KARNATAKA STATE OPEN UNIVERSITY

Mukthagangotri, Mysore – 570 006

M.S CHEMISTRY
M.Sc.
(
(FOURTH SEMESTER)

Course: MCH T 4.1 Block 1,

1,2,3 and 4
INORGANIC
ORGANIC CHEMISTRY-IV
CHEMISTRY
 M.Sc. CHEMISTRY
FOURTH SEMESTER

COURSE: MCHT 4.1

INORGANIC CHEMISTRY-IV

i
Course Design Committee
Prof. Shivalingaiah. D Prof. Devegowda .T. D
Vice-Chancellor & Chairperson Dean (Academic) & Convenor
Karnataka State Open University Karnataka State Open University
Mukthagangothri, Mysore - 570 006 Mukthagangothri, Mysore - 570 006

COURSE WRITER
Dr. Prasannakumar. C. S Blocks 4.1.1, 4.1.2 and 4.1.3
Senior scientist
Dr. Reddy’s laboratory
Bangaluru

Prof. Nagaraja Naik Block 4.1.4

Professor, Department of Studies in Chemistry
University of Mysore, Manasagangothri,
Mysuru
Course Coordinator Course editor
Dr. M. Umashankara Dr. Prasannakumar. C. S
Assistant Professor and Chairman Senior scientist
Department of Studies in Chemistry Dr.Reddy’s laboratory
Karnataka State Open University Bengaluru
Mukthagangothri, Mysore - 570 006
PUBLISHER

The Registrar
Karnataka State Open University
Mukthagangothri, Mysore - 570 006
Developed by Academic Section, KSOU, Mysore
Karnataka State Open University, 2013
All rights reserved. No part of this work may be reproduced in any form, by mimeograph or any
other means, without permission in writing from the Karnataka State Open University.
Further information on the Karnataka State Open University Programmes may obtained from the
University’s office at Mukthagangothri, Mysore - 6
Printed and Published on behalf of Karnataka State Open University. Mysore – 6 by Registrar
(Administration)

ii
 TABLE OF CONTENTS
Page No

Block
4.1.1 GROUP THEORY AND ITS APPLICATIONS

1-21
Unit-1 Definition of groups, sub groups, cyclic groups, conjugates relationships.

Unit-2 Symmetry elements and symmetry operations, point groups (of molecules) 22-37

Unit-3 Reducible and irreducible representations, characters of representation. 38-47

Unit-4 Character tables and their uses (representations, of Cn, Cnv, Cnh, Dnh groups to 48-62
be worked out)

Block SPECTROSCOPIC APPLICATIONS IN INORGANIC CHEMISTRY

4.1.2

Vibrational spectroscopy- vibrational spectra of diatomic, linear and bent 63-89

triatomic, AB3, AB4, AB5 and AB6 molecules. Spectra of metal complexes,
Unit-5 amines, amido, nitro, nitrito, latticewater, aquo and hydrido, carbonato,
sulphato, cyanato, thiocyanato complexes, mono and multinuclear carbonyl
complexes. Ethylene diamino and diketonate complexes

ESR-Spin polarization for atoms and transition metal ions, spin-orbit 90-125
coupling and significance of g-tensors, zero/non zero field splitting ,
Unit-6 Kramer’s degeneracy, applications to transition metal complexes (having one
to five unpaired electrons) including biological molecules and free radicals
such PH4 , F2 and BH3.

NMR- applications of 31P, 19F, 11B NMR spectroscopy in the structural 126-165
Unit-7 assessment of inorganic compounds, proton/ hydride interactions with
Rh103, W 183, Pt 185 and Pb207 in metal complexes/organometallic
compounds.

Mossbauer spectroscopy: principles, isomer shift, qudrupole splitting and 166-181

Unit-8 magnetic hyperfine interactions. Applications to the study of bonding and
structures Fe2+ and Fe3+ compounds, Sn2+ and Sn4+ compounds.

iii
Block
THERMAL METHODS OF ANALYSIS
4.1. 3

Unit-9 Thermogravimetric analysis- principle, factors affecting TG curves,TG curve 182-205

of calcium oxalate, instrumentation and applications of TG.

Unit-10 DTA and DSC: principles, instrumentations, and applications in the area of 206-223
polymers.

Unit-11 Thermomechanical and dynamic mechanical analysis: Principle, 224-237

instrumentation and applications.

Unit-12 Thermometric analysis: Principles, instrumentation and applications 238-244

Block HOMOGENEOUS AND HETEROGENEOU CATALYSIS

4.1.4

Unit-13 Introduction, basic principle, industrial requirements, thermodynamic and 245-356

kinetic aspects, classification of catalytic systems.

Principle, experimental techniques, acid-base catalysis, catalysis involving 257-276

Unit-14
transition metal salts and metal complexes- hydrogenation, asymmetric
hydrogenation, transfer hydrogenation, hydrosilation and hydrocyanation.
Unit-15 Fisher- tropsch process, Ziegler-Natta polymerization- Syndiotactic and 277-286
isotactic polymers.

Zeolites as shape selective catalysts. Clays as catalyst, pillard clays- 287-299

Unit-16 advantages, decomposition of isopropanol using oxide catalysts, catalytic
converters.

COURSE INTRODUCTION
Symmetry plays an central role in the analysis of the structure, bonding, and spectroscopy of

molecules. In this couse, you will explore the basic symmetry elements and operations and their

use in determining the symmetry classification (point group) of different molecules.

Spectroscopy is the study of the interaction of electromagnetic radiation with matter.

iv
Spectroscopy has many applications in the modern world, ranging from nondestructive

examination of materials to medical diagnostic imaging (e.g., MRIs, CAT scans). In a chemical

context, spectroscopy is used to study energy transitions in atoms and molecules. The transitions

are interpreted and can serve to identify the molecule or give clues about the molecular structure.

In this couse you will explore indetail application of spectroscopic methods like IR, ESR,

Mössbauer etc to the inorganic compounds you will also study the NMR spectroscopy other

than 1H, like 13F, 31P 11B etc….

Thermal analysis is the techniques in which a physical property of a substance is measured as a

function of temperature whilst the substance is subjected to a controlled temperature programme.

In this course you will going to explore different thermal analysis techniques like,

Thermogravimetry (TG); Differential thermal analysis (DTA); Differential scanning calorimetry

(DSC); etc…. and their applications.

Catalysis typically provides the technology to enable the efficient and cost-effective synthesis of

pharmaceutical products. By definition, catalysis increases the reaction rate by lowering the

activation energy of the reaction, therefore allowing the chemical transformation to take place

under much milder conditions over the uncatalyzed process. Furthermore, the catalyst typically

imparts chemo-, regio-, or stereoselectivities over the course of the reaction to enable highly

efficient syntheses of target molecules. in this course you will explore on the homogenous and

heterogeneous inorganic catalyst for various industrial applications.

v
Group theory and its applications Block 4.1.1

UNIT-1
Structure
1.0 Objectives of the unit
1.1 Introduction
1.2 Symmetry operations and symmetry elements
1.3 Rotation about an n-fold axis of symmetry
1.4 Reflection through a plane of symmetry (mirror plane)
1.5 Reflection through a centre of symmetry (inversion centre)
1.6 Identity operator
1.7 Successive operations
1.8 Point groups
1.8.1 C1 point group
1.8.2 C∞v point group
1.8.3 D∞h point group
1.8.4 Td, Oh and Ih point groups
1.9 Determining the point group of a molecule or molecular ion
a) Determination of the point group for trans-N2F2 molecule
b) Determination of the point group for PF5
c) Determination of the point group for POCl3
1.10 Summary of the unit
1.11 Key words
1.12 References for further studies
1.13 Questions for self understanding

Karnataka State Open University Page 1

Group theory and its applications Block 4.1.1

1.0 Objectives of the unit

After studying this unit you are able to

Explain the symmetry operations and symmetry elements

Explain the rotation about an n-fold axis of symmetry

Explain the reflection through a plane of symmetry (mirror plane)

Explain the reflection through a centre of symmetry (inversion centre)

Explain the identity operator

Explain the successive operations

Explain the point groups
1.1 Introduction
For understanding the chemistry of the molecules, symmetry is very important. Also,
understanding of symmetry is essential in discussions of molecular spectroscopy and
calculations of molecular properties. For qualitative purposes, it is sufficient to refer to the
shape of a molecule using terms such as tetrahedral, octahedral or square planar. However,
the common use of these descriptors is not always precise, e.g. consider the structures of BF3,
and BF2H, both of which are planar. A molecule of BF3 is correctly described as being
trigonal planar, since its symmetry properties are fully consistent with this description. all the
F-B-F bond angles are 1200 and the B-F bond distances are all identical (131 pm). It is correct
to say that the boron centre in BF2H, is in a pseudo-trigonal planar environment but the
molecular symmetry properties are not the same as those of BF3. The F-B-F bond angle in
BF2H is smaller than the two H-B-F angles, and the B-H bond is shorter (119 pm) than the B-
F bonds (131 pm).

The descriptor symmetrical implies that a species possesses a number of indistinguishable

configurations. When BF3 molecule is rotated in the plane of the paper through 1200, the
resulting structure is indistinguishable from the first; another 1200 rotation results in a third
indistinguishable molecular orientation. This is not true if we carry out the same rotational
operations on BF2H.
Group theory is the mathematical treatment of symmetry. In this unit we are going familiar to
the fundamental language of group theory ie, symmetry operator, symmetry element, point
group and character table. The unit does not set out to give a comprehensive survey of
molecular symmetry, but rather introduce some common terminology and its meaning.
Karnataka State Open University Page 2
Group theory and its applications Block 4.1.1

1.2 Symmetry operations and symmetry elements

If we applied 120o rotations to BF3, each rotation generate a representation of the molecule
that was indistinguishable from the first. Each rotation is an example of a symmetry
operation.

Figure 1: Rotation of the trigonal planar BF3 molecule through 1200 generates a
representation of the structure that is indistinguishable from the first

The Symmetry Operation is defined as A transformation in three-dimensional space that

preserves the size and shape of a molecule, and which brings it into an orientation in three
dimensional space physically indistinguishable from the original one, or
A symmetry operation is an operation performed on an object which leaves it in a
configuration that is indistinguishable from, and superimposable on, the original
configuration.
The rotations described in the above figure 1 were performed about an axis perpendicular to
the plane of the paper and passing through the boron atom. The axis is an example of a
symmetry element.
Thus Symmetry element is defined as the geometrical plane, point, or axis associated with a
particular symmetry operation or set of symmetry operations.
There are many types of symmetry operation are performed for study of symmetry of the
molecule they are
1) Rotation about an n-fold axis
2) Reflection through a plane of symmetry
3) Reflection through a centre of symmetry
4) Identity operator
1.3 Rotation about an n-fold axis of symmetry
The symmetry operation of rotation about an n-fold axis (the symmetry element) is denoted
0
by the symbol ‘Cn’, in which the angle of rotation is 360 , where n is an integer, e.g. 2, 3
n
or 4. Applying this notation to the BF3 molecule in Figure 1 gives a value of n = 3 say that
the BF3 molecule contains a C3 rotation axis. In this case, the axis lies perpendicular to the
plane containing the molecule.

Karnataka State Open University Page 3

Group theory and its applications Block 4.1.1

360 0
Angle of rotation = 1200 = ------------ (1)
n
In addition, BF3 also contains three 2-fold (C2) rotation axes, each coincident with a B-F
bond as shown in Figure 2.

Figure 2: The 3-fold (C3) and three 2-fold

(C2) axes of symmetry possessed by the
trigonal planar BF3 molecule.

If a molecule possesses more than one type of n-axis, in such case the axis of highest value of
n is called the principal axis. It is the axis of highest molecular symmetry. For example, in
BF3, the C3 axis is the principal axis.

Figure 3: The square planar molecule XeF4. (a)

One C2 axis coincides with the principal (C4)
axis; the molecule lies in a σh plane which
contains two C2’ and two C2’’ axes. (b) Each of
the two σv planes contains the C4 axis and one
C2’ axis. (c) Each of the two σd planes contains
the C4 axis and one C2’’ axis.

Karnataka State Open University Page 4

Group theory and its applications Block 4.1.1

In some molecules, the principle axis also associated with lower order symmetry axis i.e,
rotation axes of lower orders than the principal axis may be coincident with the principal axis.
For example, in square planar XeF4, the principal axis is a C4 axis but this also coincides with
a C2 axis.
If a molecule contains more than one type of Cn axis, then they are distinguished by using
prime marks, e.g. C2, C2’ and C2’’.
1.4 Reflection through a plane of symmetry (mirror plane)
If reflection of all parts of a molecule through a plane produces an indistinguishable
configuration, then the plane is called a plane of symmetry. The symmetry operation
performed is a reflection and the symmetry element is a mirror plane and it is denoted by
symbol ‘σ’. For BF3, the plane containing the molecular framework is a mirror plane.
In such case, if the plane lies perpendicular to the vertical principal axis then it is denoted by
the symbol ‘σh’.
The framework of atoms in a linear, bent or planar molecule can always be drawn in a plane,
but this plane can be labelled as σh only if the molecule possesses a Cn axis perpendicular to
the plane. If the plane contains the principal axis, it is labeled ‘σv’.
For example, consider the H2O molecule. This possesses a C2 axis as shown in figure 4. But it
also contains two mirror planes, one containing the H2O framework, and one perpendicular to
it. Each plane contains the principal axis of rotation and so may be denoted as σv but in order
to distinguish between them, we use the notations σv and σv’. The σv label refers to the plane
that bisects the H-O-H bond angle and the σv’ label refers to the plane in which the molecule
lies.

Figure 4: The H2O molecule possesses one C2 axis and two mirror planes. (a) The C2 axis
and the plane of symmetry that contains the H2O molecule. (b) The C2 axis and the plane of
symmetry that is perpendicular to the plane

Karnataka State Open University Page 5

Group theory and its applications Block 4.1.1

A special type of plane which contains the principal rotation axis, but which bisects the angle
between two adjacent 2-fold axes, is labelled σd. A square planar molecule such as XeF4
provides an example. Figure 3a shows that
XeF4 contains a C4 axis (the principal axis) and perpendicular to this is the h plane in which
the molecule lies. Coincident with the C4 axis is a C2 axis. Within the plane of the molecule,
there are two sets of C2 axes. One type (the C2’ axis) coincides with F–Xe–F bonds, while the
second type (the C2’’ axis) bisects the F–Xe–F 900 angle. We can now define two sets of
mirror planes. One type (σv) contains the principal axis and a C2’ axis (Figure 3b), while the
second type (σd) contains the principal axis and a C2’’ axis (Figure 3c). Each σd plane bisects
the angle between two C2’ axes.
In the notation for planes of symmetry, σ, the subscripts h, v and d stand for horizontal,
vertical and dihedral respectively.
1.5 Reflection through a centre of symmetry (inversion centre)
If reflection of all parts of a molecule through the centre of the molecule produces an
indistinguishable configuration, the centre is a centre of symmetry, also called a centre of
inversion. It is designated by the symbol ‘i’or ‘I’.
Each of the molecules CO2, trans-N2F2, SF6 and benzene possesses a centre of symmetry.

But H2S, cis-N2F2 and SiH4 do not.

a) Inversion Operation:
One of the simplest symmetry operations encountered is the inversion operation, whose
element is a single point in space. This operation puts a premium on the ability to recognize
the origin of the coordinate system where all symmetry elements intersect. Several examples
of molecules that contain inversion centers are shown in Figure 5

Karnataka State Open University Page 6

Group theory and its applications Block 4.1.1

Figure 5: Examples of molecules that contain an inversion center a) dioxygen; b) sulfur

hexafluoride; c) octachlorodirhenate (III) ion.

A center of inversion may be located at the center of an atom, such as on sulfur in SF6, or
between a pair of inversion related atoms, for example, midway between the O-O bond in O2
or the Re-Re bond in [Re2Cl8]2-.
The inversion operation, denoted by symbol ‘I’ derives its name because it takes an atom
with coordinates (x,y,z) and transforms them to the inverted position (-x,-y,-z). The easiest
way to perform this operation is to draw a line between an atom and the inversion center and
then to continue this lines an equal distance through the inversion center.
For example in figure 5, the three pairs of F atoms in SF6, and the four pairs of Cl atoms
related by the inversion operation have been denoted with subscripts 1,2, 3, and 4. The 6 F in
SF6 and 8 Cl in [Re2Cl8]2- are all equivalent. The inversion, operation only relates pairs of
atoms, or the unique sulfur atom to itself. Some molecules that look highly symmetrical, lack
an inversion center, for example tetrahedral TiCl4 as shown in Figure 6.

Figure 6: Illustration of the lack of an inversion center in a tetrahedral molecule,

such as TiCl4
Application of the inversion operation centered at Ti produces an orientation distinguishable
from the original one. The chlorine atoms in the drawing have been subscripted to illustrate

Karnataka State Open University Page 7

Group theory and its applications Block 4.1.1

where the inversion operation moves them. Other examples of molecules that lack an
inversion center are BF3, HCl, and trigonal bipyramidal Fe(CO)5.
b) Rotation about an axis, followed by reflection through a plane perpendicular to this axis
360 0
If rotation through about an axis, followed by reflection through a plane perpendicular
n
to that axis, yields an indistinguishable configuration, the axis is an n-fold rotation– reflection
axis, also called an n-fold improper rotation axis. It is denoted by the symbol Sn. Tetrahedral
species of the type XY4 (all Y groups must be equivalent) possess three S4 axes, and the
operation of one S4 rotation–reflection in the CH4 molecule is illustrated in Figure 7.

360 0
Figure 7: An improper rotation (or rotation–reflection), Sn, involves rotation about followed
n
by reflection through a plane that is perpendicular to the rotation axis. The diagram illustrates the
operation about one of the S4 axes in CH4; three S4 operations are possible for the CH4 molecule.

1.6 Identity operator

All objects can be operated upon by the identity operator E. This is the simplest operator and
effectively identifies the molecular configuration. The operator E leaves the molecule
unchanged.
1.7 Successive operations
As we know a particular symbol is used to denote a specific symmetry operation. For
example, if say that NH3 possesses a C3 axis means that we can rotate the molecule through
1200 results a molecular configuration that is indistinguishable from the first. And it takes
three such operations to give a configuration of the NH3 molecule that exactly coincides with
the first. The individual three 1200 rotations are identified by using the notation in Figure 8.
Actually it is difficult to distinguish between the three H atoms, but for clarity they are

Karnataka State Open University Page 8

Group theory and its applications Block 4.1.1

labelled H(1), H(2) and H(3) in the figure. Since the third rotation, C3, returns the NH3
molecule to its initial configuration, we can write equation 2, or, in general equation 3.
C 33 = E -------------------- 2

C nn = E -------------------- 3

Figure 8: Successive C3 rotations in NH3 are distinguished using the notation C3, C 32 and
C 33 . The effect of the last operation is the same as that of the identity operator acting on NH3
in the initial configuration.

Similar statements can be written to show the combined effects of successive operations. For
example, in planar BCl3, the S3 improper axis of rotation corresponds to rotation about the C3
axis followed by reflection through the σh plane. This can be written in the form of equation
4.
S 3 = C 3 Xσ h ------------------------- 4

1.8 Point groups

Point groups are a method of classifying the shapes of molecules according to their symmetry
elements. Chemists classify molecules according to their symmetry. The collection of
symmetry elements present in a molecule forms a “group”, typically called a point group. The
question arising here is why is it called a “point group”? Because all the symmetry elements
(points, lines, and planes) will intersect at a single point hence it is called point group.
Thus each molecule has a set of symmetry operations that describes the molecule's overall
symmetry. This set of operations defines the point group of the molecule. The number and
nature of the symmetry elements of a given molecule are conveniently denoted by its point
group, and give rise to labels such as C2, C3v, D3h, D2d, Td, Oh or Ih. These point groups
belong to the classes of C groups, D groups and Special groups, the latter containing groups
that possess special symmetries, i.e. tetrahedral, octahedral and icosahedral.

Karnataka State Open University Page 9

Group theory and its applications Block 4.1.1

It is important to note that the point groups to which a molecule belongs ultimately depends
on its exact molecular geometry and its specific configuration and conformation. Without
knowledge of the exact configuration or conformation, the determination of its point group is
impossible. For example the staggered and ecliptic conformations of ethane, or the chair and
boat conformations of cyclohexane have different symmetry properties. Similarly, the
stereoisomers cis- and trans-1,2-dichlorocyclopropane have different configurations and
therefore different symmetry properties belonging to different point groups.
The symmetry of a molecule in terms of one symmetry element (e.g. a rotation axis) provides
information only about this property. For example, each of BF3 and NH3 possesses a 3-fold
axis of symmetry, but their structures and overall symmetries are different. BF3 is trigonal
planar and NH3 is trigonal pyramidal. On the other hand, description the symmetries of these
molecules in terms of their respective point groups (D3h and C3v), provides information about
all their symmetry elements.
Note: It is not essential to memorize the symmetry elements of a particular point group.
Which are widely available and are listed in character tables. Table 1 summarizes the most
important classes of point group and gives their characteristic types of symmetry elements; E
is, of course, common to every group.

Table 1 Characteristic symmetry elements of some important classes of point groups. The
characteristic symmetry elements of the Td, Oh and Ih are omitted because the point groups are
readily identifie). No distinction is made in this table between σv and σd planes of symmetry.

Some particular features of significance are given below.

1.8.1 C1 point group
Molecules that appear to have no symmetry at all must possess the symmetry element E and
effectively possess at least one C1 axis of rotation. Therefore they belong to the C1 point

Karnataka State Open University Page 10

Group theory and its applications Block 4.1.1

group, although since C1 = E, the rotational symmetry operation is ignored when we list the
symmetry elements of this point group.

1.8.2 C∞v point group

C∞ signifies the presence of an ∞-fold axis of rotation, i.e. that possessed by a linear molecule
(Figure 9) . For the molecular species to belong to the C∞v point group, it must also possess
an infinite number of σv planes but no σh plane or inversion centre. These criteria are met by
asymmetrical diatomics such as HF, CO and [CN], and linear polyatomics molecules that do
not possess a centre of symmetry, e.g. OCS and HCN.

Figure 9: Linear molecular species can be classified according to whether they possess a
centre of symmetry (inversion centre) or not. All linear species possess a C∞ axis of rotation
and an infinite number of σv planes. In (a) two such planes are shown and these planes are
omitted from (b) for clarity. Diagram (a) shows an asymmetrical diatomic belonging to the
point group C∞v, and (b) shows a symmetrical diatomic belonging to the point group D∞h.

1.8.3 D∞h point group

Symmetrical diatomics (e.g. H2, [O2]2-) and linear polyatomics that contain a centre of
symmetry (e.g. [N3]-, CO2, HC≡CH) possess a σh plane in addition to a C∞ axis and an
infinite number of σv planes. These species belong to the D∞h point group.
1.8.4 Td, Oh and Ih point groups
Molecular species that belong to the Td, Oh or Ih point groups possess many symmetry
elements (Figure 10), although it is seldom necessary to identify them all before the
appropriate point group can be assigned. Species with tetrahedral symmetry include SiF4,
Karnataka State Open University Page 11
Group theory and its applications Block 4.1.1

[ClO4] , [CoCl4]2- [NH4] +, P4 and B4Cl4. Those with octahedral symmetry include SF6,
[PF6]- , W(CO)6 and [Fe(CN)6]3-

Figure 10: The tetrahedron (Td symmetry), octahedron (Oh symmetry) and
icosahedron (Ih symmetry) possess four, six and twelve vertices respectively,
and four, eight and twenty equilateral-triangular faces respectively.
There is no centre of symmetry in a tetrahedron but there is one in an octahedron, and this
distinction has consequences with regard to the observed electronic spectra of tetrahedral and
octahedral metal complexes. Members of the icosahedral point group are uncommon, e.g.
[B12H12]2- shown in figure 11.

Figure 11: The molecular structures of (a) P4, (b) B4Cl4 (c) [W(CO)6] and (d) [B12H12]2-

Karnataka State Open University Page 12

Group theory and its applications Block 4.1.1

1.9 Determining the point group of a molecule or molecular ion

The application of a systematic approach is essential for the assignment of a point group,
otherwise the symmetry elements will be missed, as a consequence an incorrect assignment is
made. Figure 12 shows a procedure that may be adopted. Some of the less common point
groups (e.g. Sn, T, O) are omitted from this. Notice that it is not necessary to find all the
symmetry elements (e.g. improper axes) in order to determine the point group.

Figure 12: Scheme for assigning point groups of molecules and molecular ions. Apart from the
cases of n = 1 or ∞, n most commonly has values of 2, 3, 4, 5 or 6.

Let us illustrate the application of Figure 10 using some worked examples. Before assigning a
point group to a molecule, it is necessary to determine its structure by microwave
spectroscopy, or X-ray, electron or neutron diffraction, etc…. methods.
a) Determination of the point group for trans-N2F2 molecule
First draw the structure.

Karnataka State Open University Page 13

Group theory and its applications Block 4.1.1

Apply the strategy shown in Figure 12

START
1) Is the molecule linear? No
2) Does trans-N2F2 have Td, Oh or Ih symmetry? No
3) Is there a Cn axis? Yes; ( a C2 axis perpendicular the plane of the paper and
passing through the midpoint of the N=N bond)
4) Are there two C2 axes perpendicular to the principal axis? No
5) Is there a σh plane (perpendicular to the principal axis)? Yes STOP
The point group is C2h.
b) Determination of the point group for PF5
First, draw the structure.

It is important to remember that in the trigonal bipyramidal arrangement, the three equatorial
F atoms are equivalent, and the two axial F atoms are equivalent.
Apply the strategy shown in Figure 12
START
1) Is the molecule linear? No
2) Does PF5 have Td, Oh or Ih symmetry? No
3) Is there a Cn axis? Yes ( a C3 axis containing the P and two axial F atoms)
4) Are there three C2 axes perpendicular to the principal axis? Yes (each lies
along a P-Feq bond)
5) Is there a σh plane (perpendicular to the principal axis)? Yes (it contains the P
and three F eq atoms). STOP
The point group is D3h.
c) Determination of the point group for POCl3
First, draw the structure

Karnataka State Open University Page 14

Group theory and its applications Block 4.1.1

Apply the strategy shown in Figure 12.

START
1) Is the molecule linear? No
2) Does POCl3 have Td, Oh or Ih symmetry? No
(Remember that although this molecule is closely considered as being tetrahedral in shape, it
does not possess tetrahedral symmetry)
3) Is there a Cn axis? Yes ( a C3 axis running along the O-P bond)
4) Are there 3 C2 axes perpendicular to the principal axis? No
5) Is there a σh plane (perpendicular to the principal axis)? No
6) Are there n σv planes (containing the principal axis)? Yes (each contains the
one Cl and the O and P atoms. STOP
The point group is C3v.

d) Determination of the point group for cyclic structure of S8

First, draw the structure
Three projections of the cyclic structure of S8 are shown below. All S-S bond distances and
all S-S-S bond angles are equivalent.

START
1) Is the molecule linear? No
2) Does S8 have Td, Oh or Ih symmetry? No
3) Is there a Cn axis? Yes (a C4 axis running through the centre of the ring,
perpendicular to the plane of the paper in diagram (a)
4) Are there 4 C2 axes to the principal axis? Yes (these are most easily seen from
diagram (c)
5) Is there a σh plane (perpendicular to the principal axis)? No

Karnataka State Open University Page 15

Group theory and its applications Block 4.1.1

6) Are there n σd planes (containing the principal axis)? Yes (these are most
easily seen from diagrams (a) and (c) STOP
The point group is D4d.
1.10 Summary of the unit
The symmetry of molecules is important for understanding the structures and properties of
compounds. In chemistry, many phenomena may be easily explained by consideration of
symmetry. The systematic discussion of symmetry is called group theory.
Atoms or groups in molecules are called symmetry equivalent if they have the same atomic
number or chemical constitution, and if they can be transposed into each other by the
application of symmetry operations. This equivalency plays an important role in the chemical
properties of these atoms or groups, and in the process of stereo differentiation of these
positions.
Symmetry operations are geometrical operations applied to molecules. The application of a
symmetry operation to a particular molecular geometry produces a spatial orientation which
is indistinguishable from the initial orientation. For example, rotating a water (H2O) molecule
by 180° about an axis bisecting the H-O-H bond angle will produce a orientation of that
molecule which looks the same as its original orientation. In fact, this rotation leads to an
exchange of both protons Ha and Hb, but as these two protons may not be distinguished from
each other, the resulting orientation of the water molecule is equivalent to the initial one.
Another rotation of 180° about this axis leads to an orientation which is identical to the
starting geometry.
The five basic symmetry operations that need to be considered are identity, rotation,
reflection (mirroring), inversion, and rotary reflection. The symmetry properties of molecules
are described as the set (combination) of valid symmetry operations for its molecular
geometry. For each symmetry operation there is a corresponding symmetry element, with
respect to which the symmetry operation is applied. For example, the rotation (a symmetry
operation) is carried out around an axis which is the corresponding symmetry element. Other
symmetry elements are planes (for reflections) and points (for inversions). All spatial points
along these symmetry elements (i.e. the symmetry plane, axis, or center of inversion) do not
change their positions during the corresponding symmetry operation. Common to all
symmetry operations is that the geometrical center of a molecule does not change its position,
all symmetry elements must intersect in this center. In fact, out of the five symmetry
operations mentioned above only two (rotation and rotary reflection) are sufficient to describe
all symmetry properties of molecules.
Karnataka State Open University Page 16
Group theory and its applications Block 4.1.1

Identity Operation (E)

The identity operation does nothing and leaves any molecule unchanged, the corresponding
symmetry element is the entire object (molecule) itself. The reason for including this
symmetry operation is that some molecules have only this symmetry element and no other
symmetry properties. Another reason is the logical completeness of the mathematical
description of group theory.
All molecules which do not have any other symmetry element than the identity operation
must belong to the C1 point group (see below), and thus must be chiral. Many natural
compounds like carbohydrates and α-amino acids belong to this group. However, all
molecules belonging to the C1 point group must be chiral, but the reverse conclusion is not
true. Chiral molecules may not necessarily be a member of the C1 point group family.
Inversion (i)
The inversion (the symmetry operation) through a center of inversion (the symmetry element,
which must be identical to the center of geometry of the molecule) takes any point in the
molecule, moves it to the center, and then moves it out the same distance on the other side
again (sometimes called point reflection). The benzene molecule, a cube, and spheres do have
a center of inversion, whereas a tetrahedron does not.
At this point, it should be noted, that molecules which contain a center of inversion as the
only symmetry element (except for the identity operation, which occurs in all molecules),
belong to the Ci point group. However, if a center of inversion is present in a molecular
geometry, the corresponding compound must be achiral, irrespective of any other type or
number of symmetry elements (mirror planes, rotation or rotary-reflection axes) which may
be present in addition.
Reflection (σ)
The reflection (the symmetry operation) in a plane of symmetry or mirror plane σ (the
corresponding symmetry element) produces a mirror image geometry of the molecule (this
symmetry operation is not present in chiral molecules). The mirror plane bisects the molecule
and must include its center of geometry. If this plane is parallel to the principal axis, it is
called a vertical mirror plane denoted σv, if it is perpendicular to the principal axis, it is
denoted a horizontal mirror plane σh. Vertical mirror planes bisecting the angle between two
Cn axes are called dihedral mirror planes σd.
The benzene molecule features all three different types of mirror planes for benzene σv and σd
planes coincide.

Karnataka State Open University Page 17

Group theory and its applications Block 4.1.1

Molecules which contain a single mirror plane as the only symmetry element belong to the Cs
point group, but any number of mirror planes will automatically result in achiral molecular
geometries.
n-Fold rotation Cn
The n-fold rotation (the symmetry operation) about a n-fold axis of symmetry (the
corresponding symmetry element) produces molecular orientations indistinguishable from the
initial for each rotation of 360°/n (clockwise and counter-clockwise). A water molecule has a
single C2 axis bisecting the H-O-H bond angle, and benzene has one C6 axis (amongst one C3
axis and seven C2 axes of which the C3 and one C2 axis coincide with the C6 axis). Linear
molecules display a C∞ axis (any infinitely small rotation about this axis produces unchanged
orientations), and perfect spheres posses an infinite number of symmetry axes along any
diameter with all possible integral values of n. If a molecule has one (or more) rotation axes
Cn or Sn, the axis with the greatest n is called the principal axis.
n-Fold rotary reflection (Sn)
The n-fold rotary reflection (or n-fold improper rotation, the symmetry operation) about an n-
fold rotary reflection axis (or n-fold axis of improper rotation) is composed of two successive
geometry transformations: first, a rotation through 360°/n about the axis of that rotation, and
second, reflection through a plane perpendicular (and through the molecular center of
geometry) to that axis. Neither of these two operations (rotation or reflection) alone is a valid
symmetry operation, but only the outcome of the combination of both transformations.
For example, a methane molecule has three S4. Any molecule featuring a Sn axes must be
achiral. In fact, the most general description of chirality is the absence of any Sn rotary
reflection in a molecular geometry.
Out of the five symmetry operations mentioned above only two (rotation and rotary
reflection) are sufficient to describe all symmetry properties of molecules. The identity
operation is equivalent to a C1 axis of rotation, as rotation of all objects around 360° about
any axis produces the initial orientation only. On the other hand, a mirror plane is equivalent
to a S1 axis of rotary-reflection perpendicular to that plane. In addition, a center of inversion
can be represented by a S2 axis of improper rotation with any arbitrary orientation of this axis.
Symmetry operations may not be combined arbitrarily with each other, but only in a limited
number of variations which are the so called point groups. Some symmetry operations
implicitly imply others, as for example any S4 or C4 axis must be accompanied by a parallel
C2 axis. For example in benzene, the principal C6 axis simultaneously must be a C3 and a C2

Karnataka State Open University Page 18

Group theory and its applications Block 4.1.1

axis of symmetry, too. Similarly, any Sn axis with odd n is identical to a Cn axis in
conjunction with a horizontal mirror plane σh.
However, certain combinations of some symmetry operations implicitly generate other
symmetries. For example, the combination of any Cn axis with even n, together with a center
of inversion i implicitly generates a horizontal mirror plane σh (which is perpendicular to the
Cn axis and runs through the inversion center). Similarly, the combination of any Cn axis
with a vertical mirror plane σv must imply (n - 1) additional vertical mirror planes σv.
In addition, combinations of two rotation axes or two rotary-reflection axes must imply a new
rotation axis, and combining a rotation axis with a rotary-reflection generates another rotary-
reflection axis.
1.11 Key words
Symmetry operations; Symmetry elements; n-fold axis of symmetry; Plane of symmetry
(mirror plane); Centre of symmetry (inversion centre); Identity operator; Point groups; C1
point group; C∞v point group; D∞h point group; Td, Oh and Ih point groups
1.12 References for further studies
1) Group theory and Symmetry in Chemistry; Gurdeep Raj; Ajay Bhagi; Vinod Jain; Krishna
Prakashan Media; 2012.
2) Symmetry: An Introduction to Group Theory and Its Applications; R. McWeeny; Courier
Corporation, 2002.
3) Symmetry and Group theory in Chemistry; M Ladd; Elsevier, 1998.
4) Molecular Symmetry and Group Theory; Robert L. Carter; Wiley India Pvt. Limited, 2009.
5) Introduction to Symmetry and Group Theory for Chemists; Arthur M. Lesk; Springer
Science & Business Media, 2007.
6) Group Theory and Chemistry; David M. Bishop; Courier Corporation, 2012.
1.13 Questions for self understanding
1) Benzene, borazine, pyridine and S6 contain a 6-membered ring. Explain why only
benzene contains a 6-fold principal rotation axis?
2) Among the following, which molecule contain a 4-fold principal rotation axis: CF4,
SF4, [BF4]- and XeF. Explain why?
3) Draw the structure of [XeF5]-. On the diagram, mark the C5 axis. The molecule
contains five C2 axes. Where are these axes located?
4) Draw the structure of B5H9. Where is the C4 axis located in this molecule?
5) N2O4 is planar. Show that it possesses three planes of symmetry.

Karnataka State Open University Page 19

Group theory and its applications Block 4.1.1

6) B2Br4 has the following staggered structure. Show that B2Br4 has one less plane of
symmetry than B2F4 which is planar.
7) Ga2H6 has the following structure in the gas phase. Show that it possesses three planes
of symmetry.
8) Show that the planes of symmetry in benzene are one σh, three σv and three σd.
9) Draw the structures of each of the following species and confirm that each possesses a
centre of symmetry. CS2, [PF6]-, XeF4, I2, [ICl2]-.
10) [PtCl4]2- has a centre of symmetry, but [CoCl4]2- does not. One is square planar and
the other is tetrahedral. Which is which? Explain why?
11) Why does CO2 possess an inversion centre, but NO2 does not?
12) CS2 and HCN are both linear. Explain why CS2 possesses a centre of symmetry
whereas HCN does not?
13) Explain why BF3 possesses an S3 axis, but NF3 does not.
14) C2H6 in a staggered conformation possesses an S6 axis. Show that this axis lies along
the C–C bond.
15) The CH4 molecule has 3 S4 axes. On going from CH4 to CH2Cl2, are the S4 axes
retained? Justify your answer.
16) How do the rotation axes and planes of symmetry in cis- and trans-N2F2 and
HFC=CHF differ?
17) How many planes of symmetry do (a) F2C=O, (b) ClFC=O and (c) [HCO2] possess?
18) The symmetry operators for NH3 are E, C3 and 3σv. (a) Draw the structure of NH3.
(b) What is the meaning of the E operator? (c) Draw a diagram to show the rotation
and reflection symmetry operations.
19) What symmetry operators are lost in going from NH3 to NH2Cl?
20) Compare the symmetry operators possessed by NH3, NH2Cl, NHCl2 and NCl3.
21) Draw a diagram to show the symmetry operators of NClF2.
22) Write a note on symmetry operations and symmetry elements
23) With an example explain the rotation about an n-fold axis of symmetry
24) With an example explain the reflection through a plane of symmetry (mirror plane)
25) With an example explain the reflection through a centre of symmetry (inversion centre)
26) What are identity operators?
27) What are successive operations?
29) What are Point groups?
30) Explain the followings with suitable example
Karnataka State Open University Page 20
Group theory and its applications Block 4.1.1

a) C1 point group.
b) C∞v point group
c) D∞h point group
d) Td, Oh and Ih point groups
31) Explain the procedure followed for determining the point group of a molecule.
32) Determine the point group for trans-N2F2 molecule.
33) Determine the point group for PF5 molecule.
34) Determine the point group for POCl3 molecule.

Karnataka State Open University Page 21

Group theory and its applications Block 4.1.1

UNIT-2
Structure
2.0 Objectives of the unit
2.1 Introduction
2.2 Properties of a group
2.3 Abelian and non- abelian group
2.4 Oder of a group (h)
2.5 Group generating elements
2.6 Sub Group
2.7 Class of a Group [Classes in a group]
2.8 An important note on classes
2.9 Group multiplication tables for symmetry operation of simple molecules
2.10 Isomorphism
2.11.1Similarity transformation
2.12 Classes
2.13 Group multiplication table
2.13 Important characteristics of a group multiplication table
2.14 Symmetry classification of molecules into point groups
2.15 Difference between point group and space group
2.16 Summary of the unit
2.17 Keywords
2.18 References for further studies
2.19Questions for self understanding

Karnataka State Open University Page 22

Group theory and its applications Block 4.1.1

2.0 Objectives of the unit

After studying this unit you are able to

List the different properties of a group

Explain the differences between bbelian and non- abelian s

Calculate the order of given group (h)

Recognize the group generating elements
2.1 Introduction
A subgroup is a “group within another group”- a subset of group elements. A supergroup is a
group obtained by adding new elements to a group (to give a larger group). The order of any
subgroup g of a group of order h must be a divisor of h: h/g = k where k is an integer.
A is said to be conjugate with B, if there exists any element of the group, X, such that (i) A =
X−1BX. Every element is conjugate with itself. (ii) If A is conjugate with B, then B is
conjugate with A. (iii) If A is conjugate with B and C, then B and C are conjugate with each
other.
A complete set of elements that are conjugate to one another within a group is called a class
of the group. The number of elements in a class is called its order. The orders of all classes
must be integral factors of the order of the group
2.2 Properties of a group
The elements of all groups obey a simple set of rules. These rules are
1. The product of any two elements of a group must also be an element of the group.
Ex. Consider C2v group
σ v1 × σ v = C 2
2. Products of elements are associative (Associative law).
Ex. Consider C2v group
(σ 1
v )
× σ v C 2 = σ v1 (σ v × C 2 )

[Note: According to correction the multiplication inside the brackets is carried out first]
3. The group contain an element which when used to multiply any other element leaser it
unchanged such an element is called identity and represent by the letter E (or I)
Ex. C2*E = E*C2=C2
4. Each element of a group has an inverse which is also an element of the group.
Ex. In C3v group C3 and C 3−1 are inverse of one another.

C3 = C 3−1 , E is its own inverse

Karnataka State Open University Page 23

Group theory and its applications Block 4.1.1

2.3 Abelian and non- abelian group

An abelian group is one in which all the elements commute with each i.e for any two
elements P and Q
P*Q = Q*P
Ex. C2v group → elements are E, C2 and σ v , σ v1

C 2 × σ v = σ v1 σ v * C 2 = σ v1
∴ C2 * σ v = σ v * C2
Simialrly
σ v * σ v1 = σ v1 * σ v = C 2
∴ C2v group an Abelian group
There are only a few abelian group. Some examples are: Cn, Sn Cnn, C2v D2 and D2h. D3h is a
non abelian group.
2.4 Oder of a group (h)
The order of the group is similarly the total number of elements in the group. For example, in
C2v group the order is form there exits there are some elements namely E, C2, σ v and σ v1 . In

C3v there are six elements E, C3, C 32 , σ v , σ v1 ∆σ v11 therefore the ordering C3r is six.

2.5 Group generating elements

In a given group there will be a small minimum number of elements called a ‘subset’. The
elements of this subset are called group generating elements or group generators. These group
generators can generate all the elements of the group.
Example.
i) C3 group has the elements E1 , C 31 , C 32 C 31 is the group generate

C31 * C32 = C32

C31 * C31 * C31 * C31 = E

ii) In C2v group σ v and σ v1 are group generator elements

σ v * σ v = E , σ v * C2 = σ v , σ v * E = C 2

iii) D3h has twelve elements of symmetry

E , C1 , C 2 , C , C1 , C11, σ , σ 1 , σ 11, σ , S1 , S 5
3 3 2 2 2 v v v n 3 3

The group generating elements are C1 , C perpendicular to C1 and σ n

3 2 3

Karnataka State Open University Page 24

Group theory and its applications Block 4.1.1

[Group generating elements or group generators will be useful in arriving at the point group
of a molecule.]
2.6 Sub Group
Smaller groups which can be found within a bigger group are called subgroups. The subgroup
must obey all the condition to be called a group. There are two types of subgroups, they are
1) Trivial subgroup, in which there is only one element E and the order of this subgroup is
one.
2) Non trivial subgroup, in which elements E is invariably present and order of these groups
begin with two
If the order of the subgroup is ‘g’ and that of full group is ‘h’ then h/g=k where ‘k’ is an
integer
Examples.
i. C1 group has no subgroup it has only element E.
ii. C2v ( elements E , σ n , σ v' , C2 ) has trivial subgroup E and more subgroups

C2→E, C2
(
C2→E, σ v ∆C s1 
→ E , σ v1 )
iii. C3v (elements E , C3' , C32 , σ v , σ v' , σ v'' ) h=6 the subgroups are

g h
g
C1 → E 1 6
C 3 → E , C 31 , C 32 3 2
C s → E,σ v 2 3
C s1 → E , σ v1 2 3
C s11 → E , σ v11 2 3
Note:
1. All subgroup contain the element E.
2. The elements of a full group may or may not commute but elements of subgroup do
necessarily commute. Therefore the subgroups are always Abelian.
2.7 Class of a Group [Classes in a group]
We have already seen how it is possible to select sets of elements constituting subgroup.
There is another way of sorting out elements of a point group into what is called classes in
order to understand how to rearrange elements into classes we need to know a new operation
called ‘smillarity transformation’

Karnataka State Open University Page 25

Group theory and its applications Block 4.1.1

If A and B are the elements of a group and X is another elements of the same group such that
X-1AX = B where X-1 is the inverse X.
The product B is called ‘similarity transform of A by X. A and B are called conjugate
elements. the following are three elements is conjugate elements
1. Every element is conjugate with itself X-1A X = A.
2. If A is conjugate with B then B is conjugate with AX-1AX = B. B is the similarity
transform of A by X. Also there must be an element Y in the group such that
Y-1BY= A, i.e A is the similarity transforms of B by Y.
3. If A is conjugate with B and C then B and C conjugate with each other (Law of
Associative conjugation)
i.e if X-1AX = B and Y-1AY = C then X-1BX = C and Y-1CY = B.
A class of a group is now defined as ‘a set of elements which are conjugate to one another’.
Example: C 3v → E , C 31 , C 32 , σ v , σ v1 , σ v11

Work out the similarity transform of each of the above six elements with every other element.
Also use the group multiplication table of C3v group to work out the products of similarity
information.

Since σ v , σ v1 , σ v11 are their own inverse and C31 and C32 are the inverse of each other the
following similarity transformation can be written on E, to begin with
E
E E E =E
C32 E C31 = E
C31 E C32 = E
σv E σv = E
σ v' E σ v' = E
σ v'' E σ v'' = E

In all these transformation E has come out as its own similarity transformation i.e, E is self
conjugate. Therefore the conclusion from this exercise is that E is in a class by itself and the
order of this calss is always one, irrespective of the point group it belongs to. This class is
called ‘trivial class ‘
The similar transformation of C31 , C32 can be worked out as given below

Karnataka State Open University Page 26

Group theory and its applications Block 4.1.1

C31 C32

E C31 E = C31 E C32 E = C32

C32 C31 C31 = C31 C32 C32 C31 = C32
C31 C31 C32 = C31 C31 C32 C32 = C32
σ v C31 σ v = C31 σ v C32 σ v = C32
σ v' C31 σ v' = C31 σ v' C32 σ v' = C32
σ v'' C31 σ v'' = C31 σ v'' C32 σ v'' = C32
From these two exercises it is clear that C31 and C32 are mutually conjugate hence they can be
in one class. The order of this class is 2. We can similarly work through the exercises for
σ v ,σ v' , σ v'' but the product transformation will not be that straight forward
σv σ v' σ v''
E σv E =σ v E σ v' E = σ v' E σ v'' E = σ v''
C32 σ v C31 = σ v'' C32 σ v' C31 = σ v C32 σ v'' C31 = σ v'
C31 σ v C32 = σ v' C31 σ v' C32 = σ v'' C31 σ v'' C32 = σ v
σ v σ v σ v =σ v σ v σ v' σ v = σ v'' σ v σ v'' σ v = σ v'
σ v' σ v σ v' = σ v'' σ v' σ v' σ v' = σ v' σ v' σ v'' σ v' = σ v
σ v'' σ v σ v'' = σ v' σ v'' σ v' σ v'' = σ v σ v'' σ v'' σ v'' = σ v''

All the planes σ v ,σ v' , σ v'' are in one class of order three. While working out the similarity

transformation on one of these planes say σ v , if the product transformation occur as σ v ,σ v' , σ v''

then it is not really necessary to carry through the exercise on σ v' and σ v'' . By recourse to

property of associative conjugation one can conclude that the three planes can be put into one
class i.e the plane ( σ v) and its two products transforms. σ v' and σ v''

Since similarity transformation involves the sequential operation of three elements, it is

sometimes difficult to work out the product transforms. We can adopt one of the two
following methods i.e,
i) Use of groups multiplication tables and/or
ii) Use of the molecular geometry for figurative illustration as shown below
Similarly transforms of C31

σ v C31σ v = C32 or
(σ C )σ
v
1
3 v = σ v' σ v = C32

Karnataka State Open University Page 27

Group theory and its applications Block 4.1.1

C3 axes and σ v plans are as in (I) planes always retain their orientation with respect to the
original configuration (I) of the molecule. Axes and planes do not move with operation
It is rather easy to visualize the transforms of C31 and C 32 . And for σ v , σ v' and σ v'' planes the

the transformation such as

Eσ vE = σ v Eσ v' E = σ v' Eσ v'' E = σ v''
σ vσ vσ v = σ v σ v' σ v' σ v' = σ v' σ v''σ v''σ v'' = σ v''

2.8 An important note on classes

A perusal of all the point groups reveals that there are only six types of Abelian groups and
all others are non-Abelian. The Abelian groups are

Cn, Cnh , C2v , D2 , D2h and Sn (n = even)

Based on this information we can further state
i. In all Abelian point groups each element is in a class by itself i.e the number of
symmetry elements of order o the group is equal to the number of classes.
Number of classes = h (order of the group)
ii. In non-Abelian groups the number of classes is always less than the order of a
group.
iii. No element of the group occurs in more than one class.
Some hints on classes
i. E is always in a class by itself i.e, E is transformed into itself by all the elements
of the group.
ii. Inversion elements ‘I’ is in a class by itself.
iii. All C nm axes are in a class.

iv. Similar C2s are in one class.

v. S nm axes like C nm are in a class if there are two or more many such types, they are

placed in as many classes.

vi. Similar vertical planes (σ v ) and similar dihedral planes (σ d ) are in separate

classes.
vii. Horizontal plane is a special plane (σ n ) and is always placed in a different class

from other planes.

Karnataka State Open University Page 28

Group theory and its applications Block 4.1.1

2.9 Group multiplication tables for symmetry operation of simple molecules

Group Multiplication Table (GMT) represents all possible products of elements of a group in
the form of a table.
Consider a molecule having ‘h’ symmetry elements. Then there will be ‘h2’ products of
symmetry elements. These can be presented as GMT. This consists of ‘h’ rows and ‘h’
columns. Each row and each column is tabulated with a group element. The entry in the table
under a given column in a given row is the product of elements which head that column and
that row. The operation which first applied is in the top of the column.
Example, C2v------- E, C2, σ v , σ v'

C2v E C2 σv σ v'
E E C2 σv σ v'
C2 C2 E σ v' σv

σv σv σ v' E C2

σ v' σ v' σv C2 E

C4 E C42 = C2 C41 C43

E E C2 C41 C43

C42 = C2 C2 E C43 C41

C41 C41 C43 C2 E

C43 C43 C41 E C2

This group with its GMTs written either way is isomorphic only with an abstract group G 24 of
the same order consisting of E A B and C elements. The one-to-one correlation of their
elements is thus given as
A← → C 41 ; C ←
→ C 2 ; B ← → C 43

Like A of G 24 , C2 is its own inverse and C 41 and C 43 have their inverse in each other, in much
the same way as do B and C. similarly S4 group like C4 can also be shown as isomorphic with
G 24 . The GMT of S4 group is given as:

Karnataka State Open University Page 29

Group theory and its applications Block 4.1.1

S4 E C2 S 41 S43
E E C2 S 41 S43

C2 C2 E S43 S 41

S 41 S 41 S43 C2 E

S43 S43 S 41 E C2

In G14 since each element A, B or C is its own inverse the above mentioned one-to-one

correlation of its elements with those of G 24 as well as C4 is found to be absent. Therefore

G14 is not isomorphic with G 24 and C4. However a numerical group formed form a set of four

elements 1,-1, I and –I is isomorphic with both C4 and G 24 .

The only groups of order four that are isomorphic with G14 are C2h, C2v and D2 whose
multiplication tables are given below.
C2h E C2( z ) σ xy i

E E C2( z ) σ xy i

C2( z ) C2( z ) E i σ xy

σ xy σ xy i E C2( z )

i i σ xy C2( z ) E

One of the important uses of GMT is in grouping a set of elements into a class particularly in
non-Abelian groups, where a class may contain more than one element in it. Abelian or cyclic
groups however have only one element in each class. Consider the GMT for a non-Abelian
group C3v of order six.
C2v E C2( z ) σ xz σ yz

E E C2( z ) σ xz σ yz

C2( z ) C2( z ) E σ yz σ xz

σ xz σ xz σ yz E C2( z )

σ yz σ yz σ xz C2( z ) E

Karnataka State Open University Page 30

Group theory and its applications Block 4.1.1

D2 E C2( z ) C2( x ) C2( y )

E E C2( z ) C2( x ) C2( y )

C2( z ) C2( z ) E C2( y ) C2( x )

C2( x ) C2( x ) C2( y ) E C2( z )

C2( y ) C2( y ) σ xy C2( z ) E

The GMTs such as above can be used with lot of advantage for determining the product
elements of similarity transformation.
2.10 Isomorphism
Two groups are supposed to be isomorphic if they obey the following rules.
1. Both have same order and structure.
2. There is a one-to-one correspondence in all respects between the members of the two
groups.
If A1, B1, C1, D1 and A2, B2, C2, D2 are the members of the two isomorphic groups, A1
corresponds to A2, B1 corresponds to B2 and so on.
3. The relationship between the any two members of a group is exactly the same as the
relationship between the corresponding members of the other group.
Let us take the three groups listed below:
(i) E, C2
(ii) E, i
(iii) E, σh
All the three are isomorphic groups.
E = C 22 ; C2E = C2
E = i2 ; iE = i
E = σ h2 ; σhE = σh etc.

