11

11.1 Physical Properties of Group 17 Elements

11.2 Chemical Properties of the Elements and their Hydrides
11.3 Redox Reactions of Halogens and Halide Ions
11.4 Other Reactions and Uses of Halogens

11.1 Physical Properties of Group 17 Elements

 There are five halogens: fluorine, chlorine, bromine, iodine and astatine. Astatine is radioactive, with a
very short half-life; fluorine is supremely reactive – the most chemically reactive of all elements. The
focus here is on the chemistry of chlorine, bromine and iodine.

Structure and Bonding

 The halogens have a simple molecular structure, with weak intermolecular forces (van der Waal’s
forces) between the molecules. The molecules are diatomic, for example, 𝐶𝑙2 .

 The atoms within each molecule are joined by a single covalent bond.

Colour and Appearance

 The colour becomes darker down the Group.

𝑪𝒍𝟐 𝑩𝒓𝟐 𝑰𝟐
Colour in pure form Pale green Red-brown Grey
Colour in aqueous solution Pale green Orange Brown
Table 11.1 Colour and appearance of Group 17 elements

Volatility
 As the number of electrons in the molecule increases down the group, the strength of the van der
Waals’ increases. Hence volatility decreases down the group.

𝑪𝒍𝟐 𝑩𝒓𝟐 𝑰𝟐
State at room temperature Gas Liquid Solid
Boiling point/ ˚C −34 59 184
Table 11.2 Physical state of the halogens at room conditions

Electronegativity
 Electronegativity is the ability of an atom to attract to electrons in a covalent bond. The halogens
become less electronegative down the Group, as the atomic size and number of shells increase.

 Fluorine is the most electronegative of all known elements.

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11.2 Chemical Properties of Group 17 Elements
Hydrogen Halides
a) Formation of Hydrogen Halides
 The hydrogen halides all form by direct combination of the elements. They are all white fumes.

 Chlorine reacts with hydrogen explosively in sunlight at room temperature or when heated. White
fumes of 𝐻𝐶𝑙 are observed:
𝑪𝒍𝟐 (𝒈) + 𝑯𝟐 (𝒈) 𝟐𝑯𝑪𝒍(𝒈)

 Bromine reacts reversibly with hydrogen at 200 ˚C in the presence of a platinum catalyst. White fumes
of 𝐻𝐵𝑟 are observed:
𝑩𝒓𝟐 (𝒈) + 𝑯𝟐 (𝒈) 𝟐𝑯𝑩𝒓(𝒈)

 Iodine also reacts reversibly and only at above 400 ˚C, also in the presence of a platinum catalyst.
White fumes of 𝐻𝐼 are observed:
𝑰𝟐 (𝒈) + 𝑯𝟐 (𝒈) 𝟐𝑯𝑰(𝒈)

b) Stability of Hydrogen Halides

 When heated, the 𝐻 − 𝑋 bond breaks and the hydrogen halide decomposes to hydrogen and the
halogen gas.

 Hydrogen iodide is easily decomposed into its elements by plunging a red hot wire into a test-tube
of the gas. Violet fumes of iodine are observed.

𝟐𝑯𝑰(𝒈) 200 ˚C 𝑰𝟐 (𝒈) + 𝑯𝟐 (𝒈)

 Hydrogen bromide decomposes at around 600˚C, depending on the exact temperature of the wire.
Hydrogen chloride is not decomposed until around 2000˚C.

 These observations show that the relative thermal stabilities of hydrogen halides decrease down the
Group. Going down the Group, the atomic size of the halogen atom increases, hence the 𝐻 − 𝑋 bond
gets longer and easier to break:

𝑯 − 𝑪𝒍 𝑯 − 𝑩𝒓 𝑯−𝑰
Bond energy/ 𝐤𝐉𝐦𝐨𝐥−𝟏 431 366 299
Table 11.3 Bond energies of the hydrogen halides

c) Acidity of Hydrogen Halides

 Hydrogen halides readily dissolve in water to form hydrohalic
(hydrofluoric, hydrochloric, hydrobromic, hydroiodic) acids.
𝑯𝑪𝒍(𝒂𝒒) + 𝑯𝟐 𝑶(𝒍) 𝑿− (𝒂𝒒) + 𝑯𝟑 𝑶+ (𝒂𝒒)

 The acids formed are all strong, except 𝐻𝐹. The acidity of the hydrohalic acids increases in the
order: 𝐻𝐹 < 𝐻𝐶𝑙 < 𝐻𝐵𝑟 < 𝐻𝐼 - the ability to donate a proton increases with increasing bond
length.

