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23 Group VII

23

Group VII

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23 Group VII

INTRODUCTION

Group VII elements are known as halogens. The term halogen means salt-bearing in Greek. This
term was coined by 18th century French scientists as the Group VII elements were well-known for
producing salts in their reactions with metals.
In general, the halogens comprise the most reactive group of non-metals. The halogens are so
reactive that they are not found as free elements in nature.
Consequently, the halogens always occur naturally as compounds with metals in which they are
present as negative ions; fluoride (F), chloride (Cl), bromide (Br) and iodide (I).
The last element in the Group, astatine, does not occur naturally. It has never been obtained in
anything other than minute amounts and the most stable isotope, 210At, has a half-life of only
8.3 hours.
Table 4.1 Sources and applications of halogens

Element

Main source

Principal method of manufacture

Main uses

Fluorine

Fluorspar, CaF2

Electrolysis of molten KF in HF

PTFE (or Teflon) in non-stick frying

pans; NaF in toothpastes; SF6 as an
insulating liquid

Chlorine

Rock salt, NaCl

Electrolysis of brine, NaCl(aq)

Sterilisation of water; manufacture of

HCl, bleach, disinfectants, weedkillers
and organic solvents

Bromine

Sea water

Extraction from sea water

Flame retardants and photography

Iodine

Chilean nitrates

By-product from extraction of

nitrates

Medicine, dyes and photography

4.1

ELECTRONIC STRUCTURE AND ATOMIC PROPERTIES OF HALOGENS

4.1.1

Electronic structure

Group VII elements are p-block elements, with a valence shell electronic configuration of ns2np5.
Table 4.2 Electronic configuration of halogens

Element

Electronic Configuration
2

10

10

1s 2s 2p

Cl

1s 2s 2p 3s 3p

Br

1s 2s 2p 3s 3p 3d 4s 4p

1s 2s 2p 3s 3p 3d 4s 4p 4d 5s 5p

10

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4.1.2

23 Group VII

Covalent and ionic radii

All the halogens exist as diatomic molecules, X2. The two atoms are linked by a single covalent bond.
Covalent radius is half the distance between two covalently bonded atoms in a diatomic molecule.

Figure 4.3 Covalent radius

Down the group, the number of quantum shells increases and electrons are further away from the
nucleus. Hence, covalent and ionic radii increase.
Table 4.3 Covalent and ionic radii of halogens

Cl

Br

Covalent radius /nm

0.072

0.099

0.114

0.133

Ionic radius /nm

0.133

0.181

0.196

0.222

Element

4.1.3

Bond energy

Table 4.5 Bond energies of halogens

Element
XX bond energy/ kJ mol

F2

Cl2

Br2

I2

159

242

193

151

Figure 4.6 Bond energies of halogens

Generally, the energy required to break the XX bond decreases down Group VII. An exception will
be for FF bond, whose bond strength is lower than expected.
From Cl to I, the atomic radius increases and hence orbital overlap between the atoms becomes less
effective. The bond length becomes longer, and the XX bond becomes weaker. Thus, the bond
energy decreases.
F is an exception due to its small size. The FF bond is so short that the lone pairs of electrons on the
F atoms repel one another and weaken the FF bond. Hence, the F-F bond is weaker than the ClCl
bond and less energy is needed to break it.

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23 Group VII

Lone pair-lone pair repulsion

Lone pair

Bonding pair
Figure 4.7 Repulsion of lone pairs in fluorine
(Adapted from www.chemguide.co.uk)

4.1.4

First ionisation energy

The first ionisation energy is the energy needed to remove 1 mole of electrons from 1 mole of
gaseous atoms to form 1 mole of unipositively charged gaseous ions.
X (g) X+ (g) + e
Table 4.7 First ionization energies of halogens

