UGSemsterSyllabus Chemistry 5Sem514Chemistry English

BS514CHE-E
B.Sc.
THIRD YEAR SEMESTER – 5
CHEMISTRY
Inorganic, Organic & Physical Chemistry-5
“We may forgo material benefits of civilization, but we cannot forgo

our right and opportunity to reap the benefitsof the highest education
to the fullest extent as the education is the greatest material benefit”
-Dr. B. R. Ambedkar
Dr. B. R. AMBEDKAR OPEN UNIVERSITY

HYDERABAD
2020
C O U R S E T EAM
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First Edition : 2020
© 2020, Dr. B. R. Ambedkar Open University, Hyderabad, T.S.
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PREFACE
This course deals with topics included in B.Sc 3 year chemistry, fifth semester
course by the Dr. B. R. Ambedkar Open University - Hyderbad.
The course material is covered in four blocks, each block comprising of three
units. Each unit contains statement of objectives, brief introduction, subject matter, summary,
check your progress - answers, model examination questions, and refferences for futher
reading.
The first block, Inorganic chemistry it covers formation, composition determiation,

stability constants, factors effecting on stability, applications in chemical analysis of Co-
ordinate complexes. Explained about General charecteristrics of metals, valance bond
and molecular orbital concepts and alloys. Also discussed about the principles of metallurgy.
The second is Organi chemistry, it deals synthesis, properties and importance of

amino acids and heterocyclic compounds. Enlightened a brief study about the vitamins
and hormones.
The third block is Physical chemistry, it deals with concepts pertaining to

thermodynamics, elcrochemistry and priciples and concepts of photochemistry .
The fourth bolck is General chemistry it deals about a basic concepts of UV-
Visible and IR spectroscopy and also discussed about the metal ions role in the biological
systems.
Keeping in view the diversity of learners in the Open University with regards to
their age, learning abilities and the minimum academic pre-requirements, the course material
is prepared in Self Instruction Mode with all the inputs to help the learner to learn by
himself/herself.
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CONTENTS
BLOCK-1: INORGANIC CHEMISTRY 1
Unit – 1: Co-ordination compounds-2 3
Unit – 2: Bonding in Metals 13
Unit – 3: Principles of Metallurgy 24
BLOCK-2 : ORGANIC CHEMISTRY 49
Unit – 4: Heterocyclic compounds 51
Unit – 5: Aminoacids and Proteins 69
Unit – 6: Vitamin and Hormones 85
BLOCK-3: PHYSICAL CHEMISTRY 105
Unit – 7: Thermodynamics - 2 (Thermochemistry) 107
Unit – 8: Electrochemistry-2 144
Unit – 9: Photochemistry 163
BLOCK-4 : GENERAL CHEMISTRY 179
Unit – 10: UV-Visible spectroscopy 181
Unit – 11: Infrared Spectroscopy (Vibrational Specroscopy) 196
Unit – 12: Metal ions in biological systems 216
Model question papers 224
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BLOCK -1
INORGANIC CHEMISTRY-1
This block deals with the formation, composition, stability of metal complexes,
general characteristics of metals, valence bond and molecular orbital theory of metalic
bonds, alloys and their properties. Aso discussed about the concepts pertaining to prin-
ciples of metullurgy.
Block-1 includes the following three units.

Unit – 1: Co-ordination compounds-2
Unit – 2: Bonding in metals
Unit – 3: Principles of metallurgy
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2
UNIT- 1: CO-ORDINATION COMPOUNDS-2
Contents
1.0. Objectives
1.1. Introduction
1.2. Formation of metal complexes
1.3. Composition of metal complexes
1.4. Stability constants of metal complexes
1.5. Factors affecting stability of metal complexes
1.6. Applications in chemical analysis
1.7. Summary
1.8. Check your progress - Answers
1.9. Examination model questions
1.10. Further reading.
1.0. OBJECTIVES
After you completed the unit you must be in a position to explain the conditions required
for the formation of metal complexes the reasons for the variation in the composition of metal
complexes. Basic principles underlying the determinations of composition and the stability of
metal complexes uses of metal complexes in chemical analysis.
1.1. INTRODUCTION
Transition metal ions form metal-complexes with chemical species (ions or molecules)
capable of donating lone pan of elections. These complexes are formed through co-ordinate
covalent compound. The metal ion in this process behaves as Lewis acid and chemical species
bond to the metal ion functions as Lewis base.
For example: Ag+, Cu2+, Ni2+ form with ammonia Ag(NH3)2+, Cu(NH3)42+ and Ni (NH3)42+.
3
Complex ions as shown below.
H 3N NH3 H3N NH3
H3N Ag+ NH3 Cu+2 Ni+2
H3N NH3 H3N NH3
The chemical species forming the bond through donation of lone pair of electrons is
known as ligand. Thus NH3 in the above examples is called the ligand. The ligand generally is
a neutral molecule or a negative ion. Some examples are
Neutral molecules
NH3, H2O, EDTA, Ethylene diamine etc.
Negative ions
CN—, CI—, Br—,I—, OH—, F— etc
The number of Co-ordinate bonds a metal ion can form with the ligands may be 2, 4, 6 or 8.
This is known as co-ordination number. The geometry of the complex species depends to a
large extent on this co-ordination number.The stability of the complex also in turn depends on
this number.
Check your progress

Note: a) Space provided below for writing your answer.
b) Compare your answer with one given at end of the unit.
1) What is a metal complex ?
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2) Which type of chemical species form metal complexes ?
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1.2. FORMATION OF METAL COMPLEXES
Formation of metal complexes depend on the conditions of the experiment. Some complexes
are formed readily in acidic solutions and some in alkaline solutions. The oxidation state of the
metal ion to some extent favours or disfavours the formation of metal complexes.
M+n + nL  MLn
The charge of the complex MLn depends on the charge of L and also the value of ‘n’. For
example
Cu2+ + 4NH3  [Cu(NH3)4]2+
Ag+ + 2NH3  [Ag(NH3)2]+
Cu2+ + 4CN-  [Cu(CN)4]2-
Fe3+ + 6CN-  [Fe(CN)6]3-
1.3. COMPOSITION OF METAL COMPLEXES
The empirical formula of the metal complex is generally referred to on the composition of
the metal complex. This is generally represented as metal ion ligand ratio of molor concentrations.
Thus the composition of metal complexes is generally represented as 1:1, 1:2, 1:3 (metal ion:
ligand) etc. This composition is determined by different methods generally. The colorimetric or
spectrophotometric methods are employed for the coloured complexes. Two of these methods
are described below
1) Slope ratio method

2) Job’s continuous variation method
The Spectrophotometric determination of the composition involves different stages as
listed below
1) Establishing of complex formation
2) Fixing up of optimum conditions for the formation of stable complex
3) Acertaining the characteristic wavelength for determining the composition
4) The method of determing the composition
1) Establishing of complex formation
To a known value (5 ml) of metal ion solution (10-3 M), a known excess (100 ml) of
ligand solution (10-1 M) is added under different pH conditions. The pH at which appearance of
a dense colour different from that of the metal ion or the ligand solution suggests the formation
of a metal complex at the pH. This fact is confirmed or established spectrophotometrically. The
absorption spectra of the following solutions are recorded in the visible wave length region (480
nm - 800 nm).
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(i) metal ion solution
(ii) ligand solution
(iii) metal ion+ ligand solution (excess)
Generally (of the solutions are coloured) each solution exhibit a characteristic wavelength
(  max) of maximum absorption. If this for the solution (iii) is quite different form the other two,
it is presumed that the complex is formed.
Check your progress
3. How is complex formed established colorimetrically?
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2) Fixing up of  max for the metal complex

The absorption spectra of metal ion solutions, ligand solution and the (metal ion + ligand)
mixed solution in the optimum pH solution are recorded. The  max of the solution (iii) which is
different from these of solutions of (i) & (ii) is used in further studies.
3) Determination of Composition of metal complex.

For the coloured complex, this is determined by spectro photometric methods. These are
a) Slope-ratio method
b) Jobs continuous variations methods.
(a) Slope- ratio methods

Under the optimum pH conditions of formation of metal complex. The following two series
of solutions are prepared and the observance of each solutions is measured at the  max
fixed.
First series of solutions
1(ml) of metal ion solutions (10-1 m)+9 ml of buffer solution + xml ligand solution (10-3 m)+
(10-x) ml water are mixed (Total= 20 ml) For each solution, The absorbance is measured at
 max. A graph is drawn between absorbance (A) and the concentration of ligand solution (x
ml). It is generally a linear graph. The slope of this linear graph is determined(m).
Second series of solution
1 ml (1-1 M) of ligand solution + 9 ml of buffer solution + x ml of metal ion solution
(10-3 M) and (10-x) ml of the H 2 O are mixed. (Total source =20ml). The absorbrance (A)
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of each solution is measured at  max.A graph is drawn between x and A. It is a linear
graph. The slope of the linear plot (n) is determined. The composition of the complex is
written as Mnm.
c) Job’s continuous variation method
A series of solutions as detailed below are prepared and the absorbance (A) of each
solution is measured at  max and a graph is drawn between absorption and mole fraction of
metal ion. A parabolic graph is obtained. The mole fraction of metal ion corresponding to the
maximum absorbance ( A max) gives the composition of the complex.
X ml of metal ion solution (10-3 M)+9 ml of buffer solution +(l0-x) ml solution of ligand
solution (10-3 M) are mixed. The absorbance of each solution is measured at  max .
1.4. STABILITY CONSTANTS OF METAL COMPLEXES
Metal ions, because of the charge and the size, do not exist freely in solutions. They are
always associated with the counter ions or other components of the solutions. In nearly all the
cases the donor property of the solvent itself is considerable. The metal ions are present as well
defined stable species called ‘solvo complexes’. If the solvent is water, these are called ‘aquo
complexes’ [Cu (H2O)4]2+. If the solution contains a more reactive ligand than the water the
stepwise substitution of the water molecules by this ligand and takes place.
For example:
When ammonia is added to a solution of Cu salt, there will be a rapid replacement of water
molecules co-ordinated to the metal ion by molecules of ammonia giving rise to a final product
[Cu (NH3)4]2+. This can be represented by the equations,
k1
2+
[Cu (H2O)4] + NH3 [Cu(NH3)(H2O)3]2+ + H2O
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k2
[Cu(NH3)(H2O)3] 2+
+ NH3 [Cu(NH3)2(H2O)2]2+ + H2O
k3
[Cu(H2O)2(NH3)2]2+ + NH3 [Cu(NH3)3(H2O)]2+ + H2O
k4
[Cu(H2O)(NH3)3]2+ + NH3 [Cu(NH3)4]2+ + H2O
According to law of mass action, ‘the equilibrium constants ‘ or otherwise called the ‘stepwise
formation constants’ K1,K2.......K4 etc., for different steps can be written as,
[Cu ( NH 3 )( H 2O)3 ]2

K1 
[Cu ( H 2O )4 ]2 + NH 3
[Cu ( NH 3 )2 ( H 2O )2 ]2
K2 
[Cu ( H 2O )3 ( NH 3 )]2 + NH 3
[Cu ( NH 3 )3 ( H 2O )]2
K3 
[Cu ( H 2O )2 ( NH 3 ) 2 ]2 + NH 3
[Cu ( NH 3 ) 4 ]2
K4 
[Cu ( H 2O )3 ( NH 3 )]2 + NH 3
The equilibrium constants characterise the stability of the complexes in solution and
are usually called ‘stability constants’. Sometimes the reciprocal values of these constants
named as ‘instability constants’ are also used. Another symbol  is used to represent the
overall formation of the complex, the overall formation constant  is the product of stepwise
formation constants. For example
 4
= K1 . K2 . K3 . K4
Or  n
= K1 . K2 . K3 .......... Kn
The numerical value of a stability constant describes the relative concentrations of

different species is equilibrium. Large stability constants indicate that the concentration of
complex is much greater than the concentrations of the components of which it is made. Then
we say that a complex is stable.
1.5. FACTORS AFFECTING STABILITY OF METAL

COMPLEXES
The factors effecting the stability of a complex in solution are:
1. Temperature
2. Nature of the medium
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3. properties of the metal ions
4. Properties of the ligand.
1. Effect of temperature: In general the formation of complex is favoured by negative

enthalpy and positive entropy change. The relative importance of these effects is found
to be dependent on variations in the ligand as well as the central metal ions.
2. Nature of the medium: The effect of dielectric constant on the stability of the complex
in solution is of two types. One is the medium in which the complex is present and the
other is due to the interaction between the metal and the ligand. The later effect is
much smaller when compared to the first one and its exact value is usually not available.
It has been observed by many that in semi aqueous media there is a linear relationship
between the mole fractions of the non aqueous solvent of the medium.
3. Properties of the metal ions: A number of attempts have been made to ascertain the
effect of the central metal ion on the stability of the metal complex. On the basis of the
observations made it is found that the most stable complexes are formed with cations
of comparatively small size and high nuclear or ionic charge. Ions with these properties
will naturally have the greatest attractive power for the electrons of the ligand. The
quantity defined to measure this attractive power is the ionic potential 
cation radius

cation radius in A 0
The values of for different cations with relative complexing ability are given in the table.
Ions Ionic Potential Relative Complex forming Ability
K+ 0.75 Forms few complexes

2+
Hg 1.8 Forms many complexes
Cd2+ 2.1 Forms many complexes
2+
Zn 2.7 Forms many complexes
2+
Co 2.8 Forms many complexes
Ni2+ 2.9 Forms many complexes
3+
Fe 4.7 Always complexes
Cr3+ 4.7 Always complexes
Co3+ 4.8 Always complexes
4+
Pt 6.2 Always complexes
It is usually true that if $ is greater than 2, the possibility for complex formation is good.
Indiscriminate use of the ionic potential to predict stability of complex can lead to discrepancies.
The availability of unfilled ‘d’ orbitals into which the electrons donated by the ligand can enter,
9
leads to the formation of greater number of complexes with greater stability. On the basis of
study of the stability constant’s of the different metals with ligands containing oxygen, nitrogen
the metal ions are grouped into three categories.
a) Metal ions that form most stable complexes with oxygen containing ligands
Ba+2 Ca2+, Mg2+, Be3+, Al3+, Ga3+, In3+, Tl3+, Ti4+, Si4+, Th4+, Ge4+, Sn4+, Mo4+, U4+, U6+, Fe3+
and
b) Metal ions showing equal affinity for oxygen and nitrogen containing ligands.
Be2+, Cr3+ , Fe2+, Pt2+ and Pt4+
c) Metal ions that form most stable complexes with nitrogen containing ligands.
d) Cu+, Cu2+, Au+, Cd2+, Hg2+, Co3+ and Ni2+
The complex forming abilities of the bivalent transition metal ions are frequently
characterised by a stability order. Irving and Williams comparing ionic radii and second ionization
potential of the metal ions rationalized such an order Mn2+<Fe2+<Co2+<Ni2+ Cu2+>Zn2+ which is
valid for nitrogen and oxygen donar ligands, irrespective of the nature of the ligand.
4. Properties of the ligand: Although the large number of ligands are known, the donor
atoms that undergo combinations with the metal ions are restricted to the strongly non metallic
elements like N, O, S and halide ions. The radius of the donor atoms and the charge or the
dipole moment of the ligand influence the stability of complexes. In the halide series the order
of the stability is F- > Cl- > Br- > I-. For a charged ligand it is observed that the greater the charge,
the strongest is the bond.
PO3–4 > SO2–4 > ClO–4
For the neutral molecules the dipole moment is the important factor. Other factors
being equal the ligands with largest permanent dipole moment will give the most stable complexes.
This is nicely illustrated in the substituted ammonia series.
NH3 >R-NH2>R2 NH>R3 N Where R is an alkyl group.
Complexes formed with poly dentate ligands like ethylenediamine, salicylaldehyde and
oxine are more stable when compared to the mono dentate ligands forming five and six membered
rings. This effect is termed as chelate effect. Introduction of the bulky group into the ligand
molecules decreases the stability of the chelate because of steric hinderance.
1.6. APPLICATIONS IN CHEMICAL ANALYSIS

The following complex formation reactions are well known in analytical chemistry.
1. In qualitative analysis
a) Formation of nitroso complex (brown ring) is used in the identification or
confirmation of nitrate (NO3–) or nitrite (NO2–) ion
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b) Formation of (Ag(NH3)2+) ion in the confirmation of chloride ions.
c) Formation of [Fe(CNS)6]3- ion (red coloured solution) is used in the confirmation
of Fe3+ ion
d) Formation of (Co (-nitro--naphthol3+)3 (red coloured solution is used in the
identification of Co2+
e) CN- ion is used in the detection of cd2+ in presence of Cu2+ ions.
2. In quantitative analysis
f) Al3+ is precipitated by 8-OH Quinoline (oxinate)3, quantitatively as [(Al(oxine)3]
complex from the solution at 4 and is estimated gravimetrically.
g) Dimethylglyoxime (DMG) is used in the precipitation of Ni from aqueous
solution as [Ni(DMG)2] complex at 8. The precipitation is quantitative, hence
it is used in the gravimetric estimation of Ni2+.
h) CNS’ ions are used in the spectrophotemetric determination of Fe3+ ion
[Fe(CNS)6 ]3+.
1.7. SUMMARY
Transition-metal complexes are formed through co-ordinate co-valent bond. These pos-
sess different structures, colours and properties. The composition of these are expressed by the
empirical formula. The ratio between the metal ion and the ligand is considered as the empirical
formula. These are 1:1, 1:2, and 1:3. The stability of these complexes in solution depends on
several factors. These complexes are useful in qualitative and quantitative chemical analysis.
1.8. CHECK YOUR PROGRESS - ANSWERS
1. Metal ions which combined to negatively charged or neutral species it can able to
donate pair of electrons are produces a complex called metal complex or coordinate
complex.
2. Negatively charged species or neutral species are donating the electron pair to the
positively charged metal ion to produce coordinate covalent bond.
3. Based on the maximum absorption wave length of the metal ion, Ligand and metal
complex solution.
1.9. EXAMINATION MODEL QUESTIONS
I. Answer the following in 10 lines each
1. What is meant by the composition of the metal complex?

2. How is this composition of metal complexes determined.
3. What are the factors that influence the stability of the metal complexes?
4. Give an account of the applications of metal complexes in chemical analysis.
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II. Answer the following in 30 lines each
1. Describe the method of determining the composition of metal complex with an
example.
2. Discuss about the stability and the factors that influences the stability
of metal complexes.
3. Write on the applications of metal complexes.
1.10. FURTHER READING
1. Text book of Inorganic chemistry by P.L. Soni

2. A New Consice Inorganic chemistry by Lee J. D.
3. Inorganic Chemistry: Principles of Structure and Reactivityby James E. Huheey.
4. Advanced inorganic chemistry by A. Cotton and G. Wilkinson.
5. Inorganic chemistry by Shriver & Atkins- fifth addition
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UNIT - 2: BONDING IN METALS
Contents
2.0. Objectives
2.1. Introduction
2.2. General characteristics of metals
2.3.Valence bond theory of metallic bond
2.4. Molecular orbital approach or bond theory of solids
2.5. Alloys
2.6. Summary
2.9. Further reading
2.0. OBJECTIVES
After the detailed study and understanding of the contents you should be able to:
 realise that the metals possess three different types of lattices. These are face centered
cubic (FCC), hexagonal close packing (HCP) and body centered cubic (BCC) packing
 find out that allotropes are the different modifications of a metal which differ in the
lattice structures.
 extend valence bond theory and molecular orbital theory to metals which explain the
metallic character satisfactorly.
2.1. INTRODUCTION
Many metals are quite hard. Therefore they should possess considerably strong attractive
forces between their atoms. But they cannot have conventional ionic or covalent bonds due to
the non-availability of so many electrons to form bonds with eight or twelve surrounding
atoms. Therefore it is proposed that metals possess special attractive forces between their
atoms called metallic bond.
2.2. GENERAL CHARACTERISTICS OF METALS
Metals are characterised by the properties like high electrical and thermal conductivity,
metallic luster, malleability (ability to be rolled into sheets) and ductility (ability to be drawn into
wires). The properties are linked to the type of bonding present in the solids. X-ray diffraction
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studies show that metals form crystals in which the atoms are arranged in one of the three
different lattice geometries. These are known as face centred cubic (FCC), the hexagonal close
packing (HCP) and body centred cubic (BCC). In the first two structures each atom is sur-
rounded by twelve atoms. Six atoms in the same plane and three atoms each above and below
as shown in figures 2.0 and 2.1.
Check your progress
1. What are the characteristic properties of metals?
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In the body centered cubic structures single atom is sand-witched between two layers
of four atoms as show in figure 2.0.
FACE CENTRED CUBIC LATTICE (FCC)
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BODY CENTRED CUBIC LATTICE (BCC)
HEXAGONAL CLOSE PACKING (HCP)

Table 2.1. Crystal structure types of some metals
The metals like iron and hafnium exist in more than one crystalline forms. Such
modifications are named as ‘allotropes’.
The deformation properties of metals, such as ductility and malleability are directly
linked to their crystal structure. Thus, when a metal is subjected to a stress, such as hamcring
or the rolling operation it deforms by planes of atoms gliding past each other. The planes of
atoms are known as glides or slip planes.
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Since these atoms are closest together (unlike the lattice diagrams shown earlier) they will
have the greatest cohesive forces and therefore will exert the greatest resistance to deformation.
The grater the number of glide planes in a given structure, the more directions there will be in
which the crystal can yield under a stress and therefore the more ductile or less brittle it will be.
The other properties like high electrical and thermal conductivity can be explained in terms of
bonding in metals (‘metallic bonding’). Two main theories are available to explain the bonding in
metals, one being the ‘valence bond theory’ and the other ‘molecular orbital approach ‘.
Check your progress
2. Why the metal of FCC crystalline structures are more malleable and ductile
over other types of metals ?
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2.3 VALENCE BOND THEORY OF THE METALLIC BOND
The valence bond approach of metals, due mainly to Pauling, is simpler than the mo-
lecular orbital approach. This approach uses the principle of electron pairing to form covalent
bonds between atoms in the metal similar to simple molecules such as H2, Cl2, O2. However,
one important difference lies between metals and these molecules. In metals, there are not
enough number of electrons between the nearest neighbour atoms to form a complete set of
electron pair bonds or in other words the metallic structure is said to be electron deficient.
As an example a unit cell of the body-centered cubic crystal of lithium is considered. In
this structure a lithium atom in the body of the unit cell is surrounded by eight nearest neighbours
at the corners of the cell and by six more next nearest neighbours at the centres of the six
surrounding cells. Thus, the central lithium atom could form covalent bonds with fourteen other
lithium atoms in a crystal. Each of the lithium atoms has only one ‘2s’ electron available to form
a covalent bond. A total of 28 electrons are required for the formation of 14 localised electron
pair bonds (covalent bonds). But only 15 electrons are available. From this one draws the
conclusion that 14 localised electron pair bonds are not formed in metals. It means the bonds in
metals are highly delocalised. This is similar to the conjugate double bonds in benzene in which
the bonds are resonating. A schematic representation of the resonating structure in the case of
lithium atoms is shown in figure 2.1.
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Li Li Li Li Li Li Li Li
Li Li Li Li Li Li Li Li
(1) (2) (3) (4)

(a) Synchronous resonance (b) Pivotal resonance resulting
resulting in non-ionic in ionic resonance forms
resonance forms
Fig.2.2. Resonating structure in Lithium
For simplicity only four atoms are shown, but of-course, this situation can be continued
throughout the three dimensional structure. The resonance occurs through the shifting of electrons
as shown by the arrowns in structure (1) of figure (a) to give new bonds between atom, as
shown in structure (2). An important feature of this type of resonance in metals should be
noted. Since only one 2s electron is available in each atom for bonding, no one atom can form
two bonds simultaneously, so that the resonance switch must be synchronous for all bonds in
the crystal. It is known that the more the number of the resonance structures, the more is the
stability of the speices. Resonance leading to the ionic structure is illustrated in figure (b) in
which the shifting of bonds are not synchronous. This leaves the lower left hand atom with a+1
charge and the upper right hand atom-1 charge (structute2) atom on the lower-right hand side,
and hence is known as pivotal resonance. The additional one electron on the right hand side of
the lithium atom is accommodated in the next higher energy empty 2p orbital, which is named
as metallic orbital. Which is equal to the difference in ionization potentials of the 2s and 2p
orbitals. This in-put of energy is more than that available from the resonance stabilization (energy
acquired from the large number of ionic resonating structures). This becomes possible through
the use of metallic orbitals. The presence of these metallic orbitals in metals allow for the
enhanced electron mobility. As a result they will have high electrical conductivity.
The availability of both s and p orbitals in many metals led Pauling to conclude that the sp
hybridization is also possible in metals like Bc. These permit greater overlap of orbitals forming
stronger bonds. Because of this, the alkaline earth metals are known to be hard having higher
melting points as compared to the alkaline metals which are soft and have low melting points.
This trend in properties continues upto the III group of the periodic table through the transition
metals. This trend in properties is due to the availability of larger number of atomic orbitals of
similar energy, to form hybridized orbitals required for the formation of strong bonds. Thus,
Pauling has assigned a valence, called metallic valence to each metallic elements. The metallic
valence parallel the properties of the metal crystal such as density and hardness. Even though
the Pauling valence bond treatment is useful in explaining the metallic properties through the
formation of bonds between the metal atoms, yet it is qualitative one.
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2.4. MOLECULAR ORBITAL APPROACH OR BOND THEORY
OF SOLIDS
To explain the metallic properties, molecular orbital concept was used by Elock in 1928. In
solids one deals with infinite number of atoms instead of small number of atoms as in descrete
molecules. In this theory starting from ‘N’ number of atomic orbitals present in the metals an
equivalent number of molecular orbitals are constructed. The total number of quantum states
with a particular quantum number does not change even when the atoms come together, to
form a crystal. Thus in lithium crystal with ‘N’ number of atoms, each atomic electron having
two possible spin states +1/2 will have 2N quantum states. This large number of states leads to
very closely spaced energy levels, which constitute an energy band in the crystal. This is
illustrated in Fig 2.2.
6N
2p
E
N
E
R
G 2N
2s
Y
1s 2N
Shell
No of atoms 1 2 3 4
Fig. 2.2. Energy bands in metals
When a second atom is brought up to the first atom, the energy level in each state is split to
give two molecular orbitals, one higher and one lower in energy than the orginal atomic orbital
as shown in the diagram. When a third atom is added three different energy levels are formed
from each atomic energy level by the combination of the atomic orbitals of three atoms. This
process continues till it reaches the value of N, in which a band of N number of closely spaced
energy levels is formed. It should be recalled that each level in the band formed from the s
atomic orbitals can accommodate two electrons with spins paired, and each energy level in the
band formed from the three p atomic orbital can accommodate six electrons with spins paired.
Thus, a band formed from Ns states will have 2-N energy levels. A band formed from N, p
states will have 6-N energy levels and a band from N, d states will have 10-N energy levels.
When the number of atoms in a system becomes equal to 10, the spacing between the levels in
a band will be the order of 10 e.v.
18
The separation between energy bands depends on the energy difference between the pure
atomic orbitals and on the distance between adjacent atoms in the solid. If the individual atomic
energy levels are widely separated or if the distance between the individual atoms is large the
individual energy bands will be separated without any overlap. In a system in which the difference
in energies of atomic orbitals is less and the distance between the individual atoms is small, we
get an overlap of energy bands. This is illustrated in figure 2.3 in which potential energy is
plotted against ‘r’ the internuclear distance for a system in which four atoms are used. At the
extreme right of the diagram, the bands formed at the distance are shown indicating the bands
which are allowed forbidden.
2.3. Overlap of energy bands
In should be noted that the band width depends not on the number of atoms present but
on the amount of interaction between the atomic orbitals with in a band. The width of a forbidden
band is greater for lower energy orbitals, compared to the higher energy orbitals. In effect, the
energy band diagram for crystal will appear very much like the energy level diagram for atoms
with the forbidden energies in crystals corresponding to the quantum jumps in energy from one
quantum level to the next in atoms. However, in crystals the energy required of transition is
small.
In the diagram the inner bands, those formed from 1s,2s and 2p atomic orbitals are
completely filled with electrons. They contain the maximum number of electrons per energy
level in a band allowed by the pauli exclusion principle. The upper bands formed form the 3s
and 3p atomic orbitals contain a partially filled band and an empty band respectively. The
partially filled band contains the valence electrons and is called the valence band. The empty
band is called the conduction band. When an electric field is applied, the electrons present in the
filled lower energy levels cannot move because the band is completely filled, and the applied
potential is not sufficient to promote the electrons to higher energy bands. In case of the electrons
present in the partially filled valence band the situation is different because the electrons can
move more freely into the unfilled valence bands and also into the conduction band resulting in
the enhanced electron mobility which in turn gives rise to the greater conduction in the metal.
19
2.5. ALLOYS
An alloy is defined as intimately mixed solid mixture of two or more different elements,
atleast one of which is a metal. Alloys are homogeneous in the molten state but heterogeneous
or homogeneous in the solid state.
Alloys containing mercury are called amalgams.
In alloys chemical properties of the component elements are retained but certain physical
properties are improved.
Alloys are prepared by the following methods.
(i) fusion (ii)electro deposition (iii)reduction and (iv)compression methods.
I) Types of Alloys
Alloys are of 3 types broadly
(i) Subtitutional solid solutions
(ii) Interstitial
(iii) Inter metallic
II) Hume-Rothery Rules
Two important rules regarding the formation of different phases of alloys and the relation
between the composition and phases of alloys are given by Hume-Rothery. These are as follows:
a) Succession of Hume-Rothery phases
The rule says that if a metal M1 of high valency is added to another metal M of lower
valency, then the same succession of alloy phases is obtained.
For example:
 ,    ,  ,    ,  ,  , 1, n1 , n, m1 , m
Pure Cu has face centered cubic structure (FCC). In adding increasing amounts of Zn
to Cu, zinc atoms first replace Cu atoms in the FCC lattice till the limit of this sample solid
solutions is reached and a new phase with body centered cube (BCC) known as -phase is
formed with increasing percentage of Zn, -phase is obtained. Further addition gives hexagonal
close packed structure known as -phase. Lastly when Zn is present in large excess a solid
solution of copper in zinc known as m-brass is formed.
b) Hume-Rothery ratio rule
Hume and Rothery pointed out that for a given structure, the ratio of the total number
of valence electrons to the number of atoms is generally constant. These ratio are 3:2; 1:13 and
7:4 for , and  structures respectively. The electrons in the orbitals of highest principal
quantum number ignoring electrons in (n-1) d orbital are considered as valence electrons the
elements of group VIII A, VIII B have no valence electrons.
20
Some examples are:
Alloy Valence electrons No. of atoms Ratio
CuZn 1+2=3 2 3:2
Cu5Sn 5+4=9 6 3:2
AgZn 1+2=3 2 3:2
Cu3As 3+3=6 4 3:2
AuCd 1+2=3 2 3:2
CoZn3 0+6=6 4 3:2
Cu5Zn8 5+16=21 13 21:13
Cu9Al4 9+12=21 13 21:13
Cu31Sn8 31+32=63 39 21:13
Au 5Cd8 5+16=21 13 21:13
Co5Cd21 0+42=42 26 21:13
CuZn3 1+6=7 4 7:4
AgCd3 1+6=7 4 7:4
Cu3Sn 3+4=7 4 7:4
AnCd3 1+6=7 4 7:4
FeZn7 0+14=14 8 7:4
Check your progress
3. What are alloys?
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4. What are Hume-Rothery rules?
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2.6. SUMMARY
Metals are differentiated from non-metals by their characteristic properties. They are
a) malleability b) ductility c) electrical and thermal conductivity d) luster e) FCC, BCC and
HCP type crystal structures. They possess special interatomic attractive forces called metallic
bond. Valence bond theory and molecular orbital theory of metal bonding try to explain the
properties of metals satisfactorily.

1. Metals are characterised by the properties like high electrical and thermal conductivity, metallic
luster, malleability (ability to be rolled into sheets) and ductility (ability to be drawn into
wires).
2. The grater the number of glide planes in a given structure, the more directions there will be
in which the crystal can yield under a stress and therefore the more ductile or less brittle it
will be.
3. An alloy is defined as intimately mixed solid mixture of two or more different elements,
atleast one of which is a metal.
4. Hume and Rothery pointed out that for a given structure, the ratio of the total number of
valence electrons to the number of atoms is generally constant
I. Answer each of the following in 10 lines

1. What is a ‘bond’ in terms of MO theory of metals? How does it originate?
2. What is the difference between synchronous and pivotal resonances, according
to the Pauling theory of metals?
3. Explain the concept of metallic orbital.
4. Explain the concept of metallic valence.
II. Answer each of the following in 30 lines.
1. How do you explain the electrical conductivity of a metal?
22
2. How is conductivity in metals explained on the basis of valence bond theory?
3. Compare Block and Pauling theories of metallic bond.

23
UNIT-3: PRINCIPLES OF METALLURGY
Contents
3.0. Objectives
3.1. Introduction
3.2. The ores of metals
3.3. Purification of ores
3.4. Fluxes and slags
3.5. Furnaces
3.6. General methods of extraction of metals
3.7. Purification of extracted metals
3.8. Extraction of nickel
3.9. Extraction of Uranium
3.10. Extraction of Thorium
3.11. Summary
3.0. OBJECTIVES
Once you completed the study and comprehension of the contents of this unit, you must be able
to:
 differentiate ores from minerals

 appreciate the classification of ores into oxides, carbonates, sulphides, sulphates, chlorides
and phosphates.
 give the steps involved in the extraction of a metal from its ores i.e., ore dressing,
concentration, roasting or calcinations, smelting and refining.
 the details regarding the extraction of Ni, U, Th.
3.1. INTRODUCTION
Metals occur in combined form as chemical compounds in nature. These are generally
referred to as minerals. These chemical compounds may be oxides. Carbonates, sulphides,
sulphates, chlorides or phosphates.
However, it may not be economical or beneficial to use each and every mineral for the
isolation of the metal from it. For example iron occurs in nature as its oxide. (Haematite Fe2O3
24
or Magnetite (Fe3 O4 ) and sulphide (Iron pyrites Fe2 S3). However haematite is generally
employed to obtain the metal from it. The mineral which is widely employed for the extraction
of the metal is commonly known as “ Ore”.
The extraction or isolation of metals from their ores (naturally occurring chemical
compounds) is known to man even from Metal Ages. Metals such as copper, iron, gold, silver
and alloys like bronze are familiar to men even in 3000B.C. The process of obtaining metal
from the ore is called “metallurgy”. In olden days metallurgy was considered as an art rather
than science.
Table 3.0: Important ores of metals.
Chemical nature Name Chemical formula Important mineral

Oxides Baddelyte ZrO2 Zirconium
Bauxite Al2O3 nH2O Aluminium
Cassiterite SnO2 Tin
Chromite FeOCr2O3 Chromium
Haematite Fe2O3 Iron
Illumenite FeTiO3 Titanium
Pitch Blende U3O8 Uranium
Pyrolusite MnO2 Manganese
Thrianite ThO2 Thorium
Zincite ZnO Zinc
Carbonates Dolomite CaCO3MgCO3 Magnesium

Lime Stone CaCO3 Calcium
Magnesite MgCO3 Magnesium
Sulphides Argentite Ag2S Silver

Cinnabar HgS Mercury
Galena PbS Lead
Pentlandite (Ni,Fe)S Nickel
Zinc Blende ZnS Zinc
Sulphates Anglesite PbSO4 Lead

Barytes BaSO4 Barium
Gypsum CaSO4 2H2O Calcium
Chlorides Carnalite KCl,MgCl26H2O Magnesium

Horn Silver AgCl Silver
Phosphates Monite Ca3(PO4)2H2O Calcium
Silicates Thorite ThSiO4 Thorium

Zinconium ZnSiO4 Zinc
25
Check your progress
1) What is an ore?
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3.2. THE ORES OF METALS

Metals as described earlier, occur in nature mostly in combined form as chemical
compounds of different types. These are oxides, carbonates, sulphides, sulphates, chlorides or
phosphates. The important ores of different metals are listed in Table 3.0.
However some metals occur in elemental form (metallic state) too in nature. Such
metals are said to occur native. These metals include silver, gold, palladium and osmium.
Ores are always associated with sand and impurities. These impurities are called gaunge.
The percentage of the impurities varies from ore to ore.
3.3. PURIFICATION OF ORES

An ore is required to be purified before it is subjected to the metallurgical processes for
the isolation of the metal. This purification process mainly involves the separation of gaunge
from the ore. This operation of separating gaunge from the ore is called ‘concentration of the
ore’ or ‘ore dressing’. The purification is effected by different methods. These are briefly
described in the foregoing paragraphs.
a) Hand picking
The ore which occurs as big rocks is powdered and then the impurities associated with
it are separated by hand picking. In this method these small bits of ore are passed over rollers
and the impurities are picked out with hand while these ore bits are moving over the rollers. For
example, the stone impurities associated with haematite are separated in this way by hand
picking.
b) Gravity concentration method
This method employs the density difference between the ore and the impurities.
i) Washing with water
The ore is powdered in Ball Mills and washed with water flowing over it with high
speeds. The lighter impurities are washed off in this water flow leaving behind the heavy ore
particles. For example when Cassiterite ore is washed with water flowing with high speeds,
sand and clay are washed away leaving behind the ore.
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ii) Using Wilfle table
The table is provided with wooden riffles. The ore is mixed with water and the slurry
obtained is passed over these riffles, while the table is shaken vigorously. In this process, the
heavy ore particles are collected (in a collector) at one side of the table.
Fig. 3.0. Wilfle Table

1. Slurry (Water + ore) 2.Wooden Riffles 3. Collector
iii) Jig’s method
When the ore is available as large lumps, this method is generally used. In this method
‘Jig’ is used and the method is therefore called Jig’s method. In the Jig, Fig 3.1 a perforated
screen immersed in water is present. The ore is placed on this screen and water is forced from
below. The mixture of ore and gaunge then gets suspended in water. By repeating this process
of forcing water a number of times, the gaunge being lighter in density floats on water and the
ore accumulates at the bottom. The gaunge is then separated.
Fig.3.1. Jig’s method