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11.3 Redox Reactions of Halogens and Halides
a) Halogens - Oxidising Agents
 The halogens are oxidising agents (electron acceptors), as they need an electron to complete the
octet.

 Oxidising strength decreases down the Group as the number of shells increases and the ability to
attract electrons therefore decreases. Therefore, chlorine is a stronger oxidising agent than bromine
and iodine.

 The oxidizing trend of the halogens is supported by electrode potential values. The 𝐸 𝜃 values become
more negative down the Group, showing the decreasing tendency of the halogens to accept electrons.
𝑪𝒍𝟐 + 𝟐𝒆− 𝟐𝑪𝒍− 𝑬𝜽 = +𝟏. 𝟑𝟔 𝑽
𝑩𝒓𝟐 + 𝟐𝒆− 𝟐𝑩𝒓− 𝑬𝜽 = +𝟏. 𝟎𝟖 𝑽
𝑰𝟐 + 𝟐𝒆− 𝟐𝑰− 𝑬𝜽 = +𝟎. 𝟓𝟒 𝑽

b) Halide Ions – Reducing Agents

 The halide ions are reducing agents – they donate electrons.

 Since oxidising strength decreases in the order 𝐶𝑙2 > 𝐵𝑟 > 𝐼2 , reducing strength increases down the
Group. Iodide ions are stronger reducing agents than bromide or chloride ions.

 The 𝐸 𝜃 values become more positive down the Group, showing the increasing ability of the halide ion
to donate electrons. Hence the halide ions become stronger reducing agents going down the Group.
𝟐𝑪𝒍− 𝑪𝒍 + 𝟐𝒆− 𝑬𝜽 = −𝟏. 𝟑𝟔 𝑽
𝟐𝑩𝒓− 𝑩𝒓𝟐 + 𝟐𝒆− 𝑬𝜽 = −𝟏. 𝟎𝟖 𝑽
𝟐𝑰− 𝑰𝟐 + 𝟐𝒆− 𝑬𝜽 = −𝟎. 𝟓𝟒 𝑽

c) Displacement Reactions Between Halogens and Halide Ions

 The displacement reactions of halogens with halide ions clearly illustrate the trends in oxidizing
properties of the halogens and the trends in reducing properties of the halide ions in aqueous
solution.

 The more reactive halogens (i.e. the strongest oxidising agents) will displace the more reactive halides
(i.e. the strongest reducing agents) from solutions of their ions:
1. Chlorine will displace bromide and iodide ions from solution.
2. Bromine will displace iodide ions from solution, but not chloride ions.
3. Iodine cannot displace either bromide or chloride ions from solution.

 An orange colour of aqueous bromine will appear on adding chlorine to an aqueous bromide solution:
𝑪𝒍𝟐 (𝒈) + 𝟐𝑩𝒓− (𝒂𝒒) 𝟐𝑪𝒍− (𝒂𝒒) + 𝑩𝒓𝟐 (𝒂𝒒)

 A brown colour of aqueous iodine will appear on adding chlorine to an aqueous iodide solution:
𝑪𝒍𝟐 (𝒈) + 𝟐𝑰− (𝒂𝒒) 𝟐𝑪𝒍− (𝒂𝒒) + 𝑰𝟐 (𝒂𝒒)

 A brown colour of aqueous iodine will appear on adding bromine to an aqueous iodide solution:
𝑩𝒓𝟐 (𝒈) + 𝟐𝑰− (𝒂𝒒) 𝟐𝑩𝒓− (𝒂𝒒) + 𝑰𝟐 (𝒂𝒒)

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d) Reactions of Halide Ions with Silver Ions

 The silver (I) ion, 𝐴𝑔+ , forms insoluble precipitates with the chloride, bromide and iodide ions. These
precipitation reactions can be used as tests for halide ions, because each precipitate has its
characteristic colour.

