KIMIA

HALOGEN

KHAIRUNNISA NASUTION
LUPITA YESSICA
RISKI SUWISTIANISA
RIDHO RAYENDRA
XII IPA 4
Halogen
The halogens or halogen elements are a series of nonmetal elements from Group 17 IUPAC
Style (formerly: VII, VIIA) of the periodic table, comprising fluorine (F), chlorine (Cl), bromine
(Br), iodine (I), and astatine (At). The artificially created element 117, provisionally referred to
by the systematic name ununseptium, may also be a halogen. The group of halogens is the only
periodic table group which contains elements in all three familiar states of matter at standard
temperature and pressure.

Abundance
Owing to their high reactivity, the halogens are found in the environment only in compounds or
as ions. Halide ions and oxoanions such as iodate (IO3−) can be found in many minerals and in
seawater. Halogenated organic compounds can also be found as natural products in living
organisms. In their elemental forms, the halogens exist as diatomic molecules, but these only
have a fleeting existence in nature and are much more common in the laboratory and in industry.
At room temperature and pressure, fluorine and chlorine are gases, bromine is a liquid and iodine
and astatine are solids; Group 17 is therefore the only periodic table group exhibiting all three
states of matter at room temperature.

Properties

Fluorine, (F); chlorine, (Cl); bromine, (Br); iodine, (I) at room temperature. The first two are
gaseous, the third is liquid and the fourth is solid.

Like other groups, the candidates of this family show patterns in its electron configuration,
especially the outermost shells resulting in trends in chemical behavior:

No. of
Z Element
electrons/shell
9 fluorine 2, 7
17 chlorine 2, 8, 7
35 bromine 2, 8, 18, 7
53 iodine 2, 8, 18, 18, 7
85 astatine 2, 8, 18, 32, 18, 7
The halogens show a series of trends when moving down the group—for instance, decreasing
electronegativity and reactivity, and increasing melting and boiling point.

Standard
Melting Boiling
Atomic Electronegativity
Halogen Point Point
Weight (Pauling)
(K) (K)
(u)
Fluorine 18.998 53.53 85.03 3.98
Chlorine 35.453 171.60 239.11 3.16
Bromine 79.904 265.80 332.00 2.96
Iodine 126.904 386.85 457.40 2.66
Astatine (210) 575 610 (?) 2.20

Diatomic halogen molecules

d(X−X) / pm d(X−X) / pm
halogen molecule structure model
(gas phase) (solid phase)

fluorine F2 143 149

chlorine Cl2 199 198

bromine Br2 228 227

iodine I2 266 272

The elements become less reactive and have higher melting points as the atomic number
increases.
Chemistry
Reactivity

Halogens are highly reactive, and as such can be harmful or lethal to biological organisms in
sufficient quantities. This high reactivity is due to the atoms being highly electronegative due to
their high effective nuclear charge. They can gain an electron by reacting with atoms of other
elements. Fluorine is one of the most reactive elements in existence, attacking otherwise inert
materials such as glass, and forming compounds with the heavier noble gases. It is a corrosive
and highly toxic gas. The reactivity of fluorine is such that if used or stored in laboratory
glassware, it can react with glass in the presence of small amounts of water to form silicon
tetrafluoride (SiF4). Thus fluorine must be handled with substances such as Teflon (which is
itself an organofluorine compound), extremely dry glass, or metals such as copper or steel which
form a protective layer of fluoride on their surface.

The high reactivity of fluorine means that once it does react with something, it bonds with it so
strongly that the resulting molecule is very inert and non-reactive to anything else. For example,
Teflon is fluorine bonded with carbon.

Both chlorine and bromine are used as disinfectants for drinking water, swimming pools, fresh
wounds, spas, dishes, and surfaces. They kill bacteria and other potentially harmful
microorganisms through a process known as sterilization. Their reactivity is also put to use in
bleaching. Sodium hypochlorite, which is produced from chlorine, is the active ingredient of
most fabric bleaches and chlorine-derived bleaches are used in the production of some paper
products.

Hydrogen halides

The halogens all form binary compounds with hydrogen known as the hydrogen halides (HF,
HCl, HBr, HI, and HAt), a series of particularly strong acids. When in aqueous solution, the
hydrogen halides are known as hydrohalic acids. HAt, or "hydroastatic acid", should also qualify,
but it is not typically included in discussions of hydrohalic acid due to astatine's extreme
instability toward alpha decay.

Interhalogen compounds

The halogens react with each other to form interhalogen compounds. Diatomic interhalogen
compounds such as BrF, ICl, and ClF bear resemblance to the pure halogens in some respects.
The properties and behaviour of a diatomic interhalogen compound tend to be intermediate
between those of its parent halogens. Some properties, however, are found in neither parent
halogen. For example, Cl2 and I2 are soluble in CCl4, but ICl is not since it is a polar molecule
due to the relatively large electronegativity difference between I and Cl.
Organohalogen compounds
Many synthetic organic compounds such as plastic polymers, and a few natural ones, contain
halogen atoms; these are known as halogenated compounds or organic halides. Chlorine is by far
the most abundant of the halogens, and the only one needed in relatively large amounts (as
chloride ions) by humans. For example, chloride ions play a key role in brain function by
mediating the action of the inhibitory transmitter GABA and are also used by the body to
produce stomach acid. Iodine is needed in trace amounts for the production of thyroid hormones
such as thyroxine. On the other hand, neither fluorine nor bromine are believed to be essential for
humans.

Polyhalogenated compounds
Polyhalogenated compounds are industrially created compounds substituted with multiple
halogens. Many of them are very toxic and bioaccumulate in humans, and have a very wide
application range. They include the much maligned PCB's, PBDE's, and PFC's as well as
numerous other compounds.

Reactivity with water

Fluorine reacts vigorously with water to produce oxygen (O2) and hydrogen fluoride (HF):[3]

2 F2(g) + 2 H2O(l) → O2(g) + 4 HF(aq)

Chlorine has minimal solubility of 0.7g Cl2 per kg of water at ambient temperature (21oC).[4]
Dissolved chlorine reacts to form hydrochloric acid (HCl) and hypochlorous acid, a solution that
can be used as a disinfectant or bleach:

Cl2(g) + H2O(l) → HCl(aq) + HClO(aq)

Bromine has a solubility of 3.41 g per 100 g of water, [5] but it slowly reacts to form hydrogen
bromide (HBr) and hypobromous acid (HBrO):

Br2(g) + H2O(l) → HBr(aq) + HBrO(aq)

Iodine, however, is minimally soluble in water (0.03 g/100 g water @ 20 °C) and does not react
with it.[6] However, iodine will form an aqueous solution in the presence of iodide ion, such as by
addition of potassium iodide (KI), because the triiodide ion is formed.
Fluorine
oxygen ← fluorine → neon