Cl

Br

+1681

+1251

+1140

+1008

Element
st

1 ionization Energy / kJ mol

Down the group, the atomic radius increases due to an increase in the number of quantum shells.
The distance between the outermost electron and the nucleus increases and therefore, the
electrostatic forces of attraction between the nucleus and the outermost electron is weaker. Less
energy is required to remove this electron, hence the first ionisation energy becomes less
endothermic.
4.1.5

First electron affinity

The first electron affinity is the enthalpy change when 1 mole of electrons is added to one mole of
gaseous atoms to form one mole of singly charged gaseous anions.
X (g) + e X(g)
Table 4.8 First electron affinity of halogens

Element
st

1 electron affinity/kJ mol

Cl

Br

328

349

325

295

From Cl to I, the number of quantum shells increases, hence any electron that is added to the atom
is less strongly attracted to the nucleus. The ability of the halogen atom to accept the electron
decreases, thus first electron affinity becomes less exothermic.
F is an exception due to the extremely small size of the atom. The added electron experiences very
strong repulsion from the electrons already present and hence it is less strongly attracted to the
nucleus. Thus, the first electron affinity of F is less exothermic than that for Cl.

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4.1.6

23 Group VII

Electronegativity

The electronegativity of an element refers to its ability to attract shared electrons in a covalent
bond.
Table 4.9 Electronegativity of halogens based on the Pauling scale

Cl

Br

3.98

3.16

2.96

2.66

Element
Electronegativity

The electronegativity of the halogens decreases down the group. As the atomic size increases down
the group, the distance between the bond pair and the halogen nucleus increases. As such, the
ability of the halogen to attract the shared pair of electrons in a covalent bond decreases.

4.2

PHYSICAL PROPERTIES OF GROUP VII ELEMENTS

4.2.1

Physical state and volatility

Table 4.10 Physical states, melting and boiling points of halogens

Element

No. of electrons

Melting point/ C

Boiling point/ C

Physical state at 20 C

F2

18

220

188

Gas

Cl2

34

101

35

Gas

Br2

70

59

Liquid

I2

106

114

184

Solid

The halogens exist as simple, non-polar diatomic molecules with dispersion forces existing between
molecules.
Down the group, the size of the electron cloud and hence, the polarizability of the halogen molecule
increases. Stronger dispersion forces exist between the molecules and more energy is needed to
overcome the intermolecular forces of attraction. Hence, the volatility of the halogens decreases
down Group VII, and the melting and boiling points increases down the group as well.
The increase in strength of dispersion forces down the group explains the change in physical state of
the elements down Group VII.
4.2.2

Solubility in water

Table 4.11 Solubility of halogens in water

Element
Solubility / g per 100g of
o
water at 20 C

F2

Cl2

Br2

I2

(Reacts readily
with water)

0.59 (about 30%

reacts)

3.6 (very little

reacts)

0.018 (very little

reacts)

Fluorine reacts violently with water even in the cold by oxidizing water to give hydrogen fluoride gas and a
mixture of oxygen and ozone. As such, it is not meaningful to discuss the solubility of fluorine in water.

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23 Group VII

Chlorine, bromine and iodine all dissolve in water to some extent, but there is no obvious trend in the
solubility of these elements in water, as shown in Table 4.11.
Chlorine and bromine can react with water to some extent to give a mixture of hydrochloric acid (HCl) and
chloric(I) acid (HOCl), or hydrobromic acid (HBr) and bromic(I) acid (HOBr) respectively (refer to Section
4.4.3 for the reactions of halogens in water). This disproportionation reaction is reversible, and occurs to a
much lower extent for bromine than chlorine. In the case of bromine, it is moderately soluble in water to
form a solution containing mainly molecular bromine as very little HBr and HOBr are actually formed.
Iodine dissolves only very slightly in water. However, in a solution containing iodide ions, iodine dissolves
readily to form a brown solution due to the formation of the complex ion, I3.
I2 (s) + I (aq) I3 (aq)
In the laboratory, iodine is often produced by oxidation of a solution containing I ions. As long as there are
excess I ions present, the iodine will react with them to produce I3 ions, causing the solution to turn
brown. Once the I ions have all reacted, the iodine is precipitated as a dark grey solid, because there are no
I ions left for iodine to react with to keep it in solution.
4.2.3

