3.4 Redox Reaction

FeSO4 + KMnO4 + H2SO4 → K2SO4 + Fe2(SO4)3 + MnSO4 +H2O
FeSO4 + K2Cr2O7 + H2SO4 → K2SO4 + Fe2(SO4)3 + Cr2(SO4)3 +H2O

KMnO4 + H2C2O4 + H2SO4 → K2SO4 + MnSO4 + CO2 + H2O
K2Cr2O7 + H2C2O4 + H2SO4 → K2SO4 + Cr2(SO4)3 + CO2 + H2O
KMnO4 + H2O2 + H2SO4 → K2SO4 + MnSO4 + O2 + H2O
K2Cr2O7 + H2O2 + H2SO4 → K2SO4 + Cr2(SO4)3 + O2 + H2O
KMnO4 + H2S + H2SO4 → K2SO4 + MnSO4 + S + H2O
K2Cr2O7 + H2S + H2SO4 → K2SO4 + Cr2(SO4)3 + S + H2O
K2Cr2O7 + KI + H2SO4→ K2SO4 + Cr3(SO4)3 + I2 + H2O
K2Cr2O7 + KI + HCl → KCl + CrCl3 + I2+ H2O
In presence H2SO4, FeSO4 is oxidized by KMnO4 as follow

FeSO4 + KMnO4 + H2SO4 → K2SO4 + Fe2(SO4)3 + MnSO4 +H2O
Balance the above Redox reaction by ion electron method.
Here FeSO4 is a reducing agent since Fe+2 is converted into Fe+3 ion by giving up one electron and
KMnO4 is an oxidizing agent since Mn+7 is converted into Mn+2 ion by accepting 5 electron. So
we can write
Fe+2+ MnO4- + H+ → Fe+3 + Mn+2 + H2O
So reduction and oxidation half reaction will be-
Oxidation half: Fe+2 → Fe+3 + e- --------(1)
Reduction half: MnO4- + 5e- + 8H+ → Mn+2 + 4H2O ----------(2)
We need to add half reactions after cross multiplying by the number of electrons in each and then
5x(1) + (২) we get

5Fe+2 + MnO4- + 8H+→ 5Fe+3 + Mn+2 + 4H2O ------------------(4)
Adding Spectator ions (K+ and SO4-2) equation (4) becomes-
KMnO4+5FeSO4+ 4 H2SO4 → ½ K2SO2 + 5/2 Fe2(SO4)3 + MnSO4 + 4H2O ------(5)
Multiplying by 2 to eliminate the fractional coefficient we get-
1
2KMnO4+ 10FeSO4 + 8 H2SO4 → K2SO2 + 5 Fe2(SO4)3 + 2 MnSO4 + 8H2O
Now we can write
2KMnO4 + 10FeSO4 + 8 H2SO4 = K2SO2 + 5 Fe2(SO4)3 + 2 MnSO4 + 8H2O
This is the balanced redox reaction
Determination of purity of iron in a given sample:

A piece of 4g of iron was dissolved in excess dilute H2SO4. The solution was completely
neutralized with 120ml of deci-molar (0.1M) KMnO4 solution. Find the percentage of purity of
the iron.
Fe + H2SO4 → FeSO4 + H2O
Sol: The balanced redox reaction
2KMnO4 +10FeSO4 + 8 H2SO4 = K2SO2 + 5 Fe2(SO4)3 + 2 MnSO4 + 8H2O
2 mole KMnO4 ≡ 10 mole FeSO4
≡ 5 mole Fe
≡ 5 x 55.85g of Fe
Mole of KMnO4 used, n = c x v = 0.1 x 0.12 = 0.012 mole
1 mole KMnO4 = 5 x55.85g Fe
Hence, 0.012 mole KMnO4 = 0.012 x5x55.85g Fe = 3.351gFe
𝟑.𝟑𝟓𝟏
Percent of purity = x100 = 83.775%
𝟒
2
In presence H2SO4, FeSO4 is oxidized by K2Cr2O7 as follow
FeSO4 + K2Cr2O7 + H2SO4 → K2SO4 + Fe2(SO4)3 + Cr2(SO4)3 +H2O
Balance the above Redox reaction by ion electron method.
Here FeSO4 is a reducing agent since Fe+2 is converted into Fe+3 ion by giving up one electron and
K2CrO7 is an oxidizing agent since Cr+6 is converted into Cr+3 ion by accepting 3 electron. So we
can write
F+2 + CrO7-2 + H+ → Fe+3 +2K+ + Cr+3 + H2O
So reduction and oxidation half reaction will be-
Oxidation half: Fe+2 → Fe+3 + e- -------------------------(1)
Reduction half: CrO7-2+ 6e- + 14H+ → 2Cr+3 + 7H2O----------(2)
We need to add half reactions after cross multiplying by the number of electrons in each and then
6 x(1) + (3) we get
CrO7-2+ 6 Fe+2 + 14 H+→ 6Fe+3 + 2Cr+3 + 7H2O ---(4)
Adding Spectator ions we get
K2Cr2O7 +6 FeSO4 + 7 H2SO4= 3Fe2(SO4)3+ K2SO4 + Cr2(SO4)3+ 7H2O
3
Acidified aqueous potassium dichromate(vi) in alcohol test:

During the reaction the orange solution containing dichromate(vi) ions is converted to a solution
containing green chromium(iii) ions:
This reaction and its associated colour change was the basis for the ‘breathalyser’ formerly used
by many police forces around the world to detect and measure alcohol levels in the breath of
drivers.
4
Large numbers of people are killed every day by car accident, many of which occur because of
excessive consumption of alcohol. A breathalyser uses sodium dichromate(vi) to oxidize alcohol
in breath to ethanoic acid. The sodium dichromate(vi) changes color from orange to green when
consumed by the reaction. The extent of this colour change is monitored and used to determine the
blood alcohol level of the person undergoing the test.
Reaction of KMnO4 with Oxalic acid in acidic medium

Sol: KMnO4 is an oxidizing agent whereas H2C2O4 is a reducing agent
In KMnO4 oxidation number of Mn is +7 and in MnSO4 oxidation number is +2.
In H2C2O4 oxidation number of C is +3 and in CO2 oxidation number is +4.
Oxidation Half reaction: C2O4-2 → 2CO2 + 2e- ---------------------------------(1)
Reduction Half reaction: MnO4-1 + 5e- + 8H+ →Mn+2 + 4H2O …….(2)
Multiplying equation (1) with 5 and equation 2 with 2we get
5
5C2O4-2 → 10CO2 + 10e- ---------------(3)
2MnO4-1 + 10e- + 16H+ →2Mn+2 + 8H2O -------(4)
Now adding equation 3 and 4
2MnO4-1 + 5C2O4-2 + 16H+ →2Mn+2 +10CO2 + 8H2O
Now putting appropriate (spectator) ions
2KMnO4 + 5H2C2O4+ 3H2SO4 → K2SO4 + 2MnSO4 + 10CO2 + 8H2O
Reaction of Potassium dichromate react with oxalic acid in acidic medium

K2Cr2O7 + H2C2O4 + H2SO4 → K2SO4 + Cr2(SO4)3 + CO2 + H2O
Sol: K2Cr2O7 is an oxidizing agent whereas H2C2O4 is a reducing agent
In K2Cr2O7 oxidation number of Cr is +6 and in Cr2(SO4)3 oxidation number is +3.
In H2C2O4 oxidation number of C is +3and in CO2 oxidation number is +4.
Oxidation Half reaction: C2O4-2 → 2CO2 + 2e- ------------------------------(1)
Reduction Half reaction: Cr2O7-2 + 6e- + 14H+ →2Cr+3 + 7H2O ………..(2)
Multiplying equation (1) with 3 we get
3 C2O4-2 → 6CO2 + 6e- ---------------(3)
Cr2O7-2 + 3 C2O4-2 + 14H+ →2Cr+3 +6CO2 + 7H2O
6
K2Cr2O7 + 3H2C2O4 + 4H2SO4 → K2SO4+ Cr2(SO4)3 + 6CO2 + 7H2O
Reaction of KMnO4 with Hydrogen peroxide in acidic medium

KMnO4 + H2O2 + H2SO4 → K2SO4 + MnSO4 + O2 + H2O
Sol: KMnO4 is an oxidizing agent whereas H2O2 is a reducing agent
In KMnO4 oxidation number of Mn is +7 and in MnSO4oxidation number is +2.
In H2O2 oxidation number of O is -1 and in O2 oxidation number is 0.
Oxidation Half reaction: O2-1 →O2 + 2e- ---------------------------(1)
Reduction Half reaction: MnO4-1 + 5e- + 8H+ → Mn+2 + 4H2O …… .(2)
Multiplying equation (1) with 5 and equation 2 with 2 we get
5O2-1 → 5O2 + 10e- ----------------------(3)
2MnO4-1 + 10e- + 16H+ → 2Mn+2 + 8H2O -------(4)
2MnO4-1 + 5O2-1 + 16H+ → 2Mn+2 + 5O2 + 8H2O
2KMnO4 + 5H2O2 + 3H2SO4 → K2SO4 + 2MnSO4 + 5O2 + 8H2O
Determination of percentage of H2O2 in given sample:

If 20ml of 0.5M acidic KMnO4 can oxidize 15ml of H2O2 solution completely then find the
percentage of H2O2 in solution.
Sol: Balanced chemical reaction
From balanced reaction,
2 mole KMnO4 ≡ 5 mole H2O2
Therefore, 1 mole KMnO4 ≡ 2.5 mole H2O2
≡ 2.5 x34g H2O2
Mole of KMnO4 used, n = c xv = 0.5 x .02 = 0.01mole
Therefore, 0.01mole KMnO4 ≡ 0.01 x2.5 x34g H2O2
≡ 0.85g H2O2
7
0.85 𝑥100
So, the percentage of H2O2 in solution is = = 5.67%
15
Reaction of Potassium dichromate with Hydrogen peroxide in acidic medium