 Procedure:
1. Make up a sample of the solution to be tested. Place 1 cm depth of this solution into a test tube.
2. To this solution, add a few drops of aqueous silver nitrate, and a little nitric acid. (The nitric acid
removes any other ions such as carbonate or hydroxide ions as carbon dioxide and water so that
they do not interfere with the precipitate.)

 Any chloride ions present will form a white precipitate; bromide ions form a cream precipitate; iodide
ions form a cream precipitate. These precipitates look fairly similar in colour, so a distinguishing test
is further done by adding ammonia solution:

Ion Add 𝑨𝒈𝑵𝑶𝟑 (𝒂𝒒) Add 𝑵𝑯𝟑 (𝒂𝒒)

White precipitate of silver chloride Precipitate dissolves in dilute ammonia:
𝑪𝒍− 𝑨𝒈+ (𝒂𝒒) + 𝑪𝒍− (𝒂𝒒) 𝑨𝒈𝑪𝒍(𝒔) 𝑨𝒈𝑪𝒍(𝒔) + 𝟐𝑵𝑯𝟑 (𝒂𝒒) 𝑨𝒈(𝑵𝑯𝟑 )+ −
𝟐 (𝒂𝒒) + 𝑪𝒍 (𝒂𝒒)

Cream precipitate of silver bromide Precipitate does not dissolve in dilute ammonia, but
𝑩𝒓 −
𝑨𝒈+ (𝒂𝒒) + 𝑩𝒓− (𝒂𝒒) 𝑨𝒈𝑩𝒓(𝒔) dissolves in concentrated ammonia:
𝑨𝒈𝑩𝒓(𝒔) + 𝟐𝑵𝑯𝟑 (𝒂𝒒) 𝑨𝒈(𝑵𝑯𝟑 )+ −
𝟐 (𝒂𝒒) + 𝑩𝒓 (𝒂𝒒)
Yellow precipitate of silver iodide Precipitate does not dissolve in dilute or concentrated
𝑰− 𝑨𝒈+ (𝒂𝒒) + 𝑰− (𝒂𝒒) 𝑨𝒈𝑰(𝒔) ammonia.

Table 11.4 Qualitative aspects of halide ions

e) Reactions of Halide Ions with Concentrated Sulphuric Acid

 These are redox reactions, where some halide ions may be oxidised by concentrated sulphuric acid,
while the halide ions reduce the sulphuric acid.

 When concentrated sulphuric acid acts as an oxidising agent, it is itself reduced to sulphur dioxide,
sulphur or hydrogen sulphide:
𝑯𝟐 𝑺𝑶𝟒 + 𝟐𝑯+ + 𝟐𝒆− 𝑺𝑶𝟐 + 𝟐𝑯𝟐 𝑶 (𝑆 is reduced from +6 to +4)
+
𝑯𝟐 𝑺𝑶𝟒 + 𝟔𝑯 + 𝟔𝒆 −
𝑺 + 𝟒𝑯𝟐 𝑶 (𝑆 is reduced from +6 to 0)
𝑯𝟐 𝑺𝑶𝟒 + 𝟖𝑯+ + 𝟖𝒆− 𝑯𝟐 𝑺 + 𝟒𝑯𝟐 𝑶 (𝑆 is reduced from +6 to −2)

Ion Reaction with concentrated 𝑯𝟐 𝑺𝑶𝟒

𝐶𝑙 − is not a strong reducing agent, and so is not oxidised by 𝐻2 𝑆𝑂4 . This is only an acid-
base reaction, not redox.
𝑯𝟐 𝑺𝑶𝟒 + 𝑪𝒍− 𝑯𝑺𝑶𝟒− + 𝑯𝑪𝒍
𝑪𝒍− For example,
𝑯𝟐 𝑺𝑶𝟒 + 𝑵𝒂𝑪𝒍 𝑵𝒂𝑯𝑺𝑶𝟒 + 𝑯𝑪𝒍
Observation:

 White acidic fumes of 𝐻𝐶𝑙 which turn damp blue litmus paper red.

