REDOX REACTIONS

“Life is like a Redox reaction, where there is oxidation, there is always a reduction.”

– Adya

The word Redox is a condensed form of reduction – oxidation reactions and this group
constitutes one of the single largest group of reactions among all the known variants. A
redox reaction is said to have taken place when one of the involved species loses
(partially or fully) electrons and the other gains electrons. Loss of Electrons (LEO)
constitutes the Oxidation half while Gain of Electrons (GER) constitutes the Reduction
half.

Oxidation Number (Oxidation State):

Oxidation number represents the actual or hypothetical charge which is assigned to

various elements in a compound. An increase in oxidation number constitutes
oxidation, while a decrease constitutes reduction. The various rules for evaluating the
oxidation number are enumerated below:

1. Oxidation number of elements in their native or uncombined form is always zero

while in combined state (compounds), it can be zero, positive, negative or even
fractional.

2. In case of ionic compounds, the actual charge on each species represents the
oxidation number.

3. In case of covalent compounds, the shared electrons are counted with the more
electronegative element. Therefore, oxidation number is hypothetical in such cases,
with the more electronegative element getting assigned a negative number while
the lesser electronegative one receives a positive number.
4. Oxidation number of an element can never exceed the number of valence electrons
on the atoms constituting the element. Whenever the calculated oxidation number
exceeds the highest possible value, the correct oxidation number is equal to the
number of valence electrons and it usually indicates the presence of peroxy
linkages.

5. Oxidation number cannot be lower than the number of electrons required for
completing the octet (with a negative sign). For example nitrogen (N) requires three
electrons to complete its octet and therefore, its oxidation number cannot be less
than −3.

6. The oxidation number of fluorine in all its compounds with other elements is −1.

7. The oxidation number of oxygen is usually −2. Some exceptions are peroxides,
super-oxides and fluorides.

8. The oxidation number of Group (I) and Group (II) elements is almost invariably +1
and +2 in their respective compounds.

9. The oxidation number of hydrogen is usually +1. Exceptions include many metal
hydrides and the compounds of hydrogen with non-metals bearing lesser
electronegativity than itself.

10. The sum of oxidation numbers of all the elements in a species is always equal to
the overall charge on the species.

Some solved examples:

1. Find the oxidation number of nitrogen in pernitric acid 𝐇𝐍𝐎𝟒

Assuming the oxidation number of N = 𝑥, we have

𝟏 + 𝒙 + 𝟒 𝐱 (−𝟐) = 𝟎

𝒙 = +𝟕

However, nitrogen has only five valence electrons and therefore, an oxidation
number of +7 is ruled out. The correct oxidation number is +5.

2. Find the oxidation number of chromium in 𝐂𝐫𝐎𝟓

 Assuming the oxidation number of Cr = 𝑥, we have

𝒙 + 𝟓 𝐱 (−𝟐) = 𝟎

𝒙 = +𝟏𝟎

However, chromium has only six valence electrons and therefore, an oxidation
number of +10 is ruled out. The correct oxidation number is +6.

3. Find the oxidation number of nitrogen in 𝐍𝐂𝐥𝟑

On the Mullikan scale, both nitrogen and chlorine have been assigned an
electronegativity of 3. Therefore, the shared electrons cannot be assigned either to
nitrogen or to chlorine. In such cases, the compound is subjected to hydrolysis – the
idea being that oxidation number of each individual element is almost invariably
retained in the products.

NCl3 + H2 O ⟶ NH3 + HOCl

Quite evidently, the oxidation number of nitrogen in NH3 is -3 and that of chlorine
in HOCl is +1. Using the principle above, we conclude that the oxidation number of
nitrogen in NCl3 is −𝟑.

4. Find the oxidation number of oxygen in 𝐇𝐎𝐅

Hydrogen is the least electronegative element in this compound, therefore, its

oxidation number has to be +1. Fluorine, being most electronegative, bears the
oxidation number of -1. Assuming the oxidation number of oxygen to be x, we have
the following equation:

+𝟏 + 𝒙 + (−𝟏) = 𝟎

𝒙=𝟎

5. Find the oxidation number of chlorine in 𝐂𝐥𝐎−

𝟒

Since oxygen is more electronegative than chlorine, we will assume its oxidation
number to be -2. Assuming chlorine to bear an oxidation number of ‘x’, we have
the following equation:

𝒙 + 𝟒(−𝟐) = −𝟏

𝒙 = +𝟕

Check: Chlorine has seven valence electrons and the oxidation number of +7 is
within this upper limit.

6. Find the oxidation number of nitrogen in nitronium ion 𝐍𝐎+

𝟐
 Once again, oxygen is more electronegative and therefore, we assign it an oxidation
number of -2. Assuming the oxidation number of nitrogen to be ‘x’, we have the
following equation:
𝒙 + 𝟐(−𝟐) = +𝟏

𝒙 = +𝟓

7. Find the oxidation number of oxygen in 𝐎𝐅𝟐

Fluorine being more electronegative bears an oxidation number of -1. Assuming

oxygen to have an oxidation number of ‘x’, we have the following equation:

𝒙 + 𝟐(−𝟏) = 𝟎

𝒙=𝟐

8. Find the oxidation number of sulphur in 𝐇𝟐 𝐒𝐎𝟒

Hydrogen being least electronegative, it bears an oxidation number of +1.

Assuming oxygen to be in -2 oxidation state and assigning sulphur an oxidation
number of ‘x’, we have the following equation:

𝟐(+𝟏) + 𝒙 + 𝟒(−𝟐) = 𝟎

𝒙=𝟔

9. Find the oxidation number of xenon in 𝐗𝐞𝐎𝟐 𝐅𝟐

Fluorine being most electronegative bears an oxidation number of -1. Assuming

oxygen to be in -2 oxidation state and assigning xenon an oxidation number of ‘x’,
we have the following equation:

𝒙 + 𝟐(−𝟐) + 𝟐(−𝟏) = 𝟎

𝒙=𝟔

Tip: Highly electronegative elements (electronegativity value of 3 units or

more) tend to avoid bonding directly to each other.

10. Find the oxidation number of oxygen in 𝐊𝐎𝟐

Potassium, being an alkali metal, bears the oxidation number of +1. Assigning
oxygen an oxidation number of ‘x’, we have the following equation:

𝟏 + 𝟐( 𝒙 ) = 𝟎

𝒙 = −𝟎. 𝟓
Types of Redox reactions:

a. Combustion Reactions
Combustion reaction represents the oxidation of one substance by the other
accompanied by significant release of heat and light. In day-to-day context,
combustion refers to vigorous oxidation of a substance by oxygen. E.g. the
combustion of methane in presence of air or oxygen.

CH4 + 2O2 ⟶ CO2 + 2H2 O

In order to determine whether a given compound is combustible or not, evaluate the

oxidation number of each and every element in the compound. Now, rule out the
elements which are in their highest oxidised states. If, among the left over elements,
any element is less electronegative than the oxidizer, then combustion will take
place.

Let’s evaluate which of the following substances are combustible in an atmosphere

of oxygen:

𝐁𝟐 𝐇𝟔 , 𝐂𝐇𝟒 , 𝐍𝐇𝟑 , 𝐇𝟐 𝐎, 𝐇𝐅

The oxidation numbers of various elements are as follows:

𝐁(+𝟑) 𝐚𝐧𝐝 𝐇(−𝟏) 𝐢𝐧 𝐁𝟐 𝐇𝟔

𝐂(−𝟒) 𝐚𝐧𝐝 𝐇(+𝟏) 𝐢𝐧 𝐂𝐇𝟒

𝑵(−𝟑) 𝒂𝒏𝒅 𝑯(+𝟏) 𝐢𝐧 𝐍𝐇𝟑

𝐇(+𝟏) 𝐚𝐧𝐝 𝐎(−𝟐) 𝐢𝐧 𝐇𝟐 𝐎

 𝐇(+𝟏) 𝐚𝐧𝐝 𝐅(−𝟏) 𝐢𝐧 𝐇𝐅

Evaluation:

𝐁𝟐 𝐇𝟔 : Since hydrogen is in a negative oxidized state and there is a large

electronegativity difference (1.4 units) between hydrogen and oxygen, diborane is
highly combustible. In fact diborane is spontaneously combustible and is not regarded
as a safe fuel.