-
↑
F
↓
Cl

9F
Periodic table

Appearance
Tan or Yellow gas

General properties
Name, symbol, number fluorine, F, 9
Pronunciation /ˈflɔːrɪn/
Element category halogen
Group, period, block 17, 2, p
Standard atomic weight 18.9984032(5) g·mol−1
Electron configuration 1s2 2s2 2p5
Electrons per shell 2, 7 (Image)
Physical properties
Phase gas
(0 °C, 101.325 kPa)
Density
1.7 g/L
Liquid density at b.p. 1.108 g·cm−3
Melting point 53.53 K−219.62 ° ,C−363.32 ° ,F
Boiling point 85.03 K−188.12 ° ,C−306.62 ° ,F
Critical point 144.13 K, 5.172 MPa
Heat of fusion (F2) 0.510 kJ·mol−1
Heat of vaporization (F2) 6.62 kJ·mol−1
(25 °C) (F2)
Specific heat capacity
31.304 J·mol−1·K−1
Vapor pressure
P (Pa) 1 10 100 1k 10 k 100 k
at T (K) 38 44 50 58 69 85
Atomic properties
−1
Oxidation states
(Weaklyacidic oxide)
Electronegativity 3.98 (Pauling scale)
Ionization energies 1st: 1681.0 kJ·mol−1
(more) 2nd: 3374.2 kJ·mol−1
3rd: 6050.4 kJ·mol−1
Covalent radius 57±3 pm
(see covalent radius of fluorine)
Van der Waals radius 147 pm
Miscellanea
Crystal structure cubic
Magnetic ordering nonmagnetic
Thermal conductivity (300 K) 27.7 m W·m−1·K−1
CAS registry number 7782-41-4
Most stable isotopes
Main article: Isotopes of fluorine
iso NA half-life DM DE (MeV) DP
18 β+ (97%) 0.64 18
O
F syn 109.77 min 18
ε (3%) 1.656 O
19 19
F 100% F is stable with 10 neutrons
v•d•e

Fluorine is the chemical element with atomic number 9, represented by the symbol F. Fluorine
forms a single bond with itself in elemental form, resulting in the diatomic F2 molecule. F2
(fluorine) is a supremely reactive, poisonous, pale, yellowish brown gas. Elemental fluorine is
the most chemically reactive and electronegative of all the elements. For example, it will readily
"burn" hydrocarbons at room temperature, in contrast to the combustion of hydrocarbons by
oxygen, which requires an input of energy with a spark. Therefore, molecular fluorine is highly
dangerous, more so than other halogens such as the poisonous chlorine gas.

Fluorine's highest electronegativity and small atomic radius give unique properties to many of its
compounds. For example, the enrichment of 235U, the principal nuclear fuel, relies on the
volatility of UF6. Also, the carbon–fluorine bond is one of the strongest bonds in organic
chemistry. This contributes to the stability and persistence of fluoroalkane based organofluorine
compounds, such as PTFE/(Teflon) and PFOS. The carbon–fluorine bond's inductive effects
result in the strength of many fluorinated acids, such as triflic acid and trifluoroacetic acid. Drugs
are often fluorinated at biologically reactive positions, to prevent their metabolism and prolong
their half-lives.

Characteristics
Physical characteristics

F2 is a corrosive pale yellow or brown[1] gas that is a powerful oxidizing agent. It is the most
reactive and most electronegative of all the elements on the classic Pauling scale (4.0), and
readily forms compounds with most other elements. It is found in the -1 oxidation state, except
when bonded to another fluorine in F2 which gives it an oxidation number of 0. Fluorine
combines with the noble gases argon, krypton, xenon, and radon. Even in dark, cool conditions,
fluorine reacts explosively with hydrogen. The reaction with hydrogen can occur at extremely
low temperatures, using liquid hydrogen and solid fluorine. It is so reactive that metals, water, as
well as most other substances, burn with a bright flame in a jet of fluorine gas. In moist air, it
reacts with water to form the also dangerous hydrofluoric acid.

Chemical characteristics

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

Occurrence

Fluorite (CaF2) crystals

Fluorine is obtained from two sources, mainly. The production of phosphate fertilizers from
apatite generates a byproduct of hydrogen fluoride that is collected. The other main source is the
mineral fluorite, CaF2, which is widespread.
Organofluorine compounds are naturally rare compounds. Though F2 is too reactive to have any
natural biological role, fluorine is incorporated into compounds with biological activity.
Naturally occurring organofluorine compounds are rare, the most notable example is
fluoroacetate, which functions as a plant defence against herbivores in at least 40 plants in
Australia, Brazil, and Africa.[2] The enzyme adenosyl-fluoride synthase catalyzes the formation
of 5'-deoxy-5'-fluoroadenosine. Fluorine is not an essential nutrient, but its importance in
preventing tooth decay is well-recognized.[3] The effect is predominantly topical, although prior
to 1981 it was considered primarily systemic (occurring through ingestion).[4]

From the perspective of cosmology, fluorine is relatively rare because the solar temperatures
needed to make it also enable it to quickly fuse with hydrogen to form oxygen and helium , or
with helium to become neon. Most fluorine is created either during a supernova when a neutrino
hits an atom of neon, or when a blue Wolf-Rayet star massing over 40 solar masses has a stellar
wind blowing the fluorine out of the star before hydrogen or helium can destroy it.[5]

Isotopes

Although fluorine has multiple isotopes, only one of these isotopes (19F) is stable, and the others
have short half-lives and are not found in nature. Fluorine is thus a mononuclidic element.

The nuclide 18F is the radionuclide of fluorine with the longest half life (about 110 minutes), and
commercially is an important source of positrons, finding its major use in positron emission
tomography scanning.

Chemistry of fluorine compounds

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

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

Hydrogen fluoride is a weak acid when dissolved in water, but is still very corrosive and attacks
glass. Consequently, fluorides of alkali metals produce basic solutions. For example, a 1 M
solution of NaF in water has a pH of 8.59 compared to a 1 M solution of NaOH, a strong base,
which has a pH of 14.00.[6]

The fluoride ion is basic, therefore hydrofluoric acid is a weak acid in water solution. However,
water is not an inert solvent in this case: When less basic solvents such as anhydrous acetic acid
are used, hydrofluoric acid is the strongest of the hydrohalogenic acids. Also, owing to the
basicity of the fluoride ion, soluble fluorides give basic water solutions. The fluoride ion is a
Lewis base, and has a high affinity to certain elements such as calcium and silicon. For example,
deprotection of silicon protecting groups is achieved with a fluoride. The fluoride ion is
poisonous.
Noble gas compounds

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

Organofluorine compounds

The carbon-fluoride bond is covalent and very stable. The use of a fluorocarbon polymer,
poly(tetrafluoroethene) or Teflon, is an example: It is thermostable and waterproof enough to be
used in frying pans. Organofluorines may be safely used in applications such as drugs, without
the risk of release of toxic fluoride. In synthetic drugs, toxication can be prevented. For example,
an aromatic ring is useful but presents a safety problem: enzymes in the body metabolize some of
them into poisonous epoxides. When the para position is substituted with fluorine, the aromatic
ring is protected and epoxide is no longer produced.

The substitution of fluorine for hydrogen in organic compounds offers a very large number of
compounds. These compounds often feature single C-F units, but -CF3 and -OCF3 group provide
further variation, and more recently the -SF5 group.[7]

