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Chemistry
Chemistry
43/16) SD - 4
Dated 25.4.2016 has given approval to prescribe this textbook in its meeting held on
30.01.2020 and it has been decided to implement it from academic year 2020-21.
CHEMISTRY
STANDARD TWELVE
2020
Maharashtra State Bureau of Textbook Production and
Curriculum Research, Pune.
First Edition : © Maharashtra State Bureau of Textbook Production and
2020 Curriculum Research, Pune - 411 004.
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- For Teachers -
Dear Teachers,
We are happy to introduce the revised textbook required for each branch of chemistry. Application
of chemistry for std. XII. This book is a sincere of this knowledge will help students to understand
attempt in continuation with the standard XI book further chapters in each unit.
to follow the maxims of teaching as well as develop • Each chapter provides solved problems on each
a ‘constructivist’ approach to enhance the quality and every concept and various laws. The solved
of learning. The demand for more activity based, problems are put into boxes. Teachers should
experiential and innovative learning opportunities explain each step of the problems to the student
is the need of the time. The present curriculum has and give them practice.
been restructured so as to bridge the credibility gap • Invite students' participation by making use of the
that exists in the experience in the outside world. boxes like ‘Can You Recall’, ‘Do you know?’
Guidelines provided below will help to enrich the • Encourage the students to collect related
teaching - learning process and achieve the desired information by providing them the websites.
learning outcomes. • Teaching- learning interactions, processes and
• To begin with, get familiar with the textbook participation of all students are necessary and so is
yourself. your active guidance.
• The present book has been prepared for • Do not use the content of the boxes titled ‘Do you
constructivism and activity based learning. know’? for evaluation.
• Teachers must skilfully plan and organize the • Exercises include parameters such as co-relation,
activities provided in each chapter to develop critical thinking, analytical reasoning etc.
interest as well as to stimulate the thought process Evaluation pattern should be based on the given
among the students. parameters. Equal weightage should be assigned
• Always teach with proper planning. to all the topics. Use different combinations of
• Use teaching aids as required for the proper questions.
understanding of the subject. • Illustrative figures are included to help assimilation
• Do not finish the chapter in short. of new concepts. Teachers should note that students
• Follow the order of the chapters strictly as listed are not expected to draw all the figures included in
in the contents because the units are introduced in this book. As a part of evaluation students can be
a graded manner to facilitate knowledge building. asked to draw schematic diagrams/structures and
• Each unit is structured in a definite manner. It interpret or label other complicated figures.
starts from the basic concepts of general chemistry
Observe and discuss... Use your brain power Can you tell ?
Cover page :
• (+) - Limonene and (-) Limonene : major contributors to the characteristic flavours of peelings of oranges and lemons respectively.
• Image of gold surface : Au (111), obtained by Scanning Tunneling Microscope (STM).
• Structures of coordination complexes : haemoglobin, chlorophyll and metal -EDTA complex.
DISCLAIMER Note : All attempts have been made to contact copy right/s (©) but we have not heard from them.
We will be pleased to acknowledge the copy right holder (s) in our next edition if we learn from them.
Competency Statements - Standard XII
Area/ Unit/ After studying the contents in Textbook students.....
Lesson
• Distinguish crystal structures illustrating unit cell and packing efficiency in cubic systems.
• Gain information on point defects and band theory in relation to electric and magnetic behavior.
• Define solubility and rationalise its dependence on various factors.
• Explain Henry and Raoult's laws.
• Derive expressions for colligative properties.
• Learn van’t Hoff factor and its correlation with dissociation constant.
• Catagorize strong and weak acid bases.
• Learn Ostwald’s dilution law.
• Derive Henderson Balch Hassel equation.
• Explain the role of buffer solutions in controlling of pH.
• Understand spontaneity of reactions.
• Know reversible/irreversible processes and PV work.
• Understand first and second laws of thermodynamics.
• Work out change in enthalpy, entropy and Gibbs' functions in physical and chemical
Physical
transformations.
Chemistry • Apply Hess’s Law in thermochemical equations.
• State what are strong and weak electrolytes.
• Define Kohlrausch law and state its importance.
• Understand functioning of electrolytic and galvanic cells. Write half cell reactions there in.
• Describe type of electrodes.
• Derive Nernst equation and understand its importance.
• Know what are dry cell, lead strong batteries and fuel cells.
• Describe the electrochemical series and its implications.
• Define average and instantaneous rate, order and molecularity in kinetics
• Formulate differential and integral rate laws for zero and first order reactions.
• Understand basis of collision theory of reaction rates
• Sketch qualitatively potential energy curve. Understand acceleration of reactions in the presence
of catalyst.
• Solve relevant numerical problems.
• Write electronic configuration of groups 16, 17, 18 and those of d and f blocks.
• Correlate atomic properties of elements with electron configuration.
• Explain the anomalous behaviour of ‘O’ and ‘F’.
• Understand allotropy in ‘O’ and ‘S’.
• Draw structures of oxyacids of ‘sulfur’ and ‘halogens’.
• Write reactions for preparation, chemical properties of O2, O3, SO2, H2SO4, Cl2, HCl, KMnO4,
K2Cr2O7.
• Draw structures of interhalogen and xenon compounds and illustrate their properties. State the
methods of preparation with reaction.
• Know chemistry of the elements belonging to groups 16, 17, 18.
Inorganic • Understand the principles of metallurgy in extraction of iron.
chemistry • Compare lanthanoides and actinoides.
• Enlist properties of the manmade post actinoide elements.
• Understand Werner theory of coordination compounds.
• Understand and apply EAN rule for stability of coordination compounds.
• Understand diverse isomerism in coordination compounds.
• Use the concept of hybridization for predicting structures and magnetic behaviour of complexes
based on the V.B.T.
• Understand C.F.T. Sketch qualitatively d-orbital splitting diagrams in octahedral and tetrahedral
ligand field environments.
• Distinguish between high spin and low spin complexes.
• Predict structure, colour and magnetic properties of the complexes based on the C.F.T.
• State common and IUPAC names of compounds and methods of preparation of halogen
derivatives, alcohols, phenols, ethers, aldehydes, ketones, carboxylic acid and amines.
• Understand structure, chemical properties, laboratory tests and reactions of the above functional
groups.
Organic • Explain acid or base strength of alcohols, phenols, carboxylic acids and amines.
Chemistry • Explain trends in boiling point and solubility of compounds of above functional groups in terms
of intermolecular forces.
• Understand optical activity, recognize chiral molecules and represent with Fischer projection
and wedge formulae.
• Understand mechanism of nucleophilic substitution reactions and influencing factors.
• Classify carbohydrates, amino acids, nucleic acids.
• Represent monosaccharides using the Fischer projection formula.
• Represent monosaccharides, disaccharides and polysaccharides using the Haworth formula.
• Correlate properties of carbohydrates to the presence or absence of potential aldehyde group.
• Learn four level structure of proteins and primary structures nucleic acid.
• Represent primary structure of dipeptide and tripeptide from data on the terminals.
• Understand enzyme catalysis and double strand DNA structure.
• Understand classification of polymers on the basis of source, structure, intermolecular forces,
polymerization, number of monomers and biodegradability.
Applied • Understand addition and condensation polymerization.
Chemistry • Know properties, structure and preparation of natural rubber, vulcanized rubber, Buna-S,
viscose, LDP, HDP, teflon, polyacrylo nitrile, polyamide, polyesters, phenol-formaldehyde
resin and PHBV.
• Understand scope of green chemistry with reference to sustainable development.
• Recognize twelve principles of green chemistry and their implementation.
• Correlate the Chemistry knowledge gained so far as pro or counter to the principles of green
chemistry.
• Understand scope and applications of nanochemistry.
• Gain knowledge of a synthetic method and properties of nanoparticles.
• Know instrumental techniques for characterization of nanomaterials.
CONTENTS
Sr. No. Title Page No.
1 Solid State 01-27
2 Solutions 28-46
3 Ionic Equilibria 47-62
4 Chemical Thermodynamics 63-89
5 Electrochemistry 90-119
6 Chemical Kinetics 120-137
7 Elements of Groups 16, 17 and 18 138-164
8 Transition and Inner transition Elements 165-191
9 Coordination Compounds 192-209
10 Halogen Derivatives 210-233
11 Alcohols, Phenols and Ethers 234-253
12 Aldehydes, Ketones and Carboxylic acids 254-281
13 Amines 282-297
14 Biomolecules 298-321
15 Introduction to Polymer Chemistry 322-339
16 Green Chemistry and Nanochemistry 340-352
1. SOLID STATE
Can you recall ? Try this...
• What are the three most common
states of matter?
• How does solid state differ from the
other two states ? (Answer with reference
to volume, shape, effect of temperature
and pressure on these and the motion
of constituent particles and interparticle
forces.)
1.1 Introduction : As studied earlier, the solid
state of matter is characterised by strong Observe the above figure carefully.
interparticle forces of attraction. As a result The two types of circles in this figure
most solids have definite shape and volume, represent two types of constituent particles
which change only slightly with change of a solid.
in temperature and pressure. The smallest
• Will you call the arrangement of particles
constituent particles of various solids are
in this solid regular or irregular ?
atoms, ions or molecules. All such smallest
constituent particles of solids will be referred • Is the arrangement of constituent
to as 'particles' in this chapter. particles same or different in directions
→ → →
1.2 Types of solids : There are two types AB, CD, and EF ?
of solids, namely crystalline solids and
amorphous solids. 1.2.1 Crystalline solids : Study of many
crystalline solids indicates that they possess
Observe and discuss... the following characteristic properties.
• Collect the following solids : i. There is a regularity and periodicity in
grannular sugar, common salt, the arrangement of constituent particles in
blue vitriol. crystalline solids. The ordered arrangement
• Observe a few grannules of these solids of particles extends over a long range.
under a magnifying lens or microscope.
• Discuss your observations with reference ii. Crystalline solids have sharp melting
to the following points : (i) Shape of the points, that is, they melt at a definite
grannules, (ii) Smoothness of faces of temperature.
the grannules and (iii) Angles between iii. All crystalline substances except those
various edges of the grannules. having cubic structure are anisotropic. In
• All the above solids are crystalline solids.
other words their properties like refractive
Name the properties of crystals that you
index, thermal and electrical conductivity,
observed in this activity.
etc, are different in different directions.
Ice, salts such as NaCl, metals such
as sodium, gold, copper and materials such
as diamond, graphite, ceramics are examples
of crystalline solids.
1
Glass, plastic, rubber, tar, and metallic glass
Do you know ? (metal-metalloid alloy) are a few examples of
• A single crystal has ordered amorphous solids.
(regular and periodic)
arrangement of constituent particles
throughout its bulk. Use your brain power
• Majority of crystalline solids, including Identify the arrangements A and B
metals, are polycrystalline in nature. as crystalline or amorphous.
Single grannule of a polycrystalline
solid is made of many single crystals or
crystallites packed together with different
orientations.
• Single crystals are difficult to obtain.
Diamond is an example of naturally
formed single crystal.
2
1.3.2 Covalent network crystals
Do you know ?
Characteristics of covalent network crystals
Many crystalline forms of
are as follows :
silica (SiO2) are found in nature.
Three of them are α-quartz, b-quartz and i. The constituent particles in covalent
cristobalite network solids are atoms.
ii. The atoms in these crystals are linked by a
continous system of covalent bonds. The
result is a rigid three dimensional network
that forms a giant molecule. The entire
crystal is a single molecule.
iii. As a result of rigid and strongly bonded
cristobalite α-quartz
structure, covalent network crystals are
very hard. In fact they are the hardest and
most incompressible of all the materials.
These crystals have high melting and
boiling points.
iv. The electrons are localised in covalent
b-quartz
bonds and hence are not mobile. As a
result, covalent solids are poor conductors
1.3 Classification of crystalline solids : of heat and electricity.
Crystalline solids are further classified into
For example : diamond, quartz (SiO2), boron
four categories : ionic solids, covalent network
nitride, carborandum are covalent network
solids, molecular solids and metallic solids.
solids.
1.3.1 Ionic crystals : Ionic crystals have the
following characteristics : Do you know ?
i. The constituent particles of ionic crystals Diamond is the hardest known
are charged ions. The cations and anions material.
may differ in size.
Try this...
ii. Each ion of a given sign of charge is
bonded to ions of opposite charge around Graphite is a covalent solid
it by coulomb force. In other words, the yet soft and good conductor of
particles of ionic crystals are held by electricity. Explain.
electrostatic force of attraction between
oppositely charged ions. Can you recall ?
iii. Ionic crystals are hard and brittle. They • What are structures of
have high melting points. diamond and graphite ?
iv. These are nonconductors of electricity • What are the types of covalent bonds
in solid state. However, they are good those link carbon atoms in diamond
conductors when melted or dissolved in and graphite ?
water. • Are all the valence electrons of
For example : NaCl, K2SO4, CaF2, KCl are carbon atoms in graphite localized to
ionic crystals. specific covalent bonds ?
3
c. Intermolecular hydrogen bonds in
Remember...
solids such as H2O (ice), NH3, HF and
Both ionic and covalent
so forth.
crystals are hard and have high
melting and boiling points. We can iii. Because of weak intermolecular attractive
use electrical properties to distinguish forces, molecular solids are usually soft
between them. Both are insulators at low substances with low melting points.
temperature. iv. These solids are poor electrical conductors
Ionic solids become good conductors and are good insulators.
only at high temperature, above their 1.3.4 Metallic crystals : These are crystalline
melting points. solids formed by atoms of the same metallic
The conductivity of covalent solids element, held together by a metallic bond.
is in general low and increases with Metallic bond : In a solid metal, the valence
temperature. However, there is no abrupt electrons are delocalised over the entire crystal
rise in conductivity when substance is leaving behind positively charged metal ions.
melted. Therefore, metallic crystals are often described
as an array of positive ions immersed in a sea
1.3.3 Molecular crystals : Substances such of mobile electrons. The attractive interactions
as Cl2, CH4, H2, CO2, O2 on solidfication between cations and mobile electrons constitute
give molecular crystals. Crystalline organic the metallic bonds. (For more details refer to
compounds are also molecular solids. section 1.9.2)
i. The constituent particles of molecular Metallic crystals have the following properties:
solids are molecules (or unbonded single
atoms) of the same substance. i. Metals are malleable, that is, they can be
hammered into thin sheets.
Can you recall ? ii. Metals are ductile, that is, they can be
What is a hydrogen bond ? drawn into wires.
iii. Metals have good electrical and thermal
ii. The bonds within the molecules are conductivity.
covalent. The molecules are held together Examples : metals such as Na, K, Ca, Li, Fe,
by various intermolecular forces of Au, Ag, Co, etc.
attraction. (Refer to XI Std. Chemistry
The properties of different types of crystalline
Textbook, Chapter 10). For example :
solids are summarized in Table 1.1.
a. Weak dipole-dipole interactions in
1.4 Crystal structure : The ordered three
polar molecules such as solid HCl,
dimensional arrangement of particles in a
H2O, SO2, which possess permanent
crystal is described using two terms, namely,
dipole moment.
lattice and basis.
b. Very weak dispersion or London
1.4.1 Crystal, lattice and basis : Lattice is a
forces in nonpolar molecules such as
geometrical arrangement of points in a three
solid CH4, H2. These forces are also
dimensional periodic array. A crystal structure
involved in monoatomic solids like
is obtained by attaching a constituent particle
argon, neon. (These substances are
to each of the lattice points. Such constituent
usually gases at room temperature.)
particles that are attached to the lattice points
form the basis of the crystal lattice. Crystal
4
Table 1.1 : Properties of four types of crystalline solids
Type Ionic solids Covalent network Molecular Metallic solids
Property solids solids
1. Particles of unit Cations and Covalently bonded Monoatomic Metallic ions in a
cell anions atoms or polyatomic sea of electrons
molecules
2. Interparticle Electrostatic Covalent bonds London, dipole- Metallic bonds
forces dipole forces and/ (attraction between
or hydrogen bonds cations and mobile
valence electrons)
3. Hardness Hard and brittle Very hard Soft Variable from soft
to very hard
4. Melting points High High Low Wide range
6000C to 30000C 12000C to 40000C (-2720C to 4000C) (-390C to 34000C)
5. Thermal and Poor electrical Poor conductors poor conductor of good conductor of
electrical conductors in Exceptions : heat and electricity heat and electricity
conductivity solid state. Good i. Graphite : good
conductors conductor of
when melted electricity.
or dissolved in ii. Diamond : good
water conductor of heat
6. Examples NaCl, CaF2 diamond, silica ice, benzoic acid Na, Mg, Cu, Au
lattice is also called space lattice of crystal. The dimensions of unit cell along the three
Thus, crystal is the structure that results by axes are denoted by the symbols a, b and c.
attaching a basis to each of the lattice points. The angles between these axes are represented
It is represented by the following equation. by the symbols ∝, β and γ as shown in Fig 1.1.
. . .
. . . + =
. . .
. . .
Lattice + Basis = Crystal b a
1.4.2 Unit Cell : The space lattice of a crystal
is built up of a three dimensional basic g
pattern. This basic pattern is repeated in three
dimensions to generate the entire crystal.
Fig. 1.1 : Unit cell parameters
The smallest repeating structural unit of a
crystalline solid is called unit cell. 1.4.3 Types of unit cell : There are four types
When the unit cells are stacked together of unit cells.
to generate the crystal, each unit cell shares i. Primitive or simple unit cell : In primitive
its faces, edges and corners with neighbouring unit cell, the constituent particles are present at
unit cells. It is important to understand that the its corners only.
geometric shape of a unit cell is same as that
ii. Body-centred unit cell : In this type of
of the macroscopic crystal. For example, if the
unit cell, one constituent particle is present at
crystal has cubic shape the unit cell will also
the centre of its body in addition to the corner
have its constituent particles arranged to form
particles.
a tiny cube.
5
iii. Face-centred unit cell : This unit cell
consists of particles at the centre of each of the
faces in addition to the corner particles.
iv. Base-centred unit cell : This unit cell
consists of particles at the centre of any two sc bcc fcc
of its opposite faces in addition to the corner
particles.
1.4.4 Crystal systems : By mathematical
analysis, it has been proved that only fourteen
different kinds of space lattices are possible. sc bcc fcc
In other words, there are only 14 ways in
which similar points can be arranged in a
three dimensional order. These 14 lattices,
which describe the crystal structure, are called
Bravais lattices.
sc bcc fcc
Fourteen Bravais lattices are divided
into seven crystal systems. The possible
combinations of lattice point spacings (a, b Fig. 1.2 : Cubic unit cell
and c) along three axes and the angles (∝, β
and γ) between these axes give rise to seven 1.5.1 Number of particles in cubic unit cells
crystal systems. In other words, seven crystal i. Primitive or simple cubic unit cell (sc) :
systems are associated with 14 Bravais lattices A simple cubic cell has particles at its eight
also called 14 unit cells. corners. When these unit cells are stacked
together, particle at each corner of a given unit
The seven crystal systems are
cell is shared with seven other neighbouring
named as cubic, tetragonal, orthorhombic,
cubes that come together at that corner. As a
rhombohedral, monoclinic, triclinic and
result the corner particle contributes its 1/8th
hexagonal system. Cubic system will be
part to the given unit cell. Thus, a simple cubic
discussed in the following section.
cell has 1/8 × 8 = 1 particle per unit cell.
1.5 Cubic system : There are three kinds of ii. Body-centred cubic unit cell (bcc) : A
unit cells in cubic system : primitive or simple bcc unit cell has eight corner particles and an
cubic (sc), body-centred cubic (bcc) and face- additional particle at the centre of the cube.
centred cubic (fcc) (Fig. 1.2). One eighth of each particle from eight corners
i. Simple cubic unit cell (sc) has a particle at belongs to the given unit cell as mentioned in
each of the eight corners of a cube. simple cubic unit cell.
ii. Body-centred cubic unit cell (bcc) has The particle at the centre of a given
particles at its eight corners and an additional cube is not shared by any other cube. Hence, it
particle in the center of the cube. belongs entirely to the given unit cell. Thus bcc
unit cell has one particle from eight corners
iii. Face-centred cubic unit cell (fcc) has plus one particle in the centre of the cube,
particle at the centre of each of six faces in making total of 2 particles per bcc unit cell.
addition to the particles at eight corners of the
iii. Face-centred cubic unit cell (fcc) : A
cube.
fcc unit cell has particles at the eight corners
plus particles at the centre of its six faces. As
described in simple cubic unit cell, one particle
6
Do you know ?
The names of fourteen Bravais lattices (unit cells) for each of the seven crystal system
are shown below.
Crystal system Bravais lattices
Name unit cell structure
1. Cubic i. simple or primitive
ii. body-centred
iii. face-centred
ii. iii.
i.
2. Orthorhombic i. simple or primitive
ii. body-centred
iii. face-centred
iv. base-centred
i. ii.
4. Monoclinic i. simple or primitive
ii. base centred
i. ii.
5. Rhombohedral i. simple or primitive
7
from eight corners belongs to the given unit
cell. Problem 1.1 : When gold crystallizes, it
forms face-centred cubic cells. The unit cell
Each particle at the centre of the six edge length is 408 pm. Calculate the density
faces is shared with one neighbouring cube. of gold. Molar mass of gold is 197 g/mol.
Thus,1/2 of each face particle belongs to the
given unit cell. From six faces, 1/2 × 6 = 3 Solution :
Mn
particles belong to the given unit cell. ρ=
a3 NA
Therefore, fcc unit cell has one corner M = 197 g mol-1, n = 4 atoms for fcc,
particle plus 3 face particles, total 4 particles NA = 6.022 ×1023 atoms mol-1,
per unit cell. a = 408 pm = 408 ×10-12m = 4.08×10-8 cm
1.5.2 Relationship between molar mass, = 19.27 g/cm3, 19.27 × 103 kg/m3.
density of the substance and unit cell edge
length, is deduced in the following steps 1.6 Packing of particles in crystal lattice
i. If edge length of cubic unit cell is a, the Constituent particles of a crystalline
volume of unit cell is a3. solid are close packed. While describing
ii. Suppose that mass of one particle is m and the packing of particles in a crystal, the
that there are n particles per unit cell. individual particles are treated as hard
spheres. The closeness of particles maximize
Mass of unit cell = m × n (1.1) the interparticle attractions.
iii. The density of unit cell (ρ), which is same The number of neighbouring spheres
as density of the sub-substance is given by that touch any given sphere is its coordination
mass of unit cell m×n
ρ = volume of unit cell = a3 = density of number. Magnitude of the coordination
substance number is a measure of compactness of
(1.2) spheres in close-packed structures. The larger
the coordination number, the closer are the
iv. Molar mass (M) of the substance is given
spheres to each other.
by
1.6.1 Close packed structures : The three
M = mass of one particle × number of particles
dimensional close packed structure can be
per mole
understood conveniently by looking at the
= m×NA (NA is Avogadro number) close packing in one and two dimensions.
Therefore, m= M/NA (1.3) a. Close packing in one dimension : A close
v. Combining Eq. (1.1) and (1.3), gives packed one dimensional structure results by
arranging the spheres to touch each other in a
nM
ρ= (1.4) row (Fig. 1.3 (a)).
a3 NA
By knowing any four parameters of Eq. (1.4), b. Close packing in two dimensions : A close
the fifth can be calculated packed two dimensional (planar) structure
results by stacking the rows together such
8
that they are in contact with each other. There the free space in this arrangement is less than
are two ways to obtain close packing in two in square packing, making it more effecient
dimensions. packing than square packing. From Fig.1.3(c)
i. Square close packing : One dimensional it is evident that the free spaces (voids) are
rows of close packed spheres are stacked over triangular in shape. These triangular voids are
each other such that the spheres align vertically of two types. Apex of the triangular voids in
and horizontally (Fig. 1.3 (b)). If the first row alternate rows points upwards and downwards.
is labelled as 'A' type, being exactly same as
the first row, the second row is also labelled as (a)
'A' type. Hence this arrangement is called A,
A, A, A..... type two dimensional arrangement.
In this arrangement, every sphere touches four
neighbouring spheres. Hence, two dimensional
coordination number, here, is 4. A square is (b)
obtained by joining the centres of these four
closest neighbours (Fig. 1.3(b)). Therefore,
this two dimensional close packing is called
square close packing in two dimension. (c)
ii. Hexagonal close packing : Close packed
Fig. 1.3 : (a) Close packing in one dimension
one dimensional row (Fig. 1.3 (a)) shows that (b) square close packing
there are depressions between the neighbouring (c) Hexagonal close packing in two dimension
spheres. If the second row is arranged in such c. Close packing in three dimensions :
a way that its spheres fit in the depressions of Stacking of two dimensional layers gives rise
the first row, a staggered arrangement results. to three dimensional crystal structures. Two
If the first row is called 'A' type row, the dimensional square close packed layers are
second row, being different, is called 'B' type. found to stack only in one way to give simple
Placing the third row in staggered manner in cubic lattice. Two dimensional hexagonal
contact with the second row gives rise to an close packed layers are found to stack in
arrangement in which the spheres in the third two distinct ways. Accordingly two crystal
row are aligned with the spheres in the first structures, namely, hexagonal close packed
row. Hence the third row is 'A' type. Similarly (hcp) structure and face centred cubic (fcc)
spheres in the fourth row will be alligned with structure are formed.
the spheres in the second row and hence the
fourth row would be 'B' type. The resulting two i. Stacking of square close packed layers:
dimensional arrangement is 'ABAB...' type Stacking of square close packed layers
(Fig. 1.3 (c)). In this arrangement each sphere generates a three dimensional simple cubic
touches six closest neighbours. Thus, the two structure. Here, the second layer is placed
dimensional coordination number in this over the first layer so as to have its spheres
packing is 6. A regular hexagon is obtained exactly above those of the first layer (Fig. 1.4).
by joining the centres of these six closest Subsequent square close packed layers are
spheres (Fig. 1.3 (c)). Hence, this type of two placed one above the other in the same manner.
dimensional close packing is called hexagonal In this arrangement, spheres of all the layers
close packing in two dimensions. Compared to are perfectly aligned horizontally as well as
the square close packing in two dimensions, vertically. Hence, all the layers are alike, and
the coordination number in hexagonal close are labelled as 'A' layers. This arrangement
packing in two dimensions is higher. Moreover of layers is described as 'AAAA... ' type. The
9
structure that results on stacking square close
packed layers is simple cubic. Its unit cell is
the primitive cubic unit cell (Fig. 1.4).
10
iii. Placing third hexagonal close packed 1 above and 1 below. Hence coordination
layer : There are two ways of placing the number of any sphere in sc is 6.
third hexagonal close packed layer on the
b. In both hcp and ccp/fcc structures that result
second.
from stacking of hexagonal close packed
One way of doing this is to align the layers in two different ways, each sphere is
spheres of the third layer with the spheres surrounded by 12 neighbouring spheres, 6 in
of the first layer. The resulting pattern of the its own layer, 3 above and 3 below. Hence, the
layers will be 'ABAB....'. This arrangement coordination number of any sphere in hcp or
results in hexagonal close packed (hcp) ccp/fcc structure is 12.
structure (Fig. 1.8(a)). Metals such as Mg,
1.6.3 Number of voids per atom in hcp and
Zn, have hcp crystal structure.
ccp : The tetrahedral and octahedral voids
The second way of placing the third occur in hcp and ccp/fcc structures. There are
hexagonal close packed layer on the second two tetrahedral voids associated with each
is to cover the octahedral voids by spheres of atom. The number of octahedral voids is half
the third layer. In such placing, the spheres of that of tetrahedral voids. Thus, there is one
the third layer do not align with the spheres octahedral void per atom.
of the second or the spheres of the first layer.
The third layer is, therefore, called 'C' layer. Remember...
The spheres of the fourth layer get aligned If N denotes number of particles,
with the spheres of the first layer. Hence, the then number of tetrahedral voids is
fourth layer is called 'A' layer. This pattern 2N and that of octahedral voids is N.
of stacking hexagonal close packed layers
is called 'ABCABC....'. This arrangement 1.7 Packing efficiency : Like coordination
results in cubic close packed (ccp) structure number, the magnitude of packing efficiency
(Fig. 1.8(b)). This is same as fcc structure. gives a measure of how tightly particles are
Metals such as copper and Ag have ccp (or packed together.
fcc) crystal structure. Packing efficiency is the fraction or a
percentage of the total space occupied by the
spheres (particles).
Packing efficiency =
Expanded volume occupied by particles in unit cell
(a) view (a) ×100
total volume of unit cell
(1.5)
1.7.1 Packing efficiency of metal crystal
in simple cubic lattice is obtained by the
Expanded
(b) view (b) following steps.
Fig. 1.8 : Formation of hexagonal closed packed Step 1 : Radius of sphere : In simple cubic
structures unit cell, particles (spheres) are at the corners
1.6.2 Coordination number in close packed and touch each other along the edge. A face of
structure simple cubic unit cell is shown in Fig. 1.9. It is
a. In the simple cubic (sc) crystal structure, evident that
that results from stacking of square close a = 2r or r = a/2 (1.6)
packed layers, each sphere is surrounded by where r is the radius of atom and ‘a’ is the
6 neighbouring spheres, 4 in its own layer, length of unit cell edge.
11
a
r r
In bcc unit cell, particles occupy the corners Step 3 : Total volume of particles : Unit
and in addition one particle is at the centre of cell bcc contains 2 particles. Hence, volume
the cube. Figure 1.10 shows that the particle occupied by particles in bcc unit cell
at the centre of the cube touches two corner 2 3 πa3
=2×
particles along the diagonal of the cube. 16
To obtain radius of the particle (sphere)
3 πa3
Pythagorus theorem is applied. = (1.12)
8
12
Step 4 : Packing efficiency 4 1 3
= 3 π a × ( 2 2)
3
Packing efficiency
volume occupied by particles in unit cell π a3
= ×100
=
total volume of unit cell 12 2
Step 3 : Total volume of particles : The unit
πa3 cell of fcc lattice contains 4 particles. Hence,
= 3 3 × 100 = 68 % volume occupied by particles in fcc unit cell
8a
π a3
=4× πa =
3
Thus, 68% of the total volume in bcc unit
12 2 32
lattice is occupied by atoms and 32 % is empty
space or void volume. Step 4 : Packing efficiency : Packing
1.7.3 Packing efficiency of metal crystal efficiency
in face-centred cubic lattice (or ccp or hcp volume occupied by particles in unit cell
= total volume of unit cell × 100
lattice)
πa3
Step 1 : Radius of particle/sphere : The corner = × 100 = π × 100 = 74%
3 2a 3
32
particles are assumed to touch the particle at
the centre of face ABCD as shown in Fig. 1.11. Thus in fcc/ccp/hcp crystal lattice, 74% of the
total volume is occupied by particles and 26%
The triangle ABC is right angled is void volume or empty space.
with ∠ABC = 900. According to Pythagorus
theorem, Table 1.3 shows the expressions for
AC2 = AB2 + BC2 = a2 +a2 = 2a2 various parameters of particles in terms of unit
cell dimension for cubic systems.
13
Table 1.4 shows the summary of coordination substitution of M gives
xNA
number of particles and packing efficiency in Number of particles in 'x' g = ρa3N /n
various cubic systems. A
15
There are three types of defects: point
Problem 1.6 : A compound forms hcp
defects, line defects and plain defects. Only
structure. What is the number of (a)
point defects will be discussed in this chapter.
octahedral voids (b) tetrahedral voids (c)
total voids formed in 0.4 mol of it. 1.8.1 Point defects : These defects are
irregularities produced in the arrangement of
Solution :
basis at lattice points in crystalline solids.
Number of atoms in 0.4 mol = 0.4 × NA
There are three major classes of point
= 0.4 × 6.022 × 1023 = 2.4098 × 1023 defects: stoichiometric point defects, impurity
(a) Number of octahedral voids = number defects and nonstoichiometric point defects.
of atoms = 2.4098 × 1023 a. Stoichiometric point defects : Chemical
(b) Number of tetrahedral voids formula of a compound shows fixed ratio of
number of atoms or number of cations and
= 2×number of atoms anions. This fixed ratio is the stoichiometry of
= 2×2.4098×1023 the compound.
= 4.818×1023 In stoichiometric defect, the stoichiometry
(c) Total number of voids remains unchanged. In other words, the ratio
of number of atoms or number of cations and
= 2.409×1023+ 4.818×1023 anions of compound remains the same as
= 7.227 × 1023 represented by its chemical formula.
1.8 Crystal defects or imperfections : The There are four types of stoichiometric
real, naturally occurring crystalline substances point defects: vacancy defect, self interstitial
do not have perfect crystal structures. They defect, Schottky defect and Frenkel defect.
have some disorders or irregularities in the i. Vacancy defect : During crystallization of
stacking of atoms. Such irregularities in the a solid, a particle is missing from its regular
arrangement of constituent particles of a solid site in the crystal lattice. The missing particle
crystal are called defects or imperfections. creates a vacancy in the lattice structure. Thus,
Defects are created during the process some of the lattice sites are vacant because of
of crystallization. The imperfections are more missing particles as shown in Fig. 1.12. The
if the crystallization occurs at a faster rate. It crystal is, then, said to have a vacancy defect.
means that the defects can be minimized by The vacancy defect can also be developed
carrying out crystallization at a slower rate. when the substance is heated.
16
Due to the absence of particles, the It is interesting to note that in this second
mass of the substance decreases. However, case, because of the displacement of a particle a
the volume remains unchanged. As a result the vacancy defect is created at its original regular
density of the substance decreases. lattice site. At the same time interstitial defect
ii. Self interstitial defect in elemental solid results at its new position. We can, therefore,
say that in this defect there is a combination of
Interstitial sites in a crystal are the vacancy defect and self interstitial defect.
spaces or voids in between the particles at
lattice points. When some particles of a This defect preserves the density of the
crystalline elemental solid occupy interstitial substance because there is neither loss nor
sites in the crystal structure, it is called self gain in mass of a substance.
interstitial defect. iii. Schottky defect : In an ionic solid, equal
This defect occurs in the following two ways : number of cations and anions are missing
from their regular positions in the crystal
Firstly, an extra particle occupies an empty lattice creating vacancies as shown in Fig.
interstitial space in the crystal structure as 1.15. It means that a vacancy created by a loss
shown in Fig. 1.13. This extra particle is same of cation is always accompanied by a vacancy
as those already present at the lattice points. formed by a loss of anion.
17
Consequences of Schottky defect Conditions for the formation of Frenkel
• As the number of ions decreases, mass defect
decreases. However, volume remains • Frenkel defect occurs in ionic compounds
unchanged. Hence, the density of a with large difference between sizes of
substance decreases. cation and anion.
• The number of missing cations and anions • The ions of ionic compounds must be
is equal, the electrical neutrality of the having low coordination number.
compound is preserved.
Consequences of Frenkel defect
This defect is found in ionic crystals such as
NaCl, AgBr and KCl. • As no ions are missing from the crystal
lattice as a whole, the density of solid and
iv. Frenkel defect : Frenkel defect arises when
its chemical properties remain unchanged.
an ion of an ionic compound is missing from
its regular lattice site and occupies interstitial • The crystal as a whole remains electrically
position between lattice points as shown in neutral because the equal numbers of
Fig. 1.16. cations and anions are present.
The cations are usually smaller than This defect is found in ionic crystals like ZnS,
anions. It is, therfore, more common to find AgCl, AgBr, AgI, CaF2.
the cations occupying interstitial sites. It is b. Impurity defect : Impurity defect arises
easier for the smaller cations to accomodate when foreign atoms, that is, atoms different
the interstitial spaces. from the host atoms, are present in the crystal
lattice. There are two kinds of impurity defects :
Substitutional and interstitial impurity defects.
i. Substitutional impurity defect : In this
defect, the foreign atoms are found at the
lattice sites in place of host atoms. The regular
atoms are displaced from their lattice sites by
impurity atoms.
For example :
18
• Vacancy through aliovalent impurity : c. Nonstoichiometric defects :
Vacancies are created by the addition Nonstoichiometric defect arises when
of impurities of aliovalent ions (that is, ions the ratio of number of atoms of one kind to
with oxidation state (o.s.) different from that that of other kind or the ratio of number of
of host ions) to an ionic solid. cations to anions becomes different from that
indicated by its chemical formula. In short,
stoichiometry of the compound is changed.
It is important to note that the change
in stoichiometry does not cause any change in
the crystal structure.
There are two types of nonstoichiometric
defects
i. Metal deficiency defect : This defect is
possible only in compounds of metals that
Fig. 1.18 : Vacancy through aliovalent ion
show variable oxidation states.
Suppose that a small amount of
SrCl2 impurity is added to NaCl during its In some crystals, positive metal ions
crystallization. The added Sr2⊕ ions (O.S. + 2) are missing from their original lattice sites.
occupy some of the regular sites of Na⊕ host The extra negative charge is balanced by the
ions (O.S.+1). presence of cation of the same metal with
higher oxidation state than that of missing
In order to maintain electrical cation.
neutrality, every Sr2⊕ ion removes two Na⊕
ions. One of the vacant lattice sites created by For example, in the compound NiO
removal of two Na⊕ ions is occupied by one one Ni ion is missing creating a vacnacy at
2⊕
Sr2⊕ ion. The other site of Na⊕ ion remains its lattice site. The deficiency of two positive
vacant as shown in Fig. 1.18. charges is made up by the presence of two Ni3⊕
ions at the other lattice sites of Ni2⊕ ions as
ii. Interstitial impurity defect : In this defect, shown in Fig. 1.20. The composition of NiO
the impurity atoms occupy interstitial spaces then becomes Ni0.97O1.0
of lattice structure. For example in steel, Fe
atoms occupy normal lattice sites. The carbon
atoms are present at interstitial spaces, as
shown in Fig. 1.19.
19
Zn atom is present in the interstitial space Cl ions diffuse to the crystal surface
as shown in Fig. 1.21(a) creating vacancies at their regular sites. These
Cl ions combine with Na atoms on the surface
to form NaCl, by releasing electron from
sodium atom.
Na + Cl NaCl +e
The electrons released diffuse into the
crystal and occupy vacant sites of anions as
shown in Fig. 1.22. The anion vacant sites
occupied by electrons are F-centres or colour-
Fig. 1.21 (a) : Neutral Zn atom at interstitial centres.
site
When ZnO is heated it turns Solids show very wide range of electrical
yellow and returns back to original conductivity. Accordingly solids are classified
white colour on cooling. What into the following three categories : conductors,
could be the reason ? insulators and semiconductors.
• By anion vacancies (Colour or F-centres) i. Conductors : Solids having electrical
conductivities in the range 104 to 107 Ohm-1m-1
This type of defect imparts colour
are called conductors. Metals and electrolytes
to the colourless crystal. For example, when
(ionic solids) are examples of electrical
NaCl crystal is heated in the atmosphere of
conductors. Metals conduct electricity by
sodium vapour, sodium atoms are deposited
movement of electrons while electrolytes
on the crystal surface.
conduct electricity by movement of ions. In
20
this section we will study some aspects of They conduct electricity when electrical
electronic conduction of electricity. potential is applied.
ii. Insulators : Solids having low electrical ii. Valence band : The band having lower
conductivities in the range 10-20 to energy than conduction band is the valence
10-10 Ohm-1m-1 are called insulators. Most band.
nonmetals and molecular solids belong to this The electrons in valence band are not
category. free to move because they are tightly bound to
iii. Semiconductors : Solids having electrical the respective nuclei.
conductivities in the range 10-6 to 104 Ohm-1 m-1 iii. Band gap : The energy difference between
are semiconductors. This range is intermediate valence band and conduction band is called
between conductors and insulators. Metalloids band gap. Size of the band gap decides whether
like silicon, germanium belong to this category. electrons from valence band can be promoted
1.9.1 Band theory : Electrical conductivities to vacant conduction band or not when band
of solid metals, nonmetals and metalloids are gap is too large to promote electrons from
explained in terms of band theory. A band valence band to vacant conduction band by
is made of closely spaced electronic energy thermal energy, it is called forbidden zone.
levels. Band formation can be correlated to When band gap is small, electrons from higher
formation of molecular orbitals (MOs) by energy levels in valence band can be promoted
interaction of atomic orbitals. (Refer to Std. to conduction band by absorption of energy
XI Chemistry Textbook, chapter 5). (such as thermal, electromagnetic).
21
depends on the atomic orbitals involved in
between these two halves. The 3s band
band formation. Band formation in metallic
in sodium is the conduction band which
conductors, thus, results in delocalization of
contains same number of electrons as the
the outermost electrons of all the metal atoms
sodium atoms. This is responsible for the
leaving behind metal ions. This is described as
high conductivity of metallic sodium.
'cations of metal are immersed in the sea of
• Metallic magnesium is an example
electrons'.
of conductor with overlapping bands.
Electronic configuration of Mg is
[Ar]3s23p0. Interaction of completely
p-band filled 3s AOs of all the Mg atoms gives
rise to the same number of MOs all of
which are filled. These together form the
3s band which is a completely filled band.
Interaction of vacant 3p AOs of all the Mg
atoms gives rise to the same number of
vacant MOs together called 3p band. This
s-band is the vacant band. The filled 3s band and
s-band overlapping bands vacant 3p band overlap each other. As a
(a) (b) result, higher energy electrons move from
Fig. 1.23: Metalic conductor 3s band to 3p band.
Do you know ?
• Metallic sodium is an example of
conductor where the conduction
band is partially filled and there is
no band gap. Electronic configuration of Fig. 1.24: Insulators
Na is [Ar]3s1. Interaction of the partially
The valence band and conduction
filled 3s AOs of all the Na atoms gives
rise to same number of MOs. All these band in insulators are separated by a large
closely spaced MOs together form a energy gap called forbidden zone as shown in
continuous band of energies which is Fig. 1.24. Here, thermal energy is insufficient
called 3s band. Lower half of 3s band to promote electrons from valence band to
corresponds of BMOs and is filled while conduction band.
the upper half of 3s band corresponds As a result the conduction band
to AMOs and is empty. There is no gap remains vacant. The material is, therefore, an
insulator.
22
1.9.4 Semiconductors : Electrical conductivity the valence band than at lower temperature.
of a semiconductor material is intermediate In fact semiconductors are insulators at
between that of metals and insulators. The low temperatures and conductors at high
metalloids Si and Ge are semiconductors. temperatures.
Like insulators, the valence band in Remember...
semiconductor is completely filled with Electrical conductivity of
electrons and conduction band is empty. metals decreases and that of
However, the energy gap between the two semiconductor increases with increasing
bands is smaller than that in an insulator. (Fig. temperature.
1.25)
1.9.5 Extrinsic semiconductors and doping :
The conductivity of a semiconductor
can be increased by doping. The process of
addition of minute quantity of impurities to a
semiconductor to increase its conductivity is
called doping. The added impurity is called
dopant.
A doped semiconductor, having higher
conductivity than pure intrinsic semiconductor,
is an extrinsic semiconductor.
There are two types of extrinsic
Fig. 1.25 : Semiconductors semiconductors, namely, n-type and p-type
At a temperature above absolute zero a semiconductors.
few electrons in the valence band have enough i. n-type semiconductor : n-type
thermal energy to jump through the small band semiconductor contains increased number of
gap and occupy higher energy conduction electrons in the conduction bond.
band. The conduction band, thus, becomes
An n-type semiconductor is obtained
partially filled and the valence band becomes
by adding group 15 element to intrinsic
partially empty.
semiconductor which belongs to group 14.
The electrons in conduction band are free
to move. When electric potential is applied to Can you tell ?
a semiconductor, it conducts a small amount Let a small quantity of
of electicity. phosphorus be doped into pure
Such a pure semiconductor material which silicon.
has a very low but finite electrical conductivity • Will the resulting material contain
is called intrinsic semiconductor. the same number of total number of
The electrical conductivity of a electrons as the original pure silicon ?
semiconductor increases with increasing • Will the material be electrically
temperature. This is because, the number neutral or charged ?
of electrons with sufficient energy so as
to get promoted to the conduction band Consider, for example, doping of Si
increases as temperature rises. Thus, at higher with phosphorus. Si has a crystal structure in
temperatures, there are more mobile electrons which each Si atom is linked tetrahedrally to
in the conduction band and more vacancies in four other Si atoms. When small quantity of
23
phosphorous is added to pure Si, the P atoms contain less number of valence electrons than
occupy some vacant sites in the lattice in place that of the pure semiconductor.
of Si atoms, as shown in Fig. 1.26. The overall Consider, for example, pure Si doped
crystal structure of Si remains unchanged. with boron. The B atoms occupy normal
positions of some of the Si atoms in the lattice
as shown in Fig. 1.28. Boron atom has only
three valence electrons. It does not have
enough electrons to form bonds with its four Si
neighbours.
Remember...
• Whether intrinsic or extrinsic
semiconductor, the material is
Fig. 1.27 : n-type and p-type semiconductor electrically neutral.
Because the charge carriers are the • An n-type semiconductor such as Si
increased number of electrons, Si or Ge doped doped with P has more electrons than
with group 15 elements such as P, As, Sb or Bi those needed for bonding and thus has
is an n-type semiconductor. electrons in the partially filled conduc-
tion band.
ii. p-type semiconductor : A p-type
• A p-type semiconductor such as Si
semiconductor is produced by doping a pure doped with B has the less electrons
semiconductor material (Si or Ge) with an than needed for bonding and thus has
impurity of group 13 elements. These elements vacancies (holes) in the valence band.
24
Because the charge carriers are holes ii. Paramagnetic solids : The substances with
which behave like positive charge, the Si or unpaired electrons are weakly attracted by
Ge doped with group 13 elements like B, Ga magnetic field. These substances are called
or In, is a p-type semiconductor. paramagnetic substances.
1.10 Magnetic properties of solids : Magnetic The spinning of unpaired electron gives
properties of solids can be understood easily rise to a magnetic moment. The substance
in terms of classical picture of electron. The is attracted by magnetic field because of
electrons spin about their own axis. The magnetic moment. It is important to understand
spinning electrons act like tiny magnets that these substances exhibit magnetism in
because their spinning action generates presence of external magnetic field only. They
induced magnetic field. lose magnetism when the external magnetic
field is removed.
If an orbital contains one electron,
the unbalanced spin exhibits magnetism. Oxygen, Cu2⊕, Fe3⊕, Cr3⊕ are some
However, when electrons are paired their examples of paramagnetic substances.
spin is balanced and no magnetic property is iii. Ferromagnetism : The substances
observed. On the basis of magnetic properties containing large number of unpaired electrons
solids are classified into three major are attracted strongly by magnetic field. These
classes : diamagnetic, paramagnetic and substances are said to be ferromagnetic.
ferromagnetic.
These substances can be permanently
i. Diamagnetic solids : The substances with magnetised. They retain magnetism even after
all electrons paired, are weakly repelled by the removal of external magnetic field.
magnetic fields. These substances are said to
be diamagnetic. Some example of ferromagnetic
substances are Fe, Co, Ni, Gd, CrO2.
Pairing of electrons balances the spins
and hence, cancels their magnetic moments.
N2, F2, NaCl, H2O and benzene are some
examples of diamagnetic substances.
Exercises
1. Choose the most correct answer.
i. Molecular solids are iii. In Frenkel defect
a. crystalline solids a. electrical neutrality of the
b. amorphous solids substance is changed.
c. ionic solids b. density of the substance is
d. metallic solids changed.
ii. Which of the follwong is n-type c. both cation and anion are missing
semiconductor? d. overall electical neutrality is
a. Pure Si preserved.
b. Si doped with As iv. In crystal lattice formed by bcc unit
cell the void volume is
c. Si doped with Ga
a. 68 % b. 74 %
d. Ge doped with In
c.32 % d. 26 %
25
v. The coordination number of atoms in having different electrical properties.
bcc crystal lattice is Classify them as insulator,
a. 2 b. 4 semiconductor or a metal.
c. 6 d. 8
vi. Which of the following is not
correct?
a. Four spheres are involved in the
formation of tetrahedral void.
b. The centres of spheres in octahedral
voids are at the apices of a regular iv. What is the unit cell?
tetrahedron. v. How does electrical conductivity
c. If the number of atoms is N the of a semiconductor change with
number of octahedral voids is 2N. temperature? Why?
d. If the number of atoms is N/2, the vi. The picture represents bands of
number of tetrahedral voids is N. MOs for Si. Label valence band,
conduction band and band gap.
vii. A compound forms hcp structure.
Number of octahedral and tetrhedral
voids in 0.5 mole of substance is
respectively
a. 3.011×1023, 6.022×1023
b. 6.022×1023, 3.011×1023
c. 4.011×1023, 2.011×1023
d. 6.011×1023, 12.022×1023 vii. A solid is hard, brittle and electrically
nonconductor. Its melt conducts
vii. Pb has fcc structure with edge length
electricity. What type of solid is it?
of unit cell 495 pm. Radius of Pb
atom is viii. Mention two properties that are
common to both hcp and ccp lattices.
a. 205 pm b. 185 pm
ix. Sketch a tetrahedral void.
c. 260 pm d. 175 pm
x. What are ferromagnetic substances?
2. Answer the following in one or two
sentences 3. Answer the following in brief.
i. What are the types of particles in i. What are valence band and
each of the four main classes of conduction band?
crystalline solids ? ii. Distinguish between ionic solids and
ii. Which of the three types of packing molecular solids.
used by metals makes the most iii. Calculate the number of atoms in fcc
efficient use of space and which unit cell.
makes the least efficient use?
iv. How are the spheres arranged in first
iii. The following pictures show layer of simple cubic close-packed
population of bands for materials structures? How are the successive
26
layers of spheres placed above this g/cm3. What is the nature of cubic unit
layer? cell? (fcc or ccp)
v. Calculate the packing efficiency of 10. An element has a bcc structure with
metal crystal that has simple cubic unit cell edge length of 288 pm. How
structure. many unit cells and number of atoms
are present in 200 g of the element?
vi. What are paramagnetic substances? (1.16×1024, 2.32×1024)
Give examples.
11. Distinguish with the help of diagrams
vii. What are the consequences of metal conductors, insulators and
Schottky defect? semiconductors from each other.
viii. Cesium chloride crystallizes in cubic 12. What are n-type semiconductors? Why
unit cell with Cl ions at the corners is the conductivity of doped n-type
and a Cs⊕ ion in the centre of the semiconductor higher than that of pure
semiconductor? Explain with diagram.
cube. How many CsCl molecules are
there in the unit cell? 13. Explain with diagram, Frenkel
defect. What are the conditions for its
ix. Cu crystallizes in fcc unit cell with formation? What is its effect on density
edge length of 495 pm. What is the and electrical neutrality of the crystal?
radius of Cu atom? 14. What is an impurity defect? What are
x. Obtain the relationship between its types? Explain the formation of
density of a substance and the edge vacancies through aliovalent impurity
length of unit cell. with example.
4. The density of iridium is 22.4 g/cm3. The
unit cell of iridium is fcc. Calculate the Activity :
radius of iridium atom. Molar mass of
• With the help of plastic balls,
iridium is 192.2 g/mol. (136 pm)
prepare models of
5. Aluminium crystallizes in cubic close
packed structure with unit cell edge 1. tetrahedral and octahedral
length of 353.6 pm. What is the radius of voids.
Al atom? How many unit cells are there 2. simple cubic, bcc and fcc unit
in 1.00 cm3 of Al? (125 pm, 2.26×1022) cells.
6. In an ionic crystalline solid atoms of
element Y form hcp lattice. The atoms 3. ccp and hcp lattices.
of element X occupy one third of • Draw structures of network of
tetrahedral voids. What is the formula carbon atoms in diamond and
of the compound ? (X2Y3) graphite. Discuss with reference to
7. How are tetrahedral and octahedral the following points :
voids formed?
1. Are the outermost electrons of
8. Third layer of spheres is added to second carbons in diamond localized or
layer so as to form hcp or ccp structure. delocalized ?
What is the difference between the
addition of third layer to form these 2. Is the energy gap between BMOs
hexagonal close-packed structures? and AMOs in diamond expected
9. An element with molar mass 27 g/mol to be large or small ?
forms cubic unit cell with edge length of
405 pm. If density of the element is 2.7
27
2. SOLUTIONS
2.1 Introduction combination of these three states of their
You are familiar with mixtures. The components. This gives rise to nine types of
mixture is a combination of two or more solutions depending on the states of solute
substances. Air is a mixture of gases, rock and solvent. These are summarised in table
is a mixture of two or more minerals and so 2.1.
forth. Table 2.1 : Types of solutions
Recall that the mixtures are (a) No. State of State of Some examples
homogeneous in which mixing of components solute solvent
is uniform or (b) heterogeneous which have 1 Solid Liquid Sea water, benzoic
nonuniform mixing of components. acid in benzene,
We studied in standard XI, that sugar in water
homogeneous mixtures are classified 2 Solid Solid Metal alloys such
according to the size of their constituent as brass, bronze.
particles as colloids or as true solutions. In 3 Solid Gas Iodine in air
this chapter we deal with the properties of 4 Liquid Liquid Gasoline, ethanol
homogeneous mixtures especially of true in water.
solutions. 5 Liquid Solid Amalgams of
Can you recall ? mercury with
The size of particles of colloids metals as mercury
and those of true solutions. in silver
6 Liquid Gas Chloroform in
The solutions are commonly found nitrogen
in all life processes. The body fluids are 7 Gas Liquid Carbonated water
solutions. The solutions are also important for (CO2 in water),
industrial processes, and many other areas. oxygen in water.
8 Gas Solid H2 in palladium
Can you recall ? 9 Gas Gas Air (O2, N2, Ar and
The terms solute and solvent. other gases)
Our focus, in this chapter, will be
The solution is a homogeneous
on the solution of solid in liquid with some
mixture of two or more pure substances. A
attention to a solution of gas in liquid. The
true solution consists of a solvent and one
solvent in most of the cases will be water.
or more solutes. We explore the properties
of binary true solutions containing only one Can you recall ?
solute. The different units used to express
2.2 Types of solutions the concentrations of solutions.
We generally think that a solution is a 2.3 Capacity of solution to dissolve solute
either solid dissolved in liquid or a mixture of
Chemists need to know the capacity of
two liquids. There are other types of solutions
solutions to dissolve a solute. Suppose that a
as well. The solute and the solvent may be
solute is added to a solvent. It dissolves readily
in any of three states namely, solid, liquid
at first. The dissolution then slows down as
or gas. The solutions thus may involve any
more solute is added. If we continue the
28
addition of solute, the dissolution stops. The and ion-ion attractions between Na⊕ and Cl
solution at this point is said to be saturated. ions are comparable.
A dynamic equilibrium can be reached where
the number of solute molecules leaving the Can you recall ?
crystal to pass into solution is equal to the The types of force between
number returning from the solution to the molecules.
crystal. Thus,
Nonpolar organic compounds like
dissolution cholesterol dissolves in nonpolar solvent such
Solute + solvent crystallization
Solution
as benzene.
A saturated solution contains
maximum amount of solute dissolved Can you tell ?
in a given amount of solvent at a given Why naphthalene dissolves in
temperature. A solution containing greater benzene but not in water?
than the equilibrium amount of solute is said
Sugar dissolves in water! The
to be supersaturated solution. Such solutions
dissolution of sugar in water is due to
are unstable. The precipitation occurs by the
intermolecular hydrogen bonding between
addition of a tiny crystal of solute and the
sugar and water.
supersaturated solution changes to saturated
solution. ii. Effect of temperatute on solubility :
How solubility of substance changes with
2.4 Solubility : The solubility of a solute is its
temperature depends on enthalpy of solution.
amount per unit volume of saturated solution
Many solids, for example KCl, dissolve in
at a specific temperature. The solubility of
water by endothermic process, that is, with
a solute is its maximum concentration and
the absorption of heat. When temperature is
expressed in the concentration units mol L-1.
increased by adding heat to the system, the
2.4.1 Factors affecting solubility : The extent solubility of substance increases according to
to which a substance dissolves in a solvent the Le-Chatelier principle. Addition of heat
varies greatly with different substances. It causes a stress on the saturated solution. This
depends on the nature of solute and solvent, stress favours endothermic process.
temperature and pressure.
Can you recall ?
i. Nature of solute and solvent : Generally the
compounds with similar chemical character Le-Chatelier principle, exothermic
are more readily soluble in each other and endothermic processes.
than those with entirely different chemical
characters. The saying that ‘like dissolves On the other hand, when the substance
like’ guides to predict the solubility of a solute dissolves in water by an exothermic process
in a given solvent. its solubility decreases with an increase of
temperature. The substances such as CaCl2
Thus, substances having similar and Li2SO4.H2O dissolve in water releasing
intermolecular forces are likely to be soluble heat.
in each other. Generally polar solutes
dissolve in polar solvents. This is because Can you tell ?
in these, solute-solute, solute-solvent and Anhydrous sodium sulphate
solvent-solvent interactions are all of similar dissolves in water with the
magnitude. For example, NaCl dissolves evolution of heat. What is the effect
in water. The strong ion-dipole interactions of temperature on its solubility ?
of Na⊕ and Cl ions with water molecules,
hydrogen bonding between water molecules
29
It is important to understand that there iii. Effect of pressure on solubility
is no direct correlation between solubility and
Pressure has no effect on the
exothermicity or endothermicity. For example,
solubilities of solids and liquids as they are
dissolution of CaCl2 in water is exothermic and
incompressible. However pressure greatly
that of NH4NO3 is endothermic. The solubility
affects solubility of gases in liquids. The
of these increases with the temperature.
solubility of gases increases with increasing
Figure 2.1 shows the result of pressure. The quantitative relationship between
experimental determination of solubilities gas solubility in a liquid and pressure is given
of some ionic solids in water at various by Henry’s law.
temperatures. Following are some
Henry’s law: It states that the solubility of a
experimental observations from Fig 2.1
gas in a liquid is directly proportional to the
pressure of the gas over the solution. Thus,
S ∝ P or S = KHP (2.1)
where, S is the solubility of the gas in
mol L-1, P is the pressure of the gas in bar
over the solution. KH, the proportionality
constant is called Henry’s law constant.
S mol L-1
Units of KH : KH = = bar
P
= mol L-1 bar-1
30
2.5 Vapour pressure of solutions of liquids
Do you know ? in liquids : Consider a binary solution of two
O2 gas has very low solubility in volatile liquids A1 and A2. When the solution
water. However, its solubility in is placed in a closed container, both the
blood is exceedingly high. This is because liquids vaporize. Eventually an equilibrium
of binding of O2 molecule to haemoglobin is established between vapor and liquid
present in blood. phases. Both the components are present in
Hb + 4O2 Hb(O2)4 the vapour phase. The partial pressure of the
components are related to their mole fractions
in the solution. This realationship is given by
Problem 2.1 : The solubility of N2 gas in Raoult’s law.
water at 25 0C and 1 bar is 6.85 × 10-4 mol
2.5.1 Raoult’s law : It states that the partial
L-1. Calculate (a) Henry’s law constant
vapour pressure of any volatile component of
(b) molarity of N2 gas dissolved in water
a solution is equal to the vapour pressure of
under atmospheric conditions when partial
pressure of N2 in atmosphere is 0.75 bar. the pure component multiplied by its mole
fraction in the solution.
Solution :
Suppose that for a binary solution
S 6.85 × 10-4 mol dm-3 of two volatile liquids A1 and A2, P1 and P2
a. KH = =
P 1 bar are their partial vapour pressures and x1 and
= 6.85 × 10-4 mol L-1 bar-1 x2 are their mole fractions in solution. Then
according to Raoult’s law,
b. S = KHP = 6.85 × 10-4 mol L-1 bar-1
we write P1 = x1P10 and P2 = x2P20 (2.2)
× 0.75 bar
where P10 and P20 are vapour pressures of
= 5.138 × 10 mol L-
-4 1
pure liquids A1 and A2, respectively.
According to Dalton’s law of partial
Problem 2.2 : The Henry’s law constant pressures, the total pressure P above the
of methyl bromide (CH3Br), is 0.159 mol solution is,
L-1 bar-1 at 250C. What is the solubility of P = P1 + P2
methyl bromide in water at 250C and at
= P10x1 + P20x2 (2.3)
pressure of 130 mmHg?
Since x1 = 1- x2, the Eq. (2.2) can also be
Solution : written as
According to Henry’s law P = P10 (1-x2) + P20x2
S = K HP = P10 - P10x2 + P20x2
1. KH = 0.159 mol L-1 bar-1 = (P20 - P10) x2 + P10 (2.4)
1 Because P10 and P20 are constants, a plot
2. P = 130 mm Hg ×
760 mm Hg/atm of P versus x2 is a straight line as shown in
= 0.171 atm × 1.013 bar/atm the Fig 2.2. The figure also shows the plots
of P1 versus x1 and P2 versus x2 according
= 0.173 bar
to the equations 2.2. These are straight lines
Hence, S = 0.159 mol L-1 bar-1 × 0.173 bar passing through origin.
= 0.271 M
31
Ideal solution 150
600 - 450 = 150 = 250x2 or x2 = = 0.6
PTotal = P1 + P2 P20 250
Vapour Pressure x1 = 1-x2 = 1-0.6 = 0.4
P10 P2 ii. Compositions of A and B in vapour are y1
and y2 respectively.
P1 P1 = y1P and P2 = y2P, P1 = P10x1 and
P2 = P20x2
x1 = 1 Mole fraction x2 = 0
x2 P P 0x 450 mm Hg × 0.4
x1 = 0 x2 = 1 y1 = 1 = 1 1 =
P P 600 mmHg
Fig. 2.2 : Variation of vapour pressure with
= 0.3
mole fraction of solute
i. For P10 versus x2 straight line, y2 = 1 - y1 = 1 - 0.3 = 0.7
P = P10 at x2 = 0 and P = P20 at x2 = 1 2.5.2 Ideal and nonideal solutions
ii. For P1 versus x1 straight line, 1. Ideal solutions
P1 = 0 at x1 = 0 and P1 = P10, at x1 = 1 i. Ideal solutions obey Raoult’s law over
entire range of concentrations.
iii. For P2 versus x2 straight line,
ii. No heat is evolved or absorbed when two
P2 = 0 at x2 = 0 and P2 = P20 at x2 = 1
components forming an ideal solution are
Composition of vapour phase : mixed. Thus, the enthalpy of mixing is
The composition of vapour in equilibrium zero. ∆mixH = 0
with the solution can be determined by iii. There is no volume change when two
Dalton’s law of partial pressures. components forming an ideal solution are
If we take y1 and y2 as the mole mixed. Thus volume of an ideal solution
fractions of two components in the vapour, is equal to the sum of volumes of two
then P1 = y1P and P2 = y2P components taken for mixing.
32
iii. Deviation from the Raoult's law : These vapour pressures of such solutions are lower
solutions show two types of deviation than those of pure components as shown in
from the Raoult's law. Fig. 2.4. The solutions of phenol and aniline,
A. Positive deviations from Raoult’s law - chloroform and acetone exhibit negative
deviations from the Raoult’s law.
Vapour Pressure 2.6 Colligative properties of nonelectrolyte
of solution
solutions : The physical properties of solutions
that depend on the number of solute particles
in solutions and not on their nature are called
Vapour Pressure
34
where n1 and n2 are the moles of solvent and
Problem 2.5 : The vapour pressure of
solute respectively, in the solution.
pure benzene (molar mass 78 g/mol) at
We are concerned only with dilute a certain temperature is 640 mm Hg. A
solutions hence n1 >> n2 and n1+n2 ≈ n1. The nonvolatile solute of mass 2.315 g is added
mole fraction x2 is then given by to 49 g of benzene. The vapour pressure
n2 of the solution is 600 mm Hg. What is the
x2 = n and
1 molar mass of solute?
∆P = n2 (2.9)
0
P 1 - P1 W2 × M1
P
0 n1 0 =
1
P1 M2 × W1
Suppose that we prepare a solution
by dissolving W2 g of a solute in W1 g of 0
P1 = 640 mm Hg, P1 = 600 mm Hg,
solvent. The moles of solute and solvent in
W1 = 49 g, W2 = 2.315 g
the solution are then,
640 mm Hg- 600 mm Hg
W2 W1 Hence, 640 mm Hg
n2 = M and n1 = M (2.10) 2.315 g - 78 g/mol
2 1 =
where M1 and M2 are molar masses of 40 g × M2
solvent and solute, respectively. Substitution 40 mm Hg 2.315 g - 78 g/mol
of Eq. (2.10) into Eq. (2.9) yields 640 mm Hg = 40 g × M 2
35
2.8.1 Boiling point elevation as a consequence higher temperature to cause it to boil than
of vapour pressure lowering : To understand the pure solvent.
the elevation of boiling point, let us compare 2.8.2 Boiling point elevation and
the vapour pressures of solution and those of
concentration of solute : The boiling point
pure solvent. The vapour pressures of solution
elevation is directly proportional to the
and of pure solvent are plotted as a function
molality of the solution. Thus,
of temperature as shown in Fig. 2.6.
∆Tb ∝ m or ∆Tb = Kbm (2.13)
where m is the molality of solution. The
proportionality constant Kb is called boiling
A point elevation constant or molal elevation
760 mm C
constant or ebullioscopic constant.
Vapour Pressure
Solvent If m = 1, ∆Tb = Kb
Thus, ebullioscopic constant is the boiling
B
D
Solution point elevation produced by 1 molal solution.
0
Tb Tb ∆T K
Temperature Units of Kb : Kb = m b = mol kg-1 =K kg mol-1
Fig. 2.6 : Vapour pressure-temperature of pure
solvent and solution Remember...
As stated in section 2.7 that at any Kb and ∆Tb are the differences
temperature the vapour pressure of solution between two temperatures. Hence,
is lower than that of pure solvent. Hence, the their values will be the same in K or in 0C.
vapour pressure-temperature curve of solution We are dealing with the systems whose
(CD) lies below that of solvent (AB). The temperature is not constant. Therefore, we
difference between the two vapour pressures cannot express the concentration of solution
increases as temperature and vapour pressure in molarity which changes with temperature
increase as predicted by the equation whereas molality is temperature independent.
∆P = x2 P10 Therefore the concentration of solute is
The intersection of the curve CD with expressed in mol/kg (molality) rather than
the line corresponding to 760 mm is the boiling mol/L (molarity).
point of solution. The similar intersection of 2.8.3 Molar mass of solute from boiling
the curve AB is the boiling point of pure point elevation
solvent. It is clear from the figure that the
boiling point (Tb) of the solution is higher The Eq. (2.13) is ∆Tb = Kbm
than that of pure solvent (Tb0) Suppose we prepare a solution by
At the boiling point of a liquid, its dissolving W2 g of solute in W1 g of solvent.
vapour pressure is equal to 1 atm. In order to W
Moles of solute in W1 g of solvent = 2
36
Substitution of this value of m in Eq. (2.13) molar mass of S
gives = atomic mass of S = 255.1
32
1000 W2 = 7.92 ≈ 8
∆Tb = Kb M W
2 1
Hence, The molecular formula would be S8 in CS2
1000 KbW2
M2 = (2.15) 2.9 Depression in freezing point
∆TbW1
Recall that freezing point of a liquid
Problem 2.6 : The normal boiling point of is the temperature at which liquid and solid
ethyl acetate is 77.06 0C. A solution of 50 are in equilibrium and the two phases have
g of a nonvolatile solute in 150 g of ethyl the same vapour pressure.
acetate boils at 84.27 0C. Evaluate the The general experimental observation
molar mass of solute if Kb for ethyl acetate is that the freezing point of a solvent is
is 2.77 0C kg mol-1. lowered by dissolving a nonvolatile solute into
Solution : it. Thus, freezing point of solution containing
1000 KbW2 a nonvolatile solute is lower than that of pure
M2 = solvent.
∆TbW1
W2 = 50 g, W1 = 150 g, If Tf 0 is the freezing point of pure
solvent and Tf that of a solution in which
∆Tb = Tb-T0b = 84.27 0C - 77.06 0C nonovolatile solute is dissolved, Tf 0 > Tf. The
= 7.210C = 7.21 K difference between the freezing point of pure
solvent and that of the solution is depression
Kb = 2.77 0C kg mol-1 = 2.77 K kg mol-1
in freezing point.
Substitution of these in above equation
Thus ∆Tf = T f0 - Tf (2.16)
1000 g Kg-1 × 2.77 K kg mol-1 × 50 g
M2 = 2.9.1 Freezing point depression as a
7.21 K × 150 g
= 128 g mol -1 consequence of vapour pressure lowering
The effect of dissolution of a
Problem 2.7 : 3.795 g of sulphur is dissolved nonvolatile solute into a solvent on freezing
in 100 g of carbon disulfide. This solution point of solvent can be understood in terms
boils at 319.81 K. What is the molecular of the vapour pressure lowering.
formula of sulphur in solution? The boiling
point of the solvent is 319.45 K.
t
(Given that Kb for CS2 = 2.42 K kg mol-1 and lv en D
so F
atomic mass of S = 32 u id
qu
1000 KbW2 B Li n
lu tio
M2 =
Vapour Pressure
∆TbW1 C So
E
t
W1 = 100 g, W2 = 3.795 g
lven
so
37
Consider the vapoure pressure- ∆Tf ∝ m or ∆Tf = Kfm (2.17)
temperature diagram as shown in Fig. 2.7. The proportionality constant Kf is
The diagram consists of three curves. AB is called freezing point depression constant or
the vapour pressure curve of solid solvent cryoscopic constant.
while CD is the vapour pressure curve of
pure liquid solvent. EF is the vapour pressure If m = 1, ∆Tf = Kf . The cryoscopic
curve of solution that always lies below the constant thus is the depression in freezing
pure solvent. point produced by 1 molal solution of a
nonvolatile solute.
It is important to note that solute does
not dissolve in solid solvent. ∆Tf K or 0C
Unit of Kf : m = mol kg-1
The curves AB and CD intersect at = K kg mol-1 or 0C kg mol-1
point B where solid and liquid phases of pure
solvent are in equilibrium. The two phases 2.9.3 Molar mass of solute from freezing
have the same vapour pressure at B. The point depression
temperature corresponding to B is the freezing Refer to Eq. (2.17), ∆Tf = Kfm
point of solvent ( T f0).
The molality m of the solution is given by
Similarly at E, the point of intersection Eq. (2.14) as
of EF and AB, the solid solvent and solution 1000W2
are in equilibrium. They have the same vapour m=
M2W1
pressure at E. The temperature corresponding Substitution of Eq. (2.14) into Eq. (2.17) gives
to E is the freezing point of solution, Tf . 1000W
∆Tf = Kf M W 2
It is clear from the figure that freezing 2 1
point of solution Tf is lower than that of pure
solvent Tf0. It is obvious because the vapour 1000KfW2
pressure curve of solution lies below that of Hence, M2 = (2.18)
∆Tf W1
solvent.
Why freezing point of solvent is lowered Problem 2.8 : 1.02 g of urea when
by dissolving a nonvolatile solute into it? dissolved in 98.5 g of certain solvent
At the freezing point of a pure liquid the decreases its freezing point by 0.211K.
attractive forces among molecules are large 1.609 g of unknown compound when
enough to cause the change of phase from dissolved in 86 g of the same solvent
liquid to solid. depresses the freezing point by 0.34 K.
Calculate the molar mass of the unknown
In a solution, the solvent molecules are
compound.
separated from each other because of solute
molecules. Thus, the separation of solvent (Molar mass of urea = 60 g mol-1)
molecules in solution is more than that in Solution :
pure solvent. This results in decreasing the
attractive forces between solvent molecules. Urea Unknown compound
Consequently, the temperature of the solution W2 = 1.02 g W2' = 1.609 g
is lowered below the freezing point of solvent
W1 = 98.5 g W1' = 86 g
to cause the phase change.
2.9.2 Freezing point depression and ∆Tf = 0.211 K ∆Tf ' = 0.34 K
concentration of solute : As varified M2 = 60 gmol-1 M2' =?
experimentally for a dilute solution the M × ∆T × W1
freezing point depression (∆Tf) is directly 1000Kf= 2 W f
2
proportional to the molality of solution. Thus,
38
the vapour pressure of solvent is greater than
M2' × ∆Tf' × W1' that of solution. The net spontaneous flow of
1000Kf = W2' solvent molecules into the solution or from
= 60 g mol × 0.211 K × 98.5 g more dilute solution to more concentrated
-1
39
As a result, some of the solvent passes ii. Hypertonic and hypotonic solutions :
through the membrane into the solution. It If two solutions have unequal osmotic
causes the liquid level in the tube to rise. The pressures, the more concentrated solution
liquid column in the tube creates hydrostatic with higher osmotic pressure is said to be
pressure that pushes the solvent back through hypertonic solution.
the membrane into the container. The column
of liquid in the tube continues to rise and The more dilute solution exhibiting
eventually stops rising. At this stage lower osmotic pressure is said to be hypotonic
hydrostatic pressure developed is sufficient solution.
to force solvent molecules back through the For example, if osmotic pressure of
membrane into the container at the same rate sucrose solution is higher than that of urea
they enter the solution. solution, the sucrose solution is hypertonic
An equilibrium is thus established to urea solution, and the urea solution is
where rates of forward and reverse passages hypotonic to sucrose solution.
are equal. The height of liquid column in the 2.10.4 Osmotic pressure and concentration
tube remains constant. This implies that the of solution
hydrostatic pressure has stopped osmosis.
For very dilute solutions, the osmotic
pressure follows the equation,
Remember...
n RT
It is important to note that π= 2 (2.19)
osmotic pressure is not the pressure V
where V is the volume of a solution in dm3
produced by a solution. It exists only when
containing n2 moles of nonvolatile solute. R
the solution is separated from the solvent by
is the gas constant equal to 0.08206 dm3 atm
a suitable kind of semipermeable membrane.
K-1mol-1 and π is osmotic pressure in atm.
The hydrostatic pressure that stops The term n2/V is concentration in
osmosis is an osmotic pressure (π) of the molarity (M). Eq. (2.19) thus can be written
solution. The hydrostatic pressure is equal to as
hρg where h is the height of liquid column π = MRT (2.20)
in the tube, ρ is density of solution and g is
Note that the solute concentration
acceleration due to gravity.
is expressed in molarity while calculating
2.10.3 Isotonic, hypertonic and hypotonic osmotic pressure rather than molality. The
solutions reason is that osmotic pressure measurements
i. Isotonic solutions : Two or more solutions are made at a specific constant temperature.
having the same osmotic pressure are said to It is not necessary to express concentration in
be isotonic solutions. a temperature independent unit like molality.