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 𝐵𝑟 − is a stronger reducing agent than 𝐶𝑙 − but only reduces the sulphur from +6 in the
𝐻2 𝑆𝑂4 to +4 in 𝑆𝑂2 . The redox reaction takes place to an extent:
𝑯𝟐 𝑺𝑶𝟒 + 𝑩𝒓− 𝑯𝑺𝑶𝟒− + 𝑯𝑩𝒓 (𝑎𝑐𝑖𝑑 − 𝑏𝑎𝑠𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛)
+ −
𝑯𝟐 𝑺𝑶𝟒 + 𝟐𝑯 + 𝟐𝑩𝒓 𝑺𝑶𝟐 + 𝑩𝒓𝟐 + 𝟐𝑯𝟐 𝑶 (𝑟𝑒𝑑𝑜𝑥 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛)
𝑩𝒓− Observations:

 White acidic fumes of 𝐻𝐵𝑟 which turn damp blue litmus paper red brown vapour
of bromine will also be seen

𝐼 − is a good reducing agent, reducing the sulphur in the 𝐻2 𝑆𝑂4 from +6 to −2 (𝐻2 𝑆).
The redox reaction takes place to a much greater extent:
𝑯𝟐 𝑺𝑶𝟒 + 𝑰− 𝑯𝑺𝑶𝟒− + 𝑯𝑰 (𝑎𝑐𝑖𝑑 − 𝑏𝑎𝑠𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛)
+ −
𝑯𝟐 𝑺𝑶𝟒 + 𝟔𝑯 + 𝟔𝑰 𝑺 + 𝟑𝑰𝟐 + 𝟒𝑯𝟐 𝑶 (𝑟𝑒𝑑𝑜𝑥 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛)
𝑯𝟐 𝑺𝑶𝟒 + 𝟖𝑯+ + 𝟖𝑰− 𝑯𝟐 𝑺 + 𝟒𝑰𝟐 + 𝟒𝑯𝟐 𝑶 (𝑟𝑒𝑑𝑜𝑥 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛)
𝑰− Observations:

 White acidic fumes of 𝐻𝐼 which turn damp blue litmus paper red.

 purple iodine vapour

 a smell of bad eggs due to the presence of 𝐻2 𝑆.

Table 11.5 Reactions of halide ions with concentrated sulphuric acid

11.4 Other Reactions and Uses of Halogens

a) Reaction with water
 Chlorine dissolves slightly in water to give a green solution. A reversible disproportionation reaction
takes place to produce a mixture of hydrochloric acid and chloric (I) acid (also called hypochlorous
acid), of pH around 2.
𝑪𝒍𝟐 (𝒈) + 𝑯𝟐 𝑶(𝒍) 𝑯𝑪𝒍(𝒂𝒒) + 𝑯𝑶𝑪𝒍(𝒂𝒒)
(𝟎) (−𝟏) (+𝟏)

 The chlorine is simultaneously oxidised from (0) to (+1) and reduced from (0) to (−1).

 Chloric (I) acid is a mild oxidising agent and effective at killing bacteria without being harmful to
humans. For this reason a small amount of chlorine dissolved in water is used to purify water for
human consumption and for swimming pools. Only small doses are used, as chlorine can be toxic in
higher doses.

b) Reactions with sodium hydroxide

 Chlorine disproportionates readily in dilute sodium hydroxide solution, forming sodium chloride and
sodium chlorate (I) among other products. Higher oxidation states chlorates form at high temperature:
𝑪𝒍𝟐 (𝒈) + 𝟐𝑵𝒂𝑶𝑯(𝒂𝒒) 𝑵𝒂𝑪𝒍(𝒂𝒒) + 𝑵𝒂𝑪𝒍𝑶(𝒂𝒒) + 𝑯𝟐 𝑶(𝒍) (cold)
sodium chlorate (I)

