Professional Documents
Culture Documents
Engineering Chemistry 9781783323555 9781783325702 1783323558 - Compress
Engineering Chemistry 9781783323555 9781783325702 1783323558 - Compress
Engineering Chemistry 9781783323555 9781783325702 1783323558 - Compress
CHEMISTRY
Ritu Singh
α
Alpha Science International Ltd.
Oxford, U.K.
Engineering Chemistry
380 pgs.
Ritu Singh
Department of Chemistry
Shri Ram Murti Smarak College
of Engineering and Technology
Bareilly
Copyright © 2020
A L P H A S C I E N C E I N T E R N AT I O N A L LT D .
7200 The Quorum, Oxford Business Park North
Garsington Road, Oxford OX4 2JZ, U.K.
www.alphasci.com
ISBN 978-1-78332-355-5
E-ISBN 978-1-78332-570-2
Any good text book, particularly in the fast changing fields such as engineering and technology, is
not only expected to cater to the current curriculum requirements of various institutions but also
provide a glimpse towards the latest developments in the concerned subject and the relevant discipline.
This book is written as per the syllabus of Engineering Chemistry course offered to First year
B.Tech students of various Indian universities and offers easy, accurate, systematic and logical leaning
of the subject.
The book aims to import knowledge of the subject so that students can understand role of
chemistry in the field of engineering and can develop a scientific reasoning of the subject.
The book includes a large number of solved and unsolved questions and numerical so that students
can understand applications of various topics at the end of each Chapter.
I hope this volume will prove beneficial to its readers.
ACKNOWLEDGEMENT
I am duty bound to express my thanks to the authors and publishers of all the books which have
been refereed during course of preparation of this book.
I deeply acknowledge my family members for their never ending encouragement.
A sincere expression of thanks to publisher and entire staff of Narosa Publication House.
I am grateful to God for what I am and My thanks giving is perpetual.
Contents
Preface iii
Experiments on
http://www.narosa.com/books_display.asp?catgcode=978-81-8487-607-9
Index I.1
Chapter 1
Chemical Bonding
1. Introduction
Atoms, except those of noble gases, do not have free existence. They readily combine together to
form molecules. The process of combination called chemical bonding involves the union of two or
more atoms through redistribution of electrons in their outer shell.
With the advancement of knowledge about atomic structure it was realized that electrons in
atoms were primarily involved in chemical combinations. According to the Lewis octet rule atoms
of all elements have a tendency to acquire an electronic configuration similar to that of inert gases
because it represents the most stable electronic configuration.
All atoms having unstable or incomplete outer shell have a tendency to gain or lose electrons
so as to acquire an electronic configuration of the nearest inert gas in the periodic table. It is this
tendency of atoms to complete and thereafter stabilize their outermost orbital of electrons which is
mainly responsible for chemical combination of the atoms.
Thus, according to electronic theory of valency, a chemical bond is formed as a result of electronic
interactions. It may, however be noted that a molecule is formed only when electrons of the constituent
atoms interact in such a way that the potential energy is lowered, greater the lowering of potential
energy, greater is the strength of the bond.
According to the electronic theory of valency, the interaction of extra nuclear electrons lead to
the formation of the following types of bonds:
1. Electrovalent bond / Ionic bond
2. Covalent bond
3. Co-ordinate bond
4. Metallic bond
5. Hydrogen bond
Subsequently, the wave mechanical theory was developed which gave logical understanding of
bonding between atoms. On the basis of wave mechanical theory, it is also possible to make fruitful
predictions regarding the geometrical structure of molecule.
However, the electronic theory had certain limitations as it could not explain the number of facts
about the molecules such as:
2. ORBITAL THEORY
2.1 Review of Valence Bond Theory
This method, applied to explain the formation of a covalent bond, was put forward by Heitler and
London in 1927 and later developed by Pauling and Slater in 1931.
According to this approach, only the valence electrons participate in the formation of chemical
bonds, the inner orbital electrons however remain undisturbed.
The main ideas of this approach are as follows:
1. A covalent bond is formed by the overlap of half filled atomic orbitals of the different
atoms.
2. The two half filled atomic orbitals taking part must have electrons with opposite spin.
3. The valency of an element is the same as the number of half filled orbitals present in it.
4. The strength of the bond formed depends upon the extent of overlap. Greater the overlapping,
stronger is the bond formation.
The above approach is called valence bond theory, according to this approach, only the valence
electrons participate in the formation of chemical bonds, the inner orbital electrons however remain
undisturbed.
(ii) The number of molecular orbitals formed is equal to the number of combining atomic
orbitals.
(iii) When two atomic orbitals combine they form two new orbitals called bonding molecular
orbital and anti-bonding molecular orbital. The bonding orbital is of lower energy and greater
stability than the corresponding antibonding orbital.
(iv) The shapes of the molecular orbitals formed depend upon the type of the combining atomic
orbitals.
(v) The bonding molecular orbitals are represented by s, p, d, etc, whereas the corresponding
anti-bonding molecular orbitals are represented by s*, p*, d*, etc.
(vi) The filling of molecular orbital takes place according to the following rules:
(a) Aufbau Principle: States that molecular orbitals are filled in order of their increasing
energies.
(b) Pauli Exclusion Principle: States that a molecular orbital can have maximum of two
electrons and these electrons must have opposite spin.
(c) Hund’s Rule of Maximum multiplicity: States that pairing of electrons in the degenerate
molecular orbitals does not take place until each of them has got one electron each.
overlap is along the internuclear axis and 1s indicating that 1s atomic orbitals have combined
to form the molecular orbital. The corresponding bonding molecular orbital s(1s) and
anti-bonding molecular orbital is designated as s*(1s) as given below:
2s with 2s Overlapping takes place exactly in the same way as between 1s with 1s. However,
in this case the bonding and anti-bonding molecular orbitals formed are designated as s (2s)
and s*(2s) respectively.
(ii) 2pz with 2pz Taking z-axis as the inter nuclear axis, the molecular orbitals formed are
shown below:
Fig. 2a Formation of bonding and anti bonding molecular orbital by pz-pz overlapping.
(iii) 2px with 2px or 2py with 2py (Fig. 2b) the bonding molecular orbital formed has been
designated a p(2px) or p(2py), indicating sideways overlapping and 2px or 2py indicating
that the two atomic orbitals involved are 2px or 2py.
The molecular orbitals in the order of increase in energy are as follows:-
s(1s) s*(1s) s(2s) s*(2s) s(2pz) p(2px) = p(2py) p*(2px) = p*(2py*) s*(2pz)
This order is followed from H2 molecule to N2 molecule because from H2 to N2 molecule the 2s
and 2p orbitals are of similar energy, so they combine with each other to form mixed atomic orbitals
which further combine giving molecular orbitals. Hence, p2px, p2py are of lower energy than s2pz
but after N2 molecule the order of filling of molecular orbital is as follows.
1.6 Engineering Chemistry
The order is changed after Nitrogen as the energies of 2s and 2p orbital are not same so they
directly form molecular orbital.
Fig. 2b Formation of bonding and anti bonding molecular orbital py2px-2px or 2py-2py
Fig. 3a Molecular energy diagram for Fig. 3b Molecular energy diagram for homonuclear
homonuclear diatomic molecules (from H2–N2). diatomic molecules (from O2 Onward).
Chemical Bonding 1.7
Bond order = 1/2 (2 – 0) = 1 i.e. two hydrogen atoms are connected by a single bond. No
unpaired electron is present so the H2 molecule should be diamagnetic in nature.
2. Helium molecule (He2 ): Electronic configuration of Helium is 1s2. Total number of
electrons in He2 should be 4.
Electronic configuration is s(1s)2 s(1s)*2.
Bond order = 1/2 (2 – 2) = 0 i.e. no bond is formed between two Helium atoms or we can
say that helium molecule does not exist but Helium exist in mono atomic state.
3. Lithium Molecule (Li2): Electronic configuration of Li is 1s2 2s1. Hence molecular orbital
configuration of Li2 molecule is s(1s)2 s(1s)*2 s(2s)2
4. Be2, B2 and C2 Molecules: The molecular orbital configurations of Be2, B2, C2 along with
their bond orders and magnetic properties are given in Table 1.
Table 1
Molecule Molecular Orbital Configuration Bond Order Magnetic Character
2 *2
Be2 KK s(2s) s(2s) 0 Be2 does not exist
B2 KK s(2s)2 s(2s)*2 p (2px)1 p (2py)1 1 Paramagnetic
C2 KK s(2s)2 s(2s)*2 p (2px)2 p (2py)2 2 Diamagnetic
Table 2
Molecule Molecular Orbital Configuration Bond Order Magnetic Character
N2+ 2
KK s(2s) s(2s) *2 2 2
p(2px) p(2py) s(2pz)1
3 Paramagnetic
N2– 2
KK s(2s) s(2s) *2 2 2 2
p(2px) p(2py) s(2pz) p(2px*)1
1 Paramagnetic
2 __
2
N2–2 KK s(2s)2 s(2s*)2 p(2px)2 p(2py)2 s(2pz)2 p(2px*)1 1 Paramagnetic
2 __
p(2py*)1 2
Relative stabilities, Bond dissociation energy and Bond length of N2, N2+, N2–, N–2
2 species. As
calculated above, the bond orders of these species are
N2 = 3, N2+ = 2.5, N2– = 2.5, N2–2 = 2
As bond dissociation energies are directly proportional to the bond orders, therefore the dissociation
energies of these molecular species are in the order:
(a) Nature of bond: Bond order is 2 which justify the presence of double bond.
(b) Paramagnetic character: Presence of two unpaired electrons p*(2px)1 p*(2py)1 molecular
orbitals accounts for its paramagnetic behavior.
The molecular orbital configuration for O2+, O2– and O2– 2 ions along with their bond order and
magnetic properties are given in Table 3
Table 3
Molecule Molecular orbital Configuration Bond Order Magnetic Character
O2+ 2 2 2 2 2
KK s(2s) s*(2s) s(2pz) p(2px) p(2py) p*(2px) 1
2.5 Paramagnetic
O2– 2 2 2 2 2
KK s(2s) s*(2s) s(2pz) p(2px) p(2py) p*(2px) 2
1.5 Paramagnetic
p*(2py)1
O2– 2 KK s(2s)2 s*(2s)2 s(2pz)2 p(2px)2 p(2py)2 p*(2px)2* 1.0 Paramagnetic
p*(2py)2
Chemical Bonding 1.11
2.9 The electronic structures and bonding properties in Hetero Nuclear Diatomic
Molecules
In case of hetero nuclear molecules (such as NO, CO and HF) the electronic distribution in between
the two atoms is not symmetrical, because the electron pair is found closer to one atom than other, due
to energy consideration. This results in a polar bond, in which the electron pair is shared unequally
between the two atoms. Now a polar covalent bond consisting of two electrons in an orbital of the
form: Y = CA Y(A) + CB Y(B) with unequal coefficients. The relative proportions of atomic orbital
Y(A) and Y(B) are CA2 and CB2 respectively. In case of homopolar covalent bond, CA2 = CB2 and for
1.12 Engineering Chemistry
pure ionic bond either CA = 0 or CB = 0. During the formation of bonding molecular orbital, the
atomic orbital, with lower energy makes the larger contribution; while during the formation of anti-
bonding molecular orbital, the dominant component comes from atomic orbital with higher energy.
Nitric Oxide (NO) Molecule:
The electronic configuration of participating nitrogen and oxygen atoms are as follows:
The molecular orbital configuration for NO +, NO – and NO +2 ions along with their bond orders
and magnetic properties are given in table 4
Table 4
Molecule Molecular orbital Configuration Bond Magnetic Character
Order
NO+ KK s(2s)2 s*(2s)2 s(2pz)2 p(2px)2 = p(2py)2 3 Diamagnetic
– 2 2 2 2 2 1 1
NO KK s(2s) s*(2s) s(2pz) p(2py) = p(2px) p*(2px) p2*py 2 Paramagnetic
+2 2 2 2 2 1
NO KK s(2s) s*(2s) s(2pz) p(2px) = p(2py) 2.5 Paramagnetic
CN Molecule: The electronic configuration of participating Carbon and Nitrogen atoms are as
follows:
Fig. 9 Molecular energy diagram for CO [a] and CO+ [b] Molecule
(i) Magnetic character: Because in the CO molecule, all the electrons are paired so it is
diamagnetic molecule.
(ii) CO + molecular ion is more stable than CO molecule because bond order of CO + is greater
than CO.
(iii) Magnetic character: Because in the CO + molecule unpaired electron is present in s*(2s)
orbital so it is a paramagnetic species.
Hydrogen Fluoride: The hydrogen and fluorine have 10 electrons in total which are needed to be
accommodated in the molecular orbital of
HF molecule.
H – 1s1
F – 1s2 2s2 2px2 2py2 2pz1
Spectroscopic evidence show that
energies of 1s2 and 2s2 electrons of Fluorine
do not participate in bonding. Out of three
2p orbital, only 2pz which is taken as inter
nuclear axis will combine with s orbital of
Hydrogen giving bonding molecular orbital.
Electrons which do not participate in
bonding will remain in their Atomic orbital.
The F (2pz) atomic orbital contributes more
than the H (1s) atomic orbital to the bonding
s*(2spz) molecular orbital.
Fig. 10 Molecular energy diagram for Hydrogen Fluoride
Molecule
Chemical Bonding 1.15
3. Metallic Bonding
The constituent particles in metals are metal atoms held together by the bonds called metallic bond.
In fact, more than 80 elements in the periodic table are metals. Except mercury and gallium, which
are liquids, all other metals are solid at ordinary temperature and pressure. It is electromagnetic
interaction between delocalized electrons called conduction electrons and metallic nuclei within the
metals, whereas most chemical bonds are localized between specific neighboring atoms, Metallic
bond extend over the entire molecular structure and it is collective in nature, Metallic bond accounts
for physical characteristics of metals like strength, malleability, ductility, lustre and conduction.
The only way in which Li atom can bond with all its neighboring Li atoms can be explained
by postulating that the covalent bond resonates among all the neighboring Li atom and the actual
structure is a resonance hybrid of all these structures. Taking the example of four Li atoms, the
resonating structures may be represented as follows:
The actual bonding includes all atoms of the crystal and as a result of resonance the crystal is
stabilized.
In the structures III, IV, V, VI ionic forms have been shown. In these structures, Li carrying
negative charge is bonded to the other Li atoms. This means that more than one valence orbital of
each Li atom is involved in the metallic bonding. It is assumed that the vacant 2p orbital, which is
not much higher than the 2s, is used. This is called the metallic bonding.
Fig. 11 2s orbitals of Li atoms combine to form molecular orbitals equal to the number of Li atoms
combining together.
Similarly we can explain conduction in Na metal (1s2 2s2 2p6 3s1). If in the crystal, N atoms
of Na are present then 1s, 2s and 2p bands are completely filled and 3s is half filled so when
n number of 3s orbitals overlap they form n number of 3s molecular orbital which appear
as a bond. If energy provides electron from filled portion will move to empty portion. This
explain the electrical conductivity of sodium.
(ii) Conduction in Completely filled orbital: For example Be, Electronic configuration of
Be is 1s2 2s2. According to the electronic configuration it should not conduct electricity as
it is completely filled but it is a good conductor. This discrepancy has been overcome by
suggesting that the 2s orbitals are not the only atomic orbitals which overlap to form band.
The 2p orbitals which are only slightly higher in energy also overlap to form empty band.
The bands of 2s and 2p are so close to one another that they overlap one another but the
two orbital bands can be differentiated. The band which holds the valence electrons is called
valence band and on the other band the one which is slightly higher in energy and is formed
by the overlap of valence atomic orbitals is called the conduction band. So if we provide
energy electrons from 2s band can move to 2p band, thus conducting electricity.
Similarly, we can explain Mg crystal, the electronic configuration is 1s2 2s2 2p6 3s2. Here
3s and 3p orbitals overlap simultaneously forming bands which overlap each other. So if we
provide energy, electrons from 3s band will move to 3p band theory conducting electricity.
Explanation of Conductors, semi Conductors and Insulators on the basis of band theory: On
application of molecular orbital theory on solids, solids can be categorized into three i.e., conductors,
semi conductors and insulators.
Insulators: The energy gap (more than 3ev) between the valence band and the bottom of the
conduction band is so large that enough energy is not available under normal conditions to promote
the electrons from the valence band to the conduction band. The in-between region is called the
forbidden zone. (Energy level diagram is represented as shown in Fig 12 (a).
Conductors: There is no energy gap between the valence band and conduction band. Electrons can
easily move from valence band to conduction band Fig. 12 (c).
Semi-Conductors: The energy gap between the valence band and conduction band is small than
in insulators (less then 3ev) Fig. 12 (b). The thermal energy available under ordinary conditions is
sufficient to excite some electrons from valence band to conduction band and thus a small amount
of current can flow through them.
1.20 Engineering Chemistry
p-Type Semiconductor: These are obtained when an impurity having lesser electron than the parent
insulator atoms e.g., when Boron/Aluminium (with 3 valence electrons) element of Third group is
added to Silicon/Germanium (with 4 valence electrons). The 4th valency of Si/Ge is free due to
electron deficiency which created a positive hole in valence band. There are as many positive holes as
boron atoms. These holes occupy the level close to the filled valence band called acceptor impurity
level. When we provide an energy these positive hole move to conduction band. The movement of
holes through the crystal lattice of a p-type semiconductor is nothing but movement of a positive
electric charge. Thus conducting electricity.
Solved Questions
1. Taking Z axis as internuclear axis, explain why 2px and 2py orbital do not combine with 2s
orbital to form molecular orbital?
Ans. 2px and 2py orbitals do not combine with 2s because 2px and 2py orbitals will form p bond
and s orbital will form s bond.
2. Give the account of electrons which occupy the bonding orbitals in H2+, H2, O2+.
Ans. 1, 2 and 15 respectively.
3. Explain why N2 has greater bond dissociation energy than N2+ whereas O2+ has greater bond
dissociation energy than O2.
Ans. B.O. of N2 (3) > B.O. of N 2+ (2.5) but B.O. of O2+ (2.5) > B.O. of O2 (2). Greater the bond
order, greater is the bond dissociation energy.
4. Can we have a diatomic molecule with its ground state molecular orbitals full with electrons?
Give a reason for your answer.
Ans. No. Because bond order becomes zero, e.g., in case of He2, Be2, Ne2, etc. Note that in H2,
s1s M.O. is full but s*1s M.O. is empty.
1.22 Engineering Chemistry
5. Compare the relative stabilities of O2– and N2– and comment on their magnetic behavior.
Ans. M.O. electronic configuration of O2– = KK s(2s)2 s*(2s)2 s(2pz)2 p(2px)2 p(2py)2 p*(2px)2
p*(2py)1
Bond order = 1/2 (8 – 5) = 3/2 = 1.5
M.O. electronic configuration of N2+ = KK s(2s)2 s(2s)*2 p(2px)2 p(2py)2 s(2pz)1
Bond order = 1/2 (7 – 2) = 5/2 = 2.5
As the bond order of N2+ > bond order of O2– , therefore, N2+ is more stable than O2–.
Each of them have unpaired electron, hence both are paramagnetic.
6. Two p-orbitals from one atom and two p-orbitals from another atom are combined to form
molecular orbitals. How many MOs will result from this combination? Explain.
Ans. Four molecular orbitals will be formed. One p-orbital of one atom will combine with one
p-orbital of another atom to form two molecular orbitals (one bonding the other antibonding).
Likewise the second p-orbital of the first atom will combine with the second p-orbital of the
second atom to form two molecular orbitals (of course, it is presumed that they have proper
orientation).
7. What is the energy gap in band theory? Compare its size in conductors, semiconductors and
insulators.
Ans. The difference of energy between the lowest level of the conduction band and the uppermost
level of the valence band is called energy gap. The size of energy gap in the order:
insulators > semiconductors > conductors
8. According to M.O. theory, what happens to the identity of the atoms after the overlap.
Ans. The identity is lost after the overlap.
9. Out of bonding and anti-bonding M.O.s which one has lower energy and which one has
higher stability.
Ans. Bonding M.O. has lower energy and higher stability.
10. How is bond order related to the stability of a molecule?
Ans. Higher the bond order, greater is the stability.
11. How is bond length related to the stability of a molecule?
Ans. Bond length is inversely related to stability.
12. When is the molecule paramagnetic in nature?
Ans. When it contains one or more unpaired electrons.
13. Define bond order.
Ans. Bond order is half of the difference of the electrons present in the bonding and anti-bonding
molecular orbitals. i.e.,
14. Indicate which of the two, O2– or O2–2 has higher bond order?
Ans. O2– has higher bond order.
15. What is metallic bonding?
Ans. A bonding between electropositive elements
Chemical Bonding 1.23
Or
A bond or a force which binds metal ions to the number of electrons within its sphere of
influences.
Or
The attractive force which holds the atoms of two or more metals together in a metal crystal
or in an alloy.
16. What type of atomic orbitals can overlap to form molecular orbitals?
Ans. Atomic orbitals with comparable energies and proper orientation or same symmetry and
similar energy.
17. Arrange O2, O2–, O2–2 and O2+ in increasing order of bond length.
Ans. O2– 2 > O2– > O2 > O2+
18. What is bonding molecular orbital and anti-bonding molecular orbital?
Ans. The molecular orbital formed by the additive effect of the wave functions of orbitals is called
bonding molecular orbital and the molecular orbital formed by subtraction of wave functions
of the atomic orbitals are called anti-molecular orbital.
19. How is bond order related to dissociation energy?
Ans. Dissociation energy is directly proportional to bond order.
20. What happens to the probability of finding the electron in the molecular orbitals after the
combination of two atomic orbitals?
Ans. Probability of finding electrons increases in the internuclear region of bonding molecular
orbital, whereas decreases in the internuclear region in the anti-bonding molecular orbital.
Unsolved Questions
1. Distinguish between orbit and orbital?
2. What are the main features of valence bond theory?
3. Give reason: H2+ and H2– ions have the same bond order but H2+ ions are more stable than
H2–.
4. Distinguish between bonding molecular orbital and anti-bonding molecular orbital.
5. Compare the relative stabilities of O2– and N2– and comment on their magnetic behavior.
6. Use molecular orbital theory to explain why Be2 molecule does not exist.
7. Compare the relative stability of the following species of N2 N+2, N–2, N2–2 and indicate their
magnetic behavior.
8. Bond order of CO + is greater than CO. Explain.
9. Give relative stability of NO +, NO, NO –.
10. Explain analogous behavior of HF molecule with the help of molecular orbital theory.
11. What is meant by bond order? Calculate the bond order of He2+, O2– and O2–2 molecule.
12. Explain why O2 is paramagnetic in behavior.
13. Compute the bond orders for H2+, H2 and He2.
14. Explain the bond order of N2 molecule with the help of molecular orbital energy level
diagram.
1.24 Engineering Chemistry
1. General Introduction
A solid is defined as that form of matter which possesses rigidity and hence possesses a definite
shape and a definite volume. Unlike gases and liquids in which the molecules are free to move about
and hence constitute fluid state, in a solid the constituent particles are not free to move but oscillate
about their fixed positions.
1.1 Classification of Solids
Solids are classified into two types, namely crystalline and amorphous. A solid is said to be
crystalline. If the various constituent particles like atoms, ions or molecules are arranged in a
definite geometric pattern within the solid. In other words, they are said to possess a long range
order. All solid elements and compounds exist in this form. On the other hand, A solid is said to be
amorphous. If the constituent particles are not arranged in any regular fashion, they may have only
short range order. Amorphous solids are generally obtained when the melts are rapidly cooled e.g.,
glass, plastics, amorphous silica, etc.
Table 1
Types of Constituent Nature of Characteristics Properties Example
Solid Particle Forces
1. Ionic Positive and Strong Hard, brittle, high melting point, NaCl, KNO3, LiF,
negative electrostatic soluble in polar solvents, insulator MgO
ions force of in solid state, good conductor in
attraction molten state
Table
2.2 Engineering Chemistry
2. Molecular Molecules Vander Waal’s Soft, low melting point, low I2, Solid CO2,
force density, volatile and insulators CH4, S, ice.
3. Covalent Atoms Covalent bonds of heat and electricity very hard Carbon (Diamond
with very high melting points and + graphite, Si,
insulators (except graphite) SiO2
4. Metallic Atoms Metallic bonds Range from soft to hard, high All metals and
melting point, good conductor of some alloys
heat and electricity
1.3 Crystal
A homogeneous anisotropic substance having a definite geometrical shape with surfaces that are
usually plane and having sharp edge is known as crystal.
1. Faces: The crystals are bounded by surfaces which are usually planar and arrange in a
definite pattern. These surfaces are called faces of the crystal.
2. Edge: When two adjacent faces intersect we get an edge.
3. Angle: When three or more edges intersect we get a solid angle.
4. Interfacial angle: The angle between the normal to the two intersecting faces is called an
inter facial angle.
1.4 Types of Symmetry
In cubic systems we have three elements of symmetry.
(a) Plane of symmetry: Is an imaginary plane which passes through the centre of symmetry
of a crystal and divides it into two equal halves. Such that one part is exactly the mirror
image of the other.
(b) Centre of Symmetry: Is an imaginary point within the crystal such that any line drawn
through it intersects the surface of the crystal at equal distances in both directions. Centre
of symmetry in a cubic system is one.
(c) Axis of Symmetry: Is an imaginary straight line about which when the crystal is rotated, it
will present the same appearance more than once during a complete revolution. If the same
appearance of crystal is repeated through an angle of 360/n about an imaginary axis. The
axis is called an n-fold axis.
The Solid State 2.3
1.6 Types of Lattice
1. Primitive unit cell
2. Non Primitive unit cell
1. Primitive unit cell: Unit cell in which constituent particles are present only at the corners is
called simple unit cell or primitive unit cell.
2.4 Engineering Chemistry
2. Non Primitive unit cell: Unit Cell in which constituent particles are not only present at the
corner but may also be present at some other special positions in the unit cell. They are also known
as centered unit cell. They may be divided as follows:
1. Face Centered (fcc): When the constituent particles are present not only at the corner but
also at the centre of each face of the unit cell, the unit cell is called face centred unit cell.
2. Body Centered (bcc): When in addition to the constituent particles at the corners, there is
one constituent particle present at the centre within the body of the unit cell. Such unit cell
is called body centered unit cell.
3. End Centered: When in addition to the particles at the corners, there are particles at the
centers of the two end faces.
Every crystal system does not have all the four types of unit cells. Hence there are only
14 types of space lattices corresponding to seven crystal systems. The fourteen lattices
corresponding to seven crystal system are known as Bravais lattice.
1. Simple cubic:
It has lattice point only at corners and each corner atom is common to eight unit cells.
Hence, contribution of each atom present at each corner = 1/8
(r + 2r + r)2 = a2 + a2
16r 2 = 2a2
____ __
÷
2a2 ÷
2
r = ___ = a ___
16
4
(c) Atomic radius of a bcc structure:
AC = r + 2r + r = 4r
AE2 = a2 + a2 = 2a2
AG 2 = AE2 + GE2
(4r)2 = 2a2 + a2
The Solid State 2.7
(4r)2 = 3a2
__
÷
3 a
r = ____
4
2. Coordination number
Coordination number of any given sphere in a crystalline structure is the number of other spheres
by which it is immediately surrounded. Greater the coordination number, the more closely packed
up will be the structure. The coordination number may be determined as explained below.
1. Simple Cubic lattice: In such a cell, there are six atoms which are the nearest neighbors
for every corner atom. Thus, there are two nearest atoms, along ± Xaxis. Similarly, there are
two nearest neighbors along ± Yaxis and two along ± Zaxis. Thus, in all, there are 2 + 2 + 2
= 6 nearest neighbors. Hence, coordination number is 6. CsCl crystallizes in simple cubic-
lattice.
2. Face Centred Cubic Lattice: Atoms are present at corners as well as at each face in a
plane. In this each atom is in direct contact with 12 nearest neighbors, 6 of which lie in
one plane, 3 are above the plane and 3 atoms are below the plane. Hence, the coordination
number is 12. Cu, Au, Al crystallize in fcc lattice.
3. Body Centred Cubic Lattice: Atoms are present at corners as well as at the centre of the
body. On drawing a sphere of this radius with any atom at the centre then it is easier to
see that eight atoms fall on it. Hence, the coordination number is 8. NaCl, Cr, Fe, Mo, W
crystallizes in bcc lattice.
2.8 Engineering Chemistry
2.1 Radius Ratio
Ionic solids possess different coordination number, because of differences in the number and relative
sizes of the cations and anions. Larger the size of cation (or anion), greater will be the number of
anions(or cations) which can be packed around it. The geometrical requirement for the structure of
an ionic solid in terms of relative sizes of the two oppositely charged ions is expressed by radius
ratio, which may be defined as:
Radius Ratio is the ratio of cation radius to that of the anion radius in an ionic solid. Thus, radius
ratio is
Radius of cation/Radius of anion = r+/r–
Greater the radius ratio, larger is the size of the cation and hence greater is its coordination
number. The relationship between the radius ratio and the coordination number and the structural
arrangement are called radius ratio rule.
The list of limiting radius is given in the Table 2 with structure and coordination number:
Table 2
+
S. No r
__ Structure Coordination Example
– (Radius Ratio)
r number
1. < 0.155 Linear 2 B2O3
2. 0.155 – 0.225 Planar triangle 3 CuCl, CuBr,
3. 0.225 – 0.414 Tetrahedral 4 CuI
4. 0.141 – 0.732 Octahedral 6 Na, KBr, MgO
5. 0.732 – 1.00 Cubic structure 8 CsI, CsBr, NH4Br
= Z × m
But, mass of an atom present in the unit cell (m)
= M/NA
Therefore, density of the unit cell of a cubic crystal (d)
Mass of unit cell
r = ________________
= i.e.
Volume of unitcell
r =Z× /NA × a3
Example 1 A face centred cube element (atomic mass 60) has a edge length of 400pm. What is
the density?
Solution: For a face centered cubic, Z = 4
The Solid State 2.9
r = Z × M/NA × a3
4 × 60 gmol–1
= __________________________________
(400 × 10 –10cm)3 × (6.023 × 1023mol–1)
= 6.23g/cm3
Example 2 Sodium has a bcc structure with nearest neighbor distance 365.9pm. Calculate its density
(atomic number of sodium = 23).
Solution: For a bcc structure, nearest neighbor distance (d) is related to the edge length (a) as
__
÷
3 a
d = ____
2
2d 2
Or a = ___
__ = _____ × 365.9
÷
3 1.732
= 422.5 pm
For bcc structure, Z = 2
For sodium, M = 23
Therefore, r = Z × M/NA × a3
2 × 23gmol–1
= ___________________________________
(422.5 × 10 –10cm)3 × (6.023 × 1023mol–1)
= 1.51g/cm3.
Example 3 The density of KBr is 2.75g/cm3. The edge length of unit cell is 654pm. Predict the type
of cubic lattice to which unit cell of KBr belongs. (N = 6.023 × 1023mol–1, atomic mass: K = 39,
Br = 80)
Solution: r = Z × M/NA × a3
r × NA × a3
Z = ___________
M
(2.75g/cm3)(654 × 10 –10 cm)3 × (6.023 × 1023mol–1)
= ___________________________________________
(39 + 80) gmol–1
= 3.89 ª 4
Example 4 The density of a face centered cubic element (atomic mass = 60.2amu) is 6.2g/cm3.
Calculate the length of the edge of a unit cell. (Avogadro’s constant NA = 6.023 × 1023mol–1)
Solution: r = Z × M/NA × a3
a3 = ZM/rNA
4 × 60.2g/cm3
a3 = _________________________
6.2g/cm3 × 6.023 × 1023mol–1
= 64.52 × 1024 cm3
a = (64.52 × 1024 cm3)1/3 = 4.01 × 10 –8 cm = 401 pm
2.10 Engineering Chemistry
2.3 Bragg’s Equation
Bragg’s equation or law gives mathematical relations to determine inter atomic distance from x-ray
diffraction patterns. They show that:
(a) The x-ray diffracted from atoms in crystal planes follows the law of reflection.
(b) The two rays reflected by successive planes will be in phase if the extra distance travelled
by the second ray is an integral number of wavelengths.
A beam of X-rays when falls on the crystal surface, two successive atomic planes of the crystal
are shown separated by distance d. Let the X-rays of wavelength l strike the first plane at on angle q.
AM and AN are two normals.
The waves reflected from different layer planes will be in phase with one another only if the
difference in path length of the waves reflected from the successive planes is equal to an integral
number of wavelength l.
Path difference = n l ...(1)
D MAB = D NAB = q
In D MAB
Sin q = BM/BA or BM = BA sin q = d sin q
In D NAB
Sin q = BN/BA or BN = BA sin q = d sin q
Path difference = BM + BN
= d sin q + d sin q
= 2d sin q ...(2)
The Solid State 2.11
= 3.68 nm
Example 6 At what glancing angle would the first order diffraction from the plane of KCl be
observed, using X ray of wavelength of 154pm? The dimension of the unit cell is 315pm.
Solution: For the first order diffraction,
n l = 2d sin q
l = 154 pm and d = 315 pm
154 pm = 2 × 315 pm sin q
Sin q = 0.244
q = 14.1°
Example 7 The distance between the two layers in a NaCl crystal is 282 pm. X-rays are diffracted
from these layers at an angle of 23.0°. Assuming that n = 1, calculate the wavelength of the Xrays
in nm.
Solution: For the first order diffraction,
n l = 2d sin q
d = 282 pm and q = 23.0°
l = 2d sin q
= 2 × 282 pm sin 23.0
= 0.220 nm
3. Imperfections in crystals
At 0 K, there is perfect order in arrangement of atom in crystals. But with the rise in temperature
some deviations occur which results in disorder. The presence of impurities also adds to the disorder.
So any deviation from perfectly ordered arrangement of atoms in crystal is called imperfections.
Imperfections not only modify the properties but also impart new properties to the solids.
2.12 Engineering Chemistry
3.1 Classification of imperfection
3.2 Electronic defects
At 0 K, in a purely covalent crystal (e.g. Silicon) or purely ionic crystal (e.g. NaCl) the electrons are
present in ground energy level. But above 0 K some electrons occupy higher energy states depending
upon the temperature. So in the crystal of pure silicon, some of the electrons from the covalent bonds
get thermally released and electrons deficient site called holes is created. Holes also provide electrical
conductivity but the holes in an electric field move in directions opposite to that in which electrons
move. Thus electrons and holes in solid give rise to electronic imperfections.
defects. The schottky defect containing one pair of holes due to missing cation and anion given
below.
3.6 Frenkel defect
An ion is missing from its lattice site and it occupies the interstitial site, electrical neutrally as well
as the stoichiometry of the compound are maintained. This type of defect is called frenkel defect.
Since cations are smaller, it is more common to find the cations occupying cation interstitial sites.
ions are in excess in a given non-stoichiometric crystal, there are two types of defects found in non
stoichiometric crystals. these are
1. Metal excess defect: this may occur on either of the following two ways:
(a) By anion vacancies:
Crystals with this type of metal excess defect contain some free electrons. Hence such materials
act as semi-conductors.
2. Metal Deficiency defects: This defect is produced when one or more cations are missing from
their lattice site and thus cation vacancies are produced. In order to maintain the electrical neutrality
of the crystal, one are more nearby cations acquire extra positive charge and are thus converted
into cation with higher oxidation state. Thus although the crystal is electrically neutral the number
of metal ions is less then that of anions i.e. there is deficiency of metal ions. This defect is found
in those ionic crystals whose positive ions show variable oxidation state. e.g. Ferrous Oxide, NiO,
Ferrous Sulphide.
The Solid State 2.15
3.7 Graphite
It is a polymorph of carbon, it has a crystal structure distinctly different from that of diamond and
is also more stable than diamond at influent temperature and pressure.
2.16 Engineering Chemistry
Graphite offers a very good example of 2-dimensional solid. The graphite structure is composed of
layers of hexagonally arranged carbon atoms (sp2 hybridized) within the layers, each carbon atom
is bonded to three coplanar neighbouring atoms by covalent bonds (1.4A°). Due to covalent bonding
graphite has high melting point i.e., 3700°C and it has a firm structure and high thermal stability.
The fourth bonding electron participates in a weak Vander Waal’s type of bond (3.4A°) between the
layers. As a consequence of these weak inter planar bonds, inter planar cleavage is facile, coefficient
of friction becomes low as a result it is soapy in touch and gives rise to the excellent lubricative
properties of graphite.
Graphite has two forms:
1. a-graphite: it is naturally occurring having hexagonal arrangement. It is of three types:
(a) Crystalline graphite
(b) Amorphous graphite
(c) Flake graphite
2. b-graphite: it is synthetic graphite having rhombohedral arrangement, for example
graphene.
Applications:
1. Used as heating elements for electric furnaces.
2. Used in batteries (crystalline graphite)
3. In metallurgical crucibles (amorphous graphite)
4. For high temperature refractors and insulations
5. In nuclear reactors as moderators
6. In Lead pencil
7. In air purifications devices.
3.8 Fullerenes
Fullerenes are Archimedian solids. They have polymorphic form of carbon which exist in discrete
molecular form and consist of hollow spherical cluster of carbon atoms. e.g. C20, C24, C32, C50, C60,
C72 etc. Out of these C60 is most important. It has truncated icosahedrons or geodesic dome structure.
Each molecule is composed of C atoms that are bonded to one another to form both hexagon and
pentagon geometrically configuration. One such molecule is found to consist of 20 hexagons and
12 pentagons which are arranged such that no. two pentagons show a common side. The molecular
surface thus, exhibits the symmetry of the soccer ball. The material composed of C60 molecules is
known as buck minister fullerene.
The Solid State 2.17
Preparation
Fullerenes are prepared by vaporizing a graphite rod in the atmosphere of helium. Mixture of
fullerenes are formed which are separated by solvent extractions or by sublimation. C60 is isolated
from the mixture by chromatographic technique using aluminate hexane.
Properties
1. It is a mustard colored solid.
2. The color changes from brown to black with increasing thickness of fullerene films.
3. In pure form, it is an insulator but functions best as super conductor by doping with alkali
metals.
4. Many higher fullerenes are chiral with increasing cage size, the number of chiral isomers
increases rapidly.
5. It can be compressed to loss 30% of its volume without destroying its carbon cage
structure.
6. It can form solid soft ferromagnetic substance if electron donor impurity is introduced .
Applications
1. It can be use as super conductor when doped with alkali metals.
2. Carbon nanotubes and nanowires. One potential important application for these C nanotubes
is the area of composite. Carbon fibers made from organic polymers are used to strength
light weight high technical materials such as the carbon. Epoxy resins used in golf clubs,
tennis racquets and yachts.
3. Catalysis: C60 participates in catalysed processes is either a part of the catalyst and or
a substrate. e.g. the complex h2-C60Pd (PPhh3)2 as the catalyst in the homogenous and
heterogeneous hydrogenation reactions.
4. Polymerization Reactions: When C60 fullerenes pellets are exposed to a pressure at 1.2 GP
at 600k for 5 hours, cycle addition occurs to give polymers.
3.9 Liquid Crystals
These are substances that exhibit a phase of matter that has properties between those of a conventional
liquid and those of a solid crystal. They may flow like liquids but have the molecules oriented in
crystal like way. They exhibit intermediate thermodynamic phase between the crystalline solid and
liquid state. These phases are called mesomorphic phases.
2.18 Engineering Chemistry
Molecules of substances with a liquid crystal state are generally oblong and rigid, that is rod
shaped. They are compounds of moderate size organic molecules which tend to be elongated and
rod shape. Typical liquid crystalline molecules are cholesterol ester, surfactants, paraffin’s phenyl
benzoates, surfactants, glycol liquids and cellulose derivatives.
Mesogen: It is the fundamental unit of a liquid crystal that induces structural order in the crystals.
Liquid crystal consists of a rigid part and a flexible part. The rigid part aligns molecules in one
direction called mesogen, whereas the flexible part induces fluidity in the liquid crystals.
Typical Behavior of Liquid crystals: In materials that form liquid crystals the inter molecular
forces are not the same in all directions, In some directions the forces are weaker than in other
directions. As such when a material is heated the increased molecular motion overcomes the weaker
forces first but its molecules remain bound by the stronger forces. Thus a molecular arrangement is
produced which is random in some direction and regular in others.
Classification of Liquid Crystals: Depending upon the amount of order in the material, liquid
crystal may be classified into following two categories.
(i) Thermotropic liquid crystal
(ii) Lyotropic liquid crystal.
Thermotropic liquid crystal: The transitions between the liquid crystals are given by the change
in temperature. They are mostly used for technical applications.
Thermotropic Liquid Crystals are Classified as:
(i) Isotropic Phase: Molecules are randomly aligned. They have low viscosity and often appear
to be crystal clear. There is no long range positional or orientational order of the molecules.
So, macroscopically appears to the like any other isotropic liquid such as water.
(ii) Nematic Phase: It is simplest liquid crystal phase. It has high degree of long range orientation
order but no translational order. They are polarizable rod. Like organic molecules have fluidity
similar to liquids but they can be easily aligned by an external magnetic electric field. A
twisted (aligned) nematic has the optical properties of a uniaxial crystal which makes it
extremely useful in LCD (Liquid crystal displays).
The Solid State 2.19
(iii) Smectic Phase: It is found at lower temperature than the nematic form well defined layers.
That can slide over one another. They are positionally ordered along one direction. They
have more degree of orientational order than nematics. There are several different categories
of smectic but the two best known are:
1. Smectic A: In which the molecules are aligned perpendicular to the layer planes.
2. Smectic C: In which the alignment of the molecules is at some arbitrary angle to
the normal. Smectics have high viscosity and this phase is generally not useful for
devices.
(iv) Chiral Nematic/Cholesteric Liquid Crystals: In this phase, the molecules twist slightly
from one layer to the next resulting in a spiral formation. Cholesteric liquid crystal should
have a chiral carbon.
(v) Columnar Liquid Crystals: They are shaped like discs instead sof long rods. It is also
called discotic liquid crystals.
2.20 Engineering Chemistry
(vi) Lyotropic liquid crystal: They are amphiphilic (Both hydrophilic and hydrophobic)
molecules. They are often called surfactants having polar head group attached to one or more
non-polar chains. When these are dissolved in an appropriate solvent they form aggregates
called micelles beyond a particular concentration called critical micelle concentration.
Lyotropic liquid crystals have biological applications (Biological membranes and cell
membranes). The outermost layer of skin is primarily a lyotropic liquid crystal made of
fatty acids.
Applications
1. Used in large displays e.g. TVs and computer screens.
2. Used in small displays for the propose of digital displays on electrical appliances.
3. Also used in portable displays e.g. laptops, PDAs, mobile phones.
4. Used in telecoms devices e.g. beam stirrers, Optical correction.
5. Used in sensors. e.g. stress and temperature sensing.
6. Used in screens e.g. office privacy screens.
7. Used as solvent for the study of structure of anisotropic molecules spectroscopically.
8. Used in gas liquid chromatography because their electrical and mechanical properties between
crystalline solids and isotropic liquids.
9. The cholesteric type of crystals is used for detecting termours in the body by the method
called thermography.
10. Used as a commercial lubricant.
solved Questions
1. At what glancing angle would the first order diffraction from (110) plane of KCl be observed,
using x-ray of wavelength of 1.54 × 10 –8 cm?
The dimension of the unit cell is 3.15 × 10 –8 cm.
Sol. For first order diffraction,
l = 2d sin q
l = 1.54 × 10 –8
d = 3.15 × 10 –8
\ 1.54 × 10 –8 = 2 × 3.15 × 10 –8
154
sin q = _______
= 0.244
2 × 315
= sin 14.1°
2. Xenon crystallises in the face centred cubic lattice and the edge of the unit cell is 620 pm.
What is the nearest neighbour distance and what is the radius of xenon atoms?
Sol. Here a = 620 pm
d =?r=?
For the face centred cubic.
a__ _____ 620
d = ___ = = 438.5 pm
÷
2 1.414
The Solid State 2.21
d 438.5
r = __
= _____
= 219.25 pm
2 2
3. Sodium has a bcc structure with nearest neighbour distance 365.9 pm. Calculate its density
(Atomic mass of sodium = 23).
Sol. For the bcc, nearest neighbour distance (d) is related to the edge (a) as
__
÷
2
d = ___
a
2
2 2
or a = ___
__ d = _____
× 365.9 = 422.5 pm
÷
3 1.732
For bcc structure, Z =2
For sodium, M = 23
Z×M
r = _______
a3 × No
2 × 23 g mol–1
= _________________________________
(4.22 × 10 –10 cm)3 × (0.2 × 1023 mol–1)
= 1.51 g/cm3.
4. Calculate the value of Avogadro’s number from the following data: density of NaCl = 2.165
g/cm–3. Distance between Na+ and Cl– in NaCl is 281 pm.
Sol.
Z = 4, M = 58.5 g/mol
r = 2.165 g/cm–3
As distance between Na+ and Cl– = 281 pm.
Edge of the unit cell = 2 × 281 = 562 pm.
Z×M
r = _______
a3 × Nc
4 × 58.5 g/mol–1
2.165 g cm–3 = ____________________
(562 × 10 –10 cm)3 × No
No = 6.09 × 1023 mol–1
5. An element occurs in the Bcc structure with cell edge of 288 pm. The density of the element
is 7.2 g/cm3. How many atoms of the element does 208 g of the element contain?
Sol. For Bcc structure, Z =2
Edge of the unit cell a = 288 pm
r = 7.2 g/cm3
Z×M
r = _______
a3 × No
2×M
7.2 g cm–3 = _________________________________
(288 × 10 –10 cm)3 × (6.02 × 1023 mol–1)
2.22 Engineering Chemistry
M = 51.8 g/mol.
By mole concept,
51.8 g of the element contains
= 6.02 × 1023 atoms.
\ 208 g of the element contains
6.02 × 1023
= __________
× 208 atoms.
61.8
= 24.17 × 1023 atoms.
6. X–rays of wavelength equal to 0.134 nm give a first order diffraction from the surface of a
crystal when the value of q is 10.5°. Calculate the distance between the planes in the crystal
parallel to the surface examined.
Sol. Here, we are given
l = 0.134 nm, n = 1, q = 10.5°
Applying Bragg’s equation
2d sin q = n l
We get
nl 1 × 0.134 nm
2d sin q = ______
= 10.5° = ____________
2 sin q 2 × sin 10.5°
= 3.68 nm.
7. Calculate the angle at which first order reflection will occur when x–rays of wavelength
1.54 Å are diffraction from the planes of the crystal separated by a distance of 4.04 Å.
Sol. According to Bragg’s equation
2d sin q = n l
Here, d = 4.04 Å, l = 1.54 Å, n = 1
\ 2 × 4.04 × sin q = 1 × 1.54
or sin q = 0.191 or q = sin–1 (0.191) = 11°
8. What will be the wavelength of the x-rays which give a diffraction angle, 2 q, equal to
16.80° for a crystal if the inter planar distance in the crystal is 0.200 nm and only first order
diffraction is observed.
Sol. 2 q = 16.80°, i.e q = 8.40°
2d sin q = n l
2d sin q _______________
2 × 0.20 × 0.146
l = _______
n = = 0.0584 nm
1
= 5.84 × 10 –11 m
9. A sample of crystalline solid scatters a beam of x-rays of wavelength 70.93 pm at an angle
of 2 q of 14.66°. If this is a second order diffraction (n = 2), calculate the distance between
the parallel planes of the atoms from which the scattered beam appears to have been
reflected.
The Solid State 2.23
Sol.
nl 2(70.93 × 10 –22 m)
d = ______
= ________________
2 sin q 2 sin 7.33
= 556.3 × 10 –12 m
= 556.3 pm.
Unsolved Questions
1. Give examples of amorphous and crystalline solids.
2. What is a body centred cube structure?
3. Define co-ordination number.
4. How many atoms are present in the unit cell of (a) simple cubic lattice (b) bcc (c) fcc?
5. On the basis of nature of bonding, how can the solids be classified into different types.
6. Explain with the help of diagrams the structural differences between three types of cubic
crystals.
7. Write Bragg’s equation. What do different symbols signify?
8. Define space lattice and unit cell?
9. Briefly explain Bragg’s x–ray method for the study of crystal structure.
10. Gold crystallizes in a face centred cubic lattice. If the length of the edge of the unit cell is
407 pm. calculate the density of gold as well as its atomic radius assuming it to be spherical.
Atomic mass of gold = 197 amu.
11. The effective radius of an iron atom is 1.42 Å. It has rock salt like structure. Calculate its
density (Fe = 56 amu).
12. The edge length of NaCl unit cell is 564 pm. What is the density of NaCl in g/cm3?
13. A compound having bcc geometry has atomic mass 50. Calculate the density of the unit cell
if its edge length is 290 pm.
14. The compound CuCl has ZnS (cubic) structure. Its density is 3.4 g cm–3. What is the length
of the edge of the unit cell? (At masses Cu = 63.5, Cl = 35.5)
15. The density of a face centred cubic element (atomic mass = 60.2 amu) is 6.25 g cm–3.
Calculate the length of the edge of the unit cell.
16. Chromium crystallizes in a body centred cubic lattice whose density is 7.20 g/cm3. The length
of the edge of the unit cell is 288.4 pm. Calculate Avogadro’s number.
17. An element of atomic mass 98.5 g/mol occurs in fcc structure. If its unit cell edge length is
500 pm and its density is 5.22 g cm–3, what is the value of Avogadro’s constant.
18. What is the distance between Na+ and Cl– in a NaCl crystal if its density is 2.165 g cm–3
NaCl crystallizes in the fcc lattice.
19. KBr has fcc structure. The density of KBr is 2.75 g cm–3. Find the distance between K+ and
Br–. (At mass of Br = 80.0)
20. Use the data given below to find the type of cubic lattice to which the crystal of iron belongs:
a/Pm = 280, P/g cm–3 = 7.86.
21. A body centred cubic element of density 10.3 g cm–3 has a cell edge of 314 Pm. Calculate
the atomic mass of the element.
22. Write a note on Fullerenes.
2.24 Engineering Chemistry
Nanomaterials
1. INTRODUCTION
The word “nano” has a Greek origin meaning dwarf (small). Technically, the prefix nano means “one
billionth” or 10–9. Therefore one nanometer is 10–9, one nano second is 10–9 sec and so on.
Today’s wide spread activities in nano science and technology are actually rooted in the ideas of
some leading scientists of the last century. Among them, the foremost name was Richard P. Feynman.
He delivered a legendary talk entitled “There is plenty of room at the bottom” in the annual general
body meeting of the American Physical society on Dec. 29, 1959 at California Institute of Technology.
In that talk he discussed about the ideas of manipulating and controlling things at the atomic scale.
Nano materials are defined as those materials which have structured components with size less
than 100 nm at least in one dimension. Bulk materials always exhibit macroscopic physical properties.
The same material at the nanoscale can have properties (e.g., optical, mechanical, electrical etc) which
are very different from the properties of the material that has at the macro scale. Non-intentionally
made nano materials, which refers to nano sized particles or materials that belong naturally to the
environment (e.g., proteins, virus, nano particles produced during volcanic eruptions, etc.) or that
are produced by human activity without intention (such as nano particles produced from diesel
combustion, chimney soot etc.). Intentionally produced nano materials, which means nano materials
produced deliberately through a defined fabrication process.
Nano science is the study of the fundamental principles of molecules and structures with at least
one dimension roughly between 1 and 100 nanometers or it is study of phenomena and manipulation
of materials at atomic, molecular and macro molecular scales. Nanotechnology is the principle of
manipulation by atom, through control of the structure of matter at the molecular level or is the
design, characterization, production and application of structures, devices and system.
Nanotechnology may also be defined as following–
• Research and technology development at the 1 to 100 nm range.
• Creating and using structures that have novel properties because of their small size.
• Ability to control or manipulate at the atomic scale.
Nanotechnology is a rapidly emerging technology with vast potential to manipulate and a
substance at the nanometer level (1 nm = 10–9 m) and create new useful materials and devices with
fascinating functions making the best use of the special physical properties of nano sized substances
and improved products for numerous applications. It is also concerned with materials and systems
3.2 Engineering Chemistry
whose structures and components exhibit novel and significantly improved physical, chemical and
biological properties, phenomena and processes, because of their small nanoscale size. Generally,
nano science aims to understand the novel properties and phenomena of all nano-based entities.
NsM particles). They can exist in single, fused, aggregated or agglomerated forms with spherical,
tabular and irregular shapes.
Nanostructured materials are classified as zero dimensional, one dimensional, two dimensional,
three dimensional nanostructures.