1. ore outlet, 2. water level, 3. screen, 4. water, 5. piston
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iv) Flotation process
This method is specially useful when it is required to separate small particles of ore from the
gaunge. This method of separation finds application in the purification of sulphide ores.
The ore is polarized and is made into pulp with water, the pulp is placed in water taken
in a tank along with some pine oil, A chemical called sodium ethyl xanthate is then added and air
is blown into the mixture with the help of tubes containing small holes. The tubes are then
rotated vigorously, when froth full of bubbles is formed. The particles of ore float on this froth.
The gaunge particles reach the bottom of the tank and settle down. The pure ore particles are
then separated from the froth.
Generally the froth formed due to air bubbles when air is bubbled through the mixture,
will not be stable and the bubbles break down. Therefore to keep the froth in the stable form,
some chemicals are added. These are called frothers.
In a similar way, chemicals such as sodium ethyl xanthate used to make the ore particles
adhere firmly to the froth are called collectors. The chemicals such as sodium cyanide used to
improve froth flotation are called activators. Substances such as lime and sodium carbonate are
added to the floatation tank to keep the PH of the mixture constant. These are called conditioners.
V) Magnetic separation
This method is employed if either the ore or the impurities associated with it (but not
both) is magnetic in nature. For example, tin ore (tin stone), is associated with the magnetic
impurity called wolfram. It is therefore easy to separate tinstone from the associated impurity.
In a similar way the method can be used in the purification of pyrolusite (manganese ore) from
the associated magnetic impurities of magnetite.
3.2. Magnetic method
1. Ore outlet, 2. Water level, 3. Screen, 4. Water, 5. Piston
28
The roller is earthed through a wire and an electrode at high negative potential is
placed near the roller. Finely powdered dry ore is then put on the roller to form a thin layer.
These ore particles get negatively charged due to the electrode and will be accumulated on the
roller. The accumulated particles being good conductors transfer the negative charge to the
roller and gradually become positively charged. The particles are also positively charged, the
low conducting gaunge particles will not be able to transfer their charge.
vi) Liquation process
This method is used in cases where the ore is relatively easily melted than the impurities.
For example, the impurities associated with the antimony ore, stitnite undergo melting at relatively
higher temperatures than the ore itself, At 5480C. The ore undergoes melting and the liquid
comes out through the pores, when the ore is subjected to high temperatures in porous pot
made from refractory material the impurities remain in the vessel.
3.4. FLUXES AND SLAGS
It is not always possible to separate the solid impurities (gaunge) completely from the
ore by the methods described earlier. It is also not possible to melt the gaunge at ordinary
furnace temperatures and separate it in the liquid form. However, by adding some foreign
substance which can chemically react with the gaunge, it is possible to melt the gaunge at lower
temperatures. The foreign substance added is called flux and the substance formed by the
chemical reaction between flux and gaunge is called slag. The melting point of slag is generally
less than the melting point of either the flux or the gaunge.
Gaunge + Flux = Slag
The fluxes are of two types a) Acid flux and b) Basic flux
Silica (SiO2) is used as acid flux. This occurs in nature in different forms such as sand,
quartz and rock. If the gaunge possesses alkaline properties, the acid flux is used. For examples
the gaunge FcO (Ferrous oxide) associated with copper pyrites is separated through the addition
of silica.
FcO + SiO2 FeSiO3
Gaunge flux slag
If the gaunge possesses acid properties, the basic flux is use. For example the gaunge,
SiO2 (sand) associated with haematite is separated through the addition of lime stone (CaCO3).
Calcium carbonate decomposes first to give calcium oxide the later combines with SiO2 to form
the slag.
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Fig. 3.3. Electromagnetic separation
1. Ore, 2. Induced magnetic rollers, 3. Electro magnetic poles, 4. Magnetised ore,
5. Non magnetised ore
vii) Electro static separation
This method is generally applicable to separate metals which occur native or in the
form of highly conducting sulphide ores from the impurities.
In this process a charged roller will be moving as shown in the figure 3.3
CaCO3 CaO+CO2
CaO + SiO2 CaSiO3
Flux gaunge slag
Types of stages
It is made clear earlier in the unit that the chemical substance is formed when a flux is
added to an ore remove the gaunge from it. For a chemical thus formed to act as a slag, it is
required to possess the following characteristics.
30
i) It should be easily liquefiable and the liquid thus formed should flow freely.
ii) It shall have lower specific gravity than the metal. This makes the slag float on the
metal.
iii) It shall have lower heat capacity. This prevents the heating of metals to high temperature.
iv) It should be able to dissolve the impurities easily.
The stages are classified as acidic and basic depending on whether the acidic oxide is
in excess or basic oxide is in excess in the slag.
For example, (CaO)4 SiO2 is called basic slag where as (CaO)4 (SiO2)3 is called acidic
slag. On the other rahand CaO SiO2 is called neutral slag since both acidic and basic oxides are
equal in proportion.
The slages are good bye-products. They are used in the laying of (a) roads and (b) in
the manufacturer of cement, fertilizers and building materials.
Check your progress
2. What do you mean by flux?
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3.5. FURNACES
In the metallurgical process i.e. in the processes of extraction of metals form their ores,
there is a need to heat a mixture of ore and another chemical substance to very high tempera-
tures. For example in the extraction of iron form its ore hematite, the ore is heated with lime to
high temperatures. The room or the device where the mixture of ore and the chemical sub-
stance is heated to higher temperatures is referred to as Furnace. The size shape and the
building material of the furnace depend on the nature of chemical reactions that takes place in
the furnace.
31
The furnaces are generally constructed with heat resistance bricks and their outer
sides are lined with steel plates. The furnaces is generally heated with a fuel (gas, liquid or
solid) or electrically. The fuels frequently used are coal, petroleum oil, natural gas, producer gas
and water gas.
Furnaces are basically classified into four types depending on
1. The chemical nature of the metallurgical process
2. The mode of burning of the fuel
3. The mode of movement of the charge in the furnace and
4. The mode of transfer of heat to the charge.
The furnaces are also usually classified on the basis of structure as
a)Shaft Furnaces
b) Reverbaratory Furnaces
c) Muffle Furnaces
d) Electrical Furnaces
a) Shaft Furnaces
This type of furnace is usually cylindrical or rectangular in shape. Coke is generally

used as the fuel. The charge added from the top of the furnace moves down due to gravity. Hot
air is blown upwards from the bottom through tuyers. These furnaces are employed in
metallurgical processes involving smelting and roasting. The Blast furnace used in the manufacture
of iron and the furnace used to prepare copper matte from copper pyrites are examples of such
furnaces.
b) Reverbaratory furnaces
These furnaces have specific shape as shown in figure 3.4. These are constructed
with furnace bricks. These contain large hearths. The proof of the furnace is curved and made
of silica bricks. Solid and liquid charges are used in theses furnace. The charge is added through
hopper fixed to the roof. Fire boxes or burners arranged at the lower part of the furnace are
used to burn the fuel. The roof of the furnace helps to reflect and radiate the heat towards the
charge.
Open hearth furnace used in the manufacture of steel belongs to this type.
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3.4. Reverberatory Furnaced
1. Fire Box, 2. Health, 3. chimney
c) Muffle furnaces
In this type of furnaces, the charge and the fuel do not have direct contact. They are
placed in two different rooms separated by heat conducting wall.
These furnaces are generally employed to burn furnace bricks.
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d) Electrical furnaces
These furnaces are important at places where electrical power is cheap. In these
furnaces, the electrical energy is used to produce heat energy. These are basically of two types
i)Are furnaces ii)Electrical resistance furnaces. These are shown in figures 3.6 and 3.7.
In the first type of furnaces, an electric are is used to produce the necessary heat.
Carbon electrodes are used for the purpose. In the second type of furnaces, electricity is
passed through the resistances and the heat produced is used in the furnaces.
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3.6. GENERAL METHODS OF EXTRACTION OF METALS
FROM ORES
The method chosen depends on the chemical nature of the ore. You have already learnt that
metals occur in nature as their oxides, or carbonates, or sulphides, or sulphates, or chlorides, or
phosphates or silicates. Therefore specific process or reactions are generally employed to
convert the compound into the metal. These processes are mainly a) reduction b) roasting c)
calicination d) smelting e) leaching.
a) Reduction
The reduction process is usually required in the extraction of metals from oxide and
chloride ores. In the reduction of oxide ores, coke (a form of carbon) is popularly used as
reducing agent. However, it offers difficulties in the case of oxides of aluminium, manganese
and magnesium. But it is highly useful in the case of oxides of iron and zinc. Therefore other
reducing agents such as hydrogen gas carbon monoxide, water gas, aluminium, calcium and
even electrical are used in the metallurgical processes. Some example to illustrate the use of
each of these reducing agents are given below.
Carbon
0
950 C
ZnO + C   Zn + CO
0
1300 C
SnO2 + 2C   Sn + 2CO
Carbon monoxide
0
700 C
Fe2O3 + 3CO   2Fe + 3CO 2
Water gas
0
300 C
2 NiO + (CO + H 2 )   2Ni + CO 2 + H 2O
Water gas
Hydrogen
MoO3 + 3H2  Mo + 3H2O
WO3 + 3H2  W + 3H2O
WCl3 + 3H2  W + 6HCl
Aluminium metal
The metal combines with oxygen in a highly exothermic process. This facts is used to
reduce the oxides of chromium and manganese to their metals. An initial temperature of 6000 C
is generally required for the purpose. The process is generally known as Alumino-thermite
process.
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CrO3 + 2Al  Al2O3 + 2Cr
3Mn3O4 + 8Al  4Al2O3+ 9Mn
Magnesium, Calcium metal
Rubdidium oxide is reduced with magnesium to get the metal.
Rb2O3 + 3Mg  3MgO + 2Rb
The halides of titanium and uranium are reduced with magnesium and calcium respectively.
b) Roasting
In the process of roasting, the ore in the non-molten state is heated alone or along with
other substances to high temperatures in presence of air. The process of roasting involves
oxidation of the metal. However the metal may be converted to its oxide, sulphate or chloride
depending on the nature of the ore and the composition of the charge. Based on this fact, the
roasting process is classified as oxidizing roasting, sulphating roasting and chloridsing roasting.
These are illustrated by the following chemical reactions.
Oxidising roasting
2ZnS + 3O2  2ZnO+2SO2
2NiS + 3O2  2NiO + 2SO2
Sulphating roastion
ZnS + 2O2  ZnSO4
2ZnS + 3O  3znO + 2SO2
ZnO + H2SO4  ZnsO4 + H2O
Chloridising roasting
AgS + 2NaCl+2O2  Na2 SO4 + 2 AgCl
c) Calcination
In this process, the ore in the non-molten state is heated to high temperatures to expel
the volatile substances in the ore. This process is widely used in the case of carbonate ores.
ZnCO3 ZnO + CO2
CaCO3  Cao + CO2
d) Smelting
In this process, the metal, or its sulphide is separated in the liquid from its ore. This is a
pyrochemical process. ie, a process where a chemical reaction is effected at high temperatures.
The conversion of heamatite into iron in the liquid state and production of a mixture of
coppersulphide and iron sulphide (matte) from copper iron pyrites are good examples for
processes involving smelting.
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e) Leaching
In this process, the ore is treated with acid, alkali or even with water a number of times
under suitable conditions to convert them into the metallic compounds of higher purity than the
ores. Few examples are given below
Acid leaching
2 Cu2S + 5O2  Cuo + 2CuSO4
2CuO + H2SO4  2CuSO4
Alkali leaching
Al2O3 + 2NaOH  2NaAlO2 + H2O
UO3 + 3Na2CO3  H2ONa4UO2(CO3)3 + 2NaOH
Cyanide leaching
2Ag2S + 8NaCN + O2  4Na[Ag(CN)2] + 2Na2SO4
3.7. PURIFICATION OF EXTRACTED METALS

The metals extracted from ores by the methods mentioned earlier are not generally of
very high purity. Hence, it is essential that these extracted metals are further purified. The
general methods of purification are a) Liquation b) Distillation c) Poling d) Cupellation
e)Electrolysis and f) Zone refining
a) Liquation
The method is useful in the purification of low melting metals. In this purification process
the impure metal is heated slowly on the roof of the inclined hearth. The metal melts and flows
down. The molten impurities remain on the hearth. Tin is purified in this way.
b) Distillation
This process is generally used to purify volatile metals. The impure metal is taken in the
retort and heated. The metal volatalizes and escapes out as the vapour leaving behind the
impurities. The vapours of the metal are condensed to get the pure metal. Zinc, cadmium and
mercury are purified by this method.
c) Poling
This method is generally applicable metals containing oxides of the same metal as
impurities. The molten metal is stirred with green logs of wood in presence of carbon powder.
The gases evolved in the process would help to reduce the oxide impurities back to metals.
d) Cupellation
Cupel is a crucible made from bone-ash. The impure metal is placed in the cupel and
melted. Hot air is blown over the cupel. In this process, the metallic impurity gets preferentially
37
oxidised. A part of the metal oxide thus formed is carried away by the air and the remaining part
is absorbed by the material of the cupel. Impure silver containing lead is purified by this method,
lead is converted into lead monoxide and is removed.
e) Electrolysis
Impure metals such as copper, silver, gold are purified by this method. In this process
the impure metal is take generally as the anode pure form of the metal is taken generally as the
cathode. A solution of the metal salt is taken together with other electrolytes as the electrolytic
bath. For example, in the purification of silver, silver nitrate and potassiumeyanide are taken as
the electrolytes in the bath. The metal from the anode in the pure form is deposited on the
cathode, while the impurities in the anode collect at the bottom of the electrolytic cell. This
collection is called anode mud.
f) Zone refining
This method is specially applicable to obtain metals of highest purity. For example
germanium of high purity used in transistors is prepared by this method. The impure metal is
made into a long rod and placed in a silica boat (Fig. 3.8). The whole set up is unclosed in quartz
tube. An induction coil surrounds the tube. The coil is first placed at one end of the boat and its
position changed gradually. When the current flows through the coil, heat is generated. The
heat thus generated melts the part of the impure metal in the boat under the coil. The position of
the coil is now changed. In the new position, the part under the coil is melted, but in the mean
time, the earlier molten metal solidifies.
By this process the pure solid metal is formed at one end and the impurities are collected
at the other end.
3.8. EXTRACTION OF NICKEL

Introduction
Kronsted in Germany isolated nickel for the first time in 1751 and named it as nickel.
However, Bergmann in 1774 studied the properties of the metal in detail. Australia Canada are
important amongest countries which produce nickel. Finland, Russia and Greece have large
deposits of nickel ores. In India, Rajasthan has large deposits of copper containing nickel.
38
Occurrence
Nickel occurs in combined form together with sulphur with sulphur, arsenic, antimony,
cobalt, copper and iron. The important ores are.
a) Nickel glance - NiAsS
b) Millerite (Nickel Blende)- Nis
c) Kup fer Nickel or Nickelite - NiAs
d) Pentlandite – (NIFo)11S10
Nickel also occurs in native state in small quantities in meteorites.
Isolation
The metal is generally extracted from sulphide ore, pentlandite or any other suphide
ore. The ore is powdered and concentrated by floatation process. The concentrated ore is put
into heaps and burnt continuously for some weeks. In this roasting process iron in the ore is
converted into iron oxide, while nickel and copper remain as sulphides.
2 FeS2 + 5O2  2FeO+4 SO2
The roasted ore is then mixed with coke and fluxes (lime stone quartz) and subjected to
smelting process in the blast furnace. FeO formed in the roasting process combines with silica
(SiO2) and forms ferrous silicate. Limestone decomposed into calcium oxide (CaO) and the
later combines with excess silica (SiO2) to form calcium silicate. These ferrous and calcium
silicate form the slag.
FeO + SiO2  Fe SiO3
CaO + SiO2  Ca SiO3
The matte is fused and taken in alkali lined Bessemer Convertor together with silica
(flux). Air is blown into the mixture. In this process sulphur is converted into SO2. All the
ferrous sulphide is converted into ferrous oxide (FeO). This FeO combines with silica to form
iron silicate. This is finally removed as the impurity. The residue of the matte contains mostly
copper sulphide and nicket sulphide with nickel ranging from 55-60% and copper 25-30%.
Recovery of nickel from matte
Nickel is obtained from matte by two processes.
a) Orford’s process
b) Mond’s process
a)Orford’s process: This is based on the following facts.
1) Copper sulphide dissolves in molten sodium sulphide while nickel sulphide does
not dissolve.
2) The density of nickel sulphide is greater than the density of copper sulphide
dissolved in sodium sulphide.
39
3) The nickel sulphide is oxidised in presence of oxygen to give nickel oxide.
 Nickel oxide when mixed with carbon and heated to high temperatures in
graphitecrucible, gives nickel.
 Mond’s process:Nickel is mostly isolated from the matte by this process.
The process is based on the following facts:
 Nickel combines with carbon monoxide at 1800C to give Ni (CO)4. Copper and iron do
not form carbonyls under similar conditions.
 Nickel carbonyl decomposes at 1800C to form nickel. The matte is roasted in special
furnaces. Copper sulphide and nickel sulphide are converted into their oxides in this
process.
Cu2S+2O2  2CuO+SO2
2NiS+3O2  2NiO+2SO3
The oxide mixture is dissolved in hot dilute sulphuric acid. Copper oxide dissolves in the
acid to give copper sulphate, while nickel oxide remains intact.
CuO+H2SO4  CuSO4+H2O
Nickel oxide is filtered and introduced into high tower (reducing tower) from the top.
The top portion of the tower is maintained at 3000 C and the bottom portion is cooled. Water gas
(CO+H2) is sent into the tower from the bottom. This gas reduces nickel oxide to nickel at the
top portion of the tower.
2NiO+(CO+H2)  2Ni+H2O+CO2
The nickel thus formed will be in the finely divided state. This finely divided nickel is
sent into a second tower (Volatalizer tower) maintained at about 800C. Carbon monoxide is
sent into the tower from the bottom. Nickel combines with carbon monoxide to give nickel
carbonyl.
Ni+4CO  Ni(CO)4
Nickel carbonyl is then sent into the third tower (decomposing tower) maintained at
o
180 C. The tower is packed with grannulated nickel. Nickel carbonyl undergoes decomposition
on contact with these granules and metallic nickel is deposited on the granules. The nickel
obtained in this process is nearly 99% pure.
Purification of Nickel
Nickel is purified electrolytically. Impure nickel is taken as anode and pure nickel as
cathode. Nickel ammonium sulphate is used as the electrolyte. Electrolysis is carried out at
30°C when pure nickel is deposited on the cathode.
Check you progress
40
3. What happens if carbon monoxide is passed over nickel powder kept at 80°C?
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Alloys of Nickel
Nickel forms many alloys such as german silver, nichrome, platinite, monel metal and
cupro nickel.
German silver contains 50.50% Copper, 10-30% Nickel and 20-30% Zinc. This is used
to make utensils.
Nichrome contains 60% Nickel, 25% Iron, 15% chromium. This is used in the
manufacture of resistance wires.
Platinite contains 60% Iron, 40% Nickel. This has the same coefficient of expansion as
glass. It is therefore used in the manufacture of filaments in electric bulbs.
Monel metal contains 70% Nickel, 30% Copper. This resists the action by alkalis. It is
therefore used in the manufacture of vessels for chemical reactions.
Cupro Nickel contains 75% copper and 25% nickel. This is used in the preparation of
coins.
Uses of Nickel
1. Nickel is used to coat metals such as iron to prevent rusting as well as to give it the
base metal bright appearance.
2. Finely divided nickel is used as a catalyst in the reduction process. This is specially
used in the hydrogenation of oils.
3. Nickel is used in the manufacture of alloys.
3.9. EXTRACTION OF URANIUM

Introduction
Uranium was discovered by Klaproth in 1789 in the mineral pitch blende. The metal is
named after the planet Uranus discovered in 1781. Uranium is now a very important metal
41
since atomic energy is being widely used these days. Monozite sands occurring in Travancore
contains Uranium. Bihar and Rajasthan also have minerals containing Uranium to less extent.
Occurence
The important ores of Uranium are
1) Pitche Blende : U3O8 This contains thoria (ThO2), lead, iron and rare earths as other
constituents. This is obtained in Canada, Belgium and South Africa.
2) Carnotite. K2O, ,UO3, V2O5nH2O
This is obtained in Canada.
3) Autanite, CaO, 2UO3,P2O5nH2 O
Isolation
The isolation process involves mainly
a) The concentration of the ore and separation of U3O8 in the pure form and (b) reduction
of U3O8 to the metallic state. The concentrated ore is subject to (i) chemical precipitation or (ii)
ion-exchange process or (iii) solvent extraction to obtain pure U3O8..
The method adopted to concentrate the ore depends on the composition of the ore. The
composition of the ore varies from place to place.
The ore is first crushed into powder and magnetic separation methods are used. Sulphide
impurities are removed by floatation process.
The ore is roasted to decompose the carbonates and sulphides and expel CO2 and SO2
formed in the process. The volatile substances such as arsenic and antimony are also removed
in the process. The roasted ore is then subjected to acid learning or alkali leaching.
Acid Leaching
The roasted ore is taken in store vessels and is leached with sulphuric acid or nitric acid
or hydrochloric acid. Generally an oxidising agent such as manganese dioxide is added to convert
lower oxides into UO3. The oxide dissolves in acid to give uranyl sulphate.
UO3 + H2SO4  UO2SO4 + H2O
The PH of the solution is generally kept at 2.8 and BaCl2 is added to remove Radium
as RaSO4 along with BaSO4. The contents are filtered to separate soluble uranyl sulphate
together with copper and iron sulphates. To this filtrate sodium carbonate is added. When
copper, iron and manganese are precipitated as hydroxides. But uranium forms a carbonato
42
complex. On filtration soluble carbonate complex of Uranium is separated. This is then treated
with sodium hydroxide solution to precipitate sodium diuranate.
2Na4 [UO2 (CO3)3 ]+6NaOH  Na2U2 O7+6Na 2CO3+3H2 O
Alkali Leaching
In this process sodium carbonate is added when UO3 reacts with it to form complex Uranyl
Carbonate.
UO3+3Na 2CO3+H2O  Na 4[UO2(CO3)3]+2NaOH
The complex carbonate reacts with NaOH to form sodium diuranate.
Preparation of U3O8 from Sodium diuranate
Sodium diurante precipitate is dissolved in HCl to form uranyl chloride. H2S is bubbled
into the solution to precipitate copper and arsenic. These precipitates are removed and excess
H2S is expelld. Later ammonium hydroxide is added and ammonium diuranate is precipitated.
This diuranate is separated and heated to 7000 C to give U3O8.
Ion exchange process
Uranyl sulphate solution obtained in acid leaching process is passed through anion
exchange resin. The complex uranium ions are retained on the resin. The impurities do not form
complexes and as such are not retained. Complex uranyl sulphate ions are later eluted from the
resin. Ammonium nitrate is generally used as elutant. U3O8 is finally precipitated from the
complex uranyl sulphate.
Solvent extraction process
When the aqueous solution contaning uranium salts is extracted with ether or methyl
ketone, the uranium salts are extracted into the organic layer. The organic liquid is again treated
with aqueous solution to extract uranium salts back into water. Uranyl nitrate is thus obtained
into the aqueous solution which is later evaporated to get the crystals. These are heated to get
U3 O 8 .
Extraction of uranium from U3O8
Uranium is obtained when U3O8 is reduced with carbon in electric are furnace
U3O8+4C  3U+4CO2
Uranium used in nuclear reactors is prepared as follows
UO3 is reduced with H2 to get UO2
43
UO3+ H2  UO2+ H2O
UO2 reacts with HF at 400°C to give UF4
UO2+4HF  UF4+2 H2O
UF4 is reduced with calcium to get uranium
UF4 +2Ca  U+2CaF2+134, kcal
Uses of uranium
1. Uranium is used as fissionable material in reactors to get nuclear energy.
2. It is used as coloring material in glass& ceramic industry.
3. It is used as catalyst in the Synthesis of ammonia.
3.10. EXTRACTION OF THORIUM
Introduction
The element was named as thorium & Bezelius in 1828 after the Scandinavian god.
The principle ore is monazite. Thorium minerals are complex in nature chemically. The chief
numerals are as follows.
Monazite- 18% Tho2 as silicate or phosphate + rare earth phosphate
Thorite ThO2.SiO2
Urano thorite (ThO2 UO2 SiO2)n H2O
Monazite is the important mineral of thorium. It is available in large quantities in India

(Travancore); Brazil, cylon, Canada, Florida and Australia.
Extraction
a) Preparation of thoria
b) Iron monazite sand. This sand contains 2-60% monazite. This is therefore concentrated
to get 90% monazite. The sand is first concentrated by washing and then electro magnetically.
The concentrated monazite is heated in cast iron pans with twice its weight of conc. sulphuric
acid till Yellow grains dissolve in water.
ThO2+2H2SO4  Th(SO4)2+2H2O
44
The product is transferred into a ladden vat. the un attacked mineral settles down. It is
removed by filteration. The solution is nentraised with alkali Thorium phosphate is precipitated.
This is dissolved in minimum acid and the process is repeated till thorium and rare earths are in
the ratio 4:1 Later phasphoric acid is removed.
Conversion of thoria to metallic thorium
It is difficult to obtain pure thorium because it readily reacts with reducing agents, air,
H2, O2, N2, C.
A high temperature is required for reduction. Thoria is obtained by the following methods.
i) By reduction of tetra chloride with sodium.
The tetra chloride is prepared by heating thoria with CoCl2
ThO2 + 2CoCl2  ThCl4 + 2CO2
ThCl4 +4Na  Th+4NaCl
ii) By reduction of thoria with calcium
ThO2 + 2Ca  Th+2CaO
iii) By thermal decomposition of tetra-iodide on tungsten filment at 17000C
Th I4  Th+2I2
Properties
Pure metallic thoria is soft, white metal melts at 18000 C and boils at 4200°C. It is malleable
and ductile.
Chemically thorium burns in oxygen to form thoria. It reacts with H2 at 300°C-400°C to form
ThH2. It reacts with N2 at 800°C to form a Th3N4. It is slowly attacked by acids. Strong HNO3
makes it possible it is not affected by alkalis.
Check your progress
4) What is the monazite Ore of thorium?
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45
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5) How is monazite concentrated?
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6) How is thorium obtained from thoria.
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U ses
i) one most important application is in the production of U-235.
ii) It is used as an addition element in alloys.
iii) It is used in slow - hits.
3.11. SUMMARY
Ores and minerals may not be same. Minerals from which metals can be extracted profitably
are ores. Some of the metals occur in the native state. Extraction of a metal from its ore
consists of the following steps-a) ore dressing b) ore concentration c) roasting or calcination d)
smelting and e) metal refining. In this unit all the above are presented in detail.
The names and composition of ores of Ni,U and Th are given. The metallurgy of these
metals is described. The purification methods and uses of these metals are described.
46
1. The mineral which is widely employed for the extraction of the metal is commonly
known as “ Ore”.
2. It is not always possible to separate the solid impurities (gaunge) completely from the
ore. It is also not possible to melt the gaunge at ordinary furnace temperatures However,
by adding some foreign substance which can chemically react with the gaunge, it is
possible to melt the gaunge at lower temperatures. The foreign substance added is
called flux
3. Nickel combines with carbon monoxide to give nickel carbonyl.
4. Monazite - 18% Tho2 as silicate or phosphate + rare earth phosphate
5. Iron monazite sand. This sand contains 2-60% monazite. This is concentrated to get
90% monazite by washing and then electro magnetically.
6. ThO2 + 2CoCl2  ThCl4 + 2CO2
ThCl4 +4Na  Th+4NaCl
3.13. MODEL EXAMINATION QUESTIONS

I. Answer the following in 10 lines each.
1. Explain in detail the gravity concentration method and floatation method used
in ore dressing.
2. Describe the magnetic and electro-static methods of ore dressing.
3. Describe briefly the reverboratory and muffle furnances.
4. Discuss briefly the reduction methods used in the extraction of metals.
5. Explain the terms roasting, calcination and smelting.
6. Describe liquation and distillation methods of purification of metals.
7. Discuss the principles underlying the metal purification methods, cupellation,

electrolysis and poling.
8. Describe steps involved in the production of “matte from the sulphide ores of
nickel”.
9. Describe the principle under lying in Oreford method.
10. How is uranium are converted into UO3?
11. How is thorium extracted from its mineral?
47
II. Answer the following in 30 lines each.
1. Discuss the general principles underlying the methods of isolation of metals

from ores.
2. Describe the different methods of purification?
3. How are impure metals purified?
4. Describe the different types of furnaces employed in the metallurgical

processes.
5. How is nickel extracted by Monds process?
6. How is uranium extracted from its ore?

48
BLOCK-2
ORGANIC CHEMISTRY
This block deals with the preparation, properties, importance and applications
of heterocyclic compounds, aminoacids and protiens, also discussed about the
physiological functions of vitamins, source of vitamins, glands, different type of hormones
and their functions.
Block -2 includes the following three units.
Unit – 4: Heterocyclic compounds
Unit – 5: Aminoacids and proteins
Unit – 6: Vitamin and Hormones
49
50
UNIT-4: HETERO CYCLIC COMPOUNDS
Contents
4.0. Objectives
4.1. Introduction
4.2. Classification and nomenclature
4.3. Aromaticity and orbital picture of pyrrole, furan and thiophene
4.4. Resonance in pyrrole, furan and thiophene
4.5. Synthesis of pyrrole, furan and thiophene
4.6. Physical properties
4.7. Chemical properties. Electrophilic substitution reactions
4.8. Relative reactivity of pyrrole, furan and thiophene
4.9. Addition reactions
4.10. Acidic character of pyrrole
4.11. Basic character
4.12. Oxidation
4.13. Summary
4.14. Check your progress - answers
4.0. OBJECTIVES
After studying this unit you must be able to:
 Classify and name the heterocyclic compounds containing one heteroatom viz,
pyrrole, furan and thiophene.
 Study the orbital picture, aromaticity, occurrence, isolation of these heterocyclic
compounds
 reactivity of pyrrole, furan and thiophene
 preferential electrophilic substitution reactions at 2 and 5 position of pyrrole, furan
and thiophene.
4.1. INTRODUCTION
Heterocyclic compounds are those cyclic compounds which contain besides carbon and
hydrogen one or more hetero atoms such as N,S and O. This definition does not include
compounds like ethylene oxide, succinic anlydride and phthalimide are easily converted into
open chain derivatives.
51
Heterocyclic compounds are widely distributed in nature in the form of vitamins,
antibiotics, plant pigments such as chlorophyll, haemin, amino acids and proteins, drugs,
enzymes and the genetic compounds such as DNA, RNA etc.
O O
C C
H 2C
H2C O O
O H 2C
C C
H2C
O O
Ethylene oxide Succinic anhydride Phthalimide
4.2. CLASSIFICATION AND NOMENCLATURE
This study is limited to the classification of five and six membered hetero cyclic
aromatic compounds.
1. Five-membered heterocyclics containing one hetero atom
These contain five atoms in the ring including the heteroatom; common examples are
 4 3 
2 
 5
S N
O 1 H
f uran thiophene
pyrrole
2. Six-membered heterocyclics
4 (g)
 5 3 
 6 2 
N N O
1
H
pyridine piperidine 4H -pyran
The ring positions are designated by numerals (or greek letters). In numeral system the
hetero atom is given the lowest number (1). In Greek system the position, next to the heteroatom
52
is designated as  -followed by  and so on in anticlock wise direction as shown in the above
compounds.
4.3. AROMATICITY AND ORBITAL PICTURE OF PYRROLE,

FURAN AND THIOPHENE
In these compounds, the four carbons and the hetero atom Z (Z=NH in pyrrole, O in
furan and S in thiophene) are sp2 hybridised. Thus each carbon has three sp2 hybrid orbitals
each containing an unpaired electron and an unhybridised p-orbital containing an electron and
being perpendicular to the plane of the hybrid orbitals. Similarly the hetero atom ‘Z’ has three
sp2 orbitals each containing one electron and an unhybridised p-orbital containing a pair of
electrons and being perpendicular to the plane of the hybrid orbitals. The carbon and heteroatom
form C-H, C-C, C-Z and Z-H (only in pyrrole) -bonds through sp2-s, sp2-sp2, sp2-sp2 and sp2-
s overlapping respectively. There still remains a p-orbital with one electron on each carbon and
a p-orbital with 2 electrons on the heteroatom (Fig. 4.0 (a) and 4.1 (a)).
Fig. 4.1. Orbital picture of furan (Z=O) and thiophene (Z=S) molecules
53
The five orbitals are one parallel to each other and overlap sideways to form a cyclic
delocalised -molecular orbital containing 6 electrons (aromatic sextet) and embracing all the
five atoms (4 carbon atoms and one heteroatom) of the ring. The localised orbital consists of
two electron clouds, one above and other below the plane of the ring. (Fig.4.0 (b) and 4.1 (b)
4.4 RESONANCE IN PYRROLE, FURAN AND THIOPHENE

The following resonance structures of pyrrole, furan and thiophene also explain their
aromaticity.
4 3
2
5
X X X X
1 IV
I II III
X = NH (Pyrrole)
(or)
= O (Furan)
= S (Thiphene) X X X
VII VI V
I, II, III, IV & V - Ressonance structures
VI & VII - Resonance hybrid
The resonance structures carrying no charge are more stable than those carrying charges.
Among the charged structures, the larger the charge separation, the less stable is the resonance
structure. Hence IV and V are less stable than II and III. Thus I, II and III are the main
contributing structures to the resonance hybrid and hence there is a larger electron density at
positions 2 and 5 than at 3 and 4. Therefore electrophilic substitution mainly take place at
positions 2 and 5.
In thiophene, it uses 3d - orbitals as sulphur is less electronegative than oxygen and
nitrogen. Hence more resonance structures (VIII to XII) are possible for thiophene than for
furan and pyrrole which is evident by the large resonance energy (30 K.cal/mole) of thiophene
than that of pyrrole and furan (20 K.cal/mole).
S S S S
S
VIII IX X XI XII
Resonance structures of thiophene using d-orbitals.

Check your progress
1) Why thiophene shows more ressonanace structures than pyrrole and furan?
54
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4.5 SYNTHESIS OF PYRROLE, FURAN AND THIOPHENE

Paal-knorr synthesis:
Pyrole, furan thiophene and their derivatives can be prepared from the following
general methods starting from 1,4-dicarbonyl compounds.
H 2C CH2 HC CH
C C C C
R R R R
O O OH HO
Enol-f orm
(NH3)2CO3  P2O 5  P2S5 
HC CH HC CH HC CH
C C C C C C
R R R R R R
N O S
H
R=H 1H-pyrrole furan thiophene
R=CH 3 2,5-dimethyl-1H -pyrrole 2,5-dimethylf uran 2,5-dimethylthiophene
Apart from the above general methods for the synthesis of pyrrole, furan and thiophene
these compounds can be prepared by the following specific methods.
4.5.1. Pyrrole
Pyrrole is the most important among all the five membered heterocyclic compounds as it
constitutes various natural products eg. chlorophyll (colouring matter of green leaves), haemin
(colouring mater of blood), bilirubin (colouring matter of bile), some alkaloids such as (nicotine,
cocaine) and vitamin B12 etc.
Isolation of pyrrole: Pyrrole occurs in coal tar and bone oil and is generally isolated from the
latter source. The oil is washed successively with dilute alkali and acid to remove acidic and
basic substances respectively. The extract is fractionally distilled when pyrrole distills over in
the fraction of 100-150°C and finally purified by fusing with potassium hydroxide. The
potassiopyrrole thus obtained gives pure pyrrole on stream distillation.
55
Synthesis:- Pyrrole may be synthesised by the following methods.
1) By passing acetylene and ammonia through a red hot tube.
HC CH
CH CH Redhot
+ CH
tube HC
CH CH
N
NH 3 H
2) By the distillation of succinimide over zinc dust
H2C CH2 HC CH HC CH
Zn
C C C C CH
O OH Dust HC
O HO
N N N
H H H
3) Pyrrole is prepared commercially by heating ammoum salt of mucic acid which is

obtained by the oxidation of lactose or galactose
H 2C CH 2 HC CH
Glycenol-Heat
HO CH HC OH HC CH
NH3, -2CO2, -4H 2O
N
COONH 4 COONH4
H
4) It is commercially prepared by the fractional distillation of coal tar or bone oil or by passing
a mixture of furan, ammonia and steam over heated alumina (4000C).
HC CH HC CH
NH3/Al2O3
HC CH HC CH
400 0C
O N
4.5.2. Furan
1) Manufacture:-Commercially furan is prepared by the catalytic decomposition of furfural
which is obtained by the distillation of agricultural wasts like oat hulls and ricebran on
maize cobs with dil H2SO4. The pentosans (Polymers of pentoses) present in oat hulls
(or) corn cobs are hydrolysed into pentoses which undergo dehydro cyclization to
furfural.
56
H H
C C
HO OH
Dil H2SO4 Heat
(C 5H8O4)n H
-3H2O
H H
Pentose O
C C O
CHO
H OH HO CaO(3500C) or Ni
-CO
Stream
O
f uran
2) It is also prepared by heating 2-furoic acid which is obtained by the dry distillation of
mucic acid
H H
C C
HO OH Distillation

-3H2O -CO2
H H
-CO2 COOH O
C C O
COOH f uran
HOOC OH HO f uran-2-carboxylic acid
2-Furoic Acid
Mucic acid
4.5.3. Thiophene
Isolation:-
Thiophene may be isolated from coaltar benzene by repeated extraction with conc.
sulphuric acid when thiophene forms the soluble thiophene sulphonic acid which on steam
distillation gives thiophene.
Alternatively the thiophene containing coaltar benzene is boiled with aqueous mercuric
acetate when only the thiophene is mercurated which on distilllation with concentrated
hydrochloric acid gives thiophene.
HCl
Coaltar Hg(COOCH3) 2
Benzene
Fraction  HgOCOCH3
S S
Thiophene
57
Preparation:-
1. Thiophene is prepared commercially by the interaction of n-butane and sulphur in
vapour phase at 6000C.
6000C
CH3CH2CH2CH3 + 4S
-3H2S
S
Thiophene
2) Passing a mixture of acetylene and hydrogen sulphide over heated alumina also
yields thiophene
Al2O3
2 HC CH + H2S
4000C
S
Thiophene
3) It is prepared in the laboratory by the distillation of sodium succinate with phosphorous
penta or trisulphide.
H2C CH2 P2S5
NaOOC COONa 
S
Thiophene
4.6. PHYSICAL PROPERTIES

The physical state, M.P, B.P and diopolemoments of pyrrole, furan and thiophene are
summarized below.
Bond length (pm)

Compound Mol.Wt State B.P(0C) Dipolemoment S.E
X -C2
1
C2-C3 C3 -C4
Pyrrole 67 Colourless 131 138 137 143 1.81 D 16

liquids
Furan 68 32 136 136 143 0.70 D 16
‘’
Thiphene 84 84 171 137 142 1.87 D 11
‘’
Benzene 78 80 equal equal equal 0.0 D 37.9
‘’
(X=Hetero atom N, O, S)
High boiling point of pyrrole as compared with furan, thiophene and benzene is due
to its molecular association through intermolecular hydrogen bonding.
N H N
58
Uv-absorption maxima (max) pyrrole shows absorption maxima in the Uv region at 172, 182,
211 and 304 nm.
Furan gives characteristic absorption bands around 190 and 205 nm while thiophene
shows two absorption maxima at 215 and 231 nm.
I.R spectra: Pyrrole, furan and thiophene show C-H (stretching) bands near 3000-3100cm-1
and characterstic bands of aromatic system around 1400, 1490 and 1590 cm-1. Besides these
pyrrole shows N-H stretching band at 3400-3500 cm-1.
Check your progress

2) Why pyrrole shows more boiling point than furan and thiophene?
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4.7. CHEMICAL PROPERTIES.