𝟐𝑪𝒍𝟐 (𝒈) + 𝟒𝑵𝒂𝑶𝑯(𝒂𝒒) 𝟑𝑵𝒂𝑪𝒍(𝒂𝒒) + 𝑵𝒂𝑪𝒍𝑶𝟐 (𝒂𝒒) + 𝟐𝑯𝟐 𝑶(𝒍) (warm)

sodium chlorate (III)

𝟑𝑪𝒍𝟐 (𝒈) + 𝟔𝑵𝒂𝑶𝑯(𝒂𝒒) 𝟓𝑵𝒂𝑪𝒍(𝒂𝒒) + 𝑵𝒂𝑪𝒍𝑶𝟑 (𝒂𝒒) + 𝟑𝑯𝟐 𝑶(𝒍) (hot)

sodium chlorate (V)

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 Sodium chlorate (I) is the active ingredient in household bleach.

 The tendency to form the ion with the halogen in the +5 oxidation state increases down the group:
with bromine, the formation of the sodium bromate (V) happens at room temperature, while sodium
iodate (V) forms at even 0 °𝐶.

Uses of the Halogens and their Compounds

 The most common use of fluorine is to make Teflon (a non-sticky coating for pans and cookware), and
as a fluoride in toothpaste (to prevent dental cavities). In some countries, fluorine is added to the
water supply to reduce tooth decay.
Fluorides are used to make many everyday products, including toothpaste, vitamin supplements, and
baby formulas.

 The most common use of chlorine is for the purification of drinking water and swimming pool water.
It is also used to make bleaches, treat waste water and sewage, and making polymers such as PVC
(poly vinyl chloride). PVC is used for making hoses, pipes, and electric cables. Chlorine is also used in
bromine extraction from sea water.

 Bromine is used to disinfect water, as it can kill the bacteria present in water.
It is also used in fumigants and flame proofing agents.

 Iodine is essential for the functioning of the body's thyroid gland. Without iodine, thyroid hormones
cannot be produced, which leads to hypothyroidism. The deficiency of iodine in the human body can
lead to 'goiter', a thyroid disease.

 Iodine has been very useful in treating acne. Iodine can also be used as a water purifying agent. It is
also used as a sterilizing agent.

 Iodoform, a compound consisting of iodine atoms, is used to treat many conditions like tuberculosis,
diabetes, bronchitis, and syphilis.

 Silver iodide is used in photography.

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 Examination Practice 11
Section A: MULTIPLE CHOICE

1. Which graph correctly shows the variation in the electronegativity, E, of the Group VII elements?

2. Which property of the halogens increases from fluorine to iodine?

A. The electronegativity of the element
B. The bond length of the halogen molecule
C. The oxidising power of the element
D. The first ionisation energy of the element

3. The given table shows the results obtained when the halogens 𝑋2 , 𝑌2 , and 𝑍2 were added to separate
aqueous solutions 𝑋 − , 𝑌 − and 𝑍 − ions.

𝑿− (𝒂𝒒) 𝒀− (𝒂𝒒) 𝒁− (𝒂𝒒)

𝑿𝟐 no reaction no reaction no reaction
𝒀𝟐 𝑋2 formed no reaction 𝑍2 formed
𝒁𝟐 𝑋2 formed no reaction no reaction

Which set correctly shows the strength (strongest first) of the ions , 𝑌 − and 𝑍 − as reducing agents?

strongest weakest
A 𝑋− 𝑌− 𝑍−
B 𝑋− 𝑍− 𝑌−
C 𝑌 −
𝑍 −
𝑋−
D 𝑍− 𝑋− 𝑌−
4. Which properties are greater in magnitude for fluorine than for chlorine?
1. Standard electrode potential, 𝐸 𝜃 for 𝑋2 /2𝑋 −
2. Boiling point of the element 𝑋2
3. Ionic radius of the 𝑋 − ion
Which of the following is the correct option?
A. 1, 2 and 3 are correct
B. 1 and 2 only are correct
C. 2 and 3 only are correct
D. 1 only is correct