Fig. 1 Classification of Nanomaterials; (a) 0D spheres and clusters, (b) 1D nanofibres, wires and rods
(c) 2D films, plates and networks (d) 3D nanomaterials
(a) Zero-dimensional nanomaterials—Materials wherein all the dimensions are measured within
the nanoscale (no dimensions, or 0D, are larger than 100nm)
The best example of zero-dimensional nanomaterials is nanoparticles. Nanoparticles can:
Be amorphous or crystalline
Be single crystalline or polycrystalline
Be composed of single or multi-chemical elements
Exhibit various shapes and forms
Exist individually or incorporated in a matrix
Be metallic, ceramic, or polymeric
(b) One-dimensional nanomaterials—Nanomaterials exist in one dimension structure. This lead to
needle like shaped nanomaterials. 1-D materials includes nanotubes, nanorods and nanowires.
1-D nanomaterials can be:
Amorphous or crystalline
Single crystalline or polycrystalline
Chemically pure or impure
Stand alone materials or embedded in within another medium
Metallic, ceramic or polymeric
(c) Two-dimensional nanomaterials—2-D nanomaterials exhibit plate like shapes. Two dimensional
nanomaterials include nanofilms, nanolayers and nanocoating.
2-D nanomaterials can be–
Amorphous or crystalline
Made up of various chemical compositions
Used as a single layer or as multilayer structures
Deposited on a substrate
Integrated into surrounding matrix material
Metallic, ceramic or polymeric
Nanomaterials 3.5
(d) Three-dimensional nanomaterials—Bulk Nanomaterials are materials that are not confined
to the nanoscale in any dimension. These materials are thus characterized by having
three arbitrarily dimensions above 100nm. Materials possess a nanocrystalline structure
or involve the presence of features at the nanoscale. In terms of nanocrystalline structure,
bulk nanomaterials can be composed of a multiple arrangement of nanosize crystals most
typically in different orientations. In nanoscale, 3-D nanomaterials can contain dispersions
of nanoparticles, bundles of nanowires and nanotubes as well as nanolayers.
Fig. 2
5. SYNTHESIS OF NANOPARTICLES
Nanoparticles with size ranging from 1 nm to 100 nm can be synthesized by means of various
techniques, physical, chemical, biological and self-assembly techniques are few common of them.
There are six widely known methods used to produce Nanoparticles, they are:
1. Mechanical alloying or high energy ball milling
2. Sputtering
3. Plasma Synthesis
4. Inert gas condensation
5. Electro deposition
6. Sol Gel synthesis
Nanomaterials 3.7
Fig. 3
3. Radio Frequency (RF) Plasma (Ionized gas) Method: Thermal plasma can also deliver the
energy necessary to cause evaporation of small micrometer size particles. Figure 3 shows a method
of Nano particles synthesis utilizing plasma generated by radio frequency heating coils. The metal
is contained in a pestle in an evacuated chamber. The RF coils are wrapped around the evacuated
system in the vicinity of the pestle. The evacuated chamber is provided with an opening to enter
helium gas. The evacuated chamber is also provided with a cluster collection device of liquid nitrogen
filled cold finger scrapper assembly.
The metal is heated above the evaporation points by R.F. coils. Now helium gas is allowed to
pass into evacuated chamber which forms high temperature plasma in the regions of coils. The metal
vapor nucleates on the helium gas atoms. It is important to mention here those ultra-fine particles
are formed by collision of evaporated atoms with residual gas molecules. They now diffuse to colder
collector rod where Nano particles are formed.
4. Chemical Method
Chemical vapor Deposition (CVD) and Chemical vapor condensation (CVC) CVD is a well
known process in which a solid is deposited on a heated surface by a chemical reaction from the
vapor or gas phase. CVC reaction requires activation energy to proceed. This energy can be provided
by several methods. In thermal CVD the reaction is activated by high temperature above 900°C.
A typical apparatus comprises of gas supply system, deposition chamber and an exhaust system.
In plasma CVD, the reaction is activated by plasma at temperatures between 300-700°C. In laser
CVD, pyrolysis occurs when laser thermal energy heats an absorbing substrate. In photo laser CVD,
the chemical reaction is induced by ultra violet radiation which has sufficient photon energy to
break the chemical bond in reactant molecules. In this process, the reaction is photon activated and
decomposition occurs at room temperature. Nano composite powder has been prepared by CVD.
SiC/Si3N composite powder was prepared using SiH3, CH4, WF6 and H2 as a source of gas at 1400°C.
Another process called chemical vapor condensation (CVC) was developed in Germany in 1994. It
involves pyrolysis of vapors of metal organic precursors in a reduced pressure atmosphere. Particles
of ZrO2, y2O3 and nanowhiskers have been produced by CVC method. A metallorganic precursor is
introduced in the hot zone of the reactor using mass flow controller. For instance, hexamethyldisilane
(CH3)3 SiNHSi(CH3)3 was used to produce SiCxNyOz powder by CVC technique. The reactor
Nanomaterials 3.9
Fig. 4
thin film using a SnO2 target and a metallic Sn target respectively for C2H5OH detection. Their
results demonstrated that the oxidation of Sn into SnO2 depends strongly on the substrate temperature.
Oxidation of Sn into SnO2 proceeds mainly on the substrate surface instead of in the ablation plume
during the condensation of Sn species onto the substrate, even if the ambient oxygen pressure reaches
100–150 Pa. Recently, Starke and Coles reported their gas sensors prepared using laser ablated
nanocrystalline metal oxides. They found that SnO2 and In2O3 are capable of detecting ozone at
concentrations well below 100 ppb with response times of less than one minute. Pt doped SnO2
and, particularly, In2O3 show some cross sensitivity to NO and NO2. WO3 shows sensing properties
superior to these two materials in terms of selectivity and response time but regrettably does not
exhibit such high sensitivity. Their CO sensor is highly sensitive to single-figure ppm concentration
with a resolution down to 1 ppm. These studies demonstrate that the laser ablated nanostructured
metal oxides can greatly enhance the sensing performance of gas sensors.
This method is used in the synthesis of Ag Nano particles. Ag NO3 Solution and a reducing agent
are arranged in a vessel (Fig. 5). A solid disc attached with a rotating device is placed inside the
solution with the help of motor. This disc is subjected to pulses from laser beam. The pulse of laser
beam produces hot spots on the surface of the disc. The reaction of AgNO3 and reducing agent at
these hot spots result in the formation of silver particles. These particles are separated from solution
by centrifuge. The size of the particles depends on the energy of incident laser pulses as well as on
the rotation speed of disc.
6. Sol Gel Method: In addition to techniques mentioned above, the sol-gel processing techniques
have also been extensively used. Colloidal particles are much larger than normal molecules or
nanoparticles. However, upon mixing with a liquid colloids appear bulky whereas the nanosized
molecules always look clear. It involves the evolution of networks through the formation of colloidal
suspension (sol) and gelatin to form a network in continuous liquid phase (gel). The precursor for
Nanomaterials 3.11
Fig. 5
synthesizing these colloids consists of ions of metal alkoxides and aloxysilanes. The most widely used
are tetramethoxysilane (TMOS), and tetraethoxysilanes (TEOS) which form silica gels. Alkoxides are
immiscible in water. They are organo metallic precursors for silica, aluminum, titanium, zirconium
and many others. Mutual solvent alcohol is used. The sol gel process involves initially a homogeneous
solution of one or more selected alkoxides. These are organic precursors for silica, alumina, titania,
zirconia, among others. Mortia et al [11-14] A catalyst is used to start reaction and control pH. Sol-
gel formation occurs in four stages.
Hydrolysis
Condensation
Growth of particles
Agglomeration of particles
Hydrolysis: During hydrolysis, addition of water results in the replacement of [OR] group with
[OH-]group. Hydrolysis occurs by attack of oxygen on silicon atoms in silica gel. Hydrolysis can be
accelerated by adding a catalyst such as HCl and NH3. Hydrolysis continues until all alkoxy groups
are replaced by hydroxyl groups. Subsequent condensation involving silanol group (Si-OH) produced
siloxane bonds (Si-O-Si) and alcohol and water. Hydrolysis occurs by attack of oxygen contained in
the water on the silicon atom.
Condensation: Polymerization to form siloxane bond occurs by either a water producing or alcohol
producing condensation reaction. The end result of condensation products is the formation of
monomer, dimer, cyclic tetramer, and high order rings. The rate of hydrolysis is affected by pH,
reagent concentration and H2O/Si molar ratio (in case of silica gels). Also ageing and drying are
important. By control of these factors, it is possible to vary the structure and properties of sol-gel
derived inorganic networks.
Growth and Agglomeration: As the number of siloxane bonds increase, the molecules aggregate
in the solution, where they form a network, a gel is formed upon drying. The water and alcohol are
driven off and the network shrinks.
At values of pH of greater then 7, and H2O/Si value ranging from 7 to 5. Spherical nano-
particles are formed. Polymerization to form siloxane bonds by either an alcohol producing or water
producing.
3.12 Engineering Chemistry
In addition on the basis of phase composition, nanomaterials in different phases can be classified
as,
• Single phase solids include crystalline, amorphous particles and layers, etc.
• Multi phase systems include colloids, aero gels, ferro fluids
6. Examples of nanomaterials
1. Creation and Use of Buckyball: Until 1985, there were only two known forms of pure
Carbon graphite and diamond. Both these substances consist entirely of carbon atoms.
However, they differ greatly in their structures and physical properties. First of all we shall
discuss the structure of diamond and graphite.
2. Diamond: In diamond all carbon atoms are stacked neatly in a three dimensional array or
lattice. Each carbon atom is bound to four other carbon atoms in a pattern of tetrahedrons.
This structure is extremely hard (Fig. 6). shows the structure of diamond.
Fig. 6 Fig. 7
6.1 Graphite
In Graphite, the carbons atoms form sheet of linked hexagons. Each carbon atom within a sheet forms
strong bonds to three other carbon atoms. However, the sheets are held together by weak bonds due
to vanderwaal’s forces. This means that sheets can slide over each other. Therefore, graphite is soft
and greasy. Figure 7 show the structure of carbon atoms connected by covalent bonds in a sheet of
graphite.
In 1985, a third form of carbon was discovered. It is a hallow cluster of 60 carbon atoms shaped
like a football. Just like the case of graphite, in which each carbon atom is bonded to three adjacent
carbon atoms and arranged in a sphere about a nano meter in diameter. It was named, Buckminister
fullerene or in short buckyballs after the famous American R. Buckminister Fuller who had already
designed domes in the structures. The shape of a buckyball is shown in fig. 8. Buckyballs is the
roundest and most symmetrical large molecule known in the world. The buckyballs has carbon atoms
at 60 chemically equivalent vertices that are connected by 32 faces, 12 of which are pentagonal and
20 hexagonal. Today a whole family of related molecules has been discovered and comes under
fullerenes.
3.14 Engineering Chemistry
Larger buckyballs such as C70, C76, C70 and C84 have also been found. In addition to it, smaller
Bucky-balls C20, C22, and C36 have also been identified.
Fig. 8
6.2.1 Properties
1. Buckyballs are stable and withstand very high temperature and pressure.
2. The carbon atoms of buckyballs can react with other atoms and molecules leaving the stable,
spherical structure still intact.
3. Buckyballs do not bond to each other they however stick together via Vanderwaal forces.
4. New molecules can be created by adding other molecules to the outside of a buckyballs and
by trapping smaller molecule inside a buckyballs.
6.2.2 Uses
Most of the commercial applications of buckyballs are still under developing stages. However various
places where buckyballs can be used are:
1. When a buckyballs is doped by inserting the right amount of potassium or cesium into empty
spaces within the crystal, it becomes a super conductor.
2. Almost every carbon atom in C60 can absorb hydrogen atom which suggest that buckyballs
can be used as a better storage medium for hydrogen fuel than metal hydrides.
3. Buckyballs can deliver medicine directly to the infected regions of the body, they are involved
in delivering elements for medical imaging, and they have ability to act as antioxidants on
counter acting free radicals in the human body. Researchers are modifying buckyballs to
fit the section of the HIV molecule that binds to proteins, possibly inhibiting the spread of
virus.
Nanomaterials 3.15
7. CARBON NANOTUBES
In 1990, Richard Smalley gave the concept if buckyballs get big enough then they can become carbon
cylinders. Sumio Lizima discovered these cylinders in 1991 and named them nano tubes. Carbon
nano tubes are sheet of graphite rolled into a tube with bonds at the end of the sheet that close.
The tube dimensions are variable and can be as small as 0.4nm in diameter & several millimeters
in length. Carbon Nanotubes (CNTs) have a length to diameter ratio greater than 10,00,000. Figure
9 gives structure of carbon nano tube.
Fig. 9
7.1 Types of Nanotubes
There are two main types of nano tubes:
• Single walled nano tubes (SWNTs) and Multi walled nano tubes (MWNTs).
3.16 Engineering Chemistry
7.2 Structure
Fig. 10
Figure 10 gives the structure of SWCNT AND MWCNT. The diameter of most single walled
nanotubes is close to 1 nanometer with a tube length of many million times longer. A one atom
thick layer of graphite is wrapped into a seamless cylinder to give the structure of SWNT. Multiwall
carbon nanotubes consist of multiple concentric nanotube cylinders i.e. they consist of multiple
layers of graphite rolled in on themselves to form a tube shape. A carbon nanotube is a cylinder of
carbon atoms covalently bonded together some of these cylinders are closed at the ends and some
are open. Each carbon atom is bonded to three other carbon atoms and forms a lattice in the shape
of hexagons except near the end. For nanotubes with closed ends, where the ends start to curve to
form a cap, the lattice forms pentagons.
Depending on the direction of roll up of graphite hexagons, carbon nanotube can be classified as
either Zigzag, armchair or Chiral as given in Fig. 11.
Fig. 11
Nanomaterials 3.17
The structure of nanotube can be specified by Chiral vector (n, m), which define how the graphite
sheet is rolled up n and m are integers if the vector equation–
R = na1 + ma2
4. Vapor Liquid Solid Growth Method Large scale production of nanotubes can be done by
vapor, liquid solid growth. The carbon containing gas, is broken apart at the surface of the
catalyst particle in VLS growth method, and the carbon is transported to the edges where
it forms nanotubes at the sites of metal catalyst. The length of the tube grown in surface
supported catalyst VLS system appears to be dependent on the orientation of the growing
tube with the surface. By properly adjusting the surface concentration and aggregation of
the catalyst particles it is possible to synthesize vertically aligned carbon nanotubes i.e. as a
carpet perpendicular to the substrate.
7.4 Properties of Nanotubes
1. Carbon nano tubes are super strong. The tensile strength of carbon nanotubes is 100 times
greater than steel. This is due to the fact that firstly, each carbon nanotube is one large
molecule and secondly the strength provided by the interlocking carbon to carbon covalent
bonds is very large.
2. Nanotubes are very elastic. The young modules of a nanotube are 5 times higher than for
steel. This is due to the fact that nanotubes have a perfect structure and bond strength between
carbon atoms is very strong.
3. In addition to being strong and elastic, carbon nanotubes are light weight with a density
about one quarter that of steel.
4. The thermal conductivity of nanotube is very high. Conduction in nanotubes takes place due
to vibration of covalent bonds holding the carbon atoms together.
5. A carbon nanotube happens to be a non-polar molecule.
6. The carbon nanotubes show negative magneto resistance (Phenomenon of change in resistance
of a material due to valuation in D.C. magnetic field).
7. Carbon nanotubes are metallic as semiconducting depending upon the diameter and how
they are rolled. The synthesis of carbon nanotubes generally results in a mixture of tubes,
two thirds are semiconducting and one third is metallic.
and lipid based nanobiomaterials. These nanobiomaterials could further be engineered to be stimuli-
responsive.
8. Water: Nanotechnology will provide efficient water purification techniques. Water from the
oceans can also be converted into drinking water.
9. Sensors: based on nanotechnology are more sensitive and more effective.
10. Computers: can be made more spowerful and smaller using nanotechnology.
11. Dendrimers are nanomaterials consisting particles between 1-100 nm, they have applications in
engineering, industry, pharmaceuticals etc,. For example Maganese dendritic nanoparticles developed
as MRI contrast agent increase hydrophobicity and relaxivities.
12. Bioimaging/Molecular imaging: The use of nanoparticles has boosted the development of
diagnostic agents for bioimaging. It of increased attention has been devoted to the development of
nanoparticles as multimodel agents for diagnosis, imaging and theory. For example Quantum dots are
used in optical imaging, for example SPIO nanoparticles are used for biomaging applications.
solved Questions
1. What are nanomaterials?
Ans. Nanomaterials are defined as those materials which have structured components with size
less than 100 nm at least in one dimension.
2. Give two techniques to manufacture quantum dots.
Ans. The two techniques to manufacture quantum dots are
(i) Top-bottom approach
(ii) Bottom-top approach
3. Why properties of materials are different at nano scale?
Ans. The properties of materials are different at the nano scale for two reasons:
1. Nano materials have a relatively large surface area.
2. Quantum effect begins to dominate.
4. Give significance of nano scale with the help of some examples.
Ans. When a material enters nano range properties change significantly for example
(i) opaque substances become transparent eg. Copper.
(ii) Inert materials can become catalyst eg. Platinum.
(iii) Stable material can turn combustible eg. Aluminium.
(iv) Insulators can become conductors eg. Silicon.
5. What are carbon nanotubes?
Ans. Carbon nanotubes are a sheet of graphite filled into a tube with bonds at the end of the sheet
that close.
UNsolved Questions
1. What is nano science?
2. What is nano technology?
3. Give preparation of carbon nanotubes.
Nanomaterials 3.21
Electrochemistry is the study of the relationship between chemical and electrical phenomena and
the laws of their interaction. Such interactions are observed at the boundaries between electrolytes
and electrodes dipping in them.
Electrochemistry is of great significance, since the laws of electrochemistry forms the basis of
technical processes like electrolysis and electro synthesis. The branch holds importance due to number
of reasons:
(i) It is of huge economical importance because of the costly destruction caused by corrosion
and the possibilities of fuel cells which generate electricity directly from fuel.
(ii) It provides techniques for measuring the thermodynamic state functions and for predicting
equilibrium concentration of dissolving and reaction of ion.
Thus the branch of electrochemistry is of major technological importance.
A bar of zinc metal is placed in zinc sulphate solution in the left container. A bar of copper
is immersed in copper sulphate solution in the right container. A salt bridge containing potassium
chloride solution interconnects the solutions in the anode and cathode compartment.
4.2 Engineering Chemistry
When the cell is set up, electrons flow from zinc electrode through the wire to the copper
electrode. As a result, zinc dissolves in the anode solution to form Zn2+ ions. The Cu+2 ions in the
cathode half cell picks up electrons and are converted to Cu atoms on the cathode. At the same time,
sulphate ions from the cathode half-cell move to the anode half-cell through the salt bridge. Likewise,
Zn2+ ions from the anode half cell move to the cathode half cell. This flow of ions from one half-
cell to the other completes the electrical circuit which ensures continuous supply of current.
As the cell operates the weight of copper rod will increase while that of zinc rod will decrease.
Consequently, the cell will function till either zinc metal or copper ion is completely used up.
A typical type of voltaic cell in which the salt bridge is replaced by porous pot is known as
Daniel cell (as shown in fig. 2).
Daniel cell resembles the above voltaic cell in all details except the Zn2+ ions and SO42– ion flow
to the cathode and the anode respectively through the porous pot instead of through the salt bridge.
Inspite of this difference the cell diagram remains the same.
Fig. 2
It provides a low resistance electrical connection between the two half cells and allows the flow
of ion from one half cell to the other half cell. Thus salt bridge completes the circuit.
It keeps the solution in the two half cells electrically neutral. An equal number of SO2–
4 ions will
move from the salt bridge toward zinc electrode and thus the positive charge around zinc electrode is
neutralized. Similarly K+ ions will move from salt thereby neutralizing the negative charge. Therefore,
the solution in two half cells are electrically neutral.
Can be expressed as the sum of the following two half cell reaction.
The half cell in which oxidation takes place is called oxidation half cell while the other in which
reduction takes place is called reduction half cell.
The reduced and oxidized substances in a half reaction form a redox couple, denoted as ox/Red.
In this reaction Cu2+/Cu and Zn2+/Zn are the redox couple.
4.4 Engineering Chemistry
As shown in figure1 in an electrochemical cell the two half reactions take place in two different
compartments. When the reaction takes place, the electron released in one compartment travels
through the external circuit and enters the cell through the other electrode. For example,
Zn will lose the electrons which will travell through the circuit. The electrode where oxidation half
reaction takes place is called anode. These electrons are given to the electrode which thus acquires
a negative charge.
When the electron flows from anode toward cathode the electrical energy is produced. Thus an
electrochemical cell converts the chemical energy into electrical energy.
The metal electrode in anode half-cell is on the left of the metal ion, while in cathode half-
cell it is on the right of the metal ion.
Anode half-cell is written on the left and cathode half-cell on the right.
(iii) In the complete cell diagram, the two half-cells are separated by a double vertical line.
The zinc-copper cell can now be written as
(iv) The symbol for an inert electrode like the platinum electrode is often enclosed in a bracket.
For example,
(v) The value of Emf of a cell is written on the right of the cell diagram. Thus, a zinc copper
cell having Emf 1.1 V and is represented as
E = + 1.1 V
Electrochemistry and Ionic Equilibrium 4.5
The negative sign indicates that the cell is not feasible in the given direction. The reaction will
take place in the reverse direction.
ECell = ER – EL.
4.6 Engineering Chemistry
Table 1
EMF Cell Potential
1. Emf is the potential difference between two Cell potential is the measure of the difference in
electrodes, when no current is flowing in the potentials of the two half cells when electric current
circuit. flows through the cell.
2. Emf is the maximum voltage which can be Cell potential is always less than the maximum
obtained from the cell. voltage obtainable from the cell.
3. Emf is measured by a potentiometer. Cell potential is measured using a voltmeter.
4. Emf corresponds to the maximum useful work Cell potential does not correspond to the maximum
obtainable from the galvanic cell. useful work.
Where ER and EL are the reduction potentials of the right-hand and left-hand electrodes respectively.
It may be noted that absolute values of these reduction potentials cannot be determined. These are
found by connecting the half cell with a standard hydrogen electrode whose reduction potential has
been arbitrarily fixed as zero.
Difference between EMF and Cell Potential are listed in Table 1 given above
More recently, the reduction potential has been adopted by the international union of pure and
applied chemistry (IUPAC) for the designation of electrode potential. When the half cell reaction
is carried out at temperature of 298 K and the electrode is suspended in a solution of one molar
concentration, the electrode potential is termed as the standard electrode potential and is represented
by E 0. The electrode potential of an electrode is measured with respect to standard hydrogen electrode.
The standard electrode potential E 0 enables one to access thermodynamic activity of various chemical
substances. But there are no methods available by which we can measure its absolute value.
The electrode potential of an electrode depends upon concentration of ions in solution in contact
with metal. Oxidation potential of an electrode is inversely proportional to the concentration of ions
whereas reduction potential is directly proportional to the concentration of ions.
In hydrogen electrode, hydrogen gas is bubbled through a solution of hydrogen ions. The inert
metal (which is often Pt) acts as a source or sink of electrons but takes no other part in the reaction
other than acting as a catalyst for it. This electrode is denoted as,
Pt | H2(g) | H+ (aq)
The hydrogen electrode may act as either a cathode or an anode, depending on the other electrode
in the cell and the spontaneous direction of the overall reaction. When the hydrogen electrode is
acting as cathode, the reaction is,
2H+ (aq) + 2e – H2(g) (Reduction)
4.8 Engineering Chemistry
To determine the electrode potential of the given electrode, the electrode is coupled with SHE.
The Emf of the cell is then determined with the help of a potentiometer. The electrode potential of
SHE is arbitrarily taken as zero the Emf of cell gives the value of electrode potential of the given
electrode.
For example when zinc electrode (Zn rod dipped in an electrode) is coupled with SHE, oxidation
takes place at the zinc electrode. (Figure 6)
The two half cell reactions are represented as:
The Emf of cell measured by a potentiometer is 0.76 V. Therefore the oxidation potential of zinc
electrode is taken as +0.76 volt and the reduction potential are taken as –0.76V.
Similarly, when copper electrode (copper rod dipped in an electrolyte) is coupled with SHE,
reduction takes place at copper electrode (fig. 7)
Hence, the reduction potential of copper electrode is taken as + 0.34 V and oxidation potential
is – 0.34 V. The negative sign of oxidation potential indicates that the oxidation at the electrode will
not be spontaneous.
Electrochemistry and Ionic Equilibrium 4.9
Fig. 7 Standard electrode potential (reduction potential) of Copper by combining with SHE.
7. Electrochemical Series
The standard potential of an electrode can be measured with reference to standard hydrogen electrode,
which has been assigned the value zero. These electrodes can be arranged in order of their increasing
reduction potential. Electrochemical series is arrangement of various electrodes in order of their
standard electrode potential value. The values are reported in Table 2 for the standard electrode
potential corresponding to half cell reaction in which reduction takes place. Therefore E0 values
are also known as standard reduction potentials. The electrochemical series is also called activity
series.
Ni Ni2+ –
(aq) + 2e Æ Ni(s) – 0.25
Sn Sn2+
(aq)
–
+ 2e Æ Sn(s) – 0.14
Pb Pb+(aq) –
+ e Æ Pb(s) – 0.13
H2 2H+ + 2e– Æ H2(g) – 0.00
– –
I2 I2(s) + 2e Æ 2I (s) + 0.54
3+ – 2+
Fe Fe + e Æ Fe + 0.77
Hg Hg2+
2(aq)
–
+ 2e Æ 2Hg(l) + 0.79
Ag Ag+(aq) + e– Æ Ag(s) + 0.80
Hg Hg2+
(aq)
–
+ 2e Æ Hg(l) + 0.85
–
Br2 Br2(aq) + 2e Æ 2Br–(aq) + 1.08
O2 1
__ + 1.23
O2(g) + 2H3O+ (ag) + 2e– Æ 3H2O
2
Cr Cr2O7– + 14H+ + 6e– Æ 2Cr3+ + 7H2O + 1.33
– -
Cl2 Cl2(g) + 2e Æ 2Cl + 1.36
Au Au3+
(aq)
–
+ 3e Æ Au(s) + 1.42
Mn MnO–4(aq) + 8H3O(aq)
+
+ 5e– Æ Mn2+
(aq) + 12H2O + 1.51
– –
F2 F2(g) + 2e Æ 2F (g) + 2.87
Fig. 8
4.12 Engineering Chemistry
The value of E0 becomes more negative down the series. This means that Cu+2 is the best oxidizing
agent (most electron attracting ion) of those in the list. That is Cu2+ shows the greatest tendency to
be reduced. Conversely, Zn+2 is the worst oxidizing agent, being the least electron-attracting ion. Of
the elements Cu, H2, Ni and Zn; Zn is the best reducing agent (best electron donor), since E0 for
the half–reaction
Zn Æ Zn2+ + 2e E0 = + 0.76 V
has the most positive value. By the same reasoning Cu is the worst reducing agent. The half reaction
potentials given in Fig. 8 above tells us that at standard condition the following reaction occur
spontaneously.
Some important points concerning the table of standard reduction potential (Table 2) are:
1. On moving upward in the table more positive value of E0, better the oxidizing ability (the
greater the tendency to reduce) of the ion or compound.
2. On moving downwards in the table more negative the value of E0, better the reducing ability
of the ions, elements or compounds.
3. Under standard conditions, any substance in this table will spontaneously oxidize any other
substance placed lower in the table.
8. Types of Cells
When various electrodes are combined, two general classes of cells are formed.
(i) Chemical cells, in which the Emf is due to a chemical reaction occurring within the cell.
(ii) Concentration cells, in which the Emf is due to transfer of material from one electrode to
the other due to species involved. Each type of the cells may or may not involve a junction
potential and it is usually said, the cell may or may not have transference.
The different types of cells are shown in Figure 9.
Fig. 9
Electrochemistry and Ionic Equilibrium 4.13
Concentration Cells
In concentration cells, Emf results from the transfer of a material from one electrode to other due to
a concentration difference between the two. The difference in concentration arises due to:
(i) Both the electrode dipping in the same electrolyte having different concentration.
These types of cells are known as electrolyte concentration cells. For example,
(a) H2 (g, 1 atm) | H+(a1) H+ (aq) | A2 (g, 1 atm)
Thus in a bid to equalize concentration of Ag+ ions in the two compartments the cell will develop
an Emf (Le Chatelier’s Priniciple) to cause the transfer of electrons equal. Eventually, the solution
in two compartments will have equal Ag+ ion concentration and there will be no Emf recorded
thereafter.
Where E is the electrode potential of the metal M and n is the valence of the ions in contact
with it. For example, the Emf, E, of the concentration cell.
Ag |Ag+ (1M)| |(0.1M) Ag+| Ag
can be calculated by substituting the values in the above equation.
[
0.0591
E = ______
n log
1 M
]
_____ = 0.0591, here n = 1
0.1 M
8.2.1 Applications
1. Determination of solubility of sparingly soluble salts
The ionic concentration of a solution is calculated from the Emf of a concentration cell. In case of a
sparingly soluble salt, the salt can be supposed to be completely ionized in saturated solution. Hence
the ionic concentration is proportional to the solubility of the salt.
Suppose we want to find the solubility of silver chloride. This can be done by measuring Emf,
E of the cell.
Electrochemistry and Ionic Equilibrium 4.15
2. Determination of valence
The expression for the Emf, E of a concentration cell is,
0.0591 C2
E = ______
n log ___
C1
Where n is the valence of the metallic ion in solution, while C1 and C2 are the concentration of
the ions in the two half-cells. Knowing the experimental values of E, C1 and C2, n can be calculated.
For example, the valence of mercury in mercurous nitrate, Hg2 (NO3)2, can be determined by the
concentration cell method. The following cell is constructed.
Hg |0.05 N Hg2 (NO3)2| |0.5 N Hg2 (NO3)2| Hg
And its Emf found experimentally is 0.029 volts.
Let C1 be the concentration of mercurous ion in 0.05 N Hg2 (NO3)2 in the left half cell and C2
be the concentration of mercurous ion in 0.5 N Hg2 (NO3)2 solution in the right half cell.
Subsitituting the values in the expression (6), we have,
0.0591 0.5
0.029 = ______
n log ____
0.05
0.0591 0.0591
= ______
n log 10 = ______
n
0.0591
Therefore, n = ______
= 2.
0.029
D G 0 = – nF E 0cell ...(7)
The significance of the above equation is:
(i) The various thermodynamic properties of a reaction can be calculated from ‘Emf’ measurement
using this equation.
(ii) This equation helps to know about the spontaneity of the reaction at constant temperature
and pressure.
When,
DG = negative The reaction is spontaneous
DG = positive The reaction is non-spontaneous
DG = zero The reaction is at equilibrium
From equation 7, it may be concluded that for any spontaneous reaction, the cell potential will
be positive, for any non-spontaneous reaction, the cell potential will be negative reaction, while for
any reaction at equilibrium, E will have to be zero. The relation between spontaneity of reaction
DG 0 and E 0 values are summarized in Table 3.
Table 3
Reaction G0 E0
Spontaneous – ve + ve
Non-spontaneous + ve – ve
Equilibrium 0 0
______ = – DS (∂(D G)
∂T )
By substituting the value of – DG from equation 7
∂(–nEF)
(
_______ = – DS
∂T P
)
Electrochemistry and Ionic Equilibrium 4.17
( )
∂E
– nF ___
= – DS
∂T P
∂E
– DS = – nF ___ ( )
∂T P
...(8)
The temperature coefficient of cell potential gives the energy of the cell reaction.
[ ( )]
∂E
DH = – nF E – T ___
∂T P
DH
nF ( )
∂E
Ecell = – ___ + T ___
∂T
...(9)
Whether the electrical work done is greater or less than the heat of reaction depends upon the
temperature coefficient of the cell, i.e. Ecell varies with T.
∂E
If ___
is negative than DG > DH and heat is absorbed from the surroundings during the working
∂T
of the cell.
∂E
If ___
is positive than DH > DG and heat is given out to the surrounding of the cell during
∂T
working.
Thus DG, DH and DS can be calculated for the cell reaction from measurements of Emf and
temperature coefficient of Emf.
nFE = – DG 0 – RT ln Q
We know that – D G = RT ln K ...(10)
Where K is the equilibrium constant for the cell reaction.
Substituting in equation 10, we get–
nFE = RT ln K – RT ln Q
[C] c [D] d
nFE = RT ln K – RT ln ________
[A] a [B] b
Changing ln into log10, we get–
2.303 2.303 RT [C] c [D] d
Ecell _____ RT log K ________ log ________ ...(11)
nF nF [A] a [B] b
2.303 RT
At 25°C, the value of ________ is
nF
2.303 × 8.313 JK–1 mol–1 × 298 K
= _____________________________
n × 96500 C mol–1
0.0591
= ______
n Volt
Where,
E = Electrode potential T = Temperature
E 0 = Standard electrode potential F = Faraday of Electricity
R = Gas Constant n = no. of electrons
Electrochemistry and Ionic Equilibrium 4.19
2.3030 RT
0
Ecell = E cell – _________ log Q ...(12)
nF
0.0591
The value of 2.303 RT/nF at 25°C is ______
n log Q
0.0591
Ecell = E 0cell – ______
n log Q
This equation gives the effect of concentration of M n+ ions on the potential of M n+. it can be
modified as:
(i) Consider the reaction–
Fe3+
(aq) + e
–
Fe2+
(aq)
Hence,
0.0591 [Fe2+]
0
Ecell = Ecell – ______
n log ______
[Fe3+]
n =1
From this, for an electrode reaction can be written as
Oxidized State + ne – Reduced State
Correspondingly the electrode potential is given by–
4.20 Engineering Chemistry
(ii) Suppose on a chlorine electrode, chlorine gas is passed at a pressure of 1 atmosphere through
a solution containing Cl– ions.
1
__
Cl2 (g) (1 atom) + e – Cl– (aq)
2
The cell potential is–
0.0591
Ecell = E 0cell – ______
Cl –
[ ]
n – ___
Cl2
Since activity of chlorine gas at 1 atmosphere pressure is taken as unity, therefore
0.0591
Ecell = E 0cell – ______
n log [Cl–]
(iii) Calculation of equilibrium constant (K) from Nernst equation. Consider the galvanic cell,
In equilibrium state the concentration of Zn 2+ (aq) and Cu2+ (aq) will be the equilibrium
concentration and Emf of the cell will be zero. Therefore the Nernst equation is modified as,
2.3030 RT [Zn2+ (aq)]equilibrium
0 = E 0cell – _________ log ___________________
nF [Cu2+ (aq)] equilibrium
0.0591
E 0cell = _____
n log K
[Zn2+ (aq)] equilibrium
\ K = ___________________
[Cu2+ (aq)] equilibrium
Where,
K = equilibrium concentration at 298 K.
0.0591
E 0cell = ______
n log K
nE 0cell
or log K = ______
0.0591
nE 0cell
K = Antilog ______ ...(15)
0.0591
Electrochemistry and Ionic Equilibrium 4.21
RT
E = E 0 – ___
1
ln ____
nF [ ]
+2
Zn
8.314 × 298
= (– 0.76) – __________
1
ln __________
2 × 96500
= 0.79 V.
(96 × 10 –3) [ ]
(ii) Nernst equation can also be used for the calculation of the potential of a cell under non
standard conditions.
Example 2 Calculate the potential of the following electro chemical cell at 25°C.
(iii) Determination of unknown concentration of one of the ionic species in a cell is possible with
the help of Nernst equation provided E 0 cell and concentration of ionic species is known.
Example 3 Determine the concentration of Cd+2 ions in the following electro chemical cell, Fe, Fe +2
(0.1 M) Cd+2 (x m), Cd, assuming that activities are of equal concentrations.
Given the emf of the cell E = – 0.02 V and E 0 = 0.04 V at 25°C.
Solution: Overall cell reaction:
Fe (s) + Cd+2 (aq) Fe +2 (aq) + Cd (s)
4.22 Engineering Chemistry
0.059
0.02 = 0.04 – _____ [ ]
0.1
log ___
2
x
x = 0.00093 or x = 0.001 M
(iv) The pH of a solution can be calculated from the measurement of emf and Nernst
equation.
Example 4 The emf of a cell measured by means of a hydrogen electrode against a saturated calomel
electrode at 298 K is 0.4188 V. If the pressure of the H2(g) is maintained at 1 atm, calculate the pH
of the unknown solution, given potential of reference calomel electrode is 0.2415 V.
The cell in this case is
Pt H2 (1 atm) H+ (aH+) Cl– (aCl–) Hg2Cl2 Hg
Hydrogen electrode Calomel electrode
with potential with potential
RT
E = ___
ln aH+ Eref = 0.2415 V
F
= ER (given)
RT
= – 2.303 ___
(– log aH+ ) = 0.0591 pH = EL
F
The emf of the cell is given by
E = ER – EL = Ecathode – Eanode
E = Eref – (– 0.0591 pH)
= Eref + 0.0591 pH
RT [Reduced state]
E = E 0 – ___
ln _____________
nF [Oxidised state]
Thus by knowing E, E 0, [oxidized state], [Reduced state], and temperature, we can easily
calculate n, the number of electrode involved in the cell reaction and hence the valency of
an ion.
Electrochemistry and Ionic Equilibrium 4.23
12. Battery
The term battery is usually applied to a group of two or more electric cells connected together
electrically in series.
Battery is a device which transforms chemical energy into electrical energy. Thus it acts as a
portable source of electrical energy. various combinations of electrolytes and electrode are employed
to make batteries for specific purposes. Thus commercial batteries can be made from different types
of electrochemical cells. There are many different types of batteries ranging from the relatively large
‘flash light’ batteries to the miniature versions used for curist watches or calculators. Batteries consist
of either two types of cells.
1. Primary Cells: Primary cells are constructed so that only one continous or intermittent discharge
can be obtained.
Primary batteries are used as a source of dc power where the following requirements are
important:
• Convenience is of major importance,
• The cost of a discharge is not much,
• Standby power is desirable without cell deterioration during periods of nonuse for day or
years
A brief account of primary cell is given below
2. Secondary cells: A secondary cell is one in which electrodes and the electrolyte are altered
by the chemical action that takes place when cell delivers the current. However, these cells can be
4.24 Engineering Chemistry
restored to their original condition by facing an electric current through them. In other words, they
can be recharged again and again number of times.
The lead storage cells and nickel cadmium cells fall under this category.
(i) The lead-acid storage cell: A storage cell can operate both as voltaic cell and as an electrical
cell. It has ability to work in both the ways to receive electrical energy and also to supply it.
When it operates as a voltaic cell, it supplies electrical energy and as a result it eventually
becomes ‘run down’. it then needs to be recharged. when being recharged the cell operates
as an electrolytic cell.
Lead storage cell is the common example of storage cell. it is so classified because the
electrolyte is an acid and the plates are largely leads. It consists of an lead antimony alloy
coated with lead dioxide as cathode and spongy lead as anode. The electrolyte is a 20%
solution of H2SO4 (specific gravity 1.15 at 25°C). In fact, a lead accumulator for car consist
of six lead acid storage cells in series. (Fig. 11)
Discharging: When the lead accumulator is used for supplying electrical energy, it is said to
be discharging. The lead electrode looses electrons which flow through the wire. (Fig. 11a)
i.e., at anode, oxidation takes place
Pb Æ Pb +2 + 2e –
The so formed Pb +2 ions then combine with SO4 –2 ions
Pb +2 + SO4–2 Æ PbSO4 Ø
The released electron flow to the cathode, where PbO2 forms Pb +2. In other words, lead
undergoes reduction at cathode.
PbO2 + 2H+ + 2e – Æ Pb +2 + 2H2O
The Pb +2 ions than combine with SO4 –2 ions
Pb +2 + SO4–2 Æ PbSO4 – Ø
Electrochemistry and Ionic Equilibrium 4.25
The released electron flow to the cathode, where PbO2 forms Pb +2. In other words, lead
undergoes reduction at cathode
PbO2 + 2H+ + 2e – Æ Pb +2 + 2H2O
The Pb +2 ions then combine with SO4 –2 ions
Pb +2 + SO4–2 Æ PbSO4 Ø
Thus, the net reaction during discharging is
Pb + PbO2 + 4H+ + 2SO4–2 Æ 2PbSO4 Ø + 2H2O + Energy
The voltage of each cell is about 2.0 volts at a concentration of 21.4% H2SO4 at 25°C.
Recharging: During the discharging PbSO4 is precipitated at both the electrodes. When
PbSO4 covers completely both anode and cathode, the cell stops functioning as a voltaic
cell. So far further use, it needs to be recharged. (Fig. 11b)
Fig. 11a Discharging of Lead acid Cell Fig. 11b Recharging of Lead acid Cell
Recharging is done by passing an external emf greater than 2 volts so that the reactions
taking place during discharging are reversed.
at cathode : PbSO4 + 2H+ Æ Pb + SO4–2
at anode : PbSO4 + 2H2O Æ PbO2 + SO4–2 + 2H+ + 2e –
Net reaction during charging is:
2PbSO4 + 2H2O + energy Æ Pb + PbO2 + 4H+ + 2SO4 –2
Obviously, during the charging cycle, the cell electrodes are restored to their original
conditions (i.e., Pb and PbO2 respectively)
Generally, overcharging does not cause any damage because continued electrolysis liberates
H2 and O2 at the electrodes. But excessive charging may reduce the acid level and may
damage the exposed electrodes.
Application of lead acid storage cells: These cells are used for supplying current to
electrical vehicles, railway, mines, laboratories, hospitals, automobiles, power station.
4.26 Engineering Chemistry
(ii) Nickel-Cadmium (Nicad) cell: Nickel–cadmium cell consists of a cadmium anode and a
paste of Ni O(OH) comprises the cathode. The cell reactions are:
Cd (s) + 2OH–(aq) Æ Cd(OH)2(s) + 2e – at anode
2NiO(OH)(s) + 2H2O + 2e – Æ 2Ni(OH)2(s) + 2OH–aq at cathode
The reaction can be easily reversed, because the reaction products, Ni(OH) 2(s) and
Cd(OH)2(s) adhere to the electrode surface.
Nicad battery has fairly constant voltage. the potential of Cd anode is below the hydrogen
potential. therefore, the cadmium electrode is completely inert to electrolyte.
Nicad batteries are used in electronic calculators, electronic flash units, transistors, etc.
solved Questions
1. A cell is prepared by dipping copper rod in 1M CuSO4 solution and Zn rod in 1M ZnSO4
solution, the standard reaction potentials of Cu and Zn are 0.34 and – 0.76 respectively?
(i) Which electrode will be positive?
(ii) How will the cell be represented?
(iii) What is the cell reaction?
(iv) What will be the emf of the cell?
Sol.
(i) Cathode is the positive electrode and has greater reduction potential than the second
electrode of the cell. Therefore, the positive electrode is copper electrode.
(ii) Oxidation reaction Zn (s) Zn+2 (aq) + 2e –
Reduction reaction Cu +2
(aq) + 2e
–
Cu (s)
Cell represented as follows.
Zn ZnSO4 CuSO4 Cu
(1M) (1M)
(iii) Cell reaction is the sum of oxidation half cell reaction plus reduction half cell reaction
so, it is written as follows:
Cu (s) + ZnSO4(aq) CuSO4(aq) + Zn (s)
(iv) E 0cell = E 0R – E L0
2. Calculate the standard reduction electrode potential of Zn+2 /Zn electrode when the cell
potential E 0 of the cell Zn (s) Zn+2 (1M) Cu+2 (1M) Cu (s) is 1.10 V.
E 0 Cu+2 /Cu = + 0.34 V.
E 0 Zn+2 / Zn = – 0.76 V.
3. Two half cell reactions with their oxidation potentials are
(a) Pb (s) – 2e– Pb +2 (aq); E 0 = – 0.13 V.
(b) Ag(s) – e– Ag+ (aq); E 0 = + 0.80 V.
Write the cell reaction and calculate its emf.
Sol. Here E 0 oxidation values are given in reduction potentials E 0 values are
0
Pb +2 /Pb = – 0.13 V E 0 Ag+/Ag = + 0.80 V
4. Standard oxidation potential of Cd/Cd +2 and Pb/Pb +2 electrodes are – 0.40 V and – 0.13 V
respectively. State whether the following cell is feasible.
Sol. The standard reduction potentials of the electrodes will have sign opposite to oxidation
potentials
E 0 Pb +2 /Pb = 0.13 V E 0 Cd+/Cd = + 0.40 V
= 1.54 + 0.139
= 1.689 V.
7. A cell is formed by dipping Zn rod in 0.01 M Zn+2 solution and Ni rod in 0.5 M Ni+2 solutions.
The standard electrode potentials of Zn and Ni are 0.76 V and – 0.25 V respectively. Write
the cell representation, cell reaction and calculate the emf of the cell.
Sol. Since E 0 (= – 0.25 V) for nickel electrode is higher than that of Zn electrode (– 0.76 V).
So nickel electrode is cathode; while zinc electrode is anode. Hence, the cell is represented
as:
Zn (s) Zn+2 (0.01 M) Ni+2 (0.5 M) Ni (s)
\ [
Ecell = E 0
Ni+2 /Ni
– E 0
Zn +2 /Zn ]
= 0.059 V
11. The potential of a hydrogen gas electrode in a solution of an acid of unknown strength is
0.29 V at 298 K, as measured against normal hydrogen electrode. Calculate the pH of acid
solution.
Sol. E 0cell = E 0hydrogen – Ehydrogen
= 0 V – (– 0.059 pH)
= 0.059 pH
Ecell 0.29
pH = _____ = _____
= 4.9
0.059 0.059
12. Find out the pH of a solution in a quinhydrone half cell, which is coupled with standard
calomel electrode. The emf of the combined cell was determined to be 0.123 V = (0.6990 V
– 0.0592 V pH) – 0.2415 V.
0.6990 – 0.2415 – 0.123
Sol. pH = _____________________
0.0592
= 5.65
4.30 Engineering Chemistry
13. A hydrogen electrode is immersed in a solution of pH = 3.5 and other half cell is SHE.
Calculate the emf of the cell, if the two half cells are connected by a salt bridge.
Sol. The cell is:
Pt, H2(g) H+ (pH) = 3.5 H+ (1M) H2 (g), Pt
0.1 × 20
[Zn+2] = _______
100 [
( Salt gives 20% of ions) ]
0.059
E 0
= E – _____
log10 [Zn+2]
OP Zn/Zn +2 OP Zn/Zn +2 2
0.059
= + 0.76 – _____
0.1 × 20
log10 _______
2 100
[ ]
E = 0.81 V
OP Zn/Zn +2
E = – 0.81 V
RP Zn/Zn +2
15. The Zinc/Siver oxide cell is used in hearing aids and electric watches. The following reactions
take place.
Zn Æ Zn+2 + 2e– E 0 = 0.76 V
Ag2O + H2O + 2e– Æ 2Ag + 2OH– E 0 = 0.344 V
(a) Which will be oxidized and which will be reduced?
(b) Find E 0 of the Cell and DG in Joules.
Sol.
(a) Zn is oxidized and Ag2O is reduced.
(b) E 0cell = E 0Ag O/Ag (Red) + E 0 +2 (ox)
2 Zn/Zn
= 0.344 + 0.76 = 1.104 V
DG = – nFE° Cell.
= – 2 × 96500 × 1.104 J
= – 2.13 × 105 J
16. Caluculate the electrode potential of a copper wire dipped in 0.1 CuSO4 solution at 25°C.
The standard electrode potential of Copper is 0.34 volt.
Electrochemistry and Ionic Equilibrium 4.31
= + 1.13 V.
UNsolved Questions
1. What is the basic difference between the voltage and emf of the cell? Explain.
2. Define electrode potential. How is it different from liquid function potential?
3. Describe the construction of a simple electro chemical cell. Indicate the positive and negative
electrodes? What are the reactions taking place at these electrodes? Give the overall reactwion
and cell diagram.
4. Differentiate between electro chemical and electrolytic cells.
5. What is a reference electrode? Describe the construction of normal hydrogen electrode.
6. Write the (a) electrode reaction (b) cell reaction and calculate the emf of the given cell:
Zn ZnSO4 CuSO4 Cu
Standard potentials of copper and zinc electrodes are + 0.34 and – 0.76 V respectively.
12. Will a reaction take place, if silver has been placed in a solution of FeSO4? Explain using
the following data:
E 0Ag+/Ag = 0.799 V and E 0 = – 0.44 V
Fe +2 /Fe
14. Consider the cell: Fe Fe +2 (0.01M) Cu+2 (0.5M) Cu. The standard electrode potential of
iron and copper are – 0.44 V and + 0.34 V respectively. Write the cell reaction and calculate
the emf of the cell.
15. What is the potential of a half cell consisting of zinc electrode in 0.01 M ZnSO4 solution at
25°C, E ° = 0.763 V.
16. Emf of the cell:
Pt, H2 (g) H+ (10 –6 M) H+ (C = ?) H2 (g), Pt is 0.11 V at 25°C. Calculate the value of C.
17. Predict whether the reaction:
2Ag (s) + Zn +(aq)
2
2Ag+ (aq) + Zn (s) is feasible or not.
Chapter 5
Corrosion
1. INTRODUCTION
When metals are exposed to atmospheric conditions they react with air or water in the environment
forming undesirable compounds, usually oxides. This process is called “corrosion”. Almost all
metals except the less reactive metals such as gold, platinum and palladium, undergo corrosion. For
example – Silver tarnishes, copper develop a green coating; lead and stainless steel lose their lustre
to corrosion. Thus, corrosion may be defined as the gradual eating away, disintegration, decaying or
deterioration of a metal by electrochemical reaction with its environment.
2. THEORIES OF CORROSION
2.1 The Electrochemical or Wet or Immersed theory
This theory is based on Nernst theory, according to which all metals have a tendency to pass into
solution. The tendency of a metal to pass into solution of its salt is measured in terms of electrode
Potential. If a metal having higher electrode potential comes into contact with another metal having a
lower electrode potential, a galvanic cell is set up and the metal having the lower electrode potential
becomes anodic and goes into solution to a measurable extent. Greater the difference in the electrode
potential of cathode and anode, greater will be the corrosion. Also the smaller the area of the anode
as compared to the cathode, the more will be the attack.
Corrosion Reactions
The corrosion process involves the formation of galvanic cells. The various reactions that occur
during corrosion are:
5.2 Engineering Chemistry
(i) Anode Reactions: The anode is the metal which undergoes oxidation and loses electrons to
the environment and passes into solution in the form of positive ions. For example:
M (s) Mn+ (aq.) + ne –
Fe (s) Fe2+ (aq.) + 2e –
Fe2+ (aq.) + 2 OH – (aq.) Fe (OH)2
This continues as long as the electrons and ions are removed from the environment. If they
are not removed, the corrosion will not proceed further.
(ii) Cathode Reactions: The electrons released at the anode are carried to the cathode and are
responsible for following reactions:
(a) Hydrogen electrode or hydrogen type corrosion: In acidic solution the common
reaction is the reduction of H+ ions to form H2 gas H+ ions are present due to the
ionization of water.
H 2O 2H+ + O2–
2H+ + 2e – H2
Such type of corrosion in which hydrogen is involved is called hydrogen type corrosion
(Fig. 2). At the anode, the metal ions pass into the solution as
M M2+ + 2e –
The overall reaction can be written as
M + 2H+ H2 + M2+
For example, iron corrosion in an acidic solution consists of two half cell reactions.
Fe Fe2+ + 2e – (Anode reaction)
2H+ + 2e – H2 (Cathode reaction)
(b) The Water Electrode: In oxidizing acids, the cathodic reaction is the formation of water
as a by-product. (Fig. 3)
O2 + 4H+ + 4e – 2 H 2O
Corrosion 5.3
(c) The Oxygen Electrode: Hydrogen ion concentration is very low in neutral or basic
solutions, thus evolution of hydrogen gas is not favorable. In such cases reduction of
oxygen to hydroxyl ion occurs.
e.g. O2 + 2H2O + 4e – 4OH –
The corrosion of iron occurs by oxygen in the presence of aqueous solution. At anode,
iron dissolves to form ions as
Fe Fe2+ + 2e –
At cathode, the electrons evolved by the above reaction will be intercepted by oxygen
in the presence of H2O
2e – + 1/2 O2 + H2O 2OH– (Cathode reaction)
The overall reaction will be
2Fe + 1/2 O2 + H2O Fe2+ + 2OH–
The OH– ion produced reactions with the positively charged Fe2+ ion forming Fe(OH)2
or rust. This process is known as rusting of iron.
1. If enough oxygen is present, ferrous hydroxide is easily oxidized to ferric hydroxide.
4Fe (OH)2 + O2 + 2H2O 4Fe (OH)3
2. This product, called yellow rust, actually corresponds to Fe2O3 ◊ H2O.
If the supply of oxygen is limited, the corrosion product may be black anhydrous magnetite,
Fe3O4.
soluble or liquid corrosion product is formed, then the metal is exposed to further attack. For example,
chlorine and iodine attack silver, generating a protective film of silver halide. During detaining of
tinned low-carbon steel cans using Cl2 gas at high temperature (over 120°C), tin is converted into
volatile SnCl4 and hence all tin is readily removed, however dry Cl2 attacks the base metal only
superficially because the FeCl3 formed on the surface protects the rest of the metal. Dry chemical
corrosion is of three main types.