Chlorine
sulfur ← chlorine → argon

F
↑
Cl
↓
Br

17Cl
Periodic table
Appearance
pale yellow-green gas

General properties
Name, symbol, number chlorine, Cl, 17
Pronunciation /ˈklɔəriːn/ KLOR-een
Element category Halogen
Group, period, block 17, 3, p
Standard atomic weight 35.453(2) g·mol−1
Electron configuration [Ne] 3s2 3p5
Electrons per shell 2, 8, 7 (Image)
Physical properties
Phase gas
(0 °C, 101.325 kPa)
Density
3.2 g/L
Liquid density at b.p. 1.5625[1] g·cm−3
Melting point 171.6 K-101.5 ° ,C-150.7 ° ,F
Boiling point 239.11 K-34.04 ° ,C-29.27 ° ,F
Critical point 416.9 K, 7.991 MPa
Heat of fusion (Cl2) 6.406 kJ·mol−1
Heat of vaporization (Cl2) 20.41 kJ·mol−1
(25 °C) (Cl2)
Specific heat capacity
33.949 J·mol−1·K−1
Vapor pressure
P (Pa) 1 10 100 1k 10 k 100 k
at T (K) 128 139 153 170 197 239
Atomic properties
7, 6, 5, 4, 3, 2, 1, -1
Oxidation states
(strongly acidic oxide)
Electronegativity 3.16 (Pauling scale)
Ionization energies 1st: 1251.2 kJ·mol−1
(more) 2nd: 2298 kJ·mol−1
3rd: 3822 kJ·mol−1
Covalent radius 102±4 pm
Van der Waals radius 175 pm
Miscellanea
Crystal structure orthorhombic
Magnetic ordering diamagnetic[2]
Electrical resistivity (20 °C) > 10 Ω·m
Thermal conductivity (300 K) 8.9x10-3 W·m−1·K−1
Speed of sound (gas, 0 °C) 206 m/s
CAS registry number 7782-50-5
Most stable isotopes
Main article: Isotopes of chlorine
iso NA half-life DM DE (MeV) DP
35 35
Cl 75.77% Cl is stable with 18 neutrons
36 β− 0.709 36
Ar
Cl trace 3.01×105 y 36
ε - S
37 37
Cl 24.23% Cl is stable with 20 neutrons
v•d•e

Chlorine is the chemical element with atomic number 17 and symbol Cl. It is a halogen, found
in the periodic table in group 17 (formerly VII, VIIa, or VIIb). As the chloride ion, which is part
of common salt and other compounds, it is abundant in nature and necessary to most forms of
life, including humans. In its elemental form (Cl2 or "dichlorine") under standard conditions,
chlorine is a powerful oxidant and is used in bleaching and disinfectants, as well as an essential
reagent in the chemical industry. As a common disinfectant, chlorine compounds are used in
swimming pools to keep them clean and sanitary. In the upper atmosphere, chlorine-containing
molecules such as chlorofluorocarbons have been implicated in the destruction of the ozone
layer.

Characteristics
Physical characteristics

At standard temperature and pressure, two chlorine atoms form the diatomic molecule Cl2. This
is a pale yellow-green gas that has its distinctive strong smell, the smell of bleach. The bonding
between the two atoms is relatively weak (only 242.580 ±0.004 kJ/mol), which makes the Cl2
molecule highly reactive.

Chemical characteristics

Along with fluorine, bromine, iodine, and astatine, chlorine is a member of the halogen series
that forms the group 17 of the periodic table. Chlorine forms compounds with almost all of the
elements to give compounds that are usually called chlorides. Chlorine gas reacts with most
organic compounds, and will even sluggishly support the combustion of hydrocarbons.[3]

Hydrolysis

At 10 °C and atmospheric pressure, one liter of water dissolves 3.10 L of gaseous chlorine,[4]
Solutions of chlorine in water contain chlorine (Cl2), hydrochloric acid, and hypochlorous acid:

Cl2 + H2O HCl + HClO

This conversion to the right is called disproportionation, because the ingredient chlorine both
increases and decreases in formal oxidation state. The solubility of chlorine in water is increased
if the water contains dissolved alkali hydroxide, and in this way, chlorine bleach is produced.

Cl2 + 2 OH- → ClO- + Cl- + H2O

Chlorine gas only exists in a neutral or acidic solution.

Compounds

Chlorine exists in all odd numbered oxidation states from −1 to +7, as well as the elemental state
of zero (see Table). Progressing through the states, hydrochloric acid can be oxidized using
manganese dioxide, or hydrogen chloride gas oxidized catalytically by air to form elemental
chlorine gas.

Oxidation
Name Formula Illustrative compounds
state
−1 chlorides Cl− ionic chlorides, organic chlorides, hydrochloric acid
0 chlorine Cl2 elemental chlorine
+1 hypochlorites ClO− sodium hypochlorite, calcium hypochlorite
+3 chlorites ClO−2 sodium chlorite
chlorine
+4 ClO2
dioxide
+5 chlorates ClO−3 sodium chlorate, potassium chlorate, chloric acid
perchloric acid, perchlorate salts such as magnesium
+7 perchlorates ClO−4
perchlorate, dichlorine heptoxide

Interhalogen compounds

Chlorine oxidizes bromide and iodide salts to bromine and iodine, respectively. But it cannot
oxidize fluoride to fluorine. It makes are variety of "interhalogen compounds" such as the
chlorine fluorides, chlorine monofluoride (ClF), chlorine trifluoride (ClF3), chlorine
pentafluoride (ClF5). Chlorides of bromine and iodine are also known.

Organo chlorine compounds

Chlorine is used extensively in organic in substitution and addition reactions. Chlorine often
imparts many desired properties to an organic compound, in part due to its electronegativity.
Organochlorine compounds are also serious pollutants, either as side products of industrial
processes or as persistent pesticidess.

Many important industrial products are produced via organochlorine intermediates. Examples
include polycarbonates, polyurethanes, silicones, polytetrafluoroethylene, carboxymethyl
cellulose, and propylene oxide. Like the other halogens, chlorine participates in free-radical
substitution reactions with hydrogen-containing organic compounds. When applied to organic
substrates, reaction is often—but not invariably—non-regioselective, and, hence, may result in a
mixture of isomeric products. It is often difficult to control the degree of substitution as well, so
multiple substitutions are common. If the different reaction products are easily separated, e.g., by
distillation, substitutive free-radical chlorination (in some cases accompanied by concurrent
thermal dehydrochlorination) may be a useful synthetic route. Industrial examples of this are the
production of methyl chloride, methylene chloride, chloroform, and carbon tetrachloride from
methane, allyl chloride from propylene, and trichloroethylene, and tetrachloroethylene from 1,2-
dichloroethane.

Like the other halides, chlorine undergoes electrophilic additions reactions, the most notable one
being the chlorination of alkenes and aromatic compounds with a Lewis acid catalyst. Organic
chlorine compounds tend to be less reactive in nucleophilic substitution reactions than the
corresponding bromine or iodine derivatives, but they tend to be cheaper. They may be activated
for reaction by substituting with a tosylate group, or by the use of a catalytic amount of sodium
iodide.

Chlorides

Chlorine combines with almost all elements to give chlorides. Compounds with oxygen,
nitrogen, xenon, and krypton are known, but do not form by direct reaction of the elements.[5]
Chloride is one of the most common anions in nature. Hydrogen chloride and its aqueous
solution, hydrochloric acid, are produced on megaton scale annually both as valued intermediates
but sometimes as undesirable pollutants.

Chlorine oxides

Chlorine forms a variety of oxides: chlorine dioxide (ClO2), dichlorine monoxide (Cl2O),
dichlorine heptoxide (Cl2O7). The anionic derivatives of these same oxides are also well known
including chlorate (ClO−3), chlorite (ClO−2), hypochlorite (ClO−), and perchlorate (ClO−4), and
chloramine (NH2Cl).[6] The acid derivatives of these anions are hypochlorous acid (HOCl),
chloric acid (HClO3) and perchloric acid (HClO4).