Solubility in non-polar solvents

Halogens, being non-polar, are more soluble in non-polar solvents such as cyclohexane and
tetrachloromethane, than polar solvents.
The halogens exist as free diatomic molecules in these non-polar solvents, just as in the gas phase.
4.2.4

Colours

The intensity of the colour of each halogen increases down the group.
Table 4.12 Colours of halogens

F2

Colour in
Colour in
gaseous state liquid state
Pale yellow

Cl2

Yellow-green

Br2

Reddish-brown

Reddishbrown

I2

Dark purple

Element

Colour in
Colour in aqueous solutions
solid state

Colourless (dilute);
Pale yellow (concentrated)

Colour in
Non-polar Solvent
Very pale yellow
Very pale green

Yellow (dilute);
Orange (Concentrated)

Orange to reddish brown

depending on
concentration

Shiny black

Pale yellow (in water);

brown (in I (aq))

Violet

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23 Group VII

4.3

PROPERTIES OF HYDROGEN HALIDES

4.3.1

Physical state

Figure 4.13 Boiling points of hydrogen halides, HX

Table 4.14 Melting and boiling points of hydrogen halides, HX

Compound

Melting point/ C

Boiling point/ C

HF

80

20

HCl

115

85

HBr

89

67

HI

51

35

All hydrogen halides are colourless gases at 25 C and fume in moist air.
From HCl to HI, the melting and boiling points increase due to increasing size of electron cloud of
the compound. The strength of van der Waals' forces increases and hence more energy is needed
to overcome these intermolecular forces during melting or boiling.
HF has abnormally high melting and boiling points due to the existence of intermolecular hydrogen
bonding which is stronger, and hence requiring more energy to overcome than van der Waals'
forces.

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4.3.2

23 Group VII

Thermal stability

Upon heating, hydrogen halides can decompose to give hydrogen and the corresponding halogen.
2HX (g) H2 (g) + X2 (g)
The thermal stability of the hydrogen halide depends on the strength of the HX bond. Down the
group, as atomic radius increases from F to I, the bond length of the HX bond increases, and hence
less energy is needed to overcome the bond as the bond strength decreases. Thus, the thermal
stability of the hydrogen halides decreases down the group.
Table 4.15 Relationship between decomposition behaviour and HX bond energy

Compound
Decomposition
behaviour

HF

HCl

HBr

HI

Does not
decompose even
on strong heating

Does not
decompose even
on strong heating

Strong heating
yields brown fumes
of Br2

Violet fumes of I2
obtained when redhot rod is plunged
into jar of HI

568

432

366

298

H-X bond energy/

kJ mol1

4.3.3

Acid strength

HCl, HBr and HI are strong acids and dissociate fully in water to give H3O+ and the corresponding
halide ion.
HX (aq) + H2O (l) H3O+ (aq) + X (aq)
X = Cl, Br or I
The acid strength increases down the group, i.e. HCl < HBr < HI. This is due to the decreasing
strength of the HX bond. A weaker HX bond breaks more easily so that H+ can be released more
readily.
An exception occurs for HF which is considered a weak acid (Ka = 5.6 104 moldm3) due to the high
strength of the HF bond amongst other factors.

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4.4

CHEMICAL PROPERTIES OF GROUP VII ELEMENTS

4.4.1

Oxidation states of Group VII elements

Table 4.16 Electronic configuration and oxidation states of halogens

Element
F

Cl

Br

Electronic Configuration
2

1s 2s 2p
2

0 or 1
2

1s 2s 2p 3s 3p

1, 0, +1, +3, +5 or +7
E.g. for iodine,

10

1s 2s 2p 3s 3p 3d 4s 4p

Oxidation state

10

10

1s 2s 2p 3s 3p 3d 4s 4p 4d 5s 5p

o.s.
I-

-1

ICl

+1

ICl3

+3

IF5

+5

IF7

+7

The most stable oxidation state of halogens is 1.