For example, 0.1 M urea solution and 2.10.5 Molar mass of solute from osmotic
0.1 M sucrose solution are isotonic because pressure
their osmotic pressures are equal. Such n RT
Consider Eq. (2.19) π= 2
solutions have the same molar concentrations V
but different concentrations in g/L. If these If the mass of solute in V litres of
solutions are separated by a semipermeable solution is W2 and its molar mass is M2 then
membrane, there is no flow of solvent in n2 = W2/M2. With this value of n2, Eq. (2.19)
either direction. becomes
W2RT W2RT
π= or M2 = (2.21)
M2V πV
40
Remember... W2 = 0.822 g
Osmotic pressure is R = 0.08205 dm3 atm K-1 mol-1
much larger and therefore more
precisely measurable property than other T = 298K
colligative properties. It is therefore, 149 (mmHg)
useful to determine molar masses of π = 149 (mmHg) = 760 (mmHg/atm)
very expensive substances and of the = 0.196 atm
substances that can be prepared in small V = 300 mL = 0.3dm3
quantities.
0.822 g × 0.08205 L atm K-1 mol-1 × 298K
M2 = 0.196 atm × 0.3dm3
2.10.6 Reverse osmosis : As mentioned
= 342 g mol-1
earlier osmosis is a flow of solvent through
a semipermeable membrane into the solution.
2.11 Collgative properties of electrolytes
The direction of osmosis can be
reversed by applying a pressure larger than Can you recall ?
the osmotic pressure. Electrolytes and nonelectrolytes.
41
dissolved in water whereas nonelctrolytes do Mtheoretical
= (2.24)
not. Stated differently, one formula unit of Mobserved
electrolyte dissolved in water produces two or Thus, i is equal to 1 for nonelctrolyte,
more ions. Consequently number of particles 2 for KNO3 and NaCl, 3 for Na2SO4 and
in solution increases. CaCl2 and so forth. The colligative properties
The colligative properties of of these electrolytes are, therefore, twice and
electrolyte solutions are thus higher than the thrice respectively as those of noneletrolytes
nonelectrolyte solutions. of the same concentration.
The foregoing arguments are valid
If 1.25 m sucrose solution has ∆Tf of 2.320C, only for infinitely dilute solutions where the
what will be the expected value of ∆Tf for dissociation of electrolytes is complete.
1.25m CaCl2 solution?
In reality especially at high
For example, when NaCl is dissolved concentrations, the colligative properties of
in water, it produces two ions, Na⊕ and strong electrolytes and their i values are
Cl , whereas sucrose does not dissociate. It usually smaller than expected. The reason is
is expected then that the colligative property that the electrostatic forces between oppositely
of 0.1 m NaCl is twice that of 0.1 m sucrose charged ions bring about the formation of ion
solution. pairs. Each ion pair consists of one or more
cations and one or more anions held together
2.11.1 van’t Hoff factor(i) by electrostatic attractive forces. This results
To obtain the colligative properties in decrease in the number of particles in
of electrolyte solutions by using relations solution causing reduction in the expected i
for nonelectrolytes, van’t Hoff suggested a value and colligative properties.
factor i. It is defined as the ratio of colligative 2.11.2 Modification of expressions of
property of a solution of electrolyte divided colligative properties : The expressions of
by the collogative property of nonelectrlyte colligative properties mentioned earlier for
solution of the same concentration. Thus nonelectrolytes are to be modified so as to
i= colligative property of elctrolyte solution make them applicable for electrolyte solutions.
colligative property of nonelectrolyte solution
The modified equations are
of the same concentration
WM
(∆T ) (∆T ) (∆P) (π) i. ∆P = i P10x2 = i 2 1
= (∆T f = (∆T b) = = (π) M 2 W1
)
f 0 b 0 (∆P)0 0
(2.22)
1000 KbW2
where quantities without subscript ii. ∆Tb = iKbm = i
M2W1
refer to electrolytes and those with subscript
to nonelectrolytes. 1000 KfW2
iii. ∆Tf = i Kf m = i
The van’t Hoff factor i is also defined M2W1
in an alternative but exactly equivalent
manner as W2RT
actual moles of particles in solution after
iv. π = i MRT = i
M2V
dissociation
i= moles of formula units dissolved in solution 2.11.3 van’t Hoff factor and degree of
(2.23) dissociation : A discussion of colligative
properties of electrolytes in the preceeding
formula mass of substance sections is based on the fact that the
= observed molar mass of substance elctrolytes are completely dissociated in their
aqueous solutions. This is approximately true
42
for solutions of strong electrolytes and not for
weak electrolytes that dissociate to a small (∆Tf)0= 1.86 K kg mol-1 × 0.2 mol kg-1
extent. The weak electrolytes involve the = 0.372 K
concept of degree of dissociation (∝), that
(∆Tf) 0.680 K
changes the van’t Hoff factor. i= = 0.372 K = 1.83
(∆Tf)0
Relation between van’t Hoff factor and
degree of dissociation
(π)0 = MRT
Consider an elctrolyte AxBy that n
dissociates in aqueous solution as = V2 RT
AxBy x Ay⊕ + y Bz (2.25) =
0.2 mol × 0.08205 L atm.mol-1K-1 × 273K
Initially : 1 mol 0 0 1L
= 4.48 atm
At equilibrium :
(1-∝) mol (x ∝ mol) (y ∝) mol π
i = 1.83 = π
If ∝ is the degree of dissociation of 0
43
Problem 2.13 : Which of following Arrange the following solutions in order
of increasing osmotic pressure. Assume
solutions will have maximum boiling point
complete ionization. a) 0.5m Li2SO4 b)
elevation and which have minimum freezing
0.5m KCl c) 0.5m Al2(SO4)3 d) 0.1m BaCl2.
point depression assuming the complete
dissociation? (a) 0.1 m KCl (b) 0.05 m NaCl
(c) 1m AlPO4 (d) 0.1 m MgSO4 Problem 2.14 : Assuming complete
dissociation, calculate the molality of an
Solution : Boiling point elevation and aqueous solution of KBr whose freezing
freezing point depression are colligative point is -2.950C. Kf for water is 1.86 K kg
properties that depend on number of particles mol-1
in solution. The solution having more Solution :
number of particles will have large boiling KBr = K⊕ + Br ,
point elevation and that having less number
i=
of particles would show minimum freezing
point depression. moles of particles after dissociation
moles of particles dissolved
(a) KCl K⊕ + Cl Total particles in
2
0.1m 0.1m 0.1m solution = 0.2 mol = =2
1
(b) NaCl Na⊕ + Cl Total particles in ∆Tf = iKfm
0.05m 0.05m 0.05m solution = 0.1 mol
∆Tf = 0 0C- (-2.95 0C) = 2.95 0C
(c) AlPO4 Al3⊕ + PO43 Total particles in
1m 1m 1m solution = 2.0mol ∆Tf 2.95 K
m = iK =
(d) MgSO4 Mg2⊕ + SO42 Total particles in f
2 × 1.86 K kg mol-1
0.1m 0.1m 0.1m solution = 0.2mole = 0.793 mol kg-1
AlPO4 solution contains highest
moles and hence highest number particles
and in turn, the maximum ∆Tb. NaCl solution
has minimum moles and particles. It has
minimum ∆Tf.
Exercises
1. Choose the most correct option. a. molarity b. molality
i. The vapour pressure of a solution c. mole fraction d. mass percent
containing 2 moles of a solute in 2 iv. Ebullioscopic constant is the boiling
moles of water (vapour pressure of point elevation when the concentration
pure water = 24 mm Hg) is of solution is
a. 24 mm Hg b. 32 mm Hg a. 1m b. 1M c. 1 mass%
c. 48 mm Hg d. 12 mm Hg d. 1 mole fraction of solute.
ii. The colligative property of a solution is v. Cryoscopic constant depends on
a. vapour pressure b. boiling point a. nature of solvent
c. osmotic pressure d. freezing point b. nature of solute
iii. In calculating osmotic pressure the c. nature of solution
concentration of solute is expressed in d. number of solvent molecules
44
vi. Identify the correct statement xii. Which of the following statement is
a. vapour pressure of solution is higher NOT correct for 0.1 M urea solution
than that of pure solvent. and 0.05 M sucrose solution?
b. boiling point of solvent is lower than a. osmotic pressure exhibited by urea
that of solution solution is higher than that exhibited
c. osmotic pressure of solution is lower by sucrose solution
than that of solvent b. urea solution is hypertonic to sucrose
d. osmosis is a colligative property. solution
vii. A living cell contains a solution which c. they are isotonic solutions
is isotonic with 0.3 M sugar solution. d. sucrose solution is hypotonic to urea
What osmotic pressure develops when solution
the cell is placed in 0.1 M KCl solution 2. Answer the following in one or two
at body temperature? sentences
a. 5.08 atm b. 2.54 atm i. What is osmotic pressure?
c. 4.92 atm d. 2.46 atm ii. A solution concentration is expressed
viii. The osmotic pressure of blood is 7.65 in molarity and not in molality while
atm at 310 K. An aqueous solution of considering osmotic pressure. Why?
glucose isotonic with blood has the iii. Write the equation relating boiling
percentage (by volume) point elevation to the concentration
a. 5.41 % b. 3.54 % of solution.
c. 4.53 % d. 53.4 % iv. A 0.1 m solution of K2SO4 in water
ix. Vapour pressure of a solution is has freezing point of -4.3 0C. What is
a. directly proportional to the mole the value of van’t Hoff factor if Kf for
fraction of the solute water is 1.86 K kg mol-1?
b. inversely proportional to the mole v. What is van’t Hoff factor?
fraction of the solute vi. How is van’t Hoff factor related to
c. inversely proportional to the mole degree of ionization?
fraction of the solvent vii. Which of the following solutions will
d. directly proportional to the mole have higher freezing point depression
fraction of the solvent and why ?
x. Pressure cooker reduces cooking time a. 0.1 m NaCl b. 0.05 m Al2(SO4)3
for food because
viii. State Raoult’s law for a solution
a. boiling point of water involved in containing a nonvolatile solute
cooking is increased
ix. What is the effect on the boiling point
b. heat is more evenly distributed in the
of water if 1 mole of methyl alcohol
cooking space
is added to 1 dm3 of water? Why?
c. the higher pressure inside the cooker
crushes the food material x. Which of the four colligative
d. cooking involves chemical changes properties is most often used for
helped by a rise in temperature. molecular mass determination? Why?
xi. Henry’s law constant for a gas CH3Br 3. Answer the following.
is 0.159 moldm-3 atm at 250 0C. What i. How vapour pressure lowering is
is the solubility of CH3Br in water at 25 related to a rise in boiling point of
0
C and a partial pressure of 0.164 atm? solution?
a. 0.0159 mol L-1 b. 0.164 mol L-1 ii. What are isotonic and hypertonic
c. 0.026 M d. 0.042 M solutions?
45
iii. A solvent and its solution containing 9. The vapour pressure of water at 20 0C is
a nonvolatile solute are separated by 17 mm Hg. What is the vapour pressure
a semipermable membrane. Does the of solution containing 2.8 g urea in 50 g of
flow of solvent occur in both directions? water? (16.17 mm Hg)
Comment giving reason. 10. A 5% aqueous solution (by mass) of cane
iv. The osmotic pressure of CaCl2 and urea sugar (molar mass 342 g/mol) has freezing
solutions of the same concentration at point of 271K. Calculate the freezing point
the same temperature are respectively of 5% aqueous glucose solution. (269.06
0.605 atm and 0.245 atm. Calculate K)
van’t Hoff factor for CaCl2 11. A solution of citric acid C6H8O7 in 50 g
of acetic acid has a boiling point elevation
v. Explain reverse osmosis. of 1.76 K. If Kb for acetic acid is 3.07 K
vi. How molar mass of a solute is kg mol-1, what is the molality of solution?
determined by osmotic pressure (0.573 m)
measurement? 12. An aqueous solution of a certain organic
vii. Why vapour pressure of a solvent is compound has a density of 1.063 gmL-1,
lowered by dissolving a nonvolatile an osmotic pressure of 12.16 atm at 250C
and a freezing point of -1.030C. What is
solute into it?
the molar mass of the compound? (334 g/
viii. Using Raoult’s law, how will you show mol)
0
that ∆P = P1 x2 ? Where x2 is the mole 13. A mixture of benzene and toluene contains
0
fraction of solute in the solution and P1 30% by mass of toluene. At 300C, vapour
vapour pressure of pure solvent. pressure of pure toluene is 36.7 mm Hg
ix. While considering boiling point and that of pure benzene is 118.2 mm Hg.
elevation and freezing point depression Assuming that the two liquids form ideal
a solution concentration is expressed in solutions, calculate the total pressure and
molality and not in molarity. Why? partial pressure of each constituent above
the solution at 300C. (86.7 mm, P = 96.5
4. Derive the relationship between degree mm)
of dissociation of an electrolyte and van’t
14. At 25 0C a 0.1 molal solution of CH3COOH
Hoff factor.
is 1.35 % dissociated in an aqueous
5. What is effect of temperature on solubility solution. Calculate freezing point and
of solids in water? Give examples. osmotic pressure of the solution assuming
6. Obtain the relationship between freezing molality and molarity to be identical.
point depression of a solution containing (-0.189 0C, 2.48 atm)
nonvolatile nonelctrolyte and its molar 15. A 0.15 m aqueous solution of KCl freezes
mass. at -0.510 0C. Calculate i and osmotic
pressure at 0 0C. Assume volume of
7. Explain with diagram the boiling point
solution equal to that of water (1.83, 6.15
elevation in terms of vapour pressure
atm)
lowering.
8. Fish generally needs O2 concentration in
water at least 3.8 mg/L for survival. What Activity :
partial pressure of O2 above the water is Boil about 100 mL of water
needed for the survival of fish? Given the in a beaker. Add about 10 to 15 g of
solubility of O2 in water at 00C and 1 atm
salt (NaCl) to the boiling water. Write
partial pressure is 2.2 × 10-3 mol/L (0.054
your observations and conclusions.
atm)
46
3. IONIC EQUILIBRIA
47
3.3.1 Arrhenius theory of acids and bases Base : Base is a substance that accepts a
According to this theory acids and bases are proton (H⊕) from another substance.
defined as follows : For example :
Acid : Acid is a substance which contains HCl + NH3 NH4⊕ + Cl
hydrogen and gives rise to H⊕ ions in aqueous Acid1 Base2 Acid2 Base1
solution. For example :
In the above reaction HCl and NH4⊕ are
water ⊕
HCl (aq) H (aq) + Cl (aq) proton donors and act as acids. The NH3 and
water
CH3COOH(aq) CH3COO (aq)+ H⊕(aq) Cl are proton acceptors and act as bases.
Further it follows that the products of the
Arrhenius described H⊕ ions in water as
Bronsted-Lowry acid-base reactions are acids
bare ions; they hydrate in aqueous solutions
bases.
and thus represented as hydronium ions H3O⊕.
We herewith conveniently represent them as The base produced by accepting the
H⊕. proton from an acid is the conjugate base of
that acid. Likewise the acid produced when a
base accepts a proton is called the conjugate
Do you know ? acid of that base. A pair of an acid and a
Hydrochloric acid, HCl base differing by a proton is said to be a
present in the gastric juice is conjugate acid-base pair.
secreted by our stomach and is essential
for digestion of food. HCl(aq) + H2O(l) H3O⊕ (aq) + Cl (aq)
Acid1 Base2 Acid2 Base1
conjugate acid-base pair2
Base : Base is a substance that contains OH
conjugate acid-base pair1
group and produces hydroxide ions (OH )
ions in aqueous solution. For example, 3.3.3 Lewis theory : A more generalized acid-
NaOH (aq) Na⊕(aq) + OH (aq) base concept was put forward by G.N. Lewis
in 1923. According to this theory acids and
NH4OH(aq) NH4⊕(aq) + OH (aq)
bases are defined as follows.
Arrhenius theory accounts for properties
Acid : Any species that accepts a share in an
of different acids and bases and is applicable
electron pair is called Lewis acid.
only to aqueous solutions. It does not account
for the basicity of NH3 and Na2CO3 which do Base : Any species that donates a share in an
not have OH group. electron pair is called Lewis base.
3.3.2 Bronsted - Lowry theory : J. N. For example :
Bronsted and T. M. Lowry (1923) proposed H H ⊕
48
3.4.1 Dissociation constant of weak acids
Use your brain power and weak bases : The dissociation of a weak
• All Bronsted bases are also acid HA in water is expressed as
Lewis bases, but all Bronsted
HA(aq) H⊕(aq) + A (aq)
acids are not Lewis acids. Explain.
The equilibrium constant called acid-
dissociation constant for this equilibrium is :
Amphoteric nature of water : Water has
the ability to act as an acid as well as a base. [H⊕][A ]
Ka = (3.3)
Such behaviour is known as amphoteric nature [HA]
of water. For example : Similarly the dissociation of weak base
H2O(l) + NH3(aq) OH (aq) + NH4⊕(aq) BOH in water is represented as :
Acid
BOH(aq) B⊕(aq) + OH (aq)
49
HA(aq) H⊕(aq) + A (aq) BOH(aq) B⊕(aq) +OH (aq)
Amount (1-∝) ∝ ∝ Amount (1-∝) ∝ ∝
present at present at
equilibrium/ equilibrium
mol concentration 1- ∝ ∝ ∝
concentration 1- ∝ ∝ ∝ at equilibrium V V V
at V V V
equilibrium/ A equilibrium,
mol dm-3
[BOH] = 1- ∝ mol dm-3,
Thus, at equilibrium [HA] = 1- ∝ , mol dm-3,
V
V [B⊕] = [OH ] = ∝ mol dm-3.
[H⊕] = [A ] = ∝ mol dm-3. V
V Substitution of these concentrations in Eq.
Substituting these in Eq. (3.3) (3.4), gives
(∝/V) (∝/V) ∝2
Ka = = (1- ∝)V (3.5) (∝/V) (∝/V) ∝2
(1- ∝)/V Kb = = (3.9)
(1- ∝)/V (1- ∝)V
If c is the initial concentration of an acid
in mol dm-3 and V is the volume in dm3 mol-1 Similar arguments in the case of weak
then c = 1/V. Replacing 1/V in Eq. (3.5) by c acid, led to
we get ∝2 c
Kb = (3.10)
(1- ∝)
Ka = ∝ c
2
(3.6) Kb
1- ∝ ∝ = Kb.V , ∝ = (3.11)
c
For the weak acid HA, ∝ is very small,
The degree of dissociation of a weak
or (1 - ∝) ≅ 1. With this Eq. (3.5) and (3.6)
base is inversely proportional to square root of
reduce.
its concentration and is directly proportional
Ka = ∝2/V and Ka = ∝2c (3.7) to square root of volume of the solution
Ka containing 1 mol of weak base.
∝= or ∝ = Ka.V (3.8)
c
Problem 3.1 : A weak monobasic acid
The Eq. (3.8) implies that the degree
is 0.05% dissociated in 0.02 M solution.
of dissociation of a weak acid is inversely
Calculate dissociation constant of the acid.
proportional to the square root of its
Solution : The dissociation constant of acid
concentration or directly proportional to
is given by Ka = ∝2 c. Here,
the square root of volume of the solution
containing 1 mol of the weak acid. percent dissociation
∝=
100
b. Weak base : Consider 1 mol of weak base 0.05
= = 5 × 10-4
BOH dissolved in V dm3 of solution. The base 100
dissociates partially as c = 0.02 M = 2 × 10-2 M
BOH (aq) B⊕(aq) + OH (aq) Hence Ka = (5 × 10-4)2 × 2 × 10-2
The base dissociation constant is = 25 × 10-8 × 2 × 10-2
[B⊕][OH ]
Kb = = 50 × 10-10 = 5 × 10-9
[BOH]
Let the fraction dissociated at equilibrium
is ∝ and that remains undissociated is (1 - ∝).
50
3.5 Autoionization of water : Pure water
Problem 3.2 : The dissociation constant of
ionizes to a very small extent. The ionization
NH4OH is 1.8 × 10-5. Calculate its degree
equilibrium of water is represented as,
of dissociation in 0.01 M solution.
Solution : The degree of dissociation is H2O (l) + H2O (l) H3O⊕(aq) + OH (aq)
given by ∝ = Kb/c . Here, The equilibrium constant (K) for the
Kb = 1.8 × 10-5; c = 0.01 = 1 × 10-2 M ionization of water is given by
1.8 × 10-5 = 1.8 × 10-3 [H O⊕][OH ]
Hence, ∝ = K= 3 (3.12)
1 × 10-2 [H2O(l)]2
= 18 × 10-4 = 4.242 × 10-2 = 0.04242 or K[H2O]2 = [H3O⊕][OH ] (3.13)
A majority of H2O molecules are
Problem 3.3 : A weak monobasic acid is
undissociated, consequently concentration of
12% dissociated in 0.05 M solution. What
water [H2O] can be treated as constant. Then
is percent dissociation in 0.15 M solution.
Solution : If ∝1 and ∝2 are the values of [H2O]2 = K'. Substituting this in Eq. (3.13)
degree of dissociation at two different we get,
concentrations c1 and c2 respectively, then K×K' = [H3O⊕][OH ] (3.14)
Ka = ∝12c1 = ∝22c2 Therefore ∝12c1 = ∝22c2 Kw = [H3O⊕][OH ]
12
∝1 = c = 0.05 M, c2 = 0.15 M, where Kw = KK' is called ionic product of
100 1
∝2 = ? water. The product of molar concentrations of
hydronium (or hydrogen) ions and hydroxyl
Substituting of these values in the equation ions at equilibrium in pure water at the given
gives temperature is called ionic product of water.
(0.12)2 × 0.05 = ∝22 × 0.15 In pure water H3O⊕ ion concentration
(12)2 × 0.05 always equals the concentration of OH ion.
∝22 = 0.15 = 0.0048
Thus at 298 K this concentration is found to be
Hence ∝2 = 0.0693 % 1.0 × 10-7 mol/L.
∴ percent dissociation = 6.93 %
Kw = (1.0 × 10-7) (1.0 × 10-7)
Problem 3.4 : Calculate [H3O⊕] in Kw = 1.0 × 10-14 (3.15)
0.1 mol dm3 solution of acetic acid.
Internet my friend
Given : Ka [CH3COOH] = 1.8 × 10-5
Find out the values of ionic
Solution : Let ∝1 be the degree of product Kw of water at various
dissociation. Concentrations of various temperatures.
species involved at equilibrium are as
follows. 273 K, 283K, 293K, 303K, 313K, 323 K
= 0.04 = 4 × 10-4
Fig. 3.1 : pH scale 100
Now [H3O⊕] = ∝ × c
= 4 × 10-4 × 0.025 M = 10-5 M
∴ pH = -log10[H3O⊕] = -log10[10-5] = 5
52
3.7 Hydrolysis of salts
Use your brain power
3.7.1 Types of salts
• Suppose that pH of monobasic These are of four types
and dibasic acid is the same. Does
I. Salts derived from strong acid and
this mean that the molar concentrations
strong base. For example : NaCl,
of both acids are identical ?
Na2SO4, NaNO3, KCl, KNO3.
• How pH of pure water vary with
II. Salts derived from strong acids and
temperature ? Explain.
weak bases. For example : NH4Cl,
CuSO4, NH4NO3, CuCl2.
Problem 3.8 : The pH of monoacidic
weak base is 11.2. Calculate its percent III. Salts derived from weak acids and
dissociation in 0.02 M solution. strong bases. For example : CH3COONa,
KCN, Na2CO3.
Solution : pOH of the solution is given as :
IV. Salts derived from weak acids and weak
pOH = 14 - pH = 14 - 11.2 = 2.8 bases. For example : CH3COONH4,
pOH = -log10[OH ] NH4CN.
log10[OH ] = - pOH 3.7.2 Concept of hydrolysis : When a salt is
dissociated in water, it dissociates completely
= - 2.8 = - 2 - 0.8 - 1 + 1
into its constituent ions. The solvent water
= - 3 + 0.2 = 3.2 dissociates slightly as,
[OH ] = antilog 3.2 = 1.585 × 10-3 mol/dm3 H2O (l) + H2O (l) H3O⊕(aq) + OH (aq)
For monoacidic base, Pure water is neutral and [H3O⊕] = [OH ].
BOH (aq) B⊕(aq) + OH (aq) If the ions of the salt do not interact with water,
the hydronium and hydroxyl ion concentrations
[OH ] = ∝c
remain equal and the solution is neutral. When
[OH ] 1.585 × 10-3 one or more of the salt ions react with water, the
∝= = 0.02 = 0.07925
c equality of concentrations of H3O⊕ and OH
ions is disturbed. The solution, does not remain
Percent dissociation = ∝ × 100
neutral and becomes acidic or basic depending
= 0.07925 × 100 on the type of the salt. Such a reaction between
= 7.925 % the ions of salt and the ions of water is called
hydrolysis of salt. Hydrolysis of salt is defined
Do you know ? as the reaction in which cations or anions or
both ions of a salt react with ions of water to
• pH is crucial for digestion of produce acidity or alkalinity (or sometimes
food and other biochemical even neutrality).
reactions in our body.
3.7.3 Salts of strong acids and strong bases
• pH of gastric juice is about 2.
NaCl is a salt of strong acid HCl and a
• pH of blood is maintained within range strong base NaOH. When it is dissolved in
7.36 to 7.42. water, it dissociates completely into its ions.
• Enzymes function effectively only at NaCl (aq) Na⊕(aq) + Cl (aq)
a certain pH. For example trypsin acts
The ions Na⊕ and Cl have no tendency to
best for alkaline pH.
react with water. This is because the possible
products, NaOH and HCl of such reactions are
53
strong electrolytes and dissociate completely CH3COONa(aq) CH3COO (aq) +
in aqueous solutions. Na⊕(aq)
In other words, Water dissociates slightly as,
Na⊕(aq) + Cl (aq) + H2O HCl(aq) +NaOH (aq)
(strong acid) (strong base) H2O (l) + H2O (l) H3O⊕(aq) + OH (aq)
[Possible products]
Solution of CH3COONa contains Na⊕,
⊕
HCl(aq) + NaOH(aq) + H2O H3O (aq) + H3O , CH3COO , OH . The Na⊕ ions of salt
⊕
The acid HF is slightly stronger than base When the salt CH3COONH4 is dissolved in
NH4OH. The two ions react with water as water, it undergoes hydrolysis :
55
CH3COONa(aq) CH3COO (aq) + Na⊕(aq)
Can you think ?
Home made jams and gellies On the other hand since the acetic acid is a
without any added chemical weak acid, the concentration of undissociated
preservative additives spoil in a few CH3COOH molecules is usually high. If a
days whereas commercial jams and jellies strong acid is added to this solution the added
have a long shelf life. Explain. What role H⊕ ions will be consumed by the conjugate
does added sodium benzoate play? base CH3COO present in large concentration.
Similarly, if small amount of base is added,
3.8.1 Types of buffer solutions the added OH ions will be neutralized by the
large concentration of acetic acid as shown in
There are two types of buffer solutions.
the following reactions :
Acidic buffer used to maintain an acidic pH,
while basic buffer maintains alkaline pH. CH3COO (aq) + H⊕(aq) CH3COOH(aq)
(large concentraion) (added acid)
a. Acidic buffer solution : A solution
CH3COOH(aq) +OH (aq) CH3COO (aq)
containing a weak acid and its salts with
(large concentraion) (added acid) + H2O(l)
strong base is called an acidic buffer solution.
The acid or base added thus can not change
For example : A solution containing weak
the [H⊕] or [OH ] concentrations and, pH of
acid such as CH3COOH and its salt such as
the buffer remains unchanged. Dilution does
CH3COONa is an acidic buffer solution.
not have any effect on pH of buffer. This is
pH of acidic buffer is given by the equation because the concentration ratio term in Eq.
[salt] (3.23) and Eq. (3.25 ) remains the same. The
pH = pKa + log10 (3.23)
[acid] dilution does not change this ratio.
where pKa = - log10Ka (3.24) 3.8.3 Properties of buffer solution
and Ka is the dissociation constant of the acid. The pH of a buffer solution does not
change appereciably
b. Basic buffer solution : A solution
containing a weak base and its salt with i. by addition of small amount of either
strong acid is the basic buffer solution. strong acid or strong base, ii. on dilution or iii.
when it is kept for long time.
For example : A solution containing a
weak base such as NH4OH and its salt such as Can you tell ?
NH4Cl is a basic buffer solution.
It is enough to add a few mL
The pOH of basic buffer is given by, of a buffer solution to maintain its
[salt] pH. Which property of buffer is used here?
pOH = pKb + log10 (3.25)
[base]
where pKb = - log10Kb (3.26)and 3.8.4 Applications of buffer solution
Kb is the dissociation constant for the base.
Equations (3.26) and (3.25) are known to Buffer solution finds extensive
Henderson Hasselbalch equation. applications in a variety of fields. Some of its
applications are given.
3.8.2 Buffer action : Let us consider
sodium acetate - acetic acid buffer. Here i. In biochemical system : pH of blood in
sodium acetate is a strong electrolyte which our body is maintained at 7.36 - 7.42 due to
dissociates completely in water producing (HCO3 + H2CO3) buffer. A mere change of 0.2
large concentration of CH3COO as follows : pH units can cause death. The saline solution
used for intravenous injection must contain
56
buffer system to maintain the proper pH of the
Problem 3.10 : Calculate the pH of buffer
blood.
solution composed of 0.1 M weak base
ii. Agriculture : The soils get buffered BOH and 0.2 M of its salt BA. [Kb = 1.8×
due to presence of salts such as carbonate, 10-5 for the weak base]
bicarbonate, phosphates and organic acids. Solution : pOH of basic buffer is given by
The choice of fertilizers depends upon pH of Henderson-Hasselbalch equation
soil. pOH = pKb + log10 [salt]
[base]
iii. Industry : Buffers play an important role
in paper, dye, ink, paint and drug industries. ∴ pKb = - log10Kb
= - log10 (1.8 × 10-5) = 5 - log10 1.8
iv. Medicine : Penicillin preparations are
= 5 - 0.2553 = 4.7447
stabilized by addition of sodium citrate as
buffer. When citric acid is added to milk of [salt] = 0.02 M, [acid] = 0.1M
magnesia (Mg(OH)2), magnesium citrate is Substitution of these in the above equation
formed, which is a buffer. gives
pOH = 4.7447 + log 0.02 = 4.7447 + log 2
v. Analytical chemistry : In qualitative 0.1
= 4.7447 + 0.3010 = 5.0457
analysis, a pH of 8 to 10 is required for
precipitation of cations IIIA group. It is pH = 14 - pOH = 14 - 5.0457
maintained with the use of (NH4OH + NH4Cl) = 13.9543 ≈ 13.95
buffer.
3.9 Solubility product
Problem 3.9 : Calculate the pH of buffer Can you recall ?
solution containing 0.05 mol NaF per litre • What is solubility of a
and 0.015 mol HF per litre. [Ka = 7.2 × 10-4 compound ?
for HF] • What is saturated solution ?
Solution : The pH of acidic buffer is given • What is meant by the sparingly soluble
by Henderson-Hasselbalch equation salt ?
pH = pKa + log10 [salt]
[acid]
Do you know ?
∴ pKa = - log10Ka = - log10 7.2 × 10-4
The process of dissolution
= 4 - log10 7.2 = 4 - 0.8573 = 3.1427 and precipitation of sparingly
[salt] = 0.05 M, [acid] = 0.015M soluble ionic compounds are of important
in our everyday life, industry and medicine.
Substitution in the above equation gives
Kidney stone is developed due to the
pH = 3.1427 + log10 0.05 precipitation of insoluble calcium oxalate,
0.015
CaC2O4. The process of tooth decay occurs
= 3.1427 + log 3.33 due to dissolution of enamel composed of
hydroxyapatite, Ca5(PO4)3OH in acidic
= 3.1427 + 0.5224 = 3.6651 ≈ 3.67 medium.
57
Suppose some powdered sparingly Consider following examples.
soluble salt such as AgCl is put into water and i. BaSO4(s) Ba2⊕ (aq) + SO42 (aq)
stirred vigorously. A very small amount of
AgCl dissolves in water to form its saturated Ksp = [Ba2⊕][SO42 ]
solution. Most of the salt remains undissolved. ii. CaF2 (s) Ca2⊕ (aq) + 2F (aq)
Thus, solid AgCl is in contact with its saturated
Ksp = [Ca2⊕][F ]2
solution. AgCl is a strong electrolyte. Hence
the quantity of AgCl that dissolves in water iii. Bi2S3 (s) 2Bi3⊕ (aq) + 3S2 (aq)
dissociates completely into its constituent Ksp = [Bi3⊕]2[S2 ]3
ions, Ag⊕ and Cl . A dynamic equilibrium
iv. Ca3(PO4)2 (s) 3Ca2⊕ (aq) + 2PO43 (aq)
exists between undissolved solid AgCl and the
dissolved ions, Ag⊕ and Cl , in the saturated Ksp = [Ca2⊕]3[PO43 ]2
solution. This equilibrium, called solubility 3.9.2 Relationship between solubility
equilibrium, is represented as : and solubility product : The solubility of
AgCl(s) Ag⊕(aq) + Cl (aq) a compound is the amount in grams that
dissolves per unit volume (which may be 100
The expression for its equilibrium constant is :
mL or 1L of its saturated solution).
[Ag⊕][Cl ]
K= [AgCl] (3.27) Molar solubility : The number of moles
of a compound that dissolve to give one
The concentration of undissolved solid
litre of saturated solution is called its molar
AgCl is constant we may write
solubility.
[AgCl] = constant = K' solubility in g/L
molar solubility (mol/L) = molar mass in g/mol
Substituting in Eq. (3.27) we write
[Ag⊕][Cl ]
K= K' Consider once again the solubility
K × K' = [Ag⊕][Cl ] equilibrium for BxAy,
The product of K × K' is another constant BxAy(s) xBy⊕ (aq) + yAx (aq)
and is called solubility product, that is the The solubility product is given by Eq.
product of concentrations of ions in a saturated (3.28) :
solution. It is denoted by Ksp.
Ksp = [By⊕]x[Ax ]y
Ksp = [Ag⊕][Cl ]
If S is the molar solubility of the
For the general salt solubility equilibrium compound, the equilibrium concentrations of
BxAy(s) xBy⊕ (aq) + yAx (aq) the ions in the saturated solution will be
58
∴ Ksp = S × S = S2
0.3
ii. For PbI2, [C2O42-] = 2 M = 0.15 mol/L
PbI2(s) Pb2⊕ (aq) + 2I (aq) These ions would react to form sparingly
x = 1, y = 2 soluble salt MgC2O4 in accordance with
Therefore, Ksp = (1)1(2)2S1+2 = 4S3 reaction
Use your brain power the Ksp value for MgC2O4 at 293 K is
8.56 × 10-5. As ionic product is greater than
What is the relationship
Ksp precipitation will take place.
between molar solubility and
solubility product for salts given below
Problem 3.12 : The solubility product of
i. Ag2CrO4 ii. Ca3(PO4)2 iii. Cr(OH)3. AgBr is 5.2 × 10-13. Calculate its solubility
in mol dm-3 and g dm-3(Molar mass of AgBr
3.9.3 Condition of precipitation : Ionic = 187.8 g mol-1)
product (IP) of an electrolyte is defined in the
same way as solubility product (Ksp). The only Solution : The solubility equilibrium of
difference is that the ionic product expression AgBr is :
contains concentration of ions under any AgBr(s) Ag⊕(aq) + Br (aq)
condition whereas expression of Ksp contains x = 1, y = 1
only equilibrium concentrations. If,
Ksp = [Ag⊕][Br ] = S2
a. IP = Ksp ; the solution is saturated and
solubility equilibrium exists. S = Ksp = 5.2 × 10-13
59
Therefore [Ba2⊕] = 0.025 M and The common ion effect states that the
ionisation of a weak electrolyte is supressed
[F ] = 0.010M in presence of a strong electrolyte containing
Hence ionic product of BaF2 is an ion common to the weak electrolyte.
IP = [Ba2⊕][F ]2 Remember...
= 0.025 × (0.01)2 Common ion effect is a special
= 2.5 × 10-6 case of Le-Chatelier's principle in
which the stress applied to an equilibrium
Ksp (BaF2) = 1.7 × 10-6 Thus, Ksp < IP system is an increase in the concentration
Ionic product in the solution is greater than of one of the product (ions). The effect
Ksp. Hence BaF2 will precipitate from the of this stress is reduced by shifting the
solution. equilibrium to the reactant side.
3.10 Common ion effect :
Can you tell ?
Can you recall ? How does the ionization of
Which reagents are used to NH4OH suppressed by addition of
precipitate (i) group II, (ii) group III NH4Cl to the solution of NH4OH ?
B, (iii) group III A of basic radicals/ 3.10.1 Common ion effect and solubility
cations ?
Consider a solution of weak acid Do you know ?
CH3COOH and its soluble ionic salt The hardness of water is due to
CH3COONa. presence of Ca2⊕ ions. It is surprising
to know that Ca2⊕ ions can be removed by
CH3COOH is weak acid, dissociates only
adding more Ca2⊕ ions in the form of lime
slightly in solution
Ca(OH)2, to the hard water. The OH ions
CH3COOH CH3COO (aq) + H⊕ (aq) of lime react with HCO3 ions present in the
CH3COONa being a strong electrolyte hard water to form CO32 ions.
dissociates almost completely in solution. OH (aq) + HCO3 (aq)
CH3COONa(aq) CH3COO + Na⊕ CO32 (aq) + H2O(l)
Both the acid and the salt produce Solubility product of CaCO3 is very low
CH3COO ions in solution. CH3COONa (Ksp = 4.5 × 10-9). Addition of lime makes
dissociates completely. Therefore it provides IP >>Ksp which results in the precipitation
high concentration of CH3COO ions. of CaCO3 and thereby removal of hardness.
According to Le-Chatelier principle, the
addition of CH3COO from CH3COONa to The presence of a common ion also
the solution of CH3COOH, shifts equilibrium affects the solubility of a sparingly soluble
of dissociation of CH3COOH to left. Thus salt. Consider, the solubility equilibrium of
reverse reaction is favoured in which AgCl,
CH3COO combines with H⊕ to form unionised AgCl(s) Ag⊕(aq) + Cl (aq)
CH3COOH. Hence dissociation of CH3COOH
The solubility product of AgCl is
is supressed due to presence of CH3COONa
containing a common CH3COO ion. Ksp = [Ag⊕][Cl ]
60
Suppose AgNO3 is added to the saturated to Le-chatelier's principle the addition of Ag⊕
solution of AgCl. The salt AgNO3 being a ions from AgNO3 to the solution of AgCl shifts
strong electrolyte dissociates completely in the the solubility equilibrium of AgCl from right
solution. to left. The reverse reaction in which AgCl
AgNO3(aq) Ag⊕ (aq) + NO3 (aq) precipitates, is favoured until the solubility
equilibrium is re-established. The value of
The dissociation of AgCl and AgNO3 Ksp however, remains the same since it is
produce a common Ag⊕ ion. The concentration an equilibrium constant. The solubility of a
of Ag⊕ ion in the solution increases owing to sparingly soluble compound, thus decreases
complete dissociation of AgNO3. According with the presence of a common ion in solution.
Exercises
1. Choose the most correct answer : vi. The conjugate base of [Zn(H2O)4]2⊕ is
i. The pH of 10-8 M of HCl is a. [Zn(H2O)4]2 NH3
a. 8 b. 7 b. [Zn(H2O)3]2
c. less than 7 d. greater than 7 c. [Zn(H2O)3OH]⊕
ii. Which of the following solution will d. [Zn(H2O)H]3⊕
have pH value equal to 1.0 ? vii. For pH > 7 the hydronium ion
a. 50 mL of 0.1M HCl + 50mL of 0.1M concentration would be
NaOH a. 10-7M b. < 10-7M
b. 60 mL of 0.1M HCl + 40mL of c. > 10-7M d. ≥ 10-7M
0.1M NaOH 2. Answer the following in one sentence :
c. 20 mL of 0.1M HCl + 80mL of i. Why cations are Lewis acids ?
0.1M NaOH ii. Why is KCl solution neutral to
d. 75 mL of 0.2M HCl + 25mLof 0.2M litmus?
NaOH iii. How are basic buffer solutions
iii. Which of the following is a buffer prepared?
solution ? iv. Dissociation constant of acetic
a. CH3COONa + NaCl in water acid is 1.8 × 10-5. Calculate percent
dissociation of acetic acid in 0.01 M
b. CH3COOH + HCl in water
solution.
c. CH3COOH+CH3COONa in water
v. Write one property of a buffer
d. HCl + NH4Cl in water solution.
iv. The solubility product of a sparingly vi. The pH of a solution is 6.06. Calculate
soluble salt AX is 5.2×10-13. Its its H⊕ ion concentration.
solubility in mol dm-3 is vii. Calculate the pH of 0.01 M sulphuric
a. 7.2 × 10-7 b. 1.35 × 10-4 acid.
c. 7.2 × 10-8 d. 13.5 × 10-8 viii. The dissociation of H2S is suppressed
v. Blood in human body is highly buffered in the presence of HCl. Name the
at pH of phenomenon.
a. 7.4 b. 7.0 ix. Why is it necessary to add H2SO4
c. 6.9 d. 8.1 while preparing the solution of
CuSO4?
61
x. Classify the following buffers into iv. Dissociation of HCN is suppressed
different types : by the addition of HCl. Explain.
a. CH3COOH + CH3COONa vi. Derive the relationship between
b. NH4OH + NH4Cl degree of dissociation and
c. Sodium benzoate + benzoic acid dissociation constant in weak
electrolytes.
d. Cu(OH)2 + CuCl2
vii. Sulfides of cation of group II are
3. Answer the following in brief :
precipitated in acidic solution (H2S
i. What are acids and bases according + HCl) whereas sulfides of cations
to Arrhenius theory ? of group IIIB are precipitated
ii. What is meant by conjugate acid- in ammoniacal solution of H2S.
base pair? Comment on the relative values of
iii. Label the conjugate acid-base pair in solubility product of sulfides of these.
the following reactions viii. Solubility of a sparingly soluble salt
a. HCl + H2O H3O⊕ + Cl get affected in presence of a soluble
b. CO32 + H2O OH + HCO3 salt having one common ion. Explain.
iv. Write a reaction in which water acts ix. The pH of rain water collected in a
as a base. certain region of Maharashtra on
particular day was 5.1. Calculate
v. Ammonia serves as a Lewis base
the H⊕ ion concentration of the rain
whereas AlCl3 is Lewis acid. Explain.
water and its percent dissociation.
vi. Acetic acid is 5% ionised in its
x. Explain the relation between ionic
decimolar solution. Calculate the
product and solubility product to
dissociation constant of acid
predict whether a precipitate will
(Ans : 2.63 × 10-4) form when two solutions are mixed?
vii. Derive the relation pH + pOH = 14.
viii. Aqueous solution of sodium Activity :
carbonate is alkaline whereas
aqueous solution of ammonium Take two test tubes and label them
chloride is acidic. Explain. as A and B. Add Zinc filings in both
the test tubes. In the test tube labelled A
ix. pH of a weak monobasic acid is 3.2
add 5 mL of 1M HCl and in test B 5 mL
in its 0.02 M solution. Calculate its
of acetic acid. Keep the test tubes on the
dissociation constant.
stand. Note down your observations.
x. In NaOH solution [OH ] is 2.87 ×
a. Do you see any effervescence coming
10-4. Calculate the pH of solution.
from the two test tubes ?
4. Answer the following :
b. Which gas is evolved ?
i. Define degree of dissociation.
c. How do you identify the gas ?
Derive Ostwald's dilution law for the
CH3COOH. d. What is the relative rate at which the
gas is evolved in the two test tubes
ii. Define pH and pOH. Derive
relationship between pH and pOH. e. Based on your observations comment
on the strength of acids used.
iii. What is meant by hydrolysis ? A
solution of CH3COONH4 is neutral.
why ?
62
4. CHEMICAL THERMODYNAMICS
Can you recall ? putting certain mass on the piston. In this case,
1. How do you define energy? a gas under study is called the system.
2. What are the different forms of
Surrounding
energy?
Surrounding
Surrounding
water or burning of carbon forming carbon
dioxide, CO2, are accompanied by a change
in energy. In dry cell, the chemical energy is
converted into electrical energy. On the other Gas
(system)
hand, in electroplating of metals electrical
energy is converted into chemical energy. Fig. 4.1 : System and surroundings
Thus it may be realized that the energy can be A part of the universe under
transformed from one form into another. thermodynamic investigation is called
the system.All other parts of the universe
Do you know ? outside the system such as cylinder, room
and others, are surroundings. The universe
At the top of dam, water is
is made of system plus surroundings.
stored in a reservoir. It has certain
potential energy due to its height from ground 4.2.2 Types of system :
level and its kinetic energy is negligible as it
is not in motion. As the water starts to fall Observe and discuss...
down through an outlet its potential energy
Observe Fig. 4.2 and discuss
decreases and kinetic energy increases due
to the downward velocity. It means that with reference to transaction of
potential energy of falling water is converted energy and matter.
into kinetic energy.
Matter Insulator
Thermodynamics is concerned with the Energy Energy
energy changes in physical and chemical Matter
transformations. Thermodynamics, however
gives no information on the rates of physical or Energy Matter
chemical processes or underlying mechanisms Open system Closed system Isolated system
involved in these. (a) (b) (c)
63
surroundings. Such a system (coffee) which
exchanges both energy and matter with the
surroundings is called an open system.
ii. Closed system : In Fig. 4.2(b), a cup
containing hot coffee is covered with a saucer.
Coffee cools down by giving away heat to the
surroundings. The water vapour from coffee
now does not pass into surroundings. Such Fig. 4.3 : Change of state
a system that exchanges energy and not the
matter with the surroundings is called a closed Suppose the pressure of the system is
system. increased to 2 bar, (P2 ) volume changes to 0.5
dm3 (V2 ) and the temperature is maintained at
iii. Isolated system : As you see in Fig. 4.2(c),
300 K (T1 ). This is the final state of the system
a cup containing hot coffee covered with a
which is different from the initial state. A
saucer is insulated from the surroundings.
change in state functions of the system brings
Coffee does not cool down. Moreover,
forth a change of its state. This is shown in Fig.
there is no escape of water vapour into the
4.3.
surroundings. Such a system that does not
allow exchange of either energy or matter with The final state of the system in Fig. 4.3. is
the surroundings is an isolated system. described by pressure 2 bar (P2 ), volume 0.5
dm3(V2 ) and temperature 300 K(T1 ). A system
4.2.3 Properties of system
continues to be in such state as long as the state
i. Extensive property : functions are unchanged. How the pressure 2
A property which depends on the amount bar is attained whether by increasing from 1
of matter present in a system is called an bar to 2 bar or decreasing from 5 bar to 2 bar,
extensive property. would not matter.
Examples : Mass, volume, internal energy, The property which depends on the state
heat capacity, number of moles. of a system and independent of a path followed
to attain it, is called the state function.
ii. Intensive property :
The term process means a physical or
A property which is independent of the amount chemical change in a system on going from
of matter in a system is called intensive one state to another. This can be achieved by a
property. number of paths by some operation. A path here
Examples : Pressure, temperature, surface refers to a sequence of situations the system
tension, viscosity, melting point, boiling point, undergoes during the accomplishment of the
specific heat. change. In other words the process in general
may not necessarily determine the change in
4.2.4 State functions : As shown in Fig.
unique way. Only isothermal and adiabatic
4.1, certain amount of a gas is enclosed in a
reversible processes follow the unique path to
cylinder fitted with a movable piston. Suppose
bring about the change of state of the system.
the pressure of the gas is 1 bar (P1 ), volume is
1 dm3 (V1 ) and temperature is 300 K (T1 ) in 4.2.5 Path Functions : The properties which
the beginning. This initial state of the system depend on the path are called path functions.
is fully defined by specifying the values of For example, work (W) and heat (Q).
these properties. Such properties defining the
state of a system, are state functions.
64
4.2.6 Thermodynamic equilibrium : carried out in a closed container is isochoric.
Consider a gas enclosed in a cylinder fitted For isochoric process ∆V = 0.
with a movable piston shown in Fig. 4.1. iv. Adiabatic process : A process in which
The gas has temperature T1, pressure P1 and there is no exchange of heat between system
volume V1. These state functions continue to and surroundings is an adiabatic process.
be constant as long as piston is motionless, (Q = 0). In adiabatic process the system is
and no heat exchange takes place. This is an completely insulated from the surroundings.
equilibrium state. For an exothermic process the heat is released
Now move the piston in upward direction which rises temperature of the system. If the
so that the gas expands. It passes through states process is endothermic the temperature falls.
for which pressure, volume and temperature This results in either increase or decrease of
are not specified and vary continuously during internal energy.
the movement of the piston. The gas would v. Reversible process : Consider a gas enclosed
then be in nonequilibrium state. in a cylinder fitted with a movable piston.
Stop the movement of the piston. Suppose Let the external pressure be Pext on the outer
at this stage the pressure and volume of the gas surface of the piston be set equal to pressure P
are respectively P2 and V2 and the temperature of the gas. Neither expansion nor compression
is constant at T1. The state functions are of the gas occurs. A system is then said to be
constant since the piston is motionless. The in mechanical equilibrium with surroundings.
gas is then in another equilibrium state. Consider Pext is reduced by an infinitesimal
A system is said to be in thermodynamic amount. Now it the Pext is infinitesimally
equilibrium when its state functions do not smaller than P the piston moves out slowly
vary with time. Thermodynamics considered allowing gas to expand.
here is limited to equilibrium states. If Pext is slightly increased so that it
4.2.7 Process and its types : A transition becomes infinitesimally greater than P, the
from one equilibrium state to another is called piston moves inward with a compression of
a process. They are of different types. the gas.
i. Isothermal process : It is the process in For the system in mechanical equilibrium
which temperature of the system remains with its surroundings, infinitesimal change
constant throughout the transformation. may cause the process to occur in the reverse
In such process heat flows from the system direction. The process is then said to be
to surroundings and vice versa so as to keep the thermodynamically reversible. A process
temperature constant. For a given temperature conducted in such a way so that at every
the internal energy (U) of the system remains stage the driving force due to pressure (P) is
constant. Thus, ∆T = 0 and ∆U = 0. infinitesimally greater than the opposing force
due to external pressure (Pext) and which can
ii. Isobaric process :
In isobaric process be reversed by a slight change of the opposing
the pressure remains constant during the force is reversible process.
transformation. In the laboratory chemical
reactions are carried out in open containers at Features of reversible process
constant atmospheric pressure or ∆P = 0 i. The driving and opposing forces differ by an
iii. Isochoric process : It is a process during infinitesimal amount.
which volume of the system remains constant ii. The process can be reversed by an
during the transformation. A chemical reaction infinitesimal change in conditions.
65
iii. A reversible process proceeds infinitely surroundings. With no heat being transferred
slowly and takes place in infinite number of a loss of energy by the system is equal to work
steps. done by the system on the surroundings. This
iv. At the end of every step of the process, the is PV expansion.
system attains mechanical equilibrium with ii. Reaction between NH3 gas and HCl gas
the surroundings. Now, consider
4.3 Nature of heat and work NH3(g) + HCl(g) NH4Cl(s)
As the reaction progresses the gases are
4.3.1 Nature of work (W) : In mechanics the
consumed resulting in a decrease of volume.
work is defined as the energy by which body
The piston moves down. A decrease in the
is displaced through a distance d with an
height of the mass is shown in Fig. 4.5.
application of force. Thus,
W=f×d
In thermodynamics the type of work
involved is pressure-volume or PV work, that
is, work is done when the system (gas) expands
or contracts against the external opposing
force.
It may be realized that the product of
pressure and volume is equal to work. Pressure
is defined as force per unit area. If d is the Fig. 4.5 : Reaction between NH3(g) and HCl(g)
distance, area A = d2 and volume V = d3. Then
f f In the process the surroundings lose
PV = × V = 2 × d3 = f d = W energy to the system and perform work on the
A d
Now let us explore the PV work with system. If no heat transfer occurs work done
two chemical reactions in a cylinder equipped by the surroundings is equal to gain in energy
with frictionless movable piston attached with by the system. This is PV work.
a certain mass on its outer surface.
Thus the work refers to a way by which
i. Decomposition of H2O2 a system exchanges energy with surroundings.
Consider 2 H2O2(l) 2 H2O(l) + O2(g)
4.3.2 Nature of heat (Q) : Like heat is a form of
energy by which the system exchanges energy
with its surroundings. When the system and its
surroundings are at different temperatures heat
either flows in or let out of the system.
O2(g) 4.3.3 Sign conventions of W and Q : The
energy changes for the system are considered
H2O2 hereafter.
The energy entering the system from the
surroundings has positive value. While the
Fig. 4.4 : Decomposition of H2O2
energy leaving the system and flowing into the
The gas produced in above reaction surroundings is negative. This is shown in Fig.
pushes the piston upwards so that the mass in 4.6.
the surroundings is raised as shown in Fig. 4.4.
+Q : Heat is absorbed by the system from the
In lifting the mass the system loses energy to
surroundings.
the surroundings or it performs work on the
66
W = f × d (4.2)
Substitution from Eq. (4.1) gives
W = - Pext × A × d (4.3)
The product of area of the piston and
Fig. 4.6 : Sign conventions
distance it moves is the volume change (∆V)
in the system.
-Q : Heat is released by the system to the
surroundings. ∆V = A × d (4.4)
+W : Work is done on the system by the Combining equations (4.3) and (4.4) we write
surroundings. W = - Pex ∆V (4.5)
-W : Work is done by the system on the
W = - Pex (V2 - V1)
surroundings.
where V2 is final volume of the gas.
Note W and Q are path functions.
When the gas expands, work is done by the
4.4 Expression for pressure-volume (PV)
work : Consider a certain amount of gas at system on the surroundings. Since V2 > V1, W
constant pressure P is enclosed in a cylinder is negative. When the gas is compressed, work
fitted with frictionless, rigid movable piston of is done on the system by surroundings. In this
area A. This is shown in Fig. 4.7. case V1< V2, and -Pext ∆V or W is positive.
Eq. (4.5) shows the external pressure
determines the work during expansion (or
compression) of the gas. A volume change
does no work unless the system is linked to the
surroundings by external pressure.
Remember...
Remember during expansion
of a gas, work is done by the
Fig. 4.7 : Pressure-volume work system on the surroundings and during
compression work is done on the system by
Let volume of the gas be V1 at temperature T. the surroundings.
On expansion the force exerted by a
gas is equal to area of the piston multiplied 4.4.1 Free expansion : A free expansion
by pressure with which the gas pushes against means expansion against zero opposing force.
piston. This pressure is equal in magnitude and Such expansion occurs in vacuum. The work
opposite in sign to the external atmospheric done by a system during such expansion is
pressure that opposes the movement and has given by Eq. (4.5), W = - Pext ∆V. When the
its value -Pext. Thus, gas expands in vacuum, there is no opposing
force that is Pext and hence, W = 0. In other
f = -Pext × A (4.1)
words no work is done when the gas expands
where Pext is the external atmospheric pressure. freely in vacuum.
If the piston moves out a distance d,
then the amount of work done is equal to the
force multiplied by distance.
67
4.4.2 Units of energy and work Problem 4.3 : 200 mL ethylene gas and 150
1 J = 1 kg m s = 1 Pa m
2 -2 3
mL of HCl gas were allowed to react at 1
1 Pa = 1 kg m-1 s-2 bar pressure according to the reaction
68
The work (W) would be maximum When the volume of a gas increases by
when ∆P is smallest. This means the opposing an infinitesimal amount dV in a single step, the
force (Pex) must be infinitesimally smaller small quantity of work done
than the driving force (P) for the work to be dW = -Pext dV (4.6)
maximum. This is required for the process to
be reversible. The maximum work is obtained As the expansion is reversible, P is greater by
from the change which is thermodynamically a very small quantity dp than pex. Thus,
reversible. P -Pext = dP or Pext = P - dP (4.7)
4.5.1 Expression for the maximum work : Combining equations (4.6) and (4.7),
Consider n moles of an ideal gas enclosed dW = - (P - dP)dV = - PdV + dP dV
in a cylinder fitted with frictionless movable
Neglecting the product dpdV which is very
rigid piston. It expands isothermally and
small, we get
reversibly from the initial volume V1 to final
volume V2 at temperature T. The expansion dW = - PdV (4.8)
takes place in a number of steps illustrated in The total amount of work done during
Fig. 4.8. entire expansion from volume V1 to V2 would
be the sum of infinitesimal contributions of
all the steps. The total work is obtained by
Step 1 Step 2 Step 3 Continued integration of Eq. (4.8) between the limits of
initial and final states. This is the maximum
work, the expansion being reversible. Thus,
dv
dv dv final
v2
V1
Gas Gas Gas Gas
∫ dW
initial
=- ∫ PdV
v1
v2
69
Replacing V2/V1 in Eq. (4.10) by P1/P2, We
have Problem 4.6 : 300 mmol of an ideal gas
P occupies 13.7 dm3 at 300 K. Calculate the
Wmax = -2.303 nRT log 1 (4.11) work done when the gas is expanded until
P2
its volume has increased by 2.3 dm3 (a)
Problem 4.4 : 2 moles of an ideal gas are isothermally against a constant external
expanded isothermally and reversibly from pressure of 0.3 bar (b) isothermally and
20 L to 30 L at 300 K. Calculate the work reversibly (c) into vacuum.
done (R= 8.314 J K-1 mol-1) Solution :
V
Solution : Wmax = -2.303 nRT log10 2 a. W = -Pex ∆V
V1
n = 2 mol, T = 300 K, V1 = 20 L, V2 = 30 L, Pext = 0.3 bar, ∆V = 2.3 dm3
R = 8.314 J/K mol W = -0.3 bar × 2.3 dm3
Substitution of these quantities into the = -0.69 dm3 bar
equation gives 100 J
= -0.69 dm3 bar ×
dm3 bar
Wmax = -2.303 × 2 mol × 8.314 J/K mol × = - 69 J
300K × log10 30 L V
20 L b. Wmax = - 2.303 nRT log10 2
= -2.303 × 2 × 8.314 J×300 × log10 1.5 V1
= -2.303 × 2 × 8.314 J×300 × 0.1761 n = 300 mmol = 300 × 10 mol = 0.3 mol,
-3
T = 300 K
= -2023 J = -2.023 kJ
Wmax = - 2.303 × 0.3 mol × 8.314 J K-1mol-1
Problem 4.5 : 22 g of CO2 are compressed
16
isothermally and reversibly at 298 K from × 300K × log10
13.7
initial pressure of 100 kPa when the work
= -2.303 ×0.3 ×8.314 J ×300 ×0.0674
obtained is 1.2 kJ. Find the final pressure.
= - 116.1 J
Solution :
P1 c. W = - Pex ∆V
W = -2.303 nRT log10 When gas is expanded to vaccum, Pext = 0
P2
22 g and W = 0
n= =0.5 mol, T = 298 K,
44 g mol-1
P1= 100 kPa, W = 1.2 kJ = 1200 J 4.6 Internal energy (U) : Every substance is
associated with a definite amount of energy.
Hence, 1200 J = -2.303 × 0.5 mol ×8.314 J This energy stored in a substance is internal
100 kPa energy denoted by U.
K-1 mol-1 × 298K × log10
P2 The internal energy of a system is made up
of kinetic and potential energies of individual
or log10 100 kPa =
P2 particles of the system.
-1200 ∆U = U2 - U1
2.303 ×0.5 ×8.314 ×298
where U1 and U2 are internal energies of initial
= -0.4206
and final states, respectively. U is a state
100 kPa function and extensive property.
= antilog (-0.4206) = 0.3797
P2
100 kPa
Therefore, P2 = 0.3797 = 263.4 kPa
70
4.7.1 Formulation of first law of
Try this...
thermodynamics : A system exchange energy
25 kJ of work is done on the with its surroundings either by transfer of
system and it releases 10 kJ of heat or by doing work. An energy supplied
heat. What is ∆U? to the system increases its internal energy.
On the other hand, removal of heat or work
A transfer of energy (as heat or work) from the system decreases its internal energy.
from the system would change its internal Suppose (Q) is heat supplied to the
energy. To know ∆U the energy supplied to or system and W work done on the system by
removed from the system need to be monitored. the surroundings. The internal energy of the
i. The energy transferred to the system by system would increase.
heating it or performing work on it is added Increase in internal energy of the system
to the system. is equal to sum of the quantity of heat supplied
ii. The energy transferred from the system to the system and amount of work done on the
by cooling or by performing work on the system or
surroundings is removed from the system. ∆U = Q + W (4.12)
The following examples illustrate how to where ∆U is an increase in internal energy
determine ∆U. of the system. Eq. (4.12) is the first law of
i. 30 kJ of heat supplied to the system. It thermodynamics. For infinitesimal changes.
would be added to internal energy of the dU = dQ +dW (4.13)
system and ∆U = +30 kJ. 4.7.2 First law of thermodynamics for
ii. If 20 kJ of work is done on the system, it various processes
is added to internal energy of the system. i. Isothermal process : Temperature is constant
Consequently, ∆U = + 20 kJ. in such process, internal energy is constant.
iii. Suppose a system releases 10 kJ of heat and Hence, ∆U = 0
performs 15 kJ of work on the surroundings. For isothermal process
These quantities are removed from internal 0 = Q +W or W = -Q (4.14)
energy of the system and ∆U = - 25 kJ
The above equation implies that heat
4.7 First law of thermodynamics : First law absorbed by the system is entirely used for
of thermodynamics is simply the conservation doing work on the surroundings. When work
of energy. According to this law the total is done on the system by the surroundings it
energy of a system and surroundings remains results in release of heat.
constant when the system changes from an
ii. Adiabatic process : In adiabatic process,
initial state to final state. The law is stated in
there is no exchange of heat between system
different ways as follows.
and its surroundings that is, Q = 0. then
i. Energy of the universe remains constant -∆U = -W (4.15)
ii. The total internal energy of an isolated Thus an increase in internal energy of
system is constant the system is the work done on it. If the work
iii. Energy is neither created nor destroyed is done by the system on the surroundings at
and can only be converted from one form to the expense of its internal energy, the internal
another. energy accompanying the adiabatic process
All above statements are equivalent. would decrease.
71
iii. Isochoric process : Substitution of From Eq. (4.19), we write
W = -Pext ∆V into Eq. (4.12) H1 = U1 + P1V1 and H2 = U2 + P2V2
∆U = Q - Pext ∆V (4.16) With these
As the reaction is carried out in a closed ∆H = U2 + P2V2 - U1 + P1V1
container, volume of the system is constant or = (U2 - U1) + (P2V2 - P1V1)
∆V = 0 and
= ∆U + ∆(PV) (4.21)
∆U = Qv (4.17)
For constant pressure, P1 = P2 = P and
Equation (4.17) shows a change in
internal energy of the system is due to heat ∆H = ∆U + P∆V (4.22)
transfer at constant volume. The subscript ‘V’ If the pressure inside and outside is the same or
indicates that heat is transferred at the constant Pext = P, Eq. (4.18) gives
volume. Further U being a state function, Qv is
Qp = ∆U + P ∆V (4.23)
also a state function.
From equations (4.22) and (4.23)
iv. Isobaric process : Usually chemical
reactions are carried out in the open containers ∆H = Qp (4.24)
under constant atmospheric pressure. In such Thus change in enthalpy of a system is
reactions, ∆V ≠ 0 equal to heat transferred from it at the constant
Replacing Q by Qp and ∆U by Qp - Pext ∆V in pressure. H and Qp are state functions.
equation (4.16) gives 4.8.1 Relationship between ∆H and ∆U for
Qp = ∆U + Pext ∆V (4.18) chemical reactions : At constant pressure, ∆H
and ∆U are related as
The reactions carried out in open
containers under constant atmospheric ∆H = ∆U + P∆V
pressure are common in chemistry, a special i. For reactions involving solids and liquids, ∆V
symbol ∆H, the enthalpy change, is given to usually is very small (solids or liquids do not
indicate heat changes occurring at constant show volume change with change of pressure)
pressure. and ∆H = ∆U
Remember... ii. For reactions involving gases, ∆V cannot be
q is not a state function. neglected and
Whereas Qv and Qp are state ∆H = ∆U + P∆V
functions.
= ∆H + P(V2 - V1)
4.8 Enthalpy (H) : Enthalpy of a system is ∆H = ∆U + PV2 - PV1 (4.25)
sum of internal energy of a system and the
where V1 is the volume of gas phase reactants
energy equivalent to PV work.
and V2 that of the gaseous products.
H = U + PV (4.19)
We assume reactant and product behave
Change in enthalpy, ∆H, is also state ideally. Applying ideal gas equation PV = nRT.
function given by When n1 moles of gaseous reactants produce
∆H = H2 - H1 (4.20) n2 moles of gaseous products. The ideal gas
equation give,
where H1 and H2 are the enthalpies of initial
and final states, respectively. PV1 = n1RT and PV2 = n2RT (4.26)
72
Substitution of Eq. (4.26) into Eq. (4.25) yields Problem 4.9 : Calculate the work done in
∆H = ∆U + n2RT - n1RT oxidation of 4 moles of SO2 at 250C if
= ∆U + (n2- n1) RT 2 SO2(g) + O2(g) 2 SO3(g)
= ∆U + ∆ng RT (4.27) R = 8.314 J K-1mol-1
where ∆ng is difference between the number of State whether work is done on the system or
moles of products and those of reactants. by the system.
Solution :
Problem 4.7 : ∆H for the reaction,
For oxidation of 4 moles of SO2, the reaction
2C(s) + 3H2(g) C2H6(g) is -84.4 is
kJ at 25 C. Calculate ∆U for the reaction
0
4 SO2(g) + 2 O2(g) 4 SO3(g)
at 25 0C. (R = 8.314 J K-1 mol-1)
W = -∆ng RT
Solution :
∆ng = 4 - 6 = - 2 mol, T = 298 K
∆H = ∆U + ∆ng RT
Hence,
∆ng = (moles of product gases) - (moles of
reactant gases) W = -2 mol × -8.314 J K-1 mol-1 × 298 K
∆H = -84.4 kJ, R = 8.314 J K-1 mol-1 Work is done on the system (since W > 0).
75
On the other hand, if l (liquid), g (gas) and aq (aqueous). ∆rH0
∑ Hproducts < ∑ Hreactants, ∆rH is negative value refers to physical states of substances
those appear in the equation.
which means that heat is released and the
iv. The given value of ∆rH0 assumes that the
reaction is exothermic.
reaction occurs in a given direction. ∆rH0 for
For example, the reverse reaction equals in magnitude and
N2(g) + O2(g) 2 NO2(g), opposite in the sign to that of the forward
reaction. A exothermic reaction on reversal
∆rH = 66.4 kJ (endothermic) becomes endothermic and vice versa.
2 KClO3(s) 2 KCl(s) + 3O2(g), v. When the coefficients indicating the
∆rH = -78 kJ (exothermic) number of moles of all substances in
thermochemical equation are multiplied or
4.10.3 Standard enthalpy of reaction(∆rH0) divided by a certain numerical factor, the
To compare enthalpy changes of different corresponding ∆rH0 need to be multiplied or
reactions they have to be reported under similar divided by the same.
set of conditions. Example of thermochemical equation
Thermodynamic standard state : The CH4(g) + 2 O2(g) CO2(g) + 2H2O(l),
standard state of a substance is the form ∆rH0 = -890 kJ
in which the substance is most stable at a
The equation signifies that when 1 mole
pressure of 1 bar and at temperature 298 K.
of gaseous CH4 and 2 moles of O2 in their
If the reaction involves species in solution its
standard states produce 1 mole of CO2 gas and
standard state refers to 1 M concentration.
2 moles of liquid water also in their standard
Standard states of certain elements and states the enthalpy change would be -890 kJ.
compounds are H2(g), Hg(g), Na(s) or
C(graphite), C2H5OH(l), CaCO3(s), CO2(g) Try this...
C2H5OH(l), H2O(l), CaCO3(s), CO2(g) refer to Given the thermochemical equation,
1 bar and 25 0C. C2H2(g)+ 5/2 O2(g)
The standard enthalpy (∆rH ) of 0 2CO2(g)+ H2O(l),
reaction is the enthalpy change accompanying ∆rH0 = -1300 kJ
the reaction when the reactants and products Write thermochemical equations when
involved are in their standard states. i. Coefficients of substances are multiplied
4.10.4 Thermochemical equation : It is by 2.
the balanced chemical equation in which ii. equation is reversed.
the enthalpy change, physical states and the 4.10.5 Standard enthalpy of formation
number of moles of reactants and products, (∆fH0)
have been specified. Here follow the guidelines
for writing thermochemical equations : Consider
1
i. Consider the balanced equation for H2(g) + 2 O2(g) H2O(l), ∆rH0 = -286 kJ
reactants and products. For the reaction where one mole of
ii. The value and appropriate sign of enthalpy liquid water in standard state is formed from
change is given on the right hand side. This H2 and O2 gases in their standard states, the
value is ∆rH0. enthalpy changes for the reaction would be the
iii. The physical states of reactants and standard enthalpy of formation of water. ∆fH
products are specified by letter, s (solid), of water is -286 kJmol-1.
76
The standard enthalpy of formation = [c ∆fH0(C) + d ∆fH0(D)] -
of a compound is the enthalpy change that [a ∆fH0(A) + b ∆fH0(B)]
accompanies a reaction in which one mole
of pure compound in its standard state is = ∑ ∆fH0 (products) - ∑ ∆fH0 (reactants)
formed from its elements in their standard (4.30)
states.
Problem 4.10
The formation of one mole of CH4 in its
Calculate standard enthalpy of reaction,
standard state from the elements carbon and
hydrogen in their standard states is represented 2C2H6(g) +7O2(g) 4 CO2(g) + 6 H2O(l)
by Given that
C(graphite)+ 2H2(g) CH4(g), ∆rH0= -74.8 kJ ∆fH0 (CO2)= -393.5 kJ mol-1,
or ∆fH0 (CH4) = -74.8 kJ mol-1 ∆fH0 (H2O)= -285.8 kJ mol-1 and
∆fH0(C2H6) = -84.9 kJ mol-1
Do you know ?
Solution -
The reaction to form a
substance from its constituent ∆rH0 = ∑ ∆fH0(products) - ∑ ∆fH0(reactants)
elements is hypothetical. It is not possible = [4 ∆fH0(CO2) + 6 ∆fH0(H2O)]
to combine C and H2 in the laboratory to
prepare CH4. The enthalpy of reaction - [2 ∆fH0(C2H6) + 7 ∆fH0(O2)]
for the formation of CH4 can be obtained = [4 mol × (-393.5 kJ mol-1) + 6 mol ×
indirectly by knowing the standard enthalpy (-285.8 kJ mol-1)]
change for system. The value -74.8 kJ mol-1
- [2 mol × (-84.9 kJ mol-1) + 0]
corresponds to the hypothetical reaction.
= -1574 kJ - 1714.8 kJ + 169.8 kJ
4.10.6 Standard enthalpy of reaction from
= -3119 kJ
standard enthalpies of formation
The standard enthalpies of formation 4.10.7 Standard enthalpy of combustion
of compounds are used to determine standard (∆cH0)
enthalpies of reactions. Consider the reaction
5
Calculations of ∆rH0 from ∆fH0 of C2H2(g) + O2(g) 2 CO2(g) + H2O(l),
2
compounds are based on the following. ∆rH0 = -1300 kJ
i. Standard enthalpies of formation of an In the above reaction, the standard enthalpy
element is zero. change of the oxidation reaction, -1300 kJ
is the standard enthalpy of combustion of
∆fH0(H2) = ∆fH0(Cl2) = ∆fH0(C) = 0
C2H2(g).
ii. Standard enthalpy of formation of a
The standard enthalpy of combustion of a
compound is equal to its standard enthalpy
substnce is the standard enthalpy change
∆fH0(compound) = H0(compound) accompanying a reaction in which one mole
Consider the reaction of the substance in its standard state is
completely oxidised.
aA + bB cC + dD
Standard enthalpy of the reaction is given by
∆fH0 = (cH0C+ dH0D) - (aH0A + bH0B)
77
Try this... Remember...
For diatomic molecules the bond
Write thermochemical equation enthalpy is the same as enthalpy
for complete oxidation of one mole of atomization.
of H2(g). Standard enthalpy change of the
reaction is -286 kJ. HCl molecule dissociates as
Is the value -286 kJ, enthalpy of HCl(g) H(g) + Cl(g), ∆rH0 = 431.9 kJ
formation or enthalpy of combustion or
both? Explain. ∆H0 (H-Cl bond) = 431.9 kJ mol-1
Average bond enthalpy in polyatomic
Problem 4.11: Estimate the standard molecules : Each covalent bond in polyatomic
enthalpy of combustion of CH4(g) if molecules is associated with its own specific
∆fH0(CH4) = -74.8 kJ mol-1, ∆fH0(CO2) = bond enthalpy. The thermochemical equation
-393.5 kJ mol-1 and ∆fH0(H2O) = -285.8 kJ for dissociation of H2O molecules is
mol-1
H2O(g) 2 H(g) + O(g), ∆rH0 = 927 kJ
Solution : The equation for the combustion
The above equation implies that the
of CH4 is
enthalpy change for breaking of two O-H
CH4(g) + 2O2(g) CO2(g) + 2H2O(l),
∆rH0 = ? bonds in one mole of gaseous H2O molecules
is 927 kJ. Two O-H bonds in H2O are identical
∆rH0 = [∆fH0 (CO2) + 2 ∆fH0(H2O)] the energies needed to break individual O-H
-[∆fH0(CH4) + 2 ∆fH0(O2)] bonds are different.
= [1 × (-393.5) + 2 × (-285.8)] The bonds in H2O are broken in
- [1 × (-74.8) + 2 × 0] successive steps as shown
∆cH0(CH4) = -890.3 kJ i. H2O(g) OH(g) + H(g) ∆rH0 = 499 kJ
ii. OH(g) O(g) + H(g) ∆rH0 = 428 kJ
4.10.8 Bond enthalpy
Consider the reaction H2O(g) 2 H(g) + O(g) ∆rH0 = 927 kJ
H2(g) H(g) + H(g), ∆rH0 = 436.4 kJ The total enthalpy change, 927 kJ, not
It shows that H-H bond in one mole twice as large of the O-H bond enthalpy. What
of H2(g) is decomposed producing gaseous H is the enthalpy of O-H bond in H2O molecule?
atoms. The enthalpy change of the reaction, For polyatomic molecules the average
436.4 kJ is bond enthalpy of the H-H bond. bond enthalpy of a particular bond would be
The enthalpy change required to break considered. Thus, the average bond enthalpy
particular covalent bond in one mole of of the O-H bond = 927 2 = 463.5 kJ or ∆H0
gaseous molecule to produce gaseous atoms (O-H) = 463.5 kJ mol-1
and/or radicals, is called bond enthalpy.
Try this...