In hot concentrated alkali solution hypochlorite disproportionates:

2 ClO− → Cl− + ClO−2

ClO− + ClO−2 → Cl− + ClO−3

Sodium chlorate and potassium chlorate can be crystallized from solutions formed by the above
reactions. If their crystals are heated, they undergo a further, final disproportionation:

4 ClO−3 → Cl− + 3 ClO−4

This same progression from chloride to perchlorate can be accomplished by electrolysis. The
anode reaction progression is:[7]

Electrode
Reaction
potential
Cl− + 2 OH− → ClO− + H2O + 2 e− +0.89 volts
ClO− + 2 OH− → ClO−2 + H2O + 2 e− +0.67 volts
 ClO−2 + 2 OH− → ClO−3 + H2O + 2 e− +0.33 volts
ClO−3 + 2 OH− → ClO−4 + H2O + 2 e− +0.35 volts

Each step is accompanied at the cathode by

2 H2O + 2 e− → 2 OH− + H2 (−0.83 volts)

Occurrence

In nature, chlorine is found primarily as the chloride ion, a component of the salt that is
deposited in the earth or dissolved in the oceans — about 1.9% of the mass of seawater is
chloride ions. Even higher concentrations of chloride are found in the Dead Sea and in
underground brine deposits. Most chloride salts are soluble in water, thus, chloride-containing
minerals are usually only found in abundance in dry climates or deep underground. Common
chloride minerals include halite (sodium chloride), sylvite (potassium chloride), and carnallite
(potassium magnesium chloride hexahydrate). Over 2000 naturally occurring organic chlorine
compounds are known.[8]

In the interstellar medium, chlorine is produced in supernovae via the r-process.[9]

Isotopes

Chlorine has a wide range of isotopes, the two principal stable isotopes being 35Cl (75.77%) and
37
Cl (24.23%); they give chlorine atoms an apparent atomic weight of 35.4527 g/mol.

Trace amounts of radioactive 36Cl exist in the environment, in a ratio of about 7x10−13 to 1 with
stable isotopes. 36Cl is produced in the atmosphere by spallation of 36Ar by interactions with
cosmic ray protons. In the subsurface environment, 36Cl is generated primarily as a result of
neutron capture by 35Cl or muon capture by 40Ca. 36Cl decays to 36S and to 36Ar, with a combined
half-life of 308,000 years. The half-life of this hydrophilic nonreactive isotope makes it suitable
for geologic dating in the range of 60,000 to 1 million years. Additionally, large amounts of 36Cl
were produced by irradiation of seawater during atmospheric detonations of nuclear weapons
between 1952 and 1958. The residence time of 36Cl in the atmosphere is about 1 week. Thus, as
an event marker of 1950s water in soil and ground water, 36Cl is also useful for dating waters less
than 50 years before the present. 36Cl has seen use in other areas of the geological sciences,
including dating ice and sediments.

Laboratory methods

Small amounts of chlorine gas can be made in the laboratory by combining hydrochloric acid
and manganese dioxide. Alternatively a strong acid such as sulfuric acid or hydrochloric acid
reacts with sodium hypochlorite or sodium chlorate solution to release chlorine gas. In the home,
accidents occur when hypochlorite bleach solutions are combined with certain acidic drain-
cleaners.

Applications
Production of industrial and consumer products

Chlorine's principal applications are in the production of a wide range of industrial and consumer
products.[25][26] For example, it is used in making plastics, solvents for dry cleaning and metal
degreasing, textiles, agrochemicals and pharmaceuticals, insecticides, dyestuffs, household
cleaning products, etc.

Purification and disinfection

Chlorine is an important chemical for water purification (such as water treatment plants), in
disinfectants, and in bleach. Chlorine in water is more than three times more effective as a
disinfectant against Escherichia coli than an equivalent concentration of bromine, and is more
than six times more effective than an equivalent concentration of iodine.[27]

Chlorine is usually used (in the form of hypochlorous acid) to kill bacteria and other microbes in
drinking water supplies and public swimming pools. In most private swimming pools, chlorine
itself is not used, but rather sodium hypochlorite, formed from chlorine and sodium hydroxide,
or solid tablets of chlorinated isocyanurates. Even small water supplies are now routinely
chlorinated.[3] (See also chlorination)

It is often impractical to store and use poisonous chlorine gas for water treatment, so alternative
methods of adding chlorine are used. These include hypochlorite solutions, which gradually
release chlorine into the water, and compounds like sodium dichloro-s-triazinetrione (dihydrate
or anhydrous), sometimes referred to as "dichlor", and trichloro-s-triazinetrione, sometimes
referred to as "trichlor". These compounds are stable while solid and may be used in powdered,
granular, or tablet form. When added in small amounts to pool water or industrial water systems,
the chlorine atoms hydrolyze from the rest of the molecule forming hypochlorous acid (HOCl),
which acts as a general biocide, killing germs, micro-organisms, algae, and so on.

Use as a weapon

• World War I

• Iraq War

Chlorine cracking
Chlorine "attack" on an acetal resin plumbing joint.

The element is widely used for purifying water owing to its powerful oxidizing properties,
especially potable water supplies and water used in swimming pools. Several catastrophic
collapses of swimming pool ceilings have occurred owing to stress corrosion cracking of
stainless steel rods used to suspend them.[31] Some polymers are also sensitive to attack,
including acetal resin and polybutene. Both materials were used in hot and cold water domestic
supplies, and stress corrosion cracking caused widespread failures in the USA in the 1980s and
1990s. One example shows an acetal joint in a water supply system, which, when it fractured,
caused substantial physical damage to computers in the labs below the supply. The cracks started
at injection molding defects in the joint and grew slowly until finally triggered. The fracture
surface shows iron and calcium salts that were deposited in the leaking joint from the water
supply before failure.

Other uses

Chlorine is used in the manufacture of numerous organic chlorine compounds, the most
significant of which in terms of production volume are 1,2-dichloroethane and vinyl chloride,
intermediates in the production of PVC. Other particularly important organochlorines are methyl
chloride, methylene chloride, chloroform, vinylidene chloride, trichloroethylene,
perchloroethylene, allyl chloride, epichlorohydrin, chlorobenzene, dichlorobenzenes, and
trichlorobenzenes.

Chlorine is also used in the production of chlorates and in bromine extraction.

Health effects

NFPA 704

0
3
0
OX
Chlorine is a toxic gas that irritates the respiratory system. Because it is heavier than air, it tends
to accumulate at the bottom of poorly ventilated spaces. Chlorine gas is a strong oxidizer, which
may react with flammable materials.[34]

Chlorine is detectable in concentrations of as low as 0.2 ppm. Coughing and vomiting may occur
at 30 ppm and lung damage at 60 ppm. About 1000 ppm can be fatal after a few deep breaths of
the gas.[4] Breathing lower concentrations can aggravate the respiratory system, and exposure to
the gas can irritate the eyes.[35] The toxicity of chlorine comes from its oxidizing power. When
chlorine is inhaled at concentrations above 30 ppm, it begins to react with water and cells, which
change it into hydrochloric acid (HCl) and hypochlorous acid (HClO).

When used at specified levels for water disinfection, the reaction of chlorine with water is not a
major concern for human health. However, other materials present in the water may generate
disinfection by-products that can damage human health.[36][37]

