GROUP 17 ELEMENTS - THE HALOGENS

The group 17 elements are also referred to as the group VIIA elements. Thay have 7 valence electrons.
The valence electron configuration is ns2np5, where ‘n’ is the highest principal quantum number.
Elemen Period Atomic Electronic configuration
t Number Short form Detailed configuration
Fluorine 2 9 [He]2s22p5 1s22s22p5
Chlorine 3 17 [Ne]3s23p5 1s22s22p63s23p5
Bromine 4 35 [Ar]4s24p5 1s22s22p63s23p64s23d104p5
Iodine 5 53 [Kr]5s25p5 1s22s22p63s23p64s23d104p65s24d105p5 .
Astatine 6 85 [Kr]6s36p5 1s22s22p63s23p63d104s24p64d105s25p64f145d106s26p5

Preparation of the Halogens

All of the halogens occur in seawater as halide ions, X- (F-, Cl-, Br- and I-). The concentration of the
chloride ion is about 0.54 M; and the concentration of the other halides is less than 10–4 M. Fluoride also
occurs in minerals such as CaF2, Ca(PO4)3F, and Na3AlF6.
Chloride also occurs in the Great Salt Lake and the Dead Sea, and in extensive salt beds that contain
NaCl, KCl, or MgCl2. Bromine compounds occur in the Dead Sea and underground brines. Iodine
compounds are found in small quantities in Chile saltpetre, underground brines, and sea kelp. Iodine is
essential to the function of the thyroid gland.
The best sources of halogens (except iodine) are halide salts and hence they are prepared from the
halides. It is possible to oxidize the halide ions to free diatomic halogen molecules by various methods,
depending on the ease of oxidation of the halide ion. Fluoride is the most difficult to oxidize because
fluorine is the most electronegative element if the periodic table. So, elemental fluorine is prepared by
electrolysis. The iodide is the easiest to oxidise as it is the strongest reducing agent among the halides.
Fluorine gas, F2 was first prepared successfully in 1886 by Henri Moissan from the electrolysis of a
mixed salt of KF and HF and noted that crystals of silicon burst into flame when mixed with this gas.
Electrolysis of molten KHF2 is still used to prepare fluorine today, as shown in the figure below.
KHF2(s) →electrolysis→ H2(g) + F2(g) + KF(s)

Chlorine gas is prepared by the chemical oxidation of the chloride ion in acid solution with strong
oxidizing agents such as manganese dioxide (MnO 2), sodium dichromate (Na2Cr2O7) or potassium
dichromate (K2Cr2O7), lead (IV) oxide, PbO2 or cerium (IV) salts, such as cerium (IV) sulphate,
Ce(SO4)2. The reaction with MnO2 is:

MnO2(s) + 2Cl−(aq) + 4H3O+(aq) ⟶ Mn2+(aq) + Cl2(g) + 6H2O(l)

Most industrial chlorine comes from the electrolysis of the chloride ion in aqueous solutions of sodium
chloride in the chlor-alkali process. Chlorine is also a product of the electrolytic production of metals
such as sodium, calcium, and magnesium from their fused chlorides.
The commercial preparation of bromine involves the oxidation of bromide ion by chlorine, because
chlorine is a stronger oxidizing agent than bromine.

2Br−(aq) + Cl2(g) ⟶ Br2(l) + 2Cl−(aq)

This method is important for the production of essentially all domestic bromine.
Some iodine comes from the oxidation of iodine chloride, ICl, or iodic acid, HlO3. The commercial
preparation of iodine utilizes the reduction of sodium iodate, NaIO3, an impurity in deposits of Chile
saltpetre, with sodium hydrogen sulphite:

2IO3−(aq) + 5HSO3−(aq) ⟶ 3HSO4−(aq) + 2SO42−(aq) + H2O(l) + I2(s)

The iodate ion can also be reduced to free iodine with the iodide ion in acidic medium.

2IO3−(aq) + 5I−(aq) = 6H+(aq) ⟶ + 3H2O(l) + 3I2(s)

Iodine can also be prepared by the oxidation of iodide ion with chlorine, because chlorine is a stronger
oxidizing agent than iodine.

