33

CHAPTER 3
STOICHIOMETRY
3.1 Stoichiometry
That part of Chemistry which deals with the quantities of substances taking part in
chemical reactions .is called stoichiometry. Stoichiometry is based on the laws and
principles of chemistry, primarily on:
1. Conservation of mass
2. Relative masses of atoms
3. The concept of the mole
The law of conservation of mass as applied to chemical reactions states that the
total mass of the products formed must be equal to the total mass of the reactants. The
masses of the substances taking part in a chemical reaction can be expressed in terms of
the masses of their constituent atoms. In the ninth standard course we have dealt with the
idea of relative masses of atoms and hence the relative masses of the elements in a
compound. Consequent to these ideas, we have learned that quantities can be expressed
in terms of numbers of atoms and molecules and this has led to the concept of the
Avogadro number and the mole. This concept is fundamental to all aspects of
stoichiometry.
What does stoichiometry involve?
Stoichiometry involves

1. Prediction of the quantities of materials required to produce a given quantity of

products or, vice versa, the determination of the quantity of product which may be
obtained from given quantities of reactants.
2. Interpreting the results of a chemical analysis.
3. Choosing the most economical way of carrying out a chemical reaction on a
commercial scale.
4. Preparing solutions containing the required concentrations of dissolved substances.

3.2 Formula Masses (Formula Weights)

A formula is used to express the composition of a substance and it denotes the relative
numbers of atoms of the respective elements in a molecule or formula unit of the
substance. The masses of the molecules or formula units relative to 12C are expressed by
their molecular masses or formula masses respectively. These are computed by simply
adding the relative atomic masses of each and every atom in the molecule or formula
unit.

3.3 Formulae and Per Cent Composition

If the formula of a compound is known, the per cent composition of the elements present
in the compound may be calculated. For this calculation, knowledge of the relative
atomic masses (or atomic weights) is essential.
 34

Example: Calculate the per cent composition of magnesium nitrate. (Relative atomic
masses of Mg = 24.31, N = 14.01, O=16)
In magnesium nitrate, Mg(NO3)2 each formula unit contains one Mg atom,
two N atoms, and six O atoms.
Formula mass = 24.31 amu + (2 x 14.01 )amu + (6x 16)amu
= 148.33 amu
Per cent of Mg = x 100
= 16.39% Mg
Per cent of N = x 100
= 18.89%N
Per cent of O = x 100
= 64.72% O

3.4 The Mole and the Millimole

A chemical formula may be used to refer to one atom, one molecule, one formula unit or
to a mole of atoms, molecules or formula units.
The quantity of a substance in terms of moles may easily be determined if the mass
of the pure substance in grams is known.
1 mole of the substance = Relative molecular mass expressed in grams
Quantity of substance in moles =

or =
Molar mass = mass in grams per mole of a substance
= relative molecular mass expressed in grams
Example: How many moles of hydrogen gas are there in 27.0 g of hydrogen?

moles of hydrogen =
= 13.4 mol H2
For experimental work It is sometimes convenient to use the millimole (mmol) as
unit. This corresponds to 0.001 mole.
Quantity of substance in millimoles =

or =
Molar mass = mass in milligrams per millimoles of a substance
= Relative molecular mass expressed in milligrams
It is evident that 1 mole is equivalent to 1000 millimoles.
3.5 Chemical Equations in Stoichiometry
 35

In every chemical reaction between a given set of reactants under a given set of
conditions the same products will always be formed. Using such equations it is possible
to predict the quantities of products which will be formed from the quantities of reactants
used. To be useful in this manner,
1. the chemical equation must be balanced
2. the physical state of each of the reactants and products must be indicated by
use of proper abbreviations in parentheses after the formulae: (s) for solid, (I)
for liquid, (g) for gas, (aq) for aqueous solution.

Example : 4 g of a mixture of calcium carbonate and sand is treated with an excess of

dilute hydrochloric acid , and 0.880 g of carbon dioxide is produced. What is
the percentage of calcium carbonate in the original mixture?

The balanced chemical equation is

CaCO3(s) + 2HC1(aq) CO2(g) + CaCl2(aq) H2 O (1)
40+12+3 x 16 12+2 x 16
100 44

1 mole of CO2 is expected from 1 mol of CaCO3

mol ...................... mol of CaCO3

or x 100g of CaCO3
or 2.00 g of CaCO3
Per cent CaCO3 in mixture = 100
= 50.0%

3.6 Limiting Quantities

When an experiment is actually conducted the relative quantities of the reactants present
may differ from those required by the balanced chemical equation. If the reacting mixture
contains one of the reactants in lesser quantity than is required by the equation, the
reaction will simply stop when the reactant in lesser quantity is exhausted. The quantities
of products formed will then be determined by the reactant present in lesser quantity.
Example: How many grams of sulphur would be precipitated on mixing 5 dm 3 of
sulphur dioxide with 12 dm3 of hydrogen sulphide if both gases were
originally at 756 mm Hg pressure and 25 C?
The gases react according to the equation
2H2S (g) + SO2 (g) 2H2O (1) + 3S(s)
2 mol + 1 mol
or 2 vol 1 vol
We shall first have to determine the limiting quantity
 36

5 dm3 of sulphur dioxide at 736 mmHg and 25 C, must first be converted to volume at
STP

V1 =

=
Volume of SO2 = 4.654 dm3 at STP
Moles of SO2 = mol or 0.2078 mol
12 dm3 of hydrogen sulphide at 756 mmHg and 25 C may similarly be converted to
volume at STP.