Bromine
selenium ← Bromine → krypton

Cl
↑
Br
↓
I

35Br
Periodic table

Appearance
gas/liquid: red-brown
solid: metallic luster
General properties
Name, symbol, number Bromine, Br, 35
/ˈbroʊmiːn/ BROH-meen
Pronunciation
or /ˈbroʊmɪn/ BROH-min
Element category halogen
Group, period, block 17, 4, p
Standard atomic weight 79.904(1) g·mol−1
Electron configuration [Ar] 4s2 3d10 4p5
Electrons per shell 2, 8, 18, 7 (Image)
Physical properties
Phase liquid
Density (near r.t.) (Br2, liquid) 3.1028 g·cm−3
Melting point 265.8 K-7.2 ° ,C19 ° ,F
Boiling point 332.0 K58.8 ° ,C137.8 ° ,F
Critical point 588 K, 10.34 MPa
Heat of fusion (Br2) 10.571 kJ·mol−1
Heat of vaporization (Br2) 29.96 kJ·mol−1
(25 °C) (Br2)
Specific heat capacity
75.69 J·mol−1·K−1
Vapor pressure
P (Pa) 1 10 100 1k 10 k 100 k
at T (K) 185 201 220 244 276 332
Atomic properties
7, 5, 4, 3, 1, -1
Oxidation states
(strongly acidic oxide)
Electronegativity 2.96 (Pauling scale)
Ionization energies 1st: 1139.9 kJ·mol−1
2nd: 2103 kJ·mol−1
3rd: 3470 kJ·mol−1
Atomic radius 120 pm
Covalent radius 120±3 pm
Van der Waals radius 185 pm
Miscellanea
Crystal structure orthorhombic
Magnetic ordering diamagnetic[1]
Electrical resistivity (20 °C) 7.8×1010Ω·m
Thermal conductivity (300 K) 0.122 W·m−1·K−1
Speed of sound (20°C) 206 m/s
CAS registry number 7726-95-6
Most stable isotopes
Main article: Isotopes of Bromine
iso NA half-life DM DE (MeV) DP
79 79
Br 50.69% Br is stable with 44 neutrons
81 81
Br 49.31% Br is stable with 46 neutrons
v•d•e

Bromine is a chemical element with the symbol Br and atomic number 35. It is in the halogen
element group. Bromine vapors are corrosive and toxic. Approximately 556,000 metric tons
were produced in 2007.[3] The main applications for bromine are in fire retardants and
manufacture of chemicals.

Characteristics
Physical

Elemental bromine exists as a diatomic molecule, Br2. It is a dense, mobile, slightly transparent
reddish-brown liquid, that evaporates easily at standard temperature and pressures to give a red
vapor (its color resembles nitrogen dioxide) that has a strongly disagreeable odor resembling that
of chlorine. It is the only nonmetallic element that is a liquid at room temperature, and one of
only two elements on the periodic table that are liquids at room temperature (mercury is the
other, but caesium, rubidium, francium and gallium are quite close).

At a pressure of 55 GPa bromine converts to a metal. At 75 GPa it converts to a face centered

orthorhombic structure. At 100 GPa it converts to a body centered orthorhombic monoatomic
form.[4]

Chemical characteristics

Being less reactive than chlorine but more reactive than iodine, bromine reacts vigorously with
metals, especially in the presence of water to give bromide salts. It is also reactive toward most
organic compounds, especially upon illumination, conditions that favor the dissociation of the
diatomic molecule into bromine radicals:

Br2 2 Br·

It bonds easily with many elements and has a strong bleaching action.

Bromine is slightly soluble in water, but it is highly soluble in organic solvents such as carbon
disulfide, aliphatic alcohols , and acetic acid.

Occurrence
World bromine production trend

View of salt evaporation pans on the Dead Sea, where Jordan (right) and Israel (left) produce salt
and bromine 31°9′0″N 35°27′0″E / 31.15°N 35.45°E

The diatomic element Br2 does not occur naturally. Instead, bromine exists exclusively as
bromide salts in diffuse amounts in crustal rock. Due to leaching, bromide salts have
accumulated in sea water (65 ppm),[5] but at a lower concentration than chloride. Bromine may
be economically recovered from bromide-rich brine wells and from the Dead Sea waters (up to
50000 ppm).[6][7] A large number of organobromine compounds are found in small amounts in
nature.

China's bromine reserves are located in the Shandong Province and Israel's bromine reserves are
contained in the waters of the Dead Sea. The largest bromine reserve in the United States is
located in Columbia and Union County, Arkansas, U.S.[8]

Isotopes

Bromine has two stable isotopes, 79Br (50.69 %) and 81Br (49.31%). At least another 23
radioisotopes are known to exist.[11] Many of the bromine isotopes are fission products. Several
of the heavier bromine isotopes from fission are delayed neutron emitters. All of the radioactive
bromine isotopes are relatively short lived. The longest half life is the neutron deficient 77Br at
2.376 days. The longest half life on the neutron rich side is 82Br at 1.471 days. A number of the
bromine isotopes exhibit metastable isomers. Stable 79Br exhibits a radioactive isomer, with a
half life of 4.86 seconds. It decays by isomeric transition to the stable ground state.[12]
Compounds and chemistry
Organic chemistry

N-Bromosuccinimide

Organic compounds are brominated by either addition or substitution reactions. Bromine

undergoes electrophilic addition to the double-bonds of alkenes, via a cyclic bromonium
intermediate. In non-aqueous solvents such as carbon disulfide, this affords the di-bromo
product. For example, reaction with ethylene will produce 1,2-dibromoethane. Bromine also
undergoes electrophilic addition to phenols and anilines. When used as bromine water, a small
amount of the corresponding bromohydrin is formed as well as the dibromo compound. So
reliable is the reactivity of bromine that bromine water is employed as a reagent to test for the
presence of alkenes, phenols, and anilines. Like the other halogens, bromine participates in free
radical reactions. For example, hydrocarbons are brominated upon treatment with bromine in the
presence of light.

Bromine, sometimes with a catalytic amount of phosphorus, easily brominates carboxylic acids
at the α-position. This method, the Hell-Volhard-Zelinsky reaction, is the basis of the
commercial route to bromoacetic acid. N-Bromosuccinimide is commonly used as a substitute
for elemental bromine, being easier to handle, and reacting more mildly and thus more
selectively. Organic bromides are often preferable relative to the less reactive chlorides and more
expensive iodide-containing reagents. Thus, Grignard and organolithium compound are most
often generated from the corresponding bromides.

Certain bromine-related compounds have been evaluated to have an ozone depletion potential or
bioaccumulate in living organisms. As a result, many industrial bromine compounds are no
longer manufactured, are being restricted, or scheduled for phasing out. The Montreal Protocol
mentions several organobromine compounds for this phase out.

Inorganic chemistry

Inorganic bromine compounds adopt a variety of oxidation states from -1 to +7.[13]

Oxidation states
of bromine
−1 HBr
0 Br2
+1 BrCl
+3 BrF3
+5 BrF5
+5 BrO−3
+7 BrO−4

Bromine is an oxidizer, and it will oxidize iodide ions to iodine, being itself reduced to bromide:

Br2 + 2 I− → 2 Br− + I2

Bromine will also oxidize metals and metalloids to the corresponding bromides. Anhydrous
bromine is less reactive toward many metals than hydrated bromine, however. Dry bromine
reacts vigorously with aluminium, titanium, mercury as well as alkaline earths and alkali metals.

Dissolving bromine in alkaline solution gives a mixture of bromide and hypobromite:

Br2 + 2 OH− → Br− + OBr− + H2O

This hypobromite is responsible for the bleaching abilities of bromide solutions. Warming of
these solutions causes the disproportion reaction of the hypobromite to give bromate, a strong
oxidising agent very similar to chlorate.

3 BrO− → BrO−3 + 2 Br−

In contrast to the route to perchlorates, perbromates are not accessible through electrolysis but
only by reacting bromate solutions with fluorine or ozone.

BrO3− + H2O + F2 → BrO−4 + 2 HF

BrO3− + O3 → BrO−4 + O2

Laboratory methods

In the laboratory, because of its commercial availability and long shelf-life, bromine is not
typically prepared. Small amounts of bromine can however be generated through the reaction of
solid sodium bromide with concentrated sulfuric acid (H2SO4). The first stage is formation of
hydrogen bromide (HBr), which is a gas, but under the reaction conditions some of the HBr is
oxidized further by the sulfuric acid to form bromine (Br2) and sulfur dioxide (SO2).

