Raffles Institution (Junior College)

H2 Chemistry 2010/11
Tutorial 23 Group VII

A. Self-Check Questions
Describe the physical states and the colours of chlorine, bromine and iodine at room temperature,
and explain the observed trend in their volatilities.
[5]

Complete the following graphs and explain the trends observed.

[7]

pH of HX(aq)

boiling point of HX / K

Cl

Br

Cl

Br

Explain why a solution containing hydrogen bromide dissolved in methylbenzene is not acidic
whereas an aqueous solution of hydrogen bromide is.
[2]

Astatine (At), the element below iodine in Group VII, is produced in trace amounts only. Using
your knowledge of the halogens, predict any changes that you might observe in the following
experiments. Write balanced equations, with state symbols, for the reactions which occur.
(a) Aqueous bromine is added into aqueous sodium astatide.
(b) Aqueous silver nitrate is added into aqueous sodium astatide, followed by excess aqueous
ammonia.
(c) Astatine vapour is heated with hydrogen gas.
(d) Hot astatine vapour is passed over metallic sodium.
[8]

B. Past Year Questions

1
2
3
4
5
6
7
8
9
10
11
12

J95/IV/15 (MCQ) variation in physical properties of halogens

N00/III/16 (MCQ) reaction of metal halide with concentrated sulphuric(VI) acid
N01/III/16 (MCQ) reaction of metal halide with aqueous silver nitrate and aqueous ammonia
N03/I/17 (MCQ) displacement reaction
N92/IV/36, J97/III/37 (MCQ) properties of hydrogen halides
N01/III/36 (MCQ) application question (properties of halides)
N90/III/6 reactions of chlorine
N97/II/3(a), (b) & (c) reactions of potassium chlorate(V)
J98/II/4 reactions of hydrogen iodide
J94/I/5a electrolysis of brine (or concentrated sodium chloride solution)
N00/II/5 properties, industrial importance and environmental significance of chlorine
N06/II/1(c) boiling points of hydrogen halides

C. Class Discussion Questions

1 (a)

Iodine is oxidised by hot concentrated nitric acid to iodic acid, HIO3, with nitrogen dioxide also
being formed.
(i)
(ii)
(iii)
(iv)

(b)

What precautions would you take if you were to perform the reaction in the laboratory?
How could you tell when the reaction has completed?
What changes in the oxidation number of the elements have taken place in the
reaction?
Write a balanced equation for the reaction.

The equation for the reaction between iodine and aqueous sodium thiosulfate is given below.
2Na2S2O3 + I2 Na2S4O6 + 2NaI
Chlorine, however, oxidises aqueous sodium thiosulfate to sodium sulfate.
(i)
(ii)

(c)

Chlorine itself is used to destroy bacteria in drinking water. Give one important use in each of
the following cases.
(i)
(ii)

Write a balanced equation for the reaction involving chlorine.

Suggest why sodium thiosulfate reacts differently with iodine and chlorine.

bromine or one of its compounds

iodine or one of its compounds

An oxide of iodine is obtained when an oxoacid of iodine, X, is dehydrated. The composition by

mass of iodine in the oxide is 76.0%.
(a) Given that the relative molecular mass of the oxide is 334, deduce the molecular formula of
the oxide of iodine. Hence, identify the oxoacid of iodine, X.
(b) 0.560 g of carbon monoxide is completely oxidised to carbon dioxide when heated with 1.34 g
of the oxide of iodine. Construct a balanced chemical equation for the oxidation of carbon
monoxide by the oxide of iodine.

Describe and explain what happens in each of the following experiments and write balanced
equations for the reactions that occur.
(a) Chlorine is passed into aqueous iron(II) sulfate and aqueous sodium hydroxide is added to the
resulting solution.
(b) Solid iodine is shaken with aqueous potassium iodide and aqueous sodium thiosulfate is then
added.

When chlorine is bubbled through a solution of iodine in hot aqueous sodium hydroxide, the two
halogens chlorine and iodine react in the mole ratio of 7:1. The products are aqueous sodium
chloride and a white precipitate A of the following composition by mass: Na, 16.9%; H, 1.1%; I,
46.7%; O, 35.3%
(a) Calculate the empirical formula of A and the oxidation number of iodine in it.
(b) Deduce the balanced equation for the reaction.