V1 =

=
Volume of H2S = 10.93 dm3 at STP
Moles of H2S = mol or 0.4879 mol
Now, according to the equation, 1 volume of sulphur dioxide will react with 2 volumes of
hydrogen sulphide. That is, 4.654 dm 3 of sulphur dioxide at STP will require 4.654 x 2 or
9.308 dm3 of hydrogen sulphide at STP. In other words, 0.2078 mole of sulphur dioxide
will require 2x0.2078 or 0.4156 mole of hydrogen sulphide. Therefore, in the mixture
there will be an excess of hydrogen sulphide and the sulphur dioxide will be the limiting
quantity. Calculations for quantity of sulphur precipitated must accordingly be based on
the amount of sulphur dioxide.
1 mol of SO2 on complete reaction with H2S deposits 3 mol S
0.2078 mol …………………… 0.2078 x 3
or 0.6234 mol S
or 0.6234 x 32 g of sulphur
or 19.948 g of sulphur

3.7 Stoichiometry in Solution: Volumetric Analysis

Molarity
The molarity (M) of a solution is the quantity in moles of the solute dissolved in one
cubic decimetre (1 dm3) of the solution.
A molar solution of a compound is one which contains one mole (the relative
molecular mass in grams or the formula mass in grams for those compounds having giant
 37

structure) of the compound in one cubic decimetre (1 dm 3) of the solution. Note that it is
one cubic decimetre of solution, not solvent, that is specified.
In common analytical use the formula usually accepted for a compound having
giant structure is assumed to be molecular formula of that compound. Consequently the
formula mass is used in place of relative molecular mass.
The formula mass or formula weight is the amount of that substance which
contains the Avogadro's number of particles as represented by the formula.
We shall use the term molar solution for all formal solution in this text.
Thus, since sulphuric acid has a relative molecular mass of 98, molar sulphuric
acid solution contains 98 g of pure sulphuric acid in one cubic decimetre of solution.
Similarly, molar sodium hydroxide solution contains 40 g of sodium hydroxide in
one cubic decimetre of solution. A 0.5 molar solution of sodium hydroxide will obviously
contain 20g of the solute in one cubic decimetre of solution.
In the case of sodium chloride which has a giant structure, the formula mass of
the formula unit NaCl is used. Thus, a molar sodium chloride solution contains 58.5 g of
sodium chloride in one cubic decimetre of solution.
1 mole of solute dissolved in 1 dm3 of solution will give a solution of 1 M.
Since, 1 mole = 1000 millimoles
3
and 1 dm = 1000 cm3
the above solution contains 1 millimole solute in 1 cm3 of the solution.
Hence, molarity is also represents the quantity in millimoles solute per cm 3 of
solution.
Example 1: Calculate the molarity of a solution prepared by dissolving. 4.0 moles of
solute in sufficient solvent to make 2.0 dm3 of solution.
molarity =
= 2M

Example 2: Calculate the molarity of a solution prepared by adding 100 g of pure

sodium carbonate to sufficient water to make 1.5 dm3 of solution.

Relative molecular mass of Na2CO3 = 2 23 + 12 + 3 16

= 106
100 g Na2CO3 = mol
= 0.9654 mol
3
Molarity of solution = mol dm
= 0.6436 M
Example 3 : What volume of 2.0 M sulphuric acid is required to react with 5.0 g of
zinc?
 38

Zn(s) + H2SO4(aq) ZnSO4(aq) + H2(g)

1 mol 1 mol
5g of Zn = mol
= 0.0765 mol of Zn
Amount of H2SO4 required= 0,0765 mol
2 mol of H2SO4 is present in 1 dm3 or 1000 cm3 of 2 M H2SO4
0.0765 ....... cm3 of 2M H2SO4
or 38.25 cm3 of 2M H2SO4

Dilution of a solution
When a given aqueous solution is diluted with water the quantity or mole of the solute
does not change but the concentration or molarity does change. Such changes in
concentration can be easily calculated from the definition of molarity.

Example: How many cubic centimetres of a 0.1 M solution must be diluted with
water to make 2.0 dm3 of 0.025 M solution?
2.0 dm3 of 0.25 M solution must be made
2.0 dm3 of 0.025 M solution must contain 2 x 0.025 mole or
0.050 mole solute
Now,
0.1 mol solute is contained in 1000 cm3 of 0.1 M solution
0.050 mol.......................... 1000 x cm3 of 0.1 M solution
or 500 cm3
Hence, 500cm3 of 0.1 M solution must be taken and diluted to 2dm3.
Alternative method
When a solution is diluted, the concentration decreases and the concentration of the
resultant solution is inversely proportional to its final volume. Generally, for the same
amount of solute,
concentration
Provided we keep the units of concentration and volume unchanged.
Concentration x volume = constant
C1V1 = C2V2 = constant

If concentration is in terms of molarity and volume in cm3

M1V1 = M2V2
3
O.I M V1cm = 0.025 M 2000 cm3
V1 in cm3 =
= 500cm3
 39

Note: This formula M1V1 = M2V2 may be used for dilution of a solution where the total
amount of solute does not change.