2.11.1Similarity transformation
Let A and X be the elements of a group and let us define B such that B = X-1 AX. B is called
the similarity transform of A by X, or A is said to be subjected to similarity transformation
with respect to X. If A and B are related by a similarity transformation they are called
conjugate elements (Figure 1).
Take the NH3 molecule, for instance. Z axis is the C3axis.

Karnataka State Open University Page 31

Group theory and its applications Block 4.1.1

Figure 1: Illustration of similarity transformation on NH3

There are three reflection planes. These are usually designated as follows
1. Plane formed by z-axis and NHa bond: σ’ or σa or σv’.
2. Plane formed by z-axis and NHb bond: σ’’ or σb or σv’.
3. Plane formed by z-axis and NHc bond: σ’’’ or σc or σv’.
Let us prefer the designation σ’, σ’’ and σ’’’.
Let us perform a reflection (σ’’’) with respect to the plane formed by NHc and z-axis. Let us
perform σ again. σ’’’2 = E.
Now let us find the similarity transform of C3 w.r.t. σ’’’, i.e., (σ’’’)-1C3σ’’’ = ?
It is seen from the Fig. that (σ’’’)-1C3σ’’’ = C 32 . Remember (σ’’’) = (σ’’’)-1. Thus C3 and C 32
are conjugate elements.
The following rules about conjugate elements are notable
1. Every element is conjugate of itself because every element is the similarity transforms
of itself w.r.t. identity (E) : E = E-1 and A = E-1 AE.
2. If A is the conjugate of B then B is the conjugate of A. This means that if A is the
similarity transform of B by X, B is the similarity transform of A by X-1. We have
A = X-1BX
But (X-1)-1AX-1 = XA X-1 = X (X-1BX) X-1
= (XX-1) B (XX-1) = B (associative law)
3. If A is the conjugate of B and B is the conjugate of C, then A, B and C are mutually
conjugate.

Karnataka State Open University Page 32

Group theory and its applications Block 4.1.1

2.12 Classes
A complete set of elements which are conjugate to one another is called a class of the group.
Let us consider NH3. Set us the coordinate system in such a manner that ZNHa is in the yz
plane. (Fig. 1) σ’ is then σyz. Without disturbing the NH3 molecule rotate the coordinate
system by 120° w.r.t z axis, i.e., subject the coordinate system to C3. Now yz plane is ZNHb.
σyz is σ’, σ’’and σ’’’are equivalent. σ’ becomes same as that of σ’’ if we change the
coordinate system by a symmetry operation (C3) of the point group. σ’ and σ’’ are therefore
in the same class.
Example:
Show that the three reflections of NH3 constitute a class. It is not difficult to show that

C 32 C 3 = E . Hence, C32 = (C3 )

−1

Let as perform the similarity transformation of σ’ by C3 in NH3.

C 3−1σ ' C 3 = C 32σ ' C 3 = σ ''
Thus σ’ and σ’’ are conjugate. Similarly we can show that σ’, σ’’ and σ’’’ are mutually
conjugate. Therefore σ’, σ’’ and σ’’’ form a class.
2.13 Group multiplication table
Every group is characterized by a multiplication table. The relationship between the elements
of the binary combinations is reflected in the multiplication table.

Figure 2: The Four symmetry elements of H2O molecules

Consider a water molecule. It has four symmetry elements, viz., E, C2(z), σv(xz) and σv’(yz)
(Figure 2).
We can easily show that the product of any two symmetry elements is one of the four
elements of the group. Thus, for instance, C2(z)σv(xz) = σv’(yz). Proceeding this way the
symmetry operations of H2O can be listed in a group multiplication table (GMT) as shown
below

Karnataka State Open University Page 33

Group theory and its applications Block 4.1.1

2.13 Important characteristics of a group multiplication table

1. It consists of h rows and h columns where h is the order of the group.
2. Each column and row is labeled with group element.
3. The entry in the table under a given column and along given row is the product of the
elements which head that column and the row (multiplication rule is strictly followed).
4. At the intersection of the column labeled by Y and the row labeled by X, we found the
element which is the product XY.
5. The following rearrangement theorem holds good for every ‘Group Multiplication Table’.
“Each row and each column in the table lists each of the group elements once and only once.
No two rows may be identical nor any two columns be identical. Thus each row and each
column is a rearranged list of the group elements”.
2.14 Symmetry classification of molecules into point groups
Molecules can be classified into point groups depending on the characteristic set of symmetry
elements possessed by them. A molecular group is called a point group since all the elements
of symmetry present in the molecule intersect at a common point and this point remains fixed
under all the symmetry operations of the molecule. The symmetry groups of the molecules
are denoted by specific symbols known as Schoenflies notations.
2.15 Difference between point group and space group
Symmetry operations do not alter the energy of the molecule. Further in all the above
operations the centre of the molecule is not altered as none of the operations involve a total
translational movement of the molecule. Whatever happens to the molecule, the centre (point)
is not changed. At least one point is fixed. Hence these are classified as ‘point group’
operations.
In case of crystals operations such as ‘screw rotations’ and glide plane reflections can be
additionally specified. Screw rotation involves a rotation with respect to an axis and then a
translation in the direction of the same axis. Glide plane reflection is a reflection in a plane
followed by a translation along a line in that plane. These are particular to crystals and the
classification comes under what is known as space group. Note that here even the centre

Karnataka State Open University Page 34

Group theory and its applications Block 4.1.1

changes. Thus in short, in point group, there is at least one point (centre) which is not altered
after all operations while in space group it is not possible to identify such a stationary point.
2.16 Summary of the unit
A group is a complete set of members which are related to each other by certain rules. Each
member may be called an element.
Basic properties of a group
Certain rules have to be satisfied by the elements so that they form a group. The rules are
listed below
1. The product of any two elements and the square of any element must be elements of group.
This property of the group is called closure property.
2. There must be one element in the group which commutes with every one of the elements
and leaves it unchanged.
3. The associative law of multiplication should be valid.
4. For every element there must be a reciprocal (inverse) and this reciprocal is also an
element of the group.
Rule 1
If A and B are the element of the group and if AB = C, C must be a member of the group.
Product AB means that we perform the operation B first and then operation A i.e., the
sequence of operations is from right to left. It should be noted that the other product BA need
not be same as AB.
BA means doing A first and then performing the operation B later. Let BA = D. D must be a
member of the group by rule 1. Usually AB BA and so C D. However, there may be some
special elements A and B each that AB = BA. Then A and B are said to commute with each
other or the multiplication of A and B is commutative. Such a group where any two elements
commute is called an abelian group.
H2O belongs to an abelian group. The four symmetry operations for H2O are E, C2z, σv(xz)
and σ’v(yz).The inter-relationships between these operations are given in the group
multiplication table.
Rule 2
Each group must necessarily have an element which commutes with every other element of
the group and leaves it unchanged.
Let A and B be the elements of the group. Let X be the element satisfying rule 2.
i.e. XA = AX = A and also XB = BX = B.
BA = BX2A; BX2 = B = BE, where we have set X2 = E (identity)
Karnataka State Open University Page 35
Group theory and its applications Block 4.1.1

It is clear BEn = B, n being any integer. This kind of element E which does not effect any
change when multiplied with any element is a unique element and is called an identity
operation E. For water, E, the identity operation satisfies this rule. It is so for all molecules.
Rule 3
Associative law of multiplication must be valid. This means ABCD is the same as (AB)
(CD), (A) (BCD) or (ABC) (D). ABC is the same as A(BC) or (AB)C.
Rule 4
Inverse of an element A is denoted by A-1 (this does not mean 1/A). It is simply an element of
the group such that A-1 * A = E. In case of symmetry groups, A-1 is that element which
undoes or annuls the effect of A. For H2O we have, for example, C2C2 = E. Therefore
C 2−1 = E i.e., C2 is its own inverse. This is true of all other elements for H2O. But this is not

general. For example, C 62 = C 3 ≠ E . Therefore C 6−1 is not C6 .

Order of group
The total number of elements present in a group is known as the order of the group. It is
denoted by n.
Example:
1. Water molecule belongs to C2v group of order 4 because it contains 4 elements namely E,
C2z, σv and σ’v.
2. Ammonia belongs to C3v group of order 6 as it contains 6 elements namely E, C 31 , C 32 , σv(1),

σv(2) and σv(3).

Abelian group
A group is said to be abelian if for all pairs of elements of the group, the binary combination
is commutative. That is AB = BC; BC = CB and so on. Example: The elements of C2v point
group E, C2z, σv and σ’v form an abelian group as all the elements of this group commute with
each other.
Non-abelian group
A group is said to be non-abelian if the commutative law does not hold for the binary
combinations of the elements of the group, i.e., AB ≠ BA.
Example:
The elements of C3v point group E, C 31 , C 32 , σv(1), σv(2) and σv(3) donot consecutive an abelian
group since the elements donot follow commutative law.

Karnataka State Open University Page 36

Group theory and its applications Block 4.1.1

2.17 Keywords
Group; Order of group; Abelian group; Non-abelian group; Isomorphism; Similarity
transformation; Classes; Group multiplication table; point groups; Space group
2.18 References for further studies
1) Group theory and Symmetry in Chemistry; Gurdeep Raj; Ajay Bhagi; Vinod Jain; Krishna
Prakashan Media; 2012.
2) Symmetry: An Introduction to Group Theory and Its Applications; R. McWeeny; Courier
Corporation, 2002.
3) Symmetry and Group theory in Chemistry; M Ladd; Elsevier, 1998.
4) Molecular Symmetry and Group Theory; Robert L. Carter; Wiley India Pvt. Limited, 2009.
5) Introduction to Symmetry and Group Theory for Chemists; Arthur M. Lesk; Springer
Science & Business Media, 2007.
2.19 Questions for self understanding
1) Explain why a set of numbers cannot form a group by the process of division.
2) Explain why the set of integers between 0 and µ do not form a group under the process of
multiplication.
3) Construct the multiplication table for the C3v point group to which NH3 molecule belongs.
4) Draw the structure of three distinct isomers of C2H2Cl2 and determine their point groups.
Which of them is polar?
5) Discuss the general properties of a group.
6) What are Abelian and non- abelian group?
7) What is mean by oder of a group (h)? Give one example.
8) Write a note on group generating elements.
9) What is mean by sub group?
10) What is mean by classes?
11) Write a note on group multiplication tables.
12) Explain Isomorphism.
14) What is similarity transformation?
15) Discuss the Important characteristics of a group multiplication table.
16) Discuss Symmetry classification of molecules into point groups.
17) Explain the differences between point group and space group.

Karnataka State Open University Page 37

Group theory and its applications Block 4.1.1

UNIT-3
Structure
3.0 Objectives of the unit
3.1 Introduction
3.2 Representation
3.3 Reducible Representation
3.4 Block diagonal matrices
3.5 The trace of a matrix
3.6 Properties of irreducible representations
3.7 Symbols used for representing irreducible representation
3.8 Motions of H2O
3.9 Point Group Representations
3.10 Summary of the unit
3.11 Key words
3.13 References for further studies
3.14 Questions for self understanding

Karnataka State Open University Page 38

Group theory and its applications Block 4.1.1

3.0 Objectives of the unit

After studying this unit you are able to

Explain the different types of representation

Identify the reducible and reducible representation in a character table

Explain the block diagonal matrices

Explain the trace of a matrix

List the properties of irreducible representations

Write the symbols used for representing irreducible representation
3.1 Introduction
The group representation plays a very important role in deducing the consequence of the
symmetries of the system. Roughly speaking, representation of a group is just some way to
realize the same group operation other than the original definition of the group. Of particular
interest to most phyical application is the realization of group operation by the matrices
whose multiplication operation can be naturally associated with group multiplication.
The basis is comprised by the labels attached to objects.
For molecules the objects can be:
1. Atoms
2. Coordinates
3. Orbitals
4. Bonds
5. Angles
The number of basic functions or labels is called the dimension.
For example, when considering molecular motions, we can assign coordinates x, y and z to
each atom. There are three coordinates for N atoms to give a total dimension of 3N.

C2(z) gives (xi → -xj), (yi→ -yj), and (zi→ +zj) where i = j for O coordinates since the O lies
along C2. But i ≠ j for the H since they do not lie along C2 and are therefore rotated into one
another, e.g., x2 → -x3. We can represent this transformation in matrix notation where each
atom will have a 3 x 3 matrix,

Karnataka State Open University Page 39

Group theory and its applications Block 4.1.1

The trace of the matrix is the sum of the diagonal elements. In this case it is -1.
3.2 Representation
The set of matrices corresponding to the symmetry operations of a group is called its
representation. Representations can be classified into
(a) Reducible representations (reps) and
(b) Irreducible representations (irreps).
Just watch what happens after the molecule undergoes each symmetry aoperation in the point
group (E, C2, 2σ)

Let us consider the C2h point group as an example. E, C2, σh and I are the four symmetry
operations present in the group. The matrix representation for this point group is given below

In the case of C2h symmetry, the matrices can be reduced to simple matrices with smaller
dimentions i.e., (1x1) matrices
3.3 Reducible Representation
A representation of a symmetry operation of a group, which can be expressed in terms of a
representation of lower dimension is called reducible representation. Or
A representation of higher dimension which can be reduced in to representation of lower
dimension is called reducible representation. They can be broken down into a simpler form
and the characters can be further diagonalized.

Karnataka State Open University Page 40

Group theory and its applications Block 4.1.1

Reducible representations are called block matrices. Example, each matrix in the C2v matrix
representation can be block diagonalized. To block diagonalize, make nonzero element into a
1x1 matrix.

3.4 Block diagonal matrices

A block diagonal matrix is a special type of matrices and it has blocks of number through its
diagonal and has zeros elsewhere.

3.5 The trace of a matrix

The trace of a matrix (χ) is the sum of its diagonal elements. i.e, χ ( A) = ∑ a ii
i

χ = 31 + 2sinθ
Because the sub-block matrices cannot be further reduce, they are called irreducible
representations. The original matrices are called reducible representations.
Irreducible representations
It ii is not possible to perform a similarity transformation matrix which will reduce the
matrices of representation T, then the representation is called irreducible representation. In
general all 1D representations are examples of irreducible representations.
The symbol Γ is used for representations

Karnataka State Open University Page 41

Group theory and its applications Block 4.1.1

Where Γred – Γ1 Γ2 Γ3………….Γn

3.6 Properties of irreducible representations
Rule 1. The sum if the square f the dimensions of the IRs of a group is equal to the order of
the group h (no proof).

∑l i
2
=l12 + l 22 + − − − − − − −− = h
2
Rule 1 can be written as ∑ [x (E )]
i
i =h

Since [xi (E )] the character of the representation of E in the ith IR = order of the
representation.
Rule 2. The sum of the square of the characters in any IR = h
2
∑ [x (R )]
R
i = h (simple test for irreducibility)

Rule 3. The vectors whose components are the characters of two different IRs are orthogonal

∑ x (R )x (R ) = 0
R
i j

Rules 4. In a given reducible or irreducible representation the character of all matrices belong
to the dame class are identical
Rule 5. The number of IRs = number of classes in a group.
From rlues 2 and 3.

∑ x (R )x (R ) = hδ
R
i j ij

Denote the number of elements in the mth class by gm, the mumber in the nth calss by gn
etc… and let there be k classes
k
Then ∑ x (R )x (R )g
p
i P j p p = hδ ij

Here Rp is any one of the operations in the pth class

This means kxi (RP ) quantities in the Γi IR behave like components of a k-dimensional vector
which is orthogonal to the k-1 other vectors,
3.7 Symbols used for representing irreducible representation
1. Dimension of the irreducible representations
If it is uni dimensional (character of E = 1), term A or B is used, for a two dimensional
representation, term E is used. If it is three dimensional term T is used
2. Symmetry with respect to principle axis

Karnataka State Open University Page 42

Group theory and its applications Block 4.1.1

If the 1-D irrep is symmetrical with respect to the principle axis (i.e, the character of the
operation is + 1) the term A is used. However if the 1-D representation is unsymmetrical with
respect to the principal acis (i.e, the character of is -1) the term B is used.
3. Symmetry with respect to subsidiary axis or plane
If the irrep is symmetrical with respect to the subsidiary axis, or in it absence to plane,
subscript , , , , are used if it is unsymmetrical subscript ,,, are used.
4. Prime and double prime marks are used over the symbol of the irrep indicate its
symmetry or anti symmetry with respect to the horizontal plane.
5. If there is a centre of symmetry in the molecule, subscripts g and u are used to
indicate the symmetry or anti symmetry of irrep. Suppose the point group has no
centre of symmetry, g or u subscripts are not used. The term g stands for gerade
(centrosymmetric) and u stands for ungerade (non-centrosymmetric).
On the basis of the above symbols can be assigned to the irreducible representations of a
point group.
This can be illustrated by considering water molecule
3.8 Motions of H2O
Since there are three atoms, the full matrix for H2O is a 9x9

The hydrogen atoms are not on the diagonal since the atoms themselves are moved as a result
of the C2 rotation. The trace of this matrix is –1. This is also called the character.
We can consider also the result of the σv mirror plane, which is also a 9x9

Karnataka State Open University Page 43

Group theory and its applications Block 4.1.1

None of the atoms are moved by the symmetry operation so all of the submatrices
representing the vectors lie along the diagonal. For this operation the trace (also known as the
character) is +3.
We can conclude with 2 general rules:
1. Only those atoms, which remain in the place following an operation can contribute to the
trace.
2. Each atom contributes the same amount to the trace since all of the atoms have the same
3x3 matrix.
Using these principles we can see that σv’ has a character of +1.
The identity always has a character equal to the number of basis functions. Here E = 9. Using
the character of the 4 symmetry operations of the C2v point group we can construct a
representation Γ.
9x9 matrix for C2 rotation in H2O

For σv(yz), no atoms are moved so the matrix representation is

Karnataka State Open University Page 44

Group theory and its applications Block 4.1.1

9x9 matrices like those above could serve as the representations of the operations for the
water molecule in this basis.
Fortunately, only the trace of this matrix is required. This sum is called the character, χ(R).
Here, χ(σv) = 3
For χ(C2) = -1

For a reflection through the plane bisecting the H-O-H bond angle, χ(σv') = +1 since only the
O is unshifted and a plane contributes +1 for each unshifted atom. The character for the
identity element will always be the dimension of the basis since all labels are unchanged. For
water then, χ(E) = 9. The representation (Γ) for water in this Cartesian basis is

3.9 Point Group Representations

A point group representation is a basis set in which the irreducible representations are the
basis vectors. The irreps form the a complete orthonormal basis for an m-dimensional space,
where m is the number of irreducible representations and is equal to the number of classes in
the group.
These considerations are summarized by the following rules.
1. The number of basis vectors or irreps (m) equals the number of classes.
2. The sum of the squares of the dimensions of the m irreps equals the order,

Karnataka State Open University Page 45

Group theory and its applications Block 4.1.1

The character of the identity operation equals the dimension of the representation, χ(E) = di
which is referred to as the degeneracy of the irrep. The degeneracy of most irreducible
representations is 1 (nondegenerate representations are 1x1 matrices) but can sometimes be 2
or 3. No character in an irreducible representation can exceed the dimension of the
representation. Thus, in non-degenenerate representations, all characters must be ±1.
3. The member irreps are orthonormal, i.e., the sum of the squares of the characters in any
irrep is equal to the order (row normalization), while the sum of the product of the
characters over all operations in two different irreps is zero (orthogonality).

• δij is the Kroniker delta (0 when i≠j and 1 when i=j), where the sum is over all of the classes
of operations,
• g(R) is the number of operations, R, in the class,
• χi(R) and χj(R) are the characters of the operation R in the ith and jth irreps,
• h is the order of the group.
4. The sum of the squares of the characters of any operation over all of the irreps times the
number of operations in the class is equal to h, i.e., columns of the representation are also
normalized.

where m is the number of irreducible representations

5. The sum of the products of the characters of any two different operations over all of the
irreps is zero, i.e., columns of the representation are also orthogonal.

6. The first representation is always the totally symmetric representation in which all
characters are +1.
7. Any reducible representation in the point group can be expressed as a linear combination of the
irreducible representations.
3.10 Summary of the unit
Mathematical techniques of group theory makes it possible to describe and analyze some of
the molecule’s chemically interesting properties. The approach we take, in general, is to
define a set of imagined vectors on the molecule’s various atoms to represent the properties
of interest. In order to apply symmetry arguments to the solution of molecular problems, we

Karnataka State Open University Page 46

Group theory and its applications Block 4.1.1

need an understanding of mathematical representations of groups - their construction,

meaning, and manipulation.
Representation; a set of symbols that will satisfy the multiplication table for the group. The
symbols themselves are called the characters of the representation. The characters may be
positive or negative integers, numeric values of certain trigonometric functions, imaginary
number, or even square matrices.
3.11 Key words
Representation; Reducible Representation; Block diagonal matrices; The trace of a matrix
Properties of irreducible representations; Symbols used for representing irreducible
representation; Motions of H2O; Point Group Representations
3.13 References for further studies
1) Group theory and Symmetry in Chemistry; Gurdeep Raj; Ajay Bhagi; Vinod Jain; Krishna
Prakashan Media; 2012.
2) Symmetry: An Introduction to Group Theory and Its Applications; R. McWeeny; Courier
Corporation, 2002.
3) Symmetry and Group theory in Chemistry; M Ladd; Elsevier, 1998.
4) Molecular Symmetry and Group Theory; Robert L. Carter; Wiley India Pvt. Limited, 2009.
5) Introduction to Symmetry and Group Theory for Chemists; Arthur M. Lesk; Springer
Science & Business Media, 2007.
3.14 Questions for self understanding
1) What is representation means?
2) What is reducible representation? Explain with example.
3) What are block diagonal matrices?
4) What is the trace of a matrix?
5) Explain the properties of irreducible representations.
6) Write the symbols used for representing irreducible representation.
7) Construct the representation table for H2O molecules.

Karnataka State Open University Page 47

Group theory and its applications Block 4.1.1

UNIT-4
Structure
4.0 Objectives of the unit
4.1 Introduction
4.2 Character tables
4.3 Symmetry of orbitals and functions
4.4 Character Tables and Bonding
4.5 The σ bonding in dichloromethane, CH2Cl2.
4.6 The σ and π bonding in SO3
4.7 The σ and π bonding in ClO4-
4.8 Summary of the unit
4.9 Key words
4.10 References for further studies
4.11 Questions for self understanding

Karnataka State Open University Page 48

Group theory and its applications Block 4.1.1

5.0 Objectives of the unit

After studying this unit you are able to

Construct the character tables for different symmetry elements

Explain the symmetry of orbitals and functions

Explain the character tables and bonding

Write the character table for σ bonding in dichloromethane, CH2Cl2.

Write the character table for σ and π bonding in SO3

Write the character table for σ and π bonding in ClO4-
4.1 Introduction
Each symmetry operation can be represented by a 3×3 matrix that shows how the operation
transforms a set of x, y, and z coordinates. The set of four transformation matrices forms a
matrix representation of the C2h point group. These matrices combine in the same way as the
operations. The sum of the numbers along each matrix diagonal (the character)gives a
shorthand version of the matrix representation, called Γ(gamma), is a reducible representation
b/c it can be further simplified. List of the complete set of irreducible representations (rows)
and symmetry classes (columns) of a point group.
4.2 Character tables
The collection of irreducible representations for a group is listed in a character table, with the
totally symmetric representation listed first. Thus each point group has a complete set of
possible symmetry operations that are conveniently listed as a matrix known as a Character
Table. As an example, we will look at the character table for the C2v point group.

Representations are subsets of the complete point group – they indicate the effect of the
symmetry operations on different kinds of mathematical functions. Representations are
orthogonal to one another. The Character is an integer that indicates the effect of an operation
in a given representation.
Karnataka State Open University Page 49
Group theory and its applications Block 4.1.1

The effect of symmetry elements on mathematical functions is useful to us because orbitals

are mathematical functions! Analysis of the symmetry of a molecule will provide us with
insight into the orbitals used in bonding.

Notes about symmetry labels and characters:

“A” means symmetric with regard to rotation about the principle axis.
“B” means anti-symmetric with regard to rotation about the principle axis.
Subscript numbers are used to differentiate symmetry labels, if necessary.
“1” indicates that the operation leaves the function unchanged: it is called “symmetric”.
“-1” indicates that the operation reverses the function: it is called “anti-symmetric”.
4.3 Symmetry of orbitals and functions
A pz orbital has the same symmetry as an arrow pointing along the z-axis.

Karnataka State Open University Page 50

Group theory and its applications Block 4.1.1

A px orbital has the same symmetry as an arrow pointing along the x-axis.

A py orbital has the same symmetry as an arrow pointing along the y-axis

Karnataka State Open University Page 51

Group theory and its applications Block 4.1.1

Rotation about the n axis, Rn, can be treated in a similar way.

The z axis is pointing out of the screen. If the rotation is still in the same direction (e.g.
counter clock-wise), then the result is considered symmetric. If the rotation is in the opposite
direction (i.e. clock-wise), then the result is considered anti-symmetric.

d orbital functions can also be treated in a similar way

The z axis is pointing out of the screen.

Karnataka State Open University Page 52

Group theory and its applications Block 4.1.1

d orbital functions can also be treated in a similar way

The z axis is pointing out of the screen. So these are representations of the view of the dz2
orbital and dx2-y2 orbital down the z-axis.

Karnataka State Open University Page 53

Group theory and its applications Block 4.1.1

Note that the representation of orbital functions changes depending on the point group – thus
it is important to be able to identify the point group correctly.

4.4 Character Tables and Bonding

We can use character tables to determine the orbitals involved in bonding in a molecule. This
process is done a few easy steps.
1. Determine the point group of the molecule.
2. Determine the Reducible Representation, Γ, for the type of bonding you wish to describe
(e.g. σ, π, π⊥, π//). The Reducible Representation indicates how the bonds are affected by the
symmetry elements present in the point group.
3. Identify the Irreducible Representation that provides the Reducible Representation; there is
a simple equation to do this. The Irreducible Representation (e.g. 2A1 + B1 + B2) is the
combination of symmetry representations in the point group that sum to give the Reducible
Representation.
4. Identify which orbitals are involved from the Irreducible Representation and the character
table.
Example,
4.5 The σ bonding in dichloromethane, CH2Cl2.

Karnataka State Open University Page 54

Group theory and its applications Block 4.1.1

The point group is C2v so we must use the appropriate character table for the reducible
representation of the sigma bonding, Γσ. To determine Γσ all we have to do is see how each
symmetry operation affects the 4 σ bonds in the molecule – if the bond moves, it is given a
value of 0, if it stays in the same place, the bond is given a value of 1. Put the sum of the 1’s
and 0’s into the box corresponding to the symmetry operation.
The E operation leaves everything where it is so all four bonds stay in the same place and the
character is 4 (1+1+1+1). The C2 operation moves all four bonds so the character is 0.
Each σv operation leaves two bonds where they were and moves two bonds so the character is
2 (1+1). Overall, the reducible representation is thus:

We now have to figure out what combination of symmetry representations will add up to give
us this reducible representation. In this case, it can be done by inspection, but there is a
simple equation that is useful for more complicated situations.

Because the character under E is 4, there must be a total of 4 symmetry representations

(sometimes called basis functions) that combine to make Γσ. Since the character under C2 is
0, there must be two of A symmetry and two of B symmetry. The irreducible representation is
(2A1 + B1 + B2), which corresponds to: s, pz, px, and py orbitals – the same as in VBT. You
can often use your understanding of VBT to help you in finding the correct basis functions
for the irreducible representation.

Karnataka State Open University Page 55

Group theory and its applications Block 4.1.1

The formula to figure out the number of symmetry representations of a given type is

4.6 The σ and π bonding in SO3

The point group is D3h so we must use the appropriate character table to find the reducible
representation of the sigma bonding, Γσ first, then we can go the representation of the π
bonding, Γπ. To determine Γσ all we have to do is see how each symmetry operation affects
the 3 σ bonds in the molecule.
The E and the σh operations leave everything where it is so all three bonds stay in the same
place and the character is 3 (1+1+1). The C3 and S3 operations move all three bonds so their
characters are 0. The C2 operation moves two of the bonds and leaves one where it was so the
character is 1. Each σv operation leaves one bond where it was and moves two bonds so the
character is 1. Overall, the reducible representation for the sigma bonding is

Karnataka State Open University Page 56

Group theory and its applications Block 4.1.1

We can stop here because the combination (A’1 + E’) produces the Γσ that we determined.
None of the other representations can contribute to the σ bonding (i.e. nA”1, nA”1 and nE” are
all 0). The irreducible representation (A’1 + E’) shows us that the orbitals involved in
bonding are the s and the px and py pair; this corresponds to the sp2 combination we find in
VBT.
Now we have to determine Γ for the π bonding in SO3

To determine Γπ we have to see how each symmetry operation affects the π systems in the
molecule. The treatment is similar to what we did for sigma bonding but there are a few
significant differences:
1) Pi bonds change sign across the inter-nuclear axis. We must consider the effect of the
symmetry operation on the signs of the lobes in a π bond.
2) There is the possibility of two different π type bonds for any given σ bond (oriented 90°
from each other). We must examine each of these.
To determine Γπ we have to see how each symmetry operation affects the π systems in the
molecule. The treatment is similar to what we did for sigma bonding but there are a few
significant differences: This means that we have to find reducible representations for both the
π system perpendicular to the molecular plane (π⊥, vectors shown in red) and the pi system in
the molecular plane (π// , vectors shown in blue).
Karnataka State Open University Page 57
Group theory and its applications Block 4.1.1

Note: These are just vectors that are associated with each sigma bond (not with any particular
atom) – they could also be placed in the middle of each SO bond. The vectors should be
placed to conform with the symmetry of the point group (e.g. the blue vectors conform to the
C3 axis).
First determine the reducible representation for the pi bonding perpendicular to the molecular
plane, Γπ⊥. The E operation leaves everything where it is so all three vectors stay in the same
place and the character is 3. The C3 and S3 operations move all three vectors so their
characters are 0. The C2 operation moves two of the vectors and reverses the sign of the other
one so the character is -1. The σh operation reverses the sign of all three vectors so the
character is -3. Each σv operation leaves one vector where it was and moves the two others so
the character is 1. Overall, the reducible representation for the perpendicular π bonding is

Karnataka State Open University Page 58

Group theory and its applications Block 4.1.1

Going through all the possibly symmetry representations, we find that the combination (A”2
+ E”) produces the Γπ⊥that we determined. The irreducible representation shows us that the
possible orbitals involved in perpendicular π bonding are the pz and the dxz and dyz pair. This
is in agreement with the π bonding we would predict using VBT.

First determine the reducible representation for the π bonding in the molecular plane, Γπ//.
The E operation leaves everything where it is so all three vectors stay in the same place and
the character is 3. The C3 and S3 operations move all three vectors so their characters are 0.
The C2 operation moves two of the vectors and reverses the sign of the other one so the
character is -1. The σh operation leaves all three vectors unchanged so the character is 3. Each
σv operation reverses the sign one vector where it was and moves the two others so the
character is -1. Overall, the reducible representation for the parallel π bonding is:

Karnataka State Open University Page 59

Group theory and its applications Block 4.1.1

Going through all the possibly symmetry representations, we find that the combination (A’2 +
E’) produces the Γπ// that we determined. The possible orbitals involved in parallel π bonding
are only the dx2-y2 and dxy pair. The A’2 representation has no orbital equivalent. Note: Such
analyses do not mean that there is π bonding using these orbitals – it only means that it is
possible based on the symmetry of the molecule.
4.7 The σ and π bonding in ClO4-

The point group is Td so we must use the appropriate character table to find the reducible
representation of the sigma bonding, Γσ first, then we can go the representation of the π
bonding, Γπ.
The E operation leaves everything where it is so all four bonds stay in the same place and the
character is 4. Each C3 operation moves three bonds leaves one where it was so the character
is 1. The C2 and S4 operations move all four bonds so their characters are 0. Each σd
operation leaves two bonds where they were and moves two bonds so the character is 2.

Karnataka State Open University Page 60

Group theory and its applications Block 4.1.1

The irreducible representation for the σ bonding is (A1 + T2), which corresponds to the s
orbital and the (px, py, pz) set that we would use in VBT to construct a the sp3 hybrid orbitals
suitable for a tetrahedral arrangement of atoms. To get the representation for the π bonding,
we must do the same procedure that we did for SO3, except that in the point group Td, one
cannot separate the representations into parallel and perpendicular components. This is
because the three-fold symmetry of the bond axis requires the orthogonal vectors to be treated
as an inseparable pair.

The analysis of how the 8 vectors are affected by the symmetry operations gives

The irreducible representation for the π bonding is (E + T1 + T2), which corresponds to the
dx2-y2 and dxy pair for E and either the (px, py, pz) set or the (dxy, dxz, dyz) set for T2, since T1
does not correspond to any of the orbitals that might be involved in bonding. Because the (px,

Karnataka State Open University Page 61

Group theory and its applications Block 4.1.1

py, pz) set has already been used in the σ bonding, only the (dxy, dxz, dyz) set may be used for π
bonding.
4.8 Summary of the unit
Each molecule has a point group, the full set of symmetry operations that describes the
molecule’s overall symmetry. We can use the decision tree to assign point groups character
tables show how the complete set of irreducible representations of a point group transforms
under all of the symmetry classes of that group. The tables contain all of the symmetry
information in convenient form. We can use the tables to understand bonding and
spectroscopy.
4.9 Key words
Character tables; Symmetry of orbitals; Character Tables and Bonding; The σ bonding in
dichloromethane, CH2Cl2.; The σ and π bonding in SO3; The σ and π bonding in ClO4-
4.10 References for further studies
1) Group theory and Symmetry in Chemistry; Gurdeep Raj; Ajay Bhagi; Vinod Jain; Krishna
Prakashan Media; 2012.
2) Symmetry: An Introduction to Group Theory and Its Applications; R. McWeeny; Courier
Corporation, 2002.
3) Symmetry and Group theory in Chemistry; M Ladd; Elsevier, 1998.
4) Molecular Symmetry and Group Theory; Robert L. Carter; Wiley India Pvt. Limited, 2009.
5) Introduction to Symmetry and Group Theory for Chemists; Arthur M. Lesk; Springer
Science & Business Media, 2007.
4.11 Questions for self understanding
1) What is meant by character tables?
2) Discuss the symmetry of orbitals and functions
3) Discuss the character tables and bonding
4) Explain the formation of the σ bonding in dichloromethane, CH2Cl2 using character table
construction.
5) Explain the formation the σ and π bonding in SO3 using character table construction.
6) Explain the formation the σ and π bonding in ClO4- using character table construction.

Karnataka State Open University Page 62

Spectroscopic applications in Inorganic chemistry Block 4.1.2

UNIT-5
Structure
5.0 Objectives of the unit
5.1 Introduction
5.2 Infra-Red spectroscopy of inorganic compounds
5.3 Di atomic molecule of the type AB or A2
5.4 Tri atomic molecules of the type AB2 or ABC
5.5 Tetra atomic molecules of the types AB3
5.6 Penta atomic molecules of the types AB4
5.7 Hexa atomic molecules of the types AB5
5.8 Hepta atomic molecules of the types AB6
5.9 IR spectral study of Lattice water and aquo and hydroxo complexes
5.9.1 Lattice Water
5.9.2 Aquo (H2O) Complexes
5.10 IR spectral study of sulfate and carbonate complexes
5.10.1 Sulfato (SO4)2- complexes
5.11 Carbonato (CO3) complexes
5.12 Mano and multinuclear carbonyl complexes
5.13 Diketonate complexes
5.14 IR spectra of Nitro and nitrato complexes
5.14.1 Chelating Nitrito Complexes
5.15 IR spectral study of thiocyanato complex
5.16 Applications in Coordination Chemistry
15.17 Complexes of ethylenediamine and related ligands
5.19 Study of isomerism
5.20 Metal Carbonyls
5.21 Organometallic Compounds
5.22 Summary of the unit
5.23 Key words
5.24 References for further studies
5.25 Questions for self understanding

Karnataka State Open University Page 63

Spectroscopic applications in Inorganic chemistry Block 4.1.2

5.0 Objectives of the unit

After studying this unit you are able to

Explain the application of Infra-Red spectroscopy for inorganic compounds

Explain the IR spectral study of Lattice water and aquo and hydroxo complexes

Explain the IR spectral study of sulfate and carbonate complexes

Explain the IR spectral study Mano and multinuclear carbonyl complexes

Explain the IR spectral study Diketonate complexes

Explain the IR spectra of Nitro and nitrato complexes
5.1 Introduction
The metal-ligand bond vibrations are sensitive to nature of ligand and metal. The stretching
and bending vibration of metal-ligand bond appears in the low frequency region due to also
the heavy mass of the metal ion/atom. Thus IR spectra studies of co-ordination compounds
provide information about nature of metal ligand bond and the special distribution of the
lignad atoms around metal atom/ion. The most common linkages in co-ordination compounds
are M-O, M-N, M-X (halogens) and M-S. In general M-O stretching vibration gives a more
intense and broad band than M-N stretching vibration. This is because large dipole moment
change taking place in M-O bond than M-N bond (O is more electronegative than N). The M-
S stretching vibration is generally of weak to medium intensity and this vibration occurs at
much lower frequencies relative to M-O and M-N stretching vibrations. The M-X stretching
vibration is usually medium to strong in infrared spectra. Compounds with bridge halogen
atoms, it is expected that a bridging vibration is located at lower frequencies than those found
for terminal vibrations. This is due to the fact that sharing of halogen between two metals in a
bridged structure causes the bond to be weaker than a terminal halogen bond
Vibratrions such as M-S, M-Se, M-P, M-C (this occurs in organometallic compounds) etc….
are expected to show only a slight change in the dipole moment, therefore such vibrations
would be of weak to medium intensity
The most important factors which are responsible for affecting the metal-ligands vibration are
i) Higher the oxidation state of the metal, higher is the frequency of vibration
ii) Greater the mass of the metal and ligand, lower is the frequency
iii) Higher the co-ordination number of the metal, lower is the frequency
iv) Greater the basicity of the ligand, the greater the frequency for sigma bonding
v) Non bridging lignads have higher frequency than bridging ligands
vi) Greater the size of counter ion smaller is the frequency

Karnataka State Open University Page 64

Spectroscopic applications in Inorganic chemistry Block 4.1.2

vii) Higher the ligand field stabilizing energy (LFSE) higher the frequency of
vibration
5.2 Infra-Red spectroscopy of inorganic compounds
Characterization of compounds via infrared spectroscopy is not limited to organic
compounds. Any inorganic compound that forms bonds of a covalent nature within a
molecular ion fragment, cation or anion, will produce a characteristic absorption spectrum,
with associated group frequencies.
Simple inorganic compounds, such as NaCl, do not produce any vibrations in the mid-
infrared region, although the lattice vibrations of such molecules occur in the far-infrared
region. This is why certain simple inorganic compounds, such as NaCl, KBr and ZnSe, are
used for infrared windows. A slightly more complex inorganic, such as CaCO3, contains a
complex anion. These anions produce characteristic infrared bands.
The cations in the complex ionorganic compounds like KNO2, K2CO3, Na2SO4 etc…
generally has negligible effect on the wavenumber of the complex anion because of the
crystal structure formed by such molecules. For example, in KNO2 crystal, ionic lattice
contains K+ ions and NO2− ions arranged in a regular array. The crystal structure consists of
essentially isolated K+ and NO2− ions. Hence the infrared bands of the cation and anion are
independent. K+ is monatomic thereforedoes not produce vibrations and, consequently no
infrared bands are absorved. However, heavier cations cause a lower wavenumber shift for
anionic vibration band. This effect is more common for the bending vibrations.
5.3 Di atomic molecule of the type AB or A2
The examples of di atomic molecules of the type A2 are H2, Cl2, O2, N2, etc... These are
called homonuclear di atomic molecules. The vibration of a homonuclear di atomic molecule
like A2 is infrared inactive. The examples of di atomic molecules of the type AB are, CO,
HCl, HBr, etc.... these are called heteronuclear di atomic molecules.

Figure 1: Variation of the dipole moment (µ) with internuclear distance ® for a di atomic
molecule AB

Karnataka State Open University Page 65

 Spectroscopic applications in Inorganic chemistry Block 4.1.2

Heteronuclear di atomic molecule AB will necessarily have a permanent dipole moment

because of asymmetry in its electron distribution. Hence the dipole moment occurs along the
bond axis. The vibration of the dipole moment with inter nuclear distance is shown in figure
1.
Obviously the dipole moment is zero both for zero and infinitely large internuclear
separations. The magnitude and sign of the dipole moment derivative depends on the
particular molecule. Thus the stretching vibration of a heteronuclear diatomic molecule is
infrared inactive
Table 1: Characteristic infrared bands of diatomic inorganic molecules

5.4 Tri atomic molecules of the type AB2 or ABC

Example of this type of molecules is CO2, NO2, SO2, ONCl, HCN, etc... Tri atomic
molecules of the general formula AB2 or ABC may have either a bent or a linear structure.
Therefore first we have to look whether molecule is linear or non-linear. In case of linear,
then we have to look whether it is symmetrical (B-A-B) or asymmetrical (B-B-A) Molecules
such as H2O, SO2, NO2, ONCl etc….. are examples of bent tri atomic molecules. Molecules
such as CO2, CS2, HCN etc…. Linear triatomic molecules.
Bent tri atomic molecules have three normal modes of vibration. Two of the vibrations are
stretching modes and the remaining one vibration is a bending mode. These are shown in
figure 2,

Figure 2: Normal modes of vibration of bent AB2 {or XY2 } molecules (+ and – denote vibrations
moving upwards and downwards, respectively, in the direction perpendicular to the plane of the
paper)

During each of the three normal vibrations of a bent tri atomic molecule, there is change in
the dipole moment of the molecule. Hence all the three vibrations are infrared active. The

Karnataka State Open University Page 66

Spectroscopic applications in Inorganic chemistry Block 4.1.2

intensity of the infrared absorption band is directly proportional to the square of the dipole
moment changes during the vibration. Hence normally polar molecules are anticipated to give
more intense infrared absorption band than non-polar molecules. It is not necessary for a
molecule to posses permanent dipole moment for infrared activity, although bent tri atomic
molecules do possess permanent dipole moment.
A linear tri atomic molecule of AB2 and ABC types has 4 normal vibrations. For example,
CO2 molecule is a typical B2A type moleculs. The vibrations of CO2 molecule are depicted in
figure 3, wherein observed frequencies are also indicated. The bending vibration (γ2) shown
in the plane of the paper and perpendicular to it are two distinct normal vibrations but they
occur at same frequency. Such vibrations are said to be degenerate. Degenerate vibrations are
found in molecules of higher symmetry.

Figure 3: Normal modes of vibration of bent AB2 {or XY2 } molecules (+ and – denote
vibrations moving upwards and downwards, respectively, in the direction perpendicular to
the plane of the paper)
Another example is the vibration of NCS- as in KNCS. The figure 4 show the vibrations of
NCS wherein the observed frequencies for the potassium compound are also given. The
bending mode of NCS- is again doubly degenerate. Appropriately one of the stretching
vibrations is termed as N≡C stretching and other as C-S stretching.

Figure 4: Normal vibrations of NCS- ion

Karnataka State Open University Page 67

Spectroscopic applications in Inorganic chemistry Block 4.1.2

There is no dipole moment change during the symmetric stretching vibration of a linear
symmetric tri atomic molecule such as CO2. However, there is change in the dipole moment
during bending and asymmetric stretching vibration. The symmetric stretching vibrations is
hence infrared inactive and other two vibrations are infrared active.
Linear unsymmetrical triatomic molecules such as HCN NCS- etc… have three infrared
bands, all the normal modes being infrared active since there is a change in the dipole
moment during each of the vibrations.
Figure 5 depict the comparison of the bending vibration of a linear triatomic molecules with
that of a nonlinear tri atomic molecules. It is clearly visible in the figure that for a non-linear
molecules the vibrations corresponding to the terminal atoms moving downwards
perpendicular to the plane of the molecule and the central atom moving upwards also
perpendicular to the plane of the molecule. It is simply a rotational motion of the molecule as
whole but this corresponding to a bending vibration in a linear triatomic molecule.

Figure 5: Comparison bween degenerate bending vibrations in a linear triatomic

molecules with the corresponding modes in a bent triatomic molecules
Table 2: Characteristic infrared bands (cm−1) of triatomic inorganic molecules

Karnataka State Open University Page 68

Spectroscopic applications in Inorganic chemistry Block 4.1.2

5.5 Tetra atomic molecules of the types AB3

Tetra atomic molecules of the type AB3 possesses either pyramidal or planar geometry. The
normal modes of ‘infrared-active’ vibrations of planar and pyramidal AB3 molecules are
illustrated in Figure 6.
The infrared ansorption bands of some of the planar and pyramidal tetra atomic molecules are
given in Table 3. Ligands may also adopt pyramidal and planar structures and the nature of
the coordination also affects the resulting infrared bands of these ligands.

Table 3: Characteristic infrared bands (cm−1) of four-atom inorganic molecules

Figure 6: Normal modes of vibration of (a) planar and (b) pyramidal AB3 molecules.

Karnataka State Open University Page 69

 Spectroscopic applications in Inorganic chemistry Block 4.1.2

5.6 Penta atomic molecules of the types AB4

The five-atom penta atomic molecule of the type AB4 and ligands commonly adopt
tetrahedral and square-planar shapes. The normal modes of tetrahedral and square-planar AB4
are shown in Figure 7. The tetrahedral AB4 molecules show two ‘infrared-active’ normal
modes of vibration, while the square-planar AB4 molecules show three infrared-active’
normal modes of vibration.

Figure 7: Normal modes of vibration of (a) tetrahedral and (b) square-planar AB4 molecules.
Table 4 summarizes the infrared bands of some common five-atom molecules.

Karnataka State Open University Page 70

Spectroscopic applications in Inorganic chemistry Block 4.1.2

Table 4: Characteristic infrared bands (cm−1) of five-atom inorganic molecules

5.7 Hexa atomic molecules of the types AB5

Six atom molecules of the AB5 type have received considerable attention vibrational
spectroscopic point of study. An AB5 molecule may adopt a trigonal bipyramidal, a square
pyramidal or a planar-pentagonal structure. The trigonal bipyramidal, (e.g. SF5− or BrF5),
shows six normal ‘infrared-active’ vibrations, while square (planar)-pentagonal AB5
molecules (e.g. XeF5−) show three ‘infrared-active’ normal vibrations.
The normal modes of vibration of an AB5 molecule in the trigonalbipyramidal and square
pyramidal geometry are depicted in Figure 8 and Figure 9 respectively.

Figure 8: Normal modes of vibration of a trigonal bipyramidal AB5 molecule

Karnataka State Open University Page 71

Spectroscopic applications in Inorganic chemistry Block 4.1.2

Figure 9: Normal modes of vibration of a square pyramidal AB5 molecule

5.8 Hepta atomic molecules of the types AB6

AB6 type of molecules invariably has an octahedral structure. A large number of inorganic
compounds particularly transition metal complexes comes under this category. Octahedral
AB6 molecules show 15 normal modes of vibration, but only two of these are ‘infrared-
active’. The normal modes of vibration of an octahedral AB6 molecule are illustrated in
Figure 10.

Figure 10: Normal modes of vibration of an octahedral AB6 molecule

Karnataka State Open University Page 72

Spectroscopic applications in Inorganic chemistry Block 4.1.2

Table 5 summarizes the infrared bands of some hexahalo molecules which show an
octahedral structure.

Table 5: Characteristic infrared bands (cm−1) of octahedral inorganic molecules

5.9 IR spectral study of Lattice water and aquo and hydroxo complexes
Water in inorganic salts may be classified as lattice or coordinated water. There is, however,
no definite borderline between the two. The former term denotes water molecules trapped in
the crystalline lattice, either by weak hydrogen bonds to the anion or by weak ionic bonds to
the metal, or by both

The latter term denotes water molecules bonded to the metal through partially covalent
bonds.
Although bond distances and angles obtained from X-ray and neutron diffraction data provide
direct information about the geometry of the water molecule in the crystal lattice, studies of
vibrational spectra are also useful for this purpose. It should be noted, however, that the
spectra of water molecules are highly sensitive to their surroundings.

Figure 11: The three rotational modes of H2O in the solid state

Karnataka State Open University Page 73

Spectroscopic applications in Inorganic chemistry Block 4.1.2

5.9.1 Lattice Water

In general, latticewater absorbs at 3550–3200 cm-1 (anti-symmetric and symmetric -OH
stretchings) and at 1630–1600 cm-1 (H-O-H bending). If the spectrum is examined under high
resolution, the fine structure of these bands is observed. For example, CaSO4.2H2O exhibits
eight peaks in the 3500–3400 cm-1 region and its complete vibrational analysis can be made
by factor group analysis. In the low-frequency region (600~200 cm-1) lattice water exhibits
“librational modes” thaare due to rotational oscillations of the water molecule, restricted by
interactions with neighboring atoms. As shown in Figure 11, they are classified into three
types depending on the direction of the principal axis of rotation. It should be noted, however,
that these librational modes couple not only among themselves but also with internal modes
of water (H-O-H bending) and other ions (SO42-, NO3-, etc.) in the crystal.
5.9.2 Aquo (H2O) Complexes
In addition to the three fundamental modes of the free water molecule, coordinated water
exhibits other modes. Vibrational spectroscopy is very useful in elucidating the structures of
aquo complexes. For example, TiCl3.6H2O should be formulated as trans-
-1
[Ti(H2O)4Cl2]Cl.2H2O since it exhibits one TiO stretching (500 cm ) and one TiCl stretching
(336 cm-1) mode . Chang and showed from infrared and Raman studies that the structures of
the tetrahydrates and dehydrates resulting from the dehydration of Mg(NO3)2.6H2O are as
follows

5.10 IR spectral study of sulfate and carbonate complexes

When a ligand of relatively high symmetry coordinates to a metal, its symmetry is lowered
and marked changes in the spectrum are expected because of changes in the selection rules.
This principle has been used extensively to determine whether acido anions such as SO42- and
CO32- coordinate to metals as unidentate, chelating bidentate, or bridging bidentate ligands.
Although symmetry lowering is also caused by the crystalline environment, this effect is
generally much smaller than the effect of coordination.
5.10.1 Sulfato (SO4)2- complexes
The free sulfate ion belongs to the high-symmetry point group Td. Of the four fundamentals,
only ν3 and ν4 are infrared-active. If the symmetry of the ion is lowered by complex

Karnataka State Open University Page 74

Spectroscopic applications in Inorganic chemistry Block 4.1.2

formation, the degenerate vibrations split and Raman-active modes appear in the infrared
spectrum. The lowering of symmetry caused by coordination is different for the unidentate
and bidentate complexes, as shown below

In [Co(NH3)6]2(SO4)3.5H2O,complex the ν3 and ν4 do not split and ν2 does not appear,

although ν1 is observed, it is very weak. , Therefore it is concluded that the symmetry of the
SO42- ion is approximately Td. In [Co(NH3)5SO4]Br, both ν1 and ν2 appear with medium
intensity. Moreover, ν3 and ν4 each splits in to two bands. This result can be explained by
assuming a lowering of symmetry from Td to C3v (unidentate coordination).
In both ν1 and ν2 appear with medium intensity, and ν3 and ν4 each splits into three bands.
These results suggest that the symmetry is further lowered and probably reduced toC2v, Thus,
the SO42- group in this complex is concluded to be a bridging bidentate as depicted in the
diagram.

5.11 Carbonato (CO3) complexes

The unidentate and bidentate (chelating) coordinations shown below are found in the majority
of carbonato complexes

In C2v and Cs*, the ν1 vibration, which is forbidden in the free ion, becomes infrared-active
and each of the doubly degenerate vibrations, ν3 and ν4, splits into two bands. Although the
number of infrared-active fundamentals is the same for C2v andCs, the splitting of the
degenerate vibrations is larger in the bidentate than in the unidentate complex. For example,
[Co(NH3)5CO3]Br exhibits two CO stretchings at 1453 and 1373 cm-1, whereas
[Co(NH3)4CO3]Cl shows them at 1593 and 1265 cm-1. In organic carbonates such as dimethyl
carbonate, (CH3O)2COII, this effect is more striking because the CH3O bond is strongly

Karnataka State Open University Page 75

Spectroscopic applications in Inorganic chemistry Block 4.1.2

covalent. Thus, the C=O stretching is observed at 1870 cm-1, whereas the C-O stretching is at
1260 cm-1. Gatehouse and co-workers showed that the separation of the CO stretching bands
increases along the following order:
Basic salt < carbonato complex < acid < organic carbonate
5.12 Mano and multinuclear carbonyl complexes
The carbonyl groups can have two modes of stretching vibrations. Both of these modes result
in change in dipole moment as shown in figure 12. Thus two bands are expected in the
infrared spectra of a terminally ligated carbon monoxide. The infrared and Raman
spectroscopy together can be used to determine the geometry of the metallic carbonyls.

