TEACHERS’ COPY ON 2015 TUTORIAL FOR REDOX PART I :

OXIDATION NUMBERS AND REDOX EQUATIONS

Level 1

1. Write down the oxidation numbers of :

(a) Chlorine in Cl2, POCl3, HClO, NaClO2, ClO2, ClO3-, and Cl2O7

Cl2 POCl3 HClO NaClO2 ClO2 ClO3- Cl2O7

0 -1 +1 +3 +4 +5 +7

(b) Nitrogen in N2, N2O, NO, NO2, NO3-, N2H4 and HCN
-
N2 N2O NO NO2 NO3 N2H4 HCN
0 +1 +2 +4 +5 -2 -3

2. Write redox equations for the following reactions.

(a) When sodium sulfite, Na2SO3 is added to acidified potassium dichromate(VI), K2Cr2O7
solution, the orange solution turns to green Cr3+ ions.

Oxidation ½ eqn: SO32- + H2O → SO42- + 2H+ + 2e- --- (1)

Reduction ½ eq: Cr2O72- + 14H+ + 6e- → 2Cr3+ + 7H2O --- (2)

Eqn(1) x 3 + Eqn(2) gives 3SO32- + Cr2O72- + 8H+ → 3SO42- + 2Cr3+ + 4H2O

orange green

(b) When aqueous potassium iodide, KI is added to acidified hydrogen peroxide, H2O2, a
brown solution of iodine is observed.

Oxidation ½ eqn: 2I- → I2 + 2e- --- (1)

Reduction ½ eqn: H2O2 + 2H+ + 2e- → 2H2O --- (2)
- +
Eqn(1) + Eqn(2) gives 2I + H2O2 + 2H → I2 + 2H2O
(brown solution of iodine)

(c) Sodium nitrite, NaNO2 decolourises acidified potassium manganate(VII), KMnO4.

Oxidation ½ eqn: NO2- + H2O → NO3- + 2H+ + 2e- --- (1)

- + - 2+
Reduction ½ eqn: MnO4 + 8H + 5e → Mn + 4H2O --- (2)

Eqn(1) x 5 + Eqn(2) x 2 gives 5NO2- + 2MnO4- + 6H+ → 5NO3- + 2Mn2+ + 3H2O

purple pale pink

(d) Chlorine gas, Cl2, reacts with cold sodium hydroxide solution to form sodium chloride
and sodium chlorate(I), NaClO.

Oxidation ½ eqn: Cl2 + 4OH- → 2ClO- + 2H2O + 2e- --- (1)

- -
Reduction ½ eqn: Cl2 + 2e → 2Cl --- (2)
- - -
Eqn(1) + Eqn(2) gives Cl2 + 2OH → ClO + Cl + H2O

1
Level 2

3. The equations for three reactions are given below:

Cl2 + 2H2O + SO2 → 2HCl + H2SO4

Cl2 + H2S → 2HCl + S
SO2 + 2H2S → 2H2O + 3S

What is the correct order of strength of the three reacting gases as reducing agents?

Weakest Strongest
A chlorine sulfur dioxide hydrogen sulfide
B chlorine hydrogen sulfide sulfur dioxide
C sulfur dioxide hydrogen sulfide chlorine
D hydrogen sulfide sulfur dioxide chlorine

Ans: A
O.A. R.A.
Cl2 + 2H2O + SO2 → 2HCl + H2SO4
O.A. R.A.
Cl2 + H2S → 2HCl + S
O.A. R.A.
SO2 + 2H2S → 2H2O + 3S
H2S is the strongest reducing agent since it reduces both SO2 and Cl2.
Cl2 is the weakest reducing agent since it cannot reduce both SO2 and H2S.
SO2 is the intermediate in strength as a reducing agent since it reduces Cl2 but
not H2S.

