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Group17 Notes
Group17 Notes
11 Group 17
The physical and chemical properties of the elements of Group 17 (the halogens) are
introduced in this topic.
GROUP 17
242
11 Group 17
The physical and chemical properties of the elements of Group 17 (the halogens) are introduced in this
topic.
Learning outcomes
Candidates should be able to:
11.1 Physical properties a) describe the colours and the trend in volatility of chlorine, bromine and
of the Group 17 iodine
elements b) interpret the volatility of the elements in terms of van der Waals’ forces
11.2 The chemical a) describe the relative reactivity of the elements as oxidising agents (see
properties of the also Section 6.3(f))
elements and their b) describe and explain the reactions of the elements with hydrogen
hydrides
c) (i) describe and explain the relative thermal stabilities of the hydrides
(ii) interpret these relative stabilities in terms of bond energies
11.3 Some reactions of a) describe and explain the reactions of halide ions with:
the halide ions (i) aqueous silver ions followed by aqueous ammonia
(ii) concentrated sulfuric acid
11.4 The reactions a) describe and interpret, in terms of changes of oxidation number, the
of chlorine with reaction of chlorine with cold and with hot aqueous sodium hydroxide
aqueous sodium
hydroxide
INTRODUCTION
dy the trends
the Group 17
Learning outcomes
The Halogens consist of the following elements:
ens. They are By the end of this topic you should be able to:
w decreasing • 11.1a)
Fluorine (F), the
describe Chlorine (Cl),the
colours and Bromine (Br), Iodine
trend in volatility (I) andbromine
of chlorine, Astatine
and (At).
asing proton iodine
All the halogens
11.1b) interpret consist of diatomic
the volatility molecules,
of the elements in terms of , linked
X2van by aforces
der Waals’ single
11.2a) bond.
covalent describe the relative
They are allreactivity of the elements as oxidising agents (see also
volatile.
Topic 23)
11.2b) describe
Fluorine (F)and explain
1s2 2sthe reactions
2 2p 5 of the elements with hydrogen
11.2c) describe and explain the relative thermal stabilities of the hydrides, and interpret
these relative
Chlorine (Cl) stabilities
1s2 2s2 in
2pterms of bond
6 3s2 3p 5 energies
11.3a) describe and explain the reactions of halide ions with aqueous silver ions
Bromine
followed(Br) 1s2 2sammonia,
by aqueous
2 2p6 3s2 3p6 3d10 4s2 4p5
and with concentrated sulfuric acid
11.4a) describe and interpret, in terms of changes of oxidation number, the reaction of
Iodine (I) 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 5s2 5p5
chlorine with cold, and with hot, aqueous sodium hydroxide
11.5a) explain the use of chlorine in water
1 purification
11.5b) state the industrial importance and environmental significance of the halogens
and their compounds (e.g. for bleaches, PVC, halogenated hydrocarbons as
solvents, refrigerants and in aerosols) (see also Topic 15).
Down the group the outer electrons get further and further away from the
same effective nuclear charge and so they are held less strongly and the
tendency to gain an extra electron decreases. Hence reactivity of
halogens decreases down the group.
4
The reactivity with hydrogen decreases down the group because the decreasing
strength of the H—X (HCl, HBr, HI) bond makes the reaction less exothermic.
Bromine slow reaction when heated H2 (g) + Br2 (g) ⟶ 2HBr (g) 366 kJ/mol
HYDROGEN HALIDES
The hydrogen halides are all colourless gases
Halogen Bond Energy
with the formula HX, where X stands for Cl, Br or
I. The bonds between hydrogen and the H—Cl 431 kJ/mol
halogens are polar. Hydrogen chloride, hydrogen
bromide and hydrogen iodide are similar in that
H—Br 366 kJ/mol
they are very soluble in water to form acidic
solutions that ionise completely in water.
H—I 299 kJ/mol
HYDROGEN HALIDES
The bond energies decrease going down Group Halogen Bond Energy
17, making it easier to break the H—X bond. This is
because the iodine atom is the largest atom, so H—Cl 431 kJ/mol
Worked example 7
Use the bond energies given in Table 11.1, and a value of 436 kJ mol −1 for the H¬H bond
energy in H2(g), to calculate the enthalpy change for the reaction between hydrogen and
chlorine, and between hydrogen and iodine.
on for the
and bromine Answer
e trend For H2 + Cl2 → 2HCl, ∆H = 436 + 242 − 2 × 431 = −184 kJ mol -1
For H2 + I2 → 2HI, ∆H = 436 + 151 − 2 × 299 = −11 kJ mol -1
HALIDES
Halide ions are the ions of the halogen elements in oxidation state −1. They include the
chloride, Cl−, bromide, Br−, and iodide, I− , ions.