Figure12: Stretching modes of carbonyl ligand

A mono nuclear pentacarbonyl can exist both in square pyramidal and trigonal bipyramidal
geometry. Performing infrared spectra after calculating the IR active and Raman active bands
in both the possible geometries can provide information about the actual geometry of the
molecule. Infrared spectroscopy of metallic carbonyls helps in determining the bond order of
ligated carbon monoxide.
The C-O bond order and the frequency related to its absorption are directly proportional.
Thus, it can be predicted that the frequencies of absorption will be in the order shown below
Free CO > metal carbonyl cation > neutral metal carbonyl > metal carbonyl anion.
Table 6: Comparison C-O stretching in representative metal carbonyls

Karnataka State Open University Page 76

Spectroscopic applications in Inorganic chemistry Block 4.1.2

It is also used to distinguish the terminal and bridging carbonyl groups. The C-O bonding in
terminal carbonyl groups is stronger than the bridged carbonyl groups. Therefore, it is
possible to differentiate the terminal carbonyls which absorb in the region of 2050–1900 cm-1
from the bridged carbonyls absorbing below 1900 cm-1 as illustrated in figure 13.
The change in the intensity of bands related to carbonyl group can provide information for
the kinetic studies of the substitution reactions involving replacement of carbonyls.

Figure 13: A partial infrared spectrum showing terminal and bridged carbonyl
5.13 Diketonate complexes
The β-diketones or 1,3-diketones bear two carbonyl groups that are separated by one carbon
atom. This carbon atom is the α-carbon. In most β-diketones, the substituents on the α-
carbon are hydrogen atoms. The substituent on the carbonyl function can be an alkyl group, a
fluorinated alkyl group, an aromatic or an heteroaromatic group. The simplest β-diketone is
acetylacetone (Hacac), were the substituents on both carbonyl groups are methyl groups. All
other β-diketones can be considered as derived from acetylacetone by substitution of the CH3
groups by other groups as shown in Figure 14.

Figure 14: Structures of β-diketones with aliphatic substituents

Karnataka State Open University Page 77

Spectroscopic applications in Inorganic chemistry Block 4.1.2

The β-diketones exhibit keto–enol tautomerism (Figure 15). In the enol form the H-atom of
the alcohol function is hydrogen-bonded to the carbonyl O-atom.

Figure 15: Keto-enol equilibrium in acetylacetone

Three main types of β-diketonate complexes with metal ion have found, they are, tris
complexes, Lewis base adducts of the tris complexes (ternary rare-earth β-diketonates) and
tetrakis complexes.
The neutral tris complexes or tris(β-diketonates) have three β-diketonate ligands for each
metal ion and they can be represented by the general formula [M(β-diketonate)3]. Because the
coordination sphere of the metal ion is unsaturated in these six-coordinate complexes, the
metal ion can expand its coordination sphere by oligomer formation (with bridging β-
diketonates ligands), but also by adduct formation with Lewis bases, such as water, 1,10-
phenanthroline, etc... It is also possible to arrange four β-diketonate ligands around a single
metal ion and in this way tetrakis complexes or tetrakis(β-diketonates) with the general
formula [M(β-diketonate)4]− are formed. These complexes are anionic and the electric
neutrality is achieved by a counter cation. The cation can be an alkali-metal ion (Li+, Na+, K+,
Cs+, Rb+).
Over the years, there has been a lot of dispute about the assignment of some absorption bands
in the infrared (IR) spectra of metal complexes of β-diketonates, including the rare-earth β-
diketonates. More particularly, the polemic was about the positions of the C=O and C=C
stretching vibrations in the infrared spectra. The bands at 1580 cm−1 and 1520 cm−1 is
assigned to the C=O and C=C stretching modes respectively.
The absorption bands observed in the infrared spectrum of [Eu(acac)3(H2O)2] at 1600 cm−1
and 1515 cm−1 to the C=O and C=C stretching vibrations respectively. Replacement of a
methyl group by a trifluoromethyl group strengthens the C=O and C=C bonds, but weakens
the Eu–O bond. The former two bands are therefore shifted to higher wavenumbers, while the
latter is shifted to lower wavenumbers.
Misumi and Iwasaki (1967) studied the infrared spectra of the tris acetylacetonate complexes
of praseodymium(III), neodymium(III), europium(III), gadolinium(III), dysprosium(III) and
erbium(III). Their assignments of the C=O and C=C stretching vibrations should be
corrected, according to the findings of Pinchas et al. (1967). The M–O vibrations were found

Karnataka State Open University Page 78

Spectroscopic applications in Inorganic chemistry Block 4.1.2

in the regions 420–432 cm−1 and 304–322 cm−1. The M–O stretching vibrations shift to
higher wavenumbers from praseodymium(III) to erbium(III).
5.14 IR spectra of Nitro and nitrato complexes
Many ligands are ambidentate, meaning they have the ability to bond a central atom in more
than one way. Examples of this include NCS-, which can coordinate via the N or S atom and
NO2- which can coordinate via the N or O atom. For example, the NO2- ligand is can form a
coordination complex with cobalt through the N atom or O atom to yield two structural
isomers as shown in figure 16, a nitrito or the more stable nitro.

O O N O
N O

Co Co

nitro nitrito
-
Figure 16: The two ways that NO2 can form coordination complexes to Co
In the nitrito complex, metal-to-ligand bonding is through one of the oxygen atoms while the
metal-to-ligand bonding for the nitro complex takes place through the nitrogen. The nitro
complex is the thermodynamically stable product while the nitrito complex is the kinetic
product and over time will transform into the more stable thermodynamic product. The two
complexes are distinguishable from one another based upon their individual IR spectrum. The
nitro complex will give a significantly different peak than that of the nitrito complex due to
the differences in the bonding of the two structures.
If the NO2 group is bonded to a metal through one of its O atoms, it is called a nitrito
complex. The two ν(NO2) of nitrito complexes are well separated, ν(N=O) and ν(NO) with at
1485–1400 and 1110–1050 cm-1 respectively. Distinction between the nitro and nitrito
coordination can be made on this basis. It is to be noted that nitrito complexes lack the
wagging modes near 620 cm1 that appear in all nitro complexes. The ν(MO) of nitrito
complexes were assigned in the 360–340 cm-1 region for metals such as Cr(III), Rh(III), and
Ir(III).

Karnataka State Open University Page 79

Spectroscopic applications in Inorganic chemistry Block 4.1.2

5.14.1 Chelating Nitrito Complexes

If the nitrito group is chelating, the ν(N=O) and ν(NO) of the nitrito group will be shifted to a
lower and a higher frequency, respectively, relative to those of unidentate nitrito complexes.
As a result, the separation between these two modes (∆) becomes much smaller than those of
unidentate complexes. It should be noted that the ∆ value depends on the degree of
asymmetry of the coordinated nitrito group; it is expected that the ∆ value is the smallest
when the two N-O bonds are equivalent and increases as the degree of asymmetry increases.
Suppose we record IR spectrum for the nitrito complex several days later, the spectrum
nearly identical to the nitro complex. This is explained by the natural degradation of the
kinetic product, nitrito, into the thermodynamically stable product, nitro.
5.15 IR spectral study of thiocyanato complex
Many of the associated group frequencies can be used diagnostically for characterization. The
structure and orientation of the ion or complex, both as an isolated entity or within a crystal
lattice, are important factors that affect the appearance and nature of the infrared spectrum.
Hydration of compounds (water of crystallization) also has a large effect on the spectrum,
and often adds a lot of complexity, in the form of additional absorption bands and structure to
existing bands. A few example group frequencies are included here (Table 7).
Table 7: Example group frequencies for common inorganic ions

a
Typically, the first absorption is intense and broad, and the second has weak to medium
intensity and is narrow. Both often exist as multiple band structures, and this may be used to
characterize individual compounds.
The degree of hydration of an inorganic compound is also a factor when interpreting spectra.
The water molecules that are incorporated into the lattice structure of a crystalline compound
produce characteristic sharp bands in the 3800–3200 and 1700–1600 cm−1 regions, due to O–
H stretching and bending, respectively. The lattice environment of the water molecules
determines the position of the infrared bands of water and whether they are single or split.

Karnataka State Open University Page 80

Spectroscopic applications in Inorganic chemistry Block 4.1.2

The hydroxy stretching bands in the 3800–3200 cm−1 range show unique patterns that may be
used to characterize the compositions of hydrated inorganic compounds.
5.16 Applications in Coordination Chemistry
Metal complexes or chelates are largely covalent in nature and the spectra of such compounds
are dominated by the contribution of the ligand and its coordination chemistry. The ligands
may be small species, such as water or ammoniummolecules, or large complex species, such
as porphyrins.
15.17 Complexes of ethylenediamine and related ligands
Chelating Ethylenediamine
When ethylenediamine(en) coordinates to a metal as a chelating ligand, it may take a gauche
(δ and λ) or a cis conformation, as shown in Figure 18. Then, there are eight different
conformations are probable for the [M(en)3]n+ ion if we consider all possible combinations of
conformations of the three chelate rings (δ or λ) around the chiral metal centre. They are
designated as ᴧ(δδδ), ᴧ(δδλ),ᴧ(δλλ),ᴧ(λλλ),D(λλλ),∆(λλδ), ∆(λδδ), and ∆(δδδ). According to
X-ray analysis, all the en ligands in the [Co(en)3]3+ion take the gauche conformation (δ), and
the configuration of the whole ion is ᴧ(δδδ). Although it is rather difficult to obtain such
information from vibrational spectra, some of these conformers can be distinguished by the
number of IR-activeC-Cstretching vibrations.
For example, [Cr(en)3]Cl33.5H2O [ᴧ(δδδ),D3 symmetry] exhibits only one band at 1003 cm-
1
whereas [Cr(en)3][Ni(CN)5] 1.5H2O [ᴧ(δδλ, δλλ), C2 symmetry] exhibits threebands at 1008,
1002 (shoulder), and 995 cm-1. Racemic (δλ) and optically active (δ) forms of [Co(en)3]Cl3
can be distinguished in the crystalline state by comparing vibrational spectra below 200 cm-1.

Figure 18: Rotational isomers of 1,2-disubstituted ethane. X= NH2 for en.

Karnataka State Open University Page 81
Spectroscopic applications in Inorganic chemistry Block 4.1.2

Bridging Ethylenediamine
Ethylenediamine takes the trans form when it functions as a bridging group between two
metal atoms. The trans configuration of ethylenediaminewas found in (AgCl)2en,
(AgSCN)2en, (AgCN)2en, Hg(en)Cl2, and M(en)Cl2(M = Zn or Cd). The structure of these
complexes may be depicted as follows

Complexes of Polyamines
Polyamines such as Diethylenetriamine(dien), Triaminotriethylamine(tren),
Triethylenetetramine(trien) shown below are coordinate to a metal as tridentate or
tetradentate ligands.

The infrared spectra of diethylenetriamine (dien) complexes [Pd(dien)X]X (X = Cl,Br,I) and

[Co(dien)(en)Cl]2+ reviles thatthe latter exists in the four isomeric forms as shown in Figure
19. 1.11. The ω and κ-isomers contain dien in the mer configuration; the π- and ε-isomers
contain dienin the fac configuration. The mer- and fac-isomers of [M(dien)X3] [M = Cr(III),
Co(III), and Rh(III); X: a halogen] can also be distinguished by infrared spectra.

Figure 19: Structures of the [Co(dien)(en)Cl] 2+ ion

Karnataka State Open University Page 82

Spectroscopic applications in Inorganic chemistry Block 4.1.2

The infrared spectra of β, β1, β11-triaminotriethylamine(tren) complexes with Co(III) and

lanthanides give three isomers (Figure 20). For example the infrared spectra of
[M(trien)X2]+, where trien is triethylene-tetramine, M is Co(III), Cr(III), or Rh(III), and X is a
halogen or an acido anion.

Figure 20: Structures of the [M(trien)X2]+ ions.

These compounds gave three isomers that can be distinguished by by the CH2 rocking
vibrations in the 920–869 cm-1 region. For [Co(trien)Cl2]ClO4 complex, cis-α-isomer exhibits
two strong bands at 905 and 871 cm-1 and cis-β-isomer shows four bands at 918, 898, 868,
and 862 cm-1; trans-isomer gives only one band at 874 cm-1 with a weak band at 912 cm-1.
5.19 Study of isomerism
Linkage and geometrical isomerisms are important issues in coordination chemistry,
producing structures with differing properties. Linkage isomerism occurs when a ligand can
coordinate to a central metal using either of two atoms within the ligand.
For example, the nitrite ion exhibits this type of isomerism. When the nitrite ion is attached to
a central metal ion via the nitrogen atom, it is known as a nitro ligand. When one of the
oxygen atoms is the donor, it is known as a nitritoligand.

When NO2− bonds undergo bonding through an oxygen bond, one of the NO bonds is
‘nearly’ a double bond, while the other is a single bond. In the other coordination, both NO
bonds are intermediate between single and double bonds. The infrared band of a bond
increases as its strength increases and so it would be expected that the wavenumbers of the
NO bonds in NO2− increase in the order:

Karnataka State Open University Page 83

Spectroscopic applications in Inorganic chemistry Block 4.1.2

Single-bond NO (in O-bonded) < NO (in N-bonded) < double-bond NO (in O-bonded).
It is observed that in complexes when NO2− is bonded through oxygen, N=O stretching
appears in the 1500–1400 cm−1 range while N–O stretching appears at 1100–1000 cm−1.
In complexes in which NO2− is bonded through nitrogen, the infrared bands appear at 1340–
1300 cm−1 and 1430–1360 cm−1, which are intermediate values when compared to the
oxygen-bonded complex.This way it is possible to use infrared spectroscopy to determine
whether a nitrite is coordinated and whether it is coordinated through a nitrogen or oxygen
atom.
Similarly the linear thiocyanate group can be present in inorganic compounds as an anion or
as a ligand. It can appear as a monodentate ligand coordinated throughsulfur or nitrogen
atom, or a bridging ligand.

This type of coordination ability and a variety of bonding modes of the thiocyanate group are
responsible for the existence of a relatively large number of coordination compounds.
Infraredspectroscopy is often used for approximative estimation of bonding modes.
Application of infrared spectroscopy for these purposes is based on the fact that the S- or N-
coordinated thiocyanate and noncoordinatedthiocyanate anion ligand gives significantly
different shifts of absorption bands.Thus Infrared spectroscopy is use full for correlating the
mode of coordination of thiocyanate ligand with changes of wavenumbers.
There are three vibrations occur, they are,
i) The pseudosymmetricstretching vibration γ(CN)
The doubly degenerated deformation frequency δ (NCS), and
ii) The pseudosymmetric stretching vibration γ (CS).
Vibrational frequencies (wavenumber) ranges of thiocyanate group with various bonding
modeslike M—NCS, M—SCN, and M—NCS—M are listed in table 8.
Table 8: Vibrational frequencies (wavenumber) ranges of thiocyanate group

Karnataka State Open University Page 84

Spectroscopic applications in Inorganic chemistry Block 4.1.2

However positions of the frequencies are slightly influenced by changes in the mass, charge, and size
of the central atom.
From the above table it is concluded that among the reported values the wavenumber of the
stretching frequency γ (CS) is the most suitable for distinguish of bonding mode.
Table 9 lists the main infrared bands observed for some common ligands capable of forming
linkage isomers
Table 9: Infrared bands of some common ligands capable of forming linkage

Infrared spectroscopy can be used to determine both the coordination mode of a ligand and
the geometrical arrangement of ligands around the metal atom. Thus geometrical isomers
canalso be differentiated by using infrared spectroscopy.
For example; The mid-infrared spectra of the cis–trans isomerism exhibited by
tetrachlorobis(N,Ndimethylformamide) tin(IV) (abbreviated as SnCl4(DMF)2) show carbonyl
stretching bands at 1651 and 1655 cm−1 for the cis- and trans-isomers, respectively.
The nature of the ligand coordination can be determined by comparing these carbonyl bands
with that of the isolated DMF molecules. The infrared spectrum of DMF inCCl4 shows a C=O
stretching band at 1687 cm−1, a notably higher wavenumber. If coordination in the
SnCl4(DMF)2 compound is through the nitrogen atom, the C–O bond order would be
increased and the C=O stretching band will shift to a higher wavenumber. In comparison,
coordination through the oxygen atom will decrease the C=O stretching wavenumber value.
Thus, the positions of the carbonyl bands of cis- and trans-SnCl4(DMF)2 indicate that the
ligand coordinates via the oxygen atoms.
There are important differences in the far-infrared spectra of the trans- and cis-SnCl4(DMF)2.
Both isomers show asymmetric Sn–O stretching at 425 cm−1and a ligand band near 400 cm−1.
However, the trans-isomer shows a single band due to Sn–Cl stretching near 340 cm−1, the
cis-isomer shows four Sn–Cl stretching bands in the 350–290 cm−1 range as shown in figure
21. The cis-isomer also shows a symmetric Sn–O stretching band, which is not present in the
spectrum of the trans-isomer. These notable differences are due to the different symmetries of
the molecules.

Karnataka State Open University Page 85

Spectroscopic applications in Inorganic chemistry Block 4.1.2

Figure 21: Far-infrared spectra of (a) trans- and (b) cis-SnCl4(DMF)2.

5.20 Metal Carbonyls

Infrared spectroscopy can be readily used to distinguish types of bonding in metal
carbonyls.A useful band in the infrared spectra of carbonyl ligands in metal complexes is that
due to C–O stretching which gives very strong sharp bands which are separated from the
bands of other ligands that may be present.The strength ofbonding between the d orbitals of
the metal into the π∗ anti-bonding orbitals of the CO ligand (known as
backbonding)determines the band position. This back bonding weakens the C–O bond
therefore appears at lower wavenumbercompare to free CO. The carbonyl ligand present in
either terminal (M–CO) and/or bridging (e.g. M–CO–M) types in metal carbonyls.The
bridging CO ligands appear at lower wavenumber values than those of the terminal ligands
in complexes with the same metal and similar electron density. Also the stretching
wavenumber for a terminal carbonyl ligand in a complex correlates with the ‘electron-
richness’ of the metal.
Terminal CO bands appear in the broad range from 2130 to 1700 cm−1, while bridging. CO
ligand bands appear in the 1900–1780 cm−1 range. However, care must be taken while
assigning such carbonyl bands. A band appearing below 1900 cm−1may aslo be due to a
terminal ligand, with a severe reduction of the carbonyl bond strength through d→π∗
bonding. However, if the complex also shows carbonyl bands well above 1900 cm−1, it may
be assumed that such electronic effects are absent and that the lower-wavenumber CO
stretching bands can be attributed tobridging ligands.

Karnataka State Open University Page 86

Spectroscopic applications in Inorganic chemistry Block 4.1.2

5.21 Organometallic Compounds

Organometallic compounds contain ligands directly bond to metal atoms or ions through
carbon bonds. The metal–carbon stretching wavenumbers of organometallic compounds are
observed in the 600–400 cm−1 range. The lighter metals shows bands at higher values. The
CH3 bending bands, arising from metal–CH3 groups, appear in the 1210–1180 cm−1region in
mercury and tin compounds, and at 1170–1150 cm−1 in lead compounds. Aromatic
organometallic molecules show a strong band near 1430 cm−1, due to benzene ring stretching
for metals directly attached to the benzene ring.
5.22 Summary of the unit
Infrared spectroscopy is used to study the vibrational motions of molecules. As shall be
described shortly, it turns out that different motion among different groups of atoms cause the
molecule to absorb different amounts of energy. Studying these transitions can sometimes
allow us to determine what kinds of atoms are bonded or grouped in an unknown compound,
which in turn gives clues as to the molecular structure. Absorption of energy in the infrared

region (ν = 4000 - 200 cm-1) arises from changes in the vibrational energy of the molecules.
There are two types of vibrations that cause absorptions in an IR spectrum. Stretching
involves rhythmical displacement along the bond axis such that the interatomic distance
alternately increases and decreases. Bending involves a change in bond angles between two
bonds and an atom common to both.
One important condition is that only those vibrations that produce a change in the electric
dipole moment of the molecule will be observed in the infrared spectrum. For example,
stretching vibrations in homonuclear diatomic molecules like O2, N2, and Br2 do not produce
a change in dipole moment and hence these molecules do not give rise to an IR spectrum. On
the other hand, CO and IBr produce IR spectra because these molecules contain a permanent
dipole moment that will change as the bond is stretched or compressed. CO2, a linear
molecule that does not have a permanent electric dipole, nevertheless produces an IR
spectrum because the two C=O bonds can stretch in an asymmetric fashion and also bend to
produce changes in the dipole moment.
5.23 Key words
Infra-Red spectroscopy of inorganic compounds; Di atomic molecule of the type AB or A2;
Tri atomic molecules of the type AB2 or ABC ; Tetra atomic molecules of the types AB3;
Penta atomic molecules of the types AB4; Hexa atomic molecules of the types AB5. Hepta
atomic molecules of the types AB6; Lattice Water; Aquo (H2O) Complexes; Sulfato (SO4)2-

Karnataka State Open University Page 87

Spectroscopic applications in Inorganic chemistry Block 4.1.2

complexes; Carbonato (CO3) complexes; Diketonate complexes; Chelating Nitrito

Complexes.
5.24 References for further studies
1) The characterization of a coordination complex using infrared spectroscopy: An
inorganic or instrumental experiment; Lawrence C. NathanJ. Chem. Educ., 1974, 51 (4), p
285. DOI: 10.1021/ed051p285
2) Infrared Spectroscopic Analysis of Linkage Isomerism in Metal−Thiocyanate
Complexes; Carl Baer and Jay Pike*J. Chem. Educ., 2010, 87 (7), pp 724–726; DOI:
10.1021/ed100284z
3) Electronic Absorption Spectroscopy and Related Techniques; D. N. Sathyanarayana;
Universities Press, 2001.
4) Infrared and Raman Spectra of Inorganic and Coordination Compounds, Applications
in Coordination, Organometallic, and Bioinorganic Chemistry; 6th Ed, Kazuo Nakamoto;
John Wiley & Sons; 2009.
5.25 Questions for self understanding
1) Red and yellow isomers exist for the coordination complex [Co(NH3)5NO2]Cl2. The red
isomer has νNO bands at 1430 and 1310cm-1 and νNO bands at 1430 and 1310 cm-1, what is
the coordination mode of the NO2 ligand in each complex?
2) Explain the general conditions of Infra-Red spectroscopy of inorganic compounds
3) Explain the Infra-Red spectroscopy of Di atomic molecule of the type AB or A2
4) Explain the Infra-Red spectroscopy of Tri atomic molecules of the type AB2 or ABC
5) Explain the Infra-Red spectroscopy of Tetra atomic molecules of the types AB3
6) Explain the Infra-Red spectroscopy of Penta atomic molecules of the types AB4
7) Explain the Infra-Red spectroscopy of Hexa atomic molecules of the types AB5
8) Explain the Infra-Red spectroscopy of Hepta atomic molecules of the types AB6
9) Explain the Infra-Red spectroscopy of IR spectral study of Lattice water and aquo and
hydroxo complexes
10) Explain the Infra-Red spectroscopy of Lattice Water
11) Explain the Infra-Red spectroscopy of Aquo (H2O) Complexes
12) Explain the Infra-Red spectroscopy of IR spectral study of sulfate and carbonate
complexes
13) Explain the Infra-Red spectroscopy of Sulfato (SO4)2- complexes
14) Explain the Infra-Red spectroscopy of Carbonato (CO3) complexes
15) Explain the Infra-Red spectroscopy of Mano and multinuclear carbonyl complexes

Karnataka State Open University Page 88

Spectroscopic applications in Inorganic chemistry Block 4.1.2

16) Explain the Infra-Red spectroscopy of Diketonate complexes

17) Explain the Infra-Red spectroscopy of Nitro and nitrato complexes
18) Explain the Infra-Red spectroscopy of Chelating Nitrito Complexes
19) Explain the IR spectral study of thiocyanato complex
20) Explain the applications of IR spectral study in Coordination Chemistry
21) Explain the applications of IR spectral study of complexes of ethylenediamine and
related ligands
22) Explain the applications of IR spectral study of isomerism
23) Explain the applications of IR spectral study of Metal Carbonyls
24) Explain the applications of IR spectral study of Organometallic Compounds

Karnataka State Open University Page 89

Spectroscopic applications in Inorganic chemistry Block 4.1.2

UNIT-6
Structure
6.0 Objectives of the unit
6.1 Introduction
6.2 Basic theory of ESR spectroscopy
6.3 Characteristics of ‘g’
6.4 Types of E.S.R. Instruments
6.5 Presentation of the Spectrum
6.5.1 Normal mode
6.5.2 Derivative mode
6.6 g-value for an electron and a complex
6.7 Factors affecting g-value in a complex
6.8 Sustaining effect
6.9 Combined effects of CFS and L-S coupling
6.10 g-value and structure
6.11 Zero– field splitting
6.12 Kramer’s degeneracy
6.13 Consequences of ZFS
6.14 Break down of selection rules
6.15 Mixing of states
6.17 Magnitude of zero- field splitting and signal
6.18 Effective spin, S’
6.19 Mixing of States and Zero–Field Splitting
6.20 Hyperfine Splitting
6.21 Characteristics of A
6.22 Hyperfine Splitting in Various Structures
6.23 Spin–Lattice relaxation
6.24 Spin–Spin relaxation
6.25 Calculation of g|| and g┴ for these two states
6.26 ESR and Jahn-Teller distortion
6.27 E.S.R. of Transition Metal Complexes
a) d1 system,2T2g: S’= ½: octahedral
b) d1tetrahedral
c) d2 system ; 3T1g

Karnataka State Open University Page 90

Spectroscopic applications in Inorganic chemistry Block 4.1.2

d) d2 tetrahedral
e) d3 system, 4A1g; S’ = 1½
f) d4 System; 5Eg; S = 2
g) d5 Spin- free, 6A1g; spin-paired, 2T2g
h) Spin-paired d5
6.28 Application of ESR spectroscopy of biological molecules
a) Iron proteins
b) Copper proteins
c) Manganese proteins
d) Cobalamin
6.29 The ESR spectrum of PH4 *
6.30 Summary of the unit
6.31 Key words
6.32 References for further studies
6.33Questions for self understanding

Karnataka State Open University Page 91

Spectroscopic applications in Inorganic chemistry Block 4.1.2

6.0 Objectives of the unit

After studying this unit you are able to

Explain the basic theory of ESR spectroscopy

Identify the Characteristics of ‘g’

Calculate the g-value for an electron and a complex

Explain the conditions in which Zero– field splitting occurs

Explain the conditions in which Kramer’s degeneracy possible

Draw the hyperfine splitting structure of various compounds

Explain the ESR and Jahn-Teller distortion

Explain the E.S.R. of Transition Metal Complexes

Explain the Application of ESR spectroscopy of biological molecules

Explain the The ESR spectrum of PH4 radical
6.1 Introduction
ESR or Electron Spin Resonance is a spectroscopic method for studies of paramagnetic
species. This method and the related NMR or nuclear magnetic resonancetechnique were
both established around 1945. Both methods make use of magnetic properties, in the first
case of electrons in the second of nuclei. The microwave technique in the frequency range
109 Hz and higher that is normally employed in ESR instruments had been developed for
Radar detection units during the Second World War. Systematic studies of transition metal
salts began at the end of the 1940s. These studies have formed the basis for continued
research on complex biochemical systems that is now one of the most active areas of
applications. Other fields have been opened by the ongoing development of resolution and
sensitivity. Free radicals – molecules with an unpaired electron have been tracked and
identified and their reactions followed both in the liquid and the solid state in many instances.
Such studies are still ongoing, nowadays more as one tool in conjunction with other methods
to obtain chemical information.
6.2 Basic theory of ESR spectroscopy
When a paramagnetic molecule absorbs a quantum of electromagnetic radiation in the
microwave region, electron is excited from one spin energy state to another spin energy state,
which has higher energy. An electron has a spin, s = ½. The spin – angularmomenta, ms ± ½,
have equal energy in the absence of magnetic field. However, when a magnetic field is
applied, the degeneracy is resolved, that is, removed. In the low energy state, the spin
magnetic moment is aligned with the external magnetic field and hence, ms=-½. In the high-

Karnataka State Open University Page 92

Spectroscopic applications in Inorganic chemistry Block 4.1.2

energy state, the magnetic moment isopposed to the external field and hence, ms= + ½. A
transition will occur between these two states, when the energy of the quantum of radiation,
ν, is equal to the difference in energy, ∆E, between the two spin states of the electron. That
is, ∆E = hν = gβH0
where, ‘h’is the Planck‘s constant,‘ν’ is the frequency of radiation,’β’ is the Bohr magneton,
‘H0’ is the external magnetic field strength and ‘g’ is the spectroscopic splitting factor.
6.3 Characteristics of ‘g’
1. It is not a constant.
2. It is a tensor quantity. That is, it depends on three parameters, namely, magnitude,
direction and arbitrary number of indices.
3. For a free electron, g = 2.00234. In metal ions, the ‘g’ values often greatly differ from the
free electron value.
5. The magnitude of ‘g’ depends up on the orientation of the molecule containing the
unpaired electron with respect to the magnetic field.
6. In solution or in the gas phase, ‘g’ is averaged over all orientations because of the free
motion of the molecules.
7. If the paramagnetic radical or ion is located in a perfectly cubic crystal site (Oh or Td site),
the ‘g’ value is independent of the orientation of the crystal and is said to be isotropic.
8. In a crystal of lower symmetry, the ‘g’ value depends up on the orientation of the crystal
with respect to the magnetic field and is said to beanisotropic.
9. The ‘z’ direction coincides with the highest fold rotation axis, which can be determined by
X – ray. When the z-axis is parallel with the external magnetic field, the ‘G’value is
called, g||, and it is also known as gz. The‘g’values along the x-and y-axes are called gx
and gy. These are referred to as g┴ . The reason is that the external magnetic field is
perpendicular to the z-axis.
10. In a tetragonal site, gx = gy.
11. If ‘θ’ is the angle between the magnetic field and the z-axis, the experimental ‘g’ value is
given by the following equation for a system with axial symmetry:

12. There will be inequality in ‘g’ values even if there are small distortions. These cannot be
detected by X-ray. However, E.S.R can detect these small distortions from the
inequalities in ‘g’values.

Karnataka State Open University Page 93

Spectroscopic applications in Inorganic chemistry Block 4.1.2

6.4 Types of E.S.R. Instruments

There are two types of E.S.R. Spectrometers
1. X – band spectrometer
2. Q – band spectrometer
X – band spectrometer
A frequency around 9400 mega cycles per second and a magnetic field strength around 3000
gauss are employed. The magnetic field strength can be varied in the range 1 – 10,000 gauss.
Q – band spectrometer
A frequency around 35,000 mega cycles per second and a magnetic field strength around
12,500 gauss are used.
6.5 Presentation of the Spectrum
The spectrum can be presented in two ways
1. Normal mode
2. Derivative mode.
6.5.1 Normal mode
In this mode, the absorption intensity is plotted against the magnetic field and a curve as
shown in Figure 1 is obtained.

Figure 1: Normal mode

In this mode, the absorption intensity is plotted against the magnetic field and a curve as
shown in Figure 1 is obtained. The disadvantage is that the absorption bands are broad.
Therefore, the field at which maximum absorption occurs cannot be determined accurately.
6.5.2 Derivative mode
Here, the first derivative of the absorption intensity, dI/dH is plotted against H. The curve
obtained is shown in Figure 2. The advantage of this curve is that this type of plot is more
accurate. When the absorption intensity is maximum, dI/dH = 0. That is, the derivative curve
crosses the x-axis. The number of peaks in an absorption curve corresponds to the number of
maxima or minima in the derivative curve.

Karnataka State Open University Page 94

Spectroscopic applications in Inorganic chemistry Block 4.1.2

Figure 2: Derivative mode

6.6 g-value for an electron and a complex
It is an inherent property of a system containing an unpaired spin. Similar to the chemical
shift observed in an NMR spectrum.
The g value for a single unpaired electron (free electron) has been calculated and
experimentally determined. It is 2.0023192778 ± 0.0000000062 (= ge). The g value for an S =
1/2 system is usually near ge, but it is not exactly at ge. This is due to spin orbit coupling
which determines both the value of g and its anisotropy (how far the 3 g values are from gav.
The g value can often be calculated and the value is characteristic for a particular spin system
The value of ‘g’ is given by the following expression

For a free electron, S = ½, L = 0, and J = S = ½. Therefore, g = 2.(J = L+S).

The ‘g’ factor is a dimensionless constant and for a free electron, g = 2.0023. A free radical
also has g = 2.0023 because in a free radical, the unpaired electron can move about freely
over orbitals and is not confined to a localized orbital. However, in a transition metal
complex, the unpaired electron is localized in a particular orbital. In a complex, the orbital
degeneracy is removed and spin–orbit coupling takes place. Therefore, the g-value for a
complex is different from 2.0023.
6.7 Factors affecting g-value in a complex
The important factors affecting the g-value in a complex are
1) Nature of the metal
2) Geometry of the complex
3) The relative magnitude of spin–orbit coupling
4) The crystal field.

Karnataka State Open University Page 95

Spectroscopic applications in Inorganic chemistry Block 4.1.2

1) Nature of the metal

Science d metal ions have 5d orbitals situations are complicated. But the spectra are
informative, in 4d and 5d series L-S/J-J coupling is stronger making the ESR hard to
interpret.
2) Geometry of the complex
Ligands and their arrangement-CFS. CFS in turn affect the electronic levels hence the ESR
transitions. The relative magnitude of CFS and L-S coupling is giving three situations.
If the complex ion is having cubic symmetry (octahedral or cubic)- g is isotropic. Complexes
with at least one axis of symmetry show two g values. Ion with no symmetry element will
show three values for g.

System with an axis of symmetry System with no symmetry

This is clear from the following equation

Thus the spin–orbit contribution makes ‘g’ characteristic property of a transition metal ion
and its oxidation state.
3) Effect of spin–orbit coupling
When the unpaired electron is placed in a chemical environment or in a transition metal
complex, the ‘g’ value does not agree with the expected value. It is explained as follows
The chemical environment or the crystal field strongly perturbs the orbital motion of the
electron. Therefore, the orbital degeneracy, if any, is partly removed or quenched. This called
quenching. On the other hand, the spin–orbit coupling tends to sustain certain amount of
orbital degeneracy. That is, complete removal of orbital degeneracy is prevented by spin–
orbit coupling but higher fold degeneracies are often decreased by this effect. This sustaining
effect implies that if an electron has orbital angular momentum, this is maintained by

Karnataka State Open University Page 96

Spectroscopic applications in Inorganic chemistry Block 4.1.2

coupling to the spin angular momentum and if it has a spin angular momentum this tends to
generate orbital angular momentum. Because of this quenching and sustaining competition,
the orbital degeneracy is partly but not completely removed and a net orbital magnetic
moment results. Hence, g-value is different from 2.0023, which would be expected if the
orbital degeneracy were completely removed.
4) Crystal field effect
Crysrtal field is not affecting the 4F and 5F electron so the ESR spectra of the lanthanides
and actinides are quite simple. If ion contains more than one unpaired electrons ZFS may
operative.
The relative magnitudes of crystal field and spin–orbit coupling determine the properties of
the transition metals to a large extent. These two have opposite effects on the orbital
degeneracy (crystal field tries to remove while the spin–orbit coupling prevents the removal
of orbital degeneracy). Three cases can be distinguished
i) Spin–orbit coupling is very much greater than the crystal field.
ii) Effect of crystal field is strong enough to break the coupling between L and S.
iii) Effect of crystal field is very large so that L-S coupling is broken down
completely.
Case i)
The effect of spin–orbit coupling is very muchgreater that of the crystal field.(e.g.) rare earth
ions:
The f-electrons are well shielded from thecrystal field effects. Therefore, L-S coupling is not
disturbed. ‘J’ is a good quantum number. Therefore, rare earth ions are very much like free
ions. The magnetic moments calculated with the help of g-value obtained from the following
equation agree with the experimental values.

Case ii)
The effect of crystal field is strong enough to break the coupling between L and S. Now, ‘J’ is
not a good quantum number. The splitting of mL levels is large. That is, orbital degeneracy is
quenched. The selection rule, mS = ±1, is obeyed.
Example; I row transition elements.
The magnetic moment corresponds to more nearly to the spin–only value.
where g = 2

Karnataka State Open University Page 97

Spectroscopic applications in Inorganic chemistry Block 4.1.2

The orbital degeneracy is not completely removed because of the effect of spin–orbit
coupling. Consequently, a net orbital magnetic moment results giving rise to a g-value
expected if the orbital degeneracy were completely removed. Ions, which have an orbitally
non-degenerate ground state such as Fe3+(6S) and Mn2+(6S), give g-values nearly equal to the
free electron value since there is practically no orbital angular momentum. The small
deviation from the free electron value is due to slight spin–orbit coupling.
Case iii)
When the crystal field is very strong, the L-S coupling is broken down completely. This
corresponds to covalent bonding and is applicable to the complexes of the 4d and 5d
transition metals and to the strong field complexes of the 3d transition metals, such as
cyanides. In many of these cases, M.O. description gives better results than the crystal field
approximation.
Symmetry of the complex ion is important because ESR is recorded in frozen solutions. In
such conditions the spins are locked. Lack of symmetry influences the applied field
considerably. If the axis is not coinciding with Z axis, the sample is rotated about three
mutually perpendicular axis and g is measured. Magnetically active nucleus causes hyperfine
splitting. If more than one unpaired electrons present in the ion, more no of transitions are
possible leads to fine structure in ESR spectrum.
In addition the following factors are also affect the g-value
1) Operating frequency of the instrument
2) Concentration of unpaired electrons
3) Ground term of the metal ion present
4) Direction and temperature of measurement
5) Inherent magnetic field in the crystals
6) Jahn-Teller distortion and ZFS
6.8 Sustaining effect
The g value for a gaseous atom or ion for which L-S coupling is applicable is given by the
expression
g = 1 + [J(J+1) + S(S+1)-L(L+ 1)]/ 2J(J+1)
For halogen atoms the g values calculate and experimental are equal, but for metal ions it
varies from 0.2-8. The reason is the orbital motions of the electrons are strongly perturbed by
the crystal field. Hence the L value is particularly or completely quenched. In addition to this
ZFS and J-T distortion may also remove the degeneracy. The spin angular momentum S of
electron tries to couple with the L. this partially retains the orbital degeneracy. The crystal

Karnataka State Open University Page 98

Spectroscopic applications in Inorganic chemistry Block 4.1.2

field tries to quench the L values and S tries to restore it. This phenomenon is called
sustaining effect. Depending up on which effect dominate the L value deviates from the
original value. So L and hence J is not a good quantum number to denote the energy of
electrons hence the g value also.
6.9 Combined effects of CFS and L-S coupling
Three cases arises depending upon the relative magnitudes of strength of crystal field and L-S
coupling
L-S coupling >>> CFS
CFS > L-S coupling and
CFS >>> L-S coupling
L-S coupling >>> CFS
When L is not affected much by CFS then J is useful in determining the g value, example rare
earth ions. 4f-electrons buried inside so not affected. G values falls in the expected regions.
All 4f-and 5f gives agreeing result other than Sm(III) and Eu(III)
CFS > L-S coupling
If CFS is larger enough to break L-S coupling then J is not useful in determining g values.
Now the transitions are explained by the selection rule and not by g values. The magnetic
⁄
moment is given by  =  + 2
All 3d ions fall in this category. System with ground terms not affected by CFS ie L = 0 are
not affected and the g values is close to 2.0036. There may be small deviation because of L-S
coupling, spin-spin interaction and gs and es mixing.
CFS >>> L-S coupling
In strong fileds L-S coupling is compleately broken and L = 0 which mweans there is
covalent bonding. Applicable to 3d strong field, 4d and 5d series. In many cases MOT gives
fair details than CFT
Example 1: Ni(II) in Oh field
For Ni(II) g calculation includes mixing 2A2g (gs) and 3T2g(es)
g = 2- [ 8λ/10Dq]
for Ni(II) the g values is 2.25 hence 8λ/10Dq must be -0.25
From the electronic spectrum 10Dq for Ni(II) in an Oh field is known to be 8500cm-1, λ is -
270cm-1. For free Ni(III) ion the λ is about -324cm-1 the decrease is attributed to the es and gs
mixing. This example shows how λ and 10Dq can affect the g value.
Example 2: Cu(II) in a tetragonal field

Karnataka State Open University Page 99

Spectroscopic applications in Inorganic chemistry Block 4.1.2

Cu (II) is a d9 system and its ground term symbol is 2D

2D → 2Eg + 1T2g (CFS)
Since Cu(II) is a d9 system it must undergo J-T distortion. So the Oh field becomes tetragonal
2
T2g → 2Eg + 2B2g, 2Eg → 2B2g + 2A1g
The unpaired electron is present in 2A1g. On applying the magnetic field the spin levels are
spilt and we get an ESR line.

Cu(II) ion in various fields

The g value is given by
gǁ = 2 - 8λ/ (E2- E0), g┴ = 2 - 2λ/ (E3- E0)
From electronic spectrum (E2- E0) and (E3- E0) can be calculated. From the above values λ
can be calculated. It is seen that when splitting by distortion is high g values approaches 2. If
the distortion splitting is lower, then resulting levels may mix with each other to give
deviated g values.

d1 system (Ti3+, VO2+)

Karnataka State Open University Page 100

Spectroscopic applications in Inorganic chemistry Block 4.1.2

d2 system (V3+ and Cr4+)

d3 system (Cr3+)

d4 system (weak field)

Karnataka State Open University Page 101

Spectroscopic applications in Inorganic chemistry Block 4.1.2

6.10 g-value and structure

From the g-value, we can obtain very importantinformation about the structure of the
complex. For a complex in solution, ‘g’ is averaged over all orientations because of the free
motion of the molecules. However, in a crystal, the motion is restricted.
Cubic field
In a cubic crystal field, the metal–ligand bond lengths are the same along the three Cartesian
axes and hence, ‘g’ remains the same. That is, gx = gy = gz.
Now ‘g’ is said to be isotropic.
Tetragonal field
If the crystal field is tetragonal, the metal–ligand distances along the x- and y-axes are the
same but different from the metal– ligand distances along the z-axis. The g-value of such a
complex is not isotropic. The anisotropic ‘g’ may be expressed as gx = gy ≠ gz.
Rhombic
If the symmetry is rhombic, three different g-values are obtained. That is, gx ≠ gy ≠ gz.
In bulk susceptibility measurements, a powderedsample is used and ‘g’ works out as an
average, gav. If a well formed single crystal is used, the E.S.R. measurements can provide the
g-values based on the orientation of the crystal.
6.11 Zero– field splitting
When the spin levels are split even in the absence of magnetic field, it is called zero–field
splitting. When a metal ion is placed in a crystal field, the degeneracy of the
‘d’ orbitals will be removed by the electrostatic interactions. That is crystal field removes the
orbital degeneracy. However, the spin degeneracy isnot removed until a magnetic field is
applied. Nevertheless, when the species contains more than one unpaired electron, crystal
field can also remove the spin degeneracy. Thus, the spin levels may be split even in the
absence of a magnetic field. This phenomenon is called zero-field splitting.
Considering a system having two unpaired electrons, there are three combinations are
possible for these electrons as shown in below figure. In the absence of external magnetic
field all three states have equal energy. Under the influence of external filed, the three levels
are no longer with same energy. Hence two transitions are possible both with same energy

Karnataka State Open University Page 102

Spectroscopic applications in Inorganic chemistry Block 4.1.2

The splitting of electronic levels even in absence of external magnetic field is possible due to
association of distortion and L-S coupling. And this is called zero filed splitting (ZFS). The
splitting may be happens when there is strong dipolar interaction of the +1 level is raised in
energy (Dipolar shift (D)) this dipolar shift reduces the gap between S= -1 and S = 0. Now
the two transitions do not have same energy resulting in two lines.

6.12 Kramer’s degeneracy

System with even number of unpaired electrons will contain a state with S = 0. But in the
case of odd electrons no state with S = 0 is appears, since Ms = ½. In such case even after
ZFS the spin state with opposite Ms values remains degenerate which is called Kramer’s
degeneracy. The levels are called Kramer’s doublets. In any system with odd number of
unpaired electrons the ZFS leaves the ground state at least two fold degenerate.

Effect of ZFS on Mn(II)

Karnataka State Open University Page 103

Spectroscopic applications in Inorganic chemistry Block 4.1.2

Thus when the species contains an odd number of unpaired electrons, the spin degeneracy of
every level remains doubly degenerate. This is known as Kramer’s degeneracy. (When the
number of unpaired electrons is even, crystal field may remove the spin degeneracy entirely).
This is schematically represented as follows

Example 1: Consider a molecule or ion with two unpaired electrons. Then S = +½ + ½ = 1.

Therefore, ms = -1, 0,+1. In the absence of zero–field splitting, two transitions are possible as
shown below

The first transition is ms = 0 to +1 and the second transition is ms = -1 to 0. These transitions

have equal energy (i.e. degenerate) and only one signal is observed. This system has even
number of unpaired electrons.

Karnataka State Open University Page 104

Spectroscopic applications in Inorganic chemistry Block 4.1.2

Hence, Kramer’s degeneracy is not operative. That is, each level will not be doubly
degenerate. If zero–field splitting is present, it removes the degeneracy in mS as shown above.
Now, the two transitions are not degenerate. Hence, two peaks are observed in the spectrum,
when zero–field splitting is present but only one when it is absent.
Example 2: Mn2+ (d5 system). In this system, there are an odd number of unpaired electrons.
Hence, Kramer’s degeneracy must exist. The term symbol for the free ion ground state is 6S.
The zero–field splitting produces three doubly degenerate spin states, namely, mS = ±5/2,
±3/2, ± ½ (Kramer’s degeneracy). Each of these is split in to two singlets by the applied field
producing six levels. As a result of this, five transitions are expected -5/2 to – 3/2, -3/2 to –
1/2, -1/2 to +1/2, +1/2 to +3/2, +3/2 to +5/2.
The spectrum is further complicated by the hyperfine splitting due to the manganese nucleus
(I = 5/2). Thus each of the five peaks split in to six hyperfine components as shown in Figure
3.

Figure 3: Zero-field splitting in Mn2+

6.13 Consequences of ZFS
In some cases ZFS magnitude is very high than the splitting by external field. Then transition
requires very high energy. Sometimes only one or no transitions occur. Example V3+ and
Co2+
Co(II) in cubic field has a ground term of 4F, since it is a d8 system it have ± 3/2 and ± ½
levels. ZFS splits the levels by 200cm-1. Since the energy gap is higher only the transition – ½ to +1/2
is seen. So it appears as if Co(II) has only unpaired electrons (Effective spin S = ½)

Karnataka State Open University Page 105

Spectroscopic applications in Inorganic chemistry Block 4.1.2

6.14 Break down of selection rules

In some cases like V(III) the magnitude of ZFS is very high. Hence it exceeds the normal
energy range of ESR transitions. In such system normal transitions occurs with ∆Ms = ± 1.
But its energy exceeds the microwave region. Then the transition from -1 to + 1 levels with
∆Ms = ± 2 occurs, which is a forbidden one.

6.15 Mixing of states

The magnitude of ZFS can be taken as originating from CFS. But orbitally singlet sate S is
not split by the crystal field even then Mn(II) shows a small amount of ZFS. This is attributed
to the mixing of g-s and e-s because of L-S coupling. The spin-spin interaction is negligible.
But dor triplet states spin-spin terms are important and they are solely responsible for ZFS.
Naphthalene trapped in durene in dilute stets shows two lines as if it has ZFS. Since there is
no crystal field or L-S coupling this is attributed to spin-spin interaction of the π electrons in
the excited triplet state.
6.17 Magnitude of zero- field splitting and signal
The effect of moderate zero-field splitting is shown in Figure 4 and that of large zero–field
splitting in Figure 5. When the zero–field splitting is very large, the allowed transition, mS =
± 1, becomes too large to be observed in the microwave region. That is, mS = 0 to mS = +1

Karnataka State Open University Page 106

Spectroscopic applications in Inorganic chemistry Block 4.1.2

transition cannot be observed. However, it has been possible to observe a weak transition
corresponding to mS = ± 2, that is, between the mS = +1 and mS = -1 levels. This transition
will be weak because it is a forbidden transition. This is the case in V3+. This signal is further
split in to eight components (I = 7/2 for V51).

Figure 5: moderate Zero-field

Figure 6: Large-Zero field splitting

6.18 Effective spin, S’
Consider a metal ion in a cubic crystal field and let the lowest state be an orbital singlet, that
is, ‘A’ state. Now, the splitting of the degeneracy is generally small and the effective spin, S’,
will be equivalent to the electronic spin. If zero–field splitting were operative 2S transitions
would be expected. For example, consider Ni2+ (d8), which has 3A2g ground state in an
octahedral field and in some cases gives rise to two transitions in the e.p.r. spectrum.
However, in the cubic field splitting, the ground state is an orbitally degenerate ground state
like a ‘T’ state.

Karnataka State Open University Page 107

Spectroscopic applications in Inorganic chemistry Block 4.1.2

The effect of lower symmetry fields and the spin–orbit coupling will resolve this orbital
degeneracy as well as the spin degeneracy. If an odd number of unpaired electrons is present,
then the lowest spin state will be doubly degenerate according to Kramer’s degeneracy. If the
splitting is large, this doublet will be well isolated from higher lying doublets. Then
transitions will be observed only in the low-lying doublet, and the effective spin will appear
to have a value only ½ (S = ½).
Example, Co2+: In an octahedral field, i.e., cubic field, the ground state is 4F. This is split by
lower symmetry fields and spin–orbit coupling to six doublets (Kramer’s degeneracy). The
lowest doublet is separated from the next by about 200 cm-1. Thus, the effective spin has a
value of ½ instead of 3/2 (three unpaired electron).
6.19 Mixing of States and Zero–Field Splitting
The magnitude of zero–field splitting in transition metal ions generally arises from the crystal
field. But Mn2+ (d5 system) has an spherically symmetric electron distribution and has 6S
ground state. It is not split by the crystal. However, this system also shows zero– field
splitting.
Explanation
The spin–orbit coupling mixes the ground state with the excited states, which are split by
crystal field. This mixing gives rise to a small zero– field splitting in Mn2+.
6.20 Hyperfine Splitting
When the unpaired electron comes in the vicinity of a nucleus with a spin I, an interaction
takes place, which causes the absorption signal to be split in to 2I+1components.
Reason
The nuclear spin–electron spin coupling arises mainly from the Fermi contact term. The two
energy levels of a free electron in a magnetic field are given in Figure 6.