1. Oxidation corrosion: This type of corrosion is brought about by the direct chemical action
of oxygen at low or high temperature on metals alkali & alkaline metals (e.g., Na, Ca, Mg etc.),
generally in the presence of moisture.
The reactions involved are:
2M 2 Mn+ + 2e – (Oxidation)
metal ion
In the case of zinc and aluminum, the outward diffusion of metal is great. As a result, the
temperature of the metal is increased and the metal undergoes melting or volatilization.
In high temperature oxidation of iron in dry air, three different oxide layers are formed on iron.
Fe2O3 is the outermost layer, FeO is the innermost and Fe3O4 is the intermediate layer.
The reactions may be written as:
4 Fe + 3O2 2 Fe2O3
3 Fe + 2O2 Fe3O4
2 Fe + O2 2FeO
The nature of the oxide film formed is very important in oxidation corrosion.
Metal + Oxygen Metal Oxide (Corrosion product)
When oxidation starts, a thin layer of oxide is formed on the metal surface and the nature of
this film decides the further action. The film may be:
(i) Stable: A stable layer is fine-grained in structure and can adhere tightly to the parent
metal surface. Such a film is protective in nature, thereby shielding the metal surface. The
oxide films on Al, Sn, Pb, Pt etc. are stable, tightly adhering and impervious in nature.
Consequently, further oxidation corrosion is prevented.
(ii) Unstable: The oxide layer formed, decomposes back into the metal and oxygen,
Metal + Oxide Metal + Oxygen
Consequently, oxidation corrosion is not possible in such a case. Thus, Ag, Au and Pt do not
undergo oxidation corrosion.
Corrosion 5.5
Fig. 4
(iii) Volatile: Here the oxide layer volatilizes as soon as it is formed. Thereby leaving the under
lying metal surface exposed for further attack. The cause’s rapid and continuous corrosion,
leading to excessive corrosion, e.g. molybolenum oxide (MoO3) is volatile.
Fig. 5
(iv) Porous: The oxide film formed is having pores or cracks. In such a case, the atmosphere
i.e., oxygen have access to the underlying surface of the metal, through the pores or cracks
of the layer, thereby the corrosion continues unobstructed, till the entire metal is completely
converted into its oxide.
Fig. 6
The formation of anodic and cathodic region on the surface of the metal can be explained due
to the following factors:
(a) Non-uniform or rough surface of metal.
(b) Presence of impurities in the bulk of metal.
(c) Difference in oxygen concentration along the metal surface.
5.6 Engineering Chemistry
2. Corrosion by other gases: Gases like CO2, SO2, Cl2, H2S, F2 etc. cause corrosion of metals.
The degree of attack depends upon the formation of protective or nonprotective films on the metal
surface.
For example, the AgCl layer formed from the attack decreases and protects the silver metal from
further attack. In the petroleum industry steel is attacked by H2S gas at high temperature and the
FeS scale is formed interfers with the normal operation of the industry. The silver metal also gets
tarnished by H2S gas in the presence of moisture.
Fe + H2S FeS + H2
3. Liquid metal corrosion: This type of corrosion is due to the chemical action of flowing liquid
metal at high temperature on solid metal or alloy. It occurs in devices used for nuclear power. The
corrosion involves dissolution of a solid metal or internal penetration of the liquid metal into solid
metal.
4. Cause of corrosion: Most metals in nature exist as compounds such as sulphides, sulphates,
oxides etc. because these compounds represent their thermodynamically stable state. The metals are
extracted from these ores and unless the nature of the metal is substantially changed, the metal will
have a natural tendency to revert back to its natural thermodynamically stable state. However, metal
existing in an elemental state naturally have excellent corrosion resistance.
3. TYPES OF CORROSION
There are a number of methods of classifying corrosion but no universally accepted terminology is
in use. In broad sense, corrosion can be classified into following types:
The use of Copper pipes in conjunction with iron pipes in water distribution systems has been
the cause of galvanic corrosion. Larger the potential difference between the two metals, greater will
be the galvanic corrosion. Galvanic corrosion is also known as differential metal corrosion.
Fig. 9
Fig. 10 Waterline corrosion occurs just underneath the meniscus and the water level
This type of corrosion is accelerated by the deposition of dirt, debris, etc. These materials
restrict the supply of oxygen underneath the covered portion which become anodic and hence suffers
corrosion. Crevice corrosion can also be attributed to concentration cell effect.
of convene stress such as rolling. These areas become very reactive chemically and may be attacked
even by trace of corrosion environment, resulting in the formation of cracks.
Stress corrosion is usually unpredictable in nature. Even after a few years of trouble free service,
a metal can suddenly crack without any warming or previous deformation.
It may be noted that stress corrosion is due to the combined effect of static tensile stress and the
corrosive environment. Moreover, stress cracking takes place only in highly selective environment i.e.
different environments are required for different alloys for stress cracking. For example, corrosion
cracking of brass takes place only in presence of traces of ammonia of amines.
Some examples of stress corrosion are:
(a) Season Cracking: Season cracking due to stress corrosion is commonly observed in cold-
drawn brass articles. In the presence of alloying atmosphere containing traces of ammonia
or amines brass show Intergranular cracking. Fissures propagate and cause cracking in the
presence of high tensile stress.
(b) Caustic Embrittlement of Mild Steel: When Mild Steel is exposed to alkaline solutions at
high temperature and stresses, it causes failure of the material due to caustic embrittlement.
This type of corrosion mainly occurs in boilers or heat transfer equipment. Boiler water
contains Na2CO3 which undergoes decomposition under high pressure.
Na2CO3 + H2O 2NaOH + CO2
The alkaline water flows into the hair cracks present at the inner surface of the boiler due
to capillary action. Eventually the concentration of NaOH in the cracks crevices increase.
The boiler material is thus under the two different concentrations of the electrolyte, higher
inside the crack, and dilute outside.
Thus a concentration cell sets in:
Anode Cathode
Fe | Conc. NaOH || Dil. NaOH | Fe
The iron of the main body containing dilute NaOH behaves as cathode whereas the iron of
the cracks and crevices surrounded by Conc. NaOH behaves as anode. The sodium ferroate
so formed decomposes as,
Corrosion 5.11
3.6 Erosion Corrosion
Erosion Corrosion is the result of relative movement between a corrosive fluid and metal surface.
This results in the development of differential cells at these points leading to corrosion. Metals that
are soft and are readily damaged due to mechanical abrasion are quite susceptible to this type of
corrosion.
Many types of corrosive medium moving with high velocities can cause erosion corrosion. For
example, hot gases may oxidize a metal and then at high velocity blow off a protective scale around
the metal.
Similarly, gray cast iron also shows the effects of selective leaching in mild environments. After
selective leaching of the iron, graphite network is left behind. Similarly white iron has no free carbon
and is not subjected to graphitization.
3.9 Hydrogen Damage
Hydrogen damage is a general term which refers to mechanical damage of a metal caused by the
presence of or interaction with hydrogen. It can be classified into the following types:
(a) Hydrogen Blistering: It is caused by penetration of hydrogen into metal. Surface bulges
appear on the surface of the metal due to hydrogen busting.
(b) Hydrogen Embrittlement: Hydrogen damage embrittlement is also caused by penetration
of hydrogen into a metal leading to loss of ductility and tensile strength.
(c) Hydrogen Attack: It refers to the interaction between hydrogen and a component of an
alloy at high temperature. For example, the oxygen containing copper gets disintegrated in
presence of hydrogen.
4. CORROSION CONTROL
Corrosion control methods may be classified into the following categories:
(ii) Protection from marine corrosion of cables, ship hulls, etc. offshore drilling platforms and
water heaters.
4.3 Protective Coatings
Protective coatings are used to isolate the anode and cathode regions. For applying any type of coating,
the metal surface is prepared in the following manner: (a) grease and other surface contamination
is removed; (b) oxide scales, rust and corrosion products are removed; (c) etching treatment to aid
in proper adhesion or buffing or polishing is given. Protective coatings are of the following two
types:
5. Corrosion Inhibitors
Inhibitors are the substances which when added to the electrolyte solution reduce the rate of corrosion.
These are of two major classes:
1. Inorganic inhibitors: Inorganic inhibitors such as silicates, chromates, borates, etc. suppress
the rate of corrosion by acting on the anode. Alkaline sodium nitrites alone or in combination
with other inhibitors such as phosphate have been used to control the corrosion of tankers
and pipelines. Sodium benzoate has been used as an inhibitor for mild steel and in preventing
corrosion in cooling system such as automobile radiators. A mixture containing 0.1% NaNO2
and 1.5% sodium benzoate has been used as inhibitors in anti-freeze solutions. Lime acts
as a cathodic inhibitor by precipitating CaCO3 in water containing temporary hardness or
dissolved CO2. Colloidal particles of CaCO3 having positive charge are attracted to the
cathodic areas and get deposited there, thus, reducing the corrosion current.
2. Organic inhibitors: Organic inhibitors act by different mechanisms e.g., organic colloidal
inhibitors form protective layers on the metal surface by adsorption. Surface active reagents
known as surfactant, containing polar groups promote spreading and oriented adhesion to
the surface, thus, forming a protective film. Organic bases e.g., amines, pyridines, quinoline
and their derivatives contain hydrophobic group or radicals. These positively charged cationic
groups attack themselves to the cathodic areas through the nitrogen and provide inhibition.
The efficiency of inhibition depends upon size and number of the alkyl groups. E.g., primary
amyl amine (C5H11NH2) has been found to be more effective as inhibitor than primary ethyl
amine (C2H5NH2).
High molecular weight amines derived from rosin have been used as corrosion inhibitors. The
product obtained by rosin amine and pentachlorophenol was used in castings for underground
pipelines to protect them from corrosion by soil bacteria. Organic inhibitors such as soluble
salts of rosin e.g., stearate or naphthenate have been used as inhibitors in the various
metal cleaning operations like acid pickling of metals, cleaning of boilers, condensers, heat
Corrosion 5.17
exchangers, chemical equipment, pipelines, etc., to prevent undue and excess corrosion of the
metal while removing rust, scales and deposits.
Some vapour phase inhibitors (VPI) such as dicyclohexylammonium nitrite and cyclohexylamine
carbonate are used to inhibit the corrosion in storing aircraft engines as well as during storage,
packing, shipping, etc.
5.1 Passivity
It is defined as a phenomenon in which metal or an alloy exhibits a much higher corrosion resistance
than its position in the electrochemical series would indicate. The passivated metal can rendered
active by a change in the environmental conditions.
Metals which exhibit passivity include iron, chromium, nickel, titanium and alloys of these
metals. However, it should be emphasized that a metal which is passive in one environment may not
necessarily be so in a different environment because passivity results from a continuous reaction at
a very slow rate.
The passivation is not static in nature but is quite stable under certain environmental conditions.
Such as oxidizing conditions, e.g., the metals or alloys of Al, Cr, Ti etc., exhibit high corrosion
resistance in oxidizing environments, but are quite unstable in reducing environments. The passivity
of some metals are in the order of:
The presence of oxide films may affect the initial rate of attack by acids. Iron dissolves readily in
a very dilute HNO3, but as the concentration of acid is raised, its oxidizing power rises and a point
is reached at which the acid directly oxidizes the metal to its oxide. The layer of oxide formed on
the surface makes the iron passive. The passive iron has high, positive electrode potential and is not
easily corroded. The oxide film is easily damaged by scratching, heating or because of the presence
of chloride ions. Under such conditions, the metal continues to corrode. However, some passive films
are not easily damaged as that of iron, and even if there are cracks in the film, these films can be
readily heal themselves in an oxidizing atmosphere, for example stainless steel composed of 18%Ni.
The highly protective coating of Cr2O3 is believed to be responsible for the corrosion resistance.
Other examples of increased resistance to oxidation by alloying are silicon containing cast iron and
silicon containing molybdenum.
It is the oxide film that is responsible for the occurrence of passivity. But in some cases films
other than those of oxides are responsible for the passivity. Therefore, any protective films other than
those of oxides are responsible for the passivity. Therefore, any protective film produced during the
chemical reaction is sufficient to cause passivity and thus the theory is termed as protective layer
theory.
The oxide film is extremely thin, transparent and invisible so long as it is in contact with the
bright reflecting metallic surface. During the formation, it is assumed that oxygen reacts extremely
fast with the metal and the rate of film growth is inversely proportional to the thickness of the film.
Therefore,
dy/dt = k/y
where, y = film thickness, t = time and k = constant.
On integration, we get
Y 2 = 2kt + I
Where I = integration constant.
Experimentally it is observed that the rate of film growth does not obey the above equation. In
other words the film is not necessarily uniform throughout its thickness.
solved Questions
1. Define Corrosion?
Ans. Any process of deterioration and consequent loss of solid metallic materials through an
unwanted chemical or electrochemical attack by its environment, starting at its surface is
called corrosion.
2. What is rust?
Ans. Hydrated feric Oxide (Fe2O3) with Fe(OH)3- brown rust, mixed ferrous & ferric oxides.
Fe3O4 FeO.Fe2O3- black rust.
3. Formation of which types of metal oxide film cause rapid and continuous corrosion?
Ans. Volatile oxide film and porous oxide film.
4. What is electro chemical corrosion?
Ans. This type of corrosion occurs due to the existence of separate ‘anodic’ and ‘cathodic’ areas
between which current flows through the conducting solution at anodic area oxidation occur
and anodic part of metal is deployed.
5. What is galvanic corrosion?
Ans. When two dissimilar metals are electrically connected and exposed to an electrolyte the
metal highest in electro chemical series undergoes corrosion.
6. Iron corrodes faster than aluminium, even though iron is placed below aluminium in the
electrical series. why?
Ans. This is because aluminium forms a nonporous, thin, tightly adhering protective oxide film
(Al2O3) on its surface and this film does not permit corrosion to occurs.
7. Wire mesh corrodes fastest at the joints. why?
Ans. The joints of wire mesh is stressed so these becomes anodic w.r.t. unjoined wires. At these
anodic parts, oxidation takes place and the metal is corroded fast, while the cathodic part
remain unaffected.
Corrosion 5.19
UNsolved Questions
1. What is corrosion of metals? Explain the basic reason of metallic corrosion.
2. Discuss briefly the consequences of corrosion.
3. Explain electrochemical theory of corrosion.
4. Differentiate chemical and electrochemical corrosion with suitable examples.
5. Discuss factors affecting rate of corrosion.
6. Explain briefly various factors influencing corrosion.
5.20 Engineering Chemistry
7. Silver and copper metals do not undergo much corrosion like iron in moist atmosphere.
Explain.
8. Explain methods for prevention of corrosions.
9. Discuss corrosion inhibitors.
10. How are metals protected against corrosion by modifying the environment?
11. How will you protect an underground pipe line from corrosion by sacrificial anodic and
impressed current cathodic protection methods?
12. What are cathodic and anodic protection methods for controlling corrosion?
13. Distinguish between anodic and cathodic coating.
14. What is meant by dry corrosion?
15. Explain passivity and its significance.
16. Discuss in detail the nature of corroding environment.
17. Discuss briefly
(i) Galvanic corrosion
(ii) Pitting corrosion
(iii) Crevice corrosion
(iv) Dropline corrosion.
Chapter 6
Water Treatment
“Water is one of the most abundant commodities in nature, but is also the most misused one”.
1. INTRODUCTION
One of the basic necessities of life is water. Living things exist on the earth because this is the only
planet that has the presence of water. Water is necessary for the survival of all living things be it
plant or animal life.
Water is one of the most abundant commodities in nature but is also the most misused one.
Although earth is a blue planet and 80% of its surface is covered by water, the hard fact of life is
that about 97% of it is locked in the oceans and sea which is too saline to drink and for direct use
for agricultural or industrial purposes. 2.4% is trapped in polar ice caps and giant glaciers, from
which icebergs break off and slowly melt at sea. > 1% water is used by man for various development,
industrial, agricultural, steam generation and domestic use.
Hydration
(b) Mg2SiO4 Mg2SiO4 XH2O
Olivine. Serpentine
(b) Rock forming minerals like silicates and alumino-silicates of Na, K. Ca and Fe are
attacked by CO2, producing soluble carbonates, bicarbonates and silica
K2O. Al2O3. 6SiO2 + 2H2O + CO2 Al2O3. 2SiO2. 2H2O + K2CO3 + 4SiO2
(c) Rocks containing felspar disintegrate and charge nearby river water with dissolved salts, fine
clay and silica in suspension.
Thus, water collects impurities from the ground, rocks or soil with which it comes in contact.
Contamination of water may also result from sewage or industrial wastes, either by actual contact
when these are allowed to flow into the running water, or by percolation through the ground.
4.1 Color
Color is found mostly in surface waters, although water from some shallow wells, springs and deep
wells may also be occasionally colored. The color of natural waters range from yellowish-brown to
dark brown. The colors and the materials which cause it are often objectionable in which the water
and the manufactured product come into contact, e.g., dyeing, scouring and laundering.
The color of natural waters is mainly due to the presence of dissolved or colloidally dispersed
organic matter. The measurement of color is usually made with a tint meter and, the result is expressed
in “Hazen units” or “Standard units of color”. In determining the color of water, it is the true color
as expressed in the standard units, that is of interest and not the apparent color.
It is known that solutions of potassium chloroplatinate tinted with small amounts of cobalt chloride
give colors similar to the colors of natural waters. The color produced by 1 mg/ litre (1 ppm) of
platinum (used as K2 Pt Cl6) is taken as the standard unit of color. The color determination is done
only after the removal of suspended matter by centrifugation.
The color standards are usually prepared by dissolving 1.2545 g of K2PtCl6 (containing 0.5 g of
Pt) and 1 g of crystallized cobaltious chloride (CoCl2. 6H2O) containing about 0.248 g of cobalt in
water with 100 ml of concentrated HCl and diluting to 1 liter with distilled water. This solution is
deemed to possess 500 units of color, as per the American Public Health Association’s books of
standard methods of water analysis.
Removal or reduction of color and organic matter is generally accomplished by coagulation,
settling, adsorption, filtration and sometimes super chlorination.
Disagreeable odours and tastes are objectionable for various industrial processes such as beverages,
food products. paper, pulp and textiles. Organic tastes and odours may be removed by means of
activated carbon, aeration, or aeration followed by activated carbon treatment. The removal of
inorganic odours and tastes due to H2S or iron will have to be removed by chemical methods like
oxidation, chlorination or precipitation.
4.4 Micro-organisms
Micro-organisms are more abundant in surface waters (since these come into contact with air, soil
and vegetation in which the organisms originally existed), whereas in deep well waters the bacterial
count is often low or even absent. The growth of these organisms in water used for industrial purposes
may cause serious problems and hence effective measures have to be taken to prevent the growth
6.6 Engineering Chemistry
of these organisms. Organic growths generally take place most readily in water at temperatures
ranging from 10°C–35°C. Many of them form coatings in pipe lines, thus reducing their carrying
capacity considerably. These coatings frequently break loose in large masses which may completely
block the flow through valves, pumps, nozzles and other parts of the water distribution systems. In
filters and water softeners employing granular media, the granules may become matted together by
such organic growths, thus impairing their operation by lowering their flow rates and also resulting
in channeling and overturning of the beds.
The commonest types of living organisms that are important from the point of view of treatment
are algae, fungi and bacteria, all of which often form slime with consequent fouling and corrosion. The
slime surrounding the organisms causes them to adhere to metal surfaces. This leads to difficulties
such as reduced heat transfers and tube blockages. The growth of marine organisms, particularly
mussels, in sea-water systems may lead to serious reduction in the carrying capacity of the pipe
lines.
Control of algal, fungal and bacterial growths is usually achieved by chlorination. Water soluble
solid sterilizing agents such as CuSO4, sodium pentachlorophenate and organic mercurials are used
in special circumstances. The growth of mussels may be prevented by chlorination.
Algae and other chlorophyll-containing plant need sunlight for their growth. Hence, the growth
of these organisms can be prevented by storing the water in covered reservoirs. In many industrial
plants, the organic growths are removed in the settling basin of the water-treatment plant. This is
usually done with chlorine and coagulation, settling and filtration, to remove the remains. The use of
chlorine in this way is called pre-chlorination, which is helpful in reducing the dosages of coagulant
required. In many other cases, the bulk of the organic matter is first removed by coagulation, settling
and filtration followed by chlorination. This method is called post-chlorination. Sometimes, both
pre-chlorination and post-chlorination are used.
Iron and manganese bacterial growths, known as “Crenothrix” are best prevented by removal of
these metals, followed by chlorination. In the case of sulphur water, the H2S should be first removed
followed by chlorination to remove the last traces of H2S and to kill any sulphate-reducing bacteria
which may be present.
Other metal ions like Fe +2, Mn2+ and Al3+ also react with the soap in the same fashion, thus
contributing to hardness but generally, these are present in natural waters only in traces. Further,
acids such as carbonic acid can also cause free fatty acid to separate from soap solution and thus
contribute to hardness. However, in practice, the hardness of a water sample is usually taken as a
measure of its Ca2+ and Mg2+ content.
Temporary and permanent hardness
When natural water is boiled, the bicarbonate ions present are decomposed to form carbonate ions
and carbon dioxide is set free. The hardness so precipitated was referred to as “temporary hardness”,
but this term is now referred to all the hardness associated with the bicarbonate content of the water
(i.e., that determinable by titration with acid). This is due to the fact that CaCO3 and more particularly
MgCO3 have appreciable, though slight, solubility in water.
D
Ca(HCO3 )2 CaCO3 + H20+ CO2
Mg(HCO3)2 Mg(OH)2 +H2O+CO2
(Insoluble)
The difference between the temporary and total hardness is referred to as “permanent hardness”,
since this is not removed by boiling the water. The permanent hardness is regarded as comprising
of the dissolved chlorides, sulphates and nitrates of calcium and magnesium.
Alkaline and non-alkaline hardness
The terms, temporary and permanent hardness, are gradually being replaced by the preferred terms
alkaline and non-alkaline hardness.
“Alkaline hardness” is defined as the hardness due to the bicarbonates, carbonates and hydroxides
of the hardness-producing metals. It is also called “carbonate hardness”.
In raw water, the alkaline hardness is almost always the hardness associated with the bicarbonates.
However, a treated or boiler water may also contain hardness due to small quantities of CaCO3 and
Mg (OH)2 in solution. The alkalinity as measured by titration with mineral acid using methyl orange
as indicator is equal to the sum of the concentrations of the bicarbonates, carbonate and hydroxide
expressed in equivalents. If this alkalinity is less than the total hardness also expressed in equivalents,
then the alkaline hardness is equal to the alkalinity. Conversely, when the alkalinity to methyl orange
is equal to or greater than the total hardness, the alkaline hardness is equal to the total hardness”.
The “non-alkaline hardness” is obtained by subtracting the “alkaline hardness” from the “total
hardness”. This is also known as “non-carbonate hardness”.
Estimation of hardness
Hardness is usually determined by the following two methods:
(1) Soap solution method
Soluble soaps consist of sodium or potassium salts of higher fatty acids, such as oleic acid, stearic
acid and palmitic acid. These soaps give lather with hard water only after sufficient quantity of the
soap is added to“precipitate all the hardness causing metal ions present in water”.
Ca or Mg (HCO3)2 + 2Cl7 H35COONa (2Cl7 H35COO)2 Ca or Mg + 2NaHCO3
Calcium or Sodium stearate Ca or Mg stearate
maginesium (soluble soap with (insoluble soap with
bicarbonate detergent value) no detergent value)
6.8 Engineering Chemistry
EDTA can be represented by H4Y. H4Y from is not used because of its limited solubility, again
Na4Y form also not used because of its extensive hydrolysis in solution which make the solution
highly alkaline Na2H2Y form is mostly used in analytical work since it can be obtained in high state
of purity.
NaOOCH2C CH2COONa
N–CH2–CH2–N
HOOCH2Cl CH3COOH
Ethylene diamine tetra acetic acid (EDTA) (Fig. 1) forms complexes with Ca2+ and Mg2+, as
well as with many other metal cations, in aqueous solution. These complexes have 3 general formula
given in Fig. 2 below:
CHzCOO M OOCH2 C
N CH2 CH2 N
– –
CH2COO OOCH2 C
Fig. 2 EDTA complex with a divalent metal cation, M2+. such as Ca2+, Mg2+. etc.
Thus, in a hard water sample, the total hardness can be determined by titrating the Ca2+ and Mg2+
present in an aliquot of the sample with Na2EDTA solution, using NH4Cl-NH4OH buffer solution of
pH 10 and, Eriochrome Black-T as the metal indicator. The color change at the end-point is from
wine red to blue.
Na2H2y Æ 2Na+ + H2y–
disodium EDTA solution
Water Treatment 6.9
2. Equivalents per million (epm): One equivalent per million is a unit chemical equivalent weight
of solute per million weight units of solution. In dilute solutions of density not differing very much
from unity, l epm = l milligram equivalent per litre; and in titrimetry, epm is conventionally taken
as equal to 1 ml of l N solution per litre.
Thus, 1 epm of Mg = 12 ppm of Mg
= 50 ppm of CaCO3
= 42 ppm of MgCO3
= 73 ppm Mg (HCO3)2
= 81 ppm Ca (HCO3)2
= 68 ppm CaSO4
= 47.5 ppm MgCl2
= 55.5 ppm CaCl2
= 60 ppm MgSO4 and so on.
It should be noted that for any dissolved substance, a concentration of l epm is equal to “50 ppm
as CaCO3”.
3. Grains per imperial gallon (gpg): In English system, hardness is expressed in terms of grains
( 1
)
l grain = _____ lb per gallon (10 lbs); i.e. parts per 70,000 parts per gallon is also called as degree
7,000
Clark. Thus, 9 degrees Clark means that 9 grains in terms of CaCO3 are present per gallon of water;
106
or 9 parts are present per 70,000 parts of water. On ppm scale, it means that 9 × ______ = 128.57
70,000
ppm of hardness (as CaCO3) is present in the water sample.
Inter-relationship between various units of hardness
Thus, 1 epm of Mg = 12 ppm of Mg
1 ppm. = 1 mg/l = 01° French = 0.07° Clark
= 0.07 grains per imperial gallon
= 0.0583 grains per US. gallon
= 0.02 epm as CaCO3
1° Clark = 14.3 ppm = l.43° French
= 1 grain per imperial gallon
= 0.833 grains per US. gallon
1 grain per US. gallon = 17.1 ppm = 17.1 mg/l
= 1.2 grains per imperial gallon
1° Fr = 10 ppm = 10 mg/l = 07° Clark
1° Russian = 1 part Cal 10° parts of water
1° German = 1 part Cal 105 parts water.
10 ppm as CaO or 17.9 ppm as CaCO3.
Water containing less than 150 ppm of hardness is classified generally as “good”. Those containing
150 to 300 ppm as fair and those exceeding 300 ppm as “bad” as per Bureau of Indian standard
BIS.
Alkalinity: By alkalinity of water we mean the total content of those substances in water that cause
an increased concentration of OH– ions upon dissociation or due to hydrolysis. The alkalinity of
natural waters is generally due to the presence of HCO3–, SiO32–, HSiO3– and sometimes CO32– ions
Water Treatment 6.11
and also due to the presence of salts of some weak organic acids, known as humates, that bind H +
ions as a result of hydrolysis, thereby increasing the concentration of OH– ions. In addition to the
above, the alkalinity of boiler water is also conditioned by the presence of PO43– and OH– ions. Also,
the presence of salts of weak acids such as silicates and borates induces buffer capacity in water
and resists the lowering of pH. Surface waters containing algae and also water treated by lime-soda
process may contain considerable quantities of alkalinity due to CO32– and OH–.
Depending on the anion that is present in water (HCO3–, CO32– or OH–), alkalinity is classified
respectively as bicarbonate alkalinity, carbonate alkalinity or hydroxide alkalinity. The maximum
contaminant level for alkalinity is 200 ppm for domestic purpose as per BIS.
Highly alkaline waters may lead to caustic embrittlement and also may cause deposition of
precipitates and sludge’s in boiler tubes and pipes.
With respect to the constituents causing alkalinity in natural waters, the following situations may
arise:
l. Hydroxides only
2. Carbonates only
3. Bicarbonates only
4. Hydroxides and carbonates
5. Carbonates and bicarbonates
(Notes: The possibility of hydroxides and bicarbonates existing together is ruled out because of the
fact that they combine with each other as follows forming the carbonates:
OH– + HCO3– = CO3– + H2O
The types and extent of alkalinity present in a water sample may be conveniently determined by
titrating an aliquot of the sample with a standard acid to phenolphthalein end-point, P, and continuing
the titration to methyl orange end-point M. The reactions taking place may be represented by the
following equations:
OH– + H+ H 2O ...(l)
– + –
CO3 + H HCO3 ...(2)
HCO3– + H+ H2CO3 H2O + CO2 ...(3)
The volume of acid run-down upto phenolphthalein end-point P corresponds to the completion
of equations (1) and (2) given above, while the volume of acid run-down after P corresponds to
the completion of equation (3). The total amount of acid used from beginning of the experiment,
i.e., the methyl orange end-point M, corresponds to the total alkalinity present which represents the
completion of reactions (1) to (3).
The results may be summarized in the following Table 2, from which the amounts of hydroxides,
carbonates and bicarbonates present in the water sample may be computed:
Table 2
Alkalinity is generally expressed as parts per million (ppm) in terms of CaCO3. 1000 ml of N/50
acid solution a 1000 mg of CaCO3. Hence
Vol.of N/ 50 acid × 1000
Alkalinity = ____________________________________
Vol.of sample taken for titration mg or ppm
On the basis of the analysis of water with respect of alkalinity and total hardness, the amounts
of carbonate hardness (temporary hardness or alkaline hardness) and non-carbonate hardness (non-
alkaline hardness or permanent hardness) present in the water can be determined as follows:
1. If the methyl orange alkalinity of the water equals or exceeds the total hardness, all the
hardness is present as carbonate hardness.
2. If the methyl orange alkalinity of water is less than the total hardness, the carbonate hardness
equals the alkalinity.
3. The non-carbonate hardness, under conditions in (2) above, is equal to the total hardness
minus the methyl organe alkalinity.
Further, on the basis of hardness and alkalinity, natural waters can be subdivided into two groups:
Non-alkaline and alkaline. If the hardness is greater than alkalinity, the water is called non-alkaline.
If the hardness of the water is lesser than alkalinity, the water is characterised as alkaline. Non-
alkaline waters are more frequently encountered in nature, which are characterized by different kinds
of hardness as follows:
Ht = (Hc+Hnc) = (HCa+HMg)
where Ht = total hardness,
Hc = carbonate hardness
Hnc = non-carbonate hardness,
HCa = calcium hardness and
HMg = magnesium hardness.
Chlorides
Chlorides are present in water generally as NaCl, MgCl2 and CaCl2. Although chlorides are not
considered as harmful as such, their concentrations over 250 mg/L impart peculiar taste to the water
which is objectionable or unacceptable for drinking purposes for most people from aesthetic point
of view. Hence the secondary standard for chlorides is 250 mg/L. Further, presence of unusually
high concentrations of chloride in water generally indicates pollution from domestic sewage or from
industrial wastewaters, presence of chlorides is also undesirable in boiler feed water. Salts like MgCl2
may undergo hydrolysis under the high pressure and temperature prevailing in the boiler, generating
hydrochloric acid which causes corrosion of boiler parts.
Sulphates
Sulphates are among the major anions present in natural water. When sulphates are present in excessive
amounts in drinking water, they may produce a laxative or cathartic effect on the people consuming
such water. The secondary maximum contaminant level (SMCL) for sulphates is 250 mg/L.
Water Treatment 6.13
Nitrates
Excessive concentrations of nitrates are objectionable particularly for infants. The maximum
contaminant level (MCL) for nitrates is 10 mg/L. In agricultural regions, ground water can have
significant concentrations of nitrates from unused fertilizer leaching into the underlying aquifers.
Surface waters can be polluted by nitrates both from discharge of municipal wastewater and from
drainage from agricultural lands. Ingestion of excessive nitrates in drinking water by infants causes
a disease known as “methemoglobinemia” (infant cyanosis or blue baby syndrome). In the intestines
of infants (particularly those below 6 months of age), nitrates can be reduced to nitrites, which are
absorbed into the blood, oxidizing the iron present in the blood, thereby resulting in cyanosis which
causes a blue color to the baby. That is why, this condition is known as “Blue-baby syndrome”. Infant
methemoglobinemia can be readily diagnosed by medical doctors and is treated readily by injecting
methylene blue into the infant’s blood.
Nitrates can be effectively removed from water with the help of strongly basic anion exchange
resins. However, high operating cost and the disposal of huge quantity of waste brine from regeneration
of the resin pose major limitations for this treatment process.
Fluorides
Flouride is found in groundwater as a result of dissolution from geologic formations. It is particularly
found in ground waters that come into contact with fluoride containing minerals such as fluorspar
(CaF2), fluorapatite [Ca10F2 (PO4) 6], cryolite (Na3AIF6) and igneous rocks containing fluosilicates.
Surface waters generally contain much smaller concentrations of fluoride, unless they are
contaminated otherwise. Water pollution by fluorides may be caused by the contaminated domestic
sewage and the run-off from agricultural lands where phosphatic fertilizers have been used. Phosphatic
fertilizers may contain 0.5 to 4% of fluorine by weight as an impurity.
The fluoride concentration found in some water samples is 1.5 to 6 mg/L, and in extreme cases,
it may be as high as 16 to 36 mg/L. Unsightly fluorosis may be caused when the fluoride level in
drinking water exceeds 4 mg/L.
Optimum fluoride concentrations prescribed in public water supplies generally are in the range
of 0.7 to 1.2 mg/L, depending on the annual average of maximum daily air temperature of the place,
on which the consumption of the water by the people depends. Beneficial health effects have been
observed where the fluoride levels are optimum. However, too low or too high concentrations of
fluoride in drinking ‘water are problematic, and such situations may have to be tackled by fluoridation
(addition of fluoride) or defluoridation (removal of fluoride) respectively.
Absence or low concentration of fluoride in drinking water causes a high incidence of dental
caries, particularly in children. On the other hand, excessive concentration of fluoride in drinking
water causes “fluorosis” which is manifested in mottling of teeth, discoloration and at times, chipping
of teeth.
Ca (HCO3)2 while bringing the pH up to about 7.2. Such filters are widely used in the household
field of water treatment and to some extent in industry also.
(ii) Oxygen: The solubility of pure oxygen at 32°F and atmospheric pressure is 48.89 ml per litre;
while under the same conditions, the solubility of nitrogen is 23.54 ml per litre. Consequently, when
air is dissolved in water, the two main components, namely N2 and O2, exist in different proportions
in solution than that existing in the atmosphere.
According to Henry’s law, the solubility of a gas is proportional to the absolute pressure. Thus, if
pressure is increased, the amount of air or O2, which can be held in solution at a given temperature,
is also increased proportionally.
Dissolved oxygen is very corrosive to metals like iron, steel, galvanized iron and brass, which
are widely used for making vessels for conducting and holding water. Low pH values and elevated
temperatures accelerate the rate of this corrosion.
Inhibition or reduction of dissolved oxygen corrosion could be achieved by deaeration of the
boiler feed water, vacuum deaeration, sodium sulphite treatment, treatment with sodium silicate plus
caustic soda, chromate treatment and by cathodic protection.
Dissolve oxygen is needed for living organisms to maintain their biological process. As per BIS
domestic water must have 4-6 ppm dissolve oxygen and 0.01-0.05 ppm for boiler water.
(iii) Nitrogen: Nitrogen is a rather inert gas which has no corrosive effects on metals. In analyzing
waters, nitrogen is practically never determined, since it is inert and is relatively unimportant as far
as water treatment is concerned.
(iv) Hydrogen sulphide: Waters which contain sulphides are known as “sulphur waters” which are
characterized by offensive odours and their marked corrosiveness. Most sulphur waters are ground
waters. H2S, like CO2, when dissolved in water is feebly ionized. Oxidation of sulphides by dissolved
oxygen is apparently a rather slow process. Chlorine may also be used to oxidize H2S, but the process
is rather expensive on raw “sulphur waters” because it takes eight atoms of chlorine to oxidize one
molecule of H2S to form a sulphate.
H2S + 4Cl2+ 4H2O H2SO4 + 8HCI
(v) Methane: In general, well waters containing methane have been found in the glacial drift and
in oil and gas well areas. While methane itself is apparently unobjectionable in drinking water, it
would be advisable to aerate the water for either industrial or household use, so as to eliminate fire
and explosion hazard.
4.8 Oxidability
Oxidability to some extent is a measure of the contamination of water by organic substances. It is
generally expressed in milligrams of oxygen required to oxidize under given conditions, the organic
substances present in 1 kg of water. However, it should be noted that oxidability does not represent
the total content of organic substances in water, since under the given experimental conditions used
for the determination of oxidability, complete oxidation of the organic substances does not take place.
Oxidability can also be expressed by the amount of KMnO4 (mg/kg) spent to oxidize the organic
substances.
5.1 Sedimentation
Sedimentation is a process of removing relatively large particles (suspended solids) into large
reservoirs of settlement tanks in which it is left for a few days or even weeks, where the suspended
impurities partially sink to the bottom. The principle involved is to slow down the flow of water so
that substances held up by the turbulence of fast moving water can fall gravitationally to the bottom
of the tank when water flow is stilled. Periodically the accumulations of the debris are to be scraped
away. In order to remove floating impurities screens of various kinds (eg., Bar screen, Band and drum
screens and microstrainers) are employed. These screens also must be continuously cleaned.
The rate of settling in still water at 10°C is known as the hydraulic settling value of a particle
and is generally expressed in millimeters/second.
During sedimentation, solid particles settle by gravity on the bottom of a settling tank in which
the water being clarified is at rest or in slow horizontal or upward motion. The velocity with which
a particle in water will fall under the action of gravity depends upon (i) the horizontal flow velocity
of the water, (ii) the size of the particle, (iii) the specific gravity of the particles (iv) the shape of
the particle and (v) the temperature of the water. Accordingly several formulae have been given to
calculate the velocity of falling spherical particles in slowly moving water on the basis of which
several types of sedimentation tanks have been designed. The sedimentation tanks commonly used
are of horizontal flow rectangular type and circular shaped upward flow type.
Sedimentation takes a long time, requires large-capacity settling tanks and cannot ensure complete
removal of coarse-dispersed impurities from water. Plain sedimentation usually removes only 70 to
75% of the suspended matter.
Water Treatment 6.17
5.2 Coagulation
Finely divided silica, clay and organic matter do not settle down easily and hence cannot be removed
by simple sedimentation. Most of these are in colloidal form (e.g., sols, gels or emulsions) and are
generally negatively charged and hence do not coalesce because of mutual repulsion. Such impurities
are generally removed by chemically assisted sedimentation, in which certain chemicals are added
which produce ions of right electrical charge that neutralize the oppositely charged calloidal particles
and bring about their coalescence. This process is called coagulation. This permits the particles to
aggregate together until a denser particle is formed which falls through still water at a reasonable
rate and is called flocculation.
Aluminium sulphate is the most common coagulating agent used for removing clay particles
and is generally called filter alum. Other coagulants which also find application in water treatment
include ferric sulphate, ferrous sulphate (copperas) chlorinated copperas, alum, ammonia alum or
potash alum and sodium aluminate.
Aluminium sulphate, when added to natural waters, hydrolyses to form colloidal aluminium
hydroxide and an equivalent quantity of sulphuric acid as follows:
Al2 (SO4)3+6H2O 2Al(OH)3+3H2SO4
The Al(OH)3 so formed acts as a floc or coagulant, which has an enormous surface area per
unit volume and removes the finely divided and colloidal impurities by neutralizing the charge on
them as well as by other mechanisms like adsorption and mechanical entrainment. Thus the smaller
particles join together to form denser particles which settle down to the bottom. Some bacteria and
color associated with these particles also get removed simultaneously. In order to render the Al(OH)3
filterable and also in order to neutralize the H2SO4 liberated to permit the hydrolysis reaction to
completion, some alkali will have to be added if the water is not sufficiently alkaline. The reaction
taking place in alkaline waters may be represented as follows:
Al2 (SO4)3 + 3Ca(HCO3)2 2Al(OH)3 + 3CaSO4 + 6CO2
With water having a little or no natural alkalinity (e.g., moorland waters) an alkali such as calcium
hydroxide or sodium carbonate is added; the latter is more commonly used as it does not increase
the hardness of the water.
Al2 (SO4)+3Na2CO3+3H2O 2Al(OH)3 + 3Na2SO4 + 3CO2
For treatment of acidic waters, sodium aluminate can be used as a source of Al(OH)3 and it is
often used in conjunction with aluminium sulphate. The reactions taking place may be represented
as under:
Na AIO2 + 2H2O NaOH + Al(OH)3,
Al2 (SO4)3, + 6Na AlO2 + 12H2O 8Al(OH)3 + 3Na2SO4
Thus the alkalinity due to aluminate is neutralized by the acidity of the sulphate and Al(OH)3
is thus precipitated from both the reagents. for treatment of alkaline water FeSO4 can be used
FeSO4 + H2O Fe(OH)2 + H2SO4
Fe(OH)2 + 1/2 O2 Fe(OH)3
In order to increase the efficiency of the coagulation process, coagulant aids such as lime, Fuller’s
earth, bentonite clay and polyelectrolytes are also added.
6.18 Engineering Chemistry
The coagulants are generally added in solution form to the water with the help of mechanical
flocculators provided with slow-moving rotating baffles or stationary baffles turning the flow of
water: thus ensuring a gentle contact with the water and the reagents.
After any sedimentation process, especially after that utilizing a chemical flocculent, there will
be a substantial reduction in the bacterial count in the water. In addition, many coagulants release
oxygen to the water as the chemical transformations take place. This oxygen helps in destroying
some bacteria, in breaking up some organic compounds and also in partial removal of color and
taste producing organisms present in water. Thus the process of ‘x coagulation, flocculation and
sedimentation has many beneficial results and is one of the most important processes of purification
of water.
Coagulation and settling equipment should be so designed that quick and thorough mixing of the
coagulant and raw water should be achieved so that the coagulant dosage required is minimized. For
this purpose, mechanical type mixers and baffled mixing troughs are widely used. Modern types of
coagulation and settling equipment include the floc-forrner type and the sludge-blanket type.
The floc-former type coagulation and settling equipment (Fig. 3) consists of (i) a flash mixer
where the coagulant is quickly and efficiently mixed with the raw water with the help of a rotating
stirrer settling (ii) rolling mix chambers where only a basin gentle mixing of the gelatinous precipitate
formed to aid in the even distribution and formation of a large-particled, easily settled-floc, and (iii)
settling basins where the floc is allowed to settle and the sludge thus formed is removed continuously
or intermittently.
The sludge-blanket type of water treatment equipment came into extensive use for coagulation
and settling well as water. It majorly differs from the floc former type of equipment in that it filters.
All of the coagulated water upwardly through a suspended sludge blanket instead of merely dropping
it to the bottom by gravity. This prolonged intimate contact with the floc helps in fully utilizing
its absorbing capacity which effects savings in the amount of coagulant or other adsorbents (such
as activated carbon used for removing colors and odours) required. The equipment is made in both
vertical and horizontal designs.
For certain industrial uses where turbidities upto 10 ppm are permissible and where the raw
water is turbid but not highly colored the effluent from the sludge-blanket type of coagulation and
settling equipment may be used directly. However, if color removal and a greater degree of clarity
are required, filtration is also necessary.
5.3 Filtration
Filtration is a process of clarification of water by passing the water through a porous material, which
is capable of retaining coarse impurities on its surface and in the pores. The porous material used is
called the filtering medium and the equipment used for filtration is known as a filter.
Filtration of water takes place due to the difference between the pressures at the of the bed of
the filtering material and that underneath it. The difference in the two pressures, Dh is called the
pressure drop through the filtering medium, but also the drop in pressure-through the filter proper
(in the pipelines, distribution devices, etc.). This pressure drop through the filtering bed depends on
the rate of filtration, height of the filtering bed, diameter (size) of the grains of the filtering material
and the extent of its contamination by the trapped impurities. Greater the numerical values of these
factors (excepting grain size), greater will be the pressure drop.
When contamination or a filter cannot be tolerated any longer, it is taken out or service tor
subsequent washing, in the course of which the impurities trapped in the filtering bed are washed out.
Then the filter can be pressed into service again. The common materials used for the filtering medium
are quartz sand (grain size 0.5 – 1.0 mm) containing not more than 96% SiO2, crushed anthracite
(piece size 0.8 – 1.5 mm) and porous clay (piece size 0.8 – 1.5 mm). It should be remembered that
when quartz sand filters are used with alkaline water, the filtrate (filtered water) gets enriched with
silicic acid (due to the solubility of quartz sand in alkaline water).
Slow sand filtration
Water for domestic use may be filtered through large area of finely graded sand beds at a slow rate
(about 2 gal/sq. ft./hour). The rate of filtration slowly diminishes due to the accumulation of sediment
in the capillaries of the filter bed, and finally the rate becomes so slow that the bed must be cleaned.
Cleaning is usually done by scarping the surface of the sand bed, or excavating, washing, and then
relaying the entire filtering medium.
Slow gravity filters are not capable of removing colloidal impurities. These can be filtered out
only when the water has been chemically treated (such as alum treatment) and the slow sand filters
cannot deal with the gelatinous type of precipitates which are produced in such treatments. Typical
equipment for Municipal water treatment with coagulation, settling and filtration tanks is shown in
Fig. 4.
Rapid-gravity filtration
Rapid gravity filters are capable of producing potable waters at flow-rates as high as 100 gal/sq. ft./
hour. This is achieved by using carefully graded quartz sand and collecting the filtrate as evenly as
6.20 Engineering Chemistry
water
Fine Sand
Coarse Sand
Water Fine Gravel
inlet Water
Course Gravel
outlet
Sludge Filtration Tank
outlet Chlorination
Coagulation cum
Setting Tank
Fig. 4 Municipal water treatment with coagulation, setting and filtration tanks
possible over the entire bottom area of the sand bed which avoids undesirable channeling. The sand
bed may be cleaned either by agitation with compressed air or in small units mechanically. This is
followed by a flush back with clean water to wash away the accumulated impurities.
Rapid Gravity filtration has the following advantages
(1) The filter bed and the quality of the filtrate can be easily inspected (2) The filter is unaffected
by pressure variations on either the inflow or draw-off sides, and (3) Large reinforced concrete filters
can be constructed at relatively low cost.
Rapid pressure filtration
Pressure filters are much more widely used than gravity filters, particularly in industrial installations.
Rapid pressure filters are used preferentially where filtration is to be effected in a rising main without
breaking the hydraulic head, or where water from an elevated source can be passed through the
filter and delivered in storage. The operation and cleaning of these filters are more or less similar
to gravity sand filters. Filtration rates are of the order of 80 to > 200 gallons/sq. ft./hour.
Pressure filters are manufactured in vertical and horizontal types. These filters consist of
cylindrical steel shells fitted with dashed heads, containing a layer of a granular filter medium
(sand or anthrafilt) supported by graded gravel (or anthrafilt), and is equipped with the required
accessories e.g., piping, under drains, valves, etc., for carrying out the cycle of operations, viz.,
filtration, backwashing and filtering to waste. Filter installations may consist of one or more units
depending upon the requirements.
Several types and designs of mechanical filters are employed (Fig. 5). The most commonly
used clarifying filter is the single-flow, single-bed, closed pressure filter, which is quite simple in
construction (Fig. 5(a)). The filtering medium is filled upto a certain volume “a’’ of the filter, on
top of which water is filled (which is known as the water cushion). Closed pressure filters operate
under the pressure created by the pumps delivering the water to be clarified.
In order to increase the rate of filtration, to improve the quality of clarified water and to raise the
mud capacity filtering material, single-flow filters are often charged with two filtering materials of
different bulk mass and grain size, as for instance, crushed anthracite (0.8 to 1.6 mm grain size) and
quartz sand (0.5 to 1.0 mm grain size). The sand, being a denser material, is arranged underneath
the anthracite filtering bed. Two-bed filters of this kind are often used in practice (Fig. 5(f)).
In open-type mechanical filters (Fig. 5(b)) which are widely used in purification and treatment
of drinking water; filtration takes place due to the pressure exerted by the column of water, h in
Water Treatment 6.21
the filter. However, the relatively small head, it restricts the use of these filters at increased filtering
rates. Horizontal closed pressure filters (Fig. 5(c)) are provided with larger filtering surface and hence
have larger throughout per filter. However, they require more floor space when installed indoor and
cumbersome to operate. Multifold mechanical filters (Fig. 5(e)) are free from such limitations. These
are filled completely with filtering material, inside which are fitted the draining and distributing
devices. They permit the water to be passed in several flows (three in the illustration given) and
ensuring increased output of a filter as many times. In radial flow filter (Fig. 5 (g)) the filtering
material is charged into the annuus formed between the filter shell (wall) and an internal tube. The
water treated is delivered into the central tube which distributes it through the filtering material
height wise. Water is passed in radial flows through the filtering material.
The clarifying filters, with a granular filtering bed discussed above, contain a high bed of
coarse-grained filtering material and a small filtering surface. In contrast to these filters, tubular-
element precoat type filters (Fig. 5(h)) contain a large filtering surface, thin filtering bed (5 to 10
mm thick), and mainly use powders as filtering media (e.g., powdery or fibrous cellulose, ionite and
perlite powders). Precoat-type ionite-exchanger filters are capable of operating at high temperatures
(100-110°C), and hence can be used to purify hot condensate and water. These filters are considered
promising for service in high-capacity steam-generator-turbine units operated at nuclear power plants.
A precoat type filter with powdery perlite (porous SiO2) as filtering material is suitable for fine
clarification of water. A mixture of powdery perlite and activated carbon is used for removing oil
from condensate.
Clarification for domestic and industrial purposes is often achieved by a combination of two to
four of the different processes as listed below:
(a) Sedimentation (b) Filtration (c) Coagulation + filtration (d) Coagulation + settling (e) Coagulation
+ settling + filtration (f) Sedimentation + coagulation + settling + filtration (g) Chlorination and (h)
Special filters (e.g., activated-carbon for removing taste and odour; manganese zeolite for removing
Fe and Mn; and Neutralizing filters such as graded calcite for removing CO2).
The organisms which should be eliminated by disinfection are divergent in character. They include
(a) the enteric bacteria belonging to Salmonella, Shigella and Vibrio groups (b) the intestinal protozoa
such as Entamoeba histolytica (c) some types of worms such as Schistosomes (d) Viruses such as
those of infectious hepatitis and (e) Coliform organisms which indicate water pollution, though not
pathogentic. Coliforms and enteric bacteria can be easily destroyed while viruses and cysts of E.
histolytica are resistant to disinfection.
Chlorine is the most common sterilizing agent in water treatment. It is capable of removing B.
Coli and substantially reducing other bacteria. Chlorine may be added in the form of bleaching
powder, or directly as a gas or in the form of concentrated solution in water. Whatever may be the
method employed, the treatment should give accurate dosage, good distribution and sufficient time
of contact (~ 30 minutes) so as to ensure effective sterilization.
CaOCl2 + H2O Ca (OH)2 + Cl2
C2 + H 2 O HOCl + HCl
HOCl [O] + HCl
Hypochlorous Nascent
Acid Oxygen
The nascent oxygen so liberated destroys the germs and bacteria by oxidation. The chlorine itself,
the hypochlorous acid and other chlorine compounds are also believed to have powerful germicidal
properties. The OCl– ions are capable of rupturing the cell membranes of the disease producing
microbes.
Bleaching powder has the limitations of being unstable during storage and also it increases the
calcium content of water rendering it more hard. Chlorine as a sterilizing agent has the advantages
of being economical, efficient, limited space requirement and convenience. Further, it does not
introduce any other impurities in the water. Both chlorine as well as bleaching power when used in
excess produce disagreeable odour in the water. Too much excess may cause irritation to the mucous
membranes. The unpleasant taste of this excess chlorine can be removed by treatment with ammonia,
which reacts with chlorine to form the tasteless compound chloramine (NH.CI). Thus, the ammonia-
chlorine treatment (chloramine process) is particularly useful, where traces of impurities are present
(e.g., phenols) which produce unpleasant tastes when chlorine alone is used. Further, chloramine
provides a more lasting effect than that of chlorine.
The chloramine process consists of adding ammonia to water in the form of gas together
with chlorine resulting in the formation of dichloramine and monochloramine as shown above.
