210

CHAPTER 12
THE HALOGENS
The four elements, fluorine, chlorine, bromine and iodine are known as the halogens.
"Halogen" is a term derived from Greek, meaning "salt formers", because they combine
readily with metals to form salts.
Halogens resemble each other very closely in general chemical behaviour, but the
first member of the group, fluorine, shows some differences from the rest. The chemical
behaviour of the individual elements such as chlorine, bromine and iodine will be
examined first, and then a comparison of their chemistry will be discussed.

12.1 Laboratory preparations of chlorine

1. Preparation of chlorine from concentrated hydrochloric acid and manganese
(IV) oxide

Fig. 12.1 Preparation of chlorine from concentrated hydrochloric acid and

manganese (IV) oxide
manganese(IV) hydrochloric manganese(II)
+ + water + chlorine
oxide acid (conc) chloride
MnO2(s) + 4HCl(aq) MnCl2(aq) + 2H2O(1) + Cl2(g)

Concentrated hydrochloric acid is oxidized to chlorine by manganese (IV) oxide.

The apparatus is set up as shown in Fig. 12.1. Some manganese (IV) oxide is
placed in the round-bottomed flask and concentrated acid poured down the dropping
funnel. The mixture in the flask is heated and effervescence will take place. A greenish
yellow gas with misty fumes is evolved. (The misty fumes are hydrogen chloride gas).
The gas mixture is passed into the first bottle which contains water. This removes
the hydrochloric acid gas which is very soluble in water. The gas is then passed into a
second bottle which contains concentrated sulphuric acid. This dries the gas which is
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collected by upward displacement of air since the gas is denser than air. Because of the
greenish yellow colour of the gas, it can be seen quite clearly when the gas jar is full of
chlorine.

2. Preparation of chlorine from concentrated hydrochloric acid and potassium

permanganate

Fig. 12.2 Preparation of chlorine from concentrated hydrochloric acid

and potassium permanganate
Note: If the chlorine is required pure and dry, insert wash-bottles containing (a)
water and (b) conentrated sulphuric acid as in Fig. 12.1.
potassium hydrochloric potassium manganese(II)
+ + + water + chlorine
permanganate acid (conc) chloride chloride
2KMnO4(s) + 16HCl(aq) 2KCl(aq) + 2MnCl2(aq) + 8H2O(g) + 5Cl2(g)

Concentrated hydrochloric acid is oxidized to chlorine by potassium

permanganate.
The apparatus is set up as shown in Fig. 12.2. Solid potassium permanganate is
put in the flat-bottomed flask and concentrated hydrochloric acid is dropped onto it from
the dropping funnel. Heat is not required.
As each drop of acid reaches the permanganate, there is evolved at once the
corresponding quantity of chlorine. Collect the gas by downward displacement of brine
(concentrated aqueous sodium chloride.)

3. Preparation of chlorine from sodium chloride

sodium
sodium manganese(IV) sulphuric manganese(II)
+ + hydrogen +
chloride oxider acid(conc) sulphate
sulphate
2NaCl(s) MnO2(s) 3H2SO4(conc) 2NaHSO4(aq) MnSO4(aq)
+ water + chlorine
2H2O(1) Cl2(g)
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Concentrated sulphuric acid acts upon the sodium chloride to form hydrogen
chloride, which is then oxidized to chlorine by manganese (IV) oxide.
The apparatus is set up as shown in Fig. 12.1. An intimate mixture of sodium
chloride and manganese (IV) oxide is placed in the round-bottomed flask and heated.
The gas evolved is washed with water, dried with concentrated sulphuric acid and
collected by upward displacement of air.

4. Preparation of chlorine from bleaching powder

(i) CaOCl2 (s) + 2HNO3(aq) Ca(NO3)2(aq) + H2O(1) + Cl2(g)
bleaching chlorine
powder
(ii) CaOCl2(s) + 2HCl(aq) CaCl2(aq) + H2O(l) +Cl2(g)
Bleaching powder chlorine
The apparatus is set up as shown in Fig. 12.2. Some bleaching powder is placed in
the flat-bottomed flask and a dilute acid, e.g., nitric acid, is dropped onto the powder.
Effervescence occurs with the evolution of a greenish yellow gas which may be collected
by either of the methods mentioned previously. Heat is not required.