Bromine has been obtained from sea salt for a number of years. For simplification, sea salt can
be considered to be sodium chloride containing some sodium bromide. One early method of
obtaining bromine is outlined below.

sea salt

chlorine
A

intense
yellow
colour

separate
with ether
B

ether recycled

yellow
solution in
ether

cold aqueous
potassium C
hydroxide
two colourless
layers

red fumes
which condense
to a red liquid
(bromine)

warm with acid

and distill
D

white
paste

aqueous layer is
concentrated

(a) (i) What causes the yellow colour produced in reaction A?

(ii) Write an equation for the reaction in A.
(b) Ether is an organic solvent immiscible with water. Explain why the yellow substance dissolves
in the ether in B, but the salt does not dissolve in ether.
(c) Suggest an equation for reaction C.
(d) Suggest an equation for reaction D, the reaction of acid on the products of reaction C.
6

Cyanogen, (CN)2, is sometimes referred to as a pseudohalogen because it behaves chemically

similar to the halogens. Its corresponding pseudohalide is the cyanide ion, CN, which behaves
chemically similar to the chloride ion. Describe and explain what happens when:
(a) cyanogen reacts with cold aqueous sodium hydroxide;
(b) aqueous silver nitrate is added into aqueous hydrogen cyanide, followed by excess aqueous
ammonia;
(c) solid sodium cyanide is heated in concentrated sulfuric(VI) acid.

When aqueous silver nitrate is added to aqueous potassium chloride, a white precipitate is formed
which dissolves in an excess of aqueous ammonia. The subsequent addition of aqueous sodium
bromide causes the precipitation of a cream solid.
Explain the chemistry for the above reactions that occur under aqueous conditions. Suggest why
the latter precipitate would dissolve if aqueous sodium cyanide is added.

Suggested Solutions to Self-Check Questions

1

property
physical state at rtp
colour

chlorine
gas
greenish-yellow

bromine
liquid
reddish-brown

iodine
solid
black

[2]

Cl2, Br2 and I2 have simple molecular structures with weak intermolecular forces. []
Boiling involves the overcoming of van der Waals forces [] (instantaneous dipole
induced dipole interactions).

Down the group from Cl2 to I2,

No. of electrons increase. []

Thus, the electron cloud becomes more easily distorted/ more easily polarisable, []

intermolecular van de Waals forces of attraction become more extensive []

Therefore, boiling point increases in the order: Cl2 < Br2 < I2 and hence volatility decreases in
the order: Cl2 > Br2 > I2 . []

Cl

Br

pH of HX(aq)

boiling point of HX / K

Cl

Br

[2]

Boiling point of HX

HCl, HBr and HI have simple molecular structures with weak intermolecular forces [].
Boiling involves the overcoming of the intermolecular van der Waals forces (VDW) [].
Molecular size and hence size of electron cloud of HX increases in the order: HCl < HBr <
HI [].
Ease of distortion of the electron cloud of HX increases in the order: HCl < HBr < HI [].
Extent of intermolecular VDW increases in the order: HCl < HBr < HI [].
Hence the boiling point of HX increases in the order: HCl < HBr < HI [].
HF has a simple molecular structure with intermolecular hydrogen bonding [], which is
much stronger than the intermolecular van der Waals forces of attraction. [].
Hence, HF has an unexpectedly higher boiling point compared to HCl, HBr and HI.

pH of HX

The acidity of the hydrogen halides depend on the bond strength of HX [].
Bond dissociation energy increases in the order: HI < HBr < HCl << HF []. Thus,
acidity increases in the order: HF << HCl < HBr < HI.

Since hydrogen bromide does not ionise in methylbenzene [1] to give H+, the solution is thus
not acidic. However, hydrogen bromide ionises in water to give H+ (or H3O+) [1] and Br ions.
Thus, an aqueous solution of hydrogen bromide is acidic, i.e. pH < 7.