Write equation for bond
enthalpy of Cl-Cl bond in Cl2
molecule ∆rH0 for dissociation of Cl2
molecule is 242.7 kJ
78
Do you know ? Examples 4.12 : Calculate the standard
In CH4 molecule there are four enthalpy of :
identical C-H bonds. The bond N2H4(g) + H2(g) 2 NH3(g)
enthalpy of all the 4 C-H bonds are different. if ∆H0(N-H) = 389 kJ mol-1, ∆H0(H-H) = 435
The breaking of C-H bonds in CH4 occurs kJ mol-1, ∆H0 (N-N) = 159 kJ mol-1
in four steps as follows:
Solution :
CH4(g) CH3(g) + H(g), ∆rH0 = 427 kJ
H H H
CH3(g) CH2(g) + H(g), ∆rH0 = 439 kJ N N (g) + H-H(g) 2N H
CH2(g) CH(g) + H(g), ∆rH0 = 452 kJ H H H
CH(g) C(g) + H(g), ∆rH0 = 347 kJ ∆rH0 = ∑ ∆H0 (reactant) -
CH4(g) C(g) + 4 H(g), ∆rH0 = 1665 kJ ∑ ∆H0 (product)
Average C-H bond enthalpy = [4∆H0(N-H) + ∆H0(N-N)
= 1665 kJ/4 = 416 kJ + ∆H0(H-H)] - [6 ∆H0(N-H)]
Hence, ∆rH0(C-H) = 416 kJ mol-1 = ∆H0 (N-N) + ∆H0(H-H) - 2 ∆H0(N-H)
= 1 × 159 + 1 mol × 435 - 2 × 389
Reaction and bond enthalpies : In a chemical
= -184 kJ
reaction bonds are broken and formed. The
enthalpies of reactions involving substances
having covalent bonds are calculated by
knowing the bond enthalpies of reactants and Example 4.13 : The enthalpy change of the
those in products. The calculations assume all following reaction
the bonds of a given type are identical. CH4(g) + Cl2(g) CH3Cl(g) + HCl(g),
Enthalpy change of a reaction ∆rH = -104 kJ. Calculate C-Cl bond
0
79
4.10.9 Hess’s law of constant heat summation
Solution :
The law states that, “Overall the
Reverse Eq.(i) and then add to Eq. (ii)
enthalpy change for a reaction is equal to
sum of enthalpy changes of individual steps 2Fe(s) + Al2O3(s) 2 Al(s) + Fe2O3(s),
in the reaction”. ∆rH0 = +847.6 kJ
The enthalpy change for a chemical 2 Al(s) + 3/2 O2(g) Al2O3(s),
reaction is the same regardless of the path by ∆rH0 = -1670 kJ
which the reaction occurs. Hess’s law is a direct
consequence of the fact that enthalpy is state 2Fe(s) + 3/2 O2(g) Fe2O3(s),
function. The enthalpy change of a reaction ∆rH0 = -822.4 kJ
depends only on the initial and final states and
not on the path by which the reaction occurs.
To determine the overall equation Example 4.15 : Calculate the standard
of reaction, reactants and products in the enthalpy of the reaction,
individual steps are added or subtracted like SiO2(s) + 3C(graphite) SiC(s) + 2 CO(g)
algebraic entities. from the following reactions,
Consider the synthesis of NH3 i. Si(s) + O2(g) SiO2(s),
i. 2H2(g) + N2(g) N2H4(g), ∆rH0 = -911 kJ
∆rH10 = + 95.4 kJ ii. 2 C(graphite) + O2(g) 2CO(g),
ii. N2H4(g) + H2(g) 2 NH3(g), ∆rH = -221 kJ 0
80
4.11 Spontaneous (irreversible) process : processes tend to occur in a direction
Spontaneous processes have a natural that leads to equilibrium.
tendency to occur and do not require any 4.11.1 Energy and spontaneity :
external influence for their occurrence. The spontaneous reaction takes place
in a direction in which energy of the system
Do you know ?
is lowered. It is accompanied by release of
i. The aqueous NaOH and energy. The reaction between NaOH and
HCl solutions mixed together. HCl is exothermic (∆rH° = -57 kJ) and is
NaOH immediately combines with spontaneous.
HCl to form NaCl and water.
On the other hand :
NaOH(aq)+HCl(aq) NaCl(aq)+ H2O(l),
∆rH0 = -57 kJ i. Ice melts spontanoeusly above 0 °C by
absorbing heat from the surroundings. It
No external force or energy is required
is endothermic.
for the reaction to occur. This is
spontaneous. The process stops when ii. Likewise, NaCl dissolves spontaneously in
HCl or NaOH is consumed. water with the absorbtion of heat from the
surroundings.
NaCl is dissolved in water, it does not
react with water to produce NaOH NaCl(s) + aq Na⊕(aq) + Cl (aq)
and HCl. ∆H0 = +3.9 kJ mol-1
These are endothermic and spontaneous. It
ii. Water flows from higher level to lower is therefore, clear that the exothermicity is
level. It is not necessary to apply
not the sufficient criterion for deciding of
external force. It is a spontaneous
spontaneity. There needs to be an another
process. The flow ceases when two
factor to describe spontaneity.
levels become equal or when the
equilibrium is reached. 4.11.2 Entropy :
To know what entropy consider the following
iii. Ice melts spontaneously above 0 °C.
processes:
iv. Hot coffee in a cup placed in a room i. In solid state water molecules in ice are
cools down releasing heat to the arranged in a definite order.
surroundings. This is spontaneous.
ii. When ice melts, this highly crystalline
arrangements of water molecules collapse.
Key points of spontaneous process The molecules become free in liquid state.
i. It occurs of its own and does not require An ordered state thus tends to become
any external agency to occur. more disordered.
ii. It proceeds in one direction and cannot
take place in the opposite direction unless
the external stimulant is present.
iii. The spontaneous processes can be rapid or
slow or spontaneity is not concerned with Ice highly H2O(l) H2O (g)
the rate of the reaction. ordered disordered highly
state state disordered
iv. The processes continues till equilibrium
state
is reached. The spontaneous (natural)
Fig. 4.10 Increasing disorder
81
iii. When liquid water vaporises, gaseous water Quantitative definition of entropy
molecules move freely and randomly in Entropy is a measure of molecular
the available space. A less disordered disorder or randomness. An entropy change
state becomes highly disordered as shown of a system is equal to the amount of heat
in Fig. 4.10. transferred (Qrev) to it in a reversible manner
During melting of ice or the vaporisation divided by the temperature in kelvin T at
of liquid water the disorder or randomness which the transfer takes place. Thus
increases. The disorder or randomness is Q
∆S = rev (4.32)
measured by entropy, denoted by S. Greater T
the disorder of a system larger is its entropy. the ∆S is thus expressed in J K-1.
The melting of ice and vaporisation of liquid Entropy or its change ∆S is a state
water show that disorder and hence, entropy function and depends on the initial and final
of substance increases as it passes from solid states of the system and not on the path
to liquid to gas. connecting two states.
In both processes entropy change i. When heat is added to a system the molecular
∆S > 0. Look at the following processes : motions increase owing to increase of their
i. Dissolution of solid I2 in water : kinetic energies. This results in increased
molecular disorder and thus entropy of the
I2(s) + aq. I2 (aq) (∆S is positive) system. ∆S is proportional to Qrev.
ordered state disordered state ii. The effectiveness of the addition of
When solid iodine dissolves in water I2 heat to increase randomness depends on
molecules move randomly. Thus disorder and temperature.
hence, entropy of the system increases or ∆S If a certain amount of heat is added to
is positive for the dissolution process. system at the higher temperature then the
ii. Dissociation of H2 molecule into atoms disorder caused is lesser than that caused
H2(g) 2H(g) (∆S is positive) by adding the same amount of heat is added
to system at the lower temperature Thus,
One mole of H2 gas is converted into two ∆S relates reciprocally to temperature at
H atoms. Larger disorder is associated with which the of heat is added.
separated H atoms than with H2 molecule.
Thus, disorder and hence entropy increases 4.11.3 Entropy and spontaneity
or ∆S is positive. (Second law of Thermodynamics)
Look at the following examples :
Try this... i. The entropy increases when ice melts
State whether ∆S is positive, above 0 °C and water vaporizes at 100
negative or zero for the following °C. Both are spontaneous.
reactions. ii. Consider the spontaneous reaction at room
i. 2H2(g) + O2(g) 2H2O(l) temperature
ii. CaCO3(s) ∆
CaO(s) + CO2(g) 2H2O2 (l) 2H2O (l) + O2 (g),
∆S = +126 J K-1
Entropy increases due to the formation of
O2 gas.
82
From above examples, it is clear that From above,
the entropy of the system increases in the i. ∆Stotal > 0, the process is spontaneous
spontaneous processes. Consider the reaction.
ii. ∆Stotal < 0, the process is nonspontaneous
2H2(g) + O2(g) 2H2O(l),
iii. ∆Stotal = 0, the process is at equilibrium
∆S = -327 J K-1.
4.11.5 Gibbs energy
The entropy of the system decreases.
Note the reaction is spontaneous. As pointed out in the preceding section, it
is necessary to determine, ∆Ssys and ∆Ssurr, for
4.11.4 Second law of thermodynamics : predicting the spontaneity of a reaction. We
The second law of thermodynamics are more interested in the system (reaction
states that total entropy of a system and mixture) . It. is, therefore convenient to
its surroundings increases in a spontaneous consider the criterion of spontaneity in terms
process. For the process to be spontaneous of the thermodynamic properties of a system.
∆Stotal = ∆Ssys + ∆Ssurr > 0 (4.33) This problem was solved by American
theoretician J. W. Gibbs. He introduced a new
Consider thermodynamic property called Gibbs energy
2H2(g) + O2(g) 2H2O(l) usually denoted by G.
∆S = -327 J K-1, and ∆H = -572 kJ (both at The Gibbs energy is defined as
298 K) G = H - TS (4.34)
To find ∆Stotal, we need to know ∆Ssurr. where H is enthalpy and S entropy of the
∆H for the reaction is -572 kJ. When 2 moles system. Since H, T and S are state functions,
of H2 and 1 mole of O2 gas combine to form G is state function. A change in Gibbs energy
2 moles of liquid water, 527 kJ of heat is depends on initial and final states of the
released which is received by surroundings at system and not on a path connecting the two
constant pressure (and 298 K). The entropy states.
change of surroundings is
The change in Gibbs energy at constant
Q 572 × 103 J
∆Ssurr = rev = = 1919 J K-1 temperature and constant pressure is given by
T 298 K
∆Stotal = ∆Ssys + ∆Ssurr ∆G = ∆H - T ∆S (4.35)
= -327 J K-1 + 1919 J K-1 4.11.6 Gibbs energy and spontaneity
= + 1592 J K-1 The total entropy change that
accompanies a process is given by
∆Stotal > 0.
∆Stotal = ∆Ssys + ∆Ssurr
The reaction is thus spontaneous. It
follows that to decide spontaneity of reactions, = ∆S + ∆Ssurr (4.36)
we need to consider the entropy of system and The subscript sys that refers to the system
its surroundings. is dropped hereafter.
The total entropy increases during a Relation between ∆G and ∆Stotal
spontaneous process that finally reaches
equilibrium. The equilibrium corresponds to According to second law of
maximum total entropy. The total entropy thermodynamics for a process to be
change, ∆Stotal must be zero for a process at spontaneous, ∆ Stotal > 0
equilibrium.
83
If ∆H is the enthalpy change 3. For ∆H negative and ∆S is positive it
accompanying a reaction (system) the follows that ∆G is negative regardless of
enthalpy change of the surroundings is -∆H. temperature.
With 4. For ∆H positive and ∆S is negative then
∆Ssurr = - ∆H (4.37) ∆G is positive regardless of temperature.
T
Such reactions are nonspontaneous at all
Substituting above into Eq. (4.36), temperatures.
84
When the reaction reaches equilibrium, ∆G0 = 0 Problem 4.17
and Qc and Qp become Kc and Kp, respectively.
Thus, For a certain reaction ∆H0 is -224 kJ
and ∆S is -153 J K-1. At what temperature
0
85
Problem 4.19 : Calculate ∆Stotal and state Problem 4.20 : Calculate ∆G for the
whether the reaction is spontaneous or reaction at 25 0C
nonspontaneous at 25 0C. CO(g) + 2 H2(g) CH3OH(g), ∆G0
HgS(s) + O2(g) Hg(l) + SO2(g), = -24.8 kJ mol The partial pressures of
-1
Exercises
86
iv. The enthalpy of formation for all x. Bond enthalpies of H-H, Cl-Cl and
elements in their standard states is H-Cl bonds are 434 kJ mol-1, 242 kJ
a. unity mol-1 and 431 kJ mol-1, respectively.
Enthalpy of formation of HCl is
b. zero
a. 245 kJ mol-1 b. -93 kJmol-1
c. less than zero
c. -245 kJ mol-1 d. 93 kJ mol-1
d. different elements
2. Answer the following in one or two
v. Which of the following reactions is sentences.
exothermic?
i. Comment on the statement: no work
a. H2(g) 2H(g) is involved in an expansion of gas in
b. C(s) C(g) vacuum.
c. 2 Cl(g) Cl2(g) ii. State the first law of thermodynamics.
d. H2O(s) H2O(l) iii. What is enthalpy of fusion?
vi. 6.24 g of ethanol are vaporized by iv. What is standard state of a substance?
supplying 5.89 kJ of heat. Enthalpy v. State whether ∆S is positive, negative
of vaporization of ethanol will be or zero for the reaction 2H(g)
a. 43.4 kJ mol-1 H2(g). Explain.
b. 60.2 kJ mol-1 vi. State second law of thermodynamics
in terms of entropy.
c. 38.9 kJ mol-1
vii. If the enthalpy change of a reaction
d. 20.4 kJ mol-1
is ∆H how will you calculate entropy
vii. If the standard enthalpy of formation of surroundings?
of methanol is -238.9 kJ mol-1 then
viii. Comment on spontaneity of reactions
entropy change of the surroundings
for which ∆H is positive and ∆S is
will be
negative.
a. -801.7 J K-1 b. 801.7 J K-1
3. Answer in brief.
c. 0.8017 J K -1
d. -0.8017 J K -1
i. Obtain the relationship between ∆G0
viii. Which of the following are not state of a reaction and the equilibrium
functions? constant.
1. Q + W 2. Q 3. W 4. H-TS ii. What is entropy? Give its units.
a. 1,2 and 3 b. 2 and 3 iii. How will you calculate reaction
c. 1 and 4 d. 2,3 and 4 enthalpy from data on bond
enthalpies?
ix. For vaporization of water at 1 bar,
iv. What is the standard enthalpy of
∆H = 40.63 kJ mol-1 and ∆S = 108.8 combustion ? Give an example.
J K-1 mol-1. At what temperature,
∆G = 0 ? v. What is the enthalpy of atomization?
Give an example.
a. 273.4 K b. 393.4 K
vi. Obtain the expression for work done
c. 373.4 K d. 293.4 K in chemical reaction.
87
vii. Derive the expression for PV work ix. Calculate standard enthalpy of reaction,
viii. What are intensive properties? Fe2O3(s) + 3CO(g) 2 Fe(s) + 3CO2(g),
Explain why density is intensive from the following data.
property. ∆fH0(Fe2O3) = -824 kJ/mol,
ix. How much heat is evolved when 12 g ∆fH0(CO) = -110 kJ/mol,
of CO reacts with NO2 ? The reaction
is : ∆fH0(CO2) = -393 kJ/mol
Ans. : (-25 kJ)
4 CO(g) + 2 NO2(g)
x. For a certain reaction ∆H0 =219 kJ and
4 CO2(g) + N2(g), ∆rH0 = -1200 kJ ∆S0 = -21 J/K. Determine whether the
4. Answer the following questions. reaction is spontaneous or nonspontaneous.
i. Derive the expression for the maximum xi. Determine whether the following reaction
work. is spontaneous under standard state
conditions.
ii. Obtain the relatioship between ∆H and ∆U
for gas phase reactions. 2 H2O(l) + O2(g) 2H2O2(l)
iii.
State Hess’s law of constant heat if ∆H0 = 196 kJ, ∆S0 = -126 J/K
summation. Illustrate with an example. Does it have a cross-over temperature?
State its applications. (Nonspontaneous, No)
iv. Although ∆S for the formation of two xii. Calculate ∆U at 298 K for the reaction,
moles of water from H2 and O2 is
-327JK-1, it is spontaneous. Explain. C2H4(g) + HCl(g) C2H5Cl(g),
(Given ∆H for the reaction is -572 kJ). ∆H = -72.3 kJ
v. Obtain the relation between ∆G and ∆Stotal How much PV work is done?
Comment on spontaneity of the reaction. Ans. : (-69.8 kJ, 2.48 kJ)
vi. One mole of an ideal gas is compressed xiii. Calculate the work done during synthesis
from 500 cm3 against a constant external of NH3 in which volume changes from
pressure of 1.2 × 105 Pa. The work involved 8.0 dm3 to 4.0 dm3 at a constant external
in the process is 36.0 J. Calculate the final pressure of 43 bar. In what direction the
volume. (200 cm3) work energy flows?
vii. Calculate the maximum work when 24 Ans. : (17.2 kJ, work energy flows into
g of O2 are expanded isothermally and system)
reversibly from the pressure of 1.6 bar to xiv. Calculate the amount of work done in the
1 bar at 298 K. (a) oxidation of 1 mole HCl(g) at 200 0C
Ans. : (-873.4 J) according to reaction.
viii. Calculate the work done in the 4HCl(g) + O2(g) 2 Cl2(g) + 2 H2O(g)
decomposition of 132 g of NH4NO3 at (b) decomposition of one mole of NO at
100 0C. 300 0C for the reaction
NH4NO3(s) N2O(g) + 2 H2O(g) 2 NO(g) N2(g) + O2
State whether work is done on the system Ans. : (a = + 983 kJ ; b = 0 kJ)
or by the system.
Ans. : (-18.6 kJ)
88
xv. When 6.0 g of O2 reacts with CIF as per is -620 J when 100 ml of ethylene and 100
2Cl F(g) + O2(g) Cl2O(g) + OF2(g) mL of H2 react at 1 bar pressure. Calculate
the pressure volume type of work and ∆U
The enthalpy change is 38.55 kJ. What is for the reaction.
standard enthalpy of the reaction ?
Ans.: (W = +10.13 J; ∆U = -609.9 J)
(∆rH0 = 205.6 kJ)
xx. Calculate the work done and comment
xvi. Calculate the standard enthalpy of on whether work is done on or by the
formation of CH3OH(l) from the following system for the decomposition of 2 moles of
data NH4NO3 at 100 0C
3
i.CH3OH(l)+ O2(g) NH4NO3(s) N2O(g) + 2H2O(g)
2
CO2(g)+ 2H2O(l), Ans. (-18.61 kJ, work is done by the system)
∆H0 = -726 kJ mol-1
ii. C (Graphite) + O2(g) CO2(g), Activity :
∆cH0 = -393 kJ mol-1 Following are some processes
1 occurrring in nature.
iii. H2(g) + O2(g) H2O(l),
2 • River originates in a mountain and
∆fH0 = -286 kJ mol-1
flows towards sea.
Ans. : (- 239 kJ mol-1) • After proper incubations for 21 days
xvii. Calculate ∆H for the following reaction
0 a chicken egg hatches and baby chick
at 298 K comes out.
H2B4O7(s) + H2O(l) 4HBO2 (aq) • List out some more processes you
come across in nature.
i. 2H3BO3(aq) B2O3(s) + 3H2O(l),
• Identify the processes that are in
∆H = 14.4 kJ mol
0 -1
accordance with the second law of
ii. H3BO3(aq) HBO2(aq) + H2O,(l) thermodynamics and those which
∆H0 = -0.02 kJ mol-1 are against it.
89
5. ELECTROCHEMISTRY
makes possible the manufacture of essential
Can you recall ? chemicals. You have learnt preparation of
• What is a redox reaction ? NaOH, widely used in the manufacture of
• Which form of energy is soaps, detergents and paper, by electrolysis of
converted into electrical energy in dry NaCl. Electrolysis is possibly the only means
cells ? to produce fluorine. The processes such as
electro-refining (for purification of metals),
electroplating (for coating one metal is on the
surface of another) are also electrochemical
processes.
In standard XI, you learnt redox reactions.
Redox reaction forms the basis for the
• How is NaOH manufactured from generation of electricity by chemical reactions
NaCl ? and also for chemical reactions brought out
by means of electricity. These processes
5.1 Introduction : Dry cell is used to power are carried out in an electrochemical cell.
our electrical and electronic equipments Electrochemistry deals with the design and
because it generates electricity. Do you operation of such cells.
know how does a dry cell generate electricity
? A chemical reaction occurs in it which The current research in electrochemistry
generates electricity. Thus in a dry cell is focused on the design of fuel cells. The
chemical energy is converted into electrical fuel cells are being explored as convenient
energy. and compact source of electricity.
You are familiar with the electrolysis 5.2 Electric conduction : We know that the
of solutions of ions. Electrolysis is breaking electric current represents a charge transfer.
down of an ionic compound by the passage A charge transfer or flow of electricity occurs
of eletricity. Breaking down of an electrolyte through substances called conductors. There
during electrolysis is a chemical reaction are two types of conductors which give rise
that takes place by the passage of electricity. to two types of conduction of electricity.
Electrical energy is, thus, converted into 5.2.1 Metallic conduction :
chemical energy.
Can you recall ?
Electrochemistry is the area of chemistry
• What is the origin of electrical
which is concerned with interconversion of
conductivity of metals ?
chemical and electrical energy.
It also deals with the resistance and Electrical conduction through metals
conductance of aqueous electrolytic solutions. involves a direct flow of electrons from one
The determination of conductivities of aqueous point to the other. The outermost electrons of
electrolytic solutions provide an information metals form conduction bond. The electrons in
on the extent of ionization of electrolytes in conduction band are free to move and hence
water. (Refer to Chapter 3). flow under the influence of applied electrical
potential (Chapter 1). Metallic conductors
The study of electrochemical cells is
are, thus, electronic conductors.
important in science and technology. It
90
5.2.2 Electrolytic or ionic conduction : i. The conducting and nonconducting
Electrolytic conduction involves conduction nature of solutions can be identified
of electric current by the movement of ions by measurement of their conductivity.
of the electrolytes. In this type of conduction Sucrose and urea do not dissociate in their
the charge transfer occurs in the form of aqueous solutions. The conductivities of
movement of ions through molten electrolytes these solutions are nearly the same as
or the aqueous solutions of electrolytes. that of water. These substances are called
Substances such as ionic salts, strong or weak nonelectrolytes.
acids and bases are the electrolytes. These On the other hand, substances like
dissociate into ions when dissolved in polar potassium chloride, acetic acid, sodium
solvents such as water. Ionic solids dissociate hydroxide, HCl dissociate in their aqueous
into ions in molten state as well. solutions. The conductivities of their
Conduction through electrolytic aqueous solutions are higher than that
conductors involves transfer of matter from of water. These are called electrolytes.
one part of the conductor to the other. It Electrolytes conduct electricity in molten
means that the current flowing through an state or when dissolved in water.
electrolytic conductor is accompanied by a ii. On the basis of high or low electrical
chemical change. conductivity electrolytes are classified
5.2.3 Information provided by measurement into strong and weak electrolytes. The
of conductivities of solutions : substances such as ionic salts, strong
acids or bases are almost completely
Try this... dissociated in aqueous solutions. These
are strong electrolytes. The solutions
of strong electrolytes exhibit high
Switch Battery
conductivities.
The weak acids and weak bases are
Non conductive weak electrolytes. They dissociate to a
frame Lamp very small extent in aqueous solutions
and show lower conductivities than those
Electrodes of strong electrolytes.
Solution Remember...
• Arrange a simple set up as shown in Electrolyte is a compound that
the diagram above. conducts electricity when molten or
in aqueous solution and breaks down into
• The lamp will glow when circuit is ions during electrolysis.
complete.
5.3 Electrical conductance of solution :
• Prepare 5 % (mass/volume) solutions
According to Ohm's law, the electrical
of cane sugar, acetic acid, sodium
resistance R of a conductor is equal to the
chloride and urea in distilled water.
electric potential difference V divided by the
• Check the electrical conductivity electric current, I :
of these solutions using the above V
R= (5.1)
assembly. Compare these with that I
observed with distilled water. The SI unit of potential is volt (V) and
that of current is ampere (A). The unit of
91
electrical resistance is ohm denoted by the From Eq. (5.2) and Eq. (5.4), we write
symbol Ω (omega). Thus, Ω = VA-1. l 1 l
k=G = (5.5)
a R a
The electrical conductance, G, of a Combination of Eq. (5.3) and Eq. (5.5)
solution is reciprocal of resistance. shows that k = 1/ρ.
1
G= (5.2) Units of electrolytic conductivity
R
The SI unit of G is siemens, denoted by
Quantity SI unit Common unit
S, which is equal to Ω-1. Therefore, we write
Length m cm
S = Ω-1 = AV-1 = CV-1s-1 where C represents
coulomb, the unit of electricity related to Area m2 cm2
current strength in ampere and time in Resistance Ω Ω
seconds as C = A s. Conductivity Ω m-1 or
-1
Ω-1 cm-1
S m-1
The electrical resistance of a conductor
is proportional to length l and inversely 5.3.2 Molar conductivity (∧) : The electrolytic
proportional to cross sectional area a. Thus, conductivity is not suitable for comparing
l l conductivities of different solutions. The
R∝ or R = ρ (5.3)
a a conductivity of a solution depends on number
where ρ, the proportionality constant is of ions present in unit volume of solution.
called resistivity of the conductor. It is the The solution of higher concentration contains
resistance of conductor of unit length and unit more ions and exhibits higher conductivity
cross sectional area. than the solution of lower concentration. To
Can you recall ? compare conductivities of different solutions,
they must have the same concentration.
What is the SI unit of In 1880, the German physicist F.W.G.
resistivity ? Kohlrausch introduced the term molar
5.3.1 Conductivity (k) : We have seen that conductivity denoted by ∧ (lambda).
G = 1/R and R is directly proportional to The molar conductivity of an electrolytic
length and inversely proportional to its cross solution is the electrolytic conductivity, k,
sectional area. It, therefore, follows that G divided by its molar concentration c.
is directly proportional to a and inversely k
∧= (5.6)
proportional to the length l. Thus c
a a SI units of k are S m-1 and that of
G∝ or G = k (5.4) c are mol m-3. Hence SI units of ∧ are
l l
The proportionality constant k is called S m2 mol-1. Common units employed for
conductivity. G = k if length and cross molar conductivity are Ω-1 cm2 mol-1.
sectional area of conductor are unity. Significance of molar conductivity : To
Thus, conductivity is the electrical understand the significance of ∧, consider
conductance of a conductor of unit length volume of a solution containing 1 mole of
and unit area of cross section. In other words, dissolved electrolyte. Suppose the solution is
the conductivity is the electrical conductance placed between two parallel electrodes 1 cm
of unit cube of material. Conductivity of apart and large enough to accommodate it.
solution of an electrolyte is called electrolytic The electrical conductance exhibited by this
conductivity which refers to the electrical solution is the molar conductivity. The molar
conductance of unit volume (1 m3 or 1 cm3) conductivity is the electrical conductance
of solution. generated by all the ions in 1 mole of the
electrolyte.
92
Remember... ∧ = 223 Ω-1 cm2 mol-1, c = 0.05 mol L-1
Conductivity is electrical Hence
conductance due to all the ions in 223 Ω-1 cm2 mol-1 × 0.05 mol L-1
k=
1 cm3 of given solution. Molar conductivity 1000 cm3L-1
is the electrical conductance due to the ions = 0.01115 Ω cm-1
-1
95
1. Determination of cell constant : The cell
Try this...
constant is determined using the 1 M, 0.1 M
Obtain the expression for or 0.01 M KCl solutions. The conductivity
dissociation constant in terms of ∧c of KCl solution is well tabulated at various
and ∧0 using Ostwald's dilution law. temperatures. The resistance of KCl solution
is measured by Wheatstone bridge. (Refer to
5.3.9 Measurement of conductivity : The standard XII Physics Textbook Chapter 9)
conductivity of a solution can be determined In Fig. 5.3 AB is the uniform wire. Rx is
from the resistance measurements by the variable known resistance placed in one
Wheatstone bridge. arm of Wheatstone bridge.
Conductivity Cell : The conductivity cell
consists of a glass tube with two platinum
conductivity cell
plates coated with a thin layer of finely
divided platinium black. This is achieved by
the electrolysis of solution of chloroplatinic
acid. The cell is dipped in a solution whose
resistance is to be measured as shown in Fig.
5.2. A.C.
solution of unknown
resistance
Fig. 5.3 : Measurement of resistance
The conductivity cell containing KCl
solution of unknown resistance is placed in
the other arm of Wheatstone bridge. D is a
current detector. F is the sliding contact that
moves along AB. A.C. represents the source
of alternating current.
The sliding contact is moved along AB
Fig. 5.2 : Conductivity cell
until no current flows. The detector D shows
Cell constant : The conductivity of an no deflection. The null point is, thus, obtained
electrolytic solution is given by Eq. (5.5), at C.
1 l
k= According to Wheatstone bridge principle,
R a
Rsolution Rx
For a given cell, the ratio of separation =
l (AC) l (BC)
(l) between the two electrodes divided by the
area of cross section (a) of the electrode is l(AC)
Hence, Rsolution = × Rx (5.15)
called the cell constant. Thus, l(BC)
l By measuring lengths AC and BC and
Cell constant = (5.13)
a knowing Rx, resistance of KCl solution can
SI unit of cell constant is m-1 which is be calculated. The cell constant is given by
conveniently expressed in cm-1. The Eq. (5.5) Eq. (5.13).
then becomes
cell constant Cell constant = kKCl × Rsolution
k= (5.14)
R The conductivity of KCl solution is
The determination of conductivity consists known. The cell constant, thus, can be
of three steps : calculated.
96
2. Determination of conductivity of given 5.4.1 Electrochemical reactions :
solution : KCl solution in the conductivity
Can you recall ?
cell in step (1) is replaced by the given
solution whose conductivity is to be measured. What is the reaction involving
Its resistance is measured by the process transfer of electrons from one
described in step (1). The conductivity of chemical species to another called?
given solution is then calculated as : The chemical reaction occuring in
Cell constant
k= electrochemical cells involves transfer
Rsolution
of electrons from one species to the
3. Calculation of molar conductivity : The
other. It is a redox reaction, we learnt in
molar conductivity of the given solution is
(Std. XI, Chapter 6).
then calculated using Eq. (5.9).
Electrochemical reactions, are made of
1000 k
∧= c oxidation and reduction half reactions. The
oxidation half reaction occurs at one electrode
Problem 5.5 : A conductivity cell containing and the reduction half reaction occurs at the
0.01M KCl gives at 250C the resistance other electrode. The net cell reaction is the
of 604 ohms. The same cell containing sum of these half reactions.
0.001M AgNO3 gives resistance of 6530 5.4.2 Electrodes : Electrodes are the surfaces
ohms. Calculate the molar conductivity of on which oxidation and reduction half
0.001M AgNO3. [Conductivity of 0.01M reactions take place. Electrodes may or may
KCl at 25 0C is 0.00141 Ω-1 cm-1] not participate in the reactions. The electrodes
Solution : which do not take part in reactions are inert
i. Calculation of cell constant electrodes.
Cell constant = kKCl × RKCl Cathode : It is an electrode at which the
= 0.00141 Ω- cm-× 604 Ω reduction takes place. At this electrode the
= 0.852 cm-1 species undergoing reduction gains electrons.
ii. Calculation of conductiviy of AgNO3' Anode : It is an electrode at which oxidation
Cell constant takes place. At this electrode, the species
k= where R = 6530 Ω undergoing oxidation loses electrons.
R
5.4.3 Types of electrochemical cells : There
0.852 cm-1
= are two types of electrochemical cells.
6530 Ω
1. Electrolytic cell : In this type of cell,
= 1.3 × 10-4 Ω-1 cm-1
a nonspontaneous reaction, known as
iii. Calculation of molar conductivity of electrolysis, is forced to occur by passing a
AgNO3 direct current from an external source into
1000k
∧= where c = 0.001 M the solution. In such cells electrical energy
c
is converted into chemcial energy. The anode
1000 cm3 L-1 × 1.3 × 10-4 Ω-1 cm-1
= of electrolytic cell is positive and cathode is
0.001 mol L-1
negative.
= 130 Ω-1 cm2 mol-1
2. Galvanic or voltaic cell : In galvanic
5.4 Electrochemical cells : An electrochemical (voltaic) cell a spontaneous chemical reaction
cell consists of two metal plates or carbon produces electricity. In these cells chemical
(graphite) rods. These electronic conductors energy is converted into electrical energy.
are dipped into an electrolytic or ionic The anode of galvanic cell is negative and
conductor. cathode is positive.
97
The carbon electrode connected to
Use your brain power terminal electrode of the battery is anode
Distinguish between
and that connected to negative terminal of
electrolytic and galvanic cells.
the battery is cathode.
5.5 Electrolytic cell
Remember...
Do you know ? In electrolysis the electrodes
Michael Faraday was the are usually inert, Pt or graphite.
first person to explain electrolysis
nearly 200 years ago. Reactions occuring in the cell : Fused NaCl
contains Na⊕ and Cl ions which are freely
Electrolytic cell consists of a container mobile. When potential is applied, cathode
in which electrolyte is placed. Two electrodes attracts Na⊕ ions and anode attracts Cl ions.
are immersed in the electrolyte and connected As these are charged particles, their migration
to a source of direct current. results in an electric current. When these
ions reach the respective electrodes, they
At anode (+) a species oxidises with
are discharged according to the following
the removal of electrons. These electrons are
reactions.
pulled from anode and pushed to cathode
through an external circuit. The electrons Oxidation half reaction at anode :
are supplied to species at cathode which are Cl ions migrate to anode. Each Cl
reduced. ion, that reaches anode, gives one electron
to anode. It oxidises to neutral Cl atom in the
Remember... primary process. Two Cl atoms then combine
Electrolysis is the process to form chlorine gas in the secondary process.
of breaking down of an ionic
2 Cl (l) Cl (g) + Cl (g) + 2e
compound in molten state or in aqueous
(primary process)
solution by the passage of electricity.
Cl (g) + Cl (g) Cl2 (g)
5.5.1 Electrolysis of molten NaCl (secondary process)
Construction of cell : The electrolytic cell 2Cl (l) Cl2 (g) + 2e
consists of a container in which fused NaCl is (overall oxidation)
placed. Two graphite electrodes are immersed
The battery sucks electrons so produced
in it. They are connected by metallic wires to
at the anode and pushes them to cathode
a source of direct current that is battery. This
through a wire in an external circuit. The
is shown in Fig. 5.4.
battery thus serves as an electron pump. The
electrons from the battery enter into solution
through cathode and leave the solution
Battery through anode.
(D.C. source)
Reduction half reaction at cathode : The
Carbon anode Carbon cathode
electrons supplied by the battery are used
in cathodic reduction. Each Na⊕ ion, that
reaches cathode accepts an electron from the
Cl2 gas Fused Na
cathode and reduces to metallic sodium.
Fused NaCl
Na⊕ (l) +e Na (l)
Fig. 5.4 : Electrolysis of fused NaCl
98
Net cell reaction The other is the reduction of water to
The net cell reaction is the sum of two hydrogen gas.
electrode reactions. ii. 2 H2O (l) + 2e H2 (g) + 2 OH (aq),
2 Cl (l) Cl2 (g) + 2e E0 = - 0.83 V
(oxidation half reaction) The standard potential (section 5.7.1) for
2 Na⊕ (l) + 2e 2 Na (l) the reduction of water is higher than that for
(reduction half reaction) reduction of Na⊕. This implies that water has
much greater tendency to get reduced than the
2 Na⊕ (l) + 2 Cl (l) 2 Na (l) + Cl2(g) Na⊕ ion. Hence reaction (ii), that is, reduction
(overall cell reaction) of water is the cathode reaction when the
Results of electrolysis of molten NaCl aqueous NaCl is electrolysed.
i. A pale green Cl2 gas is released at anode. Oxidation half reaction at anode : At anode
there will be competition between oxidation
ii. A molten silvery-white sodium is formed
of Cl ion to Cl2 gas as in case of molten
at cathode.
NaCl and the oxidation of water to O2 gas.
Decomposition of NaCl into metallic
i. 2 Cl (aq) Cl2 (g) +2e ,E0oxi = - 1.36 V
sodium and Cl2(g) is nonspontaneous. The
electrical energy supplied by the battery ii. 2H2O (l) O2 (g) + 4H⊕ (aq) + 2e
forces the reaction to occur. E0oxi = - 0.4 V
Standard electrode potential for the
Remember...
oxidation of water is greater than that of Cl
When molten ionic compound ion or water has greater tendency to undergo
is electrolysed, a metal is formed oxidation. It is, therefore, expected that anode
at the negative electrode and a nonmetal half reaction would be oxidation of water.
at the positive electrode. The experiments have shown, however, that
the gas produced at the anode is Cl2 and
5.5.2 Electrolysis of aqueous NaCl : not O2. This suggests that anode reaction is
Electrolysis of an aqueous NaCl can be oxidation of Cl to Cl2 gas. This is because
carried out in the cell used for the electrolysis of the overvoltage, discussion of which is
of molten NaCl using inert electrodes shown beyond the scope of the present book.
in Fig. 5.4. The fused NaCl is replaced by
moderately concentrated aqueous solution of It has been found experimentally
NaCl. The water involved in electrolysis of that the actual voltage required for
aqueous NaCl, leads to electrode reactions electrolysis is greater than that calculated
that differ from electrolysis of molten NaCl. using standard potentials. This additional
Reduction half reaction at cathode : At voltage required is the overpotential.
cathode, two reduction reactions compete.
One is the reduction of Na⊕ ions as in case
of molten NaCl. Do you know ?
i. Na⊕ (aq) + e Na (s), E0 = -2.71 V Refining of metal and
electroplating are achieved by
electrolysis.
99
Overall cell reaction Q (C) = I (A) × t (s) (5.16)
It is the sum of electrode reactions. ii. Calculation of moles of electrons passed
2 Cl (aq) Cl2 (g) + 2e Total charge passed is Q(C). The charge
(oxidation at anode) of one mole electrons is 96500 coulombs (C).
2 H2O (l) + 2e H2 (g) + 2 OH (aq) It is referred to as one faraday (IF). Hence,
(reduction at cathode) Moles of electrons actually passed
Q(C)
2 Cl (aq) + 2 H2O (l) Cl2 (g) + H2(g) = (5.17)
96500 (C/mol e )
+ 2 OH (aq)
iii. Calculation of moles of product formed
(overall cell reaction)
The balanced equation for the half
Results of electrolysis of aqueous NaCl reaction occuring at the electrode is devised.
i. H2 gas is liberated at cathode. The stoichiometry of half reaction indicates
ii. Cl2 gas is released at anode. the moles of electrons passed and moles of
the product formed. For the reaction,
iii. Because Na⊕ ions remain unreacted and
OH ions are formed at cathode, NaCl Cu2⊕ (aq) + 2e Cu (s), two moles of
solution is converted to NaOH solution. electrons are required for the production of
one mole of Cu. So we can calculate the moles
Do you know ? of product formed. The moles of electrons
Sea water is the source of actually passed are given by Eq. (5.16).
300000 tones of Mg produced To simplify further we introduce the
every year by electrolysis. entity mole ratio given by
Electrochemical art : Al, Cr and Sn Mole ratio =
can be coloured by an electrochemical moles of product formed in the half reaction
process called anodizing. In this process moles of electrons required in the half reaction
metal anode oxidizes to give metal oxide 1
For the reaction of Cu, mole ratio =
coat. When an organic dye is added to the 2
electrolyte, dye molecules soak forming Therefore,
spongy surface of coating and become Moles of product formed
trapped with the hardening of the metal
oxide surface. = moles of electrons actually passed × mole
ratio
Q(C)
5.5.3 Quantitative aspects of electrolysis : = × mole ratio (5.18)
96500 (C/mol e )
a. The mass of reactant consumed or
the mass of product formed at an electrode I (A) × t (s)
= × mole ratio (5.19)
during electrolysis can be calculated by 96500 (C/mol e )
knowing stoichiometry of the half reaction iv. Calculation of mass of product :
at the electrode.
Mass of product
i. Calculation of quantity of electricity
W = moles of product × molar mass of product
passed : To calculate the quantity of
I (A) × t (s)
eletricity (Q) passed during electrolysis, the = × mole ratio × molar mass
96500 (C/mol e ) of product
amount of current, I, passed through the cell
is measured. The time for which the current (5.20)
is passed is noted.
100
b. Suppose two cells containing different
electrolytes are connected in series. The same ii. Mass of Cu formed,
quantity of electricity is passed through them. W=
The masses of the substances liberated at the I (A) × t (s)
× mole ratio × molar mass
electrodes of the two cells are related as given 96500 (C/mol e ) of Cu
below :
5 A × 100 × 60 s 1 mol
The mass of the substance produced at = ×
96500 (C/mol e )
- 2 mol e-
the electrode of first cell is given by
× 63.5 g mol-1
Q(C)
W1 = × (mole ratio)1 × M1 = 9.87 g
96500 (C/mol e )
Q(C)
Hence,
96500 (C/mol e ) Problem 5.7 : How long will it take to
W1 produce 2.415 g of Ag metal from its salt
= solution by passing a current of 3 ampere ?
(mole ratio)1 × M1
Molar mass of Ag is 107.9 g mol-1.
Similarly mass of substance liberated
Solution :
at the electrode of second cell is W2 in the
equation, i. Stoichiometry :
Q(C) W2
= (mole ratio) Ag⊕ (aq) + e Ag (s)
96500 (C/mol e ) 2
× M2
1 mol
mole ratio =
M1 and M2 are the molar masses of 1 mol e
substances produced at the electrodes of cells ii. W =
1 and 2.
Q(C) I (A) × t (s)
Because is the same × mole ratio × molar mass
96500 (C/mol e ) 96500 (C/mol e ) of Ag
for both, 3A×t 1 mol
2.415 g = ×
We have 96500 (C/mol e ) 1 mol e
W1 W2 × 107.9 g mol-1
=
(mole ratio)1 × M1 (mole ratio)2 × M2
2.415 × 96500 (C = As)
(5.21) t=
3 A × 107.9
= 720 s = 12 min.
Problem 5.6 : What is the mass of Cu
metal produced at the cathode during
the passage of 5 ampere current through Do you know ?
CuSO4 solution for 100 minutes. Molar Names, galvanic or voltaic
mass of Cu is 63.5 g mol-1. are given in honour of Italian
Solution : scientists L. Galvani and A. Volta for their
work in electrochemistry.
i. Stoichiometry for the formation of Cu is
Cu2⊕ (aq) + 2 e = Cu (s)
Hence,
1 mol
mole ratio =
2 mol e
101
Problem 5.8 : How many moles of Substitution of the quantities gives
electrons are required for reduction of 3 4.36g
moles of Zn2⊕ to Zn ? How many Faradays =
1 mol/2mol e × 65.4 g mol-1
of electricity will be required ?
W2
Solution : 1 mol/3mol e- × 27 g mol-1
i. The balanced equation for the reduction
of Zn2⊕ to Zn is 4.36 g × 2 W2 × 3
or =
65.4 27
Zn2⊕ (aq) + 2e Zn (s)
The equation shows that 1 mole of Zn2⊕ 4.36 g × 2 × 27
is reduced to Zn by 2 moles of electrons. Hence, W2 = = 1.2 g
65.4 × 3
For reduction of 3 moles of Zn2⊕ 6 moles
of electrons will be required. 5.6 Galvanic or voltaic cell : In galvanic or
Faraday (96500 Coulombs) is the amount voltaic cells, electricity is generated through
of charge on one mole of electrons. the use of spontaneous chemical reactions.
Therefore, for 6 moles of electrons, 6 F A galvanic (or voltaic) cell is made of
electricity will be required. two half cells. Each half cell consists of a
metal strip immersed in the solution of its own
ions of known concentration. For example, a
Problem 5.9 : In a certain electrolysis
strip of zinc metal immersed in 1 M aqueous
experiment 4.36 g of Zn are deposited
solution of zinc ions forms an half cell.
in one cell containing ZnSO4 solution.
Calculate the mass of Al deposited in It follows that two metal plates and
another cell containing AlCl3 solution the solutions of their ions with known
connected in series with ZnSO4 cell. Molar concentrations are required for the construction
masses of Zn and Al are 65.4 g mol-1 and of a galvanic (voltaic) cell. Two half cells
27 g mol-1, respectively. are constructed by immersing the two metal
plates in solutions of their respective ions
Solution :
placed in separate containers. The two half
Cell 1 : cells so constructed are combined together
Zn2⊕ (aq) + 2e Zn (s) to form the galvanic cell. The metal plates
called electrodes are connected through
1 mol voltmeter by a conducting wire for transfer
(mole ratio)1 =
2 mol e of electrons between them. To complete the
Cell 2 : circuit the two solutions are connected by
Al3⊕ (aq) + 3e Al (s) conducting medium through which cations
and anions move from one compartment to
1 mol the other. This requirement is fulfilled by a
(mole ratio)2 =
3 mol e salt bridge.
W1 W2 5.6.1 Salt bridge : In a galvanic cell, the two
= solutions are connected by a salt bridge. It is
(mole ratio)1 × M1 (mole ratio)2 × M2
an U tube containing a saturated solution of
W1 = 4.36 g, M1 = 65.4 g mol-1, an inert electrolyte such as KCl or NH4NO3
and 5 % agar solution. The ions of electrolyte
M2 = 27 gmol-1 do not react with the ions of electrode
solutions or the electrodes.
102
Salt bridge is prepared by filling a U i. The metal electrodes or the inert electrodes
tube with hot saturated solution of the salt are denoted by vertical lines placed at the
and agar agar solution allowing it to cool. ends of the formula or the short notation.
The cooled solution sets into a gel which does The anode (-) is written at the extreme
not come out on inverting the tube. The salt left and cathode (+) at extreme right.
bridge is kept dipped in distilled water when ii. The insoluble species if any or gases are
not in use as shown in Fig. 5.5. placed in the interior position adjacent to
Saturated KCl
the metal electrodes.
solution + agar gel
iii. The aqueous solutions of ions are placed
U tube at the middle of the cell formula.
105
if [A] = [B] = [C] = [D] = 1M,
Problem 5.10 : Calculate the voltage
Ecell = E cell
0
of the cell, Sn (s)Sn2⊕ (0.02M)Ag⊕
If a gaseous substance is present in the (0.01M)Ag (s) at 25 0C.
cell reaction its concentration term is replaced E0Sn = - 0.136 V, E0Ag = 0.800 V.
by the partial pressure of the gas. Solution :
First we write the cell reaction.
The Nernst equation can be used to
calculate cell potential and electrode potential. Sn (s) Sn2⊕ (0.02M) + 2 e
(oxidation at anode)
i. Calculation of cell potential : Consider the
cell [Ag⊕ (0.01M) + e Ag (s)] × 2
Cd(s)Cd2⊕(aq) Cu2⊕ (aq) Cu. (reduction at cathode)
Let us first write the cell reaction Sn (s) + 2 Ag⊕ (0.01M)
Cd (s) Cd2⊕ (aq) + 2 e Sn2⊕ (0.02 M) + 2 Ag (s)
(oxidation at anode) (overall cell reaction)
The cell potential is given by
Cu2⊕ (aq) + 2 e Cu (s)
0.0592V [Sn2⊕]
(reduction at cathode) Ecell = E cell -
0
log10
2 [Ag⊕]2
Cd (s) + Cu2⊕ (aq) Cd2⊕ (aq) + Cu (s) E0cell = E0Ag - E0Sn = 0.8 V + 0.136 V
(overall cell reaction) = 0.936 V
Here n = 2 Hence,
0.0592V 0.02
Ecell = 0.936V - log10
The potential of cell is given by Nernst 2 (0.01)2
equation, 0.0592V
= 0.936V - log10 200
0.0592 [Cd2⊕] 2
Ecell = E0cell - log10
2 [Cu2⊕] 0.0592V
= 0.936V - × 2.301
at 25 0C. 2
(Concentration of solids and pure liquids = 0.936 V - 0.0681V = 0.8679 V
are taken to be unity.)
Problem 5.11 : The standard potential
ii. Calculation of electrode potential of the electrode, Zn2⊕ (0.02 M) Zn (s)
Consider Zn2⊕(aq)Zn(s) is - 0.76 V. Calculate its potential.
The reduction reaction for the electrode is Solution :
Zn2⊕ (aq) + 2 e Zn (s) Electrode reaction :
0.0592 0.0592V
= E0Zn + log10 [Zn2⊕] at 25 0C = - 0.76 V + log10 (0.02)
2 2
0.0592V
= - 0.76 V + × (-1.6990)
2
= - 0.76 V - 0.0503V = - 0.81 V
106
5.8 Thermodynamics of galvanic cells
Remember...
5.8.1 Gibbs energy of cell reactions and
cell potential : The electrical work done in a For chemical reaction to be
galvanic cell is the electricity (charge) passed spontaneous, ∆G must be negative.
multiplied by the cell potential. Because ∆G = - nFEcell, Ecell must be positive
for a cell reaction if it is spontaneous.
Electrical work
= amount of charge passed × cell potential.
5.8.2 Standard cell potential and equilibrium
Charge of one mole electrons is F constant : The relation between standard
coulombs. For the cell reaction involving n Gibbs energy change of cell reaction and
moles of electrons. standard cell potential is given by Eq. (5.27).
charge passed = nF coulombs - ∆G0 = nFE0cell
Hence, electrical work = nFEcell The relation between standard Gibbs
W. Gibbs in 1878 concluded that energy change of a chemical reaction
electrical work done in galvanic cell is equal and its equilibrium constant as given in
to the decrease in Gibbs energy, - ∆G, of cell thermodynamics is :
reaction. It then follows that ∆G0 = - RT ln K (5.29)
Electrical work = - ∆G Combining Eq. (5.28) and Eq. (5.29), we
and thus - ∆G = nFEcell have
or ∆G = -nFEcell (5.27) -nFE0cell = - RT ln K
Under standard state conditions, we write
RT
∆G0 = -nFE0cell (5.28) or E0cell = ln K
nF
The Eq. (5.28) explains why E0cell is an
intensive property. 2.303 RT
= log10K
nF
We know that ∆G0 is an extensive
property since its value depends on the 0.0592
amount of substance. If the stoichiometric = log10K at 25 0C
n
equation of redox reaction is multiplied by (5.29)
2 that is the amounts of substances oxidised
and reduced are doubled, ∆G0 doubles. The
moles of electrons transferred also doubles. Try this...
The ratio, Write expressions to calculate
∆G0 equilibrium constant from
E0cell = - then becomes
nF
i. Concentration data
2∆G 0
∆G 0
ii. Thermochemical data
E0cell = - =-
2 nF nF
iii. Electrochemical data
Thus, E0cell remains the same by
multiplying the redox reaction by 2. It
means E0cell is independent of the amount of
substance and the intensive property.
107
What would happen if potential of one of
Problem 5.12 : Calculate standard Gibbs
the electrodes in a galvanic cell is zero ? Can
energy change and equilibrium constant at
we measure the potential of such a galvanic
250C for the cell reaction,
cell ? There are two electrodes combined
Cd (s) + Sn2⊕ (aq) Cd2⊕ (aq) + Sn (s) together and a redox reaction results. The
Given : E0Cd = -0.403V and measured cell potential is algebraic sum of two
E0Sn = - 0.136 V. Write formula of the cell. electrode potentials. One electrode potential is
Solution : zero. Therefore, the measured cell potential is
equal to the potential of other electrode.
i. The cell is made of two electrodes,
Cd2⊕ (aq) Cd (s) and Sn2⊕ (aq) Sn (s). From foregoing arguments, it follows that
E0 value for Sn2⊕ (aq) Sn (s) electrode it is necessary to choose an arbitrary standard
is higher than that of Cd2⊕(aq) Cd electrode as a reference point. The chemists
(s) electrode. Hence, Sn2⊕ (aq) Sn (s) have chosen hydrogen gas electrode consisting
electrode is cathode and Cd2⊕ (aq) Cd (s) of H2 gas at 1 atm pressure in contact with
anode. Cell formula is Cd(s) Cd2⊕ (aq) 1 M H⊕ ion solution as a primary reference
Sn2⊕ (aq) Sn (s) electrode. The potential of this electrode has
ii. ∆G0 = - nF E0cell arbitrarily been taken as zero. The electrode
is called standard hydrogen electrode (SHE).
E0cell = E0Sn - E0Cd = - 0.136 V - (-0.403V)
We will see later that SHE is not the most
= 0.267 V.
convenient electrode. Several other electrodes
n = 2 mol e namely calomel, silver-silver chloride and
∆G0 = -2 mol e 96500 C/mol e × 0.267 V glass electrodes with known potentials are
= - 51531 V C = - 51531 J = - 51.53 kJ used as secondary reference electrodes. The
0.0592 V potentials of these electrodes are determined
iii. E0cell = log10K
2 using SHE.
A reference electrode is then defined as
0.0592 V an electrode whose potential is arbitrarily
0.267 V = log10K
2 taken as zero or is exactly known.
5.9.1 Standard hydrogen electrode (SHE) :
0.267 × 2
log10K = = 9.0203 Construction : SHE consists of a platinum
0.0592
plate, coated with platinum black used as
K = antilog 9.0203 = 1.05 × 109
electrodes. This plate is connected to the
external circuit through sealed narrow glass
5.9 Reference electrodes : Every oxidation
needs to be accompanied by reduction. The tube containing mercury. It is surrounded by
occurrence of only oxidation or only reduction an outer jacket.
is not possible. (Refer to Std. XI Chemistry The platinum electrode is immersed in
Textbook Chapter 6) 1 M H⊕ ion solution. The solution is kept
In a galvanic cell oxidation and reduction saturated with dissolved H2 by bubbling
occur simultaneously. The potential associated hydrogen gas under 1 atm pressure through
with the redox reaction can be experimentally the side tube of the jacket as shown in Fig.5.6.
measured. For the measurement of potential Platinum does not take part in the electrode
two electrodes need to be combined together reaction. It is inert electrode and serves as the
where the redox reaction occurs. site for electron transfer.
108
Pure and e e
Cu wire dry H2 gas
at 1 atm Salt bridge
Glass jacket
Zn H2
Vessel anode (g, 1atm)
Mercury SHE
Pt wire
1M
Solution Platinised ZnSO4 1M
H⊕ ions platinum soution
plate H⊕ ion
(1M) solution
Fig. 5.6 : Standard hydrogen electrode Fig. 5.7 : Determination of standard potential
using SHE
Formulation : Standard hydrogen electrode
iii. The concentration of H⊕ ion solution
is represented as
cannot be exactly maintained at 1 M.
H⊕ (1M) H2 (g, 1atm)Pt Due to bubbling of gas into the solution,
Electrode reaction : The platinum black evaporation of water may take place.
capable of adsorbing large quantities of H2 This results in changing the concentration
gas, allows the change from gaseous to ionic of solution.
form and the reverse process to occur.
Hydrogen gas electrode
The reduction half reaction at the
For hydrogen gas electrode,
electrode is
H (aq)H2(g,PH ) Pt, [H ] and pressure of
⊕ ⊕
voltaic cells which can be recharged are Fig. 5.8 : Dry cell (Leclanche' cell)
called secondary voltaic cells. Cell reactions:
It is amazing to see that secondary i. Oxidation at anode : When the cell
cells are galvanic cells during discharge and operates the current is drawn from the
electrolytic cells during recharging. Examples cell and metallic zinc is oxidised to zinc
of secondary cells are lead storage battery, ions.
mercury cell and nickel-cadmium cell. Zn (s) Zn2⊕ (aq) + 2e
5.10.1 Dry cell (Leclanche' cell) : It is a cell
ii. Reduction at cathode : The electrons
without liquid component, but the electrolyte liberated in oxidation at anode flow along
is not completely dry. It is a viscous aqueous the container and migrate to cathode. At
paste. cathode NH4⊕ ions are reduced.
Construction : The container of the cell is 2NH4⊕ (aq) + 2e 2NH3 (aq) + H2 (g)
made of zinc which serves as anode (-). It
is lined from inside with a porous paper to Hydrogen gas produced in reduction
reaction is oxidised by MnO2 and
separate it from the other material of the cell.
prevents its collection on cathode.
An inert graphite rod in the centre of the
cell immersed in the electrolyte paste serves H2(g)+2MnO2(s) Mn2O3(s)+H2O(l)
as cathode. It is surrounded by a paste of The net reduction reaction at cathode is
manganese dioxide (MnO2) and carbon black. combination of these two reactions.
The rest of the cell is filled with an 2NH4⊕(aq) + 2 MnO2(s) + 2e
electrolyte. It is a moist paste of ammonium Mn2O3 (s) + 2 NH3 (aq) + H2O (l)
chloride (NH4Cl) and zinc chloride (ZnCl2). iii. Net cell reaction : The net cell reaction is
Some starch is added to the paste to make it sum of oxidation at anode and reduction
thick so that it cannot be leaked out. at cathode.
The cell is sealed at the top to prevent Zn (s) + 2 NH4⊕ (aq) + 2 MnO2(s)
drying of the paste by evaporation of moisture.
Zn2⊕ (aq) + Mn2O3 (s) + 2 NH3 (aq) + H2O(l)
See Fig. 5.8.
The ammonia produced combines with
Zn2⊕ to form soluble compound containing
complex ion.
Zn2⊕ (aq) + 4 NH3 (aq) [Zn (NH3)4]2⊕(aq)
110
The electrodes are immersed in
Do you know ?
an electrolytic aqueous solution of
Alkaline dry cell : The Leclanche' 38 % (by mass) of sulphuric acid of density
dry cell works under acidic 1.2 g/mL.
conditions due to the presence of NH4Cl.
The difficulty with this dry cell is that Zn Notation of the cell : The cell is formulated
anode corrodes due to its actions with H⊕ as Pb(s)PbSO4(s)38%H2SO4(aq)PbSO4(s)
ions from NH4⊕ ions. PbO2(s) Pb(s)
This results in shortening the life of a. Cell reactions during discharge
dry cell. To avoid this a modified or of i. Oxidation at anode (-) : When the
the dry cell called alkaline dry cell has cell provides current, spongy lead is
been proposed. In alkaline dry cell NaOH oxidised to Pb2⊕ ions and negative charge
or KOH is used as electrolyte in place of accumulates on lead plates. The Pb2⊕
NH4Cl. ions so formed combine with SO42 ions
The alkaline dry cell has longer life from H2SO4 to form insoluble PbSO4. The
than acidic dry cell since the Zn corrodes net oxidation is the sum of these two
more slowly. processes.
Uses of dry cell : Dry cell is used as a source Pb (s) Pb2⊕ (aq) + 2 e
of power in flashlights, portable radios, tape (oxidation)
recorders, clocks and so forth. Pb2⊕ (aq) + SO42 (aq) PbSO4 (s)
5.10.2 Lead storage battery (Lead (precipitation)
accumulator) : Lead accumulator stores Pb (s)+SO42 (aq) PbSO4 (s) + 2 e ...(i)
electrical energy due to regeneration of original (overall oxidation)
reactants during recharging. It functions as
ii. Reduction at cathode (+) : The electrons
galvanic cell and as electrolytic cell, as well.
produced at anode travel through external
Construction : A group of lead plates packed circuit and re-enter the cell at cathode. At
with spongy lead serves as anode (-). Another cathode PbO2 is reduced to Pb2⊕ ions in
group of lead plates bearing lead dioxide presence of H⊕ ions. Subsequently Pb2⊕
(PbO2) serves as cathode (+). ions so formed combine with SO42 ions
from H2SO4 to form insoluble PbSO4 that
Anode (-) gets coated on the electrode.
Cathode (+)
PbO2 (s) + 4H⊕ (aq) + 2 e Pb2⊕ (aq)
+2H2O(l)
(reduction)
38 %
H2SO4 Pb (s) + SO42 (aq) PbSO4 (s)
(precipitation)
Pb Pb plates with PbO2 (s) + 4H⊕ (aq) + SO42 (aq)+ 2 e
plates PbO2 PbSO4 (s) + 2H2O (l) ...(ii)
Fig. 5.9 : Lead storage cell (overall reduction)
To provide large reacting surface, the
iii. Net cell reaction during discharge: The
cell contains several plates of each type. The
net cell reaction is the sum of overall
two types of plates are alternately arranged
oxidation at anode and overall reduction
as shown in Fig. 5.9.
at cathode.
111
Pb (s) + PbO2 (s) + 4H⊕ (aq) + 2SO42 (aq) ii. A 12 V lead storage battery constructed
2PbSO4 (s) + 2H2O (l) by connecting six 2 V cells in series is
or used in automobiles and inverters.
Pb (s) + PbO2 (s) + 2H2SO4 (aq) 5.10.3 Nickel-Cadmium or NICAD storage
2PbSO4(s) + 2H2O (l) ...(iii) cell : Nickel-cadmium cell is a secondary dry
As the cell operates to generate current, cell. In other words it is a dry cell that can
H2SO4 is consumed. Its concentration (density) be recharged.
decreases and the cell potential is decreased.
The cell potential thus depends on sulphuric Anode of the NICAD storage cell is
acid concentration (density). cadmium metal. The cathode is nickel (IV)
oxide, NiO2 supported on Ni. The electrolyte
b. Cell reactions during recharging : solution is basic.
The potential of lead accumulator is 2V. It
must be recharged with the falling of the The electrode reactions and overall cell
cell potential to 1.8 V. To recharge the cell reaction are as follows :
external potential slightly greater than 2 V Cd (s) + 2OH (aq) Cd(OH)2 (s) + 2 e
needs to be applied across the electrodes. (anodic oxidation)
During recharging the cell functions as NiO2 (s) + 2 H2O (l) + 2 e
electrolytic cell. The anode and cathode are Ni(OH)2 (s) + 2OH (aq)
interchanged with PbO2 electrode being anode (cathodic reduction)
(+) and lead electrode cathode (-).
Cd (s) + NiO2 (s) + 2 H2O (l)
iv. Oxidation at anode (+) : It is reverse
Cd(OH)2 (s) + Ni(OH)2 (s)
of reduction reaction (ii) at cathode that
occurs during discharge. (overall cell reaction)
PbSO4 (s) + 2H2O (l) The reaction product at each electrode
is solid that adheres to electrode surface.
PbO2 (s) + 4H⊕(aq) + SO42 (aq) + 2 e ...(iv)
Therefore the cell can be recharged. The
v. Reduction at cathode (-) : It is reverse potential of the cell is about 1.4 V. The cell
of oxidation reaction (i) at anode that occurs has longer life than other dry cells. It can
during discharge. be used in electronic watches, calculators,
PbSO4 (s)+2 e Pb (s)+SO42 (aq) ...(v) photographic equipments, etc.
vi. Net cell reaction : It is the sum of 5.10.4 Mercury battery : Mercury battery is
reaction (iv) and (v) or the reverse of a secondary dry cell and can be recharged.
net cell reaction (iii) that occurs during The mercury battery consists of zinc anode,
discharge amalgamated with mercury. The cathode is
a paste of Hg and carbon. The electrolyte
2PbSO4 (s) + 2H2O (l) Pb (s) + is strongly alkaline and made of a paste of
PbO2 (s) + 2 H2SO4 (aq) KOH and ZnO. The electrode ractions and
The above reaction shows that H2SO4 is net cell reaction are :
regenerated. Its concentration (density) Zn(Hg)+2OH (aq) ZnO(s) +H2O(l) + 2 e
and in turn, the cell potential increases. (anode oxidation)
Applications of lead accumulator HgO(s)+ H2O(l)+2e Hg(l) + 2 OH (aq)
i. It is used as a source of direct current in (cathode reduction)
the laboratory. Zn (Hg) + HgO(s) ZnO(s) + Hg(l)
(overall cell reaction)
112
The overall reaction involves only solid Hydrogen gas is continuously bubbled,
substances. There is no change in electrolyte through anode and oxygen gas through
composition during operation. The mercury cathode into the electrolyte.
battery, therefore, provides more constant Cell reactions
voltage (1.35V) than the Leclanche' dry cell.
It also has considerably higher capacity and i. Oxidation at anode (-) : At anode
longer life than dry cell. hydrogen gas is oxidised to H2O.
The mercury dry cell finds use in hearing 2H2 (g) + 4OH (aq) 4H2O (l) + 4 e
aids, electric watches, pacemakers, etc. ii. Reduction at cathode (+) : The electrons
5.11 Fuel cells : The functioning of fuel cells released at anode travel, through external
is based on the fact that combustion reactions circuit to cathode. Here O2 is reduced to
are of redox type and can be used to generate OH-.
electricity. O2 (g) + 2H2O (aq)+ 4 e 4OH (aq)
The fuel cells differ from ordinary iii. Net cell reaction : The overall cell
galvanic cells in that the reactants are not reaction is the sum of electrode reactions
placed within the cell. They are continuously (i) and (ii).
supplied to electrodes from a reservoir.
2H2 (g) + O2 (g) 2H2O (l)
In these cells one of the reactants is a
The overall cell reaction is combustion
fuel such as hydrogen gas or methanol. The
of H2 to form liquid water. Interestingly, the
other reactant such as oxygen, is oxidant.
fuel H2 gas and the oxidant O2 do not react
The simplest fuel cell is hydrogen-oxygen directly.
fuel cell.
The chemical energy released during the
5.11.1 Hydrogen-oxygen fuel cell : In H2 - formation of O-H bond is directly converted
O2 fuel cell, the fuel is hydrogen gas. Oxygen into electrical energy accompanying in above
gas is an oxidising agent. The energy of the combustion reaction. The cell continues
combustion of hydrogen is converted into to operate as long as H2 and O2 gases are
electrical energy. supplied to electrodes.
H2O The cell potential is given by
(anode) (cathode) E0cell = E0cathode - E0anode = 0.4V - (-0.83V)
= 1.23 V.
Advantages of fuel cells
H2 (g) O2 (g) i. The reacting substances are continuously
Aqueous supplied to the electrodes. Unlike
KOH conventional galvanic cells, fuel cells do
not have to be discarded on consuming
of chemicals.
Fig. 5.10 : H2 - O2 fuel cell
ii. They are nonpolluting as the only reaction
Construction : The anode and cathode are product is water.
porous carbon rods containing small amount
iii. Fuel cells provide electricity with an
of finely divided platinum metal that acts
efficiency of about 70 % which is twice
as a catalyst. The electrolyte is hot aqueous
as large when compared with efficiency
solution of KOH. The carbon rods immersed
of thermal plants (only 40 %).
into electrolyte are shown in Fig. 5.10.
113
Drawbacks of fuel cell ii. Below hydrogen electrode the negative
H2 gas is hazardous to handle and the standard potential increases and above
cost of preparing H2 is high. hydrogen electrode the positive standard
potential increases.
Internet my friend iii. E0 values apply to the reduction half
Fuel cells are also used in cell reactions that occur in the forward
phones and laptop computers. The direction as written.
cell proposed for use in these products
iv. Higher (more positive) E0 value for a half
is direct methanol fuel cell (DMFC).
reaction indicates its greater tendency to
Collect information of this cell.
occur in the forward direction and in
Applications of fuel cells turn greater tendency for the substance
to reduce. Conversely, the low (more
i. The fuel cells are used on experimental
negative) E0 value of a half reaction
basis in automobiles.
corresponds to its greater tendency to
ii. The fuel cell are used for electrical power occur in the reverse direction or for the
in the space programme. substance to oxidise.
iii. In space crafts the fuel cell is operated The half reactions are listed in order of
at such a high temperature that the their decreasing tendency in the forward
water evaporates at the same rate as it direction.
is formed. The vapour is condensed and
pure water formed is used for drinking Remember...
by astronauts. The left side of half reaction
has cations of metals or non-
iv. In future, fuel cells can possibly be metallic molecules (oxidants). There are
explored as power generators in hospitals, free metals or anions of non metals on the
hotels and homes. right side (reductants).
Can you tell ?
Applications of electrochemical series
In what ways are fuel cells
i. Relative strength of oxidising agents:
and galvanic cells similar and in
The species on the left side of half
what ways are they different ?
reactions are oxidizing agents. E0 value
5.12 Electrochemical series (Electromotive is a measure of the tendency of the species
series) : The standard potentials of a number to accept electrons and get reduced.
of electrodes have been determined using In other words, E0 value measures the
standard hydrogen electrode. These electrodes strength of the substances as oxidising
with their half reactions are arranged according agents. Larger the E0 value greater is
to their decreasing standard potentials as the oxidising strength. The species in the
shown in Table 5.1. This arrangement is top left side of half reactions are strong
called electrochemical series. oxidising agents. As we move down the
Key points of electrochemical series table, E0 value and strength of oxidising
agents decreases from top to bottom.
i. The half reactions are written as
reductions. The oxidizing agents and Use your brain power
electrons appear on the left side of half Indentify the strongest and the
reactions while the reducing agents weakest oxidizing agents from the
are shown on the right side in the half electrochemical series.
reaction.
114
ii. Relative strength of reducing agents: From Table 5.1 of electrochemical series we
The species on the right side of half have
reactions are reducing agents. E0Mg = -2.37 V and E0Ag = 0.8 V. For the
The half reactions at the bottom of the cell having Mg as anode and Ag cathode.
table with large negative E0 values have E0Cell = E0Ag - E0Mg = 0.8V - (-2.37V)
a little or no tendency to occur in the
forward direction as written. They tend = 3.17 V.
to favour the reverse direction. It follows, EMF being positive the cell reaction
that the species appearing at the bottom is spontaneous. Thus Ag⊕ ions oxidise to
right side of half reactions associated metallic Mg.
with large negative E0 values are the
General rules
effective electron donors. They serve as
strong reducing agents. The strength of i. An oxidizing agent can oxidize any
reducing agents increases from top to reducing agent that appears below it,
bottom as E0 values decrease. and cannot oxidize the reducing agent
appearing above it in the electrochemical
Use your brain power series.
Identify the strongest and the
ii. An reducing agent can reduce the
weakest reducing agents from the
oxidising agent located above it in the
electrochemical series.
electrochemical series.
iii. Spontaneity of redox reactions : A redox
reaction in galvanic cell is spontaneous Use your brain power
only if the species with higher E0 value From E0 values given in
is reduced (accepts electrons) and that Table 5.1, predict whether Sn can
with lower E0 value is oxidised (donates reduce I2 or Ni2⊕.
electrons).
The standard cell potential must be positive
for a cell reaction to be spontaneous under Do you know ?
the standard conditions. Noteworthy The fuel cells for power
application of electromotive series is electric vehicles incorporate the
predicting spontaneity of redox reactions proton conducting plastic membrane.
from the knowledge of standard potentials. These are proton exchange membranes
Suppose, we ask a question : At standard (PEM) fuel cells.
conditions would Ag⊕ ions oxidise
metallic magnesium ? To answer this
question, first we write oxidation of Mg
by Ag⊕.
Mg (s) Mg2⊕ (aq) + 2 e (oxidation)
2Ag2⊕ (aq) + 2 e 2Ag (s)(reduction)
Mg (s) +2Ag2⊕ (aq) Mg2⊕ (aq) + 2Ag (s)
(overall reaction)
115
Table 5.1 : The standard aqueous electrode potentials at 298 K
(Electrochemical series)
Electrode Half reaction E0 V
Left side species Right side species
(oxidizing agents) (oxidizing agents)
F F2Pt F2+ 2 e F +2.870
Au⊕Au Au⊕ + e Au +1.680
Ce , Ce Pt
4⊕ 3⊕
Ce + e
4⊕
Ce 3⊕
+1.610
Au3⊕ Au Au3⊕ + 3e Au +1.500
Cl Cl2Pt Cl2 + 2e 2Cl +1.360
Pt Pt
2⊕
Pt + 2e
2⊕
Pt +1.200
Br Br2Pt Br2 + 2e 2Br +1.080
Hg2⊕Hg Hg2⊕ + 2e- Hg +0.854
Ag Ag⊕
Ag + e
⊕
Ag +0.799
Increasing strength as oxidising agent
116
Exercises
1. Choose the most correct option.
i. Two solutions have the ratio of their ii. I2 (s) + 2e 2I (aq)
concentrations 0.4 and ratio of their E0 = 0.53V
conductivities 0.216. The ratio of iii. Pb2⊕ (aq) + 2e Pb (s)
their molar conductivities will be
E0 = -0.13V
a. 0.54 b. 11.574
iv. Fe2⊕ (aq) + 2e Fe (s)
c. 0.0864 d. 1.852
E0 = - 0.44V
ii. On diluting the solution of an
The strongest oxidising and reducing
electrolyte
agents respectively are
a. both ∧ and k increase
a. Ag and Fe2⊕ b. Ag⊕ and Fe
b. both ∧ and k decrease
c. Pb2⊕ and I d. I2 and Fe2⊕
c. ∧ increases and k decreases
vii. For the reaction Ni(s) + Cu2⊕ (1M)
d. ∧ decreases and k increases Ni2⊕ (1M) + Cu (s), E0cell =
iii. 1 S m2 mol-1 is eual to 0.57V ∆G0 of the reaction is
a. 10-4 S m2 mol-1 a. 110 kJ b. -110 kJ
b. 104 Ω-1 cm2 mol-1 c. 55 kJ d. -55 kJ
c. 10-2 S cm2 mol-1 viii. Which of the following is not correct?
d. 102 Ω-1 cm2 mol-1 a.
Gibbs energy is an extensive
iv. The standard potential of the cell in property
which the following reaction occurs b. Electrode potential or cell potential
H2 (g,1atm) + Cu2⊕(1M) is an intensive property.
2H⊕(1M) + Cu (s), (E0Cu = 0.34V) is c. Electrical work = - ∆G
a. -0.34 V b. 0.34 V d. If half reaction is multiplied by a
c. 0.17 V d. -0.17 V numerical factor, the corresponding
E0 value is also multiplied by the
v.
For the cell, Pb same factor.