Figure 6: The two energy levels of a free electron in a magnetic field

Karnataka State Open University Page 108

Spectroscopic applications in Inorganic chemistry Block 4.1.2

From magnetic considerations, interaction of a proton nuclear moment corresponding to

quantum number mI= ½ with the electron spin moment corresponding to the quantum number
mS = -½ will lead to lower energy than the interaction of moments of mI = -½ and mS = -½.
Similar theory applies to the other state. The energies of the levels are given by,
E = gβHmS = AmSmI
where ‘A’ is the hyperfine coupling constant.
Selection Rules
Only those transitions are allowed for which ∆mI = 0 and ∆mS = ±1.
6.21 Characteristics of A
1. Positive ‘A’means mS = -½, mI= +½ will have lower energy. Negative‘A’means mS= -
½, mI= -½ will have lower energy.
2. Sign of A’cannot be determined from a simple spectrum.
3. Magnitude of splitting is expressed in terms of coupling constant ‘A’.
4. The magnitude of ‘A’ depends on the following
a) The ratio of the nuclear magnetic moment to the nuclear spin.
b) Spin density in the immediate vicinityof the nucleus.
c) Anisotropic effect
6.22 Hyperfine Splitting in Various Structures
When an unpaired electron interacts with a nuclear spin, I, it will give rise to 2I+1 lines. All
the lines will be of equal intensity and equal spacing. For example, for an unpaired electron
on nitrogen, three lines are expected because I = 1 for nitrogen and 2I+1 = 2(1) + 1 = 3.When
the absorption spectrum is split by ‘n’ equivalent nuclei of equal spin, Ii, the number of lines
is given by 2nIi+1. When the splitting is caused by both a set of ‘n’ equivalent nuclei of spin
Ii and a set of ‘m’ equivalent nuclei of spin Ij , the number of lines is given
by(2nIi+1)(2mIj+1). For example, if a radical contains ‘n’ non-equivalent protons on to which
the electron is delocalised, a spectrum consisting of 2n lines will arise corresponding to the
two spin states for ‘n’ protons. Instead, if the electron is delocalised over ‘n’ equivalent
protons, a total of n+1 lines will appear in the spectrum.
Example. Bis(salicylaldimine)copper(II):

Karnataka State Open University Page 109

Spectroscopic applications in Inorganic chemistry Block 4.1.2

In the e.p.r. spectrum of the above complex, four main groups of lines are seen due to the
coupling of the Cu63 nucleus (I = 3/2) with the electron. Each group consists of eleven peaks
due to hyperfine interaction with the two equivalent nitrogen atoms and two hydrogen atoms,
H. The total number of peaks will be equal to (2nNIN + 1)(2nHIH + 1). That is, the total
number of peaks will be equal to,(2 x 2 x 1+1)(2 x 2 x ½ +1) = 5 x 3 = 15 However, only
eleven peaks are seen due to overlap. The total number of peaks obtained shows that only two
of the four hydrogens are involved in coupling. Therefore, we have to find out which set of
the hydrogens, H’or H’’, is involved in coupling. Deuteration of the N-H’’ produced a
compound, which gave an identical spectrum. However, when the H’ were replaced by
methyl groups, the e.p.r. spectrum consisted of four main groups. Each group consisted of
five lines resulting from nitrogen splitting only. Thisclearly proves that only the H’ are
involved in splitting. The spectrum furnishes conclusive evidence for the delocalisation of the
odd electron in this complex between the metal and the ligand.
Line widths in Solid State e.p.r.
The line widths are determined by three factors
1. Spin– Lattice relaxation
2. Spin–Spin relaxation
3. Exchange processes
6.23 Spin–Lattice relaxation
Spin–Lattice relaxation causes line broadening. That is, the paramagnetic ion interacts with
the thermal vibrations of the lattice leading to line broadening. The spin–lattice relaxation
times vary for different systems. This variation in time in different systems is quite large. For
some compounds, it is sufficiently long so that the spectra can be observed at room
temperature while in others it is not possible. As the temperature decreases, the relaxation
time increases. Hence, many salts of the transition metals are to be cooled to liquid nitrogen,
hydrogen or helium temperature to observe good spectra.
6.24 Spin–Spin relaxation
This results from the small magnetic fields that exist on neighboring paramagnetic ions. As a
result of these fields, the total field at the ions is slightly altered and the energy levels are
shifted. A distribution of energies results which produces broadening of the signal. This
effect depends on the distance between the ions, r, and the angle between the field and the
symmetry axis θ. These are clear from the expression, (1/r3)(1 – 3cos2θ). This kind of
broadening will show a marked dependence up on the direction of the field. This effect can

Karnataka State Open University Page 110

Spectroscopic applications in Inorganic chemistry Block 4.1.2

be reduced by increasing the distance between the paramagnetic ions by diluting the salt with
an isomorphous diamagnetic material.
Exchange processes
Exchange processes alter line widthsconsiderably. This effect can also be reduced bydilution.
If the exchange occurs between equivalentions, the lines broaden at the base and become
narrower at the center. When exchange involves dissimilar ions, the resonances of the
separate lines merge to produce a single broad line. Such an effect is observed for
CuSO4.7H2O, which has two distinct copper sites per unit cell.
Tetragonal distortion
In a tetragonally elongated octahedron, the energy of the dz2 orbital will be lower than that of
the dx2-y2 orbital. So, the unpaired ninth electron will stay in the dx2-y2 orbital. On the other
hand, if the octahedron is compressed along the z-axis, then the energy of the dz2 orbital will
be higher than that of the dx2-y2 orbital. Hence, the unpaired electron will reside in the dz2
orbital. These are shown in Figures 8 and 9.

Figure 8: the energy eleves in tetragonally elongated octahedron molecules

Karnataka State Open University Page 111

Spectroscopic applications in Inorganic chemistry Block 4.1.2

6.25 Calculation of g|| and g┴ for these two states

Ground state, dz2
This means that the copper(II) unpaired electron isin the dz2 orbital, that is, z-in distortion
and compressed. Then,

Where ‘λ’ is the spin–orbit coupling constant of the free ion. Here, λ is negative because the
system is more than half–filled (d9 system). Hence ‘g’ will be greater than two. Therefore, for
a tetragonally compressedcopper(II) complex, g┴ > g|| , where g|| = 2.
Ground state, dx2-y2
This means that the unpaired electron is in the dx2-y2 orbital. This orbital has the highest
energy. This becomes the ground state in terms of the hole.

Since λ is negative, g|| > 2

Since λ is negative, g┴ is also greater than two. Nevertheless, it is clear from the above
equations that g|| > g┴ .Thus, for a tetragonally compressed copper(II)complex,( z-in
distortion), g┴ > g|| and for a tetragonally elongated,(z-out distortion), copper(II) complex g|| >
g┴. These observations can be summarized as follows

6.26 ESR and Jahn-Teller distortion

Jahn-Teller theorem states any non-linear electronically degenerate system is unstable hence
it will undergo distortion to reduce the symmetry, remove the degeneracy and hence increase
its stability. But this theorem does not predict the type of distortion. Because of J-T distortion
the electronic levels are split and hence the number of ESR lines may increase of decrease.

Karnataka State Open University Page 112

Spectroscopic applications in Inorganic chemistry Block 4.1.2

6.27 E.S.R. of Transition Metal Complexes

a) d1 system,2T2g: S’= ½: octahedral
The ground term is 2T2g. There is considerable spin-orbit coupling. Since it contains odd
number of unpaired electrons, Kramer’s degeneracy will operate.
All of the Kramer’s doublets are close in energy. Hence, extensive mixing takes place by
spin-orbit coupling. This leads to a short relaxation time. Therefore, the ESR signal may be
obtained only at very low temperatures.(When the spin-orbit coupling is large, the
degeneracy is maintained due to extensive mixing of the orbitals. Hence, the levels do not
split and a signal is not obtained. However, at low temperatures, the mixing of orbitals does
not take place readily due to the decrease in kinetic energy. Hence, the levels split and a
signal is obtained.)
Example
1:CsTi(SO4)2.12H2O (undiluted)
In the above compound, Ti is present as Ti3+. g||= 1.24and g┴ = 1.14. The ESR signal may be
obtained only at very low temperature. The ground state of the 2T2g term is J = 1½ with g = 0.
However, the above experimental g-values have been obtained due to a tetragonal or trigonal
ligand field component of magnitude comparable to λ for the ion (λo = 154 cm-1).
Example 2: KTi(C2O4)2.2H2O.
For this compound, g|| = 1.86 and g┴ = 1.96. These results indicate that a large ligand field
component compared to λ is present. The value is nearer to two and nearly isotropic. This
indicates that the orbital angular momentum is almost quenched. Therefore, the electron is
not restricted to any particular orbital and moves like a free electron. This is supported by the
fact that the signal can be obtained at ordinary temperatures. The large ligand field
component is due to the nonequivalence of the ligand groups.
b) d1tetrahedral
In a tetrahedral ligand field, the ground state is 2E [(x2-y2); z2]. It has no first order spin-orbit
coupling. In this geometry, the ground state mixes with the nearby 2T2 excited states by
second order spin-orbit coupling. This leads to a short spin relaxation time for the electron
and broad absorption lines. The complexes must be usually studied near the liquid helium
temperature. The 2T excited state is split by spin-orbit coupling. When the ligand field is
distorted,
e.g.VO2+, the ground state becomes orbitally singlet and the excited states are well removed.
Sharper lines are obtained at higher temperatures.

Karnataka State Open University Page 113

Spectroscopic applications in Inorganic chemistry Block 4.1.2

c) d2 system ; 3T1g
The ground term is 3T1g. Extensive spin-orbit coupling is present in this state. Therefore,
ESR is usually not observed. The configuration approximates to cubic symmetry in an
octahedral complex. Very few examples of ESR spectra of these ions in octahedral
complexes have been reported because of this reason.V3+ in an octahedral environment in
Al2O3 gave g|| =1.92, g┴ = 1.63, D = +7.85, and A = 102.
d) d2 tetrahedral
Tetrahedral complexes have a 3A2 ground state and hence no spin-orbit coupling. The
relaxation time will be longer and so the ESR signal is observed readily.
e) d3 system, 4A1g; S’ = 1½
The ground term is 4A2g. S’= 1½. Since more than one unpaired electron is present, zero field
splitting will take place. The number of unpaired electron is odd and hence, Kramer’s
degeneracy will be applicable. That is, each level will remain doubly degenerate. As a result,
Kramer’s doublet will be the lowest in energy. When the zero field splitting is small as shown
in Figure 9, sometimes three transitions can be observed. The zero field parameter can be
obtained from the two effected transitions.

Figure 9: the zero field splitting of d3 system

When the zero field splitting is large compared to the spectrometer frequency, only one line
will be observed. In octahedral complexes, the metal electrons are in t2g orbitals, so that
ligand hyperfine couplings are usually small. The g-value for this system is given according
to the crystal field theory by the following expression

The ground state, 4A2g, has no spin-orbit coupling. A small amount of this state is mixed with
4
T2g state.

Karnataka State Open University Page 114

Spectroscopic applications in Inorganic chemistry Block 4.1.2

For V(H2O)6, ∆E = 11800 cm-1 and λ= 56 cm-1. These values give g = 1.964, which is close
to the observed value of 1.972.
For Cr(H2O)63+, ∆E = 17400 cm-1, λ = 91 cm-1 and the predicted value of ‘g’is smaller than
the experimental value of 1.994. This is in agreement with the fact that the crystal field
approximations are poorer and covalency becomes more important as the charge on the
central ion increases.
In K3MoCl6, Mo is present as Mo3+. When this is diluted in K3InCl6, g = 1.93 that is nearly
isotropic. Zero field splitting, D, is very large. (‘D’ specifies the zero field due to a ligand
field component of trigonal or tetragonal symmetry). The value of ‘g’ is in good agreement
with the predicted by the following equation
g = 2(1-4k2λ0)/10Dq for A2g term. ‘D’ has a higher value relative to chromium compound
because of the larger spin-orbit coupling constant for Mo3+ (λ0 = 267 cm-1).
f) d4 System; 5Eg; S = 2
The ground term is 5Eg and S = 2. Very few spectra are reported for this ‘d’ electron
configuration. In a weak crystalline Oh field, the ground state is 5Eg. This has no orbital
angular momentum. The possible states are – 2, -1, 0 , +1, +2. The zero field splitting splits
them in to three energy levels, namely, ±2, ±1, 0. That is, anon degenerate level, two fold
degenerate levels lying higher by ‘D’and two fold degenerate levels lying higher by 4D.
Example: undiluted CrSO4.5H2O
For this compound, g||= 1.95 and g┴ = 1.99 and ‘D’ is fairly large. These results indicate an
appreciably low symmetry ligand field component. The average value of ‘g’is 1.98, which is
in good agreement with predictions based up on the following equation
g = 2(1-2k2λ0)/10Dq
Since S = 2, mS= -2, -1, 0, +1, +2. The splitting of the energy levels is shown in Figure 10.

Figure 10: Splitting of energy levels in CrSO4.5H2O

Karnataka State Open University Page 115

Spectroscopic applications in Inorganic chemistry Block 4.1.2

When the splitting is large, no transition takes place because of large energy between the
levels. The Jahn-Teller distortion and the accompanying large zero field splitting make it
impossible to see a spectrum.
g) d5 Spin- free, 6A1g; spin-paired, 2T2g
For spin-free complexes, S’= 2½ and for spin-paired complexes, S’ = ½. ‘g’is isotropic. The
very small zero field splitting is neglected. The absence of zero field splitting follows from
the fact that there is no sextet term other than the ground 6A1g term. The 4T1g is the closest
other term and second order spin-orbit coupling effects are needed to mix in this
configuration, so the contributions are small. Hence, the electron lifetime is long and ESR
signals are easily detected at room temperature in all symmetry crystal fields. Because of odd
number of unpaired electrons, Kramer’s degeneracy exists even when there is large zero field
splitting. The energy levels of Mn(II) are shown in Figure 11.

Figure 11: The energy levels of Mn(II)

The isotropy of ‘g’ also follows from the same fact. The different mS values are – 5/2, -3/2, -
½, 0, +½, +3/2, +5/2.
‘g’ is very nearly 2.00 in many salts of Mn2+ and of Fe3+.
Examples are MnSO4.7H2O diluted in ZnSO4.7H2O and KFeSO4.12H2O diluted in
KAlSO4.12H2O.These results are expected for the 6A1g (6S) ground term.

Karnataka State Open University Page 116

Spectroscopic applications in Inorganic chemistry Block 4.1.2

h) Spin-paired d5
In K3Fe(CN), diluted in K3Co(CN)6, g|| and g┴ are0.92 and 2.22 respectively. The signal may
only be obtained at very low temperatures. These results indicate the presence of a ligand
field component of low symmetry of magnitude less than the spin-orbit coupling constant (λ0
= -460 cm-1) together with a small amount of t2g electron delocalisation. The splitting of the
free ion doublet state by an Oh field, by D3distortion, spin-orbit coupling, and a magnetic
field are shown in Figure 12. Since we have non-integral spin, the double group
representations are employed for the representations.

Figure 12: The splitting of the free ion doublet state by an Oh field, by D3distortion, spin-
orbit coupling, and a magnetic field

K4Mn(CN)6.3H2O diluted in K4Fe(CN)6.3H2O has g|| = 0.72 and g┴= 2.41. The signal may be
obtained only at very low temperatures. The results indicate that that ligand field component
of low symmetry and of magnitude comparable to the spin-orbit coupling constant (λ0= -355
cm-1)
For Ru(NH3)6Cl3diluted in Co(NH3)6Cl3, g|| = 1.72and g┴ = 2.04. The signal is obtained only
at low temperatures. These results indicate a tetragonal ortrigonal ligand field component,
which is either smaller or large compared to the spin-orbit coupling parameter (λ0= -1180 cm-
1
).
K2IrCl6 diluted in K2PtCl6 gives g = 1.78 and isotropic. The signal can be obtained only at
low temperatures. The results indicate the presence of some t2g electron delocalisation and
that any low symmetry ligand field component must be much smaller than the spin-orbit
coupling constant (λ0 = -5000 cm-1).

Karnataka State Open University Page 117

Spectroscopic applications in Inorganic chemistry Block 4.1.2

In a strong field, the ground state is 2T2g. Spin-orbit coupling splits this term in to three
closely spaced Kramer’s doublets. However, greater the spin-orbit coupling, shorter the
relaxation time and hence the signal can be seen only at low temperatures. Due to Jahn-Teller
distortions, the expected g-values are rarely obtained.
6.28 Application of ESR spectroscopy of biological molecules
Transition metal (d-group) ions are widespread in nature, essential for structural
characteristics and mechanistic specificity of many proteins. Iron and copper are the two most
prevalent metals in proteins responsible for the storage and transport of molecules, ions, and
electrons. Electron paramagnetic resonance (EPR) spectroscopy has been extensively used
for the determination of these metal ions without extensive disruption of the native protein
moiety. It also detects variations in coordination geometry due to ligand substitutions as well
as multiple valencies of the same metal.
a) Iron proteins
Iron is the single most abundant metal in biological systems, occurring mostly in respiratory
proteins. Haemoglobin and myoglobin are two most abundant iron-containing proteins. The
strategic presence of iron in the haem facilitates transportation and storage of oxygen by the
two proteins, respectively. Reversible binding by carbon dioxide in the forms of carbonic
acid and carbamino compounds in concert with a pH differential (Bohr effect) facilitate the
gaseous exchange mechanisms through the lungs. Both proteins are structurally similar
except that haemoglobin is a tetramer of the myoglobin-type structure. Other iron-containing
proteins found in large amounts are ferritin, transferrin, and haemosiderin. Cytochromes and
cytochrome oxidases are iron-containing proteins responsible for electron transport in the
mitochondria.
Detection of iron by EPR spectroscopy depends on the presence of unpaired electrons in
resting or intermediate reactive species. As a rule of thumb, electronic configurations of d-
group metal ions which can be detected by EPR spectroscopy would contain d1, d3, d5, d7, and
d9 terms. The presence of an odd number of electrons results in at least one unpaired electron
being available for EPR transitions.
Iron in the monovalent state FeI has the d7 configuration with spin value s = 1/2 arising from
a distribution into two sets of non-degenerate d-orbitals to give t62ge1g. Promotion of the
residual 4s1 electron to the 3d-orbital however would require such a large amount of energy
that constituent protein moiety close to the iron may be affected structurally. If at all possible,
the EPR spectrum would comprise a doublet of lines arising from a spin value s = 1/2.
Divalent FeII specie is a d6 configuration with two possibilities of spin states; a low spin

Karnataka State Open University Page 118

 Spectroscopic applications in Inorganic chemistry Block 4.1.2

t62ge0g and a high spin t42ge2gdepending on crystal field splitting energy of associated ligands.
Their respective spin values are hence s = 0 and s = 2, both of which are not observable by
EPR. Detection of nitrous oxide by binding to ferro-hemoproteins is due to formation of the
Fe–N=O complex in which nitrogen p-orbital overlaps with the Fe d-orbital such that the
unpaired electron is mainly localised on the NO ligand. The iron has a spin 3/2
The trivalent state FeIII has d5, a most stable configuration with possibilities of two spin
states; low spin t32ge2g and high spin t52ge0g . Their respective spin values of 5/2 and 1/2 are
both detectable by EPR, exhibiting many spectral characteristics depending on ligands,
molecular environment, and solvent medium.
The tetravalent state FeIV d4, t42ge0g has a spin value s = 1 which is not detectable by EPR.
This is the form of Fe in the oxo- complex of haemoglobin after its reaction with hydrogen
peroxide, known as ferryl species. Proof of formation of the ferryl [FeIV=O] specie by EPR
spectroscopy was obtained from its one-electron reduction to the easily detectable FeIII
derivative. The s = 2 state may be expected from an energy equalisation of the t2g and eg
levels so that four unpaired electrons are singly filled into four of the five degenerate energy
levels ∆ = 0. This however is purely hypothetical. Pairing of the four electrons in two levels
to give s = 0 is also not possible. Figure 16 show typical EPR spectra for FeIII derivatives of
haemoglobin in high and low spin spectroscopic states.

Figure 16: First derivative X-band EPR spectrum for methaemoglobin showing (a) high spin features
of FeIII at g = 6, low field, (b) low spin FeII features at g = 2.855, 2.226, and 1.794, mid-field.

The distinguishing features are the field positions at which resonance occurs. More precisely
these are translated to g-values, considering variations of frequencies of microwave applied.
The X-band spectrum for high spin state shows strong features at g = 6 and a complimentary
weak absorption at close to free spin, g = 2. High spin FeIII may also show up at g = 4.3 due
to quantum mechanical mixed states. For the low spin form three lines can be observed at g-
values of 2.82, 2.20, and

Karnataka State Open University Page 119

Spectroscopic applications in Inorganic chemistry Block 4.1.2

1.67, all of which arise from the same transition in axial symmetry exhibiting gx, gy, and gz
orthogonal character of a tensor. As the ligand at the sixth coordination position changes,
including pH effects, the symmetry of the central metal iron also changes creating distortions
from rhombic to axial symmetry. This is a consequence of Jahn–Teller effect. If the g-values
of low spin FeIII spectra were plotted to display gx in a linear format, the gy and gz have been
shown to follow a trend as shown in Figure 17.

Figure 17: Trends in the g-values for a range of low spin FeIII complexes
showing convergence of g-values to ‘free spin’.

The convergence point of all g-values is at ‘free spin’. This therefore is a display of EPR
spectroscopic parameters as geometry changes from axial to rhombic symmetry.
b) Copper proteins
Naturally abundant copper proteins include cerulloplasmin, hemocyanin, and Cu/Zn
superoxide dismutase.
The CuII,is a d9 species contain an odd number of electrons to give a spin s = 1/2 and
therefore EPR transitions are absorbed. With a magnetic moment MI = 3/2, CuII gives a
spectrum comprising a quartet of lines.
Major parameters for copper in proteins are the parallel and perpendicular features arising
from an axial type spectrum defined by g// and g⊥ and A// and A⊥. Typical spectra for CuII at
77 K are shown in Figure 18.
Karnataka State Open University Page 120
Spectroscopic applications in Inorganic chemistry Block 4.1.2

Figure 18: First derivative EPR spectra for CuII showing different g-values and A-
values for different structural environments.
It is important to note differences in EPR parameters of the two copper species indicating
different CuII centres by virtue of respective ligand environments. Some works have
identified copper centres as type 1, type 2 and type 3. The type 1 has an intense blue
coloration and a high extinction coefficient in its electronic absorption spectrum. The type 2
has a weaker absorption spectrum and higher hyperfine splitting constants (A-values) in its
EPR spectrum than type 1. Type 3 comprises pairs of copper so close there is
antiferromagnetic coupling and therefore not detectable by EPR spectoroscopy. On a plot of
A//vs g// types 1 and 2 are differentiated into groups as shown in Figure 4. Like iron the
copper is complexed within protein moieties such that hydrated copper ion is not observed
except where there has been denaturation in which the metal drops free of the protein. In such
a case spectroscopic parameters would be different. A common ligand is nitrogen, usually
from the side group of a histidine residue. Nitrogen hyperfines would therefore show on the
copper peaks.
c) Manganese proteins
Manganese occurs in much smaller amounts than iron and copper in nature. As a contributor
to electron transfer in the oxygen evolving photosystem, manganese is widespread in plants.
Its presence is easily determined by EPR, based on MnII, d5, s = 5/2. On interaction with the
nucleus MI = 1, a characteristic set of six isotopic lines is obtained, centred close to free spin.
Figure 6 shows MnII lines obtained from tobacco leaves at 77 K. The mitochondrial
superoxide dismutase enzyme contains manganese, though this is far less abundant than the

Karnataka State Open University Page 121

Spectroscopic applications in Inorganic chemistry Block 4.1.2

copper-zinc enzyme. The EPR spectrum for MnSOD shows features ascribed to high spin.
MnIII and MnIV and probably higher oxidation states are reported to be present in catalases
d) Cobalamin
Cobalamin, also known as vitamin B12, is an organic molecule in which a cobalt is 4
coordinated at the centre of a corrin group, a smaller haem-type structure with 4 nitrogen
donor positions. The fifth position is N-linked to a dimethylbenzimidazole to which is
attached a ribose-3-phosphate O-linked to aminopropanol. The sixth position is occupied by
5-deoxyadenosyl, but can be replaced by other substitutes as in the different derivatives of
cobalamin. The CoII nucleus has a d5 configuration with spin s = 1/2, and a magnetic moment
MI = 7/2. The EPR spectrum comprises 8 lines as shown in Figure 19. In spite of apparent
similarities of the haem and corrin structures iron and cobalt are not biologically
interchangeable. This must be due to their redox potentials being different, an important
discriminatory factor in selectivity of biological electron transfer reactions.

Figure19: First derivative EPR spectrum for CoII centres at 4 K, showing features
assigned to spin s = 1/2 and MI = 7/2.

6.29 The ESR spectrum of PH4 *

The quantum-chemically calculated PH4 structure of minimum energy is a distorted trigonal
bipyramid (TBP) with two axial (ax) and two equatorial (eq) hydrogen atoms. The unpaired
electron is placed at the position of the missing equatorial ligand. From quantum-chemical
calculations revealing significant odd-electron density to reside on the axial position it was
shown that the metastable structure B as shown in Figure 20 is equal correct with dashed
lines denoting three-electron three-centre bonding.

Karnataka State Open University Page 122

Spectroscopic applications in Inorganic chemistry Block 4.1.2

Figure 20: Structure of PH4

There is considerable evidence that the basic structure of free radicals derived from
tetravalent phosphorus (phosphoranyl radicals) is that of a distorted trigonal bipyramid in
which two ligand sites, apical and equatorial, are distinguished. ESR hyperfine interactions
show a striking disparity between the unpaired spin densities at the two positions, and
theoretical arguments favour the apical position as having the higher spin density.

Figure 21; ESR spectrum PH4 in neopentane at 100

o
K.
An analysis of the ESR spectra of PH4 (and deuterated species) in xenon and neopentane
matrices confirmed the theoretically obtained TBP-eq structure of PH4. The best resolved
ESR spectrum of PH4 was obtained in a neopentane matrix. The ESR of PH4 consisted of
eight 6.0 G, 1: 2: 1 triplets (Figure 21). It was conclusively shown by experiments with PD3
and neopentane-d12 that a large interaction of - 500 G was due to a 3lp nucleus, and that
smaller (- 6 and 200 G) interactions were due to pairs of equivalent protons.
6.30 Summary of the unit
Electron Spin Resonance (ESR) spectroscopy, also referred to as Electron Paramagnetic
Resonance (EPR) spectroscopy, is a versatile, non-destructive analytical technique based on
the absorption of microwave radiation in presence of an applied field by paramagnetic
species.
When any species that contains unpaired electron(s) is subjected to a static magnetic field, the
interaction between the magnetic moment of the electron and the applied magnetic field splits

Karnataka State Open University Page 123

Spectroscopic applications in Inorganic chemistry Block 4.1.2

the spin energy levels (Zeeman splitting), and transitions between these spin levels are
induced by applying suitable microwave radiation perpendicular to the magnetic field.
Further interactions will depend on the presence of other factors such as the nuclear spins
present in both the origin and other neigbours. The resulting absorption of the microwave
radiation is modulated to record the first derivative of the absorption. Conventionally, EPR
spectra are recorded as first derivative rather than absorption to improve the resolution. In
fact, second derivative operation is also possible when needed to get better resolution of
complex splitting patterns.
6.31 Key words
ESR spectroscopy; Characteristics of ‘g’; Types of E.S.R. Instruments; g-value for an
electron and a complex; Factors affecting g-value in a complex; Sustaining effect; Zero– field
splitting; Kramer’s degeneracy; Hyperfine Splitting; Spin–Lattice relaxation; Spin–Spin
relaxation; E.S.R. of Transition Metal Complexes
6.32 References for further studies
1) Electron Spin Resonance: Analysis and Interpretation; Philip Henri Rieger; Royal
Society of Chemistry, 2007.
2) Principles and Applications of ESR Spectroscopy; Anders Lund, Shigetaka Shimada,
Masaru Shiotani; Springer Science & Business Media, 2011.
3) EPR Spectroscopy: Applications in Chemistry and Biology; Malte Drescher, Gunnar
Jeschke; Springer Science & Business Media, 2012.
4) Biomolecular EPR Spectroscopy; Wilfred Raymond Hagen; CRC Press, 2008.
5) Foundations of Modern EPR; Gareth R. Eaton, Sandra S. Eaton; World Scientific,
1998.
6) Spectral Methods in Transition Metal Complexes; K. Sridharan; Elsevier, 2016.
6.33Questions for self understanding
1) Explain the basic theory of ESR spectroscopy
2) Discuss the characteristics of ‘g’
3) Write a note on g-value for an electron and a complex
4) Explain the factors affecting g-value in a complex
5) What is sustaining effect?
6) Discuss the combined effects of CFS and L-S coupling
7) Comment on g-value and structure of complex molecules
8) Write a note on Zero– field splitting and Kramer’s degeneracy
9) Discuss the consequences of ZFS

Karnataka State Open University Page 124

Spectroscopic applications in Inorganic chemistry Block 4.1.2

10) Write a note on break down of selection rules

11) Discuss Mixing of states
12) Write a note on magnitude of zero- field splitting and signal
13) Explain the effective spin, S’
14) Discuss mixing of states and Zero–Field splitting
15) Write a note on hyperfine Splitting
16) Discuss the characteristics of A
17) Write a note on calculation of g|| and g┴ for these two states
18) Write a note on ESR and Jahn-Teller distortion
19) With suitable example discuss the E.S.R. of transition metal complexes with following
cases
a) d1 system,2T2g: S’= ½: octahedral
b) d1tetrahedral
c) d2 system ; 3T1g
d) d2 tetrahedral
e) d3 system, 4A1g; S’ = 1½
f) d4 System; 5Eg; S = 2
g) d5 Spin- free, 6A1g; spin-paired, 2T2g
h) Spin-paired d5
20) Explain the application of ESR spectroscopy for following biological molecules
a) Iron proteins
b) Copper proteins
c) Manganese proteins
d) Cobalamin
21) Discuss the ESR spectrum of PH4 radical.

Karnataka State Open University Page 125

Spectroscopic applications in Inorganic chemistry Block 4.1.2

UNIT-7
Structure
7.0 Objectives of the unit
7.1 Introdcution
7.2 NMR spectra of Inorganic compounds
7.3 Practical limitations to metal NMR spectroscopy
7.4 Favourable properties for high-resolution NMR spectroscopy are
7.5 Chemical Shift
7.6 Chemically equivalent nuclei
7.7 Integration
7.8 Spin-Spin Splitting (Coupling)
7.9 31P NMR spectroscopy
7.9.1 Differences between 1H and 31P NMR
7.9.2 Interpreting spectra
7.9.3 Different phosphorus environments and their coupling to 1H
7.9.4 31P-1H coupling
7.9.5 Coupling to fuorine
7.9.6 31P NMR applications
19
7.10 F NMR spectroscopy
7.10.1 Chemical shift in 19F NMR
7.11 Boron NMR spectroscopy
7.11.1 Chemical Shift
7.11.2 General Comments on the Boron Chemical Shifts
7.11.3 Spin-spin coupling between Boron and Nitrogen
7.11.4 Spin-spin coupling between boron and phosphorous
7.12 other NMR active nuclei
7.12.1 Lead
7.12.2 Platinum
7.12.3 Palladium
7.13 1H NMR spectroscopy organometallic
7.14 Summary of the unit
7.15 Key words
7.16 References for further studies
7.17 Questions for self understanding

Karnataka State Open University Page 126

Spectroscopic applications in Inorganic chemistry Block 4.1.2

7.0 Objectives of the unit

After studying this unit you are able to

Explain the NMR spectra of Inorganic compounds

Explain the practical limitations to metal NMR spectroscopy

Identify the favourable properties for high-resolution NMR spectroscopy are

Explain the Spin-Spin Splitting (Coupling)

Explain the use of 31P NMR spectroscopy

Explain the use of 19F NMR spectroscopy

Explain the use of Boron NMR spectroscopy

Explain the use of other NMR active nuclei

Explain the use of 1H NMR spectroscopy for organometallic compounds
7.1 Introdcution
Nuclear Magnetic Resonance (NMR) spectroscopy takes advantage of the magnetic
properties of certain nuclei and records the absorption of energy between quantized nuclear
energy levels. In an NMR experiment, the spectrometer is tuned to the frequency of a
particular nucleus and the spectrum reveals all such nuclei in the molecule being investigated.
It is thus a very powerful technique, the closest analogy being a powerful microscope that
allows the chemist to "see" the structure of molecules in solution. Actually, the NMR
experiment does not directly show how all the atoms are connected. Accordingly, it is up to
the chemist to take the information provided by NMR spectra to build a model of the
molecule. The analysis of NMR spectra is very much like putting a puzzle together. The
structure of the molecule will be known when all of the pieces fit together.
7.2 NMR spectra of Inorganic compounds
Multinuclear NMR spectroscopy is the name given to the study of NMR active nuclei of
elements other than 1H (proton) or 13C (carbon). The 15N, 11B 19F, 31P, 77Se, 119Sn, 199Hg, etc
nucleus have spin number I ≥ ½ and are NMR active. The second most sensitive nucleus for
NMR is 19F.
In addition to charge and mass, which all nuclei have, various nuclei also possess a property
called nuclear spin, which means they were spinning. Since nuclei have a charge, they
generate a magnetic field with an associated magnetic moment. NMR is possible owing to the
magnetic properties of certain nuclei.
There are useful empirical rules relating mass number, atomic number (Z) and nuclear spin
quantum number (I), which are shown in the Table 1:

Karnataka State Open University Page 127

Spectroscopic applications in Inorganic chemistry Block 4.1.2

Table 1: Empirical rules relating mass number, atomic number (Z) and nuclear spin
quantum number (I)

Since NMR depends on the existence of a nuclear spin, nuclei with I = 0 have no NMR
12 16 18
spectrum (e.g., C, O, O). The most important class of nuclei are those with I = ½ are
NMR active and give sharp NMR spectrum. Nuclei with I >1/2 (e.g., 11B, I = 3/2; 14N, I = 1)
have quadrupole moments, a non-spherical distribution of nuclear charge, which results in
broad absorption lines and makes observation of spectra more difficult. The quadrupole
moment can even affect the lineshape of neighbouring nuclei. For example, resonances of
protons bonded to nitrogen or boron atoms are generally broad in 1H NMR spectra. We shall
thus be primarily concerned with nuclei where I = 1/2, but the effect that quadrupolar nuclei
can have on the NMR spectra of I = ½ nuclei should be remembered. A listing of isotopes
with I = 1/2 is provided in the Table 2.
Table 2: Isotopes with I = ½ and their natural abundance

7.3 Practical limitations to metal NMR spectroscopy

The NMR spectroscopy study of metal (in particular transition metal) is very much
unfavourable. This is because of the small number of nuclei with favourable nuclear
properties for high-resolution NMR. As the technology evolves, more nuclei bond types are
being brought into the spectroscopist’s net. The NMR properties of the various nuclei
tabulate in Table 3.

Karnataka State Open University Page 128

Spectroscopic applications in Inorganic chemistry Block 4.1.2

Table 3: The NMR properties of the various nuclei.

Karnataka State Open University Page 129

Spectroscopic applications in Inorganic chemistry Block 4.1.2

7.4 Favourable properties for high-resolution NMR spectroscopy are

1) Spin quantum number I = 1/2 or, for I > ½
2) A relatively small value of the nuclear electric quadrupole moment (eQ ) and
3) A large value of I, to minimize quadrupolar broadening.
Also necessary are a sufficiently large natural abundance (A) and magnetogyricratio (γ,
effectively the ratio of the magnetic moment to the spin quantum number), to which the
NMR frequency is proportional.
The intrinsic NMR receptivity, which is a measure of the intensity of signal, increases as |γ3|
AI( I+ 1). Thus, larger values of I are more favorable by a factor of 33 from I = 1/2 to 9/2.
Transition metal nuclei with natural abundance below 5% that may be usefully studied with
enrichment are 57Fe, 61Ni, 67Zn and 187Os.
Spin I = 1/2 nuclei with low γ values have a further problem of too slow relaxation, since the
rate depends on γ , and long accumulation times or sensitivity enhancement techniques may
be needed for adequate sensitivity; examples are 89Y, 183W, 57Fe, 187Os, 103Rh and 109Ag.
For the majority of metal nuclei, the spin quantum number I is greater than 1/2 and, therefore,
they possess a nuclear electric quadrupole moment eQ (in addition to their magnetic
moment), as the nuclear electric charge distribution is not spherically symmetric. The electric
quadrupole is coupled to the spin (magnetic dipole), since transitions in the one change the
magnetic environment of the other. Whereas the orientation of the spin dipole is quantized
relative to the magnetic field, that of the electric quadrupole is quantized relative to the
electric field gradient (EFG) eQ at the nucleus due to the electrons and the other nuclei.

Karnataka State Open University Page 130

Spectroscopic applications in Inorganic chemistry Block 4.1.2

Thus the interaction of the nuclear quadrupole moment with the electric field gradients
arising from the local electronic environment provides a strong relaxation mechanism for the
spin states, often resulting in short-lived states with broad resonance lines. In general,
quadrupolar nuclei display broad resonances in NMR spectra, unless they are in highly
symmetric electrical environments, which reduce the magnitude of the electric field gradients
at the nuclei.
In an NMR experiment, the sample is placed in a strong magnetic field, Bo. Since the spins of
the magnetic nuclei are quantized, they can have only certain well-defined values. If we have
nuclei with I = 1/2 (e.g., 1H, 31P), the spins can orient only in two directions: ie, either with
(mI = +1/2, α) or against (mI = -1/2, β) the applied field. NMR transitions are allowed for
cases where ∆mI = ±1. There is an energy difference, ∆E, between the two states, and this is
given by

where h is Planck’s constant, γ is the gyromagnetic ratio (a constant characteristic of each

nucleus), and Bo is the applied magnetic field. When the energy of the incoming radiation
matches the energy difference between the spin states, energy is absorbed and the nucleus is
promoted from the lower +1/2 to the higher -1/2 spin state. Since the sign of mI changes, this
is sometimes referred to as a "spin flip". NMR transitions occur in the radio frequency (rf)
range of the electromagnetic spectrum. The absorption of rf energy is electronically detected
and is displayed as an NMR spectrum.
The above equation is very important since it shows that ∆E depends only on γ and Bo. The
gyromagnetic ratio, γ, is an intrinsic property of the magnetic nucleus. Therefore, each type
of nucleus has a distinct and characteristic value of γ. Accordingly, the NMR experiment
must be tuned for a specific nucleus and one must record a different NMR spectrum for each
NMR active nucleus of interest therefore not to worry about observing signals from different
nuclei on the same NMR spectrum. In order to gather all NMR knowledge about a molecule
such as PH3, we would record two different NMR spectra - a 1H NMR spectrum to observe

Karnataka State Open University Page 131

Spectroscopic applications in Inorganic chemistry Block 4.1.2

the 1H nuclei and a 31P NMR spectrum to observe the 31P nucleus. We would not observe the
31
P nucleus in a 1H NMR spectrum and vice-versa.
The above equation also reveals that ∆E is directly proportional to Bo, the external magnetic
field. The higher the external field, the greater is the energy separation between the α (mI =
+1/2) and β (mI = -1/2) spin states. Recalling that E = hν, another way of saying this is that
the resonance frequency of the nucleus increases with increasing Bo since E increases, so also
ν. This is shown in the Table.

Table 4: The differences in resonance frequency of the nucleus under same Bo

Note that all I = 1/2 nuclei behave according to the same theoretical principles, although 1H
NMR spectroscopy is the most commonly practiced, 19F and 31P NMR spectra are generated
in exactly the same way as a 1H NMR spectrum. The main difference between the different I
= ½ nuclei is that the resonance frequency is changed when recording the spectrum.
7.5 Chemical Shift
From the previous equation it is clear that, the resonance frequency is determined only by γ
and Bo. Therefore all atoms of a given nucleus in a molecule (e.g., all 1H nuclei) should
resonate at the same frequency. If this were the case, the NMR could tell us whether a
molecule contains NMR active nuclei (1H, 31P, 13C, etc.) or not and how many different NMR
active nuclei are present in the given molecule. Fortunately, the frequency of the NMR
absorptions of a given nucleus also depends on the chemical environment of the nucleus. The
variation of the resonance frequency with chemical environment is termed the chemical shift,
and herein lies the power of the NMR method.
The origin of the chemical shift is traced by the electrons surrounding the nucleus and the
interaction of the electron cloud with the applied field Bo. The reason for this is that
circulating electrons also generate a magnetic field that orients itself in the opposite direction
to the applied field.

Karnataka State Open University Page 132

Spectroscopic applications in Inorganic chemistry Block 4.1.2

The actual field (Blocal) “felt” by a nucleus is thus less than Bo, and the ability of the electrons
to alter the field felt at the nucleus can be expressed by σ, the shielding constant.

Nuclei are said to be shielded or deshielded depending on the presence or absence of electron
density surrounding them. For example, the introduction of an electron withdrawing group
(e.g., halogen, O, etc.) will reduce the electron density around a nucleus (deshielding; σ is
small) and the resonance frequency will increase. Conversely, an electron donating
substituent (e.g., CHx, SiHx) will cause increased shielding (σ is large) and lower the
resonance frequency.
For reporting chemical shifts, one could use absolute field or absolute frequency, but this
would be cumbersome and would result in the chemical shift being dependent upon the
applied field. A simpler scale for chemical shifts has been devised. Chemical shifts (δ) are
expressed in units of parts per million (ppm) of the spectrometer frequency with respect to a
reference material whose position is arbitrarily assigned a value of 0.0 ppm.

When expressed in such dimensionless units (δ in ppm), the chemical shifts are invariant of
the frequency of the spectrometer and can be used as molecular parameters. For example, 1.0
ppm at 60 MHz is equal to a separation of 60 Hz, and at 200 MHz, 1.0 ppm equals 200 Hz.
Thus, the same two resonances that are separated by 1 ppm at 60 MHz are still 1 ppm apart at
200 MHz, because δ = 60 Hz/60 MHz = 200 Hz/200 MHz = 1 ppm. Therefore, if the same
sample is run at two different spectrometer frequencies, the chemical shifts of the resonances
will be identical.
Naturally, this statement is only true if the same reference material is used for each spectrum.
Different references are used for different nuclei. The most widely accepted reference for 1H

Karnataka State Open University Page 133

Spectroscopic applications in Inorganic chemistry Block 4.1.2

and 13C NMR is tetramethylsilane (Si(CH3)4 = TMS). For 11B NMR, F3B•OEt2 is commonly
used, as are CFCl3 for 19F NMR and 85% H3PO4 for 31P NMR spectroscopy.
In the past, NMR spectra were obtained by varying the applied field and measuring the
chemical shift as a function of the field strength. This gave rise to the terminology of a
downfield shift for nuclei that were deshielded (as they required a lower applied field to bring
the nucleus into resonance) and upfield shift for shielded nuclei. For example, one would say
that a resonance at δ 8.0 ppm is downfield of one at δ 2.0 ppm, and conversely that the signal
at δ 2.0 ppm was upfield of the signal at δ 8.0 ppm.
More modern NMR spectrometers generate spectra by varying the frequency, ν, while
keeping the magnetic field strength, Bo, constant. Nevertheless, the upfield/downfield
terminology remains in common use. Unfortunately, this result in the confusing situation that
δ is positive in the downfield direction (to the left of the standard on spectra) where
resonancefrequencies are higher. Resonances that are upfield of the reference appear at lower
frequencies and have negative δ values.

7.6 Chemically equivalent nuclei

One important consequence of chemical shift is that each chemically different type of NMR
active nucleus in a molecule will give rise to its own signal in an NMR spectrum. Nuclei are
thus referred to as chemically equivalent or chemically inequivalent in determining how
many signals will be observed in an NMR spectrum. For example, both CH3Cl and CH2Cl2
provided one resonance each in the 1H NMR spectrum in below figure.

Karnataka State Open University Page 134

Spectroscopic applications in Inorganic chemistry Block 4.1.2

From this, we can infer that the individual hydrogens in each of these molecules are
chemically equivalent. From the viewpoint of chemical structure, the reason for this is that
hydrogens are related by symmetry elements (reflection through a mirror plane or rotation
about an axis) and are thus identical.
Sometimes, determining chemical equivalence or inequivalence is straightforward. It would
not take very much to convince you that the methyl hydrogens in ethanol (CH3CH2OH) are
different from the methylene hydrogens and that both of these are different than the hydroxyl
hydrogen; we would thus anticipate three signals in the 1H NMR spectrum. Upon further
reflection though, why should the hydrogens of the methyl group all be equivalent? The
answer is simple when it is recognized that methyl groups rotate freely and rapidly, with the
result that each hydrogen experiences the same overall chemical shift as it completes one
rotation, a situation analogous to CH3Cl described above. Therefore, all methyl groups
generally give rise to one signal in 1H NMR spectra. This concept can generally be applied to
analogous groups such as tert-butyl, C(CH3)3, trimethylsilyl, Si(CH3)3, and trifluoromethyl,
CF3 (in 19F NMR spectra).
The most general method of determining whether nuclei are chemically equivalent to other
nuclei in a molecule is to determine whether they are in the same environment, and whether
one nucleus can be related to the other through a symmetry transformation such as rotation or
reflection through a mirror plane. Some examples are provided below for illustration.

SF6 is a highly symmetrical octahedral molecule it gives 1 signal in the 19F NMR spectrum

Karnataka State Open University Page 135

Spectroscopic applications in Inorganic chemistry Block 4.1.2

The axial (ax) and equatorial (eq) fluorines are chemically inequivalent hence there are 2
signals are seen in the 19F NMR spectrum

The apical fluorine is chemically distinct from the four fluorines in the square base hence 2
signals are seen in the 19F NMR spectrum

The four fluorine nuclei in the square base are chemically equivalent hence 1 signal is seen in
the 19F NMR spectrum

7.7 Integration
The area under each NMR absorption peak can be electronically integrated to determine the
relative number of nuclei responsible for each peak. The integral of each peak can be
provided numerically, and is often accompanied by a line that represents the integration
graphically. Intensities of signals can be compared within a particular NMR spectrum only.
For example, 1H intensities cannot be compared to those of 19F or 31P nuclei. It is important to
note that the integration of a peak is a relative number and does not give the absolute number
of nuclei that cause the signal. Thus, the 1H NMR spectrum of H3C–SiH3 will show two
peaks in a 1:1 ratio, as will the 1H NMR spectrum of (H3C)3C–Si(CH3)3. This is simply
because the ratios 3:3 = 9:9 = 1:1.
The concept of integration, and also that of chemical shift, is illustrated in below Figure.
Determining integration ratios is an exercise in finding the greatest common divisor for the
series of peaks (the largest whole number divisor that will produce a whole number ratio). In
the above example, this value is either 1.4 cm or 9.9 integration units. It should be
remembered that integration is a measurement that is subject to error; it is common for the
error in integrated intensity to approach 5 - 10 %. The ratio of the integrated peak intensities
Karnataka State Open University Page 136
Spectroscopic applications in Inorganic chemistry Block 4.1.2

is 1:3 = 3:9, allowing us to assign the resonance at δ 3.21 to the methyl group and that at δ
1.20 to the (CH3)3C group. It is important to note that the hydrogens of the (CH3)3C group are
more shielded than the CH3 group. This occurs because the CH3 group is directly adjacent to
the electron withdrawing oxygen, but the corresponding methyl protons in the (CH3)3C group
are separated from oxygen by a second intervening carbon centre.

At this stage, we appreciate NMR resembles a molecular microscope. For example, at one
frequency we could "see" the various protons, while the carbons, fluorines, phosphorus, and
even certain metal nuclei could be observed at other frequencies. Within one spectrum, we
can make use of the position (chemical shift) and integrated intensity of the different signals
to assign particular molecular fragments responsible for them, and to build up a model of the
molecule. There is one more aspect of NMR that is extremely helpful in determining how to
connect the parts together.
7.8 Spin-Spin Splitting (Coupling)
The appearance of a resonance may be very different when there are other neighbouring
magnetic nuclei. The reason for this is that the nucleus under observation will interact with
the magnetic spins of the different neighbouring nuclei.

Karnataka State Open University Page 137

Spectroscopic applications in Inorganic chemistry Block 4.1.2

The simplest case is that of two protons having significantly different chemical shifts
(designated A and X). Considering chemical shift and integration only, we could represent
the spectrum as

Both protons have a spin of 1/2, and both can exist in the +1/2 and -1/2 spin states. Now, it
turns out that the magnetic environment of HA is slightly different when HX is in the +1/2
state than when it is in the -1/2 state. This can be represented pictorially with arrows
(pointing either up or down) representing the two spin states of HX.

As a result, HA will split into two lines. Each half the intensity of the unperturbed signal.
Similarly, HA will influence HX which becomes a doublet also. The splitting, or coupling, is
symmetrical about the unperturbed resonances δA and δX, and is described by the means of a
coupling constant, JAX, which has units of Hz.

Note that the magnitude of JAX is identical at both signals, coupled nuclei must share the
same coupling constant.
In a similar way, the resonance of a proton attached to phosphorus will be a doublet, since the
phosphorus nucleus has I = 1/2 and may be in the +1/2 or -1/2 state. However, the key
distinction here is that we are dealing with two different nuclei, and thus two different NMR
spectra. Each NMR spectrum (1H and 31P) will show one doublet with a JPH coupling constant
that is identical in magnitude. It is important to remember that, we cannot "see" a 31P nucleus
in a 1H NMR spectrum and vice-versa. Nonetheless, the splitting of the peaks into doublets in
each spectrum tells us that the 1H and 31P nuclei are interacting.

Karnataka State Open University Page 138

Spectroscopic applications in Inorganic chemistry Block 4.1.2

The influence of the neighbouring spins is called spin-spin coupling and NMR peaks are split
into multiplets as a result. The separation between the two peaks is called the coupling
constant, J, which is expressed in Hz.
Spin-spin coupling has the following characteristics
• The magnitude of J measures how strongly the nuclear spins interact with each other.
• Coupling is normally a through-bond interaction, and is proportional to the product of the
gyromagnetic ratios of the coupled nuclei.
For example, 1JCH = 124 Hz for 1H-13C coupling in CH4, and 1JSnH = 1931 Hz for 119
Sn-H
119 13
coupling in SnH4. This happens because γ( Sn) is much larger than γ( C).
• Since coupling occurs through chemical bonds, the magnitude of J normally falls off rapidly
as the number of intervening bonds increases. e.g., 1JPH ~700; 2JPH ~20 Hz in

Coupling constants are thus labeled to show the types of nuclei and the number of bonds
separating the nuclei that give rise to spin-spin splitting.

• Since spin-spin coupling is a through-bond interaction, it is sensitive to the orientation of

the bonds between two interacting nuclei. This is particularly important for two-bond
coupling constants. The influence of the orientation of the two coupled nuclei can
occasionally render 2J < 3J. For example,

Karnataka State Open University Page 139

Spectroscopic applications in Inorganic chemistry Block 4.1.2

1
J is not affected by the orientation of the coupled nuclei, so it is generally true that 1J >> 2J
or 3J, but it is not always true that 2J > 3J.
• Spin-spin interactions are independent of the strength of the applied field. The spacing (in
Hz) between lines at two different field strengths will be the same if it is due to coupling, but
will be proportional to the field strength if it is due to a difference in chemical shift.

Cases involving more than two nuclei with I = 1/2 are direct extensions of the above.
However, because there are more nuclear spins interacting, the pattern of lines observed in
the NMR spectrum becomes more complicated. For example, let’s consider the 1H NMR
spectrum of the HF2- anion (i.e., [F--H--F]-). We are observing the 1H nucleus, but it is
19
coupled to two chemically equivalent F (I = 1/2) nuclei. There are four ways that we can
arrange the nuclear spins of the two fluorine nuclei, but only three different energy states are
created, as is explained below

Extending what we learned about the generation of a doublet, we can clearly see that the 1H
19 19
environment where both F spins are “up” is different from that where both F spins are
19
“down”. However, we can also arrange things so that one F spin is “up” and the other is
“down”. The latter case is degenerate; that is, there is more than one way of accomplishing an

Karnataka State Open University Page 140

Spectroscopic applications in Inorganic chemistry Block 4.1.2

“up/down” arrangement of nuclei, but each “up/down” arrangement has the same energy. As
a result, a pattern of three peaks (or triplet) with an intensity pattern of 1:2:1 is generated as
shown above. It is important to note that each line in the triplet is separated by the same 1JHF
19
coupling constant. As we would expect, the F NMR spectrum of [HF2]- would show a
doublet because the fluorine nuclei are chemically equivalent and couple to one 1H nucleus.
Another way of looking at this is to begin with a singlet for the 1H nucleus and then couple
each 19F nucleus one step at a time. The coupling of the first 19F nucleus generates a doublet.
When each line in this doublet is split again into a doublet, they overlap identically at the
centre of the signal, generating a single line of intensity two relative to each outer line of
intensity one.

When a similar exercise is undertaken for the 31P NMR spectrum of PF3, the nuclear spins of
the three equivalent 19F nuclei can be arranged in four ways to generate a quartet

or we can split a singlet into doublets three times to accomplish the same transformation.

In this case, when each line at the triplet stage is split again into doublets, the intensity of the
overlapping peaks is not identical; a signal of relative intensity two (from the middle peak)
overlaps with a signal of intensity one (from the outer peak) to create a peak of intensity
three.

Karnataka State Open University Page 141

Spectroscopic applications in Inorganic chemistry Block 4.1.2

Fortunately, the pattern of peaks generated by the interaction of I = 1/2 nuclei can be easily
generated by remembering that one nucleus is split by (n) equivalent nuclei into (n+1) peaks,
each separated by the coupling constant, xJAB. The number of peaks is referred as the
multiplicity. The intensity pattern is a direct consequence of the number of combinations of
the various nuclear spins that are possible and is described by a series of binomial
coefficients. In practice, it is easiest to determine the intensity pattern by use of a mnemonic
device such as Pascal's triangle.