All halogens except fluorine however, can exhibit positive oxidation states of up to +7. For a halogen
to exhibit these variable oxidation states, it must be able to accommodate an expanded octet of
more than 8 valence electrons. Since chlorine, bromine and iodine have low-lying empty d orbitals
(3d, 4d and 5d respectively), they are able to accommodate an expanded octet of electrons and
hence exhibit variable oxidation states.
On the other hand, fluorine does not have any low-lying empty d-orbitals to accommodate these
extra electrons. In addition, fluorine is the most electronegative element and hence it is always
found in the 1 oxidation state in its compounds.
4.4.2

Relative oxidising power of Group VII elements

The outermost electron shell of halogens contains 7 electrons, i.e. ns2 np5. As such, their chemistry is
dominated by a tendency to gain a completely filled outermost electron shell. Hence, halogens tend
to be reduced in a redox reaction, and their oxidising power can be measured by the value of the
standard reduction potential Eo for the process:
X2 (std) + 2e 2X (aq)
Down the group, the elements become less reactive and their electron affinity decreases. The
Eo values become less positive down the group, as shown in Table 4.17. Hence, the oxidising power
of the halogens decreases down the group and they become less likely to be reduced in a redox
reaction.

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23 Group VII

Table 4.17 Standard reduction potentials of the halogens

Element
o
E /V

4.4.3

Cl2
+1.36

F2
+2.80

Br2
+1.07

I2
+0.54

Redox reactions of Group VII elements

This section describes some of the redox reactions that Group VII elements undergo. In each of
these reactions, the relative oxidizing abilities of the halogens are further emphasized.
(I)
Reactions with water
Due to the strong oxidizing power of fluorine, it reacts vigorously with water even in the cold to form
hydrogen fluoride gas and a mixture of oxygen and ozone. As such, it is impossible to perform simple
solution reactions with fluorine.
2F2 (g) + 2H2O (l) 4HF (g) + O2 (g)
3F2 (g) + 3H2O (l) 6HF (g) + O3 (g)
On the other hand, chlorine and bromine disproportionates partially in water to give HCl and HOCl,
or HBr and HOBr repectively. The extent of disproportionation of bromine in water occurs to a
smaller extent than that for chlorine.
Cl2 (g) + H2O (l) HCl (aq) + HOCl (aq)
Br2 (l) + H2O (l) HBr (aq) + HOBr (aq)

(1)
(2)

The mixture of Cl2(aq), HCl(aq) and HOCl(aq) is called chlorine water. HOCl is responsible for the
bleaching action of chlorine water. It is also an effective disinfectant and can penetrate bacterial
membranes easily and oxidize its components.

Lecture Exercise 4.1

Using the following Eo values, explain the reaction between fluorine and water.
F2 (g) + 2e 2F (aq)
O2 (g) + 4H+ (aq) + 4e 2H2O (l)
O3 (g) + 2H+ (aq) + 2e O2 (g) + H2O (l)

Eo = +2.87 V
Eo = +1.23 V
Eo = +2.08

Step 1:
2F2 (g) + 2H2O (l) 4HF (g) + O2 (g)
Ecell = +2.87 - 1.23 = +1.64 V > 0 feasible
Step 2:
F2 (g) + O2 (g) + H2O (l) 2HF (g) + O3 (g)
Ecell = +2.87 - 2.08 = +0.79 V > 0 feasible
Combining equations for Steps 1 and 2:
3F2 (g) + 3H2O (l) 6HF (g) + O3 (g)

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(II)

23 Group VII

Displacement reactions

In general, a halogen higher in the group can oxidize a halide below it. A more reactive halogen will
hence displace a less reactive one from its compounds.

Lecture Exercise 4.2

What observation would be made for the following? Explain your answer with the aid of chemical
equations, where appropriate.
(a)

Aqueous chlorine is added to a solution of KI.