(s)Pb2⊕(1M)Ag⊕(1M) Ag (s), if
concentraton of an ion in the anode ix. The oxidation reaction that takes
compartment is increased by a factor place in lead storage battery during
of 10, the emf of the cell will discharge is
a. increase by 10 V a. Pb2⊕ (aq) + SO42 (aq) PbSO4(s)
b. increase by 0.0296 V b. PbSO4 (s) + 2H2O (l) PbO2 (s)
⊕
+ 4H (aq) + SO4 (aq) + 2e
2
c. decrease by 10 V
c. Pb (s) + SO42 (aq) PbSO4 (s) +
d. decrease by 0.0296 V 2e
vi. Consider the half reactions with d. PbSO4(s) + 2e Pb(s)
standard potentials
⊕
+ SO42 (aq)
i. Ag (aq) + e Ag (s)
E = 0.8V
0
117
x. Which of the following expressions ii. What is a salt bridge ?
represent molar conductivity of iii. Write electrode reactions for the
Al2(SO4)3? electrolysis of aqueous NaCl.
a. 3 λ0Al3⊕ + 2 λ0SO42 iv. How many moles of electrons are
b. 2 λ Al3⊕ + 3 λ SO42
0 0
passed when 0.8 ampere current is
c. 1/3 λ0Al3⊕ + 1/2 λ0SO42 passed for 1 hour through molten
CaCl2 ?
d. λ0Al3⊕ + λ0SO42
v. Construct a galvanic cell from
2. Answer the following in one or two the electrodes Co3⊕Co and
sentences. Mn2⊕ Mn. E0Co = 1.82 V,
i. What is a cell constant ? E0Mn = - 1.18V. Calculate E0cell.
ii. Write the relationship between vi. Using the relationsip between ∆G0
conductivity and molar conductivity of cell reaction and the standard
and hence unit of molar conductivity. potential associated with it, how will
iii. Write the electrode reactions during you show that the electrical potential
electrolysis of molten KCl. is an intensive property ?
iv. Write any two functions of salt viii. Derive the relationship between
bridge. standard cell potential and
v. What is standard cell potential for equilibrium constant of cell reaction.
the reaction ix. It is impossible to measure the
3Ni (s) + 2Al3⊕(1M) potential of a single electrode.
3Ni2⊕(1M) Comment.
+ 2Al(s) if E0Ni = - 0.25 V and E0Al = x. Why do the cell potential of lead
-1.66V? accumulators decrease when it
generates electricity ? How the cell
vi. Write Nerst equation. What part of potential can be increased ?
it represents the correction factor for
xi. Write the electrode reactions and net
nonstandard state conditions ? cell reaction in NICAD battery.
vii. Under what conditions the cell 4. Answer the following :
potential is called standard cell
i. What is Kohrausch law of
potential ?
independent migration of ions?
viii. Formulate a cell from the following How is it useful in obtaining molar
electrode reactions : conductivity at zero concentration of
Au3⊕(aq) + 3e Au(s) a weak electrolyte ? Explain with an
Mg(s) Mg2⊕(aq) + 2e example.
ii. Explain electrolysis of molten NaCl.
ix. How many electrons would have a
total charge of 1 coulomb ? iii. What current strength in amperes
will be required to produce 2.4
x. What is the significance of the single
g of Cu from CuSO4 solution in
vertical line and double vertical line
1 hour ? Molar mass of Cu = 63.5 g
in the formulation galvanic cell.
mol-1. (2.03 A)
3. Answer the following in brief
iv. Equilibrium constant of the reaction,
i. Explain the effect of dilution of
2Cu⊕(aq) Cu2⊕(aq) + Cu(s)
solution on conductivity ?
is 1.2 × 10 . What is the standard
6
118
potential of the cell in which the order of increasing strength under
reaction takes place ? (0.36 V) standard state conditions. The
v. Calculate emf of the cell standard potentials are given in
parenthesis.
Zn(s)Zn 2⊕ (0.2M)H ⊕ (1.6M)
H2(g, 1.8 atm) Pt at 250C. K (-2.93V), Br2(1.09V), Mg(-2.36V),
(0.785V) Ce3⊕(1.61V), Ti2⊕(-0.37V), Ag⊕(0.8
V), Ni (-0.23V).
vi. Calculate emf of the following cell at
250C. xiv. Predict whether the following
reactions would occur spontaneously
Zn (s) Zn2⊕(0.08M)Cr3⊕(0.1M)Cr under standard state conditions.
E0Zn = - 0.76 V, E0Cr = - 0.74 V a. Ca (s) + Cd2⊕ (aq)
(0.0327 V) Ca2⊕(aq) + Cd(s)
vii. What is a cell constant ? What are b. 2 Br (s) + Sn2⊕ (aq)
its units? How is it determined
experimentally? Br2(l) + Sn(s)
viii. How will you calculate the moles c. 2Ag(s) + Ni2⊕ (aq)
of electrons passed and mass of 2 Ag⊕ (aq) + Ni (s)
the substance produced during (use information of Table 5.1)
electrolysis of a salt solution using
reaction stoichiometry.
Activity :
ix. Write the electrode reactions when
lead storage cell generates electricity. 1. Write electrode reactions net
What are the anode and cathode and cell reaction in the electrolysis
the electrode reactions during its of molten barium chloride.
recharging? 2. Prepare the salt bridge and set up
the Daniel cell in your laboratory.
x. What are anode and cathode of H2-
Measure its emf using voltmeter and
O2 fuel cell ? Name the electrolyte
compare it with the value calculated
used in it. Write electrode reactions
from the information in Table 5.1
and net cell reaction taking place in
the fuel cell. 3. k1 and k2 are conductivities of two
solutions and c1 and c2 are their
xi. What are anode and cathode for
concentrations. Establish the
Leclanche' dry cell ? Write electrode relationship between k1, k2, c1, c2 and
reactions and overall cell reaction molar conductivities ∧1 and ∧2of the
when it generates electricity. two solutions.
xii. Identify oxidising agents and arrange 4. Find and search working of power
them in order of increasing strength inverters in day-to-day life.
under standard state conditions.
5. Collect information of pollution free
The standard potentials are given in
battery.
parenthesis.
Al (-1.66V), Al3⊕(-1.66V),Cl2
(1.36V), Cd2⊕(-0.4V), Fe(-0.44V),
I2(0.54V), Br (1.09V).
xiii. Which of the following species are
reducing agents? Arrange them in
119
6. CHEMICAL KINETICS
Can you recall ? change in concentration of a species
Average rate = change in time
• What is the influence of particle ∆c
size of reacting solid on rate of a = ∆t
chemical reaction ? Consider the reaction A B in which A is
• Why is finely divided nickel used in consumed and B is produced.
hydrogenation of oil ? average rate of consumption of A = - ∆[A]
∆t
• What is effect of change of temperature
∆[B]
on the rate of a chemical reaction ? Average rate of formation of B = +
∆t
120
beginning which later become slow. The In general, For
concentration of a reactant or a product plotted aA + bB cC + dD,
against time are shown in Fig. 6.1 (a) and
6.1 (b). A tangent drawn to the curve at time 1 d[A] 1 d[B]
rate = - =-
t1 gives the rate of the reaction. The slope thus a dt b dt
obtained gives the instantaneous rate of the 1 d[C] 1 d[D]
= =
reaction at time t1. The instantaneous rate dc/ c dt d dt
dt, is represented by replacing ∆ by derivative Problem 6.1 : For the reaction
dc/dt in the expression of average rate. In 2 N2O5(g) 4 NO2(g) + O2(g) in liquid
chemical kinetics we are concerned with bromine, N2O5 disappears at a rate of 0.02
instantaneous rates. moles dm-3 sec-1. At what rate NO2 and O2
For the reaction, A B, are formed? What would be the rate of
d[A] reaction?
Rate of consumption of A at any time t = -
dt Solution :
Rate of formation of B at any time t = d[B] d[N2O5] 1 d[NO2]
∆t Given : = 0.02
d [B] dt 4 dt
Rate of reaction at time t = - d[A] =
dt d[O ]
dt = dt 2
For the reaction involving one mole
of A and B each, the rate of consumption of 1 d[N2O5]
A equals the rate of formation of B. This is Rate of reaction = -
2 dt
not true for the reactions involving different 1 d[N2O5]
stoichiometries. Consider, for example, a = -
2 dt
reaction : d[O ]
Rate of formation of O2 = dt 2
A + 3B 2C
1
When one mole of A is consumed three = × 0.02
2
moles of B are consumed and two moles of d[N O ]
1 2 5 1
C are formed. The stoichiometric coefficients = - dt = × 0.02 moles dm-3 sec -1
2 2
of the three species are different. Thus the
rate of consumption of B is three times the = 0.01 moles dm-3 sec -1
d[NO5]
rate of consumption of A. Likewise the rate of Rate of formation of NO2 = dt
formation of C is twice the rate of consumption d[N2O5]
of A. We write, = 4 -
2 dt
d[B] d[A] d[C] d[A]
- = -3 and = -2 = 2 × moles dm3 sec -1
dt dt dt dt
With this = 0.04 moles dm3 sec -1
d[A] 1 d[B] 1 d[C]
- =- =
dt 3 dt 2 dt Try this...
d[A] d[B]
or rate of reaction = - =- 1 For the reaction,
dt 3 dt 3I (aq)+S2O82 (aq) I3 (aq) + 2 SO42 (aq)
1 d[C] Calculate the rate of formation of
=
2 dt I3 , the rates of consumption of I- and
Write the expression for: S2O82 and the overall rate of reaction
if the rate of formation of SO42 is
2 N2O(g) 4 NO2(g) + O2(g) ? 0.022 moles dm-3 sec -1
121
6.3 Rate of reaction and reactant (iii) If x = 0, the rate is independent of
concentration : The rate of a reaction at a concentration of A.
given temperature for a given time instant (iv) If x < 0 the rate decreases as [A] increases.
depends on the concentration of reactant. Such 6.3.2 Writing the rate law
rate-concentration relation is the rate law.
Consider the reaction,
6.3.1 Rate law : Consider the general reaction,
2H2O2(g) 2 H2O(l) + O2(g).
aA + bB cC + dD (6.1)
If the rate of the reaction is proportional
The rate of reaction at a given time is to concentration of H2O2. The rate law is given
proportional to its molar concentration at that by
time raised to simple powers or rate = k[H2O2]
Rate of reaction ∝ [A]x [B]y or
Try this...
rate = k [A]x[B]y (6.2) For the reaction,
where k the proportionality constant is called NO2(g) + CO(g) NO(g) + CO2(g),
the rate constant, which is independent of the rate of reaction is experimetally found
concentration and varies with temperature. to be proportional to the squre of the
For unit concentrations of A and B, k is equal concentration of NO2 and independent
to the rate of reaction. Equation (6.2) is called that of CO. Write the rate law.
differential rate law.
The powers x and y of the concentration Problem 6.2 : Write the rate law for the
terms A and B in the rate law not necessarily reaction, A + B P from the following
equal to stoichiometric coefficients (a and data :
b) appearing in Eq. (6.1). Thus x and y may [A] moles [B] moles Initial rate/
be simple whole numbers, zero or fraction. dm-3 sec -1 dm-3 sec -1 moles dm-3 sc -1
Realize that x and y are experimentally (Initial) (Initial)
determined. The rate law in Eq. (6.2) is
(i) 0.4 0.2 4.0 × 10-5
determined experimentally and expresses
(ii) 0.6 0.2 6.0 × 10-5
the rate of a chemical reaction in terms of
molar concentrations of the reactants and (iii) 0.8 0.4 3.2 × 10-4
not predicted from the stoichiometries of the Solution :
reactants. a. From above data (i) and (ii), when [A]
The exponents x and y appearing in the rate increases by a factor 1.5 keeping [B] as
law tell us how the concentration change constant, the rate increases by a factor
affects the rate of the reaction. 1.5. It means rate ∝ [A] and x = 1
(i) For x = y = 1, Eq. (6.2) gives b. From observations (i) and (iii), it can be
rate = k[A][B] seen that when concentrations of A and
The equation implies that the rate of a B are doubled, the rate increases by a
reaction depends linearly on concentrations of factor 8. Due to doubling of [A] the rate
A and B. If either of concentration of A or B is is doubled (because x = 1) that is rate
doubled, the rate would be doubled. increases by a factor 2.
This implies that doubling [B], the
(ii) For x = 2 and y = 1. The Eq. (6.2) then rate increases by a factor 4. or rate ∝ [B]2
leads to rate = k[A]2[B]. If concentration of A and y = 2. Therefore, rate = k[A] [B]2
is doubled keeping that of B constant, the rate
contd....
of reaction will increase by a factor of 4.
122
Problem 6.2 contd.... Try this...
Alternatively • For the reaction
The rate law gives rate = k [A] [B] .
x y
2A + 2B 2C +D, if
a. From above observations (i) and (ii) concentration of A is doubled at constant
(i) 4 × 10-5 = (0.4)x(0.2)y [B] the rate increases by a factor of 4. If
the concentration of B is doubled with [A]
(ii) 6 × 10-5 = (0.6)x(0.2)y being constant the rate is doubled. Write
Dividing (ii) by (i), we have the rate law of the reaction.
(
6 × 10-5
= 1.5 =
(0.6)x(0.2)y
y =
0.6 ( x • The rate law for the reaction
4 × 10-5 (0.4) x
(0.2) 0.4
A+B C is found to be
= (1.5)x
rate = k[A]2[B].
Hence x = 1
The rate constant of the reaction at 25 0C
b. From observations (i) and (iii) separately is 6.25 M-2s-1. What is the rate of reaction
in the rate law gives when [A] = 1.0 moles dm-3 sec -1 and
iii) 4 × 10-5 = (0.4) × (0.2)y since x = 1 [B] = 0.2 moles dm-3 sec -1?
iv) 3.2 × 10-4 = 0.8 × (0.4)y
6.3.3 Order of the reaction : For the reaction,
Dividing (iv) by (iii) we write
aA + bB cC + dD is
3.2 × 10-4 0.8 (0.4) y
=
4 × 10-5 0.4 (0.2)y If the rate of the reaction is given as
(
(y
0.6 rate = k[A]x[B]y.
or 8 = 2 ×
0.2
Then the sum x + y gives overall
or 4 = 22 = 2y order of the reaction. Thus overall order of
Therefore y = 2. the chemical reaction is given as the sum of
powers of the concentration terms in the rate
The rate law is then rate = k[A][B]2.
law expression. For example :
i. For the reaction,
Problem 6.3 : For the reaction,
2H2O2(g) 2H2O(l) + O2(g)
2 NOBr(g) 2 NO2(g) + Br2(g), experimentally determined rate law is
the rate law is rate = k[NOBr]2. If the rate
rate = k[H2O2].
of the reaction is 6.5 × 10-6 mol L-1 s-1 when
the concentration of NOBr is 2 × 10-3 mol The reaction is of first order.
L-1. What would be the rate constant for the
ii. If the experimentally determined rate law
reaction?
for the reaction
Solution :
rate H2(g) + I2(g) 2 HI(g) is
rate = k[NOBr]2 or k = [NOBr]2
rate = k[H2][I2].
= 6.5 × 10-6 mol L-1s-1
(2 × 10-3mol L-1)2 The reaction is of first order in H2 and I2 each
= 1.625 mol-1 L1 s-1 and hence overall of second order.
123
Key points about the order of reaction Solution : The reaction is first order in A
a. The order of chemical reaction is and second order in B. Hence, the rate law
experimentally determined. gives
b. The order can be integer or fractional. rate = k[A][B]2
Look at the reaction, rate
or k =
CH3CHO(g) CH4(g) + CO(g). [A][B]2
The rate law for the reaction was found to be rate = 3.6 × 10-2 mol/s,
[A] = 0.2 mol dm-3 and [B] = 0.1 mol dm-3
rate = k[CH3CHO]3/2.
Here the order of the reaction is 3/2. Substitution gives
3.6 × 10-2 mol dm-3s-1
c. The order of the reaction, can be zero for : k=
0.2 mol dm-3 × (0.1 mol dm-3)2
NO2(g) + CO(g) NO(g) + CO2(g)
3.6 × 10-2 s-1
The rate expression for this is : rate = k[NO2]2. = 0.2 × 0.01 mol2 dm-6 sec-1
This shows that order of reaction with respect
to NO2 is 2 and with CO is zero or the rate = 18 mol-2 dm-6 sec-1
is independent of concentration of CO. The
overall order of reaction is 2. Use your brain power
The rate of the reaction
d. Only a few reactions of third order are
2A + B 2C + D is 6 × 10-4 mol
known. Reactions with the orders higher than
dm s when [A] = [B] = 0.3 mol dm-3. If
-3 -1
three are scanty.
the reaction is of first order in A and zeroth
Problem 6.4 : For the reaction order in B, what is the rate constant?
A+B P is 3.6 × 10-2 mol dm-3 s-1 (i) gives rate = k [A][B]y
when [A] = 0.2 moles dm-3 and [B] = 0.1 or 6 = 3 × 2y or 2 = 2y and y =1
moles dm-3. Calculate the rate constant if The reaction is first order in A and first
the reaction is first order in A and second order in B. The overall reaction is of the
order in B. second order.
124
6.4 Molecularity of elementary reactions : these steps is slower than others. The slowest
Complex reactions are those which step is the rate determining step.
constitute a series of elementary reactions. The slowest step determines the rate of overall
6.4.1 Elementary reaction reaction.
125
The differential rate law is given by
Problem 6.7 : A reaction occurs in the d[A]
following steps rate = - = k [A] (6.4)
dt
i. NO2(g) + F2(g) NO2F(g) + F(g) (slow) where [A] is the concentration of reactant at
time t.
ii. F(g) + NO2(g) NO2F(g) (fast)
Rearranging Eq. (6.4),
a. Write the equation of overall reaction. d[A]
= -k dt (6.5)
b. Write down rate law. [A]
Let [A]0 be the initial concentration of the
c. Identify the reaction intermediate.
reactant A at time t = 0. Suppose [A]t is the
Solution : concentration of A at time = t.
a. The addition of two steps gives the overall The equation (6.5) is integrated between limits
reaction as
[A] = [A]0 at t = 0 and [A] = [A]t at t = t
2NO2(g) + F2(g) 2 NO2F(g)
[A]t
b. Step (i) is slow. The rate law of the reaction t
is predicted from its stoichiometry. Thus, ∫ d[A]
= -k ∫ dt
[A] 0 [A] 0
rate = k[NO2] [F2]
On integration,
c. F is produced in step (i) and consumed in [A]t t
step (ii) or F is the reaction intermediate. [ln[A]] [A] = -k (t)
0
0
[A]
[A]0
Because log10 [A] is unitless quantity, the
t
dimensions of k will be (time)-1. The units of k
will be s-1, min-1or (hour)-1
time
6.5.3 Half life of the first order reactions (t1/2)
Fig. 6.2 : Half life period of first order reaction
Radioactive processes follow the first
order kinetics. The half life of reaction is time 6.5.5 Graphical representation of the first
required for the reactant concentration to fall order reactions
to one half of its initial value.
i. The differential rate law for the first order
6.5.4 Half life and rate constant of the first reaction A P is
order reaction : d[A]
rate = - dt = k [A]t + 0
The integrated rate law for the first order
reaction is
[A]0 y m x c
2.303
k= log10 The equation is of the form y = mx + c. A plot
t [A]t
of rate versus [A]t is a straight line passing
where [A]0 is the initial concentration of
through origin. This is shown in Fig. 6.3. The
reactant at t = 0. It falls to [A]t at time t after
slope of straight line = k.
the start of the raction. The time required for
[A]0 to become [A]0/2 is denoted as t1/2
or
[A]t = [A]0/2 at t = t1/2
Putting this condition in the integrated rate
rate
law we write
2.303 [A]t
k= t log10
1/2 [A]0/2
2.303 intitial Concerntration
= log10 2
t1/2
Fig. 6.3 : Variation of rate with [A]
2.303
= t × 0.3010
1/2
127
ii. From Eq. (6.7) the integrated rate law is 6.5.6 Examples of first order reactions
2.303 [A]0 Some examples of reactions of first order are :
k= log10
t [A]t
On rearrangement, the equation becomes i. 2 H2O2(l) 2 H2O(l) + O2(g),
kt rate = k[H2O2]
= log10 [A]0 - log10 [A]t
2.303 ii. 2 N2O5(g) 4 NO2(g) + O2(g),
k
Hence, log10 [A]t = - t + log10 [A]0 rate = k [N2O5]
2.303
6.5.7 Integrated rate law for gas phase f
y m x c reactions
The equation is of the straight line. A graph of For the gas phase reaction,
[A]0 A(g) B(g) + C(g)
log10 versus t yields a stright line with
[A]t
slope -k/2.303 and y-axis intercept as log10[A]0 Let initial pressure of A be Pi that decreases by
x within time t.
This is shown in Fig. 6.4
Pressure of reactant A at time t
PA = Pi - x
[A]0 (6.11)
log The pressures of the products B and C at time
[A]t
t are
PB = PC = x
time
The total pressure at time t is then
Fig. 6.4 : A plot showing log [At]t/[A]0 vs time
P = Pi - x + x + x = Pi + x
iii. Eq. (6.7) gives
[A] k Hence, x = P - Pi (6.12)
log10 0 = t
[A]t 2.303
Pressure of A at time t is obtained by substitution
of Eq. (6.12) into Eq. (6.11). Thus
v m x
PA = Pi - (P - Pi) = Pi - P + Pi = 2Pi - P
The equation has a straight line form y = mx . The integrated rate law turns out to be
[A]
Hence, the graph of log10 0 versus t is 2.303 [A]0
[A]t k= log10
straight line passing through origin as shown t [A]t
The concentration now expressed in terms of
in Fig. 6.5. pressures.
Thus, [A]0 = Pi and [A]t = PA = 2 Pi - P
Substitution gives in above
[A]0 2.303 Pi
log k= log10 (6.13)
[A]t t 2 Pi - P
P is the total pressure of the reaction mixture
at time t.
conc
Fig. 6.5 :
128
Problem 6.8 : The half life of first order Problem 6.10 : Following data were
reaction is 990 s. If the initial concentration obtained during the first order decomposition
of the reactant is 0.08 mol dm-3, what of SO2Cl2 at the constant volume.
concentration would remain after 35
minutes? SO2Cl2(g) SO2(g) + Cl2(g)
Solution : Times/s Toatl pressure/bar
0.693 0.693
k= t = 990 s = 7 × 10-4 s-1 0 0.5
1/2
129
Half life of zero order reactions : The rate The metals surface gets completely
constant of zero order reaction is given by eqn covered by a layer of NH3 molecules. A number
(6.15) of NH3 molecules attached on platinum
[A]0 - [A]t surface is small compared to ammonia. A large
k= t number of the NH3 molecules tend to remain as
Using the conditions t = t1/2, [A]t = [A]1/2, gas which do not react. The molecules present
Eq. (6.15) becomes on the metal surface only react. The rate of
[A]0 - [A]0/2 [A] a reaction was thus independent of the total
k= t1/2 = 2t 0 concentration of NH3 and remains constant.
1/2
The slope of straight line is -k and its intercept rate = k' [CH3COOCH3] k''
on y-axis is [A]0. = k [CH3COO CH3]
The t1/2 of zero order reaction is where k = k'k''
directly proportional to the initial concentration.
The reaction is thus of first order.
Examples of zero order reactions :
The reaction C12H22O11(aq) + H2O (l) (excess)
Here follow some examples
C6H12O6(aq) + C6H12O6(aq)
Decomposition of NH3 on platinum metal glucose fructose
2 NH3(g) N2(g) + 3 H2(g) Can it be of pseudo-first order type ?
130
6.6 Collision theory of bimolecular reactions 6.6.4 Potential energy barrier
6.6.1 Collision between reactant molecules Consider again the reaction
Chemical reactions occur as a result A+C-B A-B+C
of collisions between the reactant species. It During a course of collision, new bond
may be expected that the rate of the reaction is A - B developes. At the same time bond C - B
equal to the rate of collision. For the gas-phase breaks. A configuration in which all the three
reactions the number of collisions is far more atoms are weakly connected together is called
and typically many powers of tens compared activated complex.
to the observed rate.
A+B-C A B C A-B+C
6.6.2 Activation : For the reaction to occur
the colliding reactant molecules must possess To attain the configuration A B C
the minimum kinetic energy. This minimum atoms need to gain energy, which comes from
kinetic energy is the activation energy. the kinetic energy of colliding molecules.
The reaction would occur only if colliding The energy barrier between reactants
molecules possess kinetic energies equal to or and products is shown in Fig. 6.7. The reactant
greater than the activation energy. molecules need to climb up and overcome this
6.6.3 Orientation of reactant molecules before they get converted to products. The
height of the barrier is called as activation
The requirement for successful collision energy (Ea). Thus the reactant molecules
described above is sufficient for reactions transform to products only if they possess
involving simple molecules (or ions) however energy equal to or greater than such activation
not for those involving complex molecules. energy. A fraction of molecules those possess
Besides the above considerations energy greater than Ea is given by f = e-Ea/RT.
the colliding molecules must have proper
orientation. The molecules need to be so
oriented relative to each other that the reacting
groups approach closely.
Consider, A + C - B A-B+C Ea
Energy
131
6.7.2 Graphical determination of activation
Do you know ? energy : Taking logarithm of both sides of eqn
For a gaseous reaction at (6.18) we obtain
298 K, Ea = 75 kJ/mol. The fraction E
of successful collisions is given by f = e-Ea/RT ln k = - a + ln A (6.19)
RT
= e-75000/8.314 × 298 = 7 × 10-14 or only 7 collisions Converting natural base to base 10 we write
Ea 1
in 1014 collisions are sufficiently energetic log10k = - + log10 A (6.20)
to lead to the reaction. 2.303 R T
y m x c
Remember... This equation is of the form of straight
All collisions of reactant line y = mx + c.
molecules do not lead to a chemical The Arrhenius plot of log10 k versus
reaction. The colliding molecules need to 1/T giving a straight line is shown in fig.
possess certain energy which is greater (6.8). A slope of the line is -Ea /2.303R with its
than the activation energy Ea and proper intercept being log10 A.
orientation.
6.7 Temperature dependence of reaction
rates
Do you know ?
It has been observed that
the rates of most of the chemical
reactions usually increase with temperature.
In everyday life we see that the fuels such as
oil, coal are inert at room temperature but
burn rapidly at higher temperatures. Many Fig. 6.8 : Variation of log10k with 1/T
foods spoil rapidly at room temperature and
From a slope of the line the activation
lasts longer in freezer.
energy can be determined. Eq. (6.18) shows
The concentrations change only a little that with an increase of temperature, -Ea/RT
with temperature. The rate constant shows a and in turn, the rate of reaction would increase.
strong dependence on the temperature. 6.7.3 Determination of activation energy :
6.7.1 Arrhenius equation: Arrhenius For two different temperatures T1 amd T2
suggested that the rate of reactions varies with
Ea
temperature as log10 k1 = log10A - (6.21)
2.303 RT1
k = A e-Ea /RT 6.18 Ea
log10k2 = log10A - (6.22)
where k is the rate constant, Ea is the activation 2.303 RT2
energy, R molar gas constant, T temperature in
kelvin, and A is the pre-exponential factor. Eq. where k1 and k2 are the rate constants
(6.18) is called as the Arrhenius equation. at temperatures T1 and T2 respectively.
Subtracting Eq. (6.21) from Eq. (6.22),
The pre exponential factor A and the
Ea 1 Ea 1
rate constant have same unit in case of the log10k2 - log10 k1 = - +
2.303 R T2 2.303 R T1
first order reactions. Besides A is found to be
related to frequency of collisions.
132
( increase with temperature. The rate of reaction
k
Hence, log10 k2 =
Ea 1
-
1 ( increases accordingly.
1 2.303 R T1 T2
(
=
Ea T2 - T1 ( ..........(6.23)
Problem 6.12 : The rate constants for a first
2.303 R T1T2 order reaction are 0.6 s-1 at 313 K and 0.045
s-1 at 293 K. What is the activation energy?
6.7.4 Graphical description of effect of Solution -
Ea
(
temperature : It has been realized that average k
log10 2 =
T2 - T1 (
kinetic energy of molecules is proportional to k1 2.303 R T1T2
temperature. The collision theory suggested a k1 = 0.045 s-1, k2 = 0.6 s-1, T1 = 293 K,
bimolecular reaction occurs only if the reacting T2 = 313 K, R = 8.314 J K-1mol-1
molecules have sufficient kinetic energies (at
least Ea) and proper orientation when they Substituting
collide. 0.6 Ea
log10 = 2.303 × 8.314 ×
At a given temperature, the fraction 0.045
[
313 - 293
of molecules with their kinetic energy equal
[
293 × 313
to or greater than Ea may lead to the product.
With an increase of temperature the fraction Ea
log10 13.33 = ×
of molecules having their energies (Ea) would 2.303 × 8.314 20
increases. The rate of the reaction thus would 293 × 313
increase. This is depicted by plotting a fraction Ea
1.1248 = × 2.18 × 10-4
of molecules with given kinetic energy versus 19.15
kinetic energy for two different temperatures Ea = 1.1248 × 19.15 J mol-1/ 2.18 × 10-4
T1 and T2 (T2 being > T1) in Fig. 6.9.
= 98810 J/mol-1 = 98.8 kJ/mol-1
133
6.8 Effect of a catalyst on the rate of reaction
A = antilog 20.89
k A catalyst is a substance added to the
= 7.78 × 1020 reactants that increases the rate of the reaction
A without itself being consumed in the reaction.
and k = 7.78 × 1020
Consider
1.6 × 10 s 13 -1 MnO2
= 2 KClO3(s)+ 3O2(g) 2 KCl(s)
7.78 × 1020
Here MnO2 is the catalyst. It has been observed
= 2.055 × 10-8 s-1
that the decomposition rate increases with
the addition of catalyst. A catalyst provides
alternative pathway associated with lower
Problem 6.14 : The half life of a first order
activation energy.
reaction is 900 min at 820 K. Estimate its
half life at 720 K if the activation energy is Fig. 6.10 compares the potential energy
250 kJ mol-1. barriers for the catalysed and uncatalysed
Solution : reactions. The barrier for uncatalysed reaction
0.693 (Ea) is larger than that for the same reaction in
t1/2 = k the presence of a catalyst Ea.
Rate constants at two different
temperatures, T1 and T2 are k1 and k2
respectively, and the corresponding half
lives (t1/2)1 and (t1/2)2.
0.693 0.693
(t1/2)1 = and (t1/2)2 =
k k
(t ) k
Hence, 1/2 1 = k2
(t1/2)2 1
k Ea
The equation, log10 2 = 2.303 RT ×
k1
T2 - T1
[
[ Fig. 6.10 : Potential energy barriers for
T1T2
catalyzed and uncatalyzed reactions
(t ) Ea
[ TT -TT Consider the decomposition of H2O2 in
log10 (t1/2)1 = 2 1
[
1/2 2 2.303 RT aqueous solution catalysed by I- ions.
1 2
[820
250 × 103 J mol-1 820 K - 720 K [ reaction is faster since the activation energy
2.303 × 8.314 J K mol -1 -1 K × 720 K decreases to 57 kJ mol-1.
= 2.212
(t1/2)1
= antilog 2.212 = 162.7
(t1/2)2
(t1/2)1 = (t1/2)2 × 162.7 = 900 × 162.7
= 1.464 × 105 min
134
Fig 6.11 shows a plot of fraction of molecules
as a function of energy. A catalyst lowers
the the threshold energy. Consequently more
molecules acquire the minimum amount of
energy and tend to cross the energy barrier. A
fraction of activated molecules is greater for
the catalyzed reaction. The rate of catalyzed
reaction thus is larger than the reaction with
no catalyst.
Fig. 6.11 : Comparison of fraction of molecules
for catalyzed and uncatalyzed reactions
Exercises
1. Choose the most correct option.
i. The rate law for the reaction v. Slope of the graph ln[A]t versus t for
aA + bB P is rate = k[A] [B]. first order reaction is
The rate of reaction doubles if a. -k b. k
a. concentrations of A and B are both c. k/2.303 d. -k/2.303
doubled.
vi. What is the half life of a first order
b. [A] is doubled and [B] is kept reaction if time required to decrease
constant concentration of reactant from 0.8 M to
c. [B] is doubled and [A] is halved 0.2 M is 12 h?
d. [A] is kept constant and [B] is a. 12 h b. 3 h
halved. c. 1.5 h d. 6 h
ii. The order of the reaction for which the vii. The reaction, 3 ClO ClO3 +2 Cl
units of rate constant are mol dm-3 s-1 occurs in two steps,
is (i) 2 ClO- ClO2
a. 1 b. 3 (ii) ClO2 + ClO ClO3 + Cl
The reaction intermediate is
c. 0 d. 2
a. Cl b. ClO2
iii. The rate constant for the reaction
c. ClO3 d. ClO
2 N2O5(g) 2 N2O4(g) + O2(g) is
4.98 × 10 s . The order of reaction is
-4 -1 viii. The elementary reaction
a. 2 b. 1 O3(g) + O(g) 2 O2(g) is
a. unimolecular and second order
c. 0 d. 3
b. bimolecular and first order
iv. Time required for 90 % completion of
c. bimolecular and second order
a certain first order reaction is t. The
d. unimolecular and first order
time required for 99.9 % completion
will be ix. Rate law for the reaction,
a. t b. 2t 2 NO + Cl2 2 NOCl is
rate = k[NO2] [Cl2]. Thus of k would
2
c. t/2 d. 3t
increase with
135
a. increase of temperature if time is expressed in seconds and
b. increase of concentration of NO concentration of reactants in mol/L?
c. increase of concentration of Cl2 vii. Write Arrhenius equation and explain
d. increase of concentrations of the terms involved in it.
both Cl2 and NO
viii. What is the rate determining step?
x. For an endothermic reaction, X Y.
ix. Write the relationships between rate
If Ef is activation energy of the forward
constant and half life of first order and
reaction and Er that for reverse reaction,
zeroth order reactions.
which of the following is correct?
x. How do half lives of the first order
a. Ef = Er b. Ef < Er
and zero order reactions change with
c. Ef > Er initial concentration of reactants?
d. ∆H = Ef - Er is negative 3. Answer the following in brief.
2. Answer the following in one or two i. How instantaneous rate of reaction is
sentences. determined?
i. For the reaction, ii. Distinguish between order and
molecularity of a reaction.
N2(g) + 3 H2(g) 2 NH3(g),
iii. A reaction takes place in two steps,
what is the relationship among d[N2] , 1. NO(g) + Cl2(g) NOCl2(g)
d[NH3] dt
d[H2]
and dt ? 2. NOCl2(g) + NO(g) 2
dt
ii. For the reaction, NOCl(g)
a. Write the overall reaction. b. Identify
CH3Br(aq) + OH-(aq)
reaction intermediate. c. What is the
CH3OH (aq) +Br (aq), rate law is molecularity of each step?
rate = k[CH3Br][OH ]
iv. Obtain the relationship between the
a. How does reaction rate changes if rate constant and half life of a first
[OH ] is decreased by a factor of 5 ? order reaction.
b.
What is change in rate if v. How will you represent zeroth order
concentrations of both reactants are reaction graphically?
doubled? vi. What are pseudo-first order reactions?
iii. What is the relationship between Give one example and explain why it
coefficients of reactants in a balanced is pseudo-first order.
equation for an overall reaction and vii. What are requirements for the colliding
exponents in rate law. In what case the reactant molecules to lead to products?
coefficients are the exponents?
viii. How catalyst increases the rate of
iv. Why all collisions between reactant reaction? Explain with the help of
molecules do not lead to a chemical potential energy diagram for catalyzed
reaction? and uncatalyzed reactions.
v. What is the activation energy of a ix. Explain with the help of Arrhenius
reaction? equation, how does the rate of reaction
vi. What are the units for rate constants for changes with (a) temperature and (b)
zero order and second order reactions activation energy.
136
x. Derive the integrated rate law for first v. The rate constant of a reaction at 5000C
order reaction. is 1.6 × 103 M-1s-1. What is the frequency
xi. How will you represent first order factor of the reaction if its activation
reactions graphically. energy is 56 kJ/mol. (9.72 × 106 M-1s-1)
xii. Derive the integrated rate law for the first vi. Show that time required for 99.9%
order reaction, A(g) B(g) + C(g) completion of a first order reaction is
in terms of pressure. three times the time required for 90%
completion.
xiii. What is zeroth order reaction? Derive its
integrated rate law. What are the units of vii. A first order reaction takes 40 minutes
rate constant? for 30% decomposition. Calculate its half
life. (77.66 min)
xiv.
How will you determine activation
energy: (a) graphically using Arrhenius viii. The rate constant for the first order reaction
equation (b) from rate constants at two is given by log10 k = 14.34 - 1.25 × 104
different temperatures? T. Calculate activation energy of the
reaction. (239.3 kJ/mol)
xv. Explain graphically the effect of
temperature on the rate of reaction. ix. What fraction of molecules in a gas at
300 K collide with an energy equal to
xvi. Explain graphically the effect of catalyst activation energy of 50 kJ/mol ? (2 × 10-9)
on the rate of reaction.
xvii. For the reaction 2A + B products, Activity :
find the rate law from the following data.
1. You wish to determine
[A]/M [B]/M rate/M s-1 the reaction order and rate
0.3 0.05 0.15 constant for the reaction, 2AB2
0.6 0.05 0.30 A2 + 2B2. a) What data would
0.6 0.2 1.20 you collect? b) How would you use
these data to determine whether the
4. Solve reaction is zeroth or first order?
i. In a first order reaction, the concentration
2. The activation energy for two
of reactant decreases from 20 mmol dm-3
reactions are Ea and E'a with Ea > E'a.
to 8 mmol dm-3 in 38 minutes. What is
If the temperature of reacting system
the half life of reaction? (28.7 min)
increase from T1 to T2, predict which
ii. The half life of a first order reaction is 1.7 of the following is correct?
hours. How long will it take for 20% of
k'1 k' k'1 k'2
the reactant to react? (32.9 min) a. = 2 b. >
k1 k2 k1 k2
iii. The energy of activation for a first order
reaction is 104 kJ/mol. The rate constant k'1 k'2 k'1 k'2
at 25 0C is 3.7 × 10-5 s-1. What is the rate c. < d. <2 k2
k1 k2 k1
constant at 300C? (R = 8.314 J/K mol)
ks are rate constants at lower
(7.4 × 10-5)
temperature and k's at higher
iv. What is the energy of activation of a temperature.
reaction whose rate constant doubles
when the temperature changes from 303
K to 313 K? (54.66 kJ/mol)
137
7. ELEMENTS OF GROUPS 16, 17 AND 18
138
Table 7.1 : Condensed electronic configuration of elements of group 16, 17 and 18
Group 16 (Oxygen family) Group 17 (Halogen family) Group 18 (Noble gases)
Condensed Condensed Condensed
Element Electronic Element Electronic Element Electronic
Configuration Configuration Configuration
2
He 1s2
8
O [He]2s22p4 9
F [He]2s22p5 10
Ne [He]2s22p6
16
S [Ne]3s23p4 17
Cl [Ne]3s23p5 18
Ar [Ne]3s23p6
34
Se [Ar]3d104s24p4 35
Br [Ar]3d104s24p5 36
Kr [Ar]3d104s24p6
52
Te [Kr]4d105s25p4 53
I [Kr]4d105s25p5 54
Xe [Kr]4d105s25p6
84
Po [Xe]4f145d106s26p4 85
At [Xe]4f145d106s26p5 86
Rn [Xe]4f145d106s26p6
7.3 Electronic configuration of elements of down the group, as a result of increase in the
group 16, 17 and 18: : The general electronic number of quantum shells.
configuration of the group 16 elements is
Across a period atomic or ionic radii decrease
ns2np4 while that of group 17 elements is
with increasing atomic number, consequent
ns2np5. The group 18 elements are shown by
to increase in (Zeff) effective nuclear charge.
ns2np6 configuration.
Group 17 elements (Halogens) have the
The elements of groups 16 and 17 smallest atomic radii in their respective
repectively have two and one electrons less periods.
than the stable electronic configuration of the
ii. Ionisation enthalpy : The group 16, 17 and
nearest noble gas.
18 elements have high ionisation enthalpy.
Table 7.1 shows the condensed electronic The ionisation enthalpy decreases down the
configuration of the elements of group 16, 17 group due to increase in the atomic size.
and 18.
Across a period ionisation enthalpy increases
7.4 Atomic and physical properties of with increase of atomic number. This is due
elements of group 16, 17 and 18. to addition of electrons in the same shell.
7.4.1 Atomic properties of Group 16, 17 However the elements of group 16 have lower
and 18 elements : These properties are given ionisation enthalpy values compared to those
in Tables 7.2, 7.3 and 7.4. of group 15 in the corresponding periods,
owing to extra stable half filled electronic
i. Atomic and Ionic radii : In group 16, configuration of p-orbitals in elements of
17 and 18 atomic and ionic radii increase group 15.
Table 7.2 : Atomic and physical properties of group 16 elements.
Ionic Ionization Electron
Atomic Atomic
Atomic radius enthalpy Electro- gain Density M.P. B.P.
Element mass radius
number E2 (∆iH1) negativity enthalpy g /cm3 (K) (K)
g/mol (pm)
(pm) kJ/mol kJ/mol
O 8 16.00 66 140 1314 3.50 -141 1.32 55 90
S 16 32.06 104 184 1000 2.44 -200 2.06 393 718
Se 34 78.96 117 198 941 2.48 -195 4.19 490 958
Te 52 127.60 137 221 869 2.01 -190 6.25 725 1260
Po 84 210.00 146 230 813 1.76 -174 - 520 1235
139
Table 7.3 : Atomic and physical properties of group 17 elements
Ionization Electron
Atomic Atomic Ionic
Atomic enthalpy Electro gain Density M.P. B.P.
Element mass radius radius
number (∆iH1) negativity enthalpy g/cm3 (K) (K)
g/mol (pm) E (pm)
kJ/mol kJ/mol
F 9 19.00 64 133 1680 4.0 -333 1.5 54.4 84.9
Cl 17 35.45 99 184 1256 3.2 -349 1.66 172.0 239.0
Br 35 79.90 114 196 1142 3.0 -325 3.19 265.8 332.5
I 53 126.90 133 220 1008 2.7 -296 4.94 386.6 458.2
At 85 210 - - - 2.2 - - - -
141
c. Group 18 elements (Noble gases) : iv. Nature of hydrides : Hydride of oxygen
Noble gases are monoatomic. (H2O) is liquid at room temperature while
hydrides of other members of the group are
They are sparingly soluble in water. gases.
Noble gases have very low melting and
boiling points. Helium has the lowest boiling Use your brain power
point (4.2 K) of any known substances. • Which of the following possess
hydrogen bonding ? H2S, H2O,
Problem 7.6 : Noble gases have very low
H2Se, H2Te
melting and boiling points. Why ?
• Show hydrogen bonding in the above
Solution : Noble gases are monoatomic,
molecule with the help of a diagram.
the only type of inter atomic interactions
which exist between them are van der
v. Common covalency of oxygen is 2. In rare
Waals forces. Therefore, they can be
cases it is four. But for the other members of
liquified at very low temperatures and
the group 16 the covalency can exceed four.
have very low melting or boiling points.
The anomalous behaviour of oxygen is due
Can you tell ? to the following reasons.
The first member of a group i. small atomic size
usually differs in properties from ii. high electronegativity.
the rest of the members of the group.
Why ? iii. absence of inner d-orbitals.
7.5.2 Anomalous behaviour of fluorine :
7.5 Anamalous Behaviour Fluorine, the first member of group 17, differs
7.5.1 Anomalous behaviour of oxygen : in properties from the other members of the
Oxygen shows the following anomalous group. The anomalous behaviour of fluorine
properties compared to other members of is due to the following reasons.
group 16 : i. small atomic size
i. Atomicity : Oxygen is a diatomic molecule ii. high electronegativity
(O2) while others are polyatomic molecules.
For example P4, S8. iii. absence of d-orbitals in valence shell
ii. Magnetic property : Oxygen is iv. low F-F bond dissociation enthalpy
paramagnetic while others are diamagnetic. Some anomalous properties of fluorine :
iii. Oxidation state : Oxygen shows -2, -1, i. Ionisation enthalpy, electronegativity,
and +2 oxidation states while other elements electrode potential are all higher for fluorine
show, -2, +2, +4, +6 oxidation states. Oxygen than expected trends shown by other halogens.
can not exhibit higher oxidation state due to
ii. Ionic and covalent radii, m.p., b.p. and
absence of vacant d orbitals.
electron gain enthalpy are quite lower than
Use your brain power expected.
• Oxygen forms only OF2 with iii. Most of the reactions of fluorine are
fluorine while sulfur forms SF6. exothermic (due to the short and strong bond
Explain. Why ? formed by it with other elements).
142
iv. It forms only one oxoacid (HOF) while All halogens exhibit -1 oxidation state.
other halogens form a number of oxoacids. However Cl, Br and I exhibit +1, +3, +5
v. Hydrogen fluoride is a liquid (b.p. 293K) and +7 oxidation states as well. This is
due to strong hydrogen bonding while other because they are less electronegative than F
hydrogen halides are gases. and possess empty d-orbitals in the valence
shell and therefore, can expand the octet. The
7.6 Chemical Properties of elements of oxidation states +4 and +6 occur in the oxides
groups 16, 17 and 18 and oxoacids of Cl and Br.
7.6.1 Oxidation state : i. The group 16 The fluorine atom has no d - orbitals
elements have the valence shell electronic in its valence shell and therefore cannot
configuration ns2np4. They attain a noble gas expand its octet. Thus fluorine being most
configuration either by gaining two electrons, electronegative exhibits mostly -1 oxidation
forming E2 ions or by sharing two electrons, state.
forming two covalent bonds. These elements,
thus, show -2 and +2 oxidation states in their iii. Group 18 elements (noble gases)
compounds. have stable valence shell electronic
configuration ns2np6 with completely filled
Oxygen being highly electronegative, orbitals. Thus they have no tendency to
shows common oxidation state of -2 except gain or lose electrons, that is, they are zero
two cases. In the case of OF2, its oxidation valent and mostly exist as monoatomic gases.
state is +2 and in peroxides, it shows oxidation However, xenon has large atomic size and
state -1 (H2O2, Na2O2). Other elements of the lower ionisation enthalpy compared to He,
group exhibit +2, +4, +6 oxidation states with Ne, Ar and Kr. Hence xenon exhibits higher
+4 and +6 being more common. The stability oxidation states. Its outermost shell has
of higher (+6) oxidation state decreases down d-orbitals. The paired electrons of the valence
the group while the stability of the lower shell can be unpaired and promoted to empty
oxidation state (+4) increases down the group d-orbitals. The unpaired electrons are shared
due to inert pair effect. Bonding in +4 and +6 with fluorine or oxygen atoms and covalent
oxidation states are primarily covalent. compounds showing higher oxidation state
Try this... such as XeF2(+2), XeF4 (+4), XeF6 (+6), XeO3
(+6) and XeOF4 (+6) are formed.
Complete the following tables
7.6.2 Chemical Reactivity towards
Element O O S F
hydrogen:
compound H 2O OF2 H2S HF
i. Group 16 elements : The elements of group
Oxidation -2
state
16 react with hydrogen to form hydrides of
Element Se Se Te Cl
the type H2E. (Where E = O, S, Se, Te, Po).
compound SeO2 SeO3 TeF6 HOCl For example, H2O, H2S, H2Se, H2Te and H2Po.
Oxidation +6 Some properties of hydrides of group 16 are
state given in Table 7.5.
ii. The group 17 elements are represented H2O is a colourless, odourless liquid, while
by their valence shell electronic configuration H2S, H2Se, H2Te and H2Po are colourless
as ns2np5. They attain noble gas configuration bad smelling, poisonous gases at ambient
either by gaining one electron forming E conditions.
ions or by sharing one electron forming one All hydrides have angular structures which
covalent bond. involve sp3 hybridisation of central atom (E).
143
The hydrides of group 16 elements are weakly Table 7.6 Properties of hydrides of group
acidic. The acidic character of the hydrides 17 elements.
increases, while thermal stability decreases
Property HF HCl HBr HI
from H2O to H2Te. This is due to decrease
m.p (K) 190 159 185 222
in the bond dissociation enthalpy of the H-E
bond down the group (Table 7.5). b.p (K) 293 189 206 238
Bond length
All hydrides except H2O possess reducing 91.7 127.4 141.4 160.9
(H-X) pm
property which increases in the order H2S < ∆dissH0
H2Se < H2Te. 574 432 363 295
kJ/mol
ii. Group 17 elements : The elements of pKa 3.2 -7.0 -9.5 -10.0
group 17 react with hydrogen to give hydrogen
iii. Group 18 elements (Noble gases) :
halides.
Noble gases are chemically inert towards
H2 + X2 2HX
hydrogen due to their stable electronic
(Where X = F, Cl, Br, I)
configuration.
Some of the properties of hydrogen halides
7.6.3 Reactivity towards oxygen :
are given in Table 7.6.
i. Group 16 elements : All the elements of
Acidic strength of halogen acids increases in
group 16 form oxides of the type EO2 and
the order :
EO3 where E = S, Se, Te, Po.
HF < HCl < HBr < HI
EO2 type oxides, Ozone (O3) and sulfur
It is due to decreasing bond dissociation dioxide (SO2) are gases, while selenium
enthalpy of H-X bond in the order dioxide (SeO2) is solid. They are acidic in
HF > HCl > HBr > HI. nature and react with water to form acids.
Thermal stability of hydrogen halides SO2 + H2O H2SO3 (Sulfurous acid)
decreases in the order HF>HCl>HBr>HI. It is
SeO2 + H2O H2SeO3 (Selenious acid)
due to decrease in bond dissociation enthalpy
of H-X bond down the group. Reducing property of dioxides decreases from
SO2 to TeO2. SO2 is reducing while TeO2
Table 7.5 Properties of hydrides of group
serves as an oxidising agent.
16 elements
EO3 type oxides, SO3, SeO3, TeO3 are also
Property H2O H2S H2Se H2Te
acidic in nature. They dissolve in water to
m.p (K) 273 188 208 222 form acids.
b.p (K) 373 213 232 269 SeO3 + H2O H2SeO4 (Selenic acid)
H-E TeO3 + 3H2O H6TeO6 (Telluric acid)
Bond length 96 134 146 169
ii. Group 17 elements : Elements of group 17
(pm)
(Halogens) form many oxides with oxygen,
∆dissH (H-E)
kJ/mol
463 347 276 238 but most of them are unstable.
∆fH kJ/mol -286 -20 73 100 Fluorine forms two oxides OF2 and O2F2.
However, only the OF2 is thermally stable at
HEH angle (°) 104 92 91 90 298 K. Both are strong fluorinating agents.
pKa 14.0 7.0 3.8 2.6 O2F2 oxidises plutonium to PuF6 and the
reaction is used in removing plutonium as
PuF6 from spent nuclear fuel.
144
Chlorine oxides, Cl2O, ClO2, Cl2O6 and Cl2O7
Internet my friend
are highly reactive oxidising agents and tend
to explode. Find and draw the structures of
ClO2 is used as bleaching agent for paper SeF4 and SCl2.
pulp and textiles and in water treatment. ii. Group 17 elements :
Bromine oxides, Br2O, BrO2, BrO3 are the Halogens (Group 17 elements) combine
least stable halogen oxides (middle row amongst themselves to form a number of
anomally). They are very powerful oxidising compounds known as interhalogen compounds.
agents.
These are of following types : XX', XX'3,
Iodine oxides, I2O4, I2O5 and I2O7 are insoluble XX'5, XX'7,
solids and decompose on heating. I2O5 is a
very good oxidising agent and used for the Where X is the halogen atom with larger size
estimation of carbon monoxide. and X', is the halogen atom with smaller size.
More details of interhalogen compounds are
The higher oxides of halogens are more stable included in section 7.12.
than the lower ones.
iii. Group 18 elements : Group 18 elements
iii. Group 18 elements : Noble gas elements (Noble gases) are chemically inert. Krypton
are chemically inert and do not directly react and xenon, however react directly with
with oxygen. fluorine to give their fluorides. For example,
7.6.4 Reactivity towards halogens : 673K
Xe(g) + F2(g) XeF2(s)
1 atm
i. Group 16 elements : Elements of group 16 Xenon fluorides XeF2, XeF4 and XeF6 are
react with halogens to give a large number crystalline and colourless which sublime
of halides of the types EX6 , EX4 and EX2. readily at 298 K. They are powerful
(Where E = S, Se, Te) fluorinating agents.
Hexahalides, SF6, SeF6 and TeF6 are formed by 7.6.5 Reactivity towards metals :
direct combination. They are colourless gases.
They have sp3d2 hybridisation and possess i. Group 16 elements : Elements of group
octahedral structure. SF6 is exceptionally 16 react with metals to form corresponding
stable halide for steric reasons. compounds.
146
Table 7.7 Allotropes of sulfur
Rhombic Sulfur (α - Sulfur) Monoclinic Sulfur (β - Sulfur)
Color Pale Yellow Bright yellow solid
Shape Orthorhombic crystals Needle shaped monoclinic crystals
M. P. 385.8 K 393 K
Density 2.069/ cm3 1.989 / cm3
Insoluble in water and soluble in
Solubility Soluble in CS2
CS2
Stable below 369 K and transforms Stable above 369 K and transforms
Stability to β - Sulphur above this into α - Sulphur below this
temperature. temperature.
S8 molecules having puckered ring S8 molecules with puckered ring
Structure
structure structure
Rhomic sulphur melted in a dish
and cooled till crust is formed. Two
Method of It is prepared by evaporation of holes are made in the crust and
preparation roll sulphur in CS2. remaining liquid is poured out to
give needle shaped crystals of
β - Sulphur
7.8 Oxoacids
Remember...
7.8.1 Oxoacids of sulfur : Sulfur forms
a number of oxoacids. Some of them are
Several modifications of sulfur unstable and cannot be isolated. They are
containing 6-20 sulfur atoms per ring, have known to exist in aqueous solutions or in the
been synsthesised. In the S8 molecule the form of their salts.
ring is puckered and has a crown shape. Some important oxoacids of sulfur and
In cyclo - S6, the ring adopts the chair their structures are given below.
form. At elevated temperature (~ 1000 K),
i. Sulfurous acid, H2SO3
S2 is the dominant species which like O2
is paramagnetic.
2.04 S S
S
pm S
S HO O
S HO
107°
S ii. Sulfuric Acid, H2SO4
S S
O
Structure of S8 ring in rhombic sulfur
S HO S
O
S HO
205.7°c S
S 02.2°
S
iii. Di or pyrosulfuric acid, H2S2O7
S O O
Chair form of S6
O S S
O O O
OH HO
147
iv. Peroxy monosulfuric acid, H2SO5 Strucutres of oxoacids of chlorine :
O i. Hypochlorous acid, HOCl
HOO S O
O H Cl
HO
ii. Chlorous acid, HOClO or HClO2
v. Peroxy disulfuric acid, H2S2O8
O O
H Cl
HO S O
O O
HO H Cl O
O
7.8.2 Oxoacids of halogens : :Halogens form 7.9 Oxygen and Compounds of oxygen
several oxoacids (See Table 7.8). Only four 7.9.1 Dioxygen
oxoacids have been isolated in pure form:
hypofluorous acid (HOF), perchloric acid a. Preparation
(HClO4), iodic acid (HIO3), metaperiodic acid i. Laboratory methods :
(H2IO6). The others are stable only in aqueous
• By heating oxygen containing salts such
solutions or in the form of their salts.
as chlorates, nitrates and permanganates.
The acid strength of the halogen oxoacids Heat
2KClO3(s) MnO 2KCl(s) + 3O2(g)
increases with the increasing oxidation state of 2
149
7.9.2 Simple Oxides : A binary compound The layer of ozone protects the earth’s surface
of oxygen with another element is called an from harmful ultraviolet (U.V) radiations.
oxide. Hence, it is called as 'ozone umbrella'.
Oxides can be classified into a. Preparation of Ozone : Ozone is prepared
a. Acidic oxides b. Basic oxides in the laboratory by passing silent electric
discharge through pure and dry oxygen in an
c. Amphoteric oxides d. Neutral oxides apparatus called ozoniser. As the conversion
a. Acidic oxides : An oxide which dissolves of oxygen to ozone is only 10%, the product
in water to give an acid or reacts with a is known as ozonised oxygen. It is an
base to give a salt is called acidic oxide. For endothermic process.
example, SO2, SO3, CO2, N2O5, Cl2O7 etc. 3O2(g) 2O3 ∆H = +142 kJ/mol
SO2 + H2O H2SO3 b. Physical properties of ozone :
SO3 + 2NaOH Na2SO4 + H2O i. Pure Ozone is a pale - blue gas, dark blue
Generally, oxides of nonmetals are acidic liquid and violet - black solid.
oxides. ii. Ozone has a characteristic smell. When
b. Basic oxides : An oxide which dissolves in inhaled in concerntration above 100 ppm, it
water to give a base or reacts with an acid to causes nausea and headache.
give salt is called basic oxide. For example, iii. It is diamagnetic in nature.
Na2O, CaO, BaO etc.
Problem 7.9 : High concerntration of ozone
CaO + H2O Ca(OH)2 can be dangerously explosive. Explain.
BaO + 2HCl BaCl2 + H2O Solution : i. Thermal stability : Ozone is
c. Amphoteric oxides : The oxide which thermodynamically unstable than oxygen
reacts with a base as well as with an acid to and decomposes into O2. The decomposition
give salt is called an amphoteric oxide. For is exothermic and results in the liberation
example, Al2O3 of heat (∆H is -ve) and an increase in
entropy (∆S is positive). This results in
Al2O3 + 6NaOH(aq) + 3H2O(l) 2Na3[Al(OH)6]
large negative Gibbs energy change (∆G).
(Acidic) Therefore high concerntration of ozone can
Al2O3(s)+ 6HCl(aq)+ 9H2O(l) 2[Al(H2O)6]3⊕ be dangerously explosive.
(Basic) Eq. O3 O2 + O
+ 6Cl (aq)
c. Chemical Properties :
d. Neutral oxides : The oxides which are
neither acidic nor basic, are called as neutral i. Oxidising property :
oxides. For example, CO, NO, N2O etc. Ozone is a powerful oxidising agents as it
7.9.3 Ozone : Ozone (O3) is an allotrope easily decomposes to liberate nascent oxygen.
of oxygen. Oxygen in the upper atmosphere (O3 O2 + O).
absorbs energy in the form of ultra-violet Ozone oxidises lead sulfide to lead sulfate
light and changes to atomic oxygen, which and iodide ions to iodine.
combines with molecular oxygen to form O3.
PbS(s) + 4O3(g) PbSO4(s) + 4O2(g)
O2 U.V. light O+O
2KI(aq) + H2O(l) + O3(g) 2KOH(aq) +
O2 + O O3 I2(g) + O2(g)
150
Ozone oxidises nitrogen oxide and gives • The depletion of ozone layer has been most
nitrogen dioxide. pronounced in polar regions, especially
over Antarctica.
NO(g) + O3(g) NO2(g) + O2(g)
• Ozone depletion is a major environmental
Hence the nitrogen oxide emmited from the
problem because it increases the amount
exhaust systems of supersonic jet aeroplanes
of ultraviolet (UV) radiation that reaches
can bringforth depletion of ozone layer in the
earth’s surface, thus causing an increase
upper atmosphere.
in rate of skin cancer, eye cataracts and
ii. Bleaching property : Ozone acts as a good genetic as well as immune system damage
bleaching agent due to its oxidising nature. among people.
O3 O + O2
Coloured matter + O colourless matter Do you know ?
Ozone bleaches in absence of moisture so it Ozone reacts with unsaturated
is also known as dry bleach. compounds containing double
bonds to form addition products called
iii. Reducing property : Ozone reduces
ozonides. Ozonides are decomposed by
peroxides to oxides.
water or dilute acids to give aldehydes
e.g. H2O2 + O3 H2O + 2O2 or ketones. This reaction is termed as
BaO2 + O3 BaO + 2O2 ozonolysis.
m
atmosphere, absorbs harmful UV
8
O O
12
O O O 117° O
radiations from the sun, thus protecting
people on the earth.
e. Uses of ozone :
• Depletion of ozone layer in the upper
• Ozone is used for air purification at
atmosphere is caused by nitrogen oxide
crowded places like cinema halls, tunnels,
released from exhausts system of car or
railways, etc.
supersonic jet aeroplanes.
• In sterilizing drinking water by oxidising
NO (g) + O3 (g) NO2 (g) + O2 (g)
all germs and bacteria.
• Depletion (thining) of ozone layer can
• For bleaching ivory, oils, starch, wax and
also be caused by chlorofluoro carbons
delicate fabrics such as silk.
(freons) used in aerosol and refrigerators
and their subsequent escape into the • In the manufacture of synthetic camphor,
atmosphere. potassium permanganate, etc.
151
7.10 Compounds of sulfur : iv. Reaction with Na2SO3 : Sulfur dioxide
7.10.1 Sulfur dioxide reacts with sodium sulfite solution to form
sodium hydrogen sulfite.
a. Preparation :
Na2SO3 + H2O(l) + SO2 2NaHSO3
i. From sulfur : Sulfur dioxide gas can be
prepared by burning of sulfur in air. v. Reducing property : Sulfur dioxide acts as
a reducing agent in the presence of moisture.
S(s) + O2 (g) SO2 (g)
• Moist sulfur dioxide reduces ferric salts
ii. From sulfite : In the laboratory sulfur into ferrous salts.
dioxide is prepared by treating sodium sulfite
with dilute sulfuric acid. 2Fe3⊕ + SO2 + 2H2O 2Fe2⊕ + SO42 + 4H⊕
152
Fig. 7.1 : Flow diagram for manufacture of Sulfuric acid
i. Sulfur or sulfide ore (iron pyrites) on iii. It freezes at 283 K and boils at 611 K.
burning or roasting in air produces sulfur iv. It is highly corrosive and produces severe
dioxide. burns on the skin.
∆
S(s) + O2(g) SO2 (g)
Do you know ?
∆
4FeS2(s) + 11O2(g) 2Fe2O3(s) + 8SO2(g)
Sulfuric acid dissolves in water
ii. Sulfur dioxide is oxidised catalytically with the evolution of a large quantity
with oxygen to sulfur trioxide, in the presence of heat. Hence care must be taken while
of V2O5 catalyst. preparing solution of sulfuric acid from
V2O5
2SO2(g) + O2 2SO3(g) concentrated sulfuric acid. Concentrated
H2SO4 must be added slowly to water with
The reaction is exothermic and reversible
constant stirring by keeping the beaker in
and the forward reaction leads to decrease
water bath.
in volume. Therefore low temperature (720K)
and high pressure (2 bar) are favourable c. Chemcial Properties :
conditions for maximum yield of SO3.
i. Acidic Property : Sulfuric acid ionises in
iii. Sulfur trioxide gas (from the catalytic aqueous solution in two steps.
converter) is absorbed in concentrated
H2SO4(aq)+H2O(l) H3O⊕(aq)+HSO4 (aq)
H2SO4 to produce oleum.
Ka > 10
Dilution of oleum with water gives sulfuric
acid of desired concentration. HSO 4(aq)+ H2O(l) H3O⊕(aq) + SO42 (aq)
154
b. Manufacture of chlorine : iv. Reaction with NH3 : Chlorine when reacted
with excess of ammonia gives ammonium
i. Deacon’s process :
chloride and nitrogen.
Chlorine is manufactured by the oxidation of
8NH3 + 3Cl2 6NH4Cl + N2
hydrogen chloride gas by atmospheric oxygen
(Excess)
in the presence of CuCl2 as catalyst at 723 K.
CuCl2 Excess of chlorine reacts with ammonia to
4HCl + O2 2Cl2 + 2H2O
give nitrogen trichloride (explosive).
ii. Electrolytic process :
NH3 + 3Cl2 NCl3 + 3HCl
By the electrolysis of brine (concentrated NaCl (Excess)
solution), chlorine is liberated at the anode.
v. Reaction with alkali : Chlorine reacts with
NaCl Na⊕ + Cl cold and dilute alkali to produce a mixture of
Cathode: 2H2O + 2e H2 + 2OH chloride and hypochlorite. When reacted with
hot concentrated alkali, chloride and chlorate
Na⊕ + OH NaOH are produced.
Anode : Cl Cl + e 2NaOH + Cl2 NaCl + NaOCl + H2O
Cl + Cl Cl2 (Cold and dilute)
c. Physical Properties of Chlorine : 6NaOH + 3Cl2 5NaCl + NaClO3 + 3H2O
(Hot and conc.)
i. Chlorine is a greenish-yellow gas having
pungent and suffocating odour. Chlorine when reacted with dry slaked lime
ii. It is poisonous in nature. gives bleaching powder.
iii. It can be easily liquified into a greenish 2Ca(OH)2 + 2Cl2 Ca(OCl)2 + CaCl2 +
yellow liquid, which boils at 293 K. 2H2O
iv. It dissolves in water to give chlorine water. vi. Reaction with hydrocarbons : Chlorine
reacts with saturated hydrocarbons to give
v. It is 2-5 times heavier than air. substitution products and with unsaturated
d. Chemical properties of chlorine : hydrocarbons gives addition products.
U.V
i. Reaction with metals : Chlorine reacts with CH4 + Cl2 CH3Cl + HCl
metals to form chlorides. Methane Methylchloride
H C = H C + Cl CH2-CH2
2Al + 3Cl2 2AlCl3 2 2 2
156
Au + 4 H⊕ + NO3 + 4Cl AuCl4 + NO neutral molecules are called Interhalogen
+ 2H2O compounds. For example, CIF, BrF3.
3Pt + 16 H⊕ + 4NO3 + 18Cl 3PtCl62 + An interhalogen compound is a compound
4NO + 8H2O formed by combination of atoms of different
halogens. The interhalogen compound
Can you recall ? is regarded as the halide of the more
electropositive halogen. A given halogen
• Which type of bonds do
forms an interhalogen compound only with
halogens form with other
the halogen having lesser electronegativity.
elements?
• Does BrF5 obey the octet rule?
Do you know ?
• What is the oxidation state of Br in
The ions formed by combination
BrF5?
of different halogens are called
• How many electrons do halogens polyhalide ions or interhalogen ions, For
require to complete their octet ? example, K⊕[Cl3 ], [NH4]⊕ [I5] , which
• What is the shape of CIF3? contain Cl3 and I5 ions.
157
In the general formula XX'n. X is
Use your brain power
the halogen having larger size and is more
electropositive. X' is the halogen having • Which halogen has tendency
smaller size and more electronegativity. to form more interhalogen
compounds?
7.12.1 General characteristics of
interhalogen compounds
Use your brain power
1. The compound is considered as the • Which will be more reactive ?
halide of X. For example, ClF. Here the
a. ClF3 or ClF, b. BrF5 or BrF
halogen having larger size is chlorine, it is
more electropositive than F and hence the • Complete the table
interhalogen compound is named as chlorine
Formula Name
monofluoride. (n) is the number of atoms of
ClF Chlorine monofluoride
X' attached to X.
ClF3
As the ratio [radius of X : radius of X']
Chlorine penta fluoride
increases the value of n also increases.
BrF
2. Interhalogen compounds have even number
of atoms 2, 4, 6, 8. For example, ClF3 has 4 Bromine penta fluoride
atoms. ICl
3. The properties of interhalogen compounds ICl3
are generally intermediate between those of
Table 7.10 : States of Interhalogen compounds
the halogens from which they are made.
at 25°C
4. The central halogen exhibits different
oxidation states in different interhalogen XX'
compounds. ClF Colorless gas
5. Number of X' atoms in the compounds is BrF Pale brown gas
always odd. BrCl Gas
6. They are all diamagnetic . ICl Ruby red solid (α- form)
Brown red soid (β - form)
Use your brain power IBr Black solid
• What will be the names of XX3'
the following compounds : ClF3 Colorless gas
ICl, BrF.
BrF3 Yellow green liquid
• Which halogen (X) will have maximum
number of other halogen (X' ) attached? IF3 Yellow powder
ICl3 Orange solid dimerises
to form (I2Cl6 having Cl -
bridges)
Do you know ? XX5'
XX' compounds are more reactive IF5 Colorless gas at R. T. but
than X2 or X'2. In the X-X' bond X' solid below 77 K
is more electronegative than X, while
BrF5 Colorless liquid
in X2 and X'2 both atoms have same
electronegativity, hence the X-X' bond ClF5 Colorless liquid
energy is less than the X-X or X'-X' bond XX7'
energy.
IF7 Colorless gas
158
Methods of Preparation of Interhalogen compounds
Method XX’ XX’3
1.Direct combination Both in equal volumes Cl2+3F2 (excess) 2ClF3
523 K
Br2+3F2 2BrF3
Cl2+F2 Cu-vessel 2ClF I2+3Cl2(excess) 2ICl3
HCl + HNO3
I2+ Cl2 boil 2ICl
Br2+Cl2 2BrCl
2.Reaction of halogen with Br2+ BrF3 3BrF Br2+ ClF3 2BrF3+ BrCl
interhalogen compounds.
Special reaction for ICl I2+KClO3 ∆
ICl+KIO3 -------
159
Table 7.11 Structures of some Interhalogen Compounds
Formula Name Structure Shape
ICl Iodine monochloride Cl I Cl Linear
F Cl F
ClF3 Chloride trifluoride 89° Bent T- shaped
F
F
86°
BrF3 Bromine trifluoride Br F Bent T- shaped
F
F F
BrF5 Bromine pentafluoride Br Square Pyramidal
F F
F
F F
ClF5 Chlorine pentafluoride Cl Square pyramidal
F F
F
Table 7.12 Oxidation states of central halogen We have studied earlier in this chapter
atom in interhalogen compounds. that group 18 elements have very high
O.S. No. of lone ionisation energies and due to this property
central pairs of Examples they are unreactive. Each noble gas atom
Halogen electrons has a completely filled valence electron shell
which makes it inert.
+7 0 IF7
The first ionization potential decreases
ClF5, BrF5,
+5 1 down the group, hence heavier noble gases
IF5
Kr, Xe and Rn can form compounds due to
ClF3, BrF3, low ionization energy.
+3 2
IF3, I2Cl6
ClF, BrF, IF, Do you know ?
+1 3 BrCl, ICl,
First true compound of noble
IBr
gas was made in 1962 by Neil
Bartelt and Lohman.
7.13 Compounds of Xenon
Xe + 2[PtF6] [XeF]⊕ [Pt2F11]
Can you recall ?
Only Xenon reacts directly with
• What is the correlation fluorine to form Xenon fluorides.
between ionization energies
and reactivity of elements?
Remember...
• Trends in ionization energy down a
XeF2, XeF4, XeF6 are stable
group.
fluoride of xenon.
Xenon also forms compounds with
oxygen, such as XeO3, XeOF2, XeOF4,
XeO2F2.
160
7.13.1 Xenon fluorides ii. Reaction with PF5 : XeF2 forms adducts
a. Preparation of Xenon Fluorides : Xenon on reaction with PF5.
fluorides are generally prepared by direct XeF2 + PF5 XeF2.PF5
reaction of xenon and fluorine in different 7.13.2 Xenon trioxide
ratios and conditions, such as temperature,
electric discharge and photochemical reaction. a. Preparation of Xenon trioxide (XeO3) :
i. Xe + F2
sealed
XeF2 Fluorides of Xenon react with water to
Ni tube, 4000C
form XeO3.
Ni tube, 4000C
iv. Xe + F2 XeF4
5-6 atmos 3XeF4 + 6H2O 2Xe + XeO3 + 12 HF
1 : 5 1
electric discharge
+ 1 2 O2
v. Xe + 2F2 -80 0C XeF4
XeF6 + 3H2O XeO3 + 6HF
electric discharge
vi. Xe + 3F2 XeF6
low temp. 7.13.3 Oxyfluorides of Xenon : Xenon forms
b. Important chemical reactions of XeF2 the following oxyfluorides :
161
a. Preparation
Use your brain power
i. Partial hydrolysis of Xenon fluorides
yields different oxyfluorides. What are the missing entries ?
XeF4 + H2O 80 C XeOF2 + 2HF Formula Name
0
162
Exercises
1. Select appropriate answers for the x. Chlorine reacts with excess of fluorine to
following. form.
i. Which of the following has highest A. ClF B. ClF3
electron gain enthalpy ? C. ClF2 D. Cl2F3
A. Fluorine B. Chlorine xi. In interhalogen compounds, which of the
C. Bromine D. Iodine following halogens is never the central
ii. Hydrides of group 16 are weakly acidic. atom.
The correct order of acidity is A. I B. Cl C. Br D. F
A. H2O > H2S > H2Se > H2Te xii. Which of the following has one lone pair
B. H2Te > H2O > H2S > H2Se of electrons ?
C. H2Te > H2Se > H2S > H2O A. IF3 B. ICl
D. H2Te > H2Se > H2O > H2S C. IF5 D. ClF3
iii. Which of the following element does not xiii. In which of the following pairs, molecules
show oxidation state of +4 ? are paired with their correct shapes ?
A. O B. S C. Se D. Te A. [I3] : bent
iv. HI acid when heated with conc. H2SO4 B. BrF5 : trigonal bipyramid
forms C. ClF3 : trigonal planar
A. HIO3 B. KIO3 D. [BrF4] : square planar
C. I2 D. KI xiv.
Among the known interhalogen
v. Ozone layer is depleted by compounds, the maximum number of
A. NO B. NO2 atoms is
C. NO3 D. N2O5 A. 3 B. 6 C. 7 D. 8
vii. In pyrosulfurous acid oxidation state of ii. What is the oxidation state of Te in TeO3 ?
sulfur is iii. Name two gases which deplete ozone
A. Only +2 B. Only +4 layer.
C. +2 and +6 D. Only +6 iv. Give two uses of ClO2
viii.
Stability of interhalogen compounds v. What is the action of bromine on
follows the order magnesium metal ?
A. BrF > IBr > ICl > ClF > BrCl
B. IBr > BeF > ICl > ClF > BrCl vi. Write the names of allotropic forms of
C. ClF > ICl > IBr > BrCl > BrF selenium.
D. ICl > ClF > BrCl > IBr > BrF vii. What is the oxidation state of S in H2SO4.
ix. BrCl reacts with water to form viii. The pKa values of HCl is -7.0 and that of
A. HBr B. Br2 + Cl2 HI is -10.0. Which is the stronger acid ?
C. HOBr D. HOBr + HCl
ix. Give one example showing reducing
property of ozone.
163
x. Write the reaction of conc. H2SO4 with viii. What is the action of chlorine on the
sugar. following
xi. Give two uses of chlorine. a. Fe b. Excess of NH3
xii. Complete the following. ix. How is hydrogen chloride prepared from
1. ICl3 + H2O ........ + ...... + ICl sodium chloride ?
2. I2 + KClO3 ....... + KIO2 x. Draw structures of XeF6, XeO3, XeOF4,
3. BrCl + H2O ....... + HCl XeF2.
4. Cl2 + ClF3 ........ xi. What are inter-halogen compounds ? Give
5. H2C = CH2 + ICl ....... two examples.
6. XeF4 + SiO2 ....... + SiF4
7. XeF6 + 6H2O ........ + HF xii. What is the action of hydrochloric acid on
8. XeOF4 + H2O ....... + HF the following ?
a. NH3 b. Na2CO3
xiii. Match the following
A B xiii. Give two uses of HCl.