NaBr (s) + H2SO4 (aq) → HBr (aq) + NaHSO4 (aq)

2 HBr (aq) + H2SO4 (aq) → Br2 (g) + SO2 (g) + 2 H2O (l)

Similar alternatives, such as the use of dilute hydrochloric acid with sodium hypobromite, are
also available. The most important thing is that the anion of the acid (in the above examples,
sulfate and chloride, respectively) be more electronegative than bromine, allowing the
substitution reaction to occur.
Reaction involving a strong oxidizing agent, such as potassium permanganate, on bromide ions
in the presence of an acid also gives bromine. An acidic solution of bromate ions and bromide
ions will also comproportionate slowly to give bromine.

Bromine is only slightly soluble in water. But the solubility can be increased by the presence of
bromide ions. However, concentrated solutions of bromine are rarely prepared in the lab because
of hazards. Sodium thiosulphate is an excellent reagent for getting rid of bromine completely
including the stains and odor.

Applications
A wide variety of organobromine compounds are used in industry. Some are prepared from
bromine and others are prepared from hydrogen bromide, which is obtained by burning hydrogen
in bromine.[3]

Illustrative of the addition reaction[24] is the preparation of 1,2-dibromoethane, the

organobromine compound produced in the largest amounts:

C2H4 + Br2 → CH2BrCH2Br

Flame retardant

Tetrabromobisphenol A

Brominated flame retardants represent a commodity of growing importance. If the material burns
the flame retardants produce hydrobromic acid which interferes in the radical chain reaction of
the oxidation reaction of the fire. The highly reactive hydrogen oxygen and hydroxy radicals
react with hydrobromic acid and form less reactive bromine radicals.[25][26] The bromine-
containing compounds can be placed in the polymers either during polymerization if a small
amount of brominated monomer is added or the bromine containing compound is added after
polymerization. Tetrabromobisphenol A can be added to produce polyesters or epoxy resins.
Epoxy used in printed circuit boards (PCB) are normally made from flame retardant resins,
indicated by the FR in the abbreviation of the products (FR-4 and FR-2. Vinyl bromide can be
used in the production of polyethylene, polyvinylchloride or polypropylene. Decabromodiphenyl
ether can be added to the final polymers.[27]

Gasoline additive
Ethylene bromide was an additive in gasolines containing lead anti-engine knocking agents. It
scavenges lead by forming volatile lead bromide, which is exhausted from the engine. This
application accounted for 77% of the bromine uses in 1966 in the US. This application has
declined since the 1970s due to environmental regulations.[28] Ethylene bromide is also used as a
fumigant, but again this application is declining.[23]

Pesticide

Methyl bromide (bromomethane)

Methyl bromide was widely used as pesticide to fumigate soil. The Montreal Protocol on
Substances that Deplete the Ozone scheduled the phase out for the ozone depleting chemical
until 2005. In 1991, an estimated 35,000 metric tonnes of the chemical were used to control
nematodes, fungi, weeds and other soil-borne diseases.[29][30]

Safety
Elemental bromine is toxic and causes burns. As an oxidizing agent, it is incompatible with most
organic and inorganic compounds. Care needs to be taken when transporting bromine; it is
commonly carried in steel tanks lined with lead, supported by strong metal frames.

When certain ionic compounds containing bromine are mixed with potassium permanganate
(KMnO4) and an acidic substance, they will form a pale brown cloud of bromine gas. This gas
smells like bleach and is very irritating to the mucous membranes. Upon exposure, one should
move to fresh air immediately. If symptoms of bromine poisoning arise, medical attention is
needed.

Iodine
tellurium ← iodine → xenon

Br
↑
I
↓
At
53I
Periodic table

Appearance
Lustrous metallic gray, violet as a gas

General properties
Name, symbol, number iodine, I, 53
/ˈaɪ.ɵdaɪn/ EYE-o-dyne,
Pronunciation /ˈaɪ.ɵdɪn/ EYE-o-dən,
or /ˈaɪ.ɵdiːn/ EYE-o-deen
Element category halogen
Group, period, block 17, 5, p
Standard atomic weight 126.90447 g·mol−1
Electron configuration [Kr] 4d10 5s2 5p5
Electrons per shell 2, 8, 18, 18, 7 (Image)
Physical properties
Phase solid
Density (near r.t.) 4.933 g·cm−3
Melting point 386.85 K113.7 ° ,C236.66 ° ,F
Boiling point 457.4 K184.3 ° ,C363.7 ° ,F
Triple point 386.65 K (113°C), 12.1 kPa
Critical point 819 K, 11.7 MPa
Heat of fusion (I2) 15.52 kJ·mol−1
Heat of vaporization (I2) 41.57 kJ·mol−1
Specific heat capacity (25 °C) (I2) 54.44 J·mol−1·K−1
Vapor pressure (rhombic)
P (Pa) 1 10 100 1k 10 k 100 k
at T (K) 260 282 309 342 381 457
Atomic properties
7, 5, 3, 1, -1
Oxidation states
(strongly acidic oxide)
Electronegativity 2.66 (Pauling scale)
Ionization energies 1st: 1008.4 kJ·mol−1
2nd: 1845.9 kJ·mol−1
3rd: 3180 kJ·mol−1
Atomic radius 140 pm
Covalent radius 139±3 pm
Van der Waals radius 198 pm
Miscellanea
Crystal structure orthorhombic
Magnetic ordering diamagnetic[1]
Electrical resistivity (0 °C) 1.3×107Ω·m
Thermal conductivity (300 K) 0.449 W·m−1·K−1
Bulk modulus 7.7 GPa
CAS registry number 7553-56-2
Most stable isotopes
Main article: Isotopes of iodine
iso NA half-life DM DE (MeV) DP
123 123
I syn 13 h ε, γ 0.16 Te
127 127
I 100% I is stable with 74 neutrons
129
I trace 15.7×106 y β− 0.194 129
Xe
131 − 131
I syn 8.02070 d β , γ 0.971 Xe
v•d•e

Iodine is a chemical element that has the symbol I and the atomic number 53.

Iodine and its compounds are primarily used in nutrition, the production of acetic acid and
polymers. Iodine's relatively high atomic number, low toxicity, and ease of attachment to organic
compounds have made it a part of many X-ray contrast materials in modern medicine.

Like the other halogens, iodine occurs mainly as a diatomic molecule I2, not the atom. In nature,
iodine is a relatively rare element, ranking 47th in abundance. It is the heaviest essential element
utilized biologically. Its rarity in many soils has led to many deficiency problems in land animals
and inland human populations, iodine deficiency affecting about two billion people and being the
leading preventable cause of mental retardation.[2] As a component of thyroid hormones, iodine is
required by higher animals. Radioisotopes of iodine are concentrated in the thyroid gland. This
property of thyroid-concentration, along with its mode of beta decay, make iodine-131 one of the
most carcinogenic nuclear fission products.

Characteristics
Iodine under standard conditions is a bluish black solid. It can be seen apparently sublimating at
standard temperatures into a violet-pink gas that has an irritating odor. This halogen forms
compounds with many elements, but is less reactive than the other members of its Group VII
(halogens) and has some metallic light reflectance.
In the gas phase iodine shows its violet color.

Elemental iodine dissolves easily in most organic solvents such as hexane or chloroform due to
its lack of polarity, but is only slightly soluble in water. However, the solubility of elemental
iodine in water can be increased by the addition of potassium iodide. The molecular iodine reacts
reversibly with the negative ion, generating the triiodide anion I3− in equilibrium, which is
soluble in water. This is also the formulation of some types of medicinal (antiseptic) iodine,
although tincture of iodine classically dissolves the element in aqueous ethanol.

The colour of solutions of elemental iodine change depend on the polarity of the solvent. In non-
polar solvents like hexane, solution are violet; in moderately polar dichloromethane the solution
is dark crimson, and in strongly polar solvents such as acetone or ethanol, it appears orange or
brown. This effect is due to the formation of adducts.

