GROUP VII

THE HALOGENS

The members of Group (VII) are called halogens. The word halogens is derived from the Greek
for salt-formers. They are all reactive non-metals and have the outer shell arrangement ns2np5
which makes them one electron short of having the full outer shell of a noble gas structure.
They show the typical properties of non-metals, having low melting and boiling points, when
solids they are brittle and when liquid they are extremely poor electrical conductors. They form
two main classes of compounds: ionic compounds containing the halide ion X- and covalent
compounds where electrons are shared with other atoms.

PHYSICAL PROPERTIES

The elements exist as diatomic molecules containing a single covalent bond X------X, (where X
represents the halogen).

The number of electrons increases with the atomic number, resulting in an increase in the
dispersion forces between the molecules. As a result the melting and boiling points of the
halogens increase as atomic number increases in the order F2 < Cl2 < Br2 < I2. At room
temperature and pressure, 25oC (298 K) and 1 bar, fluorine is a pale yellow gas, chlorine is a
greenish gas, bromine a volatile red-brown liquid and iodine a shiny black solid which gives off
a purple vapour on gentle heating. The volatility of the elements is due to the fact that the
intermolecular forces are weak Van der Waals forces.

REACTIVITY OF THE ELEMENTS

There is a clear trend in the reactivity of the group. Reactivity decreases going down the group,
partly because of the increasing size of the atoms. The electron which is added to form the X- ion
goes into a shell further from, and therefore less strongly attracted to, the nucleus. The elements
have a less negative affinity as the group is descended.

REACTIVITY AS OXIDIZING AGENTS

Oxidizing agents tend to accept electrons. All the halogens are good oxidizing agents. The
effectiveness of an oxidizing agent can be measured by the E values for the half cell reactions.
The more positive the value of E, the better the element is as an oxidizing agent.
F2

2e-

2F-

E = + 2.87v

Cl2

+ 2e-

2Cl-

E = + 1.36v

Br2

2e-

2Br-

E = + 1.07v

I2

2e-

2I-

E = + 0.54v

As the group is descended, the oxidizing strength of the element decreases. This is because the
electronegativity decreases down the group, i.e., the ability of the halogen to accept electrons
decreases down the group.
Fluorine is a strong enough oxidizing agent to oxidize water to oxygen and hydrogen fluoride.
2F2 (g)

+ 2H2O (l)

4HF(aq) +

O2 (g).

Chlorine slowly disproportionates in water forming hydrochloric acid and chloric (I) acid /
hypochlorous acid.
Cl2 (aq) + H2O (l)

HCl(aq) + HClO(aq).

A reaction where a species is simultaneously oxidized and reduced is called a

disproportionation reaction.
Chloric (I) acid decomposes in sunlight to give oxygen.
HClO(aq)

HCl(aq) + O2 (g).

Bromine undergoes a similar reaction to chlorine. Iodine has very low solubility in water.
However, it dissolves in water containing a high concentration of iodide ions, e.g. KI (aq).
Equilibrium is established in which iodide ion reacts with iodine to form the triiodide ion:
I-(aq)

I2 (s) I3-(aq).

Diagram shows chlorine reacting with the other halogens. It cannot oxidize fluorine but oxidizes bromide ions to bromine (redbrown colour) and oxidizes iodide ions to iodine (purple colour).

A halogen high in the group will oxidize the ions of another halogen lower in the group. Chlorine
can oxidize bromide ions to bromine and iodide ions to iodine.
Cl2 (aq) + 2KBr (aq) 2KCl (aq) +

Br2 (aq).

Bromine forms an orange solution.

Cl2 (aq) + 2KI (aq) 2KCl (aq) +

I2 (aq).

The iodine dissolves in potassium chloride to give a red-brown solution. Chlorine will not
oxidize fluorine.
Bromine will oxidize iodide ions to iodine.
Br2 (aq) + 2KI (aq) 2KBr (aq) +

I2 (aq).

It will not oxidize the fluoride or chloride ions. Iodine will not oxidize any of the halide ions
above it.
All the halogens can oxidize sulphate ions to sulphate ions and hydrogen sulphide to sulphur.
However, only fluorine, chlorine and bromine can oxidize iron (II) ions to iron (III) ions. Iodine
is too weak an oxidizing agent to carry out the reaction.
Fluorine, chlorine and bromine can all oxidize thiosulphate ion S2O32- to sulphate ions.
4Br2 (aq) +

S2O32-(aq) + 5H2O(l) 2SO42-(aq) + 8Br-(aq)

+ 10H+(aq).

Iodine is too weak an oxidant to achieve this. Instead it oxidizes thiosulphate ion to tetrathionate
ion:
I2 (aq) +

S2O32-(aq) S4O62 (aq) + 2I-(aq).

The oxidation number of sulphur in thiosulphate is +2. The oxidation number of sulphur in
tetrathionate is +2.5. This specific reaction of iodine is useful in quantitative analysis of oxidants.

REACTIONS WITH HYDROGEN

The halogens react directly with hydrogen to produce hydrogen halides. Fluorine reacts
explosively with hydrogen at temperatures down to -200oC.
H2 (g)

F2 (g)

2HF (g).

Hydrogen reacts slowly with chlorine in the dark but explosively when exposed to a spark or to
bright light.
H2 (g)

Cl2 (g)

2HCl (g).