Colourless solution turns reddish-brown. Chlorine is a stronger oxidizing agent than iodine.
Hence, it displaces I to form Cl and I2. The reddish-brown solution is due to a reaction
between I2 and the excess I to form I3.
Cl2 (aq) + 2I (aq) 2Cl (aq) + I2 (aq)
colourless
reddish-brown

(b)

Eocell = +1.36 0.54 = +0.82 V (feasible)

Potassium bromide solution is added over a denser layer of organic solvent in a test tube.
Chlorine is bubbled through the potassium bromide layer.
Chlorine is a stronger oxidizing agent than bromine, and hence it displaces Br to form Cl
and Br2. The Br2 formed may dissolve in the bottom organic layer to form a reddish-brown
solution, or in the top aqueous layer to form a yellow solution.
Cl2 + 2Br 2Cl + Br2

Eocell= +1.361.07 = +0.29 V (feasible)

(III)
Reactions with aqueous solutions containing iron(II) ions
In the presence of a halogen oxidizing agent, an aqueous solution of Fe2+ ions can be oxidized to Fe3+.

Lecture Exercise 4.3

By calculating the Eocell for the reaction between Fe2+ and the halogen, show that only chlorine and
bromine are able to oxidize Fe2+ while iodine will not oxidize Fe2+. (Given Eo(Fe3+/Fe2+) = +0.77V)
Equation

Eocell

Cl2 (aq) + Fe2+ (aq) 2Cl (aq) + 2Fe3+ (aq)

+1.36 0.77 = +0.59 V (feasible)

Br2 (aq) + Fe2+ (aq) 2Br (aq) + 2Fe3+ (aq)

+1.07 0.77 = +0.30 V(feasible)

I2 (aq) + 2Fe2+ (aq) 2I (aq) + 2Fe3+ (aq)

+0.54 0.77 = 0.23V (unfeasible)

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23 Group VII

(IV)
Reactions with thiosulfate, S2O32
The decrease in oxidizing power of the halogens can also be illustrated by their reaction with an
aqueous solution of thiosulfate.
Chlorine and bromine would oxidize thiosulfate to sulfate, SO42 while iodine oxidizes thiosulfate to
tetrathionate, S4O62.

Lecture Exercise 4.4

(a)

Write balanced equations for the reactions between chlorine, bromine or iodine with
thiosulfate.
4Cl2 (aq) + S2O32 (aq) + 5H2O (l) 8Cl (aq) + 2SO42 (aq) + 10H+ (aq)
+2
+6
4Br2 (aq) + S2O32 (aq) + 5H2O (l) 8Br (aq) + 2SO42 (aq) + 10H+ (aq)
+2
+6
I2 (aq) + 2S2O32 (aq) 2I (aq) + 2S4O62 (aq)
+2
+2.5

(b)

Calculate the oxidation number of sulfur in each of the reactions above, and suggest a
reason for the different sulfur-containing product formed for the reaction between iodine
and thiosulfate.
Iodine is a weaker oxidizing agent than chlorine and bromine, and hence the oxidation
number of sulfur only increases from +2 to +2.5, as compared to from +2 to +6 in the
reactions with chlorine or bromine.

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Disproportionation reactions with alkalis

Chlorine, bromine and iodine disproportionate readily in alkalis. The products formed depend on the
temparature at which the reaction occurs.
Recall from Section 4.4.3(I) that Cl2 disproportionates in water to give HCl and HOCl (Equilibrium 1).
If Cl2 was dissolved in a cold, basic solution such as NaOH (aq), Equilibrium 1 is displaced far to the
right as HCl and HOCl are neutralized. An aqueous solution of chlorate(I), ClO is formed.
15 C (cold):
Cl2 (aq) + 2OH (aq) Cl (aq) + ClO (aq) + H2O (l)

