The Chemistry of the Halogens

The HalogensNone of the halogens can be found in nature in their

elemental form. They are invariably found as salts of the halide ions (F-, Cl-,
Br-, and I-). Fluoride ions are found in minerals such as fluorite (CaF 2) and
cryolite (Na3AlF6). Chloride ions are found in rock salt (NaCl), the oceans,
which are roughly 2% Cl- ion by weight, and in lakes that have a high salt
content, such as the Great Salt Lake in Utah, which is 9% Cl - ion by weight.
Both bromide and iodide ions are found at low concentrations in the oceans,
as well as in brine wells in Louisiana, California, and Michigan.

The Halogens in their Elemental Form

Fluorine is so reactive that it is difficult to find a container in which it can be
stored. F2 attacks both glass and quartz, for example, and causes most
metals to burst into flame. Fluorine is handled in equipment built out of
certain alloys of copper and nickel. It still reacts with these alloys, but it
forms a layer of a fluoride on the surface that protects the metal from further
reaction.
Fluorine is used in the manufacture of Teflon
(C2F4)n

or poly(tetrafluoroethylene),

which is used for everything from linings for pots and pans to

gaskets that are inert to chemical reactions. Large amounts of fluorine are
also consumed each year to make the freons (such as CCl 2F2) used in
refrigerators.

Chlorine (Cl2) is a highly toxic gas with a pale yellow-green color. Chlorine is a
strong oxidizing agent, which is used commercially as a bleaching agent and
as a disinfectant. It is strong enough to oxidize the dyes that give wood pulp
its yellow or brown color, for example, thereby bleaching out this color, and
strong enough to destroy bacteria and thereby act as a germicide. Large
quantities of chlorine are used each year to make solvents such as carbon
tetrachloride (CCl4), chloroform (CHCl3), dichloroethylene (C2H2Cl2), and
trichloroethylene (C2HCl3).
Bromine (Br2) is a reddish-orange liquid with an unpleasant, choking odor.
The name of the element, in fact, comes from the Greek stem bromos,
"stench." Bromine is used to prepare flame retardants, fire-extinguishing
agents, sedatives, antiknock agents for gasoline, and insecticides.
Iodine is an intensely colored solid with an almost metallic luster. This solid is
relatively volatile, and it sublimes when heated to form a violet-colored gas.
Iodine has been used for many years as a disinfectant in "tincture of iodine."
Iodine compounds are used as catalysts, drugs, and dyes. Silver iodide (AgI)
plays an important role in the photographic process and in attempts to make
rain by seeding clouds. Iodide is also added to salt to protect against goiter,
an iodine deficiency disease characterized by a swelling of the thyroid gland.
Methods of Preparing the Halogens from their Halides
The halogens can be made by reacting a solution of the halide ion with any
substance that is a stronger oxidizing agent. Iodine, for example, can be
made by reacting the iodide ion with either bromine or chlorine.
2 I-(aq)

Br2(aq)

I2(aq)

2 Br-(aq)

Bromine was first prepared by reacting bromide ions with a solution of Cl 2

dissolved in water.

2 Br-(aq)

Cl2(aq)

Br2(aq)

2 Cl-(aq)

To prepare Cl2, we need a particularly strong oxidizing agent, such as

manganese dioxide (MnO2).
2 Cl-(aq)

+ MnO2(aq)

+ 4 H+(aq)

Cl2(aq) + Mn2+(aq)

+ 2 H2O(l)

The best way of producing a strong reducing agent is to pass an electric

current through a salt of the metal. Sodium, for example, can be prepared by
the electrolysis of molten sodium chloride.
electrolysis
2 NaCl(l)

2 Na(s)

Cl2(g)

Common Oxidation Numbers for the Halogens

Fluorine is the most electronegative element in the periodic table. As a
result, it has an oxidation number of -1 in all its compounds. Because
chlorine, bromine, and iodine are less electronegative, it is possible to
prepare compounds in which these elements have oxidation numbers of +1,
+3, +5, and +7, as shown in the table below.
Common Oxidation Numbers for the Halogens
Oxidation
Number
-1
0
+1
+3
+5
+7

Examples
CaF2, HCl, NaBr, AgI
F2, Cl2, Br2, I2
HClO, ClF
HClO2, ClF3
HClO3, BrF5, BrF6-, IF5
HClO4, BrF6+, IF7

General Trends in Halogen Chemistry

There are several patterns in the chemistry of the halogens.
1. Neither double nor triple bonds are needed to explain the chemistry of the
halogens.
2. The chemistry of fluorine is simplified by the fact it is the most
electronegative element in the periodic table and by the fact that it has no d
orbitals in its valence shell, so it can't expand its valence shell.
3. Chlorine, bromine, and iodine have valence shell d orbitals and can
expand their valence shells to hold as many as 14 valence electrons.
4. The chemistry of the halogens is dominated by oxidation-reduction
reactions.