Manufacture of chlorine
Figure 12.3 shows the apparatus for the industrial preparation of chlorine.

Fig 12.3 Manufacture of chlorine by electrolysis of aqueous sodium chloride

The reactions at the electrodes may be represented as
reaction at the cathode 2Na+ + 2e 2Na
reaction at the anode Cl Cl +e
Cl + Cl Cl2
In the electrolytic process, chlorine is liberated at the graphite anodes whilst
sodium is liberated at the mercury cathode.Sodium dissolves in the mercury forming as
amalgam which then flows into another cell where it reacts with water to form hydrogen
and a solution of sodium hydroxide.

Na/Hg(l) + H2O(l) Na+(aq) + OH (aq) + H2(g) + Hg(1)

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amalgam

Physical properties of chlorine

Chlorine is a greenish yellow gas with a choking, unpleasant smell.Chlorine is very
poisonous if inhaled even in small quantities. One part of chlorine in 50,000 parts of air
may be harmful. Chlorine is about 2 times as dense as air.
Chemical properties of chlorine
1. Affinity for hydrogen
Chlorine reacts with most compounds containing hydrogen.
(a) Action on hydrogen
When a tube containing equal volumes of chlorine and hydrogen is exposed to sunlight, it
explodes.
H2(g)+ Cl2(g) 2HCl(g)
(b) Action on warm turpentine
Chlorine reacts with warm turpentine to form carbon and hydrochloric acid.
C10H16(l) + 8Cl2(g) 10C (s) + 16HCl(g)
turpentine
(c) Action on hydrogen sulphide
Chlorine reacts with hydrogen sulphide to form sulphur ind hydrogen chloride.
H2S(g)+ Cl2(g) 2HCl(g) + S(s)
Note: In this reaction chlorine is the oxidizing agent and hydrogen sulphide is the reducing agent.
H2S 2H+ + S
S S . + 2e oxidation
Cl + 2e 2C1 reduction

2. Action on metals
(a) Action on copper
When a very thin sheet of an alloy of copper and zinc, mainly copper, is dropped into a
chlorine jar, it burns brightly with a green flame.
Cu(s) + Cl2(g) CuCl2(s)
Zn(s) + Cl2(g) ZnCl2(s)
(b) Action on iron
Hot iron wire burns in chlorine.
2Fe(s) + 3Cl2(g) 2FeCl3(s)
3. Action on non-metal
Action on phosphorus
Phosphorus burns spontaneously in chlorine.
P4(s) + 6Cl2(g) 4PCl3(g)
P4(s) + 10Cl2(g) 4PCl5(g)

4. Oxidizing properties
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(a) Bleaching action of chlorine

The chlorine reacts with water, forming hypochlorous acid, HOCl and hydrochloric acid.
Cl2(s) + H2O(l) HOCl(aq) + HCl(aq)
This hypochlorous acid is a very reactive compound and readily gives up its oxygen to
the dye, to form a colourless .compound.
dye + HOC1 HCl + (dye + O)
coloured colourless
(b) Action on iron (II) chloride solution
Chlorine reacts with iron (II) chloride solution to form iron (III) chloride.
2FeCl2(aq) + Cl2(g) 2FeCl3(aq)
(c) Action on sulphurous acid
Chlorine oxidizes sulphurous acid into sulphuric acid.
H2SO3(aq) + Cl2(g) + H2O(1) H2SO4(aq) + 2HCl(aq)
(d) Action on caustic alkalis
(i) On the cold dilute aqueous solution
When chlorine is passed into a cold ( 15°C) solution of dilute sodium hydroxide
solution, a soluble hypochlorite and chloride of the metal are formed. The colour
of this solution is yellow.
Cl2(g) + 2NaOH(aq) NaOCl(aq) + NaCl(aq) + H2O(l)
dilute solution
Cl2(g) + 2KOH(aq) KOCl(aq) + KCl(aq) + H2O(l)
dilute solution
(ii) On the hot concentrated aqueous solution
When chlorine is passed into a hot ( 70°C) concentrated sodium hydroxide
solution, a mixture of sodium chloride and sodium chlorate is formed.
6NaOH(aq) + 3Cl2(g) 5NaCl(aq) + NaClO3(aq) + 3H2O(1)
concentrated sodium chloride sodium chlorate
sodium hydroxide solution
A similar reaction occurs when chlorine is passed into concentrated potassium
hydroxide solution.
(iii) On slaked lime
When chlorine is passed over solid calcium hydroxide, bleaching powder is
formed.
Ca(OH)2(s) + Cl2(g) CaOCl2.H2O(s) bleaching powder