5. Consider the following reactions:

𝑪𝒍𝟐 (𝒈) + 𝟐𝑯𝟐 𝑶(𝒍) + 𝑺𝑶𝟐 (𝒈) 𝟐𝑯𝑪𝒍(𝒂𝒒) + 𝑯𝟐 𝑺𝑶𝟒 (𝒂𝒒)
𝑪𝒍𝟐 (𝒈) + 𝑯𝟐 𝑺(𝒈) 𝟐𝑯𝑪𝒍(𝒂𝒒) + 𝑺(𝒔)
𝑺𝑶𝟐 (𝒈) + 𝟐𝑯𝟐 𝑺(𝒍) 𝟐𝑯𝟐 𝑶(𝒍) + 𝟑𝑺(𝒔)
What can be deduced about the strength of the three reacting gases as reducing agents?
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 strongest weakest
A. chlorine hydrogen sulphide sulphur dioxide
B. chlorine sulphur dioxide hydrogen sulphide
C. hydrogen sulphide sulphur dioxide chlorine
D. sulphur dioxide hydrogen sulphide chlorine

6. Which of the following is the strongest reducing agent?

A. 𝐵𝑟 − (𝑎𝑞) B. 𝐵𝑟2 (𝑙) C. 𝐼 − (𝑎𝑞) D. 𝐼2 (𝑠)

7. Which of the following correctly describe the trends in the properties of the halogens?
1. The electronegativity decreases on descending the group
2. The volatility decreases on descending the group
3. Their reactivity as oxidising agents decrease on descending the group
Which of the following is the correct option?
A. 1, 2 and 3 are correct
B. 1 and 2 only are correct
C. 2 and 3 only are correct
D. 1 only is correct

8. Hydrogen iodide is a stronger acid than hydrogen chloride.

Which of the following explains this observation?
A. The dissociation of hydrogen chloride is suppressed by hydrogen bonding
B. The hydrogen chloride molecule is more polar than the hydrogen iodide molecule
C. The enthalpy change of hydration of the iodide ion is greater than that of the chloride ion
D. The covalent bond in the HI molecule is weaker than that in the hydrogen chloride molecule

9. Which properties of the hydrogen halides decrease on descending Group VII?

1. Bond energy of the hydrogen-halogen bond
2. Thermal stability
3. Boiling point
Which of the following is the correct option?
A. 1, 2 and 3 are correct
B. 1 and 2 only are correct
C. 2 and 3 only are correct
D. 1 only is correct

10. Which properties show an increasing trend for the sequence hydrogen chloride, hydrogen bromide, and
hydrogen iodide?
1. Thermal stability
2. Bond length
3. Ease of oxidation
Which of the following is the correct option?
A. 1, 2 and 3 are correct
B. 1 and 2 only are correct
C. 2 and 3 only are correct
D. 1 only is correct

11. On contact with a hot glass rod, which gaseous hydride most readily decomposes into its elements?
A. ammonia B. hydrogen chloride C. hydrogen iodide D. methane

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12. Which of the following are correct statements for the sequence 𝐻𝐶𝑙 – 𝐻𝐵𝑟 – 𝐻𝐼?
1. The enthalpy change of formation becomes less exothermic
2. The polarity of the hydrogen halide molecule increases
3. The thermal stability of the hydrogen halide increases
Which of the following is the correct option?
A. 1, 2 and 3 are correct
B. 1 and 2 only are correct
C. 2 and 3 only are correct
D. 1 only is correct

13. When a glass rod is inserted into a gas jar of hydrogen iodide, an immediate reaction takes place as the
hydrogen iodide decomposes.
Which of the following are correct statements about this reaction?
1. Hydrogen iodide is purple coloured
2. The hot rod provides the activation energy
3. One of the products is a solid
Which of the following is the correct option?
A. 1, 2 and 3 are correct
B. 1 and 2 only are correct
C. 2 and 3 only are correct
D. 1 only is correct