2I−(aq) + Cl2(g) ⟶ I2(l) + 2Cl−(aq)

Physical properties
At room temperature fluorine is a pale-yellow gas, chlorine is a greenish-yellow gas, bromine is a deep
reddish-brown liquid, and iodine is a greyish-black crystalline solid.

F2 gas Cl2 gas Br2 liquid I2 solid I2 vapour

Fluorine is the most electronegative element in the periodic table and as a result, it has an oxidation
number of -1 in all its compounds. Because chlorine, bromine, and iodine are less electronegative, they
can exist in compounds with different oxidation numbers as shown ibn the table below.

Element Oxidation number

F -1
Cl -1, +1, +3, +5, +7
Br -1, +1, +3, +5
I -1, +7
Illustration of the oxidation states with chlorine
Oxidation state Anion Typical Compound
Cl Formula Name Formula Name
-1 Cl- Chloride NaCl Sodium chloride
+1 ClO- Hypochlorite HClO Hypochlorous acid
+3 ClO2- Chlorite HOClO Chlorous acid
+5 ClO3- Chlorate HOClO2 Chloric acid
+7 ClO4- Perchlorate HOClO3 Perchloric acid

ionisation energies, i.e. the energy involved in the process: X(g) ⟶ X-(g) + e-
Since the atoms of the halogens have very little tendency to loose electrons they have very high

Element 1st Ionisation

energy, kJ/mol
F 1681
Cl 1256
Br 1143
I 1009

Note: The ionisation energy for hydrogen (1310 kJ/mol) is much greater than that of the halogens,
except for fluorine, yet it readily forms the proton, H + in solutions. The proton is very small compared to
the size of the halogens, therefore, in solution the very high hydration energy compensates for the high
ionisation energy, hence the overall process is more favourable.

REACTIONS OF THE HALOGENS

1. Reaction with Water
All the halogens, except for F2 dissolve in water to form the form the hypohalide, OX- and the normal
halide, X-.
X2 + H2O  HOX + HX
For example, Cl2 gas dissolves in water for from hypochlorite, OCl- and the chloride, Cl-.
Cl2(g) + H2O  HOCl(aq) +HCl(aq)

The amount of the hypohalide formed decreases down the group. Chlorine and bromine are moderately
soluble in water. When Cl2 dissolves in water, about two-thirds is converted to the hypochlorite, OCl -
and for Br2 forms only about 10 – 15% of the hypobromide, OBr -. The amount of hypoiodide formed
when I2 dissolves in water is negligible, because it is poorly soluble in water.

The standard electrode potentials of the X2/X− couples.

F = +2.866 V
Cl = +1.395 V
Br = +1.087 V
I = +0.615 V
From a standard reduction potential table, it implies that iodine and bromine cannot oxidize water to
oxygen because they have smaller reduction potentials than oxygen. However, fluorine and chlorine with
higher reduction potentials, and can oxidize water. Fluorine reacts with water vapour to form oxygen and
ozone, i.e., it oxidises water
2F2(g) + 2H2O(g) → 4HF(g)+O2(g)
3F2(g) + 2H2O(g) → 6HF(g) + O3(g)
Given that standard electrode potential for water E°(1/2O2/H2O) = +1.229 V, which is less than the
standard electrode potential for Cl2, it would be expected that Cl2 should be able to oxidise water to
oxygen and hydrochloric acid. However, the kinetics of this reaction are unfavourable, and there is also a
bubble overpotential effect to consider, so that electrolysis of aqueous chloride solutions evolves
chlorine gas and not oxygen gas, a fact that is very useful for the industrial production of chlorine.

2. Reaction with Hydrogen

All the halogens react directly with hydrogen, forming covalent bonds and at sufficient levels of purity
colourless gases at room temperature. Hydrogen reacts with fluorine, chlorine, bromine, and iodine,
forming HF, HCl, HBr, and HI, respectively.
The bond strength of these molecules decreases down the group: HF>HCl>HBr>HI

Iodine and hydrogen react non-spontaneously to produce hydrogen iodide:

H2 + I2 → 2HI
All the hydrogen halides (with the exception of HF) are soluble in water forming strong acids. The
general equation of hydrogen halide for the acid reaction is given below:
HX + H2O → H3O+ + X− (X = Cl, Br, I)
+ −
HCl + H2O → H3O + X

3. Reaction with metals

All the alkali metals react vigorously with halogens to produce salts, the most industrially important of
which are NaCl and KCl. The general equation is:
M(s) + X2 → 2MX(s)
2M(s) + Cl2(g) → 2MCl(s)
2Na(s) + Cl2(g) → 2NaCl(s)
These metal halides form white ionic crystalline solids and are all soluble in water except LiF, because
of its high lattice energy attributed to strong electrostatic attraction between the Li+ and F- ions.