5. Displacement of bromine and iodine from bromide and iodide

When chlorine is passed into a solution of sodium bromide or sodium iodide, the
respective halogen is released by the substitution action of chlorine.
Cl2(g) + 2NaBr(aq) 2NaCl(aq) + Br2(aq)
Cl2(g) + 2NaI(aq) 2NaCl(aq) + I2 (aq)

Uses of chlorine
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Chlorine is used to sterilize water for domestic and industrial use, and as a bleaching
agent. With the help of chlorine, many organic substances are prepared.

Tests for chlorides

The tests for chlorides are based on some of the reactions you have already studied.
Details of these tests are given in the experimental chemistry book for the tenth standard
students.

12.2 Bromine
Laboratory preparation of bromine

Fig. 12.4 Preparation of bromine

potassium
Potassium manganese(IV) sulphuric manganese(IV)
+ + hydrogen +
bromide oxider acid(conc) sulphate
sulphate
2KBr(s) MnO2(s) 3H2SO4(conc) 2NaHSO4(aq) MnSO4(aq)
+ water + bromine
2H2O(1) Br2(g)

Bromine is prepared in much the same way as chlorine.

A mixture of potassium bromide and manganese (IV) oxide is placed in the retort
as shown in Fig. 12.4. Concentrated sulphuric acid is added to this mixture and the
mixture warmed. A reddish brown gas of bromine is given off, together with some misty
fumes of hydrogen bromide which condense to a red liquid in the cooled receiver.

Physical properties of bromine

Bromine is a heavy, red, volatile liquid. It has a choking, irritating smell. (Bromine
means "a stench".) Liquid bromine causes burns on the flesh, which heal with difficulty.
Bromine is slightly soluble in water, forming a yellowish red solution containing about 3
percent of bromine at ordinary temperatures.

Chemical properties of bromine

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1. Affinity for hydrogen

Action on hydrogen
Bromine combines with hydrogen, but not as readily as chlorine does. A mixture of
chlorine and hydrogen will explode when merely exposed to sunlight, but a mixture of
bromine and hydrogen needs the application of heat to make them combine. Also, the
hydrogen bromide formed is not as stable as hydrogen chloride.
H2(g) + Br2(g) 2HBr(g)
2. Reaction between bromine and other elements
Bromine combines readily with most metals and non-metals to form bromides. For
example, copper, iron, sodium and sulphur give the corresponding bromides.
Bromine explodes when mixed with yellow phosphorus. Phosphorus tribromide is
made by gradually adding a solution of bromine in carbon tetrachloride to red
phosphorus. (The solution is used to moderate the action.)
3. Oxidizing property of bromine
Bromine is an oxidizing agent, but it is not as strong an oxidizing agent as chlorine.
Bromine will also give majority of oxidation reactions given by chlorine.
(a) Bleaching action of bromine
Bromine is a bleaching agent but it is not so effective as chlorine. Bromine bleaches
moist litmus papers.
(b) Action on iron (II) sulphate solution
On shaking an acidified solution of iron (II) sulphate with a few drops of bromine in a
test tube, the colour of bromine soon fades and the iron (II) sulphate becomes converted
into iron (III) sulphate.
2Fe2+(aq) + Br2(g) 2Fe3+(aq) + 2Br (aq)
(c) Action on the alkalis
Bromine reacts on solutions of akalis in the same way as chlorine.
e.g., KOH(aq) + Br2(g) KBr(aq) + KOBr(aq) + H2O(1)
dilute solution
6KOH (aq) + 3Br2 (aq) 5KBr(aq) + KBrO3 (aq) + 3H2O(1)
concentrated solution
In all these reactions bromine shows a great similarity to chlorine, but differs
from it by its lower reactivity.
4. Displacement of iodine from iodides
Action on iodide
When bromine is passed into a solution of sodium iodide, iodine is liberated.
2NaI(aq) + Br2(g) 2NaBr(aq) + I2(aq)

Test for bromides

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The tests for bromides are based on some of the reactions you have already studied.
Details of these tests are given in your experimental chemistry book for tenth standard
students.