𝐂𝐇𝟒 : Since carbon is in a negative oxidized state and there is a significant

electronegativity difference (1 unit) between carbon and oxygen, methane is
combustible and constitutes a good fuel.

𝐍𝐇𝟑 : Nitrogen is in a negative oxidized state, however, there is insignificant

electronegativity difference (0.5 units) between nitrogen and oxygen, therefore,
ammonia doesn’t burn easily and is not considered a good fuel.

𝐇𝟐 𝐎: Here oxygen bears a negative oxidation number, however, there is barely any
electronegativity difference between oxygen atom in water and molecular oxygen
atoms. Therefore, water is non-combustible in an atmosphere of oxygen.

HF: Here fluorine is in a negative oxidised state, however, the electronegativity of

fluorine is greater than that of oxygen and therefore, hydrogen fluoride is non-
combustible. Hydrogen fluoride, in fact, is non-combustible in any atmosphere.

b. Combination Reactions
The reactions in which two or more substances combine to form a single substance are
called combination reactions. Some examples are cited below:

1. Reaction between magnesium and nitrogen

3Mg + N2 ⟶ Mg 3 N2

In this reaction, magnesium undergoes oxidation from 0 to +2, while nitrogen

undergoes reduction from 0 to -3.
2. Reaction between hydrogen and Fluorine

H2 + F2 ⟶ 2HF

Here hydrogen undergoes oxidation from 0 to +1, while Fluorine undergoes

reduction from 0 to -1.

3. Reaction between Phosphorous and Chlorine

P4 + 6Cl2 ⟶ 4PCl3

c. Decomposition Reactions
These reactions represent reversal of combination reactions and involve splitting up
of a compound into two or more components. Some examples are cited below:

1. Decomposition of magnesium nitride by the action of heat

When magnesium nitride is heated above700 ℃, it decomposes into elemental

magnesium and nitrogen.

Mg 3 N2 ⟶ 3Mg + N2

2. Electrolysis of water

When water is subjected to electrolysis, it decomposes into hydrogen and

oxygen.
2H2 O ⟶ 2H2 + O2

3. Decomposition of Sodium Nitrate

When Sodium Nitrate is strongly heated, it decomposes into sodium nitrite and
oxygen gas.
2NaNO3 ⟶ 2NaNO2 + O2

Caution: All decomposition reactions are not redox reactions. For example

2CaCO3 ⟶ 2CaO + 2CO2

d. Displacement reactions

Displacement reactions are those in which one species displaces another one from
a compound.

Broadly speaking, displacement reactions can be classified into three types:

a. Metal displacing Metal

These reactions involve displacement of a less active metal from its compound by
a more active metal. Following are some examples:

1. The displacement of chromium from chromium oxide by aluminium through the

action of heat.
Cr2 O3 + 2Al ⟶ Al2 O3 + Cr

2. The displacement of copper from cupric sulphate solution by zinc rod/filings.

CuSO4 (𝑎𝑞 ) + Zn(s) ⟶ ZnSO4 (𝑎𝑞 ) + Cu(s)

3. The displacement of silver from silver nitrate solution by iron filings.

2AgNO3 (𝑎𝑞 ) + Fe(s) ⟶ Fe(NO3 )2 (𝑎𝑞 ) + 2Ag(s)

b. Metal displacing Non-metal

During such reactions, a metal displaces a non-metal from its compound. A few
examples are shown below:

1. Displacement of hydrogen from water by sodium metal.

2Na + 2H2 O ⟶ 2NaOH + H2

2. Displacement of hydrogen from sulphuric acid by zinc metal

Zn + H2 SO4 ⟶ ZnSO4 + H2

3. Displacement of nitrogen from nitrous oxide by magnesium

Mg + N2 O ⟶ MgO + N2

c. Non-metal displacing non-metal

During these reactions, a non-metal displaces another non-metal from its

compound. Some examples are depicted below:

1. Displacement of oxygen from water by fluorine

2H2 O + F2 ⟶ 2HF + O2

2. Displacement of carbon from calcium carbide by nitrogen at high temperature

 CaC2 + N2 ⟶ CaCN2 + C

3. Displacement of bromine from sodium bromide by chlorine

2NaBr + Cl2 ⟶ 2NaCl + Br2

Tip: Usually stronger non-metals (more electronegative) displace weaker non-

metals (less electronegative ones) from their compounds.

e. Disproportionation Reactions

The reactions in which the same element undergoes oxidation and reduction are
called disproportionation reactions. Some examples are cited below:

1. The disproportionation of white phosphorous in alkaline medium to yield sodium

hypo-phosphate and phosphine gas

P4 + 3NaOH + 3H2 O ⟶ 3NaH2 PO2 + PH3

2. The decomposition of potassium chlorate into potassium perchlorate and potassium

chloride through the action of heat

4KClO3 ⟶ 3KClO4 + KCl

3. The disproportionation of bromine in hot, concentrated potassium hydroxide

solution to yield potassium bromide and potassium bromate

3Br2 + 6KOH ⟶ 5KBr + KBrO3 + 3H2 O

Balancing Redox Reactions:

Depending on the nature of participating species, a variety of methods are available for
balancing redox reactions. A few of these are discussed below:

1. Oxidation Number method

It is utilized when the participating species are devoid of ions. The various steps
involved are presented below:

a. Write down the oxidation number of each and every element on the reactant and
product side.

b. Recognize the elements undergoing oxidation and reduction.

c. Segregate the reaction into oxidation half and reduction half and balance each half
by adding appropriate number of electrons on the relevant side.

d. Multiply the oxidation and reduction halves with appropriate numbers and add
the two halves such that electrons are cancelled out.

e. Add water on appropriate side and divide the entire equation by a common factor,
in any, to obtain the balanced equation.

f. Cross-check the balanced equation by counting the number of oxygens on each

side

Some solved examples:

P4 + HNO3 ⟶ H3 PO4 + NO2 + H2 O

a. Reactants: P 0 , H +1 , N +5 , O−2 ; Products: H +1 , P 0 , O−2 , N +5 , O−2 , H +1 , O−2

b. Clearly, phosphorus has oxidised from a state of 0 oxidation number to +5 oxidation

number. On the other hand, nitrogen has reduced from a state of +5 oxidation
number to +4 oxidation number.

c. Segregating the two halves and balancing, we have

Oxidation Half:
𝐏 𝟎 ⟶ 𝐏 +𝟓

Adding 𝑒 − 𝑠 to balance the charges, we obtain

P 0 ⟶ P +5 + 5e−

Multiplying both sides with four (as white phosphorous exists in nature in the form of
P4 units), we obtain

4P 0 ⟶ 4P +5 + 20e−

Or P4 0 ⟶ 4P +5 + 20e−

Or P4 ⟶ 4H3 PO4 + 20e−

Reduction Half:
 𝐍 +𝟓 ⟶ 𝐍 +𝟒

Adding 𝑒 − 𝑠 to balance the charges, we obtain

N +5 + e− ⟶ N +4

d. Multiplying reduction half with twenty, we obtain

20N +5 + 20e− ⟶ 20N +4

20HNO3 + 20e− ⟶ 20NO2

Adding the oxidation and reduction halves, we obtain

P4 + 20HNO3 ⟶ 4H3 PO4 + 20NO2

e. Adding water to balance the hydrogens, we obtain

P4 + 20HNO3 ⟶ 4H3 PO4 + 20NO2 + 4H2 O

f. The total number of oxygen atoms on each side is 60, which validates the balanced
equation.

2. Ion-electron method:

It is utilized when the participating species contain ions. The various steps involved are
presented below:

a. Write down the oxidation number of each and every element on the reactant and
product side.

b. Recognize the elements undergoing oxidation and reduction.

c. Segregate the reaction into oxidation half and reduction half and balance each half
by adding appropriate number of electrons on the relevant side.

d. In order to balance the actual charge, add requisite number of H + or OH − ions on

the appropriate side depending on whether the medium is acidic or basic
respectively.

e. In order to balance the hydrogen atoms, add requisite number of water molecules
(H2 O) on the appropriate side.
f. Cross-check the balanced half equation by observing the number of oxygen atoms
on either side.

g. Multiply the oxidation half balanced equation and the reduction half balanced
equation with appropriate factors and add the two equations so that electrons are
cancelled out. This will yield the final balanced equation.