[ELECTROPHILIC SUBSTITUTION REACTIONS]
These compounds show considerable aromatic character as they undergo electrophilic
substitution reactions readily. However these compounds also undergo some addition reactions
which show their diene character.
Electrophilic substitution reactions:- Electrophilic substitution in these cyclic compounds
occurs preferably at 2 or 5 () positions. The intermediate carbocation resulting by the attack
of an electrophile at 2 and 5-position is more resonance stabilised than that in the case of -
positions (3-or 4-). However substitution at 3 or 4- position can take place if 2 and 5-positions
are blocked because the intermediate carbocation is stabilised by the accomodation of the
+charge on the hetero atom, to some extent.
2 - (-) Substitution:
H
E
E
(Electrophile) X X
X E
Carbocation  or 2- substitution
X = NH, O, S equivalent to 5
(intermediate)
59
3 or 4- (-) substitution:
H E
H
E E E
X X X X
IV V VI
X = NH, O, S
Resonance stabilised carbocation Fewer resonating structures (less stable)
Electrophilic substitution reactions of pyrrole, furan and thiophene are summarised in figures
4.2, 4.3 and 4.4 respectively.
Reactions of Pyrrole
(CH3CO) 2/HNO3
Nitration NO2
-10 0C N
H 2-nitro-1H -pyrrole
SO 3 / Pyridine,
SO 3H
1000C N
1H -pyrrole-2-sulfonic acid
Sulphonation H
I I
I2 / NaOH
I I
N
H 2,3,4,5-tetraiodo-1H-pyrrole
N
Cl Cl
H
Pyrrole SO2Cl2
Chlorination Cl Cl
N
H
2,3,4,5-tetrachloro-1H-pyrrole
(CH 3CO)2/SnCl 4
Freidel Craft acylation COCH 3
N
H
1-(1H -pyrrol-2-yl)ethanone
HCN/HCl
Gatterman-Koch
Synthesis CHO
N
H
1H-pyrrole-2-carbaldehyde
60
ArN2X N
Ar
N
Coupling reaction N
H An Azo dye
(CH 3COO)2Hg/AcOH
HgOCOCH3
 N
N Mercuration
H
H
Pyrrole 2-Acetoxy mercuric pyrrole
CHCl3/KOH
Reimer tiemann
reaction CHO
N
H
1H-pyrrole-2-carbaldehyde
Fig 4.4 Electrophilic substitution reactions of pyrrole
Check your progress

3) In General Pyrrole, furan and thio phen undergoes electrophilic substitution at ______
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4) what is the product in the reaction of Pyrrole with Sulphuryl chloride?
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61
Reactions of Furan
(CH3CO)2/HNO3
Nitration NO2
O
2-nitrofuran
Br2 - Dioxane
Br
Bromination 00C O
2-bromofuran
Cl2/Br2 Violent reaction leading
to cleavage of ring
SO3/Pyridine (1000C)
Sulphonation SO3H
O
furan-2-sulfonic acid
(CH3CO)2O/BF3
Freidel crafts acylation
COCH3
O 1-(furan-2-yl)ethanone
C2H5Cl/SnCl4
O
Alkylation
C2 H 5
O
furan 2-ethylfuran
HCN/HCl
Gatterman Koch
CHO
O
2-formyl furan
Cl N 2X
N
Cl
Coupling reaction N
O
2-(p-chloro phenyl azo) Furan

ArN2Cl/NaOH
Ar + N2
Gomberg reaction
O
2-aryl furan
X2
X
HgCl2/CH3COONa O
HgCl
Mercuration O RCOCl
2-f uran mercuric chloride COR
O
Fig 4.4 Electrophilic substitution reactions of furan
62
Reactions of Thiophene
H2 SO4 /300 C
SO3 H
Sulphonation S
thiophene-2-sulfonic acid
Br2
Bromination Br Br
S
2,5-dibromothiophene
C6H5COCl/SnCl4
Freidel crafts acylation

COC6H5
S
phenyl(thiophen-2-yl)methanone
CH2 O/HCl
Chloroformylation
CH2Cl
S
2-(chloromethyl)thiophene
I2/HgO
S Iodination I
S
thiophene 2-iodothiophene
(CH3COO)2 Hg/ H2O CH3

O
Mercuration Hg
S O
acetoxy(thiophen-2-yl)mercury
n-C4H9 Li CO2
Li COOH
n-butyl lithium S S
thiophen-2-yl-lithium thiophene-2-carboxylic acid
Fig 4.4 Electrophilic substitution reactions of thiophene
63
Characteristic features of electrophilic substitution in pyrole, furan and thiophene
1. The high reactivity of these compounds is indicated by the fact that mild conditions are
used in freidel crafts reactions and nitration. Strong acidic condition are avoided during
nitration and sulphonation as this will cleave furan ring and polymerize pyrrole.
2. Direct halogenation of furan is violent and may cleave the ring and liberated acids
cause polymerisation. Hence halogen substituted furan is prepared indirectly as shown
below.
Br2 
-CO2
COOH Br COOH Br
O O O
3. Reactions with diazonium salts (coupling reaction) 2 – bromo furan illustrates the greater
reactivity of these compounds as compared with benzene. In the case of benzene
series, only amines on phenols can undergo coupling reactions.
4.8. RELATIVE REACTIVITY OF PYRROLE, FURAN AND

THIOPHENE
Like benzene these heterocyclic compounds exhibit aromatic character and are
resonance stabilised. The order of reactivity of these ring systems is as follows
Pyrrole > Furran > Thiophene > benzene
R.E in KJ mole-1
87.8 71.1 117 156.6
Pyrrole is so reactive towards electrophilic substitution reactions that its reactivity is

comparable to that of aniline and phenol. For instance it undergoes Kolbe - Schmidt, Reimer-
Tiemann and coupling reactions. The high reactivity of pyrrole towards electrophilic reactions
is because of the fact that one of the contributing structures of the 2 - substituted intermediate
carbocation, III is particularly more stable because every atom in it has an octet of electrons
and nitrogen accomodates the positive charge more easily than O (in furan) and S (in thophene).
Furan is less reactive than pyrrole because oxygen accomodates a positive charge less
readily than nitrogen. Thiophene is less reactive than furan because the overlap of the differently
sized p-orbitals of carbons and sulphur is less than that in the case of carton & oxygen which
reduces the +M effect of sulphur on thiophene. Due to the great reactivity of these ring systems
certain aromatic substitution reactions have to be carried out under milder condition. These are
less aromatic than benzene as evident from their NMR data.
64
4.9. ADDITION REACTIONS
Hydrogenation (Reduction)
These compounds undergo hydrogenation in the presence of suitable catalysts to give dihydro
and tetrahydro derivatives. However thiophene needs excess Pd.catalyst for hydrogenation to
overcome the poisoning effect of sulphur whereas nickel hydrogenates it with the opening of
the ring (desulphuration) to form n-butane.
H H
H H + 4H- Ni Zn/AcOH H
H
+2H
H H 2000C
N
H N
N H H H
H H H
1H-pyrrole
2,5-dihydro-1H-pyrrole
pyrrolidine
H H
H H
Raney NI
+ 2H2
H H
O
O H
H
furan
tetrahydrofuran
H H
H H
Raney NI Excess, Pd
CH3CH2CH2CH3 H
+H2 H
butane Desulphonation S
S H
thiophene H
tetrahydrothiophene
H
H
Na/liquid NH3
+ H H
H
Birch reduction
S S H
S H H
thiophene 2,5-dihydrothiophene
2,3-dihydrothiophene
Diels- Alder reaction
Furan, unlike pyrrole and thiophene is least aromatic and behaves like a conjugated diene to
give Diels-Alder reaction to form an adduct with powerful dienophile like maleic anhydride.
65
O O
 O
O + O O
f uran
O 3a,4,7,7a-tetrahydro-4,7- O
f uran-2,5-dione epoxyisobenzof uran-1,3-dione
(or) Maleic anhydride (or) Maleic anhydride f uran adduct
4.10. ACIDIC CHARACTER

Pyrrole is weakly acidic and forms alkali metal salts for ex.
KOH
+ H 2O
N
N OH
H K
1H-pyrrole Potassio pyrrole
It reacts with Grignard reagent to form N-magnesium halide salt which also indicates
its acidic character.
CH3MgBr
+ CH4
N N
H MgBr
The acidic character of pyrrole can be explained on the basis of two factors:-
-H+
N N N
N
II III
H I
Resonanace stabilisation of pyrrylanion
N
N
V IV
66
1) The lone pair of electrons of nitrogen is involved in the formation of the sextet and
hence hydrogen is less firmly held by nitrogen. So it can be removed easily as proton.
2) Pyrryl anion formed by the dissociation of pyrrole as an acid is more resonance stabilised
than pyrrole because there is no charge separation in anyone of its resonance forms as
shown above.
4.11. BASIC CHARACTER

These heterocyclics are not basic as the lone pair of electrons on the hetero atom are not
available for protonation as these are involved in the delocalization to give aromatic sextet.
N H in pyrrole destabilises the

Further protonation at the heteroatom for e.g..
system.
N -H N
H
H H
Pyrriliumcation destabilised (no resonance)
4.12. OXIDATION
Unlike furan and thiophene, pyrrole undergoes oxidation in the presence of CrO3-ACOH to
give maleinimide.
[O]
O O
N CrO3, AcOH N
H H
1H -pyrrole 1H -pyrrole-2,5-dione
(or) Maleinimide
4.13. SUMMARY
Monocyclić conjugated five membered planar systems containing one hetero atom viz
N, O, S called pyrrole, furan and thiophene respectively are aromatic and obey Huckels rule.
These are isolated form coal tar and synthesised by well known Paal- knorr reaction besides
other methods.
These are aromatic and undergo electrophilic substitution reactions preferably at 2

position. Since addition reactions which reflect olefinic behaviour are also observed. Pyrrole
exhibits acidic character. These are present in proteins, pigments, drugs and DNA, RNA.
67
1. In thiophene, it uses 3d - orbitals as sulphur is less electronegative than oxygen and

nitrogen. Hence more resonance structures are possible.
2. Dueto the presence of hydrogen bond between pyrrole molecules it shows higher
boiling point than furan and thiophene.
3. 1, 5 positions are more favorable for the electrophilic substitution reactions of pyrrole
, furan and thiophene.
4. 2,3,4,5-tetrachloro-1H-pyrrole is the product.
1. What are heterocyclic aromatic compounds? Explain the aromaticity of pyrrole?

2. Describe the synthesis of pyrrole, furan and thiophene from 1, 4 di-carbonyl
compounds
3. Explain the mechanism of electrophilic substitution in pyrole?
4. The relative reactivity of the five membered heterocyclic compounds is pyrrole >
furan> thirophene. Explain?
II. Answer each of the following in 30 lines
1. Describe the synthesis of I) furan 2) pyrrole and 3) thiophene 2. Draw the orbital
picture of furan? Explain the various electrophilic substitution reactions in it.
3. Explain the following
a) pyrrole is more reactive than furan
b) pyrrole although has NH group, it behaves as a weak acid
c) electrophilic substitution in furan takes place at 2-or 5-positions
d) pyrrole resembles phenol in its properties.
4. Discuss the aromaticity and relative reactivity in pyrrole, furan and thiophene.
1. Heterocyclic Chemistry, T.L. Gilchrist, Longman UK Ltd, London (1985).
2. Heterocyclic Chemistry, 3rd Edn J.A.Joule, K.Mills and G.F. Smith, Stanley Thornes
Ltd, UK, (1998)
3. An introduction to the chemistry of heterocyclic compounds, 2nd Edn.R.M.Acheson,

Interscience Publishers, New York, 1967.
68
UNIT-5: AMINO ACIDS & PROTEINS
Contents
5.0. Objectives
5.1. Introduction
5.2. Occurrence, structure and nomenclature of amino acids
5.3. Synthesis of -amino acids
5.4. Physical properties of amino acids
5.5. Chemical properties of amino acids
5.6. Peptide structure and nomenclature
5.7. Proteins
5.8. Summary
5.0. OBJECTIVES
After completing the reading and understanding of the contents of the unit you must be able to:
 describe the names, structures and classification of amino acids

 describe different methods of preparation of  - amino acids
 explain the properties of amino acids due to –NH2 , -COOH and both the groups
 Know about the nomenclature, elementary structure of peptides and proteins.
5.1. INTRODUCTION
Amino acids are an important class of organic compounds which have two functional groups-
an amino (NH2) group and a carboxyl (COOH) group- in their structure. They are the building
blocks from which proteins are built up.
5.2. OCCURRENCE, STRUCTURE AND NOMENCLATURE OF

AMIO ACIDS
Well over 100 amino acids have been isolated to-date, from natural sources, and identified.
The great majority of these naturally occurring amino acids are -amino acids. In these
compounds, the amino group is attached to the carbon atom alpha () to carboxyl group. The
- carbon bears a hydrogen atom. The fourth bond of the - carbon is joined to the group which
may vary. Thus most of the naturally occurring amino acids differ only in the nature of ‘R’
group on the  -carbon.
69
H

R C COOH
NH2
of the amino acids isolated from living material, only 20 are obtained upon hydrolysis of
typical proteins. These are listed in table 5.0. The remaining are found as intermediates or end
products of metabolism. The human body cannot synthesise the twenty amino acids required
for metabolic processes. Of these, eight amino acids (marked e in the table) are called “essential
amino acids.” They are called “essential amino acids” not because they are the only amino
acids required for biological functions, but because they are essential in diet and cannot be
synthesised by the human body.
Table 5.0 Naturally occurring amino acids:

H

R C COOH
NH2
In addition to the carboxyl group and the amino group on the alpha carbon, some amino acids
contain another carboxyl group (eg. aspartic acid, glutamic acid) and these are called acidic
amino acids. Some contain a second basic group which may be an amino (eg. lysine), a guanidino
(eg. arginine) group or the imidazole ring (eg, histidine). These are called basic amino acids.
R Name Abbrevation
1. Side chain is non polar H or alkyl/aryl
H glycine Gly
CH3 (+) alanine Ala

(CH3) 2CH 2- (+) valinee Val
e Leu
(CH3)2CH-CH 2- (-) leucine
CH 3-CH2-CH(CH 3)- e
(+) isoeucine Ile
H2
C (-) phenyl alaninee Phe
(-) proline Pro

COO
N
H H
70
R Name Abbrevation
2. Side chain containing -OH

HOCH2- (-) serine Ser
e
HOCH2-(CH3)- (-) threonine Thr
H2 (-) tyrosine Tyr

HO C
3. Side chain containing 'S'
HS-CH2- (-) cysteine Cys

CH3-S-CH 2-CH2- (+) methioninee Met
4.Side chai containing non basic nitrogen
O
H2
H2N C C (+) aspargine Asn
H2
C
(-) tryptophanee Trp

N
H
O
H2 H2
H2N C C C (+) glutamine Gln
5. Side chainis acid

HOOC-CH 2- (+) aspartic acid Asp
HOOC-CH2-CH 2- (+) glutamic acid Glu
6. Side chain is base

H2N-CH2-CH 2-CH2-CH3 (+) lysine Lys
NH
H H 2 H 2 H2
H2N C N C C C (+) arginine Arg
N
C
H2 (-)histidine His
N
H
e- essential amino acids
71
With the exception of glycine, in all other amino acids the -carbon is asymmetric
(attached to four different groups) and hence all amino acids except glycine are chiral molecules
i.e. exhibit optical isomerism. All the naturally occurring amino acids have L-configuration at
the asymmetric carbon. However, the  - amino acids with L-configuration may be either
dextro rotatory or levorotatory.
HOOC
H COOH
R C COOH H2N C H
H2N
H R
NH2
R
L-Amino acids
5.3. SYNTHESIS OF  - AMINO ACIDS
Many of the amino acids can be obtained from protein hydrolysate, but it is more convenient
to obtain them by synthesis. Thus all the racemic amino acids are synthetic and are prepared
commercially. Several general methods are known for the synthesis of  -amino acids. A
suitable method can be chosen keeping in view the availability of starting materials and the type
of amino acid required.
1. Amination of halo acids:  - Halo acids are easily prepared by direct halogenation of
the corresponding acids (Hell-Volhard-Zelinsky reaction). Direct amination of -halo
acids using excess of ammonium hydroxide results in the formation of amino acids.
Thus -bromopropionic acid on reaction with excess of ammonium hydroxide gives
alanine.
H2 Br2 H
H3C C COOH H3C C COOH
PBr3
Br
NH4OH
excess
H
H3C C COOH
NH2 Alanine
If ammonia is not used in excess, formation of secondary and tertiary amines are possible
in side reaction which will reduce the yield of the amino acid.
72
2. Gabriel’s Phthalimide synthesis: -Amino acids are synthesised by the reaction
-bromo derivatives of an ester with potassium phthalimidate. This is known as the
‘Gabriel’s phthalimide synthesis’.
For example, the reaction of ethyl-  -bromopropionate with potassium phthalimidate,
followed by hydrolysis of the resulting compound gives alanine.
O O
CH3
NH N K +
Br C COOC2 H5
H
O O
CH3 O CH3
COOH H3 O
+ H2 N C COOH N C COOC2H5
H H
COOH C2 H5 OH
+ O
3. From malonic ester: Monobromo derivative of diethyl malonate reacts with potassium
salt of phthalimide to give N-phthalimido malonic ester.
O
N K
O
COOC2H5 COOC2H5 COOC2H5
Br2 O
CH2 HC Br N HC
CCl4
COOC2 H5
COOC2H5 COOC2H5 O
N-pthalimido malonic ester
Base
O R O
COOC2H5 COOC2H5
RX
N C N C
COOC2H5 COOC2H5
O O
 H3O
H
R C COOH
NH2
73
The ester may be alkylated by a variety of alkyl halides. Vigorous acid hydrolysis of the
resulting compound causes hydrolysis of both ester group and phthalimido group, and
decarboxylation of the amino dicarboxylic acid.
This method is essentially a variation of malonic ester synthesis and is a useful general
method for the synthesis of  - amino acids in good yields. Some examples of the synthesis of
amino acids using this method are given below:
1. NaOC2H 5 H2 H
HOOC C C COOH
2. ClCH2CH3OOC2H5 NH2
3. H3O/ Aspartic acid (33% yield)
1. NaOC2H 5
H2 H
Ph C C COOH
H2
2. Ph C Cl NH 2
Phenyl alanine (64% yield)
3. H3 O/
O
COOC 2H5
N HC
COOC2H 5
O
1. NaOC2H5
H2 H2 H
H3C S C C C COOH
H2 NH 2
2. H C S H C C Cl
2 2
Methionine (50% yield)
3. H3O/
1. NaOC2H5 H2 H2 H
H 3C S C C C COOH
2. H2 C NH2
C COOC2H5
H
Glutamic acid (75% yield)
3. H3 O/
4. Strecker’s synthesis: In this method, an aldehyde is converted to an  - amino nitrile by

the action of hydrogen cyanide and ammonia. The amino nitrile is hydrolysed by mineral acids
to give  - amino acids.
74
H H3 O H
R CHO +NH 3 + HCN R C CN R C COOH
NH2 NH2
Amino nitrile
The formation of  -amino nitrile involves Condensation of the aldehyde and ammonia, and
addition of HCN to the resulting imine.
R CHO + NH 4 R C NH + H 2O
H
H
R C NH + HCN R C CN
H
NH2
Amino nitrile
For example, glycine can be obtained from formaldehyde, and phenyl alanine from
phenyl acetaldeyde, (74% yield).
H 2SO4 H2 BaO H2
H 2C O H2N C CN H2N C COOH
H 2O
NH4 CN (42 % Yield
H2 NH3 H2 H
Ph C C O Ph C C CN
H HCN
1 2
NH2
H2 H NaOH
Ph C C COOH
H 2O
3 NH2  H O
3
1. Phenyl acetaldehyde 2. - Amino -- Phenyl propionitrile 3. Phenyl alanine.
The methods described above are of general applicability for the synthesis of simpler amino acids.
Some of the amino acids with more complicated structures must be prepared by other methods,
which are beyond the scope of the present lesson. The synthetic amino acids are racemic, therefore
these must be resolved into optically active components for the synthesis of peptides.
5.4. PHYSICAL PROPERTIES OF AMINO ACIDS

Amino acids are colourless crystalline compounds. They are soluble in water, but sparingly
soluble in organic solvents, the melting points of amino acids are generally high, and most amino
acids decompose instead of melting. Amino acids show both acidic and basic properties. In the
solid phase, the IR spectra of amino acids show absorption bands at 3130-3000cm-1 (due to
NH3), 1600-1500cm-1 (due to COO)n and 1300-880cm-1. Except phenylalanine, tyrosine and
tryptophan, other amino acids are transparent above 250 nm, in the U.V. region.
75
5.5. CHEMICAL PROPERTIES OF AMINO ACIDS
1. Reactions due to the amino group
a) The amino acids form salts with strong mineral acids like hydrochloric acid. These
salts are sparingly soluble in water, and the free acid may be liberated by the addition of
organic bases like pyridine.
H2 HCl H2
H2 N C COOH Cl H3 N C COOH
Glycine Glycine hydrogenchloride

 - Amino acids may be acetylated by reaction with acetyl chloride or acetic anhydride.
When benzoyl chloride is used, the corresponding benzoyl derivative is formed. Benzoyl
derivative of glycine is also known as hippuric acid.
CH3COCl O
(or) H H2
H3C C N C COOH
(CH3CO)2O
H2 N-acetyl glycine
H2 N C COOH
O
PhCOCl H H2
Ph C N C COOH
Hippuric acid
c) Nitrous acid liberates nitrogen from  - amino acids. This reaction is the basis of
‘Vanslyke method’ for the estimation of amino nitrogen.
H2 O H
H HNO2 H
H3 C C COOH H 3C C COOH H3 C C COOH
HCl -Cl
-N2
NH2 N N OH
Cl
Lactic acid
Unstable diazonium salt
d) Nitrosyl Chloride (or bromide) reacts with amino acids to form chloro (or bromo) acids.
H2 NOCl H2
H2 N C COOH Cl C COOH
-N2 Chloro acetic acid
-H2O
e) When heated with hydroiodic acid at 2000C, the amino group in amino acids is eliminated
with the fomation of a fatty acid.
76
H2 H HI H2 H2
Ph C C COOH Ph C C COOH

-Phenyl propionic acid
NH2
II. Reactions due to carboxylic group
a. Amino acids form salts with heavy metals. For example, a copper salt of glycine (deep
blue needles) is formed by heating copper oxide with an aqueous solution of glycine.
O H H
O N
CuO
H2 Cu CH2
H2 N C COOH H2C
H2O
N O
H O
H
  - Amino acids react with alcohols in the presence of hydrogen chloride. The free
ester may be isolated by the neutralisation of the ester hydrochloride with sodium
carbonate.
H2 C2H5OH H2
H2N C COOH Cl H3 N C COOC2 H5 + H2 O
HCl
Na2CO3
H2
H2 N C COOC2H 5
Ethylester of glycine
c. Amino acids undergo reduction with lithium aluminum hydride (LiAlH4) to give
- amino alcohols. Thus glycine is converted into -amino ethanol.
H2 LiAlH 4 H2
H 2N C COOH H2N C CH 2OH
-Amino ethanol
d. Amino acids react with phosphorus pentachloride (PCI5) to give acid chloride
hydrochlorides.
H PCl5 H
H 3C C COOH H 3C C COCl + POCl3
NH 2 NH 3 Cl
Alanine Alanine acid chloride hydrogen chloride
77
e. When an amino acid is heated in the presence of dry barium oxide, decarboxylation
occurs to give alkyl amines.
H BaO,  H2
R C COOH R C NH2
-CO 2
NH 2
f. Sorensen formal titration of aminoacids. Amino acids exist largely as the internal salts
and hence can’t be titrated with bases. However if the amino group is protected by reacting
HCHO
with formaldehyde -NHCH2 OH the carboxylic acid group
NH2
becomes normal and can be titrated using indicators. Thus when a formalin solution is
added to glycine, dimethylol glycine is formed as shown below. This method was discovered
by the Danish scientist “Sorensen” and is known as “Formal titration”.
HO CH2
H2
H2 HCHO N C COOH
H3N C COO
HO CH2
dimethylol glycine
III Reactions due to both amino and carboxyl groups
a) The high melting points, and the large dipole moment values of amino acids, their solubility
in water and insolubility in most of the organic solvents suggest that the amino acid exist as
“Zwitter ions”.The formation of these inner salts may be visualised as due to intramolecular
neutralisation of the basic amino group and the acidic carboxyl group. X-ray analysis supports
this view.
H H
R C COOH R C COO
NH 2 NH3
Zwitter ion
In aqueous medium, the dipolar ion may be in equilibrium with its conjugate base (CB), formed
by loss of a proton, and conjugate acid (CA), formed by gain of a proton.
H -H H -H H
R COOH R C COO R C COO
C
+H NH 3 +H NH2
NH3
COnjugate base
Dipolar ion (CB)
Conjugate acid (DA)
(CA)
78
The position of this equilibrium depends upon the pH of the solution. In acidic solution, the
conjugate acid predominates, and in alkaline solution, the conjugate base predominates. For
each amino acid, there is a particular pH at which the concentration of the dipolar ion is a
maximum. Since the net charge is zero, the dipolar ion is electrically neutral, and consequently,
in this condition, the amino acid does not migrate when placed in an electric field. This pH at
which migration does not occur, is called the “isoelectric point” (or isoionic point) of the amino
acids. This point represents the pH at which the solubility of the amino acid in non-polar solvents
is at a maximum. The isoelectric point of any amino acid can be calculated by the formula.
H2 H2
H H 3N C COOH H H 2N C COO
K1 = K2 =
H2 H2
H3N C COO H 3N C COO
pk1 +pk 2
Isoelectric point of the amino acid  pHi =
2
For glycine pk1= 2.35, pk2= 9.78
2.35+9.78
= 6.06
 pHi =
2
When the amino acid contains two amino or two carboxyl groups, there are several
possibilities for the structure of the dipolar ion at the isoelectric point. In all the -amino acids,
it is the ionisation of the -carboxyl group that is involved, but the amino group could also be
the terminal one.
H H
H 3N C COO H3N C COO
H2 H2 H2 H2
H2 C C COOH H2C C C C NH2
Glutamic acid Lysine
Check your progress
1) What is isoelectric point?
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b) Ninhydrin reaction: When an aqueous solution of an amino acid is treated with

triketohydrindene hydrate (ninhydrin) a violet colour is produced.
O O
O
OH N
H
+ R C COOH
OH O HO
NH 2
O +
Ninhydrin RCHO + CO 2 + 3H2O
The violet coloured solutions show an absorption maximum at 570 nm in theU.V. region, and
the intensity of the absorption is proportional to the amount of  -amino acid present. Ninhydrin
is thus an important reagent in the identification and estimation of  -amino acids.
5.6. PEPTIDES STRUCTURE AND NOMENCLATURE
We have seen that -amino acids contain both amino and carboxylic groups. It is possible
that the amino group of one molecule and the carboxyl group of another molecule can undergo
condensation reaction to form an amide linkage. The resulting compound is known as a dipeptide.
The dipeptide can further react with a third molecule of amino acid to give a tripeptide, and so on.
R R R O R
H
H 2N C COOH 2 + H2N C COOH H 2N C C N C COOH
H H H H
a dipeptide
(Peptides or polypeptides, are thus polymeric compounds containing 2 to about 50 individual
amino acid units. Their mass number is lesser than that of proteins. The individual amino acids
are linked through an amide bond, known as peptide bond. A linear polypeptide contains a free-
NH3, group (the N-terminal unit) and a free-COO group (the C-terminal unit).
R O R
H
CH N CH
H
H3 N C N COO
H
C-Terminal amino acid
O R n
N-Terminal amino acid
Linear structure of a polypetide or protein
80
By convention, peptide structures are always written with the N-terminal unit on the left, and
the C-terminal unit on the right. They are named by prefixing the N-terminal amino acid followed
by other amino acids. While writing these structures, usually abbreviations for amino acids are
used.
O
H2 H
C N
H
H3 N C O
O CH3
Glycylalanine (Gly-Ala)
O
H2 H H2
C N C C
H
H3N C C N COO
H
O CH2
Ph
Glycyl phenyl alanyl glycine
(Gly-phe-Gly)
OH
O H2C
H2 H H COO
C N C CH N
H
H3 N C C N C C
H H2
O CH2 O
Ph
Glycyl phenyl alanyl seryl glycine (Gly-phe-ser-Gly)
Like the simpler amino acids, peptides & proteins are amphoteric compounds, since they
also contain a free amino group and a free carboxyl group, they exist as zwitterions. Like amino
acids, peptides also have isoelectric points, the PH at which the peptide is least soluble in aqueous
solution. Many polypeptides are present in plants and animals. Oxytocin and insulin hormones
are two important polypeptides present in our body.
Check your progress
2) What do you mean by a dipeptide?
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5.7. PROTEINS
Proteins (Gr. Proteos= first) are condensation polymers of. - amino acids bonded by
peptide linkages. Thus a typical protein can be represented by the structure shown in polypep-
tides where n > 100.
These are built up from 200 to 60,000 amino acids units and their relative molecular
masses range from 17,500 to 6,000,000. These undergo hydrolysis to give amino acids.
Proteins are essential constituents of all living cells. They are the principal materials of
skin, muscles, tendons, nerves, blood, enzymes antibodies and many hormones. They are
important in human and animal nutrition. Proteins like keratin (in hair) serves as structural
materials hormones like insulin (in pancrease) regulates metabolic process and haemoglobin (in
blood) transports oxygen with in the body. Enzymes catalyse biochemical reactions. Antibodies
like gamna globin destroys antigens and nucleoproteins transmit genetic message in cells.
The animals and human beings are dependent on plants for proteins which they get in
the form of food. Plants synthesise their own proteins in the presence of sunlight from carbon
dioxide, water and mineral salts, All common food stuff contain proteins. Ex, milk, cheese,
meat, egg white, wheat, peas, ground nuts, cashew nuts, almond, soyabean and maize.
Structure
Proteins are made of very long peptite chains, the amino acid units being arranged in a definite
linear sequence. This is called the primary structure.
The secondary structure of a protein shows as to how the peptite chains are arranged in a
definite linear space. These chains may be stretched side by side or coiled about one another, or
folded into spheroids. The extensive interchain or intrachain hydrogen bonding, disulphide bridges,
ion interactions bind the peptide chains into shape that determine the characteristic physiological
functions of a protein.
The primary structure of a polypeptide chain determines its tertiary structure. “Ter-
82
tiary” refers both to the folding of domains and to the final arrangement of domains in the
polypeptide.Many proteins consist of a single polypeptide chain, and are defined as monomeric
proteins. However, others may consist of two or more polypeptide chains that may be structur-
ally identical or totally unrelated. The arrangement of these polypeptide subunits is called the
quaternary structure of the protein.
5.8. SUMMARY
-Amino acids are the building blocks of proteins. These are prepared by a) amination
of  -halo acids b) Gabriels phthalimide synthesis c) phthalimide malonicester synthesis d)
strecker synthesis. -Amino acids are colorless crystalline substances with high melting and
boiling points.
These are amphoteric substances exits as Zwitter ions. Isoelectric point of amino acid
is the pH of the solution at which it does not migrate to any electrode on electrolysis. They
exhibit the properties of amines, carboxylic acids and some additional properties due to the
presence of both –NH2, and -COOH groups within the molecules.
Polypeptides are the condensation products of  -aminoacids linked through the amide
or peptide bond (-NH-C-). Their relative mass will be in the range of 10,000.
Proteins are condensation polymers of -aminoacids bonded by peptide linkages. They

possess very high mass numbers. These are the essential constituents of all living cells and
carry out vital life processes.
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1. This pH at which migration does not occur, is called the “isoelectric point” (or isoionic
point) of the amino acids.
2. Di peptide is of a molceule it formed from two same or different amino acids by
forming a peptide bond between them with evolving one water molecule.
I. Answer each of the following in 10 lines.
1) What are amino acids? Describe any three methods for their synthesis.
2) Explain “ Isoelectric point”?
3) What is peptide linkage?
4) Write the structures and the names of all possible dipeptides obtained from głycine and
alanine?
5) What are proteins? How do these differ from peptides.
6) What are “zwitter ions”?
II Answer each of the following in 30 lines?
1) Discuss the structure of the proteins? Explain their importance in life?
2) What happens when
a) glycine is treated with formaldehyde
b) alamine is treated with nitrous acid.
c) An -aminoacid is treated with 2,4-Dinitrofluorobenzene.
3) How are the following -aminoacids synthesised?
a) phenylalanine b) Valine
4) What are aminoacids? How are they classified? Give the names and the structures
of essential aminoacids?

1. Lehninger: Principles of Biochemistry (2013) 6th ed., Nelson, D.L. and Cox, M.M.,
W.H. Freeman and Company (New York), ISBN:13: 978-1-4641-0962-1 /
ISBN:10:1-4292- 3414-8.
2. Textbook of Biochemistry with Clinical Correlations (2011) 7th ed., Devlin, T.M.,
John Wiley & Sons, Inc. (New York), ISBN:978-0-470-28173-4.
84
UNIT-6: VITAMINS AND HORMONES
Contents
6.0. Objectives
6.1. Introduction
6.2. Origin of vitamins
6.3. Classification
6.4. Fat soluble vitamins
6.5. Water soluble vitamins
6.6. Water and fat insoluble vitamins
6.7. Hormones
6.8. Summary
6.9. Check your progress- Answers
6.0. OBJECTIVES
Once you complete the study of this unit, you must be able to
 give a general account of vitamins, their sources, isolation and the deficiency
diseases
 write the structures of vitamins A1, A2, D, E, K, B1, B2, B3, folic acid, B6, Niacin,
B12, C and H.
 know the importance of B12, and other vitamins.
 describe the endocrine glands, their position in the body and the hormones secreted
by them.
 give the metabolic role of thyroxine
 present the role of sex hormones secreted by reproductive organs.
 elucidate the structure of oestrone.
 describe the role of the hormones of pituitary gland.
 give an account of adrenal glands and their hormones.
 realise the physiological role of insulin secreted by islets of langerhan of pancreas.
6.1. INTRODUCTION
Vitamins are naturally occurring organic substances required in small quantities for the
life, growth and health of animals including man and certain microorganisms, besides proteins,
carbohydrates, fats, minerals and water. Their absence result in a variety of diseases. Though
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they supply very little energy but play an important role in energy transformation, reactions
(oxidation reduction) and also act as coenzymes in biochemical reactions.
6.2. ORIGIN OF VITAMINS

Eijkmann a Dutch physician (1897) observed that a disease “beriberi” in men and
polyneuritis in chick and pigeons occurred when fed on polished rice. The disease can be cured
in men by supplementing milk and vegetables in their diet. Funk isolated a crystalline compound
from rice polishing which could cure beriberi in men and polyneuritis in pigeons. It was an
amino compound and hence called it as vitamin (Vita = necessary for life = amine). Many
vitamins are free from amino groups. But the name vitamin is retained for these compounds
and used to be called as vitamin A, B, C, D, E, H and K.
6.3. CLASSIFICATION
The vitamins have been classified into the fat soluble group (vitamins A, D, E and K)
and the water soluble group (vitamin B-complex and C) Vitamin H is placed in a separate group
as it is neither water soluble nor fat soluble.
6.4. FAT SOLUBLE VITAMINS

6.4.1. VITAMIN A1
It is a di terpenoid which occurs in milk, milk products (butter, cheese, etc.), fats, curd,
shark, liver oil (free or in ester form) and in vegetables like cabbage, carrots, potatoes, tomatoes
in the form of its precursors (carotenoids) which are converted to vitamin A1 in the intestinal
tract of animals.
Structure: Vitamin A or A1 Retinol and its oxidation products are Retinol and Retinoic acid.
Double bonds are trans.
[O] H
OH
Retinal
Vitamin A1 (Reetinol)
[O]
O
OH
Retinoic acid
Physical and spectral characteristics:-Originally vitamin A1 was isolated as a yellow oil but
later obtained as a crystalline solid. It is optically inactive and sensitive to light and air but is
resistant to heat. It is destroyed by UV light. It gives blue colour with antimony chloride solution
in chloroform (carr -price reaction). It absorbs light having  max=325 nm (  51,000), 620 nm.
86
Isolation:- The substance rich in vitamin A1 (cod-liver oil ) is hydrolysed with potassium
hydroxide in the presence of hydroquinone when the vitamin A1 remains in the unsaponifiable
portion, from which it is isolated by chromatographic methods.
Function and deficiency diseases: Vitamin A1 increases resistance to disease and influences
the growth of animals Its deficiency in human causes night blindness and prolonged deficiency
leads to hardening of cornea (Xerophthalmia). The salivary glands lose their ability to secrete
saliva in its deficiency.
6.4.2. VITAMIN A2 (3,4-Dehydro retinol)
It is found in certain fish oils and isolated from fresh water fish. It is 3,4 - dehydro
retinol with the trans double bonds in the side chain.
OH
Vitamin A2
Fig: Vitamin A2 melts at 63-65°C. It shows two absorption  maxima (1) 287 (  ,
22000) and 351(  , 41,00) nm in UV spectra
6.4.3. VITAMIN D (ANTIRACHITIC FACTOR)
It is a group of closely related five fat soluble vitamins viz D1, D2, D3, D4, and D5 structurally
resembling sterols from which they can be prepared by irradiation with uv light.
Vitamin D2 (calciferol) commonly known as vitamin D or antirachitic factor is prepared

from ergosterol found in yeast and fungi, D3 from 7-dehydrocholesterol (a lipid in the skin), D4
from 22, 23- dihdroergosterol and D5 from 7 dehydrositosterol. Vitamin D1 is an equi molecular
mixture of vitamin D2 and lumisterol.
21
H 3C
20 22
18
CH3
12 17 23
19 11
16 24
CH 3 13
1 26
H3C CH 3
2 9 14 28 25
10 8 15 H3C
UV radiation
H 3 H
7 27
5
HO 4 6
HO
Vitamin -D2
Ergosterol or Ergocalciferol
D2, D3, and D4 vitamins differ only in the side chain attached to C-17 of the ring.
Occurrence:-Certain sterols found in lipoid material in grains, nuts and cod-liver oil, hens eggs
and milk are precursors from which vitamin D is obtained in the presence of UV light.
87
Uses and deficiency disease :- Deficiency of this vitamin causes a disease known as rickets
in children which is characterised by softening and bending of bones and poorteeth formation
(due to drop in calcium and phosphorous level in blood).
The administration of vitamin D2 cures the disease in such patients and hence is called
as antirachitic factor.
6.4.4. VITAMIN E OR TOCOPHEROLS OR ANTISTERILITY FACTOR
Vitamin E, represents a group of eight compounds called tocopherols viz 
and  which differ in the degree of antisterility properties. The most biologically active one
is  - tocopherols while the  and compounds exhibit about half the activity of  -compounds.
The term tocopherol is derived from normal child birth (to kos = child birth; phero = to bear and
ol = hydroxy compound)
Occurrence:-The first four tocopherols are important. The main source of - and  -
tocopherols is wheat germ oil, the compound is present in cotton seed oil.
Isolation: Wheat germ oil is subjected to chromatographic analysis to remove sterols and then
the  and - tocopherols are purified by conversion into 3,5-dinitro benzoates. Hydrolysis of
the derivatives give tocopherols isolated as pale yellow oils.
Structure:-Tocopherols structurally related phenolic compounds belong to class of organic
compounds called chroman deratives. These differ only in the nature of the substituents in the
aromatic ring of chroman, while the side chain at the 2nd position retains the same as shown
below
CH 3
1
8
CH3
H 3C 7 O 2
6
3
HO
5 4 - tocopherol ( max 294 nm)
CH 3
CH 3
R
CH 3 H 3C O
R
O R'
R' HO
HO  - tocopherol ( max 298 nm)

