NOTE

C H E M I S T R Y

Types of boundaries
REDOX REACTIONS
SPECIAL CASES

What you already know What you will learn

• Redox titrations • Volume strength of H2O2

• Back titrations • Strength of oleum
• Double indicator titrations • Concept of available chlorine
• Iodometric titrations and • Hardness of water
iodimetric titrations • Degree of hardness

BOARDS MAIN ADVANCED

Volume Strength of H2O2

The oxidation state of oxygen in oxide is −2 and that in peroxide is −1.

H2O2 as a reducing agent in acidic medium

Oxidation
(Reducing agent)

–1 0
H2O2 ⟶ 2H+ + O2 + 2e–

The oxidation state of oxygen is changing from −1 in H2O2 to 0 in O2.

Hence, H2O2 will act as a reducing agent.
n-factor = │Oxidation state of product − Oxidation state of reactant│× Number of atoms
n-factor of H2O2 = │0 − (−1)│× 2 = 2
Hence, the n-factor of H2O2 as a reducing agent in an acidic medium is 2.

H2O2 as a reducing agent in basic medium

Oxidation
(Reducing agent)

–1 0
2OH + H2O2 ⟶ 2H2O + O2 + 2e–
–

The oxidation state of oxygen is changing from −1 in H2O2 to 0 in O2

Hence, H2O2 will act as a reducing agent.

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n-factor = │Oxidation state of product − Oxidation state of reactant│× Number of atoms

n-factor of H2O2 = │0 − (−1)│× 2 = 2

H2O2 as an oxidising agent in acidic medium

Reduction
(Oxidising agent)

–1 –2
H2O2 + 2e + 2H ⟶ 2H2O
– +

The oxidation state of oxygen is changing from −1 in H2O2 to –2 in H2O.

n-factor = │Oxidation state of product − Oxidation state of reactant│× Number of atoms
n-factor of H2O2 = │−2 − (−1)│× 2 = 2

H2O2 as an oxidising agent in basic medium

Reduction
(Oxidising agent)

–1 –2
H2O2 + 2e ⟶ 2OH–
–

The oxidation state of oxygen is changing from −1 in H2O2 to −2 in OH−.

n-factor = │Oxidation state of product - Oxidation state of reactant│× Number of atoms
n-factor of H2O2 = │−2 − (−1)│× 2 = 2

Decomposition of H2O2

Reduction

–1 –2
∆
2H2O2(aq) ⟶ 2H2O(I) + O2(g)
0

Oxidation
Disproportionation redox reaction: The reaction in which same element undergoes oxidation and
reduction simultaneously.

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Volume strength of H2O2

The concentration of H2O2 is usually represented in terms of volume (vol). If a sample of H2O2
is labelled as x V, it means that 1 L of H2O2 solution gives x L of O2 gas at STP on complete
decomposition.
We know that H2O2 decomposes as,
∆
2H2O2(aq) ⟶ 2H2O(I) + O2(g)
2 moles of H2O2 gives 22.4 L of O2 at STP.
1 moles of H2O2 gives 0.5 moles of O2.
1 moles of H2O2 gives 11.2 L of O2 at STP.
1 L of 1 M H2O2 gives 11.2 L of O2 at STP, then the volume strength is 11.2 V.
1 L of 2 M H2O2 gives 22.4 L of O2 at STP, then the volume strength is 22.4 V.
2 L of 1 M H2O2 gives 22.4 L of O2at STP, then the volume strength is 11.2 V.
Volume strength in terms of normality
Volume strength of H2O2 = N × 5.6

N = nf × M

Where,
N = Normality
nf = n-factor
M = Molarity
For H2O2, nf = 2
So, volume strength of H2O2 = M × 11.2

Based on calculating the volume strength of H2O2

500 mL of H2O2 solution is added to an excess of acidified KI solution. The I2 liberated requires 25
mL of 0.1 N hypo solution for titration. Calculate the volume strength of H2O2.

Solution

The reaction for the given titration is as follows:

Reduction
(Oxidising agent)

0 –1
2S2O 3
2–
+ I2 ⟶ S4O6 + 2I–
2–

+2 +2.5

(Reducing agent)
Oxidation
Number of equivalents of S2O32− = Number of equivalents of I2

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Reduction
(Oxidising agent)

–1 –2
2H+ + H2O2 + 2I– ⟶ 2H2O + I2
–1 0

(Reducing agent)
Oxidation
Number of equivalents of H2O2 = Number of equivalents of I2
So, number of equivalents of S2O32− = Number of equivalents of H2O2
In terms of milliequivalents,
Volume of S2O32− (hypo) solution = 25 mL
Normality of S2O32− (hypo) solution = 0.1 N
Volume of H2O2 used = 500 mL
Number of milliequivalents of S2O32− = Number of milliequivalents of H2O2
25 × 0.1 = 500 × N
0.1
N= = 0.005 N
20
Volume strength of H2O2 = N × 5.6
Volume strength of H2O2 = 0.005 × 5.6 = 0.028 V