Dichloramine is a relatively stable compound and is perhaps not a sterilizing agent by itself. However,
it slowly decomposes with evolution of chlorine. Thus, the addition of ammonia stabilizes the chlorine
Water Treatment 6.23
to provide a prolonged effect. This is particularly useful when the water is passed into storage after
treatment.
A disadvantage of chlorination is the potential formation of trihalomethanes (such as
chloroform, bromodichloromethane, dibromochloromethane and bromoform) which are carcinogenic.
Trihalomethanes (THMs) may be formed when chlorine combines with natural organic substances,
such as decaying vegetation, etc., that may be present in water itself. One approach to tackle this
problem is to remove the organics completely before subjecting it to water chlorination. In future,
the actual removal of THMs from the treated water, perhaps by aeration or adsorption on activated
carbon, may become necessary.
Superchlorinatlon
In superchlorination, a large excess of chlorine is added to the water, thereby destroying not only
the micro-organisms but also the other organic impurities present. This process ensures rapid and
complete sterilization and successfully used for waters derived from wells and rivers. This process
is usually followed by dechlorination by NH3 or SO2.
A Break-point chlorination is a more precisely controlled process in which just sufficient chlorine
is added to oxidize all the organic matter, destroy bacteria and react with any ammonia, leaving a
slight excess of free chlorine. The break-through point, i.e., the appearance of free chlorine, in the
water, must be determined experimentally as follows:
If chlorine is added to a sample of water and after a few minutes, the residual chlorine available
in the water is estimated, it will be found that the residual chlorine in water is less than the amount
added initially. This is due to the fact that some of the chlorine added initially is consumed by
oxidizing bacteria and other organic matter. Now, if we take a few more aliquots of the same volume
of the water sample and add increasing doses of chlorine to different samples and analyze the residual
chlorine after the same interval of time (a few minutes), a curve of the type shown below is obtained
(Fig. 6).
Residual Chlorine
Break Point
Combined
Chlorine Free Chlorine
Chlorine dose added
It can be seen from Fig. 6 that the quantity of residual chlorine increases with increasing dose
of chlorine added giving a straight line until at a definite chlorine dose; a sudden decrease in the
residual chlorine is noticed. This is known as the break-point after which the residual chlorine
appearing more or less agrees with the chlorine dose added. The reason for such a behavior is due
to the fact that some organic compounds which defy oxidation at lower chlorine concentrations, get
oxidized when the break-point chlorine concentration is reached. Since it is these organic compounds
6.24 Engineering Chemistry
which are generally responsible for bad tastes and odours in water, it is obvious that break-point
chlorination eliminates bad tastes and odours.
Determination of free chlorine in a water sample
The principle involved in the estimation of free chlorine in water is that when a measured quantity
of water is treated with excess of potassium iodide, the free chlorine present in the water oxidizes
the corresponding amount of potassium iodide to iodine. The liberated iodine is estimated by titrating
against standard sodium thiosulphate solution using starch as indicator
Cl2 + 2KI 2KCl + I2
I2 + 2Na2S2O3 Na2SO4 + 2NaI
Dechlorinatlon
The water treated by the process of break-point chlorination may be filtered through activated carbon,
in order to remove the decomposition products formed and the excess chlorine remaining. Other
methods of dechlorination include treatment with SO2 or Na2SO3.
SO2 + Cl2 + 2H2O H2SO4 +2HCI
Na2SO3 + Cl2 + H2O Na2SO4 + 2HCl
Sterilization by Ozone
Ozone is a powerful disinfectant and is readily absorbed by water. Ozone being unstable decomposes
as follows giving nascent oxygen which is capable of destroying the bacteria.
O3 O2 + [O]
However, this process is relatively expensive but has the advantage of removing bacteria,
Color, odour and taste without leaving any harmful residual effects in the water being treated.
Sterilization by ultraviolet radiation
Ultraviolet radiation (190-380 mm) emanating from electric mercury vapor lamp is capable of
sterilizing water. This process is particularly useful for sterilizing swimming pool waters. However
this process cannot be economical for water works. Irradiation of water by ultraviolet light is
commonly used for disinfection in food industries.
Water for domestic purposes on a smaller scale may be sterilized by boiling the filtered water
for about 20 minutes. Chemicals like potassium permanganate and tincture iodine are also used
occasionally but chlorine tablets and bleaching powder are more commonly employed.
as sodium aluminate or alum helps in accelerating the coagulation of the carbonate sludge, which is
subsequently removed by filtration. Water softened by this process contains appreciable concentrations
of soluble salts, such as sodium sulphate, and cannot be used in high pressure boiler installations.
Types of cold lime-soda softeners
There are four basic types of cold lime soda softeners:
(i) The intermittent type (batch process)
(ii) The conventional type
(iii) The catalyst or spiractor type continuous processes
(iv) The sludge blanket type
(i) Intermittent or batch process
The intermittent type of cold lime-soda softener consists of a set of two tanks which are used in
turn for softening of water. Each tank is provided with inlets for raw water and chemicals, outlets for
softened water and sludge, and a mechanical stirrer (Fig. 7). Raw water and calculated quantities of
the chemicals are slowly sent into the tank simultaneously under agitation with the help of the stirrer.
Some sludge from a previous operation is also added which forms nucleus for fresh precipitation and
thus accelerates the process. Thus by the time the tank is full, the reaction is more or less complete.
Stirring is stopped and the sludge formed is allowed to settle. The clear softened water is collected
through a float pipe and sent to the filtering unit. The sludge formed in the tank is removed through
the sludge outlet. By employing a set of tanks planned for alternate cycles of reaction and settling,
continuous supply of softened water may be ensured.
Water treated by the cold lime-soda process generally produces softened water containing about
50–60 ppm of residual hardness.
(iii) Catalyst or spiractor type
The spiractor consists of a conical tank which is about two-thirds filled with finely divided granular
catalyst (Fig. 9). The tank used may be either open (for gravity catalyst operation) or closed (for
operation under pressure). In both the cases the raw water and the calculated quantities of chemicals
enter the tank tangentially near the bottom of the cone and spiral upwards through the suspended
catalyst bed. The catalyst employed is a finely granule (0.3 to 0.6 mm diameter) insoluble mineral
substance such as graded calcite or sand or green sand. The retention time is about 8 to 12 minutes.
The sludge formed during the softening reactions deposits on the catalyst grains in an adherent form
and hence the granules grow in size. The softened water rises to the top from where it is drawn
off.
The catalyst or spiractor type of continuous water softener is of interest as it gives a granular
sludge which drains and dries rapidly and can be handled easily.
(iv) The sludge blanket type
The sludge blanket type of water treatment equipment is extensively used for coagulation and settling
as well as water softening by cold lime soda process. These softeners differ from the conventional
type in that the treated water is filtered upwardly through a suspended sludge blanket composed of
previously formed precipitates. Thus in a single unit, all the three processes namely mixing, softening
and clarification take place.
In the conventional type of equipment, some of the added lime suspension is carried down in the
sludge formed by the precipitates, before it has time to dissolve and react with the hardness causing
impurities of the raw water and thus some of the lime is wasted. In the sludge blanket type, this
does not happen because the upward filtration through the suspended sludge blanket ensures complete
utilization of the added lime.
With the conventional type of equipment, it is generally observed that after-precipitates or after-
deposits form on the granules or filter media employed, and in pipe lines or distribution systems
carrying the filtered effluents. This usually necessitates recarbonation with CO2 to obviate the
formation of such deposits. However, in the sludge blanket type of equipment, the intimate contact of
the treated water with a large mass of solid phase mostly prevents super-saturation or the formation of
after-deposits. This result in the production of the effluent which is clear enough (turbidity usually less
than 10 mg/l) for many industrial applications, so that subsequent filtration is often unnecessary.
The retention period required with sludge blanket type equipment is one hour as against four
hours with the conventional units. Further, silica is removed better in sludge blanket units.
The sludge blanket type of water softening equipment, owing to its higher efficiency, shorter
detention period and smaller space requirements, is rapidly displacing the conventional type.
Hot lime-soda process
The effect of temperature on the velocity and completeness of precipitation reac involving the removal
of scaleforming constituents is shown in Fig. 10. It can be seen that at 96°C the precipitation is more
complete in 10 minutes than after several hours at 10°C. Thus effect is more pronounced with the
precipitation of magnesium compounds.
The reactions during water softening take place in very dilute solutions (about 0.001 M) and
hence proceed very slowly. The rate of these precipitation reactions can be greatly accelerated by
increasing the temperature, because, this not only increases the rate of the ionic reactions themselves,
but also the rate at which particles of measurable size are formed.
Hot lime-soda plants carry out softening at 94°–100°C which has several advantages. For efficient
softening, cold lime-soda softening plants must be of considerable area and water-storage capacity,
whereas hot lime-soda softeners are much more rapid in operation and therefore for a given through-
put, much more compact. Elevated temperatures not only accelerate the actual chemical reactions but
also reduce the viscosity of the water and increase the rate of aggregation of the particles. Thus, both
the settling rates and filtration rates are increased. Thus the softening capacity of the hot lime-soda
process will be several times higher than the cold process. Since the sludge formed settles down
rapidly, there is no need of adding any coagulants. A smaller excess of chemicals is needed than with
the cold process. Further, dissolved gases are driven out of the solution to some extent at the high
temperature. The hot lime-soda process yields softened water having relatively lower residual hardness
Water Treatment 6.29
143.0
114.4
Fig. 10 Effect of temperature on rate of precipitation of CaCO3 and Mg(OH)2 from CaSO4 and MgSO4
solutions respectively
(about 17 to 34 ppm) as against the cold process (about 50–60 ppm). A typical hot lime-soda water
softening unit is shown in Fig. 11, which includes a reaction cum settling tank and a filter. If the
water is alkaline, filtration through sand and gravel beds might steam contaminate the water with
dissolved silica, particularly if the quartz used is of inferior quality. Other filtering media used are
anthracite coal, calcite and magnetite. If the precipitation is incomplete in the softening tank, “after-
precipitation” occurs in pipes, storage tanks and even in boiler itself. If slight excess of chemicals
are used over that theoretically required, more rapid and more complete removal of hardness will
result. But if larger excess of chemicals are used, naturally they will appear in the softened water.
Lime-soda plants do not produce water of zero hardness.
Raw water
Exhaust Chemicals
or
Live
steam
Fines Anthrafilt
Coarse
Clarified
Sludge water
Sludge outlet
It is evident that in the above reaction, 2 equivalents of CO32– are generated. Thus for every one
equivalent of HCO3 present, the corresponding reduction in the dose of soda has to be t made in
the calculations for soda requirement. For solving numerical problems on lime-soda requirements for
softening of hard water, the following steps may be followed:
l. The units in which the impurities analyzed are expressed i.e., ppm (or mg/l). grains per
gallon (or degrees Clark), etc., are to be noted.
2. Substances which do not contribute towards hardness (e.g., KCl, NaCl, SiO2, Na2SO4 Fe2O3,
K2SO4, etc.) should be ignored while calculating lime and soda requirements. This fact should
be explicitly stated.
3. All the substances causing hardness should be converted into their respective CaCO3
equivalent, as a matter of convention and convenience.
wt. of the impurity
CaCO3 equivalent of a hardness causing impurity = _________________
× 50
Chemical equivalent
(since chemical equivalent weight of CaCO3 = 50).
For instance parts by weight of CaSO4 would contain the same amount of Ca as in 100 parts
by weight of CaCO3. Hence, in order to convert the weight of CaSO4 as its CaCO3 equivalent,
100 50
the weight of CaSO4 should be multiplied by a factor of a or ____
or ___
.
136 68
Conversion factors for some of the impurities in water which commonly come across are
given in Table 3.
Table 3
Salt Multiplication factor to convert into CaCO3
(1) equivalent
(2)
Ca(HCO3)2 100/162
Mg(HCO3)2 100/146
CaSO4 100/186
CaCl2 100/111
MgSO4 100/120
MgCl2 100/95
Mg(NO3)2 100/148
+2
Ca 100/40
+2
Mg 100/24
HCO –3 100/122
HCl 100/73
H2SO4 100/98
CO2 100/44
Al2 (SO4)2 100/114
FeSO4 7H2O 100/848
MgCO3 100/84
6.32 Engineering Chemistry
Notes:
(a) If the impurities are given as CaCO3 or MgCO3, these should be considered to be due to Ca(HCO3)2
or Mg(HCO3)2 respectively and they are only expressed in terms of CaCO3 and MgCO3.
(b) The amount expressed as CaCO3 does not require any further conversion. However, the amount
expressed as MgCO3 should be converted into its CaCO3 equivalent by multiplying with 100/84.
4. Calculate the lime and soda requirements as follows:
Temporary calcium hardness + (2 × Temporary
maganesium hardness) + Perm. Mg harndess +
74
(A) Lime required for softening = ____
CO2 + HCl + H2SO4 + HCO3– + salts of Fe2+,
100
Al3+ etc., –NaAlO2; all expressed in terms of
their CaCO3
1
(a) Thomsonite (Na2O, CaO) . Al2O3. 2SiO2. 2 __ H2O
2
(b) Natrolite Na2O, Al2O3.3SiO2.2H2O
(c) Laumontite CaO. Al2O3.4SiO2.4H2O
(d) Harmotome (BaO, K2O) Al2O3.5SiO2.5H2O
(e) Stilbite (Na2O.CaO), Al2O3.6SiO2.6H2O
(f) Brewsterite (BaO, SrO, CaO).Al2O3.6SiO2.5H2O
(g) Ptilolite (CaO, K2O, Na2O), Al2O3, 10SiO2.5H2O
The chemical structure of Sodium Zeolite may be represented as Na2O, Al2O3, x(2 – 10). SiO2
y(2 – 6), H2O, so that they may be regarded as hydrated sodium alumino-silicates which are capable
of exchanging their sodium ions for multivalent ions of alkaline earth group and for the divalent ions
of some of the metals in water. Thus, Zeolites find application in softening of water for domestic
and industrial purposes. Two types of Zeolites are in common use:
(a) Natural Zeolites e.g., non-porous green sands, and
(b) Synthetic Zeolites which are porous and possess a gel structure.
The natural zeolites are derived from green sands by washing, heating and treatment with NaOH.
The synthetic zeolites are prepared from solutions of sodium silicate and aluminium hydroxide. They
may also be prepared by heating together (a) China clay, felspar and soda ash and granulating the
resultant mass after cooling (b) solutions of sodium silicate, Al2 (SO4)3 and NaAlO2 (c) solutions
of sodium silicate and A12 (SO4)3 (d) solutions of sodium silicate and NaA1O2. Natural zeolites are
more durable, whereas synthetic zeolites have higher exchange capacity per unit weight. Zeolites are
now being replaced slowly by high capacity resins having greater stability.
Zeolites are also known as permutits. Sodium zeolites are used in water softening and are
simplistically represented as Na2Z, where Z stands for the insoluble zeolite radical framework. Since
these are capable of exchanging basic radicals, these are generally known as base exchangers.
When hard water passes through a bed of active granular sodium zeolite, the Ca2+ and Mg2+ ions
are taken up by the zeolite and simultaneously releasing the equivalent sodium ions in exchange for
them. The various reactions taking place may be indicated as follows:
Ca(HCO3)2 + Na2Z Æ CaZ + 2NaHCO3
Mg(HCO3)2 + Na2Z Æ MgZ + 2NaHCO3
CaSO4 + Na2Z Æ CaZ + Na2SO4
MgSO4 + Na2Z Æ MgZ + Na2SO4
CaCl2 + Na2Z Æ CaZ + 2NaCl
MgCl2 + Na2Z Æ MgZ + 2NaCl
Relatively small quantities of iron and manganese, present as the divalent bicarbonates, may also
get removed simultaneously.
Fe(HCO3)2 + Na2Z Æ FeZ + 2NaHCO3
Mn(HCO3)2 + Na2z Æ MnZ + 2NaHCO3
(Note: Soluble iron and manganese are always present in the divalent form in waters containing
bicarbonate alkalinity).
6.34 Engineering Chemistry
Regeneration
When the Zeolite bed is exhausted (i.e., saturated with Ca2+ and Mg2+), it can be regenerated and
reused. The chemicals used for regeneration are concentrated sodium chloride solution (brine),
sodium nitrate, sodium sulphate, potassium chloride or patassium nitrate. Brine is most widely used
on account of its cheapness, relatively low molecular weight and also because the products formed
by the regeneration reactions chiefly CaCl2 and MgCl2, which are highly soluble and can be readily
rinsed out from the zeolite bed.
CaZ + 2NaCl Æ Na2Z + CaCl2
MgZ + 2NaCl Æ Na2Z + MgCl2
Brine
inlet
Hard
water
Hard water
Sodium Zeolite
Fine Gravel
Coarse Gravel
Softened
water
A Simple zeolite softener is depicted in Fig. 12 and the scheme for softening and regeneration
processes are represented in Fig. 13.
Advantages of Zeolite process
1. Hardness is completely removed.
2. Equipment used is compact and occupies fewer places.
3. It automatically adjusts itself to waters of different hardness.
4. It can work under pressure. Hence the plant can be installed in the water supply line itself,
avoiding double pumping.
Water Treatment 6.35
Hard Brine
water –
2+ +
Ca Na Cl
2+
Mg
Ca Z Ca Z
Na2 Z and and Na2 Z
Mg Z Mg Z
– Regenerated
+ Cl Softening Exhausted
Na 2– progresses 2–
SO4 SO4
Softened 2+
Ca Mg
2+
Water –
Cl
(a) Softening Cycle (b) Regeneration Cycle
5. In this process, the hardness causing ions are simply exchanged with sodium ions. As the
process does not involve any precipitation, there is no problem of sludge formation and after-
precipitation in the softened water at later stages.
Limitations
1. Water, having turbidity and suspended matter should not be directly fed to the zeolite softener
because the pores of the zoelite bed will be clogged and the rate of flow will be unduly
decreased. Therefore, the raw water turbidity and suspended matter should be removed (e.g.,
by sedimentation, coagulation and filtration) before subjecting it to the Zeolite treatment.
2. Water containing excess of acidity or alkalinity may attack the Zeolite. It is preferable to
have the pH of the water passing through the Zeolite softener around 7.
3. Water containing large quantities of Fe2+ and Mn2+ when passed through the Zeolite bed are
converted into their respective Zeolites which cannot be easily regenerated.
4. Hot water should not be used as the zeolite tends to dissolve in it.
5. Acid radicals are not removed by this process. Hence, the temporary hardness present in the
raw water is converted to NaHCO3 which goes into soft water effluent. If such water is used
in the boilers, it dissociates as follows under the boiler conditions.
NaHCO3 Æ NaOH + CO2
This NaOH may cause caustic embrittlement of boiler metal. Further, CO2 goes along with
the steam and renders the condensed water acidic and corrosive. Hence, raw waters containing
large amounts of temporary hardness should be subjected to prolonged boiling or lime
treatment to remove temporary hardness, before subjecting to the Zeolite process.
6. Water treated by the Zeolite process contains about 25% more dissolved solids than that
treated by lime-soda process.
Comparison between the Zeolite process and the lime-soda process
The salient features of Zeolite process and lime-soda process are summarized in the following
table:
6.36 Engineering Chemistry
The functional groups are then introduced into the cross-linked resin network, either by subsequent
treatment of the resin or by introducing the functional groups into the starting material itself. It is
these functional groups which decide the nature of the exchanger (i.e., cationic or anionic) based on
the acidity or basicity of the functional group, exchangers are further classified as follows:
Types of ion-exchanger Functional groups
Strongly acidic cation-exchangers – SO3H
Moderately strong cation-exchangers – PO(OH)2
Weakly acidic cation-exchangers – COOH or –OH
Strongly basic anion-exchanger – NR3+;∫ P+ –CH3, etc.
Weakly basic anion-exchanger – NH2; – (C2H4): (NH) –y
Hypothetical formulations of a typical cationic and a typical anionic resin based on styrene and
divinyl benzene network are shown in Figs. 14 and 15.
Variation in polymer type and cross-linking affects the insolubility and life of the resin and the
diffusibility of ions in an exchange process.
Resins available for water treatment include cation-exchange resins of the strongly and weakly
acidic types, anion-exchange resins of the strongly and weakly basic types and highly porous
modifications of strong acid cation exchangers and strong base anion exchangers. These resins are
available in granular or bead-like form and may be obtained in an effective size and uniformity
coefficient.
For effective water treatment, ion exchangers should possess the following properties:
1. They should be non-toxic.
2. They should not discolor the water being treated.
3. They should possess a high ion-exchange capacity. (It depends upon the total number of ion
active groups per unit weight of the exchanger and is expressed as mill-equivalents per gram
of the exchanger).
6.38 Engineering Chemistry
Thus all the Ca2+ and Mg2+ are taken up by the resin in exchange of Na+. When the resin bed
is exhausted, it can be regenerated with a concentrated solution of sodium chloride.
Ca Ca
R + 2NaCl + Na2R + Cl2
Mg Mg
In the second method, hard water is passed through a bed of cation exchanger in hydrogen
form.
Ca Ca
(HCO3)2 + H2R R + 2H2O + 2 CO2
Mg Mg
Ca SO4 Ca
+ H2R R+H2SO4 or 2HCl
Mg Cl2 Mg
When the resin bed is exhausted, it can be regenerated with sulphuric acid or hydrochloric
acid.
For many industrial water supplies, chemical softening (e.g., lime soda process) is used first to
remove most of the hardness followed by a cation exchange process for completing the softening
process. For softening water, usually sodium cycle is preferred.
Water Treatment 6.39
Ca Ca
R + H2SO4 SO4 + H2R
Mg Mg
The effluent from this step is then passed through an anion exchanger bed.
Thus, all the ions present in water are removed and demineralised or deionised water is produced.
Strongly basic anion-exchanger is used when silica also is to be removed. Otherwise, weakly basic
anion exchangers are used generally. If CO2 removal is also desired, forced draft or vacuum degasifier
unit is provided. The anion exchanger may be regenerated by treating it with dilute NaOH solution.
The cation exchanger may be regenerated by passing a solution of HCl or H2SO4
Raw
water
To vacuum
pump
Alkali for
regeneration
Acid for Deionised
regeneration water
When the resins are exhausted the bed is backwashed when the two resins are separated in
different layers due to difference in their densities. Then the resins are separately regenerated, washed
and mixed again by injecting air and reused for a fresh cycle.
The deionisation process can also be used to purify highly acidic or alkaline waters. All ionizable
impurities are removed and many commercial plants produce water having as low as 3 ppm dissolved
solids and 0.1 ppm silica. However, the process is costly. The equipment and the resins as well as
the regenerants are expensive as compared to those used in zeolite process. Water having turbidity
reduces the efficiency of the process. Hence it is advisable to treat it first by lime-soda process and
then removing the residual hardness by this process. This process is recommended for very high
pressure boilers, where the specifications are more exacting.
Demineralized water is also used in the manufacture of photographic materials, fine chemicals,
synthetic rubber, pharmaceuticals, ceramics, explosives, plastics, paper products such as dielectrics,
soluble coffee, cosmetics, liquid soaps, storage batteries, catalysts, ice, cellulose products, television
tubes, for cooling purposes in broadcasting stations and diesel locomotives, power plants, oil refineries,
electroplating plants and in laboratories.
Distillation
This method of removing hardness and scale forming constituents is used in large power stations
and on steamships, where the amount of make-up water is small compared with the total amount
of water evaporated in the boilers. However, until cheaper sources of energy are available, water
softening by distillation is going to be an expensive proposition.
Removal of iron and manganese from water
Iron and manganese may be present in water as bicarbonates, sulphates, hydroxides or as chelates.
The presence or iron and manganese in water even in such low concentrations as 0.1 to 0.3 ppm may
be objectionable in industrial processes such as textile dyeing and finishing, paper making, rayon
processing, beverage manufacture, laundering and tanning.
Iron and manganese in water may be removed by the following processes:
(i) By aeration followed by settling and filtration, the metals are removed in the form of Fe
(OH)3 and Mn (OH)3
(ii) By ion exchange process using zeolites, carbonaceous or synthetic cation exchangers.
(iii) By lime-soda process, and
(iv) By manganese zeolite process
Water Treatment 6.41
Mangenese zeolite is prepared from zeolite by alternate treatments with MnSO4 and KMnO4.
This results in the precipitation of the higher oxides of Mn in and around the zeolite granules. In
this process, Fe and Mn are mostly removed by contact oxidation. The regeneration of manganese
zeolite is performed by KMnO4 or NaMnO4 solution. The manganese zeolite is used as filter medium
in pressure type filter, through which the water is filtered to remove Fe and Mn.
losses from the boiler caused by use of open steam in process work or steam otherwise lost plus the
water lost in the boiler blow-down. In certain cases, there are no condensate returns or none fit for
re-use in the boiler, so that the feed water is 100% make-up water. In some other cases, particularly
in large power plants, surface condensers employed are capable of recovering almost all of the water
evaporated and make-up may comprise of < 2% of the water fed to the boiler. All other cases lie
between the above two extremes.
The treatment of boiler feed waters may be broadly divided into two categories:
1. External treatment: In this, the scale-forming and corrosive impurities are removed from
the water before it enters the boiler.
2. Internal treatment: In this, dosages of various materials are added in the boiler to react
with the non-carbonate hardness, to reduce the sticking tendency of scale-forming materials
and to neutralise or overcome corrosive tendencies.
In many cases, both the above forms of treatment are employed. In the external treatment of
boiler feed water, one or more of the following processes are usually employed:
1. Removal of “hardness” or scale forming salts
(a) Lime-soda process (b) Zeolite process
(c) Demineralization (d) Distillation
2. Removal of silica: Magnesia process, ferric sulphate process, anion-exchange process.
Fluosilicate process.
3. Removal of suspended matter:
(a) pre-treatment: sedimentation, coagulation, settling and filtration.
(b) softening processes.
4. Removal of dissolved gases: CO2 and O2
(a) Decarbonation by aeration
(b) Deaeration
(c) Chemical treatment.
5. Removal of oil
(a) Mechanical oil-separators
(b) Sodium aluminate treatment.
Most of these processes have been discussed earlier and others will be discussed later, along with
the methods for internal treatment
8. BOILER TROUBLES
The problem of making up feed water for boilers is common to almost all industries and has been
a subject of detailed study by several workers. In treatment of boiler feed water, total elimination
of all the impurities is generally not attempted. Only those impurities which give rise to certain
operational troubles are either eliminated or maintained within tolerable limits. The major boiler
troubles caused by the use of unsuitable water are (1) carry over: priming and foaming (2) scale
formation (3) corrosion and (4) caustic embrittlement. All these troubles increase with increasing
operating pressure of the boilers. The limits of tolerance for boiler feed waters, suggested by
the committee on water quality tolerances for industrial users of the New England Water Works
Association are, given under Table 4. These tolerance limits take into account that (a) reduction in
Water Treatment 6.43
turbidity color. oxygen consumed value and total solids decrease carry over (b) reduction in hardness,
silica and alumina decrease scale formation (c) elimination of oxygen, reduction of bicarbonate ions
and increase in pH help in suppressing corrosion and (d) maintaining a high sulphate to carbonate
ratio checks caustic embrrittlement.
due to the insulating effect of these deposits, the super heater tubes also may burn out. A part of the
dried salts may be carried along with the steam farther and deposit on the high-pressure turbine blades
or in engine valves. Even a small amount of deposit on the turbine blades decreases its efficiency
considerably. In order to eliminate the bad effects of moisture, mechanical steam purifiers are often
installed in the steam drums of the boiler or between the boiler and the superheater. These devices
force the steam to take curved paths whereby due to centrifugal action, the moisture is thrown out
of the steam.
Priming is a very rapid boiling of water occurring in the boiler in such a way that some water
particles are carried away along with steam in the form of spray into the steam outlet. Priming is
mainly attributed to the presence of suspended impurities and to some extent to dissolved impurities
in the water. Thus it may be caused by imperfect filtration or precipitation of insoluble salts from the
improperly softened or unsoftened feed water. Algae and vegetable growth in tanks can also lead to
priming. Feed water containing even a small quantity of scale forming salts may cause particularly
if the total solids in the feed exceed 300 ppm. Priming may also be caused by:
(1) steam velocities high enough to carry droplets of water into the steam pipe (2) very high water
level in the boiler (3) presence of excessive foam on the surface of the water which substantially
fills the foam space (4) sudden steam demands leading to sudden drop of pressure in the steam line
followed by ebullition, which causes a large mass of water to be interspersed with fine bubbles and
(5) faulty boiler design.
Priming can be minimised by (1) good boiler design providing for proper evaporation of water
maintaining uniform heat distribution and adequate heating surfaces and also providing with
antipriming pipes and dash-plates, etc. (2) maintaining low water levels (3) avoiding rapid changes
in the steaming rate caused by sudden steam demands (4) maintaining as low a concentration of
boiler water (with respect to dissolved impurities) as is consistent with scale and corrosion prevention
and (5) minimizing foaming.
Foaming is the formation of small but persistent bubbles at the water surface. These bubbles are
carried along with steam leading to excessive priming.
According to Bancroft, foams are formed when there is a difference in concentration of solute
or suspended matter between the surface film and the bulk of the liquid. Substances which increase
the viscosity of the film favor production of foam. The bubbles may also be protected by finely
divided solids forming a protective “shell” around each of them. Any material which lowers the
surface tension of the water will collect at the interface and thus increase the foaming tendency of
the liquid.
In steam rising, the bubbles of steam may be stabilized because of the accumulation of soluble
salts in water. Clay or organic matter in raw water, oil or grease in condensed make-up water, and
finely divided particles of sludge may also cause foaming.
If the steam bubble does not collapse on reaching the surface of the water, the foam may be drawn
into the preheater or steam lines. The accompanying liquid film may carry along with it dissolved
salts, suspended solids or other stabilizing materials which will be deposited on the cylinder walls,
turbine blades or in steam lines. If the stability of the bubble is such that it breaks near the steam
outlet, tiny droplets of liquid from the collapsing film may be swept along into the steam lines giving
“wet steam”.
Foaming (and the consequent priming) can best be prevented by removal of the foaming and
stabilizing agents from the water. Clay and other suspended solids as well as droplets of oil and
grease can be removed by treatment of the feed water with clarifying agents such as hydrous silicic
Water Treatment 6.45
acid and aluminium hydroxide. The concentration of salts and sludge in the boiler can be controlled
by intermittent or continuous blow-down. Spiral or “cyclone baffles” or a series of baffle plates near
the steam outlets help to prevent water droplets from entering the steam lines.
Foaming can also be controlled by adding antifoaming agents. Some of these act by counteracting
the reduction in surface tension while others reduce foaming by simple mechanical action. For
instance, castor oil spreads on the surface of water and prevents foaming. This is used only for low
pressure boilers. Addition of a small concentration of polyamide antifoamer alters the surface tension
and leads to the formation of only large unstable bubbles at the same heat input.
Antifoaming agents may also act by reducing the charge on the protective film or its components.
Foam may be destroyed by the addition of another good foaming agent. The foam is finally destroyed
by mutual antagonistic effect of the difference in charge (positive and negative) on the colloidal
particles of the two foams. This can be illustrated by the fact that the foam obtained by a solution
of an anionic detergent (e.g., Aerosol OT) and that obtained from a cationic detergent (Ethyl Cetab)
will destroy each other on mixing the two solutions.
For avoiding priming and foaming, the following limits on total dissolved solids (in the boiler
water) are usually suggested.
Type of boiler Total dissolved solids, ppm
Water tube 2000 to 5000
Lancashire 1000 to 1500
Vertical £ 3500
In order to keep down the feed water concentration within safe limits, it is customary to remove
a portion of the concentrated boiler water by blow-down and replace it with fresh feed water. Blow-
down may be done periodically or continuously. However, blow-down will result in loss of heat.
Removal of oil
Oil present in boiler water may lead to (a) the formation of heat insulating oil films, and (b) carry
over (if the oil is fatty). Natural waters generally do not contain oil! Small amount of oil may come
from the oil used for lubrication of the pumps. A large quantity of boiler water is obtained from
the condensation of exhaust steam which usually gets contaminated with lubricating oil in the steam
cylinder. In order to remove oil, the exhaust steam is passed through mechanical separators which
contain a number of metal plates. As the steam passes over the metal plates, the oil droplets are
retained on the metal surface.
Oil is also removed by coagulation with sodium aluminate or alum and soda ash. The floc
produced by the Al(OH)3 and Mg(OH)2 precipitates enmesh the oil. The floc is then removed by
filtering through anthrafilt.
Oil can also be removed from water by cataphoresis.
Removal of Silica
Silica may cause hard deposits on turbine blades due to carry over. Silica also forms thermally
resistant boiler scales of magnesium or calcium silicate.
Silica is removed from the boiler feed water by the following methods:
1. By the addition of magnesia (MgO) to the water after the removal of the temporary
hardness.
6.46 Engineering Chemistry
2. By the addition of magnesia to the water in the boiler when magnesia silica sludge is
deposited.
3. By using magnesia or dolomitic lime in hot lime soda process of water softening. Magnesia
acts as Mg(OH)2. In all these processes, silica is removed by magnesia by adsorption or by
the formation of magnesium silicate.
4. By the use of ferrous sulphate or sodium aluminate as coagulants. They act as Fe(OH) 2 or
Mg(OH)2 and Al(OH)3 which enmesh finely suspended and colloidal impurities including
oil and silica.
5. By passing the demineralised water through a strongly basic special anion-exchanger which
removes silica as H2SiO3 or HSiO3 or in some other form. The silica content is usually
reduced to a fraction of a ppm.
6. By converting the silica into flurosilicate by the addition of Hydrofluoric acid and then
removing it by passing through an anion exchange resin.
H2SiF6 + 2R3N Æ (R3N2) . H2SiF6
7. By distillation.
formation. In very high pressure boilers, sodium aluminium silicate scales resembling the zeolite
minerals are also noticed, particularly in regions of excessive local evaporation. Several other salts
and colloidal and suspended impurities also may get deposited or entrapped in the precipitates of
salts forming the scales.
Disadvantages of scale formation
1. Scale is a poor conductor of heat. Its effect is like that of an insulator coating on the metal
surface. This result in the reduced rate of heat transfer, and thus the evaporative capacity of
the boiler will be reduced. Thus, scale formation will result in wastage of fuel and reduction
in boiler efficiency.
2. Scale formation on the boiler tubes or other heated surfaces insulates the metal so well that
it becomes overheated. The metal becomes soft and weak thus making the boiler unsafe
particularly at high pressures. The overheating also causes burning out of the metal plates
and tubes and breakdown of the expanded joints.
3. In addition to the loss of strength due to overheating, rapid reaction between water and iron
occurs at high temperatures, causing additional thinning of the tube wall.
3Fe + 4H2O Æ Fe3O4 (s)+4H2 (g)
4. Since the scale acts as heat insulator, the metal of the boiler is overheated. Under the high
pressure of steam existing in the boiler, the metal expands until the scale on it cracks. Sudden
entry of the water through these cracks to the very hot metal causes sudden cooling of the
boiler metal with the simultaneous conversion of water into steam. The sudden increase in
pressure due to this large quantity of steam thus formed may lead to explosion.
5. Excessive scaling may cause clogging of tubes. Considerable quantities of sludges may also
be entrapped in the scale which may reduce the water circulation and impair the efficiency
of the boiler.
Prevention of scale formation
Scale formation can be prevented by the following methods:
(a) External treatment: This involves removal of hardness causing impurities (such as calcium
and magnesium salts) and silica from the water before entering the boiler. The various
methods of external treatment of water are already discussed earlier.
(b) Internal treatment: Internal treatment consists of adding chemicals directly to the water in
the boilers for removing dangerous scale forming salts which were not completely removed
in the external treatment for water softening. This is mainly used as a corrective treatment to
remove the slight residual hardness and also sometimes to remove the corrosive tendencies in
water. This treatment is not usually applied to raw waters, except for small boilers, but it is
usually practiced in larger power-stations. In modern heavy-duty high pressure boilers, water
of zero hardness is required, since even an egg- shell thickness of scale may be extremely
detrimental.
1. Carbonate conditioning: For a salt to be precipitated, sufficient amount of the ions forming the
salt must be present so that the product of their concentrations (i.e., ionic product) exceed a limiting
value known as the solubility product. Thus, for a salt like CaCO3 to be precipitated, the product
of the concentration of Ca2+ and Co3–2 must exceed the solubility product of CaCO3, represented as
KCaCO .
3
6.48 Engineering Chemistry
[CO3–2] KCaCO
______ ______ 3
> ...(3)
[SO4–2] CaSO
K
4
–2
[SO4 ] CaSO
K
4
or in other words, if [CO3–2] > K’ [SO4 –2], then only CaCO3 will be precipitated in preference to
CaSO4 (because the solubility product of CaSO4 cannot be attained under these conditions).
These principles are used in the carbonate conditioning. When sodium carbonate solution is added
to boiler water, the [CO3–2] increases and when it becomes greater than K’ × [SO4 –2], only CaCO3
gets precipitated and CaSO4 remains in solution. Thus the deposition of scale-forming CaSO4 is
prevented.
Na2 CO3 + CaSO4 –> CaCO3Ø + Na2SO4
Carbonate conditioning is used only for low pressure boilers. In high pressure boilers the excess
Na2CO3 might be converted into NaOH due to hydrolysis as follows:
Na2CO3 + H2O ¤ 2 NaOH + H2CO3
H2CO3 ¤ H2O + CO2≠
NaOH causes caustic embrittlement in high pressure boilers.
2. Phosphate conditioning: Just as in the case of carbonate conditioning, if we consider a solution
saturated with both Ca3 (PO4)2 and CaSO4, the solubility product equations for both salts must be
satisfied.
Ca3 (PO4)2 3Ca+2 + 2PO4–3
Water Treatment 6.49
scales. However, precaution should be taken to inspect them at least once in six months and remove
the scale and sludge accumulations.
3. Colloidal conditioning: Scale formation can also be minimized by introducing into the boiler
some colloidal conditioning agents such as glue, agar agar, tannin, starch and sea-weed extract. These
substances act as protective colloids. They function by surrounding the minute particles of CaCO3
and CaSO4 and prevent their coalescence and coagulation. Thus, the precipitated scale-forming salts
are maintained in loose suspended form which can easily be removed by blow-down operation. Thus
the scale formation is prevented.
4. Calgon conditioning: Another approach for preventing scale formation is to convert the scale
forming salts into highly soluble complexes which are not easily precipitated under the boiler
conditions. In order to achieve this, sodium hexametaphosphate (Na PO3) 6 or Na2 [Na4P6O18] (its
trade name is calgon) is generally employed. This substance interacts with the residual calcium ions
forming highly soluble calcium hexametaphosphate and thus prevents the precipitation of scale-
forming salts.
Na2 [Na4P6O18] ¤ 2 Na+ + [Na4P6O18] 2–
2 Ca2+ + [Na4P6O18] ¤ 4 Na+ + [Ca2P6O18] 2–
5. Conditioning with EDTA: Phosphate treatment fails to prevent the formation of iron oxide and
cuprous depositions. Sometimes, the phosphate chemicals themselves become a source of deposit
formation (e.g., iron phosphate). In distinction to phosphate treatment, the conditioning of boiler water
with complexing agents can secure scale-free and sludge free operation of boiler units and sometimes,
also corrosion-free operation under certain conditions. These reagents are known as complex ones or
complexing agents such as ethylenediamine tetraacetic acid (EDTA) and its disodium salt (Na2EDTA)
known as Trylon-B, or even its tetrasodium salt (Na4EDTA).
6. Boiler compounds: Once, during the early times of Watt’s engine, is said that workmen, after
cleaning the boiler and refilling with water, hung a bag containing potatoes in the boiler to cook them.
They forgot about them and put the boiler into operation after closing it. Then, when the boiler was
shut down again for manual removing of the scale, it was found that the scale formation was much
less, much of it having come down in the form of loose sludge. The story seems to be true because,
for many years, engineers used to throw some potatoes in the boiler after every cleaning operation.
Perhaps, this is the form of internal treatment of boiler saline to reduce the adherent scale formation
by rendering it in the form of softer sludge which can be easily removed by blow-off. Slowly, potatoes
were replaced by starch and later by tannin and other organic and inorganic materials such as soda
ash and caustic soda, phosphate, coagulant such as sodium aluminate, and deoxidizer like sodium
sulphite. Natural wood and plant extracts and several synthetic products have also been used. US
Navy was reportedly using a boiler compound consisting of 47% anhydrous disodium phosphate, 44%
soda ash and 9% starch. Castor oil compounds and various synthetic antifoam compounds were also
used in locomotive boilers to reduce foaming tendency. These boiler compounds do help in reducing
scale formation when properly used under proper situations.
(c) Blow-off: In spite of external and internal treatment, the concentration of impurities in the
boiler water goes on increasing continuously as the generation of steam continues. In order
to keep the concentration of boiler water below a set figure, a part of the boiler water is
blown off to waste and fresh feed water is filled in to replace it. The blow-down (or blow-
off) may be done periodically or, preferably, continuously. During the blow-down process, a
Water Treatment 6.51
pan of concentrated water containing dissolved impurities and suspended sludge is removed
and the remaining saline get diluted with the fresh feed water make-up.
8.3 Corrosion
Corrosion of boiler tubes, plates, economizers and pipe lines can be mainly attributed to one or
more of the following factors:
(a) Presence of free acids in water.
(b) Acids generated as a result of hydrolysis of some salts in water.
(c) Acids formed by the hydrolysis of fatty lubricating oils.
(d) Presence of dissolved gases such as O2, CO2, H2S etc., in water.
(e) Presence of salts like MgCl2 which directly attack the boiler metal:
MgCl2 + Fe + 2H2O Æ Mg (OH)2 + FeCl2 + H2
(f) Presence of salts like MnS2 which may generate H2SO4 due to oxidation and hydrolysis.
(g) Formation of galvanic cells.
Some of these factors are discussed below:
(i) Dissolved oxygen: Dissolved oxygen is the chief source of corrosion in boilers and ancillary
equipment. It is highly desirable to remove the dissolved oxygen or air from softened boiler waters
by physical or by chemical means. The concentration of oxygen in boiler waters should be below
0.05 ppm for low pressure boilers and less than 0.01 ppm for high pressure boilers (~ 500 psi).
Oxygen enters the boiler through raw make up water and also through infiltration of air into the
condensate system. When the water containing dissolved oxygen is heated in the boiler, the free gas
is evolved which corrodes the metal parts under the conditions obtaining in the boiler.
The solubility of a gas is directly proportional to pressure and inversely proportional to temperature
(Dalton’s law and Henry’s law). These two principles are made use of in the design of mechanical
deaerators.
In mechanical deaerators, dissolved oxygen is removed by injecting hot feed-water, as a fine spray,
into a vacuum chamber heated externally by steam. Equipments with various designs are available.
For complete removal of dissolved oxygen, chemical methods of treatment are adopted.
Sodium sulfite is suitable for boilers operating below 650 psi. The sulphite reacts with the
dissolved oxygen to form sulphate.’
Na2SO3 + 1/2 O2 Æ Na2SO4
This method is very effective for removing oxygen in low pressure boilers but cannot be used
in high pressure boilers because (i) increasing dissolved salts concentrations produce foaming and
priming and (ii) sodium sulphate decomposes and liberates SO2 and/or H2S.
Ferrous sulphate is also used sometimes. It reacts with dissolved oxygen giving a precipitate of
Fe (OH)2 which is oxidized to Fe(OH)3
FeSO4 + 2NaOH Æ Fe(OH)2 + Na2SO4
2Fe (OH)2 + H2O + O Æ ‘2Fe(OH)3
Hydrazine, N2H4 is now extensively used to remove dissolved oxygen in high pressure boilers. The
pure compound is an explosive inflammable liquid (B.Pt. 113.5°C) but the 40% aqueous solution used
6.52 Engineering Chemistry
for water treatment is quite safe to handle. However, rubber gloves must be worn to guard against
the danger of dermatitis in some cases. One of the important advantage of hydrazine treatment is
that combination with oxygen does not produce any salts. Nitrogen and water are the only reaction
products obtained.
N2H4 + O2 Æ N2 + 2H2O
The molecular weight of hydrazine and oxygen are the same (viz. 32), so that complete elimination
of 1 ppm of oxygen would require only 1 ppm of hydrazine (which is 1/8 of the necessary concentration
of sodium sulphite). The residual hydrazine can be measured easily by a colorimeter.
The amount of hydrazine added must be closely controlled. Any excess reagent decomposes in
the boiler, liberating ammonia:
3N2H4 Æ 4NH3 + N2
Dissolved ammonia can bring about corrosion of some alloys, e.g., copper alloy condenser
tubes.
(ii) Dissolved mineral acids: Most of the natural waters are alkaline excepting waters from mining
areas or those polluted from acidic industrial wastes or those in which wet oxidation of sulphide
minerals occur. Some inorganic salts like magnesium chloride and calcium chloride are also corrosive
agents. MgCl2 hydrolyzes completely at 200°C producing hydrochloric acid as follows:
MgCl2 + 2H2O Æ Mg (OH)2 + 2HCl
CaCl2 also undergoes hydrolysis but to a lesser extent. At 600°C, its hydrolysis is about 25%.
Silicic acid catalyzes the reaction so that in water containing silica, appreciable quantities of HCl
may be formed at lower temperatures. The HCl thus produced reacts with iron as follows:
Fe+2HCl Æ FeCl2 + H2
FeCl2 + 2H2O Æ Fe(OH)2 + 2HCl
Hence, even a small amount of MgCl2 can cause considerable corrosion of the metal. If the
amount of HCl formed is small, it might get neutralized by the alkalinity present in the water, but
otherwise it should be neutralized by the addition of alkali.
(iii) Dissolved carbon dioxide: Natural waters contain CO2 water containing bicarbonates release
CO2 on heating. If CO2 is released inside the boiler, it will go along with the steam and as the
steam condenses, the CO2 is dissolved in water forming carbonic acid. This produces intense local
corrosion called pitting.
CO2, along with oxygen in water, can be removed by mechanical deaeration. CO2 in water can
be removed by lime treatment. Another method of removing CO2 from water is to filter it through
lime stone:
CaCO3 + CO2 + H2O Æ Ca (HCO3)2
but this reaction produces temporary hardness in the water.
CO2 can be converted into ammonium carbonate by the addition of ammonia.
CO2 + 2NH3 + H2O Æ (NH4)2CO3
However, the excess ammonia added to the boiler feed water may go along with steam to the
condenser. If some O2 is also present in the condensate, the ammonia may attack the condenser tubes
made of copper. Hence, a safe limit of 10 mg of NH3/litre of the condensate is prescribed.
Water Treatment 6.53
(iv) Formation of galvanic cells: Corrosion can also occur because of galvanic cell formation
between iron and other metals, present in the alloys used in boiler fittings. This may also lead to
pitting corrosion. This can be prevented by suspending zinc plates which act as sacrificial anodes.
9. DESALINATION OF WATER
Water with high levels of dissolved salt is not suitable for domestic, industrial or irrigation uses.
Sea water contain 3.5% dissolved salt. Sea water can be desalinated to separate into fresh water by
6.54 Engineering Chemistry
the process called desalination. The process of removing salt from sea water to make it suitable for
agricultural purposes or for drinking is called desalination. The people are trying to develop the
desalination process in an economical way for providing fresh water for domestic use in regions
where the availability of water is limited. Desalination can be performed by two process membrane
process and thermal process.
Reverse osmosis (RO) and electrodialysis are two membrane processes for desalination. Reverse
osmosis is a separation process forcing a solvent from a region of high solute concentration through
a membrane to a region of low solute concentration by applying a pressure in excess of the osmotic
pressure. The flow of water (or other solvent) through a semipermeable membrane called osmosis.
Normal osmosis is a process were natural movement of solvent flow from low to high concentration
through a membrane. A membrane which is permeable to solvent and not to solute is called a
semipermeable membrane.
When a solution is separated from pure water by a semipermeable membrane, osmosis of water
occurs from water to solution. This osmosis can be stopped by applying pressure equal to osmotic
pressure, on the solution. If pressure greater than osmotic pressure is applied osmosis is made to
proceed in the reverse direction to normal osmosis i.e. from solution to water.
The membranes used for reverse osmosis have a dense barrier layer in the polymer matrix where
most separation occurs. In most cases the membrane is designed to allow only water to pass through
the dense layer while preventing the passage of solutes. This process requires a high pressure to exert
on the high concentration side of a membrane usually 30-250 psi for fresh and brackish water and
600-1000 psi for sea water. This process is well known for its use in desalination. it has also been
used to purify fresh water for medical, industrial and domestic applications since 1970s.
Electrodialysis: Electrodialysis is used to transport salt ions from one solution through ion-exchange
membranes to another solution under the influence of an applied electric potential difference. The
cell consists of a feed (dilute) compartment and a concentrate (brine) compartment formed by an
anion exchange membrane and a cation exchange membrane placed between two electrodes. Cation
exchange membranes allow only cations to pass through whereas onion exchange membranes allow
passage of only anions through them.
Multiple electrodialysis cells consists of alternating anion and cation exchange membranes and
electrode. Under the influence of an electrical potential difference the negatively charged ions (CI¢)
migrate toward the positively charged anode. These ions pass through the positively charged anion
exchange membrane, but are prevented from further migration toward the anode by the negatively
charged cation exchange membrane, and stay in the C steam which becomes concentrated with the
anions. The positively charged species e.g. Na¢ in the D steam migrate toward the negatively charged
cathode and pass through the negatively charged cation exchange membrane, these cations also stay
in the C steam, prevented from further migration towards the cathode by the positively charged anion
exchange membrane. As a result of the anion and cation migration, electric current flows between
the cathode and anode, equal number of anion and cation charge equivalents are transferred from
the D stream into the C stream and so the charge balance is maintained in each stream.
The result of the electrodialysis process is an ion concentration increase in the concentration
stream with a depletion of ions in the dilute solution feed steam. E stream is the electrode stream
may consist of the same composition as the feed stream (ex. NaCl or Na2SO4) depending on the stack
configuration anions and cations from the electrode stream may be transported into the C stream or
anions and cations from the D stream may be transported into the E stream.
Water Treatment 6.55
solved Questions
Type–I
Problems based on Calcium Carbonate Equivalent and Hardness
1. A sample of water contains 204 mg of CaSO4 /l. Calculate the hardness in terms of CaCO3
equivalent.
Sol. Hardness in terms of = (Mass CaSO4 in mg/l) × Multiplication factor CaCO3 equivalent
100
= (Mass of CaSO4 in mg/l) × ____________________________
2 × chemical equivalent of CaSO4
100
= 204 × ______ = 150 mg/l
2 × 68
Hardness = 150 ppm.
2. How many grams of MgCl2 dissolved per litre gives 190 ppm of hardness?
Sol. Hardness in terms of = (Mass of MgCl2 in mg/l) × Multiplication factor CaCO3 equivalent
100
Hardness = (Mass of MgCl2 in mg/l) × _____________________________
2 × chemical equivalent of MgCl4
6.56 Engineering Chemistry
Calculate the temporary, permanent and total hardness of water in ppm, °Fr and °Cl.
Sol. Temporary hardness is due to bicarbonates of calcium and magnesium while permanent
hardness is due to sulphates and chlorides of calcium and magnesium.
Impurity Quantity (mg/L) Molecular weight MF Hardness (ppm) in CaCO3
Assumed equivalent
Ca(HCO3)2 4 162 100
____ 100
4 × ____
162 162
Mg (HCO3)2 6 146 100
____ 6 × ___
100
146 146
CaSO4 8 136 100
____ 8 × ___
100
136 136
MgSO4 10 120 100
____ 10 × ___
100
120 120
Type–II
Problems based on EDTA method
4. 20 ml of standard hard water (containing 15 gm CaCO3 per litre) required 25 ml EDTA
solution for end point. 100 ml of water sample required 18 ml EDTA solution, while same
water after boiling required 12 ml EDTA solution. Calculate carbonate and non-carbonate
hardness of water. Which buffer is used in this titration and what is its pH?
Sol. 1 L SHW ∫ 15 gm CaCO3 equivalent
\ 1 ml SHW ∫ 15 mg CaCO3 equivalent
Standardisation of EDTA
25 ml EDTA solution ∫ 20 ml
20
\ 1 ml EDT solution = ___ ml SHW
25
20
= ___ × 15 mg CaCO3 equivalent
25
1 ml EDTA solution = 12 mg CaCO3 equivalent
Calculate of total hardness
100 ml HW = 18 ml EDTA equivalent
18
\ 1 ml HW = ____
ml EDTA solution
100
18
= ____ × 12 mg CaCO3 equivalent
100
18
\ 1000 ml HW = ____
× 12 × 1000 mg CaCO3 equivalent
100
\ Total hardness = 2160 ppm
Calculate of permanent hardness (non-carbonate hardness)
100 ml BHW = 12 ml EDTA solution
12
\ 1 ml BHW = ____
ml EDTA solution
100
12
= ____ × 12 mg CaCO3 equivalent
100
12
\ 1000 ml BHW = ____
× 12 × 1000 mg CaCO3 equivalent
100
\ Total hardness = 1440 ppm
\ Carbonate hardness = 2160 – 1440 ppm
= 720 ppm.