12.3 Iodine
Laboratory preparation of iodine

Fig. 12.5 Preparation of iodine

potassium
Potassium manganese(IV) sulphuric manganese(IV)
+ + hydrogen +
iodide oxider acid(conc) sulphate
sulphate
2KI (s) MnO2(s) 3H2SO4(conc) 2NaHSO4(aq) MnSO4(aq)
+ water + iodine
2H2O(1) I2(g)

Some potassium iodide and manganese (IV) oxide are mixed and ground in a
mortar and the mixture placed in a beaker.
Concentrated sulphuric acid is added to the mixture in the beaker and a round-
bottomed flask with arrangements to circulate flowing water from the tap is placed on the
beaker as shown in Fig. 12.5.
The mixture is carefully warmed when violet vapours of iodine evolve and are
condensed on the outside of the bottom of the cooled flask, as black shiny plates.
Note: Preparation of iodine is similar to that of chlorine from common salt. However, HI is
easier to oxidize than even HBr.

Physical properties of iodine

Iodine is a black shiny solid. It sublimes when heated rapidly, forming a violet vapour
from which the black solid can again be obtained by cooling.
Iodine is almost insoluble in water but readily dissolves in aqueous potassium
iodide. This is due to the formation of a compound of potassium iodide and iodine, KI 3,
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which is very soluble. This solution is brown. Iodine also dissolves in ethanol and ether,
forming brown solutions, and in carbon disulphide and carbon tetrachloride, forming
violet solutions.

Chemical properties of iodine

1. Iodine does not bleach, and. has little affinity for hydrogen. When HI is heated it
decomposes.
2. Iodine is fairly active and will combine with many metals to form iodides, but it does
so, much less readily than either chlorine or bromine.
3. Oxidizing properties
(a) Iodine is a mild oxidizing agent, but it will not perform many of the ordinary
oxidizing actions attributed to chlorine and bromine. However, iodine oxidizes H 2S to
form hydrogen iodide and liberate sulphur.
H2S(g) + I2(g) 2HI(g) + S(s)
(b) Action on alkalis
The action of iodine on alkalis is similar to those of chlorine and bromine.
4. Action on starch
To a freshly prepared solution of starch add the smallest possible quantity of a solution of
iodine. A blue colour forms immediately. [This test is sensitive to and is capable of
detecting iodine if this element is present even in ppm (parts per million) amounts.Warm
the mixture and this blue colour will disappear. It will return on cooling.
Note: This test is given only by free iodine and is not given by a solution of KI in water.

Uses of iodine
The antiseptic properties of iodine, due to its oxidizing nature, have been used in the
treatment of small cuts and wounds. "Tincture of iodine", a dilute solution of iodine in
alcohol is a household medicinal. Iodine is used as free iodine and as iodide in medicine
to treat cases of goitre, a disease which is sometimes due to a deficiency of iodine intake
into the body.
Tests for iodides Tests for iodides are based on some of the reactions you have already
studied. Details of these tests are given in your experimental chemistry book for grade 11
students.
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12.4 Chemical characteristics of the Halogens

The halogens are the elements in the Group VIIB of the periodic table.
(See Table 12.1)
Table 12.1 Group VIIB elements : The halogens
Atomic
Symbol Name of the element
number
F Fluorine 9
Cl Chlorine 17
Br Bromine 35
I Iodine 53

Halogens are the p-block elements and hence they are non-metals.
Generally speaking, the halogens are the most reactive group of non-metals; that
is, they are the most electronegative elements in the periodic table.Halogens are
strong oxidizing agents while the alkali metals are strong reducing agents.