CH 3 CH 3
R
O
 - tocopherol ( max 297 nm)
R'
R = CH 3
HO
R' = C 16H33  - tocopherol ( max 298 nm)
Functions and deficiency diseases:- Deficiency of tocopherols cause sterility and hence
called antisterility factors. It is found that vitamin E deficient diet in male rats causes degeneration
of sperm forming tissues. These are excellent antioxidants. Vitamin E also increases concentration
of RNA and DNA in bone marrow.
88
6.4.5.VITAMIN K (ANTIHAEMORRHAGIC FACTOR)
Vitamin K refers to a group of two structurally related 2,3-di substituted naphthaquinones called
vitamin K1 and K2 which were isolated form alfaalfa leaves and purified fish meal respectively
by Doisy and his coworker in 1939. Both are Antihaemorrhagic connected with the enzymes
involved on blood clotting.
Occurrence:- Vitamin K1 occurs in cabbage, alfalfa, spinach and carrot tops; While K2 is
mainly found in bacteria and purified fish meal.
Structure: - Vitamin K1 and K2 are the derivatives of 2-methyl 1,4-naphthaquinone ( Menadione)

which differ from each other in the length and degree of unsaturation of isoprenoid side chain
at the 3-position as shown below.
O
8 1 CH3
7 2
6 3
5 4
O
Vitamin K 1
O
8 1 CH3
7 2
6 3
H
5 4
O n
Vitamin K2
Physical and spectral Characterisation
Vitamin K1 is a yellow oil and K2 is a yellow Crystalline solid (m.p.54°C). Both vitamins
show absorption maxima in UV region at 243, 249, 260, 270nm ( 20,000) and 325nm (
3000) due to the presence of the common chromophore 2,3-disubstituted 1,4-naphthaquinone.
Function and deficiency disease:- It is called anti haemorrhagic vitamin because of its important
role in blood coagulation. Vitamin K1 and its closely related derivatives serve as an antidote in
warfaring poisoning or in the case of overdosage with dicoumarol in thrombosis therapy. It is
given to pregnant women to control undue haemorrhage in both mother and child. These include
vitamin B - complex and vitamin C.
6.5. WATER SOLUBLE VITAMINS

Vitamin B complex
Vitamin - B complex is a group of water soluble organic compounds found in yeast, liver rice
polishing etc. This complex represents i) Thiamine (B1) ii) riboflavin (B2), iii) Pantothenic acid,
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iv) nicotinic acid (B5) v) Pyridoxine (B6)vi) B3 folicacid (BC) vii) biotin viii) cyanocobalamine
(B12 )
6.5.1. VITAMIN B 1 (THIAMINE (ANEURIN) OR ANTIBERIBERI FACTOR
Occurrence:-It occurs in yeast, milk, groundnut, eggs and outer seed coats of grains like rice,
wheat etc., Thiamine occurs primarily as the coenzyme thiamine pyrophosphate or cocarboxylase
in animal tissues and yeast.
Structure:- Thiamine is a pyrimidine hydrochloride linked with thiazole whose structure is
represented as follows:
H 3C
OH
Thiazole
Cl NH 3 N
Cl
CH2
N
Pyrimidine
H 3C N
Fig. Thiamine
(2 methyl -5- (4 -methyl-5hydroxy ethyl thiozolium chloride) methyl 6-amino pyrimidine
hydrochloride
Deficiency diseases:- It acts as a coenzyme, cocarboxylase (a part of carboxylase and pyruvic
acid oxidase) which functions in the breakdown of the pyruvic acid formed in Carbohydrate
metabolism. Thiamine deficiency produces a disease called beriberi in human beings. Two
types of this disease are recognised 1) dryberiberi which causes muscular disorders and loss of
weight and 2) wet beriberi which causes swelling of extremities, accumulation of fluid in body
cavities, liver congestion and dilation of heart.
6.5.2. VITAMIN B2 (RIBOFLAVIN OR LACTOFLAVIN)
It is closely related to the yellow water soluble pigments known as flavins and since it Was
first isolated from milk, vitamin B2 is also known as lactoflavin. It was named according to
source, as heptoflavin (from liver) and riboflavin (from egg yolk).
Occurrence:- It occurs free or as the phosphate or joined to specific proteins to form enzymes
and is widely distributed in nature e.g. in yeast, green vegetables, milk, meat.
Properties: Riboflavin is a bright yellow powder BP 2800 C, shows green fluorescence and is
soluble in water, ethanol but insoluble in chloroform and other organic solvents. The aqueous
solution is yellow and shows a yellowish green fluorecene (max 565nm).
Structure:- It is 6,7-dimethyl-9-[D-1-ribityl] iso-alloxazine
90
CH3 (CHOH)3 CH2OH
8 9 1
H3C 7 N N 2 O
6
4 NH 3
H3C N
5 10
O
6,7-dimethyl-9-(D-1-ribityl) iso-alloxazine
Riboflavin
Deficiency diseases: Its deficiency in human beings causes a riboflavinosis on cheilosis (cracks
on the lips and at the corners of the mouth. Glossitis (inflammation of tongue) and eye drosorders.
Its deficiency is also responsible for pellagra in humans and curled toe paralysis in chicks.
6.5.3. Vitamin B3 (pantothenic acid) or chick antidermatitis factor
The word pantothenic acid is derived from Greek word meaning everywhere.
Occurrence:-It occurs in milk, honey, sweetpotatotes vegetables and in all common sources
of B-complex.
Structure: - It is ,-dihydroxy –-dimethyl butyryl - alanide. It contains a peptide linkage
which unites the -alanine moiety and a dihydroxy caproic acid molecule).
H CH3 OH O H
   H2 H2
HO C C C C N C C COOH
H CH3 H
Pantothenic acid
Due to one asymmetric carbon it exists as d or (+) and 1-or (-) form only dextroform is
biologically active. It is usually stored in the form of white crystalline calcium salt.
Deficiency disease: - Its deficiency causes dermatitis in pigs. Its deficiency is responsible for
burning sensation, abdominal disorder, depression and muscular weakness.
6.5.4. Folic acid (B3 )
It is a growth factor for certain microorganisms and chick
Occurrence:- Green leafy vegetables are common sources of B-complex. (Latin folium = s leaf)
91
Structure:
H2 N N N H2
H O H2C C COOH
H2 H
N C N C N C COOH
N H
Glutamic acid
OH
Pteridine p-amino benzoic acid
Pteroic acid
Folic acid or Pteroyl Glutamic acid
Deficiency diseases:- Folic acid deficiency causes anemia, leucopenia (reduction in white
blood cell) mouth lesions and diarrhoea.
Importance:- It is essential for the synthesis of DNA and RNA.
6.5.6. PYRODOXINE(B 6) OR ANTIDETERMAITIC FACTOR
Vitamin B6 refers to a group of three organic compounds viz pyridoxine, pyrodoxal and
pyrodoxamine which are related to pyridine derivatives.
OH H O NH 2
OH OH OH
HO HO
HO
H3 C N H 3C N N
H 3C
p yrido xin e pyridoxa l pyridox amine
Occurrence:- Milk, green leafy vegetable, yeast, meat are the common sources of this vitamin.
Deficiency diseases:
Importance:-Pyrodoxal and pyrodoxamine are coenzymes for decarboxylases transaminares

and pyrodoxal phosphate is involved in tryptophan synthesis in Neurospora crassa Its deficiency
causes blood less, vomitings pits in children and convulsions.
6.5.7. NIACIN (NICOTONIC ACID, ANTIPELLAGRA FACTOR)

Nicotonic acid and nicotinamide have been shown to be the human pellagra preventing
factors. Niotinamide is a part of the coenzymes codehydrogenase I and II which play a part in
many biological oxidations.
Occurrence:- B3 occurs widely in plant & animal tissues like yeast, grain, cereals, coffee,
ground nut and meat products (liver and kidney).
Structure:
92
O
O
OH
NH2
N
N
Nicotinic acid Nicotinamide
Deficiency diseases :- B3 deficiency causes pellagra in humans (hence the name pellagra
preventive factor P.P.F.). The major symptoms of pellagra are stomatitis (inflammation of
stomach), glossitis and skin lessons (patches on exposed skin).
NAD+ (Nicotinamide adenine dineucleotide) and NADP (Nicotinamide adenine dinucleotide
phosphate) coenzymes with suitable apoenzymes participate in hydrogen transfer reactions.
6.5.8. VITAMIN B12 (COBALAMINE OR ANTI-PERNICIOU ANEMIA factor)
This is the first natural product containing cobalt atom centered in a porphyric nucleus to
which are attached ribose phosphate and benzimidazole.
Occurrence:- It occurs as a by-product in the production of antibiotics in fermentation residue,
dried sewage sludge and in animal tissues. It is synthesised by certain microorganisms such as
penicillin molds, streptomyces bacteria.
Deficiency diseases: Its deficiency in humans causes perniciouis anemia (lowering of red
blood cells)
6.5.9. Vitamin C OR L(+)-ascorbic acid (antiscorbutic factor)
Vitamin C is closely related to the Saccharide L glucose. The reduced form of L-ascorbic
acid obtained on oxidation is a diketone lactone (dehydro ascorbic acid). Both these forms are
biologically active and form biochemical redox system involving oxidation reduction reactions
of the cell.
Structure
HO O
OH O
O O
O OH O OH
OH OH
l-Ascorbic acid
Dehydro l-Ascorbic acid
(R)-5-((S)-1,2-
dihydroxyethyl)-3,4- (R)-5-((S)-1,2-dihydroxyethyl)furan-
dihydroxyfuran-2(5H)-one 2,3,4(5H)-trione
93
Occurrence:- Ascorbic acid occurs mainly in citrus fruits (like lemons and oranges Indian
gooseberry Amla), berries and melons it is also found in green vegetables like cabbage, tomatoes
beans and potatoes.
Deficiency diseases:- Deficiency of vitamin “C” causes a disease called scurvy whose
symptoms in human beings are weight loss, weakness, heart palpitations redness and swelling
of the gums, loosening of the teeth, haemorrhage into the skin and mucous membranes, oedema
and hyperirritability.
6.6. WATER AND FAT INSOLUBLE VITAMIN

Biotin (Vitamin h) or anti-egg white injury factor
Biotin represents two forms ( and ) which exist in nature as -biotin obtained from egg
yolk and the other  biotin obtained from liver are identical having the same molecular formula.
Occurrence:-Egg yolk, liver, yeast, kidney pancreases and milk are rich sources of biotin.
Structure: It consists of fused imidazole and thiophene rings with a fatty acid side chain as
shown below
O
O
NH H
HN OH
H S
5-((3aS,4S,6aR)-2-oxohexahydro-1H-thieno[3,4-d]imidazol-4-yl)pentanoic acid
Biotin
 - biotin crystallises as fine needles having decomposition temperature at 230°C.
It is optically active and is dextrorotatory, soluble in dilute alkali but sparingly soluble in
dilute mineral acids.
Deficiency diseases:-Its deficiency may cause dermatitis, loss of hair and progressive
paralyses. It acts as a catalyst in addition of carbon-di-oxide to actyle CoA in the formation of
malonyl co-enzyme CoA required in fatty acid synthesis. In bacteria and yeast biotin is needed
for domination of serine, threonine and aspartic acid.
O
Biotin
CO2 + CH 3CO 3CoA HOOCH2C C SCoA
AcetylCoA
Carboxylate Malonyl CoA
6.7. HORMONES
Many of the metabolic processes in the body are regulated by the secretion of chemi-
cals from some special glands. These glands are called the ductless glands or endocrine glands.
As their names indicate, they do not have any ducts or openings and the secretions from them
94
are directly introduced into the blood stream as the blood passes through the glands .These
chemicals which are secreted in the endocrine glands are called “hormones meaning chemical
messengers’. They are thus circulated throughout the body. When they reach the appropriate
part of the body, they cause certain effects to take place. The hormones control longterm
changes such as rate of growth, rate of activity and sexual maturity. The hormones, when they
pans through the liver they are converted into inactive compounds and are excreted through the
kidneys. The duration of the hormonal activity is thus regulated by the liver. The position of
some of the important endocrine glands in the body are shown in Fig 6.7.1 Table 6.7.1 gives a
list of the major endocrine glands and their secretions.
6.7.1. THYROID
The thyroid gland is situated in the throat, in front of the wind pipe. It is the largest of the
endocrine glands and weighs about 30 gms.. in man: It produces thyroxine (2), an iodine containing
hormone. In young animals the hormone controls the rate of growth and development. Thus
thyroxine brings about metamorphosis in tadpoles. In adult humans, thyroxine influences the
rate of chemical activity, particularly respiration. Too little of thyroid activity leads to overweight
and sluggishness and too much causes thinness and over activity. Enlargement of the thyroid is
known as goitre. Deficiency of thyroxine in infants causes a mental deficiency called cretinism.
This can be controlled by the administration of thyroxine.
95
I O
HO I
OH
NH2
I O
I
thyroxine
When thyroxine is treated with nitrous acid, a yellow colour deepened. When cooled and
rendered alkaline with ammonia, it gave a red colour. This colour reaction is characteristic of
phenols with iodine atoms in both ortho positions.
Table 6.7.1. Major Endocrine Glands: Their Secretions And Functions
S.No. Endocrine glands Hormones elaborated Their physiological function

1. Pituitary Prolactin Milk secretion
Growth hormone General growth and metabolism
ACTH Formation and secretion of adrenal
cortical steroids
Oxytocin Uterine contraction
Vasopressin Blood pressure
2. Thyroid Thyroxine Metabolic rate and oxygen
consumption
3. Pancreas Insulin Carbohydrate and protein
metabolism
4. Adrenals
i) Cortex Adrenal cortical steroids Metabolism of electrolytes
ii) Medulla adrenaline Blood pressure
5. Reproductive organs:
i)Ovary Oestrone Maturation. AccessorySex organ
Oestradiol growth Maturation and function
ii)Testis Testosterone of sex organ growth
6.7.2. REPRODUCTIVE ORGANS
The ovary produces several hormones. These are called the Ocstrogens. Of these, Oestrone
(3) and Oestradiol 17 (4) are most potent. The oestrogens control the female secondary sex
characteristics at puberty. They cause the lining of the uterus to thicken just before an ovum is
released. In some mammals oestradiol puts the female ‘on heat’ to get ready to mate with the
male. Progesterone (5) is another hormone which supports the pregnancy. If pregnancy does
not occur, its secretion ceases after a few days.
Testosterone (6) is the male sex hormone produced by the testis. It promotes the development
of the masculine secondary sex characteristics.
96
Check your progress
1) what is the role of testosterone?
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6.7.3. OESTRONE
Butenandt and Doisy isolated oestrone independently in 1926 from the urine of pregnant
women. Oestrone is optically active and is dextro rotatory, it melts at 259°C. It has a molecular
formula C18H22O2. It contains a phenolic hydroxyl and a ketonic function. Catalytic hydrogenation
of the compound gives an octahydro derivatives containing two hydroxyl groups. The presence
of a phenolic hydroxyl indicates a benzene ring in the molecule. Wolff-Kishner reduction of
oestrone methyl ether (7) followed by selenium dehydrogenation yields 7-methoxy 1,2-cyclo
pentenophenanthrene (8).
O
OH
H H
H H H H
HO HO
oestrone (3) oestradiol (4)
OH O
H H
H H H H
O (5)
O (6)
progesterone
testosterone
Thus the position of the phenolic hydroxyl was fixed in ring-A. Ocstrone was thus shown to
be a steroid in nature. The position of the ketone functions was shown by the following sequence
of reactions. Oestrone methyl ether (7) was treated with methyl magnesium iodide to yield the
carbinol (9) which on dehydration with potassium hydrogen sulphate gave the dehydration
product (10) which underwent a rearrangement during dehydration. Catalytic reduction of the
cyclopentene(10) yielded the cyclopentane (11) which on selenium dehydrogenation gave 7-
methoxy 3,3-dimethyl 1,2-cyciopentenophenanthrene (12).
97
O
1. Wolffkishner
reduction
H
2. Gelenium
H H dehydrogenation
H3CO
H3CO 7 8
CH3MgBr
H3C H3C
OH CH3
KHSO4
H
-H2O
H H
H3CO H3CO 10
9
H2/P
H3C
CH3
Se
H3CO 11
H3CO 12
The formation of (12) suggested the ‘position 17 for the keto group in oestrone. The structure
(13 assigned for oestrone on the basis of the above reactions and X-Ray crystallography was
confirmed by several syntheses.
6.7.4. THE PITUITARY GLAND
The pituitary gland is often called the “master gland’. It is of the size of a large pea in an
adult man and is situated at the base of the fore brain. It consists of three parts, an anterior lobe,
a posterior lobe and an intermediate part. The pituitary gland releases several different hormones.
Some of them have a direct effect on the organ systems of the body. The anterior lobe is known
to elaborate follicle stimulating hormone (FSH), luteinizing hormone (LH), thyrotrophic hormone,
prolactin and corticotropic hormone. The intermediate part of pituitary produces intermedin
while the posterior lobe elaborates the hormones, oxytocin and vasopressin. These hormones
are polypeptides in nature. Oxytocin produces (a) contraction of the uterus (oxytoxic effect
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and (b) milk ejection while vasopressin exhibits (a) an increase in the blood pressure of animals.
(b) supression of urine production (anti diuretic action) and (c) increase in the activity of intestines.
Majority of the pituitary hormones act upon and regulate the activity of other endocrine
glands. Thus one of the hormones initiates the production of oestrogen, a female sex hormone
while another stimulates the growth of the thyroid and influences the production of thyroxine.
6.7.5. OXYTOCIN
Fractionation of the extracts of the pituitary glands gave two fractions. The first one, the
pitocin fraction, gave oxytocin while the other, the pitressin fraction gave vasopressin. Purification
of the hormones was effected by counter current distribution technique. Their homogeneity
was shown by chromatographic and electrophoretic methods.
The structure of oxytocin (13) was confirmed by several syntheses.
6.7.6. ADRENAL GLANDS
The adrenal glands are situated just above the kidneys. They can be divided into two zones.
(i) the outer layer called the Cortex and (ii) the inner zone called the medulla. The cortex
produces several hormones called the cortex hormones or corticoids which are steroidal in
nature. These include cortisone (14) which accelerates the conversion of proteins to glucose.
Deficiency of these hormones produces the symptoms of Addison’s disease viz, bronzing of the
skin, muscular weakness and increase in the blood urea level, salt and water imbalance. Secretion
by the adrenal cortex is stimulated by certain pituitary hormones.
99
The zone of the adrenals producing adrenaline (15) is called medulla. When sense organs
of animals transmit signals of danger which need vigorous action, the impulses are relayed to
adrenals for the release of adrenaline into the blood. When adrenaline reaches the heart, it
increases the heart beat. It speeds up the rate of breathing and oxidation of carbohydrates. It
diverts the blood from the alimentary canal and the skin to the muscles. All these changes
prepare the animal either to run away or to put up a fight.
O
HO OH
O
HO
H
HO N H H
H
OH O
adrenaline cortisone
6.7.7. PANCREAS
This is a leaf like gland attached to the small intestine. It contains cells that secrete digestive
juices. A second type of cells called the -cells of the islets of the Langerhans control the use
of sugar in the body. The hormone responsible for this is insulin. It determines the amount of
sugar to be converted into glycogen and oxidised for energy. Insulin accelerates the conversion
of blood sugar into glycogen in the liver, promotes the uptake of glucose from the blood by the
body cells and increases the protein synthesis in some cells. The improper production of sufficient
insulin leads to diabetes. The blood glucose level of a diabetic is not effectively regulated.
Check your progress

2) What happens if the pancreas does not secrete sufficient amount of insulin?
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100
Structure of Insulin
Isolation of insulin, Insulin is commercially prepared from the pancreas of ox and the
Pig. The fresh glands are minced at a low temperature and soaked in acidified aqueous alcohol.
The extract is separated by centrifugation and made alkaline with ammonia (pH 8). It is filtered
and the filtrate acidified and evaporated in vacuum. The separated fat is filtered reacidified and
evaporated in vacuum. The separated fat is filtered off. The filtrate is treated with 25 percent
Sodium chloride solution when insulin separates out. Purification of insulin is effected by
Precipitating it at its isoelectric point at pH 5. The zinc salt of the hormone may be obtained in
a crystalline form.
Crystalline insulin melts with decomposition at 233°C. It is optically active and leaevo
rotatory. It is soluble in acids and alkalies but sparingly soluble in most other solvents.
Structure of Insulin: The structure of insulin was investigated by Sanger and co-workers
for 10 years and finally solved in 1954. It is the simplest protein which can be obtained in a pure
form. Chemically different insulines elaborated by Ox, Pig, Fish, humans differ from one
another in their composition, but they show similar action.
The molecule of beef insulin is made up of 777 atoms, the molecular formula being C254
H277 N65 O75 S6. The insulin molecule belongs to the category of peptides where the building
101
units are the amino acids attached through a peptide bond. The total number of amino acids
present insulin molecule is 51. Of the 24 natural L-amino acids are present in insulin.
Insulin contains two chains, the A chain with 21 amino acids and the B chain with 30
amino acids. Chain A was shown to have a disulphate bridge and is linked to the B chain by two
disulphide bonds. The structure assigned to human insulin is shown in Fig.6B.2. Human and
sheep insulins were synthesized. Sanger was awarded the Nobel prize in chemistry for his
remarkable work on insulin.
6.8. SUMMARY
You have studied the following in this unit the definition, importance, origin and
classification of vitamins.
The occurrence, isolation, structure of various fat soluble and water soluble vitamins
Viz vitamins A,D, E, K and B1, B2, B3 folic acid, B6, niacin, B12, C, H respectively
Various diseases caused due to the deficiency of these vitamins in the diet.
The positions of endocrine glands in the body and hormones secreted by them. The
metabolic role played by thyroxine. The role of the sex hormones secreted by reproductive
organs and elucidation of the structure of oestrone.
The role of pituitary gland hormones in the body. An account of adrenal gland hormones
and their role in the body.
The role of insulin secreted by islets of langerhans of pancreas.

1. Testosterone (6) is the male sex hormone produced by the testis. It promotes the
development of the masculine secondary sex characteristics.
2. The improper production of sufficient insulin leads to diabetes. The blood glucose
level of a diabetic is not effectively regulated.

I. Answer each of the following is 10 lines
1. What are Vitamins and how they are classified?
2. Write the structures of vitamins B1 and B2
3. Why vitamins are important for healthy living?
4. What are hormones? Explain their importance in human body.
5. What are endocrine glands? Name any two of them and the hormones secreted
by them.
6. Write the physiological role of:
a)Thyroxine b)Oestrone c)insulin and d)Oxytocin
102
1. Enumerate the various diseases caused due to the deficiency of vitamins in our diet.
2. 2 Write the structure of the following vitamins.
a)pyridoxine b) tocopherols c) vitamin –D
3. Write a brief account of the peptide hormone, Insulin.
4. Write a note on sex hormones.

ISBN:10:1-4292- 3414-8.
103
104
BLOCK-3
PHYSICALCHEMISTRY
This block deals with the concepts thermochemical reactions, exothermic and
endothermic reactions, variation of heat of reactions, spontanious and non spontanious
process, conversion of heat into work, entropy in thermodynamics. Discussed concepts
of electrochemistry, electrochemical cells, EMF, standard cell, electrode potentials,
reference electrode.Explained laws of photo chemistry, quantum yield, photochemical
reactions, fluorescence and phosphorescence.
Block – 3 includes the following three units.
Unit – 7: Thermodynamics - 2 (Thermochemistry)

Unit – 8: Electrochemistry-2
Unit – 9: Photochemistry
105
106
UNIT - 7 : THERMODYNAMICS-2
(THERMOCHEMISTRY)
Contents:
7.0. Objectives.
7.1. Introduction.
7.2. Exothermic and endothermic reactions.
7.3. Thermochemical equations.
7.4. Hess law of constant heat summation.
7.5. Indirect calculation of heat of reactions.
7.6. Heat of formation
7.7. Heat of combustion.
7.8. Heat changes in solution.
7.9. Heat of neutralization of acid and bases.
7.10. Variation of heat of reaction with temperature. The Kirchhoffs equation.
7.11. Calculation of heats of reaction from bond energies.
7.12. Spontanious processes.
7.13. Conversion of heat into work.
7.14. Entropy.
7.15. The carnot cycle.
7.16.Entropy as a thermodynamic function of state
7.17. Entropy and second law.
7.18. Molecular interpretation of entropy.
7.19. Free energy and free energy change.
7.20. G as a criterion for equilibrium and spontanious change.
7.21. free energy change of chemical reactions.
7.22. Summary.
7.23. Check your progress - Answers.
7.24. Examination model questions.
7.0. OBJECTIVES
Once you compleate the reading and understanding of various aspects of this unit, you
must be able to
 define the thermochemistry.
 classify the reactions based on heat., express the thermochemical equations.
107
 understand the various heat phenomenons.
 realise the limitations of first law of thermodynamics.
 understand the concept of spontanious and non spontanious processes.
 concept of entropy and different systems.
 free energy and its change in various systems.
7.1. INTRODUCTION
There are several reactions which are accompained by the evolution of heat like the
burning of wood coal and kerosene, action of alkali metals on water, reaction between acids
and bases. On the other hand there are also some reactions which take place only when heat is
continuously supplied to them as in the formation of nitric oxide from nitrogen and oxygen or
carbondisulphide from carbon and sulphur. These reactions take place only in the electric furnace.
Such heat changes follow the law of conservation of energy according to which the total
energy of a system before a reaction must be equal to its energy after the reaction has taken
place. Now, different substances possess different amounts of energy and it is unlikely that the
energy content of the reactants be equal to the energy content of the products. This difference
in energy is accounted for as the heat change accompanying the chemical reaction.
7.2. EXOTHERMIC AND ENDOTHERMIC REACTIONS

Consider a general of the type A + B  C + D
Let the internal energies of reactants be EA,EB products be EC and ED respectively,

then if EA + EB > EC + ED to satisfy the first law of thermodynamics some energy must
appear along with the products so that EA+EB= EC+ED+Q. Here Q is the heat evolved in the
reaction. From the above equations we may write.
(EC + ED) - ( EA + EB) = -Q or E=-Q
E (delta E) is the change in the internal energy in the reaction (Internal energy of the
products minus Internal energy of the reactants). The negative sign for Q indicates that there is
a decrease in the internal energy in the reaction. We may also write the reaction as
A + B  C + D + Q.
Such a reaction which is accompained by the evolution of heat is called an exothermic

reaction. An example of such a reaction is the formation of copper sulphide from its elements.
Cu + S  CuS + 11,600 Calories
The above reaction states that in the formation of copper sulphide from its elements,
copper and sulphur 11,600 calories of heat is liberated. The energetics of the reaction may be
written as
108
ECu+ ES= ECuS + 11,600 Cals.
The internal energy of copper sulphide is less than the internal energy of copper and sulphur put
together. This difference appears as the heat of reaction.
ECuS - (ECu+ ES) = 11,600 Cals.
E = -11,600 Cals.
By convention, the heat of reaction is shown separately from the reaction
Cu +S  CuS; E =11,600 Cals.
Exothermic reactions are very common. Some examples are:
C+O2  CO2; E =-94,050 Cals.
1
K+ Cl  KCl ; E =-93,500 Cals.
2 2
CaCl2 + 6H2O  CaCl26H2O; E =-22,500 Cals.
In all the above reactions, the internal energy of the products is less than that of the
reactants. Now we will consider reactions in which the internal energy of the products is
greater than that of the reactants.
If in the general reaction considered before EC+ ED>EA+EB then for the reaction to
take place, heat must be continuously supplied so that energy balances according to the equation.
EA + EB + Q = EC + ED
Then (EC+ ED ) - ( EA+EB) = Q or E=Q
In this reaction Q the heat of reaction is positive because E is positive. The internal energy of
the products is greater than that of the reactants and to make the reaction go towards the right,
heat must be continuously supplied. We say the reaction takes place with the absorption of
heat. Reactions which take place with the absorption of heat are called endothermic reactions.
A very good example is the formation of carbon disulphide from its elements. It is written
C + 2S + 30,600 calories  CS2
In this reaction E CS2 - (E C + 2E S ) = 30,600 calories
E=30,600 calories
109
So we write the formation of carbon disulphide reaction as
C+2S  CS2; E=30,600 calories
Two more examples of endothermic reactions are
N2+O2  2NO; E=43,200 calories
2C+H2  C2H2; E=54,190 calories
7.3. THERMOCHEMICAL EQUATIONS
Equations which also show the heat change accompanying chemical reactions are
called thermo chemical equations. To be complete in every respect they should also indicate the
state of the substances taking part in the reaction. Whether they are solid, liquid or gas and if
solid the allotropic modification if any. The equation should also indicate the temperature at
which the measurements were carried Out. Thus the formation of copper sulphide reaction is
written as
Cu(s)+ S(rombic)  CuS(s) ; E298K = -11,600 cals
the formation of carbondioxide can be shown as

C(gr)+ O2(g)  CO2(g) ; E298K = 94050 cals
The symbol (g) is written to indicate gaseous reactants and symbols (1) and (s) for as
liquids and solids respectively. Usually where there is no ambiguity regarding the state of they
substance the symbol may be dropped. The temperature indicates the temperature at which
reactants are taken and that at which products are obtained.
Again the amount of heat absorbed or evolved in a reaction depends upon the condition
in which the experiment is performed’ whether in a closed vessel under condition of constant
volume or in an open vessel at the constant pressure of the atmosphere.
We have seen in the heat absorbed or liberated at constant volume equal to E and that
at constant pressure is equal to H the heat of reaction at constant pressure. The two are
related by the equation obtained from the first law.
H =E + PV
Here  V represents the difference between the volume of products and the volume
of reactants. However if the reaction involves only solids and liquids, the change in their volume
as a result of reaction will be negligible. Hence E and H will be nearly equal. On the other hand
if the reaction involves gaseous substances, either as reactants or as products, then the volume
change will be significant, even in such cases we may neglect the volume change produced in
solids and liquids. For example in the reaction
110
Zn + H2SO4(I)  ZnSO4 (aq) + H2
Compared to the volume of hydrogen gas produced, the volume of H2SO4 used up or zinc
dissolved will be negligible. Hence V in the above reaction represents only the volume of
gaseous products-volume of gaseous reactants.
V= Vp(g) - Vr(g)
For gaseous reactants and products we may write the equation of state as
PVpr= nprRT, and PVre = nreRT
Where npr and nre are the number of moles of gaseous products and number of moles of gaseous
reactants respectively.
Therefore PV = P(Vpr-Vre) = (np-nr)RT =nRT
And therefore we get H =E +nRT
This gives the relation between heat of reaction at constant pressure and that at constant
volume.  n can easily be known from the thermo chemical equation.
Examples (i) C(g) + 2H2(g)  CH4(g)
n = 1-2 = -1
(ii) CH4 + 2O2  CO2 + 2H2O(I)
n = 1-3 = -2
It is customary to refer all the heats of reactions to constant pressure.
Example: Given that at 250 C. E = 16,548 cals for the reation
H2S(g) + I2(s)  2HI (g)+ S (rhombic)
Calculate the heat of reaction at constant pressure
H = E + nRT
E = 16,548 cals, n = 2-1 = 1, T = 298 K. Substituting we get.
H = 16,548 + 1 x 1.987 x 298 = 17,140 cals.
7.4. HESS LAW OF CONSTANT HEAT SUMMATION
Internal energy E and enthalpy H of substances are functions of state which means
E and H for any change in system must depend upon the initial and final states of the system
and not on the manner in which the change has been brought about. These are the conclusions
111
of the first law of thermodynamics. For reactions since E and H are the heats of reaction
measured at constant volume or constant pressure, it follows that the heat of reaction must also
depend upon the initial state (reactants) and final state (products) and not on the method by
which it has been carried out. The truth of this was realised from the beginning, and Hess, as
the result of a number of experiments carried out by him, stated his findings in the form of law.
This has come to be known as Hess law of constant heat summation. It may be stated as
follows. The heat evolved or absorbed in a given reaction must always be constant and
independent of the path by which it is carried out whether in one step or several steps. That this
law directly follows from the law of conservation of energy can easily be seen. For suppose a
reactant A could be converted into B in two ways (i) directly in one step when suppose Q
calories of heat is liberated (ii) through an intermediate C in two steps when Q1+Q2 calories of
heat are liberated as shown below.
A B
C
Q1 Q2
Fig.7.1. Different paths
Hess law requires that Q be equal to Q1 + Q2. If this is not so, the first law would be
violated. Suppose Q> (Q1+Q2), then A could be converted into B by path I when Q calories of
heat is liberated, and B is converted into A by the path II The reverse reaction is endothermic
reaction requiring absorption of heat=Q1+Q2. Since 9 calories of heat are liberated in path I and
since Q>Q1+ Q2 only part of Q is needed for the reverse reaction. Hence in the cycle of
reaction there is a net saving of Q-calories. This cycle may be repeated continuously to produce
a large amount of heat. Since at the end of every cycle the reactant is produced, this amounts
to producing energy from nothing. This is against the law of conservation of energy according
to which energy can neither be created nor destroyed. The same conclusion can be arrived
supposing Q> Q1 +Q2. Therefore Q=Q1 +Q2.
7.5. INDIRECT CALCULATION OF HEATS OF REACTIONS

A direct consequence of Hess law is that thermochemical equation can be added and
subtracted just as algebraic equations. Taking advantage of this, we can combine thermochemical
equations of those reactions whose enthalpy changes are known to give a required
112
thermochemical equation of action whose enthalpy change cannot be determined expermentally.
There are a large number of reactions whose heat change cannot be measure either because
the reaction does not take place to completion or more than one product results from the
reaction. To such reactions Hess’s law can applied for obtaining their H values.
For example, the enthalpy change of the following reaction cannot be determined
1
experimentally C  O2  CO .
2
This is because the reaction does not stop with the formation of CO but if oxygen is present in
CO2 may be formed.
C+O2=CO2
However carbon and carbon monoxide can be burnt separately in oxygen and the heat liberated
in these reactions can be determined (see under heat of combustion). The necessary
thermochemical equations are
C+O2=CO2; H=94,050 cals
1
CO  O2  CO2 ; H  67,900cals
2
If we subtract the second equation from the first and rearrange we get
1
C  O2  CO .
2
H of this reaction is obtained by substracting the H of the second reaction from that of the
first.
-94,050-(-67,900)=-26,150cals.
1
Hence we may write C  O2  CO .H=26,150 cals .
2
A second example is the reaction between carbon monoxide and steam. The heat change of
the reaction
CO+H2O(g)  CO2+H2
cannot be determined experimentally as it does not take place to completion and only an
equilibrium mixture containing all the four gases is obtained. H of this reaction can be obtained
from the following thermochemical reaction
113
1
CO  O2  CO2 ; H  67,900cals
2
1
H 2  O2  H 2O( g ); H  57,800cals
2
The second equation may be rewritten as
1
H2O(g)  H2+ O ; H=+57,800cals
2 2
1
adding CO+ O  CO2;H=-67,900 cals
2 2
we get CO+H2O(g)  CO2+H2; H=10,100
More examples are given later.
The heat changes accompanying reactions are given different names depending upon the
type of reaction.
7.6. HEAT OF FORMATION

The amount of heat absorbed or evolved in the formation of one mole of a compound from its
elements is called the heat of formation of the compound.
C (graphite) + O2  CO2 H =-94,050 cals.
C (graphite) + 2H2  CH4; H=17,890 cals .
The heat ehanges in these reactions are the heats of formation of the compounds formed in the
respective reactions.
However considered the thermochemical equations
2H2 +O2  2H2 O(1);=H=-136,600 cals
and H2+ Cl2  2HCl; H=-44, 120 cals
In these equations the H values do not give the heats of formation as in each case two moles
of compound are formed. The correct equations would be
1
H2+ O  H2O(1); H=-68,300cals.
2 2
1 1
H2+ Cl2  HCl; H=-22,060cals.
2 2
114
Check your progress
1) What is heat of reaction?
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If the elements and the compounds are in their standard states, the heats of fomation are
referred to as standard heat of formation. By standard state of a substance is meant its most
stable form at that temperature usually 25°C. For example at liquid mercury, solid iodine and
rhombic sulphur are the standard states for the elements. The standard heats of formation are
referred to 25°C and are expressed as H = -Ho f
The standard heats of formation of some compounds are given below. Try to write their
equations.
o
Compound C (graphite)  H f cals
Nitric Oxide (NO) 21,600
Ammonia (NH 3 ) -11,040
Hydrogen fludride (HF) -64,200
Hydrogen iodide (HI) 8,660
Methane (CH4 ) -17,890
Ethane (C2 H6 ) -20,230
Ethylene (C2 H4 ) 12,500
Acetylene (C2 H2 ) 54,190
Benzene (C6 H6 (1)) 19,820
Ethyl alcohol C2 H5 OH(1) -66,300
Two types of compounds can be recognized from the above table. Those which have
positive H values. These are compounds in the formation of which heat is absorbed. They are
called endothermic compounds. Those in the formation of which heat is liberated and have
negative H are called exothermic compounds. The enthalpies of exothermic compounds are
less than the enthalpies of the elements from which they are formed. Likewise enthalpies of
endothermic compounds are more than those of their constituent elements. Thus if we consider
CH4 Hf=-17,900 cals and ethylene C2 H4=12,500 cals) We observe that in the enthapy scale
methane would be low the level of the elements while ethylene would be above them. If the
enthalpies of carbon and hydrocarbons would be above them. If the enthalpies of all elements
115
in their standard states as zero. With the help of this convention and making use of the standand
enthalpies of formation, one may calculate Ho of any reaction. This would be given by the
relation.
H o (Products)- H o (reactants)

Consider the reaction
4 NH 3  5O2  4 NO  6 H 2O ( g )
o
 H for this reaction would be
6H 0(H2O) + 4H 0(NO) - H 0(NH3 ) - 5H 0(O2 )
6 x (-57.800)+4 (+21.600)-4(-11.040)-5x0
=-216.240 cals
7.7. HEAT OF COMBUSTION