Buffer solution used is NH4Cl + NH4OH, whose pH is 10.
5. 50 ml of standard hard water containing 1 mg pure CaCO3 per ml consumed 20 ml of EDTA.
50 ml of a water sample consumed 25 ml of same EDTA solution, using EBT. Calculate the
total hardness of water sample in ppm.
6.58 Engineering Chemistry
Type–III
Problems based on Alkalinity of water
6. 100 ml of a raw water sample on titration with N/50 H2SO4 required 12.4 ml of acid to
phenolphthalein end point and 15 ml of the same acid at methyl orange end point. Determine
the type and extent of alkalinity present in the water sample.
Sol. At phenolphthalein end point
Volume of acid used = A = 12.4 ml
Water vs Acid
N1V1 = N2V2
1
\ N1 × 100 = ___ × 12.4 [V2 = A = 12.4 ml]
50
1
\ N1 = _____
× 12.4
5000
1
\ Strength of terms of CaCO3 = _____ × 12.4 × 50 gm/L
5000
\ Phenolphthalein alkalinity = P = 0.124 × 103 mg/L
= 124 ppm.
At methyl orange end point:
Volume of acid used = A+B
= 15.0 ml = V4
Water vs Acid
N3V3 = N4V4
Water Treatment 6.59
1
\ N3 × 100 = ___ × 15.0
50
1
\ N3 = _____
× 15
5000
1
\ Strength of terms of CaCO3 = _____
× 15 × 50
5000
= 0.150 gm/L
\ Methyl orange alkalinity = M = 0.150 × 103 mg/L
= 150 ppm.
Relation:
1
( 1
P (=124 ppm) > __ M __
2 )
× 150 = 75 ppm
2
Nature:
Therefore, we have
CO3–2 alkalinity = 2 (M – P) = 2 (150 – 124)
= 52 ppm
OH– alkalinity = (2P – M) = (2 × 124 – 150)
= 98 ppm.
7. 50 ml of a sample of water required 12.5 ml of N/50 H2SO4 at phenolphthalein end point.
An additional 2.5 ml of N/50 H2SO4 was used at methyl orange end point. Calculate the
different types of alkalinity present in the water sample.
Sol. Phenolphthalein alkalinity
Volume of acid use = A = 12.5 ml
Water vs Acid
N1V1 = N2V2
1
\ N1 × 50 = ___
× 12.5 [A = V2 = 12.5 ml]
50
1
\ N1 = _____
× 12.5
2500
1
\ Strength of terms of CaCO3 = _____ × 12.5 gm/L
2500
1
\ Phenolphthalein alkalinity = _____
× 12.5 × 103 mg/L
2500
P = 250 ppm.
Methyl orange alkalinity
Further acid used = B = 2.5
Total volume of acid used = A+B
= 12.5 + 2.5 = 15.0 ml
Water vs Acid
N3V3 = N4V4 (A + B = V4 = 15.0 ml)
6.60 Engineering Chemistry
1
\ N3 × 100 = ___ × 15.0
50
1
\ N3 = _______
× 15
50 × 50
1
\ Strength of terms of CaCO3 = _______
× 15 × 50 gm/L
50 × 50
1
\ Methyl orange alkalinity = M = _______
× 15 × 50 × 103 mg/L
50 × 50
= 300 ppm.
Relation:
1
( 1
P (250 ppm) > __ M __
2 )
× 300 = 150 ppm
2
Nature:
Therefore, we have
CO3–2 alkalinity = 2 (M – P) = 2 (300 – 250)
= 100 ppm
OH– alkalinity = (2P – M) = (2 × 250 – 300)
= 200 ppm.
8. 100 ml of water sample, on titration with N/50 H2SO4 using phenolphthalein as indicator,
gave the end point when 10 ml of acid were run down. Another lot of 100 ml of the sample
also required 10 ml of the acid at methyl orange end point. What is the alkalinity of the
sample? Comment on its nature.
Sol.
Volume of acid used = A = 10 ml
Water vs Acid
N1V1 = N2V2
1
\ N1 × 100 = ___ × 10 [A = V2]
50
1 10
\ N1 = ___
× ____
50 100
1 10
\ Strength of terms of CaCO3 = ___ × ____
× 50 gm/L
50 100
1 10
= ___ × ____ × 50 × 103 mg/L
50 100
= 100 mg/L
\ Phenolphthalein alkalinity = P = 100 ppm.
Methyl orange alkalinity:
Another lot of 100 ml of the sample also required 10 ml of the acid.
Another lot of 100 ml of the sample also required 10 ml of the acid.
Volume of acid used at = A + B = 10 ml
Water Treatment 6.61
1
\ N3 × 100 = ___ × 33
50
1 1
\ N3 = ___ ____ × 33
×
50 100
1 1
\ Strength of terms of CaCO3 equivalent = ___ × ____ × 33 × 50 gm/L
50 100
1 1
\ Methyl orange alkalinity = M = ___ × ____ × 33 × 50 × 1000 mg/L
50 100
M = 330 ppm
Relation:
1
P (= 95 ppm) > __ M __
2
1
( )
× 330 = 165 ppm
2
Nature:
The alkalinity of water is due to CO3–2 and HCO3–2 ions.
CO3–2 alkalinity = 2P = 2 × 95 = 190
HCO3 – alkalinity = M – 2P = 330 – 190
= 140 ppm.
Type–IV
Problems based on Lime soda process
10. A sample of water contains following impurities: Mg (HCO3)2 = 73 mg/L, CaCl2 = 222 mg/L,
MgSO4 = 120 mg/L, Ca (NO3)2 = 164 mg/L, calculate the quantity of lime (74% pure) and
soda (90% pure) needed for softening 5000 L of water.
Sol. Conversion into CaCO3 equivalent
S. No. Constituents Amount mg/L MF CaCO3 equivalent
1. Mg (HCO3)2 73 100
____ 100
73 × ___ = 50 mg/L
146 146
100 100
2. CaCl2 222 ___ 222 × ___ = 200 mg/L
111 111
3. MgSO4 120 100
___ 100 = 100 mg/L
120 × ____
120 120
4. Ca (NO3)2 164 100
___ 100 = 100 mg/L
164 × ____
164 164
74 100
Lime required = ____
[2 × Mg(HCO3)2 + MgSO4 as CaCO3 eq] ________
× volume of
100 % purity
water
74 100
= ____
[2 × 50 + 100] × ____
× 5000
100 74
= 200 mg/L × 5000 L = 106 mg = 1 kg
Water Treatment 6.63
106 100
Soda required = ____
[CaCl2 + MgSO4 + Ca (NO3)2 as CaCO3 eq] ________
× volume of
100 % purity
water
106 100
= ____
[200 + 100 + 100] mg/L × ____
× 5000 L
100 90
= 2,356,000 mg = 2.356 kg
11. Calculate the quantities of lime and soda required for cold softening of 2, 00, 000 liters of
water using 16.4 ppm of sodium aluminates as a coagulant. The results of the analysis of
raw water and softened water are as follows:
Raw water Softened water
Ca+2 – 160 ppm CO3–2 – 30 ppm
Mg+2 – 72 ppm OH– – 17 ppm
–
HCO 3 – 732 ppm
Dissolved CO2 – 44 ppm
12. Write the chemical equations involved.
Sol.
S. No. Constituents Amount (in ppm) MF CaCO3 equivalent
Raw water
1. Ca+2 160 100
____ 100 × 160 = 400
____
40 40
2. Mg+2 72 100
____ 100 × 72 = 300
____
24 24
3. HCO3– 732 100 100
____ ____ × 732 = 600
122 122
4. CO2 44 100
____ 100 × 44 = 100
____
44 44
5. NaAlO2 16.4 100
____ 100
____
× 16.4 = 10
164 164
Treated water
1. OH– 17 100
____ 100 × 17 = 50
____
34 34
2. CO3–2 30 100
____ 100 × 30 = 50
____
60 60
74
Lime required for just softening = ____
[Mg+2 + HCO3– + CO2 – NaAlO2 as CaCO3 eq]
100
74
= ____
[300 + 600 + 100 – 10]
100
= 732.6 ppm.
106
Soda required for just softening = ____
[Ca+2 + Mg+2 – HCO3 as CaCO3 eq]
100
6.64 Engineering Chemistry
106
= ____
[400 + 300 – 600]
100
= 106 ppm.
Reactions involved to get excess OH– and CO3–2 ions are
Ca (OH)2 Æ Ca+2 + 2OH–
+2
Ca + Na2CO3 Æ CaCO3 + 2Na+
Na2CO3 Æ 2Na+ + CO3–2
Lime required for excess OH– ions in treated
74
Water = ____
[OH– as CaCO3 eq
100
74
= ____
× 50
100
= 37 ppm.
Soda required for excess OH– ions and CO3–2 ions in treated
106
Water = ____
[OH– + CO3–2 as CaCO3 eq]
100
106
= ____ [50 + 50]
100
= 106 ppm.
Total lime required for 2,00,000 litres of
Water = [6.1 + 6.3] × 2,00,000 mg
200000
= (732.6 + 37) × _______
kg
104
= 769.6 × 0.2 kg
= 153.92 kg.
Total soda required for 200000 litres of
Water = [6.2 + 6.4] × 200000 mg
200000
= [106 + 106] × _______
kg
106
= 212 × 0.2 kg
= 42.4 kg
12. Calculate the quantity of lime (74% pure) and soda (90% pure) required for softening 50,000
litres of water containing
Mg (HCO3)2 = 50 mg/L MgCl2 = 6 mg/L
Ca (HCO3)2 = 81 mg/L CO2 = 44 mg/L
HCl = 73 mg/L Al2 (SO4)3 = 57 mg/L
Sol. Conversion into CaCO3 equivalent
Water Treatment 6.65
50 × ___
100
1. Mg(HCO3)2 50 ____
100 = 34.26
146 146
81 × ___
100
2. Ca(HCO3)2 81 ____
100 = 50
162 162
6 × ___= 6.31
3. MgCl2 6 100
____ 100
95 95
44 × ___
100
4. CO2 44 ____
100 = 100
44 44
73 × ___
100
5. HCl 73 ____
100 = 100
73 73
57 × ___
100
6. Al2 (SO4)3 57 ____
100 = 50
114 114
74
Lime requirement = ____
[Ca (HCO3)2 + 2 × Mg (HCO3)2 + Al2 (SO4)3 + MgCl2 + CO2 +
100
100 Volume of water
HCl as CaCO3 eq] × ________
× ______________
kg
% purity 106
74 100 50000
= ____
[50 + 2 × 34.26 + 50 + 6.31 + 100 + 100] × ____
× ______
kg
100 74 106
50000
= 374.83 × ______
= 18.74 kg.
106
106
Soda requirement = ____
[MgCl2 + Al2 (SO4)3 + HCl as CaCO3 eq]
100
100 Volume of water
× ________
× ______________
kg
% purity 106
106 100 50000
= ____
[6.31 + 50 + 100] × ____
× ______
kg
100 90 106
74
Lime requirement = ____
[CaCO3 + 2 × MgCO3 + MgCl2 in terms of CaCO3 eq] × volume
100
of water
74 50000
= ____ [25.0 + 2 × 171.4 + 100] × ______ kg
100 106
74 50000
= ____ (467.8) × ______
= 17.31 kg.
100 106
Type–V
Problems Based on Zeolite Process
14. The hardness of 40,000 litres of a sample of water was completely removed by passing it
through a zeolite softener. The softener then required 150 litres of sodium chloride (Brine)
solution containing 100 g/litre of NaCl for regeneration. Calculate the hardness of the water
sample.
Sol. Solution of sodium chloride used for regeneration contains 100 gm NaCl per litre.
So NaCl contained in 150 litres of sodium chloride solution
= 100 gm/L × 150 L
= 100 × 150 gm
= 15,000 gm of NaCl.
100
15,000 gm of NaCl = 15,000 × ____
g CaCO3 eq
117 ( 100
MF = ____ )
117
= 12820.51 g CaCO3 eq
= 12820.51 × 103 mg CaCO3 eq
= 1.282 × 107 mg CaCO3 eq
\ Hardness of 40,000 litres of
water = 1.282 × 107 mg CaCO3 eq
Hardness of 1 litre of
1.282 × 107
Water = __________
mg CaCO3 eq
40,000
= 320.5 mg CaCO3 eq
Hardness of water = 320.5 mg/L = 320.5 ppm.
Water Treatment 6.67
15. An exhausted zeolite softener required 500 litres of sodium chloride solution containing
100 gm/L of NaCl for regeneration. If the hardness of water is 600 ppm, calculate the volume
of water softened by softener.
Sol. Sodium chloride solution used for regeneration contains 100 gm NaCl per litre.
\ NaCl contained in 500 litres of sodium chloride solution
= 100 gm/L × 500 L
= 50,000 gm of NaCl
100
Now, 50,000 of NaCl = 50,000 × ____
g CaCO3 eq
117
= 4.27 × 104 g CaCO3 eq
= 4.27 × 107 mg CaCO3 eq
Let ‘v’ litres of 600 ppm (i.e, 600 mg/L) of water contains 4.27 × 107 mg CaCO3 eq
hardness.
V × 600 = 4.27 × 107
4.27 × 107
V = _________
Litre
600
V = 7.116 × 104 Litre.
SuMMARY
1. (a) Hardness – property of water which prevents lather formation with soap solution.
(b) Types of hardness
(i) Temporary hardness – due to presence of bicarbonates of calcium, magnesium and
other heavy metals and carbonate of iron.
(ii) Permanent hardness – due to the presence of sulphates and chlorides of calcium
magnesium, iron and other heavy metals.
(a) Units of hardness and inter relation.
1 ppm = 1 mg/L = 0.1° Fr = 0.07°Cl
(b) Temporary hardness is removed by simple boiling.
(c) Permanent hardness can be removed by
(i) Zeolite process
(ii) Lime soda process
(iii) Ion exchange process
(iv) Calcium carbonate equivalent
[Mass of hardness producing substance] × 100
Calcium carbonate equivalent = ________________________________________________
2 × Chemical equivalent of hardness producing substance
2. EDTA method
(a) Is used to determine total, temporary and permanent hardness.
(b) It is complexometric titration
6.68 Engineering Chemistry
V2
Permanent hardness = ___
× 1000 ppm.
V1
V2
Temporary hardness = ___ ( V2
× 1000 – ___
V1
× 1000 ppm
V1 )
3. Alkalinity of water
(i) H+ + OH– H 2O
P=A
(ii) H+ + CO3–2 HCO3– M = A + B
(iii) HCO3– + H+ H2O + CO2 B
4. Lime – soda process
74
(a) Lime (purity %P) required for softening = ____
[Temp Ca+2 + 2 × temp. Mg+2 + perm
100
(Mg+2 + Fe +2 + Al+3) + CO2 + H+ (HCl or H2SO4) + HCO –3 - NaAlO2 in terms of
100 V
CaCO3 eq] × ________
× ___
kg
% purity 106
106
(b) Soda (Purity = %P) required = ____
[Perm (Ca+2 Mg+2 + Al+3 + Fe +2
) + H+ (HCl or
100
100 V
H2SO4) – HCO –3 in terms of CaCO3 eq] × ________
× ___
kg.
% purity 106
Where x = 2 – 10
Y =2–6
Na2Z + Ca+2 CaZ + 2Na+
Zeolite Hardness causing ions.
Unsolved Questions
1. Define hardness. What are the different types of hardness of water?
2. Differentiate between hard water and soft water.
3. Explain the causes of hardness of water.
4. Write the constituents responsible for temporary hardness of water. Discuss the treatment
method.
5. What is temporary hardness? How can it be removed?
6. Differentiate between carbonate and non carbonate hardness.
7. How is hardness expressed? Give various units of hardness. How are they related to each
other?
8. Why do we express hardness of water in terms of CaCO3 equivalent?
9. Describe a method to determine temporary, permanent and total hardness of hard water.
10. Write the names of indicator and buffer solution used in the determination of the hardness
of water by EDTA method.
11. Write the structure and complete name of EDTA and EBT.
12. Draw neat and labeled diagram of permutit (or zeolite) process of softening water. Discuss
the chemistry involved in it. Discuss its merits over lime soda process.
13. Explain the lime soda process used for softening the hard water.
14. Define zeolite. How does zeolite function in removing the hardness of water?
15. Compare zeolite and lime soda process of softening.
16. What is the principle of EDTA titration? Briefly describe the estimation of hardness of water
by EDTA method.
17. Write short notes on
(i) Scale and sludge formation
(ii) Caustic embrittlement
(iii) Boiler corrosion
(iv) Internal conditioning
18. Explain the following
(i) Hard water does not give lather with soap.
(ii) Alkalinity of water can’t be due to simultaneous presence of OH–, HCO3– and CO3–2.
(iii) Temporary hardness is removed by boiling.
(iv) Buffer solution (NH4OH + NH4Cl) is added during determination of hardness of water
by EDTA method.
19. Write short notes on
(i) Potable water
(ii) Polished water
(iii) Alkalinity of water
(iv) Zeolite process and its limitation
6.70 Engineering Chemistry
20. What are boiler troubles and what are their consequences.
21. Prove that 1 ppm = 1 mg/L.
22. Distinguish between temporary and permanent hardness of water.
23. Differentiate between scale and sludge.
24. Describe the ion exchange method of demineralisation of water.
Type–I
Problems based on Calcium Carbonate Equivalent and Harness
25. A sample of water contains 81 mg/L Ca (HCO3) 2, 73 mg/L Mg (HCO3) 2, 120 mg/L
MgSO4 and 136 mg/L CaSO4. Calculate the temporary and permanent hardness of the water
sample.
[Ans: Temporary hardness = 100 ppm, Permanent hardness = 200 ppm]
26. A sample of water on analysis has been found to contain following in mg/L Ca (HCO3)2
= 4.86, CaSO4 = 6.80, MgCl2 = 95.0, Mg (HCO3)2 = 73.0
Calculate the carbonate and non carbonate hardness also in ppm. Express your answer also
in °Fr and °Cl.
[Ans: Carbonate hardness = 53 ppm, 5.3 °F, 3.71 °Cl, Non carbonate
hardness = 105 ppm, 10.5 °F, 7.35 °Cl]
Type–II
Problems based on EDTA Method
27. 0.28 gm of CaCO3 was dissolved in HCl and the solution was made to one litre with
distilled water. 100 ml of this solution required 28 ml EDTA solution on titration. 100 ml
of an unknown hard water sample required 36 ml of the same EDTA solution on titration
using EBT as an indicator. After boiling 100 ml of this water, cooling, filtering and then
titration required 15 ml of EDTA solution. Calculate the temporary and permanent hardness
of water.
[Ans: Temporary hardness = 210 ppm, Permanent hardness = 150 ppm]
28. 1 L of a standard hard water sample contains 1 g of CaCO3. 100 ml of this standard hard
water required 25 ml EDTA on titration. 100 ml of an unknown hard water sample required
10 ml of same EDTA on titration. After boiling 100 ml of this water, cooling, filtering and
then titration, required 5 ml of EDTA solution. Calculate the carbonate and non carbonate
hardness of water.
[Ans: Non-Carbonate hardness = 200 ppm, Carbonate hardness = 200 ppm]
Water Treatment 6.71
Type–III
Problems based on Alkalinity of water
29. 100 ml of a water sample, on titration with N/50 H 2SO 4 required 12 ml of acid to
phenolphthalein end point. Further 12 ml of the same acid was used at methyl orange end
point. Calculate the different types of alkalinity present in the water sample.
[Ans: CO3–2 alkalinity = 240 ppm]
30. 500 ml of a water sample, on titration with N/50 H2SO4 gave a titre value of 7.5 ml at
phenolphthalein end point and 20.0 ml at methyl orange end point. Calculate the different
types of alkalinity present in the water sample.
[Ans: OH– alkalinity = Nil, CO3–2 alkalinity = 30 ppm and HCO3– alkalinity = 10 ppm]
Type–IV
Problems based on Lime–Soda process
31. Calculate the amount of lime (84% pure) and soda (92% pure) required for treatment of
10,000 litres of water containing:
Ca (HCO3)2 = 40.5 ppm Mg (HCO3)2 = 36.5 ppm
MgSO4 = 60.0 ppm CaSO4 = 68.0 ppm
CaCl2 = 111.0 ppm And NaCl = 20.0 ppm
[Ans: L = 1.10 kg S = 2.304 kg]
32. Yamuna canal water on analysis gave the following results:
CO2 = 22 ppm
HCO3– = 305 ppm Ca+2 = 80 ppm
Mg+2 = 48 ppm Total solid = 500 ppm
Calculate carbonate and non-carbonate hardness of the water sample. Also calculate the
amount of lime and soda that would be required for softening the above water, if 417 ppm
of FeSO4. 7H2O is used as coagulant. (At weight Ca = 40, Mg = 24, Fe = 56, S = 32)
[Ans: Carbonate hardness = 250 ppm, non-carbonate
hardness = 150 ppm, L = 629 mg/L, S = 38 mg/L]
33. Calculate the amount of lime (87% pure) and soda (91% pure) required to soften one million
litres of water containing:
Mg+2 = 25 mg/L Ca+2 = 20 mg/L
–
HCO3 = 150 mg/L
CO2 = 30 mg/L Na+ = 10 mg/L
[Ans: L = 218.9 kg, S = 33.6 kg]
Chapter 7
The phase rule is an important tool used for the quantitative treatment of systems in equilibrium.
It enables us to predict the conditions that must be specified for a system to exhibit equilibrium.
J.W. Gibbs enunciated the phase rule in 1876 while investigating heterogeneous equilibrium. According
to the phase rule, for systems in complete internal equilibrium,
F =C–P+2
Where C is the number of components; P is the number of phase and F is the number of degree
of freedom.
1. Definitions
1.1 Phase
A phase is defined as any homogeneous and physically distinct part of a system which is bounded
by a surface and is mechanically separable from other parts of the system. Examples of various
types of phases are:
(i) A gas mixture constitutes a single phase since gases are completely miscible.
(ii) Immiscible liquids constitute different phases. Thus, carbon tetrachloride and water do not
mix with each other, so form two phases.
(iii) A system consisting of a liquid in equilibrium with its vapor constitutes two phases.
(iv) Ice-liquid water – water vapor constitutes system containing three phases.
(v) Completely miscible liquids such as water and alcohol and benzene and chloroform constitute
one–phase system.
(vi) Consider the decomposition of calcium carbonate to CO2 and CaO.
Here, there are two solid phases and one gaseous phase. So it is a three-phase system. It should
be noted that each phase in a heterogeneous system is homogenous in itself. When various phases
are in equilibrium with one another in a heterogeneous system, there can be no transfer of energy
7.2 Engineering Chemistry
or mass from one phase to another. This means that at equilibrium, the various phases must be at
the same temperature and pressure.
1.2 Components
The number of components of a system at equilibrium is defined as the smallest number of
independently variable constituents by means of which the composition of each phase can be expressed
either directly or in terms of chemical equation. We may consider a few examples.
1. Water exists in three phases,
Ice liquid vapor
However, the composition of each phase can be expressed in terms of H2O. Hence it is one
component system. Components can be given by the equation C = N – E
Where E is the number of independent equations relating the concentrations of the N species
and C is component. for examples
(i) Consider a water system at equilibrium there are three phases
It is a one component system because each phase can be expressed in terms of only one
component.
2. Sulphur exists in four phases i.e., rhombic sulphur, monoclinic sulphur, liquid and vapor.
But since the composition of each phase can be expressed in term of sulphur only, it is one
component system.
3. Consider an aqueous sucrose solution. The composition of the solution phase can be expressed
by specifying the amounts of sugar and water. Hence, it is a two-component system.
4. In a chemically reactive system involving reactions between various species, the situation is
slightly different consider the thermal decomposition of CaCO3 in a closed vessel:
The system contains three phases, CaCO3(s), CaO (s) and CO2(g). However, as a result of the
existence of equilibrium, the number of components is only two. If we chose them as CaO
and Co2 then the composition of the solid CaCO3 can be given by CaO + CO2.
If CaCO3 and CO2 are taken as the components, then the composition of solid CaO can be
given by CaCO3 – CO2 and so on.
In a chemically reactive system, the number of components is given by
C =N–m–n–R
Where N is the number of chemical species, m is the number of independent equilibrium
conditions, n is the number of relations between concentrations due to initial concentrations due to
initial conditions.
The Phase Rule 7.3
In this system we have 3 substance and they are related by one equation. So number of components
are 2. Due to existence of equilibrium, composition of each of the three phases can be expressed in
terms of any two constituents, CaCO3, CaO and CO2 as shown below.
If CaCO3 and CaO constituents
Phase Component
CaCO3(s) CaCO3 + 0CaO
CaO (s) 0 CaCO3 + CaO
CO2(g) CaCO3 – CaO
If CaCO3 (s) and CO2 constituents are chosen
Phase Component
CaCO3(s) CaCO3 + 0CO2
CaO (s) CaCO3 – CO2
CO2(g) 0CaCO3 + CO2
If CaO and CO2 constituents are chosen
Phase Component
CaCO3(s) CaO + CO2
CaO (s) CaO + 0CO2
CO2(g) 0CaO + CO2
Thus in all the cases, only two components are required to express the composition of each phase.
Hence it is a two-component system and is also called binary system.
P+F =C+2
Or
F =C–P+2
7.4 Engineering Chemistry
Derivation of the Phase Rule: We shall now derive phase rule. Consider a system of C components
(C1, C2, C3....Cc) distributed between P phases (a, b, g, ....P). Assume that the passage of the
component from one phase to another does not constitute a chemical reaction. The state of each
phase of a system is completely specified by the two variables, temperature and pressure and also
by composition of each phase. In other words, the state of each phase is specified by
T, P (x1a , x2a , xCa ), (x1b , x2b , xCb ), ...(x1P, xPb , xCP) ...(1)
Where xis are composition of the compositions of the component. The total number of variables
is thus CP + 2. However, in equation (1) all the variables are not independent since in each phase,
the sum of the mole fraction must equal unity, i.e.,
In other words,
Sx i, p = 1 (i = 1, 2, 3, ...C)
For all P the phases separately. There are thus P relations of this type.
Again, for complete equilibrium to exist between the phases, the chemical potential of each
species must be same in each phase, i.e.,
m1, a = m1, b = m1, g = ... m1, P
m2, a = m2, b = m2, g = ... m2, P ...(3)
mC, a = mC, b = mC, g = ... mC, P
We see that there are P – 1 separate equations for each component. Hence, for C components,
the number for each equation is C(P – 1).
Also, the equilibrium conditions for a chemical reactions require that the chemical affinity, Af
for each reactions at equilibrium must be zero. i.e.,
F = (CP + 2) – (P + CP – C + r ¢)
= 2 + (C – r ¢) – P ...(6)
Equation 6 is known as Gibbs phase rule. If the system in non-reactive, i.e., no reaction takes place
in it, then equation of type Af = 0 will be absent, i.e., r ¢ = 0. Hence, the phase rule becomes
F =C–P+2 ...(7)
The Phase Rule 7.5
We see from this equation that for a system having a given number of components, greater
number of phases smaller will be the number of degree of freedom. Thus, for one component system
like water, the maximum number of phases that can coexist at equilibrium is three so that for this
degree of freedom is zero. In general, for a system having a given number of components where
number of phases is maximum, the degree of freedom is zero. On the other hand, the system with
the given number of phases, larger the number of components, greater will be the number of the
degrees of freedom. In these cases, variables such as T, P and concentration must be specified in
order to describe the state of the system completely.
The phase rule does not tell us anything regarding the composition of matter. It merely states that
a system having the same number of the degrees of freedom behave alike thermodynamically. The
phase rule is an important generalization that enables us to investigate highly complex heterogeneous
equilibria.
Example 1 Determine phase, component and degree of freedom in the given system
MgCO3(s) MgO (s) CO2(g)
Solution: Number of phases = 3
Components = Substance – Relation
= 3–1
= 2
Degree of Freedom = C–P+2
= 2–3+2
= 1 (System is univariant)
Example 2 Determine phase, component and degree of freedom in the given system i.e., in the
dissociation of ammonium chloride.
Solution: It dissociates as follows:
(i) NH4Cl (s) NH3(g) + HCl (g)
There are two phases, solid and gas. The system will be a one component or two components
depending upon the relative quantities of HCl and NH3.
(a) When ratio of NH3(g) and HCl (g) is 1:1 then we write one more equation with the above
equation i.e.,
(ii) Concentration of NH3 = concentration of HCl
Number of Phases = 2
Number of components = Substance – Relation
= 3 – 2
= 1
Degree of Freedom = C – P + 2
= 1 – 2 + 2
= 1 (Univariant)
(b) When ratio of NH3 : HCl is 1:2 (i.e., not same), then we cannot write (ii) equation as in
first case so,
Number of components = 3 – 1 = 2
7.6 Engineering Chemistry
Degree of Freedom = C – P + 2
= 2 – 2 + 2
= 2 (Bivariant)
Example 3 Determine phase, component and degree of freedom in the given system
N2O4(g) 2NO2(g)
Solution: Number of phases = 1
Number of components = Substance – Relation
= 2–1=1
Degree of Freedom = 1–1+2
= 2 (Bivariant)
Example 4 Determine phase, component and degree of freedom in the given system
Solution:
(i) C (s) + O2(g) CO2(g)
(ii) C (s) + 1/2O2(g) CO (g)
Number of phases = 2
Number of components = 4–2
= 2
Degree of Freedom = 2–2+2
= 2 (Bivariant)
Example 5 Determine phase, component and degree of freedom in the system of dilute solution of
H2SO4 in water.
Solution:
(i) H2SO4 + H2O Æ H3O + + HSO4 –
(ii) H2SO4 – + H2O Æ H3O + + SO4 –
(iii) Electroneutrality (Number of cations and anions are equal)
Number of phases = 1
Number of components = 5 – 3
= 2
Degree of Freedom = 2 – 1 + 2
= 3 (Trivariant)
Example 6 Determine phase, component and degree of freedom in an aqueous solution saturated
with respect to both NaCl and KCl and is in equilibrium with the vapor phase.
Solution:
(i) NaCl Na+ + Cl–
(ii) KCl K+ + Cl–
(iii) H2O (l) H2O (v)
(iv) Electroneutrality
Number of phases = 4
The Phase Rule 7.7
Number of components = 7 – 4 = 3
Degree of Freedom = 3 – 4 + 2 = 1 (Univariant)
Example 7 Determine the number of phases, components and degree of freedom in a mixture of
N2, H2 and NH3 at equilibrium.
Solution:
2N2(g) + 3H2(g) 2NH3(g)
Number of phases = 1
Number of components = 3–1
= 2
Degree of Freedom = 2–1+2
= 3 (Trivariant)
Example 8 Determine the number of phases, components and degree of freedom in the given
system:
Na2SO4.10H2O (s) Na2SO4(s) + 10H2O (g)
Number of phases = 3
Number of components = 3 – 1
= 2
Degree of Freedom = 2 – 3 + 2
= 1 (Univariant)
F = 0 i.e. to define the system completely, nothing has to be specified.
F = 1 i.e. such a system can be completely defined by specifying either pressure or temperature.
This is because on fixing one variable, the other becomes automatically fixed.
F = 2 i.e. such a system can be completely defined by specifying both temperature and
pressure.
1.5 Phase Diagram
Is a graphical representation of the pressure and temperature under which two or more physical
states can exist together in a state of dynamic equilibrium. Phase diagram illustrates the conditions
of equilibrium between various phases of a substance. If the temperature is plotted against pressure
the diagram is called P-T diagram.
The study of phase diagram is vital for proper understanding of the relative stability of equilibrium
between phases with the help of knowledge of the number of phases and components of the system,
7.8 Engineering Chemistry
phase rule enables one to predict clearly the conditions under which a system can remain in
equilibrium.
The three forms of water (Ice, water and vapor) constitute the following equilibrium:
(i) Single phase equilibrium
(a) Solid (ice) – Represented by area BOC
(b) Liquid (water) – Represented by area AOC
(c) Gas (vapor) – Represented by area AOB
(ii) Two-phase equilibrium
(a) Solid (ice) Liquid (water) – Represented by curve OC
(b) Liquid (water) Gas (water vapor) – Represented by curve OA
(c) Solid (ice) Gas (water vapor) – Represented by curve OB
(iii) Three-phase equilibrium
(a) Solid (ice) liquid (water) Gas (vapor) – Represented by triple point O.
The areas: Area BOC represents the solid phase, which is thermodynamically most stable state under
these conditions. Area AOC represents the liquid (water) phase in the system and similarly area AOB
represents the gas phase in the system. Thus these areas represent one phase equilibria.
In order to define the system completely at any point in the area, it is essential to specify both
the temperature and pressure. Therefore these areas have two degrees of freedom and are called
bivariant systems. It can be concluded by the phase rule equation.
F =C–P+2
= 1 – 1 + 2 = 2 (Bivariant system)
The Curves: The curve OC (melting or fusion curve) represents the equilibrium between ice and
water and it is known as melting point curve. The very little slope of the curve shows that very
high pressure is required to bring about significant changes in melting point of ice. The inclination
7.10 Engineering Chemistry
of the curve OC towards the pressure axis indicates that melting point of ice slightly decreases by
increasing pressure. The reason for this uncommon behavior is the decrease in the volume, when ice
melts into water. Thus ice transforms into denser water when the pressure is raised.
1.10 Triple Point
It is a point at which the gaseous, liquid and solid phases of a substance coexist in equilibrium.
For a given substance, the triple point occurs at a unique set of values of temperature, pressure and
composition. In water system the point O where all the three curves OC, OA and OB meet is known
as triple point. At this point all the three phases are in equilibrium which is attained at 0.0098°C
temperature and 4.58 mmHg pressure. Since there are three phases and one component so the degree
of freedom will be
F =C–P+2
= 1 – 3 + 2 = 0 (Non-variant system)
If either the temperature or the pressure or both are changed, the three phases would no longer
coexist and at least one of them would disappear.
On adding nucleus of ice (solid state), the system reverts to true stable system where the
equilibrium exist between solid and vapor.
Solid Vapor
2. Polymorphism
The existence of a given substance in more than one crystalline form possessing different physical
properties is known as polymorphism. It occurs in number of elements and compounds, when it
occurs in elements, it is referred as allotropy.
Each polymorphic form constitutes a separate phase. The temperature at which one form changes
in to another at a given pressure is known as the transition temperature. For example rhombic sulphur
when heated under a pressure of one atmosphere changes in to monoclinic sulphur at 95.6°C. At
the same time monoclinic sulphur when cooled under a pressure of one atmosphere changes in to
rhombic sulphur at 95.6°C. Thus 95.6°C is the transition temperature at which one form of sulphur
changes reversibly into the other. Polymorphic forms which can undergo reversible transformation
into one another at the transition temperature are called enantiotropic forms.
In some cases polymorphic forms do not undergo reversible transformations into one another
for example diamond can be converted into graphite under suitable conditions of temperature and
pressure but reverse is possible. Such forms which cannot be reversibly transformed into one another
are called monotropic and the phenomenon is known as monotropy.
The curve OC is the transition curve which gives the effect of pressure on the transition
temperature of rhombic sulphur in to monoclinic sulphur. The equilibrium involved is (SR SM)
(both solid phases). The system is monovariant. Since the transformation of rhombic sulphur into
monoclinic sulphur is accompanied by increase in volume, the increase of pressure causes a rise in
the transition temperature.
The curve BC is the fusion curve for monoclinic sulphur. This gives the effect of pressure on
the melting point of monoclinic sulphur. The two phase equilibrium (SM SL) along the curve
BC is univariant. As melting of monoclinic sulphur is accompanied by a slight increase of volume.
Therefore curve BC slopes slightly away from the pressure axis. As the slope of this curve is much
less than that of the curve OC, the two curves meet at the point C. Thus, C is another triple point
where three phases rhombic sulphur, monoclinic sulphur and liquid sulphur are in equilibrium i.e.,
SR SM SL and the system is nonvariant. At C, the temperature is 151°C and pressure is
1290 atm.
The curve CD is the fusion curve for rhombic sulfur. The equilibrium along this curve is
SR SL . As the number of phases is 2, the system is monovariant.
Thus along the line OA¢, the metastable equilibrium SR SV exist. The vapor pressure at each
temperature, as can be seen, is higher than the vapor pressure of monoclinic sulphur which is a
stable phase in this range.
Similarly, if liquid sulphur is allowed to cool along the curve BE, the solid phase may not
separate out at B unless cooling is extremely slow. The line BA’ in this case represents the metastable
equilibrium between liquid sulphur and its vapor i.e., by SL SV. The point A¢, therefore
represented the melting point of the metastable rhombic sulphur. This is another triple point where
the three phases. SR SL SV coexists in metastable equilibrium. The temperature A¢ has
been found to be about 114°C.
The curve A¢C, evidently, gives the effect of pressure on the melting point of rhombic (metastable)
sulphur. In other words, this is the fusion curve of metastable rhombic sulphur along which rhombic
sulphur is in metastable equilibrium with the liquid.
3.2 Areas
As the curves AO and OC both involve rhombic sulphur in equilibrium with the vapor, Phase in one
and bounded by these lines which represents stable existence of rhombic sulphur alone.
Similarly curves BE and BC both have liquid phase as common, in equilibrium with vapor in
the first case and with solid monoclinic sulphur in the second case, the area bounded by these lines
represented liquid sulphur as the stable phase curves. Similarly, as the curves AO, OB, and BE have
vapor phase in common, the area lying below the lines represents only vapor as the stable phase.
Lastly, the lines OC, OB, and BC have monoclinic sulphur as common phase the triangular area
bounded by these lines represents monoclinic sulphur as stable phase. The existence of this form of
sulphur, evidently is limited on all sides.
solved Questions
1. State phase rule.
Ans. Provided the equilibrium between any number of phases is not influenced by gravity, or
electrical, or magnetic forces, or by surface action but only by temperature, pressure and
concentration, then the number of degree of freedom (F) of the system is related to the
number of components (C) and of phases (P) by the phase rule equation, F = C – P + 2 for
any system at equilibrium at a definite temperature and pressure.
2. What is condensed phase rule?
Ans. When the pressure of the system remains constant (i.e., in which the vapor phase is not
considered), then the phase rule equation becomes: F = C – P + 1.
3. A system consists of benzene and water. What is the number of phases?
Ans. Two
4. How many components are present when NH4Cl is heated in a closed vessel?
Ans. One
5. Give the number of components of the system: Fe (s) + H2O (l) FeO (s) + H2(g)
Ans. Three
6. What is an invariant system?
7.14 Engineering Chemistry
Ans. In which the degree of freedom is zero i.e., no condition is required to be specified to define
the system.
7. Give an example of invariant system
Ans. A system containing ice, water and water vapor in equilibrium.
8. What is the triple point of water system?
Ans. Triple point is a point where all the there phases co exist, where the temperature is 0.0098°C
and pressure is 4.58mmHg.
9. What is the difference between a phase and a state of matter?
Ans. There are three states of matter–solid, liquid and gas. A phase is a sample of matter with
definite composition and uniform properties throughout the sample.
10. What is meant by transition?
Ans. The crossing of two-phase equilibrium curve in a phase diagram.
11. How many degrees of freedom are present in the following system?
(i) A gas in equilibrium with its solution in a liquid.
(ii) A solution of a solid in a liquid in equilibrium with solvent water.
(iii) Two partially miscible liquids in the absence of vapors.
(iv) I2(s) I2(g)
Ans. (i) F = C – P + 2 = 2 – 2 + 2 = 2
(ii) F = C – P + 2 = 2 – 2 + 2 = 2
(iii) F = C – P + 2 = 2 – 2 + 2 = 2
(iv) F = C – P + 2 = 1 – 2 + 2 = 1
12. Can four forms of sulphur, namely, rhombic, monoclinic, liquid and vapor coexist in
equilibrium at a particular temperature and pressure?
Ans. No (since F = C – P + 2 = 1 – 4 + 2 = – 1, i.e., negative)
13. What type of equilibrium exists between H2O(l) and H2O(g) at a temperature below 273K.
Ans. Metastable equilibrium
unsolved Questions
1. Explain the terms-phase, component and degree of freedom.
2. Define phase rule.
3. Write a note on (i) Triple point (ii) Metastable state.
4. Apply phase rule to water system.
5. Calculate the number of degrees of freedom in the following systems.
(i) 2KClO3(s) 2KCl (s) + 3O2(g)
(ii) KCl (s) – NaCl (s) – H2O (l)
(iii) CaCO3(s) CaO (s) + CO2(g)
(iv) 2H2S (g) 2H2(g) + S2(g)
(v) Na2SO4.10H2O (s) Na2SO4(s) + 10H2O (l)
(vi) H2O (s) H2O (g)
The Phase Rule 7.15
6. With the help of phase rule, calculate the degree of freedom of the following systems:
(i) Ice and water at equilibrium
(ii) Saturated solution of NaCl.
7. Water system is a representative system for explaining phase rule and phase equilibrium.
Explain.
8. Draw a neat and leveled diagram of water.
9. If there is no triple point in the diagram of one component system, then what inference do
you draw?
10. State the significance of triple point.
11. What is Gibbs phase rule?
12. Explain why KCl-NaCl-H2O should be regarded as a three-component system whereas KCl-
NaBr-H2O should be regarded as a four-component system.
13. Draw a neat and labeled diagram of sulphur.
14. How many triple points are there in sulphur system?
15. What is metastable state?
16. How many phases are there in following system at equilibrium?
(i) Mixture of O2 and N2.
(ii) Mixture of benzene and water.
(iii) A mixture of diamond powder and graphite.
(iv) A finely divided sulphur graphite and sodium chloride.
Chapter 8
1. INTRODUCTION
Efficiency in the use and production of heat and power is one of the major engineering problems of
the present day. The world’s energy demands are constantly increasing and to meet this expanding
requirement we look to various kinds of fuels. Material which possesses chemical energy is known
as fuel. The important fuels are carbon compounds and whole industrial society is based upon the
reaction.
Fuel + O2 Æ Combustion Product + Heat
C (s) + O2 (g) Æ CO2 (g) + DH = – 94.1 Kcal/mole
H2 + ½ O2 Æ H2O + DH = – 67.5 Kcal/mole
When C and H atom from coal and oil reacts with oxygen atoms chemical energy is released,
such reaction involves a rearrangement of the outer electron only at the atoms and the atomic nuclei
is unaffected.
A fuel may be defined as any combustible substance which is obtainable in bulk, which may be
burnt in atmospheric air in such a manner that the heat evolved is capable of being economically
used for domestic and industrial purposes for heating and generation of power.
Fuels in the broad sense, include the stored fuels that are available in the earth’s crust, viz.,
‘’fossil fuels’’ or those derived from them by an industrial process.
2. CLASSIFICATION
Fuels may be divided into two types:
(i) Primary fuels which occur in nature as such, and
(ii) Secondary fuels which are derived from the primary fuels.
Fuels may also be classified into three groups:
(a) Solid fuels,
(b) Liquid fuels, and
(c) Gaseous fuels.
8.2 Engineering Chemistry
The examples of each of these main classes of fuels are summarized in Table 1. This classification
is of practical significance because the equipment used for handling and burning of each class of
fuels is usually different for these three types of fuels:
3. CALORIFIC VALUE
One of the important properties of a fuel on which its efficiency is judged is its calorific value. The
calorific value of a fuel is defined as the amount of heat obtainable by the complete combustion of
a unit mass of the fuel.
The latent heat of steam is 587 Cal/g (or Kcal/Kg) or 1060B.Th.U./lb of water vapor produced.
H
Net C.V. = Gross C.V. – 9 × ____
× 587
100
= Gross C.V. – 0.09 × H × 587
Where H = % of hydrogen in the fuel.
In actual practical use of a fuel, it is rarely feasible to cool the combustion products at the room
temperature to allow the condensation of water vapor formed and utilize that latent heat; hence the
water vapor formed also is allowed to escape along with the hot combustion gases.
Fig. 1 (1) Strong cylindrical bomb made of stabilized austenitic steel, (2) Stainless steel rod electrode, (3)
Stainless steel tube electrode cum oxygen inlet, (4) Release valve, (5) Beckman thermometer, (6) Electrically
driven stirrer, (7) Firing terminals, (8) Calorimeter, (9) Fuse wire, (10) Crucible, (11) Screw cap, (12) Fuel pelet,
(13) Air jecket, (14) water.
Fuel and Combustion 8.5
2. A copper calorimeter vessel in which the bomb stands during the experiment.
3. An outer water-jacket enclosure.
4. A stirrer provided for stirring the water in the calorimeter at a uniform rat.
5. A thermometer graduated in one hundredths of a degree. Fixed zero or Beckman thermometers
are generally used.
6. Other necessary accessories for compressing the coal into a pellet, filling the bomb with
oxygen, etc.
Procedure
1. About 0.5 to 1 g of finely ground air-dried coal (preferably compressed into a pellet) is
accurately weighed into the crucible of the calorimeter.
2. A piece of fine platinum wire (0.0075 cm thick) is tightly stretched across the pole pieces
of the bomb and one end of a piece of a sewing cotton thread is tied round the wire. The
crucible is placed in position and the lose end of the cotton is arranged so as to be in contact
with the coal. Alternatively, a longer platinum wire is used and bent into a loop so as to
touch the coal pellet.
3. About 10 ml of distilled water are introduced into the bomb to absorb vapors of sulphuric
and nitric acids formed during the combustion and the lid of the bomb is screwed.
4. The bomb is filled with oxygen up to 25 atmospheres pressure and the firing wires are
attached to the terminals.
5. The calorimeter vessel is weighed; sufficient water is weighed to submerge the cover of the
bomb. The calorimeter vessel is then kept in the outer jacket on the insulating feet provided.
The bomb is then lowered in the calorimeter. The stirrer and the lid of the calorimeter vessel
are placed in position and the Beckman thermometer is adjusted.
6. The stirrer is started.
7. After 5 minutes, the temperature of the water is noted to the nearest 0.002°C and 5 more
readings are taken at one minute intervals.
8. At the end of the fifth minute, the electrodes are connected to a 6 to 12-volt battery to
ignite the charge and readings are continued at one-minute intervals. After the maximum
temperature is attained, readings are still continued until the rate of fall is uniform.
9. The stirrer is stopped and the bomb removed from the calorimeter. After allowing about
half an hour for the settlement of the acid mist within the bomb. The contents of the bomb
are washed into a beaker and the amounts of H2SO4 and HNO3 present in this solution are
determined.
Calculations
Let
Weight of the fuel sample taken = m grams
Higher or Gross calorific value of the fuel = L cals/gram
Weight of the water taken in the calorimeter = W grams
Water equivalent of the calorimeter, bomb, thermometer, stirrer, etc. = w grams
Initial temperature = t1°C
8.6 Engineering Chemistry
(W + w) (t 2 – t1)
\ (Gross C.V.) L = _____________
m
However, for more accurate results, the following correction will have to be incorporated in the
above equation: (i) Acids correction, tA, (ii) Fuse wire correction, tF, (iii) Cotton thread corrections,
tT and (iv) Cooling correction, tc, Accordingly, the above equation will have to be modified as:
Similarly the nitrogen present in the coal and part of that in the air in the bomb are converted
into HNO3
2N2 + 5O2 + 2H2O Æ 4HNO3; DH = – 57,160
(4 × 63) calories
(Eq. Wt. of
HNO3 = 63)
Since the above two reactions are exothermic and since the heat thus liberated is not
obtainable in practical use of coal (because SO2 and NO2 pass off into the atmosphere)
correction must be made for the heat liberated in the bomb by the formation of H2SO4 and
HNO3, as follows:
(a) 3.6 calories should be subtracted for each ml of N/10, H2SO4 formed.
(b) 1.43 calories must be deducted for each ml of N/10 HNO3 formed (as per the equations
given above)
Fuel and Combustion 8.7
(ii) Fuse wire correction, (tF): Correction has to be made for the amount of heat equivalent in
calories derived from the amount of fuse wire burnt as per the instructions furnished by the
supplier of the fuse wire.
(iii) Cotton thread correction, (tT): The correction for the cotton thread used for firing the charge
is calculated from the weight of the dry cotton thread actually used and on the basis that
the calorific value of cellulose is 4140 cals per gram.
(iv) Cooling correction, (tc): If the time taken for the water in the calorimeter to cool from the
maximum temperature attained to the room temperature is x minutes and the rate of cooling
is dt°/minute, then the cooling correction = x × dt. This should be added to the observed
raise in temperature.
For more accurate results, the cooling correction by Regnault and Pfaundler’s formula should
be used.
Cooling correction, (tc)
v¢ – v n – 1
= nv + ______
{ 1
}
(t) + __ (t0 – tn) – nt
t ¢ – t 1 2
= nv + KP
Where n = number of minutes between the time of firing and the first reading after the
temperature begins to fall from the maximum.
v = the rate of fall of temperature per minute during the period before firing.
V’ = the rate of fall of temperature per minute after the maximum temperature.
t and t’ = the average temperatures during the prefiring and final periods respectively.
(t) = the sum of the readings during the period between firing and the start of
coaling.
1
__
(t0 + tn) = mean of the temperatures at the moment of firing and the first temperature after
2
which the rate of change of temperature is constant, and
v¢ – v
K = _____ which is known as the “cooling constant’’ of the caloriment.
t¢ – t
The cooling correction so obtained should be added to the observed rise of temperature.
flame burners ‘B’ situated in a chimney ‘C’ which forms the centre of the annual vessel ‘V’ The lower
portion of “V’ is provided with a trough where water condensed from the products of combustion is
collected and can be removed through the side tube ‘T’ for measurement of its volume.
The products of combustion pass up to the chimney and are deflected downwards by the water
cooled head ‘G’ over a spiral of similar copper tubing and finally passes out through a number of
holes in the lid of the calorimeter. The inlet water passes through the outer coils downwards to
return upwards through the inner coils. Finally, it flows around suitable channels on the exterior of
the metal casting immediately above the chimney and passes into a mixer. The temperatures of the
inlet and outlet water are measured either different thermometers. The gas flows into the burners
through an accurate gas-meter.
5.3 Procedure
The apparatus is assembled as shown in the diagram (Fig. 2). After ensuring that the assembly
is leak proof, the gas is turned on and lighted. The water is turned on and the rate of flow is so
adjusted that the rise in temperature of the water in passing through the calorimeter is as nearly as
possible to 20°C. After the conditions are allowed to stabilize for about 45 minutes, the following
readings are noted: (a) the volume of the gas burnt at a given temperature and pressure during a
certain time interval (b) the amount of water passed through the cooling coils during the above time
interval (c) the steady difference in temperature of the outlet and inlet water and (d) the amount of
the water condensed from the products of combustion during the experiment. Also, the atmospheric
pressure and the gas pressure are recorded from the barometer and manometer respectively. Further,
the temperatures of the effluent gas, the ambient air and the gas meter are also noted to the nearest
degree.
Then the high calorific value of the gaseous fuel can be calculated from the following relation:
w (t 2 – t1)
Gross calorific value, J = ________
V
Fuel and Combustion 8.9
7. SOLID FUELS
The main solid fuels include wood, peat, lignite, coal, charcoal and briquetted fuels. In addition to
these, certain agricultural and industrial wastes such as bagasse, spent tan, rice husk, coconut and
nut shells are also employed as fuels.
7.1 Wood
Wood has been the main source of fuel until recent times on account of its relatively rapid growth and
production and ease of obtaining the supplies. However, large scale deforestation and the increasingly
large demands of energy by the industries led to the more extensive use of other types of fuels.
8.10 Engineering Chemistry
Freshly cut wood possesses greater water content (25 to 50%) than dry wood (15%) and its heating
value is directly proportional to the water content. Wood mainly consists of cellulose, ligno-cellulose
as well as some cell sap associated with traces of mineral ash. On the dry and ash-free basis, the
average composition of wood is 50%C, 43% O, 6% H and 1% nitrogenous and resinous material.
As a rule, dry wood is very combustible, easily kindled and burns with a long non-smoky flame. It
gives maximum heat intensity very quickly. However, the calorific value of dry wood is only 19.7
to 21.3 MJ/kg (4710 to 5085 Kcal/kg). The ash content of wood is very low and lies in the range
0.3 and 0.6%. Wood is largely used as domestic fuel. It is rarely used in industry except for special
purpose where dirt and smoke are undesirable. Due to its high flame emissivity, it is preferentially
used for space heating.