12.5 Oxidation Numbers of the Halogens

Each of the halogens has an outer shell containing seven electrons, that is, they have the
essential electronic structure of ns2 np5. In other words, all the halogens have one electron
less than the noble gas which immediately follows them in the periodic table: That is why
the halogens have a tendency to gain an electron to form a complete outermost electron
shell of eight electrons. Thus the halogens readily form X ions. This means that
halogens generally have an oxidation state of -1 in their compounds.
With the exception of fluorine, all other halogens form compound in which they
have positive oxidation numbers up to +7. Table 12.2 shows the range of oxidation
numbers for chlorine.
Table 12.2 Oxidation numbers of chlorine
Oxidation number Examples
+7 Cl2O7, NaClO4
+6 ClO3
+5 NaClO3
+4 ClO2
+3 KClO2
+2
+1 Cl2O; NaClO
0 Cl2
—1 NaCl
12.6 Occurrence of the Halogens
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The halogens are so reactive that they cannot exist free in nature. Consequently, the
halogens always occur naturally as halides of metals.
Fluorine and chlorine are the most abundant halogens. Naturally occuring
compounds of fluorine are fluorspar, CaF2 and cryolite, Na2AlF6.
The most common chlorine compound is sodium chloride, NaCI, which occurs in
sea water and in rock salt.
Bromides and iodides occur in much smaller amounts than fluorides and
chlorides. Sea water contains only small amounts of bromide.
Iodides are even scarcer than bromides. Sea water contains traces of iodide but in
sea weeds, the iodide concentration is considerably high. Most of the iodine used today
occurs as calcium iodate, Ca(IO3)2 in the sodium nitrate deposits in Chile.
Astatine does not occur naturally at all. It is a very unstable, radioactive element.
Astatine was first synthesized by chemists in 1940, but it has never been obtained in large
amounts. The most stable isotope of astatine, is At.

12.7 Preparation of the Halogens

The halogens are usually prepared by the oxidation of the halide ions, that is,
2X X2 + 2e
Fluorine is the most powerful oxidizing agent and so fluoride ions cannot be
oxidized by any of the common chemical oxidizing agents such as concentrated sulphuric
acid, manganese (IV) oxide and potassium permanganate. That is why fluorine is
manufactured by electrolysis of fused potassium fluoride.
Chlorine, bromine and iodine are much less reactive than fluorine. They can be
prepared in the laboratory by oxidizing the appropriate halide ions by manganese (IV)
oxide in the presence of concentrated sulphuric acid. The general equation far the
preparation of the halogens is
2NaX(s) + MnO2(s) + 3H2SO4(conc) 2NaHSO4(aq) + MnSO4(aq) + 2H2O(1)
+ X2(g)

Since chlorine is a gas, bromine is a liquid and iodine is a solid at room

temperature, the apparatus used in their preparation differs from one another.
Chlorine is less reactive than fluorine. It can be obtained industrially by the
electrolysis of aqueous sodium chloride (brine).
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12.8 Physical Properties of the Halogens

Some of the physical properties of the halogens are shown in Table 12.3.

Table 12.3 Physical properties of the halogens

Element Fluorine Chlorine Bromine Iodine
Atomic number 9 17 35 53
Essential electronic structure 2s2 2p5 3s2 3p5 4s2 4p5 5s2 5p5

Relative atomic mass 19.0 35.5 79.9 126.9

State at 20°C gas gas liquid solid
Colour pale yellow pale green reddish brown shiny black

Melting point °C -220 -101 -7 113

Boiling point °C -188 -35 59 183

Solubility/g per l00g of reacts 0.59 3.6 0.018

water at 20 °C readily reacts
with slightly
water

All the halogens exist as diatomic molecules, that is, the two atoms being linked
by a covalent bond. In halogens, these diatomic molecules exist in the gaseous, liquid and
solid states.
Halogens are all coloured. The depth of colour increases as their relative atomic
mass increases. Fluorine is pale yellow, chlorine i s pale green, bromine is reddish brown
and iodine is shiny black.
As the relative atomic mass of the halogens increases, their volatility decreases.
At room temperature, fluorine and chlorine are gases, whereas bromine is a liquid and
iodine is a solid. This decrease in volatility is due to the increasing strength of van der
Waals forces with increasing relative molecular mass. That is, as the relative molecular
masses of the halogens increase, their melting points and boiling points increase as well.