Example: If 20.0 cm3 of 1.0 M sulphuric acid and 60.0 cm3 of 0.2 M sulphuric acid
are mixed what will be the molarity of the final solution?
We shall first find out the total quantity of sulphuric acid in millimoles (mmol) which
will be present in the mixed solution. This will be the sum of millimoles sulphuric acid
present in each solution.
Since molarity also expresses concentration in m mol cm 3,
1 cm3 of 1.0 M H2SO4 contains 1 m mol H2SO4
20cm3........................... 20x1 m mol H2SO4
or 20 m mol H2SO4
3
60 cm of 0.2 M H2SO4 contains 60 0.2 m mol H2SO4
or 12 m mol H2SO4
Total m mol H2SO4 = 20 + 12
or 32 m mol H2SO4
This quantity is present in a total volume of (20+60) cm3 or 80cm3
Concentration in m mol cm-3 = m mol cm-3
Molarity = 0.40 M

3.8 Terms and Units used in Volumetric Analysis

Titration
The term "titration" is used for the procedure in which a solution of a standard reagent
(reactant)is added to a specific volume of a solution of unknown molarity. The volume of
standard reagent solution which just reacts completely with the unknown solution is
measured carefully. From this measurement the amount in moles of standard reagent
required for the reaction can be calculated. Knowing the equation for the reaction we can
determine the amount in moles of the other reactant. Titrations are possible if the
following conditions are fulfilled.
1. The standard reagent must react completely with the unknown solution.
2. The reaction must be reasonably fast.
3. The point at which the two reactants have just completely reacted, that is, the
equivalence point must be easily detectable.
4. The equation for the chemical reaction must be exactly known for easy
determination of the stoichiometric proportions in which the reactants react.
 40

A weighed quantity of the unknown substance or a precisely known volume of the

solution of the unknown, usually measured out by a pipette is placed in a conical flask or
beaker.
A solution of known concentration is then added gradually from a burette. This
addition is continued until the exact mole ratio required by the balanced chemical
equation is reached. To detect this equivalence point suitable indicators (dyes), which
change colour at this point are added to the solution. For example, the dye
phenolphthalein is colourless in acid, and red in alkali solutions. Its colour changes from
one to the other at the equivalence point.
The reaction between sulphuric acid and sodium hydroxide is represented by the
following equation.
H2SO4(aq) + 2NaOH(aq) Na2SO4(aq) + 2H2O(1)
This shows that one mole of sulphuric acid reacts with two moles of sodium
hydroxide and so it follows that
1 dm3 of M sulphuric acid reacts with 1 dm3 of 2M sodium hydroxide
or
1 dm of M sulphuric acid reacts with 4 dm3 of 0.5 M sodium hydroxide.
3
 41

Consider the general reaction in which compounds A and B react in the ratio of x
moles of A to y moles of B. This reaction may be represented as

xA + yB products

Suppose that in a titration V A cm3 of solution A which has molarity M A reacts

with VB cm3 of solution B whose molarity is MB.

Since 1000 cm3 of solution A contains MA moles of A

VA cm3 of solution A contains moles of A
Similarly, since 1000cm3 of solution B contains MB moles of B
VB cm3 of solution B contains moles of B

Therefore, the ratio of moles of A and B reacting is =

which on rearranging
xMBVB = yMAVA
In any titration, only one of these variables is unknown and it may be
calculated using this relationship.

Example: 1.0dm3 of sulphuric acid solution required 4.0 dm3 of 0.1 M potassium
hydroxide to neutralize it. Calculate the molarity of sulphuric acid.

H2SO4 (aq) + 2 KOH (aq) K2SO4 (aq) + 2H2O (l)

1mol 2mol

For acid For base

x = 1 mol y = 2mol
MA = ? MB = 0.1 M
VA = 1.0 dm3 VB = 4.0 d m3

x MB VB = y MA VA
MA =

=
= 0.2 M
Standard solution
 42

The reagent of exactly known concentration that is used in a titration is called a

standard solution.
The concentration of a standard solution is established either directly or
indirectly.
1. by dissolving a carefully weighed quantity of the pure reagent and diluting to
an exactly known volume,
2. by titrating a solution containing a weighed quantity of pure compound with
the reagent solution.
In either method, a highly purified chemical compound called a primary standard
is required as the reference material.

Primary standard
The accuracy of a volumetric analysis depends upon the primary standard used to
establish the concentration of the standard solution. Important requirements for a
substance to serve as a good primary standard include the following.
(1) Highest purity
(2) Stability
(3) Absence of hydrate water
(4) Ready availability at reasonable cost
(5) Reasonably high molecular mass
The requirements 1,2 and 3 are important because the compound to be used as standard
will conform to the composition prescribed by the molecular formula only if these
requirements are met.

Standardization
The process by which the concentration of a standard solution is determined
volumetrically by the use of a primary standard is called standardization.

Equivalence point and end point

In every titration the objective is to add the standard solution in an amount that is
chemically equivalent to the substance with which it reacts. This condition is achieved at
the equivalence point.
The equivalence point in a titration is a theoretical concept. In actual fact, its
position can be estimated only by observing physical changes associated with the
equivalence point. These changes occur at the end point of the titration.
A common method of end point detection in volumetric analysis involves the use
of an indicator that exhibits a change in colour as a result of concentration changes near
the equivalence points.