14. An excess of aqueous silver nitrate is added to an aqueous solution containuing both potassium
chloride and potassium iodide. The precipitate formed is filtered off and washed with distilled water.
The precipitate is then shaken withaqueous ammonia and filtered off again.
Which ion is present in the final filtrate?
A. Chloride B. iodide C. potassium D. silver

15. In an experiment, aqueous silver nitrate is treated with successive additioons of

(i) An excess of aqueous potasssium chloride
(ii) An excess of aqueous ammonia
(iii) An excess of aqueous potassium bromide
Which diagram correctly represents the mass of precipitate (ppt) present after each additiion?

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 Section B: FREE RESPONSE

16. The elements of Group VII of the Periodic Table show variation in their properties.
(a) (i) Copy and complete the table below, stating the colour of each element in its normal state at
room temperature.
halogen melting point / ℃ colour
Chlorine −101
Bromine −7
Iodine 114

(ii) Briefly explain why the melting points of the halogens increase from chlorine to iodine.
[4]
(b) The halogens form many interhalogen compounds in which two different halogens are combined.
One such compound is bromine monochloride, 𝐵𝑟𝐶𝑙.
(i) Write the electronic configurations of chlorine and bromine.
(ii) Draw a 'dot-and-cross' diagram of the 𝐵𝑟𝐶𝑙 molecule.
Show outermost electrons only.
[2]
(c) Interhalogen compounds like 𝐵𝑟𝐶𝑙 have similar properties to the halogens.
(i) By considering your answers to (a) and (b), predict the physical state of 𝐵𝑟𝐶𝑙 at room
temperature. Explain your answer.
(ii) Suggest the colour of 𝐵𝑟𝐶𝑙.
[4]
(d) 𝐶𝑙2 and 𝐵𝑟𝐶𝑙 each react with aqueous 𝐾𝐼.
(i) Describe what would be seen when 𝐶𝑙2 is bubbled through aqueous 𝐾𝐼 for several minutes.
(ii) Construct an equation for the reaction that occurs.
(iii) Suggest an equation for the reaction that occurs between 𝐵𝑟𝐶𝑙 and aqueous 𝐾𝐼.
(iv) How do 𝐶𝑙2 and 𝐵𝑟𝐶𝑙 behave in these reactions?
[5]
[Total 15 marks]
[© UCLES 2013 9701/23/O/N/13]
17. The halogens and their compounds have a wide variety of uses and the chemical and physical properties
of the elements show regular patterns related to their positions in Group VII.
(a) Chlorine, bromine and iodine all react with hydrogen.
(i) State the trend in the reactivities of the halogens with hydrogen.
(ii) Explain this trend in terms of bond energies.
[1 + 2]
(b) In the laboratory it is not very convenient to prepare hydrogen halides from their elements.
Hydrogen halides can be prepared from their salts.
(i) Write an equation for the reaction of calcium chloride, 𝐶𝑎𝐶𝑙2 , with concentrated sulfuric acid.
(ii) Explain why hydrogen iodide is not prepared in this way.
(iii) When potassium bromide, 𝐾𝐵𝑟, reacts with concentrated sulfuric acid, sulfur dioxide, 𝑆𝑂2 , is
produced. State what you would see and write an equation for this reaction.
[1 + 1 + 2]
(c) Aqueous silver nitrate solution was added to separate tubes containing chloroethane, bromoethane
and iodoethane. The tubes were heated in a water bath.
A yellow precipitate appeared first in the tube containing iodoethane, followed by a cream
precipitate in the tube containing bromoethane and finally a white precipitate appeared in the tube
containing chloroethane.
Explain these observations.
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 [2]
[Total 15 marks]
[© UCLES 2014 9701/23/M/J/14]
18. From your knowledge of the chemistry of Group VII elements, write equations for the reactions that