The heat of combustion of a compound is the amount of heat liberated when one mole
of the compound is completely burnt in oxygen. Such values are importat for fuels and foods
because heats of combustion values area measure of the energy that can be obtained from
them. In the case of fuel and foods they are referred to as calorific values.
Organic compounds that contain only carbon, hydrogen and oxygen are oxidized to carbon
dioxide and water on complete combustion reactions. For example when one mole of sucrose
(cane sugar) is completely burnt in oxygen 1348.9 calories of heat is libered. Since the products
are only CO2 and water, the thermochemical equation can easily be balanced.
C12H22O11 + 12O2  12CO2+11H2O  H=- 1348.9
Since the heats of combustion are very high, they are expressed in calories (K. calorie
= 1000 calories) A few more combustion reactions are
C2H5 OH (1)+ 3O2  2CO2+3H2O (1);  H=-326.7 K.cals
1
C6H6 (1)+ 7 O  6CO2+3H2O(1);  H=- 780.98 K.cals
2 2
Determination of heat of combustion
To ensure complete combustion of the substance, it is burned in an excess of oxygen in
a closed vessel. Since the volume remains constant, combustion is accompanied by large
increases in pressure. To withstand this large increase in pressure which is built up in a short
interval of time the vessel must be strongly built vessel. Vessel in which combustion reaction
are carried out are called bombs. They are thick walled and made of acid resistant steel.One
type of calorimeter is shown in the figure 7.2.
116
The bomb has tightly fitting screw cap which has a valve for admitting oxygen. Two metallic
supports are connected to the lid. One of them contains a ring into which can be placed a small
stainless steel crucible. A thin wire is connected to the supports are connected to the supports
and dips into the sample in the cruciable.
A known weight of the sample is placed in the crucible and the iron wire adjusted to immerse
in it. The srew cap is tightly fitted and oxygen is admitted into the bomb up to a pressure of 20
to 25 atmospheres.
Fig.7.2. Bomb calorimeter assembly

The bomb is immersed in a calorimeter containing a known weight of water. This
whole arrangement is called a bomb calorimeter. The charge is ignited by passing an electric
current through thin iron wire. Combustion takes place and the heat that is liberated causes the
temperature of water surrounding the bomb to rise. This rise in temperature t2-t1 is measured
carefully. W was the weright of the water taken, then the heat taken up by water is W (t2-t1)
calories assuming the specific heat of water to be one. If the mass of the bomb is m1 and the
specific heat of water material s1, then m1s1 (t2-t1) is the heat taken up by the bomb. In the same
way the calorimeter also get heated and the heat absorbed by it is m2 s2(t2-t1) Where m2 &s2
are the weight of the calorimeter and specific heat respectively. Thus when w gm of the
substance is burnt the heat liberated causes the temperature of the bomb, water and the
calorimeter to rise.
Therefore the heat of combustion for w gm of substance is

W(t2-t1)+m1 s1(t2 -t1 )+m2s2 (t2 -t1 )
117
= (w+m1s1+m2s2)(t2-t1)
= C(t2-t1)
where C is a constant equal to the heat capacity of calorimeter, water and the bomb. All the
quantities m1, m2, s1 , s2 can be determined separately. In the laboratory C is evaluated by
making use of a compound with known heat of combustion. The standards that are commonly
used are benzoic acid and naphthalene. The heats of combustions are expressed per mole.
Example
The molar heat of combustion of benzoic acid (C6 H5 COOH) is 771.20 k. cals 0.61 g of
benzoic acid on complete combustion in a bomb calorimeter produced a rise in temperature of
1.950c. What is the total heat capacity of the calorimeter?
One mole, i.e. 122g of benzoic acid on complete combustion produces 771.200 calories. Then
0.61
produce 7712003   38560.015 cals.
122
This heat increases the temperature of calorimeter and contents by 1.95°, Therefore Cx
1.95=3856 calories where C is the total heat capacity of calorimeter.
3856
C   1972 Calories
1.95
Heats of combusion of some organic compounds
Compound Formula Heat of combution in k.cals/mole

Methane(g) CH 4 212.8
Ethane(g) C2 H 6 372.8
Propane(g) C3 H 8 530.6
n-Butane(g) C 4 H 10 687.7
Ethylene (g) C2 H 4 337.2
Acetylene(g) C2 H 2 310.6
Benzene (l) C6 H 6 781.2
Benzene (g) C6 H 6 787.2
Methanol (l) CH 3 OH 173.6
Ethanol (l) C2 H5 OH 426.8
Acetic Acid (l) CH3 COOH 209.4
Glucose (s) C 6 H 12 O 6 6730
Sucrose(s) C 12 H 22 O 1348.9
Naphthalene (s) C 10 H 8 1.228
Benzoic acid(s) C6 H5 COOH 771.4
118
Example
A 0.45 gm of sample of an organic compound burnt in the calorimeter in the above example
causes the temperature to rise to 2.19°C what is the heat of combustion in calories per gm of
the compound?
Heat capacity of calorimeter 1972-calories.
Heat liberated on burning 0.45 gm of compound =1972x2.19=4318 cals
Heat of combustion per gram =43 18/0.45=9595. 5 cals
As indicated earlier, heat of combustion values are useful for fuel and foods. They are a
measure of energy that can be obtained from them. Heat combustion values of some organic
compounds are given in the above, table.
Heats of combustion values are important in another way. They can be used to determine the
heat of formation of organic compounds. It is not possible to determine the heat of formation of
compounds. It is not possible to determine the heat of formation of any organic compound in the
laboratary, but it is heat of combustion can easily be determined. This value together with the
heats of combustion of carbon and hydrogen can be used to estimate its heat of formation.
For example the heat of formation of ethyl alcohol cannot be determined as the reaction
C(graphite)+ 1/2O2 + 3H2  C2H5OH (I)
cannot be realized experimentally
However if its heat of combustion is known as-326.7k cals. This can be combined with the
heat of combustion of graphite (-94.050; k cals) and hydrogen (-68.3k cals) to give the following
thermochemical equations.
(i) C2H5 OH (1)+ 3O2  2CO2 + 3H(I); H=-326.7 kcals.
(ii) C(graphite) + O2  CO2 H=-94.05 kcals
(iii) H2(g)+ 1/2 O2  H2O (1); H=-68.3 kcals
These equations must be manipulated to get the reaction leading to the formation of ethyl
alcohol from its elements.
Reversing (i)We get 2CO2+3H2O(1)  C2H5OH(1)+3O2 ;H=326.7
Multiplying (ii) by 2,
119
2C(gr)+2O2  2CO2 H=-188.10
Multiplying (iii) by 3,
3H2(g)+3/2O2  3H2O (1); H=-204.9
Adding the three .
2C(gr) +1/2O2+3H2  C2H5OH (1); H= 66.3
we get the thermochemical equation for the formation of C2 H5OH.
Example
Given the following heats of combustion
n-Butane ;H = - 687.9 k cals.
C (gr) ; H = 94.05 K cals.
H2; H = -68.3 k cals.
Calculate the heat of formation of n-butane at 25°C.
First we write the balanced thermochemical equations
1
(i) C4H10(g) + 6 O  4CO2 + 5H2O (1)H1=-687.9 cals.
2 2
(ii) C + O2  CO2; H2=-94.05 kcals.
(iii) H2+ 1/2 O2  H2O H2=-68.3k cals
The above three equations must suitably be manipulated to give the thermochemical equation
for the formation of butane
4C(gr) + 5H2  C4H10(g); H=-28.8Kcal
This is done as follows,
1
Reverse equation (i) 4CO2 + 5H2O (1)  C4H10+ 6 O ; H= 687.9
2 2
Multiply (ii) by 4,
4C(gr)+4O2  4CO2; H=-376.20
120
Mulitply (iii) by 5,
5H2+ 5/2 O2= 5H2O; H=-34.5
Simiplifying and adding 4 C(gr) + 5H2 = C4H10; H=-29.8 K. cal.
7.8. HEAT CHANGES IN SOLUTION
It is known that the formation of a solution is accompanied by a heat change, that is, heat is
absorbed or evolved. Thus when compounds such as sodium hydroxide or sulphuric acid is
dissolved water the resulting solution becomes warms, that is, heat is liberated, where as solution
resulting from dissolving ammonium chloride or ammonium nitrate in water becomes cool and
the solution has to absorb heat to reach the room temperature again. The heat change produced
when a mole of solution is dissolved in solvent is called the heat of solution. The total heat
change when one mole of a solute is dissolved in infinite quantity of solvent is called the integral
heat of solution.
The integral heats of solution for various solution of H2SO4 of different molalities are given
below.
Moles of
water / moles 6 10 25 200 α
of H2 SO4
ΔH/m -14.7 -16.2 17.5 -18.13 -23.0 kcal-1 mol
If the heat changes are extrapolated to infinite dilution we get the integral heat of dilution.
Thus 23 k cals. is the total heat evolved when one mole of H2SO4 is dissolved in a very large
quantity of water. This is a solution to which further addition of water produces no thermal
change and is referred to as the aqueous solution of H2SO4 and is written H2SO4 (aq).
H2SO4(l) + H2O  H2SO4(aq); H=23.0K.cals.
When aqueous solutions of two salts are mixed, there will be no heat change produced provided
no reaction takes place. Thus when a dilute solution of sodium chloride is mixed with a dilute
solution of potassium nitrate no heat change is observed.
KNO3 (aq) + NaCl(aq) + NaNO3 (aq) H=O
This is because the same ions are present in the resulting solution No reaction has taken place.
K+(aq) + NO3 (aq)+ Na+ (aq)+ Cl (aq)  K+ (aq)+Cl+-(aq) Na+ (aq) + NO3(aq)
If a chemical reaction takes place, then the heat of reaction is not zero.
121
NaCl(aq) + Ag NO3(ag)  Ag Cl + Na NO3(aq)  H=0
It is seen that the net reaction Ag+ (aq) + Cl– (aq)  AgCl
7.9. HEAT OF NEUTRALIZATION OF ACIDS AND BASES
An important change takes place in solution when an acid is neutralized by a base. When a
dilute solution of an acid is added to a dilute solution of a base, heat is liberated. The products of
this reaction are salt and water. The heat liberated per mole of water formed is called the heat
of neutralization. When dilute solution of strong acids (HCl or HNO) are neutralized by dilute
solutions of strong bases (NaOH or KOH) the heat evoived per mole of water formed is nearly
the same as may be seen from the examples given below.
KOH (aq) + HCl (aq)  KCl (ag)+H2O (1)H=-13.695 cal
KOH (aq)+ HNO3 (aq)  KNO3 (aq)+ H2O (I) H=- 13.670 cal
Na OH (aq)+HCl (aq)  NaCl (aq) + H2O (1) H= -13.680 cal
LiOH (aq) + HCl (aq)  = LiCl (aq)+ H2O (1) H= -13.700 cal
This constancy in the value of heat of neutralization can easily be explained by the ionization
theory. Strong acids, strong bases and their salts ale completely ionized in dilute solutions.
Hence the sodium ions, potassium ions, chloride ions and nitrate ions remain unchanged in the
reaction.
For example the equation for the neutralization of HCl (a) by NaOH (aq) the ionic reaction
can be written as
Na+ (aq) + OH– (aq)+ Cl– (aq) + H+  Na+ (aq) + Cl (aq)+ H2O (1)
In this reaction Na+ and Cl remain unchanged. The only chemical reaction taking place is
therefore
OH– (aq)+ H+(aq)  H2O(I)
and the H of this reaction is- 13,610 cals
Thus we find the neutralization of any strong acid by any strong base in a dilute solution is
brought about by the combination of hydrogen and hydroxyl ions to form water.
Hence the value of heat neutralization is constant H=-13.7k cal
However this constancy of heat of neutralization is not observed if the reaction involves a
weak acid or a weak base as seen in the examples below
122
Na OH (aq) + CH3 COOH (aq)  CH5 COO Na (aq) + H2O H=-133,00
NaOH (aq)+ HCN (aq)  NaCN (aq) + H2O (1) H=-2,900
NH3+ H2O + HCl(aq)  NH4Cl(aq) + H2O H=-12,400

This means that in these reactions combination between the hydrogen and hydroxyl ions does
not take place to completion. This is so because a weak acid or a base is dissociated to a very
small extent in solution. There are very few hydrogen ions in acetic acid. solution and very few
hydroxide ions in ammonia solution. Neutralization involving weak acids and weak bases may
be imagined to take place with neutral molecules.
CH3COOH (aq) + OH– (aq)  CH COO– (aq)+ H2O (1)
NH3 (aq) + HCl (aq)  NH4 + + Cl–
These reactions do not take place to completion, hence the heat evolved is less.
7.10. VARIATION OF HEAT OF REACTION WITH

TEMPERATURE.THE KIRCHHOFFS EQUATION
The heat of a reaction depends upon the temperature at which measurements are made. It
varies with temperature because the heat capacities of the reactants and products are not the
same. However, for the applications of Hess ‘law, it is necessary to refer all H values to the
same temperature. For this reason we must know how the heat of a reaction varies with
temperature. Such a relation was first obtained by Kickoff. This can be understood from a
simple cycle.
We represent the reactants by the symbol A and the products by B. Suppose the H value for
the reaction A B is known at the temperature T1 and it is required to find its value at T2 .We
start with the reactants at the temperature T 1 and convert them into the products at the
temperature T2 This can be achieved by two paths as shown in the figure. 7.3.
Fig. 7.3. Conversion of reactants A at temperature T1 to products B at temperature T2 in two

different ways.
123
The reaction is allowed to take place at T1 when the heat change H1 occurs. The
products B at temperature T1 are heated to T2 when the heat absorbed is CP (B)(T2- T1) . Here
Cp(B) is the total heat capacity of the products.
The reactants A at T 1 are heated to T 2 when the heat absorbed is C p () (T 2 - T1). The
reaction is allowed to take place at T2 , when we obtain the products B at T2 .The heat change
in this reaction is H2 Since in both paths we started with the reactants A at the temperature T1
and obtained the products B at the temperature T2, the total heat change in both paths must be
equal.
i.e.H1 + Cp + (B) (T2- T1) = Cp(A) (T2- T1) +H1
from which we can obtain the relation
Where Cp =  Cp (Products) -  Cp (reactants)
This equation is known as Kirchhoffs equation
There is an alternate direct way of obtaining this equation.
For the reaction A  B; H = HB - HA for HB is the total enthalpy of the products and HA total
enthalpy of reactants .
:. H= HB-HA Differentiating we get
d ( H ) dH B dH A dH B
  : by definition  CP ( B)
dT dT dT dT
dH A
and  C P ( A)
dT
d ( H )
Hence  CP ( B )  CP ( A); d ( H )  CP ( B ) dT  C P ( A)dT
dT
Integrating between the limits T1, and T2 when H values are
H1, H2
H 2 T2 T2
 d H   C P ( B )dT   C P ( A)dT
H1 T1 T1
H 2  H1  C P ( B )[T2  T1 ]  C P ( A)[T2  T1 ]
from which we obtain the same equation as before
124
H 2  H 1
 CP ( B )  C P ( A)
T2  T1
In the integration it has been assumed that the CP values do not change with temperature.
Example
For the reaction H2 (g)+ 1/2 O2(g)  H2O (g)H = -57.8 K Cals at 298 K
Calculate the value at 373 K.CP (H2) and CP(O2) are C, is 6.5 cal degree mole-1 and for H2O
CP( g) CP is 7.5 cal degree-1 mole-1.
We make use of the Kirchhoff’s equation
H (373)  H (298) 1
 [C P ( H 2O )( g )  CP ( H 2 )  C P (O2 )]
373  298 2
 1 
 7.5   6.5   6.5   2.25
 2 
H (373)  H (298)  75 C P
 57,800  ( 2.25)  7.5  57,968 Cals
Check your progress
1) Why the heat of reaction changes with the variation of temperature?
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7.11. CALCULATION OF HEATS OF REACTION FROM

BOND ENERGIES
In this last section we will discuss an approximate method for calculating heat of
reactiction. This becomes necessary when Hess Law cannot be applied due to non availability
of necessary thermochemical reactions. The method involves the use of bond energies. Bond
125
energy is the energy required to break a bond and a separate the atoms. For example the H
of the reaction.
A-B  A (g) + B(g)
is the energy of the bond A-B
For diatomic molecules like N2, NO, HCl and O2 this quantity is merely the dissociation
energy of the molecules and can be obtained from experiments. However for bonds of the type
C-H, N-H, O-H etc only average values cannot be obtained. For example the bond energy for
C-H cannot be determined directly. But consider the reaction;
CH4 (g)  C(g)+ 4H (g)
Since this reaction involves the breaking of 4C -H bonds, one may suppose that one fourth the
 H of this reaction gives the bond energy of a single C-H bond. This however gives only an
average value because, with the removal of each H atom, the remaining C-H bonds become
weaker. Hence  H for the breaking of the first C-H bond in methane will be higest and that
for removal of the last hydrogen atom lowest.
The enthalpy change for the reaction
CH4  C(g) + 4H(g)
can be obtained as follows.
First the heat of formation of methane is calculated from the thermochemical equation involving
combustion of methane, hydrogen and carbon.
C(gr) + 2H2(g)  CH4 (g) : H1= 17.89 k cal.
This equation is reversed and combined with two equations
CH4 (g)  C(gr) + 2H2 (g); H= -17.89 k. cal.
Dissociation 2H2  4H; H =208.36 k. cals

of hydrogen
Sublimation C(gr)  C(g) ; H= 171.7 k. cals. of graphite

-----------------------------------------------------------------------------
Adding CH4(g)  C(gr) + 4H (g); H =397.95 k. cal.
-----------------------------------------------------------------------------
126
This is the energy required to break 4 C-H bonds. Hence the bond energy for one C-H is one
fourth this value, i.e. 99.49 k. cal. mole-1.
In this way the values of the bond energies for a number of bonds have been obtained. Some
of them are given in the table. The values in the table have been adjusted in such a way to be-
applicable to largest number of compounds.
Bond energies in k. cal mole.
H-N 104 N=N 225 C=C 145 C =O 173

H-F 135 N-H 92 C=C 198 C -Cl 76
H-Cl 102 O-H 109 C-H 98
Cl- 57 C -C 80 C-O 79
Cl
Making use of these values the enthalpy change for a number of reactions involving these
bonds can be calculated. In a chemical reaction bonds are broken and new bonds are formed.
Energy is absorbed in the breaking of a bond, and energy is released when a new bond is
formed. The net heat change in a reaction is the algebraic sum of these. However it should be
remembered that this bond energy method can be applied only for gaseous reactions and only
when covalent bonds are involved.
Example (i)
Using the values of bond energies given calculate  H for the following reaction
CH4(g) + Cl2(g)  CH3Cl(g) + HCl(g)
In this reaction one C-H bond and one Cl-Cl bond are broken and one C-Cl bond and H-Cl
bond are formed.
Energy required to break the bonds=98+57 =155 k. cals. mole-1
Energy released in the formation of bonds = 76 + 102 = 178 k. cals. mole-1
Net energy released= 178 - 155 = 23k. cals. mole-1
Therefore H = - 23 k.cals
Example (ii)
Given the heat of formation of ethane as Hf = - 20.23 k. cals. calculate the C-C bond energy
H3C-CH3  2C(gr) + 3H2 H=  20.323k.cals.
combining this with
127
2 C(gr)  2 C(g) H =2x 171.7 =343.4 k. cal
3H2 (g)  6H (g) H= 3 x 104.18= 312.54k. cal
We have H3C - CH3  2C(g) + 6H (g) ; H= 676.17 k. cal.
This is the energy required to break 6 C-H bonds and one C-C bond. Since the energy required
to break 6 C-H bonds is 6 X 98=588 k. cal, the energy required to break one C-C bond will be
676.17-588 k. cal mole-1.
7.12. SPONTANEOUS PROCESS
The first law of thermodynamics is a statement of the equivalence of different forms

of energy. While it tells us that in any process when energy of one kind disappears, an equivalent
amount of energy of another kind makes its appearance, it does not give any information about
the process itself. It cannot say whether the process is possible or not. For example, it cannot
tell us whether a metal rod at uniform temperature can by itself become hot at one end and cold
at the other. So long as the heat gained by one end is equal to the heat lost at the other, process
in no way violates the first law. However, we know from our experience that such a process is
never observed. Heat flows of its own accord (spontaneously) only from a region of higher
temperature to one at a lower temperature. We can also, from our experience predict the
course of many other processes. A solute diffuses from a concentrated solution into a dilute
solution. These are spontaneous processes. All natural process are spontaneous as water running
down a hill, decay of organic matter, demagnetization of magnets, disintegration of radioactive
elements and so on.
By observing the nature of these spontaneous processes we can arrive at some

generalisations which have become statements of the second law of thermodynamics (i) All
spontaneous processes change in direction in which they attain a final state of ‘rest’ which we
may call equilibrium. When two metal blocks at different temperatures are brought into contact,
heat flows spontaneously from the block at higher temperature to that at the lower temperature
until a uniform temperature is reached. We say there is thermal equilibrium. When two solutions
of unequal concentration are carefully brought together the solute diffuses from the concentrated
solution into the dilute solution until concentration is the same throughout. This is diffusive
equilibrium. In the same way suppose as gas under high pressure is separated from one at low
pressure by a partition. If the partition is removed the gas under higher pressure diffuses into
the low pressure gas until the pressure is the same throughout. This is called mechanical
equilibrium. These observations can be summarised as follows: Every system left to itself
changes slowly or rapidly in such a way as to approach a final state of rest called equillibrium.
This may be considered to be the origin of the second law of thermodynamics .
128
(ii) All spontaneous processes have one thing in common. They are unidirectional. They proceed
in the direction in which equillibrium may be attained. They cannot take place in direction away
from equilibrium without external aid. Work is necessary to carry water uphill. A gas that has
expanded spontaneously into an evacuated vessel can be sent back by introducing a piston in
the second vessel and compressing the gas, that is by doing work. The nonspontaneous process
of transfer of heat from low temperature to a region at high temperature is carried out in the
refrigerator, but this process is accompanied by a net input of work. These observations can be
summarised into a statement of the second law of thermodynamics.
1. The spontaneous flow of heat is always unidirectional-from a body at higher temperature to

one at lower temperature.
2. It is impossible to construct a machine which is able to convey heat by a cyclic process from
a body at constant temperature to another at a higher temperature unless work is done on the
machine by some outside agency.
Exceptions to this are observed at the microscopic level as for example in Brownian motion
where one finds occasionally particles moving from lower concentration to higher concentration.
But such violations are never observed at the macroscopic level.
7.13. CONVERSION OF HEAT INTO WORK

There is yet another limitation of the first law which gives rise to an additional statement
of the second law. While the first law states that heat is completely converted into work it does
not tell us the conditions under which this conversion can be achieved. While all other forms of
energy can be completely converted into work. Heat is one form of energy for which there are
restrictions to its being converted into work. This is because heat can be converted into work
only through a working substance, say gas enclosed in a cylinder by a piston. By placing the
cylinder in a heat reserviour the gas may absorb heat and do work by expansion against the
piston. By expanding isothermally and reversibly the absorbed heat may be completely converted
into work. Although complete conversion of heat into work has been achieved this has resulted
in a change in the state of the working substance (gas). It is now in an expanded state. To
restore the gas its original state, it must be compressed. Work must be done, when heat is given
out. To obtain work continuously from heat the gas must be brought back to its initial state after
every expansion the working substance must operate in cycles. If the expanded gas is returned
to its initial state by isothermal reversible compression the work done by the gas and heat
liberated will be identical to the heat absorbed and work done by the gas in the expansion. At
the end of the cycle, we are left with no heat absorbed and no work done. In order to retain
some of the work done in the expansion, some heat must be rejected at lower temperature.
This limitation is stated as another version of the second law of thermodynamics. It is not
possible to convert heat into work by means of an isothermal cyclic process.
129
7.14. ENTROPY
Such definition of the second law as have been made above are not convenient of
solving problems in chemistry. What is required is a criterion by which one may determine
whether a particular chemical reaction can take place spontaneously. The second law must
provide a function which has the following characteristics.
1. It must be thermodynamic function of state

2. It must change in a definite way (say increase) in an irreversible process.
3. It must not change once it reached .
A function satisfying these requirements has been ‘devised’. It is called entrophy. It

has the symbol S. For an infinitesimal change it is given by the heat absorbed (q) divided by
temperature T.
dS = q/T (for reversible process)
Check your progress
3) What are spontaneous processes?
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If the process takes place spontaneously then dS is greater than the heat absorbed (q) divided
by temperature (T).
dS > q /T (for irreversible process)
For non spontaneous processes the entrophy change is less than the heat absorbed (q) divided
by temperature(T).
dS < q/T (for non spontaneous process)
For an irreversible process the entropy change can be determined by carrying Out the same
process (same initial state to same final state) reversible and finding the heat absorbed. Hence
130
dS for change is given by qrev T where qrev is the heat absorbed had the process taken place
reversibly.
For a finite change the process is divided into a number of steps and the entropy change is the
sum of the entropy changes in the individual steps.
qrev
S  
T
Before proceeding further with this function, it should first be established that entropy is
thermodynaimc function of state. This can be done through what is called the Carnot cycle.
7.15. THE CARNOT CYCLE
Carnot devised a cycle of operations for obtaining maximum work from a cycle of operations.
In this cycle, known as Carnot cycle a working substance undergoes a series of changes and is
brought back to its initial state. Although any substance may be used as a working substance,
we choose it as a gas enclosed in a cylinder. The four stages are (i) isothermal expansion (ii)
adiabatic expansion (ii) isothermal compression (iv) adiabatic compression. Since the heat
absorbed cannot be completely converted into work, part of it must be rejected at a lower
temperature. Hence, two heat reservoirs must be provided one at a higher temperature. (T2)
called the source and another at a lower temperature (T1) called the sink.
In these reservoirs of constant temperatures isothermal processes can be carried out.

For adiabatic process therrmally insulated jackets are provided for the cylinder. The cycle of
operation is represented on a pressure- volume diagram.
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Stage I
The cylinder containing one mole of a gas under a pressure P1 and occupying V1 is placed in
the constant temperature bath at temperature T2. The gas is allowed to expand reversibly until
its final volume is V2. In this isothermal reversible expansion the gas absorbs an amount of heat
Q2 which is equal to work done.
V2
Q2  W1  RT2 .ln
V1
The path is represented by AB in the diagram.
Stage II
The cylinder is removed from the reservoirs and placed in the non-conducting jacket. The
pressure on the piston is adjusted so that the gas expands reversible until its volume increases
to V3 (point C). In this adiabatic expansion the temperature falls from T2 to T1. The work done
by the gas W2 is given by:
W2  E  Cv (T2  T1 )
This is represented by BC in the diagram
Stage III
The non conducting jacket is removed, and the cylinder is placed now in the hot reservoir at
the lower temperature T1. The gas is compressed reversibly until volume is reduced to V4. In
this isothermal compression, work W3 is done on the gas and an equivalent amount of heat Q1
given Out.
V4
Q1  W3  RT1 ln
V3
This is the isothermal CD on the diagram
Stage IV
Finally in the last stage, the cylinder is placed in the non-conducting jacket and compressed
reversibly until the initial state is reached. Actually the final volume V4 in stage III is adjusted in
such a way that it falls on the adiabatic. In the adiabatic compression the temperature rises
from T1 to T2. Work done in this compression W4 is given by
W4  E  C v (T2  T1 )
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This is represented by PA in the diagram.
The total work performed in the complete cycle
W  W1  W2  W3  W4
V2 V
 RT2 ln  Cv (T2  T1 )  RT1 ln 4  C (T2  T1 )
V1 V3 v
The second and the fourth terms cancel giving net work done as
V4
 RT2 ln V2 / V1  RT1 ln
V3
For any adiabatic reversible volume change we have relation.
 V final  T(initial )
   1  .............(17)
 Vinitial  T( final )
For the two adiabatic processes in stage II and III we can write
 1  1
 V3  T  V1  T1
   2;    ;
 V2  T1  V4  T2
From these we can get
 V3   V4  V  V 
   or  3    2 
 V2   V1   V4   V1 
Substituting this relation in the expression for net work (lone We get)
V  V V 
W  RT2 ln  2   RT1 ln 2  R ln  2  (T2  T1 )
 V1  V1  V1 
This is the net work obtained from the heat absorbed in the first stage
V2
The heat absorbed is Q2  W1  RT2 ln
V1
The efficiency of the carnot cycle is therefore
V2
R ln (T  T )
W V1 2 1 T T
  2 1
Q2 V
RT2 ln 2 T2
V1
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In this way we get the important result that the efficiency of a heat engine (mechanism for
converting heat into work) operating in a carnot cycle depends only the temperatures between
which it operates. It does not depend upon the nature of the working substance. This is the
maximum efficiency possible because every stage is conducted reversibly.
For a given temperature T2 of the source the efficiency can be increased by keeping the
W T2
temperature of the sink as low as possible. If T1=0 then   1 . This means that in a
Q T1
cycle of operation heat can be completely converted into work. Since according to the second
law heat cannot be completely converted into work in a cyclic process we arrive at the conclusion
that we cannot have reservoir at absolute zero of temperature. Of course, it can also be
shown, independent of the second law that the absolute zero is unattainable.
7.16. ENTROPY AS A THERMODYNAMIC FUNCTION OF

STATE
After going through the carnot cycle, the working substance (gas) is brought back to its
initial state, so that net change in its internal energy is zero. Then from the first law
E  Qtotal  Wtotal  0
Wtotal  Qtotal  Q1  Q2
Wtotal T2  T1

Q2 T2
But Q1 T
1  1 1
Q2 T2
Q1 T
or  1
Q2 T2
From which we can show that
Q1 Q2 Q1 Q2
 or  0
T1 T2 T1 T2
Thus, we find that in the carnot cycle the sum of the Q/T terms is zero where Q is the heat
absorbed at the temperature T. This must be true for any cyclic process. Because any such
process can be divided into a large number of carnot cycles by drawing isothermals and
134
Q
adiabatics passing through it. The   0 . Sum of the heat changes in every step, each term
T
being divided by the appropriate temperature, will be zero, if the number of steps is very large
Q
the summation can be replaced by integration and we may write T  0 . q is the heat
absorbed reversibly in each small step.
Since every step is carried out reversibly in each small step. Since every step is earned out
reversibly
qrev
q  qrev and dS  (by defination)
T
qrev
Hence,  T
  dS  0
The meaning of the expression is as follows When a substance is carried through a number of
processes but ultimately returned to its original state (cyclic process) the net change in entropy
is zero.
This is exactly the condition to be satisfied by a thermodynamic function of a state. In a cyclic

process there is no change in the value of a thermodynamic function of the state. This has been
in the case of the internal energy of a system. Hence, entropy is also a thermodynamic function
of state for which we may write
S2
S   dS  S 2  S1
S1
7.17. ENTROPY AND THE SECOND LAW
We have defined entropy change as in a reversible process to be equal to q/T and for irreversible
process ds > q/T Since entrophy is a function of state we can write these conditions
as S  Q / T and S  Q / T .
Consider the changes taking place in a thermally isolated system. These are adiabatic changes.
Heat can neither enter the system nor leave it Q=0. Hence, the changes the condition for
reversibility would be TS =0; Since T can never become zero(absolute zero cannot be reached)
H=0 for reversible process in isolated systems. For irrversible process the condition becomes
S>O.
135
From these findings we can write these conclusions (1) Since every stage of a reversible
process is an equilibrium stage, the condition for reversibility is also the condition for equilibrium.
Hence, for equilibrium S=0. (ii) Since all naturally occurring processes are irreversible, any
process occurring in nature is accompanied by an increase in entropy. Hence, we can state that
entropy of the universe (an isolated system) is constantly increasing.
This had led Clausius to state the second law in terms of entropy. This statement along with his
statement of the first law are given below:
(1) Energy of the universe is constant
(2) Entropy of the universe tends towards a maximum.
The meaning of the second statement can be appreciated better in terms of the molecular
interpretation of entropy.
7.18. MOLECULAR INTERPRETATION OF ENTROPY

Thermodynamics is concerned with the observable or bulk properties of matter. It has nothing
to do with structure of matter-the molecules and atoms the structure of these particles. However,
we can get a better understanding of thermodynamic properties, if they can be correlated with
the properties of individual molecules. Such a study is made in statistical thermodynamics.
There, the internal energy of a gas is related to, and calculated from the kinetic and potential
energies of the constituent molecules.
Entropy however is not related to any molecular property. It is regarded as a measure of the
randomness in a system. By randomness we mean the number of ways the molecules can
arrange themselves without any change in the observable properties of the system. The number
of arrangements possible obviously depends upon the number of positions available into which
they can move. The randomness in a liquid is greater than that in a solid because in a liquid the
molecules have greater freedom to move about. The randomness in a gas is much more because
in the absence of any significant attractive forces, the molecules can occupy any position in the
vessel. Randomness is thus the disorder in the system because greater the number of positions
the molecules can assume greater the disorder. Entropy is a measure of this disorder. In passing
from ordered solid state to the highly disordered gaseous state the entropy should increase.
On the basis of this interpretation it is easy to show that any spontaneous process is accompanied
by an increase in entropy. Consider the spontaneous expansion of a gas from a high pressure
(small volume) region to a low pressure (large volume) region. In the larger volume the number
of positions available for each molecule is more than in the smaller volume. Hence, the randomness
has increased and so the entropy.
136
Similarly in the diffusion from a concentrated solution into a dilute solution the molecules move
towards a more random distribution. In the spontaneous flow of heat from a hot body to cold
one, there is a more random distributions of heat among molecules. Thus in all natural process
whether it is evaporation of liquids or oxidation of organic matter (to give smaller molecules)
the systems move towards a more disorder state (greater entropy).
7.19. FREE ENERGY AND FREE ENERGY CHANGE
The conditions S=0 for and S > 0 for spontaneous process apply for isolated system For
non adiabtic systems these conditions apply for systems plus surroundings.
Ssystem+Ssurroundings=0 and Ssys+Ssurr>0
We require a criterion that is appplicable to the system alone. This is provided by another
thermodynamic property-introduced by Gibbs.
This is free energy with the symbol G. Free energy is defined by the equation
G = H - TS. ----(1)
Since enthalpy and entropy are functions of state, free energy is also a function of state.
Introducing the relation H=E+ PV into (1), we have
G =E+PV - TS. - ------(2)
For a change of state from (1) to (2) the free energy change is given by
G2  G1  E2  E1  PV
2 2  PV
1 1  (T2 S 2  T1 S1 )  (3)
At constant temperature and pressure this equation 3 becomes
G2  G1  E2  E1  P(V2 V1 )  (T (S2  S1 ))  (4)
or G  E  pV  T S    (5)
Now from the first law E= Q-W
 Qrev  Wmax (for a reversible process) - (6)
Since S  Qrev / T , Qrev  T S and E  T S  Wmax we have
G  T S  Wmax  PV  T S     (7)

 Wmax  PV
137
Which we may write as
G  Wmax  PV
This equation (8) helps us to understand the meaning of free energy change. When the
temperature and pressure are constant the decrease in free energy is equal to the maximum
work done in the process other than the pressure - volume - work, which is the work done in
displacing the environment. This is called the maximum work or net useful work. For a chemical
reaction this can be the electrical work that can be obtained from it. For example when zinc is
added to a solution of copper sulphate, copper is precipitated and heat is liberated but no work
is done. However, if the same reaction is carried out in the galvanic cell, useful electrical work
can be obtained.
7.20. G AS A CRITERION FOR EQUILIBRIUM AND

