WORKED EXAMPLES AND EXERCISES ON REDOX

TITRATIONS
A. Calculations involving Redox Titrations of acidic MnO4- with Fe2+.
1. A standard solution of 7.65 g dm-3 potassium tetraoxomanganate (VII) was titrated
against of iron (II) tetraoxosulphate (VI) solution. If 15.50 cm3 of this solution required
for complete reaction, 25.00 cm3.
(a) Write down the:
(i) reduction half equation; (ii) oxidation half equation; (iii) overall redox
equation.
(b) Calculate the concentration of:
(i) potassium tetraoxomanganate (VII) in mol dm-3;
(ii) iron (II) tetraoxosulphate (VI) solution in:
I. mol dm-3; II. g dm-3.
[Fe = 56; Mn = 55; S = 32; K = 39; O =16]

Solution
a) (i) Reduction half equation:
MnO4– + 8H+ + 5e- → Mn2+ + 4H2O
(ii) Oxidation half equation:
Fe2+ → Fe3+ + e-
(iii) Overall redox reaction:
Eq. (i) x 1: MnO4– + 8H+ + 5e- → Mn2+ + 4H2O
(ii) x 5: + 5Fe2+ → 5Fe3+ + 5e-
– 2+
MnO4 + 5Fe + 8H +
→ Mn2+ + 5Fe3+ + 4H2O
b) (i) Conc. of KMnO4 in mol dm-3.
First find the molar mass of KMnO4 = 39 + 55 + (16 x 4) = 158 g mol-1
𝑐𝑜𝑛𝑐.(𝑔 𝑑𝑚−3 ) 7.65
Conc. (𝑚𝑜𝑙 𝑑𝑚−3 ) 𝑜𝑓 𝐾𝑀𝑛4 = = = 𝟎. 𝟎𝟒𝟖𝟒 𝑚𝑜𝑙 𝑑𝑚−3
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 158

(ii) I. Conc. of FeSO4 in mol dm-3.

𝐶(𝑀𝑛𝑂 − −
4 ) 𝑥 𝑉(𝑀𝑛𝑂 4 ) 𝑛(𝑀𝑛𝑂 −
4)
=
𝐶(𝐹𝑒2+ ) 𝑥 𝑉(𝐹𝑒2+ ) 𝑛(𝐹𝑒2+)

𝐶(𝑀𝑛𝑂 − −
4 ) 𝑥 𝑉(𝑀𝑛𝑂 4 ) 𝑥 𝑛(𝐹𝑒2+ ) 0.0484 𝑥 15.50 𝑥 5
∴ 𝐶𝐹𝑒 2+ = = = 0.150 mol dm-3
𝑉(𝐹𝑒2+ ) 𝑥 𝑛(𝑀𝑛𝑂 −
4) 25.00 𝑥 1

II. Conc. of FeSO4 in g dm-3.

Molar mass of FeSO4 = 56 + 32 + (16 x 4) = 152 g mol-1
Conc. in g dm-3 = conc. (mol dm-3) x molar mass (g mol-1)
= 0.150 x 152 = 22.8 g dm-3
2. A is 0.0200 mol dm-3 KMnO4 solution.
B is FeSO4.xH2O solution of concentration 27.8 g dm-3.
C is a 2.00 mol dm-3 solution of tetraoxosulphate (VI) acid.
24.55 cm3 of A required 25.00 cm3 of B acidified with 15.0 cm3 of C for complete
oxidation.
From the information provided, calculate the:
(a) concentration of KMnO4 in A in g dm-3;
(b) concentration of FeSO4 in B in mol dm-3;
(c) concentration of FeSO4 in B in g dm-3;
(d) mass of water in FeSO4.xH2O;
(e) number of moles of water of crystallization (x) in FeSO4.xH2O;
(f) percentage of water of crystallization in FeSO4.xH2O;
(g) write down the chemical formula of B.
The equation for the reaction is:
MnO4- + 5Fe2+ + 8H+ → Mn2+ + 5Fe3+ + 4H2O
[H =1.00; O = 16.0; S = 32.0; K = 39.0; Mn = 55.0 Fe =56.0]