Iodine melts at the relatively low temperature of 113.7 °C, although the liquid is often obscured
by a dense violet vapor of gaseous iodine.

Occurrence

Iodomethane

Iodine is rare in the solar system and Earth's crust (47th in abundance); however, iodide salts are
often very soluble in water. Iodine occurs in slightly greater concentrations in seawater than in
rocks, 0.05 vs 0.04 ppm. Minerals containing iodine include caliche, found in Chile. A type of
seaweed, kelp, tends to be high in iodine as well, with from 0.03 – 0.45 dry weight percent.
Aside from tungsten, iodine is the heaviest element to be essential in living organisms, and
iodine is the heaviest element thought to be needed by higher animals. About 19,000 tons are
produced annually from natural sources.[3]

Organoiodine compounds are produced by marine life forms, the most notable being
iodomethane (commonly called methyl iodide). The total iodomethane that is produced by the
marine environment, by microbial activity in rice paddies and by the burning of biological
material is estimated to be 214 kilotonnes/year.[4] The volatile iodomethane is broken up in the
atmosphere as part of a global iodine cycle.[4][5]
Structure and bonding

Structure of solid iodine

Crystalline iodine

Iodine normally exists as a diatomic molecule with a I-I bond length of 270 pm, one of the
longest single bonds known. The I2 molecules tend to interact via van der Waals forces, and this
interaction is responsible for the higher melting point compared to more compact halogens,
which are also diatomic. The solid crystallizes in the orthorhombic space group Cmca No 64,
Pearson symbol oS8, the same as black phosphorus. The I-I bond is relatively weak, with a bond
dissociation energy of 36 kcal/mol. In fact most bonds to iodine tend to be weaker than for the
lighter halides. One consequence of this weak bonding is the relatively tendency of I2 molecules
to dissociate into atomic iodine.

Isotopes and their applications

There are 37 known (characterized) isotopes of iodine, but only one, 127I, is stable.

The longest-lived radioisotope, 129I, has a half life of 15.7 million years. This is long enough to
make it a permanent fixture of the environment on human time scales, but far too short for it to
exist as a primordial isotope today. Instead, iodine-129 is an extinct radionuclide, and its
presence in the early solar system is inferred from the observation of an excess of its daughter
xenon-129. This nuclide is also newly-made by cosmic rays and as a byproduct of human nuclear
fission, which it is used to monitor as a very long-lived environmental contaminant.

The next longest-lived radioisotope, iodine-125, has a half-life of 59 days. It is used as a

convenient gamma-emitting tag for proteins in biological assays, and a few nuclear medicine
imaging tests where a longer half life is required. It is also commonly used in brachytherapy
implanted capsules, which kill tumors by local short-range gamma radiation (but where the
isotope is never released into the body).

Iodine-123 (half life 13 hours) is the isotope of choice for nuclear medicine imaging of the
thyroid gland, which naturally accumulates all iodine isotopes.

Iodine-131 (half life 8 days) is a beta-emitting isotope which is a common nuclear fission
product. It can be administered to humans safely only in very high doses, which destroy all
tissues that accumulate it. Like other radioiodines, it accumulates in the thyroid gland, but unlike
the others, in small amounts it is highly carcinogenic there, apparently due to the high local cell
mutation due to damage from beta decay. Because of this tendency of 131I to cause high damage
to cells which accumulate it and other cells near them (0.6 to 2 mm away, the range of the beta
rays), it is the only iodine radioisotope used as direct therapy to kill tissues such as cancers that
take up artificially iodinated molecules (example, the compound MIBG). For the same reason,
only this iodine radioisotope is used to treat Grave's disease and thyroid cancers, where the
tissues that require destruction naturally take up iodide.

Nonradioactive ordinary potassium iodide (iodine-127), in a number of convenient forms (tablets

or solution) may be used to saturate the thyroid gland's ability to take up further iodine, and thus
protect against accidental contamination from iodine-131 generated by nuclear fission accidents
such as the Chernobyl disaster, as well as from contamination from this isotope in nuclear fallout
from nuclear weapons.

Applications
Catalysis

The major application of iodine is as a co-catalyst for the production of acetic acid by the
Monsanto and Cativa processes. In this technologies, which supports 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.[3]

Animal feed

The production of ethylenediammonium diiodide (EDDI) consumes a large fraction of available

iodine. EDDI is provided to livestock as a nutritional supplement.[3]

Disinfectant and water treatment

Elemental iodine is used as a disinfectant in various forms. The iodine exists 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). Alternatively, iodine may come 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:[17]

• 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 has a minimized amount of the free iodine (I2) component.
• Povidone iodine (an iodophor)

Radiocontrast agent

Diatrizoic acid, a radiocontrast

Iodine, as a heavy element, is quite radio-opaque. Organic compounds of a certain type (typically
iodine-substituted benzene derivatives) are thus used in medicine as X-ray radiocontrast agents
for intravenous injection. This is often in conjunction with advanced X-ray techniques such as
angiography and CT scanning. Presently, all water-soluble radiocontrast agents rely on iodine.

Other uses

Inorganic iodides find specialized uses. Hafnium, zirconium, titanium, 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 consumed annually for cloud seeding.[3]

The organoiodine compound erythrosine is an important food coloring agent. Perfluoroalkyl

iodides are precursors to important surfactants, such as perfluorooctanesulfonic acid.[3]

Iodine chemistry
Iodine adopts a broad range a variety of oxidation states, commonly ranging from (formally) I7+
to I-, and including the intermediate states of I5+, I3+ and I+. Practically, only the 1- oxidation state
is of significance, being the form found in iodide salts and organoiodine compounds.
Solubility

Being a nonpolar molecule, iodine is highly soluble in nonpolar organic solvents, including
ethanol (20.5 g/100 ml at 15 °C, 21.43 g/100 ml at 25 °C), diethyl ether (20.6 g/100 ml at 17 °C,
25.20 g/100 ml at 25 °C), chloroform, acetic acid, glycerol, benzene (14.09 g/100 ml at 25 °C),
carbon tetrachloride (2.603 g/100 ml at 35 °C), and carbon disulfide (16.47 g/100 ml at 25 °C).[18]
Elemental iodine is poorly soluble in water, with one gram dissolving in 3450 ml at 20 °C and
1280 ml at 50 °C. Aqueous and ethanol solutions are brown reflecting the role of these solvents
as Lewis bases. Solutions in chloroform, carbon tetrachloride, and carbon disulfide are violet, the
color of iodine vapor.

One of the most distinctive properties of iodine is the way that its solubility in water is enhanced
by the presence of iodide ions. The dissolution of iodine in aqueous solutions containing iodide
(e.g. from hydroiodic acid, potassium iodide, etc.) results from the formation of the I3− ion.
Dissolved bromides also improve water solubility of iodine.