7.9 31P NMR spectroscopy

31
P NMR spectroscopy is a simple technique that can be used alongside 1H NMR to
characterize phosphoruscontaining compounds. When used on its own, the biggest dierence
from 1H NMR is that there is no need to utilize deuterated solvents. This advantage leads to
many different applications of 31P NMR, such as assaying purity and monitoring reactions.
Phosphorus-31 nuclear magnetic resonance (31P NMR) is conceptually the same as proton
(1H) NMR. The 31
P nucleus is useful in NMR spectroscopy due to its relatively high
gyromagnetic ratio (17.235 MHzT-1). For comparison, the gyromagnetic ratios of 1H and 13C
are (42.576 MHz T-1) and (10.705 MHz T-1), respectively. Furthermore, 31
P has a 100%
natural isotopic abundance. Like the 1H nucleus, the 31
P nucleus has a nuclear spin of 1/2
31
which makes spectra relatively easy to interpret. P NMR is an excellent technique for
studying phosphorus containing compounds, such as organic compounds and metal
coordination complexes.
7.9.1 Differences between 1H and 31P NMR
There are certain significant differences between 1H and 31P NMR. While 1H NMR spectra is
31
referenced to tetramethylsilane [Si(CH3)4], the chemical shifts in P NMR are typically

Karnataka State Open University Page 142

Spectroscopic applications in Inorganic chemistry Block 4.1.2

reported relative to 85% phosphoric acid (δ = 0 ppm), which is used as an external standard
due to its reactivity. Trimethylphosphite, P(OCH3)3, is also used since unlike phosphoric acid
its shift (δ = 140 ppm) is not dependent on concentration or pH. Chemical shifts in 31P NMR
commonly depend on the concentration of the sample, the solvent used, and the presence of
other compounds. This is because the external standard does not take into account the bulk
properties of the sample. As a result, reported chemical shifts for the same compound could
31
vary by 1 ppm or more, especially for phosphate groups (P=O). P-NMR spectra are often
31
recorded with all proton signals decoupled, i.e., P-{1H}, as is done with 13
C NMR. This
gives rise to single, sharp signals per unique 31P nucleus.
7.9.2 Interpreting spectra
As in 1H-NMR, phosphorus signals occur at different frequencies depending on the electron
environment of each phosphorus nucleus. In this section we will study a few examples of
phosphorus compounds with varying chemical shifts and coupling to other nuclei.
7.9.3 Different phosphorus environments and their coupling to 1H
Consider the structure of 2,6,7-trioxa-1,4-diphosphabicyclo[2.2.2]octane [Pα(OCH2)3Pβ]
shown in below figure. The subscripts α and β are used to differentiate the two phosphorus
nuclei. According to Table 1, we expect the shift of Pα to be downfield of the phosphoric acid
standard, roughly around 125 ppm to 140 ppm and the shift of Pβ to be up field of the
standard, between -5 ppm and -70 ppm. In the decoupled spectrum shown in Figure 1, we can
assign the phosphorus shift at 90.0 ppm to Pα and the shift at -67.0 ppm to Pβ.

Figure 1: Structure and decoupled 31P spectrum (31P-{1H}) of Pα(OCH2)3Pβ.

Karnataka State Open University Page 143

Spectroscopic applications in Inorganic chemistry Block 4.1.2

Figure 2 shows the coupling of the phosphorus signals to the protons in the compound. We
expect a stronger coupling for Pβ because there are only two bonds separating Pβ from H,
whereas three bonds separate Pα from H (JPCH > JPOCH). Indeed, JPCH = 8.9 Hz and JPOCH = 2.6
Hz, corroborating our peak assignments above.

Figure 2: The 31P spin coupled spectrum of Pα(OCH2)3Pβ.

Finally, Figure 3 shows the 1H spectrum of Pα(OCH2)3Pβ (Figure 5), which shows a doublet
of doublets for the proton signal due to coupling to the two phosphorus nuclei.

Figure 3: 1H spectrum of P α(OCH2)3P β and proton splitting pattern due to phosphorus.

As suggested by the data in Figure 1 we can predict and observe changes in phosphor us
chemical shift by changing the co ordination of P. Thus for the series of compounds with the

Karnataka State Open University Page 144

Spectroscopic applications in Inorganic chemistry Block 4.1.2

different chemical shifts corresponding to different phosphorus in compound is shown in

Table 5.

Table 5: Different chemical shifts corresponding to different phosphorus in the same

compound

7.9.4 31P-1H coupling

Consider the structure of dimethyl phosphonate, OPH(OCH3)2, shown in Figure 4. As the
phosphorus nucleus is coupled to a hydrogen nucleus bound directly to it, that is, a coupling
separated by a single bond, we expect JPH to be very high. Indeed, the separation is so large
(715 Hz) that one could easily mistake the split peak for two peaks corresponding to two
different phosphorus nuclei.

Figure 4: JPH of phosphorus nucleus coupled to a hydrogen bound directly to it

This strong coupling could also lead us astray when we consider the 1H NMR spectrum of
dimethylphosphonate (Figure 5). Here we observe two very small peaks corresponding to the
phosphine proton. The peaks are separated by such a large distance and are so small relative

Karnataka State Open University Page 145

Spectroscopic applications in Inorganic chemistry Block 4.1.2

to the methoxy doublet (ratio of 1:1:12), that it would be easy to confuse them for an
impurity. To assign the small doublet, we could decouple the phosphorus signal at 11 ppm,
which will cause this peak to collapse into a singlet.

Figure 5: JPH of phosphorus nucleus coupled to a hydrogen bound directly to it and

separated by a large distance

7.9.5 Coupling to fuorine

19
F NMR is very similar to 31P NMR in that 19F has spin 1/2 and is a 100% abundant isotope.
As a result,19F NMR is a great technique for fluorine-containing compounds and allows
31 19
observance of P-F coupling. The coupled P and F NMR spectra of
ethoxybis(triuoromethyl)phosphine, P(CF3)2(OCH2CH3), are shown in Figure 6. It is worth
noting the splitting due to JPCF = 86.6 Hz.

Figure 6: The coupled 31P and 19F NMR spectra of P(CF3)2(OCH2CH3),

Karnataka State Open University Page 146

Spectroscopic applications in Inorganic chemistry Block 4.1.2

7.9.6 31P NMR applications

1) Assaying sample purity
31
P NMR spectroscopy gives rise to single sharp peaks that facilitate differentiating
phosphorus-containing species, such as starting materials from products. For this reason, 31P
NMR is a quick and simple technique for assaying sample purity. Beware, however, that a
31
clean P spectrum does not necessarily suggest a pure compound, only a mixture free of
phosphorus-containing contaminants.
31
P NMR can also be used to determine the optical purity of a chiral sample. Adding an
enantiomer to the chiral mixture to form two different diastereomers will give rise to two
unique chemical shifts in the 31P spectrum. The ratio of these peaks can then be compared to
determine optical purity.
25) Monitoring reactions
31
As suggested in the previous section, P NMR can be used to monitor a reaction involving
phosphorus compounds. Consider the reaction between a slight excess of organic diphosphine
ligand and a nickel(0) bis-cyclooctadiene.

The reaction can be followed by 31P NMR by simply taking a small aliquot from the reaction
mixture and adding it to an NMR tube, filtering as needed. The sample is then used to acquire
a 31P NMR spectrum and the procedure can be repeated at different reaction times. The data
acquired for these experiments is found in Figure 7. The changing in 31P peak intensity can be
used to monitor the reaction, which begins with a single signal at -4.40 ppm, corresponding to
the free diphosphine ligand. After an hour, a new signal appears at 41.05 ppm, corresponding
the the diphosphine nickel complex. The downfield peak grows as the reaction proceeds
relative to the upfield peak. No change is observed between four and five hours, suggesting
31
the conclusion of the reaction. There are a number of advantages for using P for reaction
monitoring when available as compared to 1H NMR:

Karnataka State Open University Page 147

Spectroscopic applications in Inorganic chemistry Block 4.1.2

Figure 7: 31P NMR spectrum recorded at different reaction times

• There is no need for a deuterated solvent, which simplies sample preparation and saves time
and resources.
31
• The P spectrum is simple and can be analyzed quickly. The corresponding 1H NMR
spectra for the above reaction would include a number of overlapping peaks for the two
phosphorus species as well as peaks for both free and bound cyclooctadiene ligand.
• Purification of product is also easy assayed.
31
P NMR does not eliminate the need for 1H NMR chacterization, as impurities lacking
phosphorus will not appear in a 31P experiment. However, at the completion of the reaction,
both the crude and purified products can be easily analyzed by both 1H and 31
P NMR
spectroscopy.
26) Measuring epoxide content of carbon nanomaterials
One can measure the amount of epoxide on nanomaterials such as carbon nanotubes and
fullerenes by monitoring a reaction involving phosphorus compounds in a similar manner to
that described above. This technique uses the catalytic reaction of methyltrioxorhenium. An
epoxide reacts with methyltrioxorhenium to form a five membered ring. In the presence of
triphenylphosphine (PPH3), the catalyst is regenerated, forming an alkene and
triphenylphosphine oxide (OPPh3). The same reaction can be applied to carbon
nanostructures and used to quantify the amount of epoxide on the nanomaterial. This way it is
easy to illustrate the quantification of epoxide on a carbon nanotube.

Karnataka State Open University Page 148

Spectroscopic applications in Inorganic chemistry Block 4.1.2

Because the amount of initial PPh3 used in the reaction is known, the relative amounts of
PPh3 and OPPh3 can be used to stoichiometrically determine the amount of epoxide on the
31
nanotube. P NMR spectroscopy is used to determine the relative amounts of PPh3 and
OPPh3.

31
The integration of the two P signals is used to quantify the amount of epoxide on the
nanotube according to

Thus, from a known quantity of PPh3, one can find the amount of OPPh3 formed and relate it
stoichiometrically to the amount of epoxide on the nanotube. Not only does this experiment
allow for such quantification, it is also unaffected by the presence of the many different
species present in the experiment. This is because the compounds of interest, PPh3 and
OPPh3, are the only ones that are characterized by 31P NMR spectroscopy

Karnataka State Open University Page 149

Spectroscopic applications in Inorganic chemistry Block 4.1.2

19
7.10 F NMR spectroscopy
19
F NMR is similar to 1H NMR. After 1H and 13
C NMR, 19
F is the most common nucleus
studied by this technique. 19F nuclei are spin ½ nuclei and a have a high gyromagnetic ratio,
19
which means that they have a high receptivity for NMR measurements. The F isotope has
19
100% natural abundance i.e, F is the only naturally occurring isotope, giving high NMR
sensitivity. The sensitivity is about 0.83 compare to H. The resonance frequency is slight
lower than 1H e.g. in the field of 1.4T 1H resonate at 60MHz, 19F resonate at 56.5MHz.
7.10.1 Chemical shift in 19F NMR
19
F chemical shift is more sensitive to solvent effects. CFCl3 is generally used as reference in
19
F NMR (as TMS (Tetramethylsilane) is used in 1H NMR). CFCl3 is inert, volatile and give
raise to a sharp singlet. Figure 8 shows the 1H and 19F spectra of trifluorotoluene (TFT)

Figure 8: 1H (top) and 19F (bottom) spectra of triflorotoluene

The chemical shift values span in wider range from 0 to 900ppm. The chemical shifts are
sensitive to electronegativity, oxidation state and stereochemistry of the neighboring groups.
For example, the chemical shift of equatorial and axial F’s of ClF3 differ by 120 ppm. Ethyl
and methyl F’s differ by 60 ppm

Karnataka State Open University Page 150

Spectroscopic applications in Inorganic chemistry Block 4.1.2

For example, (CH3)2PF3 is a triganl bipyramidal structure compound. The NMR spectra
suggested that (JP-F = 170 Hz) two methyl groups are equatorial and more electronegative
groups are at apical positions.
Similarly in the (CF3)2PF3 compound, at low temperature NMR shows that two CF3 groups
are apical position and at room temperature due to rapid exchange only one signal is appears.
19
For BrF5 molecule F NMR shows two peaks, one doublet and one quintet with intensity
ration (1:4) this suggest that 4F atoms are equivalent and one is a different type. This is
consistent with the assigned square pyramidal structure.
The 19F spectrum, shown in figure 3, consists of a single peak since the three F nuclei are in
an equivalent chemical environment and are not in close proximity to any of the H nuclei in
the molecule. The 1H spectrum is more complex since the H nuclei on the aromatic ring are
not equivalent and the homonuclear couplings give rise to splitting of the aromatic peak.
The spectrum shown in Figure 9 is a mixture of two florinecontaining chemicals;
Triflorotoluene and trifloroethanol. Triflorotoluene (TFT) is often used as a reference
material for 19F spectra. It appears as a strong, single peak with a chemical shift -63.72 ppm
with CFCl3 set at 0 ppm. It is a single peak as the structure consists of three equivalent F
nuclei isolated from any other nuclei that would couple to it. By comparison the peak in the
spectrum due to trifloroethanol, at -77 ppm, is split into a triplet. This is due to the fact that
the 19F nuclei couples with the 1H nuclei on neighbouring carbon atoms in the molecule, just
as 1H nuclei would couple with other neighbouring 1H nuclei in the molecule.

19
Figure 9: F spectrum of a mixture of triflorotoluene and trifloroethanol

Karnataka State Open University Page 151

Spectroscopic applications in Inorganic chemistry Block 4.1.2

Each of these resonances shows a complex coupling pattern due to the nuclei on the aromatic
ring. Most easily recognisable is the triplet of triplet pattern at -162 ppm, arising because the
florine at position 2 is coupled to two equivalent florines and two equivalent hydrogens. Any
coupling between the florine and the bromine is too weak to be resolved in the spectrum.
Finally, a comparison has been made of the 19F spectra of two different positional isomers of
19
bromotriflorobenzene. Figure 4 shows the F spectra of 5-bromo-1,2,3-triflorobenzene and
1-bromo-2,4,5-triflorobenzene. In contrast to the spectrum of 5-bromo-1,2,3-triflorobenzene,
19
the spectrum of 1-bromo-2,4,5-triflorobenzene shows three F resonances because each of
the florines on the ring are in different chemical environments. They all show complex
coupling patterns since each has two different florines and two different hydrogens and
potentially a bromine as coupled neighbours.
Figure 10 shows the 1H and 19
F spectra of5-Bromo1,2,3 triflorobenzene. The 1H spectrum
consists of a single multiplet of peaks resulting from the two equivalent 1H nuclei and their
19 79 81
couplings with, F and Br and Br nuclei within the molecule. The 19F spectrum consists
of two resonances, each of which are multiplets due to the two different chemical
environments of the 19F nuclei.

Figure 10: 1H and 19F spectra of5-Bromo1,2,3 triflorobenzene

Karnataka State Open University Page 152

Spectroscopic applications in Inorganic chemistry Block 4.1.2

The resonance at ~ -133 ppm arises from the florines in positions 1 and 3 on the molecule
while the resonance at -162 ppm arises from the florine in position 2.
Each of these resonances shows a complex coupling pattern due to the other nuclei on the
aromatic ring. Most easily recognisable is the triplet of triplet pattern at -162 ppm, arising
because the florine at position 2 is coupled to two equivalent florines and two equivalent
hydrogens. Any coupling between the florine and the bromine is too weak to be resolved in
the spectrum.
Finally, a comparison has been made of the 19F spectra of two different positional isomers of
19
bromotriflorobenzene. Figure 6 shows the F spectra of 5-bromo-1,2,3-triflorobenzene and
1-bromo-2,4,5-triflorobenzene. In contrast to the spectrum of 5-bromo-1,2,3-triflorobenzene,
19
the spectrum of 1-bromo-2,4,5-triflorobenzene shows three F resonances because each of
the florines on the ring are in different chemical environments. They all show complex
coupling patterns since each has two different florines and two different hydrogens and
potentially a bromine as coupled neighbours.

Figure 3. 1H (top) and 19F (bottom) spectra of 5-bromo-1,2,3-triflorobenzene

Figure 11 : 19F spectra of 5-bromo-1,2,3-triflorobenzene (top) and 1-bromo-2,4,5-

triflorobenzene

The case of PF5, The structure of PF5 has been found to be trigonal bipyramidal as shown in
Figure 12. The trigonal bipyramidal polyhedron has two distinct sites, the axial site and the

Karnataka State Open University Page 153

Spectroscopic applications in Inorganic chemistry Block 4.1.2

equatorial site. The 19F NMR spectrum of this compound shows a doublet with the separation
between the lines corresponding to the coupling constant J(P-F).

Figure 12: structure of PF5

However, for a trigonal bipyramidal structure we anticipate a more complex pattern as the
axial fluorine atoms belong to one chemically equivalent set and the equatorial fluorines
belong to another chemically equivalent set. Therefore the spectrum should have been more
complicated as shown in Figure 13.

Figure 13: Anticipated spectrum for trigonal bipyramidal structure of PF5

The question is why is only a doublet seen?
The answer lies in the fact that the molecule is stereochemically non-rigid and is continuously
changing its structure. This is known as fluxional behaviour. The mechanism that accounts
for the behaviour of PF5 is known as Berry Pseudo Rotation and is shown below. In structure
1a the angle F1-P-F2 is 180º and the F3-P-F4 angle is 120º.

Karnataka State Open University Page 154

Spectroscopic applications in Inorganic chemistry Block 4.1.2

Imagine that that the former is shrinking and the latter is expanding so that both the angles
become nearly equal and structure 2, a square pyramid, is obtained. If this process is
continued further such that the former F1-P-F2 angle now becomes 120º and the former F3-P-
F4 angle becomes 180º we get the second trigonal bipyramidal structure 1b. Thus in reaching
1b from 1a through 2, we have essentially exchanged a pair of axial fluorine atoms with a set
of equatorial fluorine atoms without breaking any bonds. In this whole process one PF5 does
not change. If this process takes place faster than the NMR time scale in the NMR
experiment only one set of fluorines is seen.
For the majority of five-coordinate main-group and transition metal compounds, the energy
difference between the trigonal bipyramid (1) and tetragonal pyramid (2) structures is
sufficiently low, so that Berry pseudorotation represents a widespread mechanism of
stereochemical nonrigidity. No angular momentum is generated by this motion, this is the
reason for the term. Important to note here that we single out one interchange path here, while
in reality all atoms will rapidly occupy all possible positions in a very dynamic way.
Having bulky substituents such as chlorine or substituents that do not prefer to occupy axial
positions can slow this process down. Accordingly in PCl2F3, although at room temperature
all the fluorine atoms are still equivalent and only a doublet is seen in the fluorine NMR
spectrum, at -143º C the exchange is stopped and one sees two sets of peaks as shown in
Figure 14(a doublet of doublet for the two axial fluorine atoms and a doublet of triplets for
the equatorial fluorine atom).

19
Figure 14: F NMR spectrum of PCl2F3 molecule at different temperature

Karnataka State Open University Page 155

Spectroscopic applications in Inorganic chemistry Block 4.1.2

At temperature of –22oC and above, the resonance of F is observed as a single doublet (31P-
19
F coupling, 1048 Hz ). However, as the temperature is lowered to –143oC, a downfield
doublet ( δ -67.4 ) for the axial F atoms and an upfield doublet (δ 41.5) for the equatorial F
atom. The single equatorial F atom is further spilt by the two axial F atoms (2nI+1; n = 2; JF-F
= 124 Hz) into two triplets. The two axial F atoms is split into doublet by the single
eaquatorial F atom ( 2nI+1; n = 2 ; JF-F = 124 Hz).
Also, the weighted average of the chemical shifts at –143oC {2x(-67.4 ppm) + 1x(41.5 ppm)}
is the same as that at –22oC {3 x (-31.1 ppm)} indicating that the structure does not change
on warming even though the F atoms exchanges positions.
7.11 Boron NMR spectroscopy
Boron is second only to carbon in its ability to bond to itself to form polyboron units. Boron
has two naturally occurring NMR active nuclei. Both nuclei have spins of greater than ½ and
11 10 11
are quadrupolar. B has a spin of 3/2 and B is spin 3. B is the better nucleus in all
respects, having the lower quadrupole moment and being more sensitive. Both nuclei have
the same wide chemical shift range. Each type of signal has a characteristic chemical shift
11
range which is the same for both nuclei. In the immense field of chemistry, B NMR
spectroscopy has been found to be the most economical, fastest, and most reliable method for
the determination of structures of compounds with boron skeletons.
The informative value of 11B chemical shifts is very high for two reasons
i) It helps significantly to analyze not only structures but also the centre of equilibrium in
fluxional molecules, and
ii) It can provide additional and significant insight into the distribution of valence-bond
electrons in some fragments of a given molecule or/and in individual atomic orbitals,
which is important for understanding both physical and chemical behaviour.
11
In many cases, analyses of individual B spectra from this point of view have indicated
unexpected deviations that called for explanation. In this way, some new principles
dominating the behaviour of B-cluster compounds have been revealed.
10 11
Both naturally occurring isotopes, B and B, are NMR active but the latter one is more
11
advantageous for NMR investigations. The success of B NMR spectroscopy stems from
several favourable factors
11
1. Strong signal of the B nucleus (0.133, i.e. 16% of the relative receptivity to 1H, or 754
relative to 13C) and 80.4% natural abundance.
2. Resonance at relatively high frequency (32.1 MHz at 2.3 T, i.e. 100 MHz for 1H).

Karnataka State Open University Page 156

Spectroscopic applications in Inorganic chemistry Block 4.1.2

11
3. Relative sensitivity of the B nucleus to different perturbations (bonding strains,
substituents, heteroatoms, etc.).
4. In most cases a sufficient spectrum span in compounds with borane skeletons (Figure 1).
5. Optimum B-H coupling (BH, 120-190 Hz; BH2, 110-130 Hz; BH3,90-11O Hz; BH4,70-80
Hz; µH, 5-60Hz).
6. An acceptable width at half height of peaks (2-100Hz, usually 30-60 Hz). Of the peak
width, only a small part must be attributed to the influence of electric quadrupole
moment (1-20 Hz), while further widening is due to the interactions of 11B with bridge
11
hydrogens, the B----H long-range coupling (ca. 0-5 Hz), the B-11B (intramolecular, 5-
11
40 Hz; exo-two-electron B-B bonds, 50-150 Hz16), and B-10B couplings (ca. 3 times
lower than the former one).
7. Short relaxation times of 11B nuclei (1-100 ms, commonly 10-50 ms, exceptionally a few
seconds).
10
In contrast, the B nucleus is present in low natural abundance (19.58%), exhibits a low
receptivity (22.1 relative to 13C), and has 3 times higher quadrupole moment, which broadens
10
its NMR signals. B is found at a lower resonance frequency on a given instrument (10.75
MHz in comparison with 32.08 MHz for 11B). This results in 2.99 times lower resolution and
l0
coupling constants (in Hz). Despite these disadvantages, the measurement of B NMR
spectra is exceptionally helpful in selected mechanistic studies including rearrangements and
other reactions.
The introduction of higher magnetic fields and, especially, the progress in computational and
programming techniques make it possible to obtain the following kinds of informations
1) The number of different types of boron atoms, their mutual ratios within a molecule, and
11
the chemical shift of each signal (from B proton decoupled spec-) δ(11B) relative to
BF3.OEt = 0 ppm with the '+" sign for signals at lower magnetic field, i.e. at higher
frequencies; δ(11B) B(OMe)3 = 18.1 ppm.
2) The number of terminal hydrogens on each boron atom, the position of each substituent,
and the splitting or broadening of relevant signals by hydrogen bridges if present (via the
11
comparison of undecoupled spectra with proton decoupled B spectra of equivalent
intensity).
3) The number of terminal H(B) and H(C) and bridge hydrogens (from 1H or lH(11B) spectra).
4) The number of different C atoms in the molecule, their mutual ratios, and the number
of hydrogen atoms they bear (from 13C NMR spectra).

Karnataka State Open University Page 157

Spectroscopic applications in Inorganic chemistry Block 4.1.2

5) The structure of boron networks and the assignment of individual signals (from llB-llB(lH)
2D COSY spectra).
6) The assignments of all H signals (from selective 1H( 11
B) spectra or from lH-llB(lH) 2D
spectra).
7) The presence of B-C links (from 13C NMR spectra decoupled by frequencies of individual
B atoms).
8) The presence of fragments with H-B-C-H links (from 11B-decoupled 1H-lH 2D spectra).
9) A relatively high J(11B-1H) of a B* signal indicates a connection of the observed B* atom
with an adjacent heteroatom such as S.
10) The magnitude of electric field gradients around various B atoms (from high and low Tl
of appropriate signals).
Practically all of this information can be obtained on commercially available FT
spectrometers; the information under items 3,6,7, and 8 is obtained when using an inverse
probe. An excellent tool for the elucidation of the skeletal connectivity is llB-llB and lH-lH 2D
NMR spectroscopy. This method is not a panacea in all cases. It fails to determine reliable
structures in the following cases
a) Symmetrical compounds in which the symmetry causes an insufficient number of cross-
peaks to be observed.
b) Missing cross-peak(s).
c) A reduced number of cross-peaks due to overlap- ping signals.
d) Heteroboranes, since these spectra do not provide information on the links of boron to the
heteroatom(s).
7.11.1 Chemical Shift
The most informative characteristic of an NMR-active nucleus is its chemical shift which
reflects
1) Its bonding surroundings, i.e. coordination, hybridization, bond angles, π-bonding, etc.
2) The charges on individual atoms originating from their positions in the skeleton, inductive,
and mesomeric effects of terminal substituents, electronegativity of skeletal heteroatoms,
etc. 3) The magnetic anisotropy of neighboring groups, i.e. the effect of heavy nuclei,
“ring current”, etc.
Hybridization is one of the most important factors influencing the chemical shift. This is well
documented in compounds of carbon (13C NMR), with which a change from sp3 to sp2
hybridization causes a shift of ca. 100 ppm to lower frequencies. A similar shift dependence

Karnataka State Open University Page 158

Spectroscopic applications in Inorganic chemistry Block 4.1.2

can also be observed for the llB nucleus. In contrast to carbon, boron can form stable
tricoordinated compounds BX3, showing the sp2 arrangement of substituents. In the case that
substituents X do not bear a free electron pair (e.g. X = H,R), the fourth orbital can remain
unoccupied (vacant), which results in a great "imbalance" of bonding electrons around the llB
nucleus and, consequently, a large shift to high frequency (-120 ppm).
In contrast, the same substituents in the tetracoordinated anions BX4- exhibit a very
symmetrical arrangement, i.e. the paramagnetic contribution vanishes, which results in
minimum deshielding originating from this very important factor. The llB chemical shift of
BX4- anions depend therefore primarily on the shielding quality of substituents R lacking a
free electron pair.
On the other hand, substituents possessing a free electron pair can interact with the
unoccupied boron orbital, decreasing the "imbalance", i.e. lowering the "deshielding". The
stronger the p-π interaction, the more the orbital electrons approximate the symmetry, and the
signal of BX3 species in the spectrum approaches the signal of the related anions BX4-. With
the first- and second-row elements as substituents, the differences ∆ = δ(sp2) - δ(sp3) very
nicely reflect the measure of p-π interactions, due to the fact that other factors are here
greatly eliminated.
7.11.2 General Comments on the Boron Chemical Shifts
a) Coordination
The addition of a ligand or base to the empty p-orbital on boron results in an upfield shift as
compared to the tricoordinate borane. This effect is also seen with coordinating solvents such
as THF. The chemical shift is dependent on the strength of the coordination complex, with
the stronger complexes shifted to higher field. Borane dimers are also found upfield from the
free monomer and may show a more complex coupled spectra due to the presence of both
terminal and bridging hydrogens coupling to the boron. The addition complex with solvent or
a basic ligand is generally found higher field than the dimer.
b) Tricoordinate Boranes containing hydrogen
The coupled 11B NMR spectra generally show a B-H coupling, unless there is a fast exchange
of the hydrogens on the NMR time scale. Since the spin of hydrogen is 1/2, the number of
peaks in the multiplet is one greater than the number of hydrogens attached to the boron. The
magnitude of the B-H splitting increases with additional ligands and greater electronegativity
of the ligand. The trivalent boranes tend to be dimeric, especially in non-coordinating
solvents in the absence of sterically large groups. In a number of cases one may observe both

Karnataka State Open University Page 159

Spectroscopic applications in Inorganic chemistry Block 4.1.2

the monomeric borane (non-coordinated to the solvent or any another weak base such as
dimethyl sulfide) and the dimeric borane. The chemical shifts of the trivalent organoboranes
having a B-H bond are more variable than that of the trialkylboranes, and are dependent on
the structure of the organic groups present.
c) Trialkylboranes
The trialkylboranes are found in a narrow low field region, 83-93 ppm. These chemical shifts
are largely independent of the structure of the alkyl group. The exception are for the tertiary
groups that shift the resonance ~ 3 ppm upfield. Cyclic boranes show a marked dependence
on the size of the ring. Six membered rings have approximately the same chemical shifts as
the acyclic compounds. The borolane compounds, five member rings, are shifted to lower
field by ~ 6 ppm. The effect of the ring size is observed for all cyclic boranes independent of
the substitutents present.
d) Substitution of Alkyl groups
Substitution at the α -carbon, R2B-CH2-X, with X = N3, OH, NH2, Cl, Br, I, PMe3, AsMe3,
SMe, BR2, SiR3, Ph, vinyl results in an upfield shift of the borane. This effect may be
attributed to inter- or intramolecular association of the lone pair electron with the empty pi-
orbital on the boron or a neighboring group anisotropic effect. The degree of upfield shift is
variable, Cl is relatively small ~ +2.9 ppm while I is much larger ~ 15.4 ppm. Silyl and boryl
groups shift upfield ~ 4-8 ppm. Similar explanation is made for phenyl and vinyl groups, ~ 0
- 6 ppm.
Boron compounds that are directly bonded to sp2 or sp carbons are shifted to higher field due
to a pi-interaction between the two p-orbitals on the adjacent carbon and boron atoms. Steric
effects are also very important, especially in the case of weaker pi-donors. The effects of
acetylenic groups is larger than that of the alkenyl groups, probably due to anisotropic effects
as opposed to pi-orbital interactions.
The presence of an OR' or OH group bonded to the boron results in 11B resonance at higher
fields as compared to the corresponding alkylborane. The OR' and OH groups are strong pi-
donors. In general, the structures of the alkyoxy groups do not affect the boron chemical
shifts for oxygen containing tricoordinate boranes. The exceptions to this are the tert -butyl,
phenoxy and Me3Si groups which give slightly higher upfield shift of ~ 2-4 ppm.
e) Boroxines
The cyclic anhydrides of the boronic acids are the boroxines, (RBO)3. These compounds are
found at slightly lower field, ~ 33 ppm, that the corresponding boronic esters or acids, ~ 30

Karnataka State Open University Page 160

Spectroscopic applications in Inorganic chemistry Block 4.1.2

ppm. Aryl and vinyl boroxines, are shifted upfield approximately 2-4 ppm from the alkyl
derivatives.
f) Borohydrides
The parent borohydrides, BH4-, is a tetrahedral compound in which all hydrogens are
magnetically equivalent. A quintet is observed in a 1:4:6:4:1 ratio. While the 1H NMR spectra
shows a 1:1:1:1 resonance. The borohydrides may be ionic or covalent in nature and this may
result in a more complex spectrum depending on the interactions of the cation with the
borohydride hydrogens. In most cases, the exchange is fast and only one type of hydrogen is
observed. The boron resonances are shifted to higher field, -26 to -45 ppm, more than most
all other boron species. The solvent has a significant effect on the chemical shift due to
solvation of the cation.
11
Replacement of an hydrogen with an alkyl group shifts the resonances downfield. The B
NMR signal of these substituted alkylborohydrides, R4-nBHn overlap but the number of
hydrogens present can readily be determined from the multiplicity of the proton coupled
boron NMR.
g) Tetraalkylborates
The tetraalkylborates do not follow this pattern. These complexes are observed over a fairly
narrow region, -15 to -22 ppm. The replacement with an aryl group shifts these
tetraorganylborates downfield in a systemic manner. The tetraphenylborates are seen ca -6.0
ppm and in general all of these borates show a slight dependence on the cation and solvent.
7.11.3 Spin-spin coupling between Boron and Nitrogen
14 15
The unfavourable mulear magnetic properties of nitrogen isotopes Nand N have not
encouraged for spin-spin coupling between B-N atoms. The rapid quadrupole relaxation of
14
N (I = 1) is thought to be responsible for the fact that no 1J(11B-14N) can be observed either
11 14
by B or N . However 1J(11B-15N) for several adducts X3BN(CH3)2 (X= F, Cl, Br) have
been reported and are too low (12-14Hz) and interesting thing is that the value is independent
of nature of the X ligand.
7.11.4 Spin-spin coupling between boron and phosphorous
Different situation exists for boron-phosphorus compounds. In many cases the coupling
constants 1J(11B-31P) were readily obtained either from 11
B or 31
P NMR spectra. While the
sign of the 1J(12C-31P) in organylphosphines is usually negative and changes to positive when
phosphorus becomes tetracoordinated, the 1J(11B-31P) in (CH3)3P-B[N(CH3)CH2]2 has been
11
shown to be positive. In Phosphine-boranes(B-P) B-31P coupling constant follows roughly
the same trends as 1J(11B-1H) and 1J(11B-13C).

Karnataka State Open University Page 161

Spectroscopic applications in Inorganic chemistry Block 4.1.2

7.12 other NMR active nuclei

7.12.1 Lead
Lead is a ubiquitous environmental contaminant. Although the use of lead (as [PbEt4]) in
gasoline and paint has now been banned in most developed countries, lead is still one of the
ten most common contaminants.
On the other hand, lead has been investigated for its potential applications in medicine. The
potentially therapeutic radioisotope 212Pb has a number of theoretical attractions including α-
emission by short-lived daughter radionuclides, and its application is encouraged by the
212
development of a new generator system and the observation that when Pb-conjugated
antibodies are internalized, radioactivity is retained inside cells
There is one lead isotope with a nuclear spin that can be exploited for NMR spectroscopy,
207
Pb, I = 1/2. This isotope has an excellent receptivity (11.8 times greater than that of 13C),
high natural abundance (22.6%), and large chemical shift range (over 16000 ppm). Although
207
Pb NMR spectroscopy has been used extensively to characterize Pb(IV)-alkyl derivatives.
7.12.2 Platinum
Platinum is a relatively inert metal and has no natural biological role. Nevertheless, platinum
complexes are now amongst the most widely used drugs for the treatment of cancer. The first
and second generation compounds cis platin and carboplatin are in widespread use to treat a
variety of cancers, either as single agents or in combination with other drugs.
195
Pt (I = 1/2) is a reasonably sensitive nucleus for NMR detection having a natural
13 195
abundance of 33.7% and receptivity relative to C of 19.1. An attractive feature of Pt
NMR for studies of platinum anticancer drugs is the very large chemical shift range (>15000
ppm), which allows ready differentiation between Pt(II) and Pt(IV), which tend to have
chemical shifts at the high-field and low-field ends of the range, respectively. The resonances
for square-planar Pt(II) complexes span some 4000 ppm and ligand substitutions produce
predictable chemical shift ranges. NMR methods have proved useful in the investigation of
platinum drugs from the time that cisplatin was firstintroduced into the clinic more than 30
195
years ago. Both 1D Pt and 2D [1H,15N] NMR techniques were used and made a major
contribution in the understanding of the molecular mechanism of action of platinum-based
anticancer drugs.
7.12.3 Palladium
Palladium is a non-essential element for life. Pharmaceutical interest in Pd(II) compounds is
driven by analogy to antitumor Pt(II) complexes, as well as antiviral, antifungal and
antimicrobial metallotherapeutics. Palladium has one naturally occurring NMR-active

Karnataka State Open University Page 162

Spectroscopic applications in Inorganic chemistry Block 4.1.2

105
isotope, Pd, with nuclear spin I = 5/2. Although it has high natural abundance (22.23%),
this quadrupolar nucleus is characterized by a low sensitivity to detection by NMR, low
resonance frequency and extremely fast relaxation times (<10−5 s). As far as we know, no
105
Pd NMR studies in solution have been reported.
7.12.4 Rhodium
Rhodium has no known biological function. Recently, rhodium complexes have been
investigated for their possible applications in medicine as antitumor, antibacterial and
antiparasitic agents. As a monoisotopic species with I = 1/2 and a wide chemical shift range
(∼8000 ppm), the 103Rh nucleus is attractive for NMR studies. Unfortunately, low receptivity,
negative magnetogyric ratio and very long relaxation times (>50 s) are major drawbacks. A
103
recent survey of Rh NMR spectroscopy has been published, but no studies of biological
relevance appear to have been reported.
7.12.5 Tungsten
183
W is the only non-quadrupolar NMR-active nucleus in the Group 6 family, but it is
characterized by low natural abundance (14.4%) and extremely low receptivity.
Thus, despite the interesting biological properties of molybdenum and tungsten, both 95/97Mo
and 183W NMR spectroscopy have not often been used to investigate the biological chemistry
183
of these two metals. W NMR has been used to characterize some heteropolytungstates
tested as anti-HIV agents
7.13 1H NMR spectroscopy organometallic
The 1H NMR spectroscopy is among the extensively used techniques for the characterization
1
of organometallic compounds. Of particular interest is the application of H NMR
spectroscopy in the characterization of the metal hydride complexes, for which the metal
hydride moiety appear at a distinct chemical shift range between 0 ppm to −40 ppm to the
high field of tetramethyl silane (TMS). This upfield shift of the metal hydride moiety is
attributed to a shielding by metal d−electrons and the extent of the upfield shift increases with
higher the dn configuration. Chemical shifts, peak intensities as well as coupling constants
from the through-bond couplings between adjacent nuclei like that of the observation of JP-H,
if a phosphorous nucleus is present within the coupling range of a proton nucleus, are often
used for the analysis of these compounds. The 1H NMR spectroscopy is often successfully
employed in studying more complex issues like fluxionality and diastereotopy in
organometallic molecules. The paramagnetic organometallic complexes show a large range
of chemical shifts, for example, (η6−C6H6)2V exhibits proton resonances that extend even up
to 290 ppm.
Karnataka State Open University Page 163
Spectroscopic applications in Inorganic chemistry Block 4.1.2

7.14 Summary of the unit

Just as in organic chemistry, it is now routine to measure 1H, 13C, and, often, 19F and 31P
NMR spectra of diamagnetic organometallic and coordination compounds. Many NMR
spectra are measured simply to see if a reaction has taken place as this approach can
sometimes take less than 5 min. Having determined that something has happened, the most
common reasons for continuing to measure are usually associated with
1) Confirmation that a reaction has taken place and, by simply counting the signals, deciding
how to proceed
2) The recognition of new and/or novel structural features via marked changes in chemical
shifts and/or J-values, and
3) The need for a unique probe with sufficient ‘‘structural resolution’’ to follow the kinetics
or the development of a reaction.
31
When a P atom is present, proton-decoupled P NMR often represents one of the simplest
analytical tools available as the spectra can be obtained quickly and do not normally contain
many lines.
7.15 Key words
31
NMR spectra of Inorganic compounds; Chemical Shift; Spin-Spin Splitting ; P NMR
spectroscopy; 19F NMR spectroscopy ; Boron NMR spectroscopy ; Other NMR active nuclei;
1
H NMR spectroscopy organometallic.
7.16 References for further studies
1) NMR Spectroscopy in Inorganic Chemistry; Jonathan A. Iggo; Oxford University Press,
1999.
2) Structural Methods in Molecular Inorganic Chemistry; D. W. H. Rankin, Norbert Mitzel,
Carole Morrison; John Wiley & Sons, 2013.
3) NMR in Organometallic Chemistry; Paul S. Pregosin; John Wiley & Sons, 2012.
4) Phosphorus-31 NMR Spectroscopy: A Concise Introduction for the Synthetic Organic and
Organometallic Chemist; Olaf Kühl; Springer Science & Business Media, 2008.
5) Guide to Fluorine NMR for Organic Chemists; W. R. Dolbier; John Wiley & Sons, 2009.
7.17 Questions for self understanding
1) Explain the practical limitations to metal NMR spectroscopy.
2) Discuss the favourable properties for high-resolution NMR spectroscopy.
3) Write a note on followings
a) Chemical Shift
b) Chemically equivalent nuclei

Karnataka State Open University Page 164

Spectroscopic applications in Inorganic chemistry Block 4.1.2

c) Integration
d) Spin-Spin Splitting (Coupling)
4) Discuss the 31P NMR spectroscopy.
5) Explain the Differences between 1H and 31P NMR.
6) With example explain the different phosphorus environments and their coupling to 1H in
31
P NMR spectroscopy.
7) Write a note on coupling of 31Pnucleus with
a) 1H
b) 19F
8) Explain the applications of 31P NMR as.
9) Discuss the 19F NMR spectroscopy.
10) Write a note on chemical shift in 19F NMR.
11) Discuss the Boron NMR spectroscopy.
12) Explain the chemical shift in Boron NMR spectroscopy.
13) Write a note on
a) Spin-spin coupling between Boron and Nitrogen.
b) Spin-spin coupling between boron and phosphorous.
14) Explain the possibility of NMR spectral study of following nuclei.
a) Lead
b) Platinum
c) Palladium
d) Rhodium
d) Tungsten
15) Discuss the 1H NMR spectroscopy in study of organometallic compound structure.

Karnataka State Open University Page 165

Spectroscopic applications in Inorganic chemistry Block 4.1.2

UNIT-8
Structure
8.0 Objectives of the unit
8.1 Introduction
8.2 Recoil effect
8.3 Conditions for MB spectra
8.4 Fe is the most studied precursor
8.5 Recording the MB spectrum
8.6 Isomeric shift/centre shift/ chemical shift
8.7 Chemical Shit values for Fe compounds
8.8 Electric Quadrupole Interactions
8.9 Information’s from quadrupole splitting
8.10 Stereochemical activity of lone pair
8.11 Magnetic interactions
8.12 Application of Mossbauer spectra
8.13 Prussian blue and Turnbull’s blue
8.14 Ferredoxin
8.15 Study of thermal spin-cross over
8.16 Summary of the unit
8.17 Key words
8.18 References for further studies
8.19 questions for self understanding

Karnataka State Open University Page 166

Spectroscopic applications in Inorganic chemistry Block 4.1.2

8.0 Objectives of the unit

After studying this unit you are able to

Explain the Recoil effect

Explain the required conditions for MB spectra

Explain the Isomeric shift/centre shift/ chemical shift

Identify the chemical shift values for Fe compounds

Explain the Electric Quadrupole Interactions

Explain the Information’s extracted from quadrupole splitting

Explain the application of Mossbauer spectra
8.1 Introduction
If a nucleus gives off radiation or any other form of energy (in this case, in the form of a γ-
ray), the nucleus must recoil with an equal and opposite momentum to preserve its energy
(E), in the same way that a gun (by analogy, the nucleus) recoils when a bullet (the γ-ray) is
fired out of it.
We describe this general case in terms of energy by saying that:
Eγ-ray emission = Etransition - ER,
where
Eγ-ray emission = the energy of the emitted γ-ray
Etransition = the energy of the nuclear transition and
ER = the energy of the recoil.
The 57Fe which is a decay product of 57Co is unstable. 57Fe decays by giving off a gamma ray
(γ-ray), along with other types of energy. Below figure shows the nuclear decay scheme
for 57Co→ 57Fe and various backscattering processes for 57Fe that can follow resonant
absorption of an incident gamma photon.

Karnataka State Open University Page 167

Spectroscopic applications in Inorganic chemistry Block 4.1.2

Below figure shows a schematic of the vibrational energy levels in a solid. On the left, the
recoil energy ER of an emitted gamma photon is less than what is needed to reach the next
higher energy level, so that excitation of a vibrational mode has low probability. The
probability that no excitation will occur is given the symbol f, which represents the fraction of
recoil-free events.

A gamma ray would be emitted without losing energy to the solid, in what is called a zero-
phonon transition. In other words, sometimes the nucleus absorbs the energy of the γ-ray and
it doesn't recoil (instead, the entire structure, rather than just the nucleus, absorbs the energy).
The variable f indicates the probability of this happening. This process of recoil-less emission
forms the basis for Mössbauer spectroscopy. On the right, ER is significantly greater in
energy than the lowest excitation energy of the solid, which is En+1- En. Absorption of the
recoil energy, ER, by the solid thus becomes probable, and the photon emerges with energy
reduced by ER and with Doppler broadening. In the figure, ω represents frequency, and ℏ is
Planck's constant divided by 2π.
The Mössbauer effect occurs because in solids, the value of f is high enough that recoil-free
absorption is possible. Thus an atom of 57Co can decay to 57Fe, which gives off a γ-ray, and
may be absorbed without recoil by a nearby 57Fe, which happens to have just the right
splitting between the energy levels in its nucleus to absorb it.

Karnataka State Open University Page 168

Spectroscopic applications in Inorganic chemistry Block 4.1.2

This scenario will only happen if the decaying Co atom is surrounded by the same atoms as
the absorbing Fe. If the receiving Fe atoms are in a different matrix (say, in a mineral) than in
the emitter, then no absorption can occur.
8.2 Recoil effect
Whenever a high energy particle/projectile is released from a body at rest, the releasing body
feels a back-kick ie, it is pushed backwards, this is true for absorption of high energy particles
also. This phenomenon is called recoil effect. The recoil happens to conserve the momentum.
When a gaseous atom or molecule emits a quantum of energy, E then emitted quantum will
always have the momentum E/C where C is the velocity of light
To conserve the momentum the emitter recoils with momentum P which is equal and in
opposite direction. Therefore
P = M. VR = -E/C where VRrecoil velocity [-ve sign shows that its direction is opposite]
ER = P2/2m = E2/2MC2
= (Et-ER)2/ 2MC2 ~ Et/2MC2
If M increases the recoil energy can be still lower, so the source and the absorber are fixed on
a larger lattice to increase mass.
8.3 Conditions for MB spectra
The energy of nuclear transition must be larger enough to give useful γ-ray photon, but not
enough to cause recoil effect.
The energy of the γ-ray photon must be in the range of 10-150keV.
A substantial amount of the nuclear decay must be with γ-ray emission.
The lifetime of the excited state must be long enough give a reasonably broad emission range.
Since, extremely narrow lines are not useful (ι must be 001 to 100nS)
The excited state of the emitter should be having a long-lived precursor, and easy to handle.
The ground state of the isotope should be stable. Its natural abundance should be high or at
least the enrichment of that isotope should be easy.
The cross section of for absorption should be high.
8.4 Fe is the most studied precursor
i) The precursor of 57Fe is 57Co which decays to 57Fe* with a half-life of 270days
(highly stable precursor).
ii) 9% of 57Fe decays to ground state directly with emission of γ-ray photon of
energy 136.32keV.
iii) 91% of 57Fe* decays to another excited state with emission 121.91keV energy.
iv) The lower excited state is having half-life times of 99.3nS (more stable).

Karnataka State Open University Page 169

Spectroscopic applications in Inorganic chemistry Block 4.1.2

v) This decay to ground state with emission of 14.41keV.

vi) This transition satisfies all the conditions for MB spectra except 2nd condition.
But this is compensated by large absorption cross section.
Other elements that can be studied are 119Sn, 121Sb, 125Te, 129I, 129Xe and 197Au.
8.5 Recording the MB spectrum
Usually the standard emitter is used as the source. Sample under investigation is the absorber.
Both the sample and absorber are embedded on a crystal lattice to minimize the recoil effect.
The source for 57Fe spectroscopy is commercially available 57Co/Rh is mounted on the shaft
of a vibrator. Source is generally kept at room temperature. Absorber (sample under study)
may be cooled down to liquid nitrogen or liquid helium temperatures in cryostat, or for
controlled heating in an oven. γ-rays are detected by a scintillation counter, gas proportional
counter or a semi-conductor detector. A constant frequency clock cynchronises a voltage
waveform which serve as a reference signal to the servo-amplifier controlling the electro-
mechanical vibrator. A difference between the monitored signal and the reference signal is
amplified and drives the vibrator at the same frequency (typically 50s-1) as the channel
address advance. Each channel corresponds to a certain relative velocity and is held open for
a fixed time interval depending on the frequency and number of channels used. The incoming
γ- counts are collected in their corresponding channels during the sequential accessing eg. 50
times per seconds, until satisfactory resolution is reached. The cryostat can be furnished with
a superconducting solenoid for measuring the sample in an applied magnetic field. It is also
possible to mount a pressure cell inide the cryostat for studying the sample properties under
pressure.
8.6 Isomeric shift/centre shift/ chemical shift
The Et values is affected by the interaction between the nucleus and the electrons present
around it. This arises because of the different sizes of nucleus in ground and excited states.
The change in nuclear radius when going from gs to es is ∆R. Z is the atomic number
The change in electrostatic energy on decay is given by (Chemical shift/ isomer shift)
δ = (ε0/5)(Ze2R2)(∆R/R) [ │Ψs(abs)│2-│Ψs(source)│2]
where
ε0= permittivity of free space
Z = atomic number of the nucleus
e = electronic charge
Ψs(abs) = s orbital wave function of absorber
Ψs(source) = s orbital wave function of source.

Karnataka State Open University Page 170

Spectroscopic applications in Inorganic chemistry Block 4.1.2

Since s electron wave functions have their maxima at the nucleus, s electron density affect the
isomer shift to a greater extent. But changes in p and d orbital occupancies affect the s
electron through screening hence have a smaller effect on isomer shift. When ∆R/R is
positive the isomer shift is also positive and negative ∆R/R reflected as negative shift. Isomer
shift is related to the oxidation state of the metal. In 119Sn spectra Sn(II) shows a positive
shift (∆R/R) with respect to Sn whereas for Sn (IV) it is negative

119
In Sn compounds, the shift values depend on the ligand present and the coordination
number of tin. Hence isomer shift values are useful in characterizing tin derivatives. My Sn
compounds appears to contain Sn(II) from the formulae but on analysing with MB spectra
Sn(IV) is present in them. Many of them are polymeric and contain Sn(IV). Generally Sn(II)
compounds shows shift > than 2.1mmS-1 and Sn(IV) shows shift < 2.1 mmS-1 (with relative
to SnO2.
The isomer shift of (SnPh2)n is 1.5 mm/S clearly showing the presence of Sn(IV). Similarly
formula Sn(C5H3)2 is having a momomeric structure in the solid state and shows a shift of
3.74mm/S.
8.7 Chemical Shit values for Fe compounds
Fe isomer shift cannot be used for determining the oxidation state of Fe in a molecule. Fe
shows oxidation state from 0 to 4 often differs in unit charge only. The electrons involved are
from d orbital, so effect on the s electron is smaller. Varying spin states (which depend on the
ligands present) also affect the shift values. Though some useful correlations had been drawn.
Fe prophyrin complexes are very important biologically. Fe can be present in +2 or +3 state
in them. The complexes can be easily reduced. The electron may be to the Fe or to the ligand.
In that ambiguous case MB spectra is useful in determining the oxidation state.

Karnataka State Open University Page 171

Spectroscopic applications in Inorganic chemistry Block 4.1.2

8.8 Electric Quadrupole Interactions

Nuclei in states with an angular momentum quantum number I > ½ have a non-spherical
charge distribution. This produces a nuclear quadrupole moment. In the presence of an
asymmetrical electric field (produced by an asymmetric electronic charge distribution of
ligand arrangement) this split the nuclear energy levels. The charge distribution is
characterized by a single quantity called the Electric Field Gradient (EFG)

Oblate and Prolate nuclei

In the case of an isotope with I = 3/2 excited state, such as 57Fe or 119
Sn, the excited state is
spilt into two sub states  = ±1/2 and  = ± 3/2. This gave a two line spectrum or doublet.
The magnitude of splitting, delta, is related to the nuclear quadrupole moment, Q and the
principle component of the EFG,  , by the relation

∆=
2

Quadrupole splitting for 57Fe and 119Sn

Karnataka State Open University Page 172

Spectroscopic applications in Inorganic chemistry Block 4.1.2

8.9 Information’s from quadrupole splitting

Appearance of quadrupole splitting shows the presence of efg at the nucleus. The efg may be
created by the ligand field or by the electron distribution around the nucleus. Single crystal or
application of magnetic field gives more information. If a nucleus with symmetric electron
distribution is in Oh filed efg is not expected.
8.10 Stereochemical activity of lone pair
Consider Te(IV) compounds with six ligands. If the lone pair of electron of Te is
stereochemically active, then it will occupy one vertex of a pentagonal bipyramide (pbp).
This will create an efg at the nucleus resulting in quadrupole splitting. But no quadrupole
splitting is observed in these classes of compounds, hence it is clear that the lone pair is
stereochemically inactive and occupies the 5s orbital.
Structurea of the [TeX4Y]2-had not been crystallographiclaay studied. The MB spectra of
these species show no quadrupole splitting but this is not a conclusive evidence for absence

Karnataka State Open University Page 173

Spectroscopic applications in Inorganic chemistry Block 4.1.2

of efg at nucleus. The efg may not be enough to cause quadrupole splitting. But in CsIF6
substantial quadrupole splitting shows the stereochemical activity of the lone pair.
8.11 Magnetic interactions
In the presence of a magnetic field the nuclear spin moment experiences a dipolar interaction
with the magnetic field ie, Zeeman splitting. There are any sources of magnetic fields that can
be experienced by the nucleus. The total effective magnetic field at the nucleus Beff is given
by
 = !"#$%&"% + #'()%&* + +),#*&' - + &,,*)+
The first three terms being due to the atom’s own partially filled electron shells."#$%&"% is
due to the spin on those electrons polarizing the spin density at the nucleus. #'()%&* is due to
the orbital momentum on those electrons, and +),#*&' is the dipolar field due to the spin of
those electrons.
Energy of the nuclear levels ./ = −12 
This magnetic field splits nuclear levels with a spin of I in to (2I + 1) substates. Transitions
between the excited state and ground state can only occur where  changes 0 or 1. This
gives six possible transitions for a 3/2 to ½ transition, giving a sextet, with the line spacing
being proportional to  .

Effect of magnetic field on 57Fe

The line positions are related to the splitting of the energy levels, but the line intensities are
related to the angle between the Mossbauer gamma-ray and the nuclear spin moment. Outer
and inner lines are always in the same proportion. The middle lines can vary in relative
intensity between 0 and 4 depending upon the angle the nuclear spin moments makes to the

Karnataka State Open University Page 174

Spectroscopic applications in Inorganic chemistry Block 4.1.2

gamma-ray. In polycrystalline samples with no applied field this value averages to 2. But in
single crystals or under applied fields the relative line intensities can give information about
moment orientation and magnetic ordering.
8.12 Application of Mossbauer spectra
Spectra of spin free Fe(II)→ FeSO4.7H2O
From the crystallographic data it was initially concluded that FeSO4.7H2O is having is having
a perfect Oh symmetry, with six H2O on each vertex. But the MB spectrum recorded showed
a large quadrupole splitting which is not possible in a regular Oh symmetry (for a perfect Oh
field efgis zero).