Solution
(a) Concentration of KMnO4 in A in g dm-3
Molar mass of KMnO4 = 39.0 + 55.0 + (16.0 x 4) = 158 g mol-1
Conc. in g dm-3 = conc. (mol dm-3) x molar mass (g mol-1)
= 0.0200 x 158 = 3.16 g dm-3

(b) Concentration of FeSO4 in B in mol dm-3

𝐶𝐴 𝑉𝐴 𝑛 𝐶 𝑥 𝑉 𝑥 𝑛
= 𝑛𝐴 . ∴ 𝐶𝐵 = 𝑨 𝑉 𝑥𝑨 𝑛 𝑩
𝐶 𝑉
𝐵 𝐵 𝐵 𝑩 𝑨
0.0200 𝑥 24.55 𝑥 5
= = 0.0982 mol dm-3
25 𝑥 1

(c) Concentration of FeSO4 in B in g dm-3 (i.e. mass of anhydrous salt)

Molar mass of FeSO4 = 56.0 + 32.0 + (16.0 x 4) = 152 g mol-1
Conc. in g dm-3 = conc. (mol dm-3) x molar mass (g mol-1)
= 0.0982 x 152 = 14.9 g dm-3

(d) Mass of water in FeSO4.xH2O.

= mass of hydrated salt – mass of anhydrous salt
= 27.8 – 14.9 = 12.9 g
 (e) Number of moles of water of crystallization or value of x in FeSO4.xH2O.
Method 1 Method 2
First find the molar mass of B from the relation, 𝑚𝑎𝑠𝑠 𝑜𝑓 𝐻2 𝑂 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝒙𝐻2 𝑂
=
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑎𝑛ℎ𝑦𝑑𝑟𝑜𝑢𝑠 𝑠𝑎𝑙𝑡 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑎𝑛ℎ𝑦𝑑𝑟𝑜𝑢𝑠 𝑠𝑎𝑙𝑡
𝑐𝑜𝑛𝑐 (𝑔 𝑑𝑚 −3 ) 27.8
Molar mass = = = 283 g mol-1
𝑐𝑜𝑛𝑐 (𝑚𝑜𝑙 𝑑𝑚 −3 ) 0.0982 12.9 𝒙[(1𝑥2) + 16]𝑔 𝑚𝑜𝑙 −1
=
14.9 56.0 + 32.0 + (16𝑥4)𝑔 𝑚𝑜𝑙 −1
FeSO4.xH2O = 283 g mol-1
12.9 18𝒙
56.0 + 32.0 + (16x4) + x[(1x2) +16] = 283 =
14.9 152
152 +18x = 283
18x = 283 – 152 = 131 12.9 𝑥 152
131 𝒙= = 7.3 ≅ 7
x= = 7.2 ≅ 7 14.9 𝑥 18
18

(f) Percentage (%) of water of crystallization in FeSO4.xH2O

𝑚𝑎𝑠𝑠 𝑜𝑓 𝒙𝐻 𝑂 𝑥 100
2 12.9 𝑥 100
= 𝑚𝑎𝑠𝑠 𝑜𝑓 ℎ𝑦𝑑𝑟𝑎𝑡𝑒𝑑 = = 46.2 %
𝑠𝑎𝑙𝑡 27.9

(g) The chemical formula of B is FeSO4.7H2O

3. A is a solution containing 0.00890 mol dm-3 acidified KMnO4.

B is a solution containing a mixture of Fe2+/Fe3+ of concentration 10.00 g dm-3.
22.20 cm3 of A required 25.00 cm3 of B for complete oxidation.
From the information provided, calculate the:
(a) concentration of KMnO4 in A in g dm-3;
(b) concentration of Fe2+ in B in mol dm-3;
(c) concentration of Fe2+ in B in g dm-3;
(d) percentage of Fe2+ in B.
The equation for the reaction is:
MnO4– + 5Fe2+ + 8H+ → Mn2+ + 5Fe3+ + 4H2O
[O = 16.0; K = 39.0; Mn = 55.0 Fe =56.0]