would take place and state any observations made in the situations given below:
(a) A mixture of 𝐶𝑙2 (𝑔) and 𝐻2 (𝑔) is exposed to sunlight
[2]
(b) Concentrated sulphuric acid is added to solid sodium bromide.
[2]
(c) Chlorine gas is bubbled through aqueous sodium thiosulphate.
[2]
(d) Bromine is added to warm sodium hydroxide.
[2]
(e) 𝑁𝑎𝐶𝑙(𝑎𝑞) is mixed with 𝐴𝑔𝑁𝑂3 (𝑎𝑞) followed by 𝑁𝐻3 (𝑎𝑞).
[4]
[Total 12 marks]
[© ZIMSEC 9189/1 J2011]
19. With the aid of balanced equations, explain the following statements:
(a) Hydrogen chloride can be prepared in the laboratory by the action of concentrated sulphuric acid
on solid sodium chloride, but hydrogen bromide cannot be prepared by a similar method.
[3]
(b) On reacting with aqueous thiosulphate solution, chlorine and bromine increase the oxidation state
of sulphur from +2 to +6 while iodine can only increase it to +2.5
[3]
(c) The extent and rate of reaction for the formation of hydrogen halides decreases from chlorine to
iodine. (Use of the Data Booklet is recommended.)
[3]
(d) Both chlorine and bromine can be used to extract iodine from sea water.
[2]
(e) Aqueous silver nitrate can be used to confirm the presence of halide ions.
[1]
[Total 12 marks]
[© ZIMSEC 9189/1 J2012]
20. (a) Compare and contrast the chemistry of bromine and iodine with respect to each of the following
reactions. Suggest explanations for any differences in behaviour towards each reagent:
(i) Reactions of the elements with hydrogen gas
(ii) Reactions of silver bromide and silver iodide with aqueous ammonia.
[6]
(b) An excess of aqueous potassium iodide was added to a portion of 25.0 𝑐𝑚3 of aqueous bromine.
The iodine liberated required 9.5 𝑐𝑚3 of a 0.120 𝑚𝑜𝑙 𝑑𝑚−3 solution of sodium thiosulphate.
(i) Write equations for the reactions that occurred.
(ii) Calculate the number of moles of iodine liberated.
(iii) A second portion of 25.00 𝑐𝑚3 of the aqueous bromine required 2.45 𝑐𝑚3 of the 0.120 𝑚𝑜𝑙 𝑑𝑚−3
solution of sodium thiosulphate and sulphate ions were detected as one of the products.
1. Calculate the number of moles of thiosulphate that reacted with the bromine.
2. Hence derive an equation for the reaction between bromine and thiosulphate ions.
(iv) Explain the differences in the reactions of bromine and iodine with aqueous sodium
thiosulphate.
[6]
[Total 12 marks]
[© ZIMSEC 9189/1 J2013]

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21. The elements in Group VII show trends in physical and chemical properties.
element melting point
chlorine −101
bromine −7
iodine 114
(a) Explain the trends in the melting points of the elements shown above.
[3]
(b) Describe the trend in colour and physical state of chlorine, bromine and iodine at ordinary
temperature.
[2]
(c) (i) With the aid of equations, explain how concentrated sulphuric acid reacts with 𝑁𝑎𝐶𝑙, 𝑁𝑎𝐵𝑟 and
𝑁𝑎𝐼. How does the reaction for 𝑁𝑎𝐶𝑙 differ from that of 𝑁𝑎𝐵𝑟 and 𝑁𝑎𝐼?
[4]
(ii) What observations are made in each reaction?
[3]
[Total 12 marks]
[© ZIMSEC 9189/1 N2006]
22. Chlorine is a yellow-green gas whilst iodine is a black solid.
With the aid of chemical equations, compare and contrast the chemistry of chlorine and iodine by
describing and explaining the following:
(a) Reactions of the two elements with sodium thiosulphate.
[3]
(b) Reactions of solid halides of the two elements with concentrated sulphuric acid.
[5]
(c) Reactions of the two elements with hydrogen.
[4]
[Total 12 marks]
[© ZIMSEC 9189/1 N2010]

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