12.9 Chemical Properties of the Halogens

Since the electronic structure of the halogen is ns 2 np5, the addition of one more electron
to each of the halogens will complete the outermost shell of eight electrons. That is why
in most of their compounds, halogens exist as X ions.
1. Action on metals
The halogens are very reactive with mtals. Halogens react with metals to form ionic
compounds containing the halide X ion.
2M + X2 2MX
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M + X2 MX2
The reactivity of the halogens decreases with increase in their relative atomic
masses. Fluorine is the most reactive of all the electronegative elements. Fluorine
combines readily and directly with all metals, whereas iodine reacts slowly with metals
even on heating. That is, in Group VIIB, the reactivity of the elements decreases as their
relative atomic masses increase. This trend is the reverse of that of the elements, in Group
IA. For the alkali metals, the reactivity increases as the relative atomic mass increases.
2. Action on non-metals
Fluorine reacts directly with all non-metals except nitrogen, helium, neon and argon.
Fluorine reacts even with diamond and xenon on heating.
C (diamond) + 2F2(g) CF4(g)
carbon tetrafluoride
Xe(g) + 2F2(g) XeF4(s)
xenon tetrafluoride
Fluorine attacks glass, and silica forming silicon tetrafluoride.
SiO2(s) + 2F2(s) SiF4(g) + O2(g)
silica
Chlorine and bromine are much less reactive than fluorine. They will not .react
directly with any of the noble gases, carbon, nitrogen or oxygen.
Iodine does not combine with these elements nor with sulphur, but it reacts
readily with phosphorus forming phosphorus tri iodide.
P4(s) + 6I2 (vapour) 4PI3(s)
The relative reactivity of the halogens with non-metals can be studied by their
reaction with hydrogen. Fluorine explodes with hydrogen even in the dark at -200°C.
Chlorine and hydrogen explode in bright sunlight but react slowly in the dark. Bromine
reacts with hydrogen only on heating and in the presence of a platinum catalyst. Iodine
combines only partially and slowly with hydrogen even on heating.
H2(g) + X2(g) 2HX(g)
When the halogens combine with metals or non-metals they normally act as
oxidizing agents and the elements with which they react have positive oxidation numbers
in the resultant compounds.
2Na(s) + Cl2(g) 2Na+Cl (s)
During these reactions, the halogens accept electrons and act as oxidizing agents.
X2 + 2e 2X
3. Action on water
Fluorine reacts with water vapour to form oxygen and ozone.
2F2(g) + 2H2O(g) 4HF(g) + O2(g)
3F2(g) + 3H2O(g) 6HF(g) + O3(g)
Chlorine reacts slowly with water forming hypochlorous acid and hydrochloric acid.
 223

Cl2(g) + H2O(l) HCl(aq) + HOCl(aq)

This hypochlorous acid is a very reactive compound and readily gives up its oxygen to
coloured dyes, to form colourless compounds.
dye + HOC1 HCl + (dye+O)
coloured colourless
4. Action on alkalis
Fluorine reacts with alkalis in a different way from the other halogens, forming a mixture
of fluoride and oxygen difluoride in both of which the oxidation number fluorine is -1.
2F2(g) + 2NaOH(aq) OF2(g) + 2NaF(aq) + H2O(1)
Chlorine, bromine and iodine undergo very similar reactions with alkalis, the products
depending upon the temperature at which the reaction occurs.
With cold, dilute alkali at 15°C, the halogen reacts to form a mixture of halide X
and hypohalite XO .
X2(g) + 2MOH(aq) MX(aq) + MXO (aq) + H2O
The MXO which is produced in the first reaction then decomposes to form halide X and
halite XO .
3MXO 2MX + MXO3
For chlorine, the decomposition of hypochlorite to chlorate is very slow at 15 C but rapid
at 70°C. Therefore, sodium hypochlorite can be obtained by passing chlorine into sodium
hydroxide at 15°C, while sodium chlorate is obtained carrying out the same reaction at
70°C.
With bromine, both reactions are rapid at 15°C, but decomposition of BrO is
slow at 0°C.
With iodine, the decomposition of IO occurs rapidly even at 0°C, so it is
difficult to prepare NaIO free from NalO3.
Unlike the alkali metals of Group IA which have only one oxidation number in
their compounds, the halogens, other than fluorine, have several oxidation numbers.
Their highest positive oxidation number is the same as their group number 7. But the
most stable oxidation state for the halogens is —1 and the relative stability of the —1 state
decreases as the group is descended and the electronegativity of the halogen decreases.
Fluorine, which is the most electronegative element, never shows a positive
oxidation number, since it cannot form a compound in which it is the less electronegative
element.
The relative stability of the positive oxidation states increases with increasing
relative atomic mass of the halogen. This is due to the decreasing electronegativity down
Group VIIB elements. For example, the ease of decomposition of XO into XO and X
is in the order IO > BrO > ClO suggesting that IO is relatively more stable than
BrO which in turn is more stable than ClO .
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12.10 Interhalogen Compounds