When hot alkaline solutions are treated with Cl2, the above reaction occurs but chlorate(I) is further
oxidized to chlorate(V), ClO3.
70 C (hot):
Cl2 (aq) + 2OH (aq) Cl (aq) + ClO (aq) + H2O (l)
3ClO (aq) 2Cl (aq) + ClO3 (aq)
Overall: 3Cl2 (aq) + 6OH (aq) 5Cl (aq) + ClO3 (aq) + 3H2O (l)

The reactions involving bromine and iodine are essentially similar to that for chlorine, the difference
being the temperature at which the reactions happen. The tendency to form the ion with the
halogen in the +5 oxidation state increases rapidly down the group.
With bromine, the formation of bromate(V) occurs at a much lower temperature. If a solution of
bromate(I) is required, the reaction needs to be performed at about 0C.
0 C:
Br2 (aq) + 2OH (aq) Br (aq) + BrO (aq) + H2O (l)
15 C:
Br2 (aq) + 2OH (aq) Br (aq) + BrO (aq) + H2O (l)
3BrO (aq) 2Br (aq) + BrO3 (aq)
Overall: 3Br2 (aq) + 6OH (aq) 5Br (aq) + BrO3 (aq) + 3H2O (l)

In the case of iodine, iodate(V) is obtained regardless of temperature.

I2 (aq) + 2OH (aq) I (aq) + IO (aq) + H2O (l)
3IO (aq) 2I (aq) + IO3 (aq)
Overall: 3I2 (aq) + 6OH (aq) 5I (aq) + IO3 (aq) + 3H2O (l)

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Reactions with metals

When halogens combine with metals, they act as oxidizing agents (themselves being reduced) to
form ionic compounds containing the halide ion, X. Fluorine, being the strongest oxidizing agent,
combines readily and directly, with all metals. However, other halogens do not react with unreactive
metals like gold, platinum and silver. The reactions of halogens with sodium and iron are further
elaborated below.
(I)

Reaction with sodium

All of the halogens react with sodium to produce sodium halides. In each case, the sodium burns
with a bright orange flame in the halogen vapour and a white solid product is formed at the end of
the reaction.
2Na (s) + X2 (g) 2NaX (s)

(X = F, Cl, Br, I)

Video of reaction between Na and Cl2 - http://www.youtube.com/watch?v=Mx5JJWI2aaw

(II)

Reaction with iron

With the exception of iodine, iron burns in the halogen vapour to give iron(III) halides. Iodine, being
a weaker oxidizing agent, only produces iron(II) iodide. The reaction becomes less vigorous down
the group.
2Fe (s) + 3X2 (g) 2FeX3 (s)
Fe (s) + I2 (g) FeI2 (s)

(X = F, Cl, Br)

Reactions with non-metals

With non-metals, halogens tend to form simple molecular compounds in which the halogen is linked
by a single covalent bond to the other element. Fluorine reacts directly with all non-metals except
nitrogen, helium, neon and argon. It will even react with diamond and xenon upon heating.
However, chlorine and bromine are much less reactive and will not react directly with any of the
noble gases, carbon, nitrogen or oxygen. The reactions of the halogens with phosphorus and
hydrogen are further elaborated below.

(I)

Reaction with phosphorus

All of the halogens react vigorously with phosphorus at room temperature to give, in the first
instance, phosphorus(III) halides, PX3.
2P + 3X2 2PX3
Video of reaction between red phosphorus and Br2 - http://www.youtube.com/watch?v=IVZjNeqerdk

For chlorine and bromine, there is actually a reversible reaction involving the phosphorus(III) halide
and phosphorus(V) halide. Hence, to produce PCl3 for example, it is necessary to remove it from the
reaction mixture once it is formed.
PX3 (l) +
Colorless liquid

X2 (g)

PX5 (s)
White solid (PCl5)
Yellow solid (PBr5)