SPONTANEOUS CHANGE
We start with the equation,
G = H - TS = E + PV - TS
Differentiating we get
dG = dE + PdV + VdP - TdS - SdT
dE = q - W = q - PdV if only pressure-volume work is involved.
Substituting
dG = q - TdS
dS  qrev / TdS  qrev where qrev is the heat absorbed when the process is carried out
reversibly.
Hence, dG = q - qrev
Here q is the heat absorbed in the actual process and qrev is the heat absorbed had the process
taken place reversibly.
For a reversible process q = qrev and dG = 0.
For an irreversible process q < qrev and dG < 0.
138
Since all spontaneous processes are irreversible, the free energy change should decrease in a
spontaneous process and we may state that all natural processes proceed in the direction in
which free energy decreases. When the free energy reaches a minimum, there is no furthur
tendency to change, the system is at equilibrium and dG = 0. Since G is a function of state we
can replace dG by  G and write
G = 0 for equilibrium
G < 0 for spontaneous change.
Check your progress
4. What is the relation between free energy and spontaneous processes?
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7.21. FREE ENERGY CHANGE OF CHEMICAL REACTIONS
The free energy change equation is written
G=H-TS
For a chemical reaction  H is the heat of reaction. It is negative for exothermic reactions
and positive for endoothermic reactions.  G and  S are the differences in the values of
products and reactants. For a reaction to proceed spontaneously  G of the reaction must be
negative. This is possible under three conditions.
H is negative S is positive
H is negative S is negative but TS < H
H is positivee S is positive but TS > H
Entropy values do not vary significanly from molecule so that  S values are usually
small. Hence, at ordinary temperatures T  S values can never be expected to be greater than
 H values. Hence, for most reactions at ordinary temperatures the sign of  H alone decides
the direction of the reaction. This means that a reaction is possible if it is exothermic. Examples
of exothermic reaction with negative  G values are many..
139
H2 +1/2 O2  H2O (I) H =-68.3 k. cal G =-56.7k. cals.
CCl4 (g) + 2H2O (g)  CO2(g) + 4HCl(g)
H=-41.2 k. cals. G= 61.2k. cals.
Endothermic reactions are not favored at ordinary temperatures, but at high temperature the
product TS may exceed H to make G negative .
An example for the reaction
Ca CO3+ (S)  CaO(S) + CO2(g)
H= 42.5 k. cals, S= 38.36 Cals= 0.0384 k Cals.
At room temperature TS =298 X0.0384 1=11.4 k, Cals
G =H-TS=42.5-11.4 =31.1 k.Cals.
The reaction cannot take place. But at high temperatures T S values may exceed 42.5. For
example at 12000C, TS =1200 x 0.0384 46.1 k. Cals.
G = 42.5-46.1 = -35 k Cals. and the reaction may take place spontaneously.
Nevertheless there are few examples of endothermic reactions for which  G is negative at
room temperature and they proceed spontaneously.
CH3OH (I) + NH3(g)  CH3 NH2(g) + H2O (g)
H=3.5 k.Cals.; G =-4.3k.Cals
Free energy change is therefore the criterion we have been looking for, to predict the direction
of a reaction. It is a better criterion because. It takes into account two rival tendencies shown
by the reacting molecules.
(i) Tendency to form stable products. The atoms in the reacting molecules prefer a configuration
in which they form stable bonds. This requires the reaction re-proceed in the direction in which
heat is liberated or enthaply decreases.
(ii) Tendency to form products which have greater randomness. This requires the reaction to
proceed in the direction in which entropy increases.
Sometimes the two tendencies may require the reaction to go in opposite directions as in the
reaction,
140
H2  2H
Molecular hydrogen is more stable hence the reverse reaction should be favoured on the basis
of stability. Atomic hydrogen represents a more random state and is to be favoured if entropy
change alone is considered.
Actual reaction tendency is a balance between the two tendencies. This is achieved through
free energy change. The reaction takes, place in the direction in which free energy decreases.
However, thermodynamics only guides us in predicting whether a reaction is possible or not.
This depends upon other factors. For example for the reaction
H2+1/2O2  H2 O
G is negative indicating the reaction can takes place. The rate at which it takes place at room
temperature is immeasurably slow. We may take a mixture of hydrogen and oxygen but it will
be ages before we can discover a drop of water. The presence of a catalyst like finely divided
platinum would make the reaction go fast and an electric spark would cause the the mixture to
explode.
7.22. SUMMARY
Chemical reactions are usually accompanied by heat changes. Some are exothermic reactions
and other are endo-thermic. Heat of a reaction is constant and it is independent of the path
chosen, it may be carried out in one step or several steps. The thermochemical concepts heat
of formation, heat of combusion, heat of solution and heat of neutralisation are briefly introduced.
Heat of a reaction changes with the change of the temperature. Reactions between covalent
substances proceed with the bond breakage of reactants and new bond formation. From the
bond energies it is possible to calculate the heat of reaction.
First law of thermodynamics is unable to predict the spontaneity of processes. Therefore

other thermodynamic functions entropy and free energy have been proposed. Process which
proceed at their own accord are called spontaneous processes. Different forms of energy get
completely converted into heat, but there are obstacles for the complete conversion of heat into
other forms of energy.
Carnot cycle is cyclic process of operations of a system from which maximum amount of work
is obtained. Entropy is the measurement of the disorderliness of a system accompanied by free
energy decrease.
141
1. Heat of reaction is nothing but enthalpy of reaction. The change of enthalpy of products
and reactants depends on T & P. The reaction is carried out by the absorption or
liberation of heat energy will give heat content or enthalpy of reaction.
2. The physical or chemical change of the reaction depends or heat of the reaction. By
increasing or decreasing the temparature, rate of the reaction will varies.
3. If the reaction is feasible or occurs by increasing the entropy from reactants to products
will give spontanious process. ex: solids to liquid S= Sl-Ss the process becomes
spontanious.
4. G = H - TS, by substituting entropy and enthalpy of the reaction, if we get G is

negative, the process becomes spontanious. G is zero that is reversible process and
G is positive the process is non spontainious process.
I. Answer the following in 10 lines each.
1. In which of the following pair would you expect the difference in entropy to be least?
(i) Solid iodine and iodine vapour (ii) Solid glass and molten glass (iii) Ice and water.
2. Show that free energy decreases in a reversible process.
3. Under what conditions can an endothermic reaction proceed spontaneously?
II. Answer the following in 30 lines each.
1. Give the different statements of the second law of thermodynamics and explain each one of them.
2. Derive an expression for the maximum efficiency of a heat engine.
3. From the bond energy data given in this lesson, deduce Hf for propane.
4. State and explain the Hess’s Law of constant heat summation. Show how it is in agreement
with the first law of thermodynamics. Mention two applications of the law
5. What is meant by heat combustion of a compound? Described the method by which heats of
combustion are obtained. What is their importance for foods and fuels? Show how these
values can be used to determine the heat of formation of organic compounds.
142
Solve the following problems.
1. A heat engine operates between the temperature 120°C and 30°C. Find the maximum
efficiency of this engine.
2. A steam engine operates between the temperatures 140°C and 40°C. What is the
minimum amount of heat that should be withdrawn from the hot reservoir to obtain 250
calories of work?
3. A refrigerator (reverse of a carnot cycle) transfers heat from 0° C (inside the

refrigerator) to 25°C (room). Find the work that must be done to freeze I Kg of water.
(Hint:Amount of heat to be withdrawn is 1000 g x 80 Cal gm).
143
UNIT-8 : ELECTROCHEMISTRY-II GALVANIC CELLS
AND ELECTRO MOTIVE FORCE (EMF)
Contents
8.0. Objectives
8.1. Introduction
8.2. Galvanic or voltaic cells
8.3. Irreversible and reversible cells
8.4. Reversible electrodes
8.5. Electromotive force (EMF)
8.6. Standard cell
8.7. Free energy change and electrical energy
8.8. Electrode potential
8.9. Standard hydrogen electrode
8.10 Sign convention of electrode potential
8.11. Secondary reference electrodes
8.12. Summary
8.0. OBJECTIVES
Once you complete the study and understanding of various aspects of this unit, you must be
able to:
 Differentiate galvanic voltaic cells which consist two electrodes immersed in an
electrolyte solution.
 Cells are classifies as reversible and irreversible based on the nature of the cell reaction.
 Explain the electromotive force (EMF) of cells and its measurement.
 Relate electrical energy and free energy change of cell reaction.
 Account for the sign convention of electrode potentials.
 Describe the utility of standard hydrogen electrode and subsidiary reference electrodes
calomel and silver-silver chloride electrodes.
8.1. INTRODUCTION
In electro chemistry, we encounter two situations that involve electrochemical changes.
144
i) Situation where chemical changes are brought out a passage of electric current. Such
a process where chemical change is brought out by applied voltage is called electrolysis.
ii) Situations where chemical changes (EMF) help to produce electrical energy. Such
changes occur in chemical cells.
In either of these situations, we require at least one electrolyte solution in which two
metal rods are dipped. Chemical cells used to produce electrical energy are of two types
a) Primary cells and b) Secondary cells.
Primary cell: A cell which produces electric energy (current) directly by a chemical
reaction. Voltaic or galvanic cells are considered as primary cells.
Secondary cell: A cell which generates electric energy (current) if a current is earlier
passed through it for sometime from an external source of EMF. In the former process (the
charging process) the electric energy is converted into chemical energy chemical cells used to
produce electrical energy and this chemical energy is converted in a latter process (discharging
process) back into electrical energy. Thus it functions as a source of voltage in the latter
process. Lead accumulators, and batteries are examples of secondary cells.
8.2. GALVANIC OR VOLTAIC CELLS (PRIMARY CLELS)
A galvanic or a voltaic cell consists essentially of two electrodes combined in such

manner that when they are connected by a conducting material, for example, a metal wire, an
electric current flows through it. Each electrode, in general, involves an electronic (metal rod)
conductor and an electrolytic conductor in contact with each other. There exists a potential
difference called electrode potential at the surface of separation between the metal and the
solution. If there is no other potential difference in the cell the electromotive force (EMF) of the
cell is taken as equal to the algebraic sum of the electrode potentials; due allowance being
made with respect to the sign of each electrode potential. During the operation of a voltaic cell
a chemical reaction lakes place at each electrode, and it is free energy of this reaction that
provides the electrical energy of the cell. In general there will be an overall chemical reaction
when we take into consideration all the processes occurring in the cell. Such a cell is referred
to as a chemical cell. In other type of cells the reaction occurring at one electrode is exactly
reversed at the other, but there may be a net change of free energy because of a difference in
concentration of one or other of the reactants concerned at the two electrodes. Such cells are
called concentration cells. The electrical energy arises in these cases from the energy change
accompanying the transfer of the same material from one concentration to another.
Check your progress
1. Differentiate a galvanic cell from an electrolytic cell.
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8.3. REVERSIBLE AND IRREVERSIBLE CELLS

Cells may further be classified into i) reversible and ii) irreversible cells The first category
of cells where no net flow of current takes place unless the two electrodes are connected is
called reversible cells. The extent of chemical reaction occurring in such cells is proportional
the quantity of electricity passing in accordance with the Faraday’s laws. A reversible cell shall
satisfy the following conditions.
i) When the cell is connected to an external source of EMF, exactly equal to that of the
cell, no chemical reaction should occur within the cell.
ii) If the driving force is decreased by an infinitesimally small amount, then the current
should flow from the cell to the external source.
iii) When the driving force is increased by an infinitesimally small amount ,the current
should flow from the external source to the cell.
If chemical reaction takes place at either electrodes even when there is no net flow
of current, they are called irreversible cells. The following are the example of the two categories
of cells.
The first type of cell illustrated by the Daniel cell, is made up of a zinc electrode dipped
in zinc sulphate solution and copper electrode dipped in copper sulphate solution. The two
solutions are usually separated by means of a porous partition. Neither metal is attacked until
the electrodes are connected and a current is allowed to flow. This cell is an example of the
reversible cell.
The second type cell consists of zinc and copper electrodes dipped in dilute sulphuric acid.
The zinc electrode reacts with the acid spontaneously even if there is no passage of current.
This type of cells, where there is spontaneous reaction are examples of the irreversible cells.
It is necessary to relate the electrical energy produced in a galvanic cell thermodynamically

to the process occurring in the cell. This can be done only when the cell behaves as a reversible
one.
The Daniel cell, mentioned above, satisfies these requirements and so it is a reversible cell.
It may be noted that galvanic cells are excepted to behave reversibly only when the currents
passing through are infinitesimally small, so that the system is always virtually at equilibrium.
146
8.4. REVERSIBLE ELECTRODES
The electrodes of a reversible cell are called reversible electrodes. There are three main
types of reversible electrodes.
The first type of reversible electrode consists of a metal or non-metal in contact with
the solution of its ions. zinc in zinc sulphate solution, copper in copper sulphate solution. Hydrogen
gas in contact with hydrogen ions, oxygen gas in contact with hydroxyl ions, and chlorine gas in
contact with chloride ions are some examples. In the case of non metal electrodes, platinum or
any other unattackable metal is generally used for electrical contacts. In these cases, the metal
comes rapidly into equilibrium with the gases.
The reaction taking place in the reversible electrodes of the first kind can be written in
the following manner. If the electrode material is a metal (M), the reaction can be written as
follows:
M+ + e–  M
Where M+ is corresponding ion of the metal and e indicates an electron. In the case of
non metal electrodes, the reactions may be represented by the following examples.
1
O2 + H2 O + 2e  2[OH]
2
Cl2 + 2e—  2Cl—
In the case of hydrogen electrode the reaction is similar to a metal, metal ion electrode,
since hydrogen gives a positive ion i.e.
1
H + e  H2
2
ii) Reversible electrodes of the second type involve a metal and a sparingly soluble salt of
this metal in contact with a solution of a soluble salt of the same anion. An example of this kind
is the silver chloride. Electrode in contact with a solution of a soluble chloride like KCl. The
electrode reaction can be written as
AgCl(s) + e–  Ag(s) + Cl—
The above reaction is virtually equivalent to the cell reaction of a chlorine gas electrode
except that the silver
1
Cl2 + e  Cl
2
147
chloride can be regarded as the source of chlorine. In fact the silver-silver chloride electrode is
thermodynamically equivalent to a chlorine electrode with chlorine at a pressure equivalent to
the dissociation pressure of the silver chloride into silver and chlorine at the experimental
temperature. The other examples of the second kind of reversible electrodes are:
i) Hg, Hg2 Cl2, (s), KCI Solution

ii) Ag, AgBr (s), HBr Solution
The electrodes of this kind are of great value in electrochemistry because they permit
the ready establishment of an electrode reversible with respect to anions like (chloride, bromide,
sulphate and oxalate, which could not be obtained in a direct manner.
The third type of reversible electrode consists of an unattackable metal, e.g; platinum
or gold, immersed in a solution containing both oxidised and reduced species of an oxidation-
reduction system e.g.
Sn4+, Sn2+
Fe3+ , Fe2+
Fe (CN)3—6, Fe (CN)4—6
The unattackable metal serves as the conductor for making electrical contact. The
oxidized and reduced states need not be ionic always. For example, in a system consisting of
quinone is the reduced form. This also constitutes an electrode of the third type. These electrodes
are known as oxidation-reduction electrodes. These electrodes are represented as
a) Pt/ Sn4+, Sn2+
b) Pt/ Fe3+ , Fe2+
The electrode reactions are written as
Sn4+ + 2e  Sn2+
Fe3+ + e  Fe2+
In order that the electrode may behave reversibly, it is essential that the system contains
both oxidised and reduced states.
Since a reversible electrode always involves an oxidised and reduced state using the
terms oxidised and reduced in the broadest sense, all the reactions taking place at an electrode
may be considered as an oxidation reduction reaction in the most general sense. So the reaction
at any electrode may be written as general form, reduced form = oxidised form + ne–
Where n is the difference in the number of electrons of the oxidised and the reduced forms.
8.5. ELECTROMOTIVE FORCE (EMF) AND ITS MEASUREMENT
Electric current cannot flow from one point to another unless there is a potential
difference between the two points. Hence the flow of electric from one electrode to another in
a galvanic cell indicates that the two electrodes have different potentials. The difference of
148
potential which causes the flow of current from one electrode to another in a galvanic cell
indicates that the two electrodes have different potentials, The difference of potential which
causes the flow of current from one electrode to another is called the electromotive force
(EMF). As stated earlier, the EMF of a cell is equal to the algebraic sum of the two electrode
potentials, due allowance being made to the sign of the electrode potential.
The EMF of a cell cannot be measured by directly connecting the cell terminals to a
voltmeter. It is because during such a measurement some current is drawn from the cell and a
chemical reaction occurs in the cell to some extent. This brings a change in the concentration of
the electrolytes and hence in the potential. Because of the flow of current, a part of the EMF is
used to overcome the internal resistance of the cell. Because of these two reasons, the EMF of
the cell given by the voltmeter will not correctly represent its voltage.
To overcome this difficulty the Poggendroff compensation method is used. This method
has got the advantage of measuring the EMF of the cell on ‘’open circuit” ie, when it is producing
no current. As mentioned earlier, the cell can be expected to behave reversibly only when it is
producing an infinitesimally small current and hence use of an open Circuit is ideal one for
determining the EMF of a reversible cell.
The device used for the measurement of EMF of galvanic cells is called the
potentiometer. The experimental setup is given in fig 8.1. It consists of storage battery B of a
constant EMF which is much larger than the EMF of the cell to be measured.
Fig. 8.1. Measurement of EMF
This is connected across the ends uniform conductor AC of high resistance. The cell
X, whose EME is being measured is connected through a galvanometer G to a sliding contact
D which can be moved along AC. The position of D is adjusted until no current flows through
the galvanometer i.e., it gives no deflection. The potential fall between A and D due to the
battery compensated by the EMF of X, that is Ex. The cell X is replaced by a standard cell S of
accurately known EMF (E2). The sliding contact is readjusted until a point of balance (D1) is
reached. The fall of potential between A and Dl is equal to Es. Since conductor AB is supposed
to be uniform, it follows that
149
Ex AD

E s AD1 …….(1)
AD
 E x  Es X
AD1 ……..(2)
Since Es is known, and AD and AD1, can be measured, the EMF (Ex) of the unknown
cell can be evaluated.
In the simplest form of the potentiometer, AC is 1 meter long and the EMF of Battery
is 2 volts. Then the corresponding error in the evaluation of EMF is 0.001 volt.
8.6. STANDARD CELL
The accuracy of the measurement of EMF depends on the accuracy of the standard
cell used. The cell now widely used for the purpose is the Weston Standard cadmium cell. The
characteristics of the cell are i) it is highly reproducible, ii) its EMF remains constant over long
periods of time and ii) it has a small temperature coefficient. In order to retain constancy of
EMF while in use, only very minute currents are drawn from the cell, as is actually done if the
potentiometer is operated properly. One electrode of the cell is a 12.5 percent cadmium amalgam
placed in a saturated solution of cadmium sulphate (3CdSO4.8H2O) and the other electro consists
of mercury and solid mercurous sulphate placed in the same cadmum sulphate solution. The
cell is represented as follows:
Fig. 8.2. Weston Cadmium cell
12.5% Cd (Hg)/3 CdSO4 8H2O Hg2SO4 (s)/Hg salt, solution
The Westom cell is set up generally in a H-shaped tube as shown in Fig.8.2.
150
The right hand limb contains cadmium amalgam and the left hand limb the mercury.
The amalgam is covered with crystals of 3CdSO48H2O and the mercury with Mercurous
sulphate and 3CdSO48H2O crystals. The whole cell is filled with a saturated solution of cadmium
sulphate. The EMF of the Weston Cadmium cell is 1.018636 (international) absolute volts at
200C and its temperature coefficient is 4 x 105 volt (The EMF decreases by this quantity for
every degree rise of temperature). For ordinary purposes unsaturated Weston cell is used
which makes use of a solution of cadmium sulphate saturated at 4°c and becomes unsaturated
at normal temperature. The temperature coefficient is negligibly small and so its EMF can be
taken as equal to 1.0186 volt.
8.7. FREE ENERGY CHANGE AND ELECTRICAL ENERGY
The second law of thermodynamics is applicable to reversible processes. Since the

study here involves reversible cells, it is possible to apply thermodynamics to the results. If the
EMF of a voltaic cell is E volts and the process taking place in it is accompanied by the passage
of n faradays (nF coulombs) where F represents 96500 coulombs, the work done by the system
in the cell is nFE volt-coulombs or Joules. If the cell is a reversible one, this work represents the
maximum work, and it may be taken as equal to the change of free energy accompanying the
cell reaction. Hence it follows that
G  nFE .........(3)
Where  G is the increase in free energy for the process taking place in the cell under
consideration. According to the Gibbs-Helmholtz equation.
 G 
G  H  T   ……………(4)
 T  p
Where H is increase of heat content for the cell reaction. Introducing -nFE for G in the
equation the result is
 E 
 nFE  H  nFT   ………..(5)
 T  p
 E 
H   nFE  nFT   ………..(6)
 T  p
  E  
 nF  E  T    ……….(7)
  T  p 
151
It is seen from the equation that if the EMF of the reversible cell E and its temperature
coefficient at dE/dT at constant pressure are known, it is possible to evaluate the heat change
of the reaction occurring in the cell.
Further since G = H - TS (from thermodynamics), the above measurements of E and dE

can be used to calculate S, the entropy change in the process. It can also be shown that
 E 
G  nF  T  ……………….(8)
 p
8.8. ELECTRODE POTENTIAL
Suppose the reaction occurring in a reversible cell is represented by me equation.
A+B  C+D
The decrease in free energy - G accompanying the process is given by van’t Hoff reaction
isotherm.
G  G o  RTQn ...................(9)
Where -Go is the decrease in free energy accompanying the same process when all
the reactants and the products are in their standard states of unit activity and Qn stands for the
reaction quotient of the activities of the products and the reactants. Substituting the value of Qn
we have
aC xaD
G  G o  RT ln
aA xaB ……………. (10)
If E is the e.m.f. of the cell in volts and the cell reaction involves the passage of n Faradays
i.e., nF coulombs, the electrical work done by the cell is nFE Volt coulombs, or joules. It is
known that this electrical energy is equal to decrease in free energy. The above equation can
be written as
aC xaD
nFE  G o  RT ln
a A xaB ………..(11)
aC xaD
nFE  nFE o  RT ln
aA xaB ………..(12)
RT a xa
E  Eo  ln C D …………….(13)
nF a A xaB
152
Where Eo is the EMF of the cell in which the activity or as an approximation the
concentration of each reactant and each resultant of the cell reaction is equal to unity. Eo is
known as the standard EMF of the cell. The above equation is often referred as Nernst
equation. Nernst equation can be written in the following form by replacing the activity terms
by the concentration terms as an approximation.
This equation helps us to calculate the EMP of the cell when the concentrations of the
reactants and products of the cell reaction and E are known.
We know that the reversible cells are made up of two reversible electrodes. The over all cell
reaction and in turn the EMF of the cell can be split up into two, one for each electrode. This
can be explained by the following example,
The cell reaction for the cell
H2 / HCl, (c) AgCl (s)/ Ag
is 1/2H2 +AgCl(s)  H++Cl-+Ag(s)
for the passage of one faraday. Then Nernst equation takes the form
RT a H   aCl  a Ag
E  Eo  In
F a 1  a AgCl ............(15)
H2
2
We can write the individual electrode reactions as
1/2 H2  H+ + e–
AgCl (s) + e–  Ag+ + Cl-
Based on these two reactions equation (15) can be split up as
 
 RT a   o RT a Ag  aCl 
E   E1o  ln H     E 2  nF ln a  ---------- (16)
nF a 1
 2
H2   AgCl 
RT a 
 E1  E10  In H
F a1 ---------- (17)
H2
2
RT a Ag xaCl 
 E2  E20  In
F AAgCl ---------- (18)
153
Where E1 and E2 are the single electrode potentials.
The standard slate of hydrogen is the gas at 1 atmosphere pressure and the standard states of
silver and silver chloride are the solids, it therefore follows that aH2 and aAgCl are unity, so
equations 17 and 18 are written as
RT
E 1  E H 2  E 10  ln a cl ---------- (19)
H  F
RT
E2  E Ag / AgCl  E2o  In aCl  ---------- (20)
F
Where Eo terms are the standard potentials of H2/H+ and Ag/AgCl, Cl- electrodes, It is
seen, therefore, that in the cell under consideration the potential of each electrode depends only
on the activity of one ionic species apart from the standard potential of the system.
A general expression for an electrode potential can be obtained by writing the general
electrode reaction as
Reduced State  oxidised state + ne–
Where n is the number of electrons by which the reduced state and the oxidised state
differ. The electrode potential is given by
RT  Re ducedState
E  Eo  n
nF  Oxidi sin gState 
Where E° is the standard potential
Thus if the electrode is formed from a metal M of valency z+ reversible with respect to
MZ+ ions, the electrode reaction is written as
M z   ze  M
The equation for the potential is written as
RT aM
E  EO  ln
z F aM z  ---------- (21)

Where aM , aM z  , are respectively the activities of the solid metal M and Mz+. The
cations Mz+ and M are in equilibrium in solution with each other. By convention the solid
state of the metal is taken as the standard state (unit activity) for an electrode consisting of
the pure metal, therefore aM may be replaced by unity. The equation (21) is then written as
154
RT 1
E  EO  In
z F aM z ---------- (22)

Similarly for an electrode involving a non-metal A, reversible with its anions Az-, the
electrode reaction is
A  ze  A z 
The equation for the electrode potential
RT aA 
E  EO  
In Z ---------- (23)
z F aA
As before, the activity aA of A is taken as unity. The equation for electrode potential is
written as
RT
E  EO ln a z ---------- (24)
zF A
Thus the magnitude of tendency of a substance to lose or gain electrons when it is in

contact with its ions is expressed by the electrode potential. Since the tendency to lose electrons
means the tendency to get oxidised, the potential is called oxidation potential. Similarly the
tendency to gain electrons means the tendency to get reduced, and hence the potential is called
reduction potential. It may be noted, that the reduction potential is the reverse of the oxidation
and vice versa.
Check your progress
2. Why iron cannot precipitate zinc from the aqueous solution of a zinc salt?
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8.9. STANDARD HYDROGEN ELECTRODE

It is not possible to determine experimentally the potential of a single electrode, it is
only the difference of potentials between two electrodes that we can measure by combining
them to give a complete cell. By arbitrarily fixing the potential of one electrode as zero, it is
therefore possible to assign numerical values to potentials of the each other electrode. Accordingly
the potential of a reversible hydrogen electrode in which the H gas at atmospheric pressure is
155
bubbled through a solution of hydrogen ions at unit activity, has been fixed as zero. This electrode
is known hydrogen electrode and is represented as
Pt, H2 (1atm)/H+ (a= 1)
Fig.8.3. Hydrogen Electrode
Where Pt is Platinum used for getting the electrical contact. The potentials of all other
single electrodes are generally expressed on this hydrogen scale. If it is required to find the
electrode potential, of, say zinc electrode, in a solution of zinc sulphate (i.e., Zn/Zn2+) it is
needed to combine it with a standard hydrogen electrode and construct the cell.
Zn/ Zn2+(Solution) // H+ (a= 1), H2(1atm.)Pt.
The EMF of this cell, determined potentiometrically, is equal to the potential of the Zinc electrode,
since the potential of the standard hydrogen electrode is zero. In this cell, oxidation takes place
at the zinc electrode and reduction at the hydrogen electrode as shown below.
Zn(s)  Zn2++2e–
2H+ +2e–  H2(g)
The net cell reaction is
Zn(s) + 2H+  Zn2+ +H2 (g)
156
8.10. SIGN CONVENTION OF ELECTRODE POTENTIAL
According to one convention the electrode potential is given a negative sign if the
electrode reaction involves oxidation when connected to the standard hydrogen electrode and a
positive sign if the electrode reaction involves reduction reaction when connected to standard
hydrogen electrode whose potential is arbitrarily taken as zero. This can be explained by the
following examples.
i) When copper electrode is connected to the standard hydrogen electrode, reduction

takes place at the copper electrode. The electrode reactions are:
At Hydrogen electrode H2(g)  2H++ 2e– (Oxidation)
 At Copper electrode Cu2++ 2e–  Cu Rreduction)
Hence according to the above convention, the potential of copper electrode is taken as positive.
However, if the zinc electrode is connected to the standard hydrogen electrode, oxidation takes
place at the zinc electrode. The reactions that take place at the electrodes are:
At zinc electrodes Zn(s)  Zn2++2e–
At hydrogen electrode 2H++2e–  H2(g) (1atm)
The potential of the zinc electrode is therefore taken as negative. The standard potential (Eo) of
any substance (electrode) is the potential of the electrode where the substance is in equilibrium
with its ions in solution present at unit activity.
In a cell the electrode reactions are written as oxidation relations. The electrode with
more positive potential is represented as left hand electrode and the one with negative (less
positive) potential as the right hand electrode. The overall cell reaction is obtained by subtracting
the right hand electrode reaction from that of the left hand electrode reaction. In a similar way
the standard potential of the cell (Eo cell) is given as the difference between the standard
oxidation potentials of the right hand electrode and the left hand electrode.
Zn/Zn2+//Cu2+/Cu
EO=Zn/Zn2+ -E° Cu2+/Cu
8.11. SECONDARY REFERENCE ELECTRODES
The standard hydrogen electrodes as mentioned earlier is used as a reference electrode

for determining the single electrode potentials. But it is not always convenient to set up this
electrode on account of difficulties involved in maintaining the activity of hydrogen ions at unity
and in keeping the pressure of the gas uniformly at one atmosphere. Hydrogen electrode also
157
gets poisoned if there are traces of impurities in the gas. To overcome these difficulties, other
electrodes, called secondary reference electrodes have been employed. Two such electrodes
in common use are i) calomel electrode and ii) silver-silver chloride electrode.
Fig.8.4. Secondary reference electrodes (Calomel electrodes)
i) Calomel Electrode:
This is the commonly used reference electrode. It Consists of mercury, solid mercurous
chloride, and a solution of potassium chloride of a definite concentration. The electrode reaction
that takes place is
Hg 2Cl2  S   Hg 2 2  2Cl 
Hg22  2e  2Hg ( I )
-------------------------------------------
Hg 2Cl2 (s )  2e  2 Hg  2Cl 
The electrode is therefore treated as an electrode reversible with chloride ions. The
potential hence depends on the concentration of the chloride ipotential of this electrode therefore
varies with the concentration of potassium chloride solution.
Three different concentrations of potassium chloride are generally employed in constructing

the electrode. These are 0.1. N, 1.0 N and a saturated solution. The following potentials are
obtained for the three calomel electrodes on the hydrogen scale.
0.1 N KCI, Hg2 Cl2, (s), Hg +0.3338 V Vs SHE
1.0N KCI, Hg2 Cl2 (s), Hg +0.2800 V Vs SHE
Saturated KCI, Hg2Cl2, (S), Hg +0.2415 V Vs SHE
158
ii)Silver- Silver Chloride electrode.
In recent years, the silver, silver chloride electrode has been extensively used as reference
electrode for accurate work. It is normally obtained by the following method. A small sheet or
short coil of platinum is first coated with silver by electrolysis of argentocyanide solution. This
coated silver is partly converted into silver chloride by using it as an anode and electrolysis is
carried out in a chloride solution. The electrode thus prepared is kept in a solution of KCl or HCl
of unit activity. The electrode is represented as (a =1) Cl–/AgCl (S)/Ag. It is an electrode reversible
with respect to chloride ion. The standard potential of this electrode is +0.2224 V on the hydrogen
scale.
Fig. 8.5. Slver-Silver Chloride electrode

Worked Problems
Write the electrode reactions and cell reaction for the Daniel cell Zn/ZnSO4 /CuSO4/Cu
Solution: Let us consider that the reactions at the electrodes as oxidation reactions, we first
write the right hand electrode reaction and then the left hand electrode reaction.
Cu2++ 2e–  Cu i) Right hand electrodes.
Zn  Zn+++2e– ii) Left hand electrodes.

The over all cell reaction is obtained by adding (i) & (ii)
Zn + Cu2+  Zn+2 + Cu
The over all cell reaction is
2) Calculate the standard EMF of the cell,
Cd (s)/ Cd2+ / Cu2+/ Cu(s)
given that
E0Cd/Cd2+ = -0.40 V. E 0Cd2+ /Cd = + 0.34V
Solution: Write the cell reaction. According to convention, the standard EMF of the cell is
equal to the difference in the standard potentials of the left hand electrode and the standard
potential of the right hand electrode.
159
EoCell = Eoright hand - Eoleft hand
E 0 Cell = 0.34 - (-0.40) = 0.74

3) Calculate the standard EMF standard free energy change and the equilibrium constant for
the following reaction that takes place in a cell at 25°C.
1 1 1
Cu ( s )  Cl2 ( g )  Cu   Cl 
2 2 2
Solution: The overall cell reaction can be split up into two half cell reactions (both as reduction
reactions)
1
(i) Cl2  e  Cl 
2
1
(ii) Cu 2  e  Cu
2
The reaction (1) is considered as the reaction at the right hand electrode and (ii) as the
reaction at the left hand electrode on the basis of their potentials.
The standard EMF of the cell is the difference in standard potentials of the left hand and
right hand electrodes.
From tables it is known that
ECl0 
0
=1.36 V, ECu ++ /Cu =+0.34 V
2 /Cl
 E0 = +1.36 - 0.34 = 1.02 V..

 E0 for the given reaction is 1.02 V..
Standard free energy change is given by the equation Go = -nFEo
If n the number of electrons involved in the reaction and Fo the standard EMF are known,
Go can be calculated since F is equal to 96500 coulombs. In this reaction n= 1 and Eo=1.02 V
and so
Go=-IX 96500 X 1.02
Go=-98430 Joules.
The equilibrium constant for the reaction is calculated making use the thermodynamic relationship
between standard free energy change and the equilibrium constant K
-G° =RT ln K.
Since we got the value of G° it is possible for us now to calculate K for the reaction, making use
of the equation.
-G° =RT ln K=nFEO
160
nFE O
ln K 
RT
nFE O
or log K 
2.303RT
In this n=1, F=96500, Eo=1.02, R=8.314 Joules and T=273+25=2980. By substituting these
values in the above equation we get
1 96500  1.02
log K   17.2507
2.303  8.314  298
 K  1.781 1017
Thus the equilibrium constant for the given reaction =1.781 x1017
8.12. SUMMARY
Galvanic cell is a device of converting chemical energy into electrical energy. These cells are
two types called reversible and irreversible. EMF of a cell can be measured by Poggendorfis
compensation method. Weston cell is a standard cell which gives constant EMF if considerable
quantity of electricity is not drawn out from it. If the signs are changed oxidation potentials
become reduction potentials. In order to develop a scale the potential of standard hydrogen
electrode is taken as zero. EMF of a cell is the sum of the oxidation potential of anode (left side
electrode) and the reduction potential of cathode) (right side electrode).

1. A galvanic cell or voltaic cell, named after Luigi Galvani or Alessandro Volta, respectively,
is an electrochemical cell that derives electrical energy from spontaneous redox reactions
taking place within the cell. It generally consists of two different metals immersed in
electrolytes, or of individual half-cells with different metals and their ions in solution
connected by a salt bridge or separated by a porous membrane.
2. Iron is less reactive than Zinc to produce coresponding cation due to this reaon Zinc can
form Zinc salt easily than iron.

1. Explain the meaning of a reversible electrode.
2. How are reversible electrodes classified?
3. Discuss the principal underlying the sign conventions of electrode potentials.
4. Explain the meaning and construction of a standard Cell.
1. Obtain the relation between the free energy change and the EMF of a galvanic Cell.
161
2. Describe hydrogen electrode and silver-silver chloride electrodes
3. Write the cell reaction for the Daniel Cell.
4. Write a brief account of the construction of Calomel electrode.
1. Physica chemistry by Gurdeep Raj.
2. Physical chemistry by Puri Sharma Pathania.
3. Atkins, P.W & Paula, J.D. Physical Chemistry, 10th Ed., Oxford University Press (2014).
4. Castellan, G. W. Physical Chemistry 4th Ed., Narosa (2004).
5. Mortimer, R. G. Physical Chemistry 3rd Ed., Elsevier: NOIDA, UP (2009).
6. Barrow, G. M., Physical Chemistry 5th Ed., Tata McGraw Hill: New Delhi (2006).
7. Engel, T. & Reid, P. Physical Chemistry 3rd Ed., Prentice-Hall (2012).
8. Rogers, D. W. Concise Physical Chemistry Wiley (2010). 29
9. Silbey, R. J.; Alberty, R. A. & Bawendi, M. G. Physical Chemistry 4th Ed., John Wiley &
Sons, Inc. (2005).
162
UNIT-9: PHOTO CHEMISTRY
Contents
9.0. Objectives
9.1. Introduction
9.2. Laws of photo chemistry
9.3. Fluorescence and phosphorescence
9.4. Photo chemical reactions
9.5. Summary
9.8. Further Reading
9.0. OBJECTIVES
After you completed the unit you must be able to understand

 the difference between chemical reactions & photo chemical reactions
 the significance of laws of photochemistry
 what is fluorescence and phosphoresce?
 The photo chemical reactions-mechanism.
9.1. INTRODUCTION
The study of chemical reactions that occur under the influence of light is known as
photo chemistry. In these reactions molecules taking part in the reaction are activated by the
absorption of protons (light energy). The well known natural reaction that occurs in plants is
photochemical synthesis of carbohydrates from CO2 and H2O.
hv
CO2 + H2O Carbohydrate
Chlorophyll
But some chemical compounds absorb light but will not undergo chemical reactions in
the excited state. These return to ground state or lower energy state with emission of light.
Such processes called photo physical processes. For example fluorescence and
phosphorescence.
9.2 LAWS OF PHOTO CHEMISTRY

1. Grotthus - Draper Law
It is a law of fund amental importance in all photo processes. The law states that those
radiations which are absorbed by the reacting substances are effective in producing a chemical
change.
163
But the converse is not true. It does not necessarily mean that the absorbed light will
always bring about the chemical reactions.
Other factors such as structure of the molecule, nature of the medium etc. also play
significant role.
2. Lambert - Beer law
J.H Lambert (1758) stated that if a mono chromatic light of intensity I passes through
a medium of thickness dl its intensity decreases by dI. This decrease in intensity dI is proportional
to the thickness d-l and the intensity of incident light.
dl -I.dl
= -I . dl .............. (1)
= proportionality construct
This is also referred to as absorption coefficient or extinction coefficient. This depends

on the nature of the medium and the wavelength of the light.
dI
Equation (1) can be written as   dl
I
On integration we have
In I=  l+c
when l=0, I=I0
 C   ln I 0
ln I=  l+ln I0
I
ln   l
I0
I  I 0 .e  l
I als=I0-I
I abs  I 0  I 0 .e  l
 I 0 (1  e l )
if ' ' is large e  l  0
and Iabs=I0
164
Beer law
Beer showed that for solutions of absorbing solutes in non-absorbing solvents. The constant
' ' is proportional to the concentration ‘C’ of solution.
  c
Therefore the equation
I
In   l
I0
Can be written as
I
In   cl
I0
I  cl
or log   (3)
I0 2.303
This is known as Lambert - Beer law. In the exponential form, equation (3) can be written as
I  I 0 .e  cl    (4)
Where e= extinction coefficient
c =concentration
I= thickness of the absorbing medium
Each of the concentration is expressed in moles/litre. ‘  ’ is called molar extinction coefficient.
Problem
Intensity of light 200 nm when passed through a path length of 10-3 m of an optical cell
containing 0.05 M solutions is reduced to 15% of its initial value, calculate the optical density
and molar extinction coefficient of the sample.
Solution
Lambert - Bear law is
I
 10 cl
I0
C  50  102 M / litre
l  1 103 m
I/I0=0.15
165
2
)  (1  1 0  3 )
 0 .1 5  1 0   ( 5 .0  1 0
  1 .6 5  1 0 4 M o l  1 l i t . m 1
Optical density c.l
 1.65  104  5  102  1 103

 0.824
Stark - Einsterin law of photo chemical equivalence
This law deals with efficiency of photo -chemical reactions. The law states that each molecule
that participates in a primary photo chemical process absorbs one quantum of light causing the
reaction.
The law is also stated as for every one quantum of light absorbed in a photo chemical
process, one molecule undergoes chemical reaction.
The ratio of the number of molecules reacted to the number of quantum of light absorbed
is called quantum efficiency (  )
number of molecules reacted in a given time


number of quanta absorbed in the given time
rate of reaction
=
number of quanta absorbed per sec
rate of reaction
=
labs
The intensity of radiation is generally measured with the help of thermopile or actinometer.
In commonly used ‘actinometers’ uranyl. Oxalate is used 0.05M oxalic acid and 0.01 uranyl
sulphate in water are mixed.
O22  hv  (O22 )*
(O22 )*  H 2C2O4  CO2  CO  H 2O
By titrating the oxalic acid remaining, oxalic acid reacted is determined. The reaction has a
quantum yield of 0.5.
4.Reactions of unusual quantum yields : As per Einsterin law quantum efficiency must be
one. It was observed that many reactions showed quantum yields less or more than one. This
appears to be a deviation from Einsterin law of photo chemical equivalence. The reason for
these deviations is that the quantum yield is worked for the entire reaction but not for the
primary photo chemical process only Einstein’s law is applicable to primary photo chemical
process only.
166
a) Reaction of high quantum yield
The photo chemical reaction between H2 and Cl2 is an example of high quantum yield.
The yield is about 106. The reason for this abnormality is that it is a chain reaction. But
the primary process involving absorption of light still obeys Einsterin law.
Cl2+ hv  2Cl•
b) Reaction of law quantum yield
The decomposition of NH3 in the vapour state and the conversion of maleic acid into
fumaric acid in the liquid state are the examples.
2 NH 3  N 2  3H 2   0.02
molaric acid  fumaric acid   0.04

But in these reactions too the primary processes follow the Einsterin law.
Problems
1.200 Cals of energy is absorbed when 2530A0 light is absorbed by HI. 0.0037 moles
of HI decomposed. What is quantum yield?
2.859
Ans: Energy of 2530 A° = Cals
2530  108
2.859
Cals----------1 moles
2530  108
200 Cals--------?
200  2530  108

 moles
2.859
0.0037  2.859
  2.09
200  2530  10 8
2. What is the energy of 6000A°
Nhc 6.023  1023  6.624  1027  2.887  1010

Ans: E 
 6000  108
=1.994  1012 ergs/mole
1.994  1012
 7
 0.4769  105 cals/mole
4.18 10
= 47.69K.cal/mol
167
Check your progress
1. What are photochemical laws?