K2Cr2O7 + H2O2 + H2SO4 → K2SO4 + Cr2(SO4)3 + O2 + H2O
Sol: K2Cr2O7 is an oxidizing agent whereas H2O2 is a reducing agent
In H2O2 oxidation number of O is -1 and in O2 oxidation number is -2.
Oxidation Half reaction: O2-1 →O2 + 2e- ------------------------------------(1)
Reduction Half reaction: Cr2O7-2 + 6e- + 14H+ → 2Cr+3 + 7H2O ……..(2)
3 O2-1 → 3O2 + 6e
-
---------------(3)
Cr2O7-2 + 3O4-1 + 14H+ → 2Cr+3 + 3O2 + 7H2O
K2Cr2O7 + 3H2O2 + 4H2SO4 → K2SO4 + Cr2(SO4)3 + 3O2 + 7H2O
8
Reaction of KMnO4 with H2S in acidic medium
The ionic reaction can be given as

MnO4-1 + S-2 + H+ → Mn+2 + S + H2O
KMnO4 is an oxidizing agent whereas H2S is a reducing agent
In H2S oxidation number of S is -2 and in S, oxidation number is 0.
Oxidation Half reaction: S-2 → S + 2e- -----------------------------(1)
Multiplying equation (1) with 5 and equation (2) with 2 we get
5S-2 → 5S + 10e ---------------(3)
2MnO4-1 + 10e- + 16H+ → 2Mn+2 + 8H2O -------(4)
2MnO4-1 + 5S-2 + 16H+ → 2Mn+2 + 5S + 8H2O
Now adding appropriate (spectator) ions
2KMnO4 + 5H2S + 3H2SO4 → K2SO4 + 2MnSO4 + 5S + 8H2O
Reaction of Potassium dichromate with H2S in acidic medium

K2Cr2O7 + H2S + H2SO4 → K2SO4 + Cr2(SO4)3 + S + H2O
Sol: K2Cr2O7 is an oxidizing agent whereas H2O2 is a reducing agent
In H2S oxidation number of O is -2 and in S oxidation number is 0.
Oxidation Half reaction: S-2 → S + 2e
-
----------------------------------------(1)
Reduction Half reaction: Cr2O7-2 + 6e- + 14H+ → 2Cr+3 + 7H2O ………..(2)
3 S-2 → 3S + 6e- ---------------(3)
Cr2O7-2 + 3S-2 + 14H+ → 2Cr+3 + 3S + 7H2O
9
K2Cr2O7 + 3H2S + 4H2SO4 → K2SO4 + Cr2(SO4)3 + 3S + 7H2O
Reaction of KMnO4 with KI in acidic medium

KMnO4 + KI + H2SO4 → K2SO4 + MnSO4 + I2 + H2O
Sol: KMnO4 is an oxidizing agent whereas KI is a reducing agent
In KI oxidation number of I is -1 and in I2,oxidation number is 0.
Oxidation Half reaction: 2I-1 → I2 + 2e- ----------------------------(1)
Multiplying equation (1) with 5 and equation (2) with 2 we get
10I-1 → 5I2 + 10e- ---------------(3)
2MnO4-1 + 10e- + 16H+ → 2Mn+2 + 8H2O -------(4)
2MnO4-1 + 10I-1 + 16H+ → 2Mn+2 + 5I2 + 8H2O
2KMnO4 + 10KI + 8H2SO4 →6 K2SO4 + 2MnSO4 + 5I2+ 8H2O
Reaction of Potassium dichromate with KI in acidic medium

K2Cr2O7 + KI + H2SO4→ K2SO4 + Cr3(SO4)3 + I2 + H2O
K2Cr2O7 is an oxidizing agent whereas KI is a reducing agent
In KI oxidation number of I is -1 and in I2oxidation number is 0.
Oxidation Half reaction: 2I-1 → I2 + 2e- ---------------------------------------(1)
6I-1 → 3I2 + 6e- ---------------(3)
Cr2O7-2 + 6I-1 + 14H+ → 2Cr+3 + 3I2 + 7H2O
10
K2Cr2O7 + 6KI + 7H2SO4 → K2SO4 + Cr2(SO4)3 + 3I2 + 7H2O
Reaction of Potassium dichromate with KI in acidic medium

K2Cr2O7 + KI + HCl → KCl + CrCl3 + I2+ H2O
K2Cr2O7 is an oxidizing agent whereas KI is a reducing agent
In KI oxidation number of I is -1 and in S, oxidation number is 0.
Oxidation Half reaction: 2I-1 → I2 + 2e- -----------------------------------------(1)
6I-1 → 3I2 + 6e- ---------------(3)
Cr2O7-2 + 6I-1 + 14H+ → 2Cr+3 + 3I2 + 7H2O
K2Cr2O7 + 6KI + 14HCl → 2KCl + 2CrCl3 + 3I2 + 7H2O
Iodimetric and Iodometric

Iodimetric Titration: When a reducing agent is titrated directly with a standard iodine solution,
this titration method is called "iodimetric titration".
Iodometric Titration: When an oxidizing agent is added to excess iodide to produce iodine, and
the iodine produced is determined by titration with standard sodium thiosulfate, this titration
method is called "iodometric titration”
2CuSO4 + 4KI → Cu2I2 + 2K2SO4 + I2

I2 + 2Na2S2O3 → 2NaI + Na2S4O6
Determination of purity of Cu in a given sample:

Iodometric Titration can be used to determine the purity of copper in any given sample:
11
CQ. If 15 mlof 0.25M Na2S2O3 is needed to titrate liberated iodine after adding excessive KI
solution in 20 ml CuSO4 solution, then determine the amount of Cu in CuSO4 solution.
Sol: 2CuSO4 + 4KI → Cu2I2 + 2K2SO4 + I2
From Reaction,
2 mole Na2S2O3 ≡ 1 mole I2 = 2 mole CuSO4
Hence, 1 mole Na2S2O3 ≡ 1 mole CuSO4
≡ 1 mole Cu
≡ 63.5g of Cu
Mole of Na2S2O3used , n = cx v = 0.015 x 0.25 = 0.00375 mole
Therefore, 0.00375 mole of Na2S2O3 ≡ 0.00375 X 63.5g of Cu = 0.238g Cu
Problem for self-practice:

0.5 g mixture of K2Cr2O7 and KMnO4 was treated with excess of KI in acidic medium. Iodine
liberated required 150 cm3 of 0.10N solution of thiosulphate solution for titration. Find the
percentage of K2Cr2O7 in the mixture.
Uses of chlorine in everyday life

Chlorine is a powerful oxidizing agent and is widely used as a disinfectant and antiseptic. Calcium
hypochlorite, Ca(OCl)2, is often used in hospitals by healthcare professionals to disinfect their
hands. Sodium hypochlorite, NaOCl, is another disinfectant, often used in our homes as household
bleach. The sharing of needles and syringes among drug users is a contributory factor in the
transmission of the human immune deficiency virus (HIV), which can lead to acquired immune
deficiency syndrome (AIDS). The US Centers for Disease Control and Prevention (CDC) has
reported that disinfection of syringes and needles with household bleach may go some way to
alleviating this risk.
Use of chlorine and ozone as disinfectants in drinking water

Access to a supply of clean drinking water has been recognized by the United Nations as a
fundamental human right, yet it is estimated that over one billion people worldwide do not have
that. Water supplies are disinfected using strong oxidizing agents such as chlorine, Cl2 or ozone,
O3 to kill microbial pathogens. In Bangladesh, chlorine is used for this purpose. Chlorine can be
added in three forms: chlorine gas, Cl2; sodium hypochlorite, NaOCl; and calcium hypochlorite,
Ca(OCl)2. All three of these solutions yield hypochlorous acid, HOCl, which is the antibacterial
agent. The use of chlorine can cause problems for the general public. Some people object to the
taste and general odor of residual chlorine in water. Residual chlorine can also react with other
chemicals to form toxic products such as trichloromethane, CHCl3, commonly known as
chloroform.
12
In Europe, France was one of the first countries to use ozone to disinfect water supplies. The first
industrial ozone plant was established in Nice in 1906 for this purpose. The following table
compares the use of ozone and chlorine for water treatment.
An environmental application of redox chemistry: The Winkler method

In the Winkler method, an iodine/thiosulfate redox titration is carried out to measure the dissolved
oxygen present in a water sample. The procedure developed by Winkler is an indirect one, as the
dissolved oxygen does not directly react with the redox reagent.
The basic chemistry behind the Winkler method is that manganese(II) sulfate is added to the
water and the manganese(II) ions are oxidised under alkaline conditions to manganese(IV) by the
oxygen in the water:
MnSO4 + 2NaOH → Mn(OH)2 + Na2SO4
2Mn(OH)2(s) + O2(aq) → 2MnO(OH)2(s)
manganese(II) manganese(IV)
The sample is acidified with sulfuric acid to produce manganese(IV) sulfate:
MnO(OH)2(s) + 2H2SO4 (aq) → Mn(SO4)2 (aq) + 3H2O(l)
There is no change in oxidation number in this reaction. After adding excess KI in the mixture,
the Iodide ions are oxidised to I2 by the manganese(IV) ions:
Mn(SO4)2 (aq) + 2KI(aq) → Mn(SO4)2 aq) + I2(aq) + 2KI
This iodine can then be titrated against a standard sodium thiosulfate solution:
I2(aq) + 2Na2S2O3(aq) → Na2S4O6 aq) + 2NaI (aq)
From above reactions we can write,
1 1
2 mole Na2S2O3 = 1 mole I2 = 1 mole Mn(SO4)2 = 2 mole O2 = 2 x 32g of O2 = 18g O2 = 18000mg
O2
Or, 1 mole Na2S2O3 = 9000mg O2

1000mL 1M Na2S2O3 = 9000mg O2
This Winkler method is carried out to measure the dissolved oxygen content in the water sample
before and after the 5-day incubation period to determine the BOD.
13
Problem: A 50.0 mL of sample of water taken from a location where treated effluent is discharged
into a marina at Narayangonj, was first saturated with oxygen and then left for a period of 5 days
at 293 K in the dark. It was found that 5.25 cm3 of a 0.00500 mol dm-3 solution of sodium
thiosulfate, Na2S2O3(aq) was required to react with the iodine produced.
a) Determine the concentration of dissolved oxygen, in ppm, in the sample of water.

