ANSWERS TO 2012 TUTORIAL SUPPLEMENTARY QUESTIONS

FOR OXIDATION NUMBERS AND REDOX EQUATIONS

1. Write down the oxidation numbers of :
Manganese in Mn2(CO)10, MnCl2, MnF3, MnO2, Na3MnO4, KMnO4
Mn2(CO)10

MnCl2

MnF3

MnO2

Na3MnO4

KMnO4

+2

+3

+4

+5

+7

2. In each of the following reactions, state what (if any) has been reduced or oxidised.
Write ion-electron half equations (where appropriate) to explain your answer.
(a) 3Cl2 + 6OH 5Cl + ClO3 + 3H2O
Cl2 is reduced and oxidised.
Cl2 + 12OH- 2ClO3- + 6H2O + 10eCl2 + 2e- 2Cl(b)

(ON from 0 to +5)

(ON from 0 to -1)

HNO3 + 2H2SO4 NO2+ + H3O+ + 2HSO4

No redox

3. Write redox equations for the following reactions.

(a)

Chlorine dioxide, ClO2 disproportionates to a mixture of chlorate(III), ClO2- and

chlorate(V), ClO3- in alkaline solution.
Oxidation eqn: ClO2 + 2OH- ClO3- + H2O + eReduction eqn: ClO2 + e- ClO2Eqn(1) + Eqn(2) gives

(b)

2ClO2 + 2OH- ClO2- + ClO3- + H2O

NH2OH is oxidised to N2O by Fe3+(aq), which is itself reduced to Fe2+(aq).

Oxidation eqn: 2NH2OH N2O + H2O + 4H+ + 4eReduction eq: Fe3+ + e- Fe2+
Eqn(1) + Eqn(2) x 4 gives

(c)

----(1)
----(2)

----(1)
----(2)

4Fe3+ + 2NH2OH 4Fe2+ + N2O + H2O + 4H+

Reaction of potassium iodide, KI with aqueous potassium manganate (VII), KMnO4

gives a mixture of black and brown precipitate. The black precipitate dissolves in
excess KI solution.
Oxidation eqn: 2I- I2 + 2e----(1)
Reduction eqn: MnO4- + 2H2O + 3e- MnO2 + 4OH- ----(2)
Eqn(1) x 3 + Eqn(2) x 2 gives 6I- + 2MnO4- + 4H2O 3I2 +
black
Black ppt of I2 dissolves in excess KI solution: I2 + I I3-

2MnO2 + 8OHbrown

4. The head of the first self-igniting match, called a lucifer, contained a mixture of
antimony(III) sulfide and potassium chlorate(V). When the match was struck, the
following reaction took place.
1

Sb2S3(s) + 3KClO3(s) Sb2O3(s) + 3KCl(s) + 3SO2(g)

Which element is reduced in the reaction?
A
B
C
D

[H1 N10/I/10]

antimony
chlorine
oxygen
sulfur

Ans: B
ON of chlorine decreases from +5 in KClO3 to -1 in KCl
5. Ten percent of the copper produced in the USA comes from bacterial leaching of lowgrade copper ores. In this process acidified water is sprayed onto the ore chalcopyrite.
Bacteria then convert the insoluble ore into a solution containing iron and copper ions.
4CuFeS2 + 17O2 + 4H+ 4Cu2+ + 4Fe3+ + 8SO42- + 2H2O
No change occurs in the oxidation state of copper.
What changes in oxidation state occur for the iron and the sulfur in this reaction?
[H1 N09/I/9]
change in oxidation state
Fe

-1

-6

-1

+6

+1

-8

+1

+8

Ans: D
ON of iron increases from +2 in CuFeS2 to +3 in Fe3+;
ON of sulfur increases from -2 in CuFeS2 to +6 in SO426. When aqueous hydrogen peroxide, H2O2, is mixed with acidified potassium
dichromate(VI), there is a colour change from orange to green. When aqueous
hydrogen peroxide is added to acidified potassium iodide solution, there is a colour
change from colourless to brown.
The oxidation number of oxygen in H2O2 is -1.
What are the oxidation numbers of oxygen after the reactions with potassium
dichromate(VI) and potassium iodide?
[N09/I/16]

A
B
C
D

After reaction with

potassium
dichromate(VI)
-2
-2
0
0

After reaction with

potassium
iodide
-2
0
-2
0

Ans: C
K2Cr2O7 oxidises H2O2 to O2 (ON: 0) while KI reduces H2O2 to H2O (ON: -2).

ANSWERS TO 2012 TUTORIAL SUPPLEMENTARY QUESTIONS

FOR REDOX REACTIONS IN VOLUMETRIC ANALYSIS
1. Sodium sulfite acts as a preservative in sausages. The amount of sulfite present in a
sausage can be determined by boiling the sausage with a strong acid, and measuring
the amount of sulfur dioxide evolved.
50 g of sausage together with 200 cm3 of water and 20 cm3 of 10 mol dm-3 HCl are
boiled in a distillation flask. The sulfur dioxide gas liberated is dissolved in water in
collecting flask.
The resulting solution in the collecting flask required 7.00 cm3 of 0.0250 mol dm-3 iodine
solution in order to completely oxidize the sulfur dioxide gas to sulfate(VI) ion.
As a check on the titration, excess BaCl2 solution is then added and the resulting
precipitate collected and weighed.
(a) Give an ion-electron half-equation for the oxidation reaction of sulfur dioxide to
sulfate(VI) ion and hence write the balanced chemical equation for the reaction
between sulfur dioxide and iodine solution.
[2]
2+
SO2 + 2H2O SO4 + 4H + 2e
I2 + 2e- 2IOverall: SO2 + 2H2O + I2 SO42- + 4H+ + 2I(b) Calculate the mass of the sulfur dioxide gas evolved from 50 g of sausage.