Some solved examples:

Balance the following equation in acidic medium

𝐌𝐧𝐎−
𝟒 + 𝐅𝐞
𝟐+
⟶ 𝐌𝐧𝟐+ + 𝐅𝐞𝟑+ + 𝐇𝟐 𝐎

a. Write the reactants and products along with their oxidation numbers

𝐑𝐞𝐚𝐜𝐭𝐚𝐧𝐭𝐬: 𝐌𝐧+𝟕 , 𝐎−𝟐 , 𝐅𝐞+𝟐 ; 𝐏𝐫𝐨𝐝𝐮𝐜𝐭𝐬: 𝐌𝐧+𝟐 , 𝐅𝐞+𝟑 , 𝐇+𝟏 , 𝐎−𝟐

b. Clearly, iron has undergone oxidation from a state of +2 oxidation number to +3

oxidation number. On the other hand, manganese has reduced from a state of +7
oxidation number to +2 oxidation number.

c. Oxidation half:

𝐅𝐞+𝟐 ⟶ 𝐅𝐞+𝟑

Adding 𝑒 − 𝑠 to balance the charges, we obtain

𝐅𝐞+𝟐 ⟶ 𝐅𝐞+𝟑 +e−

𝐅𝐞𝟐+ ⟶ 𝐅𝐞𝟑+ +e− … (1)

Reduction half:
𝐌𝐧+𝟕 ⟶ 𝐌𝐧+𝟐

Adding 𝑒 − 𝑠 to balance the charges, we obtain

𝐌𝐧+𝟕 + 5e− ⟶ 𝐌𝐧+𝟐

𝐌𝐧𝐎− −
𝟒 + 5e ⟶ 𝐌𝐧
𝟐+
d. In order to balance actual charges, add requisite number of H + ions on left hand side
of the equation above

𝐌𝐧𝐎− + −
𝟒 + 𝟖𝐇 + 𝟓𝐞 ⟶ 𝐌𝐧
𝟐+

e. In order to balance hydrogen atoms, add requisite number of water molecules (𝐻2 𝑂)
on right hand side of the equation above

𝐌𝐧𝐎− + −
𝟒 + 𝟖𝐇 + 𝟓𝐞 ⟶ 𝐌𝐧
𝟐+
+ 𝟒𝐇𝟐 𝐎 … (𝟐)

As a cross-check, we observe the number of oxygen atoms on either side of the equation
above and find it same (equal to four).

Now multiplying equation (1) with 5 and adding it to equation (2) yields

𝐌𝐧𝐎−
𝟒 + 𝟓𝐅𝐞
𝟐+
+ 𝟖𝐇 + ⟶ 𝐌𝐧𝟐+ + 𝟓𝐅𝐞𝟑+ + 𝟒𝐇𝟐 𝐎

This is the final balanced equation.

n – factor and the Concept of Equivalents

n – factor is used for estimating the number of equivalents of a given reactant and its
value depends on the type of reaction.

1. Redox Reactions:

For a redox reaction, the n – factor is defined as the number of moles of electrons
lost or gained per mole of the reactant. For example, the n – factor of permanganate
and oxalate ions in the following reaction are calculated as shown below:

𝐌𝐧𝐎− 𝟐− +
𝟒 + 𝐂𝟐 𝐎𝟒 + 𝐇 ⟶ 𝐌𝐧
𝟐+
+ 𝐂𝐎𝟐 + +𝐇𝟐 𝐎

Oxidation numbers of elements undergoing redox reaction on reactant and product

side:

𝐑𝐞𝐚𝐜𝐭𝐚𝐧𝐭𝐬: 𝐌𝐧+𝟕 , 𝐂 +𝟑 ; 𝐏𝐫𝐨𝐝𝐮𝐜𝐭𝐬: 𝐌𝐧+𝟐 , 𝐂+𝟒

n – factor of permanganate: |1 × 7 − 1 × 2 | = 5

n – factor of oxalate: |2 × 3 − 2 × 4 | = 2
2. Acid – Base Reactions:

For an acid, the n – factor is defined as the number of protons donated per mole by
the acid during reaction with a base. Similarly, for a base, the n – factor is defined
as the number of protons accepted per mole by the base during reaction with an
acid.

𝑯𝟐 𝑺𝑶𝟒 + 𝑵𝒂𝑪𝒍 → 𝑵𝒂𝑯𝑺𝑶𝟒 + 𝑯𝑪𝒍

∆

In this reaction, the n – factor of sulphuric acid is one as only one proton per mole
is being transferred.

𝑴𝒈(𝑶𝑯)𝟐 + 𝑯𝟑 𝑷𝑶𝟒 ⟶ 𝑴𝒈𝑯𝑷𝑶𝟒 + 𝟐𝑯𝟐 𝑶

In this reaction, the n – factor of magnesium hydroxide is two as two protons per
mole are being accepted by magnesium hydroxide.

3. Salt – Salt Reactions or Precipitation Reactions:

For these reactions, the n – factor is defined as the magnitude of charge on all the
cations or all the anions constituting the salt. Some examples are shown below:

𝟑𝑩𝒂𝑪𝒍𝟐 + 𝟐𝑵𝒂𝟑 𝑷𝑶𝟒 ⟶ 𝑩𝒂𝟑 (𝑷𝑶𝟒 )𝟐 + 𝟔𝑵𝒂𝑪𝒍

n – factor of Barium Chloride:

|𝒎𝒂𝒈𝒏𝒊𝒕𝒖𝒅𝒆 𝒐𝒇 𝒄𝒉𝒂𝒓𝒈𝒆 𝒐𝒏 𝑩𝒂𝟐+ 𝒊𝒐𝒏| = 𝟐

−
𝒐𝒓 |𝒎𝒂𝒈𝒏𝒊𝒕𝒖𝒅𝒆 𝒐𝒇 𝒄𝒉𝒂𝒓𝒈𝒆 𝒐𝒏 𝒕𝒘𝒐 𝑪𝒍 𝒊𝒐𝒏𝒔| = 𝟐

n – factor of Sodium Phosphate:

|𝒎𝒂𝒈𝒏𝒊𝒕𝒖𝒅𝒆 𝒐𝒇 𝒄𝒉𝒂𝒓𝒈𝒆 𝒐𝒏 𝒕𝒉𝒓𝒆𝒆 𝑵𝒂+ 𝒊𝒐𝒏𝒔| = 𝟑

𝟑−
𝒐𝒓 |𝒎𝒂𝒈𝒏𝒊𝒕𝒖𝒅𝒆 𝒐𝒇 𝒄𝒉𝒂𝒓𝒈𝒆 𝒐𝒏 𝑷𝑶𝟒 𝒊𝒐𝒏| = 𝟑
 Number of Equivalents

Number of equivalents represents the true combining capacity of a reactant. In a

given balanced reaction, the coefficient of various reactants and products depends
on the nature of reactants and the reaction conditions. However, the number of
equivalents of each reactant used up and the number of equivalents of each product
formed is the same.

The number of equivalents can be calculated either through the product of number
of moles of a reacting substance and its n – factor or through the product of
Normality of a solution and its volume in litres.

𝐍𝐮𝐦𝐛𝐞𝐫 𝐨𝐟 𝐞𝐪𝐮𝐢𝐯𝐚𝐥𝐞𝐧𝐭𝐬 = 𝐧 × 𝐧 − 𝐟𝐚𝐜𝐭𝐨𝐫 (𝐮𝐬𝐞𝐟𝐮𝐥 𝐟𝐨𝐫 𝐬𝐨𝐥𝐢𝐝𝐬)

𝐍𝐮𝐦𝐛𝐞𝐫 𝐨𝐟 𝐞𝐪𝐮𝐢𝐯𝐚𝐥𝐞𝐧𝐭𝐬 = 𝐍𝐨𝐫𝐦𝐚𝐥𝐢𝐭𝐲 × 𝐕𝐨𝐥𝐮𝐦𝐞 (𝐋) (𝐮𝐬𝐞𝐟𝐮𝐥 𝐟𝐨𝐫 𝐬𝐨𝐥𝐮𝐭𝐢𝐨𝐧𝐬)

Titration

It is the process of finding the concentration of one chemical through reaction with
another chemical whose concentration is known. Based on the nature of reacting
substances, titration could be of three types:

1. Acid – Base Titrations

2. Redox Titrations

3. Salt – Salt Titrations

1. Acid – Base Titrations

In this type of titration, an acid or a base is neutralized in the presence of a suitable

indicator. For example, the strength of hydrochloric acid solution can be calculated
by subjecting it to neutralization in presence of phenolphthalein.
Procedure:

A small beaker containing the sample of hydrochloric acid solution is taken and a
few drops of phenolphthalein (HPh) are added to it. The solution stays colourless
as hydrochloric acid prevents the dissociation of phenolphthalein (which happens
to be a weak acid).