b) Deduce the BOD, in ppm, of the water sample, assuming that the maximum solubility of
oxygen in the water is 9.00 ppm at 293 K.
Redox Titration
Since both KMnO4 and K2Cr2O7 themselves change color during a redox reaction so when we
carry out titration using KMnO4 and K2Cr2O7, we don’t need to use extra indicator. Both KMnO4
and K2Cr2O7 can act as self-indicator.
Mn+7 (purple) → Mn+2 (almost colorless)

Cr+6 (orange) → Cr+3(green)
1. Standardising potassium manganate (VII) against sodium oxalate
A 25.0cm3 sodium oxalate solution of concentration 0.2M is warmed and titrated against a solution
of potassium manganate (VII). If 17.2 cm3 of potassium manganate (VII) are required, what is its
concentration?
Sol:
2KMnO4 + 5Na2C2O4 + 8H2SO4 → K2SO4 + 2MnSO4 + Na2SO4 + 10CO2 + 8H2O
𝑚𝑜𝑙𝑒 𝑜𝑓 𝐾𝑀𝑛𝑂4 2
=
𝑚𝑜𝑙𝑒 𝑜𝑓 𝑁𝑎2 𝐶2 𝑂4 5
Mole, n = volume x concentration = V x S
𝑉𝑜 𝑆𝑜 2
=
𝑉𝑟 𝑆𝑟 5
Vo = volume of KMnO4 = 17.2cm3
S0 = Concentration of KMnO4 = ?
Vr = volume of Na2C2O4 = 25.0 cm3
14
S0 = Concentration of Na2C2O4 = 0.2M
17.2 𝑥 𝑆 2
Hence, 25 𝑥 0.2𝑜 = 5
2 25 𝑥 0.2
Hence, So = 5 = 0.116M
17.2
Equivalent method:
Mole equivalent of KMnO4 = Mole equivalent of Na2C2O4
Vo x So x equivalent number of KMnO4 = Vr x Sr x equivalent number of Na2C2O4
17.2 x S0 x 5 = 25 x 0.2 x 2
Hence, So = 0.116M
2. Oxidising Iron(II) Compounds:

Ammonium iron (II) sulphate commonly known as Mohr’s salt having general formula
(NH4)2SO4. FeSO4.nH2O. In an experiment to determine n, 8.492g of the salt were
dissolved and made up to 250cm3 with distt\illed water and dilute sulphuric acid. A
25.0cm3 of the solution was further acidified and titrated against potassium manganate(VII)
solution of concentration 0.015M. A volume of 22.5cm3 was required.
Sol:
𝑚𝑜𝑙𝑒 𝑜𝑓 𝐾𝑀𝑛𝑂4 2 1
= =5
𝑚𝑜𝑙𝑒 𝑜𝑓 𝐹𝑒𝑆𝑂4 10
𝑉𝑜 𝑆𝑜 1
=
𝑉𝑟 𝑆𝑟 5
S0 = Concentration of KMnO4 = 0.015M
Vr = volume of FeSO4 = 25.0 cm3
S0 = Concentration of FeSO4 = ?
22.5 𝑥0.015 1
Hence, 25 𝑥 𝑆 = 5
𝑟
5 𝑥 22.5 𝑥0.015
Hence, Sr = 1 = 0.0675M
25
Hence, concentration of mohr’s salt is 0.0675M
𝑤 𝑥 1000
Again we know that, Molarity, S = 𝑀 𝑥 𝑣
𝑤 𝑥 1000 8.492 𝑥 1000
Or, M = = 0.0675 𝑥 250 = 503.2
𝑆𝑥𝑣
Molar mass of (NH4)2SO4. FeSO4.nH2O = 284 + 18n = 503.2
Or, n = 12
So, the formula of Mohr’s salt is (NH4)2SO4. FeSO4.12H2O
Oxidising by Hydrogen peroxide:

A solution of hydrogen peroxide was diluted 20times. A 25.0 cm3 of the diluted solution was
acidified and titrated against 0.015M potassium manganate (VII) solution. 45.7cm3 of the oxidant
were required. Calculate the concentration and percentage of the original hydrogen peroxide
solution.
15
Sol:
𝑚𝑜𝑙𝑒 𝑜𝑓 𝐾𝑀𝑛𝑂4 2
=
𝑚𝑜𝑙𝑒 𝑜𝑓 𝐻2 𝑂2 5
𝑉𝑜 𝑆𝑜 2
=
𝑉𝑟 𝑆𝑟 5

S0 = Concentration of KMnO4 = 0.015M
Vr = volume of H2O2 = 25.0 cm3
S0 = Concentration of H2O2 = ?
45.7𝑥0.015 2
Hence, 25 𝑥 𝑆𝑟 5
=
5 𝑥 45.7 𝑥0.015
Hence, Sr = 2 = 0.0685M
25
Concentration of original H2O2 solution = 4 x 0.0685 = 1.37M
1.37 𝑥 34
% H2O2 = x 100 = 4.658% (w/v)
1000
Finding the percentage of iron in ammonium iron (II) sulphate:

To determine the percentage of iron in Ammonium iron (II) sulphate, 8.492g of the salt
were dissolved and made up to 250cm3 with distt\illed water and dilute sulphuric acid. A
25.0cm3 of the solution was further acidified and titrated against potassium manganate(VII)
solution of concentration 0.015M. A volume of 22.5cm3 was required.
Sol: The balanced redox reaction

