] These are the
minerals that occur as trace impurities in
the caliche, found in Chile, whose main
product is sodium nitrate. In total, they can
contain at least 0.02% and at most 1%
iodine by weight.[68] Sodium iodate is
extracted from the caliche and reduced to
iodide by sodium bisulfite. This solution is
then reacted with freshly extracted iodate,
resulting in comproportionation to iodine,
which may be filtered off.[17]

The caliche was the main source of iodine

in the 19th century and continues to be
important today, replacing kelp (which is
no longer an economically viable
source),[69] but in the late 20th century
brines emerged as a comparable source.
The Japanese Minami Kanto gas field east
of Tokyo and the American Anadarko
Basin gas field in northwest Oklahoma are
the two largest such sources. The brine is
hotter than 60 °C from the depth of the
source. The brine is first purified and
acidified using sulfuric acid, then the
iodide present is oxidised to iodine with
chlorine. An iodine solution is produced,
but is dilute and must be concentrated. Air
is blown into the solution to evaporate the
iodine, which is passed into an absorbing
tower where sulfur dioxide reduces the
iodine. The hydrogen iodide (HI) is reacted
with chlorine to precipitate the iodine.
After filtering and purification the iodine is
packed.[68][70]

2 HI + Cl2 → I2↑ + 2 HCl

I2 + 2 H2O + SO2 → 2 HI + H2SO4
2 HI + Cl2 → I2↓ + 2 HCl

These sources ensure that Chile and

Japan are the largest producers of iodine
today.[67] Alternatively, the brine may be
treated with silver nitrate to precipitate out
iodine as silver iodide, which is then
decomposed by reaction with iron to form
metallic silver and a solution of iron(II)
iodide. The iodine may then be liberated by
displacement with chlorine.[71]

Applications
Unlike chlorine and bromine, which have
one significant main use dwarfing all
others, iodine is used in many applications
of varying importance. About half of all
produced iodine goes into various
organoiodine compounds; another 15%
remains as the pure element, another 15%
is used to form potassium iodide, and
another 15% for other inorganic iodine
compounds. The remaining 5% is for
minor uses. Among the major uses of
iodine compounds are catalysts, animal
feed supplements, stabilisers, dyes,
colourants and pigments, pharmaceutical,
sanitation (from tincture of iodine), and
photography; minor uses include smog
inhibition, cloud seeding, and various uses
in analytical chemistry.[17]

Chemical analysis

Testing a seed for starch with a solution of iodine

Potassium tetraiodomercurate(II), K2HgI4,
is also known as Nessler's reagent. It is
often used as a sensitive spot test for
ammonia. Similarly, Cu2HgI4 is used as a
precipitating reagent to test for alkaloids.
The iodide and iodate anions are often
used for quantitative volumetric analysis,
for example in iodometry and the iodine
clock reaction (in which iodine also serves
as a test for starch, forming a dark blue
complex),[17] and aqueous alkaline iodine
solution is used in the iodoform test for
methyl ketones.[61] The iodine test for
starch is still used to detect counterfeit
banknotes printed on starch-containing
paper.[72]
Spectroscopy

The spectra of the iodine molecule, I2,

consists of (not exclusively) tens of
thousands of sharp spectral lines in the
wavelength range 500-700 nm. It is
therefore a commonly used wavelength
reference (secondary standard). By
measuring with a spectroscopic Doppler-
free technique while focusing on one of
these lines, the hyperfine structure of the
iodine molecule reveals itself. A line is now
resolved such that either 15 components,
(from even rotational quantum numbers,
Jeven), or 21 components (from odd
rotational quantum numbers, Jodd) are
measurable.