Wood charcoal is obtained by the destructive distillation of wood. The carbonisation is performed
usually in closed retorts. The charcoal is not pure carbon because even when the carbonisation is
conducted at high temperatures, it rapidly absorbs some gas and moisture. It also contains some
inorganic residues derived from the wood. Charcoal was widely used for metallurgical operations
formerly, but it has now been replaced by coke excepting for some special applications. The major
use of wood charcoal today is for producing activated carbon which finds extensive application for
decolorisation (e.g., in sugar industry), adsorption of gases and vapors and recovery of solvents from
gases and air. Charcoal is also used in the production of CaC2, ferro-alloys, and special quality pig
iron in small furnaces.
7.2 Peat
Peat is generally considered as the first stage in the conversion of vegetable debris to coal and is
produced under water-logged conditions by the action of fungi and anaerobic bacteria. Peat is generally
found in high altitudes.
Three main types of peat are usually distinguished: (1) upland type consisting mainly of
decomposed heaths and mosses (2) lowland type derived from sedges, grasses and willows and (3)
Forest peat formed from accumulations of leaves, twigs, etc. and is mostly found in tropical countries.
The bog peats derived from the smaller forms of vegetation are mainly found in USSR, Ireland,
U.K., Canada, Finland, Poland, Siberia, France, Germany and Italy. About 42% of the world’s peat
deposits occurs in the USSR.
Freshly won peat from a well-drained bog may contain even 90% of water, which can be brought
down to the level of 15 to 20% by air-drying. Most of the commercial peat blocks contain about
20-25% moisture. Thus the utilization of peat depends on its economical drying. On the dry basis its
calorific value is around 5450 Kcal/Kg. Peat as such is used only as a local fuel. It is not considered
as an economic furl on account of the cost of drying and handling, cost of transportation as it is
voluminous, relatively low calorific value and also because of its property of getting powdered during
burning. It is mostly used, after briquetting with other substances, as a domestic fuel. Carbonisation
of peat at low temperature (500-600°C) produces a char, oils and light spirit. Carbonisation of peat
under proper conditions may yield coke and gas as well. Peat is largely used as domestic fuel in
Europe but its use as such in India is limited. Dried peat is used as a fuel for the domestic appliances
(e.g., cookers and space heaters), for steam rising, for thermal insulation, packing, gas purification
and soil conditioning. Due to the shortage of coal, peat is used for generation of electricity in Russia.
In India, peat deposits are found in Nilgiri Hills (Tamil Nadu), Sundarbans (West Bengal), Kashmir
and Kolkata.
Fuel and Combustion 8.11
7.5 Anthracite
Anthracites are considered to be the highest rank of coal and contain the maximum percentage of
carbon (92 to 96%). They are black, hard and lustrous. They have a conchoidal fracture. They have
a very low percentage of volatile matter (about 6%) and hence produce a very little flame which is
short, non-smoky and blue. Their calorific value is about 8600 Kcals/kg. They burn with intense local
heating. Owing to their smokeless combustion, they are used for domestic heating in Canada and
in the Continent. Anthracites are used in metallurgical operations, naval purposes, slow combustion
stoves, central heating furnaces. Generation of producer gas, for drying malt and hops (because
of its low arsenic content), and curing rubber. They are also used for special applications such as
manufacture of cathode for aluminum industry and as a filter medium of water treatment. In India
anthracites are found in Jammu, Darjeeling and Rajhara.
The variation in average composition from wood to anthracite is summarized in the following
Table 2.
7.6 Rank of Coal
The different stages of coalification are called as peat-anthracite series. Each stage in the above
series is considered to belong to higher rank or maturity than their respective preceding member in
the series. As the coalification progresses, the percentage of carbon and hardness increases, while
the percentage of hydrogen, oxygen, moisture and volatile matter generally decrease. The calorific
value gradually increases from peat to semi-bituminous coal. There is a slight fall in the calorific
value of anthracite because the percentage of hydrogen decreases.
8. COAL
8.1 Origin of coal formation
Coal is regarded as a fossil fuel produced from large accumulations of vegetable debris due to partial
decay and alteration by the action of heat and pressure over millions of years.
Fuel and Combustion 8.13
extraneous ash. Only the extraneous or free ash can be removed by washing. Many Indian coals
have high ash content.
The nature of the ash and its amount in a coal and the softening temperature are very vital in
determining the quality of a coal. Ash reduces the heating value of coal.
Ash usually consists of silica, alumina, iron oxide and small quantities of line, magnesia, etc.
Its composition is of considerable importance in metallurgical operations as it affects the slag and
metal composition and consequently is a prime consideration in selecting the flux.
When coal is used in a boiler, the fusion temperature of the ash is of particular significance.
Fusion temperature of coal ash is generally between 1000°–1700°C. Ash with fusion temperatures
below 1200°C is called fusible ash and that above 1430°C is called refractory ash. If the ash fuses at
the working temperatures when coal is burnt on grates, it leads to the formation of clinkers (lumps of
ash) which reduces the primary air supply and the efficiency of production and distribution of heat are
adversely affected. Clinkers cause uneven temperature on the grates, which may contribute to further
clinker formation. Some coal particles also gen embedded in the fused ash thereby causing loss of
fuel. Fused particles of the ash may stick to the boiler tubes and reduce heat transfer. Removal of
clinkers from grates is difficult and laborious. Ash with low melting point forms molten slag which
is absorbed in the pores of the refractory lining of the boiler furnace. On account of differences
in the coefficients of expansion and contraction of the refractory material and ash, the life of the
refractory material might be reduced due to spalling. In view of all the above considerations, coals
used in boilers should have high ash fusion temperatures.
Fixed carbon. It is reported as the difference between 100 and the sum of percentages of moisture,
volatile matter and ash content of a coal. The fixed carbon content increases from low ranking coals
such as lignite to high ranking coals such as anthracite. It is the fixed carbon which burns in the
solid state. Hence, information regarding the percentage of fixed carbon helps in designing of the
furnace and the fire box.
Procedure for proximate analysis
1. Moisture. Moisture is generally determined by heating a known quantity of air-dried coal
to 105°C to 110°C for one hour and calculating the loss in weight as percentage.
2. Volatile Matter. Volatile matter is determined by heating 1g of air-dried coal exactly for 7
minutes in a translucent silica crucible of specified dimensions at a steady temperature of
925°C in a muffle furnace. The loss in weight calculated as percentage minus the % moisture
gives the % volatile matter.
3. Ash. Ash is determined by heating at 400°C a known quantity of the powdered sample
until most of the carbonaceous matter is burnt off and then heating for 1 hour at 750°C to
complete the combustion. The weight of residue remaining in the crucible corresponds to the
ash content of the coal, which is reported on percentage basis.
4. Fixed Carbon. The sum total of the percentages of volatile matter, moisture and ash
subtracted from 100 gives the percentage of fixed carbon.
Nitrogen is determined by digesting 1g of the coal sample in a Kjeldahl flask with Con. H2SO4,
K2SO4 and HgSO4 when the nitrogen present is converted to ammonium salts. The sample is then
made alkaline with NaOH and the liberated ammonia is distilled into a measured amount of standard
acid. The residual acid is determined by back titration with NaOH. From the amount of the standard
acid neutralized by the liberated ammonia, the nitrogen present in the sample is calculated.
Sulfur is determined conveniently from the bomb washings obtained from the combustion of a
known mass of coal in the bomb calorimeter experiment for the determination of calorific value. The
washings contain sulfur in the form of sulfate from which it is precipitated as BaSO4. The precipitate
is filtered, ignited and weighed. Form the weight of BaSO4 obtained the sulfur present in the coal
is calculated.
Sulfur can also be determined by heating the coal with Eschka mixture (2 Parts of MgO: 1 Part
of Na2CO3) and estimating the sulfates produced as BaSO4.
Ash is determined as described under proximate analysis.
Oxygen is determined by difference as follows:
% Oxygen = 100 – % of (C + H + S + N + Ash)
8.3.3 Significance
Carbon and Hydrogen in coal directly contribute towards the calorific value of the coal. Higher the
percentages of C and H, better is the quality of the coal and higher is its calorific value. Hydrogen
is mostly associated with the volatile matter of the coal and thus influence the use of coal for the
byproduct manufacture or otherwise. Nitrogen in the coal does not contribute any useful value
to the coal and since it is generally present only in small quantities (~1%), its presence is not of
much significance. Sulfur present in coal contributes towards the heating value of the coal but its
combustion products (SO2 and SO3) have corrosive effects on the equipments, particularly in presence
of moisture. Further, the oxides of sulfur are undesirable from the atmospheric pollution point of
view. Sulfur containing coal is not suitable for the preparation or metallurgical coke as it adversely
affects the properties of the metal. Oxygen content of coal is generally associated with moisture.
The lower the oxygen content, the more is the maturity of the coal and greater is its calorific value.
As the oxygen content increases, the capacity of the coal to hold moisture increases and the caking
power decreases.
Use of proximate and ultimate analysis in the theoretical determination of the calorific value
of coal
The calorific value is determined by burning 1g of coal sample in an oxygen bomb calorimeter
equipment and measuring the rise of temperature thus produced in the water content of the calorimeter.
However, quite often, an engineer may have to estimate the thermal efficiency of a process when
the calorific value of the fuel has not been determined. In such circumstances, formulae for the
calculation of calorific value from ultimate and proximate analysis are very helpful.
(
Calorific value in B.Th.U./lb = 14,544 + 62,028 H – __
0
)
+ 4,050 S
8
Where C, H, O and S represent the respective percentages of carbon, hydrogen, oxygen and
sulfur. Several modifications to it have been proposed to this formula and one of them is as
follows:
8.18 Engineering Chemistry
(
% Ash
calorific value in B.Th.U. per lb} = a V – ______
10 )
+ 140.4 C,
Where ‘a’ depends on the % volatiles and caking prosperity as shown in table below. The
deduction of Ash/10 from the volatiles is made to allow for that part of the volatiles as
determined which is derived from the combined water and pyritic sulfur in the mineral
matter and not from the coal substance.
The main use of all these formulae is that they provide a means for calculating the calorific
values of coals approximately when their compositions are known but of which the samples are not
available.
9. CHARACTERISTICS OF COAL
Apart from proximate and ultimate analysis, the assessment of a coal is based on the following
characteristics:
1. Colour: Lignites are brown or brownish black and the color darkens with increasing rank
of the coal.
Fuel and Combustion 8.19
2. Texture: Lignites are earthy and fibrous in structure. With increasing maturity, the coals
tend to be more tough, hard and brittle.
3. Specific gravity: The specific gravity depends upon the type of the coal and its ash content.
The specific gravity increase from lignite (1.2) to anthracite (1.5).
4. Heat of combustion (calorific value): The calorific value increases with increasing rank
of the coal (except in case of anthracites whose calorific value may be lesser than semi-
bituminous coals because of lesser percentage of hydrogen). High volatile coals having long
flame have less heating value than those of low volatile short-flame coals. Coals with 20%
volatiles generally have the best heating value.
5. Grind ability: This shows the ease with which a coal can be ground and is generally
expressed as grind ability index. It is a measure of the power required for grinding a coal
and is of special significance for pulverized coals. The coals which can be easily pulverized
have grind ability index of about 100.
6. Friability: This is the tendency of coal to break to pieces on handling and is tested by drop
shatter test. Non-friability is essential for coals used with stoker firing. Splint and cannel
coal are less friable than others.
7. Caking and coking properties: Caking is the ability of coal to form a coherent cake on
carbonisation. This is an important property used to assess the value of a coal and is tested
by various tests such as Swelling Number, Gray-King Assay, Roga Index and Audibert Arnu
test. If the residue formed on carbonisation is strong and porous, then the coal is called
coking coals which is used for preparing metallurgical coke.
8. Weathering or slaking index: This is a measure of the tendency of a coal to break on
exposure to weather or alternate cycles of dry and wet climate.
9. Bulk density: This is an important characteristic of coal on which the design of bunkers
and containers for storage of coal and for manufacturing coke depends.
(ii) Calorific value: The coke should possess a high calorific value.
(iii) Cost: The coke should be cheaply available near the plant site.
(iv) Calorific intensity: The calorific intensity of the fuel should be high enough to melt
the metal.
(v) Combustibility: The coke should burn easily but at the same time should not be very
reactive.
(vi) Reactivity: Reactivity of coke refers to its ability to react with CO2, steam, air and O2,
the reactivity of the coke should not be very high. Coke of low reactivity gives a higher
fuel bed temperature than what is produced by a coke of high reactivity.
Coal cannot be used as a metallurgical fuel (excepting in reverberatory furnaces) because it does
not have the necessary purity, porosity and strength. During the process of carbonisation from coking
coals, much of the volatile matter and sulfur compounds are removed and a strong and porous coke
is produced.
c value is about 6300 to 9300 Kcals/m3 depending on the coal and the process used and the yield
is about 150 to 330m3/tonne of the coal carbonised. Hence it is a more valuable gaseous fuel.
are converted into gaseous fuels and simultaneously the various byproducts formed are
recovered.
2. Gaseous fuels are very clean to operate. They are ashless and smokeless. Ash and smoke
cause lots of difficulties while using solid and liquid fuels.
3. They can be ignited instantaneously. As the feed of the gas to the burners can be easily
controlled, the combustion process can be kept under better control.
4. Gases are miscible with air and hence the excess air needed is much less than that required
for solid or liquid fuels. This leads to fuel economy and efficiency of operation.
5. Both oxidizing and reducing atmospheres can be easily maintained.
6. Sensible heat from the hot flue gases can be recovered and used for preheating the incoming
fuel gas using furnaces operating with regenerative principle of heat economy.
15.2 Disadvantages
1. As they are highly inflammable, special care should be taken to avoid fire hazards.
2. As they occupy large volumes, more space is required for storage. However, this problem is
not there at the consumer end for “Town gas’’ which is supplied from a central place.
The gas thus produced was known originally as synthetic natural gas, but language purists argued
that synthetic could not be natural, so now it is called substitute natural gas. The sulfur and carbon
dioxide are removed from the gas before it is methanated. The operating pressure in the gasifier,
depending upon the process, can be atmospheric to over 6.9 Mpa and the temperature can vary from
800°C to about 1650°C. The higher pressure and lower temperture result in the formation of a large
amount of methane.
100
[ ( 0
32 × C + 8 H – __
= ____
3 12 ) ]
+ S kg.
8
Where C, H, O and S are the respective weights of carbon, hydrogen oxygen and sulfur
present in 1 kg. of the fuel.
9. Calorific Value If the ultimate analysis of coal is available, its calorific value may be
calculated by Dulong’s formula as follows:
Calorific value (Kcal/kg.)
0
= [8080 C + 34460 H – __( )
+ 2250 S]
8
Where C, H, O and S represent the respective weight of carbon, hydrogen, oxygen and sulfur
per kg. of coal.
10. % Excess Air
(Actual air used–Theoretical air)
% Excess Air = ____________________________
× 100
Theoretical air
Fuel and Combustion 8.27
11. The mass of dry flue gases formed should be calculated by balancing the carbon in the fuel
and the carbon present in the flue gases.
12. The composition of a solid or liquid fuel is usually expressed on weight basis whereas the
composition of a gaseous fuel is expressed on volume basis unless otherwise stated.
16. Biomass
Biomass refers to living and recently dead biological material that can be used as a fuel or for
industrial production. It is referred to material derived from recently living organisms. This includes
plants, animals and their byproducts. For example, manure, cattle dung, garden waste, sugarcane
waste and crop residue are all sources of biomass. Biomass include biodegradable wastes that can
be burnt as fuel.
Biomass is a renewable energy source based on carbon cycle. It is grown from several plants,
including miscanthus, switichgrass, hemp, corn, poplar, willow, sugarcane and oil palm.
Biomass is a part of carbon cycle. Carbon from the atmosphere is converted into biological matter
by photosynthesis. On the death or combustion the carbon goes back to atmosphere as carbon dioxide.
Thus, during a life span of animal or plant total carbon content remains same.
Production of biomass is a growing industry as interest in sustainable fuel sources is growing.
Biomass consists of carbon compounds which may be used as a source of energy by using either of
the following methods:
1. Biomass such as cattle dung, wood, bagasse, plant wastes, agricultural wastes, dry vegetable
waste, etc. is used directly in chulhas for getting energy. However, by doing so a lot of heat
energy is wasted and lot of smoke is liberated, thereby causing blackening of utensils and
houses. Moreover, it librates poisonous gas carbon monoxide and leaves ash as residue.
2. Biomass is converted into biogas, which is used for heating and lightening purposes.
Advantages of converting biomass into biogas are:
(i) Biogas production is very economical. It has been found that 1kg of dry cattle dung
gives about 160 litres of gabar gas, which can supply 800kJ of heat. On the other hand,
1kg of dry dung on direct burning gives only 100kJ of effective heat.
(ii) The gas has all the advantages of gaseous fuel like cleanliness, absence of smoke,
flexibility, etc., It does not have poisonous gas, CO as an ingredient.
(iii) It provides simultaneously yield of good manure.
16.1 Biogas
Biogas refers to a gas produced by the biological breakdown of organic matter in the absence of
oxygen. Biogas produced by the fermentation of biomass comprises primarily of methane and carbon
dioxide.
The average composition of biogas is:
CH4 50-65%
CO2 30-40%
H2 5-10%
N2 2.6%
H 2S Traces
8.28 Engineering Chemistry
Biogas can provide a clean, easily controlled source of renewable energy from organic waste
materials for a small labour input, replacing firewood or fossil fuels.
Process
Biogas is generated when bacteria degrade biological material in the absence of oxygen, in the process
known as anaerobic decomposition. Anaerobic decomposition is a two-stage process as specific
bacteria feed on certain organic materials.
1. In the first stage, acidic bacteria (such as E.coli, bacteriods etc) break down the complex
organic molecules into peptides, glycerol, alcohol and the simple sugars.
2. In the second stage, a second type of bacteria (methangenoic bacteria) starts to convert
these simpler compounds into methane. These methane producing bacteria are particularly
influenced by the ambient conditions.
The main features that influence biogas production are:
pH; It is well established that a biogas plant works at an optimal pH of 7 or just above, Temperature
is 32°C.
Raw material for biogas: Animal dung, poultry wastes, vegetable wastes, waste paper and cotton
clothes, plants wastes, human excreta, birds excreta, etc,.
Fig. 3
and a gas valve. On the left side of the tank there is a sloping inlet chamber and on the right side
there is rectangular outlet chamber, both made up of bricks and cement. Fresh cattle dung plus water
slurry is introduced from the inlet chamber while spent slurry gets collected in the outlet chamber.
The inlet chamber is connected to the mixing tank; while the outlet chamber is connected to the
overflow tank.
Working: Slurry (made by mixing cattle dung and water in a definite proportion in mixing tank)
is fed into the digestive tank via the inlet chamber, till the slurry level becomes equal to cylindrical
top level. In about 50 to 60 days, the biogas plant starts functioning. During this time period, cattle
dung undergoes fermentation in the presence of anaerobic bacteria with gradual evolution of biogas,
which starts collecting in domed shaped space. As the time passes more and more biogas collects
inside the dome, thereby exerting pressure on the slurry in the digestive tank and this in turn forces
the spent slurry to the overflow tank via outlet chamber. From the over flow tank spent slurry is
withdrawn periodically and used as a good manure.
From time to time fresh slurry is fed to the digestive tank so as to get the regular supply of
biogas. The biogas collected in the dome is taken out through outlet pipe by opening the gas valve
and then used as a fuel.
Fixed dome type biogas plant is cheap, since only bricks and cement are used for its construction
and there is no danger of corrosion for such a plant.
Biogas is considered as an ideal fuel:
1. It burns without smoke hence causes no pollution.
2. Its calorific valve is high
3. It is cheapest gaseous fuel
4. It has no storage problem
Uses of biogas: (i) For cooking food (ii) As a fuel to run engines (iii) As a illuminant in
villages.
Limitations of biogas: It is necessary to have the gas lamp or stove or burner within 10 metres
of the plant.
solved Questions
Type–I
1. Classify the following fuels in to primary and secondary fuels.
Lignite, Dung, Gasoline, Biogas, Kerosene.
Sol. Fuels which occur in nature as such are known as primary fuels while those which are
derived from the primary fuels are known as secondary fuels.
2. Classify the following into conventional and non conventional energy sources:
Petrol, diesel, Coal, Biogas, Solar energy, Tidal energy, Geothermal energy.
8.30 Engineering Chemistry
Sol.
Conventional energy sources are exhaustible and non-renewable on the other hand, the non-
exhaustible and renewable energy sources are non-conventional.
3. List the raw materials which can be utilized for biogas manufacture.
Sol. Animal dung (mainly cow dung), poultry wastes, human excreta, plant wastes, waste papers
etc are the raw materials which can be utilized for biogas manufacture.
4. Arrange the following in increasing order of their calorific value and moisture content.
Peat, Lignite, Anthracite, Bituminous.
Sol.
Coal Calorific value (kcal/kg)
Peat 5400
Lignite 6500 – 7100
Bituminous 7000 – 8600
Anthracite 8650 – 8700
Type–II
Problems Based on Bomb Calorimeter
5. The following data is obtained in a Bomb calorimeter experiment:
Weight of crucible = 3.649 gm.
Weight of crucible + fuel = 4.687 gm.
Weight equivalent of calorimeter = 570 gm.
Water taken in calorimeter = 2200 gm.
Observed rise in temperature = 2.3°C.
Cooling correction = 0.047°C.
Acid correction = 62.6 calories.
Fuse wire correction = 3.8 calories.
Cotton thread correction = 1.6 calories.
Calculate the gross calorific value of the fuel sample. If the fuel contains 6.5% hydrogen,
determine the net calorific value.
Fuel and Combustion 8.31
Sol.
(W + w) (t 2 – t1 + Cc) – (CA + CF + CCr)
HCV = __________________________________
m
Type–III
1
HCV = ____ [ ( 0
8080 C + 34500 H – __
100 ) ]
+ 2240 S cal/gm
8
...(7.1)
Given that
C = 85% H = 8% S = 1%
Nitrogen and ash, don’t contribute to the calorific value.
1
HCV = ____
So, [ 0
8080 × 85 + 34500 8 – __
100 (
+ 2240 × 1 cal/gm
8 ) ]
1
= ____
[686800 + 276000 + 2240] cal/gm
100
1
= ____
[965040] = 9650.4 cal/gm.
100
Fuel and Combustion 8.33
10. A coal has the following composition by weight: C = 90%, O = 3.0%, S = 0.5%, N = 0.5%
and ash 2.5%. Net calorific value of coal was found to be 8490.5 kcal/kg. Calculate the
percentage of hydrogen and higher calorific value of coal.
Sol. Given that C = 90%, O = 3%, S = 0.5%,
LCV = 8490.5 kcal/kg.
HCV = LCV + 0.09H × 587 kcal/kg.
Or HCV = 8490.5 + 0.09 × H × 587
HCV = (8490.5 + 52.8H) kcal/kg ...(7.2)
According to Dulong’s formula
1
HCV = ____ [ ( 3.0
8080 × 90 + 34500 H – ___
100 ) ]
+ 2240 × 0.5 kcal/gm
8
Or HCV = [7272 + 345H – 129.4 + 11.2] kcal/gm
Or HCV = (7754.8 + 345H) kcal/kg ...(7.3)
From 2 and 3 we have
7754.8 + 345H = 8490.5 +52.8H
Or (345 – 52.8) H = 8490.5 – 7754.8
1335.7
Or %H = ______
= 4.575% ...(7.4)
292.2
From 2 and 4
HCV = (8490.5 + 52.8 × 4.575) kcal/kg
= (8490.5 + 241 .3) = 8731.8 kcal/kg
Type–IV
Problems Based on Boy’s Gas Calorimeter
11. The following data were obtained in a Boy’s gas calorimeter experiment:
Volume of gas used = 0.1 m3 at STP.
Weight of water heated = 50 kg.
Temperature of inlet water = 20°C.
Temperature of outlet water = 30°C.
Weight of steam condensed = 0.15 kg.
Calculate the higher and lower calorific value per m3 at STP. Take the heat liberated in
condensing water vapour and cooling the condensate as 580 kcal.gm.
Sol. Given that V = 0.1 m3, W = 50 kg, T1 = 20°C, T2 = 30°C, = 0.15 kg
W(T2 – T1) 50 × (30 – 20)
HCV = _________ = _____________
V 0.1
50 × 10
Or HCV = _______
= 5000 kcal/m3
0.1
M
LCV = HCV – __ × 580
V
8.34 Engineering Chemistry
0.15
= 5000 – ____
× 580 = 5000 – 3 × 290
0.1
= 5000 – 870
LCV = 4130 kcal/m3.
Type–V
Problems Based on Combustion of Fuel
12. Calculate the weight and volume of air required for the combustion of 500 gm of carbon.
Sol. Air contains 23% oxygen by weight while it contains 21% oxygen by volume.
Combustion reaction
C + O2 CO2
12 32
Weight of oxygen required for combustion of 12 gm of carbon = 32 gm
32
\ Weight of oxygen required for combustion of 500 gm of carbon = ___
× 500 gm
12
= 1333.3 gm
= 1.33 kg
100
Weight of air required = ____
× 1.33 kg = 5.782 kg
23
\ 32 gm of oxygen occupies 22.4 L at NTP.
22.4
\ 1333.3 gm of oxygen occupies ____
× 1333.3 L at NTP = 933.31 L
32
100
____
\ Volume of required = × 933.3 = 4444.28 L = 4.44 m3.
21
13. A gas sample has the following composition by volume:
H2 = 30%, CH4 = 5%, CO = 25%, CO2 = 11%, O2 = 10%, N2 = 19%. If 40% excess air
is supplied, calculate the volume of air required for the complete combustion of 1 m3 of the
fuel.
Sol. Nitrogen and CO2 are incombustible matters and hence they take any oxygen during
combustion.
% of component Combustion reaction Volume of O2 required
3
H2 = 30% = 0.3 m H2 + ½ O2 Æ H2O 0.3 × 0.5 = 0.15 m3
CH4 = 5% = 0.05 m3 CH4 + 2O2 Æ CO2 + 2H2O 0.05 × 2 = 0.1 m3
CO = 25% = 0.25 m3 CO + ½ O2 Æ CO2 0.25 × 0.5 = 0.125 m3
Total volume of O2 required = 0.375 m3
O2 available in fuel gas 5% Net oxygen required = 0.375 – 0.05
= 0.05 m3 = 0.325 m3
\ Volume of air required for the complete combustion of 1 m3 of the gas using
100 140
40% of excess air = 325 × ____
× ____
= 2166.6 L
21 100
14. A sample of coal was found to have the following % composition by weight:
C = 75%, H = 5.2%, O = 12.1%, N = 3.2% and ash = 4.5%
Calculate (i) The minimum amount of O2 and air by weight necessary for complete combustion
of 1 kg of coal (ii) Weight of air required, if 40% excess air is supplied. (iii) Gross and net
calorific value of coal sample using Dulong’s formula.
Sol. Given that weight of coal = 1 kg
100
1
[ (O
(iii) Gross calorific value = ____ 8080 C + 34500 H – __ )]
8
1
= ____ [ ( 12.1
8080 × 75 + 34500 5.2 – ____
100 )]
= 7332 kcal/kg
8
Type–VI
Problem Based on Proximate and ultimate analysis
15. A sample of coal was analysed as follows: Exactly 1.40 gm was weight into a silica crucible.
After heating for one hour at 105 – 110°C, the residue weight 1.10 gm. The crucible next
was covered with a vented lid and strongly heated for exactly 7 minutes at 950 ± 20°C. The
residue was weight 1.0 gm. The crucible was then heated without cover, until a constant
weight was obtained. The last residue was found to weight 0.21 gm. Calculate the ash content,
moisture content, volatile matter and percentage of fixed carbon.
8.36 Engineering Chemistry
UNsolved Questions
1. Define a chemical fuel. What are the characteristics of a good fuel?
2. Classify the following fuels into primary and secondary fuels: Coal, Coke, Natural gas,
Diesel, Kerosene, Briquette, Producer gas, LPG.
3. Distinguish between natural and synthetic fuels.
4. Define calorific value of a fuel and write the units.
5. Differentiate between net calorific value and gross calorific value.
6. Describe how the calorific value of a solid fuel is determined using a bomb calorimeter.
7. Describe a suitable method for the determination of the calorific value of a solid fuel. What
are the corrections needed?
8. How is the higher calorific value and the lower calorific value of a coal sample
determined?
9. Give the determination of calorific value by Boy’s gas calorimeter.
10. Describe how the calorific value of coal or liquid fuel is determined by Bomb calorimeter.
11. What are chemical fuels? How are they classified?
12. What are non-conventional fuels? List a few of them.
13. Write the approximate composition and applications of biogas.
14. Give the examples of non-conventional sources of energy.
15. List the raw materials which can be utilized for biogas manufacture. How is biogas obtained
from cattle dung?
16. Discuss the manufacturing of biogas. Write its merits and demerits.
17. Write short notes on:
(i) Biogas (ii) Solar energy
18. Explain the process involved in the conversion of solar energy into electrical energy and heat
energy in solar plaints.
19. Describe the reasons for not using solar energy at domestic and industrial levels economically
in spite of the free availability of sunlight.
20. Justify that solar energy is a very good source of non conventional energy. What do you
understand by renewable and non renewable fuels?
21. Discuss the process of conversion of solar energy into electrical energy.
22. Discuss p-type and n-type silicones used in solar energy plants.
23. Write a short note on biomass.
24. Explain the following:
(i) Gaseous fuels are more advantageous than solid fuels.
(ii) An ideal fuel should have moderate ignition temperature.
(iii) Net calorific value is less than gross calorific value.
25. Distinguish between solid, liquid and gaseous fuels.
26. What are fuels? Discuss their classification.
27. Write a short note on biomass as a source of energy. How does this technique differ from
biogas technique?
8.38 Engineering Chemistry
28. A sample of coal containing 89% C, 8% H, 3% ash, when tested in the laboratory for its
calorific value in the bomb calorimeter, the following data were obtained:
Weight of coal burnt = 0.85 gm.
Weight of water taken = 650 gm.
Water equivalent of bomb calorimeter = 2500 gm.
Rise in temperature = 2.5°C.
Cooling correction = 0.03°C.
Fuse wire correction = 10 Cal.
Acid correction = 50 Cal.
Assuming that the latent heat of condensation of steam as 580 cal/gm, calculate (i) the gross
and (ii) the net calorific values of the coal in cal/gm.
[Ans: GCV = 9305.29 cal/gm, NCV = 8887.69 cal/gm]
29. The following data were obtained in a bomb calorimeter experiment:
Weight of coal burnt = 0.95 gm.
Weight of water taken in calorimeter = 1000 gm.
Water equivalent of bomb calorimeter = 2500 gm.
Rise in temperature = 2.8°C.
Cooling correction = 0.03°C.
Acid correction = 60.0 calories.
Cotton thread correction = 2.0 calories.
Calculate the gross calorific value of the fuel sample. If the fuel contains 5% hydrogen
determines the net calorific value.
[Ans. GCV = 10361.05 cal/gm, NCV = 10096.9 cal/gm]
30. A gas has the following compaction by volume: H2 = 20%, CH4 = 6%, CO = 22%, CO2 = 4%,
O2 = 4% and N2 = 44%, 20% excess air is used. Find the weight of air actually supplied
per m3 of the gas [Ans. 2143g]
31. Calculate the weight of air needed for complete combustion of 5.0 kg of a coal containing
80% carbon, 15% hydrogen and the rest oxygen. [Ans. 7139 kg]
32. A sample of coal was found to contain following percentage composition: C = 75%, H = 5.2%,
O = 12.8%, S = 1.2%, N = 3.7%, ash = 2.1%. Calculate the minimum amount of air necessary
for complete combustion of 1 kg of carbon.
33. A sample of coal was analysed as fallows: 1 g of an air dried coal, sample was weighed in a
silica crucible. After heating far 1 hour at 105-110°C, the dry coal residue weighed 0.985 g.
The crucible was covered with a rented lid and then heated strongly far exactly 0.800 g.
The crucible was then heated strongly in air, until a constant weight was obtained. The lost
residue was found to weight 0.10 g calculate the proximate analysis.
[Ans. Moisture = 1.5, Volatile matter = 18.5%, ash = 10.0% and fixed C = 70%]
34. 1.56 g of the coal was kjeldahlized and NH3 gas thus evolved was absorbed in 50.0 ml of
0.1 N H2SO4. After absorption, the excess (residual) acid required 6.25 ml of the 0.1 N NaOH
far exact neutralization, 2.60 g of the coal sample in a quantitative analysis gave 0.1755 g of
BaSO4. Calculate the percentage of N and S in the Coal sample.
[Ans. N = 3.93%, S = 0.93%]
Fuel and Combustion 8.39
35. A coal sample gas the following analysis: C = 66.2%, H = 2%, O = 6.1%, N = 1.4%, S = 2.9%,
moisture = 9.7% and ash = 9.5%. Determine the quantity of products of combustion, if 1 kg
of coal in burnt with 25% excess air. [Ans. 12.17 kg]
36. A coal sample was found to contains the following: C = 81%, H = 4%, O = 2%, N = 10% the
remaining being ash. Estimate the quantity of minimum air required for complete Combustion
of 1 kg of the sample. [Ans. 10.69 kg]
37. Calculate the mass of air needed for Complete Combustion of 5 kg of coal containing 80%
Carbon, 15% hydrogen and rest in oxygen. [Ans. 71.034 kg]
38. A gas used in an internal combustion engine had the following composition by volume
H2 = 45%, CH4 = 36%, CO = 15% and N2 = 4%.
Find the volume of air required for the combustion of 1 m3 of gas. [Ans. 4.85 m3]
Chapter 9
Spectroscopic Methods
of Analysis
1. INTRODUCTION
Molecular spectroscopy is defined as the study of interaction of electromagnetic radiations with
matter. It provides valuable information regarding molecular structure such as molecular symmetry,
bond distances, bond angles; chemical structure such as chemical properties, electronic distribution,
bond strength, molecular reactions; and thermodynamic properties.
2. ELECTROMAGNETIC SPECTRUM
The wavelength of visible light range from 400mm (violet) to 800mm (red). The visible region
however, is a very small part to the entire electromagnetic spectrum. Some components of the
electromagnetic spectrum are listed in Table along with their wavelength, the energy associated with
them, and the type of effect they are capable of producing in a molecule.
Common symbols used in spectroscopy are given in Table 2
Light Source
Monochromotor
Recorder
2. The Monochromator: Except for microwave spectroscopy, some element is necessary by means
of which the radiations can be separated in space according to wavelength, after it has passed the
sample. Sometimes filters transparent over limited wavelength ranges can be used in combination
with gratings.
3. The Detector: In all spectrometers, the emitted radiations from the sample must be analyzed with
regard to radiation intensity as a function. The “transformer” is called the detector.
In the microwave region, the detector is a crystal rectifier. At the higher frequencies in the infrared
region, thermocouples are used. In the visible and the ultraviolet region the photocells are used.
4. Spectrum recording: When there is no sample present, the detector output will be constant
over the range of frequencies covered by the instrument. However, when the radiations are passed
through a sample, having just two possible energy levels E1 and E2, the detector output will show
a sudden fall at frequency given by V = [(E2 – E1)/h]. The spectrum has been scanned between
the beginning and ending frequencies. Such a spectrum is referred to as “frequency domain”, which
indicates records of detector output against frequency.
It is evident from the record (11) that the ideal situation represented in (1) is seldom attained.
Thus, the base line is seldom horizontal. The reasons for this are–
• It is impossible to make the self life infinitely narrow. Therefore, a range of frequencies
rather than a single frequency reaches the detector.
Spectroscopic Methods of Analysis 9.5
Fig. 4
• Energy transitions in atoms or molecules are not absolutely sharp but always occur over a
range of frequencies.
• The sensitivity of the delector is also frequency dependent.
4. UV SPECTROSCOPY
• introduciton: UV absorption spectrum arises from the transition of electrons within a molecule
or ion. When a molecule absorbs ultraviolet radiation of frequency (v), the electrons in that molecule
may undergo transitions from a lower to higher energy level, the energy difference between the two
states is given by.
DE = hn
Where, h is plank’s constant. Also,
DE = E2 – E1
E1 = Energy of the ground state.
E2 = Energy of the excited state.
We know that the total energy of the molecule is equal to the sum of the electronic, vibrational,
and rotational energies. Therefore,
Etotal = Eelectronic + Evibrational + Erotational
The absorption in the UV region involves single electronic transition, from lower energy state to
higher energy state. So the spectrum must contain a single discrete line. This is because the electronic
transitions are also accompanied by vibrational and rotational transitions. As the energy required for
these transitions is much less, so the broad band appears.
In UV range, the absorbed energy produce changes in the valance electrons of the molecules.
The electrons involved are–
(i) p-electrons: These are involved in unsaturated compounds such as dienes, trienes, aromatic
compounds, etc.
(ii) s-electrons: These are involves the electrons of the saturated bond between carbon and
hydrogen.
(iii) n-electrons: These electrons are not involved in bonding between atoms in the molecules.
For example, one pair of electrons in nitrogen, oxygen, sulphur or halogens.
• Electronic transitions: When a molecule absorbs energy in the UV or visible region, its electrons
are promoted from a bonding molecular orbital to an antibonding molecular orbital. The electronic
transitions involved in the UV and visible region are of the following types:
9.6 Engineering Chemistry
s Æ s* transitions
(i)
n Æ s* transitions
(ii)
n Æ p* transitions
(iii)
p Æ p* transitions
(iv)
s * Antibonding
p* Antibonding
N Nonbonding
p Bonding
s Bonding
(i) s Æ s* transitions: These transitions occur by the promotion of sigma electrons from
the bonding to antibonding (s*) orbitals. These transitions require high energy and thus
absorb radiation in far UV region (126 mm – 136 mm). These transitions are seen in
saturated hydrocarbons. For example, propane shows absorption around 135 mm and
methane shows l max at 121.9 mm.
(ii) n Æ s* transitions: These transitions are seen in saturated compounds, containing
heteroatom in addition to s Æ s* transitions. The energy required for the transitions is
less than that required for s Æ s* transitions. For example, CH3OH absorbs at ordinary
UV region and l max at 183 mm, for methyl chloride l max at 173 mm and water absorbs
at 167 mm.
(iii) n Æ p* transitions: Unsaturated compounds containing heteroatom such as O, N and
S show this type of transition. The electron from n-orbitals are transferred to p* orbitals
and require less amount of energy and occur at longer wavelength.
C=O C=O
N Æ p* transition
(iv) p Æ p* transitions: The electron transfer occurs from the bonding p-orbital to the
antibonding p* orbital. These transitions are only associated with compounds containing
double or triple bond and aromatic compounds. These transitions require less energy and
occur at higher wavelengths.
C=O C—O
p Æ p* transitions
For example, unconjugated alkenes show an absorption bond around 170 mm to 190 mm and
saturated aldehydes and lactones absorb at about 180 mm.
• chromophores and auxochromes: A group of atoms in a molecule that is responsible for the
absorption of radiations called Chromophores.
Chromophores are of two types–
1. Chromophores which contains p-electrons only and under p Æ p* transitions. For example,
ethylenes, acetylenes, etc.
2. Chromophore which contain both p-electrons and n–electron. Such Chromophores undergo
p Æ p* and n Æ p* transitions. For example, carbonyl, nitrites, azo compounds, nitro
Spectroscopic Methods of Analysis 9.7
compounds, etc. The carbonyl group in acetone shows absorption at 190 mm (p Æ p*) and
270 mm (n Æ p*).
Examples of some of the molecular types in which electronic transitions occur are given in
Table 3.
Identical functional groups in different molecules will not necessarily absorb at exactly the
same wavelength. The energy change depends upon the structural environments of the molecule.
The position and intensity of an absorption bond of a simple Chromophore may be modified by
the attachment of certain groups in the basic Chromophore system known as auxochromes. The
auxochromes produce the following shifts:
(a) Bathochromic Shift: This effect causes the absorption maximum to shift towards longer
wavelength (l) or lower frequencies. This is called red shift and is due to solvent effect.
(b) Hypsochromic Shift: This is the shift in which absorption maxima shifts to shorter
wavelength. This is called blue shift.
(c) Hyperchromic shift: This is the effect in which intensity of absorption maxima shifts up.
(d) Hypochromic shift: This is the effect in which intensity of absorption maxima shifts
down.
The bathchromic shift can be brought about in two ways.
(i) By Conjugation of chromophoric groups: When two chromophoric groups present in the
molecule are separated by two or more single bonds, their effect on the spectrum is usually
additive and there is little interaction between the isolated chromophoric groups.
9.8 Engineering Chemistry
When the two chromophoric groups are conjugated, separated by only single bond, the
electron system is spread over atleast four atomic centers. The shift is of 15nm-45nm to
longer wavelength, for example:
l max Transition
(a) 217 p Æ p*
1, 3 Butadiene
(b) – C – C = C – C = O 218 p Æ p*
(ii) By attaching auxochromes to the system: Auxochromes generally deepen the color of a
Chromophore but cannot by themselves impart color to a compound. These lead to shifts in
the absorption to a longer wavelength and result in increase in the intensity of the absorption
peak. Some typical auxochromes are–
–NH2, – NHCH3, – N(CH3) 2, – OH, – Cl, – CH3, – CN and – CONH2 etc.
These groups contain nonbonding electrons and the transitions involving non-bonding electrons
are responsible for this effect.
For example, benzene shows an absorption bond l max at 255nm and aniline shows l max at
280nm.
NH2
(ii) CH3–CH–CH=CH–CH3
Basic Value = 217 nm
Alkyl residues = 2 × 5 = 10 nm
Calculate Value = 227 nm
Spectroscopic Methods of Analysis 9.9
The value l max depends upon the nature of substituent and interaction, for example:
(i) Cl Cl
COOH COOH
lmax 204 nm 210 nm 230 242
(ii)
9.10 Engineering Chemistry
In the first case, there is no resonance interaction and both Cl and COOH groups show additive
effect in l max. Therefore, l max for P – Chlorobenzoic acid should be 210 + 230 – 204 = 236 nm,
which is very close to the observed value. On the other hand, in the second case, the – NH2 and
– COCH3 groups have opposing electrical effect. Therefore, l max for P–amino acetophenone should be
230 + 246 – 272 nm. But its observed value is quite higher. The UV spectrum of diphenyl suggests
considerable resonance interaction between rings as shown below:
If two rings carry substituents in a suitable position, the molar extinction coefficient diminished
due to hindrance of the co-planarity of the rings.
But hydrocarbon, like dipheny methane, has typical benzene like spectrum.
On the basis of the above discussion we may conclude that UV spectroscopy is useful only in
compounds which have extended conjugation between carbon–carbon double and bonds and between
in compound carbon–carbon or corbon–oxyten/nitrogen multiple bonds or between carbon–carbon
double bonds and a benzene ring.
The values of l max for some unsaturated compounds are given in Table 4.
Cyclohexene 182
CH3 CH CH2
Cis-1, 3-pentadiene C C 223
H H
CH3 H
Trans-1, 3-pentadiene C C 223.5
H CH CH2
• APPLICATION OF UV SPECTROSCOPY:
1. Qualitative Analysis: For qualitative analysis, a curve is plotted between wavelength (l)
and degree of absorption (E). Now, by comparing the absorption spectrum of known and
unknown compounds, the unknown compounds may be identified.
2. Quantitative analysis: The qualitative analysis may be carried out on the basis of Beer’s law.
In this technique l max is selected for the compound then optical densities are measured for
some known compounds. A straight line is obtained and from this graph, the concentration
of the unknown compound is evaluated very easily.
3. Detection of Impurities: With the help of UV absorption spectroscopy, the impurities
present in organic compounds can be detected. This is because:
(a) The bonds due to impurities are very intense.
(b) The organic compounds may be classified into saturated & unsaturated; the former has
little absorption while the latter has strong absorption bonds.
4. Determination of Molecular Weight:
According to Beer’s law:
Io
log __
= C.Emax.L
It
Io
log __
It
C = _______
Emax ×L
From the above equation, C, i.e. molar concentration of the solution, is calculated. If
the amount of solute dissolved (w) is known, the molecular weight of the solute may be
calculated.
5. Tautomeric Equilibrium: UV absorption spectroscopy may be used in determining the
percentage of Keto and enol forms in Tautomeric equilibrium.
Consider the case of ethylacetoacetate.
The Keto form l max = 275 nm and E = 16 while enol form has l max = 244 nm and E = 1600.
We can measure the proportion of tautomers present in ethyl acetoacetate from the length of
244 nm band.
6. Determination of the dissociation constant of acid and bases.
9.12 Engineering Chemistry
m A mB (m A + mB) 2
= _______________
r
(m A + mB)2
Spectroscopic Methods of Analysis 9.13
m A mB
= _______ r 2
m A + mB
= m r 2
(m AmB)
Where m = _______ is called reduced mass of the molecule.
m A + mB
Classically, the angular momentum L of a rotating molecule is given by
L = Iw, w is angular velocity energy of a rotating molecule
1
E (g) = __
Iw2
2
Let J = rotational quantum number and it can have integrial values from zero onwards.
__________
÷ ___h
L = J (J + 1)
J = 0, 1, 2, 3
2p
Since angular momentum is quantized
h2
Now. EJ = ____ J (J + 1) Joule
8p2 I
J = 0, 1, 2
The energies can also be expressed in cm–1 units, which is normally reported as rotational
term F(J).
EJ h
Thus, F(J) = ___ = _____
J (J + 1) cm–1
hc 8p2 Ic
h
Let _____ = B = Rotational Constant
8p2 Ic
Hence, F(J) = BJ (J + 1) cm–1
Next, we need a selection rule to determine the radiative transitions between the rotational energy
levels.
The rotational transitions for a rigid diatomic molecule are governed by the selection rule.
DJ = ±1
i.e. only those transitions are allowed in which the rotational quantum number changes by unity.
The + sign refers to absorption and – sign to emission of radiation. Microwave spectra are usually
observed as absorption spectra so that the cooperative part of the selection rule is D J = +1. For a
transition taking place from J to J + 1, the rotational frequency is given by.
_ __
n(J Æ J + 1) = B (J + 1) (J + 2) – B
J (J + 1)
__
= (J + 3J + 2) – (J2 + J)
B 2
__
= 2 B (J = 1) cm–1
Thus
_ __ _ _ __
v0 – 1 = 2B, v
= 4B, v
(2 Æ 3) = 6B,
_ __ (1 Æ 2)
v(3 Æ 4) = 8B etc.
__ __ __
__ So rotational spectrum of a rigid diatomic molecule consist of a__ series of lines at 2B, 4B, 6B,
8B etc. Evidently, these lines are equally spaced by an amount of 2B.
9.14 Engineering Chemistry
Fig. [B] Rotation of HCl molecule having parmanent dipole moment and fluctuation
in the vertical component of the dipole moment.
Spectroscopic Methods of Analysis 9.15
Thus, a molecule with permanent dipole moment generates the oscillating electric field on rotation
and hence can interact with the electric field component of microwave radiation which oscillates in
a plane perpendicular to the direction of propagation of the wave.
It is noted that the rotational spectra are observed in the gaseous state only because the rotational
energy levels are not quantized in solid and liquid states.
÷ ÷
I h
\ r = __
= _______
2 = Internuclear distance
m 8p Bcm
2. Determination of symmetry in a molecule.
3. Determination of dipole moments of gaseous molecules is also possible by recording the
spectra in the presence of electric field.
It is found that in the presence of external electric field (E), the splitting of rotational energy
levels of the molecule occurs (starck effect).
If Dv = Shift of rotational v
m = dipole moment of the molecule.
and E = External electric fuild.
then DV µ (m × E)2.
Thus, by knowing E and measuring DV, m can be determined.
Limitations
1. By using this technique, molecule with permanent dipole moment can be analyzed.
2. The molecules to be studied must be in gaseous form so that they are free to rotate.
3. Difficulties are encountered to study large molecules because they have more than one
internuclear distance which connot be easily sorted out from the determind moments of
inertia.
6. INFRARED SPECTROSCOPY
• Introduction: IR spectroscopy is the most powerful analytical technique for the identification
of chemical constitution. IR radiations range from 2mm to 16mm and are not energetic enough
9.16 Engineering Chemistry
to produce electronic excitations in most organic molecules. These radiation causes stretching
and bending of organic bonds.
After absorption of IR radiations the molecules thus give close-packed absorption bands
known as Infrared Absorption Spectrum. A number of bonds may be present in the 1R
spectrum corresponding to the characteristic functional group and bonds present in the
substance.
• Vibrational Model of Polyatomic Molecules: The atoms in a molecule, which may be
of different types, are always in motion. This type of vibration movement is called bond
stretching and the atoms remains in the same bond axis. This mode of vibration does not
cause any dipole change in the symmetrical molecules e.g., O = C = O and therefore is not
an infrared active vibration.
In the case of polyatomic molecules, the actual vibration is complicated. However, it can be
resolved into simple modes called normal modes of vibration. Each normal mode of vibration
give rise to vibrational bond. The modes of vibration are (3n – 5) for linear polyatomic
molecules and for a nonlinear polyatomic molecules the number of modes of vibrations are
(3n – 6), where n is the number of atoms in the molecule. The various types of vibration
are:
1. Stretching Vibration: In this vibration, the distance between the two atoms increases or
decreases but the bond axis remains the same. It may be symmetric or asymmetric. In
the former case, movement of an atom with respect to a particular atom in a molecule
is in the same direction, while in the later case, one atom approaches the central atom
and other is moving away.
O O O O
Symmetric Asymmetric
2. Bending Vibration: In this case the distance between the two atoms remains constant,
the position of the atom changes with respect to original bond axis. It is of two types:
1. In the plane bending, which is of two types
(a) Scissoring: In this mode of vibration two atoms approach each other.
(b) Rocking: The movement of both the atoms take place in same direction.
2. Out of plane bending which is also of two types
(a) Wagging: The two atoms move up and below the plane while the other moves down
the plane with respect to central atom.
(b) Twisting: In this type, one of the atoms move up the plane while the other moves
down the plane with respect to central atoms.
Spectroscopic Methods of Analysis 9.17
O O O
H H H H H
All the three vibrations in water molecule involve a change in dipole moment and
therefore are IR active.
(ii) Carbon Di-oxide (CO2): It is a linear molecule and has normal modes of vibration =
3 × 3 – 5 = 4. The fourth mode of vibration is identical with third except in direction
and such modes are called degenerate. Thus, for linear CO2, we get two bands in the
spectrum.
O C O O C O
O C O O C O
Bending Bending
–1 –1
V = 667 cm V = 667 cm
• Group Frequencies and Analysis: A particular part of the infrared spectrum is referred
to either by wavelength or more preferably by its frequency. The wave number is simply
9.18 Engineering Chemistry
the number of waves per centimeter, and is equal to the reciprocal of the wavelength in
centimeters. The IR spectrum may be divided into two parts:
(a) Characteristic Frequencies: The region 4000 cm–1 to 1400 cm–1 (approx.) contains the
peak characteristic of individual groups. Hence, the frequencies corresponding to such
groups are known as characteristic frequencies.
(b) Fingerprint Region: The region 1400 cm–1 to 650 cm–1 is referred to as the fingerprint
region. This position is extremely valuable when examined with reference to other
regions. For example, if alcoholic phenolic stretching frequency appears in the high
frequency region and absorption also occurs at 1260 cm–1 to 1000 cm–1. This is the
region usually checked for identification, since it is associated with vibrational energy
changes of the molecules skeleton and so is characteristic of the compound.
Wave length (nm)
2.5 3 4 5 6 7 8 9 10 12 15
100
Transmittance (%)
80
60
40 Fingerprint Region
4000 3500 3000 2500 2000 1800 1600 1400 1200 1000 800 600
–1
Frequency (cm )
• Characteristic Infrared Bands: The above absorption ranges of the major functions groups
in organic compounds are summarized in Table 5. All the bands in the IR spectrum need
not be attempted, but the presence or absence of function group such as carbonyl, hydroxyl,
amino etc. is ascertained by this technique and these finding should be used in conjugation
with the information obtained from UV, NMR and mass spectra.
1. Alkane and Alkane Residue: Precise position of CH3, symmetrical and unsymmetrical
vibration frequencies is well known. Since most organic molecules possess alkane
residues the groups of saturated C – H absorption bands are of little diagnostic value,
whereas the absence of saturated C – H absorption in a spectrum is of diagnostic value.
Unsaturated and aromatic C – H stretching frequencies can be distinguished from the
saturated C – H absorption since the latter occurs below 3000 cm–1 while the former
gives rise to much less intense absorption above 3000 cm–1.
2. Alcohol and Phenols: Compounds containing O – H bands exhibit a peak between
3700 and 320 cm–1. The position of this band dependent on the existence and strength
of a hydrogen band. The IR spectrum of ethanol in vapor state show a sharp band near
3700 cm–1 which is described as a free hydroxyl group. However, when the spectrum
is taken in solution, Sharp band is a almost replaced by a broad band at 3350 cm–1.