Now sodium hydroxide solution is dripped slowly from a burette into the solution,
causing the neutralization of acid and an increase in the P H of solution. Once
hydrochloric acid is completely neutralized, the base starts to deprotonate
phenolphthalein (HPh) and generate the conjugate base of phenolphthalein (𝑃ℎ− ).

HPh (colourless) ⇋ 𝐻 + + 𝑃ℎ− (𝑝𝑖𝑛𝑘)

Therefore, the solution turns pale pink and it represents the end point of titration.
At this stage, the volume of hydrochloric acid solution used up is noted from the
burette and the following equation holds:

𝑵𝒐. 𝒐𝒇 𝒆𝒒𝒖𝒊𝒗𝒂𝒍𝒆𝒏𝒕𝒔 𝒐𝒇 𝑵𝒂𝑶𝑯(𝒂𝒒) = 𝑵𝒐. 𝒐𝒇 𝒆𝒒𝒖𝒊𝒗𝒂𝒍𝒆𝒏𝒕𝒔 𝒐𝒇 𝑯𝑪𝒍(𝒂𝒒)

𝑵𝟏 × 𝑽𝟏 = 𝑵𝟐 × 𝑽𝟐

𝑴𝟏 × 𝟏 × 𝑽𝟏 = 𝑴𝟐 × 𝟏 × 𝑽𝟐

𝑴𝟐 × 𝑽𝟐
𝑴𝟏 =
𝑽𝟏
 Since M2,V2 and V1 are known, M1 can be calculated.

2. Redox Titrations

This type of titration involves reaction between an oxidizing agent and a reducing
agent with the purpose of finding the concentration of either of them. For example,
the concentration of oxalic acid solution can be determined by subjecting it to
oxidation using potassium permanganate. Usually, redox titrations do not require a
separate indicator.

Procedure:

A weighed sample of potassium permanganate is added to a measured volume of

water, thereby obtaining a known concentration of permanganate in water. Doing
so imparts a bright purple colour to the solution. Since potassium permanganate
acts as a self-indicator, there is no need to add another indicator separately. Now
oxalic acid is dripped slowly into the solution and the following redox reaction
commences:

𝐌𝐧𝐎− 𝟐− + 𝟐+
𝟒 (𝐩𝐮𝐫𝐩𝐥𝐞) + 𝐂𝟐 𝐎𝟒 + 𝐇 ⟶ 𝐌𝐧 (𝐩𝐢𝐧𝐤) + 𝐂𝐎𝟐 + +𝐇𝟐 𝐎

When the colour of solution changes from purple to pale pink, it indicates the end
point of titration. At this stage, the volume of oxalic acid solution used up is noted
from the burette and the following equation holds:

𝑵𝒐. 𝒐𝒇 𝒆𝒒𝒖𝒊𝒗𝒂𝒍𝒆𝒏𝒕𝒔 𝒐𝒇 𝑪𝟐 𝐎𝟐− −

𝟒 = 𝑵𝒐. 𝒐𝒇 𝒆𝒒𝒖𝒊𝒗𝒂𝒍𝒆𝒏𝒕𝒔 𝒐𝒇 𝐌𝐧𝐎𝟒
 𝑵𝟏 × 𝑽𝟏 = 𝑵𝟐 × 𝑽𝟐

𝑴𝟏 × 𝟐 × 𝑽𝟏 = 𝑴𝟐 × 𝟓 × 𝑽𝟐

𝟓 × 𝑴𝟐 × 𝑽𝟐
𝑴𝟏 =
𝟐 × 𝑽𝟏

Since M2,V2 and V1 are known, M1 can be calculated.

3. Precipitation (Salt – Salt) Titrations

This type of titration involves reaction between two salt solutions, resulting in the
formation of a precipitate. For example, the concentration of sodium chloride
solution can be determined by reacting it with a known concentration of silver
nitrate solution in presence of chromate ions as indicators. Precipitation titrations
may or may not require a separate indicator.

Procedure:

A sample of sodium chloride solution is taken and a few drops of potassium

chromate are added to it, rendering the solution yellow. A weighed amount of silver
nitrate is added separately to a measured volume of water, thereby obtaining a
known concentration of silver ions in water. This solution is introduced into a
burette. Now silver nitrate solution is dripped slowly from the burette into the
sodium chloride solution and the following reaction commences:

𝐀𝐠𝐍𝐎𝟑 (𝐚𝐪) + 𝐍𝐚𝐂𝐥(𝐚𝐪) ⟶ 𝐀𝐠𝐂𝐥 ↓ +𝐍𝐚𝐍𝐎𝟑 (𝒂𝒒)

 Once all the chloride ions are precipitated, the added silver ions start to react with
chromate ions, leading to discharge of yellow colour and the formation of reddish-
brown precipitate.

𝐂𝐫𝐎𝟐− +
𝟒 (𝐲𝐞𝐥𝐥𝐨𝐰) + 𝟐𝐀𝐠 ⟶ 𝐀𝐠 𝟐 𝐂𝐫𝐎𝟒 (𝐫𝐞𝐝𝐝𝐢𝐬𝐡 − 𝐛𝐫𝐨𝐰𝐧)

This represents the end point of titration and the following equation holds:

𝑵𝒐. 𝒐𝒇 𝒆𝒒𝒖𝒊𝒗𝒂𝒍𝒆𝒏𝒕𝒔 𝒐𝒇 𝐍𝐚𝐂𝐥 = 𝑵𝒐. 𝒐𝒇 𝒆𝒒𝒖𝒊𝒗𝒂𝒍𝒆𝒏𝒕𝒔 𝒐𝒇 𝐀𝐠𝐍𝐎𝟑

𝑵𝟏 × 𝑽𝟏 = 𝑵𝟐 × 𝑽𝟐

𝑴𝟏 × 𝟏 × 𝑽𝟏 = 𝑴𝟐 × 𝟏 × 𝑽𝟐

𝑴𝟐 × 𝑽𝟐
𝑴𝟏 =
𝑽𝟏

Since M2,V2 and V1 are known, M1 can be calculated.

Back Titration and Double Titration

These two belong to the class of acid – base titrations and are used when simple
titration cannot be utilized.

1. Back Titration

This titration is used when the titrand or analyte has a solute which is either highly
volatile or of low solubility in the given solvent. In case the solute is highly volatile,
then the concentration of solute will go on decreasing during the process of titration
and if the solute is of low solubility, then the indicator may not work. For example,
the simple titration of ammonium hydroxide solution is not possible as the solution
keeps losing ammonia in an open beaker. Also, the simple titration of calcium
carbonate is not feasible as calcium carbonate does not dissolve sufficiently in water
to bring about a significant increase in PH and give a pink solution with
phenolphthalein.
 Back titration involves treating the analyte with an excess of acid or base and then
titrating the left over acid or base with a suitable titrant. For example, the purity of
a sample of calcium carbonate can be obtained through the following procedure.

Procedure:

The given sample of calcium carbonate is weighed and then dissolved in excess of
hydrochloric acid.