If the n-factor of I2 is the same in both the reactions, then,

Equivalents of S2O32− = Equivalents of H2O2
But suppose if the reactions are:
(Oxidising agent)
Reduction

–1 –2
2H + H2O2 + 2I ⟶ 2H2O + I2
+ –

–1 0

Oxidation
(Reducing agent)

The oxidation number of I in iodide ion is −1, and that in I2 is 0, so the nf of I2 is 1 × 2 = 2

And the other reaction is,
I2 ⟶ 2IO3–
The oxidation number of iodine is 0 in I2 and +5 in IO , so the 3
−

nf of I2 is 5 × 2 = 10 0 +5
So, if the n-factors are not the same, then the equivalents of I2 (Reducing agent)
in both the reactions will not be the same.
Oxidation

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BOARDS MAIN ADVANCED

Strength of Oleum

Percentage labelling of oleum

Oleum is a mixture of H2SO4 and SO3 that is, H2S2O7.

O O
O

S S
H H
O O
O O

Fig. 1: Structure of oleum

This is obtained by passing SO3 in the H2SO4 solution.
SO3(g) + H2SO4(aq) ⟶ H2S2O7 (aq)
To dissolve free SO3, water is added to it. Dilution is continued till the entire SO3 gets converted
into H2SO4.
SO3(g) + H2O(I) ⟶ H2SO4(aq)
H2SO4 (aq) + SO3(g) + H2O(I) ⟶ 2H2SO4(aq)
Free SO3 reacts with H2O to form H2SO4 and the mass of the solution increases.
Let us take 100 g oleum having 80 g SO3 and 20 g H2SO4 in composition.
The molar mass of SO3 is 80 g mol–1.
80 g SO3 + 18 g H2O ⟶ 98 g H2SO4
We know that 1 mol of SO3 reacts with 1 mol of H2O to form 1 mol of H2SO4.
100 g oleum + 18 g H2O ⟶ 118 g H2SO4
98 g H2SO4 is formed from SO3, and 20 g H2SO4 is already present.
So, 100 g oleum upon addition of water gives 118 g of H2SO4.
Hence, % labelling of oleum is 118% in this case.
Percentage labelling in oleum
When a 100 g sample of oleum is diluted with the desired weight of H2O (in g), then the total mass
of H2SO4 obtained after dilution is known as the % labelling in oleum.
So, The % oleum is always more than 100.
Let weight of (100 g oleum + Weight of H2O added) be ‘y’
Or if % labelling in oleum = y
Then the percentage of free SO3​in oleum sample is given as :
( y – 100 ) × 80%
% Free SO3 =
18

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Based on calculating the composition of oleum

Calculate the composition of 109% oleum.

Solution

Given,
109% oleum means 9 g of water is required, i.e.,
100 g oleum + 9 g H2O = 109 g H2SO4
9 g H2O means 0.5 mol of H2O
We know that 0.5 mol SO3 reacts with 0.5 mol H2O to form 0.5 mol H2SO4. That is,
40 g SO3 + 9 g H2O ⟶ 49 g H2SO4
The percentage composition of 109% oleum is 40% SO3 and 60% H2SO4.

Based on labelling the sample of oleum

The percent free SO3​in a sample of oleum is 20%. Label the sample in terms of percent H2SO4.

Solution

Let weight of (100 g oleum + Weight of H2O added) be y

( y – 100 ) × 80%
The percent free SO3​in oleum is given as:
18
( y – 100 ) × 80 = 20
18
y = 104.5%
So, the % labelling in oleum is 104.5%

BOARDS MAIN ADVANCED

Hardness of Water

Water

Hard water Soft water

Hard water: It does not generate lather with soap.

Soft water: It generates lather with soap.

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(After shaking)

Hard water Soft water (Addition of soap solution) Doesn't form Forms lather
lather
Fig. 2: Illustration of hard and soft water

Types of hardness

Temporary hardness Permanent hardness

Temporary hardness

Temporary hardness is due to the presence of soluble bicarbonates of Ca and Mg.

Examples: Ca(HCO3)2and Mg(HCO3)2
Removal of temporary hardness
By boiling:
Ca (HCO3 )2 ( aq) 
→ CaCO3 ( s ) + CO2 ( g) + H2O (l)
Mg (HCO3 )2 ( aq) 
→ MgCO3 ( s ) + CO2 ( g) + H2O (l)
Bicarbonates of Ca and Mg are water soluble, but carbonates of Ca and Mg are insoluble. So,
carbonates of Ca and Mg can be separated by filtration.