Hydrogen and bromine reacts more slowly at very high temperatures of 300oC and a platinum
catalyst.
H2 (g)

Br2 (g)

2HBr (g).

Iodine and hydrogen react even more slowly and the reaction is reversible.
H2 (g)

I2 (g)

2HI (g).

STABILITY OF THE HYDRIDES

The hydrogen halides are all gases at room temperature and pressure with the exception of
hydrogen fluoride. Hydrogen fluoride is a liquid at room temperature and pressure which boils at
293K.

It has the highest boiling temperature of the hydrogen halides owning to the formation of strong
hydrogen bonds. In fact the F ------- H----- F ------ H hydrogen bond is the strongest known
having bond energy of 125kJmol-1, which approaches the strength of some covalent bonds.
Hydrogen fluoride dissolved in water is a weak acid:
HF(aq) + H2O(l) F-(aq) + H3O+(aq).
This is due to the very strong H-----F bond. The other hydrogen halides dissolve in water to form
strong acids. The strength of the acids increase going down the group i.e., HI < HBr < HCl < HF.

This is because the bond energy for the hydrogen halides decreases down the group so they
dissociate more easily. They dissociate according to the equation:
HX(g) + H2O(l) X-(aq) + H3O+(aq).
As the group is descended, the bond lengths of the hydrides increase. Longer bonds are weaker
bonds.

The order of ease of decomposition increases going down the group. This is due to the H-----X
bond weakening going down the group. The size of the atoms increases from fluorine to iodine;
bond length increases and bond enthalpy decreases in the same order.

Thermal stability of the hydride can be investigated by dipping a red-hot wire into each halide. In
the case of hydrogen iodide, copious violet clouds of iodine is seen. Hydrogen bromide would
produce reddish-brown bromine gas.
2HI(g)

H2 (g) + I2 (g).

REACTIONS OF HALIDE IONS

1. AQUEOUS SILVER NITRATE FOLLOWED BY AQUEOUS

AMMONIA
The silver halides are used to identify the chloride, bromide and iodide ions. These halides may
be identified in a solution by adding silver nitrate and observing the colour of the precipitate
formed. Fluorides cannot be identified by this test as they do not form a precipitate with silver
nitrate. Silver fluoride is soluble and its solution is colourless. This is a reflection of its pure ionic
character. Silver chloride, silver bromide and silver iodide are insoluble in water and are
precipitated. The colours of the precipitates are as follows:

Silver chloride is white

Silver bromide is cream
Silver iodide is yellow

The ionic equation for the precipitation of the halide is:

Ag+(aq)

+ X-(aq)

AgX(s).

Confirmation is obtained by observing the behaviour when aqueous ammonia is added to these
precipitates:

Silver chloride dissolves in dilute aqueous ammonia

Silver bromide dissolves in concentrated aqueous ammonia
Silver iodide remains as a precipitate in both dilute and concentrated aqueous ammonia.

The precipitate dissolves because a complex ion is formed between the silver ion and ammonia:
AgCl(s) +

2NH3 (aq) [Ag(NH3)2]+(aq) + Cl-(aq).

2. CONCENTRATED SULPHURIC ACID

Concentrated sulphuric acid can be used to prepare hydrogen chloride by reacting it with a metal
halide e.g sodium chloride.
NaCl(s) +

H2SO4 (aq. conc.) HCl(g)

+ NaHSO4 (aq).

Concentrated sulphuric acid is a powerful oxidant, and may not be used to prepare HBr and HI as
it would HCl because these substances are reductants and so are oxidized by concentrated
sulphuric acid to bromine and iodine respectively. Example:
2HBr(aq) + H2SO4 (aq. conc) 2H2O(l) + SO2 (g) + Br2 (g).
Hydrogen iodide reduces concentrated sulphuric acid further to sulphur and hydrogen sulphide.

REACTIONS OF CHLORINE WITH SODUIM HYDROXIDE

Chlorine reacts faster with dilute alkalis than with water. Chlorine bromine and iodine undergo
similar reactions with alkalis. The products of the reaction depend on the temperature at which
the reaction is occurring.

1. COLD AQUEOUS SODIUM HYDROXIDE

When chlorine is added to cold aqueous sodium hydroxide a mixture of sodium chloride and
sodium chlorate (I) is formed.
Cl2 (g) + 2NaOH(aq)

NaCl(aq) + NaClO(aq) + H2O(l).

The sodium chlorate (I) formed decomposes slowly to sodium chloride and sodium chlorate (V).
The decomposition is slow at room temperature but fast at 70oC.
3NaClO(aq)

2NaCl(aq) + NaClO3 (aq).

Both reactions are fast at 15oC for bromine and iodine. Decomposition of the iodate (I) to iodate
(V) occurs rapidly at even 0oC.

2. HOT AQUEOUS SODIUM HYDROXIDE

When chlorine is added to hot aqueous sodium hydroxide at about 70oC, a mixture of sodium
chloride and sodium chlorate (V) is formed.
3Cl2 (g) + 6NaOH(aq)

5NaCl(aq) + NaClO3(aq) + 3H2O(l).

The reaction forms sodium chlorate (I) first which rapidly decomposes to sodium chlorate (V).
Sodium chlorate (I) is a mild antiseptic and sodium chlorate (V) is a powerful weed killer.