Medicine

Elemental iodine

Elemental iodine is used as a disinfectant

either as the element, or as the water-
soluble triiodide anion I3− generated in situ
by adding iodide to poorly water-soluble
elemental iodine (the reverse chemical
reaction makes some free elemental
iodine available for antisepsis). Elemental
iodine may also be used to treat iodine
deficiency.[73]
In the alternative, iodine may be produced
from iodophors, which contain iodine
complexed with a solubilizing agent
(iodide ion may be thought of loosely as
the iodophor in triiodide water solutions).
Examples of such preparations include:[74]

Tincture of iodine: iodine in ethanol, or

iodine and sodium iodide in a mixture of
ethanol and water.
Lugol's iodine: iodine and iodide in water
alone, forming mostly triiodide. Unlike
tincture of iodine, Lugol's iodine has a
minimised amount of the free iodine (I2)
component.
Povidone iodine (an iodophor).
The antimicrobial action of iodine is quick
and works at low concentrations, and thus
it is used in operating theatres.[75] Its
specific mode of action is unknown. It
penetrates into microorganisms and
attacks particular amino acids (such as
cysteine and methionine), nucleotides, and
fatty acids, ultimately resulting in cell
death. It also has an antiviral action, but
nonlipid viruses and parvoviruses are less
sensitive than lipid enveloped viruses.
Iodine probably attacks surface proteins
of enveloped viruses, and it may also
destabilise membrane fatty acids by
reacting with unsaturated carbon
bonds.[76]
Other formulations

In medicine, a saturated solution of

potassium iodide is used to treat acute
thyrotoxicosis. It is also used to block
uptake of iodine-131 in the thyroid gland
(see isotopes section above), when this
isotope is used as part of
radiopharmaceuticals (such as
iobenguane) that are not targeted to the
thyroid or thyroid-type tissues.[77][78]

Iodine-131 (usually as iodide) is a

component of nuclear fallout, and is
particularly dangerous owing to the thyroid
gland's propensity to concentrate ingested
iodine and retain it for periods longer than
this isotope's radiological half-life of eight
days. For this reason, people at risk of
exposure to environmental radioactive
iodine (iodine-131) in fallout may be
instructed to take non-radioactive
potassium iodide tablets. The typical adult
dose is one 130 mg tablet per 24 hours,
supplying 100 mg (100,000 micrograms)
of ionic iodine. (The typical daily dose of
iodine for normal health is of order 100
micrograms; see "Dietary Intake" below.)
Ingestion of this large dose of non-
radioactive iodine minimises the uptake of
radioactive iodine by the thyroid gland.[79]
Diatrizoic acid, an iodine-containing radiocontrast
agent

As an element with high electron density

and atomic number, iodine absorbs X-rays
weaker than 33.3 keV due to the
photoelectric effect of the innermost
electrons.[80] Organoiodine compounds
are used with intravenous injection as X-
ray radiocontrast agents. This application
is often in conjunction with advanced X-ray
techniques such as angiography and CT
scanning. At present, all water-soluble
radiocontrast agents rely on iodine.

Others

The production of ethylenediamine

dihydroiodide, provided as a nutritional
supplement for livestock, consumes a
large portion of available iodine. Another
significant use is a catalyst for the
production of acetic acid by the Monsanto
and Cativa processes. In these
technologies, which support the world's
demand for acetic acid, hydroiodic acid
converts the methanol feedstock into
methyl iodide, which undergoes
carbonylation. Hydrolysis of the resulting
acetyl iodide regenerates hydroiodic acid
and gives acetic acid.[81]

Inorganic iodides find specialised uses.