𝐂𝐚𝐂𝐎𝟑 (𝐬) + 𝐇𝐂𝐥 (𝐞𝐱𝐜𝐞𝐬𝐬) ⟶ 𝐂𝐚𝐂𝐥𝟐 + 𝐂𝐎𝟐 + 𝐇𝟐 𝐎 + 𝐇𝐂𝐥 (𝐥𝐞𝐟𝐭 𝐨𝐯𝐞𝐫)

From the principle of equivalents, we have

𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇 𝐇𝐂𝐥 (𝐮𝐬𝐞𝐝 𝐮𝐩) = 𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇 𝐂𝐚𝐂𝐎𝟑

𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇 𝑯𝑪𝒍 (𝒆𝒙𝒄𝒆𝒔𝒔) − 𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇 𝑯𝑪𝒍 (𝒍𝒆𝒇𝒕 𝒐𝒗𝒆𝒓) = 𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇 𝑪𝒂𝑪𝑶𝟑

𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇 𝑪𝒂𝑪𝑶𝟑 = 𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇 𝑯𝑪𝒍 (𝒆𝒙𝒄𝒆𝒔𝒔) − 𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇 𝑯𝑪𝒍 (𝒍𝒆𝒇𝒕 𝒐𝒗𝒆𝒓) … (𝟏)

The left – over hydrochloric acid is now titrated with a known concentration of
sodium hydroxide solution in presence of phenolphthalein as indicator.

𝐇𝐂𝐥 (𝐥𝐞𝐟𝐭 𝐨𝐯𝐞𝐫) + 𝐍𝐚𝐎𝐇 (𝐚𝐪) ⟶ 𝐍𝐚𝐂𝐥 (𝐚𝐪) + 𝐇𝟐 𝐎

The end point is attained when the solution changes from colourless to pink. At this
stage,

𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇 𝑯𝑪𝒍 (𝒍𝒆𝒇𝒕 𝒐𝒗𝒆𝒓) = 𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇 𝐍𝐚𝐎𝐇 (𝐚𝐪) … (𝟐)

From (1) and (2), we obtain

𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇 𝑪𝒂𝑪𝑶𝟑 = 𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇 𝑯𝑪𝒍 (𝒆𝒙𝒄𝒆𝒔𝒔) − 𝒏 𝒐𝒇 𝐍𝐚𝐎𝐇 (𝐚𝐪)

𝒆𝒒𝒗𝒔.
 Since, the number of equivalents of both hydrochloric acid and sodium hydroxide
are known, the number of equivalents of calcium carbonate can be calculated. From
the number of equivalents, the number of moles and mass can be calculated.

𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇 𝑪𝒂𝑪𝑶𝟑 = 𝒏 × 𝒏 − 𝒇𝒂𝒄𝒕𝒐𝒓

𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇 𝑪𝒂𝑪𝑶𝟑 = 𝒏 × 𝟐

𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇 𝑪𝒂𝑪𝑶𝟑
𝒏=
𝟐

Therefore, mass of calcium carbonate

𝑾𝑪𝒂𝑪𝑶𝟑 = 𝒏 × 𝒎𝒐𝒍𝒆𝒄𝒖𝒍𝒂𝒓 𝒎𝒂𝒔𝒔 𝒐𝒇 𝑪𝒂𝑪𝑶𝟑

𝑾𝑪𝒂𝑪𝑶𝟑 = 𝒏 × 𝟏𝟎𝟎

𝑾𝑪𝒂𝑪𝑶𝟑
𝑷𝒆𝒓𝒄𝒆𝒏𝒕𝒂𝒈𝒆 𝒑𝒖𝒓𝒊𝒕𝒚 𝒐𝒇 𝑪𝒂𝑪𝑶𝟑 = × 𝟏𝟎𝟎
𝑾𝑺𝒂𝒎𝒑𝒍𝒆

2. Double Titration

It is utilized when there are two or more salts present in a mixture and the percentage
of each salt needs to be calculated. The sample is titrated using two indicators either
in a sequential mode or in a parallel mode. For example, the percentage composition
of a mixture of sodium bicarbonate, sodium carbonate and sodium chloride can be
obtained by adopting the following procedure:

Procedure:

1. Sequential mode:

The sample is weighed and then dissolved in a given volume of water. A few
drops of phenolphthalein are added which turns the solution pale pink. Now the
solution is titrated against hydrochloric acid of known strength until the solution
 turns colourless. This represents the end point and at this stage, all the carbonate
in the solution is converted into bicarbonate, with sodium chloride and the
original bicarbonate ions remaining unreacted. The reaction is given below:

𝐍𝐚𝟐 𝐂𝐎𝟑 (𝐚𝐪) + 𝐇𝐂𝐥 (𝐚𝐪) ⟶ 𝐍𝐚𝐇𝐂𝐎𝟑 (𝐚𝐪) + 𝐍𝐚𝐂𝐥 (𝐚𝐪)

𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇 𝐍𝐚𝟐 𝐂𝑶𝟑 (𝐚𝐪) = 𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇𝐇𝐂𝐥 (𝐚𝐪)

𝒂 × 𝒏 − 𝒇𝒂𝒄𝒕𝒐𝒓 = 𝑵 × 𝑽(𝑳)

𝒂 × 𝟏 = 𝑵 × 𝑽𝟏 (𝑳) … (𝟏)

Since normality and volume of hydrochloric acid used are known, the number
of moles (a) of sodium carbonate can easily be calculated.

Now Methyl Orange is added to the solution and the solution turns yellow. The
titration is continued with hydrochloric acid until the solution turns reddish –
orange. This represents the end point of titration. At this stage all the
bicarbonate ions in the solution have been converted to carbonic acid, which
being unstable decomposes into carbon dioxide and water. The reaction is given
below:

𝐍𝐚𝐇𝐂𝐎𝟑 (𝐚𝐪) + 𝐇𝐂𝐥 (𝐚𝐪) ⟶ 𝐍𝐚𝐂𝐥 (𝐚𝐪) + 𝐂𝐎𝟐 + 𝐇𝟐 𝐎

𝒏𝒆𝒒𝒗𝒔. 𝐍𝐚𝐇𝐂𝐎𝟑 (𝐟𝐫𝐨𝐦 𝐍𝐚𝟐 𝑪𝑶𝟑 ) + 𝒏𝒆𝒒𝒗𝒔. 𝐍𝐚𝐇𝐂𝐎𝟑 (𝐨𝐫𝐢𝐠𝐢𝐧𝐚𝐥) = 𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇𝐇𝐂𝐥 (𝐚𝐪)

𝒂 × 𝒏 − 𝒇𝒂𝒄𝒕𝒐𝒓 + 𝒃 × 𝒏 − 𝒇𝒂𝒄𝒕𝒐𝒓 = 𝑵 × 𝑽𝟐 (𝑳)

𝒂 × 𝟏 + 𝒃 × 𝟏 = 𝑵 × 𝑽𝟐 (𝑳) … (𝟐)

Substituting the value of ‘a’ from equation (1) into equation (2), ‘b’ can be
obtained since the normality of hydrochloric acid and its volume used up are
known.
 Now the mass of sodium carbonate and sodium bicarbonate in the sample can
be easily calculated from their number of moles and their respective molecular
masses.

𝑾𝐍𝐚𝟐 𝐂𝐎𝟑 = 𝐚 × 𝟏𝟎𝟔

𝑾𝐍𝐚𝐇𝐂𝐎𝟑 = 𝐛 × 𝟖𝟒

The percentages of various constituents are:

𝑾𝐍𝐚𝟐 𝐂𝐎𝟑
𝑷𝒆𝒓𝒄𝒆𝒏𝒕𝒂𝒈𝒆 𝒐𝒇 𝐍𝐚𝟐 𝐂𝐎𝟑 (𝒔𝒂𝒚 𝒙) = × 𝟏𝟎𝟎
𝑾𝐬𝐚𝐦𝐩𝐥𝐞

𝑾𝐍𝐚𝐇𝐂𝐎𝟑
𝑷𝒆𝒓𝒄𝒆𝒏𝒕𝒂𝒈𝒆 𝒐𝒇 𝐍𝐚𝐇𝐂𝐎𝟑 (𝒔𝒂𝒚 𝒚) = × 𝟏𝟎𝟎
𝑾𝐬𝐚𝐦𝐩𝐥𝐞

𝑷𝒆𝒓𝒄𝒆𝒏𝒕𝒂𝒈𝒆 𝒐𝒇 𝐍𝐚𝐂𝐥 = 𝟏𝟎𝟎 − (𝐱 + 𝐲)

2. Parallel mode:

Two samples of equal masses are added to two beakers containing equal
volumes of water. Phenolphthalein is added to one of the beakers while methyl
orange is added to the other one. Now, both the solutions are titrated against
hydrochloric acid. The following observations are noted:

Titration in beaker containing Phenolphthalein

The end point is reached when the PH of solution drops just below 8 and the
solution becomes colourless. At this stage, all the carbonate ions in the solution
have converted to bicarbonate while the bicarbonate ions originally present are
unaffected. The reaction is shown below.