Redox reactions

In every day life, iodides are slowly oxidized by atmospheric oxygen in the atmosphere to give
free iodine. Evidence for this conversion is the yellow tint of certain aged samples of iodide salts
and some organoiodine compounds.[3] The oxidation of iodide to iodine in air is also responsible
for the slow loss of iodide content in iodized salt if exposed to air.[19]

Iodine is easily oxidized and easily reduced. Most common is the interconversion of I- and I2.
Molecular iodine can be prepared by oxidizing iodides with chlorine:

2 I− + Cl2 → I2 + 2 Cl−

or with manganese dioxide in acid solution:[20]

2 I− + 4 H+ + MnO2 → I2 + 2 H2O + Mn2+

Iodine is reduced to hydroiodic acid by hydrogen sulfide and hydrazine:[21]

I2 + H2S → 2 HI + 1/8 S8
2 I2 + N2H4 → 4 HI + N2

When dissolved in fuming sulfuric acid (65% oleum), iodine forms an intense blue solution. The
blue color is due to I+2 cation, the result of iodine being oxidized by SO3:[22]

2 I2 + 2 SO3 + H2SO4 → 2 I+2 + SO2 + 2 HSO−4

The I+2 cation is also formed in the oxidation of iodine by SbF5 or TaF5. The resulting I+2Sb2F−11
or I+2Ta2F−11 can be isolated as deep blue crystals. The solutions of these salts turn red when
cooled below −60 °C, due to the formation of the I2+4 cation:[22]

2 I+2 I2+4

Under slightly more alkaline conditions, I2+4 disproportionates into I+3 and an iodine(III)
Oxides of iodine

The best known oxides are the anions, IO3− and IO4−, but several other oxides are known, such as
the strong oxidant iodine pentoxide.

By contrast with chlorine, the formation of the hypohalite ion (IO–) in neutral aqueous solutions
of iodine is negligible.

I2 + H2O H+ + I− + HIO (K = 2.0×10−13)[20] In basic solutions (such as aqueous sodium

hydroxide), iodine converts in a two stage reaction to iodide and iodate:[20]
I2 + 2 OH− → I− + IO− + H2O (K = 30)
3 IO− → 2 I− + IO3− (K = 1020)

Organic derivatives of hypoiodate (2-Iodoxybenzoic acid, and Dess-Martin periodinane) are used
in organic chemistry.

Iodic acid (HIO3), periodic acid (HIO4) and their salts are strong oxidizers and are of some use in
organic synthesis. Iodine is oxidized to iodate by nitric acid as well as by chlorates:[23]

I2 + 10 HNO3 → 2 HIO3 + 10 NO2 + 4 H2O

I2 + 2 ClO3− → 2 IO3− + Cl2

Inorganic iodine compounds

Iodine forms compounds with all the elements except for the noble gases. From the perspective
of commercial applications, an important compound is hydroiodic acid, used as a co-catalyst in
the Cativa process for the production of acetic acid. Titanium and aluminium iodides are used in
the production of butadiene, a precursor to rubber tyres.[3]

Alkali metal salts are common colourless solids that are highly soluble in water. Potassium
iodide is a convenient source of the iodide anion; it is easier to handle than sodium iodide
because it is not hygroscopic. Both salts are mainly used in the production of iodized salt.
Sodium iodide is especially useful in the Finkelstein reaction, because it is soluble in acetone,
whereas potassium iodide is less so. In this reaction, an alkyl chloride is converted to an alkyl
iodide. This relies on the insolubility of sodium chloride in acetone to drive the reaction:

R-Cl (acetone) + NaI (acetone) → R-I (acetone) + NaCl (s)

Despite having the lowest electronegativity of the common halogens, iodine reacts violently with
some metals, such as aluminium:

3 I2 + 2 Al → 2 AlI3

This reaction produces 314 kJ per mole of aluminum, comparable to thermite's 425 kJ. Yet the
reaction initiates spontaneously, and if unconfined, causes a cloud of gaseous iodine due to the
high temperature.
Interhalogen compounds

Interhalogen compounds are well known; examples include iodine monochloride and trichloride;
iodine pentafluoride and heptafluoride.

Organic compounds

Many organoiodine compounds exist, the simplest is iodomethane, approved as a soil fumigant.
Iodinated organics are used as synthetic reagents, and also radiocontrast agents.

The thyroid hormones are naturally occurring organoiodine compounds.[24]

Organic synthesis

With phosphorus, iodine is able to replace hydroxyl groups on alcohols with iodide. For
example, the synthesis of methyl iodide from methanol, red phosphorus, and iodine.[25] The
iodinating reagent is phosphorus triiodide that is formed in situ:

3 CH3OH + PI3 → 3 CH3I + H3PO3

Phosphorous acid is formed as a side-product.

The iodoform test uses an alkaline solution of iodine to react with methyl ketones to give the
labile triiodomethide leaving group, forming iodoform which precipitates.

Iodine is sometimes used to activate magnesium when preparing Grignard reagents; aryl and
alkyl iodides both form Grignard reagents. Alkyl iodides such as iodomethane are good
alkylating agents. Some drawbacks to use of organoiodine compounds in chemical synthesis are:

• iodine compounds tend to be more expensive than the corresponding bromides and
chlorides, in that order
• iodides tend to be much stronger alkylating agents, and so are more toxic (e.g. methyl
iodide is very toxic (T+)[26]
• low molecular weight iodides tend to have a much higher equivalent weight, compared
with other alkylating agents (e.g. methyl iodide versus dimethyl carbonate), due to the
atomic mass of iodine.

Deficiency

In areas where there is little iodine in the diet,[5] 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.[40] Iodine deficiency is the leading cause of
preventable mental retardation, a result which 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 the wealthier nations, but as of March 2006, iodine deficiency
remained a serious public health problem in the developing world.[41] Iodine deficiency is also a
problem in certain areas of Europe. In Germany it has been estimated to cause a billion dollars in
health care costs per year.[29]

Other possible health effects being investigated as being related to deficiency include:

• Breast cancer. The breast strongly and actively concentrates iodine into breast-milk for
the benefit of the developing infant, and may develop a goiter-like hyperplasia,
sometimes manifesting as fibrocystic breast disease, when iodine level are low. Studies
indicate that iodine deficiency, either dietary or pharmacologic, can lead to breast atypia
and increased incidence of malignancy in animal models, while iodine treatment can
reverse dysplasia.[42][43][44] The role of iodide in breast dysplasia and development of breast
cancer is an area of active research.[42]

• Stomach cancer. Some researchers have found an epidemiologic correlation between

iodine deficiency, iodine-deficient goitre and gastric cancer.[45][46][47] A decrease of the
incidence of death rate from stomach cancer after implementation of the effective iodine-
prophylaxis has been reported also.[48]

Precautions and toxicity of elemental iodine

Elemental iodine is an oxidizing irritant and direct contact with skin can cause lesions, so 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 use for cleaning
and antisepsis is prolonged.

Elemental iodine (I2) is poisonous if taken orally in larger amounts; 2–3 grams of it is a lethal
dose for an adult human.

Iodine vapor is very irritating to the eye, to mucous membranes, and in the respiratory tract.
Concentration of iodine in the air should not exceed 1 mg/m³ (eight-hour time-weighted
average).

When mixed with ammonia and water, elemental iodine forms nitrogen triiodide which is
extremely shock sensitive and can explode unexpectedly.

Toxicity of iodide ion

Excess iodine has symptoms similar to those of iodine deficiency. Commonly encountered
symptoms are abnormal growth of the thyroid gland and disorders in functioning and growth of
the organism as a whole. Iodides are similar in toxicity to bromides.[citation needed]

Excess iodine can be more cytotoxic in the presence of selenium deficiency.[49] Iodine
supplementation in selenium-deficient populations is theoretically problematic, partly for this
reason.[29]
Iodine sensitivity

Some people develop a sensitivity to iodine. Application of tincture of iodine can cause a rash.
Some cases of reaction to Povidone-iodine (Betadine) have been documented to be a chemical
burn.[50] Eating iodine-containing foods can cause hives. Medical use of iodine (i.e. as a contrast
agent, see above) can cause anaphylactic shock in highly iodine sensitive patients. Some cases of
sensitivity to iodine can be formally classified as iodine allergies. Iodine sensitivity is rare but
has a considerable effect given the extremely widespread use of iodine-based contrast media.[51