4. When iron is reacted with aqueous iron(III) ions, iron(II) ions are formed.

Assuming the reaction goes to completion, how many moles of Fe and Fe3+(aq) would
result in a mixture containing equal numbers of moles of Fe3+(aq) and Fe2+(aq) once the
reaction had taken place? [N07/I/2]

moles of Fe moles of Fe3+(aq)

A 1 2
B 1 3
C 1 5
D 2 3

Ans: C

Oxidation ½ eqn: Fe → Fe2+ + 2e- --- (1)

Reduction ½ eqn: Fe3+ + e- → Fe2+ --- (2)

Eqn(1) + Eqn(2) x 2 gives a balanced redox eqn of Fe + 2Fe3+ → 3Fe2+

Hence, 1 mol Fe will react with 2 mol Fe3+ to produce 3 mol Fe2+.

--THE END--
2
 TEACHERS’ COPY ON 2015 TUTORIAL FOR REDOX PART II:
REDOX REACTIONS IN VOLUMETRIC ANALYSIS

Level 2

Potassium Manganate(VII) & Potassium Dichromate(VI) Titration

1. Compounds of iron and strontium are usually found in food.

Spinach is considered to be a rich source of iron. However, it contains iron absorption

inhibiting substances such as oxalate which can bind to the iron to form iron(II) oxalate,
which renders much of the iron in spinach unusable by the body.

35.0 cm3 sample of iron(II) oxalate, FeC2O4 was extracted from 150 g of spinach,
diluted in water and the solution made up to 250 cm3. A 25.0 cm3 portion of this solution
was acidified and required 13.45 cm3 of 0.020 mol dm-3 potassium manganate(VII) for
oxidation of iron(II) to iron(III) and oxalate ions to carbon dioxide.

Solution:
(a) State the change in oxidation number for manganese and carbon in the reaction.

Mn: From +7 to +2 [or decrease by 5]

C: From +3 to +4 [or increase by 1]

(b) Write down all the relevant ionic half equations and hence the overall redox equation
for the reaction between potassium manganate(VII) and iron(II) oxalate.

MnO4- + 8H+ + 5e- → Mn2+ + 4H2O

C2O42- → 2CO2 + 2e-
Fe2+ → Fe3+ + e-
3MnO4- + 24H+ + 5C2O42- + 5Fe2+ → 3Mn2+ + 5Fe3+ + 12H2O + 10CO2

(c) Calculate the concentration, in mol dm-3, of iron(II) oxalate in the original sample.

13.45
Number of moles of KMnO4 = x 0.020
1000
= 2.69 x 10-4 mol
5
Number of moles of FeC2O4 in 25.0 cm3 = x 2.69 x 10-4
3
= 4.48 x 10-4 mol
250
Number of moles of FeC2O4 in 250 cm3 = 4.48 x 10-4 x
25.0
-3
= 4.48 x 10 mol
4.48 x 10 -3
Concentration of FeC2O4 in the original sample =
35.0 x 10 -3
= 0.128 mol dm-3

3
Iodine – Thiosulfate Titration
2. The halogens form many interhalogen compounds and ions, in which a halogen atom
lower down the group is surrounded by atoms of halogens higher in the group. Two
such species are the compound ClF5 and the ion ICl4-.

Solution:
(a) Calculate the oxidation number of iodine in ICl4-. [1]

+3

(b) N-chlorosuccinimide (Mr = 133.5) is used in some water purification tablets. It

dissolves in water to give a weak acid, HClO, which kills waterborne bacteria.

N-chlorosuccinimide

The amount of N-chlorosuccinimide in a tablet can be estimated by dissolving it in

water, and adding an excess of acidified KI(aq). The HClO is quantitatively reduced to
Cl- by I- ions, which are oxidised to I2. The I2 is titrated with standard sodium
thiosulfate. The following reaction takes place during the titration.

I2 + 2S2O32- → 2I- + S4O62-

(i) Construct a balanced equation for the reaction between HClO and acidified
KI(aq).