XeOF2 Xenon trioxydifluoride xiv. Write the names and structural formulae
XeO2F2 Xenon monooxydifluoride of oxoacids of chlorine.
XeO3F2 Xenon dioxytetrafluoride
xv. What happens when
XeO2F4 Xenon dioxydifluoride
a. Cl2 reacts with F2 in equal volume at
xiv. What is the oxidation state of xenon in the 437 K.
following compounds. b. Br2 reacts with excess of F2.
XeOF4, XeO3, XeF6, XeF4, XeF2.
xvi. How are xenon fluorides XeF2, XeF4 and
XeF6 obtained ? Give suitable reactions.
3. Answer the following.
xvii. How are XeO3 and XeOF4 prepared ?
i. The first ionisation enthalpies of S, Cl
and Ar are 1000, 1256 and 1520 kJ/mol-1, xviii. Give two uses of neon and argon.
respectively. Explain the observed trend. xix. Describe the structure of Ozone. Give two
ii. “Acidic character of hydrides of group uses of ozone.
16 elements increases from H2O to H2Te” xx. Explain the trend in following atomic
Explain. properties of group 16 elements.
iii. How is dioxygen prepared in laboratory i. Atomic radii ii. Ionisation enthalpy
from KClO3 ?
iii. Electronegativity.
iv. What happens when
a. Lead sulfide reacts with ozone (O3). 4. Answer the following.
b. Nitric oxide reacts with ozone. i. Distinguish between rhombic sulfur and
v. Give two chemical reactions to explain monoclinic sulfur.
oxidizing property of concentrated H2SO4. ii. Give two reactions showing oxidising
vi. Discuss the structure of sulfure dioxide. property of concentrated H2SO4.
vii. Fluorine shows only -1 oxidation state iii. How is SO2 prepared in laboratory
while other halogens show -1, +1, +3, +5 from sodium sulfite? Give two physical
and +7 oxidation states. Explain. properties of SO2.
iv. Describe the manufacturing of H2SO4 by
contact process.
164
8. TRANSITION AND INNER TRANSITION ELEMENTS
3d Sc(21) Ti(22) V(23) Cr(24) Mn(25) Fe(26) Co(27) Ni(28) Cu(29) Zn(30)
4d Y(39) Zr(40) Nb(41) Mo(42) Tc(43) Ru(44) Rh(45) Pd(46) Ag(47) Cd(48)
5d La(57) Hf(72) Ta(73) W(74) Re(75) Os(76) Ir(77) Pt(78) Au(79) Hg(80)
6d Ac(89) Rf(104) Db(105) Sg(106) Bh(107) Hs(108) Mt(109) Ds(110) Rg(111) Cn(112)
165
s - block p - block
1 18
1
2 13 14 15 16 17
2
d - block
3 3 4 5 6 7 8 9 10 11 12
4
5
Series
and
f - block
Since zinc has completely filled Table 8.2 indicates that the expected
(n - 1)d orbital in the ground state (3d10,4s2) electronic configuration of chromium (Z = 24)
and (3d10) in its common oxidation state +2, differs from the observed configuration.
it is not regarded as transition element. On the This can be explained on the basis of
same ground, cadmium and mercury from 4d the concept of additional stability associated
and 5d series are not considered as transition with the completely filled and half filled
elements. Copper in the elementary state (3d10 subshells.
4s1) contains filled 3d orbitals but in the +2 Remember...
oxidation state it has partly filled 3d orbital
Any subshell having a half filled
(3d9), hence copper is a transition element.
or completely filled electronic
General electronic configuration of configuration has extra stability.
four series of d-block elements of periodic
table can be represented as given below: The general electronic configuration
of the elements of the 3d series is 3d1-10 4s2
i. 3d series : [Ar] 3d1-10 4s2
with the exceptions of Cr and Cu. The 3d and
ii. 4d series : [Kr] 4d1-10 5s0-2 4s orbitals are close in energy and in order to
iii. 5d series : [Xe] 5d1-10 6s2 gain extra stability the last electron instead of
occupying 4s orbital occupies the 3d orbital
iv. 6d series : [Rn] 6d1-10 7s2 that assigns Cr the 3d5, 4s1 and Cu 3d10, 4s1
configuration.
166
Table 8.2 Electronic configuration of 3d series of d-block elements
2nd series
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
Z 39 40 41 42 43 44 45 46 47 48
valence 4d15s2 4d25s2 4d45s1 4d65s1 4d85s1 4d105s0 4d105s2
shell
electronic
configuration
3rd series
La Hf Ta W Re Os Ir Pt Au Hg
Z 57 72 73 74 75 76 77 78 79 80
valence shell 5d 6s2
1
5d 6s2
3
5d 6s2
4
5d66s2 5d 6s2
7
5d 6s1
9
5d106s2
electronic
configuration
4th series
Ac Rf Db Sg Bh Hs Mt Ds Rg Uvb
Z 89 104 105 106 107 108 109 110 111 112
valence shell 6d 7s2
1
6d27s2 6d47s2 6d57s2 6d67s2 6d77s2 6d87s2 6d107s2
electronic
configuration
167
Remember... From Table 8.3 it is clear that as the number
of unpaired electrons in 3d orbitals increases,
Electronic configuration of Cr
the number of oxidation states shown by the
is [Ar] 3d5 4s1 and
element also increases. Scandium has only one
Cu is : [Ar]3d10, 4s1. unpaird electron. It shows two oxidation states
8.4 Oxidation states of first transition while manganese with 5 unpaired d electrons
series shows six different oxidation states.
The elements which give the greatest
One of the notable features of transition number of oxidation states occur in or near the
elements is the great variety of oxidation states middle of the series. Manganese, for example,
they show in their compounds. Table 8.3 lists shows oxidation states from +2 to +7.
the common oxidation states of the first row 8.5 Physical properties of first transition
transition elements. series : All transition elements are metals
and show properties that are characteristic of
Can you tell ?
metals. They are hard, lustrous, malleable,
Which of the first transition series ductile and form alloys with other metals. They
elements shows the maximum are good conductors of heat and electricity.
number of oxidation states and why? Except Zn, Cd, Hg and Mn, all the other
Which elements in the 4d and 5d series will transition elements have one or more typical
show maximum number of oxidation states? metallic structures at ambient temperature.
These transition metals (with the exception
Loss of 4s and 3d electrons progressively of Zn, Cd and Hg) are very hard and have
leads to formation of ions. The transition low volatility. They possess high melting and
elements display a variety of oxidation states boiling points.
in their compounds. Loss of one 4s electron
leads to the formation of M⊕ ion, loss of two
4s electrons gives a M2⊕ ion while loss of
unpaired 3d and 4s electrons gives M3⊕, M4⊕
ions and so on. Some examples are as shown
in Table 8.4
Try this...
Write the electronic configuration
of Mn6⊕, Mn4⊕, Fe4⊕, Co5⊕, Ni2⊕
Fig. 8.2 : Trends in melting points of transition
elements
168
8.6 Trends in atomic properties of the first
atomic radii in nm
transition series
8.6.1 Atomic and ionic radii
Atomic radii of the elements of the
transition series decrease gradually from left
to right (Fig. 8.3 and Table 8.5). As we move
across a transition series from left to right the
nuclear charge increases by one unit at a time.
The last filled electron enters a penultimate
Fig. 8.3 : Trends in atomic radii of d block
(n-1)d subshell. However, d orbitals in an elements
atom are less penetrating or more diffused and,
therefore d electrons offer smaller screening Ionic radii of transition elements show
effect. The result is that effective nuclear the same trend as of the atomic radii (Table
charge also increases as the atomi number 8.5)
increases along a transition series. Hence The elements of first transition series
the atomic radii decrease gradually across a show variable oxidation states. The trends
transition series from left to right. in ionic radii, thus, can be studied with (i)
The explanation for the minor variation elements having same oxidation state or (ii)
in atomic radii within a particular transition considering various oxidation states of the
series is out of the scope of this textbook. same element.
(i) For the same oxidation state, with an
increase of nuclear charge a gradual decrease
in ionic radii was observed. The trend is
pronounced for the divalent ions of the first
transition series (Cr2⊕ - 82 pm, Cu2⊕ - 72 pm).
169
(ii) The oxidation states of the same element The atoms of elements of third
shows difference of one unit such as M⊕, M2⊕, transition series possess filled 4f- orbitals. 4f
M3⊕, M4⊕ and so on. With higher oxidation state orbitals show poor shielding effect on account
the effective nuclear charge also increases and of their peculiar diffused shape. As a result,
hence, decrease of ionic radii can be observed the valence electrons experience greater
from M2⊕ to M3⊕ (Table 8.5). Ionic radii of nuclear attraction. A greater amount of energy
transition elements are smaller than ionic radii is required to ionize elements of the third
of representative elements of the same period. transition series. The ionisation enthalpies of
8.6.2 Ionisation Enthalpy : The ionisation the elements of the third transition series are,
enthalpies of transition elements are therefore much higher than the first and second
intermediate between those of s-block or series (Fig.8.4).
p-block elements. This suggests that transition 8.6.3 Metallic character : Low ionization
elements are less electropositive than elements enthalpies and vacant d orbitals in the
of group 1 and 2. Depending on the conditions, outermost shell are responsible for the metallic
they form ionic or covalent bonds. Generally in character of the transition elements. These
the lower oxidation states these elements form favour the formation of metallic bonds and
ionic compounds while in the higher oxidation thus these elements show typical metallic
states they form covalent compounds. properties. The hard nature of these elements
Ionisation enthalpies shown in suggests the formation of covalent bonds in
Table 8.6 reveal that for a given element there them. This is possible due to the presence of
is substantial increase from the first ionisation unpaired (n-1)d electrons in these elements.
enthalpy IE1 to the third ionisation enthalpy
Nearly all transition metals have simple
IE3.
hexagonal closed packed (hcp), cubic closed
As we move across the transition series, packed (ccp) or body centered cubic (bcc)
slight variation is observed in the successive lattices which are characteristic of true
enthalpies IE1, IE2, IE3 of these elements (Table metals (You have learnt more about this in
8.6). Chapter 1).
Remember...
Hardness, high melting points
and metallic properties of the
transition elements indicate that the
metal atoms are held strongly by metallic
bonds with covalent character.
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
IE
IE1 632 659 650 652 717 762 756 736 744 906
IE2 1245 1320 1376 1635 1513 1563 1647 1756 1961 1736
IE3 2450 2721 2873 2994 3258 2963 3237 3400 3560 3838
(IE = Ionisation Enthalpy in kJ/mol)
170
In all the transition series the melting Each unpaired electron gives rise to a
points steadily increase upto d5 configuration. small magnetic field (magnetic moment) due
Cr, Mo and W show highest melting points to its spin angular momentum and orbital
in their respective series. Mn and Tc display angular momentum. In case of the first row
anomalous values of melting points. After this transition elements, the contribution from
with increasing atomic number the melting the orbital angular momentum is quenched
point decreases regularly. and hence, can be neglected. The spin-only
8.6.4 Magnetic Properties : formula for magnetic moment is :
Can you recall ? m = n(n + 2) BM
1. What happens when magnetic where n is the number of unpaired
field is applied to substances ? electrons and m is the magnetic moment
2. What is meant by the terms expressed in Bohr Magneton (BM). A single
paramagnetism and diamagnetism ? unpaired electron has magnetic moment
m = 1.73 BM.
The compounds of transition metals
exhibit magnetic properties due to the unpaired From the magnetic moment (m)
electrons present in their atoms or ions. When measurements of the metal complexes of the
a magnetic field is applied, substances which first row transition elements, the number of
are attracted towards the applied magnetic unpaired electrons can be calculated, with the
field are called paramagnetic, while the ones use of spin-only formula. As magnetic moment
which are repelled are called diamagnetic. is directly related to number of unpaired
electrons, value of m will vary directly with
Some substances are attracted very the number of unpaired electrons.
strongly and these are called ferromagnetic
substances. Try this...
What will be the magnetic
Remember... moment of transition metal having
Paramagnetism and 3 unpaired electrons ?
ferromagnetism arises due to a. equal to 1.73 BM,
presence of unpaired electrons in a species. b. less than 1.73 BM or
When all electron spins are paired, the c. more than 1.73 BM ?
compound becomes diamagnetic.
Magnetic moments are determined
Among transition metals Fe, Co, Ni experimentally in solution or in solid state
are ferromagnetic. When magnetic field is where the central metal is hydrated or bound
applied externally all the unpaired electrons in to ligands. A slight difference in the calculated
these metals and their compounds align in the and observed values of magetic moments thus
direction of the applied magnetic field. Due to can be noticed.
this the magnetic susceptibility is enhanced.
These metals can be magnetized, that is, they Use your brain power
aquire permanent magnetic moment. A metal ion from the first transition
series has two unpaired electrons.
Try this... Calculate the magnetic moment.
Pick up the paramagnetic species Table 8.7 gives the calculated and
Cu1⊕, Fe3⊕, Ni2⊕, Zn2⊕, Cd2⊕, Pd2⊕. observed magnetic moments of cations of 3d
series.
171
Table 8.7 Magnetic moments of ions of first transition series elements (values in BM)
Ion Outer electronic Number of Calculated value Experimental
configuration unpaired of magnetic value
electrons moment
Sc3⊕ 3d0 0 0 0
Ti3⊕ 3d1 1 1.73 1.75
V3⊕ 3d2 2 2.84 2.76
Cr3⊕ 3d3 3 3.87 3.86
Cr2⊕ 3d4 4 4.90 4.80
Mn2⊕ 3d5 5 5.92 5.96
Fe2⊕ 3d6 4 4.90 5.3-5.5
Co2⊕ 3d7 3 3.87 4.4-5.2
Ni2⊕ 3d8 2 2.84 2.9-3.0, 4.0
Cu2⊕ 3d9 1 1.73 1.8-2.2
Zn2⊕ 3d10 0 0 0
172
the compound appears blue. The ions having Thus the colour of a transition metal ion
no unpaired electrons are colorless for example relates to
Cu⊕(3d10); Ti4⊕(3d0). Table 8.8 enlists colours 1. presence of unpaired d electrons
of 3d transition metal ions. 2. d - d transitions
620 nm
3. nature of ligands attached to the metal ion
800 nm 4. geometry of the complex formed by the
580 nm
400 nm red orange metal ion
Do you know ?
violet yellow
Colour of transition metal ions
may arise due to a charge transfer.
blue green
560 nm
For example, MnO4 ion has an intense purple
colour in solution. In MnO4 , an electron is
430 nm momentarily transferred from oxygen (O) to
490 nm metal, thus momentarily changing O2 to O
Let us see how colour of the transition and reducing the oxidation state of manganese
metal ion depends upon ligand and geometry from +7 to +6. For charge transfer transition
to take place, the energy levels of the two
of the complex formed by metal ion.
different atoms involved should be fairly close.
When cobalt chloride (Co2⊕) is dissolved Colours of Cr2O72 , CrO4 , Cu2O and Ni-DMG
in water, it forms a pink solution of the (where DMG = dimethyl glyoxime) complex
complex [Co(H2O)6]2⊕ which has octahedral thus can be explained through charge transfer
transitions.
geometry. But when this solution is treated
with concentrated hydrochloric acid, it turns 8.6.6 Catalytic Properties : Transition metals
deep blue. This change is due to the formationand their compounds exhibit good catalytic
of another complex [CoCl4]2 which has a properties. They have proven to be good
tetrahedral structure. homogeneous and heterogeneous catalysts.
Partly because of their ability to participate in
[Co(H2O)6]2⊕ + 4Cl [CoCl4]2 + 6H2O different oxidation-reduction steps of catalytic
reactions.
Table 8.8 Colour of 3d transition metal ions
Ion Outer electronic configuration Number of unpairedelectrons Colour
Sc 3⊕
3d 0
0 Colourless
Ti3⊕
3d 1
1 Purple
Ti4⊕
3d 0
0 Colourless
V 3⊕
3d 2
2 Green
Cr 3⊕
3d 3
3 violet
Mn2⊕ 3d5 5 Light pink
Mn 3⊕
3d 4
4 Violet
Fe 2⊕
3d 6
4 Pale green
Fe 3⊕
3d 5
5 Yellow
Co 2⊕
3d 7
3 Pink
Ni 2⊕
3d 8
2 Green
Cu 2⊕
3d 9
1 Blue
⊕
Cu 3d 10
0 Colourless
Zn 2⊕
3d 10
0 Colourless
173
These steps involve changes in the formed are called interstitial compounds.
oxidation states of these metal ions. Sometimes sulphides and oxides are also
Compounds of Fe, Co, Ni, Pd, Pt, Cr, etc. are trapped in the crystal lattice of transition
used as catalysts in a number of reactions. elements. Steel and cast iron are examples of
Their compounds enhance the rate of the interstitial compounds of carbon and iron. Due
chemical reactions. to presence of carbon, the malleability and
ductility of iron is reduced while its tenacity
In homogeneous catalysis reactions, the
increases.
metal ions participate by forming unstable
intermediates. In heterogeneous catalysis Some properties of interstitial compounds
reactions on the other hand, the metal provides i. They are hard and good conductors of heat
a surface for the reactants to react. and electricity.
Examples : ii. Their chemical properties are similar to the
1. MnO2 acts as a catalyst for decomposition parent metal.
of KClO3. iii. Their melting points are higher than the
2. In manufacture of ammonia by Haber’s pure metals.
process Mo/Fe is used as a catalyst. iv. Their densities are less than the parent
3. Co-Th alloy is used in Fischer Tropsch metal.
process in the synthesis of gasoline. v. The metallic carbides are chemically inert
4. Finely divided Ni, formed by reduction of and extremely hard as diamond.
the heated oxide in hydrogen is an extremely vi. Hydrides of transition metals are used as
efficient catalyst in hydrogenation of ethene powerful reducing agents.
to ethane at 140 0C.
H2C = CH2 + H - H
∆
H3C - CH3 Remember...
Ni, 140 0C
• Tungsten carbide is used for
Commercially, hydrogenation with nickel as
cutting tools.
catalyst is used to convert inedible oils into
solid fat for the production of margarine. • Iron carbide is used in manufacture
of steel.
5. In the contact process of industrial
production of sulfuric acid; sulphur dioxide 8.6.8 Formation of Alloys
and oxygen from the air react reversibly
over a solid catalyst of platinised asbestos. Can you recall ?
platinised • What is an alloy ?
2SO2 + O2 2SO3
asbestos
• Do atomic radii of 3d transition
6. Carbon dioxide and hydrogen are
elements differ largely ?
formed by reaction of the carbon monoxide
and steam at about 500 0C with an Fe-Cr Transition metals form alloys where
catalyst. atoms of one metal are distributed randomly
Fe-Cr
CO + H2O CO2 + H2 in the lattice of another metal. The metals with
catalyst
(steam)
similar radii and similar properties readily
form alloys.
8.6.7 Formation of interstitial compounds
Alloys are classified into ferrous and non-
When small atoms like hydrogen, carbon ferrous.
or nitrogen are trapped in the interstitial spaces
within the crystal lattice, the compounds
174
Ferrous alloys have atoms of other elements 3MnO2 + 6KOH + KClO3 ∆
3K2MnO4 +
distributed randomly in atoms of iron in the KCl + 3H2O
mixture. As percentage of iron is more, they
In neutral or acidic medium the green potassium
are termed ferrous alloys eg. nickel steel,
manganate disproportionates to KMnO4 and
chromium steel, stainless steel etc. All steels
MnO2.
have 2% carbon.
3K2MnO4 + 4CO2+ 2H2O 2KMnO4 +
Non-ferrous alloys are formed by mixing
MnO2 + 4KHCO3
atoms of transition metal other than iron with
a non transition element. eg. brass, which is 3MnO42 + 4H⊕ 2MnO4 +
an alloy of copper and zinc. Ferrous and non- MnO2 + 2H2O
ferrous alloys are of industrial importance. The liquid is filtered through glass
Uses of alloys wool or sintered glass and evaporated
until crystallisation occurs. Potassium
• Bronze, an alloy of copper and tin is tough,
permanganate forms small crystals which are
strong and corrosion resistant. It is used for
almost black in appearance.
making statues, medals and trophies.
ii. Electrolytic oxidation
• Cupra-nickel, an alloy of copper and nickel
is used for making machinary parts of In electrolytic oxidation, alkaline solution
marine ships, boats. For example, marine of manganate ion is electrolysed between iron
condenser tubes. electrodes separated by a diaphragm. Overall
reaction is as follows :
• Stainless steels are used in the construction
of the outer fuselage of ultra-high speed air 2K2MnO4 + H2O + [O] 2KMnO4 + 2KOH
craft. The oxygen evolved at the anode converts
• Nichrome an alloy of nickel and chromium manganate to permanganate.
in the ratio 80 : 20 has been developed The solution is filtered and evaporated to
specifically for gas turbine engines. get deep purple black coloured crystals of
• Titanium alloys withstand stress up to KMnO4.
high temperatures and are used for ultra- 8.7.2 Chemical properties of KMnO4 :
high speed flight, fire proof bulkheads and
a. In acidic medium :
exhaust shrouds.
The oxidizing reactions of KMnO4 in acidic
8.7 Compounds of Mn and Cr (KMnO4 and
medium
K2Cr2O7)
i. Oxidation of iodide to iodine :
Remember...
Both KMnO4 and K2Cr2O7 are 2MnO4 + 10 I + 16H⊕ 2Mn2⊕ +
strong oxidising agents. 8H2O + I2
ii. Oxidation of Fe2⊕ to Fe3⊕
8.7.1 Preparation of potassium permaganate
MnO4 + 5Fe2⊕ + 8H⊕ 5Fe3⊕ + Mn2⊕
i. Chemical oxidation
+4H2O
When a finely divided manganese dioxide
iii. Oxidation of H2S
(MnO2) is heated strongly with fused mass
of caustic potash (KOH) and an oxidising H2S 2H⊕ + S2
agent, potassium chlorate (KClO3), dark green 5S2 + 2MnO4 + 16H⊕ 2Mn2⊕ + 5S + 8H2O
potassium manganate, K2MnO4 is formed.
175
iv. Oxidation of oxalic acid : Na2Cr2O7 + 2KCl K2Cr2O7 + 2NaCl
⊕
2MnO4 + 5H2C2O4 + 6H 2Mn + 2⊕
8.7.5 Chemical properties of K2Cr2O7 :
10CO2+ 8H2O
i. Oxidation of I- from aq. solution of KI
b. In neutral or weakly alkaline medium : by acidified K2Cr2O7 gives I2. Potassium
i. Oxidation of iodide I to iodate IO3 . dichromate is reduced to chromic sulphate.
Liberated I2 turns the solution brown.
2MnO4 + H2O + I 2MnO2 + 2OH + IO3
K2Cr2O7 + 6KI + 7H2SO4 4K2SO4 +
ii. Thiosulphate (S2O32 ) is oxidised to sulphate
Cr2(SO4)3 + 7H2O + 3I2
(SO42 )
ii. When H2S gas is passed through acidified
8MnO4 + 3S2O32 + H2O 8MnO2 +
K2Cr2O7 solution, H2S is oxidised to pale
6SO4 + 2OH
2
yellow precipitate of sulphur. Simultaneously
iii. Manganous salt is oxidised to MnO2. potassium dichromate is reduced to chromic
2MnO4 + 3Mn2⊕ + 2H2O 5MnO2 + 4H⊕ sulphate, which is reflected as colour change
of solution from orange to green.
8.7.3 Uses of KMnO4 :
K2Cr2O7 + 4H2SO4 + 3H2S K2SO4 +
• An antiseptic. Cr2(SO4)3 + 7H2O + 3S
• For unsaturation test in laboratory. 8.8 Common properties of d block elements
• In volumetric analysis of reducing agents. Physical properties
• For detecting halides in qualitative i. All d block elements are lustrous and
analysis. shining.
• Powerful oxidising agent in laboratory and ii. They are hard and have high density.
industry.
iii. Have high melting and boiling points.
8.7.4 K2Cr2O7 : Preparation of potassium
iv. Are good electrical and thermal conductors.
dichromate
v. Have high tensile strength and malleability.
In the industrial production, finely powdered
chromite ore (FeOCr2O3) is heated with vi. Can form alloys with transition and non
anhydrous sodium carbonate (Na2CO3) and a transition elements.
flux of lime in air in a reverbatory furnace. vii. Many metals and their compounds are
4(FeO.Cr2O3) + 8Na2CO3 + 7O2 8Na2CrO4 ∆ paramagnetic.
+ 2Fe2O3 + 8CO2. viii. Most of the metals are efficient catalysts.
Sodium chromate (Na2CrO4) formed in this Chemical properties
reaction is then extracted with water and
i. All d block elements are electropositive
treated with concentrated sulphuric acid to
metals.
get sodium dichromate and hydrated sodium
sulphate : ii. They exhibit variable valencies and form
colored salts and complexes.
2Na2CrO4 + H2SO4 Na2Cr2O7 + 2NaCl +
iii. They are good reducing agents.
Na2Cr2O7.H2O
iv. They form insoluble oxides and hydroxides.
Addition of potassium chloride to concentrated
v. Iron, cobalt, copper, molybdenum and
solution of sodium dichromate precipitates
zinc are biologically important metals
less soluble orange-red coloured potassium
dichromate, K2Cr2O7. vi. catalyse biological reactions.
176
Differences : Although most properties Table 8.9 : List of minerals and ores of some
exhibited by d block elements are similar, the transition metals.
elements of first row differ from second and Metals Mineral Ore
third rows in stabilization of higher oxidation Iron Haematite Fe2O3 Haematite
states in their compounds. Magnetite Fe3O4
For example, Mo(V) and W (VI) compounds Limonite 2Fe2O3, 3H2O
Iron pyrites FeS2
are more stable than Cr(VI) and Mn (VIII).
Siderite FeCO3
Highest oxidation state for elements of first row Copper Chalcopyrite CuFeS2 Chalcopyrite
is +7, and in the case of 3rd row +8 oxidation Chalcocite Chalcocite
state as in (RuO4) and (OsO4). Cuprite Cu2O
Zinc Zinc blende ZnS Zinc blende
Can you recall ?
Zinccite ZnO
Calamine ZnCO3
• How are metals found in nature?
• Name two the salts of metals that Metallurgy
are found in nature.
Pyrometallurgy Hydrometallurgy Electro-
Internet my friend metallurgy
8.9.1 Metallurgy : Commercial extraction of
1. Collect the information on metals from their ores is called metallurgy.
different steps involved in the Different methods are used for their extraction
extraction of metals from their ores. depending on the nature of a metal and its ore.
2. Collect information about place where a. Pyrometallurgy: A process in which the
deposits of iron ores are found. ore is reduced to metal at high temperature
using reducing agents like carbon, hydrogen,
8.9 Extraction of metals aluminium, etc. is called pyrometallurgy.
Most metals are found in the earth’s b. Hydrometallurgy : The process of
crust in the form of their salts, such as extracting metals from the aqueous solution
carbonates, sulphates, sulphides and oxides. of their salts using suitable reducing agent is
called hydrometallurgy.
A few metals are nonreactive and occur in
the free state in the earth’s crust, for example, c. Electrometallurgy : A process in which
silver, gold, and platinum. metal is extracted by electrolytic reduction of
molten (fused) metallic compound is called
Mineral : A naturally occuring substance electrometallurgy.
found in the earth’s crust containing inorganic
Steps Involved in Process of Extraction
salts, solids, siliceous matter etc, is called a
mineral. Do you know ?
The mineral which contains high 1. Extraction of iron has been
percentage of the metal and from which the known to Indians since 700 BC.
metal can be extracted economically is called Indian blacksmiths also knew the
an ore. thermo-mechnical process for forging.
During Archaeological studies in Harappa,
Madhya Pradesh different iron objects
belonging to middle iron age were found.
2. Famous iron pillar in Delhi is 1300 years
old and is free of rust till to date.
177
Concentration : After mining the ore from the Iron is extracted from haematite by its
earth’s crust it is subjected to concentration. reduction using coke and limestone. Carbon in
In this step, impurities termed as gangue the limestone is reduced to carbon monoxide.
are removed from the ore and the ore gets Carbon and carbon monoxide together reduce
concentrated. Fe2O3 to metallic iron.
The sand, mud and other unwanted Limestone acts as flux, it combines with
impurities which remain mixed with the ore the gangue material to form molten slag.
deposit are called gangue. Extraction of iron from haematite ore involves
During the process of concentration, the following steps.
the ore is separated from the gangue material i. Concentration : The powdered ore is washed
using different methods such as washing, in a powerful current of water introduced into
hydraulic classification, magnetic separation, the hydraulic classifier.
froth floatation, etc. The lighter gangue particles are
The method chosen for concentration separated and the concentrated ore is collected
depends upon the nature of the ore. at the bottom.
8.9.2 Extraction of Iron from Haematite ore ii. Roasting : The concentrated ore is heated
using Blast furnace in a current of air. The sulfur and arsenic
impurties present in the ore get converted into
Do you know ? their oxides and escape as vapour. Ferrous
Iron is the fourth most oxide in the ore is converted to Fe2O3.
abundant element in the earth’s
4FeO + O2 2Fe2O3
crust
The roasted ore is converted into lumps
Composition of Haematite ore : by sintering.
Fe2O3 + SiO2 + Al2O3 + phosphates iii. Reduction (Smelting) : This step is carried
out in a blast furnace. Blast furnace is a tall
{
Reduction by coke
Iron ore Crushing and grinding
Reduction by CO
Reduction by heat
Concentration Reduction
Reduction by Al
Reduction by electrolysis
178
Burden charging
179
Table 8.9 : Summary of reactions taking place in blast furnace at different temperature zones
Temp K Changes taking place Reaction
500 loss of moisture from ore
900 Reduction of ore by CO Fe2O3 + 3CO 2 Fe + 3CO2
1200 Decomposition of lime CaCO3 ∆ CaO + CO2
1500 Reduction of ore by C Fe2O3 + 3C 2Fe + 3CO
Fusion of iron CaO + SiO2 CaSiO3
2000
Slag formation 12CaO + 2Al2O3 4Ca3AlO3 + 3 O2
3. Zone of slag formation (20 m unit) : 5. Refining : Pure iron can be obtained
The gangue present in the ore is converted by electrolytic refining of impure iron or
to slag. This slag can be used for making other methods given in the flow chart. The
road foundation. Temperature of this zone is choice of extraction technique is governed
1200 K. The gangue contains silica, alumina by the following factors. 1. Nature of ore
and phosphates. A removal of this gangue is 2. Availability and cost of reducing agent,
effected by adding lime-stone in the charge, generally cheap coke is used. 3. Availability of
which acts as flux. Limestone decomposes to hydraulic power. 4. Purity of product (metal)
give CaO (quick lime) required. 5. Value of byproducts for example,
CaCO ∆ CaO + CO
3 2
SO2 obtained during roasting of sulphide ores
is vital for manufacture of H2SO4. Knowledge
CaO combines with gangue to form of electrochemical series provides solutions to
molten slag of calcium silicate and calcium many problems.
aluminate.
Commercial forms of Iron
CaO + SiO2 CaSiO3
Iron
12 CaO + 2Al2O3 4Ca3 AlO3 + 3 O2
4. Zone of fusion (15 m ht) : MnO2 and Cast Wrought Steel
Ca3(PO4)2 present in the iron ore are reduced
to Mn and P. Some of the silica is also reduced Remember...
to Si.
1. Iron melts at a very high
The spongy iron coming down in the temperature (1800 K). On
furnace melt absorbs impurities like C, Si, Mn, addition of carbon its melting
P and S. This molten iron collects at the bottom point decreases depending upon
in the furnace. The slag which is lighter floats percentage of carbon.
on the surface of molten iron. Molten slag and
2. Mechanical properties of steel can
iron are collected through separate outlets. be modified by addition of small
Molten iron is poured into moulds. amounts of suitable elements such
These solid blocks are called pigs. This iron as manganese, chromium, sulfur,
contains about 4% of carbon. When pig iron nickel etc. These elements are
is remelted, run into moulds and cooled, it called alloying elements and steels
becomes cast iron. The waste gases containing are alloy steels.
N2, CO and CO2 escape through the outlet at
the top. These hot gases are used for preheating
the blast of air.
180
Differences between cast iron, wrought iron and (n-1)f orbitals are very similar and are
and steel sensitive to electronic configurations.
Cast iron Wrought Steel
iron Do you know ?
1. Hard and 1. Very soft 1. Neither too Glenn Seaborg first proposed a
brittle hard nor too
revised design of periodic table with
soft.
2. Contains 2.Contains 2. Contains a whole new series of elements. When
4% carbon. less than 0.2 to 2% he showed his design to two prominent
0.2% carbon inorganic chemists of the time, they warned
carbon
him against publishing it. They told him
3. Used for 3. Used for 3. Used in
making pipes, making buildings that tampering with the established periodic
manufacturing pipes, infrastructure, table will affect his career. Seaborg went
automotive bars for tools, ships, ahead and published it. He later remarked
parts, pots, stay bolts, automobiles,
“I did not have any scientific reputation, so
pans, utensils engine bolts weapons etc.
and rivetts. I published it anyway”. Now we see that
elements 89 -102 (filling of 5f orbitals) fit
Do you know ? in Seaborg’s proposed order.
Iron possesses a high degree
of magnetism below 1042 K. This is
known as ferromagnetism.
8.11 Properties of f-block elements
8.10 Inner Transition (f-block) Elements:
i. Properties are similar to d block elements
Lanthanoids and Actinoids : Elements whose
f orbitals get filled up by electrons, are called ii. Electrons are added to f subshells of (n-2)
f block elements. These elements are placed level
separately at the bottom of the periodic table. iii. Placed between (n-1)d and ns block
They are a subset of 6th and 7th periods. elements
Can you tell ? Lanthanoids begin with atomic number 57 and
• Why f-block elements are end at 71. Although, historically, lanthanoids
called inner transition metals? are termed as rare earth elements, they are
• Are there any similarities between fairly abundant in earth’s crust. For example,
transition and inner transition metals? thulium is found more in abundance than silver
(4.5 x 10-5 vs 0.79 x 10-5 percent by mass). The
Since f orbital lies much inside the d orbital, name rare earth elements was coined because
in relation to the transition metals the f block of difficulty in extracting them economically
elements are called inner transition elements. in pure form from other lanthanoids having
These elements have 1 to 14 electrons in their similar chemical properties. Now, due to newer
f orbital, 0 or 1 in the penultimate energy level separation methods like ion exchange resins,
and 2 electrons in the outermost orbital. The the separation of these elements has become
lanthanoids are characterized by gradual easier and more economical.
filling up of 4f and actinides by the 5 f orbitals.
There are 14 elements filling the f orbital in
each series. The relative energies of the nd
181
These metals are soft with moderate decreases. La(OH)3 is the strongest base
densities of about 7 g cm-3. They have high while Lu(OH)3 is the weakest base.
melting (~1000 0C) and boiling points (~3000 Lanthanoids react with nitrogen and
0
C). Similar to groups 1 and 2, lanthanoids halogens to give nitrides and halides of the
in the metallic state are very reactive and formulae LnN and LnX3 repectively. While
resemble alkali and alkaline earth metals in doing so, lanthanoids lose their outermost
their reactivities than transition metals. For 3 electrons to form stable compound in +3
example, they react with water to give the oxidation state. When lanthanoids are heated
metal hydroxide and hydrogen gas at elevated temperatures (~ 2800 K) with
2M(s) + 6 H2O (l) 2M(OH)3(s) + 3H2(g) carbon, the carbides with general formula
LnC2 are obtained.
Although, the common oxidation state
for lanthanoids is +3, the +2 oxidation state In +3 oxidation state, many of the
is also important. They all form stable oxides lanthanoids are coloured, mostly green, pink
and yellow. This is attributed to the electronic
of the type M2O3 where M is metal ion. Eu2+
transitions among the f orbitals. Like transition
and Yb2+ are the most stable dipositive metal
metals the electronic spectra of lanthanoids
ions. Higher oxidation states are unusual for
however, do not get affected with different
lanthanoids with the only exception of cerium
ligands.
which forms a stable +4 species. The energy
required to break up the metal lattice is heat 8.12 Properties of Lanthanoids
of atomization. Lanthanoids have lower heat i. Soft metals with silvery white colour and
of atomization than transition metals. This moderate densities of ~ 7 g cm-3. Colour and
is because with d electrons, transition metals brightness reduces on exposure to air
are much harder and require high heat of ii. Good conductors of heat and electricity.
atomization. Europium and ytterbium have the
iii. Except promethium (Pm), all are non-
lowest enthalpies of vaporization and largest
radioactive in nature.
atomic radii of lanthanoids, resemble barium.
These two elements resemble alkaline earth iv. The atomic and ionic radii decrease from
elements; they dissolve in liquid ammonia to lanthanum (La) to lutetium (Lu). This is known
give blue conducting solutions. as lanthanoid contraction.
Their ionic radii decrease from 117 pm of v. Binding to water is common (i.e.) such that
La to 100 pm for Lu. This is because 5f orbitals H2O is often found in products when isolated
do not shield the outer 5s and 5p electrons from aqueous solutions.
effectively, leading to increase in effective vi. Coordination numbers usually are greater
nuclear charge and decrease in the ionic size. than 6, typically 8, 9,... (up to 12 found).
Such large ions have higher coordination vii. The lanthanoides are strongly
number that varies from 6 (most common) to paramagnetic. Gadolinium becomes
9, 10 and upto12 in some cases. For example, ferromagnetic below 16 C (Curie point). The
0
182
Table 8.11 : Electronic configuration and atomic ionic radii of lanthanoids
183
Europium Eu 63 [Xe]4f 76s2 [Xe]4f 76s2 4f 6 199 94.7
184
8.12.2 Oxidation state : +3 oxidation state is 4f subshell. Thus the 4f electrons shield each
common to all elements in which 2 electrons other from the nuclear charge poorly owing to
of s- subshell and one from d or f- subshell their diffused nature. With increasing atomic
are removed. The 4f electrons are strongly number and nuclear charge, the effective
screened by inner electrons of 5s and 5p nuclear charge experienced by each 4f
electrons. Thus, 4f electrons are not involved in electrons increases. As a result, the whole of
the bonding. Besides these, some lanthanoids 4f electron shell contracts at each successive
show oxidation states +2 and +4. They are element.
formed in case of f0, f7 , f14 configurations or
resulting ions.
For example : Ce4⊕ (f 0) ; Eu2⊕ and Tb4⊕ (f 7) ;
Yb2⊕ (f 14) Refer Table 8.11.
8.12.3 Colour and Spectra :
Some trivalent ions (M3⊕) are coloured in
solid state as well as in solution. The colour of
lanthanoid ion is due to f-f transitions which
Fig. 8.6 : Ionic radii of lanthanoids in +3
correspond to energy in the visible region of
the electromagnetic spectrum. The colour of oxidation state
ions having nf electrons is about the same as In section 8.3.4 we have learnt about
those having (14 – n)f electrons. (where n is an the magnetic behaviour of transition metal
integer 1-13). complexes.
Ln No. of Colour
ion f-electrons Use your brain power
Pr 3⊕
4f 2
green (14 -n) • Do you think that lanthanoid
f-electrons complexes would show
=14-2 =12 magnetism?
Tm3⊕ 4f 12 green n f-electrons
• Can you calculate the spin only
=12
magnetic moment of lanthanoid
Nd3⊕ 4f 3 pink (14 -n) complexes using the same formula
f-electrons that you used for transition metal
=14-3 =11 complexes?
Er3⊕ 4f 11 pink nf-electrons • Calculate the spin only magnetic
=11 moment of La3+. Compare the value
8.12.4 Atomic and ionic radii (Lanthanoid with that given in Table 8.13 Is it same
Contraction) : As we move along the or different?
lanthanoid series, there is a decrease in
atomic and ionic radii (Fig.8.6). This steady
decrease in the atomic and ionic radii is called
Lanthanoide contraction. As we move from
one element to another the nuclear charge
increases by one unit and one electron is added.
The new electrons are added to the same inner
185
Table 8.13: Effective magnetic moments of For example, mixed oxide of europium and
lanthanoids in +3 oxidation state yttrium (Eu,Y)2O3 releases an intense red
colour when bombarded with the high energy
Ln Ln3+ No. of Observed electrons.The optoelectronics applications use
oxidation unpaired magnetic lanthanoid ions as active ions in luminescent
state electrons moment, materials. The most notable application is the
μeff B.M Nd: YAG laser (Nd: YAG = neodymium doped
La 4f0 0 0 yttrium aluminium garnet). Erbium-doped fibre
Ce 4f1 1 2.3-2.5 amplifiers are significant devices in the optical-
fibre communication systems. Lanthanoids
Pr 4f2 2 3.4-3.6 are used in hybrid cars, superconductors and
Nd 4f 3
3 3.5-3.6 permanent magnets.
Pm 4f4 4 -- 8.14 Actinoids : The last row of elements in the
Sm 4f 5
5 1.4-1.7 periodic table is the actinoid series. It begins
Eu 4f6 6 3.3-3.5 at thorium (Z =72) and ends at lawrencium
(Z=103). Most of these elements are not
Gd 4f7 7 7.9-8.0 found in nature. They are all radioactive and
Tb 4f 8
6 9.5-9.8 man-made. The half-lives of the isotopes
Dy 4f9 5 10.4-10.6 of thorium (Th-232=1.4 x 1010 years) and
uranium (U-238=4.5 x 109 years) are so long
Ho 4f10 4 10.4-10.7
that these elements exist in rocks on earth.
Er 4f11 3 9.4-9.6 The long lived isotopes such as thorium,
Tm 4f 12
2 7.1-7.6 protactinium, uranium, neptunium, plutonium
Yb 4f13 1 4.3-4.9 and americium, are studied in more details.
These elements have high densities (~ 15-20
Lu 4f14 0 0
g cm-3), high melting points (~1000 oC) and
8.13 Applications high boiling points (~3000 oC). Actinoids are
less reactive than lanthanoids. For example,
The lanthanoid compounds are present
they react with hot, but not cold water to
in every household. It is inside the colour
give the hydroxide and hydrogen gas. Unlike
television tubes. When electrons are bombarded
lanthanoids, they exhibit a range of oxidation
on certain mixed lanthanoid compounds, they
numbers in their compounds which varies
emit visible light over a small wavelength
from +2 to +8. The most common oxidation
range. Therefore, the inside surface of a
numbers of the actinoids are shown in Fig. 8.7.
television tube or computer monitor is coated
with tiny patches of three different lanthanoid As can be seen from Fig.8.7, the most
compositions to give three colours that make common oxidation state of early actinoids
the colour image. reflects the loss of all outer electrons which
is similar to transition metals than the
lanthanoids. A ready loss of 5f electrons by
early actinoids indicates that these electrons
are much closer in energy to 7s and 6d electrons
Promethium Europium Actinium Brekelium
than the 4f electrons to 6s and 5d electrons as
in lanthanoids. All three sets of orbitals that
is 6d, 5f and 7s have similar energies. For Th,
Pa and Np difference in energy levels is small
Nobelium Mendelenium Sebargium
186
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With the help of internet find out the applications of the elements listed in
table below. Share this information with your friends
Element Applications
Lanthanum
Ytterbium
Erbium
Praseodymium
Samarium
Promethium
6
5
4
3
2
1
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
iv. They experience decrease in the atomic and Uranium is another actinoid which
ionic radii from actinium (Ac) to lawrencium is in great demand as it is used in
(Lw), known as actinoid contraction the nuclear reactors. One of the extraction
v. They usually exhibit +3 oxidation state. methods for uranium has a very interesting
Elements of first half of the series usually chemistry. The ore containing U(IV) oxide,
exhibit higher oxidation states.
UO2, is first treated with Fe(III) ion to give
8.16 Applications of actinoids : We have U(VI) oxide, UO3
seen that the half-lives of natural thorium
UO2 (s) + H2O(l) UO3 (s) + 2H⊕ (aq)
and uranium isotopes are so long that we get
very negligible radiation from these elements. + 2e
We find them in everyday use. For example, Fe (aq) + e Fe (aq)
3⊕ 2⊕
Th(IV) oxide, ThO2 with 1% CeO2 was used Addition of H2SO4 to this solution produces
as a major source of indoor lighting before uranyl sulphate containing UO22⊕ cation:
incandescent lamps came into existence only
UO3 (s) + H2SO4 (aq) UO2SO4 (aq) +
because these oxides convert heat energy from
burning natural gas to an intense light. Even H2O (l)
today, there is a great demand for these lights After purification, ammonia is added to the
for outdoor camping. solution giving bright yellow precipitate of
ammonium diuranate, (NH4)2U7O7:
2 UO2SO4 (aq) + 6 NH3 (aq) + 3 H2O (l)
(NH4)2U7O7 (s) + 2 (NH4)2SO4 (aq)
This yellow cake is the marketable form of
uranium!
The electronegativity of all the elements in Lanthanoids do not form oxocations, but actinides
both the series is low and are said to be highly form oxocations such as UO+, PuO+, NpO2+
reactive
The nitrates, perchlorates and sulphates of all Most of the lanthanoids are colourless in nature
the elements are soluble while the hydroxides, whereas the actinoids are coloured ions
fluorides and carbonates are insoluble
188
Table 8.14 Electronic configuration of actinoids and their ionic radii in +3 oxidation state
Element Symbol Atomic *Atomic *Ionic radii
Electronic configuration
number radii, pm (Ac3⊕), pm
ground state +3
oxidation
state
Actinium Ac 89 [Rn]5f 06d17s2 5f 0 203 126
Thorium Th 90 [Rn]5f 06d27s2 5f 1 180 -
Protactinium Pa 91 [Rn]5f 6d 7s
2 1 2
5f 2
162 118
Uranium U 92 [Rn]5f 36d17s2 5f 3 153 118
Neptunium Np 93 [Rn]5f 46d17s2 5f 4 150 116
Plutonium Pu 94 [Rn]5f 6d 7s
6 0 2
5f 5
162 115
Americium Am 95 [Rn]5f 76d07s2 5f 6 173 114
Curium Cm 96 [Rn]5f 6d 7s
7 1 2
5f 7
174 112
Berkelium Bk 97 [Rn]5f 96d07s2 5f 8 170 110
Californium Cf 98 [Rn]5f 6d 7s
10 0 2
5f 9
186 109
Einsteinium Es 99 [Rn]5f 116d07s2 5f 10 186 98
Fermium Fm 100 [Rn]5f 126d07s2 5f 11 198 91
Mendelevium Md 101 [Rn]5f 6d 7s
13 0 2
5f 12
194 90
Nobelium No 102 [Rn]5f146d07s2 5f 13 197 95
Lawrencium Lr 103 [Rn]5f 6d 7s
14 1 2
5f 14
171 88
Table 8.15 : Some comparison between Pre-Transition, Lanthanoids and Transition Metals
Pre-Transition Metals Lanthanoids Transition Metals
Essentially in (+3)
Essentially monovalent - Show variable oxidation
oxidation state
show group (n+) oxidation states
(+2/+4 for certain
state
configurations)
Periodic trends dominated Lanthanoid contraction of
Size changes of Mn⊕, less
by effective nuclear charge Ln3⊕ marked
at noble gas configuration
Similar properties for a Similar properties Substantial changes in
given group properties
Always 'hard' (O, X, Always 'hard' (O, X, heavier metals
N donors, preferably N donors, preferably (increasingly from Fe-Cu)
negatively charged) negatively charged) may show a 'soft' character
Insignificant ligand field Substantial ligand field
No ligand field effects
effects effects
Poor coordination High coordination Coordination number 6
properties(C.N. determined numbers (C.N. determined is typical maximum (many
by size) by size) exceptions)
Fixed geometries (ligand
Flexibility in geometry Flexibility in geometry
field effects)
No magnetism Show magnetism Show magnetism
189
8.17 Postactinoid elements : You have seen With half-lives of miliseconds only a little is
that elements with atomic number greater than known about the chemistry of these elements.
92 are called ‘Transuranium’. Elements from Rutherfordium forms a chloride, RfCl4, similar
atomic number 93 to 103 now are included to zirconium and hafnium in the +4 oxidation
in actinoid series and those from 104 to 118 state. Dubnium resembles to both, group 5
are called as postactinoid elements. The transition metal, niobium(V) and actinoid,
postactinoid elements that are known so far protactinium(V).
are transition metals. They are included as
postactinoids because similar to actinoid Do you know ?
elements, they can be synthesized in the Traditionally, no element was
nuclear reactions. So far, nine postactinoid
named after a still-living scientist.
elements have been synthesized. It is difficult
to study their chemistry owing their short half- This principle was put to an end with
lives. For example, element 112 has a half-life naming the element 106 as ‘Seaborgium’.
of only 2.8 x 10-4 seconds.
Exercises
191
9. COORDINATION COMPOUNDS
9.1 Introduction : A coordination compound ligands depending on the number of electron
consists of central metal atom or ion surrounded donor atoms they have.
by atoms or molecules. For example, a
chemotherapy drug, cisplatin, Pt(NH3)2Cl2, is 9.2.1 Monodentate ligands : A monodentate
a coordination compound in which the central ligand is the one where a single donor atom
platinum metal ion is surrounded by two shares an electron pair to form a coordinate
ammonia molecules and two chloride ions. The bond with the central metal ion. For example:
species surrounding the central metal atom or the ligands Cl , OH or CN attached to metal
ion are called ligands. The ligands are linked have electron pair on Cl, O and N, respectively
directly to central metal ion through coordinate which are donor atoms :
bonds. A formation of coordinate bond occurs Cl O-H C≡N
when the shared electron pair is contributed
by ligands. A coordinate bond is conveniently Use your brain power
represented by an arrow →, where the arrow Draw Lewis structure of the
head points to electron acceptor. The central following ligands and identify the
metal atom or ion usually an electron deficient donor atom in them : NH3, H2O
species, accepts an electron pair while the
9.2.2 Polydentate ligands : A polydentate
ligands serve as electron donors. Coordination
ligand has two or more donor atoms linked
compounds having a metal ion in the centre are
to the central metal ion. For example,
common. In cisplatin two ammonia molecules
ethylenediamine and oxalate ion. Each of these
and two chloride ligands utilize their lone pairs
ligands possesses two donor atoms. These are
of electrons to form bonds with the Pt(II).
bidentate ligands.
NH3 i. Ethylenediamine binds to metal using
Cl Pt NH3 electron pair on each of its two nitrogens.
Cl
The donor nitrogen and chlorine atoms of H 2N NH2
CH2 - CH2
the ligands are directly attached to and form
bonds with platinum. Similarly oxalate ion (C2O4)2 utilizes
electron pair on each of its negatively charged
Can you recall ? oxygen atoms upon linking with the metal.
What are Lewis acids and bases ?
O O
Formation of a coordination compound C-C
O O
can be looked upon as the Lewis acid-base
ii. Ethylenediaminetetraacetate ion
interaction. The ligands being electron pair
(EDTA)4 binds to metal ion by electron pairs
donors are Lewis bases. The central metal ion
of four oxygen and two nitrogen atoms. It is a
being electron pair acceptor serves as Lewis
hexadentate ligand.
acid.
O O
9.2 Types of ligands : The ligands can O - C - H2C CH2 - C - O
be classified as monodentate and polydentate N - CH2 - CH2 - N
O - C - H2C CH2 - C - O
O O
192
9.2.3 Ambidentate ligand : The ligands which [Fe(CN)6]4 has charge number of -4. It can be
have two donor atoms and use the electron utilised to calculate O.S. of Fe. Thus,
pair of either donor atoms to form a coordinate charge number of complex = -4
bond with the metal ion, are ambidentate
ligands. For example, the ligand NO2 links to = (O.S. of Fe + charge of ligands)
metal ion through nitrogen or oxygen. = (O.S. of Fe + 6 × charge of CN ion)
O = (O.S. of Fe + 6 × (-1))
M N or M O-N=O Therefore, O.S. of Fe = -4 + 6 = +2.
O
Can you tell ?
Similarly, SCN has two donor atoms A complex is made of Co(III)
nitrogen and sulfur either of which links to and consists of four NH3 molecules
metal depicted as M ← SCN or M← NCS. and two Cl ions as ligands. What is the
9.3 Terms used in coordination chemistry: charge number and formula of complex ion ?
The following terms are used for describing
coordination compounds. 9.3.3 Coordination number (C.N.) of central
9.3.1 Coordination sphere : The central metal metal ion : Look at the complex [Co(NH3)4Cl2]⊕.
ion and ligands linked to it are enclosed in a Here four ammonia molecules and two chloride
square bracket. This is called a coordination ions, that is, total six ligands are attached to
sphere, which is a discrete structural unit. When the cobalt ion. All these are monodentate since
the coordination sphere comprising central each has only one donor atom. There are
metal ion and the surrounding ligands together six donor atoms in the complex. Therefore,
carry a net charge, it is called the complex the coordination number of Co3⊕ ion in the
ion. The ionisable groups shown outside the complex is six. Thus, the coordination number
bracket are the counter ions. For example, of metal ion attached to monodentate ligands
the compound K4[Fe(CN)6] has [Fe(CN)6]4- is equal to number of ligands bound to it.
coordination sphere with the ionisable K⊕ Consider the bidentate ligand C2O42
ions representing counter ions. The compound or ethylenediamine (en). The complexes,
ionizes as : [Fe(C2O4)3]3 and [Co(en)3]3⊕, have three
K4[Fe(CN)6] 4K⊕ + [Fe(CN)6]4 bidentate ligands each. The total donor atoms
in three of ligands is six and the C.N. of Fe3⊕
Try this... and Co3⊕ in these complexes is six.
193
The secondary valencies for a metal ion are
Can you tell ?
fixed and satisfied by either anions or neutral
What is the coordination
ligands. Number of secondary valencies is
number of Co in [CoCl2(en)2]⊕,
equal to the coordination number.
of Ir in [Ir(C2O4)2Cl2]3⊕ and of Pt in
[Pt(NO2)2(NH3)2]? Postulate (iv) The secondary valencies have
a fixed spatial arrangement around the metal
9.3.4 Double salt and coordination complex ion. Two spheres of attraction in the complex
Combination of two or more stable [Co(NH3)6]Cl3 are shown.
compounds in stochiometric ratio can give two
types of substances, namely, double salt and NH3
H 3N NH3
coordination complexes.
Co Cl3
Double salt : A double salt dissociates in water
H 3N NH3
completely into simple ions. For example (i)
NH3
Mohr's salt, FeSO4(NH4)2SO4.6H2O dissociates
as : coordination ionization
water
FeSO4(NH4)2SO4.6H2O Fe2⊕(aq) (secondary) sphere (primary) sphere
+ 2NH4⊕(aq) +2SO42 (aq)
ii. Carnalite KCl.MgCl2.6H2O dissociates as Remember...
water
When a complex is brought
KCl.MgCl2.6H2O K⊕(aq) +
into solution it does not dissociate
Mg (aq) + 3Cl (aq)
2⊕
into simple metal ions. When [Co(NH3)6]
Coordination complex : A coordination Cl3 is dissolved in water it does not give the
complex dissociates in water with at least test for Co3⊕ or NH3. However, on reacting
one complex ion. For example, K4[Fe(CN)6] with AgNO3 a curdy white precipitate of
dissociates as the complex ion and counter ion. AgCl corresponding to 3 moles is observed.
K4[Fe(CN)6] 4K⊕(aq) + [Fe(CN)6]4
Problem 9.1 : One mole of a purple coloured
(counter ion) (complex ion) complex CoCl3 and NH3 on treatment with
9.3.5 Werner theory of coordination excess AgNO3 produces two moles AgCl.
complexes : The first attempt to explain nature Write the formula of the complex if the
of bonding in coordination compounds was coordination number of Co is 6.
put forth by Werner. The postulates of Werner Solution : One mole of the complex gives
theory are as follows. 2 moles of AgCl. It indicates that two Cl
Postulate (i) Unlike metal salts, the metal in ions react with Ag⊕ ions. The complex has
a complex possesses two types of valencies two ionisable Cl ions. The formula of the
: primary (ionizable) valency and secondary complex is then [Co(NH3)5Cl]Cl2.
(nonionizable) valency.
Postulate (ii) The ionizable sphere consists Can you tell ?
of entities which satisfy the primary valency One mole of a green coloured
of the metal. Primary valencies are generally complex of CoCl3 and NH3 on
satisfied by anions. treatment with excess of AgNO3
produces 1 mole of AgCl. What is the
Postulate (iii) The secondary coordination
formula of the complex ? (Given : C.N. of
sphere consists of entities which satisfy the
Co is 6)
secondary valencies and are non ionizable.
194
A complex with coordination number six has anionic sphere complex. For example,
octahedral structure. When four coordinating [Ni(CN)4] and K3[Fe(CN)6] have anionic
2
groups are attached to the metal ion the coordination sphere; [Fe(CN)6]3 and
⊕
complex would either be with square planar three K ions make the latter electrically
or tetrahedral structure. neutral.
9.4 Classification of complexes: The iii. Neutral sphere complexes : A neutral
coordination complexes are classified coordination complex does not possess cationic
according to types of ligands and sign of or anionic sphere. [Pt(NH3)2Cl2] or [Ni(CO)4]
charge on the complex ion. have neither cation nor anion but are neutral
sphere complexes.
9.4.1 Classification on the basis of types of
ligands
i. Homoleptic complexes : Consider Use your brain power
[Co(NH3)6]3⊕. Here only one type of ligands Classify the complexes
surrounds the Co3⊕ ion. The complexes in as cationic, anionic or neutral.
which metal ion is bound to only one type of Na4[Fe(CN)6], Co(NH3)6Cl2,
ligands are homoleptic. Cr(H2O)2(C2O4)23 , PtCl2(en)2 and
Cr(CO)6.
ii. Heteroleptic complexes : Look at the
complex [Co(NH3)4Cl2]⊕. There are two types 9.5 IUPAC nomenclature of coordination
of ligands, NH3 and Cl attached to Co3⊕ compounds : Tables 9.1, 9.2 and 9.3 summarize
ion. Such complexes in which metal ion is the IUPAC nomenclature of coordination
surrounded by more than one type of ligands compounds.
are heteroleptic.
Rules for naming coordination compounds
recommended by IUPAC are as follows:
Use your brain power
1. In naming the complex ion or neutral
Classify the complexes molecule, name the ligand first and then the
as homoleptic and heteroleptic metal.
[Co(NH3)5Cl]SO4, [Co(ONO)(NH3)5]Cl2 2. The names of anionic ligands are obtained
[CoCl(NH3)(en)2]2⊕ and [Cu(C2O4)3]3 . by changing the ending -ide to -o and -ate to
-ato.
9.4.2 Classification on the basis of charge on 3. The name of a complex is one single word.
the complex There must not be any space between
i. Cationic complexes : A positively charged different ligand names as well as between
coordination sphere or a coordination ligand name and the name of the metal.
compound having a positively charged 4. After the name of the metal, write its
coordination sphere is called cationic sphere oxidation state in Roman number which
complex. appears in parentheses without any space
For example: the cation [Zn(NH3)4]2⊕ and between metal name and parentheses.
[Co(NH3)5Cl]SO4 are cationic complexes. The 5. If complex has more than one ligand of the
latter has coordination sphere [Co(NH3)5Cl]2⊕; same type, the number is indicated with
the anion SO42 makes it electrically neutral. prefixes, di-, tri-, tetra-, penta-, hexa- and
ii. Anionic sphere complexes : A so on.
negatively charged coordination sphere or a 6. For the complex having more than one type
coordination compound having negatively of ligands, they are written in an alphabetical
charged coordination sphere is called order. Suppose two ligands with prefixes
195
Table 9.1 : IUPAC names of anionic and neutral ligands
Anionic ligand IUPAC name Anionic ligand IUPAC name
Br , Bromide Bromo CO3 , Carbonate
2
Carbonato
Cl , Chloride Chloro OH , Hydroxide Hydroxo
F , Fluoride Fluoro C2O42 , Oxalate Oxalato
I Iodide Iodo NO2 , Nitrite Nitro (For N - bonded ligand)
CN , Cyanide Cyano ONO , Nitrite Nitrito(For O-bonded ligand)
Thiocyanato (For ligand do-
SO42 , Sulphate Sulphato SCN , Thiocyanate
nor atom S)
Isothiocyanato (For ligand
NO3 , Nitro Nitrato NCS , Thiocyanate
donor atom N)
Neutral ligand IUPAC name Neutral ligand IUPAC names
Ammine (Note the
NH3, Ammonia H2O, water Aqua
spelling)
CO, Carbon monoxide Cabonyl en, Ethylene diamine Ethylenediamine
Table 9.2 : IUPAC names of metals in anionic complexes
Metal IUPAC name Metal IUPAC name
Aluminium, Al Aluminate Chromium, Cr Chromate
Cobalt, Co Cobaltate Copper, Cu Cuprate
Gold, Au Aurate Iron, Fe Ferrate
Manganese, Mn Maganate Nickel, Ni Nickelate
Platinum, Pt Platinate Zinc, Zn Zincate
Table 9.3 : IUPAC names of some complexes
Complex IUPAC name
i. Anionic complexes :
a.[Ni(CN)4]2 Tetracyanonickelate(II) ion
b. [Co(C2O4)3]3 Trioxalatocobaltate(III) ion
c. [Fe(CN)6]4 Hexacyanoferrate(II) ion
ii. Compounds containing complex anions and metal cations :
a. Na3[Co(NO2)6] Sodium hexanitrocobaltate(III)
b. K3[Al(C2O4)3] Potasium trioxalatoaluminate(III)
c. Na3[AlF6] Sodium hexafluoroaluminate(III)
iii. Cationic complexes :
a. Cu(NH3)42⊕ Tetraamminecopper(II) ion
b.[Fe(H2O)5(NCS)]2⊕ Pentaaquaisothiocyanatoiron(III) ion,
c.[Pt(en)2(SCN)2]2⊕ Bis(ethylenediamine)dithiocyanatoplatinum(IV).
v. Neutral complexes :
a. [Co(NO2)3(NH3)3] Triamminetrinitrocobalt(III)
b. Fe(CO)5 Pentacarbonyliron(0)
c. [Rh(NH3)3(SCN)3] Triamminetrithiocyanatorhodium(III)
196
are tetraaqua and dichloro. While naming rule states that a metal ion continues to accept
in alphabetical order, tetraaqua is first and electrons pairs till it attains the electronic
then dichloro. configuration of the next noble gas. Thus if the
7. If the name of ligand itself contains EAN is equal to 18 (Ar), 36 (Kr), 54 (Xe), or
numerical prefix then display number 86 (Rn) then the EAN rule is obeyed.
by prefixes with bis for 2, tris for 3, EAN can be calculated with the following.
tetrakis for 4 and so forth. Put the ligand Formula
name in parentheses. For example, EAN = number of electrons of metal ion + total
(ethylenediamine)3 or (en3) would appear number of electrons donated by ligands
as tris(ethylenediamine) or tris(ethane-1, = atomic number of metal (Z) - number
2-diamine). of electrons lost by metal to form the
8. The metal in cationic or neutral complex ion (X) + number of electrons donated
is specified by its usual name while in the by ligands (Y).
anionic complex the name of metal ends =Z-X+Y
with 'ate'. Cosider Co[NH3]63⊕
Oxidation state of Cobalt is +3, six ligands
Try this... donate 12 electrons.
Write the representation of Z = 27; X = 3; Y = 12
EAN of Co3⊕ = 27 - 3 + 12 = 36.
• Tricarbonatocobaltate(III) ion.
• Sodium hexacyanoferrate(III). Try this...
• Aquachlorobis(ethylenediamine)
cobalt(III). Cr(CO)6 and [Fe(CN)6]4 are some examples
• Tetraaquadichlorochromium(III) of coordination compounds which obey
chloride. the EAN rule. Certain other coordination
compounds however do not obey the EAN
• Diamminedichloroplatinum(II).
rule. For example, [Fe(CN)6]3 and Cu[NH3]42⊕
9.6 Effective Atomic Number (EAN) Rule : have EAN 35.
An early attempt to explain the stability
of coordination compounds was made by Use your brain power
Sidgwick who proposed an empirical rule Do the following complexes follow
known as effective atomic number (EAN) rule. the EAN rule ? Cr(CO)4, Ni(CO)4,
EAN equals total number of electrons around Mn(CO)5, Fe(CO)5.
the central metal ion in the complex. EAN
Isomers
3⊕ 3⊕
en en 9.7.2 Structural isomers (Constitutional
en Co Co en isomers) : Structural isomers possess different
linkages among their constituent atoms and
en en have, their chemical formulae to be the same.
d mirror l They can be classified as linkage isomers,
ionization isomers, coordination isomers and
solvate isomers.
Remember...
a. Linkage isomers : These isomers are formed
Our hands are non
when the ligand has two different donor atoms.
superimposable mirror images.
It coordinates to the metal via different donor
When you hold your left hand upto a
atoms. Thus the nitrite ion NO2 having two
mirror the image looks like right hand.
donor atoms show isomers as :
[Co(NH3)5(NO2)]2⊕ and [Co(NH3)5(ONO)]2⊕
The nitro complex has Co-N bond and the
ii. Octahedral complexes existing as both nitrito complex is linked through Co-O bond.
geometric and optical isomers These are linkage isomers.
[PtCl2(en)2]2⊕
Can you tell ?
In this type of complex, only the cis isomer
exists as pair of enantiomers Write linkage isomers of
[Fe(H2O)5SCN]⊕. Write their IUPAC
names.
199
b. Ionization isomers : Ionization isomers the free solvent molecule. I and II represent
involve exchange of ligands between solvate (hydrate) isomers.
coordination and ionization spheres. For 9.8 Stability of the coordination compounds:
example:
The stability of coordination compounds
[Co(NH3)5SO4]Br and [Co(NH3)5Br]SO4 can be explained by knowing their stability
(I) (II) constants. The stability is governed by metal-
In compound I, anion SO42 , bonded to ligand interactions. In this the metal serves
Co is in the coordination sphere while Br is as electron-pair acceptor while the ligand as
in the ionization sphere. In compound II, anion Lewis base (since it is electron donor). The
Br is in the coordination sphere linked to Co metal-ligand interaction can be realized as the
while SO42 is in the ionisation sphere. These Lewis acid-Lewis base interaction. Stronger
complexes in solution ionize to give different the interaction greater is stability of the
ions. complex.
200
is called Irving-William order. In the above list iii. The number of vacant hybrid orbitals
both Cu and Cd have the charge +2, however, formed is equal to the number of ligand
the ionic radius of Cu2⊕ is 69 pm and that of donor atoms surrounding the metal ion
Cd2⊕ is 97 pm. The charge to size ratio of Cu2⊕ which equals the coordination number of
is greater than that of Cd2⊕ . Therefore the Cu2⊕ metal.
forms stable complexes than Cd2⊕. iv. Overlap between the vacant hybrid
b. Nature of the ligand. orbitals of the metal and filled orbitals of
the ligand leads to formation of the metal-
A second factor that governs stability
ligand coordinate bonds.
of the complexes is related to how easily the
ligand can donate its lone pair of electrons to v. The hybrid orbitals used by the metal ion
the central metal ion that is, the basicity of the point in the direction of the ligand.
ligand. The ligands those are stronger bases vi. The (n-1)d or nd orbitals used in
tend to form more stable complexes. hybridisation allow the complexes to be
classified as (a) outer orbital and (b) inner
Use your brain power orbital complexes.
The stability constant K of the vii. For hybridisation in the outer orbital
[Ag(CN)2] is 5.5 × 1018 while that complex nd orbitals are used, whereas
for the corresponding [Ag(NH3)2]⊕ is 1.6 × in the inner orbital complexes (n-1)d
107. Explain why [Ag(CN)2]2 is more stable. orbitals are used.
Type of hybridisation decides the structure
9.9 Theories of bonding in complexes : of the complex. For example when the
The metal-ligand bonding in coordination hybridisation is d2sp3 the structure is octahedral.
compounds has been described by Valence Steps to understand the metal-ligand bonding
bond theory (VBT) and Crystal field theory include :
(CFT). i. Find oxidation state of central metal ion
9.9.1 Valence bond theory (VBT) ii. Write valence shell electronic configuration
of metal ion.
Can you recall ?
iii. See whether the complex is low spin or
What is valence bond theory and
high spin. (applicable only for octahedral
the concept of Hybridisation?
complexes with d4 to d8 electronic
The hybridized state is a theoretical step that configurations).
describes how complexes are formed. VBT iv. From the number of ligands find the
is based on the concept of hybridization. The number of metal ion orbitals required for
hybrid orbitals neither exist nor can be detected bonding.
spectroscopically. These orbitals, however, v. Identify the orbitals of metal ion
help us to describe structure of coordination available for hybridisation and the type of
compounds. The steps involved in describing hybridisation involved.
bonding in coordination compounds using the vi. Write the electronic configuration after
VBT are given below. hybridisation.
i. Metal ion provides vacant d orbitals
vii Show filling of orbitals after complex
for formation of coordinate bonds with
formation.
ligands.
viii.Determine the number of unpaired
ii. The vacant d orbitals along with s and
electrons and predict magnetic behaviour
p orbitals of the metal ion take part in
of the complex.
hybridisation.
201
vi. Six orbitals available for hybridisation
Remember...
are two 3d, one 4s, three 4p orbitals
Complete the missing entries.
3d 4s 4p
Coordination Geometry Hybridization
number of complex
2 sp
d2sp3
4 Tetrahedral
The orbitals for hybridization are decided
Square from the number of ammine ligands which
4
planar is six. Here (n-1)d orbitals participate in
6 d2sp3/ sp3d2 hybridization since it is the low spin complex.
vii. Electronic configuration after complex
formation.
Try this...
3d 4s 4p
Give VBT description of
bonding in each of following
complexes. Predict their magnetic
behavior. d2sp3
a. [ZnCl4]2 3⊕
b. [Co(H2O)6]2⊕ (high spin) NH3
c. [Pt(CN)4]2 (square planar) H3N NH3
Co
d. [CoCl4]2 (tetrahedral) H3N NH3
e. [Cr(NH3)6]3⊕ NH3
9.9.2 Octahedral, complexes viii. As all electrons are paired the complex is
a. [Co(NH3)6]3 ⊕ low spin diamagnetic.
i. Oxidation state of Cobalt:3⊕ b. [CoF6]3 high spin
ii. Valence shell electronic configuration i.Oxidation state of central metal Co is 3+
of Co3⊕ is represented in box diagram as ii.Valence shell electronic configuration of
shown below : Co3⊕ is
3d 4s 4p 3d 4s 4p
iii. Number of ammine ligands is 6, number iii. Six fluoride F ligands, thus the number of
of vacant metal ion orbitals required for vacant metal ion orbitals required for bonding
bonding with ligands must be six. with ligands would be six.
iv. Complex is low spin, so pairing of electrons iv. Complex is high spin, that means pairing
will take place prior to hybridisation. of electrons will not take place prior to
v. Electronic configuration after pairing would hybridisation. Electronic configuration would
be remain the same as in the free state shown
3d 4s 4p above.
202
v. Six orbitals available for the hybridisation. one 4s, three 4p. The complex is tetrahedral.
Those are one 4s, three 4p, two of 4d orbitals 3d 4s 4p
3d 4s 4p 4d
sp3
sp3d2
The four metal ion orbitals for bonding with
Six metal orbitals after bonding with six Cl ligands are derived from the sp3
F ligands led to the sp3d2 hybridization. The d hybridization.
orbitals participating in hybridisation for this vi. Four vacant sp3 hybrid orbital of Ni2⊕
complex are nd. overlap with four orbitals of Cl ions.
vi. Six vacant sp3d2 hybrid orbital of Co3+ vii. Configuration after complex formation
overlap with six orbitals of fluoride forming would be.
Co - F coordinate bonds. 3d 4s 4p
vii. Configuration after complex formation.
3d 4s 4p 4d
sp3
viii.The complex has four unpaired electrons
and hence, paramagnetic.
sp3d2
viii. The complex is octahedral and has four 2
Cl
unpaired electrons and hence, is paramagnetic.
Ni Cl
3 Cl
F
F F Cl
Co 9.9.4 Square planar complex
F F [Ni(CN)4]2
F i. Oxidation state of nickel is +2
ii. Valence shell electronic configuration of
Ni2⊕
9.9.3 Tetrahedral complex
3d 4s 4p
[Ni(Cl)4]2
i. Oxidation state of nickel is +2
ii. Valence shell electronic configuration of
Ni2+ iii. Number of CN ligands is 4, so number
3d 4s 4p of vacant metal ion orbitals required for
bonding with ligands would be four.
iv. Complex is square planar so Ni2⊕ ion uses
iii. number of Cl ligands is 4. Therefore dsp2 hybrid orbitals.
number of vacant metal ion orbitals v. 3d electrons are paired prior to the
required for bonding with ligands must be hybridisation and electronic configuration
four. of Ni2⊕ becomes :
iv. Four orbitals on metal available for
hybridisation are 3d 4s 4p
203
vi. Orbitals available for hybridisation are In an isolated gaseous metal ion the five d
one 3d, one 4s and two 4p which give dsp2 orbitals, d x2-y2 ,dz2, dxy,dyzd,zx have the same
hybridization. energy i.e. they are degenerate.
vii. Four vacant dsp2 hybrid orbitals of Ni2⊕ ii. When ligands approach the metal ion they
overlap with four orbitals of CN ions to form create crystal-field around the metal ion. If
Ni - CN coordinate bonds. it were symmetrical the degeneracy of the d
vii. Configuration after the complex formation orbitals remains intact.
becomes. Usually the field created is not symmetrical
3d 4s 4p
and the degeneracy is destroyed. The d orbitals
thus split into two sets namely, (dxy, dyz, dxz)
usually refered by t2g and ( d x2-y2 ,dz2) called
dsp2
as eg. These two sets of orbitals now have
viii.The complex has no unpaired electrons
different energies. A separation of energies of
and hence, dimagnetic.
these two sets of d orbitals is the crystal field
2 splitting parameter. This is denoted by Δo (O
for octahedral).
NC CN iii. The Δo depends on strength of the ligands.
Ni The ligands are then classified as (a) strong
NC CN field and (b) weak field ligands. Strong field
ligands are those in which donor atoms are
C,N or P. Thus CN , NC , CO, NH3, EDTA,
Try this...
en (ethylenediammine) are considered to be
Based on the VBT predict strong ligands. They cause larger splitting of
structure and magnetic behavior of d orbitals and pairing of electrons is favoured.
the [Ni(NH3)6]3⊕ complex. These ligands tend to form low spin complexes.