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9.4. FLUORESCENCE AND PHOSPHORESCENCE

Reacting molecules after absorbing light of characteristic frequencies go to excited state in
the primary process.
A + hv  A*
A*- excited state of molecule
Some molecules exhibit chemical reaction in the excited, such reactions are called photo
chemical reactions
A* +B  C+ D+ hv
Some molecules in the excited state emit back light simultaneously or after a time gap.
A* 
- hv
 A1 or A
A ground state or A1 = different lower energy state. This type of light emission
phenomenon is referred to as fluorescence or phosphorescence. If the emitted radiation ceases
immediately when the exciting radiation is removed the phenominon is called fluorescence. If
the emitted radiation persists for a longer period even after the exciting radiation is removed the
phenominon is called phosphorescence. Thus in phosphorescence the energy is stored in the
excited molecule for some time and is then emitted or released slowly.
Fluorescence
Atoms of elements or molecules of compounds when exposed to light (characteristic of

them) are excited to higher electronic states. The process is represented as
A + hv  A*
(A=atom or molecule)
168
In photo chemical reactions or deactivation processes, the excited atoms or molecules collision
with other atoms or molecules. During the process the energy absorbed is utilised by the reacting
atoms or molecules and participate in chemical reaction.
But if the excess energy in the excited species is not removed by collisions the excited
species is returned to lower energy state or ground state by releasing the excess energy absorbed.
A* 
 hv A* or A
In this dexitation process light of characteristic frequences are emitted out.
This emission may take place in a single step or in several steps.
A*  A1*+ hv1
A*1  A1+hv2 etc
Organic dyes such as eosin, fluorescein and ultra marine starch etc exhibit such phenomenon
of fluorescence.
If the “absorption of light” process and the “emission of light” process occur simultaneousness
with absorption of light. The phenomenon is referred to as fluorescence.
The emitted radiation will be of lower frequency than that of the absorbed light. This typeof
fluorescence is referred to as stokes fluorescence. In some cases the frequency of the absorbed
radiation and emitted radiation is the same. Such florescence is resonance fluorescence. For
example Hg vapour at low pressure when exposed to radiation of wave length 253.7 nm exhibit
resonance fluorescence. Some atoms or molecules may not be able to absorb light directly and
hence are incapable of exhibiting florescence. But these when mixed Hg vapour or some other
similar substance exhibit fluorescence. Such type of fluorescence is known as sensitized
fluorescence. Hg vapour is known as sensitizer. For example Ag, TI, Pb, or Zn do not exhibit
fluorescence individually. But when mixed with Hg vapour these metals exhibit fluorescence.
This is called sensitized fluorescence.
Hg atom absorb light in the primary process and get excited. These excited Hg atoms colloide
with the metal atoms mentioned above and transfer energy to them. The metal atoms in turn
get excited (M*) and exhibit fluorescence.
Hg + hv  Hg*
Hg* + M  M*
M*  M1(fluorescence)
(M = Ag, TI, Pb, Zn)
169
In some cases, The frequency of the emitted radiation is more than that of the absorbed
radiation. Such fluorescence is referred to as anti - stokes fluorescence.
A +hv1  A
A*  A1+hv2
(v2>v1 )
In all the above examples if the excited atom or molecule collides with other atoms or
molecules collides with other atoms or molecules and get deactivated with out even undergoing
chemical reaction, the phenomenon of fluorescence is not observed. Such phenomenon is called
quenching of fluorescence.
A+hv  A*
A  A1+hv1(fluorescence)
A* +B  A +B*(no fluorescence)
‘B’ quenches the fluorescence of A
Check your progress

2. What is fluorescence?
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Phosphorescence
Phosphorescence resembles fluorescence broadly but differs fundamentally in respect of

time of emission of radiation.
In the case of fluorescence, the absorption and the emission of light occurs
simultaneously. But if the process of emission is delayed by few seconds the phenomenon is
called phosphorescence. Thus phosphorescence is exhibited even after the exciting radiation is
removed but the fluorescence ceases as soon as the radiation is removed. Phosphorescence is
more intense in solids compared to fluorescence. ZnS and alkaline earth sulphides exhibits
phosphorescence. Hence these are called phosphorescent. There is a fundamental difference
in the deactivation process between fluorescence and phosphorescences.
170
Mechanisms
In molecules containing even number of electrons, these electrons are paired in the ground
state. Their spins opposite each other (  ). If the total spin of the electrons is denoted by ‘S’,
its value is zero (S =O) in the case of molecules or atoms with paired electrons. But in other
case the spin value is not equal to zero. In such cases the result spin value is given by (2s+1).
So atoms or molecules in much (2S + 1)is equal to 1, the state is called” singlet” spin state. This
1 1 1 1
is denoted by ‘S’ In case where the spins are not paired (+ ,+ or - , - ) the (2S+1)value
2 2 2 2
 1   1  
is 2  1  1  3          2  1  3 .
 2   2  
This state is referred to as triplet spin state. This is denoted by ‘T’ If the principal quantum
number of the electron is 1 or 2, or 3 or 4, the states are referred t as S1, S2, S3,S4 or T1, T2, T3,
T4 .
Therefore every molecule in So state after absorbing light will go to S1 or S2 or S3 or S4

depending on the light absorbed. For every singlet state, there will be a corresponding triplet
state T1, T2, T3, T4 etc. Thus in the phenomenon of fluroscence or phosphorescences the excited
species may exhibit different types of changes in the spin states.
These changes are as follows
1) a) from a) S2, S3  S1 or
T 2, T 3  T 1
This is called internal conversions
c) But it is also possible the conversion may be
S1  T1 or
S2  T 2
This type is called inter system crossing.
d) But it is also possible that the species may under go conversion from S1 or T1 to So
directly.
S1  SO
T 1  SO
The convention from S1  SO is allowed as per spectral rules, therefore it occures

rapidly. This is known as fluorescence.
171
But the transition from T1 to So is not allowed, therefore it occurs slowly. This is
known as phosphorescence.
Therefore simply we can say that
S1-S O- fluorescence
T1 –SO- phosphorescence
Check your progress

3. What is singlet state ?
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4. What is triplet state?
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5. What is Phosphorescence ?
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9.5. PHOTO CHEMICAL REACTION

Photo chemical reactions are those which are initiated by absorption of light. Many reactions
occur in this way. But only few reactions are presented below. These are
172
hv
1) 2HI   H2 + I2
hv
2) H2 + Br2   2HBr
3) H2 + Cl2  hv
 2HCl
4) Photosynthesis of carbohydrate
1) The decomposition of HI
The decomposition is brought about by the light in the region 200-300 nm. The primary
process is
hv
HI 
I abs
HI rate  I abs
This is followed by secondary processes

k2
H  I   HI rate  K 2 [ H ][ HI ]
k3
I  I   I2 rate = K[I]2
The overall reaction is therefore obtained by adding the three steps.

hv
2HI   H2 + I2
d [ HI ]
The overall rate =   I abs  K 2  H  HI 
dt
d[H ]
But 0
dt
I abs  k2 [ H ][ HI ]  O
I abs
[H ] 
K 2 [ HI ]
d [ HI ]
  I abs  I abs  2 I abs
dt
The quantum efficiency is 2

2) Photochemical combination of H2+ Br2  2 HBr
This occurs in presence of light(  <510 nm).
The primary process is
Br2 hv
 2HBr
The secondary processes are
k2 •
Br + H2   HBr + H
H• + Br2 
k3
 HBr + Br
•
173
H• + HBr 
k4
 H2 + Br
•
Br• + Br• 
k5
 Br2
The rate of formulation can be expressed by the equation
1/2
 2I 
2k2  abs  [ H2 ]
d [HBr ]
  k5 
dt k [HBr ]
1 4
k5 [Br2 ]
The quantum yield is 0.01
3) The reaction between H2 and Cl2

The reaction occurs in presence of light of  less than 480 nm
The primary step is
hv
Cl2 
I abs
Cl 
The secondary processes
k2 •
Cl + H2   HCl + H
H• + Cl2 
k3
 HCl + Cl
•
Cl• + Cl• 
k4
 Cl2
The rate expression is
d  HCl  2 K 2 I abs
 [H2 ]
dt k
The quantum efficiency is 106
(4) Photosynthesis of Carbohydrates
Plants with the help of chlorophyll present in green leaves, make use of CO2 and H2O
vapour present in the atmosphere to synthesise carbohydrates. Thus plants synthesis there
food by the photo-chemical process. In the process O2 is given out into the atmosphere. Thus
plants absorb CO2 and release O2 into the atmosphere. This is a very important process in
nature. To prevent CO2 pollution (green house effect) growing of trees is very essential.
hv
nCO 2 + nH 2 O 
600 nm
 (CH 2 O)N + nO 2
Chlorophyll
174
CO2. H2O vapour can not absorb solar radiation directly. Therefore chlorophyll absorbs it, gets
excited and in turn releases energy to CO2 & H2O. This can therefore be called photo sensitised
process.
Primary process
hv
2H2O 
Chlorophyll
 4H+ + 4e + O2
Dark process
nH 
CO2 carbohydrates.
ne 
To release one molecule of O2, approxnules 3000 molecules of chlorophyll is required

photosynthesis occurs through two systems PSI, PS II.
In PS II strong oxidising agent & weak reducing agent are formed.
In PS I weak oxidising agent and strong reducing agent are formed.
The weak reducing agent of PS II and strong oxidising agent of PS I participate in the
reaction.
Chl  hv  Chl *
H 2O  Chl *  e   Chl 
A  Chl *  A  Chl 
e   A  A  H 2O
1
Chl   H 2O  Chl   H   1/ 2O2
2
Chl  Chl   2Chl  hv1

Chl- chlorophyll ; Chl*= excited chlorophyll A=electron acceptor.
9.6 SUMMARY
1. Chemical reactions that occur under the influence of light are called photo chemical
reactions.
2. These are governed by photo-chemical laws.
a) Grothus - Draper Law
b) Lambert Beer Law
c) Stark - Einstein Law
175
3. The rates of number of molecules reaching /sec to the number of quanta absorbed is
called photo-chemical yield(  )
4. This yield is generally one. But there are many reactions where I is less than 1 or
greater than 1.
5. But all photo chemical processes followed Einstein law in the primary process.
6. The physical processes occuring under the influence of light are fluorescence, and
phosphorescences.
7. Fluorescence occurs simultaneously with incident light. Phosphorescence occurs with

lapse of time.
8. Fluorescence is explained by
Sn  So
and phosphorescence is given by
T n  So
9. Photo chemical reactions are many. Some important are
H2 + Cl2  2 HCl
H2+ Br2  2HBr
H2 + I2  2 HI
nCO2 + n H2O  nC6H12O6+ nO2

1. Grotthus – Draper law
Lambert – Beer law
Stark- Einstein law
2. When electron exited from ground state to excited state its spin is retained is called
siglet state.
3. When electron exited from ground state to excited state its spin becomes inverted is
called siglet state.
4. Fluorescence is brought about by absorption of photons in the singlet ground state
promoted to a singlet excited state. The spin of the electron is still paired with the
ground state, electron emits light when it decay to ground state.
5. Phosporescence is brought about by absorption of photons in the singlet ground state
promoted to a triplet excited state. The spin of the electron is inverted with the ground
state electron when Triplet excited electron reached to ground state it emits radiation
and it is timelapsed light emission.
176
1. What is a photo chemical reaction? Give examples
2. What are the laws of photochemistry? Explain one of them.
3. What is fluorescence and phosphorescence?
4. Give the mechanisms of any one photochemical reaction.
1. State and explain laws of photochemistry.
2. Explain fluorescence and phosphorescence with examples and mechanisms
3. Describe the mechanism of H2+ Cl2  2 HCl reaction.
1. Physica chemistry by Gurdeep Raj.

2. Physical chemistry by Puri Sharma Pathania.
3. Atkins, P.W & Paula, J.D. Physical Chemistry, 10th Ed., Oxford University Press (2014).
4. Castellan, G. W. Physical Chemistry 4th Ed., Narosa (2004).
5. Mortimer, R. G. Physical Chemistry 3rd Ed., Elsevier: NOIDA, UP (2009).
6. Barrow, G. M., Physical Chemistry 5th Ed., Tata McGraw Hill: New Delhi (2006).
7. Engel, T. & Reid, P. Physical Chemistry 3rd Ed., Prentice-Hall (2012).
8. Rogers, D. W. Concise Physical Chemistry Wiley (2010). 29
9. Silbey, R. J.; Alberty, R. A. & Bawendi, M. G. Physical Chemistry 4th Ed., John Wiley &
Sons, Inc. (2005).
177
178
BLOCK-4
GENERAL CHEMISTRY
In this block we included basic concepts of electronic transitions, terminology

involved in UV spectroscopy and vibrational spectroscopy. This block also deals with
importence, functions of different metal ions in biological systems.
Block – 4 includes the following three units.
Unit – 10: UV-Visible spectroscopy
Unit – 11: IR-Spectroscopy (Vibrational Specroscopy)
Unit – 12: Metal ions in biological systems
179
180
UNIT-10 : UV - VISIBLE SPECTROSCOPY
Contents
10.0. Objectives
10.1. Introduction
10.2. Electromagnetic radiation
10.3. Absorption spectroscopy
10.4. Principle of UV - Visible Spectroscopy
10.5. Instrumentation of UV - Visible Spectroscopy
10.6. Selection rules for Electronic transitions
10.7. Summary
10.0. OBJECTIVES
Once you complete the study and understanding of the contents of this unit, you
must be able to:
• Remember different types of electromagnetic radiation, their wavelength
and frequency
• Realise the importance of absorption spectroscopy in structure determination
• Electronic transitions, chromophores and auxochromes, conjugated systems
U.V.spectroscopy.
10.1. INTRODUCTION
Spectroscopy has become the most widely used tool in chemistry today. It has been
used in the elucidation of structure of complex organic and inorganic compounds. Spectroscopy
deals with the interaction of electromagnetic radiation with matter.
10.2. ELECTROMAGNETIC RADIATION
Electromagnetic radiation is a form of energy. Visible light is an example of radiation

which occupies only a small region in the spectrum of electromagnetic radiation. The
electromagnetic radiation may be regarded as electric waves moving through space in a wave
like motion. A wave of electromagnetic radiation can be described by its wavelength.
Following are the wavelength ranges of different regions of electromagetic radiation:
181
Radiation Wavelength
X-rays 0.1-10m
Ultraviolet light 10 to 400 m
Visible light 400-800 m
Near infrared light 0.8 -2.5
Infrared light 2.5 -25
Microwave region >25
10.3. ABSORPTION SPECTROSCOPY

Absorption of radiation causes certain changes in the molecules. The exact nature of the
change depends on the wavelength of radiation absorbed. Absorption of U.V. and visible radiation
by oganic molecules causes electronic excitation i.e., an electron from bonding or nonbonding
orbital is promoted to antibonding orbital. Infrared radiation, on the other hand, influences the
vibrational and rotational states of covalent molecules.
An absorption spectrum is obtained by placing the compound (in the suitable state) between
the spectrometer and the source of appropriate radiation viz. I.R. or U.V.-visible light. The
spectrometer analyses the relative intensities of incident and transmitted lights at ditferent
wavelengehs Plot of these absorbed light (or transmitted light) versus wavelength is called an
absorption spectrum. The ultraviolet and infrared spectra are extremely useful in the structure
elucidation of organic compounds. The former are useful in understanding the nature of multiple
bonds or conjugation in the molecules. The latter, however, gives valuable information about the
functional groups.
10.4. PRINCIPLES OF UV-VISIBLE SPECTROSCOPY

The principles of UV-visible spectroscopy can be explained based on the math-
ematical concept and origin of molecular spectra.
Mathematical Concept
When a beam of light falls on a solution /homogenous medium, a portion of light is reflected
from the surface of medium at the interface, a portion is absorbed within the medium, a
portion is refracted and scattered and the remaining portion is transmitted through the media.
However, how much of light is reflected, refracted, absorbed, scattered or transmitted depends
upon the nature of medium as well as the container. Figure 6.1 shows different phenomena of
light passing through the medium. Thus, it is clear from the above figure that the intensity of
incident light decreases as the beam passes through the medium.
182
Absorbing solution
concentration C
Reflection
Refraction
Incident Beam Transmitted beam

Intensity I0
Intensity It
Scattering
b
Thickness of solution
Figure 6.1 Different phenomena of light passing through a medium
In the most of spectroscopic measurements, the amount of radiation lost by refraction

and scattering is small and can be ignored. If Io is the initial intensity of the incident radiation of
light beam falling on the media. Ia is the amount of light absorbed by the media and It is the
amount of light transmitted and Ir is amount of reflected light then one can obtain.
Io = Ia + It + Ir …..Equation 6.1
However the amount of radiation lost by reflection Ir when using glass cells is very
small , (about 4% of the incident light is reflected). Ir is usually eliminated by use of control,
such as a comparison cell. Hence the above equation can be written as,
Io = Ia + Ir …..Equation 6.2
Thus from the equation 6.2 it can be concluded when an beam of incident light falls on
absorbing media, a portion of incident light falling on a media is absorbed and the remaining
portion is transmitted ,under controlled experimental conditions.
The relation between intensity of incident light and the amount of light absorbed and
concentration of the absorbing substance is given by Bear – Lamberts law.
183
According to the Beer-Lambert law, absorbance A is linearly related to the
concentration of the absorbing species c and path length b of the radiation in the
absorbing media.
Thus,
A = log (I o/It) = abc …..Equation 6.3
Where a is the proportionality constant constant called as absorptivity. This is the fundamental
equation of absorption spectroscopic. This law forms the basis of all quantitative spectroscopic
analysis, since this law expresses the relationship between the amount of light absorbed and the
concentration of absorbing substance.
Check your progress

1. Define Beer-Lamberts law.
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The various terms involved in Beer – Lamberts law are,
TRANSMITTANCE(T) – of a solution is defined as fraction of incident radiation transmitted

by the solution, it is given by the equation
T = It/Io ….Equation 6.4
Transmittance is a unit-less quantity. Transmittance is often expressed as percentage

and is given by the equation.
% T = It/Io x 100% …..Equation 6.5
ABSORBANCE (A) is given by
A = log (Io / It) = log ( I / T ) …..Equation 6.6
From above equation when t = 1.00 A = 0.00 T = 0.10, T = 0.01 A = 2.00 etc.
This, when the amount, of light transmitted decreases there is a corresponding increase
in absorbance by the same solution. Absorbance is also a unit-loss quantity.
ABSORPTIVITY (a) In the Beer-Lamberts law is proportionality constant. It is independent

of concentration path length and intensity of incident radiation. Absorptivity is dependent on
184
temperature, solvent, molecular structure and wavelength of radiation. Units of absorptivity
depend upon the units of path length b and concentration c. when b is in centimeters and c is in
grams per liter, the absorptivity has unit liters per gram-centimeter.
MOLAR ABSORPTIVITY (  ) – The absorptivity expressed in units of liter/mole cm is

called as molar absorptivity. Here the concentration c is in moles per liter and the path length h
is in centimeters. This is given by equation
  A  M / be …..Equation 6.7
Where M is molecular weight
1%
A1cm – is the absorbance of a 1% w/v solution with 1cm path length. When c is expressed in wt/
1% 1%
volume (gm/100ml) and b is in cm. the absorptivity may be written as A1cm ..
For example, A1cm
280nm = 325 means that for substance in question at wavelength of 280 nm in, a solution of
length of 1cm and concentration 1% w/v solution has absorbance of 325.
Figure 6.2 Beer – Lamberts law plots. Curve 1 – obeyed, curve 2 – positive deviation. Curve
3- negative deviation
According to Beer – Lamberts law, when Absorbance A is plotted against concentration

c, if a straight line passing through the origin is obtained (Refer curve 1 of figure 6.2). then
Beer-Lamberts law is obeyed by the solution over the concentration range investigated. However,
sometimes positive deviation (curve 2) or negative deviation (curve 3) is observed from the
law. The above deviations are observed in Beer-Lamberts law due to the following reasons.
1. If monochromatic light is not used.

2. Presence of impurities in solution under analysis
3. Solute ionizes, dissociates, and associates in solution,
4. Solution under analysis is not dilute.
5. Solution under analysis is not clear: it is turbid or contains sonic suspended
particles.
185
6. Sample reacts with solvent.
7. Due to defect in detector amplification system of the spectroscopic instrument.
8. Stray radiations are reaching the detector of the spectroscopic instrument.
9. The radiation source of the instrument shows fluctuation.
10.5. INSTRUMENTATION FOR UV-VISIBLE SPECTROSCOPY
Various types of instruments are used to measure the absorbance in UV and visible
region. They are spectrometer, spectroscope. Spectrograph, photometers, spectrophotometers
and colorimeters. Basic components for all the above instruments are same. See figure 6.7. As
informed earlier, most modern instruments are capable of measuring absorbance in range of
200-800nm i.e. In both UV and visible regions. Instrumentation specifically devoted to measure
only visible range is discussed separately in unit 7.
Source Wavelength Sample Detecor Single processor

selector and Readout
Figure 6.7 Block diagram of various components of UV-visible spectrophotometer.
A) COMPONENTS
Radiation source – Continuous radiation source of UV region is produced by Deuterium /

hydrogen lamp, Xenon are lamp or Mercury arc lamp. Tungsten filament lamp is used as
common source of visible radiation. Tungstem-halogen lamps are used in many modern
equipments due to more efficiency, longer life, greater intensity and with wider output range in
both UV and visible regions.
Wavelength selector – Monochromators are used to select required wavelength in most

modern equipments. Prism or grating type of monochromators is used. Material of construction
is usually quartz or fused silica. Glass absorbs UV radiation and hence not used.
Sample container – Cells or cuvcttes made of quartz or fused silica are used. Glass cells are
not used since glass absorbs IJV radiation. For double beam UV spectrophotometers. Two
matched cells are used. Matched cells are those cells in which the absorption of one is equal or
very nearly equal to absorption of other cell.
Quality and accuracy of absorption data is dependent on the way the matched cells are
used and maintained. The cells must be cleaned before and after use. At all times, when not in
use, cells must be kept clean and dry. Any sample left in cell will tend to dry out and cause stain
on cell walls. This leads to analytical error. Similarly, surface of cell windows must not be
touched. Handling should always be done by ground surfaces and never by polished surfaces.
The cells must also be calibrated against each other regularly with an absorbing solution.
Radiation detectors – Phototubes or Photo multiplier tubes are widely used in most Instruments
as radiation detectors.
186
Recording system – Electrical signal from the detector is received by recording system.
Recording is done by pen recorder/ computers/digital display devices.
B) INSTRUMENTS
Two types of UV-visible spectrophotometers are available single beam and double
beam instruments.
Single beam spectrophotometers
Figure 6.8 Schematic representation of UV-visible single beam spectrophotometer
The image of interchangeable light source is focused by a condensing mirror and the
diagonal mirror on the entrance slit. The entrance slit is the lower of two slits placed vertically
one above another. See figure 6.8 . The light then passes on to a collimating mirror and reflected
on to the quartz prism. The isolated wavelength is then reflected back through the exit slit
(upper slit) to the sample cells. The transmitted radiation is detected by photomultiplier tube.
The response is amplified and recorded on a meter. In modem instruments, the prism will be
replaced by grating monochromator. Commercial model available is Backman DU model.
Double beam spectrophotometers
Most modern UV-visible spectrophotometers are double beam instruments that cover
a range of 200-800nm by a continuous automatic scanning process producing the spectrum on
a display screen.
The monochromatic beam of radiation from a tungsten or deuterium lamp is divided

into two identical beams. See figures 6.9. One portion of beam passes through reference cell
(containing solvent or blank) and other through sample cell. The power of the two beams is
compared to give transmittance of the sample. The splitting and recombination of beam is done
by two rotating sector or mirrors geared to the same electric motors so that they work in
187
unison. Commercial models are available from Perkin Elmer, Hitachi, Hewlet-Packard Systronic,
etc.
Figure 6.9 Schematic representation of double beam UV-visible spectrophotometer
10.6. SELECTION RULES FOR ELECTRONIC TRANSITIONS
The absorption of light in the U.V. and visible range excites the valence electrons in the
molecules. The electrons in a molecule will be present in bonding orbitals (  and  orbitals),
non-bonding orbitals (n-orbitals) and probably also in antibonding orbitals [a (  * sigma starred)
and  * (pi starred) orbitals]. By absorption of U.V.-visible radiation of appropriate wavelength,
an electron from  ,  or n molecular orbital is promoted to an empty (  * or  * molecular
orbital. Different electronic transitions that can be envisaged in a molecule are, (    *     *
and n   * . The energy required to bring about the transition,    *     *  and n   * .
n 

n 

In spectral phenomena such as the Zeeman effect it becomes evident that transitions
are not observed between all pairs of energy levels. Some transitions are “forbidden” (i.e.,
highly improbable)while others are “allowed” by a set of selection rules .The number of split
Components observed in the Zeeman effect is consistent with the selection rules:
188
l  1(notzero)
ml  0, 1
These are the selection rules for an electric dipole transition. One can say that the oscillating
electric field associated with the transitions resembles an oscillating electric dipole. When this
is expressed/in quantum terms, photon emission is always accompanied by a change of 1in the
orbital angular momentum quantum number. The magnetic quantum number can change by
zero or one unit.
Another approach to the selection rules is to note that any electron transition which
involves the emission of a photon must involve a change of 1 in the angular momentum. The
photon is said to have an intrinsic angular momentum or “spin” of one, so that conservation of
angular momentum in photon emission requires a change of 1 in the atom’s angular momentum.
The electron spin quantum number does not change in such transitions, so an additional selection
rule is:
ms  0
The total angular momentum may change be either zero or one:
j  0, 1
An exception to this last selection rule it that you cannot have a transition from j=0 to j=0;i.e.,
since the vector angular momentum must change by one unit in a electronic transition, j=0-> 0 can’t
happen because there is no total angular momentum to re-orient to get a change of 1.
Some Typical Applications
In ethane    * transition (of C-Ca bond) occurs at 154 nm i.e., in the vaccum U.V..
region. Similarly in ethylene the    * transition (of C=C double bond) occurs at 180nm.
Therefore we say that saturated molecules and simple olefins do not absorb in the regular U.V
and visible region and therefore are colorless. Two transitions, n   * and    * are possible
in formaldehyde, which has a pi bond and nonbonding electrons. These occur at 185nm and
270nm respectively.The absorption at 185nm results in a strong band whereas that at 270nm is
responsible for a weak band.
HC CH H2 C CH 2 H C O
3 3
H
ethane ethene formaldehyde
Transition    

nm =180 nm =185 nm
n *
l=270 nm
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Chromophores
Multiple bonds, such as C=C and C= O, which are responsible for    or n transition are
called chromophores. Multiple bonds such as, C=N, N=N, C=S and N=O are examples of
other chromophores. These chromophores in simple molecules absorb at different Wavelengths
and explain the colour of compounds.
Chromophore wavwlength (nm) Colour of the

Compound compound
C C H2 C CH2 180 Colour less
C N (H3C)2HC C N CH(CH3 )2 250 Colour less

H
C O 280 Colour less
C(H3 C)2 O
347 Pale yellow

N N H3 C N N CH3
400 light yellow

C S C(H3 C)2 S
H2 H2 Blue green
H3 C C C N O 665
N O
Check your progress

2. What do you mean by a chromophore?
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Auxochromes
Functional groups that do not absorb in the U.V - visible region (above 200nm) but
(when attached to a chromophoric system) influence the absorption of chromophores are called
auxochromes. Auxochromes cause a shift in the absorption to longer wavelength (bathochromic
shift) and increase the intensity of the absorption peak. Common auxochromic groups are
hydroxy, amino, mercapto groups (and their derivatives) and halogens. - bonds are not present
in these groups, but they all contain nonbonding electrons.
Bathochromic shift:
This term stands for “lower frequency colour shift”, i.e., “Red Shift”. A shift of
absorption maximum ( max ) to a longer wave length takes place by the presence of electron
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donor substituents such as alkyl, hydroxyl, alkoxyl and amino groups attached to a chromophore.
Such groups are called auxochromes since their effects are auxilliary, i.e. secondary to those of
chromophores. The auxochrome has a synergistic influence on the chromophore by extending
conjugation of a chromophore by sharing of non-bonding electrons. Practically then, the
auxochrome becomes part of a new extended chromophore.
Without Auxochrome Wth auxochrome

compound max compound max
HCN 175 300
N C C C C N
2
H H 2
(Tetracyano ethylene
Benzene 255 Toluene 261
(  max =204) (  max =225)
Chlorobenzene 263.5
(  max = 190)
Phenol 270
(  max =1450)
Aniline 280
(  max =1430)
Bathochromic shift occurs for phenol in basic medium due to the formation of the new
chromophore of phenoxide anion with max of 287nm ( =2,600).
max
Hypsochromic shift:
This term derives from “higher frequency colour shift”, i.e., blue shift. A shift of
absorption maximum ( max ) to a shorter wavelength takes place by the presence of electron
withdrawing substituents such as  NO2 and C  N groups. Usually groups causing
hypsochromic shift are themselves chromophores; hence, the hypsochromic shift of the original
chromophore is ignored.
Examples: 1. Benzene
2. Aniline with max of 280nm ((max=1430) undergoes hypsochromic shift to

254nm ((max=160) in acid medium due to the formation of anilinium cation.
Hyperchromic effect is increased intensity of absorption which usually takes place with
bathochromic shift.
Hypochromic effect is decreased intensity of absorption that usually takes place with
hypsochromic shift.
The uniqueness of these shifts is that they are additive, i.e., of a chromophore or
substituent or extension can be calculated by certain rules of summation, originally proposed by
RB Woodward, and hence called as Woodward rules of additivity.
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Conjugated systems
Two or more chromophores may be present in molecules. When these groups are directly
linked by a single bond a conjugated system results. In a conjugated diene two sets of doubly
bonded carbons are directly linked by a single bond: >C=C-C=C<(conjugated diene).
Different conjugated systems result when a carbon-carbon double bond is directly linked by
a single bond to other chromophores. Due to conjugation, electron excitation in these systems
occurs readily i.e., absorb radiation of longer wavelength. In butadiene    * transition occurs
at 217nm. The presence of conjugated multiple bonds in molecules leads to bathochromic shift.
The wavelength of radiation absorbed by some of the simple conjugated systems are given
below:
Chromophore Compound  nm
C=C-C=C 1,3 Butadiene 217 nm
C=C-C=C Vinylacetylene 219 and 228 nm
C=C  C=O Crotonaldehyde 218 and 320 nm
C=C-C=N- N-n-butyl cortanaldimine 219 nm
C=C-NO2 1-Nitro-l-propene 229 and 235 nm
O C C O glyoxal 195 and 463 nm
Benzene absorbs at 203 nm but in conjugated systems like aniline (230nm) and
Benzophenone (252nm) the absorption shifts to longer wavelength (Fig 10.1).
Fig. 10.1. UV Spectra of 1) Aniline and 2) benzophenone

AI= Absorption Intensity WL= Wavelength
The colour of polynuclear aromatic compounds incresaes with the increase in the number
of benzene rings. This is due to the presence of extended conjugation in the molecules.
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Benzene Napthalene Anthracene Napthacene
max 203 nm max 314 nm max 480 nm
max 380 nm
Colourless Yellow
Colourless
buff colour
Pentacene Hexacene
max 580 nm max 600 nm
Blue Green
If two or more chromophoric groups, in a molecule, are separated by two or more single
bonds, an isolated unsaturated system results. Penta- 1,4-diene is an isolated diene.
CH2 =CH-CH2- CH=CH2
(Penta-1,4-diene)
The effect of two isolated chromophores on the intensity of absorption band of the molecule
is additive; but does not significantly influence the wavelength of absorption.
Ultraviolet spectra do not provide information about individual bonds (functional groups);
rather they are characteristic of multiple bonds. They reflect the extent of conjugation of multiple
bonds, and other structural features such as steric hindrance and hydrogen bonding which
influence conjugation.
Check your progress
3. What do you mean by a bathochromatic shift?
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10.7. SUMMARY
Spectroscopy is the study of interaction of electromagnetic radiation with the matter. It

is an important method of structure determination.
193
Based on wavelength electromagnetic radiation is classified into different
types.Absorption spectrum of a compound is a plot or graph between Io/Ic and wavelength or
wave number.
Absorption of U.V. radiation by organic molecules usually causes n   * and    *

electron transitions. Functional groups which undergo these transitions are called chromophores.
Those groups without  - bonds that affect the absorption bands of chromophores are called
auxochromes. Shift of absorption to longer wavelength region is called bathochromic shift and
the opposite shift is hypsochromic shift. Based on U.V. spectroscopy the type of conjugation in
organic compounds can be determined.
1. Absorbance A is linearly related to the concentration of the absorbing species ‘c’

and path length b of the radiation in the absorbing media.
2. Multiple bonds, such as C=C and C= O, which are responsible for    * or n   *

transition are called chromophores.
3. A shift of absorption maximum ( max ) to a longer wave length called Bathochromic

shift.
10.9. EXAMINATION MODEL QUESTION
I. Answer the following in about 30 lines
1. Explain the principles of UV-visible spectroscopy.