X = Cl or Br

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23 Group VII

Hence, in an excess of chlorine or bromine, phosphorus reacts to form phosphorus(V) chloride or

phosphorus(V) bromide.
E.g.
2P + 5Cl2 2PCl5
(II)
Reaction with hydrogen
The reactivity of the halogens with hydrogen to form hydrogen halides decreases down the group.
This is mainly due to the decreasing bond energy of the H-X bond down the group, which causes the
enthalpy of reaction to become less exothermic. The lessening vigour of this reaction also illustrates
the decreasing oxidizing power of the halogens down the group.
H2 (g) + X2 (g) 2HX (g)
Table 4.18 Reactions of halogens with hydrogen

Halogen

F2

Cl2

Br2

I2
Reacts reversibly and
o
slowly at 300 C with Pt
catalyst. Reaction is
incomplete and an
equilibrium mixture is
obtained.

Very rapid
reaction;
explosive
reaction even in
the dark at
o
200 C

Rapid reaction;
explosive
reaction under
direct sunlight;
slow reaction in
the dark below
o
200 C

XX bond
energy/
1
kJ mol

158

244

193

151

HX bond
energy/
1
kJ mol

568

432

366

298

H reaction /
1
kJ mol

271

93

36

+26

Vigour of
reaction

Slow reaction;
o
heat at 300 C
with Pt catalyst

H2 + I2 2HI

Reasons for the exceptional reactivity of fluorine with hydrogen are the low FF bond
energy, and high HF bond energy, which leads to a very exothermic enthalpy change of
reaction.

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4.5

REACTIONS OF HALIDE IONS

4.5.1

Precipitation reactions

This section describes some of the precipitation reactions that halide ions undergo.
Reaction with aqueous silver nitrate
Silver halide (other than silver fluoride), is precipitated when halide ions react with aqueous silver
nitrate.
Ag+ (aq) + X (aq) AgX (s) ------------------------ (a)
The subsequent addition of ammonia
diammine silver(I) complex, [Ag(NH3)2]+.

results

in

the

formation

of

the

stable

Ag+ (aq) + 2NH3 (aq) [Ag(NH3)2]+ (aq) --------- (b)

Addition of NH3 shifts the position of equilibrium (b) to the right, causing [Ag+] to decrease. This in
turn causes the position of equilibrium (a) to shift to the left, hence increasing the solubility of AgX.
The solubility of the silver halides in ammonia depends on the Ksp of the silver halides, which are low
and decrease in the order: AgCl > AgBr > AgI. To be soluble, the ionic product, [Ag+][X], must not
exceed Ksp.
For AgCl, when dilute NH3 is added, the precipitate becomes soluble as the ionic product is smaller
than Ksp of AgCl.
For AgBr, despite its lower Ksp, the ionic product is still greater than Ksp when dilute NH3 is added.
Hence, the precipitate remains insoluble in dilute NH3. However, when concentrated NH3 is added, it
will sufficiently lower [Ag+] such that the ionic product becomes smaller than Ksp and the precipitate
dissolves.
For AgI, the value of Ksp is extremely low, thus the ionic product is greater than Ksp regardless of the
concentration of NH3. Hence the precipitate remains insoluble when dilute or concentrated NH3 is
added.
The table below summarizes the reaction of the halide ions with aqueous silver nitrate and the
subsequent solubility of the silver halides in dilute and concentrated ammonia.
Table 4.19 Reactions of halides with aqueous silver nitrate

Halide ion

F (aq)

Cl (aq)

Br (aq)

I (aq)

Reaction with AgNO3 (aq)

No ppt

White ppt

Cream ppt

Yellow ppt

(i) in dilute NH3

Soluble

Insoluble

Insoluble

(ii) in conc. NH3

Soluble

Soluble

Insoluble

Solubility of
AgX

Ksp of AgX/ mol dm

10

1.6 10

13

7.7 10

17

8.3 10

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Reaction with aqueous solutions of lead(II) ions

Lead(II) halides are precipitated when aqueous solutions of halides are treated with Pb2+ (aq).
Pb2+ (aq) + 2X (aq) PbX2 (s)
White ppt (X = F, Cl, Br)
Yellow ppt (X = I)
The ppt formed may become soluble upon addition of excess halide ions due to the formation of the
soluble [PbX4]2 complex ion.
Pb2+ (aq) + 4X (aq) [PbX4]2 (aq)
4.5.2