𝐍𝐚𝟐 𝐂𝐎𝟑 (𝐚𝐪) + 𝐇𝐂𝐥 (𝐚𝐪) ⟶ 𝐍𝐚𝐇𝐂𝐎𝟑 (𝐚𝐪) + 𝐍𝐚𝐂𝐥 (𝐚𝐪)

𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇 𝐍𝐚𝟐 𝐂𝑶𝟑 (𝐚𝐪) = 𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇𝐇𝐂𝐥 (𝐚𝐪)

 𝒂 × 𝒏 − 𝒇𝒂𝒄𝒕𝒐𝒓 = 𝑵 × 𝑽(𝑳)

𝒂 × 𝟏 = 𝑵 × 𝑽𝟏 (𝑳) … (𝟏)

Since normality and volume of hydrochloric acid used are known, the number
of moles (a) of sodium carbonate can easily be calculated.

Titration in beaker containing Methyl Orange

The end point is reached when the PH of solution drops just below 3 and the
solution becomes reddish – orange. At this stage, all the carbonate and
bicarbonate ions in the solution are completely protonated to carbonic acid,
which being unstable decomposes to carbon dioxide and water. The reactions
are shown below.

𝐍𝐚𝟐 𝐂𝐎𝟑 (𝐚𝐪) + 𝟐𝐇𝐂𝐥 (𝐚𝐪) ⟶ 𝟐𝐍𝐚𝐂𝐥 (𝐚𝐪) + +𝐂𝐎𝟐 + 𝐇𝟐 𝐎

𝐍𝐚𝐇𝐂𝐎𝟑 (𝐚𝐪) + 𝐇𝐂𝐥 (𝐚𝐪) ⟶ 𝐍𝐚𝐂𝐥 (𝐚𝐪) + 𝐂𝐎𝟐 + 𝐇𝟐 𝐎

𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇 𝐍𝐚𝟐 𝐂𝑶𝟑(𝐚𝐪) + 𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇 𝐍𝐚𝐇𝐂𝐎𝟑 (𝐚𝐪) = 𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇𝐇𝐂𝐥 (𝐚𝐪)

𝐚 × 𝟐 + 𝐛 × 𝟏 = 𝐍 × 𝐕𝟐 (𝐋) … (𝟐)

Substituting the value of ‘a’ from equation (1) into equation (2), ‘b’ can be
obtained since the normality of hydrochloric acid and its volume used up are
known.

Once ‘a’ and ‘b’ are evaluated, the masses and percentages of sodium carbonate
and sodium bicarbonate can be calculated as discussed in sequential mode.
From these the percentage of the remaining inert salt, sodium chloride, is easily
found out.
 Iodometry and Iodimetry
These two belong to the class of Redox Titrations and are often employed in
laboratory to find the strength of oxidising and reducing agents.

1. Iodometry

This titration is used to find the strength of an oxidizing agent. The procedure is
described with the help of reactions involving potassium dichromate as the
oxidizing agent.

Procedure:

A weighed sample of potassium iodide (in excess) is dissolved in a given volume

of water and the solution containing oxidizing agent is now introduced. The reaction
produces iodine which dissolves in the left over potassium iodide. Now the
indicator – starch – is added to this solution, which turns the solution distinctly
blue. This solution is now titrated with sodium thiosulphate (hypo) solution until
the blue colour is discharged. Number of equivalents of oxidizing agent are equal
to the number of equivalents of iodine produced which in turn are equal to the
number of equivalents of hypo solution. From the number of equivalents of
oxidizing agent and its n – factor, the strength can be easily calculated.

𝑪𝒓𝟐 𝑶𝟐− − +
𝟕 + 𝑰 (𝒆𝒙𝒄𝒆𝒔𝒔) + 𝑯 ⟶ 𝑰𝟐 + 𝑪𝒓
𝟑+
+ 𝑯𝟐 𝑶 + 𝑰− (𝒍𝒆𝒇𝒕 𝒐𝒗𝒆𝒓)

∴ 𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇 𝑪𝒓𝟐 𝑶𝟐−

𝟕 (𝐚𝐪) = 𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇 𝑰𝟐 𝒑𝒓𝒐𝒅𝒖𝒄𝒆𝒅 … (𝟏)

𝑰− (𝒍𝒆𝒇𝒕 𝒐𝒗𝒆𝒓) + 𝑰𝟐 ⇋ 𝑰−
𝟑

Starch is now added to the solution and it is titrated with sodium thiosulphate,
leading to the following reaction:

𝑰𝟐 + 𝟐𝑺𝟐 𝑶𝟐− − 𝟐−
𝟑 ⟶ 𝟐𝑰 + 𝑺𝟒 𝑶𝟔

∴ 𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇 𝑰𝟐 = 𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇 𝑺𝟐 𝑶𝟐−

𝟑 … (𝟑)

From (1) and (3), we obtain

 𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇 𝑪𝒓𝟐 𝑶𝟐− 𝟐−
𝟕 (𝐚𝐪) = 𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇 𝑺𝟐 𝑶𝟑

𝑴𝟏 × 𝒏 − 𝒇𝒂𝒄𝒕𝒐𝒓 × 𝑽𝟏 = 𝑴𝟐 × 𝒏 − 𝒇𝒂𝒄𝒕𝒐𝒓 × 𝑽𝟐

𝑴𝟏 × 𝟔 × 𝑽𝟏 = 𝑴𝟐 × 𝟏 × 𝑽𝟐

𝑴𝟐 𝑽𝟐
𝑴𝟏 =
𝟔𝑽𝟏

Since all variables on the right hand side of above expression are known, the
molarity of oxidizing agent (M1) can be easily calculated.

2. Iodimetry

This titration is used to find the strength of reducing agents such as sulphite,
arsenite, thiosulphate etc. The procedure is described with the help of reactions
involving sodium sulphite as the reducing agent.

Procedure:

A weighed sample of iodine is added to a given volume of water containing

dissolved potassium iodide. Potassium iodide serves the twin purposes of increasing
the solubility of iodine in water significantly and decreasing the volatility of iodine.
The following equilibrium is established:

𝑰− (𝒂𝒒) + 𝑰𝟐 (𝒂𝒒) ⇋ 𝑰−
𝟑 (𝒂𝒒)

Starch is now added to this solution, turning it distinctly blue. This solution is now
titrated with a solution containing the reducing agent until the blue colour is
discharged.

𝐈𝟐 (𝒂𝒒) + 𝐍𝐚𝟐 𝐒𝐎𝟑 (𝒂𝒒) + 𝐇𝟐 𝐎 ⟶ 𝐍𝐚𝟐 𝐒𝐎𝟒 + 𝟐𝐇𝐈

 𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇 𝐍𝐚𝟐 𝐒𝐎𝟑 (𝒂𝒒) = 𝒏𝒆𝒒𝒗𝒔. 𝒐𝒇 𝑰𝟐 (𝒂𝒒)

𝑴𝟏 × 𝒏 − 𝒇𝒂𝒄𝒕𝒐𝒓 × 𝑽𝟏 = 𝑴𝟐 × 𝒏 − 𝒇𝒂𝒄𝒕𝒐𝒓 × 𝑽𝟐

𝑴𝟏 × 𝟐 × 𝑽𝟏 = 𝑴𝟐 × 𝟐 × 𝑽𝟐

𝑴𝟐 𝑽𝟐
𝑴𝟏 =
𝑽𝟏

Since all variables on the right hand side of above expression are known, the
molarity of reducing agent (M1) can be easily calculated.

Volume Strength of hydrogen peroxide

A sample of hydrogen peroxide is said to have a volume strength of ‘x’ if a one
litre solution of it releases ‘x’ litre of oxygen gas on decomposition.