The Hydrogen Halides (HX)

The hydrogen halides are compounds that contain hydrogen attached to one
of the halogens (HF, HCl, HBr, and HI). These compounds are all colorless
gases, which are soluble in water. Each of the hydrogen halides ionizes to at
least some extent when it dissolves in water.
H2O
H+(aq)

HCl(g)

Cl-(aq)

Several of the hydrogen halides can be prepared directly from the elements.
Mixtures of H2 and Cl2, for example, react with explosive violence in the
presence of light to form HCl.
H2(g)

Cl2(g)

2 HCl(g)

Because chemists are usually more interested in aqueous solutions of these

compounds than the pure gases, these compounds are usually synthesized
in water. Aqueous solutions of the hydrogen halides are often called mineral
acids because they are literally acids prepared from minerals. Hydrochloric
acid is prepared by reacting table salt with sulfuric acid, for example, and
hydrofluoric acid is prepared from fluorite and sulfuric acid.
2 NaCl(s)
CaF2(s)

+ H2SO4(aq)
+ H2SO4(aq)

2 HCl(aq)
2 HF(aq)

+ Na2SO4(aq)
+ CaSO4(aq)

These acids are purified by taking advantage of the ease with which HF and
HCl gas boil out of these solutions. The gas given off when one of these
solutions is heated is collected and then redissolved in water to give
relatively pure samples of the mineral acid.
The Interhalogen Compounds
Interhalogen

compounds

are

formed

by

reactions

between

different

halogens. All possible interhalogen compounds of the type XY are known.

Bromine reacts with chlorine, for example, to give BrCl, which is a gas at
room temperature.
Br2(l)

Cl2(g)

2 BrCl(g)

Interhalogen compounds with the general formulas XY3, XY5, and even XY7
are formed when pairs of halogens react. Chlorine reacts with fluorine, for
example, to form chlorine trifluoride.
Cl2(g)

3 F2(g)

2 ClF3(g)

These compounds are easiest to form when Y is fluorine. Iodine is the only
halogen that forms an XY7 interhalogen compound, and it does so only with
fluorine.

ClF3 and BrF5 are extremely reactive compounds. ClF 3 is so reactive that
wood, asbestos, and even water spontaneously burn in its presence. These
compounds are excellent fluorinating agents, which tend to react with each
other to form positive ions such as ClF 2+ and BrF4+ and negative ions such as
IF2- and BrF6-.
[BrF4+][BrF6-](s)

2 BrF5(l)

Neutral Oxides of the Halogens

Under certain conditions, it is possible to isolate neutral oxides of the
halogens, such as Cl2O, Cl2O3, ClO2, Cl2O4, Cl2O6, and Cl2O7. Cl2O7, for
example, can be obtained by dehydrating perchloric acid, HClO 4. These
oxides are notoriously unstable compounds that explode when subjected to
either thermal or physical shock.

Oxyacids of the Halogens and Their Salts

Chlorine reacts with the OH- ion to form chloride ions and hypochlorite (OCl -)
ions.
Cl2(aq)

+ 2 OH-(aq)

Cl-(aq)

+ OCl-(aq)

+ H2O(l)

This is a disproportionation reaction in which one-half of the chlorine atoms

are oxidized to hypochlorite ions and the other half are reduced to chloride
ions.

When the solution is hot, this reaction gives a mixture of the chloride and
chlorate (ClO3-) ions.
3 Cl2(aq)

+ 6 OH-(aq)

5 Cl-(aq)

+ ClO3-(aq)

+ 3 H2O(l)

Under carefully controlled conditions, it is possible to convert a mixture of

the chlorate and hypochlorite ions into a solution that contains the chlorite
(ClO2-) ion.
ClO3-(aq)

ClO-(aq)

2 ClO2- (aq)

The names of the oxyanions of the halogens use the endings -ite and -ate to
indicate low and high oxidation numbers and the prefixes hypo- and per- to
indicate the very lowest and very highest oxidation numbers, as shown in the
table below. Each of these ions can be converted into an oxyacid, which is
named by replacing the -ite ending with -ous and the -ate ending with -ic.

Oxyanions and Oxyacids of Chlorine

Oxidation

Oxyanions
Compoun Name

Oxyacids
Compoun

State

Name

of the Chlorine
+1
+3
+5
+7

ClOClO2ClO3ClO4-

hypochlorite
chlorite
chlorate
perchlorate

HClO
HOClO
HOClO2
HOClO3

hypochlorous acid
chlorous acid
chloric acid
perchloric acid