Reaction of solid halides with concentrated acids

With concentrated sulfuric acid

When concentrated sulfuric acid is added to solid halides, a H+ ion is donated to the halide ion to
produce a hydrogen halide. This is an acid-base reaction. Being relatively volatile, the hydrogen
halides are evolved as gases, and white misty fumes are observed in moist air.
NaX (s) + H2SO4 (l) HX (g) + NaHSO4 (s)
However, concentrated sulfuric acid is also an oxidizing agent and it is sufficiently strong to oxidize
HBr and HI (but not HF and HCl) to Br2 and I2 respectively. This is a redox reaction where the
hydrogen halide is oxidized while sulfuric acid is reduced. The reducing power and the ease of
oxidation of hydrogen halides increase down the group. Hence, HI is readily oxidized by
concentrated sulfuric acid, while HBr is oxidized to a lesser extent than HI. The reducing power of
HCl and HF is too low to cause a redox reaction to occur with concentrated sulfuric acid.

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The table below summarizes the reactions of halide ions with concentrated sulfuric acid.
Table 4.20 Reactions of halides with concentrated sulfuric acid

Halide (solid)

Products formed

Equations and observations

HF (g)

NaF (s) + H2SO4 (l) HF (g) + NaHSO4 (s)

Observation: White fumes of HF evolved.

Cl

HCl (g)

NaCl (s) + H2SO4 (l) HCl (g) + NaHSO4 (s)

Observation: White fumes of HCl evolved.

Br

HBr (g)
+ a little Br2(g)

NaBr (s) + H2SO4 (l) HBr (g) + NaHSO4 (s)

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

Observations: White fumes of HBr and some red-brown fumes of
Br2 evolved.
NaI (s) + H2SO4 (l) HI (g) + NaHSO4 (s)
2HI (g) + H2SO4 (l) I2 (g) + SO2 (g) + 2H2O (l)

A little HI (g)
+ I2(g)

6HI (g) + H2SO4 (l) 3I2 (g) + S (s) + 4H2O (l)

8HI (g) + H2SO4 (l) 4I2 (g) + H2S (g) + 4H2O (l)
Observations: Violet fumes of I2 and some white fumes of HI
evolved. Some I2(g) may condense into black I2 solid. Pungent SO2
or H2S and yellow solid of S may be produced.

With concentrated sulfuric acid in the presence of MnO2

MnO2 is a stronger oxidising agent than concentrated sulfuric acid and hence it can oxidise HCl (g) to Cl2(g).
NaCl (s) + H2SO4 (l) HCl (g) + NaHSO4 (s)
4HCl (g) + MnO2 (s) Cl2 (g) + MnCl2 (s) + 2H2O (l)
With concentrated phosphoric acid
If HBr and HI are to be obtained from NaI and NaBr respectively, concentrated phosphoric acid, H3PO4 can
be used instead of concentrated sulfuric acid because H3PO4 is a weaker oxidizing agent, hence it will not
oxidise HBr and HI.
NaI (s) + H3PO4 (l) HI (g) + NaH2PO4 (s)
NaBr (s) + H3PO4 (l) HBr (g) + NaH2PO4 (s)

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Lecture Exercise 4.5

Astatine (At) is the element below iodine in the Periodic Table. Predict what happens when concentrated
sulfuric acid is added to solid sodium astatide. Write equations for the reactions that take place.
NaAt(s) + H2SO4(l) HAt(g) + NaHSO4(s)
2HAt(g) + H2SO4(l) At2(s) + 2H2O(l) + SO2(g)
As the reducing power of At is high, H2S or even S, may result.
8HAt(g) + H2SO4(l) 4At2(s) + 4H2O(l) + H2S(g)
6HAt(g) + H2SO4(l) 3At2(s) + 4H2O(l) + S(s)

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