[2]

Amount of SO2 = Amount of I2

= 0.0250 x (7.00/1000)
= 1.75 x 10-4 mol
Mass of SO2 = 1.75 x 10-4 x [32.1+2(16.0)]
= 0.0112 g
(c) Express the mass of sulfur dioxide in sausage parts per million (ppm).

[1]

Mass of SO2 in sausage = (0.0112/50) x106

= 224 ppm
(d) Identify and calculate the mass of the precipitate formed when BaCl2 solution is added
to the solution at the end point of the titration?
[2]
Precipitate is BaSO4.
Amount of BaSO4 = Amount of SO42- = Amount of SO2
= 1.75 x 10-4 mol
Mass of BaSO4 = 1.75 x 10-4 x [137.3 + 32.1 + 4(16.0)]
= 0.0408 g

2.

Wines often contain a small amount of sulfur dioxide that is added as a preservative.
The sulfur dioxide content of a wine is found using the following method:
A 50 cm3 sample of white wine is reacted with 40.0 cm3 of 0.0100 mol dm-3 of excess
aqueous iodine. The sulfur dioxide in the wine is oxidized to sulfate(VI) ion in the
process. The unreacted iodine requires exactly 23.60 cm3 of 0.0200 mol dm-3 of sodium
thiosulfate for complete reaction.
3

(a) Give the ion-electron half-equation for the oxidation reaction of sulfur dioxide to
sulfate(VI). Hence, write the redox equation for the reaction between sulfur dioxide and
aqueous iodine.
[2]
SO2 + 2H2O SO42- + 4H+ + 2eI2 + 2e- 2IOverall: SO2 + 2H2O + I2 SO42- + 4H+ + 2I(b) Write the redox equation for the reaction between aqueous iodine and sodium
thiosulfate.
[1]
222S2O3 + I2 S4O6 + 2I
(c) Determine the concentration of sulfur dioxide, in mol dm-3, in the 50 cm3 sample of
wine.
[3]
Amount of unreacted I2 = x amount of S2O32= x [0.0200 x (23.60/1000)]
= 2.36 x 10-4 mol
Amount of original I2 = 0.0100 x (40.0/1000)
= 4.00 x 10-4 mol
Amount of reacted I2 = 4.00 x 10-4 2.36 x 10-4
= 1.64 x 10-4 mol
amount of SO2 = amount of reacted I2 = 1.64 x 10-4 mol

Concentration of SO2 in sample = (1.64 x 10-4) / (50/1000)

= 3.28 x 10-3 mol dm-3
3. Chlorine dioxide, ClO2 oxidises thiosulfate, S2O32- under acidic conditions.
ClO2(aq) + 4H+(aq) + 5e- Cl-(aq) + 2H2O(l)
In an experiment, 25.0 cm3 portion of the solution containing 11.2 g of thiosulfate ions
per dm3 were oxidised by 20.00 cm3 of 0.0250 mol dm-3 of chlorine dioxide in acidic
medium.
(a) State the oxidation state of sulfur in thiosulfate ion.
+2
(b) Calculate the new oxidation number of sulfur after the reaction.
[Ar: S = 32.1, O = 16.0, Cl = 35.5]
Conc. of S2O32-

= 11.2 / [2(32.1) + 3(16.0)]

= 0.0998 mol dm-3
Amount of S2O32- = 0.0998 x (25.0/1000)
= 2.50 x 10-3 mol
Amount of ClO2 = 0.0250 x (20.00/1000)
= 5.00 x 10-4 mol
Amount of e- = 5 x 5.00 x 10-4
= 2.50 x 10-3 mol

[1]

[3]

nS O 2
2

2.50 10

2.50 10

=1

Therefore, 1 mole of S2O32- will give out 1 mole of ei.e. 1 mole of S in S2O32- will give out 0.5 mole of eHence, new oxidation number of sulfur = +2.5
4. Potassium dichromate(VI) can be used to determine the concentration of Fe2+ ions in a
solution by titration. The reaction of the dichromate(VI) ions is shown in the equation
below:
Cr2O72-(aq) + 14H+(aq) + 6e- 2Cr3+(aq) + 7H2O(l)
a) (i) Acidified potassium dichromate(VI) is an oxidising agent. Justify this statement by
using oxidation numbers in the above equation.
Oxidation number of Cr in Cr2O72 = +6
Oxidation number of Cr in Cr3+ = +3
Cr has undergone reduction from Cr2O72 to Cr3+. Cr2O72 is thus an oxidising
agent as it has the ability to oxidise another substance through accepting
electrons to undergo reduction.
(ii) Write an ionic equation for the oxidation of Fe2+ ions.
Fe2+ Fe3+ + e
(iii) Write an overall equation for the reaction between dichromate(VI) and iron(II)
ions.
Cr2O72 + 14H+ + 6Fe2+ 2Cr3+ + 7H2O + 6Fe3+
b) A piece of iron wire weighs 0.1389 g. It is dissolved in acid. The Fe2+ ions formed are
titrated with 20.40 cm3 of 0.0200 mol dm-3 potassium dichromate(VI) solution. What
is the percentage purity of the iron wire?
[H1 N07/2/7]
Number of moles of Cr2O72 titrated:

20.40
0.020 =4.08 10 4 mol dm3
1000

From (a)(iii), nFe2 + = 6nCr O2

2

Therefore, number of moles of Fe2+ formed = 6 (4.08 x 10-4)

= 2.45 103 mol
Since nFe = nFe2 + , number of moles of Fe in wire = 2.45 x 103 mol
Mass of iron in sample = (2.45 10-3) 56.0 = 0.137 g
0.137
Hence, percentage purity of iron wire =
100%
0.1389
= 98.7%

--THE END--