3.9 Standard Solutions in Acid-Base Titrations

For volumetric analysis a standard solution is required as a starting point. Actually few
compounds are suitable for the direct preparation of standard solution. Some compounds,
 43

such as, sodium hydroxide, potassium hydroxide, and concentrated sulphuric acid absorb
water from air. For this reason, these substances cannot be weighed out accurately.
Sodium hydroxide and potassium hydroxide also react with carbon dioxide from
the air.
2NaOH(s) + CO2(g) Na2CO3(s) + H2O(l)
2KOH (s) + CO2(g) K2CO3(s) + H2O(l)

A compound which is commonly used for the direct preparation of a standard

solution is anhydrous sodium carbonate. It is best prepared from sodium
hydrogencarbonate of high purity. This is done by heating the sodium hydrogencarbonate
to constant mass, which ensures completion of the decomposition.

2NaHCO3(s) Na2CO3(s) + H2O(l) + CO2(g)

The anhydrous sodium carbonate so obtained is very pure and can be regarded as a
primary standard if prepared just prior to its use. It can be used in ordinary weighings
with no appreciable change in composition.
The preparation of a standard solution of sulphuric acid cannot be done directly
because concentrated sulphuric acid absorbs water rapidly from the air and is never
reliably pure. A solution is prepared which is a little above 0.1 M in concentration and it
is then standardized against a primary standard and diluted with distilled water to exactly
0.1 M.
A molar solution of sulphuric acid contains 98 g of pure acid in I dm 3 of solution.
So the 0.1 M acid contains 9.8 g of the acid in 1dm 3. The concentrated acid has a density
of about 1.8 g cm 3, so 10 g of it will occupy about 5.6 cm3.

Thus, the preparation of a standard solution of sulphuric acid involves

(a) diluting a concentrated solution of sulphuric acid to an approximate molarity,
and
(b) the standardization of the dilute acid solution using a previously standardized
alkali solution.

3.10 Calculation
Example 1: Two drops of phenolphthalein solution was added to 10.00 cm 3 of
hydrochloric acid solution, and this solution was titrated with 0.10 M sodium hydroxide.
When 7.5 cm3 of the sodium hydroxide solution had been added, part of the solution
turned pink, but the colour disappeared upon mixing the solution. From this point
onwards the sodium hydroxide solution was added dropwise with thorough mixing of the
solution after each addition, until a lasting pink colour was developed. The equivalence
point is now reached and the volume of 0.10 M sodium hydroxide added was 8.00 cm 3.
What was the concentration of the hydrochloric acid solution?

NaOH(aq) + HCl(aq) NaCl (aq) + H2O(1)

 44

1 mol 1 mol
The added NaOH in millimoles = 8.0cm3 x 0.1 mmol cm-3
= 0.8 mmol

This base will neutralize an equivalent amount of HCl, i.e.,

0.8 mmol of HC1.

Hence, 0.8 mmol of HCl must have been present in 10cm3 of the HC1 solution.
Molarity of HCl =
= 0.080 M
Example 2: Vinegar contains the organic acid, acetic acid (ethanoic acid), HC 2H3O2.
When 6g of vinegar was titrated with 0.10 M sodium hydroxide, 40.00 cm 3 of this base
had to be added to reach the equivalence point. What is the percentage by mass of acetic
acid in this sample of vinegar?

HC2H3O2(aq) + NaOH(aq) NaC2H3O2(aq) + H2O(1)

1 mol 1 mol
Molecular mass = 60

Millimoles of base required for neutralization

= 40.00 cm3 x 0.10 mmol cm-3
= 4.00 mmol NaOH

4 mmol of acetic acid must be present in the vinegar

Weight of acetic acid = 4.00 mmol x 60 mg mmol-1
= 240mg
Per cent acetic acid in vinegar = x 100
= 4% acetic acid

Example 3: 25 cm3 of 0.1 M sodium carbonate solution required 24 cm3 of sulphuric

acid to neutralize it.
(a) Calculate the molar concentration of sulphuric acid.
(b) What volume of water should be added to 24 cm3 of sulphuric acid so that the
concentration becomes exactly 0.1 M?
(a) In calculating the molarity of any solution from the results of an acid-base
titration, it is necessary to write the equation for the reaction taking place.
Na2CO3(aq)+ H2SO4 (aq) Na2SO4 (aq) + CO2 (g) + H2O (1)

From the above equation it can be seen that one mole of Na 2CO3 reacts with one mole of
H2SO4 for complete neutralization.
 45

Therefore the amount in moles of sodium carbonate in 25 cm 3 of solution is equal to the

amount in moles of sulphuric acid added at the end point.

Since the sodium carbonate solution is 0.1 M, 1 dm 3 of sodium carbonate solution

contains 0.1 mole sodium carbonate. 25 cm3 of sodium carbonate solution contains
mole of sodium carbonate = 0.0025 mole.
For complete neutralization 24 cm3 of sulphuric acid are required.
Therefore,
24 cm3 of sulphuric acid solution contains 0.0025 mole of sulphuric acid
1 dm3 of sulphuric acid solution contains mole of sulphuric acid
= 0.104 mol
(b) To make the acid exactly equal in molar concentration to the sodium carbonate
solution, that is. 0.1 M, 24 cm3 of the acid must be diluted to 25 cm 3. Therefore 1 cm3 of
distilled water must be added to 24 cm 3 of the acid. You may confirm it by doing the
actual calculation.