The halogens combine among themselves to give interhalogcn compounds. (See Table
12.4)
Table 12.4 The known interhalogen compounds
ClF ClF3 BrF5 IF7
BrF BrF3 IF5
BeCl ICl3
ICl
IBr

These compounds are of the type XY, XY3, XY5 and XY7. They can be prepared
by the direct combination of the corresponding halogens under suitable conditions.
Interhalogen compounds are more reactive than the elemental halogens (except fluorine),
because the heteroatomic bonds in the interhalogen compounds are weaker than the
homoatomic bond in the individual halogens.
Some physical properties and their uses are tabulated below.
Halogen Color Odour Hazard Uses
Chlorine Pale green Choking Poisonous when -To sterilize
yellow (gas) unpleasant smell inhaled water
-Bleaching agent
Bromine Reddish brown Choking irritating Causes burns on -
(liquid) smell the flesh
Iodine Shiny black Unpleasant smell - To treat small
(solid) cuts and wounds
(as antiseptic)
To treat goiter (I2
deficiency
disorder)

The general equation for the preparation of the halogen is

2 NaX(s) + MnO2(s) + 3 H2SO4(conc.) 2 NaHSO4(aq)+MnSO4(aq) + 2 H2O(l)
+ X2(g)
Action on metals, action on non-metal, action on water and action on alkalis of
halogens were presented in this chapter.
SUMMARY
Fluorine, chlorine, bromine and iodine are known as halogens. They have
oxidizing properties. Chlorine and bromine have bleaching power but iodine cannot
bleach. With the exception of fluorine, all other halogens form compound in which they
have positive oxidation numbers up to +7.The preparation, physical and chemical
properties and their uses are also presented in this chapter. Questions and problems are
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given at the end of the chapter so that students can understand and practice about
various aspects of halogens.

Questions and Problems

1. What does the term "halogen" mean?

2. What are the halogens?

3. Why are all the halogens in Group VII B of the periodic table?

4. Write the name and these members of the halogens other than chlorine.
State whether each of these halogens would react with hydrogen more vigorously
or less vigorously, than would chlorine.
5. How would prepare pure, dry chlorine? Describe what you would observe and say
what is formed when
(a) a lighted candle is placed in a jar of chlorine?
(b) chlorine is passed into a potassium iodide solution? (Candle is made of a
hydrocarbon)

6. Describe a method of manufacturing chlorine by an electrolytic process. Name the

electrolyte and give the name, sign and material of each electrode. Name also the
products for the reaction occuring at the etectrodes.

7. When dry hydrogen burns at a jet in a gas jar of dry chlorine the following
changes are observed;
(a) the colour of the chlorine disappears
(b) a gas is formed which fames in moist air and turns moist blue litmus red.
Explain these observations.

8. Chlorine can be prepared by the oxidation of concentrated hydrochloric acid.

Name three oxidizing agents which will bring about this oxidation.

9. Give equations for the three reactions which show the oxidizing property of
chlorine.

10. Write equations in words and symbols for the following reactions.
(a) Fe(s) + 3Cl2(g) ?
(b) Ca(OH)2(s) + Cl2(g) ?
(c) Cl2(s) + NaOH (aq) (dilute) ?
(d) KBr(s) + MnO2(s) + H2SO4(aq) ?
(e) NaI(aq) + Br2(g) ?
(f) H2S(g) + I2(g) ?
(g) F2(g) + H2O(g) ?
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(h) Cl2(g) + H2O(l) ?

11. How many grams of potassium chlorate will be formed when chlorine is passed
into a concentrated solution of potassium hydroxide containing 8 g of the alkali?
(K = 39, O =16, H = 1, Cl = 35.5)

12. You are shown two colourless salts which are supposed to be an alkali chloride
and an alkali iodide. How will you distinguish the two by chemical means?