The alkaline earth metals react to form hydrated halides. These halides are ionic except for those
involving , the least metallic of the group.
M+X2→MX2
Mg(s) + Cl2(g) → 2MgCl2(s)
where M represents an alkali or alkaline earth metal and X represents fluorine, chlorine, bromine or
iodine

4. Reaction dilute alkali

The halogens react with cold aqueous alkalis to form the hypohalides, OX - and the halide, X-. The
halogen is oxidised and reduced at the same time. The process is known as disproprtionation. Chlorine
disproportionates readily in cold dilute alkalis to the hypochlorite, OCl - (or chlorate (I) ion) and reduced
to chloride, Cl-.
 Cl2(g) + 2OH-(aq)  Cl- (aq) + OCl-(aq) + H2O(l)
Cl2(g) + NaOH(aq)  NaCl(aq) + NaOCl(aq) + H2O(l)

Bromine and iodine react in a similar manner, but in the case of iodine, the hypoiodide formed is not
stable even at room temperature, it decomposes into the iodate and iodide.
I2(g) + 2OH-(aq)  I- (aq) + IO3-(aq) + H2O(l)
I2(g) + NaOH(aq)  NaI(aq) + NaIO3(aq) + H2O(l)

In hot alkali solution the products are the halate ion (or halate (V) ion) and halide.
X2(g) + 2OH-(aq)  X- (aq) + XO3-(aq) + H2O(l)
X2(g) + NaOH(aq)  NaX(aq) + NXlO3(aq) + H2O(l)
For example,
Cl2(g) + 2OH-(aq)  Cl- (aq) + OCl-(aq) + H2O(l)
Cl2(g) + NaOH(aq)  NaCl(aq) + NaOCl(aq) + H2O(l)

The ClO- ion is an important oxidising agent and is the active ingredient in domestic bleach, NaClO.

5. Reactions with concentrated sulphuric acid

When concentrated sulphuric acid is added to a potassium halide, hydrogen halide is formed. With a
chloride, misty white fumes appear.

KCl(s) + H2SO4(aq)  KHSO4(aq) + HCl(g)

The chloride ion is not a strong enough reducing agent to react further with the oxidising agent, H2SO4.

Concentrated sulphuric acid is an oxidising agent is strong enough to and reacts further with the
hydrogen bromide and hydrogen iodide. Moreover, the bromide and iodide ions are relatively stronger
reducing agent hence they can react further with the concentrated sulphuric acid. The hydrogen bromide
reduces the sulphuric acid to sulphur dioxide and it is oxidised to free bromine, an orange-brown misty
fumes appear. The hydrogen iodide is also oxidised to free iodine, a purple vapour.
KBr(s) + H2SO4(aq)  KHSO4(aq) + HBr(g)
2HBr + H2SO4  Br2 + 2H2O + SO2

KI(s) + H2SO4(aq)  KHSO4(aq) + HI(g)

2HI(g) + H2SO4  I2 + 2H2O + SO2(g)

Iodide ions can produce a variety of reactions forming sulphur dioxide, sulphur and hydrogen sulphide.
Iodide ions are stronger reducing agents than bromide ions are. Hence the ions are readily oxidised to
iodine by the concentrated sulphuric acid.
2I-  I2 + 2e-
The reduction of the sulphuric acid is more complicated than in the case of bromide. The iodide ions are
powerful enough reducing agents to reduce it first to sulphur dioxide (sulphur +4) then to elemental
sulphur itself (sulphur 0) and all the way to hydrogen sulphide (sulphur -2).
H2SO4 + 2H+ + 2I-  I2 + SO2 + 2H2O
H2SO4 + 6H+ + 6I-  3I2 + S + 4H2O
H2SO4 + 8H+ + 8I-  4I2 + H2S + 4H2O