Titanium, zirconium, hafnium, and thorium
are purified by the van Arkel process,
which involves the reversible formation of
the tetraiodides of these elements. Silver
iodide is a major ingredient to traditional
photographic film. Thousands of
kilograms of silver iodide are used
annually for cloud seeding to induce
rain.[81]
The organoiodine compound erythrosine is
an important food coloring agent.
Perfluoroalkyl iodides are precursors to
important surfactants, such as
perfluorooctanesulfonic acid.[81]

Biological role

The thyroid system of the thyroid hormones T3 and T4

Comparison of the iodine content in urine in France (in
microgramme/day), for some regions and departments
(average levels of urine iodine, measured in
micrograms per liter at the end of the twentieth century
(1980 to 2000)[82]

Iodine is an essential element for life and,

at atomic number Z = 53, is the heaviest
element commonly needed by living
organisms. (Lanthanum and the other
lanthanides, as well as tungsten with Z =
74, are used by a few
microorganisms.)[83][84] It is required for
the synthesis of the growth-regulating
thyroid hormones thyroxine and
triiodothyronine (T4 and T3 respectively,
named after their number of iodine
atoms). A deficiency of iodine leads to
decreased production of T3 and T4 and a
concomitant enlargement of the thyroid
tissue in an attempt to obtain more iodine,
causing the disease known as simple
goitre. The major form of thyroid hormone
in the blood is thyroxine (T4), which has a
longer half-life than T3. In humans, the
ratio of T4 to T3 released into the blood is
between 14:1 and 20:1. T4 is converted to
the active T3 (three to four times more
potent than T4) within cells by deiodinases
(5'-iodinase). These are further processed
by decarboxylation and deiodination to
produce iodothyronamine (T1a) and
thyronamine (T0a'). All three isoforms of
the deiodinases are selenium-containing
enzymes; thus dietary selenium is
essential for T3 production.[85]

Iodine accounts for 65% of the molecular

weight of T4 and 59% of T3. Fifteen to
20 mg of iodine is concentrated in thyroid
tissue and hormones, but 70% of all iodine
in the body is found in other tissues,
including mammary glands, eyes, gastric
mucosa, fetal thymus, cerebro-spinal fluid
and choroid plexus, arterial walls, the
cervix, and salivary glands. In the cells of
those tissues, iodide enters directly by
sodium-iodide symporter (NIS). The action
of iodine in mammary tissue is related to
fetal and neonatal development, but in the
other tissues, it is (at least) partially
unknown.[86]

Dietary intake

Recommendations by the United States

Institute of Medicine are between 110 and
130 µg for infants up to 12 months, 90 µg
for children up to eight years, 130 µg for
children up to 13 years, 150 µg for adults,
220 µg for pregnant women and 290 µg
for lactation.[4][87] The Tolerable Upper
Intake Level (UL) for adults is
1,100 μg/day.[88] This upper limit was
assessed by analyzing the effect of
supplementation on thyroid-stimulating
hormone.[86]

The thyroid gland needs no more than

70 μg/day to synthesise the requisite daily
amounts of T4 and T3.[4] The higher
recommended daily allowance levels of
iodine seem necessary for optimal
function of a number of body systems,
including lactation, gastric mucosa,
salivary glands, brain cells, choroid plexus,
thymus, and arterial walls.[4][89][90][91]

Natural sources of dietary iodine include

seafood, such as fish, seaweeds (such as
kelp) and shellfish, dairy products and
eggs so long as the animals received
enough iodine, and plants grown on iodine-
rich soil.[92][93] Iodised salt is fortified with
iodine in the form of sodium iodide.[93][94]

As of 2000, the median intake of iodine

from food in the United States was 240 to
300 μg/day for men and 190 to
210 μg/day for women.[88] The general US
population has adequate iodine
nutrition,[95][96] with women of childbearing
age and pregnant women having a
possible mild risk of deficiency.[96] In
Japan, consumption was considered
much higher, ranging between
5,280 μg/day to 13,800 μg/day from
dietary seaweed or kombu kelp,[86] often in
the form of Kombu Umami extracts for
soup stock and potato chips. However,
new studies suggest that Japan's
consumption is closer to 1,000–
3,000 μg/day.[97] The adult UL in Japan
was last revised to 3,000 µg/day in
2015.[98]
After iodine fortification programs such as
iodisation of salt have been implemented,
some cases of iodine-induced
hyperthyroidism have been observed (so-
called Jod-Basedow phenomenon). The
condition seems to occur mainly in people
over forty, and the risk appears higher
when iodine deficiency is severe and the
initial rise in iodine intake is high.[99]