𝟐𝐇𝟐 𝐎𝟐 ⟶ 𝟐𝐇𝟐 𝐎 + 𝐎𝟐

𝟐 𝐦𝐨𝐥𝐞𝐬 𝐨𝐟 𝐇𝟐 𝐎𝟐 ≡ 𝟏 𝐦𝐨𝐥𝐞 𝐨𝐟 𝐎𝟐 ≡ 𝟐𝟐. 𝟒 𝐥𝐢𝐭𝐫𝐞 𝐨𝐟 𝐎𝟐

𝟐
𝟏 𝐥𝐢𝐭𝐫𝐞 𝐨𝐟 𝐎𝟐 ≡ 𝐦𝐨𝐥𝐞𝐬 𝐨𝐟 𝐇𝟐 𝐎𝟐
𝟐𝟐. 𝟒

𝐱
𝐱 𝐥𝐢𝐭𝐫𝐞 𝐨𝐟 𝐎𝟐 ≡ 𝐦𝐨𝐥𝐞𝐬 𝐨𝐟 𝐇𝟐 𝐎𝟐
𝟏𝟏. 𝟐

𝐱
∴ 𝐌𝐨𝐥𝐚𝐫𝐢𝐭𝐲 = 𝐚𝐬 𝐯𝐨𝐥𝐮𝐦𝐞 𝐢𝐬 𝟏 𝐥𝐢𝐭𝐫𝐞
𝟏𝟏. 𝟐

𝐕𝐨𝐥𝐮𝐦𝐞 𝐒𝐭𝐫𝐞𝐧𝐠𝐭𝐡
∵ 𝐌𝐨𝐥𝐚𝐫𝐢𝐭𝐲 =
𝟏𝟏. 𝟐

𝐕. 𝐒. = 𝟏𝟏. 𝟐 × 𝐌 … (𝟏)

𝐍𝐨𝐫𝐦𝐚𝐥𝐢𝐭𝐲 (𝐍) = 𝐌𝐨𝐥𝐚𝐫𝐢𝐭𝐲 (𝐌) × 𝐧 − 𝐟𝐚𝐜𝐭𝐨𝐫

𝐍 = 𝐌 × 𝟐 … (𝟐)
 Substituting (2) in (1), we obtain

𝐍
𝐕. 𝐒. = 𝟏𝟏. 𝟐 ×
𝟐

𝐕. 𝐒. = 𝟓. 𝟔 × 𝐍

Percentage of labelled oleum

A sample of oleum labelled ‘x percentage’ indicates that ‘x’ grams of sulphuric
acid is obtained when 100 grams of oleum is diluted with water. Therefore,
percentage of labelled oleum will always be greater than 100 percent and this
represents the lower limit.

Oleum represents a class of compounds with the general formula H2 Sn+1 O3n+4
and its reaction with water is given below.

𝐇𝟐 𝐒𝐧+𝟏 𝐎𝟑𝐧+𝟒 + 𝐧𝐇𝟐 𝐎 ⟶ (𝐧+𝟏) 𝐇𝟐 𝐒𝐎𝟒

From this equation, it is observed that 1 mole of oleum produces (n+1) moles
of sulphuric acid.

𝟏𝟎𝟎
𝐍𝐨𝐰, 𝟏𝟎𝟎 𝐠𝐫𝐚𝐦𝐬 𝐨𝐟 𝐨𝐥𝐞𝐮𝐦 ≡ 𝐦𝐨𝐥𝐞𝐬 𝐨𝐟 𝐨𝐥𝐞𝐮𝐦
(𝟗𝟖 + 𝟖𝟎𝐧)

𝟏𝟎𝟎 𝟏𝟎𝟎 × (𝐧 + 𝟏)
∴ 𝐦𝐨𝐥𝐞𝐬 𝐨𝐟 𝐨𝐥𝐞𝐮𝐦 𝐩𝐫𝐨𝐝𝐮𝐜𝐞 ≡ 𝐦𝐨𝐥𝐞𝐬 𝐨𝐟 𝐇𝟐 𝐒𝐎𝟒
(𝟗𝟖 + 𝟖𝟎𝐧) (𝟗𝟖 + 𝟖𝟎𝐧)

𝟏𝟎𝟎 𝟏𝟎𝟎 × (𝐧 + 𝟏)
𝐦𝐨𝐥𝐞𝐬 𝐨𝐟 𝐨𝐥𝐞𝐮𝐦 𝐩𝐫𝐨𝐝𝐮𝐜𝐞 ≡ × 𝟗𝟖 𝐠𝐫𝐚𝐦𝐬 𝐨𝐟 𝐇𝟐 𝐒𝐎𝟒
(𝟗𝟖 + 𝟖𝟎𝐧) (𝟗𝟖 + 𝟖𝟎𝐧)

𝟏
𝟏𝟎𝟎 𝟏𝟎𝟎 × (𝟏 + 𝒏)
𝐦𝐨𝐥𝐞𝐬 𝐨𝐟 𝐨𝐥𝐞𝐮𝐦 𝐩𝐫𝐨𝐝𝐮𝐜𝐞 ≡ × 𝟗𝟖 𝐠𝐫𝐚𝐦𝐬 𝐨𝐟 𝐇𝟐 𝐒𝐎𝟒
(𝟗𝟖 + 𝟖𝟎𝐧) 𝟗𝟖
( 𝒏 + 𝟖𝟎)

𝐔𝐧𝐝𝐞𝐫 𝐭𝐡𝐞 𝐥𝐢𝐦𝐢𝐭 𝒏 → ∞

 𝟏𝟎𝟎 𝟏𝟎𝟎 × 𝟗𝟖
𝐦𝐨𝐥𝐞𝐬 𝐨𝐟 𝐨𝐥𝐞𝐮𝐦 𝐩𝐫𝐨𝐝𝐮𝐜𝐞 ≡ = 𝟏𝟐𝟐. 𝟓 𝒈𝒓𝒂𝒎𝒔 𝒐𝒇 𝐇𝟐 𝐒𝐎𝟒
(𝟗𝟖 + 𝟖𝟎𝐧) 𝟖𝟎

Therefore, percentage of labelled oleum will always be lesser than 122.5 percent and
this represents the upper limit.

Hardness and Hard Water

A sample of water is said to be hard if it doesn’t produce lather with soap easily.
Hardness in water is due to the presence of calcium and magnesium ions which form
precipitates called scum with water, resulting in wastage of soap. Hardness could be of
two types:

1. Temporary Hardness
2. Permanent Hardness

1. Temporary Hardness

The hardness which can be removed through physical means such as boiling the
sample of water is called temporary hardness. It is due to the presence of
bicarbonates of calcium and magnesium in water.

Means of removing temporary hardness:

1. Boiling:

Boiling the sample of water converts the bicarbonates into carbonates, thereby
precipitating the calcium and magnesium ions.

2𝑯𝑪𝑶− 𝟐−
𝟑 (𝐚𝐪) ⟶ 𝑪𝑶𝟑 (𝒂𝒒) + 𝐇𝟐 𝐎

𝑪𝒂𝟐+ (𝒂𝒒) + 𝑪𝑶𝟐−

𝟑 (𝐚𝐪) ⟶ 𝐂𝐚𝐂𝐎𝟑 (𝒔)

𝑴𝒈𝟐+ (𝒂𝒒) + 𝑪𝑶𝟐−

𝟑 (𝐚𝐪) ⟶ 𝐌𝐠𝐂𝐎𝟑 (𝒔)

2. Adding Washing Soda:

Addition of washing soda floods the aqueous solution with carbonate ions, thereby
precipitating the calcium and magnesium ions.
 𝐍𝐚𝟐 𝐂𝐎𝟑 (𝐚𝐪) ⟶ 𝟐𝑵𝒂+ (𝒂𝒒) + 𝑪𝑶𝟐−
𝟑 (𝐚𝐪)

𝑪𝒂𝟐+ (𝒂𝒒) + 𝑪𝑶𝟐−

𝟑 (𝐚𝐪) ⟶ 𝐂𝐚𝐂𝐎𝟑 (𝒔)

𝑴𝒈𝟐+ (𝒂𝒒) + 𝑪𝑶𝟐−

𝟑 (𝐚𝐪) ⟶ 𝐌𝐠𝐂𝐎𝟑 (𝒔)

3. Clarke’s Process :

Addition of calcium hydroxide converts bicarbonates to carbonates, resulting in

precipitation of calcium and magnesium ions as their carbonates.