Weak field ligands are those in which donor
9.9.5 Limitations of VBT atoms are halogens, oxygen or sulphur. For
i. It does not explain the high spin or low spin example, F , Cl , Br , I , SCN , C2O42 . In
nature of the complexes. In other words, strong case of these ligands the Δo parameter is
and weak field nature of ligands can not be smaller compared to the energy required for
distinguished. the pairing of electrons, which is called as
ii. It does not provide any explanation for the electron pairing energy. The ligands then can
colour of coordination compounds. be arranged in order of their increasing field
iii. The structure of the complexes predicted strength as
from the VBT would not always match
I < Br < Cl < S2 < F < OH < C2O42
necessarily with those determined from the
<H2O<NCS <EDTA< NH3,< en< CN < CO.
experiments.
To overcome these difficulties in VBT, the Let us understand splitting of d orbitals and
Crystal field theory has been proposed which formation of octahedral complexes
has widely been accepted. In octahedral environment the central metal
9.9.6 Crystal Field theory (CFT) ion is surrounded by six ligands.
C.F.T. is based on following assumptions Ligands approach the metal ion along the x, y,
i. The ligands are treated as point charges. z axes. As the ligands approach the metal ion
The interaction between metal ion and ligand the degeneracy of d orbitals is resolved.
is purely electrostatic or there are no orbital
interactions between metal and ligand.
204
eg
t2g
205
eg eg Try this...
Energy Sketch qualitatively crystal
t2g t2g field d orbital energy level diagrams
Ground state Excited state for each of the following complexes:
Fig. 9.3 : d - d transition in d' system a. [Ni(en)3]2⊕ b. [Mn(CN)6]3
The absorption of the wavelength of light c. [Fe(H2O)6]2⊕
corresponding to Δo parameter promotes an Predict whether each of the complexes is
electron from the t2g level. Such energy gap in diamagnetic or paramagnetic.
case of the [Ti(H2O)6]3⊕ complex is 20,300 cm-1
(520 nm, 243 kJ/mol) and a complimentary The dxy, dyz, dzx orbitals with their lobes
colour to this is imparted to the complex. A lying in between the axes point toward the
violet color of the [Ti(H2O)6]3⊕ complex arises ligands. On the other hand, dx2-y2 and dz2
from such d-d transition. orbitals lie in between metal-ligand bond
9.9.9 Tetrahedral complexes axes. The dxy, dyz and dzx orbitals experience
more repulsion from the ligands compared to
A pattern of splitting of d orbitals, that by dx2-y2 and dz2 orbitals.
which is a key in the crystal field theory, is
dependent on the ligand field environment. Due to larger such repulsions the dxy, dyz
This is illustrated for the tetrahedral ligand and dzx orbitals are of higher energy while the
field environment. dx2-y2 and dz2 orbitals are of relatively lower
z energy.
Each electron entering in one of the
dxy,dyz and dzx orbitals raises the energy by
4 Dq whereas that accupying d x2-y2 and dz2
orbitals lowers it by 6 Dq compared to the
M x
energy of hypothetical degenerate d orbitals
in the ligand field.
A splitting of d orbitals in tetrahedral
crystal fields (assumed to be 10 Dq) thus is
y much less (typically 4/9) compared to that
Fig. 9.4 : Tetrahedral structure for the octahedral environment. The crystal
The tetrahedral structure having the field splitting of d orbitals in a tetrahedral
metal atom M at the centre and four ligands ligand field is compared with the octahedral
occupying the corners is displayed along with one in Fig. 9.5. Thus the pairing of electrons
in Fig. 9.4. is not favoured in tetrahedral structure. For
example, in d4 configuration an electron
Tetrahedral Octahedral
would occupy one of the t2g orbitals. The low
eg
spin tetrahedral complexes thus are not found.
t2g Typically metal complexes possessing
Δtet Δo the cetral metal ion with d8 electronic
eg
configuration, for example, Ni(CO)4, favours
Free-ion t2g the tetrahedral structure.
Exercises
1. Choose the most correct option.
i. The oxidation state of cobalt ion in the 3. [PtCl2Br2]2 (square planar)
complex [Co(NH3)5Br]SO4 is
4. [FeCl2(NCS)2]2 (tetrahedral)
a. +2 b. +3
c. +1 d. +4 a. 1 and 3 b. 2 and 3
ii. IUPAC name of the complex c. 1 and 3 d. 4 only
[Pt(en)2(SCN)2] is
2+
v. Which of the following complexes are
a. bis (ethylenediamine chiral ?
dithiocyanatoplatinum (IV) ion
1. [Co(en)2Cl2]⊕ 2. [Pt(en)Cl2]
b. bis (ethylenediamine)
dithiocyantoplatinate (IV) ion 3. [Cr(C2O4)3]3 4. [Co(NH3)4Cl2]⊕
c. dicyanatobis (ethylenediamine) a. 1 and 3 b. 2 and 3
platinate IV ion
d. bis (ethylenediammine)dithiocynato c. 1 and 4 d. 2 and 4
platinate (IV) ion vi. On the basis of CFT predict the number of
iii. Formula for the compound sodium unpaired electrons in [CrF6]3 .
hexacynoferrate (III) is a. 1 b. 2 c. 3 d. 4
a. [NaFe(CN)6] b. Na2[Fe(CN)6] vii. When an excess of AgNO3 is added to the
c. Na[Fe(CN)6] d. Na3[Fe(CN)6] complex one mole of AgCl is precipitated.
The formula of the complex is
iv. Which of the following complexes exist
as cis and trans isomers ? a. [CoCl2(NH3)4]Cl
207
c. [CoCl3(NH3)3] v. Write formulae of the following complexes
d. [Co(NH3)4]Cl3 a. Potassium amminetrichloroplatinate
viii. The sum of coordination number and (II)
oxidation number of M in [M(en)2C2O4]Cl b. Dicyanoaurate (I) ion
is vi. What are ionization isomers ? Give an
a. 6 b. 7 c. 9 d. 8 example.
2. Answer the following in one or two vii. What are the high-spin and low-spin
sentences. complexes ?
i.
Write the formula for viii. [CoCl4]2 is tetrahedral complex. Draw its
tetraammineplatinum (II) chloride. box orbital diagram. State which orbitals
ii. Predict whether the [Cr(en)2(H2O)2]3+ participate in hybridization.
complex is chiral. Write structure of its ix. What are strong field and weak field
enantiomer. ligands ? Give one example of each.
iv. Name the Lewis acids and bases in the x. With the help of crystal field energy-
complex [PtCl2(NH3)2]. level diagram explain why the complex
v. What is the shape of a complex in which [Cr(en)3]3⊕ is coloured ?
the coordination number of central metal 4. Answer the following questions.
ion is 4 ?
i. Give valence bond description for the
vi. Is the complex [CoF6] cationic or anionic bonding in the complex [VCl4] . Draw
if the oxidation state of cobalt ion is +3 ? box diagrams for free metal ion. Which
vii. Consider the complexes [Cu(NH3)4][PtCl4] hybrid orbitals are used by the metal ?
and [Pt(NH3)4] [CuCl4]. What type of State the number of unpaired electrons.
isomerism these two complexes exhibit? ii.
Draw qualitatively energy-level
viii. Mention two applications of coordination diagram showing d-orbital splitting in
compounds. the octahedral environment. Predict
the number of unpaired electrons in the
3. Answer in brief. complex [Fe(CN)6]4 . Is the complex
i. What are bidentate ligands ? Give one diamagnetic or paramagnetic? Is it
example. coloured? Explain.
ii. What is the coordination number and iii. Draw isomers in each of the following
oxidation state of metal ion in the complex a. Pt(NH3)2ClNO2
[Pt(NH3)Cl5] ?
b. Ru(NH3)4Cl2
iii. What is difference between a double salt
and a complex ? Give an example. c. [Cr(en2)Br2]⊕
iv. Classify following complexes as iv. Draw geometric isomers and enantiomers
homoleptic and heteroleptic of the following complexes.
208
v. What are ligands ? What are their types ? vii.
How stability of the coordination
Give one example of each type. compounds can be explained in terms of
vi. What are cationic, anionic and neutral equilibrium constants ?
complexes? Give one example of each. viii.
Name the factors governing the
equilibrium constants of the coordination
compounds.
Activity :
1. The reaction of chromium metal with H2SO4 in the absence of air gives blue
solution of chromium ion.
Cr(s) + 2H⊕(aq) Cr2⊕(aq) + H2(s)
Cr2⊕ forms octahedral complex with H2O ligands.
a. Write formula of the complex
b. Describe bonding in the complex using CFT and VBT.
Draw crystal field splitting and valence bond orbital diagrams.
2. Reaction of complex [Co(NH3)3(NO2)3 with HCl gives a complex
[Co(NH3)3H2OCl2]⊕ in which two chloride ligands are trans to one another.
a. Draw possible stereoisomers of starting material
b. Assuming that NH3 groups remain in place, which of two starting isomers would give
the observed product ?
209
10. HALOGEN DERIVATIVES
Can you recall ? CH3 - CH2 - X CH2 = CH - X
Identify the functional group (Haloalkane) (Haloalkene)
in the following compounds.
HC ≡ C - X X
i. ii. CCl2F2
Br (Haloalkyne)
(Haloarene)
(Benzyl bromide) (Freon - 12) b. On the basis of number of halogen atoms,
iii. Cl iv. Cl - CH = CCl2 halogen derivatives are classified as mono,
Cl Cl di, tri or poly halogen compounds.
(Westrosol)
X
Cl Cl CH3 - CH2 - X
Cl
(Hexachlorobenzene) Monohalogen compounds
Cl
211
10.2 Nomenclature of halogen derivatives a wide variety. The hydroxyl group may be
replaced by halogen atom using (a) halogen
Can you recall ? acid, (b) phosphorous halide or (c) thionyl
• In IUPAC system of chloride.
nomenclature does the a. By using halogen acid or hydrogen
functional group 'halogen' appear halide (HX) : The conditions for reaction
as a suffix or prefix ? of alcohol with halogen acid (HX) depend
• What are the trivial names of laboratory on the structure of the alcohol and particular
solvents CHCl3 and CCl4 ? halogen acid used. The order of reactivity of
alcohols with a given haloacid is 30>20>10.
The common names of alkyl halides are (Refer to section 11.2.1 a)
derived by naming the alkyl group followed R - OH + HX
suitable
R - X + H2O
condition
by the name of halogen as halide. For
example, methyl iodide, tert-butyl chloride. (Alcohol) (Alkyl halide)
According to IUPAC system of nomenclature Hydrogen chloride is used with zinc
(Std. XI Chemistry Textbook Chapter 14, chloride (Grooves' process) for primary and
section 14.4.7) alkyl halides are named as secondary alcohols, but tertiary alcohols
haloalkanes. Aryl halides are named as readily react with concentrated hydrochloric
haloarenes in common as well as IUPAC acid in absence of zinc chloride.
system. For dihalogen derivative of an arene, anhydrous
R - OH + HCl ZnCl2 R - Cl + H2O
prefix o-, m-, p- are used in common name
system but in IUPAC system the numerals
1,2 ; 1,3 and 1,4 respectively are used. Do you know ?
Common and IUPAC names of some halogen Zinc chloride is a Lewis acid
derivatives are given in Table 10.1. and consequently can coordinate
with the alcohol, weakening R - O bond.
Use your brain power Mixture of concentrated HCl and anhydrous
Write IUPAC names of the ZnCl2 is called Lucas reagent.
following.
Constant boiling hydrobromic acid
i. CH3 - CH - CH3 ii. CH3 - CH - CH2I (48%) is used for preparing alkyl bromides.
Br CH3 Primary alkyl bromides can also be prepared
by reaction with NaBr and H2SO4. Here HBr
iii. CH3 - CH = CH - CH2Cl is generated in situ.
NaBr, H2SO4
iv. CH3 - C ≡ C - CH2 - Br R - OH + HBr heat R - Br + H2O
213
When toluene is brominated in presence
Do you know ? of iron, a mixture of ortho and para bromo
When alkenes are heated toluene is obtained.
with Br2 or Cl2 at high temperature,
hydrogen atom of allylic carbon is CH3 CH3 CH3
substittued with halogen atom giving Fe
Br
+ Br2 dark
+
allyl halide.
CH2 = CH - CH3 + Cl2 Br
(o - Bromotoluene) (p-Bromotoluene)
CH2 = CH - CH2Cl + HCl
+ HBr
10.3.3 Halogen exchange : Alkyl iodides Aromatic electrophilic substitution
are prepared conveniently by treating alkyl with iodine is reversible. In this case use
chlorides or bromides with sodium iodide in of HNO3/HIO4 removes HI by oxidation to
methanol or acetone solution. The sodium I2, equilibrium is shifted to right and iodo
bromide or sodium chloride precipitates from product is formed. F2 being highly reactive,
the solution and can be separated by filtration. fluoro compounds are not prepared by this
acetone method.
R - Cl + NaI R - I + NaCl ↓
10.3.5 Sandmeyer's reaction : Aryl halides
The reaction is known as Finkelstein reaction.
are most commonly prepared by replacement
Alkyl fluorides are prepared by heating of nitrogen of diazonium salt. (For details
alkyl chlorides or bromides with metal refer to Chapter 13 section 13.6).
fluorides such as AgF, Hg2F2, AsF3, SbF3 etc.
10.4 Physical properties : Physical properties
R - Cl + AgF R - F + AgCl ↓ of alkyl halides are considerably different
The reaction is known as Swartz reaction. from those of corresponding alkanes. The
boiling point of alkyl halides is determined
10.3.4 Electrophilic substitution :
by polarity of the C-X bond as well as the
size of halogen atoms.
Can you recall ?
10.4.1 Nature of intermolecular forces:
• Identify the product of the Halogens (X = F, Cl, Br and I) are more
following reaction. electronegative than carbon.
+ Cl2
anhyd. Carbon atom that carries halogen
AlCl3
develops a partial positive charge while the
• Name the type of halide produced in halogen carries a partial negative charge.
the above reaction. Thus carbon-halogen bond in alkyl halide is a
• What type of reactions are shown by polar covalent bond. Therefore alkyl halides
benzene ? are moderately polar compounds.
δ⊕ δ
C X
Aryl chlorides and bromides can be
prepared by direct halogenation of benzene Size of the halogen atom increases from
and its derivatives through electrophilic fluorine to iodine. Hence the C-X bond length
substitution. It may be conveniently carried increases. The C-X bond strength decreases
out in dark at ordinary temperature in presence with an increase in size of halogen. This is
of suitable Lewis acid catalyst like Fe, FeCl3 because as the size of p-orbital of halogen
or anhydrous AlCl3. increases the p-orbital becomes more diffused
214
and the extent of overlap with orbital of Haloalkane Boiling point (K)
carbon decreases. Some typical bond lengths,
CH3CH2CH2CH2Br 375
bond enthalpies and dipole moments of C-X
bond are given in Table 10.2. CH3 - CH - CH2 - CH3
364
Br
Table 10.2 : Bond parameters of C-X bond
CH3
Bond Bond Bond en- Dipole CH3− C − CH3 346
length/ thalpy/ moment/ Br
(pm) (kJ mol-1) debye
CH3 - F 139 452 1.847 10.4.3 Solubility : Though alkyl halides
are moderately polar, they are insoluble in
CH3 - Cl 178 351 1.860
water. It is due to inability of alkyl halides to
CH3 - Br 193 293 1.830 form hydrogen bonds with water. Attraction
CH3 - I 214 234 1.636 between alkyl halide molecules is stronger
than attraction between alkyl halide and
10.4.2 Boiling point : Boiling points of alkyl
water. Alkyl halides are soluble in non-polar
halides are considerably higher than those of
organic solvents.
corresponding alkanes due to higher polarity
and higher molecular mass. Within alkyl Aryl halides are also insoluble in water
halides, for a given alkyl group, the boiling but soluble in organic solvents. If aryl halides
point increases with increasing atomic mass are not modified by presence of any other
of halogen, because magnitude of van der functional group, they show properties similar
Waals force increases with increase in size to corresponding alkyl halides. The isomeric
and mass of halogen. dihalobenzenes have nearly the same boiling
points, but melting points of these isomers
Thus boiling point of alkyl halide
show variation. Melting point of para isomer
decreases in the order RI > RBr > RCl > RF
is quite high compared to that of ortho or meta
For example, : isomer. This is because of its symmetrical
structure which can easily pack closely in
Haloal- CH3F CH3Cl CH3Br CH3I
kane
the crystal lattice. As a result intermolecular
forces of attraction are stronger and therefore
Boiling
194.6 248.8 276.6 315.4 greater energy is required to overcome its
point (K)
lattice energy.
For the given halogen, boiling point rises
with increasing carbon number. Cl
Cl Cl
For example, Cl
Haloalkane Boiling point (K)
Cl
CH3Cl 248.8 Cl
CH3CH2Cl 285.5 b.p./K 453 446 448
CH3CH2CH2Cl 320.0 m.p./K 256 249 323
CH3CH2CH2CH2Cl 351.5
For isomeric alkyl halides, boiling point
decrease with increased branching as surface
area decreases on branching and van der
Waals forces decrease. For example :
215
Let us, now, jot down the atoms/groups
Problem 10.2 Arrange the following attached to each carbon in 2 - chlorobutane.
compounds in order of increasing boiling 1 2 3 4
points : bromoform, chloromethane, CH3 - CHCl - CH2 - CH3
dibromomethane, bromomethane. 2 3 4
C-1 : - H, -H, -H, -CHCl-CH2-CH3
Solution : The comparative boiling points
of halogen derivatives are mainly related 1 3 4
C-2 : -H, -Cl, -CH3, -CH2-CH3
with van der Waals forces of attraction
4 2 1
which depend upon the molecular size. In C-3 : -H, -H, -CH3, -CHCl-CH3
the present case all the compounds contain
3 2 1
only one carbon. Thus the molecular size C-4 : -H, -H, -H, -CH2-CHCl-CH3
depends upon the size of halogen and
number of halogen atoms present. It can be seen that the four groups bonded
to C-2 are all different from each other.
Thus increasing order of boiling point is, Carbon atom in a molecule which carries
CH3Cl < CH3Br < CH2Br2 < CHBr3 four different groups/atoms is called chiral
carbon atom. Thus, the C-2 in 2-chlorobutane
10.5 Optical isomerism in halogen is a chiral carbon. Chiral atom in a molecule
derivatives : is marked with asterisk (*). For example,
CH3-*CHCl-CH2-CH3.
Can you recall ? When a molecule contains one chiral
• What is the relationship between atom, it acquires a unique property. Such a
two compounds having the same molecule can not superimpose perfectly on its
molecular formula? mirror image. It is called chiral molecule. A
• What is meant by stereoisomerism ? chiral molecule and its mirror image are not
identical (see Fig. 10.1).
Isomers having the same bond connectivities,
that is, structural formula are called
CH3
stereoisomers. Knowledge of optical CH3
isomerism, which is a kind of stereoisomerism *C
will be useful to understand nucleophilic C* Cl H
H Cl C2H5
substitution reactions of alkyl halides (see
C2H5 mirror plane
10.6.3).
10.5.1 Chiral atom and molecular chirality CH3 CH3
Try this... C * *C
H Cl Cl H
• Make a three - dimensional C2H5 C2H5
model of 2 - chlorobutane.
• Make another model which is a mirror Fig. 10.1 : Nonsuperimposable mirror images
image of the first model. A chiral molecule and its mirror image
• Try to superimpose the two models on both have the same structural formula and,
each other. of course, the same molecular formula. The
• Do they superimpose on each other spatial arrangement of the four different
exactly ? groups around the chiral atom, however, is
• Comment on whether the two models different. In other words, a chiral molecule
are identical or not. and its mirror image are stereoisomers of each
216
other. (Refer to Std. XI Chemistry Textbook,
Chapter 14). Do you know ?
Nicol prism is a special type of
The relationship between a chiral prism made from pieces of calcite,
molecule and its mirror image is similar to a crystalline form of CaCO3, arranged
the relationship between left and right hands. in a specific manner. Nicol prism is also
Therefore it is called handedness or chirality. called polarizer.
(Origin : Greek word : Cheir means hand)
10.5.3 Optical activity : When an aqueous
The stereoisomerism in which the isomers
solution of certain organic compounds like
have different spatial arrangements of groups/
sugar, lactic acid is placed in the path of
atoms around a chiral atom is called optical
plane polarized light, the transmitted light
isomerism. The optical isomers differ from
has oscillations in a different plane than
each other in terms of a measurable property
the original. In other words, the incident
called optical activity.
light undergoes rotation of its plane of
To understand optical activity, we must polarization. The plane of polarization rotates
know what is plane polarized light. either to the right (clockwise) or to the left
(anticlockwise). This property of a substance
Remember... by which it rotates plane of polarization
of incident plane polarized light is known
The phenomenon of optical as optical activity. The compounds which
isomerism in organic compounds rotate the plane of plane polarized light are
was observed first and its origin in called optically active compounds and those
molecular chirality was recognized later. which do not rotate it are optically inactive
compounds. Optical activity of a substance
10.5.2 Plane polarized light : An ordinary is expressed numerically in terms of optical
light consists of electromagnetic waves having rotation. The angle through which a substance
oscillations of electric and magnetic field in rotates the plane of plane polarized light on
all possible planes perpendicular to direction passing through it is called optical rotation.
of propagation of light. In accordance with the direction of optical
When ordinary light is passed through rotation an optically active substance is either
Nicol's prism, oscillations only in one plane dextrorotatory or laevorotatory. A compound
emerge out. Such a light having oscillations which rotates the plane of plane polarized
only in one plane perpendicular to direction light towards right is called dextrorotatory
of propagation of light is known as plane and designated by symbol d- or by (+)
polarized light. sign. A compound which rotates plane of
plane polarized light towards left is called
laevorotatory and designated by symbol l-
or by (-) sign.
Isomerism in which isomeric compounds
have different optical activity is known as
optical isomerism. French scientist Louis
Pasteur first recognized that optical activity is
associated with certain type of 3-dimensional
structure of molecules. Pasteur introduced
the term enantiomers for the optical isomers
having equal and opposite optical rotation.
217
Figure 10.2 indicates a few objects in our Enantiomers have identical physical
day to day life which exhibit superimposable properties (Such as melting point, boiling
and non-superimposable mirror image points, densities, refractive index) except the
relationship. sign of optical rotation. The magnitude of
their optical rotation is equal but the sign
of optical rotation is opposite. They have
identical chemical properties except towards
optically active reagent.
An equimolar mixture of enantiomers
(dextrorotatory and laevorotatory) is called
racemic modification or racemic mixture.
A racemic modification is optically inactive
because optical rotation due to molecules
of one enatiomer is cancelled by equal and
Non superimposable Superimposable opposite optical rotation due to molecules of
the other enantiomer. A racemic modification
Fig. 10.2 : Superimposable and is designated as (dl) or by (±) sign.
nonsuperimposable mirror image 10.5.5 Representation of configuration of
molecules :
219
10.3 Nucleophilic substitution reactions of alkyl halides
Ag - O - N = O ⊕ O
8. R-X + R N + AgX ↓
(silver nitrite) O
(nitroalkane)
⊕
Tertiary halides undergo nucleophilic CH2 CH2 CH2
substitution by SN1 mechanism while primary ⊕
⊕
halides follow SN2 mechanism. Secondary
⊕
halides react by either of the mechanism or ⊕
CH2 CH2
by mixed mechanism depending upon the
exact conditions.
Resonance stabilization of benzylic carbocation
223
b. Nucleophilicity of the reagent : carbocation is relatively poor and solvation
of anion is particularly important. Anions are
Can you recall ? solvated by hydrogen bonding solvents, that
• Give some examples of is, protic solvents. Thus SN1 reaction proceeds
nucleophiles that are electrically more rapidly in polar protic solvents than in
neutral. aprotic solvents.
• Give some examples of anionic Polar protic solvents usually decrease the
nucleophiles. rate of SN2 reaction. In the rate determining
step of SN2 mechanism substrate as well
• What is the difference between a base as nucleophile is involved. A polar solvent
and a nucleophile ? stabilizes nucleophile (one of the reactant)
by solvation. Thus solvent deactivates the
A nucleophile is a species that uses its nucleophile by stabilizing it. Hence aprotic
electron pair to form a bond with carbon. solvents or solvents of low polarity will
Nucleophilic character of any species is favour SN2 mechanism.
expressed in its electron releasing tendency,
which can be corelated to its strength as
Problem 10.5 : Which of the following
Lewis base.
two compounds would react faster by SN2
A more powerful nucleophile attacks the mechanism and Why ?
substrate faster and favours SN2 mechanism.
CH3-CH2-CH2-CH2Cl CH3-CH-CH2-CH3
The rate of SN1 mechanism is independent of
the nature of nucleophile. Nucleophile does Cl
1-Chlorobutane 2-Chlorobutane
not react in slow step of SN1. It waits till
the carbocation intermediate is formed, and Solution : In SN2 mechanism, a
reacts fast with it. pentacoordinate T.S. is involved. The order
of reactivity of alkyl halides towards SN2
Do you know ? mechanism is,
1. A negatively charged Primary > Secondary > Tertiary, (due to
nucleophile is more powerful increasing crowding in T.S. from primary
than its conjugate acid. For example to tertiary halides. 1-Chlorobutane being
R-O is better nucleophile than R-OH. primary halide will react faster by SN2
mechanism, than the secondary halide
2. When donor atoms are from same 2-chlorobutane.
period of periodic table, nucleophilicity
decreases from left to right in a period. Can you recall ?
For example H2O is less powerful
nucleophile than NH3. • How are alkenes prepared
3. When donor atoms are from same group from alkyl halides ?
of the periodic table, nucleophilicity • Which is stronger base from the
increases down the group. For example, following ?
I is better nucleophile than Cl . i. aq. KOH ii. alc. KOH
c. Solvent polarity : SN1 mechanism proceeds
via formation of carbocation intermediate.
A good ionizing solvent, polar solvent,
stabilizes the ions by solvation. Solvation of
224
10.6.5 Elimination reaction : The different products of elimination do
Dehydrohalogenation not form in equal proportion. After studying
When alkyl halide having at least one a number of elimination reactions, Russian
β-hydrogen is boiled with alcoholic solution of chemist Saytzeff formulated an empirical rule
potassium hydroxide, it undergoes elimination given below.
of hydrogen atom from β-carbon and halogen In dehydrohalogenation reaction, the
atom from α - carbon resulting in the formation preferred product is that alkene which has
of an alkene. greater number of alkyl groups attached to
doubly bonded carbon atoms.
Remember...
Therefore, in the above reaction but-2-ene
The carbon bearing halogen is
is the preferred product, and is formed as the
commonly called α-carbon (alpha
major product. It turned out that more highly
carbon) and any carbon attached to α-carbon
substituted alkenes are also more stable alkenes.
is β-carbon (beta carbon). Hydrogens
Hence Saytzeff elimination is preferred
attached to β-carbon are β-hydrogens.
formation of more highly stabilized alkene
during an elimination reaction. The stability
This reaction is called β-elimination order of alkyl substituted alkenes is :
(or 1,2 - elimination) reaction as it involves
elimination of halogen and a β - hydrogen R2C = CR2 > R2C = CHR > R2C = CH2,
atom. RCH = CHR > RCH = CH2
H
β α alc. KOH
B+ C C ∆ C = C + B⊕H +X Do you know ?
X Elimination versus substitution:
(base) (alkyl halide) (alkene)
Alkyl halides undergo sunstitution as
As hydrogen and halogen is removed well as elimination reaction. Both reactions
in this reaction it is also known as are brought about by basic reagent, hence
dehydrohalogenation reaction. there is always a competition between these
two reactions. The reaction which actually
If there are two or more non-equivalent
predominates depends upon following
β-hydrogen atoms in a halide, then this
factors.
reaction gives a mixture of products. Thus,
2-bromobutane on heating with alcoholic a. Nature of alkyl halides : Tertiary alkyl
KOH gives mixture of but-1-ene and but-2- halides prefer to undergo elimination
ene. reaction where as primary alkyl halides
prefer to undergo substitution reaction.
β1 α β2
CH3 − CH2 − CH − CH3 b. Strength and size of nucleophile :
Br Bulkier electron rich species prefers to act
(2-bromobutane) as base by abstracting proton, thus favours
alc. KOH ∆
elimination. Substitution is favoured in the
case of comparatively weaker bases, which
loss of β - hydrogen loss of β1 -hydrogen
2
prefer to act as nucleophile
c. Reaction conditions : Less polar solvent,
HC3 − CH2 − CH = CH2 high temperature fovours elimination where
(But-1-ene) as low tempertaure, polar solvent favours
CH3− CH = CH - CH3 substitution reaction.
(But-2-ene)
225
10.6 Reaction with active metals b. Wurtz reaction : Alkyl halides react with
Active metals like sodium, magnesium metallic sodium in dry ether as solvent, and
cadmium readily combine with alkyl chlorides, form higher alkanes containing double the
bromides and iodides to form compounds number of carbon atoms present in alkyl halide.
containing carbon-metal bonds. These are This reaction is called Wurtz reaction. (Refer
known as organometallic compounds. to Std. XI Chemistry Textbook sec. 1.5.3)
dry
a. Reaction with magnesium : When alkyl 2 R-X + 2 Na ether R - R + 2 NaX
halide is treated with magnesium in dry ether 2C2H5 Br + 2Na
dry
CH3-CH2-CH2-CH3
ether
as solvent, it gives alkyl magnesium halide. It
(Ethyl bromide) (Butane)
is known as Grignard reagent.
+ 2 NaBr
dry ether When a mixture of two different alkyl halides is
R-X + Mg R - Mg - X
alkyl magnesium halide used, all the three possible alkanes are formed.
(Grignard reagent)
For example : CH3-CH3
Grignard reagents are very reactive compounds. (ethane)
They react with water or compounds containing Na
CH3Br + C2H5Br CH3-CH2-CH3
hydrogen attached to electronegative element. dryether
(Methyl (Ethyl (propane)
X bromide) bromide)
CH3-CH2-CH3-CH3
R - Mg -X + CH3OH R - H + Mg
(butane)
(Hydrocarbon)
OCH3 10.6.1 Reaction of haloarenes :
X
R - Mg -X + NH3 R - H + Mg a. Reactions of haloarene with metals
(Hydrocarbon) NH2 The reaction of aryl halide with alkyl
halide and sodium metal in dry ether to give
substituted aromatic compounds is known as
Do you know ? Wurtz- Fittig reaction. This reaction is an
extension of Wurtz reaction and was carried
Carbon-magnesium bond in out by Fittig. This reaction allows alkylation
Grignard reagent is a polar covalant of aryl halides.
bond. The carbon pulls electrons from the CH3
Br
electropositive magnesium. Hence carbon dry
in Grignard reagent has negative polarity + CH3-Br + 2Na ether + 2NaBr
and acts as a nucleophite (Bromobenzene) (Toluene)
δ δ⊕
R- Mg X
In case only aryl halide takes part in the
Victor Grignard received Nobel Prize reaction, the product is biphenyl and the
in 1912 for synthesis and study of organo- reaction is known as Fittig reaction.
magnesium compounds. Grignard reagent
Cl
is a very versatile reagent used by organic
chemist. Vinyl and aryl halides also form dry
+ 2Na ether + 2NaCl
Grignard reagent.
(Chlorobenzene) (Biphenyl)
226
b. Nucleophilic substitution SN of haloarenes: Thus nuclophilic substitution reaction
involving cleavage of C-X bond in haloarene
Can you recall ? proceeds with difficulty. However, the presence
• What is resonance? of certain groups at certain positions of the
• Draw resonance structures of ring, markedly activate the halogen of aryl
bromobenzene. halides towards substitutuion. For example,
presence of electron withdrawing group at
• Identify the type of hybridization of
ortho and/or para postion greatly increases the
carbon to which halogen is attached in
reactivity of haloarenes towards subsitution of
haloarene.
halogen atom. Greater the number of electron
Aryl halides show low reactivity withdrawing groups at o/p position, greater
towards nucleophilic substitution reactions. is the reactivity. Electron withdrawing group
The low reactivity of aryl halides is due to : at meta position has practically no effect on
i. Resonance effect and reactivity.
ii. sp2 hybrid state of C . i. Cl OH
i. One of the lone pairs of electrons (i)NaOH 433 K
on halogen atom is in conjugation with (ii)H3O⊕
: Cl :
NO2 NO2
(i)aq.Na2CO3 403 K
(ii)H3O⊕
NO2 NO2
I II III
(2,4-dinitrochlorobenzene) (2,4 - dinitrophenol)
+ Cl :
:
:
: Cl :
iii. Cl OH
NO2 NO2 NO2 NO2
warm
H2O
IV V NO2 NO2
Resonance structures II, III and IV show (2,4,6-trinitrochlorobenzene) (2,4,6 - trinitrophenol)
double bond character to carbon-chlorine bond.
Thus carbon-chlorine bond in chlorobenzene
is stronger and shorter than chloroalkane Can you tell ?
molecule, C-Cl bond length in chlorobenzene Conversion of chlorobenzene
is 169 pm as compared to C-Cl bond length to phenol by aqueous sodium
in alkyl chloride 178 pm. Hence it is difficult hydroxide requires high temperture of
to break. Phenyl cation produced due to self- about 623K and high pressure. Explain.
ionization of haloarene will not be stabilised OH
Cl
by resonance, which rules out possibility of SN1
(i) 623K, OH 300 atm
mechanism. Back side attack of nucleophile is
(ii) H3O⊕
blocked by the aromatic ring, which rules out
SN2 mechanism. Chlorobenzene Phenol
227
Do you know ? • Identify the product A of following
reaction.
Occurrence of nucleophilic
substitution in p-nitrochlorobenzene + HNO3 conc. H2SO4
A
can be explained on the basis of resonance
stabilization of the intermediate.
Aryl halides undergo electrophilic
Cl Cl OH substitution reaction slowly as compared to
benzene.
+ OH slow
step In resonance structures of chlorobenzene
N N (see section 10.6.5) elelctron density is
O ⊕ O O ⊕ O relatively more at ortho and para position.
(I) Therefore incoming electrophilic group is
more likely to attack at these positions. But
Cl OH Cl OH
due to steric hinderance at ortho position, para
product usually predominates. In haloarenes,
halogen atom has strong electron withdrawing
N N inductive effect (-I). This deactivates the ring
O ⊕ O O ⊕ O and electrophilic substitution reaction occurs
(II) (III) slowly.
Cl OH OH
Remember...
fast
step + Cl The -I effect of Cl is more
powerful than its +R effect.
N N Therefore Cl is o-/p- directing but ring
O ⊕ O O ⊕ O deactivating group.
(IV)
i. Halogenation : It is carried out by reacting
The resonance structure (III) shows haloarene with halogen in presence of ferric
that the electron withdrawing nitro group salt as Lewis acid catalyst.
(-NO2) in the p-position extends the
conjugation. As a result, the intermediate Cl
carbanion is better stabilized which favours
nucleophilic substitution reaction. + Cl2
c. Electrophilic substitution (SE) in (Chlorobenzene)
arylhalides
anhydrous Cl
Can you recall ? FeCl3
2
• What is an electrophile?
Cl Cl
• Give some examples of Cl
electrophiles + + HCl
• What type of reactions are observed in
benzene? Cl
(1,4 - Dichlorobenzene) (1,2 - Dichlorobenzene)
(major) (minor)
228
ii. Nitration : It is carried out by heating Cl
haloarene with conc. HNO3 in presence of O
conc. H2SO4. + CH3-C -Cl
Cl (Chlorobenzene)
229
nervous system and it is suspected to be 10.7.6 Dichlorodiphenyltrichloroethane
carcinogenic. Prolonged exposure may cause (DDT) : It is colourless, tasteless and odorless
death. It is a green house gas. crystalline compound having insecticidal
10.7.4 Idoform or triiodomethane (CHI3): property.
230
Exercises
231
viii. Choose the compound from the c. CH3-CH-CH=CH2 + HBr peroxide
Cl CH3
b. CH3-CH=CH2 Red P/Br2
A Ag2O/H2O
B
Cl Cl OH
c. d.
CH3
CH3 c. CH3-C-CH2-Cl Na/dry ether
A
C2H5 Cl
CH3
ii. Write structure and IUPAC name
of the major product in each of the Cl
following reaction. d. Mg
dry ether A
a. CH3-CH-CH2Cl + NaI Acetone
CH3
b. CH3-CH2Br + SbF3
232
vi. Name the reagent used to bring about iv. But-1-ene to n-butyl iodide
the following conversions. v. 2-Chloropropane to propan-1-ol
a. Bromoethane to ethoxyethane vi. tert-Butyl bromide to isobutyl bromide
b.1-Chloropropane to 1 nitropropane vii. Aniline to chlorobenzene
c.
Ethyl bromide to ethyl viii. Propene to 1-nitropropane
isocyanide 7. Answer the following
d. Chlorobenzene to biphenyl i. HCl is added to a hydrocarbon 'A'
vii. Arrange the following in the increase (C4H8) to give a compound 'B' which
order of boiling points on hydrolysis with aqueous alkali
forms tertiary alcohol 'C' (C4H10O).
a. 1-Bromopropane Identify 'A' , 'B' and 'C'.
b. 2- Bromopropane ii. Complete the following reaction
c. 1- Bromobutane sequences by writing the structural
formulae of the organic compounds
d. 1-Bromo-2-methylpropane
'A', 'B' and 'C' .
viii. Match the pairs. alc.KOH
a. 2-Bromobutane A Br2 B NaNH C2
Column I Column II ∆
b. Isopropyl alcohol PBr3 A NH excess B
a. CH3CH-CH3 i. vinyl halide 3
11.1 Introduction : Alcohols are organic 11.2 Classification : Let us first consider
compounds whose molecules contain hydroxyl classification of alcohols, phenols and then
group, (-OH) attached to a saturated carbon ethers.
atom. 11.2.1 Mono, di, tri and polyhydric
C OH compounds : Alcohols and phenols are
classified as mono, di-, tri, or polyhydric
Hydroxyl group can also be present in aromatic
compounds on the basis of one, two, three
compounds. There are two types of aromatic
or more hydroxyl groups present in their
hydroxy compounds: phenols and aromatic
molecules as :
alcohols. Phenols contain a hydroxyl group
directly attached to the carbon atom of benzene CH3 - CH2 - OH H2C - OH H2C - OH
ring. When the hydroxyl group is present in the H2C - OH HC - OH
side chain of aromatic ring, the compound is H2C - OH
termed as aromatic alcohol.
OH OH
OH
OH OH
OH OH
OH
Monohydric Dihydric alcohols/ Trihydric
Phenols alcohols/phenols phenols alcohols/phenols
234
Primary
b. Alcohols contianing sp2C -OH bonds :
H Secondary
carbon R carbon In these alcohols -OH group is attached
R C OH R C OH to a sp2 hybridised carbon atom which is part of
H H a carbon-carbon double bond. These alcohols
10 alcohol 20 alcohol are known as vinylic alcohols. For example
tertiary CH2 = CH - OH (Vinyl alcohol)
R carbon
11.2.2 Classification of Ethers : Ethers are
R C OH
classified as symmetrical ethers (simple
R ethers) or unsymmetrical ethers (mixed
30 alcohol
ethers) depending on whether the two alkyl/
Fig. 11.1 : Primary, secondary and tertiary aryl groups bonded to oxygen atom are same
alcohols or different respectively. For example :
Each of these three types of alcohols can also R - O - R/Ar - O - Ar
be either allylic or benzylic if the sp3 carbon
carrying -OH is further bonded to sp2 carbon. CH3 - O - CH3
symmetrical ethers (simple ethers)
• Allylic alcohols : In this type of alcohols
-OH group is attached to sp3 hybridised R - O - R'/Ar - O - Ar'
carbon atom which is further bonded to a
carbon-carbon double bond. Allylic alcohol CH3 - O - C2H5, C6H5 - O - CH3
may be primary, secondary or tertiary. unsymmetrical ethers (mixed ethers)
235
11.3.2 Nomenclature of phenols : The
Use your brain power hydroxyl derivative of benzene is called
Name t-butyl alcohol using phenol. The IUPAC system name of phenol is
carbinol system of nomenclature. benzenol. The common name phenol is also
accepted by IUPAC. The common names have
c. IUPAC system : Accoriding to IUPAC
prefixes ortho, meta and para in subsituted
system (Std XI Chemistry Text book, Chapter
phenols. IUPAC system uses the locant 2-, 3-,
14), alcohols are named as alkanols. The
4-, etc. to indicate the positions of substituents
ending ‘e’ in the name of the parent alkane,
(see Table 11.2).
alkene or alkyne is replaced by the suffix
‘ol’. For naming polyhydric alcohol, ‘e’ in the 11.3.3 Nomenclature of Ethers : In the
ending of alkane is retained, the ending ‘ol’ is common system of nomenclature, the ethers
added and number of -OH groups is indicated are named by writing names of the alkyl groups
by prefix di, tri, etc., before ‘ol’. The positions attached to the oxygen atom in alphabetical
of -OH groups are indicated by appropriate order and word ether is added. If two alkyl
locants. For example ethane -1,2-diol (see. groups are same, prefix di- is used. According
Table 11.1). Similarly cyclic alcohols are to the IUPAC system of nomenclature, ethers
named by using prefix cyclo to the parent are named as alkoxyalkanes (see Table 11.3).
alkane and considering -OH group attached to The larger alkyl group is considered to be the
C-1 carbon atom. parent alkane. The name of the smaller alkane
is prefixed by the name of alkoxy group and its
locant. For example :
OH
C2H5 Some alkoxy group
1 CH3-CH2O- Ethoxy
OH CH3
Cyclobutanol 2- Ethylcyclopentanol 2 3 CH3-CH2-CH2-O- n-Propoxy
CH3 - O - CH - CH3 CH3-CH-O- Isopropoxy
CH3
2-Methoxypropane
Table 11.1 Common/Trivial and IUPAC Names of some alcohols
Structural formula Common/ Trivial Name IUPAC Name
H3C-OH Methyl alcohol Methanol
H3C-CH2-OH Ethyl alcohol Ethanol
H3C-CH2-CH2-OH n -Propyl alcohol Propan -1-ol
H3C-CH2-CH-OH sec-Butyl alcohol Butan -2-ol
CH3
H3C-CH-CH2-OH Isobutyl alcohol 2- Methylpropanol
CH3
CH3 tert-Butyl alcohol 2-Methylpropan-2-ol
H3C C OH
CH3
H2C CH2 Ethylene glycol Ethane-1, 2-diol
OH OH
H2C − CH − CH2 Propylene glycerol Propane-1,2,3-triol
OH OH OH
H3CCH = CHCH2OH Crotonyl alcohol But-2-en-1-ol
236
Table 11.2 Common and IUPAC names of some phenols
OH
CH3
o- Cresol 2-Methylphenol
HO
p-Nitrophenol 4-Nitrophenol
NO2
OH
OH
Catechol Benzene-1,2-diol
OH
Resorcinol Benzene-1,3-diol
OH
HO
Hydroquinone/
Benzene -1,4-diol
quinol
OH
OH
Phloroglucinol Benzene-1,3,5-triol
HO OH
OH
HO OH
Pyrogallol Benzene-1,2,3-triol
CH3
H3C OCH3 2- Methoxy-1,1-
-
dimethylcyclobutane
237
alcohol. (Refer to Std. XI Chemistry Textbook
Problem 11.1 : Draw structures of
following compounds. section 15.2.4). This is an antimarkownikoff
hydration of alkene.
i. 2,5-Diethylphenol ii. Prop-2-en-1-ol
iii. 2-methoxypropane iv. Phenylmethanol Do you know ?
The mechanism of acid catalyzed
Solutuion : hydration of alkene involves the
i. OH ii.
3 2 1
following three steps:
1 C2H5
6 H2C = CH - CH2 - OH Step 1: Formation of carbocation
2
5 intermediate.
3
H5C2 4 H
iii. CH3-CH-CH3 iv. CH2 - OH H-O-H+ C=C H 2O + C - C
⊕ ⊕
O-CH3 H
Step 2: Nucleophilic attack of H2O on C⊕
H
Try this... C-C +H-O C-C
Write IUPAC names of the ⊕
H H O⊕
following compounds.
H H
OH OH
i. ii. H3C-CH-CH2- CH3
Step 3: Deprotonation
OCH2- CH3
H2O
C-C C-C + H3O⊕
iii. CH2 - CH2 - OH iv. H C OH
H O⊕ H OH
3
H H
238
O H2/Ni or Pd
∆ R CH OH Problem 11.2 : Predict the products for the
R C R (i)LiAlH4
R following reaction.
(ii) H3O⊕
20 alcohol ?
H2/Ni
H⊕
R - COOH + R'OH R - COOR' + H2O
Ni/Pd
This reaction is useful in synthesis of a variety
RCOOR' + 2H2 ∆
R - CH2OH + R'OH of alcohols (see Table 11.4).
Table 11.4 Preparation of alcohols by Grignard
Remember... reagent
The advantage of LiAlH4 over Aldehyde/ Grignard Type of
Final product
H2/Ni is that it does not reduce the ketone reagent alcohol
isolated olefinic bond and hence it can H - CHO
R - Mg Br R - CH2OH 10
reduce unsaturated aldehyde and ketones to (formaldehyde)
unsaturated alcohols. R' - CHO R - CH - OH
R - Mg Br 20
(aldehyde) R'
e.By addition of Grignard reagent to R''
aldeheydes and ketones : Grignard reagent R' - CO - R''
R - Mg Br R - C - OH 30
reacts with aldehyde or ketone to form an (ketone)
adduct which on hydrolysis with dilute acid R'
gives the corresponding alcohols.
δ Do you know ?
O OMgX
δ δ⊕
δ⊕C + R - Mg - X dry
Epoxide reacts with Girgnard
ether -C-
R reagent followed by acidic hydolysis
to give primary alcohols
(adduct) dry
H2C - CH2 + R Mg X ether
OH
H3O⊕ X O
- C - + Mg
H3O⊕
R OH [R - CH2- CH2 - OMgX]
X
R-CH2CH2-OH + Mg
OH
239
11.4.2 Preparation of phenol : d. From aniline : Aniline is treated with nitrous
acid [NaNO2 + HCl] at low temparature to
a. From chlorobenzene (Dow Process) :
obtain benzene diazonium chloride, which on
Chlorobenzene is fused with NaOH at high
hydrolysis gives phenol (Also refer to chapter
temperature and pressure (623K and 150atm)
13 for this reaction).
followed by treatment with dilute HCl to
obtain phenol.
NH2 ⊕
⊕ N2Cl
Cl O Na OH
NaNO2
NaOH + HNO2 HCl
623 K/150atm H3O⊕ 273 K
(Aniline) (Benzene diazonium
(Chloro (Sodium (Phenol) chloride)
benzene) phenoxide)
b. From Cumene : This is the commercial OH
method of preparation of phenol. Cumene H2O
∆
+ N2
(isopropylbenzene) on air oxidation in
presence of Co-naphthenate gives cumene (Phenol)
hydroperoxide, which on decomposition with
dilute acid gives phenol with acetone as a 11.4.3 Physical Properties of alcohols and
valuable by product. phenols
CH3 CH3
H3C CH H 3C C O O H Try this...
Co-naphthenate Arrange O-H, C-H and N-H
+ O2 423K bonds in increasing order of their
bond polarity.
(Cumene) (air) (Cumene hydroperoxide)
a. Nature of intermolecular forces : Alcohols
OH CH3 and phenols are very polar molecules due to
C=O presence of -OH groups. The polar -OH groups
dil. HCl
∆
+ CH3 are held together by the strong intermolecular
(Phenol) (Acetone)
forces, namely hydrogen bonding.
240
Table 11.5 M.P/B.P and solubilities of some alcohols and phenols
Name Formula M.P. (0C) B.P. (0C) Solubility (g/100g H2O)
Methyl alcohol H3C-OH -97 65 0.793
Ethyl alcohol H3C-CH2-OH -115 78 0.789
n-Propyl alcohol H3C-CH2-CH2-OH -126 97 0.804
Isopropyl alcohol H3C-CH-OH -86 83 0.789
CH3
n-Butyl alcohol H3C-CH2-CH2-CH2-OH -90 118 0.810
Isobutyl alcohol H3C-CH-CH2-OH -108 108 0.802
CH3
sec-Butyl alcohol H3C-CH2-CH-OH -114 99.5 0.806
CH3
tert-Butyl alcohol H3C 25.5 83 0.789
H3C C-OH
H3C
Phenol 41 182 9.3
OH
241
Ar - OH + NaOH(aq) Ar-O Na⊕(aq)
Problem 11.4 : The solubility of o-nitrophenol
+ H2O(l)
and p-nitrophenol is 0.2 g and 1.7 g/100 g of
H2O respectively Explain the difference. Ar - O Na⊕(aq) + HCl(aq) Ar - OH↓
+ NaCl(aq)
Solution :
δ-
O δ⊕ Do you know ?
H (intramolecular hydrogen
Sodium bicarbonate, sodium
⊕ O - bonding in o-nitrophenol) hydroxide, sodium metal are
N
Oδ - increasingly strong bases. Weak and strong
acids can be distinguished from each other
O δ⊕
δ⊕ ⊕ δ⊕ δ- H qulitatively by testing their reactivity
H δ⊕ N O-H O
O-H O towards bases of different strengths. A
δ- - H
δ⊕ weak acid does not react with a weak
(intermolecular hydrogen bonding in p-nitrophenol base, it requires a stronger base instead.
and water) Hence phenols react with NaOH but not
p-Nitrophenol has strong intermolecular with NaHCO3. A strong acid shows high
hydrogen bonding with solvent water. On reactivity towards weak as well as strong
the other hand, o-nitrophenol has strong base. For example : HCl is a strong acid.
intramolecular hydrogen bonding and Its reacts with both NaHCO3 and NaOH as
therefore the intermolecular attraction shown below:
towards solvent water is weak. The stronger
HCl(aq)+NaHCO3(aq)
the intermolecular attraction between solute
and solvent higher is the solubility. Hence H2O(l)+ NaCl(aq)+ CO2↑
p-nitrophenol has higher solubility in water HCl(aq)+NaOH(aq) NaCl(aq)+H2O(l)
than that of o-nitrophenol.
11.4.4 Chemical properties of Alcohols and • Alcohols show no acidic character in
Phenols aqueous solution, thus, alcohols do
not react with either aqueous NaHCO3
a. Laboratory tests of alcohols and phenols :
or aqueous NaOH. Very weak acidic
i. Litmus test : Water soluble alcohols and character of alcohol is revealed in the
phenols can be tested with litmus paper. reaction with active metal. When alcohols
Aqueous solution of alcohols is neutral to are treated with very strong base like alkali
litmus (neither blue nor red litmus change metal Na or K they react to give sodium
colour). Aqueous solutions of phenols turn or potassium alkoxide with liberation of
blue litmus red. Thus, phenols have acidic hydrogen gas.
character.
2R - OH + 2Na 2R-O Na⊕ + H2↑
ii. Reaction with bases :
Liberation of H2 gas is used to detect the
• Acid strength of phenols being very low, presence of alcoholic -OH group in a molecule.
phenols cannot react with NaHCO3 but
iii. Characteristic test for phenols : Phenols
react with NaOH.
reacts with neutral ferric chloride solution to
Ar - OH + NaHCO3(aq) No reaction give deep (purple/violet/green) colouration of
Phenols dissolve in aqueous NaOH by forming ferric phenoxide.
water soluble sodium phenoxide and are 3Ar - OH + FeCl3 (Ar -O)3 Fe + 3HCl
reprecipitated/regenerated on acidification (deep colour)
(neutral)
with HCl.
242
iv. Distinguishing test for alcohols (Lucas Electron donating inductive effect (+I effect) of
test) :
Primary, secondary and tertiary alkyl group destabilizes the alkoxide ion (the
alcohols can be distinguished from each other conjugate base of alcohol). As a result alcohol
in the laboratory using Lucas reagent (conc. does not ionize much in water, and behaves
HCl and ZnCl2). The reaction involved is : like neutral compound in aqueous medium.
R - OH
HCl
R - Cl • Ionization of phenol is represented by the
ZnCl2
equilibrium shown in Fig. 11.1.
Alcohols are soluble in Lucas reagent but
the product alkyl chloride is not. Hence, the
clear solution becomes turbid when product O-H O
starts forming. Tertiary alcohols reacts fast
+ H2O + H3O⊕
and the reagent turns turbid instantaneously.
Secondary alcohols turn the reagent turbid (phenoxide)
Phenol
slowly. Primary alcohols turn the reagent
turbid only on heating. O O O
b. Reactions due to breaking of O -H bond.
i. Acidic character of alcohols and phenols :
I II III
From the laboratory tests it is
understood that in aqueous medium phenols O O
show weak acidic character while alcohols are
neutral. It is clear, therefore, that the reactivity
of alcohols and phenols towards ionization IV V
of O-H bond in them is different. The reason
behind this difference lies in the extent of Fig. 11.1 Ionization of phenol and resonance
stabilization of their respective conjugate stabilization phenoxide ion
bases by electronic effects as shown below. Phenoxide ion, the conjugate base of
• Ionization of alcohols is represented by the phenol, is resonace stabilized by delocalization
following equilibrium of the negative charge.Therefore phenol ionizes
in aqueous medium to a moderate extent, and
R - OH + H2O R O + H3O⊕ thereby shows a weak acidic character.
(alcohol) (alkoxide)
Problem 11.5 : Arrange the following compounds in decreasing order of acid strength and
justify.
Solution : Compounds (iii) and (iv) are phenols and therefore are more acidic than the alcohols
(i) and (ii). The acidic strenghts of compounds depend upon stabilization of the corresponding
conjugate bases. Hence let us compare electronic effects in the conjugate bases of these
compounds :
Alcohols : H3C
C O (Conjugate base of (ii))
CH3 CH2 O (Conjugate base of (i)) and H3C
H3C
243
The conjugate base of the alcohol (i) is destabilized by +I effect of one alkyl group,
where as conjugate base of the alcohol (ii) is destabilized by +I effect of three alkyl groups.
Hence (ii) is weaker acid than (i)
O O O O O O
N N N N N N
O ⊕ O O ⊕ O O ⊕ O O ⊕ O O ⊕ O O ⊕ O
I II III IV V VI
Phenols : The conjugate base of p-nitrophenol (iv) is better resonance stabilized due to six
resonance structures compared to the five resonance structures of conjugate base of phenol (iii)
(see Fig. 11.1). The resonance structure VI has -ve charge on only electronegative oxygens.
Hence the phenol (iv) is stronger acid than (iii). Thus the decreasing order of acid strength is
(iv) > (iii) > (i) > (ii)
244
The reaction of alcohol and phenols with ii. Reaction with phosphorous halide :
acid chloride is carried out in the presence of Alcohols react with phosphorous pentahalide
pyridine (base), which neutralizes HCl. (PX5) and phosphorous trihalide (PX3) to form
O O alkyl halides. (refer to Chapter 10 section
pyridine
R-OH + Cl-C -R' R'-C -OR + HCl 10.3.1).
(alcohol) (acid chloride) iii. Dehydration of alcohols to alkenes :
(ester)
O O Alcohol when treated with concerntrated
pyridine
Ar-OH+ Cl-C -R' R'-C -O-Ar + HCl sulphuric acid or phosphoric acid or alumina
(phenol) (acid chloride) (ester) undergoes dehydration to form alkene and
water. (refer to Std. XI Chemistry Textbook
Acetyl derivatives : The CH3-CO- group section 15.2) The reaction gives more
is called acetyl group. The acetate esters of substituted alkene as the major product, in
alcohols or phenols are also called ‘acetyl accordance with Saytzeff rule.
derivatives’ of alcohols or phenols repectively.
The number of alcoholic or phenolic -OH
groups in the given compound can be deduced
from the number of acetyl groups introduced Problem 11.6 : Write the reaction showing
in it as a result of acetylation. Aspirin, a major and minor products formed on heating
well known generic medicine, is an acetyl butan-2-ol with concentrated sulfuric acid.
derivative of salicylic acid formed by its Solution : In the reaction described
acetylation using acetic anhydride. butan-2-ol undergoes dehydration to give
but-2-ene (major) and but-1-ene (minor) in
COOH accordance with Saytzeff rule.
OH O O
H⊕ OH CH3-CH=CH-CH3
+ CH3-C -O-C -CH3
CH3-CH -CH2-CH3Conc H2SO4 But-2-ene (major)
∆
(Salicylic acid) (Acetic anhydride) (Butan-2-ol) CH2=CH-CH2-CH3
COOH But-1-ene (minor)
O
-O-C -CH3 + CH3COOH
(Acetic acid)
Do you know ?
(Aspirin/
Acetyl salicyclic acid) According to the common accepted
mechanism dehydration involves
c. Reaction due to breaking of C-O bond in
following three steps.
alcohols : ⊕
1. Formation of protonated alcohols R-OH2
i. Reaction with hydrogen halides :
Alcohols reacts with hydrogen halides to form 2. Its slow dissociation into carbocation
alkylhalides (refer to Chapter 10 section 10.3.1) 3. Fast removal of hydrogen ion to form
In general, tertiary alcohols react rapidly with alkene.
hydrogen halides; secondary alcohols react
⊕ -H2O -H⊕
somewhat slower; and primary alcohols, -C -C- H -C - C- -C -C - -C = C-
fast slow ⊕ fast
even more slowly. The order of reactivity of H OH H ⊕OH2 H
hydrogen halides is
(Alcohol) (Protonated (Carbocation) (Alkene)
HI > HBr > HCl alcohol)
HCl reacts only in the presence of anhydrous
ZnCl2. No catalyst is required in the case of
HBr and HI.
245
KMnO4/K2Cr2O7/HNO3
Problem 11.7 : Write and explain reactions R-CH2-OH (O)
[R-CHO]
(10 alcohol) (aldehyde)
to convert propan-1-ol into propan-2-ol ?
O
Solution : The dehydration of propane-1-ol R-C -OH
to propene is the first step. Markownikoff (carboxylic acid)
hydration of propene is the second step to
get the product propan-2-ol. This is brought Tertiary alcohols are difficult to oxidise.
about by reaction with concerntrated On oxidation with strong oxidising agents at
H2SO4 followed by hydrolysis. high temperature tertiary alcohol undergoes
breaking of C-C bonds and gives a mixture
Al2O3
of carboxylic acids containing less number of
CH3-CH2-CH2-OH 623K
CH3-CH=CH2 carbon atoms than the starting 3° alcohol.
(Propan-1-ol) (Propene)
i. Con H2SO4
CH3-CH -CH3 Heating with Cu : When vapours of various
ii. H2O
types of alcohols are passed over hot copper
OH
(Propan-2-ol) the following reactions are observed.
Cu/573K
R-CH2-OH R-CHO
iv. Oxidation of alcohols : Oxidation
(10 alcohol) (aldehyde)
Can you recall ?
Cu/573K
What are the various definitions of R-CH -R' Oxidation R-C -R'
oxidation ? OH O
(2 alcohol)
0
(ketone)
On reaction with oxidising agent Cu/573K
primary and secondary alcohols undergo H3C- C(OH) -CH3 dehydration
H3C- C = CH2
CH3 CH3
dehydrogenation to form carbonyl compounds,
namely aldehydes and ketones respectively (3 alcohol)
0
(alkene)
Seondary alcohol on oxidation with chromic
anhydride (CrO3) forms ketone. Problem 11.8 : An organic compound
CrO3 gives hydrogen on reaction with sodium
R-CH -R' R-C -R'
(O) metal. It forms an aldehyde having
OH O
(20alcohol) (ketone) molecular formula C2H4O on oxidation
Primary alcohol on oxidation with CrO3 with pyridinium chlorochromate Name the
forms aldehyde. However, a better reagent to compounds and give equations of these
bring about this oxidation is PCC (pyridinium reactions.
chlorochromate). Solution : The given molecular formula
PCC C2H4O of aldehyde is written as
R-CH2-OH (O)
R-CHO CH3 -CHO. Hence the formula
(1 alcohol)
0
(aldehyde)
of alcohol from which this is
When common oxidizing agents like obtained by oxidation must be
nitric acid, potassium permanganate or CH3-CH2-OH. The two reactions can,
potassium dichromate are used to oxidise therefore, be represented as follows.
primary alcohol, the oxidation does not stop 2CH3-CH2-OH 2Na 2CH3-CH2O Na⊕+ H2
at aldehyde stage, but the aldehyde formed is (Ethyl alcohol) (Sodium ethoxide)
further oxidized to carboxylic acid containing [O]
the same number of carbon atoms. CH3-CH2-OH CH3-CHO + H2O
PCC
(Ethyl alcohol) (Acetaldehyde)
246
d. Reactions of phenols : Phenol undergoes OH
electrophilic substitution reactions more readily HO-SO3H SO3H
as compared to benzene. The -OH group in 293K
H C2H5-O-C2H5
Ni
+ 3H2 433 K
(Phenol) (Cyclohexanol) b. Williamson Synthesis : Simple as well as
mixed ethers can be prepared in laboratory
viii. Reduction of phenol : Phenol is reduced by Williamson Synthesis. In this method
to benezene on heating with zinc dust. alkyl halide is treated with sodium alkoxide
OH or sodium phenoxide to give dialkyl ethers or
alkyl aryl ethers.
+ Zn + ZnO R-X + Na⊕ O -R R-O-R + NaX
(Phenol) (Benzene) R-X + Na⊕ O -Ar R-O-Ar + NaX
11.5 Ethers This reaction follows SN2 mechanism. Ether
is formed as a result of backside attack by
11.5.1 Preaparation of ethers
alkoxide/ phenoxide ion (a nucleophile) on
a. Dehydration of alcohols : When alcohol is alkyl halide. The alkyl halide used in this
heated with dehydrating agent like concentrated reaction must be primary. For example : t-butyl
H2SO4 or H3PO4 two products, either an ether methyl ether can be synthesised by reaction of
or an alkene, can form depending upon the methyl bromide with sodium t-butoxide.
temperature. For example : dehydration of
ethanol by H2SO4 gives ethoxyethane at 413 (CH3)3C-O Na⊕ + CH3-Br
K, while ethene is formed at 443 K. (sodium t-butoxide) (methyl bromide)
2C2H5OH
H2SO4/413K
C2H5-O-C2H5 (CH3)3C-O-CH3 + NaBr
-H2O
(ethanol) (Ethoxyethane) (t-butyl methyl ether)
248
If secondary or tertiary alkyl halides are used,
C2H5-Cl + Na⊕O -CH-CH3 C2H5-O-CH-CH3
the reaction leads mainly to alkene formation
(Ethyl CH3 CH2
(elimination reaction). For example :
chloride) (Sodium (ethyl isopropyl
CH3
CH3
isopropoxide) ether)
CH-C - Cl + Na⊕O -C2H5 CH3-C = CH2 + NaCl
CH3 (sodium ethoxide) (isobutene)
( t-butyl chloride) + C2H5OH + NaCl 11.5.2 Physical properties :
(ethanol)
a. Physical states and boiling points
Aryl halides do not give Williamson’s
synthesis. i. Dimethyl ether and ethyl methyl ether are
gases. Other ethers are colourless liquids with
Can you think ?
pleasant odour.
Williamson synthesis is effectively
a method of preparation of ethers ii. Lower ethers are highly volatile and highly
from two hydroxy compounds. The inflammable substances.
two substrates of Williamson synthesis, iii. Boiling points of ethers show gradual
namely the nucleophile and alkyl hadlides increase with the increase in molecular mass.
are obtained from hydroxy compounds as
shown below. Ether B.P. / K
OH ONa CH3-O-CH3 248
+ NaOH C2H5-O-CH3 284
Phenol (Phenoxide)
HX C2H5-O-C2H5 308
C2H5X (alkyl halide)
C2H5-OH Na b. Polarity and solubility : Since -C-O-C-
C2H5ONa (alkoxide)
bond angle is 110° and not 180°, the bond
dipole moments of the two C-O bonds donot
Problem 11.9 : Ethyl isopropyl ether does
cancel each other; therefore ethers posses a
not form on reaction of sodium ethoxide
small net dipole moment (For example, dipole
and isopropyl chloride.
moment of diethyl ether is 1.18 D)
C2H5-ONa + Cl-CH-CH3
CH3 R
× C2H5-O-CH-CH3 net dipole
CH3 110° O moment
R
i. What would be the main product of this
reaction ?
Weak polarity of ethers does not affect their
ii. Write another reaction suitable for the boiling points, which are about the same as
preparation of ethyl isopropyl ether. those of alkanes having comparable molecular
Solution : i. Isopropyl chloride is a mass. (see table 11.6).
secondary chloride. On treating with sodium Table 11.6 Comparative boiling points of
ethoxide it gives elimination reaction to alkane, ether and alcohol
form propene as the main product . Methyl
n-Hep- n-Hexyl
C2H5-ONa + Cl-CH-CH3 CH3-CH=CH2 Name n-pentyl
tane alcohol
CH3 (Propene) ether
(Sodium (isopropyl
ethoxide)
+ C2H5OH + NaCl Molecular
chloride) 100 102 102
(Ethyl alcohol) mass
ii. Ethyl isopropyl ether can be prepared as
follows using ethyl chloride (10chloride) as Boiling
371 373 430
as substrate. point / K
249
The intermolecular hydrogen bonding that R-O-R + H-O-H
H 3O ⊕
2R-OH
∆
holds alcohol molecules together strongly, is ⊕
H
not present in ethers and alkanes. However, R-O-R' + H-O-H ∆ R-OH + R'-OH
solubility/miscibility of ethers in water is H⊕
Ar-O-R + H-O-H ∆ Ar-OH + R-OH
similar to that of alcohols of comparable
molecular mass. This is because ethers can ii. Reaction with PCl5 : Ethers react with PCl5
form hydrogen bonds with water through the to give alkyl chlorides
ethereal oxygen.
R-O-R' + PCl D R-Cl + R'-Cl + POCl
5 3
δ δ⊕
R- O H -O iii. Reaction with hot concentrated acid :
R H Alkyl ethers react with hot and concentrated
HI and HBr to give an alcohol and an alkyl
For example diethyl ether and n-butyl alcohol
halide.
have respective miscibilities of 7.5 and 9g per
100 g of water. R-O-R + HX R-X + R-OH HX R-X
11.5.3 Chemical properties of ethers : R-OH HX R-X + H2O
a. Laboratory test for ethers : Ethers are The order of reactivity of HX is HI>HBr>HCl
neutral compounds in aqueous medium.
Ethers do not react with bases, cold dilute
Do you know ?
acids, reducing agents, oxidizing agents and
active metals. However, ethers dissolve in Mechanism of first stage : Reaction
cold concerntrated H2SO4 due to formation of of ether with hot concentrated
oxonium salts. HI involves formation of oxonium ion by
H protonation in the first step and subsequent
R-O-R' + H2SO4 R-O-R' HSO4 nucleophilic substitution reaction brought
⊕ about by the powerful nucleophile I . The
This property distinguishes ethers from least substituted carbon in oxoinium ion is
hydrocarbons. attacked by I following SN2 mechanism.
∆ ⊕
b. Reaction involving alkyl group of ether : CH3-O-CH2-CH3 + H-I CH3-O-CH2-CH3
i. Formation of peroxide : Ethers combine H
+ I
with atmospheric oxygen to form peroxide. 1 1
O-OH ⊕ 2 2
⊕
I CH3-O-CH2-CH3 I CH3 O-CH2-CH3
CH3-CH2-O-C2H5 + O2 Long CH3-CH-O-C2H5 H
contact H
(diethyl ether)
with air (peroxide of
(oxygen) diethyl ether)
CH3- I + CH3-CH2-OH
For example :
All ethers which have been exposed to • Use of excess HI converts the alcohol into
the atmosphere contain peroxide. This is very alkyl iodide.
undesirable reaction. Peroxides are hazardous • In case of ether having one tertiary alkyl
because they decompose violently at high group the reaction with hot HI follows SN1
temperature. mechanism, and tertiary iodide is formed
rather than tertiary alcohol.
c. Reaction involving C-O bond ⊕ slow
Step 1 : (CH3)3C-O-CH3 (CH3)3C⊕ +
i. Reaction with hot dilute sulphuric acid H
(Hydrolysis) : Ethers when heated with CH3OH
dilute sulfuric acid undergo hydrolysis to give
alcohols/phenols. Step 2 : (CH3)3C⊕ + I fast (CH3)3C-I
250
Aryl alkyl ethers have stronger and shorter OCH3 OCH3 OCH3
bond between oxygen and the aromatic ring. CH3
Anhydrous
Hence an aryl alkyl ether undergoes cleavage + CH3Cl AlCl3 +
of oxygen - alkyl bond and yields a phenol
(Anisole) CH3
and an alkyl halide on reaction with HI.
(4-Methoxy (2-Methoxy
toluene) toluene)
CH3 (major) (minor)
O OH
OCH3 OCH3
+ HI 398K + CH3I
Anhydrous
(Anisole) (Phenol) (Methyl iodide) + CH3COCl AlCl3 +
(Anisole) COCH3
d. Electrophilic substitution in aromatic (4-Methoxy
ethers : The alkoxy group in aromatic acetophenone)
ether is a ring activating and ortho-, para- (major)
directing group toward electrophilic aromatic
OCH3
substitution. This is evident from the resonance
COCH3
structures:
⊕ R ⊕ ⊕ R
O
R
O O
R
O OR (2-Methoxy
acetophenone)
(minor)
iii. Nitration : Anisole reacts with concentrated
(I) (II) (III) (IV) (V) nitric acid in presence of concentrated sulfuric
acid (Nitrating mixture) to give a mixture of
+R Effect of -OR group results in increased o-nitro anisole and p-nitro anisole.
electron density at the para- and two ortho- OCH3 OCH3 OCH3
positions (see resonance structures II, III and conc HNO3 NO2
IV). +
conc H2SO4
i. Halogenation : Anisole undergoes (Anisole) NO2
bromination with bromine in acetic acid even (4-Nitroanisole) (2-Nitroanisole)
in the absence of ferric bromide catalyst. It (major) (minor)
is due to activation of benzene ring by the
methoxy group. 11.6 Uses of alcohols, phenols and ethers
OCH3 OCH3 OCH3 Alcohols :
Br2 Br 1. Methyl alcohol is used as a solvent for
CH3COOH +
paints and varnishes.
Br 2. Ethyl alcohol is used as antifreeze agent
(Anisole) 90% 10% in automobile radiators. It is also used as
(p-bromo anisole) (o-bromo anisole) solvent.
ii. Friedel Crafts reaction : Anisole reacts Ethers :
with alkyl halide and acyl chloride in presence 1. Earlier diethyl ether was used as a general
of anhydrous AlCl3 (Lewis acid) as catalyst. anaesthetic in surgical operations.
2. Diethyl ether is used as a solvent for
Grignard reagents, fats, waxes, oil, etc.
251
Phenols :
1. Phenol is used in preparation of phenol formaldehyde resin For example : bakelite.
2. Phenols are used as antiseptic in common products like air freshners, deodarants, mouthwash,
calamine lotions, floor cleaners, etc.
Exercises
A. (1) < (2) < (3) B. (2) < (1) < (3) A. Iodobenzene
C. (3) < (2) < (1) D. (2) < (3) < (1) B. Phenol + Methanol
ii. Which is the best reagent for carrying out C. Phenol + Iodomethane
following conversion ? D. Iodobenzene + methanol
CH3 CH3
vii. Which of the following is the least acidic
OH compound ?
OH
OH
A. LiAlH4 B. Conc. H2SO4, H2O A. B.
C. H2/Pd D. B2H6, H2O2-NaOH
CH3
iii. Which of the following substrate will give
OH OH
ionic organic product on reaction ?
C. D.
A. CH3-CH2-OH + Na
B. CH3-CH2-OH + SOCl2 NO2
NO2
C. CH3-CH2-OH + PCl5
viii. The compound incapable of hydrogen
D. CH3-CH2-OH + H2SO4
bonding with water is ......
iv. Which is the most resistant alcohol
A. CH3-CH2-O-CH3
towards oxidation reaction among the
follwoing ? B. CH3-CH2-CH2-CH3
A. CH3-CH2-OH B. (CH3)2CH-OH
OH
C. (CH3)3C-OH D. C2H5 CH -OH C.
CH3
D. CH3-CH2-CH2-OH
252
ix. Ethers are kept in air tight brown bottles 4. An ether (A), C5H12O, when heated
because with excess of hot HI produce two
alkyl halides which on hydrolysis form
A. Ethers absorb moisture
compound (B)and (C), oxidation of (B)
B. Ethers evaporate readily gave and acid (D), whereas oxidation
C. Ethers oxidise to explosive peroxide of (C) gave a ketone (E). Deduce the
structural formula of (A), (B), (C), (D)
D. Ethers are inert and (E).
x. Ethers reacts with cold and concentrated 5. Write structural formulae for
H2SO4 to form
a. 3-Methoxyhexane
A. oxonium salt B. alkene
b. Methyl vinyl ether
C. alkoxides D. alcohols
c. 1-Ethylcyclohexanol
2. Answer in one sentence/ word.
d. Pentane-1,4-diol
i. Hydroboration-oxidation of propene
gives..... e. Cyclohex-2-en-1-ol
ii. Write the IUPAC name of alcohol having 6. Write IUPAC names of the following
molecular formula C4H10O which is
HO CH3
resistant towards oxidation. i.
iii. Write structure of optically active alcohol
having molecular formula C4H10O
ii. CH3-CH -CH -CH2-OH
iv. Write name of the electrophile used in
OH CH3
Kolbe’s Reaction.
3. Answer in brief.
OH O-CH3
i. Explain why phenol is more acidic than iii. iv.
ethyl alcohol. NO2
ii. Explain why p-nitrophenol is a stronger
acid than phenol.
iii. Write two points of difference between Activity :
properties of phenol and ethyl alcohol.
iv. Give the reagents and conditions necessary • Collect information about
to prepare phenol from production of ethanol as byproduct
a. Chlorobenzene in sugar industry and its
importance in fuel economy.
b. Benzene sulfonic acid.
v. Give the equations of the reactions for • Collect information about phenols
the preparation of phenol from isopropyl used as antiseptics and polyphenols
benezene. having antioxidant activity.
vi. Give a simple chemcial test to distinguish
between ethanol and ethyl bromide.
253
12. ALDEHYDES, KETONES AND CARBOXYLIC ACIDS
254
12.2.2 Classification of ketones : Ketones are
classified as aliphatic and aromatic ketones: Use your brain power
• Classify the followings as
a. Aliphatic ketones : The compounds in
simple and mixed ketones.
which >C=O group is attached to two alkyl
• Benzophenone, acetone, butanone,
groups are called aliphatic ketones.
acetophenone.