On further increasing the concentration the band at 3700 cm–1, completely disappears,
the broad band at 3350 cm–1 is characteristics of hydrogen bonded hydroxyl group and
since the intensity of this band changes with concentration. It is a case of intermolecular
hydrogen bonding.
25 mm 15
CH3CH2OH
3640
–1
4000 Cm 800
15 mm 15
3540 CH3CH2OH
3350
–1
4000 Cm 800
The position of absorption of the carbonyl stretching of esters (Fig. 10) is somewhat
higher than Ketones and is dependent, as with Ketones, on conjugation, unsaturation,
and ring size.
The IR spectrum (Fig. 11) in addition to showing (figure) Keto and ester carbonyl
frequencies, also shows a band at 1650 cm–1 which has been ascribed to ab–hydroxyl–a,
b–unsaturated ester carbonyl.
25 mm 15 25 mm 15
O O O
CH3–C–OC2H3 CH3–C–CH2–C–OC2H5
–1 –1
4000 Cm 800 4000 Cm 800
Fig. 10 The IR Spectrum of Ethyl Acetate Fig. 11 The IR Spectrum of Ethyl aceto Acetate
4. Carboxylic acids: The IR spectra of carboxylic acid reveals the presence of a hydrogen
bond. Comparison of the IR spectrum of acetic acid (Fig. 12) with ethanol (Fig. 5) clearly
shows the absence of a free hydroxyl groups in the molecule of acetic acid.
25 mm 15
CH3–C–CH
–1
4000 Cm 800
• Applications of IR Spectroscopy
1. Qualitative Analysis: The qualitative analysis can easily be done by comparing the spectrum
of the compound under examination and the standard one.
9.22 Engineering Chemistry
7. Raman Spectroscopy
Raman Spectroscopy deals with the scattering of light in contrast whereas other branches of
spectroscopy which deal with absorption of light.
Origin: When a sample is irradiated with a beam of monochromatic light, a very small fraction
of it is scattered in all directions. if the scattered light in a direction perpendicular to the incident
beam is spectrographed it shows strong line (Rayleigh line) corresponding to the frequency of the
incident light and weak lines on either side of it. These lines are symmetrically arrayed above and
below the frequency of the Rayleigh line and are known as Anti-Stokes and stokes. The plot of these
frequency shifts against their intensities is a Raman.
The quantum theory of Raman effect is quite simple. Consider a photon of frequency n falling on
a molecule of the collision is elastic then the scattered photon will be of same energy as the incident
Spectroscopic Methods of Analysis 9.23
photon. if on the other hand collision is inelastic the scattered photon will have either a higher or a
lower energy than the incident photon. if the kinetic energy of the photon and the molecule remains
unchanged before and after the collision, then from the law of conservation of energy,
hn + E = hn¢ + E¢ ...(1)
where hn is the energy of the incident photon and hn¢ in the energy of the scattered photon after
collision. E is the energy of the molecule (rotational, vibrational, and electronic) before collision and
E¢ is the molecular energy after collision. Rearranging eq (1) we get
E¢ – E
______ = n – n¢ ...(2)
h
Consider the following cases:
Case 1 n = n¢ so that E = E¢
Case 1 is referred as Rayleigh scattering, where scattered photon has the same frequency as the
incident photon as given in Fig 13.
Fig. 13
9.24 Engineering Chemistry
When the molecule, excited to the higher unstable vibrational state, returns to the original
vibrational state, we get Rayleigh scattering.
The Rayleigh scattering and the Raman scatting.
Case II (a) When the molecule excited to the higher unstable vibrational state, returns to the
original vibrational state this gives rise to Raman scattering (Stokes lines).
Case II (b) When the molecule, initially in the first excited vibrational state is promoted to a higher
unstable vibrational state and returns to the ground state, this again gives rise to Raman Scattering
(anti-stokes lines).
Thus, the Raman spectrum of a molecule consists of Stoke’s lines and anti-Stokes lines situated
symmetrically about the Rayleigh line.
The Rayleigh line is far more intense than the stoke’s lines which in turn have greater intensity
than the anti-Stokes lines. In a conventional Raman spectroscopy, the anti Stokes lines are difficult to
be observed because they correspond to the return of a molecule form the unstable excited vibrational
state to the ground state and initially there are very few molecules in the excited vibrational state.
Criteria for a molecule to be Raman spectra
The Raman spectroscopy is observed only when a molecule shows periodic change in polarizability
due to its vibrational or rotational osciallation.
Pure Rotational Raman Spectra of Diatomic Molecules
When the polarizability of a molecule depends on the direction in which the applied field lies,
rotational transitions can also be observed by Raman effect. Since, on every revolution, the
polarizability of a molecule returns to its initial value, twice the rotational selection rule in Raman
spectra is therefore DJ = ± 2.
The expression for rotational term F (J) is
F (J) = B J(J + 1) cm–1
When a molecule makes transition with D J = ± 2 i.e., from J to J + 2 ; the scattered light emerges
with a lower frequency and we get stokes lines in the spectrum.
__
Stokes n(J Æ J + 2) = F(J + 2) – F(J)
= B(J + 2) (J + 3) – BJ(J + 1)
= B[J + 2) (J + 3) – J(J + 1]
= B[J2+ 5J + 6 – J2+ J]
= B[4J + 6]
Where J = 0, 1, 2 ...
Similarly, expression for anti-Stokes lines can be observed with the help of selection rule D J = – 2
i.e., transition from J to J – 2.
When D J = 0 only Rayleigh Scattering takes __
place and Rayleigh line is observed at the same
wave number as that of incident radiation (i.e., n0).
Thus, Raman lines will appear at wave numbers given by
__ __
n = n 0 ± B (4 + 6) ; J = 0, 1, 2.
__
Where n0 is wave number of Rayleigh line
__ __
When n > n
0 Æ Anti-Stokes lines are observed.
__ __
And when n < n
– Stokes lines are observed
__ 0 __
When J = 0 – n = n0 ± 6B
Spectroscopic Methods of Analysis 9.25
Hence, the first stokes and anti-stokes line will be at a separation of 6B from the Rayleigh line.
However, the separation between the successive lines is 4B cm–1 as shown in Figure (14) below.
Fig. 14 Anti-Stokes and Stokes rotational Raman lines in pure rotational Raman
spectrum of diatomic molecule.
From the constant separation of 4B cm–1 between the neighbourning lines in Stokes and anti-Stokes
series, calculation of B is possible. Once we know the value of B, moment of inertia of the molecule.
can be determined. From this bond length and bond, angles can be calculated.
Vibrational Raman Spectra
The selection rule for vibrational Raman effect is Dn = ± 1.
When Dn = + 1, Stokes lines corresponding to low frequency of side of the incident light are
observed.
When Dn = –1, anti-stokes lines corresponding to high frequency side of the incident light are
observed.
Rotation Vibration Raman Spectrum
Let us now briefly consider the rotational transition accompanying a vibrational raman transition
of a diatomic molecule. The selection rules now involve the changes in both the vibrational and the
rotational quantum numbers. For a diatomic molecule the selection rules are
Dn = + 1
D J = 0, ± 2
Since at room temperature most of the molecules are in the ground vibrational state (v = 0), only
the vibratinal transitions, v = 0 to v = 1, is of interest. The transitions with D J = 0 forms a Q branch.
those with D J = +2 form an S branch and those with D J = – 2 form an O branch. The rotational
Raman transitions accompanying a 0 Æ 1 vibrational transitions are shown in the figure (16) given
9.26 Engineering Chemistry
below. Here D n measures the displacement from the exciting mercury line. The Q band exhibits an
_
intense ‘narrow line’ at vexc that is usually unresolved while the S and Q branches form weak wings
which extend to lower s higher wave numbers respectively, from the intense narrow line.
The Raman spectra of gases are generally weaker than those of liquids. It is necessary to use very
long discharge lamps and cells, the latter containing mirror at both ends arranged so as to increase
the effective path length of the cell.
It is to be recalled here that selection rule for IR and Raman spectra is same. It does not mean
that IR and Raman spectra are identical. But most of the time, they supplement each other for the
determination of molecular structure.
For example, if a molecular has a centre of symmetry, then IR inactive vibrational modes are
Raman active and vice–versa. This is known as role of mutual exclusion.
This can be exemplified by taking the example of CO2, a linear triatomic molecule with 3N – 5
= 3 × 3 – 5 = 4 vibrational modes.
Another example is that of the planes dichloroethylene C2H2Cl, which consist of cis and trans-
configuration in equilibrium proportions. Only the trans-configuration has a centre of symmetry.
Thus, the coincident frequencies observed in IR and Raman spectra of the sample can be assigned
to this cis–configuration. In this manner the analyses of the mixture of this cis and trans–isomers
can be carried out.
Again, for CS2, all the vibrations that are Raman active are infared inactive and vice-versa,
whereas for N2O the vibrations are simultaneously Raman and IR active.
From the spectral data we conclude that CS2 has a centre of symmetry where as N2O has no
centre of symmetry. Thus the CS2 structure is of the type S – C – S while the N2O structure must
be N – N – O rather than N – O – N.
Raman shift D V generally lies within the far and near infrared regions of the spectrum. But it
is not necessary that all Raman lines will have corresponding infrared bands and vice-versa Raman
Spectrum is different from Infrared spectrum in the following respects:
by I called the spin quantum number. Spin quantum number is associated with the angular momentum
by the following relation:
_______ h
I = ÷I (I + 1) ___
2p
where,
h, is the Plank’s constant.
• Rules for Nuclei showing NMR Spectroscopy: Nuclei with an even number of protons and an
even number of neutrons (i.e., even atomic and mass number) have hero spin and they do not give
rise to NMR signals. For example Cl12, O16, S32 etc.
Nuclei with an odd number of protons and an odd number of neutrons (i.e., odd atomic and even
mass number) have integral spins. For example the nuclei H2, N14 have I = 1 and for B10, I = 3.
Nuclei with odd mass numbers have half-integral spin, for example H1 and N15 have I = 1/2 and
17
O have I = 5/2 etc.
• Principle of H1 NMR Spectroscopy: Consider the nucleus of a hydrogen atom (proton). It
behaves as a tiny spinning bar magnet because of posses both electric and magnetic spin. Like any
other spinning charged body, it will generate a magnetic field.
Applied magnetic field
Precessional
orbit
Spinning
nucleus
Fig. 18
If the sample contain many identical nuclei with spin quantum number I = 1/2, it can have two
possible orientations (2I + 1), i.e., 1/2 or –1/2 or a and b nuclear spin. When the external magnetic
field is applied the magnetic nuclei (protons), like the spinning top, will process around the axis of
an applied external field. It precessionals frequency is given by:
V µ Bo
The precessional frequency V is directly proportional to the strength of the external field Bo. In
the presence of an external magnetic field, two changes can occur.
(i) The precessional proton can adopt two principal orientations with respect to the applied
external field.
(a) Aligned with the field, corresponding to low energy state, a – state.
E1 = 1/2 gBnH
Spectroscopic Methods of Analysis 9.29
Instrumentation
For the observation of the absorption of radiation by protons, difficulty in setting up the arrangement
is encountered because (1) of obtaining the magnetic field of sufficient high field strength, and (2)
uniformity of the field. In contrast to most other absorption methods, in NMR spectroscopy the
frequency of radiation is kept constant and the magnitude of applied magnetic field is varied, until
absorption of radiation by protons occurs. This slight variation in magnetic field is achieved by
passing current through wire coils, wrapped round the two pole pieces of the magnet. Absorption
of radiation is detected on the radiofrequency bridge (a type of wheatstone bridge arrangement),
which goes out of balance, when absorption of radiation occurs and the resulting signal is amplified
and recorded instantaneously on the chart Fig. 19 showing schematically the basic arrangement for
NMR spectrometer.
Chemical Shift
Chemical shift may be defined as a shift in position of a spectrum peak due to a small change in
environment. When a molecule is placed in a magnetic field, its electrons are caused to circulate,
thereby producing a induced magnetic field, which may be either:
(i) Oppose the applied field: Evidently, the effective field experienced by the protons is
diminished. Under this state, proton is said to be shielded. The shielded protons in turn shift
the absorption position upfield in the NMR spectrum. This effect is also called diamagnetic
shift. Consequently, the value of the applied field necessary to bring the nucleus in the
resonance will be more. For example, acetylic protons exhibit this type of chemical shift.
(ii) Reinforce the applied field: Evidently, the effective field experienced by the protons turn
shift the absorption position downfield in the NMR spectrum. This effect is also called
paramagnetic shift. Consequently, the value of the applied field necessary to bring the nucleus
in the resonance will be less. For example, ethylenic and aldehydic protons exhibit this type
of chemical shift.
Expression for chemical shift: It is not possible to measure in absolute term the precessional
frequency for a group of nuclei. Usually, chemical shift is measured with respect to some standard.
TMS [tetramethy silane (CH3) 4Si] is taken as standard. Usually, chemical shift positions are expressed
in delta (d) units, which is equal to differences in ppm from TMS signals. Thus:
go
d = gs – __
g
gs = frequency of the sample
go = frequency of TMS
g = operating frequency.
Most chemical shift values have to be found to lie between 0 and 10. So TMS has been assigned
d value of 0.
TMS is used as a standard compound to carry out NMR spectra for the following reasons;
1. It has 12 protons but only one signal is obtained as their environment is same.
2. It is soluble in all organic solvents without showing molecular interaction with the sample.
3. It is volatile so need not be removed.
(a) (b)
2. C H3– OH Two Signals
3. Three Signals
(a) (a)
H H
4. C=C One Signal
H H
(a) CH3 H(c)
5. C=C Four Signals
(b) H H(d)
(a)
CH3 (b)
H
6. C=C Three Signals
C1 H(c)
(c)CH3
H(d)
7. Four Signals
(a) H H(a)
(b) H H(b)
(b) Position of signal (Chemical Shift): The number of signals in an NMR spectrum tells the
number of the sets of equivalent protons in the molecule. The protons have a precessional
frequency by ~60MHz. However, the precessional frequency of all the protons in the same
as the exact value depends upon the chemical environment of the protons. Since the shift in
frequency depends upon the chemical environment it is called chemical shift. For example,
case of a molecule of methanol CH3OH, there are two types of precessional frequencies of
the proton in the spectrum. The differences in precessional frequency are very small but can
be detected by high resolution instruments
(c) Splitting of Signals/ Spin-Spin coupling: Each signal in NMR spectra represents one set
of protons in a molecule. However, in certain molecules, instead of a signal peak, a group of
peaks (multiple) is absorbed. The number of lines observed in the NMR signal for a group
of protons is not related to the number of protons in the group but it is related to the number
of protons in the neighboring group. The simplest rule to find the multiplicity of the signal
from a group of protons is (n + 1), where ‘n’ is the number of neighboring protons. This
can illustrated by the following examples:
(i) Ethyl Alcohol
(a) (b) (a)
CH3– CH2– OH
It contains three types of protons, namely three methyl protons, two methylene protons and
one hydroxyl proton. Hence, three NMR signals are obtained under low resolution. This is
due to the spin interaction or coupling between the adjacent sets of non-equivalent protons.
The adjacent methylene protons as shown in the following table. The intensities of the lines
9.32 Engineering Chemistry
in the triplet are in the ratio of 1 : 2 : 1, corresponding to the number of like orientation in
each case.
Thus, the relative intensities of the individual lines of the multiple correspond to the numerical
coefficient of the lines in the binomial expression where, n = number of protons.
(ii) CH3-CH2-O-CH3
a b c
This has three types of protons. Splitting of signals is as follows;
a =2+1=3
b =3+1=4
c=1
(iii) CH3-CH2-CH2-CHO
a b c d
This has four types of protons. Splitting is as follows;
a =2+1=3
b = (3 + 1) (2 + 1)
c = (2 + 1) (1 + 1)
d =2+1=3
(iv) CH3-CH2-OH(aq)
a b c
This molecule has three types of protons but because the medium is aqueous c proton
is involved in hydrogen bonding so b and c protons are not present in environment of
each other. Splitting is as follows;
Spectroscopic Methods of Analysis 9.33
a = 2 + 1 =3
b = 3 + 1 =4
c =1
1
How to interpret H NMR spectra?
Following points may be considered for the interpretation of NMR spectra:
(1) Number of signals tells the number of different environments in the molecule.
(2) The relative areas of different peaks corresponds to the number of protons present in
different environment is the molecule. In other words, area under each NMR signal
is proportional to the number of H-atoms present in the environment.
(3) Multiplicity of lines in an NMR signal for a group of protons is dependent on
hydrogen atoms present in the neighbouring groups. If there are n protons, then
multiplicity of signals = (n + 1).
(4) The intensities of signals are asymmetric about the midpoint of the group. Pascal’s
triangle gives the relative intensities of various signals in the NMR spectrum
solved Questions
1. What is molecular spectroscopy?
Ans. The study of interaction of electromagnetic radiation with matter.
2. What is electromagnetic radiation?
Ans. The emission and propagation of electromagnetic waves.
3. What are electromagnetic waves?
Ans. A wave comprising of two interdependent mutually perpendicular transverse waves of electric
and magnetic field.
4. What is the wavelength range of electromagnetic waves?
Ans. Wavelengths of 10 –15 to 103.
5. Names the forms of electromagnetic radiations.
Ans. Gamma rays, Xrays, ultraviolet radiations, visible light, infrared radiation, microwaves and
radiowaves.
9.34 Engineering Chemistry
Unsolved Questions
IR spectroscopy
1. What is the difference between absorption and emission spectra?
2. Distinguish between atomic and molecular spectroscopy.
3. Explain Beer’s Lamberts law.
4. What are electromagnetic radiations? Give the regions of electromagnetic radiations in the
increasing order of frequency.
5. What type of molecules gives pure rotational spectra?
6. Explain how a vibrational rotational spectrum is obtained.
7. What do you understand by fundamental bands and overtone bands?
8. Distinguish between the following from their IR spectra.
(i) Ethanol and dimethyl ether
(ii) Primary, secondary and tertiary amides
9. What modes of vibrations are active in IR absorption spectra and why taking CO molecule
show the various types vibrations which will be observed in IR spectra.
10. Three test tubes contain three ketones–one of them absorbs near 1785, one near 1750 and
one near 1710 cm–1. What types of ketones are they?
11. How many vibrational modes are there in a linear and a non-linear molecule having n atoms?
Explain with the help of degrees of freedom.
12. What are different kinds of electronic transitions?
13. Distinguish between the following pairs from their IR spectra.
(i) 2 propanol and propanone.
(ii) Ethanol and dimethyl ether.
(iii) Ethylamine and acetamide.
UV–Visible Spectroscopy
1. What are absorption spectra?
2. Write short note on the electronic transitions caused by energy absorbed in the U.V.
region.
3. Why molecules absorb in UV visible region? What are the types of electronic transitions
that can occur in the molecules?
4. Give one example each of s Æ s*, n Æ s*, n Æ p and p Æ p* transitions.
5. How will you distinguish between benzene and anthracene by UV spectroscopy?
6. Write a note one (i) Chromophores (ii) Auxochromes
7. Define the following terms:
(i) Batho chromic shift (ii) Hypo chromic shift
9.36 Engineering Chemistry
(b) H H
C=C
Br Br
(c) H Cl
C=C
Br H
(d) CH3 – C = O
(e) CH3
C=O
CH3
12. An organic compound C3H6O contains a carbonyl group > C = O.
How will its NMR spectrum decide whether it is an aldehyde or a ketone?
13. State and explain the principle of NMR spectroscopy.
14. Explain the term coupling constant with examples.
15. Why TMS is used as internal standard in NMR spectroscopy?
16. Predict the NMR spectrum of the compound CH3COCH2C ∫ CCH3.
Spectroscopic Methods of Analysis 9.37
17. What is the multiplicity of each proton in (i) Iso butyl bromide (ii) Butyl bromide
18. Give the structure consistent with the following NMR data: C3H5Cl3
(a) Singlet, d 2.20, 3H
(b) Singlet, d 4.20, 2H
Rotational Spectra
1. Explain applications of Rotational spectra.
2. Give the principle of Rotational spectra.
3. Explain Rotation in diatomic molecules.
4. She pure rotational spectrum of CN molecule in gaseous phase shows series of equally spacel
lines with interspacing 3.8 cm–1. Calculate the internclear distance of CN molecule.
Raman Spectra
1. How is Raman spectra different from other spectra?
2. Explain Rayleigh Scattering and Raman Scattering.
3. Explain Rotational-Viluational spectra in Raman.
4. How is Raman spectra different from IR Spectra?
Chapter 10
Polymers
Polymers form the backbone of the modern civilization and are the chief products of the modern
chemical industries. In almost all walks of life, starting from household utensils, clothes, furniture etc.,
to automobiles to space aircrafts and biochemical and surgical operations, polymers are extensively
used.
A polymer may be defined as high molecular weight compound formed by the combination of
large number of one or more types of small units or molecular of low molecular weight.
The simple molecules from which the repeating structural units are derived are called monomers
and the process by which these simple molecules i.e. monomers are converted into polymers is called
polymerization.
H H
* * * – Two Bonding sites
C=C C–C Functionality = 2
H H
1. Characteristics of polymers
• Polymeric molecules are very big molecules. Their average molecular weights may approach
105 or more. That’s why, they are also known as macromolecules. They are in fact sub-
microscopic particles.
• Polymers are semi-crystalline materials. It means they have both amorphous and crystalline
regions. In fact, polymers have regions of crystallinity, called crystallites, embedded in
amorphous regions. Crystallites provide strength and hardness and the amorphous regions
provide flexibility to the polymeric material.
• The intermolecular forces in polymers can be vander waal’s forces, dipole-dipole attractions
or hydrogen bonding. These intermolecular forces are in addition to covalent bonds which
connect the repeating units into a macromolecule.
• The chemical, electrical, optical, mechanical and thermal properties of polymers depend
on (i) size and shape of the polymers, and (ii) the presence or absence of characteristic
intermolecular forces. These parameters not only determine the properties of the polymers,
but also the performance of these materials in a given applications.
• Polymers show time-dependent properties. They show “creep”.
• Polymers are combustible materials.
• Generally, polymers are thermal and electrical insulators.
• Polymeric materials are tailor-made and are easily mould able even into complex shapes with
reproducible dimensions with a minimum of fabrication and finishing cost.
Polymers 10.3
2. Advantages of polymers
Advantages offered by polymers in comparison with metals, wood, ceramics and other conventional
materials:
(a) Polymers have low densities, this leads to production of light weight products, hence costs
of transportation is low and general handling are easy.
(b) Polymers have low absolute strength and stiffness but their specific strength and specific
stiffness values are favorable.
(c) Polymers have excellent resistant to corrosion. They do not require any protective covering
and the maintenance of exposed surfaces is easy and economical.
(d) Polymers are usually thermal and electrical insulators.
(e) Some polymers, especially rubbers are inherently flexible. They have excellent elasticity and
damping qualities.
(f) Polymeric materials are easily moulded even into complex shapes and reproducible dimensions
with a minimum of fabrication and finishing cost. This is because they require low processing
temperatures, hence energy requirements are less (hence small amount of energy required).
(g) Polymeric materials have the ability to take variety of colors, shades, etc. which does not fade
easily since coloring is not usually restricted to the surface but is throughout the mass.
(h) Polymeric materials are tailor-made. Depending on the need they can be synthesized as:
(i) Transparent or opaque
(ii) Rigid or flexible
(iii) Brittle or tough
(iv) Malleable or elastic and
(v) Fibers, Elastomers and Plastic
(c) We sit and stand on them (by making furniture from them);
(d) They are used in leisure industry;
(e) We sleep on them (by using foamed matrices and bed sheets);
(f) We eat and drink from them (by using plastic crockery);
(g) We see sights far away from us in time and space and we hear sound with their help (by
making electrical appliances like TV and radio cabinets and telephone body parts);
(h) We turn knobs, pull switches and grasp handles made from them;
(i) Damaged organs can be repaired or replaced with their help;
(j) We use them for purification of water;
(k) By their use blind people can be made to see and cripples to walk;
(l) In the form of coating they prevent rusting and decay of traditional materials;
(m) We employ them for electrical insulation for protecting ourselves against electric shock.
(n) We also employ them from heat and sound insulation in refrigeration and air conditioning.
(o) We also make overhead tanks and pipes to convey water, gases etc., from them.
5. Polymer Classification
In this modern world, polymers are an integral part of everyone’s life style. They have very diverse
structures and applications ranging from domestic articles to sophisticated scientific and medical
instruments. These materials have penetrated into almost all the applications like transport, agriculture,
construction, education etc. These materials are used as fibers, rubber, plastics, adhesives, paints etc.
In fact, the very existence of life is virtually the formation, transformation and decomposition of
biopolymers viz. carbohydrates, proteins and nucleic acid therefore, in view of their importance, a
proper understanding of polymeric materials is very essential.
Polymers can be classified into several ways as described below:
5.1
[A] On the Basis of structure of polymer there are three types of polymers:
(i) Linear chain (ii) Branched chain (iii) Cross linked polymer
(i) Linear Chain: Linear chain polymers are those in which monomers are joined like links in a
chain. They have high density, high tensile strength and high melting point because of well packed
structure.
For example, Poly ethylene, Nylons, Polyesters etc.
Monomer structure
Linear chain
(ii) Branched Chain Polymer: They are the polymers having side chains or branches in addition to
main chain, branching hinders the close packing of the polymeric chains and hence are less tightly
packed in comparison to the linear chain polymers. Branched polymers have low melting point,
density and tensile strength as compared to linear polymers.
e.g. LDPE, Glycogen, Starch etc.
Polymers 10.5
(iii) Network or Cross Linked Polymers: Polymers in which monomers are cross linked together in
all the three dimensions to form three-dimensional network type of structure are known as network
or cross linked polymers. These are generally obtained by the polymerization of poly functional
monomers. Cross linked polymers are hard, rigid and brittle because of network structures.
e.g. Bakelite
5.2
[B] On the Basis of Stereochemistry or Tacticity:
Alkenes of the type H2C = CHZ may undergo polymerization to form polymer – (H2C – CHZ) n– in
which function group Z are on the
(i) Same side of the main carbon chain or
(ii) Alternate side of the main carbon chain or
(iii) Randomly arranged along the main carbon chain.
The difference in the configuration of polymers is known as tacticity.
Depending upon the tacticity polymers are of three types.
(i) Isotactic (ii) Syndiotactic (iii) Atactic
(i) Isotactic: Polymers, in which all the functional group Z, is on the same side of the main
carbon chain, are known as Isotactic polymers.
e.g. Cis – Polyisoprene.
H ZH ZH ZH Z
H H
H Z
Same
or H H
side
H Z
H H
H HH HH HH H
Isotactic Polymer
10.6 Engineering Chemistry
(ii) Syndiotactic: Polymers where functional group ‘Z’ is present in alternating fashion on the
main carbon. e.g. Gutta Purcha.
H HH ZZ H H H
H Z
H H
or
Z Z
H H
H HH HH HH H Z
(iii) Atactic: Polymer where the functional group Z is arranged randomly along the main carbon
chain. e.g. Polypropylene.
H HZ HH ZZ H H H
H H
H H
or
Z Z
H H
Z H
H HH HH H H H
5.3
[C] On the basis of type of monomers there are two types of polymers;
(i) Homopolymer (ii) Copolymer
(i) Homopolymer: A polymer formed by repeated combination of one type of monomer is
known as homopolymer. For example PE, PMMA, PVC etc.
nA [– A ]n
(ii) Copolymer: A polymer formed by repeated combination of two or more types of monomer
is known as copolymer. For example; Nylon 6, 6, Terylene, Vinyon.
Depending upon the arrangement of A (monomer) and B (monomer) in the polymeric chain
copolymers may be subdivided into following types:
(a) Alternating copolymers: Monomers are arranged alternatively in the polymeric
chain.
nA + nB [ A–B–A–B–A–B–A [
nd nd
II Block II Block
nA + nB [ A–A–A–B–B–A–A–A–B–B [
st st
I Block I Block
For example, Polystyrene-block-polybutadiene.
(d) Graft copolymers: One type of monomer segment is grafted on the backbone chain of
another type of monomer segment.
B
–
B
–
nA + nB A–A–A–A–A–A
–
B
Back
–
B
Bone graft Chain
–
Chain B
–
For example, Polybutadiene-graft-polystyrene.
5.4
[D] On the basis of mode of synthesis polymers are classified into two:
(i) Addition Polymers (ii) Condensation Polymers
(i) Addition Polymers: Polymers which are formed by the polymerization of monomers without
elimination of atoms or groups are known as addition polymers. They are also known as
chain growth polymers. Polymerization takes place in the presence of initiators. For example;
Ethylene
(ii) Condensation Polymers: Polymers which are formed by the polymerization of monomers
with elimination of small molecules like NH3, H 2O, HCl, CH3OH etc are known as
condensation polymers. They are generally formed by different types of monomers and are
also called step growth polymers. Initiators are not required in condensation polymerization.
For example, Terylene.
6. This is also known as chain growth 6. This is also known as step growth
polymerization. polymerization.
7. Initiator is needed. 7. No initiator is used.
8. Addition polymerization gives rise to 8. Generally copolymers are formed.
homopolymers.
9. For example, PE, PVC, PMMA, etc. 9. For example, Nylon 6,6, Bakelite.
5.5
[E] On the Basis of action of heat, polymers there are of two types;
(i) Thermoplastic (ii) Thermosetting
(i) Thermoplastic: These are polymers which gets soften on heating and hardened on cooling
without or with very little change in their properties.
(ii) Thermosetting: These are polymers which once hardened cannot be softened again.
5.6
[F] On the basis of origin:
Polymers can be broadly classified into two types:
(i) Natural Polymers (ii) Synthetic Polymers
(i) Natural Polymers: Polymers which are obtained from the nature (animal or vegetable origin)
are called natural polymers. e.g. Starch, Cellulose, Proteins, Natural rubber etc.
(ii) Synthetic Polymers: Polymers which are prepared in laboratory. They are of two types.
(a) Organic polymers: Main chain of polymer is made of carbon. For example. PVC, PE,
Nylon, PTFE etc.
(b) Inorganic polymers: Main chain of polymer is made of elements other than carbon.
For example, silicon polymers.
Polymers 10.9
e.g. Pe, PVC, PMMA, Nylons, Polysterene e.g. Phenolic resin, Epoxyresin, Bakelite
5.7
[G] On the basis of molecular force: Polymers are three types of polymers:
(i) Elastomers (ii) Fibres (iii) Plastics
(i) Elastomers: The group of polymers exhibiting high degree of elasticity (reversible elongation
300% to 1000%) stretching at least twice of their original length under the action of tensile
force and recover their dimensions after the removal of the applied force, just like rubber
are known as elastomers.
Elastomers have long coiled chains, amorphous structure and a few widely separated cross
links. The polymeric chains are held together by weakest inter molecular forces. When such
polymers are subjected to external force the coils open up partially and get aligned in the
direction of elongation. The aligned chains have a natural tendency to revert back in their
original state as soon as the force is removed.
Example: Natural rubber [cis-poly isoprene] is elastomer. The average initial modulus of
elasticity ranges from 10 to 102 psi.
There are two types of elastomers.
(a) Natural elastomers. For example, natural rubber
(b) Synthetic elastomers. For example, Synthetic rubber like Buna S, Buna N, neoprene,
Butyl rubber.
(ii) Fibres: These are polymers having thread like structure with high aspect ratio (length to
diameter ratio).
6. Thermosetting Resin
These polymers undergo permanent change on heating i.e. the changed occurred in structure of
polymers is chemical. These polymers are cross linked or heavily branched molecules which on
heating undergo extensive cross linking and again become infusible. Cross linked polymers are always
thermosets due to the presence of three-dimensional networks.
Novalac Formation: In the presence of acid catalyst, when the P/F (phenol formaldehyde) ratio is
less than unity, the methylol derivatives condense with phenol to form a linear polymer with little
methylol group. The product is thermoplastic in nature and known as novalac.
Resole Formation: In the presence of alkaline catalysts with P/F (phenol formaldehyde) ratio greater
than 1, the methylol phenols condense to form linear structure called resoles.
The resoles have excess of methylol groups capable of further reaction during continued heating.
Resoles, therefore have limited shelf life. However the reaction may be stopped at the deserved step
by cooling.
OH OH
HOH2C CH2OH + CH2OH
OH OH
HOH2C CH2
Resoles
Bakelite: Further heating of novalac, in the presence of hexa methylene tetramine as curing agent
produces 3 dimensional, cross linked network polymer (Bakelite) which is hard, rigid and insoluble
solid. Cross linked of resoles can be done by heating in either neutral of just acidic conditions. Cross
linked product from resole is called resites.
OH OH OH
CH2 CH2 CH2
Uses: They have moulding applications. They are widely used in making telephone parts, cabinets for
radio, television and automobile parts, for making electric insulator parts like switches, plugs boards,
heater handle, for producing brake linings, abrasive wheels and sand paper, used in varnishes, paints
and protective coating, in production of ion exchange resin for water softening.
O=C O=C
Uses: It shows remarkable chemical resistance and good adhesion, works as very tough materials,
used in industrial flooring foams, potting material for electrical insulation, as a reinforcing material
Polymers 10.13
in many of the fibres reinforced plastics, used for surface coating and as laminating and casting
material, used as decorative articles like plates, drinking glasses, dishes, etc.
NH2 NHCH2OH
N N + 3HCHO N N
The methylol derivative is further condensed with melamine to give a linear polymer. This
linear polymer reacts with excess of formaldehyde producing a cross linked melamine formaldehyde
resin.
NHCH2NH NHCH2NH
N N N N
N HNCH2NH N HNCH2NH
N N
HNCH2HN N NHCH2NH
N N
HNCH2HN N NHCH2NH
Uses: Uncross linked (known as amino resins) used in the paper industry to improve the wet strength
of paper, finds use as sizing agents and textile finishing resins, in the plywood industry they are
used as adhesives, used in the manufacture of decorative laminates and lacquers.
Final curing is done by adding di- and poly-anhydrides and acids (which react with the hydroxyl
groups and epoxide rings) or by adding diamines (which react with the epoxide groups). The formation
of three dimensional, cross linked structure in epoxy resins (by using diamine) can be written in
following ways:
Uses
1. In surface coating particularly for making skid-resistant surfaces for highways, road junctions
and round about.
2. Is used as adhesives for glass, metals etc. and are popularly known as araldite.
3. Due to low water absorption tendency, dimensional stability, good heat and electrical resistance
make them very good material for electronic applications particularly in mouldings containing
inserts and encapsulation.
Polymers 10.15
7. Thermoplastics
These are polymers which can be easily softened repeatedly when heated and hardened when cooled
with little change in their properties. The inter molecular force of attraction is more than elastomer
and less than that of fibres. There is no cross linking between the chains of polymers. Some common
examples are polyethene, polystyrene, polyvinyl chloride, polyvinyl acetate, polyesters and nylons
etc.
Some thermoplastic polymers are discussed below:
Presence of chlorine atoms on the alternate carbon atoms of PVC causes an increase in the inter
molecular attraction which increases the hardness and stiffness of polymer.
Uses: Used in an insulating material, making hand bags, bathroom curtain, kitchen upholstery, used
in membrane separation technology. Chlorinated PVC increases the heat distortion temperature of PVC
which can be used for the manufacture of hot water pipe. It is widely used synthetic polymer.
10.16 Engineering Chemistry
7.3 Polyvinyl Acetate
It is prepared by emulsion or suspension polymerization of vinyl acetate in the presence of benzoyl
peroxide or acetyl acetate as catalyst.
CH2 = CH Polymerization
CH2 – C H
CO – O – CH3 COOCH3 n
It is insoluble in water and is saponified with great difficulty and hence is not absorbed by
the digestive system. Polyvinyl acetate is used as a basic material for chewing gums and surgical
dressings.
Uses: The production of water based emulsion paints, making chewing gums and surgical dressings
making records, finishing textiles and other fabrics, PVA adhesives are used for bonding of paper
leather textiles and woods etc.
7.4 Polyethylene
Polyethylene is the simplest addition homo polymer. Monomer is ethylene
(ii) High density polyethylene (HDPE): High density polyethylene is obtained by polymerization
of ethylene in presence of Zeigler Natta catalyst at lower temperature and pressure. Zeigler Natta
catalyst used is TiCl4 + (C2H5)3Al.
7. It is used for making squeeze bottles, bags, toys, 7. For making pipes, food tube, containers, gas
etc. piping, drug packaging, etc.
7.5 Polycarbonates
They are derivatives of phenol and carbonic acid. It is prepared by interaction of diphenyl carbonate
with bisphenol-A[2,2-bis(4-hydroxyphenyl) propane] also called lexan, Merlon.
Uses: It is transparent plastic so it can be used to make safety goggles, making telephone parts and
machinery parts, as electrical insulators in electronics and electrical industries.
7.6 Polyamides
They are a group of polymers which contains the amide (-CONH-) linkage in the main polymer
chain. These are synthetic linear aliphatic polyamides which are capable of fiber formation. Nylon
is generic name for synthetic polyamides, capable of forming fibers. Polyamides are prepared by the
polycondensation between dicarboxylic acids and diamines.
Typical polyamides are describes below:
Nylon 6, 6: Prepared by poly condensation of hexa methylene diamine with adipic acid. By heating
equimolar proportion of the two reactants, a polymeric salt is formed.
10.18 Engineering Chemistry
N – (CH2)6 – N – C – (CH2)4 – C
+ nH2O
H H O O n
nylon 6,6
Nylon 6: This polymer can be made either from e amino caproic acid or e caprolactum by self
condensation. Nylon 6 is also known as perlon
Nylon 6, 10: This is prepared by the condensation between hexa methylene diamine and sebacic
acid. It is generally not used as a fiber, but it is suitable for monofilaments.
H O
Self — N – (CH2)10 – C —
n – [H2N – (CH2)10 – COOH]
Condensation n
w amino decanoic acid
Nylon 11
Uses: Nylon 6, 6 is used as a plastic as well as fiber, manufacture of automobile tyre cards, ropes,
threads, textile fiber for use in tresses, Nylon 6, 6 being a tough plastic, is used as a substitute for
metals in gears and bearings etc. Nylon 11 is used as textile fibers, used as moulding purposes for
gears. Nylon 6, 10 is not used much as synthetic fiber, but is used in making brushes and bristles.
Kelvar: It is aromatic polyamides similar to nylon. It is prepared by the condensation polymerization
of terephthalic acid dichloride and 1,4-diaminebenzene.
Uses: (a) Tyres, brakes, clutch lining and other car parts; (b)Bullet proof vests; (c) Motorcycle
helmets; (d) Aerospace and air-craft industries.
— C – R – O – C – (R¢) – C —
n
O O
Uses: It has good fibre forming property with high tensile strength and excellent crease resistant
garments. Terycot is a blend of Terylene with cotton, used as films in the manufacture of magnetic
recordings tapes and aluminum sheets.
7.8 Glyptal resins
Its is made by condensation polymerization of polybasic acids (or anhydride) with polyhydric alcohols
(like glycerol) in the presence of heat and catalyst.
O H O
O
C – O – CH2 – C – CH2 – O – C
C
n O + n OH – CH2 – CH – CH2 – OH –O–C C–O
C O O
OH
O
Phthalic
anlydride
Uses: In paints, enamels, varishes, car panels, car body, binding material for cements, circuit break
insulators, switches and gears.
7.9 Poly urethanes
Poly urethanes (poly isocyanate) resins are produced by the reaction of a di isocyanate with a
compound containing at least two active hydrogen atoms such as diol or diamine. The principal
linkage in poly urethane is
— NH – C – O —
n
O
The poly addition between di-isocyanate for example toluene di isocyanate with diol or triol is
used to prepared poly urethanes.
Uses: The poly urethane foams or U-foam have the uridest, used in coatings, adhesives, elastomers,
in insulation of wire.
Polymers 10.21
7.10 Polypropylene
It is lightest known industrial polymer. It is prepared by the polymerization of propylene using
Zeigler Natta catalyst.
Zeigler – natta
n CH2 = CH — CH2 – CH —
Catalyst n
CH3 CH3
Uses: Fibres made from PVA are found to possess a higher water absorption property. PV alcohol
fibres have excellent dimensional stability.
7.12 Poly Formaldehyde
It can be obtained by cationic polymerization of formaldehyde or trioxane
10.22 Engineering Chemistry
Uses: Due to high degree of hardness and rigidity it is useful as engineering plastics.
Teflon is a linear, inert polymer. It is inert because of the presence of highly electronegative
fluorine atoms. There are very strong attractive forces between different chains due to which it is
highly dense polymer.
Uses:
1. Used for making gaskets and seals, used as insulating material for transformer cables, wires
and fittings, as non lubricating bearings, as a non stick coating for pots and pans.
7.14 Poly Styrene
It is also known as polyvinyl benzene, has the following structure.
CH = CH2
Because of the presence of bulky phenyl groups it is amorphous, atactic, linear and chemical
inert.
Uses: It is used in manufacturing the articles such as moulded containers, bottles, lids, jars, toys,
foam, radio and television cabinets and many household items.
It is produced from acrylonitrile by the free radical polymerization technique using peroxide
initiators.
Uses: It is used to produce PAN fibres. The copolymer of acrylonitrile with butadiene called nitrile
rubber has great importance.
ABS polymers are made by copolymerizing acrylonitile, butadiene and styrene.
CN
— CH2 — CH CH2 – CH = CH – CH2 CH2 – CH —
x y z
They are structural plastics or rubber possessing good strength and toughness.
Uses: Telephones, pipes, moulded articles (like furniture, suit-cases, etc.), packing containers.
7.16 Elastomers (Rubber)
Elastomers are the polymers which we capable of being stretched rapidly at least 150% of their
original length without breaking and return to their original shape on release of stress.
(a) It should be a high polymer.
(b) It must be cross linked and amorphous.
(c) It should have flexibility of chains.
(d) Its glass transition temperature should be low and flow temperature should be high as
possible.
Properties of Typical Elastomers are
1. They must stretch rapidly and considerably when stretched reaching high elongation
(500 – 1000%).
2. They must exhibit high tensile strength and high stiffness when fully stretched.
3. They must shape back to their original length, once the stretching force is withdrawn or the
stress is released.
Natural rubber is mainly extracted from the tree, ‘Hevea Basilienesis’. The rubber is obtained
from latex collected from the cuts made in the bark of the tree. Latex is an emulsion, of
poly hydrocarbon droplets in an aqueous solution and looks like milk.
The negatively charged particles of poly hydrocarbons stabiles the emulsion. Chemically, natural
rubber is cis poly isoprene
2 methyl 1, 3 butadiene)
CH2 = C – CH = CH2
CH3
Processing
[Composition of Latex water = 60%, Rubber = 35%, Protein, Enzymes and Nucleic acid = 3%, Fatty
Acid & Ester = 11% and Inorganic Salts = 0.5%]
10.24 Engineering Chemistry
Gutta Percha: It is obtained from the mature leaves of dicopsis gutta and palagum gutta tree. Gutta
percha has the same empirical formula as the rubber. But it is trans poly isoprene while rubber is
cis poly isoprene.
Vulcanization: It is a process by which rubber is converted from plastic condition to elastic condition
by heating it with certain chemicals like sulphur, sulphur mono chloride (S2Cl2), hydrogen sulphide.
Raw rubber is heated with sulphur at 100–140°C. Chemically sulphur adds to the double bonds
of different polymeric chains providing cross linking between them and hence it stiffens the raw
rubber.
The degree of vulcanization depends on the amount of sulphur added. In tyre industry, about 3
to 4% sulphur and filler like carbon is added.
If the percentage of sulphur is increased beyond 30%, full saturation of the bonds takes place
resulting in a rigid non flexible rubber called ebonite.
CH3 CH3
CH2 – C = CH – CH2 – CH2 – C = CH – CH2 –
+ + S
CH2 – C = CH – CH2 – CH2 – C = CH – CH –
CH3 CH3
unvulcanized rubber
CH3 CH3
CH2 – C – CH – CH2 – CH2 – C – CH – CH2 –
Sulphur cross S S S S
link.
CH2 – C – CH – CH2 – CH2 – C – CH – CH2 –
CH3 CH3
vulcanized rubber
7.17 Synthetic Rubber
SBR (Buna –S– rubber) Styrene butadiene rubber is first commercially made synthetic rubber. It is
a copolymer obtained by the copolymerization of butadiene (75%) and styrene (25%) in an emulsion
system at 50°C in the presence of cumene hydro peroxide as catalyst.
10.26 Engineering Chemistry
Its resilience is poor than that of natural rubber. It has high abrasion resistance and high load
bearing capacity.
Uses: It is used in manufacturing of automobile tyres-rubber soles, Motor tyre, Shoe soles, Footwear
components, Insulation of wire and cables, Gaskets, Adhesive and Floor tiles.
Buna N or Nitrile Rubber (NBR) or GR-A
The nitrile rubbers are polymers of butadiene and acrylonitrile in the ratio of 75% and 25%
respectively. It is prepared by emulsion polymerization using cumene hydro peroxide as initiator.
Hydrogen peroxide and ferrous sulphate can also be used as initiators vulcanization is done by
conventional means by adding sulphur.
Due to the presence of cyano group it is less resistant to alkalis than natural rubber.
It has good tensile strength, abrasion resistance good heat resistance. It possesses excellent
resistance to heat, sunlight, acids and salt.
Uses: Nitrile rubber are used for oil resistance, Conveyer belts, Lining of tanks, Gaskets, Printing
rollers, Oil resistance form, Automobile parts and high altitude aircraft components and Adhesive.
Neoprene or GR-M Rubber
This is also known as polychloroprene or poly chloro butadiene or duprene.
Neoprene is prepared by polymerization of chloroprene which is 2 chloro 1,3 butadiene.
Cl Cl
Polymerization
CH2 = C – CH = CH2 — CH2 – C = CH – CH2 —
n
Chloroprene Neoprene
The polymerization of chloroprene takes place through free radical emulsion polymerization.
Polymers 10.27
The vulcanization of neoprene is different because it can be vulcanized by heat alone. Neoprene
can also be vulcanized using ZnO or MgO.
Neoprene is closely related to the natural rubber. It is superior to natural rubber as far as ageing
and effects of high temperature are concerned. It is soluble in polar solvents due to the presence of
chloro group. It has excellent oil resistance through inferior to nitrile rubber but better than natural
rubber or SBR.
Uses
1. It is used in oil resistant wire and cable coating, industrial houses, shoes soles, latex is used
for the manufacture of gloves and coated fabrics, for making tubes for carrying corrosive
gases and oils, used in manufacture of sponges, converges belts, lining of reaction vessels
etc.
7.18 Silicone Polymers
Like carbon silicone has a valency of four. There are many compounds of silicon which apparently
resemble carbon compound e.g. CH4, SiH4. Unlike carbon, however, silicon cannot form Si = Si
double bonds. Hence the polymers of silicon are produced through condensation. The Si – Si linkage
is thermally unstable in the case of large molecules and hence silicon forms polymer mainly through
silicon bonds represented as – Si – O – Si –.
Silicon is organo silicon polymers. They are prepared from alkyl chloro silanes obtained from
Grignard reagent and silicon tetra chloride (SiCl4).
CH3MgCl + SiCl4 Æ CH3SiCl3 + MgCl2
Methyl tri chlorosilane
The di methyl di chloro silane can also be prepared by passing methyl chloride over powdered
silicone in the presence of Cu catalyst at 275° – 375°C.
Cu
2CH3Cl + Si (CH3)2 SiCl2
Hydrolysis of the chlorides yields the corresponding silanols which polymerise by condensation.
For example dichloro dimethyl silane on hydrolysis gives the diol which reacts as below.
10.28 Engineering Chemistry
Since O an active (– OH) group is left at each end of the chain, polymerization continues at both
the ends and ultimately form a linear thermoplastic polymer.
7.19 Types of polymerization
1. Addition or chain growth polymerization is a reaction that yields a product, which is an exact
multiple of the original monomeric molecule. Such a monomeric molecule, usually contains one or
more double bonds, which by intermolecular rearrangement, may make the molecule bifunctional.
The addition polymerization reaction must be instigated by the application of heat, light, pressure or
a catalyst for breaking down covalent bonds of monomers. Thus:
H H rearrangement H H H H
Polymerizalion
n C=C (heat, light n C=C C–C
pressure or
H H catalyst) H H H H
H H H OH H OH –2nH2O H H
Condenlation
n N – C –N + C – C – C —N – C – N – C – C – C —
Polymerization
H H6H O H 4 O H H 6H O H 4 O n
3. Copolymerization is the joint polymerization of two or more monomers species. High molecular-
weight compounds obtained by copolymerization are called copolymers. For example, butadiene and
styrene copolymerize to yield GR-S rubber.
1. Initiation
A reagent that is either itself a free radical O2 molecule, or that which easily decomposes to form
free radicals, such as organic peroxides or aliphatic azo compounds are used as radical initiator.
Commonly used radical initiator are:
1. Benzoyl peroxide
2. Azo-bis isobutyronitrile
R + CH2 = CH R–CH2 – CH
X X
3. Chain propagation. The FR, RCH2CHX, further adds to a monomer molecule forming another
FR, and successive addition of monomer to these radicals results in the formation of larger
chain radicals.
The chain propagation results in the change of p–bonds into s bonds. This step always occurs
with the liberation of heat.
In vinyl polymerization free radicals attach monomers at the methylene group, giving head-to-tail
addition. This addition is also favored because this carbon atom is less sterically hindered than the
other carbon atoms. This addition also leads to reasonance stabilization. For example,
R +
etc
Polymers 10.31
Chain termination: The growing polymer chains can be terminated in the following two ways:
(i) Coupling or Recombination: It involves the addition of two growing radical chains to
form a saturated macromolecules.
(ii) Disproportionation: It involves the transfer of a hydrogen atom from one growing chain to
another with the formation of an unsaturated end group on the chain by losing the hydrogen
atom.
Ionic polymerization
This type of polymerization may be anionic when electron withdrawing groups such as chlorine are
present or cationic when electron donating groups such as methyl are present. These reactions occur
at very low temperature as the initiation reaction requires only small activation energy.
1. Anionic polymerization: Monomers containing electronegative substituent’s such as acrylonitrile,
methylmethacrylate and styrene are polymerized by initiators. The initiators used in liquid ammonia,
alkali metals such as sodium, potassium and lithium in liquid ammonia, alkali metal alkyls,
triphenylmethyl sodium and Grignard reagents.
Mechanism: It consists of following three steps:
(a) Chain initiation. In this step the initiator produces an anion which adds to the monomer
molecule to generate a carbanion as an active centre for chain growth.
K–NH2 Æ K+ + NH2–
10.32 Engineering Chemistry
2. Synthesis of polystyrene
Polymers 10.33
(b) Chain propagation. This step involves addition of monomer molecules with regeneration
of carbonium ion.
– ≈
[SnCl4] CH2 – CH – CH – CH + nCH2 = CH
– ≈
[SnCl4] – CH2 – CH – CH2 – CH – CH2 – CH
n
C6H5 C6H5 C6H5
– ≈
[SnCl4] – CH2 – CH – CH2 – CH – CH2 – CH
n
C6H5 C6H5 C6H5
Other examples include, polymerization of ethylene derived compounds using BF3 (lewis acid)
and H2O as catalyst.
(a) Chain initiation
10.34 Engineering Chemistry
8. Conducting Polymers
Conventional polymers are poor conductor of electricity, because of non availability of large number
of free electrons in the conduction process. Within past several years, polymeric material has been
synthesized which possess electrical conductivity as per metallic conductors. Such polymers are
called conducting polymers. Conductivities as high as 1.5 × 107ohm–1m–1 have been attained in
these polymeric materials. On a volume basis, this value is equal to one-fourth of the conductivity
of copper, or is twice its conductivity on the basis of weight.
Different types of conducting polymers are discussed below:
1. Intrinsically conducting polymer or
(a) conjugated p electron conducting polymers. In this polymer backbones or associated
group consist of delocalized electron pair or residual charge. Such polymers essentially
contain conjugated p electrons backbone, which is responsible for conducting electrical
charge. In an electric field, conjugated p electrons of the polymer gets excited, thereby
can be transported through the solid polymeric material. Overlapping of orbitals of
conjugated p electrons over the entire backbone results in the formation of valence bands
as well as conduction bands, this extends over the entire polymer molecule. Presence of
conjugated p electrons in a polymer increases its conductivity to a larger extend.
Important commercially produced conducting polymers:
(i) Polyacetylene polymers e.g., poly-p-phenylene, polyquinoline, polyphenylene-co-
vinylene, poly-m-phyenylene sulphide, etc.
(ii) With condensed aromatic rings, e.g., polyaniline, polyanthrylene etc.
(iii) With aromatic heteroaromatic and conjugated aliphatic units, e.g., polypyrrole,
polythiophene, polyazomethine, polybutadienylene, etc.