HClO + 2I- + H+ → I2 + Cl- + H2O

When one tablet was subjected to the above procedure, 6.0 cm3 of 0.0050 mol dm-3
sodium thiosulfate was required to discharge the colour of I2.

(ii) Calculate the mass of N-chlorosuccinimide in the tablet. [4]

6.0
nS O 2 − = 0.0050 × = 3.00 × 10 -5 mol
2 3
1000
1
nI2 = × 3.00 × 10 -5 = 1.50 × 10 -5 mol
2
nN-chlorosuccinimide = nHClO = nI2 = 1.50 × 10 -5 mol

mN-chlorosucc inimide = 1.50 × 10 -5 × 133.5 = 2.00 × 10 −3 g

[N11/III/1]

4
Further Redox Reactions

3. The compound Na3CrO4, is an instable dark green solid. The addition of dilute sulfuric
acid to this produces a solution containing chromium(III) ions and dichromate(VI) ions.
When a 1.00 g sample of the impure green solid was reacted in this way, the Cr(VI) in
the resulting solution reacted with an excess of potassium iodide to liberate
5.00 x 10-3 moles of iodine, I2.

Solution:
(a) Calculate the oxidation state of chromium in Na3CrO4, and construct a balanced
equation for its reaction with dilute acid.

O.N of Cr in Na3CrO4 = +5

3CrO43- + 10H+ → Cr3+ + Cr2O72- + 5H2O (ionic eqn)

∴ 6Na3CrO4 + 10H2SO4 → Cr2(SO4)3 + 2Na2Cr2O7 + 10H2O + 7Na2SO4 (full eqn)

(b) Write an equation for the reaction between Cr(VI) and iodide ions, and hence
calculate the number of moles of Cr(VI) produced in solution.

Cr2O72- + 14H+ + 6I- → 3I2 + 2Cr3+ + 7H2O

Number of moles of I2 produced = 5.00 x 10-3 mol

1
Number of moles of Cr2O72- = x 5.00 x 10-3
3
= 1.67 x 10-3 mol

∴ number of moles of Cr(VI) produced = 2 x 1.67 x 10-3

= 3.34 x 10-3 mol

(c) By using your results in (a) and (b), calculate the number of moles of Na3CrO4, in the
1.00 g sample and hence the percentage purity.

6
Number of moles of Na3CrO4 = moles of Cr2O72-
2

Mass of Na3CrO4 in 1 g sample = 3 x 1.67 x 10-3 x 185.0

= 0.925 g

0.925
∴ % purity of Na3CrO4 sample = x 100%
1
= 92.5 %
[N96/II/2]

5
Level 3

4. 1.50 g of a copper(II) compound was dissolved in water and then made up to

250 cm3. 25.0 cm3 portion of this solution were treated with excess potassium iodide
solution. Iodine and solid copper(I) iodide were formed. The iodine liberated was titrated
with a standard sodium thiosulfate solution containing 2.80 g of thiosulfate ions per dm3.
The average titre was 24.00 cm3.

Calculate the percentage of copper(II) in the compound.

[Titration video: http://vimeo.com/18901164. Password: vjcchemistry]

Solution:
2S2O32- + I2 → S4O62- + 2I-
Number of moles of S2O32- used = conc. (mol dm-3) x volume
= [2.8 ÷ (2(32.0) + 3(16.0))] x 0.024
= 6.00 x 10-4 mol

Number of moles of I2 evolved = ½ x 6.00 x 10-4

= 3.00 x 10-4 mol

2Cu2+ + 4I- → 2CuI + I2

Number of moles of Cu2+ in 25.0 cm3 = 2 x 3.00 x 10-4
= 6.00 x 10-4 mol

250
Number of moles of Cu2+ in 250 cm3 = 6.00 x 10-4 x
25.0
= 6.00 x 10-3 mol

Mass of Cu(II) in 1.5 g of compound = 6.00 x 10-3 x 63.5

= 0.381 g

0.381
Percentage of Cu(II) in compound = x 100%
1 .5
= 25.4 %

5. In one experiment, 30.0 cm3 of a solution of M5+ of concentration 0.100 mol dm-3 was
reduced by sulfur dioxide to a solution of Mn+. In order to reoxidise Mn+ to M5+, 50.0 cm3
of acidified potassium dichromate(VI) solution of concentration 0.0200 mol dm-3 was
required.