2. Discuss the instrumentation for UV-visible spectroscopy.
3. Explain following
a. Bathochromic shift
b. Hyperchromic shift
c. Hypochromic shift
d. Hypschromic shif
4. Write a note o seclection rules for electronic transitions in UV- Specroscopy.
II. Answer the following in about 10 lines

1. State Beer-Lamberts law and explain the terms therein.
2. Define chromophore and auxochrome with suitable example.
3.. Sketch single beam spectrophotometer.
4. Exlain about double beam spectrophotometer
194
1. Banwell, C. N. & McCash, E. M. Fundamentals of Molecular Spectroscopy 4th Ed. Tata

McGraw-Hill: New Delhi (2006).
2. Kakkar, R. Atomic & Molecular Spectroscopy: Concepts & Applications, Cambridge

University Press (2015).
3.Kemp, W. Organic Spectroscopy, Palgrave.
4. Pavia, D. L. et al. Introduction to Spectroscopy 5th Ed. Cengage Learning India Ed. (2015).
195
UNIT-11 : INFRARED SPECTROSCOPY
((Vibrational Specroscopy))
CONTENTS
11.0. Objectives
11.1. Introduction
11.2. Vibrational energy levels of diatomic molecules
11.3. Selection rules
11.4. Calculation of force constant
11.5. Anharmonic nature of vibrations
11.6. Fundamental bands, overtones and hot bands
11.7. Charecteristric infrared absorption frequencies of functional groups.
11.8. Summary
11.9. Check your progress – Answers
11.0. OBJECTIVES
After completing this lesson you should be able to

• Explain the nature of interaction of electromagnetic radiation with a vibrating
molecule
• Calculate the force constant for harmonic oscillator
• Calculate the anharmonicity constant, zero point energy, equilibrium
vibrationalfrequency and force constant of an anharmonic oscillator
• Explain the terms fundamental bands, overtones and hot bands
11.1. INTRODUCTION
A vibrating molecule absorbs energy in the infrared region of the electromagnetic

spectrum resulting in an increase in the amplitude of vibration. An infrared spectrum is a plot of
percentage of transmission against wave number (4000 cm-1 to 200 cm-1). A molecular vibration
may be described as a periodic change in the internuclear distance. A diatomic molecule can
have only one type of vibration that involves a periodic increase and decrease of internuclear
distance. This type of vibration is called as a symmetric stretch. The dipole moment depends on
the magnitude of charges and their separation, in the case of molecules, which possess a
permanent dipole moment, there is a periodic change in the dipole moment. It means, during the
196
symmetric stretch vibration of hetero nuclear diatomic molecules, there is a change in inter-
nuclear distance as the molecule is alternatively stretched and compressed. This in turn changes
the dipole moment of the molecule. Therefore, a vibrating molecule with a permanent dipole
moment is equivalent to an oscillating electric dipole.
Fig. 11.1. Oscillating electric dipole of a hetero-nuclear diatomic molecule.
This oscillating electric dipole can interact with the electric component of the electromagnetic
radiation. This happens when the frequency of oscillating dipole is equal to the frequency of
electromagnetic radiation. Homo-nuclear diatomic molecules such as H2, O2, N2, cannot interact
with electromagnetic radiation, as these molecules do not possess a permanent dipole moment.
Therefore, the essential condition for a particular vibrational mode of a molecule to be infrared
active is that there must be a change in dipole moment during the vibration.
Fig. 11.2. Variation of potential energy of a diatomic molecule with inter nuclear distance
197
When two atoms combine to form a molecule, the atoms finally settle at a mean inter
nuclear distance such that all the force acting are just balanced and the energy of the whole
system is minimum. Attempt to bring the atoms more closely together and the repulsion forces
rises rapidly; attempt to pull them further apart and we are resisted by the attractive forces., In
either case an attempt to distort the bond requires an input of energy and so we may plot energy
against inter nuclear distance.
At the minimum, the inter-nuclear distance is referred to as the equilibrium distance re or

more simply as the bond length. The compression and extension of a bond may be likened to the
behaviour of a spring.
11.2. VIBRATIONAL ENERGY LEVELS OF DIATOMIC MOLECULES

Harmonic Oscillator:
As a first approximation, a diatomic molecule may be assumed to behave like a harmonic

oscillator. It means the molecule can be stretched or compressed to any extent without a
breakage of the bond. A harmonic oscillator can be characterized by its frequency of vibration
and energy.
Frequency of vibration of harmonic oscillator:
A harmonic oscillator obeys Hooke’s law, which states that the restoring force is directly
proportional to the extent of stretch. Now let us consider a spring one end of which is fixed to
a wall and the other end to a ball. The ball is now displaced to an extent of ‘x’ along a
reference direction, such that the spring which is assumed to be perfectly elastic is stretched to
the same extent. The restoring force acting on the ball is proportional to the extent of stretch,
i.e. F=-k .x.
Fig. 11.3. Hooke’s law
The negative sign indicates that the restoring force ‘F’ has a direction opposite to that
of the displacement ‘x’. The constant ‘k’ is called the force constant that is characteristic of
the spring and is independent of the nature of the ball.
198
Now let us consider a model containing two balls of masses m1 and m2 attached by a
spring. The dotted circles in the figure indicate the new positions of the balls after stretching the
spring by a small extent on either side.
Fig. 11.4. A model of hetero - nuclear diatomic molecule
let x1, and x2 be the displacement of the two balls. As the displacement is a vector which has
magnitude and direction, the extension of the spring x = (x2-x1).
Now by Hooke’s law,
Restoring force acting on ball 1, F1=k.(x2-x1) ——(1)
Restoring force acting on ball 2, F2=-k.(x2-x1)——(2)
According to Newton’s second law, we have
d 2 x1
Restoring force acting on ball 1 is given by m1. ———(3)
dt 2
d 2 x2
Similarly, restoring force acing on ball 2 is m2. ——(4)
dt 2
From equations (1).(2),(3) and (4), it follows that
d 2 x1
m1. = k.(x2-x1)————(5)
dt 2
d 2 x2
m2. =-k. (x2-x1)—————(6)
dt 2
The coordinates x1 and x2 will follow either the cosine or sine relations as given below
x1=A1cos(2..v.t) or x1=A1sin(2..v.t)
x2=A2cos(2..v.t) or x2=A2sin(2..v.t)
199
Where A1 and A2 are the amplitudes of vibration of balls 1 and 2 respectively and ‘v’ is
the frequency of vibration. Substituting cosine values in equations (5) and (6), we get
d 2 A1 cos(2. .v.t )
m1.  k ( A2  A1 ) cos(2. .v.t )
dt 2
and
d 2 A2 cos(2. .v.t )
m2 .  k ( A2  A1 ) cos(2. .v.t )
dt 2
on differentiation,
m1 . A1 (2. .v )2  k ( A2  A1 )    (7)

and
m2 . A2 (2. .v )2  k ( A2  A1 )      (8)
Multiplying equation (7) with m2 and (8) with m1 and adding we get,
m1, m2.A2(2.v )2(A2 –A1) = (A2 –A1)k(m1 + m2)
(m1  m2 )
i.e. (2. .v ) 2  k . or
m1 .m2
1 k
v    (9)
2 
m1.m2
Where  
(m1  m2 ) is the reduced mass of the system under consideration.
The equation (9) represents the equilibrium or classical frequency of a harmonic oscillator.
Energy of Harmonic Oscillator:
Classically, the potential energy of the system at any instant can be evaluated from
the expression, dE
F 
dx
dE
In the present case we have  k .x  
d ( x )
200
( x ) 2
On integration, we get, E  k I
2
Where ‘I’ is the constant of integration, whose value may be determined from the
fact that if x = 0, E = 0. Thus I=0 and the potential energy expression becomes
1
E k (x) 2      (10)
2
The variation of potential energy with displacement is shown in figure 11.5. Classically
speaking, the molecule can vibrate with any amount of potential energy i.e. the potential energy
of the molecule is a continuous function of the displacement from the equilibrium position.
Fig. 11.5. Potential diagram of harmonic oscillator
Since classical laws do not hold good for particles of very small size, the classical
equation of potential energy 1/2 k ( x )2 is not applicable to diatomic molecules. The potential
energy expression for such a case has to be derived quantum mechanically by solving the
appropriate Schrondinger equation. In the present case solution of Schrondinger equation yields
the following expression of potential energy.
1
E  (v  ).h.vclassical
2
1 k
Where vclassical is the classical frequency of vibration given by v  and ‘v’ is
2 
the vibrational quantum number. The allowed values of ‘v’ are 0,1,2...etc. Thus the vibrational
energies are quantized i.e. the molecule cannot vibrate with any arbitrary amount of energy but
with only certain Vibrational energies.
201
1 h k
E  (v  ). ergs or joules
2 2 
1 1 k
Ev  (v  ). cycles/sec
2 2 
1 1 k 1
E  (v  ). m
2 2 c 
1 k
The energy levels are equally spaced and E 
2 c 
The lowest Vibrational energy (v=0) is not zero as in the case of classical vibrator but
1 1 1 k  1
has a value of .h.vclassical or   m
2 2  2 c  
The lowest energy is known as zero point energy. This means that the atoms in a
molecule can never be completely at rest relative to each other. This fact is in agreement with
the Heisenberg’s uncertainty principle. If the atoms were stand still, the uncertainty in the
position would be zero. The zero point energy is just half of the energy difference between the
two nearest Vibrational energy levels.
11.3. SELECTION RULES FOR HARMONIC OSCILLATOR

The quantum mechanical calculations show that the selection rule for vibrational transitions
is, It means that only transitions between adjacent energy levels are allowed.
Inter nuclear distance

11.6. Allowed vibrational transitions of harmonic oscillator
202
The transition v=1 v =0 is the most intense transition, as at room temperature
the population of v= 0 level is very high when compared to other energy levels. This is because
the energy difference between v=0 and v=1 levels is very high when compared to room
temperature energy. The energy difference between adjacent energy levels is constant
given by
1 k 1
E  m
2 c 
Therefore, from the position of the spectral line, the force constant ‘k’ can be
calculated using the equation, k  42  2 c 2  (E )2 .
11.4. CALCULATION OF FORCE CONSTANT

The vibrational transition, ‘v=1v=0’ for hydrogen chloride molecule is found to occur at
2890cm-1. Calculate the bond strength of the molecule.
The reduced mass,
1 35
 23
103 kg  1.615  10 27 kg
(1  35)  6.023  10
K = 4 (3.14)2 (2  108ms-1)2 (1.615  10-27kg) (2890  102m-1)2 = 4.7812 Nm-1
11.5. ANHARMONIC NATURE OF VIBRATIONS
11.7. Potential Energy diagram for an anharmonic oscillator

The vibrational quantum number in the energy expression of a harmonic oscillator can have
any value starting from the minimum value of zero to any large integral value. This means that
a diatomic molecule that is considered to execute harmonic oscillations can have any higher
allowed energy without exhibiting any sign of breaking into two atoms. This fact is contrary to
the experimental behaviour that the molecule breaks into atoms if it is stretched beyond a
certain limit. The maximum displacement from the equilibrium bond length increases with increase
203
of vibrational quantum number. For large displacements, the bonds are no longer elastic and
hence deviation from the harmonic vibration energy is expected for the larger vibrational quantum
numbers. The potential energy diagram for an anharmonic oscillator (Fig.11.7) rises more steeply
in the lower bond length region and less steeply on the higher side when compared to harmonic
oscillator and approaches a limiting value corresponding to the dissociation energy of the molecule.
Energy level diagram:
The potential energy of a few low Vibrational levels are given below.
1  1 
v0 E0  .h.ve . 1  xe 
2  2 
Inter nuclear Distance
1  3 
v 1 E1  .h.ve . 1  xe 
2  2 
E1 - E0 = h.ve.[1-2xe]
Since the anharmonicity constant has a small positive value, it follows from the above
equation that E between the two closest levels decreases with increasing value of Vibrational
quantum number. Thus the Vibrational levels are no more equally spaced as in the case of a
harmonic oscillator but becomes closer to each other with increasing value of ‘v’.
11.6. FUNDAMENTAL BANDS, OVERTONES AND HOT BANDS

The selection rule for anharmonic oscillator is v = ±1, 2, 3,... . Hence all types of
transitions from any lower vibrational level to any of the higher Vibrational levels are allowed.
Since only the lowest level is thickly populated and because the population decreases very
rapidly with increasing v, only a few transitions from the lowest vibrational level (v=0) to the
next nearest vibrational levels are actually observed at room temperature.
The transition v=1v=0 is found to be the most intense and is known as fundamental
absorption. The transition v=2 v=0, is found to have a poor intensity and is known as the first
Overtone. The transition, v=3v=0,is found to have negligible intensity and is known as the
second overtone. The higher overtones are too weak to be realized experimentally, the energies
of the observed transitions are given below.
Fundamental absorption, v=1  v=0 E = h.ve.[1-2xe] Joules
First overtone v=2  v=0 E =2h.ve.[1-3xe] Joules
Second overtone v=3  v=0 E =3h.ve.[1-4xe] Joules
In the wave number units, we have,
v  1  v  0ve .[1  2 xe ]m 1
v  2  v  02ve .[1  3 xe ]m 1
v  3  v  03ve .[1  4 xe ]m 1
204
The transition from v=1 to the higher levels are not observed unless the temperature of the
sample is high. This is due to the fact that population at v=1 level is negligible at room temperature
and it becomes appreciable at higher temperatures. These transitions are known as hot bands
as they appear only at higher temperatures. The intensities of hot bands are usually very weak
and become more intense on increasing temperature of the sample.
11.7. TYPES OF MOLECULAR VIBRATIONS
The number of vibrations possible in linear and nonlinear molecules containing ‘n’ atoms
are 3n-5 and 3n-6 respectively. For example the number of vibrations in CO2 is 4 (3x3 - 5) and
the number of vibrations in H2O is 3 (3x3 - 6). The molecular vibrations are broadly classified
into two types viz. stretching and bending (or deformation) vibrations. In stretching vibration of
a bond the distance between two atoms increases and decreases but the atoms remain in the
same bond axis. Stretching víbrations are further classified as symmetric and asymmetric
stretching vibrations.
H H H H
C C
a b
a. Symmetric stretching vibration b. Asymmetric stretching vibration (the
(the bond distance increases in bond distance increases inone C-H
both the C-H bonds) as shown by bonds and in the other it decreases) as
the arrow head. shown by the arrow head.
Stretching vibrations
In bending vibrations the position of the atoms changes relative to the original bond axis.
Bending vibrations are differentiated into in plane bending, (scissoring and rocking) and out-of-
plane bending vibrations (wagging and twisting).
+ + + -
H H H H H H H H
C C C C
Ia Ib IIa IIb
I. In- plane bending vibrations II. Out-of-plane bending vibration
I.a. Scissorind I.b. Rocking II. a. Wagging II.b. Twisting
205
Bending vibrations
The sign + and - represent the vibration above and below the plane of paper.
Infrared spectrum of compound is a plot of the relative intensity of the light transmitted
by the compound at different frequencies (or wavelengths) of radiation in the I.R. range. Only
vibrations that cause change in the dipolemoment of a molecule result in the absorption of
characteristic frequencies of I.R. radiation and also transmit characteristic frequencies. The
frequencies of stretching vibrations increase with increasing bond strength. The force constants
of the bonds increase from the single bond to triple bond i.e., the strength of the bonds: C  N
> C=N > C-N. Accordingly the absorpton frequencies of these bonds are about 2250 cm-
1
.,1650 cm-1,1250cm-1 respectively. The frequency of absorption of a bond also increases with
decreasing atomic masses. The stretching frequencies of the C-Br (500-600 cm-1.), C-C1(600-
800 cm-1.) and C-F (1000-1400 cm-1.) bonds, O-H (3570cm-1.) and O-D (2630 cm-1.) bonds
illustrate this point.
From the spectra of a large number of organic compounds chemists assigned frequency
ranges for different bonds. Some of the values are given below:
Bending vibrations generally require less energy and occur at longer wavelength (lower
wave number) than stretching vibrations of the same bond. Absorption peaks resulting from the
stretching vibrations are usually most intense peaks in the spectrum. Many of the absorption
bands cannot be assigned accurately. But those that can be assigned provide valuable information
about the structure of a molecule.
Check your progress

1) State Hooke’s law?
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2) How many tpes of molecular vibrations ?
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206
FREQUENCY cm-1 BOND FUNCTIONAL GROUP
3640-3610(s,sh), O-H stretch Free hydroxyl alcohols, phenols
3500-3200(s,b) O-H stretch, H-bonded alcohols, phenols
3400-3250(m) N-H stretch 10, 20 amines, amides
3300-2500(m) O-H stretch Carboxylic acids
3330-3270(n,s) -C  C-H:C-H stretch Alkynes (terminal)
3100-3000(s) C-H stretch aromatics
3100-3000(m) =C-H stretch alkenes
3000-2850(m) C –H stretch alkanes
2830-2695(m) H-C=O:C-H stretch aldehydes
2260-2210(v) C  N stretch nitriles
2260-2100(w) -C  C-stretch alkynes
1760-1665(s) C=O stretch Carbonyls (general)
1760-1690(s) C=O stretch Carboxylic acids
1750-1735(s) C=O stretch Esters, saturated aliphatic
1740-1720(s) C=O stretch Aldehydes, saturated aliphatic
1730-1715(s) C=O stretch , -unsaturated esters
1715(s) C=O stretch Ketones, saturated aliphatic
1710-1665(s) C=O stretch , -unsaturated
aldehydes,ketones
1680-1640(m) -C=C-stretch alkenes
1650-1580(m) N-H bend 10 amines
1600-1585(m) C-C stretch(in-ring) aromatics

1550-1475(s) N-O asymmetric stretch Nitro compounds
1500-1400(m) C-C stretch (in-ring) aromatics
1470-1450(m) C-H bend alkanes
1370-1350(m) C-H rock alkanes
1360-1290(m) N-O symmetric stretch Nitro compounds
1335-1250(s) C-N stretch Aromatic amines
1320-1000(s) C-O stretch Alcohols, carboxylic acids, esters,
ethers
1300-1150(m) C-H wag (-CH2 X) Alkyl halides
1250-1020(m) C-N stretch Aliphatic amines
1000-650(s) =C-H Bend alkenes
950-910(m) Carboxylic acids
11.7. CHARACTERISTIC INFRARED ABSORPTION

FREQUENCIES OF FUNCTIONAL GROUPS
Some of the functional groups whose absorptions can be easily interpreted are givem below.
If a spectrum does not contain a peak at the frequency assigned to a certain functional group,
the molecule does not contain that functional group.
207
a) Carbonyl compounds
A peak due to absorption by carbonyl group is expected in these compounds. The frequency
of stretching vibration varies with the nature of the carnonyl compound.
Aldehyes and ketones
Aliphatic carbonyl compounds 1720-1740 cm-1.
Carbonyl group in cyclohexanone 1715cm-1.
Aromatic carbonyl compounds and  ,  -unsaturated
aliphatic carbonyl compounds 1670-1690cm-1.
Carbonyl group involved in hydrogen bond 1600-1640 cm-1.
Saturated cyclic ketones
4 membered = 1775 cm-1.

5 membered = 1740-1750 cm-1.
6 membered and higher = 1705-1725cm-1.
The carbonyl compounds are best identified by IR spectra. The strong band due to C=O
stretching appears at about 1700 cm-1. It is one of the most useful bands. Typical IR spectra of
an aliphatic aldehyde (n-butyraldehude) and an aromatic ketone (acetophenone) are presented
in below
b) Esters
saturated acyclic esters = 1735-1750 cm-1.
saturated cyclic esters
5 membered (P-lactones) = 1820 cm-1.
6 numbered ( y- lactones) = 1760-1780 cm-1.
7 membered (lactones) = 1735-1750 cm-1.
larger rings
208
Esters (-COOR) are distinguished from acids (-COOH) by the absence of band due
to OH group. They are also differentiated from ketones (C=O) by two strong C-O stretching
bands in the region 1050-1300cm-1 . The exact position of the bands depends on the structure
of the ester. Typical IR spectrum of methyl acetate is presented below.
C) Alcohols and phenols
In these compounds absorption by OH group results in a peak. The stretching vibrations

of the hydroxyl groups in different compounds are given below:
i) Alcohols
Monomolecular unassociated alcohols = 3590-3650 cm-1
Intermolecularly hydrogen
bonded OH group (changes on dilution) = 3450-3550 cm-1
Intramolecularly
hydrogen bonded -OH group (no change on dilution) = 3450-3570 cm-1
The most significant feature is a strong broad band in 3200-3600cm-1 region due to O-H
stretching. Another strong broad band due to C-O stretching appears in the 1000-1200 cm-1
region. The exact value depends on the nature of alcohol. Typical IR spectra of an aliphatic
alcohol (Sec-butyl alcohol) and an aromatic alcohol (benzyl alcohol) are presented in figures
below
209
ii) Phenols
Monomolecular phenols - 3650 cm-1
Intermolecularly associated phenols -3610 cm-1
Intramolecularly associated phenols - 3100cm-1.
Phenols also show the bands like alcohols. But the C-O stretching appears at higher frequencies.
The spectrum of a typical phenol (p-Cresol) is shown in below. Phenols show peak at about
1230cm-1 while alcohols show at 1050-1200 cm-1.
d)Carboxylic acids
The stretching vibrations of carbonyl and hydroxyl groups in these compounds occur at 1700-
1725 cm-1 and 3520cm-1 respectively,
It is obvious that -COOH group is made up of both C=O group and -OH group. The IR
spectrum reflects both these structural units. For hydrogen bonded (dimeric) acids, O-H stretching
band (broad) occurs at 2500-3000cm-1. Acids show C-O stretching band at about 1250cm-1 and
OH bending near 1400cm-1 and 920cm-1 (broad). Spectra of typical acids propionic acid and o-
toluic acid are presented in below.
210
Check your progress
3) What are the stretching frequencies of ester?
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e)Amines
Following are the stretching vibrations in amines due to N-H function: Primary amine, free
(two bands) 3400 cm-1 and 3500 cm-1. Secondary amine (free one band) 3310-3500 cm-1.
Amines exhibit bands whose position and number depend on the class to which the amine
belongs. -NH stretching bands as/mentioned above and NH bending bands at 650-900cm-1
(broad) and at 1560-1650cm-1.
211
Besides these CN stretching at 1030-1230 cm-1 (weak) for aliphatic compounds there are
two at 1180-1360cm-1 (strong) for aromatic compounds. Spectra of typical compounds;
isobutylamine and N-methyl aniline are presented in below.
f)Amides
(i) Carbonyl stretching vibrations
Primary 1650cm-1
Secondary 1630-1680cm-1
Tertiary 1630-1670cm-1
(ii) NH stretching vibrations
Primary amide, free (two bands) 3400cm-1 and 3500cm-1
Primary amide, bonded (two bands) 3180cm-1 and 3350cm-1
Secondary amide, free (one band) 3430cm-1
Secondary amide, bonded (one band) 3140cm-1 3320 cm-1
Amides (-CO NH2) show absorption due to N-H stretching in the region 3050-3550cm-1
besides C=O band. N-H bending band occurs in the region 1600-1640cm-1. Typical spectra of
benzamide is shown in below.
212
g) Azides
These absorb at 2120-2160 cm-1
h) Nitro compounds
The nitro group in nitro aromatic compounds give two strong peaks at 1300-1370 cm-1 and
1500-1570 cm-1. In aliphatic nitro compounds these peaks are observed at 1370-1380 cm-1 and
1550-1570 cm-1. These are four absorption bands in the region 1430-1670 cm-1 that are
particularly diagnostic of aromatic structure. The absence of absorption in this region is fair
assurance that the compound is not aromatic.
The region of infrared spectrum, 910-1430 cm-1 (  7-11) is particularly rich in absorption
bands and is characteristic of a compound. This region of spectrum is called the finger print
region. Although similar molecules show very similar spectra in the region 1430-4000 cm-1,
but they will have different spectral characteristics in the finger print region. Perhaps the
most powerful function of IR spectroscopy is establishing conclusively the identity of two
samples that have identical spectra when determined in the same medium.
11.8. SUMMARY
By the absorption of infrared radiation usually the frequencies of stretching and bending
vibrations of bonds get increased. Based on the position of absorption bands in the infrared
spectrum of a compound it is possible to detect its functional groups. In the infrared spectra the
region 910-1430cm-1 is called finger print region, which is characteristic of every compound.
Two samples indicate the same compound if they possess super imposable infrared spectra.
A vibrating diatomic molecule can be approximated to a harmonic oscillator. The vibrational

mode is an infrared active only if there is a change in the dipole moment of the molecule during
the vibration. The frequency of vibration of a harmonic oscillator is given by the equation,
1 k
v , where ‘k’ is the force constant and  is the reduce mass of the molecule. The
2 
1
classical energy equation, E  k (x) 2 , could not explain the quantization of vibrational
2
213
1 1 k 1
energies. Thequantum mechanical equation of energy ,. E  (v  ). m where, ‘v’
2 2 c 
is the vibrational quantum number that can be explained. the behaviour of a harmonic oscillator.
The selection rule for spectral transitions is v  1 , which means that only the transitions
between adjacent energy levels are allowed. The harmonic oscillator approximation assumes
that the molecule can be stretched to any extent without breaking the bond. The real situation,
where the molecule dissociates into respective atoms beyond certain amplitude of vibration can
be approximated by the Morse equation of energy.
The selection rule for spectral transition in the case of anhames Oscillator is
v  1, 2, 3 The higher overtones are in general not observed due to their extremely low
intensities. From the positions ofthe spectral lines. the equilibrium vibrational frequency.
anhamanicity constant, zero point energy and force canstant can be calculated. The transitions
from v=1, v=2 etc. to high levels can be observed onlyat high temperatures. Therefore these
absorptions are called ‘hot bands.
1. a law stating that the strain in a solid is proportional to the applied stress within the
elastic limit of that solid.
2. Stretching vibrations, bending vibrations (In-plane bending, out-plane bending, Scissoring,
rocking, wagging and twisting)
3. saturated acyclic esters = 1735-1750 cm-1.
saturated cyclic esters
5 membered (P-lactones) = 1820 cm-1.
6 numbered ( y- lactones) = 1760-1780 cm-1.
7 membered (lactones) = 1735-1750 cm-1.
I Answer each of the following in 10 lines
1. What are the units for expressing wavelengths of different regions of electromagnetic
radiation?
2. Discuss ditferent types of bond vibrations in molecules.
3. What are the selection rules for hrmonic and anharmonic oscillators?
4. How do you calculate the amplitude of vibration at v = 0 level for a diatomic molecule given
the reduced mass and force constant.
5. Explain the procedure for the calculation of the force constant for a diatomic molecute using
infrared spectral data.
6. What is Zero point energy? How do you calculate the zero point energy of an anharmonic
oscillator?
214
II Answer each of the following in 30 lines
1. Discuss application of IR spectroscopy in differentiating various classes of organic compounds

containing carbonyl group.
2. Explain the tems overtones and hot bands.
3. How are different types of amines and amides distinguished by I.R. spectroscopy?
4. How do you differentiate the following functional groups by IR spectroscopy?
a) CH3-CH2- OH and
b) H3C-CH=CH-CH3 and CH3- CH2- C  C-H
1. Banwell, C. N. & McCash, E. M. Fundamentals of Molecular Spectroscopy 4th Ed. Tata

McGraw-Hill: New Delhi (2006).
2. Kakkar, R. Atomic & Molecular Spectroscopy: Concepts & Applications, Cambridge

University Press (2015).
3.Kemp, W. Organic Spectroscopy, Palgrave.
4. Pavia, D. L. et al. Introduction to Spectroscopy 5th Ed. Cengage Learning India Ed. (2015).
215
UNIT-12: METAL IONS IN BIOLOGICAL SYSTEMS
Contents
12.0. Objectives
12.1. Introduction
12.2. The importance of Na+, K+, Fe2+, Co2+, Zn2+ in biological systems.
12.3. Bio inorganic chemistry of Fe, Co, and Zn
12.4. Summary
12.0. OBJECTIVES
After you completing this unit you must be able to
 Why metals ions are essential in biological systems
 The importance of different metal ions such as Na+, K+, Fe2+, and Co2+ in living
organisms
 The adverse effects, if these metal ions are absent
12.2. INTRODUCTION
Living organisms consist of two types of chemical constituent they are inorganic and
organic. Organic compounds are proteins, Carbohydrates and fats. This type of components
constitute 90% of the total.
Inorganic components constitute the remaining 10%. Most of these are chemical
elements. These elements are classified into essential and nonessential elements. Essential
elements present in more than 1mg are called macro elements.
12.3. THE IMPORTANCE OF Na+, K+, Fe2+, CO2+ IN

BIOLOGICAL SYSTEMS
Na, K, Mg and Ca ions were be in greater amounts in biological systems than the other
metal ions. These metals constitute 99% of the total metal ion concentration. The next abundant
metal is iron. Zn, Cu, Co are present to less extent.
216
The bio inorganic chemistry of Na, K: The concentrations of metal ions with in the living
cell and outside the living cells are different from one another. In any living cell the concentration
of K+ is more than that of Na+. Therefore the concentration of Na+ is more than that of K+
outside the living cell. Thus K+ ions are connected with the reactions into cell where as Na+ ions
are important for reactions outside the cell. K+ ions activate the enzymes in the cell and Na+
ions activate the enzymes outside the cell.
Those which are required in very small amounts (< 1mg) are called micro elements. These
are called trace elements or aligo elements. These include Cu, Zn, Co, Mn, Mo, I, Fe. Non-
essential elements are about 10 in number. Their function is not definitely known and hence are
called non-essential. These are Br, B, Si, As, Ni, Al, Pb, V, Ti, and Sn.
Check your progress
1) What is the percentage of inorganic components in living organisms?
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2) What are essential elements?
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3) What are non-essential elements?
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217
12.4 BIO INORGANIC CHEMISTRY OF Fe, CO AND Zn
Iron has two oxidation state Fe2+, Fe3+. Iron is useful in the transport of O2 and electrons
besides in many other body functions. Iron is mostly present in haemoglobin, myoglobin and
cytochromes. It is also present in non-haeme substances such as peritein and trans periterin.
The iron-protein distribution in human body is illustrated approximately in the table 12.1
Iron -protein distribution
Protein % Fe No of atoms of Fe Oxidation Function

in the molecule state
1. Haemoglobin 65 4 Fe2+ O2 Transport
2. Mayoglobin 6 1 Fe2+ Storage of O2 in Muscles
3. Transperitin 2 2 Fe3+ Transport of Iron
4. Peritien 13 4300 Fe3+ Storage of Iron in cells
5. Cytochinm 0.1 1 Fe2+/Fe3+ Terminal Oxidation
6. Haemo seridim 12 15000 Fe3+ Storage of Iron in cells
The enzymes activated by K+ ions are not activated by Na+ ions and vice-versa. K+
ions play a significant role in the synthesis of RNA/DNA. The concentration gradient of K+,
and Na+, with in the cells and outside the cell causes a potential difference between the two
sides of the cell - membrane. This potential difference influences the expansion and contraction
of muscles. These metal ions are generally present as their chlorides Na+, K+ and Cl– ions help
to keep protein molecules in the liquid form and to regulate the blood density and viscosity. The
action of retina in the eye is also controlled by Na+, K+. Thus the absence of these ions in the
body leads to many health problems.
Check your progress

4) Name two functions of Na+, K+ ions in the living cell
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Haemoglobin and Myoglobin
These two are intimately related. Myoglobin molecule contains a peptide chain with one
haemo group. The molecular weight is 17,000. The peptide chain contains 100-160 amino acids.
218
Hemoglobin molecule contain 4 peptide chains each containing 1 heame group. The molecular
weight is 64,454. Fe is present as Fe2+.
Both these molecules form bonds with O2 molecules. But their functions are different.
Haemoglobin receives O2 from lungs and transports it to different tissues of the body. The
O2 thus transported is received by myoglobin and stores sufficient amount for the digestion
process Haemoglobin receives CO2 and takes to the lungs.
HC CH2
H3C
H
H
N CH3
H3C
N Fe N
CH2
H2C C
N H
H2C
H H
COOH
H2C CH3
CH2
COOH
Haemoglobin readily combines with oxygen to form oxyhaemoglobin, and this when treated
with glacial acetic acid form haematin. The chloride of haematin is known as haemin. Its
molecular formula is C34 H32 O4 FeIII Cl, in which iron atom is in Ferric state.
Cyto chromes
These play an important role in the transport of electrons in photosynthesis. These are of
three types A, B, and C. In these ‘C’ is the most important. This receives electrons from
strong reducing agent and gives to oxidising agents. This contains iron in the +2 and +3
oxidation states. The molecular weight is about 12,000.
The energy released in the reduction process of O2 to H2O by cytochromes is utilised for
digestive processes of food.
219
4H+O2  2H2O+ energy
Proteins containing Iron but no haemo group
In these, iron is bound to sulphur. These are useful for the electron-transfer
processes. These participate in reduction processes. The structure can be broadly
represented as
S SCys
CysS
Fe Fe
CysS SCys
S
Rubindoxin and peridoxin illustrate this type of proteins. These are stores iron in them and
supply whenever it is needed.
Check your progress
5) What are the functions of proteins containing Iron?
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6) Name proteins containing iron but no haeme group.
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Bio Inorganic chemistry of Co
Vitamin B12 is a Cobalt complex. This is present in liver. Cobalt (III) is present as the central
mental ion in the complex compound vitamin B12 is an octahehedral Cobalt (III) complex. In the
6th co-ordination position CN– is bound to the cobalt. In youth B12 is present to the extent of 2-
5 mg. B12 is mainly responsible for the synthesis of red blood corposules in bone marrow. It is
for this reason, deficiency of cobalamine (B12 ) in the body leads to anemia. But at the same
220
time If B12 is present excessively is leads to over production of red blood cells and this is known
polycythemia.
Bio inorganic Chemistry of Zn

It is now realised that zinc is required for all living organisms. In youth zinc is present in
amounts equal to 4 to 6 g. Two enzymes containing Zn namely carbonic anhydrase and carboxy
peptidase were discovered in the years 1940 & 1955 respectively. But today more enzymes
were known for they containing Zn. There enzymes are useful for different types of reactions
such as alcohol dehydrogenation, trans phosphorilation, polymerization (DNA, RNA) etc. Two
important functions are discussed below.
Carbonic an hydrase
This is present in blood red cells. The molecular weight is 300,00. This is used in
hydration reaction of CO2.
CO2 + H2O  H3CO3
This usually occurs slowly but the enzyme accelates the HCO-3 dehydration and the
hydration of CO2 reactions.
Carboxy peptidase
This is present in pancreas. The molecular weight 34600. This enzyme catalyses the
hydrolysis of peptide linkage. Insulin contain Zn. In diabetic patients, Zn content decreases to
5%. In leucamia patients it is reduced to 10%. Deficiency of Zn retards reaction in kidneys and
liver. This leads to retardtion of body development.
Check your progress
7. What is the role of Zn in human body?
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12.5. SUMMARY
1. Metals play an importent role in biological systems.
2. Bio chemicals include both organic and inorganic components. The chemical elements required
for living organisms are classified into essential and non-essential.
221
3. There elements are classified based on their quantity into macro and micro elements.
4. Na, K, Fe, Mg, Co, and Zn play significant role in living organisms.
5. There are associated into the enzymes and enzyme actions.
6. Fe, Co are the most importent
7. Fe is present in haemoglobin and Co is present in B12
8. Deficiency of metal leads to various types of disorders.
9. Enzyme actions are slowed down body development is retarded.

1. 90% is the organic component and remaining 10% is inorganic component is present.
2. Metal ions which are required to lead important function in the biological systems are
called essential elements Ex: Na, K, I, Zn, Cu, Co, Mo, Mn etc..
3. Metal ions their function is not known definitely are called non essential elements Ex:
Br, B, Si, As, Ni, Al, Pb, V, Ti and Sn.
4. K+ ion activates the enzymes inside the cell K+ ion plays an important role in the
synthesis RNA/DNA. Na+, K+ required to maintain blood density and viscosity.
5. Proteins containg Iron function as transportation of O2, storing of Iron and
transportation of CO2 from cells to lungs.
6. Rubindoxin and peridoxin.
7. Zn contain enzymes play important role in biological functions ex Carbonic
anhydrase used to hydration reaction of CO2 and Carboxy peptidase used regulate
the production of insulin.
12.7. MODEL EXAMINATION QUESTIONS

1) What are the percentages of organic and inorganic components in living organisms?
How are chemical elements classified?
2) Name the essential and non-essential elements needed for the proper functioning of
living organisms
3) What is haemoglobin? Discuss its functions
4) What is B12? Discuss its functions
5) Describe the functions of Zn in living organisms.
6) What are the disorders caused by the deficiency of Na, K, Fe, Co and Zn in living
organisms?
222
1) What is the role of metals in living organisms? Discuss with suitable examples.
2) Discuss the role of Na, K, Fe, Co & Zn in biological systems.
3) Write notes on haemoglobin and vitamin B12.

ISBN:10:1-4292- 3414-8.
3. Bioinorganic Chemistry, I.Bertini, H.B.Gray, S.J.Lippard and S.J.Valentine, Viva

LowPriced Student Edition, New Delhi (1998).
4. Bioinorganic Chemistry: Inorganic Elements in the Chemistry of Life, W.Kain and

B.Schwederski, John Wiley and Sons, NY (1999).
5. Lippard, S.J. & Berg, J.M. Principles of Bioinorganic Chemistry Panima Publishing
Company 1994.
223
DR. B. R. AMBEDKAR OPEN UNIVERSITY
FACULTY OF SCIENCE
2nd YEAR (3 YEARS DEGEREE COURSE)
MODEL QUESTION PAPER
CHEMISTRY SEMESTER - 5
Chemistry - 5 : Inorganic, organic & physical chemistry - 5
[Time : 3 hours] [Max Marks : 60]
————————————————————————————————————
Section - A
[Short Answer questions]
[Marks : 4 x 5 = 20]
Note : a) Answer any four of the following in about 10 lines each.
b) Each question carries 5 Marks.
1. [Block - 1] How the composition of metal complexes determined?
2. [Block - 1] What is a ‘bond’ in terms of MO theory of metals? How does it

originate?
3. [Block - 2] Explain the mechanism of electrophilic substitution in pyrole?
4. [Block - 2] What are Vitamins and how they are classified?
5. [Block - 3] Under what conditions can an endothermic reaction proceed

spontaneously? explain
6. [Block - 3] What is fluorescence and phosphorescence?
7. [Block - 4] Discuss the instrumentation for UV-visible spectroscopy.
8. [Block - 4] Discuss ditferent types of bond vibrations in molecules.
Section - B
[Short Answer questions]
[Marks : 4 x 10 = 40]
Note : a) Answer any four of the following in about 30 lines each.
b) Each question carries 10 Marks.
9. [Block - 1] Discuss about the stability and the factors that influences the stability
of metal complexes.
(or)
10. [Block - 1] Describe the different methods of purification?
224
11. [Block - 2] Describe the synthesis of I) furan 2) pyrrole and 3) thiophene 2. Draw
the orbital picture of furan?
(or)
12. [Block - 2] What happens when

a) glycine is treated with formaldehyde
b) alamine is treated with Nitrous acid
13. [Block - 3] Derive an expression for the maximum efficiency of a heat engine.
(or)
14. [Block - 3] Write a brief account of the construction of Calomel electrode.
15. [Block - 4] Explain the tems overtones and hot bands.
(or)
16. [Block - 4] Discuss the role of Na, K, Fe, Co & Zn in biological systems.
SECTION - C
Total Number of Questions 20
I. Multiple Choice Questions.
1. The Spectrophotometric determination of the composition metal complexes involves
a) Establishing of complex formation [ ]
b) Fixing up of optimum conditions for the formation of stable complex
c) Acertaining the characteristic wavelength for determining the composition and the
method of determing the composition.
d). All
2. Metal ions showing equal affinity for oxygen and nitrogen containing ligands ——————
a. Be2+, Cr3+, Pt2+ b. Fe2+, Pt2+ , Pt4+ [ ]
c. Cr3+ , Fe2+, Pt2+ d. All
3. Magnetite ———————— [ ]
a. MgSO4 b. Fe3O4 c. Fe5O8 d. Fe6O10
4. Pyrrole undergoes electrophilic substitution reactions at ______________
a. 2 ,5 b. 3,4 c. 1 d. 2,3 [ ]
225
5. Acetylene and hydrogen sulphide over heated alumina yields ____________
a. Furan b. Pyrrole [ ]
c. Thiophene d. benzene
6. Ninhydrin is used for _____________ [ ]
a. Detecting for hetero cyclics b. Detecting for Amino acids
c. Detecting for vitamins d. Detecting for hormones
7. B-complex vitamins are __________ [ ]
a. water soluble b. Fat soluble
c. water and fat insoluble d. Water insoluble
8. Spontaneous process ΔG =_____________ [ ]
a. negative b. Positive c. Zero d. Not effected
9. In photosynthesis Activator is ____________ [ ]
a. Chlorophil b. Haemoglobin c. Water d. CO2
10. Vibrational Stretching frequency of N-H bond of primary amine ____________
a. 3400cm-1 and 3500cm-1 [ ]
b. 3180cm-1 and 3350cm-

c. 3140cm-1 3320 cm-1
d. None
II. Match the follwing
1. Slope- ratio methods [ ] a. Bonding in metals

2. Metallic bonding [ ] b. Composition of metal complex
3. valence bond theory [ ] c. Elock
4. Molecular orbital theory [ ] d. Pauling
5. Carnalite [ ] e. yellow colur
f. KClMgCl26H2O
g Ca 3 (PO4 )2H2 O
III. Fill in the blanks.
1. Dolomite molecular formula _________________.
226
2. Slag is _____________________.
3. Sketch the Furan structure _________
4. Sketch the Glycene structure ______________
5. Hypsochromic shift is ————————————-
******
227
228

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BS514CHE-E

“We may forgo material benefits of civilization, but we cannot forgo

Dr. B. R. AMBEDKAR OPEN UNIVERSITY

First Edition : 2020

© 2020, Dr. B. R. Ambedkar Open University, Hyderabad, T.S.

The text forms part of Dr. B. R. Ambedkar Open University Programme.

Further information on Dr. B. R. Ambedkar Open University courses may be obtained

Printed on behalf of Dr. B. R. Ambedkar Open University, Hyderabad by the Registrar.

The first block, Inorganic chemistry it covers formation, composition determiation,

The second is Organi chemistry, it deals synthesis, properties and importance of

The third block is Physical chemistry, it deals with concepts pertaining to

BLOCK-1: INORGANIC CHEMISTRY 1

Unit – 1: Co-ordination compounds-2 3

Unit – 2: Bonding in Metals 13

Unit – 3: Principles of Metallurgy 24

BLOCK-2 : ORGANIC CHEMISTRY 49

Unit – 4: Heterocyclic compounds 51

Unit – 5: Aminoacids and Proteins 69

Unit – 6: Vitamin and Hormones 85

BLOCK-3: PHYSICAL CHEMISTRY 105

Unit – 7: Thermodynamics - 2 (Thermochemistry) 107

Unit – 8: Electrochemistry-2 144

Unit – 9: Photochemistry 163

BLOCK-4 : GENERAL CHEMISTRY 179

Unit – 10: UV-Visible spectroscopy 181

Unit – 11: Infrared Spectroscopy (Vibrational Specroscopy) 196

Unit – 12: Metal ions in biological systems 216

Model question papers 224

Block-1 includes the following three units.

Unit – 2: Bonding in metals

Unit – 3: Principles of metallurgy

1.2. Formation of metal complexes

1.3. Composition of metal complexes

1.4. Stability constants of metal complexes

1.5. Factors affecting stability of metal complexes

1.6. Applications in chemical analysis

1.8. Check your progress - Answers

1.9. Examination model questions

1.10. Further reading.

H 3N NH3 H3N NH3

H3N Ag+ NH3 Cu+2 Ni+2

H3N NH3 H3N NH3

NH3, H2O, EDTA, Ethylene diamine etc.

Check your progress

1) What is a metal complex ?

2) Which type of chemical species form metal complexes ?

Cu2+ + 4NH3  [Cu(NH3)4]2+

Ag+ + 2NH3  [Ag(NH3)2]+

Cu2+ + 4CN-  [Cu(CN)4]2-

Fe3+ + 6CN-  [Fe(CN)6]3-

1.3. COMPOSITION OF METAL COMPLEXES

1) Slope ratio method

1) Establishing of complex formation

(ii) ligand solution

(iii) metal ion+ ligand solution (excess)

2) Fixing up of  max for the metal complex

3) Determination of Composition of metal complex.

(a) Slope- ratio methods