2KMnO4 +10FeSO4 + 8 H2SO4 = K2SO2 + 5 Fe2(SO4)3 + 2 MnSO4 + 8H2O
≡ 5 mole Fe
≡ 5 x 55.85g of Fe
1000mL 1M KMnO4 = 5 x 55.85g of Fe
5 x 55.85 x22.5 x0.015
Hence, 22.5mL 0.015M KMnO4 = = 0.0942 of Fe
1000
𝟎.𝟎𝟗𝟒𝟐
Percent of iron = x100 = 11.1%
𝟖.𝟒𝟗𝟐
16
Potassium dichromate (VI) titrations:
Determination of the percentage of iron in iron wire:
A piece of iron wire of mass 2.225g was dissolved in sulfuric acid and made up to 250 mL in
a graduated flask. 25mL of the solution were acidified and titrated against a 0.0185M
solution of potassium dichromate(VI). The volume required was 31.0mL. Calculate the
percentage of iron in the iron wire.
Sol:
K2Cr2O7 +6 FeSO4 + 7 H2SO4= 3Fe2(SO4)3+ K2SO4 + Cr2(SO4)3+ 7H2O
1 mole K2Cr2O7 = 6 mole FeSO4 = 6 mole iron = 6 x 55.85g Fe
So, 1000mL 1M K2Cr2O7 = 6 x 55.85g Fe
6 𝑥31.0 𝑥0.0185 𝑥 55.85
Hence, 31.0mL 0.0185M K2Cr2O7 = = 0.192 g Fe
1000
Amount of total iron in 250mL solution = 0.192 x10 =1.92g

1.92
% Fe = 2.225 x 100 = 86.7%
Sodium Thiosulphate Titration:

Sodium thiosulphate reduces iodine to iodide ions, and forms sodium tetrathionate, Na2S4O6
Sodium thiosulphate, Na2S2O3.5H2O is not used as a primary standard as the water content of the
crystal is variable. A solution of sodium thiosulphate can be standardized against a solution of
iodine or a solution of potassium iodate (V) or potassium dichromate or potassium manganate
(VII).
Iodine has a limited solubility in water. It dissolves in a solution of potassium iodide because it
forms the very soluble complex ion, I3-.
I2(S) + I- (aq) ↔ I3-(aq)
Standardization of a sodium thiosulphate solution using iodine:

1. 2.835g of iodine and 6g of potassium iodide are dissolved in distilled water
and made up to 250mL. A 25mL solution titrated against sodium thiosulphate
solution required 17.7mL of the solution. Calculate the concentration of the
thiosulphate solution.
Sol:
17
𝑚𝑜𝑙𝑒 𝑜𝑓 𝑁𝑎2 𝑆2 𝑂3 2
= =2
𝑚𝑜𝑙𝑒 𝑜𝑓 𝐼2 1
𝑉𝑜 𝑆𝑜 2
=
𝑉𝑟 𝑆𝑟 5
Vo = volume of Na2S2O3 = 17.7cm3

S0 = Concentration of Na2S2O3 = ?
Vr = volume of I2 = 25.0 cm3
2.835 𝑥 1000
S0 = Concentration of I2 = 250 𝑥 254 = 0.0446M
17.7𝑥 𝑆
𝑜
Hence, 25 𝑥 0.0446 =2
2 𝑥 25 𝑥0.0446
Hence, S0 = = 0.126M
17.7
So, Concentration of Na2S2O3 is 0.126M
Standardization of thiosulphate solution with potassium dichromate (VI):

K2Cr2O7 + 6KI + 7H2SO4 → K2SO4 + Cr2(SO4)3 + 3I2 + 7H2O
1 mole K2Cr2O7 = 3 mole I2 = 6 mole Na2S2O3
A standard solution is made by dissolving 1.015g potassium dichromate (VI) and making up to
250mL. A 25mL solution is added to excess of KI and diluted sulfuric acid, and the iodine liberated
is titrated against sodium thiosulphate solution. 19.2 mL of this solution are needed. Find the
concentration of the thiosulphate solution.
CQ.1.
30mL KMnO4 2g Fe in 50mL 0.1M
Solution Excess dilute K2Cr2O7
(acidic)
H2SO4 C
A
( B দ্রবনটি C দ্রবন দ্বারা সম্পূন জাররত
ন B
হয়)
c) Balance the redox reaction by ion electron method that will take place after passing H2S into
solution A.
d) Analyze whether the iron added in solution B is pure or not?
Ans
C) The redox reaction that will take place after passing H2S into solution A.
18
d) Fe + H2SO4 → FeSO4 + H2O