(a) 2NaAt(aq) + Br2(aq) 2NaBr(aq) + At2(s) [1] (Displacement reaction)

The orange colour of Br2(aq) will be decolourised. A black solid, At2, is formed. [1]
(b) AgNO3(aq) + NaAt(aq) AgAt(s) + NaNO3(aq) [1]
A yellow precipitate, AgAt, which is insoluble in excess NH3(aq), is formed. [1] (The Ksp of
AgAt is too small hence the ionic product easily exceeds the Ksp)
(c) H2(g) + At2(g) 2HAt(g) [1]
The black colour of At2(g) is decolourised. Colourless fumes of HAt are formed. [1] (Heat is
required for reaction to happen. Reactivity decreases down the group.)
(d) 2Na(s) + At2(g) 2NaAt(s) [1]
The black colour of At2(g) is decolourised. A white solid, NaAt, is formed. [1]

Suggested Solutions to Class Discussion Questions

1 (a)

(i)
Experiment should be done in a fume cupboard
Heating should be done over a sand bath.
Reason: Hot concentrated HNO3 is very corrosive and poisonous NO2 gas is evolved.
(ii) Reaction is completed when the black I2 crystals disappear leaving only the white
crystals of iodic acid.
(iii)

I2 +
(0)

HNO3
(+5)

HIO3
(+5)

NO2 +
(+4)

H2O

Iodine is oxidised from 0 to +5 state

Nitrogen is reduced from +5 to +4 state
+

5HNO3(l)

(iv)

I2(s)

HIO3(s)

5NO2(g) +

2H2O(l)

(i)

4Cl2(aq) + S2O32-(aq) + 5H2O(l) 2SO42-(aq) + 10H+(aq) + 8Cl-(aq)

(b)

(ii)

(c)

Chlorine is a much stronger oxidising agent than iodine; hence chlorine can oxidise
S2O32 to SO42- (i.e sulphur is oxidised from +2 to +6 state.)

Iodine is a weaker oxidising agent; hence iodine can oxidise S2O32- to S4O62- (i.e
sulphur is oxidised from +2 to +2.5 state.)

(i) Making silver bromide for photographic film

(ii) Used in the preparation of dyes and in colour photography

(a)

127

16

76.0
76.0
0.60
127.0
1
:
2
:

24.0
24.0
1.5
16.0
2.5
5
[1] empirical formula: I2O5

mass per 100 g of oxide / g

amount / mol
mole ratio
simplest integer ratio

Mr of I2O5 = 2 x 127 + 5 x 16.0 = 334

molecular formula: I2O5 [1]
2HIO3(aq) I2O5(s) + H2O(g)
The oxoacid is iodic(V) acid or HIO3. [1]
1.34
= 0.004012 mol
334
0.560
Amount of CO oxidised by I2O5 =
= 0.02 mol
12.0 16.0
Amount of CO : Amount of I2O5 = 0.02 : 0.004012 = 5 : 1 [1]
I2O5(s) + 5CO(g) I2(s) + 5CO2(g) [1]

(b) Amount of I2O5 used to oxidise CO =

(a) Reaction 1: Cl2 and Fe2+

Analysis
Fe2+ will be oxidised to Fe3+
Cl2 will be reduced to ClOxidation:
Reduction:
Overall :

Fe2+ Fe3+ + e
Cl2 + 2e 2Cl2Fe2+(aq) + Cl2(g) 2Fe3+(aq) + 2Cl-(aq)

Observation: Pale green solution of Fe2+ turns to pale yellow due to formation of Fe3+
Reaction 2: NaOH and Fe3+
Equation: Fe3+(aq) + 3OH-(aq) Fe(OH)3(s)
Observation: A reddish brown ppt of Fe(OH)3 is formed which is insoluble in excess
NaOH.
(b) Reaction 1: I2 is shaken with KI
I2(s)
I2(aq)
I2(aq) + I-(aq)

I3-(aq)

------------------------- (1)

Observation: Black crystals of I2 dissolves to form brown solution due to the formation of the
complex I3-.
Reaction 2: Na2S2O3 reacts with I2
2S2O32(aq) + I2(aq) S4O62(aq) + 2I(aq) -------------- (2)
From (2), S2O32 reacts with I2, thus reducing [I2(aq)] in (1). By Le Chateliers Principle,
position of eqm (1) shifts to the left, reducing [I3], until all I2 is reacted with S2O32.
Observation: The brown solution is decolourised. (Note: S4O62(aq) is colourless).