𝑪𝒂(𝑶𝑯)𝟐 (𝒂𝒒) ⟶ 𝑪𝒂𝟐+ (𝒂𝒒) + 𝟐𝑶𝑯− (𝒂𝒒)

𝑯𝑪𝑶− − 𝟐−
𝟑 (𝐚𝐪) + 𝑶𝑯 (𝒂𝒒) ⟶ 𝑪𝑶𝟑 (𝐚𝐪) + 𝐇𝟐 𝐎

𝑪𝒂𝟐+ (𝒂𝒒) + 𝑪𝑶𝟐−

𝟑 (𝐚𝐪) ⟶ 𝐂𝐚𝐂𝐎𝟑 (𝒔)

𝑴𝒈𝟐+ (𝒂𝒒) + 𝑪𝑶𝟐−

𝟑 (𝐚𝐪) ⟶ 𝐌𝐠𝐂𝐎𝟑 (𝒔)

Permanent Hardness

The hardness which cannot be removed through physical means is called permanent
hardness. Permanent hardness is due to the presence of chlorides and sulphates of
calcium and magnesium. Such hardness can be removed only through chemical
means.

Means of removing permanent hardness:

1. Adding Washing Soda:

Addition of washing soda floods the aqueous solution with carbonate ions, thereby
precipitating the calcium and magnesium ions.

𝐍𝐚𝟐 𝐂𝐎𝟑 (𝐚𝐪) ⟶ 𝟐𝑵𝒂+ (𝒂𝒒) + 𝑪𝑶𝟐−

𝟑 (𝐚𝐪)

𝑪𝒂𝟐+ (𝒂𝒒) + 𝑪𝑶𝟐−

𝟑 (𝐚𝐪) ⟶ 𝐂𝐚𝐂𝐎𝟑 (𝒔)

𝑴𝒈𝟐+ (𝒂𝒒) + 𝑪𝑶𝟐−

𝟑 (𝐚𝐪) ⟶ 𝐌𝐠𝐂𝐎𝟑 (𝒔)
2. Adding Calgon (Calcium gone):

Addition of Calgon swaps the calcium and magnesium ions present in hard water
with sodium ions, thereby removing the hardness.

𝐍𝐚𝟐 [𝐍𝐚𝟒 (𝑷𝑶𝟑 )𝟔 ](𝐚𝐪) ⟶ 𝟐𝑵𝒂+ (𝒂𝒒) + [𝐍𝐚𝟒 (𝑷𝑶𝟑 )𝟔 ]𝟐− (𝐚𝐪)

[𝐍𝐚𝟒 (𝑷𝑶𝟑 )𝟔 ]𝟐− (𝐚𝐪) + 𝑪𝒂𝟐+ (𝒂𝒒) ⟶ [𝐍𝐚𝟐 𝑪𝒂(𝑷𝑶𝟑 )𝟔 ]𝟐− + 𝟐𝑵𝒂+ (𝒂𝒒)

3. Permuit Process:

Hard water is allowed to seep through zeolite which exchanges the calcium or
magnesium ions with sodium ions. The zeolite is later regenerated by passing brine
(concentrated sodium chloride solution) water through zeolite.

𝐍𝐚𝟐 𝒁 + 𝑪𝒂𝟐+ (𝒂𝒒) ⟶ 𝑪𝒂𝒁 + 𝟐𝑵𝒂+ (𝒂𝒒)

𝐍𝐚𝟐 𝒁 + 𝑴𝒈𝟐+ (𝒂𝒒) ⟶ 𝑴𝒈𝒁 + 𝟐𝑵𝒂+ (𝒂𝒒)

Regeneration of zeolite

𝑪𝒂𝒁 + 𝟐𝑵𝒂𝑪𝒍 (𝒂𝒒) ⟶ 𝐍𝐚𝟐 𝒁 + 𝑪𝒂𝑪𝒍𝟐

𝑴𝒈𝒁 + 𝟐𝑵𝒂𝑪𝒍 (𝒂𝒒) ⟶ 𝐍𝐚𝟐 𝒁 + 𝑴𝒈𝑪𝒍𝟐

 1. Ion exchange resin process:

The hard water is first passed through an acidic resin chamber which exchanges the
calcium and magnesium ions (present as their chlorides and sulphates) for protons
(𝐻 + 𝑖𝑜𝑛𝑠).

𝟐𝐑𝐒𝐎𝟑 𝑯(𝒂𝒄𝒊𝒅𝒊𝒄 𝒓𝒆𝒔𝒊𝒏) + 𝑪𝒂𝑪𝒍𝟐 (𝒂𝒒) ⟶ 𝑪𝒂(𝐑𝐒𝐎𝟑 )𝟐 + 𝟐𝑯+ (𝒂𝒒) + 𝟐𝑪𝒍− (𝒂𝒒)

𝟐𝐑𝐒𝐎𝟑 𝑯(𝒃𝒂𝒔𝒊𝒄 𝒓𝒆𝒔𝒊𝒏) + 𝑴𝒈𝐒𝐎𝟒 (𝒂𝒒) ⟶ 𝑴𝒈(𝐑𝐒𝐎𝟑 )𝟐 + 𝟐𝑯+ (𝒂𝒒) + 𝐒𝐎𝟒 𝟐− (𝒂𝒒)

Since the water coming out of acidic resin chamber is significantly acidic, it cannot
be used for most domestic or industrial purposes. Therefore, this water is now
passed through a basic resin chamber which neutralises the protons, thereby making
the water fit for consumption.

𝐑𝐍𝐇𝟑 + 𝑶𝑯− (𝒃𝒂𝒔𝒊𝒄 𝒓𝒆𝒔𝒊𝒏) + 𝑯+ (𝒂𝒒) + 𝑪𝒍− (𝒂𝒒) ⟶ 𝐑𝐍𝐇𝟑 𝑪𝒍 + 𝐇𝟐 𝐎

𝟐𝐑𝐍𝐇𝟑 + 𝑶𝑯− (𝒃𝒂𝒔𝒊𝒄 𝒓𝒆𝒔𝒊𝒏) + 𝟐𝑯+ (𝒂𝒒) + 𝐒𝐎𝟒 𝟐− (𝒂𝒒) ⟶ (𝐑𝐍𝐇𝟑 )𝟐 𝐒𝐎𝟒 + 𝟐𝐇𝟐 𝐎

Once the resins are depleted, they are regenerated by adding a strong acid and a
strong base to the acidic and basic resin chambers respectively.

Acidic Resin Chamber:

𝑪𝒂(𝐑𝐒𝐎𝟑 )𝟐 + 𝟐𝑯𝑪𝒍 (𝒂𝒒) ⟶ 𝟐𝐑𝐒𝐎𝟑 𝑯 + 𝑪𝒂𝑪𝒍𝟐 (𝒂𝒒)

𝑴𝒈(𝐑𝐒𝐎𝟑 )𝟐 + 𝟐𝑯𝑪𝒍 (𝒂𝒒) ⟶ 𝟐𝐑𝐒𝐎𝟑 𝑯 + 𝑴𝒈𝑪𝒍𝟐 (𝒂𝒒)

 Basic Resin Chamber:

𝐑𝐍𝐇𝟑 𝑪𝒍 + 𝑵𝒂𝑶𝑯(𝒂𝒒) ⟶ 𝐑𝐍𝐇𝟑 + 𝑶𝑯− + 𝑵𝒂𝑪𝒍(𝒂𝒒)

(𝐑𝐍𝐇𝟑 )𝟐 𝐒𝐎𝟒 + 𝟐𝑵𝒂𝑶𝑯(𝒂𝒒) ⟶ 𝟐𝐑𝐍𝐇𝟑 + 𝑶𝑯− + 𝑵𝒂𝟐 𝐒𝐎𝟒 (𝒂𝒒)

Degree of Hardness

It is defined as the number of parts by mass (or equivalent mass) of Calcium Carbonate
present in million parts by mass of water and which is precipitated through addition of
washing soda.

𝑴𝒂𝒔𝒔 𝒐𝒇 𝐂𝐚𝐂𝐎𝟑 (𝒔)

𝑫𝒆𝒈𝒓𝒆𝒆 𝒐𝒇 𝑯𝒂𝒓𝒅𝒏𝒆𝒔𝒔 = × 𝟏𝟎𝟔
𝑴𝒂𝒔𝒔 𝒐𝒇 𝑾𝒂𝒕𝒆𝒓