Solution
(a) Concentration of KMnO4 in A in g dm-3
Molar mass of KMnO4 = 39.0 + 55.0 + (16.0 x 4) = 158 g mol-1
Conc. in g dm-3 = conc. (mol dm-3) x molar mass (g mol-1)
= 0.00890 x 158 = 1.41 g dm-3
(b) Concentration of Fe2+ in B in mol dm-3
𝐶𝐴 𝑉𝐴 𝑛𝐴 𝐶𝑨 𝑥 𝑉𝑨 𝑥 𝑛𝑩 0.00890 𝑥 22.20 𝑥 5
= . ∴ 𝐶𝐵 = = = 0.0395 mol dm-3
𝐶 𝑉
𝐵 𝐵 𝑛 𝐵 𝑉 𝑥 𝑛 𝑩 25 𝑥 1
𝑨
(c) Concentration of Fe2+ in B in g dm-3
Molar mass of Fe2+ = 56.0 g mol-1
Mass conc. or conc. in g dm-3 = conc. (mol dm-3) x molar mass (g mol-1)
= 0.0395 x 56 = 2.21 g dm-3

(d) Percentage of Fe2+ in B

𝑚𝑎𝑠𝑠 𝑐𝑜𝑛𝑐. 𝑜𝑓 𝐹𝑒 2+ 𝑖𝑛 𝑩 2.21
= 𝑚𝑎𝑠𝑠 𝑐𝑜𝑛𝑐. x 100 = 10.00 x 100 = 22.1 %
𝑜𝑓 𝑚𝑖𝑥𝑡𝑢𝑟𝑒 (𝐹𝑒 2+ /𝐹𝑒 3+ )
EXERCISES
Question 1. (WASSCE, CHEMISTRY 3 [Alternative to practical]: NOVEMBER 2017)
E was prepared by dissolving 33.60 g of a mixture of FeSO4.7H2O and NaCl to make 1.0 dm3
solution.
F was 0.0200 mol dm-3 KMnO4.
25 cm3 of E was pipetted into a conical flask acidified with 20.0 cm3 of dilute H2SO4 and titrated
with F.
The results were recorded in the table below.
Burette Readings/cm3 1 2 3
Final Reading 33.10 30.00
Initial Reading 7.50 2.40
Volume of F used/cm3 23.50 22.60

(a) (i) Copy and complete the table.

Burette Readings/cm3 1 2 3
Final Reading 33.10 30.00 …………..
Initial Reading ……………. 7.50 2.40
Volume of F used/cm3 23.50 …………… 22.60
(ii) Calculate the average volume of F used.
…………………………………………………………………………………………………………
…………. ……………………………………………………………………………………………
Answer: 22.55 cm3
Equation of reaction is: 5Fe2+ + MnO4– + 8H+ → 5Fe3+ + Mn2+ + 4H2O.
(b) From your results and the information provided, calculate the:
(i) concentration of FeSO4.7H2O in E in mol dm-3;
…………………………………………………………………………………………………………
…………………………………………………………………………………………………………
………………………………………………………………………… Answer: 0.0902 mol dm-3
(ii) concentration of FeSO4.7H2O in E in g dm-3;
…………………………………………………………………………………………………………
…………………………………………………………………………………………………………
……………………………………………………………………………… Answer: 13.7 g dm-3
(iii) percentage by mass of FeSO4.7H2O in the mixture.
…………………………………………………………………………………………………………
…………………………………………………………………………………………………………
…………………………………………………………………………………… Answer: 40.8 %
[O = 16.0; S = 32.0; H = 1.00; Fe = 56.0]