K2Cr2O7 +6 FeSO4 + 7 H2SO4 = 3Fe2(SO4)3+ K2SO4 + Cr2(SO4)3 + 7H2O
1 mole K2Cr2O7 ≡ 6 mole FeSO4
≡ 6 mole Fe
≡ 6 x 55085g of Fe
1000mL 1M K2Cr2O7 = 6 x 55.85g of Fe
6 x 55.85 𝒙 𝟓𝟎 𝒙 𝟎.𝟏
Hence, 50mL 0.1M K2Cr2O7 = g Fe
𝟏𝟎𝟎𝟎
= 1.6755g Fe
𝟏.𝟔𝟕𝟓𝟓
𝟐
CQ.2.
25mL 0.1M 15mL 12mL FeSO4
H2C2O4 KMnO4 + H2SO4
≡ solution ≡
C
(acidic) B
A
C) Balance the Redox reaction by ion electron method that will take place after mixing Solution
A and B together.
d) Using solution A and B determine the amount of iron in solution C.
5 xS1 x V1 = 2 x S2 x V2 V2 = Volume of H2C2O4 = 25mL
S2 = concentration of H2C2O4 = 0.1M
2 𝑥𝑆2 𝑉2 2 𝑥25 𝑥 0.1 V1 = Volume of KMnO4 = 15mL
Therefore, S1 = = = 0.067M
5 𝑥 𝑉1 5 𝑥 15

Balanced chemical reaction
19
≡ 5 mole Fe
≡ 5 x 55085g of Fe
1000mL 1M KMnO4 = 5x55.85g Fe
CQ.3.
30mL KMnO4 2g Fe in 50mL 0.1M K2Cr2O7
Solution (acidic) Excess dilute H2SO4 C
A B
( Solution B is completely oxidized by solution C)

c) Balance the redox reaction by ion electron method that will take place after passing H2S
into solution A.
d) Analyze whether the iron added in solution B is pure or not?
C) The redox reaction that will take place after passing H2S into solution A.
d) The balanced redox reaction
K2Cr2O7 +6 FeSO4 + 7 H2SO4 = 3Fe2(SO4)3+ K2SO4 + Cr2(SO4)3 + 7H2O
1 mole K2Cr2O7 ≡ 6 mole FeSO4
≡ 6 mole Fe
≡ 6 x 55085g of Fe
1000mL 1M K2Cr2O7 = 6 x 55.85g of Fe
6 x 55.85 𝒙 𝟓𝟎 𝒙 𝟎.𝟏
Hence, 50mL 0.1M K2Cr2O7 = g Fe
𝟏𝟎𝟎𝟎
= 1.6755g Fe
𝟏.𝟔𝟕𝟓𝟓
𝟐
20
CQ.4.
25mL 0.1M 15mL 12mL FeSO4
H2C2O4 (acidic) KMnO4 solution + H2SO4
≡ ≡
A B C
C) Balance the Redox reaction by ion electron method that will take place after mixing
Solution A and B together.
c)

5 x S1 x V1 = 2 xS2 x V2 V2 = Volume of H2C2O4 = 25mL
2 𝑥𝑆2 𝑉2 2 𝑥25 𝑥 0.1 S2 = concentration of H2C2O4 = 0.1M
Therefore, S1 = = = 0.067M
5 𝑥𝑉1 5 𝑥15
V1 = Volume of KMnO4 = 15mL
Balanced chemical reaction
≡ 5 mole Fe
≡ 5 x 55085g of Fe
1000mL 1M KMnO4 = 5x55.85g Fe
21
1.3g Cu
CQ.5.
100mL 0.2M
Dilute H2SO4 KI solution
50mL Na2S2O3
B
A C
Solution A is completely neutralized by solution B and C respectively.
a) How will you convert solution C in the stem into a decimolar solution?
b) Find the percentage of impurity of copper used in the stem.
Sol:
a)
S1V1 = S2V2 S1 = concentration of Na2S2O3 solution =

𝑆 𝑉 0.2 𝑥100 0.2M
V2 = 1𝑆 1 = 0.1 = 200mL
2 V1 = Volume of Na2S2O3 solution
= 100mL
S2 = concentration of Na2S2O3 solution
to be made = 0.1M
By adding (200-100) = 100 mL water in solution C we can convert it into a decimolar solution.
e)
2CuSO4 + 4KI → Cu2I2 + 2K2SO4 + I2
From Reaction,
2 mole Na2S2O3 ≡ 1 mole I2 = 2 mole CuSO4
Hence, 1 mole Na2S2O3 ≡ 1 mole CuSO4 ≡ 1 mole Cu ≡ 63.5g of Cu
1000mL 1M Na2S2O3 = 63.5g of Cu
63.5 𝑥100𝑥0.2
100mL 0.2M Na2S2O3 = =1.27gCu
1000
1.27
% of purity of Copper = 𝑥100 = 97.69 %
1.3
% of impurity of Copper = 100-97.69 = 2.31%
22
CQ.6.
a) If K2Cr2O7 is taken in burette then balance the redox reaction that will take place with the
reducing agent taken in conical flask in acidic medium.
b) If 22.5mL of 0.5M Na2S2O3 is needed to neutralize the solution taken in conical flask then
find the amount Cu and explain with logic whether the stem titration is iodometric or
iodemetric?
CQ.7.
c) Balance the redox reaction in ion electron method that will take place in conical flask.
d) If we use K2Cr2O7 instead of CuSO4 then the process will be iodometric or iodimetric?
Analyze with logic.
CQ.8.
25mL 0.1M KMnO4 15mL 12mL FeSO4
H2C2O4 ≡ Solution With≡H2SO4
Solution (A) B C
c) Determine the amount of iron in solution C by using solution B.