Deficiency

In areas where there is little iodine in the

diet,[100] typically remote inland areas and
semi-arid equatorial climates where no
marine foods are eaten, iodine deficiency
gives rise to hypothyroidism, symptoms of
which are extreme fatigue, goitre, mental
slowing, depression, weight gain, and low
basal body temperatures.[101] Iodine
deficiency is the leading cause of
preventable intellectual disability, a result
that occurs primarily when babies or small
children are rendered hypothyroidic by a
lack of the element. The addition of iodine
to table salt has largely eliminated this
problem in wealthier nations, but iodine
deficiency remains a serious public health
problem in the developing world today.[102]
Iodine deficiency is also a problem in
certain areas of Europe. Information
processing, fine motor skills, and visual
problem solving are improved by iodine
repletion in moderately iodine-deficient
children.[103]

Toxicity
 Iodine
Hazards

GHS pictograms

GHS signal word Danger

GHS hazard statements H312, H332, H315,

H319, H335, H372,
H400

GHS precautionary P261, P273, P280,

statements
P305, P351, P338,
P314[104]

NFPA 704 0
[105]
3 0

Elemental iodine (I2) is toxic if taken orally

undiluted. The lethal dose for an adult
human is 30 mg/kg, which is about 2.1–
2.4 grams for a human weighing 70 to
80 kg (even if experiments on rats
demonstrated that these animals could
survive after eating a 14000 mg/kg dose).
Excess iodine can be more cytotoxic in the
presence of selenium deficiency.[106]
Iodine supplementation in selenium-
deficient populations is, in theory,
problematic, partly for this reason.[86] The
toxicity derives from its oxidizing
properties, through which it denaturates
proteins (including enzymes).[107]

Elemental iodine is also a skin irritant, and

direct contact with skin can cause damage
and solid iodine crystals should be
handled with care. Solutions with high
elemental iodine concentration, such as
tincture of iodine and Lugol's solution, are
capable of causing tissue damage if used
in prolonged cleaning or antisepsis;
similarly, liquid Povidone-iodine (Betadine)
trapped against the skin resulted in
chemical burns in some reported
cases.[108]

Occupational exposure

People can be exposed to iodine in the

workplace by inhalation, ingestion, skin
contact, and eye contact. The
Occupational Safety and Health
Administration (OSHA) has set the legal
limit (Permissible exposure limit) for
iodine exposure in the workplace at 0.1
ppm (1 mg/m3) during an 8-hour workday.
The National Institute for Occupational
Safety and Health (NIOSH) has set a
Recommended exposure limit (REL) of
0.1 ppm (1 mg/m3) during an 8-hour
workday. At levels of 2 ppm, iodine is
immediately dangerous to life and
health.[109]

Allergic reactions

Some people develop a hypersensitivity to

products and foods containing iodine.
Applications of tincture of iodine or
Betadine can cause rashes, sometimes
severe.[110] Parenteral use of iodine-based
contrast agents (see above) can cause
reactions ranging from a mild rash to fatal
anaphylaxis. Such reactions have led to
the misconception (widely held, even
among physicians) that some people are
allergic to iodine itself; even allergies to
iodine-rich seafood have been so
construed.[111] In fact, there has never
been a confirmed report of a true iodine
allergy, and an allergy to elemental iodine
or simple iodide salts is theoretically
impossible. Hypersensitivity reactions to
products and foods containing iodine are
apparently related to their other molecular
components;[112] thus, a person who has
demonstrated an allergy to one food or
product containing iodine may not have an
allergic reaction to another. Patients with
various food allergies (shellfish, egg, milk,
etc.) or asthma are more likely to suffer
reactions to contrast media containing
iodine.[112] As with all medications, the
patient's allergy history should be
questioned and consulted before any
containing iodine are administered.[113]

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