Example 4: 25 cm3 of a sodium carbonate solution required 23.5 cm 3 of 0.5 M

hydrochloric acid solution to neutralize it. Calculate the molarity of sodium carbonate
solution and convert the concentration into g dm -3. ( The relative atomic masses of Na =
23, C= 12, 0=16)
Na2CO3 (aq) + 2HCl(aq) 2NaCl (aq) + H2O(l) + CO2(g)
From the above reaction it can be seen that one mole of Na2CO3 reacts with two moles of
HC1 for complete neutralization.
Since the hydrochloric acid is 0.5 M,
1 dm3 of hydrochloric acid solution contains 0.5 mole of hydrochloric acid

23.5 cm3 of hydrochloric acid solution contains mole of hydrochloric acid

= 0.01175 mol
Therefore,
25 cm3 of sodium carbonate solution contains mole of sodium carbonate.

1 dm3 of sodium carbonate solution contains

= 0.235 mol
Molecular mass of Na2CO3 = 106
Therefore 1 dm3 of 0.235 M Na2CO3 contains 106 x 0.235
= 24.91 g
Example 5: 3g of a mixture of sodium carbonate and sodium chloride were made up to
250 cm3 of solution. 25 cm3 of this solution required 21 cm 3 of 0.1050 M hydrochloric
acid for neutralization. Calculate the percentage by mass of sodium chloride in the
 46

mixture. Sodium chloride does not react with hydrochloric acid, but sodium carbonate
reacts according to the equation.
Na2CO3(aq) + 2HCl(aq) 2NaCl(aq) + H2O(l) + CO2(g)
2 moles of HCl reacts with l mole of Na2CO3
1 mole of HC1 reacts with 0.5 mole of Na2CO3
Molecular mass of Na2CO3 = 106
The mass of 0.5 mole of Na2CO3 = 53 g
3
1000 cm of 1 M HCl reacts with 53 g of Na2CO3

21 cm3 of 0.1050 M HCl reacts with

ie., 25 cm3 of the given solution contains g

250cm3 of the given solution contains

3 g of mixture contains

100 g of mixture contains

= 38.95%
The percentage of sodium carbonate = 38.95 %
The percentage of sodium chloride = (100 - 38.95 ) %
= 61.05%
You may refer to the experimental chemistry book for further examples on acid-base
titration.

3.11 Volumetric Analysis involving Oxidation- Reduction Reactions

Oxidation- reduction titrations (or redox titrations) are based upon the reaction of. the
substance with a standard solution of an oxidizing agent or reducing agent. For the
titration to be meaningful, the substance must exist entirely in a single oxidation state at
the start of the titration.

Potassium permanganate (Potassium manganate (VII))

Potassium permanganate is perhaps the most widely used of all standard oxidizing
agents. The colour of a permanganate solution is so intense that an indicator is not
ordinarily required.

Reaction of permanganate ion

Potassium permanganate is most commonly employed with solutions that are 0.05 M or
greater in mineral acid concentration. Under these conditions, the product is manganese
(II) ion.
 47

MnO (aq)+ 8H+(aq) + 5e Mn2+(aq) + 4H2O(1)

Preparation and standardization of permanganate solutions

Solid potassium permanganate is always contaminated with manganese (IV) oxide to
some extent. Therefore, preparation of standard permanganate solutions of exact
concentrations is not possible by direct weighing. Potassium permanganate solution of
approximate concentration is first prepared and then the solution is standardized using the
solution of sodium salt of ethanedioic acid as primary standard.
In acidic solution, ethanedioic acid is released and the permanganate oxidizes it to
carbon dioxide and water. The permanganate oxidizes ethanedioic acid according to the
ionic half- equations.
MnO (aq) + 8H+ (aq) + 5e Mn2+(aq) + 4H2O(1)
H2C2O4 (aq) 2H+(aq) + CO2(g) + 2e

Adding together the two ionic half-equations, we obtain

2MnO (aq)+ 5H2C2O4(aq) + 6H+ (aq) 2Mn2+(aq) + 10CO2(g) +8H2O(l)

Application of standard permanganate solutions

Permanganate may be used for the titration of iron (II) in acid solution.
The ionic half-equations for the oxidation of iron (II) salt by the permanganate are
MnO (aq)+ 8H+(aq) + 5e Mn2+ (aq) + 4H2O(1)
Fe2+ (aq) Fe3+ (aq) + e
Combining the half- equations, we obtain
5Fe2+(aq) + MnO (aq) + 8H+(aq) 5Fe3+(aq) + Mn2+(aq) + 4H2O (1)

Potassium dichromate
In its applications, dichromate ion is reduced from the hexavalent to the trivalent state.
Cr2O (aq) + l4H+(aq) + 6e 2Cr3+(aq) + 7H2O(1)
The advantage of using dichromate is that its solutions are very stable.
For most purposes, commercial reagent grade or primary standard grade
potassium dichromate can be used to prepare standard solutions.