Spectra of spin free Fe(III)→ FeSO4.7H2O

Fe(II) is a d6 system, in weak field created by H2O an orbitally degenerate system results.
This under goes J-T distortion (Zin) to remove the degeneracy and form a tetragonal field.
This creates an efg at the nucleus and hence quadrupole splitting occurs. The structure
assigned is a distorted Oh with all angels 900 and x ≠ y ≠ z

Karnataka State Open University Page 175

Spectroscopic applications in Inorganic chemistry Block 4.1.2

8.13 Prussian blue and Turnbull’s blue

Prussian blue is a dark blue pigment with the idealized formula Fe7(CN)18. It is prepared by
adding a ferric salt to ferrocyanide.
3 45 + [3 5
(67)8 ]9: → 3945 [3 5 (67)
8 ]4

Trnbull’s blue is the same substance but is made from different reagents, ie, addition ferrous
salt to ferricyanide
3 5
+ [3 45 (67)8 ]4: → 3945 [3 5 (67)
8 ]4

Its lightly different colour systems from different impurities.For a long time they considered
as chemically different compounds. Prussian blue with [3  (67)8 ]9: anions and Turnbull’s
blue with [3  (67)8 ]4: anions, according to the different way of preparing them. However
the Mossbauer were nearly identical for both PB and TB showing only the presence of
[3  (67)8 ]9: and Fe3+ in the high spin state. This was confirmed by use of <9 [3  (67)8 ]
and <4 [3  (67)8 ] as a reference compounds. Immediately after adding a solution of Fe2+ to
a solution of [3  (67)8 ]4: a rapid electron transfer takes place from Fe2+ to the anion of
the same material. A singlet for Fe(II) and a quadrupole doublet for Fe(III) were which
confirmed Prussian blue and Turnbull’s blue are identical.

The Fe(II) centres which are low spin are surrounded by six cyanide ligands in an octahedral
configuration. The Fe(III) centres which are high spin are ocahedrally surrounded on average
by 4.5 nitrogen atom and 1.5 oxygen atoms (the oxygen from the six coordinated water
molecules. This introduces am efg at Fe(III) nucleus and hence quadrupole splitting occurs.

Karnataka State Open University Page 176

Spectroscopic applications in Inorganic chemistry Block 4.1.2

Sodium nitroprusside → Na2[Fe(CN)5(NO)]

The oxidation state of Fe in nitroprusside was a matter of controversy for a long time.
Initially it was assumed that it contained Fe(II) and +NO since it was diamagnetic . [Fe(II) is a
d6 and Fe(III) is a d5 systems]. But the MB spectrum of the sample showed a doublet with δ =
-0.165 mm/S. this value is too negative for a Fe(II) complex.

This suggests that the Fe may be in Fe(IV) state. The magnetism and MB spectrum are in
consistent with the structure which has an extensive π-bondinf with +NO ligand. The t2g
orbital of Fe and the p-orbital of N present in +NO containing the off electron to form a π-
bond. The Fe(II) is transferring the electrons from filled t2g level to an vacant π-antibonding
orbital of NO. This makes the shift value to approach Fe(IV) values. Now because of this the
shielding of s electrons by the d electrons decreases and hence the shift becomes more. This
is supported by the decrease in N-O stretching frequency in IR since the anti-bonding levels
is field.

Karnataka State Open University Page 177

Spectroscopic applications in Inorganic chemistry Block 4.1.2

K4[Fe(CN)6] is a 3d6 LS complex with Oh symmetry, where all six electrons are
accommodated in the three t2g orbitals. Both contributions (EFG)val and (EFG)lat vanish, there
is no quadrupolar interaction. Na2[Fe(CN)5NO]2H2O has C4V symmetry with d-orbital
splitting as shown.

Its LS behaviour requires that all six electrons are accommodated in the lowest three orbitals
arising from the tetragonal splitting of the former cubic t2g (Oh) subgroup. (EFG)val is still
zero but (EFG)lat ≠ 0 arises from the ligand replacement in the iron coordination sphere. The
isomer shift data for the pentacyano complexes of iron(II) with different sixth ligand X.

Normalizing the isomer shift to that of the petacyanonitrosylferrate complex as zero point.
The ordering expresses the varying effects of dπ-pπ back donation for the different sixth
ligand X. the isomer shift values becomes more positive on going from +NO to H2O.
dπ-pπbackdonation decrease causing an increasing d-electron density residing near the iron
centre. Stronger shielding of s-electrons by d-electrons which finally creates lower s-electron
density at the nucleus. The nuclear factor ∆R/R is negative for 57Fe explains the increasingly
positive isomer shift values in the given sequence from +NO to H2O.

Karnataka State Open University Page 178

Spectroscopic applications in Inorganic chemistry Block 4.1.2

8.14 Ferredoxin
Study of ferredoxin a Fe-S protein which assists in in-vivo electron transfer reactions. The
two-iron centres are not equivalent in the reduced form. The oxidized form with two Fe(III)-
high spin centres can be distinguished from the reduced form with one Fe(III)-high spin
centre only by using MB spectrum.

8.15 Study of thermal spin-cross over

Many coordination compounds possessing intermediate ligand field strengths show thermal
spin crossover {ie, HS↔LS}. For example [Fe(phen)2(NCS)2] undergoes thermal spin
transition. The main result is that in the temperature region, where the MAS spectra refelect
the transition to the LS state the MES spectra still show the typical HS signals arising from
excited ligand field states.

Karnataka State Open University Page 179

Spectroscopic applications in Inorganic chemistry Block 4.1.2

8.16 Summary of the unit

Nearly fifty years ago Rudolf L Mössbauer discovered the recoilless nuclear resonance
absorption of gamma rays and it is referred as Mössbauer spectroscopy. It gives very precise
information about the chemical, structural, magnetic and time-dependent properties of a
compound. Key feature of this technique is the recoilless gamma ray emission and absorption
of a nucleus (referred as the 'Mössbauer Effect').
Nuclei in atoms undergo a variety of energy level transitions and these energy levels are
influenced by their surrounding environment (both electronic and magnetic) which can
change or split these energy levels. These changes in the energy levels can provide
information about the atom's local environment within a system and ought to be observed
using resonance-fluorescence. There are two major obstacles in obtaining this information
they are
i) The 'hyperfine' interactions between the nucleus and its environment (which are extremely
small) and
ii) The recoil of the nucleus as the gamma-ray is emitted or absorbed prevents resonance.
A nucleus with Z protons and N neutrons in an excited state of energy Ee undergoes transition
to the ground state of energy Eg by emitting a gamma quantum of energy Ee – Eg. The gamma
quantum may be absorbed by the nucleus of the same kind (same Z and N) in its ground state,
whereby transition to the excited state of energy Ee takes place (resonance absorption). The
subsequent transition to the ground state emits a conversion electron e- or a -γ-quantum
(resonance fluorescence).
8.17 Key words
Recoil effect; Conditions for MB spectra; Isomeric shift/centre shift/ chemical shift;
Chemical Shit values for Fe compounds; Electric Quadrupole Interactions; Magnetic
interactions; Application of Mossbauer spectra ; Prussian blue and Turnbull’s blue;
Ferredoxin; Study of thermal spin-cross over
8.18 References for further studies
1) Mössbauer Spectroscopy: Tutorial Book; Yutaka Yoshida, Guido Langouche; Springer
Science & Business Media, 2012.
2) Mössbauer Spectroscopy Applied to Inorganic Chemistry; G.J Long; Springer Science &
Business Media, 2013.
3) Mossbauer Spectroscopy: Applications in Chemistry, Biology, and Nanotechnology;
Virender K. Sharma, Gostar Klingelhofer, Tetsuaki Nishida; John Wiley & Sons, 2013.

Karnataka State Open University Page 180

Spectroscopic applications in Inorganic chemistry Block 4.1.2

4) Mössbauer Spectroscopy and Transition Metal Chemistry: Fundamentals and

Applications; Philipp Gütlich, Eckhard Bill, Alfred X. Trautwein; Springer Science &
Business Media, 2010.
5) Mössbauer Spectroscopy; Dominic P. E. Dickson, Frank J. Berry; Cambridge University
Press, 2005.
8.19 questions for self understanding
1) What is Recoil Effect?
2) Explain the necessary Conditions for MB spectra
3) Why Fe is the most studied precursor in MB spectra?
4) Explain the recording of the MB spectrum
5) What is Isomeric shift/centre shift/ chemical shift?
6) Discuss the chemical shit values for Fe compounds
7) What is Electric Quadrupole interaction?
8) What are the informations obtained from quadrupole splitting?
9) Discuss the stereochemical activity of lone pair
10) Explain the magnetic interactions
11) Discuss the application of Mossbauer spectra for following cases
a) Prussian blue and Turnbull’s blue
b) Ferredoxin
c) Study of thermal spin-cross over

Karnataka State Open University Page 181

Thermal methods of analysis Block 4.1.3

UNIT-9
Structure
9.0 Objectives of the unit
9.1 Introduction
9.2 Thermogravimetric analysis (TGA)
9.3 Principle
9.4 Types of TGA
9.5 Instrumentation
9.6 Types of TGA instruments
9.7 Thermogravimatic curves
9.8 Sources of errors in TGA
9.9 Calibration of thermobalance for the measurement of mass
9.10 Interpretation of TG curves
9.11 Types of TG curves
9.11.1 Plateau
9.11.2 Procedural decomposition temperature
9.11.3 Final temperature
9.11.4 The reaction interval
9.11.5 Isobaric mass change determination
9.11.6 Evolved gas detection (EGD)
9.11.7 Evolved gas analysis (EGA)
9.12 Information from TG curve
9.13 Factors affecting TG curve
9.14 Applications of thermogravimetric analysis
9.15 Analysis of inorganic and organic mixtures
9.15.1 Binary mixtures
9.15.2 Analysis of a mixture of calcium and magnesium carbonates
9.15.3 Mixture of calcium and magnesium oxalates
9.15.4 Analysis of a mixture of AgNO3 and Cu(NO3)2
9.15.5 Complex mixture
9.16 Summary
9.17 Key words
9.18 References for further studies

Karnataka State Open University Page 182

Thermal methods of analysis Block 4.1.3

9.0 Objectives of the unit

After studying this unit you are able to

Explain the principle of TGA,

Describe the experimental setup of TGA,

Interpret the analytical information from TGA curves

Describe the applications of TGA in qualitative and quantitative analysis of inorganic,
organic and polymer material.
9.1 Introduction
Thermogravimetric analysis (TGA) is the most widely used thermal method. It is based on
the measurement of mass loss of material as a function of temperature. In thermogravimetry a
continuous graph of mass change against temperature is obtained when a substance is heated
at a uniform rate or kept at constant temperature. A plot of mass change versus temperature
(T) is referred to as the thermogravimetric curve (TG curve). For the TG curve, we generally
plot mass (m) decreasing downwards on the y axis (ordinate), and temperature (T) increasing
to the right on the x axis (abscissa). Sometime we may plot time (t) in place of T. TG curve
helps in revealing the extent of purity of analytical samples and in determining the mode of
their transformations within specified range of temperature. In thermogravimetry, the term
‘decomposition temperature’ is a complete misnomer. In a TG curve of single stage
decomposition, there are two characteristic temperatures; the initial Ti and the final
temperature Tf. Ti is defined as the lowest temperature at which the onset of a mass change
can be detected by thermo balance operating under particular conditions and Tf as the final
temperature at which the particular decomposition appear to be complete. Although Ti has no
fundamental significance, it can still be a useful characteristic of a TG curve and the term
procedural decomposition temperature has been suggested. The difference Tf – Ti is termed
as reaction interval. In a dynamic thermogravimetry a sample is subjected to continuous
increase in temperature usually linear with time whereas in isothermal or static
thermogravimetry the sample is maintained at a constant temperature for a period of time
during which any change in mass is noted. Now we will take up the instrumentation
commonly used to obtain TG Curve.
9.2 Thermogravimetric analysis (TGA)
Thermogravimetric analysis (TGA) is an analytical technique used to determine a material’s
thermal stability and its fraction of volatile components by monitoring the weight change that
occurs as a specimen is heated. The measurement is normally carried out in air or in an inert

Karnataka State Open University Page 183

Thermal methods of analysis Block 4.1.3

atmosphere, such as Helium or Argon, and the weight is recorded as a function of increasing
temperature.
Sometimes, the measurement is performed in a lean oxygen atmosphere (1 to 5% O2 in N2 or
He) to slow down oxidation. In addition to weight changes, some instruments also record the
temperature difference between the specimen and one or more reference pans (differential
thermal analysis, or DTA) or the heat flow into the specimen pan compared to that of the
reference pan (differential scanning calorimetry, or DSC). The latter can be used to monitor
the energy released or absorbed via chemical reactions during the heating process.
In the particular case of carbon nanotubes, the weight change in an air atmosphere is typically
a superposition of the weight loss due to oxidation of carbon into gaseous carbon dioxide and
the weight gain due to oxidation of residual metal catalyst into solid oxides.
9.3 Principle
Changes in the mass of a sample are studied is a subject of a program.
Changes in temperature affect the sample. Not all thermal changes/events brings a changes in
mass of sample, i.e, melting, crystallization but some thermal events i.e, desorption,
absorption, sublimation, vaporization, oxidation, reduction and decomposition brings changes
in mass of sample
it is used in analysis of volatile products, gaseous products lost during the reaction in
thermoplastics, thermosets, elastomers, composites, films, fibers, coatings, paints ect….
9.4 Types of TGA
There are three types of themogravimetry they are
Dynamic TGA: In this type of analysis, the sample is subjected to condition of continuous
increase in temperature usually linear with time.
Isothermal or static TGA: in this type of analysis, sample is maintained at a constant
temperature for a period of time during which change in weight is recorded.
Quasistatic TGA: in this technique sample is heated to a constant weight at each of a series of
increasing temperature.
9.5 Instrumentation
The instrument used in thermogravimetry (TG) is called a thermobalance. It consists of
following basic components in order to provide the flexibility necessary for the production of
useful analytical data in the form of TGA Curve.
Basic components of a typical thermobalance are
i) Balance

Karnataka State Open University Page 184

Thermal methods of analysis Block 4.1.3

ii) Furnace (heating device)

iii) Unit for temperature measurement and control (Programmer)
iv) Recorder( automatic recording unit for the mass and temperature changes)
a) Balance
The essential requirements of an automatic recording thermobalance are accuracy, sensitivity,
reproducibility, and capacityThe simple block diagram of thermobalcae is shown in figure 1.

Figure 1: Block diagram of a thermobalance

Two types or recording thermobalances are generally used in thermogravimetry analysis they
are null point type balance and deflection type balance.
The null type balance, are more widely used. A sensing element is incorporated to balance
which detects a deviation of the balance beam from its null position. A sensor detects the
deviation and triggers the restoring force to bring the balance beam to back to the null
position. The restoring force is directly proportional to the mass change.
Deflection balance type involve the conversion of the balance beam deflection about the
fulcrum into a suitable mass–change trace by
a) Photographic recoding i.e change in path of a reflected beam of light available of
photographic recording
b) Recording electrical signals generated by an appropriate displacement measurement
transducer and
c) Using an electrochemical device.
The different balances used in TG instruments are having measuring range from 0.0001 mg
to 1 g depending on sample containers used.
b) Furnace
The furnace and control system are designed to produce linear heating at over the whole
working temperature range of the furnace and provision is made to maintain any fixed

Karnataka State Open University Page 185

Thermal methods of analysis Block 4.1.3

temperature. A wide temperature range generally -150°C to 2000 °C of furnaces is used in

different instruments. The range of furnace basically depends on the types of heating
elements are used.
c) Temperature measurement and control
Temperature measurement are commonly done using thermocouples, chromal–alumel
thermocouple are often used for temperature up to 1100°C whereas Pt/(Pt–10%Rh) is
employed for temperature up to 1750°C. Temperature may be controlled or varied using a
program controller with two thermocouple arrangement. The signal from one actuates the
control system whilst the second thermocouple is used to record the temperature.
d) Recorder
Graphic recorders are preferred to meter type recorders. X-Y recorders are commonly used as
they plot weight directly against temperature. The present instrument facilitate
microprocessor controlled operation and digital data acquisition and processing using
personal computer with different types recorder and plotter for better presentation of data.
9.6 Types of TGA instruments
The schematic TGA instrument is shown in Figure 2. The sample is heated under nitrogen or
synthetic air with constant heat rate while the difference of the mass during this process is
measured. A mass loss indicates that a degradation of the measured substance takes place.
The reaction with oxygen from the synthetic air for example could lead to an increase of
mass.

Figure 2: Schematic principle of TGA measurement

TGA instruments can be divided into two general types: vertical and horizontal balance.
Vertical balance instruments have a specimen pan hanging from the balance. It is necessary
to calibrate these instruments in order to compensate for buoyancy effects due to the variation

Karnataka State Open University Page 186

Thermal methods of analysis Block 4.1.3

in the density of the purge gas with temperature. Vertical balance instruments generally do
not have reference pan and are incapable of true DTA measurements.
Horizontal balance instruments normally have two pans (sample and reference) and can
perform DTA and DSC measurements. They are considered free from buoyancy effects, but
require calibration to compensate for differential thermal expansion of balance arms.
9.7 Thermogravimatic curves
TG curves represent the variation in the mass (m) of the sample with the temperature (T) or
time (t). Normally, plot of mass loss in downward and mass gain in upwards on the ordinate
(y) axis was done as shown in Figure 3.

Figure 3: TG Curve. The plateau of constant weight (region A), the mass loss portion
(region B), and another plateau of constant mass (region C)

Sometime (when substance is heated at uniform rate) a derivative thermogravimetric (DTG)

curves is recorded. A DTG curve presents the rate of mass change (dm/dt) as a function of
temperature, or time (t) against T on the abscissa (x axis) as shown in Figure 4. In this figure,
the derivative of the curve is shown by dotted lines.
9.8 Sources of errors in TGA
There are a number of sources of error in TGA, and they can lead to inaccuracies in the
recorded temperature and mass data. Some of the errors may be corrected by placing the
thermobalance at proper place and handling it with great care.
i) Buoyance effect
If a thermally inert empty crucible is heated, there is usually an apparent weight change as
temperature increases. This is due to effect of change in buoyancy of the gas in the sample

Karnataka State Open University Page 187

Thermal methods of analysis Block 4.1.3

environment with the temperature, the increase convection and possible effect of heat from
the furnace in the balance itself. In modern thermobalances, this effect is negligible.
However, if necessary, a blank run with empty crucible can be performed over the
appropriate temperature range. The resultant record can be used as a correction curve for
subsequent experiment performed in the same condition.
i) Condensation on balance suspension
Condensation of the sample will also affect the mass of the sample and consequently the
shape of TG curve .This can be avoided by maintaining a dynamic atmosphere around the
sample in the furnace so that the entire condensable product may be driven by the flowing
gases.
ii) Random fluctuation of balance mechanism
iii) Reaction between sample and container
iv) Convection effect from furnace
v) Turbulence effect from gas flow
vi) Induction effect from furnace
Errors of type (iii) can be avoided by proper placing of balance in the laboratory and error (v)
can be avoided by sensible choice of sample container. Last three errors (v-vii) have to be
considered in the design of the furnace, the balance and its suspension system. By avoiding
excessive heating rate and proper gas flow rate some of above mentioned errors may be
avoided.
9.9 Calibration of thermobalance for the measurement of mass
It can be done by adding known mass of the sample container and noting the reading of the
chart. Temperature calibration: ferromagnetic standards are used for this purpose. In a
magnetic field there substances have shown detectable mass changes. The ferromagnetic
standards are quite suitable for the temperature range from 242 to 771°C.
9.10 Interpretation of TG curves
TG curves of a pure compound are characteristic of that compound. Using TG curve we can
relate the mass changes to the stoichiometry involved. This can often lead us directly to the
quantitative analysis of samples whose quantitative composition is known. To further
illustrate, let’s consider the example of TGA curve of CaCO3 shown in figure 5. This curve
indicates that CaCO3 decomposes in a single step between 800° C and 950° C to form stable
oxide CaO and the gas carbon dioxide. This can be explained the chemistry of CaCO3 when it
is heated.

Karnataka State Open University Page 188

Thermal methods of analysis Block 4.1.3

CaCO3(s) → CaO(s) + CO2 (g) ----------- (1)

Mr 100.1 56.1 44
Figure 4 indicates the % mass lost by the sample is 44 (100.1–56.1) between 800 and 950°C.
This exactly corresponds to the mass changes calculations based on stoichiometry of the
decomposition of CaCO3. The percentage weight loss of CaCO3 will be
M r (CO2 )
m% = X 100
M r (CaCO3 )
44
m% = X 100
100.1

Figure 4: TG and DTG Curve of CaCO3 at various heating rates (b =10 oC, c = 3 oC)
(DTG = Rate of Change of mass, dm/dt) curve

We have seen above how TG Curves is related to stoichiometry (quantitative interpretation).

In next example we will see how it can be used to compare thermal stability of materials
(qualitative interpretation). Such information can be used to select material for certain end-
use application, predict product performance and improve product quality etc….
Figure 5 gives TG curves of some polymers. TG Curves clearly indicate that polymer (PVC)
is the least thermally stable and polymer (PS) is most thermally stable. Polymer (PS) looses
no weight at all below about 500oC and then decomposes abruptly by about 600oC. The other
three polymers have all decomposed by about 450oC. Polymers (PMMA) decomposes more

Karnataka State Open University Page 189

Thermal methods of analysis Block 4.1.3

slowly than the others as indicated by slopes of TG curves. TG curve of polymer (PMMA)
has less slope than the others.

Figure 5: TG Curves of some polymers: PVC = polyvinyl chloride; PMMMA = polymethyl

methacrylate, LDPE = low density poly ethylene; PTFF = ploytetra fluoroethylene; and PS =
polystyrene.
9.11 Types of TG curves
TG curves are classified according to their shapes in to seven types as shown in Figure 6.
Type A: This cruves shows no mass change over the entire range of temperature. it can be
concluded that the decomposition temperature for a sample is greater than the
temperature range of instrument.
Type B: this curve shows that there is large mass loss followed by mass plateau and is
formed when evaporation of volatile product(s) during drying, desorption or
polymerization takes place. If a non-interacting atmosphere is present in the chamber,
type B curve will change in to type A curve.
Type C: this curve shows the singlet-stage decomposition temperatures (Ti and Tf).
Type D: this curve shows the multi-stage decomposition processes where reaction is
resolved.
Type E: this curve shows the multi-stage decomposition reaction where reaction is not
resolved.
Type F: this curve shows the increase in mass in the presence of an interacting atmosphere,
example, surface oxidation reaction.

Karnataka State Open University Page 190

Thermal methods of analysis Block 4.1.3

Type G: this curve showa multiple reaction one after the other, example, surface oxidation
reaction followed by decomposition of reaction product(s)

Figure 6: Classification of TG curves

9.11.1 Plateau
A plateau is the part of the TG curve where the mass is essentially constant or there is no
change in mass.
9.11.2 Procedural decomposition temperature
The initial temperature Ti is that temperature at which the cumulative mass change reaches a
magnitude that the thermobalance can detect.
9.11.3 Final temperature
The final temperature Tf, is that temperature at which the cumulative mass changes reaches
maximum.
9.11.4 The reaction interval
The reaction interval is the temperature difference between Tf and Ti.
9.11.5 Isobaric mass change determination
A technique in which the equilibrium mass of a substance at constant partial pressure of the
volatile product(s, is measured as a function of temperature while the substance is subjected
to a controlled temperature program. the record is the isobaric mass change curve, the mass is
plotted on Y-axis and temperature on X-axis increasing from the left to right.
9.11.6 Evolved gas detection (EGD)
A technique in which evolution of gas from a substance is detected as a function of
temperature while the substance is subjected to a controlled temperature program.
9.11.7 Evolved gas analysis (EGA)

Karnataka State Open University Page 191

Thermal methods of analysis Block 4.1.3

A technique in which the nature and/or amount of volatile product(s) released by a substance
are measured as a function of temperature while the substance is subjected to a controlled
temperature program. the method of analysis should be clearly stated.
9.12 Information from TG curve

Figure 7: Formalized TG curve

Plot of weight/mass against temperature of time produced by a thermalgravimeter is called
thermogram. The following features of TG curve should be noted from above figure 7.
Plateau: a region of no mass change indicates the thermal stability of the sample/substance.
Thermal stability is the ability of a substance to maintain its properties as nearly unchanged
as possible on heating. this information about the thermal stability is significant for engineers
as they then know the temperature ranges of in which substances like alloy, building
materials polymers etc…. can be used.
Weight/mass loss: heating a sample to given temperature causes it to lose weight/mass.
Mass/weight loss is informative to inorganic chemist who can then determine the
composition of substance/sample and understand the reaction involved in decomposition.
Procedural decomposition temperature: by looking at thermogram, one can determine the
procedural decomposition temperature Ti indicating the decomposition or evaporation of
sample/substance.
Composition: Weight/mass lost by heating helps determine the composition of
substance/sample, also allows analytical chemist to identify unknown compound or
determine the amount/percentage/weight of a compound in mixture of different compounds.
9.13 Factors affecting TG curve
We have already discussed that the lowest temperature, Ti at which the onset of a mass
change can be detected by the thermobalance operating under particular conditions and Tf is
the final temperature at which the decomposition completed. Actually in TGA experiments,

Karnataka State Open University Page 192

Thermal methods of analysis Block 4.1.3

both Ti and Tf do not have fundamental significance, but they can still be a useful
characteristic of a TG curve. The term procedural decomposition temperature is often used
for the temperature at which mass change appears to commence. This indicates that
procedural decomposition temperature does not have a fixed value, but depends on the
experimental procedure employed to get it. Similar to this there are many factors which
influence a TGA curve. These factors may be due to instrumentation or nature of sample. The
main factors affect the shape precision and accuracy of the experimental results in
thermogravimetry are listed below
1. Instrumental factors
i) Furnace heating rate
ii) Recording or chart speed
iii) Furnace atmosphere
iv) Geometry of sample holder/ location of sensors
v) Sensitivity of recording mechanism
vi) Composition of sample container
2. Sample Characteristics
a) Amount of sample
b) Solubility of evolved gases in sample
c) Particle size
d) Heat of reaction
e) Sample packing
f) Nature of sample
g) Thermal conductivity.
a) Furnace heating rate
At a given temperature, the degree of decomposition is less in the case of slower heating rate.
therefore the shape of the TG curve is influenced by the heating rate. For a single stage
endothermic reaction it has been found that
i) (Ti)F > (Ti)S
ii) (Tf)F > (Tf)S
iii) (Tf –Ti)F > ( Tf –Ti )S
where subscripts F and S indicate fast and slow heating rate respectively.
For example, calcium carbonate would not show any mass loss below 600 °C, when heated in
a thermobalance at heating rate of 3°C per min., and yet it is known that CO2 is evolved at

Karnataka State Open University Page 193

Thermal methods of analysis Block 4.1.3

250 °C. Similarly, polystyrene decomposes 10% by mass when heating rate is 1°C per min by
357 °C and 10% by mass when heating rate is 5°C per min by 394°C. More specifically, it is
observed that the procedural decomposition temperature Ti, and also Tf (the procedural final
temperature) will decrease with decrease in heating rate and the TG curve will be shifted to
the left. The appearance of an inflection in a TG curve at a fast heating rate may well be
resolved into a plateau at a slower heating rate. Therefore, in TGA there is neither optimum
no standard heating rate, but a heating rate of 3°C per min. gives a TG curve with maximum
meaningful resolution.
b) Recording or chart speed
The chart speed on the recording of the TG curve of rapid or slow reaction has pronounced
effect on the shape of the TG curves. For a slow decomposition reaction low chart speed is
recommended for recording the TG curve because at high chart speed the curve will be
flattened and it will not show the sharp decomposition temperature. For a slow reaction
followed by a rapid one at the lower chart speed the curve will show less separation in the
two steps than the higher chart speed curve. For fast-fast reaction followed by slower one
similar observation was observed in shorter curve plateaus.
c) Furnace atmosphere
The effect of atmosphere on the TG curve depends on
i) The types of the reaction
ii) The nature of the decomposition products and
iii) Type of the atmosphere employed.
The effect of the atmosphere on TG curve may be illustrated by taking the example of
thermodecomposition of a sample of monohydrates of calcium oxalate in dry O2 and dry N2
as shown Figure 8.

Figure 8: TG Curve of Calcium Oxalate in O2 and N2 atmosphere

[ N2 ,---------------O2]

Karnataka State Open University Page 194

Thermal methods of analysis Block 4.1.3

The first step, which is dehydration is reversible reaction.

∆
CaC2O4.H2O(s) 
→ CaC2O4(s) + H2O(g ) ………… (2)
This is unaffected because both gases are equally effective in sweeping the evolved water
vapours away from the sample surface. For the second step,
∆
CaC2O4(s) 
→ CaCO3(s) + CO(g) …………. (3)
The curve diverges in O2 atmosphere because the oxygen reacts with evolved CO, giving a
second oxidation reaction which is highly exothermic and so raises the temperature of the un-
reacted sample. The temperature accelerates the decomposition of the compound more
rapidly and completely at a lower temperature as shown in the above diagram in dry O2 then
in N2 atmosphere.
The third step in decomposition reaction is also reversible reaction.
∆
CaCO3(s) 
→ CaO(s) + CO2 (g) …………… (4)
This step should not be influenced by O2 or N2. However there is a slight difference in curves
for the two gases as shown in diagram. The small difference was due to the difference in the
nature/composition of CaCO3 formed in the two atmospheres. This is due to the particle size,
surface area, lattice defects or due to the other physical characteristics of CaCO3 formed.
d) Sample holder
The sample holders range from flat plates to deep crucible of various capacities. The shape of
the TG curve will vary as the sample will not be heated in identical condition. Generally, it is
preconditioning that the thermocouple is placed on near the sample as possible and is not
dipped into the sample because it might be spoiled due to sticking of the sample to the
thermocouple on heating. So actual sample temperature is not recorded, it is the temperature
at some point in the furnace near the sample. Thus it leads to source of error due to the
thermal lag and partly due to the finite time taken to cause detectable mass change. If the
sensitivity of recording mechanism is not enough to record the mass change of the sample
then this will also cause error in recording the weight change of the sample. If the
composition of the sample contains is such that it reacts either with the sample, or product
formed or the evolved gases then this will cause error in recording the mass change of the
sample.
e) Effect of sample mass
The sample mass affects the TG curve in following
i) The endothermic and exothermic reactions of the sample will cause sample temperature to
deviate from a linear temperature change.
Karnataka State Open University Page 195
Thermal methods of analysis Block 4.1.3

ii) The degree of diffusion of evolved gases through the void space around the solid particles.
iii) The existence of large thermal gradients throughout the sample particularly, if it has a low
thermal conductivity.
Thus, it is preferable to use as small a sample as possible depending on the sensitivity of the
balance.
f) Effect of sample particle size
The particle size will cause a change in the diffusion of the evolved gases which will alter the
reaction rate and hence the curve shape. The smaller the particle size, greater the extent of
decomposition at any given temperature. The use of large crystal may result in apparent vary
rapid mass loss during heating. This may be due to the mechanical loss of part of the sample
by forcible ejection from the sample container, when the accumulated evolved gases within
the coarse grains are suddenly released.
g) Effect of heat of reaction
The heat of reaction will affect the extent to which sample temperature proceeds or succeeds
the furnace temperature. This depends on whether the reaction is exothermic or endothermic
and consequently the extent of decomposition will also be affected. The other sample
characteristics such as sample packing, nature of the sample and its thermal conductivity will
also affect the shape of TG curves. If the sample is packed loosely then the evolved gases
may diffuse more easily than if the sample packed tightly.
If the sample reacts with the sample container on heating then it will not give the mass of the
product formed so the sample will change. We can avoid this effect by a sensible choice of
sample container.
9.14 Applications of thermogravimetric analysis
So far we have studied how TGA can be used to understand the chemistry of decomposition
of a particular compound. Information regarding the temperature range over which a
particular sample appears to be stable or unstable can also be studied by TGA. Beside these
thermogravimetric analysis can be used for various other applications. Some of are listed
below
i) Purity and thermal stability
ii) Solid state reactions.
iii) Decomposition of inorganic and organic compounds.
iv) Determining composition of the mixture
v) Corrosion of metals in various atmospheres

Karnataka State Open University Page 196

Thermal methods of analysis Block 4.1.3

vi) Pyrolysis of coal, petroleum and wood.

vii) Roasting and calcinations of minerals.
viii) Reaction kinetics studies.
ix) Evaluation of gravimetric precipitates.
x) Oxidative and reductive stability.
xi) Determining moisture, volatile and ash contents.
xii) Desolvation, sublimation, vaporizations, sorption, desorption, chemisorptions.
It is not possible to discuss all these applications at this level; it is worth to describe some of
the applications which are more common.
9.15 Analysis of inorganic and organic mixtures
The single and pure compound gives characteristic TG curves. Now, we will see how TG
Curves can be used in predicting relative quantities of the components of a mixture.
9.15.1 Binary mixtures
Consider a mixture of two compounds AB and CD having characteristic TG Curves which
are different from each other as shown in Figure 9

Figure 9: (a)Thermogravimetric curves of two compounds AB and CD and (b) their mixture

The decomposition of pure compound AB and CD occur at T1, (labeled as bc) and
temperature T2, (labeled as fg) respectively, as illustrated in Figure 9(a). The TG curve of
mixture of AB and CD together is shown in Figure 9(b). We can see form this figure, the
plateaus (corresponding to the regions of constant mass) commence at about the same
temperature as they do in the TG Curves for the pure compounds AB and CD. We can also
notice that the mass loss overall up to T1 is x mg and from T1 to T2 it is an additional y mg. By

Karnataka State Open University Page 197

Thermal methods of analysis Block 4.1.3

measuring these two quantities x and y from the TG curves we can determine the relative
quantities of AB and CD in the original binary mixture.
For example; consider the mixtures of calcium and magnesium carbonates.
9.15.2 Analysis of a mixture of calcium and magnesium carbonates
A typical TG curve of a mixture of calcium and magnesium carbonates is shown in Figure
10. We can notice that a significant mass loss occurs before 210°C. This is due to the
moisture present in the mixture. Another mass loss at about 480°C is due to the following
reaction
MgCO3(s) → MgO(s) + CO2(g) … (1)
Earlier we mentioned that CaCO3 decomposes at about 800°C. In Figure 9 mass loss between
about 600°C and 900°C can be interpreted due to decomposition of CaCO3.
CaCO3(s) → CaO(s) + CO2(g) … (2)
Portion of the curve ab represents a mixture of MgO and CaCO3 and cd represents a residue
of the mixture of MgO and CaO. Both these plateaus ab and cd represent weight m1 and m2,
respectively. In fact mass m1 is due to CaCO3 + MgO.

Figure 10: TG curve of mixture of calcium and magnesium carbonate

Thus, m1–m2 is the loss of CO2 between 500°C and 900°C due to the decomposition of
CaCO3. Using TGA curve we can relate the mass of different components formed during
TGA experiment. The mass of CaO (m3) formed can be calculated using following Eq. (3)
m3 = 1.27(m1 – m2) … (3)
This equation can be obtained as follows

Karnataka State Open University Page 198

Thermal methods of analysis Block 4.1.3

The CaO is formed by the evolution of CO2 on the decomposition of CaCO3,

CaCO3(s) → CaO(s) + CO2(g)
Mr 100.1 56.1 44
From the above equation 1mole of CaCO3 gives 1 mole of CO2 and 1mole of CaO. Thus,

moles of CO2 in the given examples = (m1 − m2 ) and this is equal to moles of CaO formed.
M r (CO2 )

Thus the amount of CaO must be, m3 = (m1 − m2 ) M r (CO2 )

44
where, Mr(CaO) is the relative molar mass of CaO.

m3 = (m1 − m2 ) X 56 g
44
m3 = 1.27(m1 – m2) g
We know the mass of residue left, i.e., m2, the mass of MgO (m4) can be calculated.
m4 = m2 – m3
Here m3 is the mass of CaO formed, which is equal to 1.27 (m1 – m2). Thus
m4 = m2 – 1.27 (m1 – m2)
Mass of the Ca (mca) in the original sample can also be related to m1 and m2 by the following
formula
mca = 0.91 (m1 – m2)
This can be obtained as follows:
We know, amount of Ca in CaCO3 and CaO will be equal in moles, therefore amount of Ca in
Ar (Ca) Ar (Ca)
mCa = m3 X = 1.27(m1 − m2 ) X
Mr (CaO) Mr (CaO)
where, Ar(Ca) and Mr (CaO) are the relative atomic mass and relative molar mass of Ca and
CaO, respectively. Thus,
= 1.27 (m1 – m2) × 40/56 = 0.91 (m1 – m2)
Similarly, mass of magnesium in the original sample can be related to m1 and m2
Thus, the mass of Mg in original sample (mMg)
Ar ( Mg )
= (mass of residue – mass of CaO) X
M r ( MgO)
Ar ( Mg ) 24.3
mMg = (m2-m3)X = (m 2 - m 3 )X
M r ( MgO) 40.3
mMg = 0.60(m2 − m3 )

Karnataka State Open University Page 199

Thermal methods of analysis Block 4.1.3

9.15.3 Mixture of calcium and magnesium oxalates

Calcium oxalate monohydrate is unsatisfactory weighing form for determining calcium as
oxalate because its tendency to retain excess moisture even at 110°C, co-precipitated
ammonium oxalate remain un-decomposed. The anhydrous calcium oxalate is hygroscopic
but CaCO3 is excellent weighing form if heated to 500 ± 25 °C as can be seen in TG curve of
CaC2O4.H2O. Above 6350C the decomposition of CaCO3 commences to become significant
under usual laboratory conditions and completely converted to CaO at 900°C. Thus, calcium
oxalate monohydrate decomposes in three steps,
First step is dehydration,
Second step involves removal of CO and formation of CaCO3
Third step includes CaCO3 decomposes to CaO. See Figure 11.
CaC2O4.H2O → CaC2O4 + H2O at about 135-220°C
CaC2O4 → CaCO3+ CO at about 400-480 °C
CaCO3 → CaO + CO2 at about 635-900 °C
But magnesium oxalate dihydrate decomposes in two steps instead of three steps.
First, dehydration then removal of CO and CO2 simultaneously and forming MgO, there is no
horizontal corresponding to MgCO3 as it is thermally unstable at this temperature.
MgC2O4.2H2O → MgC2O4 + 2H2O at about 135-220°C
MgC2O4 → MgCO3 + CO → MgO + CO2 at about 500 °C
The TG curve for the mixture of CaC2O4.H2O and MgC2O4.2H2O shows two mass losses up
to 500 °C, first at about 200°C due to loss of water and the second mass loss occurs in the
390-500°C range which is due to decomposition of both calcium and magnesium oxalates.
Thus, at 500°C, the composition of the mixture will be CaCO3 and MgO.

Figure 11: DTG/TG curve of calcium oxalate

Karnataka State Open University Page 200

Thermal methods of analysis Block 4.1.3

Third mass loss after 500°C is due to only the decomposition of CaCO3. If m1 and m2 are the
mass of the mixture at 500°C and 900°C then similar to the previous example we can
calculate the amount of calcium and magnesium in the original sample.
9.15.4 Analysis of a mixture of AgNO3 and Cu(NO3)2
The TG curve of pure AgNO3, Cu(NO3)2 and their mixture are given in Figure 12. Curve a is
the curve of dry crystalline AgNO3. A horizontal extends to 340°C and is followed by
descent as far as 473°C. At this temperature decomposition sets in abruptly and nitrous fumes
are expelled up to 610°C. After that there is much slower mass loss from 610°C to 810°C.
Decomposition of AgNO2, which is not observed when CuO is present, no doubt the latter
catalyses the decomposition. Above 810°C the weight is again constant due to the formation
of pure Ag metal.
2AgNO3(s) → 2AgNO2 (s) + O2(g)
2AgNO2(s) → 2Ag(s) + 2NO2(g)
While the copper nitrate hexahydrate gives a quite different curve b. Water and nitrogen
oxide are driven off up to 150°C to 200°C, then a horizontal indicates the existence of zone
of a new compound, which has been analysed and it corresponds to a basic nitrate Cu(NO3)2
2Cu(OH)2. After that between 200°C and 610°C this compound decomposes vigorously from
250°C and subsequently more slowly. The residue is CuO which only become constant at
940°C.
3Cu(NO3).6H2O → Cu(NO3)2.2Cu(OH)2 +H2O + NO → CuO

Figure 12: TG curve of nitrates: a: AgNO3, b: Cu(NO3)2 and c: AgNO3 + Cu(NO3)2 mixture
If a mixture of AgNO3 and Cu(NO3)2 is placed in thermobalance , the curve c is recorded.
The horizontal related to the basic copper nitrate is, nevertheless, well marked. From 240°C

Karnataka State Open University Page 201

Thermal methods of analysis Block 4.1.3

to 400°C there is a residue keeping constant mass (AgNO3 + CuO), while above 900°C a
mixture of Ag + CuO is present.
If m1 and m2 are the mass of the sample at 400 °C and 700 °C, respectively, the amount of
silver and copper in the sample can be calculated similar to previous example.
A binary alloy of Ag and Cu can be analyzed with ± 3 % error by this method by dissolving
the alloy in HNO3 and then running thermogram and recording successive weight at 400 °C
and 700 °C by solving following simultaneous equations:
(170/108) x + (79/63) y = m1
x + (79/63) y = m2
where x and y are the masses of Ag and Cu in the alloy, m1 and m2 are the masses of the
sample at 400 °C and 700 °C, respectively, 170 is the molar mass of AgNO3, 1000 is the
relative atomic mass of Ag, 79 is molar mass of CuO and 63 is the relative atomic mass of
Cu.
9.15.5 Complex mixture
In this category we are considering the analysis of a mixture of calcium, strontium and
barium oxalates. In the thermogram of a mixture of Ca, Sr and Ba oxalates it is noticed that in
between 100 °and 250 ° C the water of hydration is evolved from all metal oxalates, after the
loss of the water of hydration, the curve exhibited a horizontal weight level from 250-360 °C,
which corresponds to the composition for anhydrous metal oxalates. Then all the three
oxalates decomposed simultaneously to the carbonates and the process completed at
500°C.Then from 500 °C to 620 °C the anhydrous carbonates were stable. On further heating,
the CaCO3 decomposed in the temperature range 620°C- 860 °C to oxide followed by the
decomposition of SrCO3 from 860 °C to 1100°C at which temperature BaCO3 began to
decompose (see Figure 13 ). From weight loss curve, the following data are obtained.

Figure 13: TGA Curve of the mixture of Calcium, Strontium and Barium oxalate

Karnataka State Open University Page 202

Thermal methods of analysis Block 4.1.3

I- mass of hydrated oxalates at 100 °C(mass of the sample) = ms

II- mass of water of hydration = m1
III- mass of CO formed by the decomposition of metal oxalates = m2
IV- mass of CO2 formed by the decomposition of CaCO3 = m3
V- mass of CO2 formed by the decomposition of SrCO3 = m4
We can calculate the amount of Ca, Ba and Sr as follows
From the amount of CO2 (m4) formed by the decomposition of SrCO3, we can calculate the
mass of SrCO3. Simultaneously from the mass of CO2 (m3) formed by the decomposition of
CaCO3, we can calculated the amount of CaCO3.
From thermogram we know the total mass of all the carbonates, so by subtracting the amount
of carbonates of Ca + Sr, we will get the mass of BaCO3.
From the mass of CaCO3, SrCO3 and BaCO3 we can calculate easily the amount of Ca, Sr
and Ba present in the mixture. From the steps discussed above we can arrived on the
following formula to calculate the amount of Ca = mCa, Sr = mSa, Ba = mBa.
Amount of Ca (mCa) = 0.91068 × m3
Amount of Sr (mSr) = 1.9911 × m4
Amount of Ba (mBa) = 0.58603 × ms– 1.9457 × m3 – 2.5788 × m4
9.16 Summary
Thermal analysis comprises a group of techniques where the properties of material are
studied as they change with temperature. To determine the thermo-physical properties several
methods are commonly used: differential thermal analysis (DTA), differential scanning
calorimetry (DSC), thermogravimetric analysis (TGA), dilatometry (DIL), evolved gas
analysis (EGA), dynamic mechanical analysis (DMA), dielectric analyse (DEA) etc. In
metallurgy, material science, pharmacy and food industry the main application of the DTA
and DSC is used for studying phase transition under different atmospheric influences,
temperatures and heating / cooling rates. Common laboratory equipment has a combination
of two thermal analysis techniques. Most common is the simultaneous thermal analysis
(STA) apparatus as the combination of thermogravimetric analysis (TGA) and differential
thermal analysis (DSC).
9.17 Key words
Thermogravimetric analysis (TGA); Types of TGA; Thermogravimatic curves; Plateau
Isobaric mass change determination ; Evolved gas detection (EGD); Evolved gas analysis
(EGA)

Karnataka State Open University Page 203

Thermal methods of analysis Block 4.1.3

9.18 References for further studies

1) Principles and Applications of Thermal Analysis; Paul Gabbott; John Wiley & Sons, 2008.
2) Basic Concepts of Analytical Chemistry; S M Khopkar; New Age International, 1998.
3) Instrumental Methods of Chemical Analysis; Dr. B. K. Sharma; Krishna Prakashan
Media, 2000.
4) Characterization and Analysis of Polymers; Arza Seidel; John Wiley & Sons, 2008.
5) Pharmaceutical Drug Analysis; Ashutosh Kar; New Age International, 2007.
9.19 Questions for self understanding
1) List the different components of a thermobalance.
2) What are common source of errors in thermogravimetric analysis?
3) Calculate the percentage mass change (m %) for the following reactions.
∆
i) Ca(OH)2(s) 
→ CaO(s) + H2O (g)
∆
ii) 6PbO(s) + O2 (g) 
→ 2Pb3O4 (s)
∆
iii) NH4NO3 (s) 
→ N2O(g) + 2H2O(g)
∆
iv) CuSO4.5H2O 
→ CuSO4 .4H2O + H2O
∆
v) CuSO4 
→ CuO + SO3
4) A thermogram of a magnesium compound shows a loss of 91.0 mg from a total of 175.0
mg used for analyte. Identify the compound either as MgO, MgCO3, or MgC2O4
5) What are the common instrumental factors affecting TG curves.
6) A mixture of CaO and CaCO3 is analysed by TGA. The result indicates that mass of the
sample decreases from 250.6 mg to 190.8 mg only between 600°C and 900°C. Calculate
the percentage of calcium carbonate in the mixture.
7) Formulate the solid state reaction of sodium bicarbonate when heated. It decomposes
between 100 and 225 °C with evolution of water and carbon dioxide. The combined loss
of water and carbon dioxide totaled 36.6% by mass whereas the mass loss due to carbon
dioxide alone was found to be 25.4 %.
8) Thermogravimetric studies of carbon black filled rubber sample is performed in inert
atmosphere upto 950 °C and then quickly changing the atmosphere to air. The observed
weight loss is ~ 66.41% upto 500 °C and the mass becomes constant and further the mass
loss between 1300 °C to 2800 °C . Predict the composition of rubber.
9) The TGA and DTA data Manganese Phosphate Monohydrate are shown in Table

Karnataka State Open University Page 204

Thermal methods of analysis Block 4.1.3

Explain the probable transition of unidentified peaks in TGA.

10) What types of standard are required to calibrate the mass variation obtained with a TGA
equipment?
11) What type of standards are required for temperature calibration of any TGA.
12) A mixture of CaCO3 and CaO is analysed using TGA technique. TG curve of the sample
indicates that there is a mass change from 145.3 mg to 115.4 mg between 500–900 °C.
Calculate the percentage of CaCO3 in the sample.
13) A 250 mg hydrated sample of Na2HPO4 decreases to a mass of 145.7 mg after heating to
15 ° C. What is the number of water hydration in Na2HPO4.
14) Draw a labeled diagram of the TG curve obtained by heating a mixture of 80 mg of
CaC2O4.H2O and 80 mg of BaC2O4.H2O to 1200 °C. Calculate the amount of all mass
losses.

Karnataka State Open University Page 205

Thermal methods of analysis Block 4.1.3

UNIT-10
Structure
10.0 Objectives of the unit
10.1 Introduction
10.2 Theory
10.2.1 Static Thermogravimetric Analysis
10.2.2 Dynamic Thermogravimetric Analysis
10.3 Principle
10.4 Characteristics of DTA Curves
10.4 Instrumentation
10.5 Methodology
10.6 Applications
10.7 Differential Scanning Calorimetry DSC
10.8 The difference between a heat flow and a heat flux DSC
10.9 Instrumentation
10.10 Theory of DSC
10.11 Information is obtainable from a DSC curve
10.12 Applications in the area of polymers
10.12.1 Energy (Ordinate) Calibration
10.12.2 Transformation temperatures of a shape memory alloy
10.12.3 Epoxy Mixtures
10.13 Summary of the unit
10.14 Key words
10.15 References for further study
10.16 Questions for self understanding

Karnataka State Open University Page 206

Thermal methods of analysis Block 4.1.3

10.0 Objectives of the unit

After studying this unit you are able to

Explain the principle of DTA, DSC and thermometric titration,

Describe the experimental setup of DTA, DSC and thermometric titration,

Interpret the analytical information from DTA and DSC curves and enthalpogram,

Describe the applications of DTA, DSC and thermometric titration,
10.1 Introduction
Differential thermal analysis (DTA) is a thermal analysis using a reference. The sample and
the reference material (sample) are heated in one furnace. The difference of the sample
temperature and the reference material temperature is recorded during programmed heating
and cooling cycles.
Differential Scanning Calorimetry (DSC) measures the change of the difference in the heat
flow rate to the material (sample) and to a reference material while they are subjected to a
controlled temperature program.
Like differential thermal analysis (DTA), differential scanning (DSC) is also an alternative
technique for determining the temperatures of the phase transitions like melting point,
solidification onset, re-crystallization onset, evaporation temperature etc. With differential
thermal analysis DTA, which is an older technique than differential scanning calorimetry, the
result is a DTA curve (Figure 1b). DTA curve is a curve of temperature difference between
the sample material and the reference material versus temperature or time. The result of DSC
is a curve of heat flux versus time or temperature and is therefore used also for determination
of the enthalpy, specific heat (Cp ) etc.
Broadly speaking the thermoanalytical methods are normally classified into the following
three categories, namely
i) Thermogravimetric Analysis (TGA),
ii) Differential Thermal Analysis (DTA), and
iii) Thermometric Titrations
10.2 Theory
A large number of chemical substances invariably decompose upon heating, and this idea of
heating a sample to observe weight changes is the underlying principle of thermogravimetric
analysis (TGA).
However, TGA may be sub-divided into two heads, namely
a) Static (or Isothermal) Thermogravimetric Analysis, and

Karnataka State Open University Page 207

Thermal methods of analysis Block 4.1.3

b) Dynamic Thermogravimetric Analysis.