(c) (i) Explain briefly why hydrochloric acid cannot be used to provide an acidic
medium in titration involving KMnO4.
…………………………………………………………………………………………………………
…………………………………………………………………………………………………………
(ii) Explain why the upper rim of the meniscus is read in KMnO4 titrations.
…………………………………………………………………………………………………………
…………………………………………………………………………………………………………
(iii) Explain why no indicator was used in the titration.
…………………………………………………………………………………………………………
Question 2.
A is a solution containing 0.100 mol dm-3 acidified KMnO4.
B is a solution containing a mixture of Fe2+/Fe3+ of concentration 7.50 g in 250 cm3.
24.00 cm3 of A required 25.00 cm3 of B for complete oxidation.
The equation for the reaction is: MnO4– + 5Fe2+ + 8H+ → Mn2+ + 5Fe3+ + 4H2O
[O = 16.0; K = 39.0; Mn = 55.0 Fe =56.0]

From the information provided, calculate the:

(a) concentration of KMnO4 in A in g dm-3;
…………………………………………………………………………………………………………
…………………………………………………………………………………………………………
……………………………………………………………………………… Answer: 15.8 g dm-3
(b) concentration of B (i.e. mixture) in g dm-3;
…………………………………………………………………………………………………………
…………………………………………………………………………………………………………
……………………………………………………………………………… Answer: 30.0 g dm-3
(c) concentration of Fe2+ in B in mol dm-3;
…………………………………………………………………………………………………………
…………………………………………………………………………………………………………
…………………………………………………………………………… Answer: 0.480 mol dm-3
(d) concentration of Fe2+ in B in g dm-3;
…………………………………………………………………………………………………………
…………………………………………………………………………………………………………
……………………………………………………………………………… Answer: 26.9 g dm-3
(e) percentage of Fe2+ in B.
…………………………………………………………………………………………………………
……………………………………………………………………………………Answer: 89.7 %
Note: Percentage of Fe3+ in B = 100 – 89.7 = 10.3 %
Question 3.
A is 0.0100 mol dm-3 potassium tetraoxomanganate (VII) solution, KMnO4.
B is an acidified aqueous solution of iron (II) tetraoxosulphate (VI), FeSO4 containing 12.18 g per
500 cm3.
43.85 cm3 of solution A reacted completely with 25.0 cm3 of B.
The equation for the reaction is:
MnO4– + 5Fe2+ + 8H+ → Mn2+ + 5Fe3+ + 4H2O
[H =1.00; O = 16.0; S = 32.0; K = 39.0; Mn = 55.0 Fe =56.0]

Calculate the:
(a) concentration of FeSO4 in B in mol dm-3;
……………………………………………………………………………………………………
……………………………………………………………………………………………………
………………………………………………………………………Answer: 0.0877 mol dm-3
(b) concentration of FeSO4 in B in g dm-3 (mass concentration of anhydrous salt)
……………………………………………………………………………………………………
……………………………………………………………………………………………………
…………………………………………………………………………… Answer: 13.3 g dm-3
(c) mass of water in FeSO4.xH2O;
First find the concentration in g dm-3 of hydrated salt (in the question)
……………………………………………………………………………………………………
……………………………………………………………………………………………………
…………………………………………………………………………… Answer: 24.4 g dm-3
Then the mass of water in FeSO4.xH2O.
………………………………………………………………………………… Answer: 11.1 g
(d) number of moles of water of crystallization (x) in FeSO4.xH2O;
First find the molar mass of FeSO4.xH2O.
……………………………………………………………………………………………………
……………………………………………………………………………………………………
…………………………………………………………………………… Answer: 278 g mol-1
Then equate the molar mass to FeSO4.xH2O and find x.
……………………………………………………………………………………………………
……………………………………………………………………………………………………
………………………………………………………………………………………Answer: 7
(e) percentage of water of crystallization in FeSO4.xH2O;
……………………………………………………………………………………………………
……………………………………………………………………………………………………
……………………………………………………………………………… Answer: 45.5 %
(f) write down the chemical formula of B. ………………………………….