Application of standard dichromate solution

The principal use of dichromate involves titration of iron (II).
6Fe2+(aq) + Cr2O (aq) + l4H+(aq) 6Fe3+(aq)+ 2Cr3+(aq) + 7H2O(1)
Example 1: An approximately 0.02 M potassium permanganate solution was
standardized against exactly 0.1 M iron (II) sulphate solution. 25 cm 3 of the solution of
the iron (II) salt were oxidized by 24.6 cm 3 of the permanganate solution. What is the
molarity of the permanganate solution?
 48

5Fe2+(aq) + MnO (aq) + 8H+(aq) 5Fe3+(aq) + Mn2+(aq) + 4H2O(1)

From this reaction five moles of Fe(II) react with one mole of MnO . Since the iron (II)
sulphate is exactly 0.1 M,
1dm3 of iron (II) sulphate contains 0.1 mole of iron (II) sulphate
25 cm3 of iron (II) sulphate solution contains mole of iron (II) sulphate
= 0.025 mot
3
For complete reaction 24.6 cm of the permanganate solution are required. Therefore,
24.6 cm3 of the permanganate solution contains mole of permanganate.

1 dm3 of permanganate solution contains mole

= mol
= 0.0203 mol
The molarity of permanganate solution is 0.0203 M

Example 2: 9.85 g of pure ammonium iron (II) sulphate FeSO 4 . (NH4)2 SO4 . 6H2O
were made up to 250 cm3 of the solution in sulphuric acid. 25 cm 3 of the solution reacted
completely with 24.75 cm3 of a potassium permanganate solution. Calculate
(a) the molarity of the solution
(b) its concentration in g dm 3
(c) the volume of water needed to convert 1.8 dm 3 of such a solution to exactly 0.02 M
concentration.

Essentially the Fe2+ ion in the ammonium iron (II) sulphate is oxidized to Fe3+ ion.
(a) The ionic half-equations for the oxidation of the iron (II) salt by the permanganate are
MnO (aq)+ 8H+(aq)+ 5e Mn2+(aq) + 4H2O(1)
Fe2+(aq) Fe3+(aq) + e
Combining these two half-equations, we obtain
5Fe2+(aq) + MnO (aq) + 8H+(aq) 5Fe3+(aq) + Mn2+(aq) + 4H2O(1)
Molecular mass of ammonium iron (II) sulphate,
FeSO4. (NH4)2 SO4. 6H2O 392
250cm3 of the iron (II) salt contain 9.85 g pure ammonium iron (II) sulphate
25cm3 of the iron (II) salt contain 0.985 g " " " "
25 cm3 of the iron (II) salt contain mole which contains the same
quantity in moles of Fe2+ ion
 49

From the reaction between Fe2+ and MnO in acid solution, 1 MnO reacts with 5 Fe2+

and therefore 24.75 cm3 of the permanganate solution must contain mole of

MnO .

1 dm3 of the permanganate solution contains

= 0.0203 mol.
(b) The potassium permanganate solution is 0.0203 M.
1 mole of potassium permanganate is 158 g.
Therefore the concentration of the potassium permanganate solution is 0.023
158 =3.21 gdm 3.
(c) Since 1 dm3 of permanganate solution contains 0.0203 mole, 1.8 dm3 of this
solution contains 0.0203 x 1.8 mole
= 0.03654 mole of KMnO4.
When this solution is diluted to make exactly 0.02 M solution, it will still contain
0.03654 mole.

Therefore the volume of a 0.02 M KMnO4 solution containing

0.03654 mole = 1000
= 1827cm3
= 1.827dm3
The difference in the two volumes = 1.827-1.8
= 0.027dm3
= 27cm3
Therefore 27 cm3 of distilled water must be added to l.8 dm 3 (1800 cm3) of potassium
permanganate solution in order to make the solution exactly 0.02 M.

Example 3: A solution contains ethanedioic acid and sodium salt of ethanedioic acid.
25 cm3 of this solution required 14.75 cm 3 of 0.1 M sodium hydroxide solution for
neutralization. The same volume, 25 cm 3 of the solution required 30.5 cm3 of 0.0205 M
potassium permanganate solution for oxidation in acidic condition at about 70 C.
Calculate the number of grams of each constituent (anhydrous form) per dm 3 of the
solution.
The sodium hydroxide reacts with free ethanedioic acid only. The reaction is
2 NaOH(aq) + H2C2O4 (aq) Na2C2O4(aq) + 2H20 (1)
2 moles of NaOH react with 1 mole of H2C2O4
1 mole of NaOH react with 0.5 mole of H2C2O4
Mass of anhydrous H2C2O4 = 90 g
Mass of 0.5 mole H2C2O4 = 45 g
 50

l000 cm3 of 1 M NaOH reacts with 45 g of H2C2O414.75 cm3 of 0.1

M NaOH reacts with 45 0.1 g

This is the mass of ethanedioic acid in 25 cm3 of solution.

= 45
= 2.66 g
Potassium permanganate oxidizes all the ethanedioic acid and sodium salt of ethanedioic
acid which are present as ethanedioate according to the ionic half-equations.
MnO (aq) + 8H+(aq) + 5e Mn2+(aq) + 4H2O(1)
C2O (aq) 2CO2(g) + 2e
Combining these two half-equations, we obtain
2MnO (aq) + 5C2O (aq) +16H+(aq) 2Mn2+(aq)+ 10CO2(g)+8H2O(1)
From this reaction,
1 mole of MnO oxidizes 2.5 moles of ethanedioate ions
1000 cm3 of lM KMnO4 oxidizes 2.5 moles of ethanedioate ions
30.5cm3 of 0.0205 M KMnO4 oxidizes 2.5 0.0205 mol
Therefore, the total ethanedioate ions present in 25 cm3 = 0.001545 mol
1 dm3 of the solution contains 2.66 g of ethanedioic acid
1 dm3 of the solution contains mol of ethanedioic acid