In Group 17, a more reactive halogen oxidises the ions of a less reactive halogen. And
as halogens are oxidising agents, a halogen that is a more powerful oxidising agent
displaces one that is less powerful. For example, bromine reacts with a solution of an
iodide to produce iodine and a bromide. This is because bromine has a stronger
tendency to gain electrons and turn into ions than iodine.
But iodine will not displace bromide or chloride ions as iodine is the weakest of the
three oxidising agents.
9
Silver chloride is a white solid. This distinguishes it from silver bromide, which is a
creamy colour, and silver iodide, which is a brighter yellow.
The colour changes are not very distinct, but a further test with ammonia helps to
distinguish the precipitates. Silver chloride easily dissolves in dilute ammonia
solution. Silver bromide dissolves in concentrated ammonia solution, but silver
iodide does not dissolve in ammonia solution at all.
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of the halide ions Halide ion Appearance and formula Solubility of precipitate in NH3(aq)
248
of precipitate
Cl− white, AgCl soluble in dilute NH3(aq)
−
Br cream, AgBr soluble in concentrated NH3(aq)
−
I yellow, AgI insoluble in concentrated NH3(aq)
HALIDE REACTIONS WITH SILVER IONS
f the silver halides
de ions.
Worked example 11
Write fully balanced, and ionic, equations for the reactions between:
a HCl and AgNO3
b KI and AgNO3
Answer
onic, equations a HCl + AgNO3 → AgCl + HNO3
aqueous solutions Cl−(aq) + AgCambridge
+
(aq) → AgCl(s)International AS Level Chemistry
MgBr2, and silver b KI + AgNO3 → AgI + KNO3
I−(aq) + Ag+(aq) → AgI(s)
HALIDES AS REDUCTANTS
Halogen anions (halides) are powerful reducing agents.
This is due to halides requiring to lose only one electron to form halogens.
Down the group, reducing power increases. Hence, Fluoride ion is the
weakest reducing agent.
This is due to the fact that down a group, an increased ionic radius means
an electron can easily be removed from the halide ion.
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REDOX REACTIONS
The forward reaction is reduction of halogens, and
the backward reaction is the oxidation of halides.
• Hydrogen halides are displaced from their salts, all of which give white fumes in
air.
• Down the group halides are strong reducing agents, they can further react to
reduce the sulfuric acid into many oxidation states.
• These reactions demonstrate that the strength of the halides as reducing agents
is in the order I— > Br— > Cl—
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2HBr (g) + H2SO4 (aq) ⟶ 2H2O (l) + SO2 (g) + Br2 (g)
HI is so easily oxidised that only a trace of it is found. The sulfuric acid is reduced not
only to SO2 (+4), but further to sulfur (0), and even to hydrogen sulphide (—2).
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H2S —2
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DISPROPORTIONATION OF CHLORINE
Chlorine oxoanions form when chlorine reacts with water and alkalis. When chlorine
dissolves in water, it reacts reversibly to form a mixture of weak chloric(I) acid and
strong hydrochloric acid.
Cl2 + H2O ⇌ HCl + HOCl
This is an example of a reaction in which the same element both increases and
decreases its oxidation number.
In other words, some of the element is oxidised while the rest of the element is
reduced. Reactions of this type are called disproportionation reactions.
Bromine reacts in a similar way but to a much lesser extent. Iodine is almost insoluble
in water and hardly reacts at all.
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DISPROPORTIONATION OF CHLORINE
When chlorine dissolves in sodium (or potassium) hydroxide solution at room
temperature, it produces chlorate(I) and chloride ions.
Chlorine itself, being an element, has the oxidation number 0. In the chloride ion, it
has an oxidation number of −1. In the ClO− ion, the chlorine has an oxidation
number of +1 in order to give an overall charge of −1 on the ion. This is another
example of disproportionation.
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DISPROPORTIONATION OF CHLORINE
When chlorine is passed into hot, concentrated aqueous sodium
hydroxide, it produces sodium chloride and sodium chlorate(V).
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