P VII Lecture Notes
P VII Lecture Notes
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
Main uses
Fluorine
Fluorspar, CaF2
Electrolysis of molten KF in HF
Chlorine
Bromine
Sea water
Iodine
Chilean nitrates
4.1
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
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.
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
0.072
0.099
0.114
0.133
0.133
0.181
0.196
0.222
Element
4.1.3
Bond energy
Element
XX bond energy/ kJ mol
F2
Cl2
Br2
I2
159
242
193
151
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
Bonding pair
Figure 4.7 Repulsion of lone pairs in fluorine
(Adapted from www.chemguide.co.uk)
4.1.4
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
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
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
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
4.2.1
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
Element
Solubility / g per 100g of
o
water at 20 C
F2
Cl2
Br2
I2
(Reacts readily
with water)
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
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)
Shiny black
Violet
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23 Group VII
4.3
4.3.1
Physical state
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
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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23 Group VII
4.4
4.4.1
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 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
Element
o
E /V
4.4.3
Cl2
+1.36
F2
+2.80
Br2
+1.07
I2
+0.54
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.
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.
(b)
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
(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+.
Eocell
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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.
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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23 Group VII
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)
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23 Group VII
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)
(II)
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)
(I)
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
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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23 Group VII
4.5
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
Halide ion
F (aq)
Cl (aq)
Br (aq)
I (aq)
No ppt
White ppt
Cream ppt
Yellow ppt
Soluble
Insoluble
Insoluble
Soluble
Soluble
Insoluble
Solubility of
AgX
10
1.6 10
13
7.7 10
17
8.3 10
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23 Group VII
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23 Group VII
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
HF (g)
Cl
HCl (g)
Br
HBr (g)
+ a little Br2(g)
A little HI (g)
+ I2(g)
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23 Group VII
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