10.2.1 Static Thermogravimetric Analysis
In this particular instance the sample under analysis is maintained at a constant temperature
for a period of time during which any changes in weight are observed carefully.
10.2.2 Dynamic Thermogravimetric Analysis
In dynamic thermogravimetric analysis a sample is subjected to conditions of predetermined,
carefully controlled continuous increase in temperature that is invariably found to be linear
with time.
Differential thermal analysis is the most widely used and is probably a very suitable method
for the identification and estimation purposes especially in the case of soils (clays) and
minerals. The chemical or physical changes which are not accompanied by the change in
mass on heating are not indicated in thermogravimetric but there is a possibility that such
changes may be indicated in DTA.
10.3 Principle
Differential thermal analysis is a technique in which the temperature of the substance under
investigation is compared with the temperature of a thermally inert material such as α- lumina
and is recorded with furnace temperature as the substance is heated or cooled at a
predetermined uniform rate. The range of temperature measurable in the course of DTA is
much larger than TG determination. Thus, during TG, pure fusion reactions, crystalline
transition, glass transition and crystallization and solid state reactions with no volatile product
would not be indicated because they provide no change in mass of the specimen. However,
these changes are indicated during DTA by endothermal or exothermal departure from the
base line. Since DTA is a dynamic method, it is essential that all aspects of the technique be
standardized in order to obtain reproducible results. These include pretreatment of specimen,
particle size and packing specimen, dilution of the specimen and nature of the inert diluent.
The principle of method consists in measuring the change in temperature associated with
physical or chemical changes during the gradual heating of the substance. Thermal changes
due to fusion, crystalline structure inversions, boiling, dissociation or decomposition
reactions, oxidation and reduction reactions, destruction of crystalline lattice structure and
other chemical reactions are generally accompanied by an appreciable rise or fall in
temperature. Hence, all these are accounted in DTA. Generally speaking, phase transitions,
dehydration, reduction and some decomposition reactions produce endothermic effects
whereas crystallization, oxidation and some decomposition reactions produce exothermic

Karnataka State Open University Page 208

Thermal methods of analysis Block 4.1.3

effects. In DTA a sample of material under investigation (specimen) is placed by the side of
thermally inert material (the reference sample) usually calacite or α- alumina in suitable
sample holder or block. The temperature difference between the two is continuously recorded
as they are heated. The block is heated in an electric furnace i.e. both are heated under
identical conditions.
10.4 Characteristics of DTA Curves
An idealized representation of the two major processes observable in DTA is illustrated in
Figure 1, where ∆T is plotted on y-axis and T on x-axis. Endotherms are plotted downwards
and exotherms upwards. Similarly, the temperature of the sample is greater for an exothermic
reaction, than that of the reference, for endotherms the sample temperature lags behind that of
the reference

Figure 1: A representation of the DAT curve showing exotherm, endotherm and base line
changes
When no reaction occurs in the sample material, the temperature of the sample remains
similar to that of reference substance. This is because both are being heated exactly under
identical condition i.e. temperature difference ∆T(Ts–Tr) will be zero for no reaction. But as
soon as reaction starts, the sample becomes either hot or cool depending upon whether the
reaction is exothermic or endothermic. A peak develops on the curve for the temperature
difference ∆T against temperature of furnace or time. Let us consider the DTA curve in
Figure 1 again, where ∆T along the line AB is zero indicating no reaction but at B where the
curve begins to deviate from the base line corresponds to the onset temperature at which the
exothermic reaction starts and give rise to a peak BCD with a maximum at point C. Where
rate of heat evolution by the reaction is equal to the difference between the rate of evolution
of heat and inert reference material. The peak temperature C corresponds to the maximum
rate of heat of evolution. It does not represent the maximum rate of reaction nor the

Karnataka State Open University Page 209

Thermal methods of analysis Block 4.1.3

completion of the exothermic process. Thus, the position of C does not have much
significance in DTA experiments. At some determinant point the heat of evaluation process is
completed and after this point heat evaluation goes on decreasing up to D. The usefulness of
the method arises from the fact that peak temperature is normally characteristic of the
material in the sample. Area of the peak BCD is proportional to the amount of reacting
material. For endothermic reaction the peak EFG will be obtained as shown in the idealised
curve. This peak shows that the ∆Ti.e. (Ts–Tr) will be negative because heat is absorbed and
consequently Ts will be smaller than Tr. Note the levels of base lines of extotherm curve, AB
and DE. Both are at different levels above x-axis. This is due to the fact that heat capacity of
the sample has changed as a result of the exothermic process. Similar explanation can be
given for the difference in levels of base lines of endotherm curve i.e. DE and GH. DTA
curves are not only help in the identification of materials but their peak areas provide
quantitative information regarding mass of sample (m), heat of reactions (enthalpy change,
∆H).
10.4 Instrumentation
A differential thermal analyzer is composed of five basic components, namely
i) Sample holder with built-in thermocouple assembly,
ii) Flow-control system,
iii) Furnace assembly,
iv) Preamplifier and Recorder, and
v) Furnace Power Programmer and Controller.
A typical commercial differential thermal analyzer is schematically illustrated in Figure 2.

Figure 2: Schematic representation of thermal analyzer

Karnataka State Open University Page 210

Thermal methods of analysis Block 4.1.3

a) Thermocouples employed are normally unsheathed Platinum Vs Platinum and Sodium Vs

10% Rhodium. The said two thermocouples help in measuring the difference in temperature
between a sample S and an absolutely inert reference substance R, as both are subjected to
heating in a ceramic or metal block inside a furnace being operated by a temperature
programmer and controller.
b) The output of the differential thermocouple is amplified adequately through a high gain,
low-noise preamplifier and subsequently hooked to the recorder, one axis of which is driven
by the block temperature signal and is measured by a third thermocouple.
c) Heating/Cooling Device, a sufficient versatility is achieved by the aid of a pressure-
vacuum, high-temperature electric furnace. An almost constant heating rate is usually
achieved by using a motor-driven variable auto transformer. Both heating rates and cooling
rates may be conveniently adjusted continuously:
i) From 0°-30°C/minute by some instruments, and
ii) From a choice of several commonly employed heating rates viz., 2°, 4°, 8° and
16°C/minute. Usual workable sample temperatures are upto : 500°C. Exceptional maximum
temperatures are upto : 1000°C.
d) Relatively small sample volumes help in two ways: first, they make evacuation easy ; and
secondly, they minimize thermal gradients.
10.5 Methodology
i) Insert a very thin thermocouple into a disposable sample tube 2 mm in diameter
and containing 0.1-10 mg of sample,
ii) ii) Another identical tube is either kept empty or filled with a reference substance,
such as quartz, sand, alumina or alundum powder,
iii) iii) The two tubes are simultaneously inserted into the sample block and
subsequently heated (or cooled) at a uniform predetermined programmed rate, and
iv) iv) DTA—being a dynamic process, it is extremely important that all aspects of
the technique must be thoroughly standardised so as to obtain reproducible results.
A few of these aspects vital aspects are
• Pretreatment of the specimen,
• Particle size and packing of the specimen,
• Dilution of the specimen,
• Nature of the inert diluent,
• Crystalline substances must be powdered, and sieved through 100-mesh sieve,

Karnataka State Open University Page 211

Thermal methods of analysis Block 4.1.3

• For colloidal particles (e.g., clays), micelle-size is very critical, and

• Either to supress an unwanted reaction (e.g., oxidation), or to explore the study of a
reaction
(e.g., gaseous reaction product)—the atmosphere should be controlled adequately. Figure 3,
depicts the differential thermal analysis investigation of calcium acetate monohydrate at a
uniform programmed heating rate of 12°C/minute.

Figure 3: DTA-Investigation of Calcium Acetate Monohydrate, 12°C. min–1

The chemical reactions involved in the differentiated thermal analysis of calcium acetate
monohydrate may be expressed as follows

Stage I: The endothermal dehydration of calcium acetate monohydrate occurs giving rise to
the anhydrous salt. It is easily noticed by an endothermal band on DTA curve between 200°C
and 250°C.
Stage II: The anhydrous salt undergoes endothermal decomposition reaction at 350-400°C
resulting into the formation of CaCO3. It has been observed that this decomposition reaction
seems to be almost alike in the presence of either CO2 or Ar.
Stage III: The decomposition of calcium carbonate to calcium oxide, which is a function of
the partial pressure of the CO2 in contact with the sample. The endothermal band for the

Karnataka State Open University Page 212

Thermal methods of analysis Block 4.1.3

carbonate decomposition is sharply peaked spread over a relatively narrower temperature

range in an atmosphere of CO2.
10.6 Applications
The various important applications of DTA are
i) Rapid identification of the compositions of mixed clay
ii) Studying the thermal stabilities of inorganic compounds
iii) Critically examining in a specific reaction whether a new compound is actually
formed or the product is nothing but an unreacted original substance, and
iv) DTA offers a wide spectrum of useful investigations related to reaction kinetics,
polymerization, solvent retention, phase-transformations, solid-phase reactions
and curing or drying properties of a product.
10.7 Differential Scanning Calorimetry DSC
Differential Scanning Calorimetry (DSC) is a thermal analysis technique that looks at how a
material’s heat capacity (Cp) is changed by temperature. A sample of known mass is heated
or cooled and the changes in its heat capacity are tracked as changes in the heat flow. This
allows the detection of transitions such as melts, glass transitions, phase changes, and curing.
The biggest advantage of DSC is the ease and speed with which it can be used to see
transitions in materials. For these reasons, DSC is the most common thermal analysis
technique and is found in many analytical, process control, quality assurance, and R&D
laboratories.
10.8 The difference between a heat flow and a heat flux DSC
The term differential scanning calorimetry refers to both the technique of measuring
calorimetric data while scanning, as well as a specific instrument design. The technique can
be carried out with other types of instruments
The DSC can be used to obtain the thermal critical points like melting point, enthalpy specific
heat or glass transition temperature of substances. The schematic principle of the DSC is
described in Figure 4. The sample and an empty reference crucible is heated at constant heat
flow. A difference of the temperature of both crucibles is caused by the thermal critical points
of the sample and can be detected.
10.9 Instrumentation
In DSC the instrument used is a differential scanning calorimeter. There are two types, heat-
of instruments are in use, they are
i) flux DSC and

Karnataka State Open University Page 213

Thermal methods of analysis Block 4.1.3

ii) Power compensation DSC, depending on the method of measurement used.

In a heat-flux DSC instrument, the temperature difference between sample and reference is
recorded, after suitable calorimetric calibration, as a direct measure of the difference in heat
flow rate or the difference in power.
In a power compensation DSC instrument the difference in power supplied to the sample and
to the reference, to keep their temperatures as nearly the same as possible, is measured
directly.
The power difference in units of watts (∆P) should be plotted as ordinate. Since endothermic
reactions require a positive input of power into the sample, the DSC convention demands that
endothermic peaks should be plotted upwards, and t or T increasing from left to fight.
However, the DTA convention (endotherms downwards) is quite often used, and it is
recommended that the ordinate axis be labelled with the endothermic (or exothermic)
direction.
10.10 Theory of DSC
Differential scanning calorimetry (DSC) monitors heat effects associated with phase
transitions or chemical reactions as a function of temperature. In a DSC the difference in heat
flow to the sample and a reference at the same temperature is recorded as a function of
temperature. The reference is an inert material such as alumina, or just an empty aluminum
pan. The temperature of both the sample and reference are increased at a constant rate. Since
the DSC is at constant pressure, heat flow is equivalent to enthalpy changes
 dq  dH
  = --------------- (1)
 dp  p dt

Here dH/dt is the heat flow measured in mcal sec-1. The heat flow difference between the
sample and the reference is
 dH   dH   dH 
∆ =  −  -------------- (2)
 dt   dt  samole  dt  reference
and can be either positive or negative. In an endothermic process, such as most phase
transitions, heat is absorbed and, therefore, heat flow to the sample is higher than that to the
reference. Hence ∆dH/dt is positive. Other endothermic processes include helix-coil
transitions in DNA, protein denaturation, dehydrations, reduction reactions, and some
decomposition reactions. In an exothermic process, such as crystallization, some cross-
linking processes, oxidation reactions, and some decomposition reactions, the opposite is true
and ∆dH/dt is negative.

Karnataka State Open University Page 214

Thermal methods of analysis Block 4.1.3

Figure 5: Differential scanning calorimeter sample and reference holder

The calorimeter consists of a sample holder and a reference holder as shown in Figure 5.
Both are constructed of platinum to allow high temperature operation. Under each holder is a
resistance heater and a temperature sensor. Currents are applied to the two heaters to increase
the temperature at the selected rate. The difference in the power to the two holders, necessary
to maintain the holders at the same temperature, is used to calculate ∆dH/dt. A schematic
diagram of a DSC is shown in Figure 6. A flow of nitrogen gas is maintained over the
samples to create a reproducible and dry atmosphere. The nitrogen atmosphere also
eliminates air oxidation of the samples at high temperatures. The sample is sealed into a small
aluminum pan. The reference is usually an empty pan and cover. The pans hold up to about
10 mg of material.

Figure 2: Schematic of a DSC

Karnataka State Open University Page 215

Thermal methods of analysis Block 4.1.3

During the heating of a sample, for example, from room temperature to its decomposition
temperature, peaks with positive and negative ∆dH/dt may be recorded; each peak
corresponds to a heat effect associated with a specific process, such as crystallization or
melting (Figure. 7).

Figure 7: Typical DSC scan. The heat capacity of the sample is calculated
from the shift in the baseline at the starting transient

10.11 Information is obtainable from a DSC curve

The first and most direct information is the temperature at which a certain process occurs, for
example, the melting point of a polymer. The temperature at which a reaction, such as
decomposition, starts is another important parameter. The decomposition peak temperature is
associated with the temperature at which maximum reaction rate occurs. A special case in
which the temperature of a phase transformation is of great importance in polymers is the
glass transition temperature, Tg. The Tg is the temperature at which amorphous
(noncrystalline) polymers are converted from a brittle, glasslike form to a rubbery, flexible
form. The glass transition is not a first-order phase transition but one that involves a change
in the local degrees of freedom through changes in the torsion angles along the polymer
backbone. Above the glass transition temperature, segmental motions of the polymer are
comparatively unhindered by the interaction with neighboring chains. Below the glass
transition temperature, such motions are hindered greatly, and the relaxation times associated
with such hindered motions are usually long compared to the duration of the experiment.
The operative definition of glass transition temperature is that at this temperature the specific
heat, the coefficient of thermal expansion, the free volume, and the dielectric constant (in the
case of a polar polymer) all change rapidly. The glass transition temperature is an important
characteristic of every polymer, because the mechanical behavior of the polymer changes
markedly.

Karnataka State Open University Page 216

Thermal methods of analysis Block 4.1.3

In the DSC experiment, Tg is manifested by a sudden increase in the base line, indicating an
increase in the heat capacity of the polymer (Figure 8). The glass transition is a second-order
transition; no enthalpy is associated with the transition. As a result, the effect in the DSC
thermogram is slight and is observable only if the instrument is sufficiently sensitive. The
second direct information obtainable from a DSC thermogram is the enthalpy associated with
processes.

Figure 8: Glass transition

If there are sloping baselines before and after the glass transition, extroplate the baselines
forwards and backwards (as shown by dotted lines) and take the baseline shift when the
transition is about 63% complete (as shown by arrows).
The integral under the DSC peak, above the baseline, gives the total enthalpy change for the
process,
 dH 
∫  
dt  sample
dt = ∆H sample ------------------ (3)

Assuming that the heat capacity of the reference is constant over the temperature range
covered by the peak, ∆Hreference cancels out because the integral above the baseline is
taken. Therefore, equation 3 is also valid when the integral is taken from the DCS plot of
∆dH/dt. Heat capacities and changes in heat capacity can be determined from the shift in the
baseline of the thermogram. The heat capacity is defined as
 dq   dH 
Cp =   =  ------------------ (4)
 dT  p  dT  p
The temperature scan rate is
dT
Scan rate = ------------- (5)
dt
Using the chain rule

Karnataka State Open University Page 217

Thermal methods of analysis Block 4.1.3

 dH  dH dt
Cp =   = − ------------ (6)
 dT  p dt dT

where the last derivative is just the inverse of the scan rate. For differential measurements, we
determine the difference in the heat capacity of the sample and the reference:
∆C p = C p ( sample ) − C p (reference ) ----------------(7)

dH dt
∆C p = ∆ ------------------(8)
dT dT
where ∆dH/dt is the shift in the baseline of the thermogram (Figure 3-4). The units of the heat
flow are mcal sec-1 and the temperature scan rate is usually expressed as °C min-1. So to be
consistent with units you must multiply by 60 sec min-1.
 mcal  min  60 sec 
∆C p =   0   --------------------- (9)
 sec  C  min 
For determination of the bulk heat capacity of substances, greater accuracy is obtained by
determining the baseline shift at several temperature scan rates. Rearranging Eq. 7 gives the
difference in heat capacity between the sample and reference as the slope of the plot of
baseline shift versus scan rate
dH dT
∆ = ∆C p ------------------------ (10)
dt dt
10.12 Applications in the area of polymers
The study of polymers example, ABS, polystyrene, and polyethylene. Acrylonitrile butadiene
styrene, ABS, is a co-polymer made from the monomers acrylonitrile, butadiene, and styrene,
ABS is stronger than polystyrene. ABS is the plastic in Lego blocks and is commonly used in
3D-printing. Polystyrene is widely used in rigid packaging, including plastic petri dishes.
Polystyrene is also used in foams, including polystyrene insulated beverage cups.

By themselves, styrene and acrylonitrile polymerize to give a random copolymer, Figure 9.

ABS is a graft copolymer. ABS is produced by the polymerization of monomeric acrylonitrile
and styrene in the presence of polybutadiene. The result is to “graft” polybutadiene
sidechains on the acrylonitrile-styrene backbone.

Karnataka State Open University Page 218

Thermal methods of analysis Block 4.1.3

Figure 9: Copolymer types. ABS has a random copolymer backbone with grafted
sidechains of polybutadiene.
ABS and polystyrene are amorphous polymers, which correspondingly have no distinct
melting transition. The viscosity of ABS or polystyrene smoothly decreases with increasing
temperature above Tg. 3D-printing with ABS is done at 230°C.
10.12.1 Energy (Ordinate) Calibration
In practice, the measurement of energy flow will necessarily involve an instrument
calibration constant, the recorder chart speed, the sensitivity used, the units employed for area
measurement, etc. The range switch on the instrument control panel gives nominal values for
the rate of energy change, in millicalories per second, for a full scale displacement, to within
+-5%. There are two methods which may be used to calibrate the ordinate on the Model
DSC-4. We will use "automatic" ordinate calibration, to yield an overall accuracy of ±1% in
our results. In this method, the instrument will electronically generate a 10 mCal/Sec
calibration signal, which will be used to check the mV output at full scale. Set the Range
setting on the DSC to 10 mcal/sec. Depress the black rocker switch. The output voltage for
the 10 mCal/Sec calibration should give 10.0 mV. The Range setting gives the mCal/Sec
value that corresponds to 10 mV output. The calibration constant, which should be close to
1.00, is then

Other applications of Differential Scanning Calorimetry

• Metal alloy melting temperatures and heat of fusion.
• Metal magnetic or structure transition temperatures and heat of transformation.
• Intermetallic phase formation temperatures and exothermal energies.
• Oxidation temperature and oxidation energy.

Karnataka State Open University Page 219

Thermal methods of analysis Block 4.1.3

• Exothermal energy of polymer cure (as in epoxy adhesives), allows determination of

the degree and rate of cure.
• Determine the melting behaviour of complex organic materials, both temperatures and
enthalpies of melting can be used to determine purity of a material.
• Measurement of plastic or glassy material glass transition temperatures or softening
temperatures, which change dependent upon the temperature history of the polymer or
the amount and type of fill material, among other effects.
• Determines crystalline to amorphous transition temperatures in polymers and plastics
and the energy associated with the transition.
• Crystallization and melting temperatures and phase transition energies for inorganic
compounds.
• Oxidative induction period of an oil or fat.
• May be used as one of multiple techniques to identify an unknown material or by
itself to confirm that it is the expected material.
• Determine the thermal stability of a material.
• Determine the reaction kinetics of a material.
TMA can also be used to measure glass transition temperatures, melting temperatures,
crystalline phase formation temperatures, and crystalline to amorphous transition
temperatures. It is often more sensitive to detecting the transition, but cannot measure the
energy of the transition as DSC does. It also may measure the temperature more accurately
when sample thermal conductivity is low or its dimensions are large since DSC has to have a
higher rate of temperature change commonly to detect the transitions.
Illustrative Example 1
10.12.2 Transformation temperatures of a shape memory alloy
Cu-Al-Ni alloy shape memory material undergoes a martensite to austenite transformation
upon heating. The lower curve of the DSC plot in the figure below shows the endotherm
which results when the sample was heated at a rate of 5°C/min. from 30°C to 190°C in
nitrogen gas flowing at a rate of 25ml/min. Upon cooling down, the austenite to martensite
transformation yields an exotherm seen in the upper trace of the DSC plot. The temperatures
of these transitions are a function of the alloy composition. There is a hysteresis in the
transformation on heating and cooling which is notable. The on-set temperatures, 145.06°C
on heating and 145.88°C on cooling are close, however.

Karnataka State Open University Page 220

Thermal methods of analysis Block 4.1.3

Example 2
10.12.3 Epoxy Mixtures
The figure below shows DSC curves of a two-part room-temperature cured, low-shrinkage
epoxy, with different resin to hardener ratios. The epoxies were held at room temperature for
several weeks prior to the DSC measurements. The red curve shows the epoxy mixed in
accordance with the manufacturer’s instructions: 5 parts of epoxy resin with 1 part of epoxy
hardener. The blue DSC curve shows the result for a 4 part epoxy resin to 1 part epoxy
hardener ratio. The endothermic peak temperature of the prescribed mixture is 53.64°C and
that of the 4:1 ratio mixture is higher at 55.89°C. The total endothermic energies are also
different. Therefore, DSC can be used as a tool for quality control of epoxy mixture ratios

10.13 Summary of the unit

Differential Thermal Analysis (DTA) is a technique in which the difference in temperature
between the sample and a reference sample (∆TsR) is monitored against time while the
samples are exposed to a temperature programme.

Karnataka State Open University Page 221

Thermal methods of analysis Block 4.1.3

The instrument is a differential thermal analyser and the record is the differential thermal or
DTA curve. The temperature difference (∆T) should be plotted on the ordinate with
endothermic reactions downwards and t or T increasing from left to fight.
The first recommendations clarified the terminology to be used, such as the sample, reference
material, block and differential thermocouple. It is stated that "in DTA it must be
remembered that, although the ordinate is conventionally labelled AT the output from the
thermocouple will in most instances vary with temperature and the measurement recorded is
normally the e.m.f, output, E, i.e. the conversion factor, b in the equation
∆T = bE
is not constant since b = f(T), and that a similar situation occurs with other sensor systems".
There should be clear distinction between different instrumental conditions and experimental
regimes. The ICTAC recommendations specify that the nature, history and size of the sample,
the geometry of the system, and sample holder, the temperature programme used, the gaseous
atmosphere and flow rate, and the type, sensitivity and placement of the sensors, as well as
the design of the sample holder should ideally be given. It has already been pointed out that
the methods of data collection and processing also need to be described carefully.
Differential Scanning Calorimetry (DSC) is a technique in which the difference in heat flow
rate (or power) to the sample and to the reference sample is monitored against time while the
samples are exposed to a temperature programme.
The instrument is a differential scanning calorimeter and may be one of two types, heat-flux
DSC or power compensation DSC, depending on the method of measurement used.
In a Heat-flux DSC instrument, the temperature difference between sample and reference is
recorded, after suitable calorimetric calibration, as a direct measure of the difference in heat
flow rate or the difference in power.
In a power compensation DSC instrument the difference in power supplied to the sample and
to the reference, to keep their temperatures as nearly the same as possible, is measured
directly.
The power difference in units of watts (∆P) should be plotted as ordinate. Since endothermic
reactions require a positive input of power into the sample, the DSC convention demands that
endothermic peaks should be plotted upwards, and t or T increasing from left to fight.
However, the DTA convention (endotherms downwards) is quite often used, and it is
recommended that the ordinate axis be labelled with the endothermic (or exothermic)
direction.

Karnataka State Open University Page 222

Thermal methods of analysis Block 4.1.3

10.14 Key words

Static Thermogravimetric Analysis; Dynamic Thermogravimetric Analysis; Characteristics of
DTA Curves; Differential Scanning Calorimetry DSC; Theory of DSC; Energy (Ordinate)
Calibration
10.15 References for further study
1) Introduction to Thermal Analysis: Techniques and applications; Michael Ewart Brown;
Springer Science & Business Media, 2012.
2) Handbook of Thermal Analysis of Construction Materials; V.S. Ramachandran, Ralph M.
Paroli, James J. Beaudoin, Ana H. Delgado; William Andrew, 2002.
3) Handbook of Thermal Analysis and Calorimetry: From Macromolecules to Man; Richard
B. Kemp; Elsevier, 1999.
4) Principles of Thermal Analysis and Calorimetry; Peter J. Haines; Royal Society of
Chemistry, 2002.
5) Thermal analysis of Micro, Nano- and Non-Crystalline Materials: Transformation,
Crystallization, Kinetics and Thermodynamics; Jaroslav, Peter Simon; Springer Science
& Business Media, 2012.
10.16 Questions for self understanding
1) Discuss the theory of DTA
2) Explain the followings
a) Static Thermogravimetric Analysis
b) Dynamic Thermogravimetric Analysis
3) Explain the principle of DTA
4) Write a note on characteristics of DTA Curves
5) Discuss the followings
a) Instrumentation of DTA
b) Methodology involved in DTA analysis
6) Explain the applications of DTA
7) What is Differential Scanning Calorimetry (DSC)
8) Explain the difference between a heat flow and a heat flux DSC
9) Discuss the instrumentation of DSC
10) Explain the Theory of DSC
11) Discuss the Information is obtainable from a DSC curve
12) Explain the applications of DSC in the area of polymers

Karnataka State Open University Page 223

Thermal methods of analysis Block 4.1.3

UNIT-11
Structure
11.0 Objectives of the unit
11.1 Introduction
11.2 Thermomechanical analysis
11.3 Instrumentation
11.3.1 TMA probe types
11.4 TMA temperature calibration
11.5 Thermal expansion measurement
11.6 Glass transition temperature by TMA
11.7 Dynamic Mechanical Analysis (DMA)
11.8 Basic principles
11.9 Theory
11.10 Equipment
11.11 Free Vibration
11.12 Forced Vibration (Non-resonant)
11.13 Procedure
11.15 Evaluation
11.16 Summary of the unit
11.17 Key words
11.18 References for further studies
11.19 Questions for self understanding

Karnataka State Open University Page 224

Thermal methods of analysis Block 4.1.3

11.0 Objectives of the unit

After studying this unit you are able to

Explain the thermomechanical analysis

Explain the procedure of determining glass transition temperature by TMA

Define the Dynamic Mechanical Analysis (DMA)

Explain the basic principles of DMA
11.1 Introduction
The dimensional and mechanical stability of materials is of paramount importance to their
use in the everyday world where they may encounter a wide variation in temperature through
design or by accident. Many polymers are processed at elevated temperatures so as to enable
them to flow and be more amenable to fabrication. Food items are cooked, pasteurised or
otherwise heated or frozen. Ceramics are fired so as to consolidate their final structure. The
relationship between a material’s dimensional and mechanical properties and its temperature
is studied by the techniques described in this unit and, due to common concepts, the effect of
heat on the electrical properties of materials is also considered.
11.2 Thermomechanical analysis
Thermomechanical analysis (TMA) determines dimensional changes of solids, liquids or
pasty materials as a function of temperature and/or time under a defined mechanical force.
Or
Thermomechanical Analysis (TMA) is defined as the measurement of a specimen’s
dimensions (length or volume) as a function of temperature whilst it is subjected to a constant
mechanical stress.
It is closely related to dilatometry, which determines the length change of samples under
negligible load. In this way thermal expansion coefficients can be determined and changes in
this property with temperature (and/or time) is monitored. Many materials will deform under
the applied stress at a particular temperature which is often connected with the material
melting or undergoing a glass-rubber transition.
Stress (σ) is defined as the ratio of the mechanical force applied (F) divided by the area over
which it acts (A).
The stress is usually applied in compression or tension, but may also be applied in shear,
torsion, or some other bending mode as shown in Figure 1. The units of stress are Nm-2 or Pa.
If the applied stress is negligible then the technique becomes that of thermodilatometry. This

Karnataka State Open University Page 225

Thermal methods of analysis Block 4.1.3

technique is used to determine the coefficient of thermal expansion of the specimen from the
relationship.
11.3 Instrumentation
A schematic diagram of a typical instrument is shown in Figure 1. The sample is placed in a
temperature controlled environment with a thermocouple or other temperature sensing
device, such as a platinum resistance thermometer, placed in close proximity. The facility to
circulate a cryogenic coolant such as cold nitrogen gas from a Dewar vessel of liquid nitrogen
is useful for subambient measurements. The atmosphere around the sample is usually
controlled by purging the oven with air or nitrogen from a cylinder. Because of the much
larger thermal mass of the sample and oven compared to a differential scanning calorimeter
or a thermobalance, the heating and cooling rates employed are usually much slower for
TMA.

Figure 1: A schematic diagram of a typical TMA instrument

For compression measurements a flat-ended probe is rested on the top surface of the sample
and a static force is applied by means of a weight or an electromagnetic motor similar in
principle to the coil of a loudspeaker. Some form of proximity sensor measures the
movement of the probe. This is usually achieved by using a linear variable differential
transformer (LVDT) which consists of two coils of wire which form an electrical transformer
when fed by an AC current. The core of the transformer is attached to the probe assembly
and the coupling between the windings of the transformer is dependent upon the
displacement of the probe.

Karnataka State Open University Page 226

Thermal methods of analysis Block 4.1.3

11.3.1 TMA probe types

Following probe types are commonly employed in TMA (Figure 2). The compression,
penetration, tension, volumetric

Figure 2: Different probe types commonly employed in TMA

 Compression probe used for applying low load over a wide area of sample for thermal
expansion measurements (thermodilatometry)
 Penetration probe applies a high load over a small area for the purpose of measuring
softening temperatures.
 Tension probe used for measuring non-self supporting specimens - such as thin films
and fibres under tension.
 Volumetric probe used for measuring the thermal volumetric expansion of irregularly
shaped specimens surrounded by an inert packing material (alumina powder or
silicone oil).
11.4 TMA temperature calibration
TMA temperature calibration is usually done by using indium (156.6°C), tin (232.0°C) and
bismuth (271.4°C). Heating rate: 5°C min-1, force 1 N, static air atmosphere. A multi-layered
sandwich of specimens is prepared separated by alumina spacers. When the metal standard
melts, the stack collapses slightly. The onset of the length change is taken as the melting
point of the metal.
11.5 Thermal expansion measurement
Measurements of thermal expansion coefficients are useful in assessing the compatibility of
different materials for fabrication into components. Mismatches in behaviour can causes
stresses to build up when temperature changes occur resulting in eventual weakening and

Karnataka State Open University Page 227

Thermal methods of analysis Block 4.1.3

failure of the structure. Many crystalline materials can exist in a number of polymorphic
forms which are stable at different temperatures. The transition between crystal structures is
usually accompanied by a change in density and thermal expansion
expansion coefficient which can be
detected by TMA.
11.6 Glass transition temperature by TMA
Supporting information from differential scanning calorimetry is often useful in interpreting
information from TMA, particularly when softening point determinations are made – since
loss of mechanical integrity can occur due to melting, which gives an endothermic peak in
DSC or a glass-rubber
rubber transition, which causes
causes a step change in heat capacity.

Figure 3: Change in length of a silicone

ne gum rubber
Plots of the change in length of a sample of a silicone
silicone gum rubber are shown in Figure 3.
Three experiments were carried out on the material with different applied forces. At zero
force a change in slope of the curve can be seen around –60°C
60°C due to the sample undergoing
a change from
m glassy to rubbery behaviour. At this temperature the polymer chains acquire
additional degrees of mobility which is seen as an increase in thermal expansion coefficient.
The glass transition temperature (T
( g) can be defined by finding the intercept of tangents to the
linear portions of the length versus temperature plot
plot above and below this region. When a
force is applied to the specimen the probe deforms the material in inverse proportion
prop to its
stiffness. Below Tg the polymer is rigid and is able to resist the applied force therefore its
deformation is negligible. Above Tg the polymer becomes soft and the probe penetrates into
the specimen. The temperature at which this occurs is called
called the materials’ softening
temperature and is highly dependent on the force applied to the sample.
sample

Karnataka State Open University Page 228

Thermal methods of analysis Block 4.1.3

11.7 Dynamic Mechanical Analysis (DMA)

Dynamic mechanical analysis is concerned with the measurement of the mechanical
properties (mechanical modulus or stiffness and damping) of a specimen as a function of
temperature.
DMA is also called forced oscillatory measurements, dynamic mechanical, thermal analysis
(DMTA), dynamic thermomechanical analysis, and even dynamic rheology [Rheology is the
study of the deformation and flow of materials]. DMRT is the preferred name because this
mode of thermal analysis is rooted in the science of rheology.
Dynamic mechanical properties refer to the response of a material as it is subjected to a
periodic force. These properties may be expressed in terms of a dynamic modulus, a dynamic
loss modulus, and a mechanical damping term. Typical values of dynamic moduli for
polymers range from 106 -1012 dyne/cm2 depending upon the type of polymer, temperature,
and frequency
DMA is a sensitive probe of molecular mobility within materials and is most commonly used
to measure the glass transition temperature and other transitions in macromolecules, or to
follow changes in mechanical properties brought about by chemical reactions. For this type of
measurement the specimen is subjected to an oscillating stress, usually following a sinusoidal
waveform. Thus dynamic mechanical analysis yields information about the mechanical
properties of a specimen placed in minor, usually sinusoidal, oscillation as a function of time
and temperature by subjecting it to a small, usually sinusidal, oscillating force.
11.8 Basic principles
DMA can be simply described as applying an oscillating force to a sample and analyzing the
material’s response to that force. From this, one can calculates properties like the tendency to
flow (called viscosity) from the phase lag and the stiffness (modulus) from the sample
recovery. These properties are often described as the ability to lose energy as heat (damping)
and the ability to recover from deformation (elasticity). One way to describe what we are
studying is the relaxation of the polymer chains.
The applied force is called stress and is denoted by the Greek letter, σ. When subjected to a
stress, a material will exhibit a deformation or strain, γ. The stress–strain curves of most
materials are look like as shown in Figure 4.

Karnataka State Open University Page 229

Thermal methods of analysis Block 4.1.3

Figure 4: Stress–strain curves relate force to deformation

11.9 Theory
In DMA a sinusoidal oscillating stress is applied to a specimen, a corresponding oscillating
strain will be produced. Unless the material is perfectly elastic, the measured strain will lag
behind the applied stress by a phase difference (δ) shown in Figure 5. The ratio of peak stress
to peak strain gives the complex modulus (E*) which comprises an in-phase component or
storage modulus (E’) and a 90° out-of-phase (quadrature) component or loss modulus (E”).

Figure 5: the measured strain lag behind the applied stress by a phase difference (δ)

The storage modulus, being in-phase with the applied stress, represents the elastic component
of the material’s behaviour, whereas the loss modulus, deriving from the condition at which
dε /dt is a maximum, corresponds to the viscous nature of the material. The ratio between the
loss and storage moduli (E ”/E’) gives the useful quantity known as the mechanical damping
factor (tan δ) which is a measure of the amount of deformational energy that is dissipated as
heat during each cycle. The relationship between these quantities can be illustrated by means
of an Argand diagram, commonly used to visualise complex numbers, which shows that the
complex modulus is a vector quantity characterised by magnitude (E*) and angle (δ) as
shown in Figure 6. E’ and E” represent the real and imaginary components of this vector
thus:

Karnataka State Open University Page 230

Thermal methods of analysis Block 4.1.3

E* = E’ + iE" = √(E'2 + E"2)

So that:
E’ = E* cos δ
and
E" = E* sin δ

Figure 6: a vector quantity characterised by magnitude (E*) and angle (δ)

Thus in DMA instruments apply an oscillating force (stress) and record an oscillating sample
response. Modulus is calculated from the elastic response; e.g. sample response “in phase”
with applied oscillatory stress. Damping is calculated from the viscous response; e.g. sample
response “out of phase” with applied oscillatory stress.
11.10 Equipment
There are basically two types of DMA measurement. Deformation-controlled tests apply a
sinusoidal deformation to the specimen and measure the stress. Force-controlled tests apply a
dynamic sinusoidal stress and measure the deformation. Dynamic load may essentially be
achieved in free vibration or in forced vibration. There are two designs of apparatus,
i) Torsion type,
ii) Bending, tension, compression, shear type.
11.11 Free Vibration
In free torsional vibration, one end of the specimen is clamped firmly while a torsion
vibration disc at the other end is made to oscillate freely. The resultant frequency and
amplitude of the oscillations, along with the specimen’s dimensions, are used to calculate the
torsion modulus. Measurements are conducted at various temperatures to establish how the

Karnataka State Open University Page 231

Thermal methods of analysis Block 4.1.3

torsion modulus varies with temperature. The term torsion modulus is intended to convey the
idea that the stress is not necessarily purely shear and that the observation is not necessarily a
shear modulus (except in the case of cylinders). On being twisted, the flat, clamped specimen
is placed in torsional stress and, to an extent depending on the way it is clamped and on its
shape, its two free edges are placed in tension and its center is placed in compression.
Another free-vibration method is flexural vibration. In this, the specimen is firmly clamped
between two parallel oscillation arms. One arm keeps the specimen oscillating so that the
system attains a resonance frequency of almost constant amplitude. The modulus is
calculated from the resonance frequency, the resultant amplitude, and the dimensions of the
specimen.
Free-vibration apparatus (resonant) is highly sensitive and is eminently suitable for studying
weak effects. The disadvantage is a drop in frequency combined with falling modulus due to
elevated temperatures. Frequency-dependent measurements are difficult to perform and
require the use of different test-piece geometries. They thus entail considerable experimental
outlay
11.12 Forced Vibration (Non-resonant)
Variable frequency apparatus applies constant amplitude (stress or deformation amplitude).
The frequency may be varied during the measurement. Figure 7 shows the design of a torsion
apparatus.

Figure 7: Schematic design of a torsion vibration apparatus with variable frequency

Firmly clamped at both ends, the specimen is electromagnetically excited into sinusoidal
oscillation of defined amplitude and frequency. Because of the damping properties of the

Karnataka State Open University Page 232

Thermal methods of analysis Block 4.1.3

material or specimen, the torque lags behind

behind the deformation by a value equal to the phase
angle δ.. The observed values for torque, phase angle, and geometry constant of the specimen
may be substituted into the formulae to calculate the complex modulus E*, the storage
´, the loss modulus E´´, and the loss factor tan δ.
modulus E´,
The specimen should be dimensionally stable and of rectangular or cylindrical cross section.
Suitable specimens have modulus values ranging from very high (fiber composites) down to
low (elastomers). If appropriate plane-parallel
plane rallel plates are attached to the drive shafts, it is also
possible to measure soft, gelatinous substances and viscous liquids. Most types of apparatus
utilize vertical loading, which allows measurements under bending, tension, compression,
and shear. Usually,
lly, the same apparatus is employed, with interchangeable clamping
mechanisms applying
lying the various types of load.
11.Procedure
A sample is held in place between two grips or confining elements. Next, an oscillatory
(dynamic) force is applied to the sample. This is applied using an electric motor moving
rotationally (typically back and forth) and linearly (typically up and down), and contains a
frequency
cy (speed of oscillation), and a force
rce (energy input into sample). Resulting strain
(displacement) is measured using LVDT measurement or by a force transducer. Plots Storage
Modulus and Tan Delta (damping) vs. Temperature (Figure 8) calculates Tg (the “glass
transition”, melting of amorphous phase) and Beta transitions (low temperature
temperature declines in
Modulus).

Figure 8: plots Storage Modulus and Tan Delta (damping) vs. Temperature

Karnataka State Open University Page 233

Thermal methods of analysis Block 4.1.3

The following different methods of analysis can be done in DMA instrument

Temperature scan: Modulus and damping is recorded as the sample is heated
Frequency scan: Modulus and damping is recorded as the sample is vibrated at increasing
speeds
Stress scan: Modulus and damping is recorded as the sample stress is increased
Strain scan: Modulus and damping is recorded as the sample strain is increased
Transient testing (not oscillatory): Creep-Relaxation and Stress-Recovery
Multiplexed scan: Combinations of above methods
Evaluation
Because DMA is sensitive to variations in the stiffness of a material, it may be used to
determine not only modulus and damping values directly, but also glass transition
temperatures. It is particularly suitable for determining glass transitions because the change in
modulus is much more pronounced in DMA than, for example, the cp change in a DSC
measurement. Owing to discrepancies between the proposals made in various standards and
the information provided by apparatus manufacturers, confusion has arisen about how to
determine and state glass transition temperatures in practice. Although the modulus step that
occurs during the glass transition can be evaluated much in the manner of a DSC curve, it is
difficult to do so in practice.
For example,
The DMA curve of polycaprolactone measured at a meachnical vibration frequency of 1 Hz
is shown in Figure 9.

Figure 9: The DMA curve of polycaprolactone

Karnataka State Open University Page 234

Thermal methods of analysis Block 4.1.3

The drop in storage modulus (E') and peak in damping factor (tan delta) between -60 and -
30°C is due to the glass transition (Tg) of the amorphous polymer in this semi-crystalline
material. Above 50°C the sample begins to melt and flow, thus loosing all mechanical
integrity. Below the Tg small peaks are evident in the tan delta curve at -80 and -130°C.
These are the beta and gamma transtions in this polymer (the glass transition is known also as
the alpha transition) and are caused by local motion of the polymer chains as opposed to large
scale co-operative motion that accompanies the Tg. These small transitions are very difficult
to observe by DSC but are often very important in determining the impact resistance of the
polymer.
Summary of the unit
In the 50’s, the term "thermal analysis" meant simply heating a sample in a capillary melting
point tube to measure the melting point, or incinerating it to measure its ash content. And that
was about all there was to thermal analysis. Now the term is applied to a host of tests,
including DSC (differential scanning calorimetry),TGA (Thermogravimetric analysis), and
DMA (dynamic mechanical analysis). DMA is a shortened form of Dynamic Mechanical
Thermal Analysis (DMTA), which is another name for Dynamic Mechanical Rheological
Testing (DMRT). Many materials undergo changes of their thermomechanical properties
during heating or cooling. For example, phase changes, sintering steps or softening can occur
in addition to thermal expansion. TMA analyses can hereby provide valuable insight into the
composition, structure, production conditions or application possibilities for various
materials. The application range of instruments for thermomechanical analysis extends from
quality control to research and development. Typical domains include plastics and
elastomers, paints and dyes, composite materials, adhesives, films and fibers, ceramics, glass
and metals.
Dynamic mechanical analysis (DMA) is a technique used to study and characterize materials.
It is most useful for studying the viscoelastic behavior of polymers. A sinusoidal stress is
applied and the strain in the material is measured, allowing one to determine the modulus.
The temperature of the sample or the frequency of the stress is often varied, leading to
variations in the modulus. This approach can be used to locate the glass transition
temperature of the material.
DMA measures stiffness and damping, these are reported as modulus and tan delta. Because
sinusoidal stress is applied, modulus can be expresesed as
In-phase component, the storage modulus (E‘) and

Karnataka State Open University Page 235

Thermal methods of analysis Block 4.1.3

Out of phase component, the loss modulus (E")

Storage modulus (E‘) is a measure of elastic response of a material. It measures the stored
energy.Loss modulus (E") is a measure of viscous response of a material. It measures the
energy dissipated as heat.
Tan delta is the ratio of loss to the storage and is called damping. It is a measure of the energy
dissipation of a material. It tells us how good a material will be at absorbing energy.
Basically tan delta can be used to characterize the modulus of the material. Delta should
range between 0° and 90° and as delta approaches 0° it also approaches a purely elastic
behaviour. As delta approached 90° the material approaches a purely viscous behaviour.
The tan of delta is defined below
tan(δ) = E"/E'
E" = storage modulus
E' = loss modulus
Increasing Tan delta indicates that your material has more energy dissipation potential so the
greater the Tan delta, the more dissipative your material is.
Decreasing Tan delta means that your material acts more elastic now and by applying a load,
it has more potential to store the load rather than dissipating it!
For example, in case of nano-composites (and filled polymers), increasing the nano-particle
content diminishes the value of Tan delta as nano-particles impose restrictions against
molecular motion of polymer chains (due to the adsorption of polymer chain on the surface of
the particles) resulting in more elastic response of the material.
Key words
Thermomechanical analysis; TMA probe types; TMA temperature calibration; Thermal
expansion measurement; Glass transition temperature by TMA ; Dynamic Mechanical
Analysis (DMA)
References for further studies
1) Dynamic Mechanical Analysis: A Practical Introduction; Kevin P. Menard; CRC
Press, 2008.
2) Principles and Applications of Thermal Analysis; Paul Gabbott; John Wiley & Sons,
2008.
3) Introduction to Thermal Analysis: Techniques and applications; Michael Ewart
Brown; Springer Science & Business Media, 2012.

Karnataka State Open University Page 236

Thermal methods of analysis Block 4.1.3

4) Principles of Thermal Analysis and Calorimetry; Peter J. Haines; Royal Society of

Chemistry, 2002.
5) Thermal analysis of Micro, Nano- and Non-Crystalline Materials: Transformation,
Crystallization, Kinetics and Thermodynamics; Jaroslav, Peter Simon; Springer
Science & Business Media, 2012.
6) Thermal Analysis of Polymers: Fundamentals and Applications; Joseph D. Menczel,
R. Bruce Prime; John Wiley & Sons, 2014.
Questions for self understanding
1) What is thermomechanical analysis?
2) Explain the instrumentation of thermomechanical analysis
3) Discuss the TMA probe types
4) How TMA temperature calibration can be done?
5) Explain the thermal expansion measurement in thermomechanical analysis
6) Discuss the measurement of glass transition temperature by TMA
7) What is Dynamic Mechanical Analysis (DMA)?
8) Explain the basic principles of DMA
9) Explain the theory of DMA
10) Discuss the equipment used in DMA

Karnataka State Open University Page 237

Thermal methods of analysis Block 4.1.3

UNIT-12
Structure
12.0 Objectives of the unit
12.1 Introduction
12.2 Theory
12.3 Instrumentation
12.4 Procedure
12.5 Methodology
12.6 Precautions
12.7 Applications
12.8 Estimation of Benzene in Cyclohexane
12.9 Summary of the unit
12.10 Key words
12.11 References for further studies
12.12 Questions for self understanding

Karnataka State Open University Page 238

Thermal methods of analysis Block 4.1.3

12.0 Objectives of the unit

After studying this unit you are able to

Explain the theory of thermometric analysis

Discuss the instrumentation of thermometric analysis

Explain the procedure of thermometric analysis

Discuss the methodology followed in thermometric analysis

Explain the precautions need to take in thermometric analysis

Discuss the applications of thermometric analysis

Explain the estimation of Benzene in Cyclohexane using thermometric analysis
12.1 Introduction
Thermometry is the science and practice of temperature measurement. Any measurable
change in a thermometric probe (e.g. the dilatation of a liquid in a capillary tube, variation of
electrical resistance of a conductor, of refractive index of a transparent material, and so on)
can be used to mark temperature levels, that should later be calibrated against an
internationally agreed unit if the measure is to be related to other thermodynamic variables (if
the measure is only needed to establish an ordering in thermal levels, no calibration is
required). Thermometry is sometimes split in metrological studies in two subfields: contact
thermometry and noncontact thermometry. As there can never be complete thermal
uniformity at large, thermometry is always associated to a heat transfer problem with some
space-time coordinates of measurement, given rise to time-series plots and temperature maps
(profiles, if one-dimensional).
12.2 Theory
The thermometric titrations (TT) make use of ‘heats of reaction’ to obtain titration curves. In
usual practice, the temperature of solution is plotted against the volume of titrant. TT is
performed by allowing the titrant to flow from a thermostated-burette directly into a solution
contained in a thermally-insulated vessel, and subsequently the observed change in
temperature of the solution is recorded precisely either during continuous addition of titrant
or after every successive incremental addition. The end-point is aptly indicated by a sharp
break in the curve. As the dielectric constant of a solvent exerts little effect on the
thermometric titrations, the latter may be employed effectively in most non-aqueous media.
Hence, in a broader-sense TT may be utilized in a number of reactions with greater efficacy,
for instance : complexation, precipitation, redox, neutralization. Further, TT can be used to

Karnataka State Open University Page 239

Thermal methods of analysis Block 4.1.3

titrate gases against other gases devoid of a liquid-phase ; and to titrate liquid solutions with
gaseous reagents.
12.3 Instrumentation
A standard thermometric titration assembly essentially consists of the following four vital
components, namely
i) Motor-driven Burette,
ii) Adiabatic Titration Chamber
iii) Thermister Bridge Assembly, and
iv) Recorder.
Fiaure 1, represents the schematic thermometric titration assembly complete with a bridge-
circuit. To minimise heat transfer losses from the solution by its immediate surroundings, the
thermometric titrations are usually carried out in an isolated-beaker tightly closed with a
stopper having provision for a burette-tip, a motorized-glass stirrer, and a temperature-
monitoring arrangement.

Figure 1: Schematic Thermometric Titration Assembly Complete with a Bridge-Circuit

12.4 Procedure
a) Introduce the titrant from a burette that is duly mounted in a thermostated-water-jacket to
maintain the temperature of the titrant within ± 0.05°C,
b) Experimental parameters are predetermined in such a fashion such that the volume of
titrant needed for each titration must lie between 1-3 ml,

Karnataka State Open University Page 240

Thermal methods of analysis Block 4.1.3

c) Automated device delivering reagent at a steady and constant rate of 600 µl per minute
usually permits recording,
d) Constant-speed motorized stirrer at 600 rpm is employed to effect uniform mixing of
solution,
e) Variations in temperature are measured with the help of a sensitive thermister-sensing-
element with fast response, that is sealed completely in glass and immersed in solution,
f) In the course of a thermometric titration, the thermister attached to the insulated-beaker is
connected to one arm of the Wheatstone Bridge as displayed in Figure 11.5. The values of the
circuit component listed are for a thermister having an approximate resistance of 2 KΩ and a
sensitivity of –0.04 Ω/Ω/°C in the 25°C temperature range. Hence, an observed change of
1°C ≡ an unbalanced potential of 15.7 mV, and
g) The heat of reaction is either absorbed or generated upon addition of the titrant to the
beaker, thereby unbalancing the Wheatstone Bridge caused by simultaneous variations in the
resistance (temperature) in the insulated-beaker thermister. Thus, the bridge unbalance
potential is promptly plotted by the recorder.
Note: i) To minimise the temperature variations between the titrant and the solution and also
to obviate volume corrections, the concentration of the titrant is invariably maintained 10–
100 times higher than that of the reactant, and
ii) To obtain optimum results, temperatures of the titrant and the solution must be always
within 0.2°C of each other before a titration is commenced.
12.5 Methodology
Thermometric titration curves usually represent both the entropy and the free energy
involved. The titrant is added to the solution at a constant rate in order that the voltage output
of the thermister-temperaturetransducer changes linearly with time upto the equivalence
point. TT-method affords exact end-point due to
a) Coloured solutions, and
b) Poisoning of Electrodes.
In usual practice it has been observed that thermometric titrations are mostly feasible with
such systems that provide rates of temperature change more than 0.01°C/second. A few
typical examples are cited below

Karnataka State Open University Page 241

Thermal methods of analysis Block 4.1.3

12.6 Precautions
i) Lower limit of concentrations which can be titrated effectively is 0.002 M, ii) No transfer
of heat between the titration vessel and its immediate surroundings is allowed, and
iii) During titration temperature fluctuation must not exceed 0.001°C.
12.7 Applications
Various important applications of thermometric titrations are enumerated below
i) Precipitation Reactions: e.g., Chloride ions (Cl–) with Ag+ ions. Besides, phase relations
have been studied extensively in precipitation reactions.
ii) Ion-combination Reactions:e.g., divalent cations like Ca2+, Mg2+ with EDTA
(complexometric estimation),
iii) Conversion of Amides to Amines : e.g.,

iv) Estimation of H2O and (CH3CO)2O concentrations in a mixture : The concentration of

either of these reactions in the presence of the other may be determined successfully by
measuring the rise in temperature taking place during the exothermic reactions of water
and acetic anhydride in glacial acid solution along with a trace of perchloric acid (HClO4
) acting as a catalyst, and
v) Benzene in Cyclohexane : Benzene may be estimated rapidly with fairly good accuracy in
cyclohexane by measuring the heat of nitration, whereby a previously prepared standard
nitrating acid mixture (benzene and cyclohexane) and the subsequent temperature rise is
noted which is a direct function of the quantity of benzene present. Details involving
various experimental parameters for the above estimation are enumerated below
12.8 Estimation of Benzene in Cyclohexane
Materials Required
Thermometric titration assembly as per Figure 11.5, minus the burette; a stopwatch or timer ;
standard nitrating acid mixture [mix 2 volumes of 70% HNO3 (d = 1.41) with 1 volume of
95% H2SO4 (d = 1.82)] ; Bakelite screw-cap bottle (4 oz. capacity) 2:
Procedure
1) Weigh 50 g of sample in a Bakelite screw-cap bottle and in a similar bottle put the
standard nitrating mixture. Place these two bottles in a thermostat maintained at 20°C until
the contents have attained an equilibrium temperature,

Karnataka State Open University Page 242

Thermal methods of analysis Block 4.1.3

2) Transfer 50 ml of the standard nitrating-acid to the insulated vessel and insert the
motorised stirrer. Just wait for about 3-5 minutes and then start the motorized stirrer. After
exactly 1 minute record the initial temperature,
3) Stop the motor. Insert the sample into the reaction vessel and start the stirrer. Now, start
taking readings of the rise in temperature after each interval 1, 2, 3 and 5 minutes
respectively, and
4) Plot a ‘calibration curve’ between the observed temperature-rise in a 3 minute interval Vs
percent benzene present in cyclohexane. Run pure cyclohexane and standards containing 0.5-
5.0 percent benzene by weight.
12.9 Summary of the unit
The titration is a basis quantitative analytical method. It allows a simple analysis to determine
the amount of product in the sample following a chemical reaction without need do a
comparison with a standard. The potentiometric titration following the potential of a solution
also it is a differential method between a reference and a measurement electrodes. This
potential can be interpret as a pH or a potential redox par example. Thermometry is the
science and practice of temperature measurement. Any measurable change in a thermometric
probe (e.g. the dilatation of a liquid in a capillary tube, variation of electrical resistance of a
conductor, of refractive index of a transparent material, and so on) can be used to mark
temperature levels, that should later be calibrated against an internationally agreed unit if the
measure is to be related to other thermodynamic variables (if the measure is only needed to
establish an ordering in thermal levels, no calibration is required).
12.10 Key words
Thermometric analysis; Instrumentation; Procedure of thermometric analysis; Methodology
followed in thermometric analysis
12.11 References for further studies
1) A Practical Guide to Instrumental Analysis; Erno Pungor, G. Horvai; CRC Press, 1994.
2) Thermometric Titrimetry: International Series of Monographs in Analytical Chemistry; L.
S. Bark, S. M. Bark; Elsevier, 2013.
3) Instrumental Methods of Chemical Analysis; Dr. B. K. Sharma; Krishna Prakashan
Media, 2000.
4) Undergraduate Instrumental Analysis, 7th Ed. James W. Robinson, Eileen Skelly Frame,
George M. Frame II; CRC Press, 2014.
5) Pharmaceutical Drug Analysis; Ashutosh Kar; New Age International, 2007.