Soft water
Hard water
Precipitate

Solution turns milky The precipitate can

Precipitate starts forming be filtered out
Fig. 3: Removal of temporary hardness through boiling

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Permanent hardness

Permanent hardness is due to the presence of soluble chlorides and sulphates of Mg and Ca.
Examples: CaCl2, CaSO4, MgCl2, MgSO4
This type of hardness is referred to as permanent because unlike temporary hardness, it cannot be
removed by simple methods like boiling.
Degree of hardness
Hardness is generally represented in terms of ppm of CaCO3.
Mass of CaCO 3
Hardness of water in ppm = × 106
Mass of hard water
If there is no information about the given salt, then the hardness of water is calculated in terms of
CaCO3.
The hardness of water can also be represented in terms of other salts like CaCl2, MgCl2, CaSO4,
and more.
For the same hard water sample,
1 g equivalent of CaCO3 (nf = 2) = 1 g equivalent of MgCl2 (nf = 2) = 1 g equivalent of CaCl2 (nf = 2)
Given mass
Number of equivalents =
Equivalent mass
Number of equivalents of all three are 1, so given mass = equivalent mass.
Molar mass
Equivalent mass = , so
n-factor
100 95 111
g of CaCO3 = g of MgCl2 = g of CaCl2
2 2 2
100 g of CaCO3 = 95 g of MgCl2 = 111 g of CaCl2
100 ppm CaCO3 = 95 ppm of MgCl2 = 111 ppm of CaCl2

Based on calculating the degree of hardness in terms of CaCO3

A sample of water contains 2 mg of MgCl2 and 2 mg of CaCl2 per litre. Calculate the degree of
hardness in terms of CaCO3.

Solution

100 g of CaCO3. = 95 g of MgCl2

100 g of CaCO3. = 111 g of CaCl2
2 × 10–3
2 mg of MgCl2 = × 100 g of CaCO3
95
2 × 10–3
2 mg of CaCl2 = × 100 g of CaCO3
111
 2 × 10–3   2 × 10–3 
Total mass of CaCO3 =  × 100 g  +  × 100 g 
 95   111 
Total mass of CaCO3 = ( 0.0021) + ( 0.0018 ) g = 0.0039 g
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1 L of solution = 1000 g (Density = 1 g L–1 for water)
 95
–3
092 mg of CaCl = 2 × 10 × 100 g of CaCO
2 3
111
 2 × 10–3   2 × 10–3 
Total mass of CaCO3 =  × 100 g  +  × 100 g 
 95   111 
Total mass of CaCO3 = ( 0.0021) + ( 0.0018 ) g = 0.0039 g
1 L of solution = 1000 g (Density = 1 g L–1 for water)
Mass of CaCO 3
Hardness of water in ppm = × 106
Mass of hard water
0.0039
Hardness of water in ppm = × 106 = 3.9 ppm
1000
The degree of hardness in terms of CaCO3 is 3.9 ppm

BOARDS MAIN ADVANCED

Concept of Available Chlorine

Bleaching Powder is CaOCl2.

Available chlorine
The weight of available Cl2 released from the given sample of bleaching powder on reaction with
dilute acids or CO2 is known as available chlorine.
CaOCl2 is dissolved in water to form a suspension.
Bleaching powder
CaOCl2 ( aq) + H2SO4 ( aq) → CaSO4 ( s ) + Cl2 ( g) + → H2O (l )
CaOCl2 ( aq) + 2HCl ( aq) → CaCl2 ( s ) + Cl2 ( g) + H2O (l)
CaOCl2 ( aq) + CO2 ( g) → CaCO3 ( s ) + Cl2 ( g)
Sample of bleaching powder
CaOCl2 ( aq) + 2CH3COOH ( aq) → Ca ( CH3COO )2 + Cl2 ( g) + H2O (l )
Cl2 ( g) + 2KI ( aq) → 2KCl ( s ) + I2 ( aq)
I2 ( aq) + 2Na2S2O3 ( aq) → Na2S4O6 ( aq) + 2NaI ( aq)
v.f. (of I2 ) = 2 and v.f. (of Na2S2O3 ) = 1
Where v.f. is the valency factor
The endpoint is indicated by the disappearance of blue colour.
M×V
= Millimoles of Cl2 produced = Millimoles of I2 used by hypo
2
M = Molarity of Na2S2O3 ,
V = Volume of Na2S2O3
If, W = Amount of bleaching powder taken in gram.
M × V × 10– 3
Mass of Cl2 produced = × 71
2
Mass of Cl2 produced = 35.5 × M × V × 10–3
35.5 × M × V × 10–3
% of available chlorine = × 100
W
3.55 × M × V
% of available chlorine =
W

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