13. Sea water contains about 2.5 % by mass of sodium chloride and traces of
potassium bromide. Suggest practical methods for obtaining from sea water.
(a) water, free from sodium ions and potassium ions.
(b) reasonably pure sodium chloride
(c) a sample of chlorine

14. Fluorine reacts with sodium to form fluoride. What properties would you expect
this fluoride to have?

15. Which of the naturally occurring halogens provide examples of

(a) the largest atom
(b) the smallest ionization energy and
(c) the weakest acid HX?

16. Write an account of the positive oxidation states shown by the halogens.

17. From your knowledge of the halogens, predict what happens in the following
situations and write equations for any reactions which take place. (Ignore the
radioactive nature of astatine.)
(a) Astatine vapour is mixed with hydrogen at 100°C.
(b) Astatine is added to aqueous sodium hydroxide.
(c) Concentrated sulphuric acid is added to solid sodium astatide.
(d) Aqueous silver nitrate is added to aqueous sodium astatide.

18. Fluorine, chlorine, bromine and iodine from a well-defined group of elements
known as halogens.
(a) Explain how the following support this statement :
(i) electronic structure
(ii) redox behaviour
(iii) physical properties of the elements
(iv) usual oxidation state.
(b) Describe two specific properties that show a regular gradation as the group
is descended from F to I.
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(c) How does electron affinity vary among the halogens? How is it related to
their reactivity?
(d) Fluorine shows some properties not typical of the rest of the group.
Mention three of these properties and suggest a reason or reasons for the
difference.

19. Explain the following observations.

(a) In its compounds, fluorine shows only one oxidation state, whereas
chlorine shows several.
(b) As Group VIIB of the periodic table is descended, the halogens become
weaker oxidizing agents.

20. "The relative stability of the positive oxidation states increases with increasing
relative atomic mass of the halogen". What chemical evidence can you give to
support the above statement?

21. State TRUE or FALSE for each of the following statements.

(i) All halogens always take positive oxidation number.
(ii) All halogens have similar properties but not identical.
(iii) Halogens are usually found as metal halides.
(iv) Chlorine is stronger than bromine to bleach the colour.
(v) Bromine can displace the chlorine from chloride.

22. Fill in the blanks with a suitable word or phrase or numerical value with unit as
necessary.
(i) Chlorine gas can be dried by passing through ..................
(ii) Chlorine can be collected by downward displacement of ..............
(iii) The most abundant halogen in sea water is .....:..........
(iv) In halogens ..................exists as solid at room temperature.
(v) The most abundant halogens are chlorine and .................

23. Select the correct term or terms given in the brackets.

(i) Sea weeds contain relatively high content of (chlorine, bromine, iodine).
(ii) (Chloride, Fluoride, Bromide) can not be oxidized by concentrated
sulphuric acid.
(iii) The most reactive halogen is (fluorine, chlorine, bromine).
(iv) (Chlorine, Bromine, Fluorine) never shows the positive oxidation number.
(v) (Cl2, Br2, I2) is a liquid at room temperature.

24. Match each of the, items given in List A with the appropriate item in List B.
List A List B
(a) Amalgam (i) Br2
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(b) Solvent for Iodine (ii) Cl2

(e) Sterilizing agent (iii) potassium iodide solution
(d) Halogen in solid form (iv) Na/Hg
(e) Reddish brown liquid (v) I2

25 Answer the following questions

(a) Which compound is formed when chlorine is passed over heated iron ?
Write equation in symbols only.
(b) Which of the following statements about chlorine is NOT TRUE ?
(A) In industry it is produced by the electrolysis of lime .
(B) It is used for purifying water.
(C) It is one of the most reactive of halogens.
(D) It combines directly with metals and non-metals.
(c) Which of the following pairs would react together most violently?
(A) sodium and iodine (C) magnesium and bromine
(B) potassium and chlorine (D) calcium and astatine
(d) Which of the following statements is the correct use of chlorine ?
(A) Chlorine is used in tooth paste to protect
(B) Chlorine gas is used to sterilize drinking water.
(C) Chlorine is used to make the plymer Teflon.
(D) Chlorine is used in the manufacture of fertilizers.

26. Complete the following table on halogen family.

Name Symbol State Colour
Fluorine
pale green
Br
solid
Astatine Artificial
radioactive
element., first
synthesized in
1940
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