255
a. Aliphatic carboxylic acids : The organic
compounds in which carboxyl (-COOH) Remember...
group is bonded to an alkyl group are called The aromatic compounds in which
aliphatic carboxylic acids or fatty acids. the –COOH group is not attached
(Exception : Formic acid, H-COOH is also directly to the ring are called side-chain
classified as aliphatic carboxylic acid though aromatic acids. For example :
–COOH group is not attached to any carbon).
For example : CH2 - COOH
H3C - COOH H3C - CH2 - COOH (Phenyl acetic acid)
(Acetic acid) (Propionic acid )
Carboxylic acids are widely distributed
O
Carboxyl in nature; they are found in both the plants and
R C
OH
functional group animals. L-lactic acid is present in curd , citric
acid is found in citrus fruit (Lemons). Acetic
General formula
(R= H or alkyl group) acid is the key ingredient of vinegar.
COOH
(Benzoic acid) (Phthalic acid)
OCOCH3
COOH
(Acetyl salicylic acid) ( Aspirin)
256
When two –CHO groups are present at
Do you know ? the two ends of the chain the ending ‘e’of
A series of straight chain
alkane is retained and the suffix –‘dial’ is
dicarboxylic acids are
added to the name of parent aldehyde. In case
commercially known by the following
of dicarboxylic acids, ‘dioic acid’ is added
common names:
COOH COOH COOH COOH COOH to the name of the parent alkane. In IUPAC
COOH CH2 (CH2)2 (CH2)3 (CH2)4 nomenclature an alicyclic compound in
(oxalic COOH COOH COOH COOH which –CHO group is attached directly to the
acid) (malonic (succinic (glutaric (adipic
acid) acid) acid) acid)
ring is named as a carbaldehyde. The suffix
A series of lower fatty acids are commercially ‘carbaldehyde’ is added after the full name
known by the following common names. of parent cycloalkane structure. Similarly an
CH3 CH3 CH3 CH3 CH3 alicyclic compound having a carboxyl group
COOH CH2 (CH2)2 (CH2)3 (CH2)4 directly attached to alicyclic ring is named as
(Acetic COOH COOH COOH COOH cycloalkane carboxylic acid.
acid) (propionic (butyric (valeric (caproic
acid) acid) acid) acid) Substituted aromatic aldehydes and
carboxylic acids : When two or more different
b. IUPAC names of aldehydes and carboxylic functional groups are attached to a ring ,
acids : the higher priority group (std. XI Chemistry
Can you recall ? Textbook, Chapter 14, sec.14.4.7) is given
lower number. When –CHO group, appears
Which suffix do appear in the as substituent prefix ‘formyl’ is used in the
IUPAC names of aldehydes and IUPAC name.
carboxylic acids ?
CHO
According to IUPAC system, the name of an
aliphatic aldehyde is derived from the name of
the corresponding alkane by replacing ending CH3
‘e’ of alkane with ‘ al ’. Aldehyde is named OH
as alkanal (Table 12.1). The IUPAC name of
(4-Hydroxy-3-methylbenzaldehyde)
aliphatic carboxylic acid is derived from the
name of the corresponding alkane by replacing COOH
ending ‘ e’ of alkane with ‘ oic acid ’. (Refer to
Std. XI Chemistry Textbook sec. 14.4.7).
Alkane Alkanal OH
CH3
Alkane Alkanoic acid
(3-Hydroxy-4-methylbenzoic acid)
The longest chain including –CHO or –
COOH group is identified as the parent chain. CHO
Numbering of the chain is done by giving
number 1 to the –CHO or –COOH carbon. The COOH
name of substituent is included along with its (2-Formylbenzoic acid)
locant.
4
CH3-3CH2-2CH2-1CHO ; 4CH3-3CH2-2CH2-1COOH Trivial and IUPAC names of some aldehydes
and carboxylic acids are given in Table 12.1.
Aldehyde (-CHO) group and carboxyl
(-COOH) group are always present at the end
of the parent straight chain.
257
Table 12.1 Trivial and IUPAC names of carboxylic acids and aldehydes
258
(Benzenecarboxylic (Benzenecarbaldehyde)
acid)
COOH o-Toluic acid 2-Methylbenzoic acid CHO o-Tolualdehyde 2-Methylbenzaldehyde
CH3 CH3
COOH Salicyclic acid 2-Hydroxybenzoic acid CHO Salicylaldehyde 2-Hydroxybenzaldehyde
OH OH
COOH Phthalic acid Benzene-1,2- CHO Phthalaldehyde Benzene-1,2-
dicarboxylic acid dicarboaldehyde
COOH CHO
COOH Cyclohexylcarboxylic Cyclohexanecarboxylic CHO Cyclohexane aldehyde Cyclohexanecarbaldehyde
acid acid
In case of substituted aliphatic ketones the
Do you know ? position of substituent is indicated by labelling
The trivial names of carboxylic the carbon serially as α, β, γ and so on. The
acids are often derived from Latin carbon atom adjacent to carbonyl carbon
names of their original natural source. is labelled as α and next one is β and so on.
For example, Formic acid is obtained Names of aromatic ketones are based on a
from red ants (Formica means ant), acetic phenone. (see Table 12.2)
acid is obtained from acetum (acetum b. The IUPAC names of aliphatic ketones are
means vinegar), propionic acid is from basic derived from the name of the corresponding
fat (propion means first fat), butyric acid is alkanes by replacing ending ‘e’ of alkane
from butter (butyrum means butter). with ‘one’. They are named as alkanone. The
longest chain of carbon atoms containing the
12.3.2 Trivial and IUPAC names of ketones:
ketonic carbonyl group is numbered from the
a. The trivial names of aliphatic ketones are end closer to the carbonyl carbon.
based on the names of alkyl groups or aryl
Alkane Alkanone
groups attached to carbonyl carbon .Names of
alkyl or aryl groups are written in alphabetical When two >C=O groups are present,
order followed by the word ketone. then ending ‘e’of alkane is retained and
the suffix –‘dione’ is added to the name of
parent ketone indicating the locants of ketonic
Table 12.2 Trivial and IUPAC names of some ketones
11 O ----------------------- 2-Chloro-4-
Cl methylcyclohexanone
259
carbonyl groups. In case of polyfunctional ii. By dehydrogenation of alcohols : This
ketones, higher priority group is given lower method has industrial application. Aldehydes
number. When ketonic carbonyl is a lower and ketones are prepared by passing the
priority group it is named as 'oxo', preceded vapours of primary and secondary alcohols
by the locant. In alicyclic ketones, carbonyl respectively over hot copper powder. (See
carbon is numbered as 1. (Refer Table 12.2). Chapter 11)
b. From hydrocarbons :
Use your brain power
Write IUPAC names for the Can you recall ?
following compounds.
• What is ozonolysis ?
i. H
• What is the role of zinc dust in
Br Br ozonolysis process?
O
i. By ozonolysis : Alkene reacts with ozone to
O
ii. give ozonide which on decomposition with zinc
dust and water gives aldehyde and/or ketones.
O (See Std. XI Chemistry Textbook, Chapter 15)
iii. H
ii. By hydration of alkynes : Alkynes react
O with water in presence of 40% sulfuric acid
and 1% mercuric sulfate to give aldehydes
or ketones. (See Std. XI Chemistry Textbook,
iv. CHO v. O Chapter 15)
12.4.2 Other methods of preparation of
aldehydes and ketones : Some methods of
preparation of aldehydes and ketones involve
common starting functional groups but
Try this...
different types.
Draw structures for the following
a. 2-Methylpentanal a. From acyl chlorides (Acid chlorides) :
b. Hexan-2-one Aldehydes and ketones both can be obtained
from acyl chloride, but the reactions involved
12.4 Preparation of aldehydes and ketones : are different.
12.4.1 General methods of preparation of • Preparation of aldehyde from acyl
aldehydes and ketones : chloride
a. By oxidation of alcohols : i. Aldehydes Acyl chloride is reduced to corresponding
and ketones are prepared by the oxidation of aldehyde by hydrogen using a palladium
primary and secondary alcohols respectively. catalyst poisoned with barium sulfate. This
(See Chapter 11 ) reaction is known as Rosenmund reduction.
Can you tell ? O O
H2
What is the reagent which R - C - Cl Pd-BaSO4 R - C - H + HCl
oxidizes primary alcohols to
only aldehydes and does not oxidize (Acyl chloride) (Aldehyde)
aldehydes further into carboxylic acid ?
260
hydrochloric acid which on acid hydrolysis
Use your brain power give corresponding aldehydes. This reaction
Write the structure of the is called Stephen reaction.
product formed on Rosenmund SnCl2, HCl
reduction of ethanoyl chloride and benzoyl R - C ≡ N + 2[H] R - HC = NH.HCl
(Alkane nitrile) (imine hydrochloride)
chloride.
H3O⊕
R - CHO + NH4Cl
(Aldehyde)
Can you think ?
For example,
What is the alcohol formed when SnCl2, HCl
benzoyl chloride is reduced with H3C - C ≡ N + 2[H] (reduction)
pure palladium as the catalyst ? (Ethanenitrile)
H3O⊕
CH3 - HC = NH.HCl CH3-CHO+NH4Cl
b. Preparation of ketone (aliphatic and (ethanimine hydrochloride) (Ethanal)
aromatic) from acyl chloride :
SnCl2, HCl
i. Preparation of aliphatic ketones from C6H5 - C ≡ N + 2[H]
acyl chloride: ketones are obtained from acyl (Benzonitrile)
chloride by reaction with dialkyl cadmium H3O⊕
C6H5 - HC = NH.HCl C6H5-CHO+NH4Cl
which is prepared by the treatment of cadmium
(Benzanimine hydrochloride) (Benzaldehyde)
chloride with Grignard reagent.
Alternatively, nitriles are also reduced by
2R - MgX + CdCl2 R2Cd + 2Mg(X)Cl
diisobutylaluminium hydride (DIBAl-H)
2R' - COCl + R2Cd 2 R' - CO - R or AlH (i-Bu)2 to imines followed by acid
(Acyl chloride) (Ketone) hydrolysis to aldehydes. An advantage of this
+ CdCl2 method is that double or triple bond present in
For example, the same molecule is not reduced..
AIH (i-Bu)2
2CH3 - COCl + (CH3)2Cd H3C - CH = CH - CH2 - C ≡ N H O ⊕
3
262
b. Anhydrides on hydrolysis with water give
Try this...
Draw the structure of the product carboxylic acids.
formed by the combination of O O O
carbon monoxide and HCl. R - C - O - C - R + H2O 2R - C - O - H
(Anhydride) (Carboxylic acid)
Use your brain power
12.5.3 From esters : Carboxylic acids can be
Identify the reagents necessary obtained from esters either by acid hydrolysis
to achieve each of the following or alkaline hydrolysis.
transformation a. Acid hydrolysis of ester : Esters on
O O hydrolysis with dilute mineral acid like dilute
Cl H HCl or dilute H2SO4 give the corresponding
carboxylic acid .
O O O
R - C - O - R' + H2O dil.H
∆
SO 2
R -4
C -O-H
(Ester) (Carboxylic acid)
O O + R' - OH
(Alcohol)
OCH3 H
O2N b. Alkaline hydrolysis of ester using dilute
O2N
alkali like dilute NaOH or dilute KOH form
solution of water soluble sodium or potassium
12.5 Preparation of carboxylic acids : salt of the acid (carboxylate). On acidification
12.5.1 From nitriles and amides : Alkyl with concentrated HCl, free acid is formed.
nitriles or aryl nitriles on acid hydrolysis give O
amides . Amides on further acid hydrolysis give H5C2 - C - O - CH3 + dil.NaOH ∆
COOH
H3O⊕
(Benzoic acid)
Use your brain power
CH3
H3C ⊕ Predict the products (name and
C COOK
H KMnO4.KOH structure) in the following reactions.
∆ ∆
CH3CH2CN dil. HCl ?
(Cumene) (Potassium benzoate) ∆
CH3-CONH2 dil. HCl ?
COOH
H3O⊕ alk.KMnO4
C6H5-CH2-CH3 ∆ ?
∆
(Benzoic acid) C6H5-COO-C2H5 dil. H2SO4 ?
12.5.5 From alkenes : Carboxylic acids can CH3MgBr
(i) dry ice/dry ether
?
(ii) dil. HCl
also be prepared by the oxidation of alkenes
by KMnO4 in dilute H2SO4. 12.6 Physical properties :
KMnO4.dil.H2SO4
H5C6 - CH = CH2 ∆ H5C6 - COOH 12.6.1 Nature of intermolecular forces :
(Phenyl ethene) (Benzoic acid) The carbonyl bond ( C=O) in aldehydes and
ketones is a polar covalent bond. As a result,
KMnO4.dil.H2SO4 COOH these compounds contain dipole-dipole forces
∆ COOH
of attraction. (Fig. 12.1) The molecules orient
(Cyclohexene) (Adipic acid) in such a way as to have oppositely polarized
atoms facing each other.
12.5.6 From Grignard reagent : Grignard δ δ⊕
reagent in dry ether solvent is added to solid O C
carbon dioxide (dry ice) to give a complex
C O
which on acid hydrolysis gives corresponding δ⊕ δ
carboxylic acid.
Fig. 12.1 Dipole-dipole attraction in carbonyl
dry ether
R - Mg - X + O = C = O R - COOMgX compounds
(Alkyl (dry ice) (complex) Carboxyl group of carboxylic acid contains
magnesium halide) O-H bond which is responsible for formation
HOH of hydrogen bonding. Thus, carboxylic acids
dil.HCl R - COOH + Mg(X)OH have the strongest intermolecular forces of
(carboxylic acid) attraction. (Fig.12.3 in section 12.6.4).
264
Table 12.4 Boiling points of aldehydes and ketones
Number of carbon atoms Aldehyde Boiling point Ketone Boiling point
1 Methanal 252 K ----- --------
2 Ethanal 294 K ------- ---------
3 Propanal 319 K Propanone 329 K
4 Butanal 348 K Butan -2-one 353 K
5 Pentanal 376 K Pentan-2-one 375 K
6 Hexanal 392 K Hexan-2-one 400 K
12.6.2 Physical state and boiling points of 12.6.4 Physical state, boiling points and
aldehydes and ketones : solubilities of carboxylic acids : Lower
Formaldehyde is a gas at room temperature aliphatic carboxylic acids upto nine carbon
and has irritating odour. Acetaldehdye is atoms are colourless liquids with irritating
extremely volatile, colourless liquid. Higher odours. The higher homologues are colourless,
aldehydes have pleasant odour. Acetone is a odourless wax like solids, have low volatility.
liquid at room temperature and has pleasant Boiling points of lower carboxylic acids are
odour but most of the higher ketones have listed in Table 12.5.
bland odours. Carboxylic acids have higher boiling
Increasing boiling points in the homologous points than those of alkanes, ethers, alcohols
series of aldehydes and ketones are listed in aldehydes and ketones of comparable mass
Table 12.4. (Table 12.6). The reason is that , in liquid
phase, carboxylic acids form dimer in which
12.6.3 Solubility of aldehydes and ketones : two molecules are held by two hydrogen
The oxygen atom of ( C=O) can involve bonds. Acidic hydrogen of one molecule form
in hydrogen bonding with water molecule hydrogen bond with carbonyl oxygen of the
(Fig 12.2). As a result of this, the lower other molecule (Fig.12.3). This doubles the
aldehydes and ketones are water soluble (For size of the molecule resulting in increase in
example : acetaldehyde, acetone). As the intermolecular van der Waals forces, which in
molecular mass increases, the proportion of turn results in high boiling point. In the case of
hydrocarbon part of the molecule increases acetic acid dimers exist even in the gas phase
which cannot form hydrogen bond; and the (Fig.12.3).
water solubility decreases. δ δ⊕
O H O
δ δ⊕ δ H3 C - C C - CH3
δ⊕ C = O H -O δ⊕
H O H O
Fig. 12.2 : Hydrogen bonding in carbonyl δ⊕ δ
compound and water Fig. 12.3 : Dimer of acetic acid (Two molecules
held by two hydrogen bonds)
Table 12.5 Increasing boiling points of carboxylic acids
Name Formula Boiling point in K
Formic acid HCOOH 373 K
Acetic acid CH3COOH 391 K
Propionic acid CH3CH2COOH 414 K
Butyric acid CH3CH2CH2COOH 437 K
Valeric acid CH3CH2CH2CH2COOH 460 K
265
Table 12.6 : Variation of boiling point with functional group
Compound Family Molecular mass Boiling point Strength of intermolecular
forces
CH3-CH2-CH2-CH3 Alkane 58 272 K
CH3-O-CH2-CH3 Ether 60 281 K
increases
CH3-CH2-CHO Aldehyde 58 322 K
CH3-CO-CH3 Ketone 58 329 K
CH3-CH2-CH2-OH Alcohol 60 370 K
CH3-COOH Carboxylic acid 60 391 K
266
The carbonyl carbon has positive polarity
Try this...
(see structures (A) and (D)). Therefore, it is
electron deficient. As a result, this carbon Draw structure of propanone and
atom is electrophilic (electron loving) and is indicate its polarity.
susceptible to attack by a nucleophile (Nu: ).
12.8 Chemical properties of aldehydes and
12.7.1 Reactivity of aldehydes and ketones ketones :
: Reactivity of aldehydes and ketones is
due to the polarity of carbonyl group which 12.8.1 Laboratory tests for aldehydes and
results in electrophilicity of carbon. In general, ketones : Aldehydes are easily oxidized to
aldehydes are more reactive than ketones carboxylic acids and therefore, act as reducing
toward nucleophilic attack. This can be well agents toward mild oxidizing agents. Ketones,
explained in terms of both the electronic effects do not have hydrogen atom directly attached to
and steric effect. carbonyl carbon. Hence, they are not oxidized
by mild oxidizing agents. On the basis of this
1. Influence of electronic effects : Alkyl difference in the reactivity, aldehydes and
groups have electron donating inductive effect ketones are distinguished by the following
(+I). A ketone has two electron donating alkyl tests:
groups bonded to carbonyl carbon which are
responsible for decreasing its positive polarity a. Tests given by only aldehydes :
and electrophilicity. In contrast, aldehydes 1. Schiff test : When alcoholic solution of
have only one electron donating group bonded aldehyde is treated with few drops of Schiff 's
to carbonyl carbon. This makes aldehydes reagent, pink or red or magenta colour appears.
more electrophilic than ketones. This confirms the presence of aldehydic
2. Steric effects : Two bulky alkyl groups (-CHO) group.
in ketone come in the way of incoming 2. Tollens' test or silver mirror test : When
nucleophile. This is called steric hindrance to an aldehyde is boiled with Tollens' reagent
nucleophilic attack. (ammonical silver nitrate), silver mirror
On the other hand, nucleophile can easily is formed. The aldehyde is oxidized to
attack the carbonyl carbon in aldehyde because carboxylate ion by Tollens' reagent and Ag⊕
it has one alkyl group and is less crowded or ion is reduced to Ag.
sterically less hindered . Hence aldehyde are R - CHO + 2 Ag (NH3)2⊕ + 3OH ∆
267
R - CHO + 2Cu2⊕ + 5OH boil a. Addition of hydrogen cyanide (H-CN) :
Hydrogen cyanide (weak acid) adds across
(Aldehyde) (Fehling solution) the carbon-oxygen double bond in aldehydes
R - COO + Cu2O↓ + 3H2O and ketones to produce compounds called
(carboxylate ion) red ppt
Do you know ?
Can you tell ?
1. Schiff 's reagent is a colourless
Simple hydrocarbons, ethers, solution obtained by passing sulfur
ketones and alcohols do not dioxide gas (oxidant) through magenta
get oxidized by Tollens' reagent. coloured solution of p-rosaniline
Explain, Why ? hydrochloride .
268
cyanohydrins. The negative part of the reagent H3C CH3
( CN) attacks the electrophilic carbon of C = O + NaHSO3 H3C − C − OH
carbonyl group. The reaction requires either H3C SO3Na
acid or base as catalyst. (Acetonesodium
(Acetone)
R R bisulfite adduct)
C = O + HCN R' − C − OH
Use your brain power
R' CN
(Aldehyde when R' = H
Sodium bisulfite is sodium salt
(cyanohydrin)
Ketone : R' = alkyl/aryl group) of sulfurous acid, write down its
detailed bond structure .
For example ,
H3C R Do you know ?
C = O + H - CN H3C − C − OH Sodium bisulfite addition product
H CN so formed can be split easily to
(Acetaldehyde) (acetaldehyde cyanohydrin) regenerate aldehydes and ketones on
treatment with dilute acid or base. Thus,
H3C CH3 this reaction is used to separate and purify
C = O + H - CN the aldehydes and ketones from other
H3C − C − OH
H3C organic compounds.
CN
(Acetone) (Acetone cynohydrin) c. Addition of alcohols : Aldehyde reacts
with one molecule of anhydrous monohydric
Remember... alcohol in presence of dry hydrogen chloride
i. Cyanohydrin formation is a to give alkoxyalcohol known as hemiacetal,
'step-up' reaction as a new carbon which further reacts with one more molecule
- carbon single bond is formed. of anhydrous monohydric alcohol to give a
geminaldialkoxy compound known as acetal
ii. The - C ≡ N group can be converted to as shown in the reaction.
–COOH, - CH2 - NH2 and so on.
Step 1 :
iii. Therefore, cyanohydrins are used as
intermediate in step up synthesis. R H
dry HCl
C = O +R' - OH R − C − OR'
dil. HCl
b. Addition of NaHSO3 (Sodium bisulphite) H OH
: Aldehydes and ketones react with saturated
(Aldehyde) (Hemiacetal) unstable
aqueous solution of sodium bisulfite to give
crystalline precipitate of sodium bisulfite
Step 2 :
adduct (addition compound). For example ,
H H
dry HCl
H3C H R − C − OR' +R' - OH R − C − OR'
dil. HCl
C = O + NaHSO3 H3C − C − OH OH OR'
H SO3Na (Hemiacetal) (Acetal) stable
269
For example ,
Do you know ?
Step 1 :
Cyclic ketal is used as protecting
H3C
group for ketone in reactions of
C=O + H5C2 - OH
multifunctional compound to which
H
ketone is sensitive.
(Acetaldehyde)
H
dry HCl
H3C − C − OC2H5 Use your brain power
dil. HCl
OH Predict the product of the
(Hemiacetal) unstable following reaction :
O HO-CH2-CH2-OH
Step 2 : Br
Mg in dry ether
H
dry HCl
H3C − C − OC2H5 + H5C2 - OH Acetals and ketals are hydrolysed with
dil. HCl
OH aqueous mineral acids to give corresponding
(Hemiacetal) (unstable) aldehydes and ketones respectively.
H
H3C − C − OC2H5 + H2O Remember...
OC2H5 Organic molecule containing
(1,1-Diethyoxyethane) an alcohol and carbonyl group can
(stable) undergo intramolecular reaction with dry
HCl to form cyclic hemiacetals/hemiketals.
Similarly, Ketones react with alcohol in
presence of acid catalyst to form hemiketal
and ketal. d. Addition of Grignard reagent : Aldehydes
and ketones on reaction with alkyl magnesium
Ketones react with 1,2- or 1,3- diols in halide followed by acid hydrolysis give
presence of dry hydrogen chloride to give five- alcohols.(Refer to Chapter 11, sec. 11.4.1 d.)
or six -membered cyclic ketals .
e. Nucleophilic addition –elimination of
R HO -CH2 aldehydes and ketones with ammonia
C=O + derivatives : Aldehydes and ketones undergo
R HO -CH2
addition elimination with some ammonia
(ketone) (ethane-1,2-diol)
derivatives (NH2-Z ) to give product
dry HCl R O CH2 containing C = N bonds (imines). The reaction
dil. HCl C is reversible and takes place in weakly acidic
R O CH2 medium. The substituted imine is called a
(cyclic ketal) Schiff 's base.
270
Table 12.7 Nucleophilic addition – elimination reactions of aldehydes and ketones with
ammonia derivatives
Sr. Aldehyde(R'=H)/ + NH2 - Z imine (a crystalline
-H2O
No. Ketone(R'≠H) derivative)
R NH2 OH R
1. C=O + Hydroxyl amine -H2O R' C N OH
R' oxime
R NH2 NH2 R
2. C=O + Hydrazine -H2O R' C N NH2
R' hydrazone
R NH2 NH C6H5 R
3. C=O + Phenyl hydrazine -H2O R' C N NH C6H5
R' phenylhydrazone
R NH2 NH CONH2 R
4. C=O + Semicarbazide -H2O R' C N NH CONH2
R' semicarbazone
NO2 NO2
H R H
R
+H2N N NO2 C = N N NO2
5. C=O -H2O
R
R' 2, 4 - Dinitrophenyl 2, 4 -
hydrazine Dinitrophenylhydrazone
271
f. Haloform reaction : This reaction is g. Aldol condensation :
given by acetaldehyde, all methyl ketones
(CH3-CO-R) and all alcohols containing CH3- Try this...
(CHOH)- group. When an alcohol or methyl When acetaldehyde is treated
ketone is warmed with sodium hydroxide and with dilute NaOH, the following
iodine, a yellow precipitate is formed. Here reaction is observed.
the reagent sodium hypoiodite is produced
dil. NaOH
in situ. During the reaction, sodium salt of 2CH3-CHO CH3 -CH-CH2-CHO
carboxylic acid is formed which contains OH
one carbon atom less than the substrate. The • What are the functional groups in the
methyl group is converted in to haloform. product ?
For example : Acetone is oxidized by sodium • Will there be another product formed
hypoiodite to give sodium salt of acetic acid during the same reaction ? (Deduce
and yellow precipitate of iodoform. the answer by doing atomic audit of
reactant and product)
O • Is this an addition reaction or
NaOH, I2
H3C C CH3 + 3 Na OI condensation reaction ?
∆
(Acetone) (Sodium
hypoiodite)
Aldehydes containing at least one
O α –hydrogen atom undergo a reaction in
⊕
CHI3 ↓ + H3C C ONa + 2 NaOH presence of dilute alkali ( dilute NaOH, KOH
(Iodoform) (Sodium acetate) or Na2CO3) as catalyst to form β-hydroxy
aldehydes (aldol). This reaction is known
as aldol reaction. Formation of aldol is an
Remember...
addition reaction. Aldol formed from aldehyde
1. If C=C bond is present in a given having α-hydrogens undergoes subsequent
aldehyde or ketone or methyl elimination of water molecule on warming,
ketone, it is not attacked by hypohalite. giving rise to a, b - unsaturated aldehyde.
2. Non methyl ketones do not give a aq. NaOH
R-CH2-CH-CHR-CHO
2R-CH2-CHO
positive iodoform test.
OH
3.
Secondary alcohols having CH3- (aldehyde) (aldol)
CHOH- group give positive iodoform -H2O
test because the reagent first oxidizes it R-CH2-CH-CHR-CHO warm
R-CH=CR CHO
to a CH3-CO- group which subsequently OH
forms iodoform. (aldol) (a, b - unsaturated aldehyde)
For example :
Try this...
(i)
Write chemical reactions taking H
place when propan-2-ol is treated α dil. NaOH
H C C H + H CH2 C H
with iodine and sodium hydroxide.
H O O
(Ethanal) (Ethanal)
272
b a ∆ b a
H3C CH CH CHO-H O H3C CH CH CHO Use your brain power
2
O H H O H3C O
Self
H3C- C-H condensation
H3C - C = C - C - H + H3C - CH2 - CH = C - C - H
(Ethanal) i. dil.NaOH (Crotonaldehyde / But-2-enal) (2-Methylpent-2-enal)
+ ii. heat
O H3C O H H O
H3C-CH2-C-H Cross H3C - CH = C - C- H + H3C - CH2 - C = C - C - H
condensation
(Propanal) (2-Methylbut-2-enal) (Pent-2-enal)
274
For example : Wolf-Kishner reduction is used to
CH3 synthesize straight chain alkyl substituted
Zn-Hg, conc. HCl benzenes which is not possible by Friedel-
(i) H3C C O + 4[H] ∆
Crafts alkylation reaction.
(Acetone) CH3
12.8.4 Electrophilic substitution reactions:
H3C C H2 + H2O Aromatic aldehydes and ketones undergo
(propane) electrophilic substitution reactions such as
Zn-Hg, conc. HCl
nitration ,sulfonation and halogenation. The
(ii) CH3 CH2 CHO + 4[H] ∆ aldehydic ( -CHO) and ketonic (>C=O)
(Propanal) groups are electron-withdrawing by inductive
CH3 CH2 CH3 + H2O as well as resonance effects. They deactivate
(Propane) the benzene ring at ortho- and para- positions.
This results in the formation of meta-product.
Wolf-Kishner reduction : For example ,
H2N-NH2 CHO
C O -H2O
C N NH2 conc. H2SO4
+ HO NO2
(Carbonyl group (conc. HNO3)
(Hydrazone)
in aldehydes and (Benzaldehyde)
ketones)
CHO
KOH, HO-CH2-CH2-OH + H2O
∆ CH2 + N2
(Methylene group)
NO2
For example : (m-Nitrobenzaldehyde)
12.9 Chemical properties of carboxylic
H2N-NH2
(i) C2H5 CHO acids :
-H2O C2H5 CH N NH2
12.9.1 Acidic character of carboxylic acids:
(Propanal) (Hydrazone)
The carboxyl group (- COOH) imparts acidic
KOH, HO-CH2-CH2-OH
character to carboxylic acids. A carboxyl
CH3 CH2 CH3 + N2 group is made of -OH group bonded to a
∆
(Propane) carbonyl group. In aqueous solution the H
atom in OH of carboxyl group dissociates as
proton and carboxylate ion is formed as the
C2H5 conjugate base,
H2N-NH2
(ii) C O R - COOH + H2O R - COO + H3O⊕
-H2O
(carboxylate ion)
(Ethyl phenyl ketone) Carboxylate ion is resonance stabilized by
C2H5 two equivalent resonance structures as shown
KOH, HO-CH2-CH2-OH below.
C N-NH2 ∆
(Hydrazone) O O
C2H5 O
R C R C R C
CH2 + N2 O O O
(n-Propyl benzene) (i) (ii) resonance
hybrid
275
Carboxylate ion has two resonance structures Table 12.8 : pKa values of haloacetic acids
(i) and (ii) and both of them are equivalent to
Acid pKa Acid
each other (Refer to Std. XI Chemistry Textbook
strength
Chapter 14). This gives good resonance
F-CH2-COOH 2.56
stabilization to carboxylate ion, which in turn
Cl-CH2-COOH 2.86
decreases
gives acidic character to carboxylic acids.
Br-CH2-COOH 2.90
Can you recall ?
I-CH2-COOH 3.18
What is the numerical parameter
to express acid strength? CH3-COOH 4.76
276
Try this... ring exerts electron withdrawing inductive
effect (-I effect) which stabilizes the conjugate
Compare the following two base and increases the acid strength of
conjugate bases and answer. aromatic acids.
O O Table 12.9 illustrates that more the number of
CH3 C Cl - CH2 C electron withdrawing substituents higher is the
O O acid strength.
(a) (b)
Try this...
• Indicate the inuctive effects of CH3 -
Arrange the following acids in
group in (a) and Cl - group in (b) by
order of their decreasing acidity.
putting arrowheads in the middle of
appropriate covalent bonds. CH3-CH-CH2-COOH, CCl3-CH2-COOH,
• Which species is stabilized by Cl
CH3COOH
inductive effect, (a) or (b) ?
• Which species is destabilized by Electron–withdrawing groups like -Cl, -CN,
inductive effect, (a) or (b) ? and -NO2 increase the acidity of substituted
benzoic acids while electron –donating group
like –CH3, - OH , - OCH3 and -NH2 decrease
Use your brain power the acidity of substituted benzoic acids .
• Compare the pKa values and COOH COOH COOH
arrange the following in an
increasing order of acid strength.
Cl3CCOOH, ClCH2COOH, CH3COOH,
Cl2CHCOOH
NO2 CH3
• Draw structures of conjugate bases
of monochloroacetic acid and (4-Nitrobenzoic (Benzoic acid) (4-Methylbenzoic
acid) (pKa = 4.2) acid)
dichloroacetic acid. Which one is more (pKa = 3.41) (pKa = 4.4)
stabilized by -I effect ?
Try this...
Acidity of aromatic carboxylic acids :
Benzoic acid is the simplest aromatic acid. Arrange the following carboxylic
From the pKa value of benzoic acid (4.2) we acids in order of increasing acidity.
understand that it is stronger than acetic acid m-Nitrobenzoic acid, Trichloroacetic acid,
(pKa 4.76). The sp2 hybrid carbon of aromatic benzoic acid, α-Chlorobutyric acid.
277
12.9.2 Laboratory tests for carboxyl 12.9.3 Formation of acyl chloride
(-COOH) group : The presence of -COOH Reaction with PCl3, PCl5, SOCl2 : Carboxylic
group in carboxylic acids is identified by the acids on heating with PCl3, PCl5, SOCl2 give
following tests: the corresponding acyl chlorides. Thionyl
a. Litmus test : (valid for water soluble chloride (SOCl2) is preferred because the
substances) byproducts formed are in gaseous state so they
Aqueous solution of Organic compound can easily escape from the reaction mixture.
containing –COOH group turns blue litmus In this reaction –OH group of –COOH is
red which indicates the presence of acidic replaced by –Cl .
functional group. (It may be noted that ∆
R COOH + SOCl2 R - COCl + SO2↑
aqueous solutions of water soluble phenols (Carboxylic acid) (acyl chloride)
also turn blue litmus red.) +HCl ↑
∆
b. Sodium bicarbonate test : 3 R COOH + PCl3 3 R - COCl + P(OH)3
∆
When sodium bicarbonate is added to an R COOH + PCl5 R - COCl + POCl3
organic compound containing –COOH + HCl
group, a brisk effervescence of carbon
dioxide gas is evolved. Water insoluble acid
goes in solution and gives precipitate on Use your brain power
acidification with conc.HCl. This indicates
Fill in the blanks and rewrite the
the presence of –COOH group.
-CO2
balanced equations.
R - COOH + NaHCO3(aq) -H2O ∆
(water insoluble)
• CH3COOH + thionyl chloride
HCl + +
R - COONa(aq) R - COOH↓
∆
+ NaCl(aq) • CH3-CH2-COOH +
+ + H3PO3
(Phenol does not evolve CO2 gas with
∆
sodium bicarbonate. Hence, carboxylic • C6H5-COOH + +
acid and phenol are distinguished by this phosphorous oxylchloride + HCl
test.) • CH3-COOH + phosphorous trichloride
∆
c. Ester test : One drop of concentrated +
NH3
sulfuric acid is added to a mixture of given • CH3-COOH ∆
278
Acyl chloride and sodium salt of acid
Do you know ? are prepared by reacting carboxylic acid
separately with thionyl chloride and sodium
hydroxide respectively.
COOH COONH4
+ 2NH3
COOH COONH4 SOCl2
Phthalic acid R COOH R COCl
O ∆
CONH2 C ⊕
∆ -NH3 R COOH NaOH R COONa
-2H2O NH
CONH2 C
O O
O
Phthalimide R C O C R + NaCl
(Anhydride)
b. Acid amides can also be prepared by
reacting acid chloride with ammonia. Can you recall ?
R COCl + NH3 R CONH2 + HCl Which molecule is eliminated in a
(Acyl chloride) (Acid amide) decarboxylation ?
12.9.5 Formation of acid anhydride :
12.9.6 Decarboxylation of carboxylic acids :
Can you tell ?
Sodium salts of carboxylic acids on heating
What is the term used for
with soda lime give hydrocarbons which
elimination of water molecule ?
contain one carbon atom less than the
Mono carboxylic acids on heating with carboxylic acid. For example,
⊕ CaO
strong dehydrating agent like P2O5 concentrated R COONa + NaOH R H + Na2CO3
∆
H2SO4 give acid anhydrides. The reaction is
reversible. Anhydrides are readily hydrolyzed
back to acids on reaction with water. ⊕ CaO
CH3 COONa + NaOH ∆ CH4 + Na2CO3
O O (Sodium acetate) (Methane)
R C R C
O H ∆ P2O5
+ O
+H2O
R C 12.9.7 Reduction of carboxylic acids :
R C O H
O Carboxylic acids are reduced to primary
O alcohols by powerful reducing agent like
(Carboxylic acid) (Acid anhydride) lithium aluminium hydride. Carboxylic acid
Better yield of acid anhydride is obtained can also be reduced by diborane (diborane
by heating sodium carboxylate with acyl does not reduce –COOR , -NO2 , -X).
chloride. (Note : Sodium borohydride (NaBH4 )does
⊕
R COONa + R COCl not reduce-COOH group).
(sodium carboxylate) (acyl chloride) dry
R COOH + LiAlH4 R CH2OH
ether
O O
∆ R C O C R + NaCl
(acid anhydride)
279
Exercises
280
ix. Arrange the following compounds in the 4. Answer the following
increasing order of their boiling points : i. Write a note on –
Formaldehyde, ethane, methyl alcohol. a. Cannizaro reaction
x. Acetic acid is prepared from methyl b. Stephen reaction.
magnesium bromide and dry ice
in presence of dry ether. Name the ii. What is the action of the following
compound which serves not only reagent reagents on toluene ?
but also as cooling agent in the reaction. a. Alkaline KMnO4 , dil. HCl and heat
3. Answer in brief. b. CrO2Cl2 in CS2
i. Observe the following equation of c.
Acetyl chloride in presence of
reaction of Tollens' reagent with anhydrous AlCl3.
aldehyde. How do we know that a redox
iii. Write the IUPAC names of the following
reaction has taken place. Explain.
structures :
∆
R CHO + 2 Ag(NH3)2+ + OH- a. O b. COOH
R COO- + 2 Ag + 4 NH3 + 2 H2O
COOH
ii. Formic acid is stronger than acetic acid.
Explain. iv.
Write reaction showing conversion
iii. What is the action of hydrazine on of p- bromoisopropyl benzene into
cyclopentanone in presence of ---. p-Isopropyl benzoic acid ( 3 steps).
KOH in ethylene glycol ? v.
Write reaction showing aldol
condensation of cyclohexanone.
iv.
Write reaction showing conversion
of Acetaldehyde into acetaldehyde
dimethyl acetal. Activity :
v. Aldehydes are more reactive toward Draw and complete the
nucleophilic addition reactions than following reaction scheme which
ketones. Explain. starts with acetaldehyde. In each empty
vi. Write reaction showing the action of the box, write the structural formula of
following reagent on propanenitrile – the organic compound that would be
formed.
a. Dilute NaOH
HCN reduction
b. Dilute HCl ? CH3CHO
vi. Arrange the following carboxylic acids dilute H2SO4, heat Tollens' reagents
with increasing order of their acidic
strength and justify your answer.
COOH
281
13 AMINES
Can you recall ? Use your brain power
Classify the following amines
• Write some examples of nitrogen as simple/mixed; 1°, 2°, 3° and
containing organic compounds. aliphatic or aromatic.
• What are the types of amines?
(C2H5)2NH, (CH3)3N, C2H5-NH-CH3,
CH3 NH-C6H5
Amines are nitrogen containing organic
compounds having basic character. Amines C6H5-NH2, CH3-CH- NH2, ,
are present in structure of many natural
compounds like proteins, vitamins, hormones N(CH3)2
CH3
and many plant products like nicotine.
CH3-C-NH2, ,
N
13.1 Classification of Amines : Amines are CH3
classified as primary (1°), secondary (2°)
and tertiary (3°) amines. Their structures are
obtained in simple way by replacing one, two Remember...
or three hydrogen atoms of NH3 molecule by
Other organic compopunds
alkyl/aryl groups (see Table 13.1).
like alkyl halides or alcohols are
Secondary and tertiary amines are further classified as 1°, 2°, 3° depending upon
classified as simple / symmetrical amines and the nature of the carbon atom to which
mixed / unsymmetrical amines. When all the functional group is attached where as
alkyl or aryl groups on nitrogen are same, it is amines are classified depending upon the
a simple amine. If these groups are different, number of alkyl or aryl groups directly
then the amine is a mixed amine. attached to the nitrogen atom. Thus,
Amines are also divided into two major isopropyl amine is 10 amine, but isopropyl
classes, namely, aliphatic and aromatic amines alcohol is 20 alcohol.
on the basis of nature of the groups attached to
the nitrogen atom.
Table 13.1 Types of amines
282
13.2 Nomenclature of Amines : 13.3 Preparation of Amines :
13.2.1 Common names : Common names 13.3.1 : By ammonolysis of alkyl halides :
of aliphatic amines are given by writing the When alkyl halide is heated with alcoholic
name of alkyl group followed by suffix-amine, solution of excess ammonia it undergoes
that is, ‘alkyl amine’. In the case of mixed nucleophilic substitution reaction in which the
amines, the names of alkyl groups are written halogen atom is replaced by an amino (-NH2)
in alphabetical order. If two or three identical group to form primary amine. This process of
alkyl groups are attached to nitrogen atom, the breaking of C-X bond by ammonia is known
prefix ‘di-’ or ‘tri-’ is added before the name of as ammonolysis. The reaction is also known
alkyl group. The parent arylamine, C6H5-NH2, as alkylation of ammonia. The reaction is
is named as aniline. Other aromatic amines carried out in a sealed tube at 373 K. It may be
are named as derivatives of aniline (see Table noted that the primary amine obtained in the
13.2). 1st step is stronger nucleophile than ammonia.
13.2.2 IUPAC names : In IUPAC system, Hence, it further reacts with alkyl halide to
primary amines are named by replacing form secondary and tertiary amines and finally
the ending ‘e’ of the parent alkane by suffix quaternary ammonium salt if NH3 is not used
-amine (alkanamine). A locant indicating the in large excess.
position of amino group is added before the R-X +NH3(alc). ∆ R-NH2
suffix amine. When two or more amino groups (excess) 10 amine
are present, the prefix ‘di-’, ‘tri-’ etc. are used
with proper locant. In this case the ending ‘e’ The order of reactivity of alkyl halides
of parent alkane is retained. with ammonia is R-I > R-Br > R-Cl.
Try this...
283
Table 13.2 : Common and IUPAC names of some alkyl and arylamines
Amines Common names IUPAC names
a. Primary amines :
CH3-NH2 Methylamine Methanamine
CH3-CH2-CH2-NH2 n-Propylamine Propan-1-amine
CH3-CH-CH3
Isopropylamine Propan-2-amine
NH2
H2N-CH2-CH2-NH2 Ethylenediamine Ethane-1, 2-diamine
CH2=CH-CH2-NH2 Allylamine Prop-2-en-1-amine
NH2
Aniline/ Phenylamine Aniline or Benzenamine
CH2-NH2
Benzylamine Phenylmethanamine
Br 4-Bromoaniline or
p-Bromoaniline
H 2N 4-Bromobenzenamine
b. Secondary Amines
CH3-NH-CH3 Dimethylamine N-methylmethanamine
CH3-CH2-NH-CH3 Ethylmethylamine N-methylethanamine
NH-CH3 N-methylaniline or
Methylphenylamine
N-methylbenzenamine
C6H5-NH-C6H5 Diphenylamine N-Phenylbenzenamine
c. Tertiary Amines
CH3-N-CH3
Trimethylamine N, N-Dimethylmethanamine
CH3
C2H5-N-CH3
Ethyldimethylamine N, N-Dimethylethanamine
CH3
CH3-N-C3H7 N-Ethyl-N-methyl propan-1-
Ethylmethyln-propylamine
C2H5 amine
CH3-CH-CH3 N-Ethyl-N-methyl
Ethylmethylisopropylamine
C2H5-N-CH3 propan-2-amine
N-CH3
CH3 N, N-Dimethylaniline N, N-Dimethylbenzenamine
284
Do you know ? Solution : Methyl bromide can be converted
into ethyl amine in two stage reaction
When tert-butyl bromide sequence as shown below.
is treated with alcoholic NH3,
isobutylene is formed. This is the result CH3-Br + KCN CH3-CN + KBr
of elimination reaction preferred over CH3-CN
Na/C2H5OH
CH3-CH2-NH2
(reduction)
nucleophilic substitution through the stable
tertiary butyl carbocation intermediate. The starting compound methyl bromide
contains one carbon atom while the product
CH3 CH3
-Br ethylamine contains two carbon atoms.
H3C-C-CH3 NH (alc) H3C-C-CH3
3 ⊕ A reaction in which number of carbons
Br increases involves a step up reaction. The
(tert-Butyl bromide) -H⊕
overall conversion of methyl bromide into
CH2 ethyl amine is a step up conversion.
H3C-C-CH3
(isobutylene)
Use your brain power
13.3.2 Reduction of nitrocompounds : Use your brain power:
Aliphatic and aromatic nitrocompounds Identify ‘A’ and ‘B’ in the following
can be reduced to primary amines by using conversions.
metal-acid mixture (Sn/HCl or Fe/HCl or Zn/ Na/C2H5OH
HCl) or catalytic hydrogenation (H2/Ni or Pt (i) CH3-I KCN A B
AgNO2
or Pd) or LiAlH4 in ether. (ii) CH3-Br A Sn/HCl B
R-NO2 + 6[H] Sn/HCl R-NH2 + 2H2O Na/C2H5OH
(iii) C2H5-I AgCN A B
13.3.3 Reduction of alkyl cyanide
(alkanenitriles) : 13.3.4 By reduction of amides :
Primary amines having same number of
Can you recall ?
carbon atoms can be obtained by the reduction
• How is alkyl halide converted of amides by LiAlH4 in ether or by Na/C2H5OH.
into alkyl cyanide ?
O
LiAlH4 / ether
Primary amines can be obtained by the CH3-C-NH2 + 4[H] CH3-CH2-NH2
or Na/C2H5OH
reduction of alkyl cyanide with sodium and (Acetamide) (Ethylamine)
ethanol. This is known as Mendius reduction. 13.3.5 Gabriel phthalimide synthesis : This
The reaction can also be brought about by method is used for the synthesis of primary
lithium aluminium hydride. amine. It involves the following three stages.
R-C N + 4[H] Na/C H OH
or LiAlH
2R-CH2-NH2
5
i. Formation of potassium salt of phthalimide
4
285
O O O
i. C C The overall result is removal of the -C-
⊕
N-H alc.KOH
-H O NK group from the amide. As the product contains
2
C C one carbon atom less than the original amide.
O O It is a step down reaction.
(Phthalimide) (Potassium salt of
phthalimide) Use your brain power
O O
ii. C ⊕
C Write the chemical equations for
NK
R-X N-R
-KX the following conversions :
C C
O O i. Methyl chloride to ethylamine.
(N-Alkylphthalimide)
ii. Benzamide to aniline.
O O
iii. iii. 1, 4 - Dichlorobutane to hexane - 1, 6 -
C C-ONa
N-R NaOH (aq) diamine.
⊕
C C-ONa iv. Benzamide to benzylamine.
O O
(sodium phthalate) 13.4 Physical properties of Amines :
13.4.1 Intermolecular forces, boiling points
+ R-NH2
and solubility : The N-H bond in amines
(1° amine)
is polar because the electronegativities of
Aromatic amines cannot be prepared
Nitrogen (3.0) and Hydrogen (2.1) are different.
by this method because aryl halides do not
Due to the polar nature of N-H bond primary
undergo nucleophilic substitution with the
and secondary amines have intermolecular
anion formed by phthalimide.
hydrogen bonding. The intermolecular
13.3.6 By Hofmann degradation (Hofmann hydrogen bonding is to greater extent in
rearrangement / Hofmann bromamide primary amine than in secondary amines,
degradation / Hofmann hypobromite because primary amines have two hydrogen
degradation ) : atoms bonded to nitrogen for hydrogen bond
This is a good laboratory method for the formation (see Fig 13.1).
conversion of an amide into primary amine
δ⊕ δ⊕
containing one carbon less. The reaction is H δ⊕ R δ⊕ H
brought about by warming the amide with R-N-H δ N-H δ N-R
bromine and concentrated aqueous KOH Hδ⊕ H
solution. δ
Hydrogen bond H-N-R
O H
∆
R-C-NH2 + Br2 + 4KOH(aq) Fig. 13.1 : Intermolecular hydrogen bonding in
(Amide) primary amines
R-NH2 + 2KBr+ K2CO3 + 2H2O
(1° amine) Tertiary amines do not have intermolecular
hydrogen bonding as there is no hydrogen
atom on nitrogen of tertiary amine. But due
For example :
to polar N-C bonds, tertiary amines are polar
O molecules, and have intermolecular dipole-
∆ dipole attractive forces. Thus intermolecular
CH3-C-NH2 + Br2 + 4KOH (aq) CH3-NH2
(Acetamide) (methylamine) forces of attraction are strongest in primary
+2KBr + K2CO3 + 2H2O amines and weakest in tertiary amines.
286
The observed order of boiling points of Table 13.3 Boiling points of alkane, alcohol
isomeric amines is : primary amine > secondary and amines of similar molar masses
amine > tertiary amine (see Table 13.3 serial
Sr. Molar
numbers 1, 2, 3). It can be explained on the Compound B.P. (K)
No mass
basis of the intermolecular forces in them.
1 n-C4H9NH2 73 350.8
The lower aliphatic amines are gases
with fishy odour, middle members are liquids
2 (C2H5)2NH 73 329.3
and higher members are solids under ordinary
temperature and pressure.
3 C2H5N(CH3)2 73 310.5
Aniline and other arylamines are usually
colourless liquids but get coloured as they are 4 C2H5COOH 74 414.4
easily oxidised by air.
Due to their ability to form hydrogen 5 n-C4H9OH 74 390.3
bond with water molecule, lower aliphatic
amines are soluble in water (see Fig. 13.2). 6 (CH3)3C-NH2 73 318.15
Solubility of amines decreases with increase
in molar mass of amines due to increase in size 7 C2H5CH(CH3)2 72 300.8
of hydrophobic alkyl group. Aromatic amines
13.5 Basicity of Amines
and higher aliphatic amines are insoluble in
water. The basic nature of amines is due to
presence of a lone pair of electrons on the
Hydrogen bond nitrogen atom. In terms of Lewis theory, amines
δ δ⊕ R δ δ⊕ δ are bases because they can share a lone pair of
H-O H-N H-O electrons on ‘N’ atom with an electron deficient
H H H species. For example : Trimethylamine shares
its lone pair of electrons with the electron
Fig. 13.2 : Hydrogen bonding between deficient boron trifluoride.
amine and water molecule
⊕
Since N-H bonds in amines are less polar Me3N + BF3 Me3N-BF3
than O-H bond in alcohol, water solubilities of
alcohols, amines and alkanes of comparable Basic strength of amines is expressed
molar mass in water are in the decreasing quantitatively as Kb or pKb value. In terms of
order: alcohols > amines > alkanes. Lowry-Bronsted theory, the basic nature of
The order of boiling points of alkanes, amines is explained by writing the following
amines, alcohols and carboxylic acid of equilibrium.
comparable molar mass is as follows : ⊕
N + H2O N-H + OH ........... (13.1)
Alkanes < Amines < Alcohols < Carboxylic (amine) (conjugate acid)
acid. (Table 13.3, serial number 4, 5, 6, 7)
In this equilibrium amine accepts H⊕,
Use your brain power hence an amine is a Lowry-Bronsted base.
Arrange the following : For stronger base, this equilibrium shifts
a. In decreasing order of the b.p. towards right, thereby the Kb value is larger
C2H5-OH, C2H5-NH2, (CH3)2NH and pKb value is smaller and vice versa (refer
b. In increasing order of solubility in water: to Chapter 3). Table 13.4 gives pKb values of
C2H5-NH2, C3H7-NH2, C6H5-NH2 some amines.
287
Table 13.4 : pKb Values of some amines in aqueous medium
NH3 > R-NH2 > R2NH < R3N Basicity of amines is related to the structural
Order of basic strength : effects which influence stabilization of various
species. Greater is the stabilization of the
NH3 < R-NH2 < R2NH > R3N (13.2) protonated amine, that is, the conjugate acid,
Thus as per the observed pKb values of the greater is the basicity of the amine.
aliphatic amines, secondary amines are the
strongest bases. Basic strength increases as Use your brain power
we move from NH3 to R-NH2 and from R-NH2 Refer to pKb values from Table
to R2NH, but basic strength decreases as we 13.4 and answer which compound
move from R2NH to R3N (Table 13.4). from the following pairs is stronger base ?
The basic strength and the corresponding i. CH3-NH2 and (CH3)2NH
pKb value depends upon the position of the
ii. (C2H5)2NH and (C2H5)3N
equilibrium shown in Eq. (13.1). Greater the
stabilization of the conjugate acid more on iii. NH3 and (CH3)2CH-NH2
right side the equilibrium will lie and stronger
will be the base and smaller will be its pKb
value.
288
a. Influence of +I effect on stabilization of H H
O R⊕
conjugate acids of aliphatic amines and NH3
can be represented as shown below : H⊕ R-N-R
R-N-R , H
H H H H H
⊕ ⊕ ⊕ ⊕ O
HNH R NH R N R R N R O H H
H H H H H
R
An alkyl group exerts electron releasing The solvent water stabilizes the conjugate
inductive effect (+I) which stabilizes positive acid by hydrogen bonding through the ‘H’
charge on atom bonded to it. As we move bonded to the ‘N⊕’. The number of ‘H’ atoms
from conjugate acid of ammonia (NH4⊕) to bonded to the ‘N⊕’ decreaes from 4 in NH4⊕
that of tertiary amine (R3NH⊕), the number of to 1 in R3NH⊕. As a result NH4⊕ is best
alkyl groups (R) bonded to Nitrogen goes on stabilized by solvation while the stabilization
increasing steadily. This results in increasing by solvation is very poor in R3NH⊕.
stabilization of the conjugate acids and
c. Combined influence of +I effect and
thereby an increasing order of basic strength
solvation on stabilization if conjugate acids
is expected.
of aliphatic amines decides the observed basic
Order of stabilization : strength and pKb value. These two influencing
⊕ ⊕ ⊕ ⊕
NH4 < R-NH3 < R2NH2 < R3N-H factors operate in opposite directions.
Expected order of basic strength : increases
Solvation
NH3 < R-NH2 < R2NH < R3N ⊕ ⊕ ⊕ ⊕
NH4 R-NH3 R2NH R3NH
The expected order of basic strength on the
basis of +I effect differs from the observed order +I effect
increases
(Eq.13.2). It is seen that the observed increasing
basic strength from ammonia to amine and The net results is that as we move from
from 1° amine to 2° amine is explained on the NH3 to RNH2 to R2NH, the basic strength
basis of increased stabilization of conjugate increases due to better stabilization of the
acids by +I effect of increased number of corresponding conjugate acids. But 3° amine
alkyl (R) groups. However, decreased basic is weaker base than 2° amine because the
strength of 3° amine implies that the conjugate stabilization of conjugate acid of 3° amine by
acid of 3° amine is less stabilized even solvation is very poor.
though
⊕
the +I effect of three alkyl groups in 13.5.2 Basicity of arylamines :
R3NH is expected to be large. This is suggestive
of existance of another influencing factor in Can you recall ?
stabilization of conjugate acids of amines. Refer to Table 13.4 and answer :
b. Influence of solvation by water on
Are the pKb values of aniline,
stabilization of conjugate acids of aliphatic
N-methylaniline and N, N-dimethylaniline
amines and ammonia can be represented as
larger or smaller than those of NH3 and
shown below :
CH3NH2 ?
H H H H
O O Which one of the two, aniline or CH3NH2, is
H H⊕ stronger base ?
H H H
O H-N-H ⊕
O R-N-H O
H H , H,
H H
O O
H H H H
289
From the pKb values we understand that As a result the equilibrium (13.3) is
arylamines in general are weaker bases than shifted towards left side. This makes aniline
ammonia and aliphatic amines. Strength (and also other arylamines) weaker bases than
of arylamines is explained in accordance aliphatic amines and ammonia.
with Lowery Bronsted theory by writing the
following equilibrium (Eq. 13.3) For aniline Use your brain power
(similar to eq. 13.1). Arrange the following amines
⊕ in decreasing order of their basic
NH2 NH3
strength -
+ H 2O + OH ....... (13.3) NH3, CH3-NH2, (CH3)2NH, C6H5NH2.
290
The reaction involved in this test will be 13.6.3 Hofmann Elimination :
discussed in section 13.6.5. When tetraalkylammonium halide is
13.6.2: Alkylation of amines : Hofmann’s hetated with moist silver oxide, it gives
exhaustive alkylation : When a primary amine quanternary ammonium hydroxide which is
is heated with excess of primary alkyl halide it a deliquescent crystalline solid, and strongly
gives a mixture of secondary amine, tertiary basic like NaOH or KOH. Quaternary
amine along with tetraalkylammonium halide ammonium hydroxides on strong heating
(also refer to sec. 13.3.1). undergo b-elimination to give an alkene, the
reaction is called Hofmann elimination. The
⊕
R-NH2 R-X
R2NH R-X
R3N R-X
R4NX least substituted alkene is obtained as major
-HX -HX -HX
(1° Amine) (2° Amine) (3° Amine) (Tetraalkyl product (in contrast to Saytzeff elimination)
ammonium For example :
halide)
⊕
If excess of alkyl halide is used tetraalkyl CH3CH2CH2-N(CH2CH3)3 I + AgOH
ammonium halide is obtained as major (N,N,N-triethylpropylammonium iodide)
product. The reaction is known as exhaustive moist
∆ Ag2O
alkylation of amines. a b
The tetraalkylammonium halides are CH2-CH3
b' a' ⊕
called quaternary ammonium salts which are CH3-CH2-CH2-N-CH2-CH3 OH
crystalline solids. They are the derivatives CH2-CH3
of ammoium salts in which all the four (N,N,N-triethylpropanammonium hydroxide)
hydrogen
⊕
atoms attached to nitrogen in ∆ -H2O
NH4 are replaced by four alkyl groups (same
or different). Primary, secondary and tertiary CH2= CH2 + CH3CH2CH2-N-CH2CH3
amines consume three, two and one moles of (ethene) CH2CH3
alkyl halide respectively to get converted into (N,N-diethylpropylamine)
quaternary ammonium salt. The reaction is
carried out in presence of mild base NaHCO3,
to neutralize the large quantity of HX formed. Use your brain power
If the alkyl halide is methyl iodide, the reaction Complete the following reaction:
is called exhaustive methylation of amines.
⊕ Moist ∆
CH3-CH2-N(CH3)3I Ag O ? 2
292
Aryl diazonium salts are resonance stabilized Reaction with fluoroboric acid :
and useful as versatile intermidiates to obtain Arene diazonium salt on reaction with
a variety of products. fluoroboric acid gives precipitate of diazonium
⊕ ⊕ ⊕ ⊕
fluoroborate which on heating decomposes to
N N N=N N=N N=N
yield fluoroarene. On the other hand when
⊕ ⊕ heated with aqueous sodium nitrite in presence
of copper it gives nitroarene.
⊕ ⊕ ⊕
⊕ HBF4
N N Ar-N2Cl Ar-N2BF4
∆ ∆,Cu aq. NaNO2
293
Azo coupling with b-naphthol in NaOH O
is used as a confirmatory test for primary S-Cl + H-N-C2H5
aromatic amines. Benzenediazonium chloride O C2H5
reacts with aniline in mild alkaline medium to (2° amine)
give p-aminoazo-benzene (yellow dye.)
O
⊕
OH
S-N-C2H5 + HCl
N NCl + NH2 O C2H5
(Benzenediazonium (Aniline) (N, N-diethylbenzene sulfonamide)
chloride)
N,N-diethylbenzenesulfonamide does not
N=N NH2 + HCl contain any H-atom attached to nitrogen atom.
Hence it is not acidic and does not dissolve in
(p-Aminoazobenzene)
alkali.
Do you know ?
Can you tell ?
The acid-base indicator methyl
• Do tertiary amines have ‘H’
orange is an azo dye.
bonded to ‘N’ ?
⊕
(CH3)N N=N SO3Na • Why do tertiary amines not react with
benzene sulfonyl chloride ?
13.8 Reaction with arenesulfonyl chloride :
(Hinsberg’s test) : Benzenesulfonyl Use your brain power
chloride (C6H5SO2Cl) is known as Hinsberg’s
reagent. How will you distinguish between
methylamine, dimethylamine and
a. Ethyl amine (primary amine) reacts with trimethylamine by Hinsberg’s test ?
benzenesulfonyl chloride to form N-ethyl
benzenesulfonyl amide.
13.9 Electrophilic aromatic substitution in
O
aromatic amines : Amino group is ortho and
S-Cl + H-N-C2H5
para directing and powerful ring activating
O H
(Benzenesulfonyl (1° amine)
group. As a result aromtic amines readily
chloride) undergo electrophilic substitution reactions.
O
a. Bromination : Aniline reacts with bromine
S-N-C2H5 + HCl
OH water at room temperature to give a white
(N-Ethylbenzene sulfonamide)
precipitate of 2,4,6- tribromoaniline.
(Soluble in alkali)
NH2 NH2
The hydrogen attached to nitrogen in Br Br
Br2/H2O
sulfonamide ethanamine (a primary amine) is + 3Br2 + 3HBr
strongly acidic. Hence it is soluble in alkali.
(Aniline) Br
b. Diethyl amine reacts with benzene-sulfonyl (2,4,6-tribromoaniline)
chloride to give N, N- diethyl benzene
sulfonamide.
294
NH2 NH2 NH2
Problem 13.1 : Write the scheme for
preparation of p-bromoaniline from aniline. Conc. HNO3 + Conc H2SO4
+ +
288 K
Justify your answer.
NO2
Solution : NH2- group in aniline is highly (Aniline) NO2
(51%) (47%)
ring activating and o-/p- directing due to (p-nitroaniline) (m-nitroaniline)
involvement of the lone pair of electrons NH2
on ‘N’ in resonace with the ring. As NO2
a result, on reaction with Br2 it gives
2,4,6-tribromoniline. To get a monobromo
(2%)
product, it is necessary to decrease the (o-nitroaniline)
ring activating effect of -NH2 group. This
is done by acetylation of aniline. The lone
Internet my friend
pair of ‘N’ in acetanilide is also involved in
resonance in the acetyl group. To that extent Search the pKa or pKb values
ring activation decreases. of ortho, meta and para nitroaniline
on internet and arrange them in
O O
⊕ increasing order of their basic strength.
NH-C-CH3 NH=C-CH3
However, to get p-nitroaniline as major
Hence, acetanilide on bromination gives a product, -NH2 group is first protected by
monobromo product p-bromoacetanilide. acetylation, nitration is carried out and then
After monobromination the original -NH2 amide is hydrolysed.
group is regenerated. The protection of O
-NH2 group in the form of acetyl group is NH2 NH-C-CH3
removed by acid catalyzed hydrolysis to get (CH3CO)2O Conc. HNO3 + Conc H2SO4
p-bromoaniline, as shown in the following Pyridine 288 K
scheme. O
O (Aniline) (Acetanilide)
NH-C-CH3
NH2 NH-C-CH3
O
CH3-C-Cl Br2
base (Acetic acid
solvent)
(Aniline) (acetanilide) NO2
O (p-nitroaetanilide)
NH-C-CH3 NH2 H⊕ or OH
hydrolysis
H⊕
NH2
Br Br
(p-bromoacetanilide) (p-bromoaniline)
NO2
b. Nitration : Direct nitration of aniline yeilds (p-nitroaniline)
a mixture of ortho, meta and para nitroanilines.
c. Sulfonation : Aniline reacts with
In acidic medium -NH2 group is protonated concerntrated sulfuric acid to form anilinium
⊕
to -NH3 group which is meta-directing and hydrogen sulfate which on heating with sulfuric
deactivating. Hence considerable amount of acid at 453-473K produces p-aminobenzene
m-nitroaniline is obtained. sulfonic acid (sulfanilic acid) as major product.
295
⊕ Sulfanilic acid exists as a salt; called
NH2 NH3HSO4 NH2
dipolar ion or zwitter ion. It is produced by
H2SO4 453-473 K the reaction between an acidic group and a
basic group present in the same molecule.
(Aniline) (Anilinium SO3H
hydrogensulfate) (Sulfanilic acid)
Use your brain power
⊕
NH3 • Can aniline react with a Lewis
acid ?
• Why aniline does not undergo Friedel
Craft’s reaction using aluminium chloride ?
SO3
(Zwitter ion)
Exercises
1. Choose the most correct option.
i. The hybridisation of nitrogen in primary vii. Which one of the following compounds
amine is ............ does not react with acetyl chloride ?
a. sp b. sp2 c. sp3 d. sp3d a. CH3-CH2-NH2 b. (CH3-CH2)2NH
ii. Isobutylamine is an example of ............ c. (CH3-CH2)3N d. C6H5-NH2
a. 2° amine b. 3° amine viii.
Which of the following compounds
c. 1° amine will dissolve in aqueous NaOH after
d. quaternary ammonium salt. undergoing reaction with Hinsberg
iii. Which one of the following compounds reagent ?
has the highest boiling point ? a. Ethylamine b. Triethylamine
a. n-Butylamine b. sec-Butylamine c. Trimethylamine d. Diethylamine
c. isobutylamine d. tert-Butylamine ix. Identify ‘B’ in the following reactions
iv. Which of the following has the highest CH3-C N Na/C H OH A NaNO /dilHCl B
2 5 2
296
iii. Which amide does produce ethanamine 4. Answer the following.
by Hofmann bromamide degradation i. Write the IUPAC names of the following
reaction? amines :
iv. Write the order of basicity of aliphatic a. CH3-CH2-N-CH2-CH2-CH3
alkylamine in gaseous phase. CH3
v. Why are primary aliphatic amines
CH3
stronger bases than ammonia ? b. CH3-C-CH2-CH2-NH2
vi. Predict the product of the following
CH3
reaction.
Nitrobenzene Sn/Conc. HCl ? c. CH3-CH-NH-CH2-CH3
vii. Write the IUPAC name of benzylamine. CH3
viii. Arrange the following amines in an ii. What are amines ? How are they
increasing order of boiling points. classified ?
n-propylamine, ethylmethyl amine, iii. Write IUPAC names of the following
trimethylamine. amines.
ix. Write the balanced chemical equations for a. H2N-(CH2)6-NH2
the action of dil H2SO4 on diethylamine.
NH2 NH2
x. Arrange the following amines in the CH3 c.
b.
increasing order of their pKb values.
Aniline, Cyclohexylamine, 4-Nitroaniline CH3 NH2
3. Answer the following iv. Write reactions to prepare ethanamine
i. Identify A and B in the following reactions. from
C6H5CH2Br alco. KCN
A Na/ethanol B. a. Acetonitrile b. Nitroethane
ii. Explain the basic nature of amines with c. Propionamide
suitable example. v. What is the action of acetic anhydride
iii. What is diazotisation ? Write diazotisation on ethylamine, diethylamine and
reaction of aniline. triethylamine ?
iv. Write reaction to convert acetic acid into vii. Distinguish between ethylamine,
methylamine. diethylamine and triethylamine by using
v. Write a short note on coupling reactions. Hinsberg’s reagent ?
vi. Explain Gabriel phthalimide synthesis. viii.
Write reactions to bring about the
following conversions :
vii. Explain carbylamine reaction with
suitable examples. a. Aniline into p-nitroaniline
viii. Write reaction to convert (i) methanamine b. Aniline into sulphanilic acid ?
into ethanamine (ii) Aniline into
p-bromoaniline. Activity :
ix. Complete the following reactions : • Prepare a chart of azodyes,
a. C6H5N2⊕Cl + C2H5OH colours and its application.
b. C6H5NH2 + Br2(aq) ? • Prepare a list of names and structures
x. Explain Ammonolysis of alkyl halides. of N-containing ingredients of diet.
xi. Write reaction to convert ethylamine into
methylamine.
297
14. BIOMOLECULES
Can you recall ? Try this...
• What are the constituents of Observe the following
balanced diet ? structural formulae carefully and
• What are the products of digestion of answer the questions.
carbohydrates? CHO CH2OH CHO
• Which constituent of diet is useful for (CHOH)4 CO (CHOH)3
building muscles? CH OH (CHOH)3 CH2OH
2 (ribose)
• Which constituent of diet is a source (glucose) CH2OH
(fructose)
of high energy?
• What is the genetic material of 1. How many OH groups are present in
organisms? glucose, fructose and ribose respectively?
2. Which other functional groups are
14.1 Introduction : Principal molecules of present in these three compounds?
the living world : Bodies of living organisms
contain large number of different molecules Greek word for sugar is sakkharon. Hence
which constitute their structure. They are carbohydrates are also called saccharides.
also part of various physiological processes Origin of the term carbohydrate lies in the
taking place in them. Primary structural finding that molecular formulae of many of
materials of organisms are proteins and them can be expressed as Cx(H2O)y(hydrates
cellulose. By means of the unique process of of carbon). For example: glucose (C6H12O6 Or
photosynthesis plants produce carbohydrates. C6(H2O)6, sucrose (C12H22O11 or C12(H2O)11),
Plants utilize the minerals absorbed by their starch [(C6H10O5)n or [C6(H2O)5]n].
roots to produce proteins. Lipids are the main 14.2.1 Classification of carbohydrates :
ingredient of vegetable oils and milk fats.
Nucleic acids constitute the genetic material Carbohydrates are clssified into
of organisms. three broad groups in accordance with
their behaviour on hydrolysis. These are
In this chapter we are going to study monosaccharides, oligosaccharides and
some aspects of three principal biomolecules, polysaccharides (Fig. 14.1).
namely, carbohydrates, proteins and nucleic
acids. Monosaccharides do not hydrolyse
further into smaller units of polyhydroxy
14.2 Carbohydrates : From the simple aldehydes or ketones. Oligosaccharides
chemical reactions of many carbohydrates it is on hydrolysis yield two to ten units of
understood that carbohydrates are polyhydroxy monosaccharides and accordingly they
aldehydes or ketones or compounds which are further classified as disaccharides,
give rise to such units on hydrolysis. Some trisaccharides and so on. Polysaccharides
carbohydrates like glucose, fructose are give very large number of monosaccharide
sweet in taste, and are called sugars. The units on complete hydrolysis.
most commonly used sugar is sucrose which
is obtained from sugarcane or sugar beet.
The sugar present in milk is called lactose.
298
Carbohydrates (Saccharides)
299
b. Prepartion of glucose from starch : 4. The carbonyl group in glucose is in the
form of aldehyde. This was inferred from the
Commercially glucose is obtained by
observation that glucose gets oxidised to a six
hydrolysis of starch by boiling it with dilute
carbon monocarboxylic acid called gluconic
sulfuric acid at 393K under 2 to 3 atm
acid on reaction with bromine water which is
pressure.
a mild oxidizing agent.
H⊕
(C6H10O5)n + n H2O n C6H12O6
393K, 2-3 atm CHO COOH
(O)
(Starch) (Glucose) (CHOH)4 (CHOH)4
CH2OH Br2 water
14.2.4 Structure and properties of glucose CH2OH
(Glucose) (Gluconic acid)
Glucose has an aldohexose structure.
In other words, glucose molecule contains
one aldehydic, that is, formyl group and the Problem 14.1 :
remaining five carbons carry one hydroxyl An alcoholic compound was found to have
group (-OH) each. The six carbons in glucose molcular mass of 90 u. It was acetylated.
form one straight chain. This aldohexose Molecular mass of the acetyl derivative
structure of glucose was established on the
was found to be 174 u. How many alcoholic
basis of the following chemical properties.
(-OH) groups must be present in the original
1. Molecular formula of glucose was found compound?
to be C6H12O6, on the basis of its elemental Solution : In acetylation reaction H atom
compostion and colligative properties. of an (-OH) group is replaced by an acetyl
2. The six carbons in glucose molecule form group (-COCH3). This results in an increase
a straight chain. This was inferred from in molcular mass by [(12+16+12+3×1)-1],
the following observation : Glucose gives that as, 42 u.
n-hexane on prolonged heating with HI. In the given alcohol,
CHO - (CHOH)4 - CH2OH increase in molecular mass = 174 u - 90 u
(Glucose) = 84 u
HI, ∆ 84 u
CH3 - (CH2)4 - CH3 ∴ Number of -OH groups = =2
(n-Hexane) 42 u
300
CHO CHO O 14.2.5 Optical isomerism in glucose :
(CHOH)4 Acetic (CH-O-C-CH3)4 Structural formula of glucose shows that it
CH2OH contains four chiral carbon atoms. You have
anhydride
CH -O-C-CH +CH3COOH
(Glucose) 2 3 learnt that every chiral carbon can have two
O distinct spatial arrangements of groups around
(glucose pentacetate) (acetic acid)
it (section 10.5.1). In other words, two distinct
6. Glucose contains one primary alcoholic configurations are possible for each of the four
(- CH2OH) group : This was inferred from chiral carbons of glucose. Stereostructure of
the following observation : Glucose and glucose is therefore one out of several possible
gluconic acid both on oxidation with dilute stereostructures of an aldohexose.
nitric acid give the same dicarboxylic acid
called saccharic acid.
Do you know ?
CHO COOH A structural formula containing
(CHOH)4 (CHOH)4 ‘n’ number of chiral carbon can
CH2OH CH2OH have maximum ‘2n’ numbers of
(Glucose) (O (Gluconic acid) stereostructures or optical isomers. An
) )
HN (O
O
3 HN
O3 aldohexose therefore, can exist as sixteen
(24 = 16) optical isomers, and glucose is
COOH
one of them.
(CHOH)4
COOH Can you recall ?
(Saccharic acid)
• What are the ways to
Use your brain power represent three dimensional
• Write structural formula of structure of an organic molecule?
glucose showing all the bonds • How is a Fischer projection
in the molecule. formula drawn?
• Number all the carbons in the molecules
giving number 1 to the (-CHO) carbon. On the basis of very elaborate chemical
evidence and measurement of optical activity
• Mark the chiral carbons in the molecule
of various chemicals involved, Emil Fischer,
with asterisk (*). a German Nobel laureate (1902), determined
• How many chiral carbons are present the configuration of the four chiral carbons
in glucose? (C-2, C-3, C-4, C-5) in glucose.
1 1 1
CHO COOH COOH
H *2 OH H 2
OH 2
H OH
HO *3 HO 3
H H HO 3
H
H * 4 4
OH H OH H 4
OH
* 5 5
H OH H OH 5
H OH
6 6
CH2OH CH2OH 6
COOH
(Glucose) (Gluconic acid)
(Saccharic acid)
I II III
Fig 14.2 : Fischer projection formulae of glucose, gluconic acid and saccharic acid
301
Figure 14.2 shows the Fisher projection
formulae of glucose (I), gluconic acid (II) and Do you know ?
saccharic acid (III).