d) If we Amix up solution A and B together then analyze whether both oxidation and
reduction reaction will take together or not?
CQ.9.
FeSO4
20mL 0.1M 10mL K2Cr2O7
With H2SO4
H2C2O4 Solution
≡ ≡ ≡ C
Solution (A) B
23 A
c) Balance the redox reaction by ion electron method that will take place if we mix up B and C.
d) Using solution A and B determine the amount of Fe in solution C.
CQ.10.
Acidic K2Cr2O7 45 mL 2g CuSO4

containing
148mL 0.01M ≡ Na2S2O3 solution ≡
A 33mL KI solution
B
C
c) Why do we use KI when doing titration of B with C?

d) Analyze whether it is possible to oxidize solution B completely by solution C or not?
CQ. 11. 400mL of solution was prepared by dissolving 3.04g of bleaching powder. To neutralize
25mL of this solution if 40mL 0.075M Na2S2O3 is needed.
c) Find the amount of chlorine in bleaching powder.
d) Using the stem iodometric titration how will you determine the amount of iron? Explain.
CQ.12.
24
CQ.13.
14. 1.2L of standard solution was prepared by dissolving hydrated sodium thiosulphate (
Na2S2O3.5H2O). To neutralize a mixture of 10mL 0.2M K2Cr2O7, 10mL con H2SO4 and 10mL
15% KI 15mL of sodium thiosuphate solution was needed. What was the concentration of sodium
thiosulphate solution?
Sol: K2Cr2O7 + 6KI +7 H2SO4 = 4K2SO4 + Cr2(SO4)3 + 7H2O +3I2

2 Na2S2O3 +I2 = Na2S4O6 + 2NaI
So, 1mole K2Cr2O7 = 3 mole I2 = 6mole Na2S2O3

Hence, 1mole K2Cr2O7 = 6mole Na2S2O3
25

3.4 Redox Reaction

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3.4 Redox Reaction

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FeSO4 + KMnO4 + H2SO4 → K2SO4 + Fe2(SO4)3 + MnSO4 +H2O

FeSO4 + K2Cr2O7 + H2SO4 → K2SO4 + Fe2(SO4)3 + Cr2(SO4)3 +H2O

In presence H2SO4, FeSO4 is oxidized by KMnO4 as follow

5x(1) + (২) we get

Determination of purity of iron in a given sample:

Acidified aqueous potassium dichromate(vi) in alcohol test:

Reaction of KMnO4 with Oxalic acid in acidic medium

Reaction of Potassium dichromate react with oxalic acid in acidic medium

Reaction of KMnO4 with Hydrogen peroxide in acidic medium

Determination of percentage of H2O2 in given sample:

Reaction of Potassium dichromate with Hydrogen peroxide in acidic medium

The ionic reaction can be given as

Reaction of Potassium dichromate with H2S in acidic medium

Reaction of KMnO4 with KI in acidic medium

Reaction of Potassium dichromate with KI in acidic medium

Reaction of Potassium dichromate with KI in acidic medium

Iodimetric and Iodometric

2CuSO4 + 4KI → Cu2I2 + 2K2SO4 + I2

Determination of purity of Cu in a given sample:

Problem for self-practice:

Uses of chlorine in everyday life

Use of chlorine and ozone as disinfectants in drinking water

An environmental application of redox chemistry: The Winkler method

Or, 1 mole Na2S2O3 = 9000mg O2

a) Determine the concentration of dissolved oxygen, in ppm, in the sample of water.

Mn+7 (purple) → Mn+2 (almost colorless)

1. Standardising potassium manganate (VII) against sodium oxalate

2. Oxidising Iron(II) Compounds:

Molar mass of (NH4)2SO4. FeSO4.nH2O = 284 + 18n = 503.2

Oxidising by Hydrogen peroxide:

Mole, n = volume x concentration = V x S

Finding the percentage of iron in ammonium iron (II) sulphate:

Sol: The balanced redox reaction

Amount of total iron in 250mL solution = 0.192 x10 =1.92g

Sodium Thiosulphate Titration:

Standardization of a sodium thiosulphate solution using iodine:

Mole, n = volume x concentration = V x S

Vo = volume of Na2S2O3 = 17.7cm3

So, Concentration of Na2S2O3 is 0.126M

Standardization of thiosulphate solution with potassium dichromate (VI):

d) Fe + H2SO4 → FeSO4 + H2O

2KMnO4 + 10FeSO4 + 8 H2SO4 = K2SO2 + 5 Fe2(SO4)3 + 2 MnSO4 + 8H2O

( Solution B is completely oxidized by solution C)

d) Using solution A and B determine the amount of iron in solution C.

Solution A is completely neutralized by solution B and C respectively.

S1V1 = S2V2 S1 = concentration of Na2S2O3 solution =

% of impurity of Copper = 100-97.69 = 2.31%

c) Determine the amount of iron in solution C by using solution B.

Acidic K2Cr2O7 45 mL 2g CuSO4

c) Why do we use KI when doing titration of B with C?

Sol: K2Cr2O7 + 6KI +7 H2SO4 = 4K2SO4 + Cr2(SO4)3 + 7H2O +3I2

So, 1mole K2Cr2O7 = 3 mole I2 = 6mole Na2S2O3

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