Polymers 10.35
(c) Trans-Polyacetylene
(d) Polythiophene
H H
N N N
N N
H H
(f) Polyaniline
H
N N
N N
H
(b) Doped conducting polymers are obtained by exposing a polymer to a charge transfer agent
in either gaseous phase or in solution. Intrinsically conducting polymers (ICP) possess
low conductivity but these possess low ionization energy and high electron affinities, so
these can be easily oxidized or reduced. Consequently, the conductivity of (ICP) can be
increased by creating either positive or negative charges on the polymer backbone by
oxidation or negative charges on the polymer backbone by oxidation or reduction. This
technique called doping is of two types:
10.36 Engineering Chemistry
(i) P-doping involves treating an intrinsically conducting polymer with lewis acid,
thereby oxidation process takes place and positive charges on the polymer backbone
are created. Some of the common p-dopents used are I2, Br2, AsF5, PF6, etc. For
example:
(C2H2)n + 2FeCl3 Æ (C2H2) +FeCl4 – + FeCl2
2(C2H2)n + 3I2 Æ 2[(C2H2)n+ I3]
(ii) N-doping involes treating an intrinsically conducting polymer with a lewis base
thereby reduction process takes place and negative charges on the polymer backbone
are created. Some of the common N-dopant used are Li, Na, Ca, tetrabutyl
ammonium, FeCl3, etc. For example:
2. Extrinsically conducting polymers are those polymers whose conductivity is due to the
presence of externally added ingredient in them. These are of following types:
(i) Conductive element filled polymer is a resin or polymer filled with conducting elements
such as carbon black, metallic fibres, metal oxides, etc. In this, the polymer acts as
a binder to hold the conductive elements together as a solid entity. These polymers
possess reasonably good bulk conductivity and are generally low in cost, light in weight,
mechanically durable, and strong and easily process able in different forms, shapes and
sizes.
Generally special grade conducting carbon black is used as filler due to its
(a) very high surface area
(b) high porosity and
(c) filamentous properties. Minimum concentration of conductive filler in the polymer
to start the conducting process is called percolation threshold.
(ii) Blended conducting polymer is product obtained by blending a conventional polymer
with a conducting polymer either by physical or chemical change. Such polymers can
be easily processed and possess better physical or chemical and mechanical properties.
3. Coordination conducting polymer (inorganic polymer) is a charge transfer complex containing
polymers obtained by combining a metal atom with a polydentate ligand. Although the degree
of polymerization in such a polymer is small, yet they exhibit corrosion characteristics, and
are usually undoubtable in most solvents.
Applications: Conducting polymers are finding increased use as they are light weight, easy to
process and have good mechanical properties. Some of the important applications of the conducting
polymers are:
Polymers 10.37
9. Biodegradable polymer
Biodegradation is caused by attack of ester groups by non-specific esterases produced by ground
microflora combined with hydrolytic attack or it is the breakdown of polymer by microbial organism
in to smaller components. The polymer of molecular weight below 9000 is accessible to bacteria
for degradation.
The essentials for biodegradation process are
(a) Microorganism
(b) Environment e.g. Temperature, pressure, moisture, O2, light
(c) Substrate (biodegradable polymer): It should have following essential features
1. It should have suitable functional group which is susceptible to hydrolysis or oxidation
by microorganism
2. Greater hydrophilicity
3. Low molecular weight
4. Less crystalline structure
Biodegradable polymers do not have solid waste and they do not cause marine pollution. They
can enter geochemical cycles over
They are of two types:
(a) Naturally occurring polymers: e.g.
Polysaccharides – starch, cellulose
Proteins – gelatin, casein
Polyesters – poly hydroxyl alkanoates
Others – lignin, natural rubbers
10.38 Engineering Chemistry
10. Organometallics
Organometallic chemistry is an important subdiscipline that bridges the fields of organic and
inorganic chemistry together. The term organometallics is usually restricted to those compounds in
which a metal atom (including non metallic elements like boron, silicon, phosphorus, arsenic etc.
which are less electronegative than carbon) is bonded directly to a carbon atom of at least one organic
group. Organometallic compounds contain atleast one direct metal-carbon bond. The bond may be
simple covalent or p-dative or even predominantly ionic. Organometallic compounds would include
various hydrocarbon derivatives such as carbonyls and carbides.
Carbon metal bond
Where M may be Mg, Ca, Na, Li, Al, Sn, Pb, etc.
The reactivity of organometallic compounds depends upon percentage ionic character of carbon
metal bond. The greater the percentage ionic character of carbon metal bond the higher is the
reactivity of the compound examples of organometallics compounds are Grignard reagent, tetraethyl
lead, Ferrocene etc.
11. Classification
Polymers 10.39
H3
C
CH3 CH3
Al Al
CH3 CH3
C
H3
Structure of [Al(CH3)]2
CH3
CH3
CH3 s CH3 CH3 CH3
s Al Al Al Al
CH3 CH3 CH3 CH3
CH3
CH3 Banana shaped as
three centre Bond.
Three centred Bonds in
[Al(CH3)3]2
4. Transition metal organometallic compounds: Transition metals are well known to form
a variety of organometallic compounds with unsaturated organic compounds. In these
compounds, the transtion metal forms bond to more than one carbon atoms of the same
organic compound. This type of bonding is of considerable importance in transition metal
chemistry. The interaction primarily occurs between the p-orbitals of organic ligand and the
appropriate p or d-orbitals of the transition metal atom.
10.40 Engineering Chemistry
Some of the typical organometallic compounds in this category are the following:
–
Cl CH2
K
+
Pt CH2 Fe Cr
Cl Cl
Zeise salt
+
K [PtCl3 (C2H4)] Ferrocene Dilenzene chromium
(C5H5)2Fe (C6H6)2 Cr
Sandwich structures
It is important to note that in this type of bonding each carbon atom must be sp2 hybridized so
that it becomes a part of the planar carbon atom network.
There are four Organometallic compounds of transition metals:
1. Aryl/alkyl complexes: Simple organometallic compounds of transition metals prepared by
reaction like e.g.,
dry ether
TiCl4 + 4 LiCH3 Ti(CH3) 4 + 4 LiCl
12. Preparation
1. Direct reaction of metals: Metals (M) react directly with alkyl halides (RX) in ether leading
to the formation of alkyl/aryl metal halides.
M + RX RMX
M + C6H5 X C6 H5 MX
2. Using alkylating agent: Here alkylating agents such as Grignard and lithium reagents,
aluminum and mercury alkyls etc are used to make organometallics compounds
PCl3 + 3C6H5MgCl P (C6H5)3 + 3MgCl2
H H
This general method may be applied to M = Li Be Al, Ga, Sn, Pb, Bi, Zn, Cd. RM are
found among the heavy elements (Hg, Tl, Pb and Br). Few examples are given below:
Zn + Me2Hg Me2Zn + Hg
P + Ph3Br Ph3P + Br
7. Preparation of p complex
(a) Zeise’s salt:
CH2 = CH2 + K2 (PtCl4) [PtCl3 (C2H5)] K– + KCl
(b) Ferrocene:
FeCl2 + 2C5H5MgBr Fe(C6H5)N2 + 2 MgBrCl
300°C
Fe + 2 C6H5 Fe(C5H5)2
325 K
(c) Ni + 4CO Ni(CO) 4
HT/HP
(d) Fe + 5CO Fe(CO)5
13. Applications
1. Tetra ethyl lead is used as anti-knock compound
2. Used to enhance agriculture production e.g. C2H5HgCl acts as fungicide
3. Aryl arsenic compounds are used as chemotherapentic agents
4. Used to prepare organic compounds e.g. Grignard reagent
5. Wilkinson’s catalyst [(PPh3)3] RhCl is used for selective hydrogenation of certain double
bonded compounds
Cl (PPh3)3
C=C + H2 –C–C–
H H
6. In heterogeneous catalysis: e.g. Ziegler Natta catalyst it permits stereo regular polymerization
of alkenes. i.e. unchanged and stereo regular i.e. isotactic polymer is obtained. These polymers
have high density and high melting point due to efficient packing.
1. Bimetallic mechanism:
Complexation of Ti atom through alkyl group is due to empty orbital on Ti atom. This is
followed by ionization of transition metal alkyl bond and formation of 6 membered transition state
and insertion. The alkyl group goes to olefin and a new metal alkyl bond is bond
2. Monometallic mechanism:
The active site is a penta coordinate transition metal atom with an empty orbital. The monomer
is complexed to this atom. An insertion reaction then occurs with the alkyl group (R) migrating to
the monomer olefin and a shifting of vacant octahedral position.
Polymer chain migrates back so that the vacant site resumes its original position which is
necessary to preserve stereoregularity.
10.44 Engineering Chemistry
15. Grignard reagent
It is an organometallic compound discovered by Victor Grignard and is used as synthetic reagent.
Almost all classes of organic compound can be prepared from Grignard reagent.
The general formula for Grignard reagent is R – Mg – X or R – MgX or RMgX.
Where R – alkyl, alkenyl, alkynyl or aryl group and X – Cl, Br. I.
15.1 Preparation
By the action of alkyl halides on magnesium metal in the presence of dry ether (anhydrous diethyl
ether).
Diethyl ether
R – X + Mg R – Mg – X
Alkyl halide Grignard reagent
Di ethyl ether
CH3 – I + Mg CH3MgI
Methyl Magnesium Iodide
Grignard reagent is produced by dropping a solution of the alkyl halide in dry ether into the
reaction flask containing magnesium ribbon suspended in dry ether. Solvents which can be used are
diethyl ether, Et2O or tetrahydrofuran, dimethoxyethane, dioxane. Ether solvent is best suitable for
the preparation of Grignard reagents as it is not only unreactive with magnesium but also stabilize
the Grignard reagent by forming lewis acid base comlpexs
In the preparation of Grignard reagent, apparatus and reactants should be absolutely dry. Even
traces of moisture/impurities prevent the formation of grignard reagent as grignard reagent reacts
with water forming alkanes.
CH3CH2MgBr + H2O CH3CH3 + Mg(OH)Br
Polymers 10.45
15.2 Physical properties
1. Non volatile, colorless solids
2. They are explosive in nature, therefore, for synthetic purpose the Grignard reagent are always
prepared and used in ether solution.
Nucleophilic addition reaction: Carbonyl compounds are attacked by Grignard reagents to form
addition products which on acid–hydrolysis yield alcohols, acids, and esters etc. In addition reaction
positive part of the Grignard reagent combines with the oxygen atom of the carbonyl group. The
negative part of Grignard reagent goes to the carbon atom of the carbonyl group.
10.46 Engineering Chemistry
4. Reaction with epoxides: Grignard reagent react with carbons of epoxides which results
in ring opening and formation of an alcohol. Reaction occurs at the least substituted ring
carbon of the epoxides.
5. Reaction with aldehyde and ketones to give primary/secondary and tertiary alcohols.
(a) Formaldehyde reacts with Grignard reagent to give addition products which on protonation
yield – primary alcohols.
(b) Other aldehyde reacts with Grignard reagent to give addition products which on
protanation yield secondary alcohols.
Polymers 10.47
(c) Reaction with Ketones: Grignard reagent reacts with ketones to give addition products
which on protonation form tertiary alcohols.
6. Formation of Ketones: Grignard reagent reacts with acid chlorides and cyanides to form
Ketones.
(a) Reaction with acid chlorides:
(b) Reaction with cyanides: Grignard reagent reacts with cyanides to give addition
products which on hydrolysis with dilute HCl yield ketones.
7. Formation of carboxylic acid: Grignard reagent reacts with carbon dioxide to give addition
products which on protonation yield carboxylic acids.
8. Formation of organometallic compounds: Grignard reagent reacts with inorganic halides
to form other organometallic compounds.
4C2H5MgBr + 2PbCl2 (C2H5) 4Pb + 4MgBr (Cl)
4CH3MgI + SiCl4 (CH3) 4Si + 4MgI (Cl)
solved Questions
1. Give common name and IUPAC name of monomer of natural rubber.
Ans. Isoprene, 2-1,3-butadiene
2. What is a copolymer?
10.48 Engineering Chemistry
Ans. Polymer whose repeating structural units are derived from two or more types of monomer
units are called copolymers. For example Polyester, Bakelite, SBR etc.
3. What does PMMA stands for?
Ans. Poly(methyl methacrylate).
4. Give the chemical name for teflon.
Ans. Poly(tetrafluoroethylene).
5. Write the monomers of Bakelite.
Ans. Phenol and formaldehyde.
6. Define addition polymers.
Ans. The molecules of same or different monomers simply add on one another leading to formation
of a macromolecule in which the molecular formula of the repeating unit is the same as that
of the starting monomer. The polymer thus formed is called addition polymers.
7. Could a copolymer be formed in both addition and condensation or not? Explain with
example.
Ans. Copolymers can be formed both by addition and condensation polymerization. For example,
styrene butadiene rubber is a copolymer which is obtained by addition polymerization while
nylon 66 is a copolymer obtained by condensation polymerization.
8. What is the function of sulphur in vulcanization of rubber?
Ans. During vulcanization, natural rubber is heated with suphur. The function of sulphur is to
introduce sulphur cross links between polymer chains thereby imparting more tensile strength,
elasticity and resistance to abrasion.
9. Write names of monomers of terylene or Dacron.
Ans. Ethylene glycol and terephthalic acid or it is methyl ester.
10. What is thermoplastics polymer?
Ans. Polymers which softens on heating and hardens on cooling. They have a linear polymer and
different chains are held by weak vander waal’s force of attraction.
11. Give examples of thermosetting polymers.
Ans. The examples of thermosetting polymers are Bakelite, Urea formaldehyde resin, Melamine
etc.
12. On basis of molecular forces, how will you classify polymers?
Ans. On the basis of force of attraction polymers are classified as elastomers, fibres and
plastics.
13. What are monomers of SBR?
Ans. The monomers of SBR are butadiene and styrene.
14. What are conducting polymers?
Ans. Conventional polymers are bad conductors of electricity but polymeric material can be
synthesized which possess electrical properties as per metallic conductors. Such polymers are
called conducting polymers. Their electrical conductivity is as high as 1.5 × 107 ohm–1m–1.
15. What are organometallic compound?
Ans. The term organometallics is usually restricted to those compounds in which metal atom is
bonded directly to a carbon atom of atleast one organic group.
Polymers 10.49
unsolved Questions
• What does PVC stand for?
• Name a synthetic polymer which is an ester?
• Name the polymer which is used for making non stick utensils.
• How is nylon 66 synthesized?
• Give the name and structure of neoprene rubber.
• Give the monomers of SBR.
• Why is Bakelite a thermosetting polymer?
• Give chemical name of Teflon.
• What does PMMA stands for?
• Write equation for the preparation of poly acrylonitrite.
• How is nylon 6, 10 prepared?
• What is the difference in the structure of natural rubber and gutter percha?
• Define Fibres.
• Differentiate between addition and condensation polymerization.
• Give monomers of glyptal.
• What are organic polymers? Give the structure of few organic polymers.
• What is the difference between a monomer and a polymer?
• Classify polymers on the basis of occurrence and chemical nature.
• What are graft and block copolymers?
• What is an addition polymer? Give five examples.
• What are vinyl monomers?
• Define the terms:
(a) Degree of polymerization and functionality.
10.50 Engineering Chemistry
• Distinguish between
(i) Thermoplastics and thermosetting
(ii) Homopolymers and copolymers
(iii) LDPE and HDPE
• Give the structure of following polymers:
(a) Nylon 6, 6 (b) Terylene
(c) Orlon (d) Chloroprene
• What are biopolymers? Give three examples.
• Write two uses of the following polymers: low density polyethylene, polystyrene, Nylon 6,
epoxy resin.
• Write structures of phenol formaldehyde resin, urea formaldehyde resin, polyamide.
• Explain the mechanism of the polymerization of ethylene monomers on Zieglarnatta
catalysts.
• Write a note on conducting polymers.
• Write the mechanism of cationic and anionic polymerization.
• How is Bakelite formed? Explain the reactions with equation?
• Describe vulcanization of rubber.
• Explain the structure of ion exchange resin.
Chapter 11
1. Introduction
The term titrimetric analysis refers to quantitative chemical analysis carried out by determining the
volume of a solution of accurately known concentration which is required to react quantitatively with
a measured volume of a solution of the substance to be determined. The solution of accurately known
strength is called the standard solution. The weight of the substance to be determined is calculated
from the volume of the standard solution used and the chemical equation and relative molecular
masses of the reacting compounds.
The term volumetric analysis was formerly used for this form of quantitative determination but
it has now been replaced by titrimetric analysis. It is considered that titrimetric analysis expresses
the process of titration better and ‘volumetric analysis’ is likely to be confused with measurements
of volumes, such as those involving gases. In titrimetric analysis the reagent of known concentration
is called the titrant and the substance being titrated is termed the titrand.
The alternative name has not been extended to apparatus used in the various operations; so the
terms ‘volumetric glassware’ and ‘volumetric flasks’ are still common, but it is better to employ the
expressions ‘graduated glassware’ and ‘graduated flasks’.
The standard solution is usually added from a long graduated tube called a burette. The process
of adding the standard solution until the reaction is just complete is called a titration, and the
substance to be determined is titrated. The point at which this occurs is called the equivalence
point or the theoretical or stoichiometric end point. The completion of the titration is detected by
some physical change, produced by the standard solution itself (e.g., the faint pink color formed by
potassium permanganate) or, more usually, by the addition of an auxiliary reagent, known as an
indicator, alternatively some other physical measurement may be used. After the reaction between the
substance and the standard solution is practically complete, the indicator should give a clear visual
change (either a color change or the formation of turbidity) in the liquid being titrated. The point at
which this occurs is called the end point of the titration. In the ideal titration the visible end point
will coincide with the stoichiometric or theoretical end point.
In practice, however, a very small difference usually occurs, this represents the titration error.
The indicator and the experimental condition should be selected so the difference between the visible
end point and the theoretical end point is as small as possible.
11.2 Engineering Chemistry
For using in titrimetric analysis a reaction must fulfill the following conditions:
(i) There the reaction should be relatively fast. (Most ionic reactions satisfy this condition). In
some cases the addition of a catalyst may be necessary to increase the speed of reaction.
(ii) There must be an alteration in some physical or chemical property of the solution at the
equivalence point.
(iii) An indicator should be available which, by a change in physical properties (color of formation
of a precipitate), should sharply define the end point of the reaction, if no visible indicator
is available, the detection of the equivalence point can often be achieved in other ways.
(a) Measuring the potential between and indicator electrode and a reference electrode
(potentiometric titration).
(b) Developing the titrant by electrolysis (coulometric titration).
(c) Measuring the current which passes through the titration cell between an indicator electrode
and a depolarized reference at a suitable applied e.m.f. (amperometric titration).
Titrimetric methods are normally capable of high precision and wherever applicable they posses
obvious advantages over gravimetric methods. They need simpler apparatus and are generally
performed quickly; any tedious and difficult separation can easily perform.
There are many areas in which titrimetric procedures are invaluable. The main advantages of
these methods include–
(i) The precision (0.1%) is better than most instrumental methods.
(ii) Methods are usually superior to instrumental techniques for major component analysis.
(iii) When the sample throughout is small, simple titration are often preferable.
(iv) Unlike instrumental methods, the equipment does not require constant recalibration.
(v) Methods are relatively inexpensive with low unit costs per determination.
(vi) They are often used to calibrate and/or validate routine analysis using instruments.
(vii) The method can be automated.
There are, however, several disadvantages to classical titrimetric procedures, these include–
(i) They are normally less sensitive and frequently less selective than instrumental methods.
(ii) When a large number of similar determinations are required, then instrument methods are
usually much quicker and often cheaper than the more labor intensive titrimetric methods.
Nevertheless, despite the widespread popularity of instrumental techniques, it can be seen
from the above discussion we find that there is considerable scope for the use of titrimetric
procedures, especially for practicing laboratory skills.
temperature. However, molality does not change with temperature because mass of the solvent
does not change with change in temperature.
6. Mole Fraction: It is the ratio of number of moles of one component to the total number of
moles (solute and solvent) present in the solution. It is denoted by x. Let us suppose that a
solution contains n A moles of solute and nB moles of the solvent. Then,
nA
Mole fraction of solute (x A) = _______
n A + nB
nB
Moe fraction of solvent (xB) = _______
n A + nB
The sum of mole fraction of all the components in solution is always equal to one as shown
below:
nA nB
x A + xB = _______ + _______ = 1
n A + nB n A + nB
Thus, if the mole fraction of one component of a binary solution is known, than that of the
other can be calculate. For example, the mole fraction x A is related to xB as
x A = 1 – xB or xB = 1 – x A
It may be noted that the mole fraction is independent of temperature.
7. Normality: It is number of gram equivalents of the solute dissolved per litre of the solution.
It is denoted by N.
Number of gram equivalents of solute
Normality (N) = ________________________________
Volume of solution in litres
Number of gram equivalents of solute
Or Normality (N) = ________________________________
× 1000
Volume of solution in ml
Gram equivalent of solute can be calculated as
Mass of solute
Gram equivalents of solute = ______________
Equivalent mass
Like molarity, normality of a solution also changes with temperature.
Relationship between normality and molarity of solution.
The normality and molarity of solution are related as
Molar mass
Normality = Molarity × ______________
Equivalent mass
For acids,
Normality = Molarity × Basicity
Where basicity is the number of H+ ion that a molecule of an acid can give in solution.
For bases,
Normality = Molarity × Acidity
Where acidity is the number of OH– ions that a molecule of base can give in solution.
11.6 Engineering Chemistry
8. Formality: It is number of formula masses of the solute dissolved per litre of the solution.
It is represented by F.
Number of formula masses of solute
Formality = _______________________________
Volume of the solution litre
The term formality is used to express the concentration of ionic substance. The ionic
compounds such as NaCl, KNO3.CuSO4 etc. do not exist as discrete molecules. The sum of
the atomic masses of various atoms constituting the formula of the ionic compound is called
gram formula mass instead of molar mass.
Types of Titrimetric Analysis
1. Acid Alkali, Acid–Base or Neutralization Titrations: These are those analysis in which the
two solutions used are acid and alkali respectively. These reactions involve neutralization i.e. the
combination of hydrogen and hydroxyl ions to from water.
H+ + OH– Æ H2O
The process of determining the strength of unknown by titrating with a standard alkali solution
is called acidimetry. Acid base of pH indicators are either weak organic acids or weak organic
bases. They possess different colors in dissociated and undissociated forms and also in different pH
conditions. Phenolphthalein and methyl orange the most commonly used pH indicates.
2. Oxidation-Reduction or Redox Titrations: These are those titrations in which the two solutions
used are the solutions of oxidizing and reducing agents respectively. The important oxidants are
KMnO4, K 2CrO7, Ce(SO4) 2, I2, K 2BrO3 and K 2IO3 while the common reductants are FeSO4,
(NH4)2SO4.6H2O (Mohr’s salt), SnCl2, Na2S2O3, As2O3 and TiCl3. The reduction of KMnO4 and
K2Cr2O7 by FeSO4 may be represented as;
MnO4 – + 8H+ + 5e – Æ Mn2+ + 4H2O (Reduction)
(Oxidant)
(a) Direct method or Iodimetric method involve the use of a standard iodine solution to
titrate easily oxidizable substance, e.g., the titration of AS2O3 and I2.
AS2O3 + 2I2 + 2H2O AS2O5 + 4HI
They are of limited application because I2 is a weaker oxidant than MnO4, Cr2O7–2 and
Ce +4 salts.
(b) Indirect method or Iodometric technique are those titrations in which I2 liberated
form iodide (say KI) is titrated against standard hype or sodium thiosulphate (Na2 S2 O3)
solution. e.g. the titration of Cu SO4 and hypo of K2 Cr2 O7 and hypo of KMnO4 etc.
2Cu2+ + 2 I– Æ 2 Cu+ + I2 ≠
Cr2O7–2 + 14 H+ + 6 I– Æ 2 Cr3+ + 7 H2O + 3I2 ≠
2S2O32– + I2 Æ I2 S4O62– + 2 I–
Iodine solution can be used as a self indicator. However to get a better result 1% such starch
solution is used as an indicator with which even traces of I2 can give a deep blue color due
to the formation of an adsorption complex called starch iodide, (C24H40O20)I3.
(iv) Precipitation Titrations or Precipitimetry: Precipitimetry involves the combination of
cations and anions (other than H+ and OH–) so as to produce a precipitate or turbidity due
to the formation of an insoluble salt and the strength of unknown solution is determined by
complete precipitation with the help of standard solution. e.g. The titration of AgNO3 and
KI, Na2CrO4, KCNS or NaCl, where AgI (yellow), AgCl (white) precipitate out. Precipitation
Titration is also called argentometric titrations as the one of the solutions of either known
or unknown concentration has Ag+ ions.
Three types of such titrations are mentioned below:
(a) Mohr’s Method: Mohr’s procedure was given in the year 1856 for the determination of
CI– or Br– in neutral solution. It is a little inferior to Fajan’s and Volhard’s method for
the determination of CI– ions.
(b) Volhard’s Method: It was given in the year 1878 for the determination of Ag in diluted
HNO3 by direct titration with standard KSCN or NH4SCN solution in the present of
Fe3+ ions or ferric alum as indicator.
The end point is judged by the formation of a soluble blood red colored [Fe (SCN)3]
with the Ist slight excess of thiocyanate ions. The Cl– or Br– ions are detected indirectly
by this method.
(c) Fajans’s Method involves the chloride content determination of a sample by direct
titration with standard AgNO3 solution using dichlorofluorescein as an adsorption
indicator.
The formation of a clear supernatant solution of a colored complex ion on a colored
secondary precipitate or of a colored adsorption compound indicates the end point in
precipitimetry.
(v) Complexometric Titration or Compleximetry: They are the titrations involving the
following formation of a complex ion. Only a few reactions of complexation can be used as
a basis for volumetry partly due to the lack of s suitable indicator and partly because in some
cases varying mixture of products are obtained. A large number of estimations have been
carried out by using complexing agents mostly ethylene diamine tetra acetic acid (EDTA).
11.8 Engineering Chemistry
3. Standard Solution
In titrimetric analysis, the required solutions must be standard. A standard solution is one whose
strength (concentration) is known. Standard solution of accurately known concentration need to be
stored correctly. They may be classified into four types.
(i) Reagents solution which are of approximate concentration.
(ii) Standard solution which have a known concentration of some chemical.
(iii) Standard reference solution which have a known concentration of a primary standard
substance.
(iv) Standard titrimetric solution which have a known concentration (determined either by
weighing or standardization) of a substance other a primary standard.
Primary and Secondary Standards: In titrimetry certain chemicals are used frequently in defined
concentration as reference solution. They are known as primary standards or secondary standards.
Primary standard is a compound of sufficient purity from which a standard solution can be prepared
by direct weighing of a quantity of it, followed by dilution to give a defined volume of solution. A
primary standard should satisfy the following requirements:
(i) It must be easy to obtain to purity, to dry and to preserve in a pure state.
(ii) The substance should be unaltered in air during weighing. This condition implies that if
should not be hygroscopic, oxidized by air, or affected by carbon dioxide. The standard
should maintain an unchanged composition during storage.
(iii) The substance should be capable of being tested for impurities by quantitative and other tests
of known sensitivity.
(iv) It should have a high relative molecular mass so that the weighing errors may be negligible.
(The precision in weighing is ordinarily 0.1 – 0.2 mg; for an accuracy of 1 part in 1000, it
is necessary to employ samples weighing at least about 0.2 g).
In practice, an ideal primary standard is difficult to obtain, and a compromise between
the ideal requirements is usually necessary. The substance commonly employed as primary
standards are indicated below:
Acid–Base reactions: Sodium carbonate Na2 CO3. Sodium tetra borate Na2 B4 O7, potassium hydrogen
phthalate KH (C8H4O4), Potassium hydrogen iodate [KH (IO3)2]
Complex formation reactions: Pure metals (e.g. Zinc, magnesium, copper and manganese) and salt
depending upon the reaction used.
Precipitation reactions: Silver nitrate, Silver, Sodium Chloride, Potassium chloride, and Potassium
Bromide.
Oxidation-Reduction reactions: Potassium dichromate K 2Cr2O7, potassium bromate KBrO3,
Potassium iodate KIO3, Potassium hydrogeniodate [KH (IO3)2], arsenic (III) oxide As2O3, and pure
iron.
A Secondary Standard is a substance which may be used for standardizations, and whose content of
the active substance has been found by comparison against a primary standard. A secondary standard
solution is a solution in which the concentration of dissolved solute has not been determined from
Concepts of Titrimetric Analysis 11.9
the weight of the compound dissolved but by reaction of a volume of the solution against a measured
volume of a primary standard solution.
Standardization of Solutions: The process of determining the exact strength of a standard solution
is known as standardization and may be accomplished in several ways. an accurately weighed
amount of the chemical is transferred to a volumetric flask and diluted to the mark with solvent.
This procedure is not generally used in preparing standard solution of acids and bases.
The usual technique is to weigh an amount of solute appearing the exact quantity which, upon
dissolving in water will give the desired normality. The exact normality and date of analysis are
placed on the label of the container. The problem can be minimized in this instance by protecting the
solution from carbon dioxide by using soda–lime absorption tubes. If a solution of definite normality
is required, such as exactly 0.1N sulphuric acids, a solution is prepared which is slightly stronger
than 0.1N. The solution is standardized and the diluted with the exact volume of water to produce
the desired normality.
The expression
ml × N (acid1) = ml × N (acid2)
is used to calculate the final volume of the solution which has the desired normality. The final
solution is then standardized.
In standardizing a solution, an accurately weighted sample of the primary standard is dissolved
in water and titrated to the end point with the solution being standardized. From the volume of
titrant consumed the sample weight of primary standard and its equivalent that is all quantitative
procedures an accuracy of at least 1 part in 1000 burette readings should be maintained. Therefore,
weighing should be carried out to the fourth decimal place, and burette readings should be made to
the nearest 0.02ml.
4. Acid–Base Titrations
Before discussing acid-base titrations we must be familiar with certain general concepts of acid and
bases. These are described in following sections.
Theory of Acid-Base Indicators: In the acid alkali titrations, the equivalence point is detected by
the use of substance called acid base indicators which change their color at or near the equivalence
point. The actual color that produces in solution depends on the pH of the solution. The change in
color of the indicator is not sudden and abrupt but takes place in a small pH range. Let us examine
briefly how the acid-base indicators works.
(i) Ostwald Theory: The first attempt in the theory of indicators was made by Oswald. The unionized
form of the acid indicator HIn or the basic indicator inOH had one color and the corresponding
ionized form has another colour. The ionization equilibrium in aqueous solution may be written as
HIn + H2O H3O + + In–
And In OH OH– + In+
Let us apply the law of mass action to the ionization equilibrium of an acid indicator HIn.
The ionization constant of the indicator is given by
[H3O +] [In–]
Kind = __________
[HIn]
11.10 Engineering Chemistry
[HIn]
[H3O +] = K ind _____
[In–]
[Unionized form]
Or [H3O +] = K ind _______________
[Ionized form]
In acid solution presence of excess of H3O + ions will suppress the ionization of the acid indicator
and [In–] will be small. On the other hand, in alkaline solution the ionization equilibrium is shifted
to the right increasing the concentration. Indicator will exist mainly in the ionized form and the
colour of the ionized form become apparent.
(ii) Quinonoid Theory: The colour in most of the naturally occurring organic compounds has been
attributed to be due to the presence of quinonoid structure.
Concepts of Titrimetric Analysis 11.11
This may be illustrated changes by reference to phenolphthalein where (I) represents the structure
of phenolphthalein which in the presence of dilute alkalis changes to structure (II). This monoanion
then yield a red resonating dianion (III). If phenolphthalein is treated with excess of concentration
of alkalis the red colour first produced disappears owing to the formation of carbinol form (IV).
Similarly, the two forms of methyl orange are:
CH3
O 3S N N N
CH3
– +
OH H 3O
+ CH3
O 3S N N N
–
CH3
H
Methyl orange in Presence of acids
(Quinonoid structure - Red)
Table contains a selected list of some indicators along with their colour change intervals.
By suitably mixing certain indicators the colour change may be made to extend over a considered
pH range. Such a mixture is known as universal indicator. These are mostly employed for determining
the appear pH of solution. It converse a pH range of 3 – 11 and gives colour changes at different
pH values as shown below.
pH 3 4 5 6 7 8 9 10 11
Colour Red Orange Orange Yellow Yellowish Greenish Blue Violet Reddish
11.12 Engineering Chemistry
Acid–Base Titration in Aqueous Media: The changes in hydrogen ion concentration accompanying
the addition of a base to an acid are important for analytical purpose. A plot of pH against the volume
of base (or acid) added from the burette is called a pH titration curve. Changes in pH values in the
neighborhood of the equivalence point are of importance and enable us to select an indicator which
will give the least titration error.
(a) Titration of a Strong Acid by a Strong Base: Shows the variation of pH with the volume
of alkali added during the titration of an acid like HCl with a base like NaOH. It will be
observed that pH of the solution starts increasing slowly at first, then rise more rapidly until
at the equivalence point there is a sharp increase in pH for small volumes of alkali added.
After the equivalence point increase in pH is small on addition of excess alkali.
pH
7.0
ml of alkali added
Fig. 1 Titration of 1.0M hydrochloric acid with 1.0M sodium hydroxide.
(b) Titration of a weak acid by a strong base: The titration curve of weak acid with a strong
base (CH3COOH Vs NaOH) is depicted in fig 2. As sodium acetate is a salt of a weak acid
and a strong base if gives excess of OH– ions in aqueous solution thereby increasing the pH
at equivalence point beyond 7. Hence phenolphthalein or thymol blue would be satisfactory
indicators. For titration of acid like boric acid against sodium hydroxide the titration curve
does not show any sharp rise in pH. The pH, therefore goes on increasing gradually without
showing a sharp increase. Thus very weak acids can not be successfully titrated.
14
12
10
8
pH
6
7.0
4
2
0
0 40 80
ml of alkali added
Titration of 100ml of 0.1 N acetic
acid with 0.1 N sodium hydroxide
Fig. 2
Concepts of Titrimetric Analysis 11.13
(c) Titration of a Weak Base by a Strong Acid: The titration curve of a weak base against
a strong acid (ammonium hydroxide Vs hydrochloric acid) is depicted in fig. 3. The pH at
equivalence point is this case lies in the acid range i.e., below 7. Thus the pH change at
equivalent lies in range 6 to 4. Thus the indicator having pH range on acidic side i.e., methyl
red or methyl orange can be used successfully.
Fig. 3
(d) Titration of a Weak Acid by a Weak Base: The titration curve for a weak acid say, acetic
acid, by a weak base like NH3 is shown in fig 4. Hence no sharp end point can be obtained
with the commonly employed indicators. However, a mixed indicator which shows a sharp
color change over a limited pH range may sometimes be used. Such titration is usually
avoided.
14
12
10
8
pH
6
4
2
0
0 40 80
ml of alkali added
Titration curve for the titration of
acetic acid with ammonium hydroxide
Fig. 4
11.14 Engineering Chemistry
5 Redox Titrations
The chemical reaction involving oxidation reactions are more widely used in titrimetric analysis than
acid base, complex formation, or precipitation reactions. Oxidation is defined as the loss of one or
more electrons by an atom (deelectronation), molecule or ion, while reduction is the gain in electrons
(electronation). Thus oxidation and reduction occur simultaneously. The redox reaction may also be
referred to as electron transfer reactions.
Consider the reaction,
2 HgCl2 + Sn Cl2 Æ Hg2Cl2 Ø + Sn Cl4
Here the element Sn is said to be oxidized from Sn2+ (in SnCl2) to Sn4+ (in SnCl4) i.e., an increase
in oxidation state is oxidation. The element that causes oxidation must itself decrease in oxidation
state, here the oxidation state of Hg has changed state +2(Hg2+ in HgCl2) to 1 (Hg+ in Hg2Cl2), thus
decrease in oxidation state is reduction. Here the electrons pass from Sn2+ to Hg2+, hence SnCl2 is
a reducing agent while HgCl2 is an oxidizing agent. If a reagent acts both as oxidizing as well as
reducing agent it is said to be undergoing auto oxidation or disproportionation.
Many redox reactions can satisfy the requirement for use in titrimetric analysis provided that
equilibrium is reached immediately following each addition of titrant and also that the indicator is
capable of locating the end point with a reasonable accuracy. In such titrations a table of standard
electrode potential serves as a guide to equilibrium condition as no other information such as the
rate or mechanism of reaction is known generally the course of a titration reaction is followed by
plotting a graph of potential versus volume (cm3) of the titrant.
Theory of Redox Titration Curves: In constructing titration curves in redox reaction titration it is
costomary to plot of graph of emf of E cell (against SCE) versus volume of titrant. This is necessary
because most redox indicators are sensitive but they are themselves oxidizing or reducing agents and
hence the change in potential of the system is considered during titration let us consider a typical
titration curve by considering the potential of the oxidation reduction system at the equivalence point
(Eeq). The nernst equation states.
RT [reductant]
E = E 0 – ___ log _________
nF [oxidant]
For the simple reaction of
Fe2+ + Ce4+ Fe3+ + Ce3+
At equilibrium the electrode potentials for the two half reaction is the same.
4+
ECe 3+ = Esystem
+ EFe
This is the potential of the system. For the redox indicator the potential is the same as for the
4+
system Endicator = ECe 3+ = Esystem
+ EFe
Ce3+
Eeq = E0Ce4+ – 0.0591 ____
And also by Ce4+
[Fe2+]
Eeq = E0Fe3+ – 0.0591 log _____
3+
Adding both equations [Fe ]
[Ce3+] _____
[Fe2+]
2Eeq = E0Ce4+ + E0Fe3+ - 0.0591 log ______
4+
3+
Since at the equivalence point [Ce ] [Fe ]
[Fe3+] = [Ce3+] and [Ce4+] = [Fe3+]
We can calculate the equilibrium concentration of the reacting species from the equivalence point
potential.
Fig. 5
The aqueous solution is not stable and oxidizes water in the following way.
4MnO4 – + 2H2O + 6H+ 2Mn2+ + 10CO2 + 8H2O
3. Potassium dichromate: This reaction proceeds as follows;
Cr2O72– + 14H+ + 6e – Cr3+ + 7H2O E0 = 1.33V.
It has limited application in comparison with KMnO4 or Ce (IV) due to lesser oxidising
characteristics and slowness of some of its reaction K 2Cr2O7 is indefinitely stable and inert
towards HCl. It is mainly used for the analysis of iron (III) with reaction.
6Fe2+ + Cr2O72– + 14H+ 6Fe3+ + 2Cr3+ + 7H2O
There are several other applications for this titrant.
4. Potassium Bromate: It is a strong oxidising agent. It reacts as
BrO3– + 6H+ + 6e – Br– + 3H2O E0 = 1.44V.
In acidic solutions BrO3– reacts with Br– (aq) + 3H2O. KBrO3 is a primary standard and is
stable indefinitely. Postassium bromate finds extensive application in organic chemistry e.g.,
titration with oxine. Most titrations involve back titrations with arsenous acid.
5. Potassium Iodate: It has extensive use in analytical chemistry.
IO3– + 5I– + 6H+ Æ 3I2 + 3H2O and the reaction in Andrew’s titration is
IO3– + CI– + 6H+ + 4e – Æ ICI + 3H2O E0 = + 1.20V.
Redox indicators: Several types of indicators used in redox titrations are:
(i) Self indicators: The KMnO4 solution are quite deeply coloured and a slight of this reagent in
a titration is easily detected. Thus in the titration of oxalic acid hydrogen peroxide etc., with
KMnO4, as soon as the reaction is complete, and a drop of the latter is in excess, indicating
that the reaction is complete and the end point has reached.
(ii) Specific indicator: This is a substance which reacts in a specific manner with one of the
reagents in a titration to exhibit a colour. Thus starch produces a deep blue colour with iodine,
SCN– (usually KSCN or NH4SCN are used) produces a red colour with Fe (III) ion.
(iii) External (or Spot test) indicator: These were usually employed when no internal indicators
were known. For example, Fe(CN) 63–, Ferric cyanide ion is still used to detect Fe(II) ion
by the formation of a deep blue green complex (Turnbull’s blue) on a spot plate outside the
titration mixture. Thus K3Fe(CN) 6 is used in the titration of Fe(II) with K2Cr2O7 solution
in acid medium
2[Fe(CN) 6]3– + 3Fe2+ Æ Fe3 [Fe(CN) 6] 2
Ferro–Ferri cyanide
(deep blue to green precipitate)
Concepts of Titrimetric Analysis 11.17
2. Ferroin: The well known redox is ferroin, the Fe(II) complex of 1, 10 – phenanthrolin:
Each N-atom in 1,10 phenanthroline possesses a lone pair of electrons which is shared with
Fe(II) ion. Since the coordination number of Fe(II) is 6, three such organic molecules bind
themselves to the Fe(II) ion to Fe(II) ion to form a blood red chelate complex ion. The colour
of the Fe(III) complex is pale blue, and hence a sharp colour takes places when Fe(II) is
oxidised to Fe(III) in the presence of 1,10 phenanthroline.
The indicator is prepared by mixing equivalent quantities of Fe(II) sulphate and 1,10
phenanthroline. This complex chelate is ferroin.
11.18 Engineering Chemistry
Complexometric Titrations
Introduction: The formation of a complex during a chemical reaction may serve as the basis of a
titrimetric assay. The complex formed should be soluble, stable (but slightly disscociated) and posses
a stoichiometric composition at the equivalence point (complexometric titrations). The groups (anion/
neutral) attached to the central cation (or a metal) are called ligands. The number of bonds formed
by the central cation, is called the coordination number of the metal. A complex formation reaction
may also be viewed as a Lewis acid-base reaction. For example, the formation of a stable complex
ion Ag(CN)2–:
The bond formed between the central cation and the ligand is usually covalent but the bonding
interaction may be coulombic attraction also. Ligands such as H2O, NH3, CN– and Cl– etc. Which
possess only one electronegative donor atom (O, N, S, C or Cl– etc), containing only one unshared pair
of electrons are called as bi, tri, penta, hexa, dentate ligands respectively. The process of ring formation
is called chelation. Thus the chelation between Cu2+ and two molecules of ethylenediamine is:
Chelating Agents: It may be noted that in the formation of [Cu (NH3) 4] 2+ not all of the added
ammonia is used up in one step to form this complex, rather all the lower complex species such
as, CuNH32+, Cu (NH3)22+, Cu (NH3)32+ are still present in appreciable concentration [i.e., these
have not changed into Cu (NH3) 42+]. Schwarzenbach (1945) realized that the difficulty arising from
the formation of lower complexes can be overcome by the use of chelating agents as titrant. Thus,
for example, the compound triethelene (trien), can satisfy co-ordination number 4 of copper in one
step.
2+
CH2 CH2
H2N
NH CH2
Cu
NH CH2
H2N
CH2 CH2
Concepts of Titrimetric Analysis 11.19
However, only a few metals such as cobalt, nickel, zinc, cadmium and Hg (II) form stable
complexes with ligands as trien. Schwarzenbach noted that certain chelating agents containing both
oxygen and nitrogen are especially effective in forming stable chelates with a wide variety of metals.
The most important of these is ethylene diamimetetra acetic acid, EDTA with the structure.
Since it has been shown that in EDTA, two N–atoms are held in the form of Zwitter ions, EDTA
is potentially a hexadentate ligand which may co-ordinate with a metal ion through its two N-atoms
and 4-carboxyl groups. IR spectra and other measurements indicate that EDTA forms octahedral
complexes with metal ions such as CO2+, Ca2+, Cu (II) and Fe (II) etc. The structure of CO2+ -EDTA
complex is:
To void its long name, usually abbreviation likes H4Y (Free acid form), H4Y– , H2Y22– are used
and then the complexes because CoY2–, CuY2– and FeY2– etc. In some cases EDTA may function
as a quinquedentate or quadridentate ligand with one or two of its carboxyl groups remain free not
attaching to the metal. In general the reaction with M2+ ion may be:
M2+ + H2Y2– MY2– + 2H+
M3 + H2Y2– MY – + 2H+
Mn + H2Y2– (MY)(n–4)+ + 2H+
11.20 Engineering Chemistry
The disodium salt, Na2H2Y, affords the complex forming ion H2Y22– in aqueous solution, it react
with all the metals in a 1:1 ratio. In each case, one mole of the complex forming ion H2Y2– reacts
with one mole of the metal ion and releases two moles of hydrogen ion. Titrations involving EDTA
as titrate are referred to as chelometric titrations.
The more stable the complex, the lower the pH at which an EDTA titration of the metal ion under
study may be performed. Below are indicated minimum pH values for the existence of selected metal
EDTA complexes.
Table 2
It is thus evident in general that M2+ EDTA complexes are stable in alkaline or slightly acidic
solution, while M3+ or M4+ EDTA complexes exist in solutions of much higher acidity.
Titration Curves: Complexometric titration curves are constructed and consists of a plot of the
negative logarithm of the metal ion concentration (pM) versus milliliters of titrant; a point of inflexion
occurs at the equivalence point; in some cases this sudden increase may exceed 10PM units. These
are analogous to acid base titration curves and likewise are helpful in knowing the feasibility of a
complexometric titration and in choosing a proper metal ion sensitive indicator.
Fig. 6
Such indicators form complexes with specific metal ions, which differ in colour from the free
indicator and hence a sudden change of colour occurs at the equivalence point.
Concepts of Titrimetric Analysis 11.21
Types of EDTA Titrations: EDTA titrations have been performed for nearly all common cations.
The important types of EDTA titrations of metal ions are:
1. Direct Titrations: The direct titration with EDTA may be performed on at least 25 cations
using metallochromic indicators. The metal ion in solution is buffered to the desired pH (say
to pH = 10 with NH4 + aqueous NH3) and titrated directly with the standard EDTA solution.
The total hardness of water (Ca + Mg) is determined by direct titration with EDTA using
Eriochrome Black T or calmagite indicator.
2. Substitution (or Replacement) Titrations: Such titrations are used for metal ions. Which
do not react with a metal indicator, or for metal ions which form EDTA complexes that are
more stable than those of other metals such as Mg2+ and Ca2+, The metal cation Mn+ to be
determined is treated with Mg– EDTA complex, when the reaction occurs:
The amount of Mg2+ liberated is equivalent to the cation present and can be titrated with
standard EDTA solution using a suitable metal indicator, such as calmagite.
3. Alkali Metric Titrations: When a solution of disodium salt (EDTA), Na2H2Y, is added to
a solution of metal ions, complexes are formed and two equivalents of hydrogen ions are set
free.
These liberated hydrogen ions can be titrated with a standard solution of NaOH using a usual
acid base indicator to locate the end point.
4. Miscellaneous Methods: Silver and gold cannot be titrated complexometrically but by the
exchange reactions between the Ni(CN) 42– ion and Ag+ or Au+, the Ni2+ ions are set free
and hence can be determined:
Such reactions take place with sparingly soluble silver salts AgSCN, AgCl, AgBr and AgI
etc., and hence provide a method for the determination of these anions. The anion is first
precipitated as the silver salt and is then dissolved in a solution of Ni (CN) 42–, the equivalent
amount of Ni2+ is set free and is determined by immediate titration with EDTA using
murexide or bromopyrogallolred as an indicator.
Indicators for Complexometric (EDTA) Titration: At present a wide variety of good indicators
are available and usually the visual titrations are easier to perform such indicators are also referred
to as metallochromic indicators.
The metal indicator complex should be sufficiently stable, otherwise due to dissociation, a sharp
colour change is not obtained. However, the metal indicator complex must be less stable than the
metal EDTA complex, thereby ensuring that at the end point, EDTA can remove metal ions from
the metal indicator complex. Some important indicators of this type are described here.
11.22 Engineering Chemistry
2. Murexide: It was probably the first metal ion indicator to be used in EDTA titrations. It is
the ammonium salt of purpuric acid and the anion has the structure (III). The 0.5g of dye
staff is suspended in 100cm3 water, shaken well and allowed to settle. The clear supernatant
liquid is used as the indicator.
Fig. 6
6. Precipitation Titrations
Introduction: The precipitation method is based on titration with the use of reactions accompanied
by formation of sparingly soluble compounds. Although many such reaction are known, only a few
of them can be used in titrimetric analysis. They must satisfy a number of conditions, namely:
(a) The precipitate must be practically insoluble.
(b) The titrations results should not be distorted appreciably by adsorption effects.
(c) It must be possible to detect the equivalence point during the titration.
These conditions restrict severely the range of reactions which are suitable for volumetric
analysis. The most important methods are those based on precipitation of insoluble silver
salts in accordance with the equation.
Concepts of Titrimetric Analysis 11.23
Ag+ + X– Æ AgX Ø
Or reactions giving rise to weakly dissociated salts such as HgCl2, HgBr2, Hg (CNS)2, etc.
In addition to precipitation of chlorides and bromides as AgCl and AGBr, they can be
determined by the mercurimetric method by means of the reactions.
2NaCl + Hg (NO3)2 Æ HgCl2 + 2NaNO3
2KBr + Hg (NO3)2 Æ HgBr2 + 2KNO3
A serious obstacle to the use of many reactions of complex formation in volumetric analysis
is the fact that the same cation and ligand can form complexes differing in composition, i.e,
with different proportions of metal and ligand. This makes the reaction complex as in such
cases they do not conform to the same stoichiometric equation.
Principle of Precipitation: solubility, which is dependent on the solvent and temperature, is the
concentration of the dissolved solute in moles per litre, when the solution is in equilibrium with a
solid solute. This repeating pattern depends upon the molecular structure of the compound.
The solute molecules are held together in that pattern by intermolecular forces of attraction. Now
in order to dissolve a solid, these forces of attraction must be overcome so that solute–solute attraction
is replaced by solute–solvent attraction. During precipitation, however, the opposite condition is
aspired for, where the intermolecular forces between the molecules of product are high and solute–
solute forces replace the solute solvent forces.
Solubility Product and Precipitation: Consider an aqueous solution of a slightly soluble salt BA
in equilibrium with excess of the solid at constant temperature. The equilibrium can be represented
by:
BA(s) B+ + A–
Where BA(s) represents the solid phase, in dilute aqueous solution essentially no undissociated
BA will be present in the solution. Since the activity of solid is constant, the equilibrium constant
for (i) may be written as:
Ksp = [B]+ [A–]
Ksp is the solubility product which is a constant for solute solvent and temperature. In a more
complex case
11.24 Engineering Chemistry
Fig. 7
Such precipitation titration in which silver nitrate is used as a reagent are of high importance
and are called argentiometric titration.
Thus, the chloride ions form the primary adsorbed layer, which in turn will hold the secondary
adsorbed layer of oppositely change Na+ ions.
–
NO3
+ +
Na – Na + +
Cl Cl
– Ag Ag
– –
AgCl NO3 AgCl NO3
– – + +
Cl Cl Ag Ag
+ +
Na Na
– –
Fluoresceinate NO3
+ +
– Ag Ag –
Fluoresceinate AgCl Fluoresceinate
+ +
Ag Ag
–
Fluoresceinate
solved Questions
1. What is alkalinity?
Ans. Alkalinity is amount of OH– present in a given water sample which can be increased by
hydrolysis and dissociation of carbonates and bicarbonates, respectively
2. Give types of neutralization titration.
Ans. Neutralization titrations are of four types–
Strong acid and Strong base
Strong acid and weak base
Weak acid and Strong base
Weak acid and weak Base
3. What is buffer solution?
Ans. Buffer solution resists the change in pH.
4. Give the complexes formed in EDTA method for softening water.
Ans. Two complexes are formed in EDTA method first is of wine red color formed between EBT
and cations causing hardness and second is formed between EDTA and cations causing
hardness.
5. Why precipitation titration is also called argentometric titration?
Ans. One of the two solutions in precipitation titration is having silver ions in it so precipitation
is also known as argentometric.
6. Give the conditions for precipitation to take place.
Ans. For precipitation to take place ionic product should be greater than solubility product.
7. What is the pH range of phenolphthalein and methyl orange?
Ans. pH range of phenolphthalein is 8.1 to 9.8 and methyl orange is 3.1 to 4.4.
Concepts of Titrimetric Analysis 11.27
UNsolved Questions
1. Distinguish between qualitative and quantitative analysis.
2. Explain types of titration.
3. Distinguish between
(a) End point and equivalence point
(b) Primary standard solution and secondary standard solution
(c) Acidimetry and alkalimetry
(d) Self, internal and external indicator.
4. Give pH range of phenolphthalein and methyl orange.
5. Distinguish between iodometry and iodimetry.
6. Give the structure of EDTA and EBT.
7. Give the structure of phenolphthalein and methyl orange.
8. Explain Ostwald’s theory of acid base indicators.
9. Gibe types and examples of acid base titrations.
10. What is precipitation titrations?
11. Why do we use buffer in complexometric titration?
12. Explain Redox titration.
13. What are colors of AgCl and Ag2CrO4 in precipitation titration?
11.28 Engineering Chemistry