4. (a) Na2H3IO6 (Students: please show working for determining the empirical formula.)
Let the oxidation number of Iodine in A be x.
2(1) + 3(1) + x + 6(-2) = 0
x = +7
(b)

Analysis:
Cl2 : I2 ratio = 7:1
white ppt is Na2H3IO6
add H2O as a product to balance the equation
7Cl2 (g) + I2 (aq) + 18NaOH (aq) 2Na2H3IO6 (s) + 14NaCl (aq) + 6H2O (l)
5

(a) (i) dilute aqueous bromine

(ii) 2NaBr(aq) + Cl2(g) 2NaCl(aq) + Br2(aq)

[2x1]

(b) Bromine is non-polar, so it dissolves better in an non-polar solvent like ether. However, the
salt is ionic in nature and is insoluble in a non-polar solvent.
[2x1]

(c) 2KOH(aq) + Br2(org) KBr(aq) + KBrO(aq) + H2O(l)

[1]

(d) KBr(aq) + KBrO(aq) + 2H+(aq) Br2(g) + H2O(l) + 2K+(aq)

[1]

(a) Cyanogen disproportionates in cold aqueous sodium hydroxide.

(CN)2(g) + 2OH(aq) CN(aq) + CNO(aq) + H2O(l)

[2x1]

(b) A white precipitate of silver cyanide, which is soluble in excess aqueous ammonia,
forms.
Ag+(aq) + CN(aq) AgCN(s) --------(1)
Ag+ ions forms a insoluble ppt with the cyanide ion. [1]
AgCN (s)
Ag+ (aq) + CN- (aq) -----(2)
Ag+ (aq) + 2NH3(aq)
[Ag(NH3)2]+(aq) ----(3)
Upon addition of NH3, the formation of the soluble [Ag (NH3)2]+ complex, causes [Ag+ (aq)] to
decrease. By Le Chateliers principle, the position of equilibrium (2) will shift to the right,
causing more AgCN to dissolve to form Ag+ (aq). [2]
(c) Sodium cyanide is acidified [1] by concentrated sulfuric(VI) acid to form hydrogen cyanide
gas.
NaCN(s) + H2SO4(l) NaHSO4(s) + HCN(g)
[1]
7

Analysis:
Four reactions occurring :
1 KCl + AgNO3
2 Solubility in excess aq NH3
3 Formation of cream solid on adding NaBr
4 Solubility of the cream ppt in NaCN

Reaction 1: KCl and AgNO3

KCl(aq) + AgNO3(aq) AgCl(s) + KNO3(aq)
Observations: White ppt of AgCl observed.
Reaction 2: AgCl and NH3
AgCl(s)
Ag+ (aq) + Cl- (aq) ------------------------------------ (1)
AgCl(s) + 2NH3(aq)
[Ag(NH3)2]+(aq) + Cl-(aq) ---------(2)
The aq NH3 will react with free Ag+ to form the soluble diammine complex. By Le
Chateliers Principle, position of equilibrium (1) shift right hence AgCl dissolves.
Observation: The white ppt of AgCl dissolve in ammonia to form the soluble complex
and a colourless solution is obtained.
Reaction 3: NaBr and AgNO3
NaBr (aq) + AgNO3(aq) AgBr(s) + NaNO3(aq)
Observation: Cream ppt of AgBr is seen.
Reaction 4 : AgBr dissolve in NaCN
On adding NaCN,
AgBr(s)

Ag+ (aq) + Br-(aq) ------------------------------------ (3)

The free Ag+ reacts with the strong CN- ligand to form stable [Ag(CN)2]- complex
Ag+(aq) + 2CN-(aq)

[Ag(CN)2]- (aq)

By Le Chateliers Principle, position of equilibrium (3) shifts to the right to increase [Ag+].
Therefore, AgBr dissolves.