25 cm3 of the solution contains mol of ethanedioic acid

= 0.0007375 mol
The corresponding quantity in mole of ethane dioate present in the solution is contributed
by the ethane dioic acid.
Therefore the amount in moles of ethane dioate ions from
sodium ethane dioate = 0.001545 — 0.0007375 = 0.0008075mol
But one mole of Na2C2O4 is 134g
Therefore the mass of Na2C2O4 in 25 cm3 = 0.0008075 134g
3
and the mass of Na2C2 O4 in 1000cm = 0.0008075 134 40
= 4.33 g

3.12 Calculations involving formulae and chemical equations

There are two kinds of formulae (i) the simplest or empirical formula and(ii) the
molecular formula.
 51

The simplest formula or the empirical formula gives us only the relative number
of atoms of different elements in a compound. The molecular formula tells us show many
atoms of various elements exist in an individual molecule. Usually the empirical formula
is calculated first, since it is obtained directly from the chemical analysis of the
compound. Other data are needed to determine the molecular formula.
When the empirical formula of a compound is known, the percentages by mass of
each of the elements in a compound can be calculated. For example, let us calculate the
percentages by mass of calcium, oxygen and carbon present in calcium carbonate.
The empirical formula of calcium carbonate is CaCO3
The formula mass of CaCO3 is 40 + 12 + (3 x 16)= 100.
Out of 100 units of mass of CaCO3, 40 units of mass are from calcium. That is,
the fractional mass of calcium is . Therefore the percentage by mass of Ca in

CaCO3 = 100 = 40 %. Similarly the percentage by mass of C in

CaCO3= l00 = 12%. The percentage by mass of oxygen need not be calculated
because-
percentage of oxygen = 100 — (% of Ca + % of C)
= 100 — (40 + 12) = 48%
We have seen that a chemical reaction can be represented by chemical equation.
A balanced chemical equation can be used as summary of the mass changes that occur
when reactants are converted to products.
Let us consider the chemical equation:
CaCO3 + 2HCl CaCl2 + H2O + CO2
40+12+(3 xl6) + 2(1+35.5) 40+(2x35.5) + (2x1)+16 + 12+(2 x 16)
100 73 111 18 44

This equation tells us that one mole of calcium carbonate reacts with two moles of
hydrochloric acid to form one mole of calcium chloride, one mole of water and one mole
of carbon dioxide. When the appropriate formula masses are inserted as shown above, the
equation also means 100 parts by mass of calcium carbonate reacts with 73 parts by mass
of hydrochloric acid to form 111 parts by mass of calcium chloride, 18 parts by mass of
water and 44 parts by mass of carbon dioxide.
Various problems can be solved by using balanced chemical equations.
Relative Atomic masses (nearest values) of elements for solving the problems are
given in Table(3.1).

Table (3.1) Relative atomic Masses (nearest values)

Aluminium 27 Hydrogen 1 Phosphorous 31
Barium 137 Iodine 127 Potassium 39
Bromine 80 Iron 56 Silver 108
 52

Calcium 40 Lead 207 Sodium 23

Carbon 12 Magnesium 24 Sulphur 32
Chlorine 35.5 Mercury 201 Zinc 65
Chromium 52 Nitrogen 14
Copper 64 Oxygen 16

SUMMARY
In this chapter, the chemistry which deals with the quantities of substances taking
part in chemical reactions is termed ‘ Stoichiometry’. Stoichiometry is based on the laws
and principles of chemistry, such as conservation of mass, relative masses of atoms, and
the concept of the mole. It involves formula masses (formula weights), formulae and per
cent composition , mole , millimole of substances . It introduces the concept of limiting
quantities in an experiment In volumetric analysis (stoichiometry in solution), it
explains the concepts of molarity, standard solution, primary standard, standardization,
equivalence point, end point involve in acid-base titration. Various types of volumetric
analysis have been presented with appropriate worked out examples followed by
problems and questions.

Questions and Problems

1. What is the molarity of the following solutions?
(a) 3.2 g of sulphuric acid in 500 cm3 of solution.
(b) 0.56g of sodium carbonate in 100 cm3 of solution.
(c) 1 g of caustic potash in 1 dm3 of solution.
(d) 3.6 g of hydrogen chloride in 100 cm3 of solution.
2. How many cubic centimetres of l M hydrochloric acid are needed to neutralize 0.40
g of caustic potash?
3. 5g of a mixture of sodium chloride and anhydrous sodium carbonate were made up
to 500 cm3 of aqueous solution. 25 cm 3 of this solution required 18 cm 3 of 0.1 M
sulphuric acid for neutralization. What was the mass of sodium chloride in this
mixture?
4. 0.48 g of magnesium was dissolved in 50 cm 3 of 1 M hydrochloric acid. How many
cubic centimetres of 0.1 M potassium hydroxide solution will be necessary to
neutralize the excess acid?
5. 2.5 g of mixture of anhydrous sodium carbonate and sodium chloride were made up
to 250 cm3 with distilled water. 25 cm 3 of this solution required 20 cm 3 of 0.1 M
hydrochloric acid. Calculate the percentage by mass of sodium chloride in the
mixture.
6. 100 cm3 of concentrated hydrochloric acid were dilute to 1 dm 3 with distilled water.
26.8 cm3 of this diluted acid were needed to neutralize 25 cm 3 of 0.5 M sodium
carbonate solution. What is the concentration in g dm 3 of the original acid?
7. Calculate the percentage of iron in a sample of iron wire from the following data:
1.4 g of the wire were dissolved in excess of oxygen free dilute sulphuric acid and
the solution made up to 250cm3;25cm3of this solution needed 25.37 cm3 of 0.0196
M potassium permanganate for oxidation.
8. Calculate the molecular mass or formula mass of each of the following compounds.
 53