What is the value of n?

Solution:
[O] half-eqn: Mn+ → M5+ + (5 - n)e-
[R] half-eqn: Cr2O72- + 14H+ + 6e- → 2Cr3+ + 7H2O
50.0
nCr O 2− = 0.020 × = 1.00 × 10 -3 mol
1000
∴
2 7

n e- = 6 × (1.00 × 10 3 ) = 6.00 × 10 -3 mol

30.0
nM5+ = 0.10 × = 3.00 × 10 -3 mol
1000

6
n 6.00 × 10 3
e-
= 3
=2
nM3 + 3.00 × 10
⇒ 1 mol M5+ will take in 2 mol e-. i.e. M5+ + 2e- → M3+
∴n = 3

6. Iodine and chlorine react together to form compound X (ICln). When 0.0010 mol of X
was reacted with an excess of KI (aq), all of its iodine was converted into I2. The iodine
liberated required 40.0 cm3 of 0.10 mol dm-3 sodium thiosulfate, Na2S2O3 for complete
reaction.

Solution:
(a) Calculate the amount (in moles) of iodine produced.

I2 + 2S2O32- → 2I- + S4O62-

1 40.0
Amount of iodine produced = × × 0.10
2 1000
= 0.00200 mol

(b) Hence calculate the value of n in ICln.

ICln + nKI → [(1 + n)/2] I2 + nKCl

0.001 mol 0.002 mol

nI 2 0.002 (1 + n ) / 2
= =
nICl n 0.001 1

∴n=3

(c) Write a balanced equation for the reaction between Cl2 and I2.

Substitute n = 3 into the equation ‘I2 + nCl2 → 2ICln’

∴ I2 + 3Cl2 → 2ICl3
[N03/III/5 either]

--THE END—

7
 ANSWERS TO 2015 TUTORIAL SUPPLEMENTARY QUESTIONS
FOR OXIDATION NUMBERS AND REDOX EQUATIONS

3. Write down the oxidation numbers of :

Manganese in Mn2(CO)10, MnCl2, MnF3, MnO2, Na3MnO4, KMnO4

Mn2(CO)10 MnCl2 MnF3 MnO2 Na3MnO4 KMnO4

0 +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 + 10e- (ON from 0 to +5)
Cl2 + 2e- → 2Cl- (ON from 0 to -1)

(b) 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 ½ eqn: ClO2 + 2OH- → ClO3- + H2O + e- ----(1)

Reduction ½ eqn: ClO2 + e- → ClO2- ----(2)

Eqn(1) + Eqn(2) gives 2ClO2 + 2OH- → ClO2- + ClO3- + H2O

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

Oxidation ½ eqn: 2NH2OH → N2O + H2O + 4H+ + 4e- ----(1)

Reduction ½ eq: Fe3+ + e- → Fe2+ ----(2)

Eqn(1) + Eqn(2) x 4 gives 4Fe3+ + 2NH2OH → 4Fe2+ + N2O + H2O + 4H+

(c) 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 ½ eqn: 2I- → I2 + 2e- ----(1)

Reduction ½ eqn: MnO4- + 2H2O + 3e- → MnO2 + 4OH- ----(2)

Eqn(1) x 3 + Eqn(2) x 2 gives 6I- + 2MnO4- + 4H2O → 3I2 + 2MnO2 + 8OH-

black brown
Black ppt of I2 dissolves in excess KI solution: I2 + I- → I3-
8
5. 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

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

Which element is reduced in the reaction?