Optical rotation is an
Glucose is an optically active compound experimentally measurable property
and has its specific rotation, [∝]20
D
, equal to of a compound. Configuration of chiral
+52.7 . Due to its dextrorotation glucose is
0
carbon, on the other hand, is difficult to
also called dextrose. The designations (+)- observe by simple experiment. In 1951
glucose or d-glucose imply the dextrorotatory X-ray crystallographic studies of (+) -
nature of glucose. D-glucose is another sodium rubidium tartarate established its
designation of glucose, which is more common. configuration as :
This designation indicates the configuration
COO
of glucose rather than the sign of its optical
rotation. H OH
D/L configuration system : The prefix D- or HO H
L- in the name of a compound indicates relative
configuration of a stereoisomer. It refers to COO
a particular enantiomer of glyceraldehyde. This was the first instance of determining
Glyceraldehyde has one chiral carbon(C-2) absolute configuration.
and exists as two enantiomers. These are
represented by two Fischer projection formulae A monosaccharide is assigned D/L
(see Fig. 14.3). configuration on the basis of the configuration
of the lowest chiral carbon in its Fischer
CHO CHO projection formula. Figure 14.4 illustrates the
D-configuration of (+) - glucose.
H * OH HO * H
CHO 1
CHO
2
CH2OH CH2OH H OH H OH
D-(+)- Glyceraldehyde L -(-)- Glyceraldehyde 3
HO H
IV V
4
Fig. 14.3 : Enantiomers of glyceraldehyde CH2OH H OH
IV 5
H OH
Conventionally (+)-glyceraldehyde is D-(+)-glyceraldehyde
6
represented by the Fischer projection formula CH2OH
having OH group attached to C-2 on right I
side (IV) and this configuration is denoted D-(+)-glucose
by symbol ‘D’. Similarly, configuration of Fig. 14.4 : Relative configuration of
(-) glyceraldehyde (V) is denoted by symbol (+) - glucose
‘L’. All the compounds which can be 14.2.6 Ring structure of glucose : On the
correlated by a series of chemical reactions basis of chemical evidence stereostructure
to (+) - glyceraldehyde are said to have of D-glucose was represented by the Fischer
D-configuration. The compounds which are projection formula I (Fig. 14.2 and Fig. 14.4).
chemically correlated to (-) - glyceraldehyde Glucose, however, was found to exhibit some
are said to have L- configuration. This is the more chemical properties which could not be
system of relative configuration of chiral explained on the basis of the structure I. It was
compounds. necessary to write another structure for glucose
which will explain all the properties. Ring
structure of glucose fulfils this requirement.
302
Glucose is found to have two cyclic structures
Problem 14.2 : Assign D/L configuration
(VI and VII) which are in equilibrium with
to the following monosaccharides.
each other through the open chain structure
i. CHO ii. CHO (I) in aqueous solution (Fig.14.5).
HO H HO H The ring structure of glucose is formed
H OH HO H by reaction between the formyl (-CHO) group
H and the alcoholic (-OH) group at C-5. Thus,
HO
CH2OH the ring structure is a hemiacetal structure
CH2OH
(Threose) (Ribose) (section 12.8.2 c). The two hemiacetal
structures (VI and VII) differ only in the
Solution :
configuration of C-1 (Fig. 14.5), the additional
D/L configuration is assigned to Fischer chiral centre resulting from ring closure.
projection formula of monosaccharide on The two ring structures are called ∝- and
the basis of the lowest chiral carbon. β- anomers of glucose and C-1 is called
i. 1 CHO Threose has two chiral the anomeric carbon. The ring of the cyclic
2 carbons C-2 and C-3. structure of glucose contains five carbons and
HO H
3 The given Fischer one oxygen. Thus, it is a six membered ring.
H OH projection formula of It is called pyranose structure, in analogy
with the six membered heterocyclic compound
CH2OH threose has -OH groups
4
at the lowest C-3 chiral pyran (Fig. 14.6). Hence glucose is also
(Threose)
carbon on right side. called glucopyranose. Haworth formula is
a better way than Fischer projection formula
∴ It is D-threose.
to represent structure of glucopyranose (Fig.
ii. 1 Ribose has three chiral 14.6). In the Haworth formula the pyranose
CHO
2 carbons C-2, C-3 and ring is considered to be in a perpendicular
HO H C-4. The given Fischer plane with respect to the plane of paper.
3
HO H projection formula of The carbons and oxygen in the ring are in
4
HO H ribose has -OH group the places as they appear in Fig. 14.6. The
5 CH OH at the lowest C-4 chiral lower side of the ring is called ∝-side and
2
(Ribose) carbon on left side. the upper side is the β-side. The ∝-anomer
∴ It is L-ribose has its anomeric hydroxyl (-OH) group (at
C-1) on the ∝-side, whereas the β-anomer has
1
CHO 1
1 HO H
H OH 2 2
2 H OH H OH
H OH 3 O
O HO H 3
3 HO H
HO H 4
H OH 4
4 H OH
H OH 5
H OH 5
5 H
H
6
CH2OH 6
6 CH2OH
CH2OH
(∝-D-(+) Glucose) β-D-(+) glucose
I VII
VI
Fig. 14.5 Ring structures of glucose: Fischer projection formulae
303
14.2.8 Representation of Fructose structure
Fructose (C6H12O6) is a laevorotatory
ketohexose. Fructose is also called laevulose
O 20
b- side b- side
6 1 6 1
HO- H2C O CH2 - OH HO- H C O OH
2
O 2 2
5 5
H H HO OH H H HO C H2 - OH
4 3 4 3
Furan
HO H α- side OH H a- side
α- D - (-) - Fructofuranose b - D - (-) - Fructofuranose
Fig. 14.7 : Representations of fructose structure
304
6
CH2-OH
5 O
H H 6 1
H CH2-OH HO-H2C H
4
OH H
1 O
5 O
HO 3 2 α H H 2 5
H 1 6
H OH or 4
OH H H CH2 - OH
α- D - glucose unit HO
O HO 3 2 α b
OH O 3 4
6 H
O b HO H
HO-H2C α- D - glucose unit
5 2 b- D - fructose unit
1
H CH2 - OH
H HO
4 3
OH H α, b - 1, 2- glycosidic linkage
b- D - fructose unit
Fig. 14.8 : Haworth formula of sucrose
(-OH) groups from two monosaccharide units. b. Maltose : Maltose (C12H22O11) is a
At least one of the two monosaccharide disaccharide made of two units of D-glucose.
units must use its anomeric hydroxyl group The glycosidic bond in maltose is formed
in formation of the glycosidic linkage. Three between C-1 of one glucose ring and C-4
most common disaccharides are sucrose, of the other. The glucose ring which uses its
maltose and lactose. hydroxyl group at C-1 is ∝-glucopyranose.
a. Sucrose : Sucrose (C12H22O11) is Hence the linkage is called ∝-1,4-glycosidic
dextrorotatory (+66.50). On hydrolysis with
dilute acid or an enzyme called invertase Do you know ?
sucrose gives equimolar mixture of D-(+) Invert sugar is commerically
glucose and D-(-) fructose. available as invert syrup. It is
H ⊕ used as sweetene in bakery and
C12H22O11 + H2O or C6H12O6 + C6H12O6 confectionary products and also in fruit
invertase
(Sucrose) (D-(+) glucose) (D-(-)fructose) preserves and beverages. It is sweeter
Since the laevoratotion of fructose (-92.40) than sucrose and glucose. It is resistant to
is larger than the dextrorotation of glucose crystallization and promotes retention of
(+52.70), the hydrolysis product has net moisture, enhances flavour and texture and
also prolongs shelf life.
laevorotation. Hence hydrolysis of sucrose
is also called inversion of sucrose, and the
linkage. The hemiacetal group at C-1 of the
product is called invert sugar. Structure of
second ring is not involved in glycosidic
sucrose contains glycosidic linkage between
linkage. Hence maltose is a reducing sugar.
C-1 of ∝-glucose and C-2 of β-fructose (Fig.
Maltose gives glucose on hydrolysis with
14.8).
dilute acids or the enzyme maltase. Figure
Try this... 14.9 shows Haworth formula of maltose.
6 6
Make models corresponding to the CH2OH CH2OH
5 O 5 O
two Haworth formulae of sucrose H
H
H H
H
H
4 1 4 1
in Fig. 14.8. Check that both are identical. OH H OH H
OH
HO 3 2 α 3 2
O
Since the potential aldehyde and ketone H OH H OH
α- D-glucose glucose
groups of both the monosaccharide units are
α- 1, 4- glycosidic bond
involved in formation of the glycosidic bond,
sucrose is a non reducing sugar. Fig. 14.9 : Haworth formula of maltose
305
6 6
HOCH2 HOCH2 Use your brain power
5 O 5 O
HO H OH
4
H 1 O 4
H 1
• Is galactose an aldohexose or
OH H OH H
H H 3 2
H a ketohexose?
3 2
H OH H OH • Which carbon in galactose has different
b- D - galactose b-D-glucose configuration compared to glucose?
b- 1, 4- glycosidic linkage • Draw Haworth formulae of
∝-D-galactose and β-D-galactose.
Fig. 14.10 : Haworth formula of lactose • Which disaccharides among sucrose,
c. Lactose : Lactose (C12H22O11) is a maltose and lactose is/are expected to
disaccharide present in milk. It is formed give positive Fehling test?
from two monosaccharide units, namely • What are the expected products of
D-galactose and D-glucose. The glycosidic hydrolysis of lactose?
linkage is formed between C-1 of β-D-
galactose and C-4 of glucose. Therefore the Starch, cellulose and glycogen are the most
linkage in lactose is called β-1,4-glycosidic common natural polysaccharides. Starch is
linkage. The hemiacetal group at C-1 of the storage carbohydrate of plants and important
glucose unit is not involved in glycosidic nutrient for humans and other animals.
linkage but is free. Hence lactose is a Cellulose is the main constituent of cell wall
reducing sugar. Figure 14.10 shows Haworth of plant and bacterial cells. It is also main
formula of lactose. constituent of wood and cotton. Glycogen
14.2.10 Polysaccharides : Polysaccharides constitutes storage carbohydrate of animals
are formed by linking large number of and is present in liver, muscles and brain. It
monosaccharide units by glycosidic linkages. is also found in yeast and fungi.
6 6 6 6
CH2OH CH2OH CH2OH CH2OH
5 O 5 O 5 O 5 O
H H H H H H H H
H H 1
H 1
H 1
4 1 4 4 4
OH H OH H OH H OH H
3 2 3 2 O 3 2 O 3 2 O-
-O O
H OH H OH H OH H OH
α- 1, 4 - glycosidic linkages
Fig. 14.11 : Amylose
6 6
CH2OH CH2OH
5 O 5 O
H H H H
H H 1
4 1 4
OH H OH H
-O 3 2 3 2
O
H OH H OH O α- 1, 6 - glycosidic linkage (branch)
6 6 6
CH2OH CH2 CH2OH
5 O 5 O 5 O
H H H H H H
H H H 1
4 1 4 4
OH H OH H OH H
-O 3 2 O 3 2
O
3 2 O-
H OH H OH H OH
α- 1, 4 - glycosidic linkage
Fig. 14.12 : Amylopectin
306
6 6 6
HOCH2 HOCH2 HOCH2
5 O 5 O 5 O
H H H
H O H O H O
O 4
OH H 1 4
OH H 1 4
OH H 1
3 2 H 3 2 H 3 2 H
H OH H OH H OH
b- 1, 4 - glycosidic link
Fig. 14.13 : Cellulose
c. Glycogen : Glycogen has its structure
Can you think ? similar to that of amylopectin, but it is more
When you chew plain bread, highly branched.
chapati or bhaakari for long time, it
tastes sweet. What could be the resason ? Do you know ?
The symbiotic bacteria in guts
a. Starch : Starch is a polymer of of insects called termites have
∝-D-glucose.Starch has two components, enzymes that can hydrolyse
namely, amylose (15-20%) and amylopectin β-1,4- glycosidic linkage in cellulose.
(80-85%). Amylose is soluble in water and
forms blue coloured complex with iodine. 14.3 Proteins
It contains 200-1000 ∝-glucose units linked
Can you recall ?
by ∝-1,4- glycosidic linkages giving rise to
unbranched chain of variable length (Fig. • What is the product of reaction
14.11). Amylopectin is water insoluble of acetic acid with ammonia ?
component of starch which forms blue-violet • Write the structural formula of N-methyl
coloured complex with iodine. It is a branched acetamide. What is the name of the
chain polysaccharide. In amylopectin, chains functional group in this compound?
are formed by ∝-1,4- glycosidic linkages
• What are the nitrogenous nutrients in
between ∝-glucose units, where as branches
human diet?
are formed by ∝-1,6- glycosidic linkages
(Fig. 14.12). Proteins are the fundamental structural
b. Cellulose : Cellulose is a straight chain materials of animal bodies. Proteins in the
polysaccharide of β-glucose units linked by form of enzymes play prime role in all the
β-1,4- glycosidic bonds. Chemical hydrolysis physiological reactions. The name protein is
of cellulose requires use of concerntrated strong derived form the Greek word, ‘proteios’ which
acids at high temperature and pressure. This means ‘primary’ or ‘of prime importance’.
implies that the β-1,4- glycosidic bond is very Nutritional sources of proteins are milk,
strong and difficult to hydrolyse. Humans do pulses, nuts, fish, meat, etc. Chemically
not have enzymes which can hydrolyse this proteins are polyamides which are high
linkage. Hence cellulose cannot be digested molecular weight polymers of the monomer
by human beings; it serves as the fibrous units called ∝-amino acids.
content of food useful for bowel movement. 14.3.1 ∝-Amino acids : Proteins on complete
Figure 14.13 shows the Haworth formula of hydrolysis give rise to a mixture of ∝-amino
cellulose. acids. ∝-Amino acids are carboxylic acids
having an amino (-NH2) group bonded to
307
Table 14.1 Natural α - amino acids : L - RCH (NH2) COOH (* Essential α - amino acids)
308
types as neutral, acidic or basic. Ten ∝-amino for example, zwitter ion and the other forms
acids from this list cannot be synthesised in of alanine (Fig. 14.16).
human body and have to be obtained through
diet. These are called essential amino acids
Lone pair can
and are marked with asterisk (*) in Table bond to a proton
14.1.
H O H O
proton trasfer ⊕
:
Use your brain power H 2N C O H H3N C O
Tryptophan and histidine R carboxyl group
R
can donate proton Zwitter ion
have the structures (I) and (II)
respectively. Classify them into neutral/ Fig. 14.15 : Zwitter ion
acidic/basic ∝-amino acids and justify
your answer.(Hint : Consider involvement H H
of lone pair in resonance). ⊕ ⊕
H3N COOH H 3N COO
CH2 - CH - COOH CH3 CH3
NH2 (B) (A)
N Zwitter ion of alanine
N overall +1 charge
H (No net charge)
pH < 2 pH ~~6
CH2 - CH - COOH
(I) N
H NH2
H
(II) H 2N COO
CH3
Can you think ? (C)
Overall -1 charge
Compare the molecular masses of pH < 10
the following compounds and explain
Fig. 14.16 : Three forms of alanine
the observed melting points.
Formula Molecular mass Melting point
Do you know ?
CH3 - CH - COOH 89 293.50C
At the physiological pH of 7.4,
NH2
neutral ∝-amino acids are primarily
C5H11 - NH2 87 -550C
in their zwitterionic forms. On the other
C3H7 - COOH 88 -7.90C hand, at this pH acidic ∝-amino acids
exist as anion (due to deprotonation of
∝-Amino acids are high melting, water the carboxyl group), while basic ∝-amino
soluble crystalline solids, unlike simple acids exist as cation (due to protonation
amines or carboxylic acids. These properties of the amino groups). Ionic structures of
are due to a peculiar structure called zwitter constituent ∝-amino acids result in ionic
ion structure of ∝-amino acids. An ∝-amino nature of proteins.
acid molecule contains both acidic carboxyl
(-COOH) group as well as basic amino (-NH2)
group. Proton transfer from acidic group to Can you recall ?
basic group of amino acid forms a salt, which • What does the enzyme pepsin
is a dipolar ion called zwitter ion (Fig. 14.15). do?
Amino acid can exist in different forms • What are the initial and final products
depending upon the pH of the aqueous of digestion of proteins?
solution in which it is dissolved. Consider,
309
14.3.2 Peptide bond and protein : respectively. When the number of ∝-amino
Proteins are known to break down into acids linked by peptide bonds is more than
peptides in stomach and duodenum under ten, the products are called polypeptides.
the influence of enzymes, pepsin being The -CHR- units linked by peptide bonds are
one of them which is secreted by stomach. referred to as ‘amino acid residues’. Proteins
Polypeptides are further broken down to are polypeptides having more than hundred
∝-amino acids. This implies that proteins amino acid residues linked by peptide bonds.
are formed by connecting ∝-amino acids to It may be, however, noted that distinction
each other. The bond that connects ∝-amino between proteins and polypeptides is not
acids to each other is called peptide bond. sharp. The two ends of a polypeptide chain of
Consider, for example, linking of a molecule protein are not identical. The end having free
of glycine with that of alanine. One way of carboxyl group is called C-terminal while the
doing this is to combine carboxyl group of other end having free amino group is called
glycine with ∝-amino group of alanine. This N-terminal. In the dipeptide glycylalanine
results in elimination of a water molecule and glycine residue is N-terminal and alanine
formation of a dipeptide called glycylalanine residue is C-terminal.
in which the two amino acid units are linked 14.3.3 Types of proteins : Depending upon
the molecular shape proteins are classified
H2N - CH2 - COOH + H2N - CH - COOH into two types.
CH3 a. Globular proteins : Molecules of globular
(glycine) (alanine)
proteins have spherical shape. This shape
-H2O results from coiling around of the polypeptide
chain of protein. Globular proteins are usually
H2N - CH2 - CO - NH - CH - COOH soluble in water. For example : insulin, egg
CH3 albumin, serum albumin, legumelin (protein
(peptide bond)
(glycylalanine) in pulses)
Fig. 14.17 : Peptide bond b. Fibrous proteins : Molecules of fibrous
proteins have elongated, rod like shape. This
by a peptide bond (Fig. 14.17). It can be
shape is the result of holding the polypeptide
seen that a peptide bond or peptide linkage
chains of protein parallel to each other.
is same as what is described as secondary
Hydrogen bonds and disulfide bonds are
amide in organic chemistry. Combination of
responsible for this shape. Fibrous proteins
a third molecule of an ∝-amino acid with
are insoluble in water. For example : keratin
a dipeptide would result in formation of a
(present in hair, nail, wool), myosin (protein
tripeptide. Similarly linking of four, five
of muscles).
or six ∝-amino acids results in formation
of tetrapeptide, pentapeptide or hexapeptide The shapes of protein molecules are the
result of four level structure of proteins.
Use your brain power
14.3.4 Structure of proteins : Proteins are
• Write the structural formula of
responsible for a variety of functions in
dipeptide formed by combina-
organisms. Proteins of hair, muscles, skin
tion of carboxyl group of alanine and
give shape to the structure, while enzymes
amino group of glycine.
are proteins which catalyze physiological
• Name the resulting dipeptide.
• Is this dipeptide same as glycyalanine reactions. These diverse functions of proteins
or its structural isomer? can be understood by studying the four
310
O O O O
- NH - CH - C - NH - CH - C - NH - CH - C - NH - CH - C -
N - terminal R' R'' R''' R' C - terminal
level structure of proteins, namely primary, symbols are separated by dashes. According
secondary, tertiary and quaternary structure to the convention, the N-terminal amino acid
of proteins. residue as written at the left end and the
a. Primary structure of proteins : Primary C-terminal amino acid residue at the right
structure of proteins is the sequence of end (Fig. 14.18).
constituent ∝-amino acid residues linked Problem 14.4 : Write down the structures
by peptide bonds. Any change in the of amino acids constituting the following
sequence of amino acid residuce results peptide.
in a different protein. Primary structure of
proteins is represented by writing the three CH3-CH-CO-NH-CH-CO-NH-CH-COOH
letter symbols of amino acid residuces as per NH2 CH2OH CH2SH
their sequence in the concerned protein. The Solution : The given peptide has two
amide bonds linking three amino acids.
Problem 14.3 The structures of these amino acids are
Chymotrypsin is a digestive enzyme obtained by adding one H2O molecule
that hydrolyzes those amide bonds for across the amide bond as follows :
which the carbonyl group comes from HO H HO H
phenylalanine, tyrosine or tryptophan. CH3-CH-CO-NH-CH-CO-NH-CH-COOH
Write the symbols of the amino acids and NH2 CH2SH CH2OH
peptides smaller than pentapeptide formed
by hydrolysis of the following hexapeptide → CH3-CH-COOH + H2N-CH-COOH +
with chymotrypsin. NH2 CH2SH
Gly-Tyr-Gly-Ala-Phe-Val H2N-CH-COOH
Solution : In the given hexapeptaide CH2OH
hydroylsis by chymotripsin can take b. Secondary structure of proteins :
place at two points, namely, Phe and Tyr.
The carbonyl group of these residuces The three-dimensional arrangement of
is towards right side, that is, toward localized regions of a protein chain is called
the C-terminal. Therefore the hydrolysis the secondary structure of protein. Hydrogen
products in required range will be : bonding between N-H proton of one amide
linkage and C=O oxygen of another gives
Gly-Tyr, Gly-Ala-Phe and Val rise to the secondary structure. Two types
(a dipeptide) (a tripeptide) (∝-amino acid) of secondary structures commonly found in
proteins are ∝-helix and β-pleated sheet.
311
β-Pleated sheet : The secondary structure
R is called β-pleated sheet when two or more
polypeptide chains, called strands, line
H
up side-by-side (Fig. 14.20). The β-pleated
R
H sheet structure of protein consists of extended
H strands of polypeptide chains held together
by hydrogen bonding. The characteristics of
R
Hydrogen β-pleated sheet structure are :
H
R bond
H
R
H
R R
H
3.6 residues
H
R O
H R H R H
R N N
N N
H O R H O R
Fig. 14.19 : Backbone of ∝ - Helix
O H R O H R
∝-Helix : The ∝-helix forms when a N N
polypeptide chain twists into a right handed N
or clockwise spiral (Fig. 14.19). Some R O H R O
characteristic features of ∝-helical structure
of protein are: Fig. 14.20 : β - pleated sheet
• Each turn of the helix has 3.6 amino acids.
• The C=O and N-H bonds lie in the planes
• A C=O group of one amino acid is of the sheet.
hydrogen bonded to N-H group of the
fourth amino acid along the chain. • Hydrogen bonding occurs between the
N-H and C=O groups of nearby amino
• Hydrogen bonds are parallel to the axis
acid residues in the neighbouring chains.
of helix while R groups extend outward
from the helix core. • The R groups are oriented above and
Myosin in muscle and ∝-keratin in hair below the plane of the sheet.
are proteins with almost entire ∝-helical The β-pleated sheet arrangement is favoured
secondary structure. by amino acids with small R groups.
Most proteins have regions of ∝-helix
Do you know ? and β-pleated sheet, in addition to other
In collagen, the protein of random regions that cannot be characterised
connective tissue, the polypeptide by either of these secondary structures. For
chains have unusual left-handed helix example: Spider dragline silk protein is strong
structure. Three strands of these chains due to β-pleated sheet region, yet elastic due
wind around each other in a right-handed to ∝-helical regions in it.
triple helix.
312
c. Tertiary structure of proteins : The Haemoglobin can do its function of oxygen
three-dimensional shape adopted by the transport only when all the four subunits are
entire polypeptide chain of a protein is together. Figure 14.22 summerizes the four
called its tertiary structure. It is the result of levels of protein structure.
folding of the chain in a particular manner
that the structure is itself stabilized and also a - amino
has attractive interaction with the aqueous acids Primary structure
environment of the cell. The globular and (sequence of
fibrous proteins represent two major molecular a - amino acids)
shapes resulting from the tertiary structure.
The forces that stabilize a particular tertiary b - pleated
a - helix
sheet Secondary structure
structure include hydrogen bonding, dipole-
dipole attraction (due to polar bonds in the
side chains), electrostatic attraction (due to
the ionic groups like -COO , NH3⊕ in the side
chain) and also London dispersion forces. b - pleated Tertiary structure
Finally, disulfide bonds formed by oxidation sheet
of nearby -SH groups (in cysteine residues)
are the covalent bonds which stabilize the a - helix
tertiary structure (Fig. 14.21). Quaternary structure
(multiple units of
tertiary structure)
hydrogen
bond
Fig. 14.22 : Four levels of protein structure
313
14.3.5 Denaturation of proteins Chemically enzymes are proteins. Every living
High temperature, acid, base and cell contains at least 1000 different enzymes.
even agitation can disrupt the noncovalent Most enzymes catalyse only one reaction or
interactions responsible for a specific shape one group of similar reactions. Thus, enzyme
of protein. This is denaturation of protein. catalysis is highly specific. You have learnt
Denaturation is the process by which the that a mineral acid can catalyse hydrolysis
molecular shape of protein changes without of many types of compounds such as esters,
breaking the amide/peptide bonds that acetals and amides. In contrast, an enzyme
form the primary structre. that catalyses hydrolysis of amide will not
work on ester or acetal.
Do you know ? substrate
Globular proteins are typically
folded with hydrophobic side chains
active site
in the interior and polar residues on the
outside, and thereby are water soluble. enzyme
Denaturation exposes the hydrophobic
region of globular proteins and makes
them water insoluble.
enzyme -
substrate
denaturation
complex
315
HO-CH2 HO-CH2 OH Remember...
O OH O
H H H H RNA contains : D-ribose, A, G, C, U
H H H H
OH OH HO H
DNA contains : D-2-deoxyribose, A, G, C, T
or or
5
5
HO-CH2 HO-CH2 OH bases with two rings (adenine and guanine)
O OH O
1
are derived from the parent compound
1 4
4
2 3 2 purine. Each base in designated by a one-
3
OH No OH letter symbol (Fig. 14.25). Uracil (U) occurs
OH OH at C-2 only in RNA while thymine (T) occurs only
D - Ribose 2 - Deoxy-D-ribose in DNA.
(present in RNA) (present in DNA)
A nucleoside is formed by joining
Fig 14.24 : Sugar Components of nucleic acids the anomeric carbon of the furanose with
nucleotides. nitrogen of a base. While numbering the
atoms in a nucleoside, primes (') are used
The nucleotide monomers consist of three
for furanose numbering to distinguish them
components : a monosaccharide, a nitrogen-
from the atoms of the base (Fig. 14.26). With
containing base and a phosphate group.
pyrimidine bases, the nitrogen atom at the 1
Nucleotides of both RNA and DNA position bonds with the 1' carbon of the sugar.
contain five-membered ring monosaccharide With purine bases, the nitrogen atom at the
(furanose), often called simply sugar 9 position bonds with 1' carbon of the sugar.
component. In RNA, the sugar component of
Nucleotides are formed by adding
nucleotide unit is D-ribose, while in DNA, it
a phosphate group to the 5'-OH of a
is 2-deoxy-D-ribose (Fig. 14.24).
nucleoside (Fig. 14.27). Thus, nucleotides are
Total five nitrogen - containing bases are monophosphates of nucleosides. Abridged
present in nucleic acids. Three bases with one names of some nucleotides are AMP, dAMP,
ring (cytosine, uracil and thymine) are derived UMP, dTMP and so on. Here, the first capital
from the parent compound pyrimidine. Two letter is derived from the corresponding base.
NH2 O O
4
5 H 3C
N3 N NH NH
6 2
N N O N O N O
1
H H H
Pyrimidine Cytosine Uracil Thymine
(Parent compound) C U T
7
NH2 O
6
N 5 N N
N1 N NH
8
9 2
N 4 N N N N N NH2
H 3 H H
Purine Adenine Guanine
(Parent compound) A G
NH2
HO-CH2 NH2 N
O OH N
N 5'
N
+ HO-CH2 N
O 9 N
N N
OH 4' 1'
H 3' 2'
OH
(D - 2 - deoxyribose) (Adenine) (a deoxyribonnucleoside)
317
NH2 NH2
N
O N N
5'
O 5'
O-P-O-CH2
O N O + O-P-O-CH2 O N N
O O
3` 3'
OH OH
(dCMP) (dAMP)
NH2
O N
5'
5' end O-P-O-CH2 N O
O
O NH2
3'
N
{
O N
5'
Phosphodiester O P-O-CH2
O N N
linkage
O
3'
OH 3' end
Fig 14.28 : Formation of a dinucleotide
Sugar-phosphate
backbone } 5'
Phosphate Sugar Phosphate Sugar Phosphate Sugar
3'
(a)
base base base
5'
(b) P S P S P S P S 3'
B B B B
A C T
318
name CATG means there are four nucleotides base pairs and the two strands of the
in the segment containing the bases cytosine, double helix are complementary to each
adenine, thymine and guanine, in the indicated other.
order from the 5' end. It may be noted that RNA exists as single
Remember... stranded structure.
• A nucleic acid contains
a backbone consisting of 30 50
alternating sugar and phosphate groups. Axis of helix
A T
• Backbone of all types of DNA contains G C
the sugar 2-deoxy-D-ribose while that T A
of RNA contains the sugar D-ribose. C G
• The identity and sequence of bases Hydrogen bond
distinguish one polynucleotide from the T A
other. C G
• A polynucleotide has one free phosphate A T Sugar phosphate
backbone
group at the 5' end. T A
319
Problem 14.6 : Write the sequence of the complementary strand of the following portion of a
DNA molecule : 5' - ACGTAC-3'
Solution : The complementary strand runs in opposite direction from the 3' end to the 5' end. It
has the base sequence decided by complementary base pairs A - T and C - G.
Original strand 5' - A C G T A C - 3'
Exercises
b. It is present in all the human iii. α - Amino acids have high melting
proteins. points compared to the corresponding
amines or carboxylic acids of
c. It cannot be synthesised by human comparable molecular mass.
body.
iv. Hydrolysis of sucrose is called
d. It is essential constituent of inversion.
enzymes.
v. On boiling egg albumin becomes
opaque white.
320
3. Answer the following 4. Draw a neat diagram for the following:
i. Some of the following statements i. Haworth formula of glucopyranose
apply to DNA only, some to RNA ii. Zwitter ion
only and some to both. Lable them
accordingly. iii. Haworth formula of maltose
a.
The polynucleotide is double iv. Secondary structure of protein
stranded. ( ) v. AMP
b. The polynucleotide contains uracil. vi. dAMP
( )
vii. One purine base from nucleic acid
c.
The polynucleotide contains
viii. Enzyme catalysis
D-ribose ( ).
d.
The polynucleotide contains
Guanine ( ). Activity :
ii. Write the sequence of the • Draw structure of a segment
complementary strand for the of DNA comprising at least ten
following segments of a DNA nucleotides on a big chart paper.
molecule.
• Make a model of DNA double
a. 5' - CGTTTAAG - 3' stranded structure as group
b. 5' - CCGGTTAATACGGC - 3' activity.
iii. Write the names and schematic
representations of all the possible
dipeptides formed from alanine,
glycine and tyrosine.
iv. Give two evidences for presence of
formyl group in glucose.
321
15. INTRODUCTION TO POLYMER CHEMISTRY
Can you recall ? aspects of organic polymers. You have learnt
i. Classify the following in Chapter 14 about carbohydrates, proteins
materials as bio-degradable and nucleic acids which are important organic
and non-bio-degradable : biopolymers playing crucial role in living
Thermocol, glass, wood, cotton world.
clothes, paper bags, polythene bags, In this chapter we will consider mainly
nylon ropes, fruit peels. man made organic polymers with reference
ii. Give examples of man made materials to aspects such as types, preparation and
we use in our daily life. applications.
iii. Which material is used in manufacture Do you know ?
of toys, combs ?
Nobel prizes for pioneering work
iv. Write examples of thermosetting in 'Polymers' :
plastic articles. • The polymeric substances, that we
v. List various properties of plastic. know today as macromolecules,
were considered hundred years ago
15.1 Introduction : Today the overall as associated molecules. Staudinger
development in polymer science and received Nobel prize (1953) for his work
technology has enriched human life. The world which established macromolecular
would be at totally different place without nature of polymers.
polymers such as artificial fibres, plastics • In 1963 Natta received Nobel prize for
and elastomers. From the throwaway candy recognizing stereospecific regularity in
wrapper to the artificial heart, polymers touch vinyl polymers.
our lives as does no other class of material. • In 1974 Flory received Nobel prize for
In short we are living in the world of elucidating the three step mechanism
polymers. Polymer chemistry emerged as of chain-reaction in polymerization
a separate branch of chemistry during the involving initiation, propagation and
last several decades due to the voluminous termination.
knowledge built up in this field and the ever 15.2 Classification of polymers : Polymers
increasing applications in everyday life. are classified in number of ways on the basis
Chemically polymers are complex, giant of their source, chemical structures, mode of
macromolecules made from the repeating units polymerization, molecular forces, type of
which are derived from small molecules called monomers and biodegradability.
'monomers'. The term 'polymer' originates 15.2.1 Classification of polymers on the basis
from Greek word 'poly' meaning many and of source or origin : Poylmers are divided
'mer' meaning part or unit. Interlinking of into three categories : a. Natural b. Synthetic
many units constitutes polymers. c. Semisynthetic
Polymers are high molecular mass a. Natural polymers : The polymers obtained
macromolecules (103 - 107 u). from natural source are said to be natural
Both inorganic as well as organic polymers polymers. They are further subdivided into two
are known. In this chapter we will study some types.
322
i. Plant polymers : These are obtained from bifunctional monomers or alkenes. (Fig.
plants. For example, cotton and linen are 15.1(a)). For example : PVC, high density
obtained from cotton plant and flax plant polythene.
respectively. Natural rubber is another example b. Branched chain polymers : The second
of natural polymer which is manufactured most common arrangement is that of branched
from the latex obtained from bark of rubber chain. Monomer having 3 functional groups
trees. or already having side chains give rise to
ii. Animal polymers : These are derived from branched chain polymers. (Fig. 15.1 (b)). For
animal sources. For example, wool is obtained example : low density polythene.
from hair of sheep. Silk is obtained from c. Cross-linked polymers : Third type of
silkworm. arrangement is said to be cross linked or
b. Synthetic Polymers : These are man- made network polymers where cross links are
polymers. These polymers are artificially produced between linear chains as shown
prepared by polymerization of one monomer in Fig. 15.1 (c). Cross linking results from
or copolymerization of two or more monomers. polyfunctional monomers. For example,
Nylon, terylene, neoprene are synthetic bakelite, melamine.
polymers. These are further divided into three
subtypes, namely, fibres, synthetic rubbers and
plastics.
c. Semisynthetic polymers : These are derived
from natural polymers. These are also called
regenerated fibres.Cellulose derivatives such
as cellulose acetate rayon, cellulose nitrate,
viscose rayon, cuprammonium rayon are a
few examples of this category.
Semisynthetic polymers are used in
preparation of non-inflammable photographic
films, cinema films, varnishes, etc. Fig. 15.1 : Different chain configurations of
Use your brain power polymers
• Differentiate between natural 15.2.3 Classification of polymers on the basis
and synthetic polymers. of mode of polymerization : Polymerization
is the fundamental process by which low
15.2.2 Classification of polymers on the molecular mass compounds are converted
basis of structure : Depending upon how into high molecular weight compounds by
the monomers are linked together, that is, the linking together of repeating structural units
chain configuration, polymers are classified with covalent bonds. This process is illustrated
in three general types : a. linear b. branched below.
and c. three dimensional cross - linked Low molecular
polymers (Fig. 15.1). The nature of linking mass material High temprature High molecular
the monomers depends upon the nature and (Possessing and/or pressure mass material
number of functional groups in them. reactive groups) and/or catalyst
a. Linear or straight chain polymers : When There are three modes of polymerization
the monomer molecules are joined together according to the types of reactions taking place
in a linear arrangement the resulting polymer between the monomers.
is straight chain polymer. It is obtained from
323
a. Addition polymerization (or chain growth
R + CH2 = CHY R - CH2 - CHY
polymerization)
(free (vinyl (new radical)
b. Condensation polymerization (or step radical) monomer)
growth polymerization)
c. Ring opening polymerization Step 2 : Chain propagation : The new radical
formed in the initiation step reacts with
a. Addition polymerization : Addition
another molecule of vinyl monomer, forming
polymerization is a process of formation of
another still bigger sized radical, which in turn
polymers by addition of monomers without
reacts with another monomer molecule. The
loss of any small molecules. The repeating unit
repetition of this sequence takes place very
of an addition polymer has the same elemental
rapidly. It is called chain propagation.
composition as that of original monomer.
R - CH2 - CHY + nCH2 = CHY
Compounds containing double bond
undergo addition polymerization. It is also R (CH2 - CHY)n CH2 - CHY
referred as vinyl polymerization, since This step is very rapid and leads to high
majority of monomers are from vinyl category. molecular mass radical.
For example : vinyl chloride (CH2=CHCl),
acrylonitrile (CH2=CHCN). Formation of Step 3 : Chain termination : Ultimately,
polyethylene from ethylene is well known at some stage,termination of the growing chain
example of addition polymerization. Addition takes place. It may occur by several processes.
polymerization produces high molecular mass One mode of termination is by combination of
polymeric materials without formation of any two growing chain radicals.
intermediate low molecular mass polymeric 2 R (CH2 - CHY)n CH2 - CHY
materials.
R (CH2CHY)n+ 1 (CHYCH2 )n+ 1 R
Free radical mechanism is most common
(polymer)
in addition polymerisation. It is also called
chain reaction which involves three distinct
steps chain initiation, chain propagation and Internet my friend
chain termination. Study audiovisual free
radical mechanism of addition
Step 1 : Chain initiation : The chain reaction
polymerization. (Refer/search for free
is initiated by a free radical. An initiator
radical polymerization.Animation (IQOG-
(catalyst) such as benzoyl peroxide, acetyl
CSIC) on youtube channel)
peroxide, tert-butyl peroxide, etc. can be used
to produce free radical. For example acetyl b. Condensation polymerization :
peroxide generates methyl radical as shown
Consider the formation of terylene, a
below :
poly ester polymer, from ethylene glycol and
O O O terephthalic acid.
CH3 - C - O - O - C - CH3 2CH3 - C - O
(acetyl peroxide) n HO - CH2 - CH2 - OH + n HOOC COOH
- CO2 CH3
(methyl radical) (ethylene glycol) (terephthalic acid)
O O
The free radical (say R) so formed
attaches itself to the olefin (vinyl monomer)
- nH2O
HO [CH - CH - O - C
2 2 ]Cn
OH
ester link
and produces a new radical, made up of two (terylene or dacron)
parts, namely, the attached radical and the
monomer unit.
324
In this reaction an alcoholic OH group
in ethylene glycol condenses with a carboxyl Use your brain power
group in terephthalic acid by eliminating a What is the type of
water molecule to form an ester linkage. polymerization in the following
The process of formation of polymers from examples ?
(i)
polyfunctional monomers with the elimination 2n CH2 = CH - CH3
CH 3
325
forces the fibres are crystalline in nature. For 15.2.5 Classification of polymers on the basis
example : polyamides (nylon 6, 6), polyesters of type of different monomers : Polymers are
(terylene), etc. divided into two classes :
a. Homopolymers : The polymers which
have only one type of repeating unit are called
homopolymers. Usually they are formed from
a single monomer. In some cases the repeating
unit is formed by condensation of two
distinct monomers. For example : polythene,
polypropene, Nylon 6, polyacrylonitrile,
c. Thermoplastic polymers : Plasticity is a Nylon 6, 6.
property of being easily shaped or moulded. b. Copolymers : The polymers which have
Thermoplastic polymers are capable of two or more types of repeating units are called
repeated softening on heating and hardening copolymer. They are formed by polymerization
on cooling. These polymers possess of two or more different types of monomers in
moderately strong intermolecular forces that presence of each other. The different monomer
are intermediate between elastomers and units are randomly sequenced in the copolymer.
fibres. For example : polythene, polystyrene, For example : Buna-S, Buna-N.
polyvinyls, etc. : Problem 15.1 : Refer to the following table
listing for different polymers formed from
respective monomer. Identify from the list
whether it is copolymer or homopolymer.
Sr. Monomer Polymers
No.
1. Ethylene Polyethylene
d. Thermosetting polymers : Themosetting 2. Vinyl chloride Polyvinyl chloride
polymers are rigid polymers. During their
3. Isobutylene Polyisobutylene
formation they have property of being shaped
4. Acrylonitrile Polyacrylonitrile
on heating; but they get hardened while hot.
5. Caprolactum Nylon 6
Once hardened these become infusible; cannot
6. Hexamethylene Nylon 6, 6
be softened by heating and therefore cannot diammonium
be remoulded. This characteristic is the result adipate
of extensive cross linking by covalent bonds 7. Butdiene + Buna-S
formed in the moulds during hardening/setting styrene
process while hot. For example : bakelite, urea Solution : In each of first five cases,
formaldehyde resin, etc. there is only one monomer which gives
corresponding homopolymer. In the sixth
case hexamethylene diamine reacts with
adipic acid to form the salt hexamethylene
diammonium adipate which undergoes
condensation to form Nylon 6, 6. Hence
nylon 6, 6 is homopolymer. The polymer
Buna-S is formed by polymerization of
the monomers butadiene and styrene in
presence of each other. The repeating units
corresponding to the monomers butadiene
and styrene are randomly arranged in the
polymer. Hence Buna-S in copolymer.
326
Fig. 15.2 Shows all the classes of polymers in the form of a tree diagram.
Polymers
Thermosetting Non-biodegradable
Fig. 15.2 : Classification of polymers
327
The process by which a network of cross
links is introduced into an elastomers is Use your brain power
called vulcanization. The profound effect • From the cis-polyisoprene
of vulcanization enhances the properties like structure of natural rubber
tensile strength, stiffness, elasticity, toughness; explain the low strength of
etc. of natural rubber. Sulfur vulcanization van der Waals forces in it.
is the most frequently used process. Sulfur • Explain how vulcanization of natural
forms crosslinks between polyisoprene chains rubber improves its elasticity ? (Hint :
which results in improved properties of consider the intermolecular links.)
natural rubber.
Do you know ?
Do you know ?
Natural Rubber first came into
Vulcanizing is carried out the market in early 19 th century. It
by heating raw rubber with sulfur was entirely recovered from wild Hevea
powder in presence of some organic brasiliensis trees which usually grew on the
compounds called accelerators at about banks of Amazon river and its tributaries in
150 0C. (The most common accelerator South America. The amount of hydrocarbon
is ZBX or zincbutyl xanthate). By present in Hevea Tree is very high (35%).
increasing amount of sulfur the rubber As per the demand the production of natural
can be hardened. For example when the rubber increased by leaps and bounds and
amount of sulfur is raised to 40-45 % at present 1.5 million tons of natural rubber
a non-elastic hard material known as is sent to the market.
ebonite is obtained. The latex is collected from a mature
One or more sulfur atoms cross-link Hevea tree by making deep cuts on the
two polyisoprene chains. Cross-linking bark and by allowing the latex stream in a
takes place by opening of a double pot attached below the cut. The latex is an
bond and produces three dimensional emulsion like milk.
vulcanised rubber. When a coagulant like acetic acid is
added to the latex the rubber hydrocarbon
Probable 3-D structure of vulcanized gets coagulated in the amorphous solid
rubber is form.
CH3 S
15.3.2 Polythene :
CH - C - CH - CH2
S Can you recall ?
S How is ethylene prepared ?
S
Polythene is the simplest and most
H2C - HC - C - CH2- CH2
commonly used hydrocarbon thermoplastic
S CH3
and has following structure.
S
[CH2 − CH2]n
S CH3
H2C - CH - C - CH2- CH2 The IUPAC name of polyethylene is
S
polythene. Polythene is of two kinds, namely
low density polythene (LDP) and high density
polythene (HDP) .
328
a. Low density polyethylene (LDP) : b. High density polyethylene (HDP) : It is
LDP is obtained by polymerization of ethylene essentially a linear polymer with high density
under high pressure (1000 - 2000 atm) and due to close packing.
333 K - 343 K
temperature (350 - 570 K) in presence of CH2 = CH2 6 - 7 atm, catalyst HDP
traces of O2 or peroxide as initiator.
Traces of O2 HDP is obtained by polymerization of
CH2 = CH2 peroxide at 350 - 370K, LDP ethene in presence of Zieglar-Natta catalyst
1000 - 2000 atm
which is a combination of triethyl aluminium
The mechanism of this reaction with titanium tetrachloride at a temperature
involves free radical addition and H-atom of 333K to 343K and a pressure of 6-7 atm.
abstraction. The latter results in branching.
Properties of HDP : HDP is crystalline,
As a result the chains are loosely held and
melting point in the range of 144 - 150 0C. It
the polymer has low density.
is much stiffer than LDP and has high tensile
strength and hardness. It is more resistant to
Do you know ?
chemicals than LDP.
In the H-atom abstraction,
process involved in formation Uses of HDP : HDP is used in manufacture
of LDP; the terminal carbon radical of toys and other household articles like
abstracts H-atom from an internal carbon buckets, dustbins, bottles, pipes etc. It is used
atom in the form of an internal carbon to prepare laboratory wares and other objects
radical. Termination step in addition where high tensile strength and stiffness is
polymerization gives rise to branching required.
of these internal carbons.
H
H intramolecular R R
H-atom abstraction Termination
329
C - F bond is very difficult to break Polyamides contain - CO - NH - groups
and remains unaffected by corrosive alkali, as the inter unit linkages. Two important
organic solvents. polyamide polymers are nylon 6, 6 and nylon
Uses : Telflon is used in making non-stick 6.
cookware, oil seals, gaskets, etc. a. Nylon 6,6 : The monomers adipic acid and
hexamethylendiamine on mixing forms nylon
salt, which upon condensation polymerization
under conditions of high temperature and
pressure give the polyamide fibre nylon 6,6.
n HOOC-(CH2)4-COOH + n H2N-(CH2)6-NH2
(adipic acid) (hexamethylene
diamine)
Internet my friend
Collect the information of O O ⊕ ⊕
Teflon coated products used in n O - C ( CH2 )4 C - OH3N ( CH2 )6 NH3
daily life and in industries. (nylon salt)
553K high
15.3.4 Polyacrylonitrile : Polyacrylonitrile -nH2O pressure
is prepared by addition polymerization of
O O H
acrylonitrile by using peroxide initiator.
[ C-(CH2)4-C-NH-(CH2)6-N]n
Polymerization (nylon 6,6)
nCH2 = CHCN Peroxide
[CH2 − CH]n
CN The numerals 6,6 in the name of this
(Acrylonitrile) (Polyacrylonitrile) polymer stand for the number of carbon atoms
in the two bifunctional monomers, namely,
Polyacrylonitrile resembles wool and is adipic acid and hexamethylenediamine.
used as wool substitute and for making orlon Nylon 6,6 is high molecular mass (12000-
or acrilan. 50000 u) linear condensation polymer. It
possesses high tensile strength. It does not
soak in water. It is used for making sheets,
bristles for brushes, surgical sutures, textile
fabrics, etc.
330
b. Nylon 6 : When epsilon (ε)-caprolactam Polycarbonates are also a kind of
is heated with water at high temperature it polyester polymers. These are high melting
undergoes ring opening polymerization to give thermosetting resins.
the polyamide polymer called nylon 6.
15.3.7 Phenol - formaldehyde and related
e NH O
H2C C H 2O polymers :
n δ α
533 - 543 K
[NH ( CH2 )5 CO ]n
H2C CH2 a. Bakelite : Bakelite, the thermosetting
CH2 CH2 (Nylon 6) polymer obtained from reaction of phenol and
γ β
331
Stage 1: OH OH OH OH
CH2OH CH2OH HOH2C CH2OH
Acid
+ CH2O
or base + +
(Phenol) (Formaldehyde) CH2OH CH2OH
Stage 2 :
OH OH OH OH
CH2OH H2C CH2 CH2 CH2
H⊕
n -H2O
(Novolac)
Stage 3 : OH OH
OH
H2C CH2 CH2 CH2
Novolac
CH2
CH2 CH2
OH
H2C CH2 CH2 CH2
OH OH
CH2 (Bakelite)
H H
H2N N NH2 (HOH2C)NH N NH(CH2OH) N
N N - CH2
N + CH2O N H2C
N N H3O⊕
N N
NH2 NH(CH2OH) N n
H2C H
(Melamine) (Formaldehyde)
(cross linked melamine formaldehyde resin)
C6H5
CH2 - CH = CH - CH2 - CH2 - CH = CH - CH2 - CH2 - CH - CH2 - CH2 - CH = CH
(SBR)
Fig. 15.5 Formation of SBR (Buna - S)
332
Cl Cl
Polymerization
nCH2 = C - CH = CH2 [CH2 - C = CH - CH2 ]n
(chloroprene) (Neoprene)
(a) : Polymerization
333
⊕
Cell - OH + NaOH Cell - ONa + H2O
(cellulose pulp wood) (alkali cellulose)
⊕ ⊕
Cell - ONa + CS2 Cell - O - C - SNa
S
(cellulose xanthate)
⊕
Cell - O - C - SNa + H2O Cell - O - C - SH + NaOH
S S
Cell - O - C - SH + H2O Cell - OH + CS2
S (viscose rayon)
(Regenerated cellulose filaments)
334
Problem 15.2 : The critical degree of Can you recall ?
polymerization is low for nylon 6 while
• What are the structural formulae
high for polythene. Explain.
of glycine and e - amino caproic
Solution : Nylon 6 is a polyamide acid ?
polymer, and has strong intermolecular
hydrogen bonding as inter molecular this problem biodegradable polymers are being
forces. On the other hand polythene chains developed. These polymers contain functional
have only weak van der Waals forces as groups similar to those in biopolymers such
intermolecular interaction. Because of the as proteins. Aliphatic polyesters are also an
stronger intermolecular forces the critical important class of biodegradable polymers.
DP is lower for nylon 6 than polythene.
Use your brain power
15.5 Biodegradable polymers : • Represent the copolymerization
reaction between glycine and
Can you recall ?
e - amino caproic acid to form the
• Name some materials which copolymer nylon 2- nylon 6.
undergo degradation after use.
• What is the origin of the numbers 2 and
• List the materials which do not decay 6 in the name of this polymer ?
even after a long time.
• How is the environment affected by non 15.5.1 PHBV : PHBV is a copolymer of
decaying substances ? two bifunctional b- hydroxy carboxylic
acids, namely, b- hydroxybutyric acid (3 -
• Which bonds are broken during digestion hydroxybutanoic acid) and b- hydroxyvaleric
of proteins and carbohydrates ? acid (3 - hydroxypentanoic acid). Hydroxyl
• What happens to disposed natural wastes group of one monomer forms ester link by
such as stale food, fruit peels, torn cotton reacting with carboxyl group of the other. Thus
cloth ? PHBV is an aliphatic polyester with name poly
b- hydroxy butyrate - co - b- hydroxy valerate
Inspite of large number of useful (PHBV). PHBV is degraded by microbes in the
applications, polymers are blamed for creating environment.
environmental pollution. To strike the golden b a
n(HO - CH - CH2 - COOH) + n(HO - CH - CH2 - COOH)
mean, certain new biodegradable synthetic
CH3 CH2 CH3
polymers have been developed.
(b - hydroxy butyric acid) (b - hydroxy valeric acid)
Aliphatic polyesters and polyamides
- nH2O
with large proportion of polar linkages are
one of the important classes of biodegradable O
polymers. Some important examples are [ O - CH - CH2 - C - O - CH - CH2- C ]n
discussed below. CH3 O CH2 - CH3
(PHBV)
Disposed natural wastes are usually
attacked by soil microbes and get degraded
to humus. But most synthetic polymers and 15.5.2 Nylon 2 - nylon 6 : Nylon 2 - nylon 6
plastics cannot be degraded by microbes and is a polyamide copolymer of two amino acids,
stay in the environment for very long period of namely, glycine and e - amino caproic acid. It
time posing pollution problems. To overcome is a biodegradable polymer.
335
15.6 Commercially important polymers : Apart from the polymers already discussed in this
chapter, many more polymers are used extensively. Structures and applications of some of them
are given in the Table 15.1.
Table 15.1 : Commercially important polymers
Butadiene and
adhesives, rubber belts,
acrylonitrile [H2C-CH=CH-CH2-CH2-CH ]n
Buna N shoe soles, O-rings,
CN
gaskets
CN
a. ethyleneglycol
Glyptal paints and lacquers
b. phthalic acid [ O - CH2 - CH2 - OOC CO ]n
336
Exercises
1. Choose the correct option from the given viii. PET is formed by ----
alternatives.
A. Addition B. Condensation
i. Nylon fibres are ----
C. Alkylation D. Hydration
A. Semisynthetic fibres
ix. Chemically pure cotton is ----
B. Polyamide fibres
A. Acetate rayon
C. Polyester fibres
B. Viscose rayon
D. Cellulose fibres
C. Cellulose nitrate
ii. Which of the following is naturally
D. Cellulose
occurring polymer ?
x. Teflon is chemically inert, due to
A. Telfon B. Polyethylene
presence of ...........
C. PVC D. Protein
A. C-H bond B. C-F bond
iii. Silk is a kind of ---- fibre
C. H- bond D. C=C bond
A. Semisynthetic
2. Answer the following in one sentence
B. Synthetic each.
C. Animal i. Identify 'A' and 'B' in the following
D. Vegetable reaction ----
O C6H5
v. Write structural formula of the
b. -(CH2-CH=CH-CH2)n
following synthetic rubbers :
c. -(CO(CH2)4-CONH(CH2)6NH-)n
a. SBR rubber
d. -(OCH2-CH2-O-CO CO-)n
b. Buna-N rubber
c. Neoprene rubber
338
ii. Write the chemical reactions involved 5. Answer the following.
in manufacture of Nylon 6,6 i. How is polythene manufactured ?
iii. Explain vulcanisation of rubber. Give their properties and uses.
Which vulcanizing agents are used ii. Is synthetic rubber better than natural
for the following synthetic rubber. rubber ? If so, in what respect?
a. Neoprene b. Buna-N iii. Write main specialities of Buna-S,
iv. Write reactions involved in the Neoprene rubber?
formation of --- 1) Teflon iv. Write the structure of isoprene and
2) Bakelite the polymer obtained from it.
v. What is meant by LDP and HDP? v. Explain in detail free radical
Mention the basic difference between mechanism involved during
the same with suitable examples. preparation of addition polymer.
vi. Write preparation, properties and uses
of Teflon.
Activity :
vii. Classify the following polymers as
straight chain, branched chain and
cross linked polymers. i. Collect the information of
the process like extrusion and
a. -(CH2-CH-)n moulding in Textile Industries.
−
CN
b. -(CH2-CH2-CH-CH2-CH2-)n ii. Make a list of polymers used to
make the following articles
− −
CH2
CH2 a. Photographic film
b. Frames of spectacles
c.
OH OH OH c. Fountain pens
H2C CH2 CH2 CH2
d. Moulded plastic chains
e. Terywool or Terycot fabric
CH2
iii. Prepare a report on factors
CH2 CH2 responsible for degradation of
polymers giving suitable example.
OH iv. Search and make a chart/note
H2C CH2 CH2 CH2 on silicones with reference to
OH OH monomers, structure, properties
and uses.
CH2 (Bakelite)
v. Collect the information and data
about Rubber industry, plastic
industry and synthetic fibre (rayon)
industries running in India.
339
16. GREEN CHEMISTRY AND NANOCHEMISTRY
340
Illustration : The concept of atom economy For example : Adipic acid is widely used in
gives the measure of the unwanted product polymer industry. Benzene is the starting
produced in a particular reaction. material for the synthesis of adipic acid but
% atom economy = benzene is carcinogenic and benzene being
volatile organic compound (VOC) pollutes air.
Formula weight of the desired product
In green technology developed by Drath and
sum of formula weight of all the reactants used in Frost, adipic acid is enzymatically synthesised
the reaction
from glucose.
× 100
5. Use Safer solvent and auxilaries :
For example : conversion of Butan-1-ol to 1 - Choose the safer solvent available for
bromobutane any given step of reaction. Minimize the total
CH3CH2CH2CH2OH + NaBr + H2SO4 amount of solvents and auxilary substances
CH3CH2CH2CH2-Br + NaHSO4 + H2O used, as these make up a large percentage of
the total waste created.
% atom economy =
Illustration : The main aim behind this
mass of (4C + 9H + 1Br) atoms
principle is to use green solvents. For example,
mass of (4C + 12H + 5O + 1Br + 1Na + 1S)atoms water, supercritical CO2 in place of volatile
× 100
halogenated organic solvents, for example,
137 u CH2Cl2, CHCl3, CCl4 for chemical synthesis
= × 100
275 u and other purposes. Solvents as chemicals that
= 49.81 % dissolve solutes and form solutions, facilitate
many reactions. Water is a safe benign solvent
3. Less hazardous chemical synthesis :
while dichloromethane is hazardous. Use of
Designed chemical reactions and toxic solvent affects millions of workers every
synthesis routes should be as safe as possible. year and has implications for consumers and
So that we can avoid formation of hazardous the environment as well. Many solvents are
waste from chemical processes. used in high volumes and many are volatile
Illustration : Earlier DDT (Dichlorodiphenyl organic compounds. Their use creates large
trichloroethane) was used as insecticide and amounts of waste, air pollution and other
which was effective in controlling diseases like health impacts. Finding safer, more efficient
typhoid and malaria carrying mosquitos. It was alternatives or removing solvents altogether is
realized that DDT is harmful to living things. one of the best ways to improve a process or
Nowadays benzene hexachloride (BHC) product.
is used as insecticide. One of the ϒ-isomer 6. Design for energy efficiency : Chemical
(gamma) of BHC is called gammexane or synthesis should be designed to minimize the
lindane. use of energy. It is better to minimize the energy
4. Desigining Safer Chemicals : This principle by carrying out reactions at room temperature
is quite similar to the previous one. To develop and pressure.
products that are less toxic or which require This can be achieved by use of proper
less toxic raw materials. catalyst, use of micro organisms for organic
Illustration : In Chemical industries workers synthesis, use of renewable materials, ... ,etc.
are exposed to toxic environment. In order to Illustration : The biocatalyst can work at
prevent the workers from exposure to toxicity, the ambient condition. Similarly, in chemical
we should think of designing safer chemicals. synthesis, refluxing conditions require less
341
energy, improving the technology of heating 8. Reduce derivatives : [Minimization of
system, use microwave heating, .... , etc. steps]
7. Use of renewable feedstocks : The A commonly used technique in
perspective of this principle is largely toward organic synthesis is the use of protecting or
petrochemicals. Use chemicals which are blocking group. Unnecessary derivatization
made from renewable (plant based) sources (for example installation / removal of use of
rather than other (for example : Crude Oil). protecting groups) should be minimized or
avoided if possible, because such steps require
Illustration : Overexploitation of
additional reagents and can generate waste.
nonrenewable feed stocks will deplete the
resources and future generation will be Illustration : In organic synthesis, we need
deprived. Moreover, use of these nonrenewable very often protection of some functional
resources puts burden on the environment. groups. Finally, we again need their
deprotection. It is explained in the following
On the other hand, use of renewable resources
example of synthesis of m-hydroxybenzoic
for example agricultural or biological product
acid from m-hydroxy benzaldehyde.
ensures the sharing of resources by future
generation. This practice generally does not Obviously, in such cases, atom economy
put much burden on environment. The products is also less. The green chemistry principle
and waste are generally biodegradable. aims to develop the methodology where
unnecessary steps should be avoided, if
practicable biocatalytic reactions very often
need no protection of selective group.
COOH
OH
(m-hydroxybenzoic acid)
9. Use of catalysis : Use of catalyst in the chemical reaction speeds up its rate. Catalyst helps
to incease selectivity, minimize waste and reduce reaction times and energy demands.
Complete the chart
Reaction Name of Catalyst used
1. Hydrogenation of oil (Hardening)
2. Haber’s process of manufature of ammonia
3. Manufacture of HDPE polymer
4. Manufacture of H2SO4 by contact process
5. Fischer-Tropsch process (synthesis of gasoline)
342
10. Design for degradation : Design chemicals
Do you know ? that degrade and can be discarded easily. Ensure
Does plastic packaging impact the that both chemicals and their degradation
food they wrap ? products are not toxic, bioaccumulative or
Phthalates leach into food through environmentally persistent.
packaging so you should avoid Illustration : The aim behind this principle
microwaving food or drinks in plastic and is that the waste product should degrade
not use plastic cling wrap and store your automatically to clean the environment. Thus,
food in glass container whenever possible. the biodegradable polymers and pesticides are
Try to avoid prepackaging, processed food always preferred. To make separation easier
so that you will reduce exposure to harmful for the consumer an international plastic
effect of plastic. recycle mark is printed on larger items.
1 2
PETE
Number 1 : PETE or PET HDPE
(Polyethylene terephthalate) Number 2 : HDPE (high
Used In : microwavable food trays; density polyethylene)
salad dressing, soft drink, water and Used In : household cleaner and
beer bottles shampoo bottles
Status : hard to clean; absorbs bacteria Status : transmits no known chemicals
and flavors; avoid reusing into food
Is Recycled To Make : carpet, Is Recycled To Make : detergent
furniture, new containers, polar bottles, fencing, floor tiles, pens
fleece
7
Other
Number 7 : Other 3
(Miscellaneous) V
Used In : 3- and 5- gallon waterjugs, Number 3 : V or PVC
nylon, some food containers (vinyl)
Status : Contains bisphenol A, which Used In : cooking oil bottles, clear
has been linked to heart disease and HOUSEHOLD food packaging, mouthwash bottles
obesity; avoid PLASTICS Status : is belived to contain
Is Recycled To Make : custom- phalates that interfere with hormonal
made products development; avoid
Is Recycled To Make : cables.
mudflaps, paneling, roadway
gutters
6
PS
Number 6 : PS 5 4
(Polystyrene)
PP LDPE
Used In : disposable cups and plates,
Number 5 : PP Number 4 : LDPE (Low
egg cartons, take-out containers
(Polypropylene) density polyethylene)
Status : is belived to leach styrene,
Used In : ketchup bottles, medicine, Used In : bread and shopping bags,
a possible human carcinogen into
and syrup bottle, drinking straws carpet, clothing, furniture
food; avoid
Is Recycled To Make : foam Status : transmits no known chemicals Status : Transmits no known
packaging, insulation, light into food chemicals into food
switchplates, rulers Is Recycled To Make : battery Is Recycled To Make : envelopes,
cables, brooms, ice scrapers, rakes floor tiles, lumber, trash-can liners
343
11. Real-time Analysis Pollution Prevention: negative environmental effects. Right now
Analytical methods need to be further the green chemistry revolution is beginning
developed to allow for real-time, in process and it is an exciting time with new challenges
monitoring and control prior to the formation for chemists involved with the discovery,
of hazardous substances. manufacture and use of chemicals.
Illustration : Analytical methodologies Green chemistry helps to protect the
should be developed or modified, so that presence of ozone in the stratosphere essential
continuous monitoring of the manufacturing for the survival of life on the earth. Green
and processing units is possible. This is very chemistry is useful to control green house
much important for the chemical industries effect (Global warming). So we should think
and nuclear reactors. about save environment and save earth.
12. Safer chemistry for Accident prevention:
Can you recall ?
We need to develop chemical processes
1. What are the shapes of a
that are safer and minimize the risk of
bacillus and coccus? (Refer to
accidents.
chapter from Biology, Std. XI)
Illustration : The substances to be used in a
2. Which instrument is used to observe the
chemical reaction should be selected in such
cells ? (Refer to chapter 5 from Biology,
a way that they can minimize the occurrence
Std. XI)
of chemical accidents, explosions, fire and
emission. For example, if the chemical process 3. What is the size range of molecules of
works with the gaseous substances, then the lipids and proteins ?
possibility of accidents including explosion
is relatively higher compared to the system 16.5 Introduction to nano chemistry : From
working with non volatile liquid and solid clothes, sunglasses you wear to computer
substances. hard drives and even cleaning products,
nanotechnology plays a big part in the
16.4 The role of Green chemistry : The green
manufacture of many materials. We have been
chemistry approach recognizes that the Earth
using Lasers in DVD, CD players for a long
does have a natural capacity for dealing with
time which contain nanosize components.
much of the waste and pollution that society
Look at Fig. 16.1 which shows comparative
generates, it is only when that capacity is
scales from macro-materials to atoms.
exceeded that we become unsustainable.
Also observe another Fig. 16.2 which depicts
To promote innovative chemical
the materials in nature, as well as devices that
technologies that reduce or eliminate the use
are man made. In both figures some objects
or generation of hazardous substances in the
like tennis ball (Fig. 16.1), ant, human hair
design, manufacture and use of chemical
(Fig. 16.2) we can see with our own eyes
products.
whereas bacteria, virus, red blood cell, we can
The green chemistry helps to reduce not observe with naked eye. These are known
capital expenditure, to prevent pollution. as nanomaterials.
Green chemistry incorporates pollution
a. What is nanoscience ?
prevention practices in the manufacture of
chemicals and promotes pollution prevention Nanoscience is the study of phenomena and
and industrial ecology. Green chemistry is a manipulation of materials at atomic, molecular
new way of looking at chemicals and their and macromolecular scales where properties
manufacturing process to minimize any differ significantly from those at a larger scale.
344
Fig. 16.1 Macro-materials to atoms
345
be nanoparticles, nanowires and nanotubes materials science as well as engineering,
according to dimensions. Nanostructured biological and medical applications.
materials may be large organic molecules,
inorganic cluster compounds and metallic or Do you know ?
semiconductor particles. A very highly useful application
of nanochemistry is ‘medicine’. A
What are zero, one and two dimensional
simple skin care product of nanochemistry
nanoscale system ?
is sunscreen. Sunscreen contains
i. Zero-Dimensional Nanostructures : For nanoparticles of Zinc oxide, (ZnO) and
example, Nanoparticles. Titanium dioxide, (TiO2). These chemicals
A zero dimensional structure is one in which protect the skin against harmful UV
all three dimensions are in the nanoscale. (ultraviolet) rays by absorbing or reflecting
the light and prevent the skin from damage.
ii. One-Dimensional Nanostructures : For
example, Nanowires and Nano rods.
Internet my friend
A one dimensional nanostructure is one in Find out similar applications in
which two dimensions are in the nanoscale. medicine related to wounds, healing
iii. Two-Dimensional Nanostructures : For process. Also find out applications of TiO2
example, Thin films. and ZnO in other areas.
A two-dimensional nanostructure is one in 16.6 Characteristic features of Nanoparticles
which one dimension is in the nanoscale. : What makes the science at nanoscale special
Nanomaterial Nanomaterial is that at such a small scale, different laws
Example
Dimension Type dominate over those that we experience in our
everyday life.
Nanoparticles,
All three Quantum dots, 16.6.1 Colour : It is an optical property that
dimensions < nanoshells, is different at nanoscale. Elemental gold as
100 nm nanorings, we know, has nice shining yellow colour.
microcapsules However, if you had only 100 gold atoms
arranged in cube, its colour would be much
Two dimen- more red.
Nanotubes, fibres,
sions < 100
nanowires
nm
One dimen-
Thin films, layers
sion < 100
and coatings
nm
Fig. 16.3 Illustration of zero, one, two
dimensions
e. Definition of Nanochemistry : It is the Fig. 16.4 Formation of gold nanoparticles
combination of chemistry and nanoscience. solution
It deals with designing and synthesis of 16.6.2 Surface area : High surface-to-volume
materials of nanoscale with different size and ratio is a very important characteristic of
shape, structure and composition and their nanoparticles. If a bulk material is sub divided
organization into functional architectures. into a group of individual nanoparticles,
Nanochemistry is used in chemical, physical, the total volume remains the same, but the
346
collective surface area is largely increased. sodium clusters (Nan) of 1000 atoms appeared
With large surface area for the same volume, to melt at 288 K while cluster of 10,000 atoms
these small particles react much faster because melted at 303 K and bulk sodium melts at
more surface area provides more number 371K.
of reaction sites, leading to more chemical 16.6.5 Mechanical properties
reactivity. Explanation of increase in surface
area with decrease in particle size. Mechanical strength : Nanosized copper and
palladium clusters with diameter in the size
range of 5-7 nm can have hardness upto 500%
greater than bulk metal.
16.6.6 Electrical conductivity : Electrical
conductivity is observed to change at nanoscale.
For example, carbon nanotube can act as a
Area = 6 × 1m2 = 6 m2 Area = 6×(1/2m)2 ×8 = 12 m2
conductor or semiconductor in behaviour.
16.7 Synthesis of nanomaterials
16.7.1 : There are two approaches to the
synthesis of nanomaterials. Bottom up and Top
down. Fig. 16.6 shows schematic illustration
Area = 6 × (1/3m)2 × 27 = 18 m2
of the preparation methods of nanoparticles.
Fig. 16.5 : Surface area of nanoparticles
Fig. 16.5 shows the surface areas when a cube Top-Down
of 1m3 were progressively cut into smaller
cube until cube of 1nm3 formed.
16.6.3 Catalytic activity : Due to increase
in surface area with decrease in particle Bottom-up
size, nanomaterial-based catalysts show
increased catalytic acitivity. Usually they are Fig. 16.6 : Schematic illustration of the
heterogeneous catalysts that means catalysts preparation of nanoparticles
are in solid form and the reactions occur on the In the bottom approach, molecular
surface of the catalyst. Nanoparticle catalysts components arrange themselves into more
can be easily separated and can be recycled. complex assemblies atom by atom, molecule
Example, Pd, Pt metal nanoparticles used in by molecule and cluster by cluster from the
hydrogenation reactions. bottom. Example : synthesis of nanoparticles
TiO2, ZnO are used in photocatalysis. Gold in by colloidal dispersion.
bulk form is unreactive, but gold nanoparticles In the top-down approach, nanomaterials
are found to be very good catalyst for various are synthesized from bulk material by breaking
organic reactions. the material. The bulk solids are dis-assembled
into finer pieces until they are constituted of
Internet my friend
only few atoms.
Find out various applications or
use of gold nanoparticles. 16.7.2 Wet chemical synthesis of
Nanomaterials : Sol-gel process : Sols are
16.6.4 Thermal properties : melting point dispersions of colloidal particles in a liquid.
The melting point of nanomaterial changes Colloids are solid particles with diameters of
drastically and depends on size. For example, 1-100nm. A gel is interconnected rigid network
347
with pores of submicrometer dimensions and 2. Gelation resulting from the formation of an
polymeric chains whose average length is oxide or alcohol-bridged network. (gel) by a
greater than a micrometer. polycondensation reaction.
A sol-gel process is based on inorganic 3. Aging of the gel means during that period
polymerization reactions. It is generally carried gel transforms into a solid mass.
out at room temperature and includes four 4. Drying of the gel : In this step, water and
steps : hydrolysis, polycondensation, drying other volatile liquids are removed from the
and thermal decomposition. This method is gel network.
widely employed to prepare oxide materials.
5. Dehydration : The material is heated at
temperatures upto 800 0C.
16.7.3 Analysis or characterization of
nanomaterials :
The synthesized material is analyzed by
various analytical tools or techniques. The
name of the technique and its use is described
in the following Table 16.1.
16.7.4 Photographs of instruments
348
16.8 History of nanotechnology :
Electron Gun Vaccum Chamber Richard
Watson Von
Anode and Crick Feynman Neumann
Condenser Lens 1959
1953 Machines
Condenser Lens Electron Beam 1966
Filament Gun
Wehnelt Gun Deflectors
Anode
Condenser lens 1
Fixed Aperture
Condenser lens 2
Condenser stigmator
Beam Deflectors
Condenser Aperture
Objective lens upper
Objective stigmator Specimen holder
Objective Aperture Objective lens lower
Selective Area Aperture Image Deflectors
or intermediate Aperture Intermediate Lens
Different stigmator Projector Lens 1
Projector Lens 2
CCD Camera
Beam axis
Viewing screen
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Disadvantages : Despite the possibilities and
Do you know ? the advancements that the nanotechnology
Sol-gel processes are used in the offers to the world, there also exist certain
motor vechicle industry to produce potential risks involved with the disadvantages
water repellent coatings for wind screens of it.
or exterior mirrors.
Nanotechnology has raised the standard
16.10 Nanoparticles and Nanotechnology : of living but at the same time, it has increased
the pollution which includes air pollution. The
Advantages : pollution caused by nanotechnology is known
1. Revolution in electronics and computing. as nano pollution. This kind of pollution is
2. Energy sector - nanotechnology will make very dangerous for living organisms.
solar power more economical. Energy storage Nanoparticles can cause lung damage.
devices will become more efficient. Inhaled particulated matter can be deposited
3. Medical field : throughout the human respiratory tract and
then deposit in lungs.
Manufacturing of smart drugs, helps cure
faster and without side effects. Curing of life The characteristics of nanoparticles
threatening diseases like cancer and diabetes. that are relevant for health effects are size,
chemical composition and shape.
Exercises
1. Choose the most correct option.
i. The development that meets the needs iv. Which of the following information
of present without compromising the is given by FTIR technique ?
ability of future generations to meet
a. Absorption of functional groups
their own need is known as
b. Particle size
a. Continuous development
c. Confirmation of formation of
b. Sustainable development
nanoparticles
c. True development
d. Crystal structure
d. Irrational development
v. The concept of green chemistry was
ii. Which of the following is ϒ-isomer coined by
of BHC?
a. Born Haber
a. DDT b. lindane
b. Nario Taniguchi
c. Chloroform
c. Richard Feynman
d. Chlorobenzene
d. Paul T. Anastas
iii. The prefix 'nano' comes from
2. Answer the following
a. French word meaning billion
i. Write the formula to calculate % atom
b. Greek word meaning dwarf economy.
c. Spanish word meaning particle ii. Name the ϒ-isomer of BHC.
d. Latin word meaning invisible
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iii. Ridhima wants to detect structure vi. Which nanomaterial is used in
of surface of materials. Name the sunscreen lotion ? Write its use.
technique she has to use. vii. How will you illustrate the use of
iv. Which nanomaterial is used for tyres safer solvent and auxiliaries ?
of car to increase the life of tyres ? viii. Define catalyst. Give two examples.
v. Name the scientist who discovered 4. Answer the following
scanning tunneling microscope (STM)
in 1980. i. Explain any three principles of green
chemistry.
vi. 1 nm = .....m ?
ii. Explain atom economy with suitable
3. Answer the following example.
i. Define (i) Green chemistry (ii) iii. How will you illustrate the principle,
sustainable development. minimization of steps ?
ii. Explain the role of green chemistry. iv. What do you mean by sol and gel?
iii. Give the full form (long form) of the Describe the sol-gel method of
names for following instruments. preparation for nanoparticles.
a. XRD b. TEM. c. STM v. Which flower is an example of self
d. FTIR e. SEM cleaning ?
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