(a) Nitric acid (f) Barium carbonate

(b) Lead (II) chloride (g) Magnesium hydrogencarbonate
(c) Calcium carbide (h) Sodium dihydrogenphosphate
(d) Tetraphosphorus decaoxide (i) Disodium hydrogenphosphate
(or) Phosphorus (V) oxide (j) Potassium chlorate
(e) Dinitrogen tetroxide
9. Calculate the percentage by mass of the elements in each of the following
compounds.
(a) Potassium chloride (d) Nitrogen dioxide
(b) Iron (II) sulphate (e) Trilead tetroxide
(c) Dinitrogen oxide (f) Tetraphosphorus hexaoxide
(g) Sodium thiosulphate
10. Find the percentage by mass of water present in copper (II) sulphate crystals.
11. 1.92 g of copper was obtained from reduction of 2.4 g of an oxide of copper by
hydrogen. From experimental result, calculate the empirical formula for this oxide
of copper.
12. Oxidation of 2.01 g of mercury yields 2.17 g of oxide of mercury. What is the
empirical formula of this oxide?
13. Increase in mass of 88.89% was found on the oxidation of aluminium metal. What is
the empirical formula of this oxide?
14. 0.87 g of phosphorus reacts with chlorine to form 4.29 g of chloride.
0.33 g of phosphorus reacts with chlorine to give 2.22 g of another chloride. From
this data
(a) show that law of multiple proportion is valid.
(b) find the empirical formulae of two chlorides of phosphorus.
15. How many grams of calcium chloride will be formed by the action of dilute
hydrochloric acid on 10 g of calcium carbonate?
16. How many grams of copper (II) sulphate crystals can you get from 50 g of malachite
ore of formula Cu(OH)2. CuCO3?
17. 1.905 g of silver is converted to silver nitrate. This silver nitrate is dissolved in
distilled water and to this solution dilute hydrochloric acid is added in slight excess.
The precipitate formed is filtered, washed and dried. The weight of this dried
precipitate is 2.535 g. From this experimental result, formulate the equation for the
precipitation reaction.
18. 5 g of a mixture of anhydrous sodium sulphate and sodium sulphate decahydrate on
heating to constant mass produces 3.2 g of anhydrous salt. What percentages of
anhydrous and hydrated salt are present in the mixture?
19. 0.02 g of hydrogen gas was evolved when 0.65g of a divalent metal was treated with
dilute sulphuric acid. Calculate the atomic mass of this divalent (combining capacity
of 2) metal.
20. 100cm3 of iron (III) chloride solution is boiled and ammonium hydroxide is added in
slight excess. The reddish brown precipitate is washed, dried and ignited. The
weight of the residue obtained is 0.72 g. How many grams of iron (III) chloride is
dissolved in 1 dm3 of solution?
21. Write TRUE or FALSE for each of the following statements.
(i) A standard solution is the reagent of exactly known concentration.
 54

(ii) Sodium hydroxide may be used as primary standard.

(iii) An indicator is required in the redox titration using potassium
permanganate.
(iv)Equivalent point and end point are identical in all types of titration.
(v) A hygroscopic compound is preferrable to use as a primary standard.
22. Fill in the blanks with a suitable word or phrase or numerical value with unit as
necessary.
(i) One of the reactants in a reacting system that has the lesser quantities than is
required by chemical equation is the ......... substance.
(ii) A molar solution dissolves.......... of solute in 1 dm3 of the solution.
(iii) The amount of........ does not change due to dilution.
(iv)One cubic centimetre of a molar solution contains.........of solute.
(v) The process of determining the accurate volume of solution that is exactly
reacted with other is called ...............
23. Choose the correct term or terms given in the brackets.
(i) The (amount of solute, amount solvent, molarity) does not change due to
dilution.
(ii) A (pipette, burette, conical flask) is used to measure the amount of a solution.
(iii) Molarity means (mol dm-3, m mol dm-3, g dm-3).
(vi) An indicator indicates the (equivalent point, end point, stoichiometric amount
of reactants).
(v) The compound with (hydrate water, low molecular mass, high purity) is
preferable to use as a primary standard.
24. Match each of the items given in List A with the appropriate item in List B.
List A List B
(a) pipette (i) to indicate the end point
(b) indicator (ii) formula mass
(c) molarity (iii) finding the concentration of a solution
(d) standardization (iv) mol dm-3
(c) giant structure (v) to withdraw a known volume
25. How will you assign the physical states of each of the reactants and products in a
chemical equation ?
26. Define the term ‘ Molarity ‘.
27. Discuss the differences between molarity and a molar solution of a compound.
28. How many cm3 of 0.1 mol dm-3 hydrochloric acid will be required to neutralize 25
cm3 of 0.2 mol dm-3 sodium hydroxide. ?
29. If 25 cm3 of potassium hydroxide is neutralized by 20 cm 3 of 2.5 mol dm-1
sulphuric acid . What is the molarity of the alkali ?
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