A antimony
B chlorine
C oxygen
D sulfur
[H1 N10/I/10]
Ans: B
ON of chlorine decreases from +5 in KClO3 to -1 in KCl

6. Ten percent of the copper produced in the USA comes from bacterial leaching of low-
grade 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?

change in oxidation state

Fe S
A -1 -6
B -1 +6
C +1 -8
D +1 +8
[H1 N09/I/9]
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 SO42-

9
7. 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]

After reaction with After reaction with

potassium dichromate(VI) potassium iodide
A -2 -2
B -2 0
C 0 -2
D 0 0

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

10
 ANSWERS TO 2015 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 oxidise 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]

SO2 + 2H2O → SO42- + 4H+ + 2e-

I2 + 2e- → 2I-
Overall: 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

7.00
= 0.0250 x
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]

0.0112
Mass of SO2 in sausage = x106
50
= 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

11
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.

(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+ + 2e-

I2 + 2e- → 2I-
Overall: SO2 + 2H2O + I2 → SO42- + 4H+ + 2I-

(b) Write the redox equation for the reaction between aqueous iodine and sodium
thiosulfate. [1]

2S2O32- + I2 → S4O62- + 2I -

(c) Determine the concentration of sulfur dioxide, in mol dm-3, in the 50 cm3 sample of
wine. [3]

1
Amount of unreacted I2 = x amount of S2O32-
2
1 23.60
= × 0.0200 ×
2 1000
= 2.36 x 10-4 mol

40.0
Amount of original I2 = 0.0100 ×
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

1.64 × 10 −4 × 1000
Concentration of SO2 in sample =
50
= 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.

12
(a) State the oxidation state of sulfur in thiosulfate ion. [1]

+2

(b) Calculate the new oxidation number of sulfur after the reaction. [3]

Conc. of S2O32- = 11.2 / [2(32.1) + 3(16.0)]

= 0.0998 mol dm-3
25.0
Amount of S2O32- = 0.0998 ×
1000
= 2.50 x 10-3 mol

20.00
Amount of ClO2 = 0.0250 ×
1000
= 5.00 x 10-4 mol
Amount of e- = 5 x 5.00 x 10-4
= 2.50 x 10-3 mol

n _ 2.50 × 10
_
3
e
∴ = _
3
=1
nS O 2− 2.50 × 10
2 3

Therefore, 1 mol S2O32- will give out 1 mol e-

i.e. 1 mol of S in S2O32- will give out 0.5 mol e-
Hence, new oxidation number of sulfur = +2.5

4. An acidified solution of the salt KClOx (x = 1,2 or 3) will oxidise Fe2+(aq) to Fe3+(aq)
quantitatively, the chlorine being reduced to Cl-(aq).

When 0.150 g of the salt KClOx was reacted with 0.500 mol dm-3 Fe2+ (aq) in the
presence of H+ (aq), 11.30 cm3 of Fe2+ (aq) was needed for complete reaction.

Calculate the value of x and construct an equation for the reaction between Fe2+(aq)
and acidified KClOx (aq). [N11/III/5f]

Oxidation ½ eqn: Fe2+ → Fe3+ + e- ----(1)

Reduction ½ eqn: ClOx- + 2xH+ + 2xe- → Cl- + xH2O ----(2)

11.30
nFe 2+ = 0.500 × = 5.65 × 10 - 3 mol
1000

∴ ne- = 1× (5.65 × 10 -3 ) = 5.65 × 10 -3 mol

0.150
nClO − = mol
x
39.1 + 35.5 + 16 x

n 5.65 × 10 −3
e-
= = 2x
nClO − 0.150
x
39.1 + 35.5 + 16 x

∴ x=2

13
Oxidation ½ eqn: Fe2+ → Fe3+ + e- ----(1)
Reduction ½ eqn: ClO2- + 4H+ + 4e- → Cl- + 2H2O ----(2)
2+ - + 3+ -
Eqn(1) x 4 + Eqn(2) gives 4Fe + ClO2 + 4H → 4Fe + Cl + 2H2O

--THE END--

14