Karnataka State Open University Page 243

Thermal methods of analysis Block 4.1.3

12.12 Questions for self understanding

1) Explain the theory of thermometric analysis
2) Discuss the instrumentation of thermometric analysis
3) Explain the procedure of thermometric analysis
4) Discuss the methodology followed in thermometric analysis
5) Explain the precautions need to take in thermometric analysis
6) Discuss the applications of thermometric analysis
7) Explain the estimation of Benzene in cyclohexane using thermometric analysis

Karnataka State Open University Page 244

Homogeneous and Heterogeneous catalysis Block 4.1.4

UNIT-13
Structure
13.0 objectives of the unit
13.1 Introduction
13.2 Principle (Mode of action of catalysts)
13.3 Activity
13. 4 Industrial requirements of catalysis
13.5 Industrial processes using heterogeneous catalysis.
13.6 Thermodynamics and Kinetics aspects
13.6.1 Thermodynamics Studies
13.7 Activation energy(∆Ga)
13.8 Classification of Catalytic system
13.9 Summary of the unit
13.10 Key words
13.11 References for further studies
13.12 Questions for self understanding

Karnataka State Open University Page 245

Homogeneous and Heterogeneous catalysis Block 4.1.4

13.0 objectives of the unit

After studying this unit you are able to

Explain the mode of action of catalysts

Discuss the activity of catalyst

Explain the Industrial requirements of catalysis

Discuss the industrial processes using heterogeneous catalysis.

Explain the thermodynamics and kinetics aspects of catalytic action

Calculate the Activation energy (∆Ga) of a reaction with and without catalyst

Write the classification of catalytic system
13.1 Introduction
Catalysis is the key to chemical transformations. Most industrial syntheses and nearly all
biological reactions require catalysts. Furthermore, catalysis is the most important technology in
environmental protection, i.e., the prevention of emissions. A well-known example is the
catalytic converter for automobiles. Catalytic reactions were already used in antiquity, although
the underlying principle of catalysis was not recognized at the time. For example, the
fermentation of sugar to ethanol and the conversion of ethanol to acetic acid are catalyzed by
enzymes (biocatalysts). However, the systematic scientific development of catalysis only began
about 200 years ago, and its importance has grown up to the present day.
The term “catalysis” was introduced as early as 1836 by Berzelius in order to explain various
decomposition and transformation reactions. He assumed that catalysts possess special powers
that can influence the affinity of chemical substances. A definition that is still valid today is due
to Ostwald (1895): “a catalyst accelerates a chemical reaction without affecting the position of
the equilibrium.” Ostwald recognized catalysis as a ubiquitous phenomenon that was to be
explained in terms of the laws of physical chemistry. While it was formerly assumed that the
catalyst remained unchanged in the course of the reaction, it is now known that the catalyst is
involved in chemical bonding with the reactants during the catalytic process. Thus catalysis is a
cyclic process: the reactants are bound to one form of the catalyst, and the products are released
from another, regenerating the initial state.
13.2 Principle (Mode of action of catalysts)
The suitability of a catalyst for an industrial process depends mainly on the following three
properties:

Karnataka State Open University Page 246

Homogeneous and Heterogeneous catalysis Block 4.1.4

• Activity
• Selectivity
• Stability (deactivation behavior)
The question which of these functions is the most important is generally difficult to answer
because the demands made on the catalyst are different for each process. First, let us define the
above terms.
13.3 Activity
Activity is a measure of how fast one or more reactions proceed in the presence of the catalyst.
Activity can be defined in terms of kinetics or from a more practically oriented viewpoint. In a
formal kinetic treatment, it is appropriate to measure reaction rates in the temperature and
concentration ranges that will be present in the reactor.
• Reaction rate
• Rate constant k
• Activation energy Ea
Empirical rate equations are obtained by measuring reaction rates at various concentrations and
temperatures. If, however, different catalysts are to be compared for a given reaction, the use of
constant concentration and temperature conditions is often difficult because each catalyst
requires it own optimal conditions. In this case it is appropriate to use the initial reaction rates
obtained by extrapolation to the start of the reaction.
The number of active centers per unit mass or volume of catalyst can be determined
indirectly by means of chemisorption experiments, but such measurements require great care,
and the results are often not applicable to process conditions.
For optimization of catalyst production conditions, and deactivation studies, the following
activity measures can be used:
– Conversion under constant reaction conditions
– Space velocity for a given, constant conversion
– Space–time yield
– Temperature required for a given conversion
Catalysts are often investigated in continuously operated test reactors, in which the conversions
attained at constant space velocity are compared.
13. 4 Industrial requirements of catalysis

Karnataka State Open University Page 247

Homogeneous and Heterogeneous catalysis Block 4.1.4

Catalysts are substances that speed up reactions by providing an alternative pathway for the
breaking and making of bonds. Key to this alternative pathway is a lower activation energy than
that required for the uncatalysed reaction.
Catalysts are often specific for one particular reaction and this is particularly so for enzymes
which catalyse biological reactions, for example in the fermentation of carbohydrates to
produce biofuels.
Much fundamental and applied research is done by industrial companies and university research
laboratories to find out how catalysts work and to improve their effectiveness. If catalytic
activity can be improved, it may be possible to lower the temperature and/or the pressure at
which the process operates and thus save fuel which is one of the major costs in a large-scale
chemical process. Further, it may be possible to reduce the amount of reactants that are wasted
forming unwanted by-products.
If the catalyst is in the same phase as the reactants, it is referred to as a homogeneous catalyst.
A heterogeneous catalyst on the other hand is in a different phase to the reactants and products,
and is often favoured in industry, being easily separated from the products, although it is often
less specific and allows side reactions to occur.

The most common examples of catalysis in industry involve the reactions of gases being passed
over the surface of a solid, often a metal, a metal oxide or a zeolite.

Karnataka State Open University Page 248

Homogeneous and Heterogeneous catalysis Block 4.1.4

Process Catalyst Equation

Making ammonia Iron
Making synthesis Nickel
gas (carbon monoxide and
hydrogen)
Catalytic cracking of gas Zeolite Produces:
oil a gas (e.g. ethene, propene)
a liquid (e.g.petrol)
a residue (e.g. fuel oil)
Reforming of naphtha Platinum and
rhenium on
alumina
Making epoxyethane Silver on alumina

Making sulfuric acid Vanadium(V)

oxide on silica
Making nitric acid Platinum and
rhodium
13.5 Industrial processes using heterogeneous catalysis.
The gas molecules interact with atoms or ions on the surface of the solid. The first process
usually involves the formation of very weak intermolecular bonds, a process known as
physisorption, followed by chemical bonds being formed, a process known as chemisorption.
Physisorption can be likened to a physical process such as liquefaction. Indeed the enthalpy
changes that occur in physisorption are cal-20 to -50 kJ mol-1, similar to those of enthalpy
changes when a gas condenses to form a liquid. The enthalpies of chemisorptions are similar to
the values found for enthalpies of reaction. They have a very wide range, just like the range for
non-catalytic chemical reactions.
An example of the stepwise processes that occur in heterogeneous catalysis is the oxidation of
carbon monoxide to carbon dioxide over palladium. This is a very important process in everyday
life. Motor vehicles are fitted with catalytic converters. These consist of a metal casing in which
there are two metals, palladium and rhodium, dispersed very finely on the surface of a ceramic

Karnataka State Open University Page 249

Homogeneous and Heterogeneous catalysis Block 4.1.4

support that resembles a honeycomb of holes. The converter is placed between the engine and
the outlet of the exhaust pipe.
The exhaust gases contain carbon monoxide and unburned hydrocarbons that react with the
excess oxygen to form carbon dioxide and water vapour, the reaction being catalysed principally
by the palladium

The exhaust gases also contain nitrogen(II) oxide (nitric oxide, NO), and this is removed by
reactions catalysed principally by the rhodium

The accepted mechanism for the oxidation of carbon monoxide to carbon dioxide involves the
chemisorption of both carbon monoxide molecules and oxygen molecules on the surface of the
metals. The adsorbed oxygen molecules dissociate into separate atoms of oxygen. Each of these
oxygen atoms can combine with a chemisorbed carbon monoxide molecule to form a carbon
dioxide molecule. The carbon dioxide molecules are then desorbed from the surface of the
catalyst. A representation of these steps is shown in Figure 1.

Figure 1: A mechanism for the oxidation of carbon monoxide

13.6 Thermodynamics and Kinetics aspects

Kinetics aspects
The rate constant, k, measures how fast a chemical reaction reaches equilibrium assuming the
reactants were supplied with enough activation energy to enable the reaction to proceed in the
forward direction—reactants to products. This requirement for input of energy symbolizes the
fact that the reactants are unreactive under certain conditions The reaction must have some sort

Karnataka State Open University Page 250

Homogeneous and Heterogeneous catalysis Block 4.1.4

of energy input before it can proceed; otherwise, the reactants cannot cross the activation energy
threshold and convert to products. The reaction is activated by energy supplied to the reactants
by different energy sources. The rate of reaction, the rate constant, and the kinetic energy
required for activation of reaction indicate how fast the reaction reaches equilibrium.
The transition state represents a threshold the reactants must pass before the reaction can proceed
in the forward direction. The activation energy is the energy required to reach the transition state.
Once this threshold is reached, the reaction proceed in the favorable "downhill" direction. It is
important to remember that each reaction has a different transition state threshold, with different
activation energies, and determined by the reactants and the conditions in which the reaction is
taking place. The value of k is affected by these two factors, and can be increased in the presence
of a catalyst (such as an enzyme), which increases reaction rate. In chemical reactions,
specifically, the catalyst can both provide more energy to the reactants and lower the transition
state energy. The provider of activation energy can also be a spark, heat, or anything else that
gives off energy. Regardless of what provides the activation energy, a kinetic or nonspontaneous
reaction is one in which the most stable state is that of the reactants. The change in energy
between the reactants and products, also known as ∆G, relates to thermodynamics and will be
discussed shortly.
A process concerned for Kinetics could be a chemical reaction (change between different
molecules or materials), or a transformation between two material structures (or phases), for
which only the crystalline structure (atomic arrangement) changes, while the chemical
compositions (concerned elements, ionic valence state, etc) remain the same. Indeed, such
“phase transformation” will be one of the major topic throughout this Kinetics course. Typical
examples of “phase transformation” include freezing of water, eutectoid transformation of steel
between austenite (γ-Fe) and pearlite (α-Fe + Fe3C), transition between graphite and diamond
(but takes forever), etc.
In all processes of materials transformation, atomic (ionic) rearrangement takes place. When an
atom (ion) moves in an environment surrounded by other atoms or ions, bonds are broken, new
bonds are formed and the surrounding atoms are displaced (during the transition) from their
equilibrium positions. This leads to a momentary increase in local energy, forming an
intermediate (non-equilibrium) state, so-called transition (or activated) state. Thus, two

Karnataka State Open University Page 251

Homogeneous and Heterogeneous catalysis Block 4.1.4

equilibrium states which are characterized by local minima in free energy (G, stands for Gibbs
free energy) are separated by a maximum represented by the activated state, as shown below:2
The local minima are state function, and intrinsic to the molecular (materials) structure, where
inter-atomic interaction plays important role in determining the system energy. The energy-
minimized state can usually be calculated by theoretical and computational methods. However,
this is not true for the maximum (activated state), for which the structure is not in equilibrium
and hard to predict.
For a process to occur, it must overcome the energy maximum. The larger the barrier (∆Ga), the
difference between the maximum and the initial minimum, the harder the process to occur, the
slower the rate.
For a process or a reaction to occur, the thermodynamics must be favorable (i.e., ∆G < 0), and
the kinetics must be fast enough (small ∆Ga).
In general: Rate ∝(Kinetic factor) × (Thermodynamic factor)
Kinetic factor refers to ∆Ga, activation energy; while the thermodynamic factor refers to ∆G
=G2-G1, the driving force.
Understanding of ∆G =G2-G1, the driving force
Kinetic theory: the rate of reaction is proportional to the probability to reach activated state, thus,
rate ∝/KTG-ae∆
13.6.1 Thermodynamics Studies
Thermodynamics can be considered in terms of the energy stored within a reaction, a reactant, or
a product. Most often, thermodynamics is thought of as the different forms of energy that are
converted every time a reaction emits energy or is initiated by energy. With respect toGibbs free
energy (∆G), thermodynamics refers to either the energy released during a reaction, in which
case ∆G will be negative and the reaction exergonic or spontaneous. the energy consumed during
a reaction, in which case ∆G will be positive and the reaction endergonic or nonspontaneous. A
thermodynamic reaction favors the products, resulting in a spontaneous reaction that occurs
without the need to constantly supply energy. This indicates that the reactions' most stable state
is that of the products.
Thus, going back to Diagram 2, thermodynamics is what describes the free energy between the
reactants and the products. Because thermodynamic values apply only after the reactants have
turned into products, they are said to describe the equilibrium state. The relationship between

Karnataka State Open University Page 252

Homogeneous and Heterogeneous catalysis Block 4.1.4

free energy (aka, Gibbs free energy) and other thermodynamic quantities is expressed
mathematically in the following equation:
G = U + pV−TS
Because "U" is the variable representing the internal energy of a system, it is closely correlated
with the free energy. Changes in internal energy change the value of the free energy, in
turn affecting chemical reactions in several ways: the rate of reaction, whether the reaction is
spontaneous or non-spontaneous, and even whether or not activation energy will be needed to
initiate the reaction.

Figure 2: Thermodynamic graph

A thermodynamically favorable reaction or process means ∆G < 0, that’s to say, highly driven.
The products are at a lower free energy, or more stable, than the reactants. Because of this, the
reactants "want" to be converted into the products.
13.7 Activation energy(∆Ga)
It is the maximum in energy separating the two equilibrium states; overcoming this barrier
represents the bottle-neck for the reaction to finish, thus a rate determining step. The rate can be
given in terms of the transition state (often called activated complex) by considering the
activation energy, ∆Ga. The high hump of activation energy also indicates the high energy of the
transition state, or activated complex that is at the top of the hump is so unstable.
It is often gets confused between thermodynamic quantities like free energy with kinetic ones
like activation energy. Probably for this reason, “thermodynamics” and “kinetics” are often
taught in separate courses as in our department.

Karnataka State Open University Page 253

Homogeneous and Heterogeneous catalysis Block 4.1.4

The free energies are average energies over a large number of atoms. As a result of random
thermal motion of the atoms (depending on temperature), the energy of any particular atom will
vary with time and occasionally it may be sufficient for the atom to reach the activated state,
which is called “thermal activation”.
13.8 Classification of Catalytic system
The numerous catalysts known today can be classified according to various criteria: structure,
composition, area of application, or state of aggregation. Here we shall classify the catalysts
according to the state of aggregation in which they act. There are two large groups:
heterogeneous catalysts (solid-state catalysts) and homogeneous catalysts. There are also
intermediate forms such as homogeneous catalysts attached to solids (supported catalysts), also
known as immobilized catalysts.
In supported catalysts the catalytically active substance is applied to a support material that has a
large surface area and is usually porous. By far the most important catalysts are the
heterogeneous catalysts. The market share of homogeneous catalysts is estimated to be only ca.
10–15 %. In the following, we shall briefly discuss the individual groups of catalysts.
 Heterogeneous catalysts
 Bulk catalysts
 Homogeneous catalysts
 Acid/base catalysts
 Supported catalysts
 Transition metal compounds Catalysts
 Heterogenized Biocatalysts (enzymes)
Catalytic processes that take place in a uniform gas or liquid phase are classified as
homogeneous catalysis. Homogeneous catalysts are generally well-defined chemical compounds
or coordination complexes, which, together with the reactants, are molecularly dispersed in the
reaction medium. Examples of homogeneous catalysts include mineral acids and transition metal
compounds (e. g., rhodium carbonyl complexes in oxo synthesis).
Heterogeneous catalysis takes place between several phases. Generally the catalyst is a solid, and
the reactants are gases or liquids. Examples of heterogeneous catalysts are Pt/Rh nets for the
oxidation of ammonia to nitrous gases (Ostwald process), supported catalysts such as nickel on

Karnataka State Open University Page 254

Homogeneous and Heterogeneous catalysis Block 4.1.4

kieselguhr for fat hardening, and amorphous or crystalline aluminosilicates for cracking
petroleum fractions.
Of increasing importance are the so-called biocatalysts (enzymes). Enzymes are protein
molecules of colloidal size [e. g., poly(amino acids)]. Some of them act in dissolved form in
cells, while others are chemically bound to to cell membranes or on surfaces. Enzymes can be
classified somewhere between molecular homogeneous catalysts and macroscopic heterogeneous
catalysts.
Enzymes are the driving force for biological reactions. They exhibit remarkable activities and
selectivities. For example, the enzyme catalase decomposes hydrogen peroxide 109 times faster
than inorganic catalysts. The enzymes are organic molecules that almost always have a metal as
the active center. Often the only difference to the industrial homogeneous catalysts is that the
metal center is ligated by one or more proteins, resulting in a relatively high molecular mass.
Apart from high selectivity, the major advantage of enzymes is that they function under mild
conditions, generally at room temperature in aqueous solution at pH values near 7. Their
disadvantage is that they are sensitive, unstable molecules which are destroyed by extreme
reaction conditions. They generally function well only at physiological pH values in very dilute
solutions of the substrate.
Enzymes are expensive and difficult to obtain in pure form. Only recently have enzymes, often
in immobilized form, been increasingly used for reactions of nonbiological substances. With the
increasing importance of biotechnological processes, enzymes will also grow in importance.
It would seem reasonable to treat homogeneous catalysis, heterogeneous catalysis, and
enzymatic catalysis as separate disciplines.
13.9 Summary of the unit
Catalysts are compounds that accelerate the rate of a reaction. Catalysts accelerate reactions by
reducing the energy of the rate-limiting transition state. Catalysts do not affect the equilibrium
state of a reaction. Transition state is an intermediate state in a chemical reaction that has a
higher free energy than both the reactants the products. Reactions can be sped up by the addition
of a catalyst, including reversible reactions involving a final equilibrium state. Recall that for a
reversible reaction, the equilibrium state is one in which the forward and reverse reaction rates
are equal. In the presence of a catalyst, both the forward and reverse reaction rates will speed up
equally, thereby allowing the system to reach equilibrium faster. However, it is very important to

Karnataka State Open University Page 255

Homogeneous and Heterogeneous catalysis Block 4.1.4

keep in mind that the addition of a catalyst has no effect whatsoever on the final equilibrium
position of the reaction. It simply gets it there faster.
Catalysts are compounds that accelerate the progress of a reaction without being consumed.
Common examples of catalysts include acid catalysts and enzymes. Catalysts allow reactions to
proceed faster through a lower-energy transition state. By lowering the energy of the transition
state, which is the rate-limiting step, catalysts reduce the required energy of activation to allow a
reaction to proceed and, in the case of a reversible reaction, reach equilibrium more rapidly.
13.10 Key words
Mode of action of catalysts; Activity; Industrial requirements of catalysis; Heterogeneous
catalysis.; Thermodynamics and Kinetics aspects; Thermodynamics Studies; Activation
energy(∆Ga) ; Classification of Catalytic system
13.11 References for further studies
1) Homogeneous Catalysis: Mechanisms and Industrial Applications; Sumit Bhaduri, Doble
Mukesh; John Wiley & Sons, 2014.
2) Homogeneous Catalysis with Metal Complexes: Fundamentals and Applications; Gheorghe
Duca; Springer Science & Business Media, 2012.
3) Industrial Catalysis: A Practical Approach; Jens Hagen; John Wiley & Sons, 2015.
4) Handbook of Asymmetric Heterogeneous Catalysis; Kuiling Ding, Yasuhiro Uozumi; John
Wiley & Sons, 2008.
5) Principles and Practice of Heterogeneous Catalysis; John Meurig Thomas, J. M. Thomas, W.
John Thomas; John Wiley & Sons, 2015.
6) Organometallic Chemistry and Catalysis; Didier Astruc; Springer Science & Business Media,
2007.
13.12 Questions for self understanding
1) Discuss the mode of action of catalysts.
2) Explain briefly activity of catalyst.
3) Discuss the industrial requirements of catalysis;
4) With example explain the industrial processes using heterogeneous catalysis
5) Explain the catalytic action in terms of thermodynamics and kKinetics aspects.
6) What is activation energy (∆Ga)? Explain its significance.
7) Discuss the classification of catalytic system.

Karnataka State Open University Page 256

Homogeneous and Heterogeneous catalysis Block 4.1.4

UNIT-14
Structure
14.0 Objectives of the unit
14.1 Introduction
14.2 Acid–base catalysis
14.3 Catalysis involving transition metal salts and metal complexes
14.4 Condition to be satisfied by a Metal to act as a catalyst
14.5 Hydrogenation of olefins
14.6 Importance of Wilkinson’s catalyst
14.7 Role of Rhodium Mmetal in the catalytic process
14.8 Mechanism of hydrogenation of olefins using Wilkinson’s catalyst
14.9 Advantages
14.10 Disadvantages
14.11 Modification over the original Catalyst
14.12 Asymmetric hydrogenation
14.12.1 Industrial Catalytic asymmetric hydrogenation
14.13 The mechanism of Asymmetric Hydrogenation using a Chiral catalyst
14.14 Asymmetric Hydrogenation of Ketones and Isomerisation
14.15 Hydrosilylation
14.16 Hydrocyanation
14.17Hydrocyanation of Alkenes
14.18 Summary of the unit
14.19 Key words
14.20 References for further studies
14.21 Questions for self understanding

Karnataka State Open University Page 257

Homogeneous and Heterogeneous catalysis Block 4.1.4

14.0 Objectives of the unit

After studying this unit you are able to

Explain the Acid–base catalysis process

Write the mechanism of hydrogenation of olefins

Explain the importance of Wilkinson’s catalyst

Discuss the catalyst used for Asymmetric hydrogenation

Explain the industrial catalytic asymmetric hydrogenation

Explain the Hydrosilylation reaction

Explain the Hydrocyanation reaction

Explain the Hydrocyanation reaction of Alkenes
14.1 Introduction
Until the 1950, organometallic chemistry was an unexplored are of chemistry. Tremendous
interest in this filed originated predominantly from the two discoveries of i) synthesis of
ferrocene in 1952 and ii) the low pressure catalytic polymerization of ethylene, discovered by
Ziegler in 1952.
No area of chemistry has produced more suppresses and challenges during the past few decade
as organimetallic chemistry. This field continues to be one of great excitement and research
activity. Elegant and skilful synthetic programmers are being supplemented by an unusual
number of chance discoveries.
Synthetic chemists take an intellectual approach. Structural chemists are able to press their
various techniques in elucidating the structure of various products formed. Industrial chemists
exploit and extent the result by developing numerous catalytic processes of great importance.
Some organometallic compounds of transition metals with both saturated and unsaturated
organic systems are of great utility as catalysts in organic chemistry and also in some industrial
process. For example, [RhCl(PPh3)3], Wilkinson’s catalyst in the hydrogenation of olefins,
HCo(CO)4 in the hydroformylation of olefins, TiCl3-Al(C2H5)3 in polymerization of olefins, [Ni
(acac)2] in cyclooligomerization of acetylenes etc….
14.2 Acid–base catalysis
Acceleration of a chemical reaction by the addition of an acid or a base, the acid or base itself not
being consumed in the reaction. The catalytic reaction may be acid-specific (acid catalysis), as in
the case of decomposition of the sugar sucrose into glucose and fructose in sulfuric acid; or base-

Karnataka State Open University Page 258

Homogeneous and Heterogeneous catalysis Block 4.1.4

specific (base catalysis), as in the addition of hydrogen cyanide to aldehydes and ketones in the
presence of sodium hydroxide. Many reactions are catalyzed by both acids and bases.
The mechanism of acid- and base-catalyzed reactions is explained in terms of the Brønsted–
Lowry concept of acids and bases as one in which there is an initial transfer of protons from an
acidic catalyst to the reactant or from the reactant to a basic catalyst. In terms of the Lewis
theory of acids and bases, the reaction entails sharing of an electron pair donated by a base
catalyst or accepted by an acid catalyst.
Acid catalysis is employed in a large number of industrial reactions, among them the conversion
of petroleum hydrocarbons to gasoline and related products. Such reactions include
decomposition of high-molecular-weight hydrocarbons (cracking) using alumina–silica catalysts
(Brønsted–Lowry acids), polymerization of unsaturated hydrocarbons using sulfuric acid or
hydrogen fluoride (Brønsted–Lowry acids), and isomerization of aliphatic hydrocarbons using
aluminum chloride (a Lewis acid). The generalacid basecatalysis mechanism can be represented
as

Mechanism of general acid catalysis

Mechanism of general base catalysis

Karnataka State Open University Page 259

Homogeneous and Heterogeneous catalysis Block 4.1.4

14.3 Catalysis involving transition metal salts and metal complexes

The d orbitals are what give transition metals their distinguished properties. The transition metal
ions the outermost d orbitals are incompletely filled with electrons so they can easily give and
take electrons. This makes transition metals prime candidates for catalysis. The outermost s and
p orbitals are usually empty and therfore less useful for electron transfer.
The principal reasons why transition metals contribute the essential ingredient in catalyst systems
can be summarized as the following headings,
a) Bonding ability
b) Catholic choice of ligands
c) Ligand effects
d) Variability of oxidation state
e) Variablility of co-ordination number
A d-block metal ion has nine valence shell orbitals to accommodate its valence electrons and to
form hybrid molecular orbitals in bonding with other groups. The d orbitals are illustrated in the
following figure. The special configuration enable the d metal to form both σ- and π- bonds
which is one of the key factors in imparting catalytic properties to the transition metals and their
complexes. The interactions between the catalyst and the substrate should be "just right"; that is,
neither too strong nor too weak. If the interaction is too weak, the substrate will fail to bind to the
catalyst and no reaction will take place. On the other hand, if the interaction is too strong, the
catalyst gets blocked by substrate or product that fails to dissociate
14.4 Condition to be satisfied by a Metal to act as a catalyst
1. At least two moderately stable oxidation states for the metal separated by two units should
exist.
Example, Rh+ and Rh3+ in Wilkinson’s Catalyst.
2. It should be capable of forming complexes with a range of coordination numbers and of
forming moderately stable co-ordinatively unsaturated species.
Example, coordination numbers 3, 4, 5 and 6 for rhodium in Wilkinson’s catalyst.
3. It must have the ability to match the substrate orbitals.
For example, if the substrate is an alkene, then this means that the metal must have an empty
orbital capable of accepting σ- donating from the alkenes and a filled orbital of π- back donating
to the alkene.

Karnataka State Open University Page 260

Homogeneous and Heterogeneous catalysis Block 4.1.4

The metals Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and Pt meet all of these requirements most effectively.
As a consequence the most versatile catalyst comes from this group o metal.
14.5 Hydrogenation of olefins
Hydrogenation of olefins is a reaction of major industrial importance, being used in the
petrochemical industries and in the pharmaceutical industries where the preparation of drugs
often involves the hydrogenation of specific double bonds. it is for the hydrogenation of specific
double bonds in compounds containing several double bonds that the search for new more
efficient and above all more selective catalysts has been most vigorous. One very successful
catalyst for this process is [Rh(Cl)(PPh3)], chlorotris (triphenylphosphine) rhodium(I). This is an
effective homogeneous catalyst in solution of aromatic hydrocarbon such as benzene and
toluene. As it very often happens with important discoveries this particular catalyst was
discovered independatly by two groups and now almost universal referred to as catalyst. The net
reaction is

14.6 Importance of Wilkinson’s catalyst

An ideal hydrogenation catalyst should be capable of catalyzing hydrogenations at or near
atmospheric pressure and room temperature. This is because it eliminates the need for expensive
vessels capable of withstanding high pressure and high temperature. In this respect this catalyst
is remarkably effective because the hydrogenation of isolated double or triple bonds takes place
at atmospheric pressure and at room temperature. The applications of Wilkinson’s catalyst are
important in pharmaceutical industries for making specific drugs in spite of the high cost of the
catalyst.
Preparation of the Catalyst [RhCl(PPh3)3]
This red-violet colored compounds is prepared by refluxing ethanolic RhCl3. 3H2O with an
excess of PPh3.
14.7 Role of Rhodium Mmetal in the catalytic process
The role of the metal in the catalytic process is three-stage. Firstly the metal provides a low
energy path for cleaving the H-H bond in H2. Secondly the metal coordinates with the alkene
thereby weakening the bonding between the carbon atoms. Thirdly the metal provides a

Karnataka State Open University Page 261

Homogeneous and Heterogeneous catalysis Block 4.1.4

mechanism for transferring the two hydrogen fragments to the alkene carbon atoms yielding an
alkane.
14.8 Mechanism of hydrogenation of olefins using Wilkinson’s catalyst
On passing hydrogen into a solution of the catalyst in benzene followed by the addition of olefin
the alkane is formed. The precise mechanism of this process is complicated and has been the
subjected of much speculation and controversy. But the following scheme is a simplified but a
reasonable one. For the sake of simplicity PPh3 is represented as L in the catalytic cycle

Step-1 Involves a reasonable loss of one PPh3. This is indicated by two lines of evidence.
1. In less sterically hindered phosphine complexes, the catalytic effect disappears as small
ligands do not readily dissociate which is essential for catalysis, they render the catalyst
ineffective.
2. In the corresponding iridium complex in which the metal-phosphrous bond is stronger
apparently no dissociation takes place and hence catalytic behavior disappears.
Step- II Is oxide addition leading to the formation of a 5-coordianted species [RhCl(H)2L2] in
which the oxidation state of Rh is +3 this step is an oxidation reaction. The coordination number
of the central metal ion is increased from 4 to 5 in this step. Hence this step is also an addition
reaction. Since this step involves both oxidation and addition, it is referred to as an oxidative

Karnataka State Open University Page 262

Homogeneous and Heterogeneous catalysis Block 4.1.4

addition reaction or oxad reaction. In this reaction which is reversible the first role of the catalyst
i.e cleavage of the H-H bond is accompanied. This is identified by NMR peaks characteristics of
Rh-H bond.
Note: The term oxidative addition was introduced by Vaska, who studied some addition
reactions of the complex, trans –[Ir(Cl)(CO)(PPh3)2(O2)] which is called Vaska’s compounds
[Ir(Cl)(CO)(PPh3)2] + (O2) → [Ir(Cl)(CO)(PPh3)2(O2)]
Ir Oxidation number +1 → +3
Co-ordination number 4 → 6
Oxidative addition reaction involves an increase in the formal oxidation state and co-ordiantion
number of the metal in the complex. The reaction,


→
[Ir(Cl)(CO)(PPh3)2] + Cl2 ←
 [Ir(Cl)3(CO)(PPh3)2]
also involves oxidative addition. The reverse reaction is known as reductive elimination. which
involves a decrease in the formal oxidation state and co-ordination number of the central metal in
a complex.
Conditions to be satisfied for an oxidative addition reaction to take place are,
1. The metal should posseses non-bonding electrons density
2. Two vacant co-ordination sites on the complex should be available to aloe formation of two
new bonds to addendum (that is the complex should be coordinatively unsaturated) and
3. The metal should possess two stable oxidation state separated by two units.
Step-III involves the coordination of the alkene to the potential vacant site on the 5-coordinate
dihydrido complex to form the 6-coordianted species. In this step the metal has not only
weakened the alkene double bond by coordination, but has also brought the alkene and the
hydrogen atoms into close proximity where they react probably in a two-step process to give an
alkane (product) and [RhClL2S] which can restart the catalytic cycle. In this step the second role
of the catalytic namely the weakening of the bond between the two carbon atoms is
accomplished.
Step- IV is an insertion reaction. It involves the insertion of olefins into metal-H bond to give
metal-alkyl derivatives.
Note: The concept of insertion is of wide applicability in chemistry when defined as a reaction
where an atom or a group of atom is inserted between two atoms initially bound together. For
example,

Karnataka State Open University Page 263

Homogeneous and Heterogeneous catalysis Block 4.1.4

LnM-X + YZ →LnM-(YZ)-X
Some representative examples are

Carbonyl insertion into M-alkyl bond to give metal-acyl derivatives and olefin insertion into M-
H bond to give metal alkyl derivatives are the partial steps in most of the catalytic cycles in
industrial process. In addition insertion into M-N and M-O bonds are also known.
Step V- Is the reductive elimination step. The metal is reduced form +3 state to +1 state and
coordination number of the central metal is reduced from 6 to 4. In this step the product alkane is
formed. The third role of the catalyst namely the transfer of hydrogen fragments to the alkene
yielding the product alkane is achieved in steps IV and V.
Note: In this reductive elimination reaction two substrates X and Y present in the catalyst system
bonded to one or more centres combine to form a product XY, which then leaves the
coordination sphere of the metal. This is essentially the reverse of oxad reaction.
An example of reductive elimination is the elimination of acetyliodide in the Rh- catalysed
carbonylation of methanol. One of the steps in the above reaction is

This is reductive elimination reaction.

Another example of reductive elimination is the elimination of an aldehyde in the cobalt
catalysed hydroformylation of olefins one step in the process in which reductive elimination
occurs is

14.9 Advantages
1. Compared with the older process which was likewise homogeneously catalyzed and marked
by high reaction temperature of about 2500C and by pressure around 750 atmosphere this new
process under considerably milder reaction condition.

Karnataka State Open University Page 264

Homogeneous and Heterogeneous catalysis Block 4.1.4

2. It is possible selectively hydrogenate biologically active substrate such as steroids. The value
of this catalyst is based upon the fact that the hydrogens are transferred specifically to cis
position.
3. This catalyst is specific for the hydrogenation of terminal olefins due to steric reasons.
14.10 Disadvantages
1. Being a soluble catalyst it cannot be removed easily at the end of the reaction by simple
filtration. Due to this imperfect separation of alkane and rhodium complex at the end of
hydrogenation, rhodium is lost in practice although the catalytic cycle shows no loss of
rhodium. The separation of the catalyst at the end of the reaction is a major problem and it is
one of the reasons why industries have been unwilling to adopt homogneous catalyst more
widely.
2. Because of the high cost of rhodium and the higher cost of converting it into Wilkinson’s
catalyst this process is highly expensive.
14.11 Modification over the original Catalyst
Removal of the catalyst at the end of the catalytic reaction is made easy by building the catalyst
on an insoluble support. The types of support used are beds either of cross-linked polymers such
as polystyrene or polyvinylchloride or of inorganic materials such as silica. the resulting
polymer-supported catalyst is a solid and hence can be easily filtered off at the end of catalytic
process. This process of converting a homogeneous catalyst into a heterogeneous catalyst into a
heterogeneous one is called anchoring of catalyst. In the anchored catalyst all the rhodium atoms
have identical coordination sites leading to high selectivity thus the selectivity are retained in this
modified process.
Note: in recent years the discovery and utility of homogeneous hydrogenation, isomerisarion,
oligomerization, carbonylation reactions etc… have expanded enormously. Commercial
processes based on homogeneously catalyzed routes are becoming increasingly important as
evidenced by the Wacker process and others. However, homogeneous catalysis can exhibit the
problems of product contamination and catalyst loss, where the products are not easily separated
from the catalyst. Anchoring homogeneous catalysts to polymers or other supports effectively
heterogenise them, allowing their use in fixed beds and simplifying catalyst recovery. Thus, the
anchoring of homogeneous catalyst has become the objective of the several groups of the
chemist.

Karnataka State Open University Page 265

Homogeneous and Heterogeneous catalysis Block 4.1.4

When a homogeneous catalyst is heterogenised in such a way that it can react mechanistically in
the same manner of its homogeneous counterpart, the greater se
selectivity
lectivity and activity of the
homogeneous catalyst are thus preserved.
In general, polymer-bound
bound catalyst appears to offer great promise for practical applications in
specific and selective chemical transformations at comparatively mild conditions.
Polymer- supported Wilkinson’s catalyst is prepared as follows. Phosphine groups are introduced
on to the polymer support by the following series of reactions.

14.12 Asymmetric hydrogenation

Asymmetric hydrogenation is a chemical reaction that adds two atoms of hydrogen preferentially
to one of two faces of an unsaturated substrate molecule, such as an alkene or ketone. The
selectivity derives from the manner that the substrate binds to the chiral catalysts.
catalysts In jargon, this
binding transmits spatial information (what chemists refer to aschirality)
as ) from the catalyst to the
target, favoring the product as a single enantiomer. This enzyme-like
like selectivity is particularly
applied to bioactive products such aspharmaceutical
as agents and agrochemicals.
agrochemicals

14.12.1 Industrial Catalytic asymmetric hydrogenation

Knowles aim was to develop an industrial synthesis of the amino acid L
L-DOPA which has
proved useful in the treatment of Parkinson’s disease. By testing enantiomers of phosphines with

Karnataka State Open University Page 266

Homogeneous and Heterogeneous catalysis Block 4.1.4

varied structures, Knowles and his colleagues quickly succeeded in produced usable catalysts
that provided a high enantiomeric excess of the product L-DOPA.

The ligand used in Monasnto’s industrial synthesis of L-DOPA was the diphosphine lignd
DIPAMP a cationic rhodium complex with this ligand afforded extraordinarily high levels of
enantio selectivity in the hydrogenation of achiral enamides. This was the first demonstration
that a chiral transition metal complex could effectively transfer chirality to a nonchiral substrate
with selectivities that even rival those given by enzymes The synthesis gave a mixture of the
enantiomers of DOPA in 100% yield with 97.5% of L-DOPA Thus Knowles has in a short time,
succeeded in applying his own basic research and that of the others to come up with an industrial
synthesis of an important drug. This was the first catalytic asymmetric synthesis. A variety if
chiral diphosphines are nowadays used and many of them are found to give very good in
hydrogenation reactions. These phosphines can be broadly classified as follows.
Diphosphines having chiral phosphorus atoms (DIPAMP).
Diphosphines having a chiral backbone(DIOP)
Ligands having atropisomerism(BINAP)
Those carrying chiral substituents on the phosphorus site.
Ligands having a planar symmetry.

Karnataka State Open University Page 267

Homogeneous and Heterogeneous catalysis Block 4.1.4

14.13 The mechanism of Asymmetric Hydrogenation using a Chiral catalyst

Transition metal say rhodium, when bound to the chiral diphosphine, has the ability to
multaneosuly bind both H2 and substrate. The complex obtained then undergoes an igratory
insertion and H2 is added to the double bond in the substrate. This is the vital stage ring
hydrogenation when a new chiral complex is formed the chiral product is released from is
complex. Thus using a substrate that is prochiral the chirality has been transferred from the urial
catalyst to the product. This product contains more of one enantiomer than the other that the
synthesis is asymmetric.
The reason for the enantimeric excess lies in the hydrogenation stage as hydrogen can in two
ways that give different enantiomers at different rates. These two pathways utilize different
transition state complex which are diasteromers and therefore have different strategies.
Hydrogenation takes place are rapidly via the complex with the lowest energy thus producing an
excess of one of the enantiomers. To develop better asymmetrical hydrogenation catalyst it is
important to increase the energy difference between the transition state complexes in order to
obtain better enantiomeric excess. This is of vital intrest in industrial applications in which the
aim is to achieve economy in the process as well as to use environmentally acceptable methods
that is the process with as few waste products as possible. This development has been led by
Noyori.

Karnataka State Open University Page 268

Homogeneous and Heterogeneous catalysis Block 4.1.4

14.14 Asymmetric Hydrogenation of Ketones and Isomerisation

In 1980 Noyori and cowokers synthesized both enantiomers of the diphosphine ligand BINAP.
The ruthenium complexes containing this ligand catalyse the synthesis of sertain amino acids
with an enantiomeric excess of up to 100%
Noyori also saw the need for more general catalysts with broader applications for example
exchanging Rh(I) with Ru(II) proved to be very successful. The Ru(II)-BINAP complex
hydrogenates many molecules having other types of functional groups. A well known example is
hydrogenation of ketones and aldehydes. Although relatively high pressure are required the
enantioselectivity is very good and the reaction can be scaled up for industrial use. Noyori’s Ru-
BINAP is used as catalyst in the production of (R)-1,2 Propanediol for the industrial synthesis of
an antibiotic, levofloxacin similar reactions are used for the synthesis of other antibiotics.

Karnataka State Open University Page 269

Homogeneous and Heterogeneous catalysis Block 4.1.4

The Takasago International Company has been using BINAP in the industrial synthesis of a
chiral aromatic compounds, menthol since the early 1980. The key reaction in this process is the
enantioselective isomerisation of an allylamine to an asymmetric enamine. The enamine is then
hydrolysed followed by a Lewis acid (ZnCl) catalyzed ring closer reaction that gives the menthol
skeleton. In the final step, the isopropenyl group is hydrogenated over Raney nickel to (-)
menthol

Karnataka State Open University Page 270

Homogeneous and Heterogeneous catalysis Block 4.1.4

14.15 Hydrosilylation
Hydrosilylation, also called catalytic hydrosilation, describes the addition of Si-H bonds
across unsaturated bonds. Ordinarily the reaction is conducted catalytically and usually the
substrates are unsaturated organic compounds. Alkenes and alkynes give alkyl and vinyl
silanes; aldehydes and ketones give silyl ethers. The process was first reported in academic
literature in 1947. Hydrosilylation has been called the "most important application of platinum in
homogeneous catalysis."
The catalytic transformation represents an important method for preparing organosilicon
compounds. An idealized transformation is illustrated by the addition of triethylsilane to
diphenylacetylene
Et3SiH + PhC≡CPh → Et3Si(Ph)C=CH(Ph)
The reaction is related mechanistically to hydrogenation, and similar catalysts are sometimes
employed for the two catalytic processes. Popular industrial catalysts are "Speier's
catalyst," H2PtCl6, and Karstedt’s catalyst (an alkene-stabilized platinum(0) catalyst. One
prevalent mechanism, called the Chalk-Harrod mechanism, assumes an intermediate metal
complex that contains a hydride, a silyl ligand (R3Si), and the alkene substrate. The reaction
usually produces anti-Markovnikov addition alkane, i.e., silicon on the terminal
carbon.[1] Variations of the Chalk-Harrod mechanism. Some cases involve insertion of alkene
into M-Si bond followed by reductive elimination. In certain cases, hydrosilylation results in
vinyl or allylic silanes resulting from beta-hydride elimination.

Karnataka State Open University Page 271

Homogeneous and Heterogeneous catalysis Block 4.1.4

14.16 Hydrocyanation
Hydrocyanation of alkenes and alkynes refers to the transition-metal-mediated or -catalyzed
addition of hydrogen cyanide across a carbon-carbon π bond. This reaction may be used to
synthesize nitriles from alkenes or alkynes in a Markovnikov or anti-Markovnikov fashion.
The addition of hydrogen cyanide across activated carbon-carbon π bonds, such as the C=C bond
of α,β-unsaturated carbonyl compounds, is a well-known, synthetically useful transformation.
Because this process requires a sufficiently electrophilic substrate, unactivated alkenes will not
undergo addition under conditions useful for activated substrates. However, the addition of
hydrogen cyanide across a π bond is a thermodynamically favorable process, and the high
activation barriers associated with addition to unactivated alkenes and alkynes may be
surmounted using transition-metal catalysis. Transition-metal catalyzed addition of cyanide
across π bonds may occur in a Markovnikov or anti-Markovnikov fashion to provide fully
saturated nitriles or vinyl nitriles.

Karnataka State Open University Page 272

Homogeneous and Heterogeneous catalysis Block 4.1.4

14.17Hydrocyanation of Alkenes
Hydrocynation is a process by which H+ and CN- ions are added to a molecular substrate, usually
substrate is an alkene and the product is a nitrile. Since cyanide is a good σ donor and acceptor
ligand, its presence accelerates the rate of substitution of the ligand trans to it by the trans effect.
A key step in hydrocyanation is the oxidative addition of hydrogen cyanide to low metal
complexes. The most important industrial application of hysrocyanation is in the induction of
Nylon-6,6.
Condensation polymerization of hexamethylenediamine (HMD) and adipic acid is the common
route to obtain Nylon-6,6. Traditionally this was prepared by using benzene as a starting
material. This method of production involved a complex set of steps

Alternative procedures using homogeneous catalysis and 1,3- butadiene as precursor have
developed. BASF demonstrated selective dicarbonylation of butadiene to give adipic acid
Dupont developed double anti-Markownikov addition of HCN to butadiene using
Nickelphosphite catalysts to make adiponitrile. The process for adiponitrile developed during
1960 and commercialized in 1971 operates in three stages. Today more than nine adiponitrile
prapred annually is by catalytic hydrocyanation.
Nature of the phosphours ligand is significant in these reactions and only phosphites catalysts of
sustained activity. If instead of phosphate an alkyl phosphine is used catalysts of sustained
activity. If instead of phosphate an alkyl or aryl or aryl phosphine is used in addition of Ni(0) to

Karnataka State Open University Page 273

Homogeneous and Heterogeneous catalysis Block 4.1.4

Ni(II) will occur with the formation of complexes of the type L2Ni(CN)2 lead to catalyst
deactivation.

Karnataka State Open University Page 274

Homogeneous and Heterogeneous catalysis Block 4.1.4

14.18 Summary of the unit

Many catalytic hydrogenations with molecular hydrogen actually involve atomic hydrogen
dispersed in and over the catalyst. In many reductions with hydrogen donors, it may not be easy
to decide just how hydrogen transferred. For example, formic acid may be regarded as providing
a proton and a hydride or two hydrogen atoms. However, for suitable hydrogen donor properties,
it seems clear that compounds containing hydrogen bonded to elements or groups with similar
electronegativity to that of hydrogen itself provide the best hydrogen donors. In this respect
formic acid, ammonium formate, triethylammonium formate, hydrazinium monoformate,
phosphinic acid and phosphinates, phosphorus acid and phosphites, hydrazine, alcohols, amines,
hydrocarbons, hydrides of boron, aluminium, silicon and tin are all hydrogen donors to catalytic
transfer reductions. An added advantage gained when the products of the decomposing donors
have large negative enthalpies of formation. Thus, CO2 from formic acid provide added driving
force to the reactivity of these substances as hydrogen donors.
Hydrocyanation is the process in which HCN is added across a double bond of an alkene to form
a nitrile. In the last decades, more studies have therefore focused on the synthesis of nitriles,
based on HCN addition to alkenes or to related systems in the presence of a transition metal
catalyst, most commonly based on nickel. The most outstanding example for the application of
hydrocyanation is the DuPont adiponitrile process The synthesis of adiponitrile (AdN) based on
a nickel-catalyzed double hydrocyanation of butadiene is a major industrial success for
homogeneous catalysis. In the first step, hydrocyanation of butadiene leads to a mixture of
mononitriles, the desired 3-pentenenitrile (3PN) and the undesired 2-methyl-3-butenenitrile
(2M3BN). The branched isomer needs to be isomerized to the linear 3PN. The second
hydrocyanation of 3PN produces AdN. This reaction only proceeds with the assistance of a
Lewis acid co-catalyst.
14.19 Key words
Acid–base catalysis; transition metal salts and metal complexes; Metal to act as a catalyst;
Hydrogenation of olefins; Wilkinson’s catalyst; Asymmetric hydrogenation; Hydrosilylation
Hydrocyanation; Hydrocyanation of Alkenes
14.20 References for further studies
1) Homogeneous Catalysis: Mechanisms and Industrial Applications; Sumit Bhaduri, Doble
Mukesh; John Wiley & Sons, 2014.

Karnataka State Open University Page 275

Homogeneous and Heterogeneous catalysis Block 4.1.4

2) Homogeneous Catalysis with Metal Complexes: Fundamentals and Applications; Gheorghe

Duca; Springer Science & Business Media, 2012.
3) Industrial Catalysis: A Practical Approach; Jens Hagen; John Wiley & Sons, 2015.
4) Handbook of Asymmetric Heterogeneous Catalysis; Kuiling Ding, Yasuhiro Uozumi; John
Wiley & Sons, 2008.
5) Principles and Practice of Heterogeneous Catalysis; John Meurig Thomas, J. M. Thomas, W.
John Thomas; John Wiley & Sons, 2015.
6) Organometallic Chemistry and Catalysis; Didier Astruc; Springer Science & Business Media,
2007.
14.21 Questions for self understanding
1) What are Acid–base catalysis? Explain their actions
2) Discuss the catalysis involving transition metal salts and metal complexes.
3) Explain the condition to be satisfied by a Metal to act as a catalyst.
4) Discuss the Hydrogenation of olefins.
5) Explain the importance of Wilkinson’s catalyst.
6) Explain the role of Rhodium metal in the catalytic process.
7) Discuss the mechanism of hydrogenation of olefins using Wilkinson’s catalyst.
8) Discuss the advantages and disadvantages Wilkinson’s catalyst.
9) Write a note on modification over the original Wilkinson’s Catalyst.
10) What is Asymmetric hydrogenation?
11) Discuss the industrial catalytic asymmetric hydrogenation.
12) Explain the the mechanism of Asymmetric Hydrogenation using a Chiral catalyst.
13) Discuss the Asymmetric Hydrogenation of Ketones and Isomerisation.
14) Explain the catalytic Hydrosilylation process.
15) Discuss the catalytic Hydrocyanation reaction.
16) Explain the Hydrocyanation reaction of Alkenes.

Karnataka State Open University Page 276

Homogeneous and Heterogeneous catalysis Block 4.1.4

UNIT-15
Structure
15.0 Objectives of the unit
15.1 Introduction
15.2 Fischer–Tropsch process
15.3 Fisher-Tropsch synthesis
15.4 Mechanism of Fisher- Tropsch synthesis
15.5 Ziegler–Natta catalyst
15.6 Importance of Ziegler-Natta catalyst
15.7 Mechanism of Ziegular-Natta catalysis
15.8 Summary of the unit
15.9 Key Words
15.10 References for further studies
15.11 Questions for self understanding

Karnataka State Open University Page 277

Homogeneous and Heterogeneous catalysis Block 4.1.4

15.0 Objectives of the unit

After studying this unit you are able to

Explain the Fischer–Tropsch process

Write the scheme of Fisher-Tropsch synthesis

Write the mechanism of Fisher- Tropsch synthesis

Draw the structure of Ziegler–Natta catalyst

Explain the importance of Ziegler-Natta catalyst

Write the mechanism of Ziegular-Natta catalysis
15.1 Introduction
The Fischer-Tropsch (FT) process, originally developed by Franz Fischer and Hans Tropsch in
early 1920s, is a series of chemical reactions that involve the conversion of hydrogen and carbon
monoxide into liquid hydrocarbons by using a catalyst.
This process is a key component of gas to liquid technology. It produces synthetic lubrication oil
and synthetic fuel including natural gas, biomass or coal. Generally, these products are of higher
quality than those derived through conventional means, having no sulphur or aromatics.
In the FT process, typical cobalt catalysts are produced using Oxford Catalysts' patented
technology with superior stability, selectivity and activity to conventional catalysts, and without
any loss of performance.
The FT process has gained importance as a source of low-sulfur diesel fuel and in addressing the
cost and supply of petroleum-derived hydrocarbons.
Although several catalysts can be used for Fischer-Tropsch synthesis, the transition metals of
ruthenium, nickel, cobalt and iron are some of the most common catalysts. Selection of FT
process catalysts is based on the diesel fuels production and high molecular weight linear
alkanes. Nickel can be also be used as the catalyst, but it tends to promote methane formation.
Cobalt is more active and usually preferred over ruthenium owing to the high cost of ruthenium.
On the other hand, iron is relatively inexpensive and has high water-gas-shift activity, so it is
more suitable for obtaining synthetic gas with low hydrogen/carbon monoxide ratio like those
derived through coal gasification. In addition to the active metal, the catalysts include various
promoters such as copper, potassium and high surface area binders such as alumina or silica. The
presence of sulfur compounds in the synthetic gas can poison the FT catalysts. The cobalt-based
catalysts have higher sensitivity to sulfur than its iron counterparts, which in turn contributes to

Karnataka State Open University Page 278

Homogeneous and Heterogeneous catalysis Block 4.1.4

higher catalyst replacement costs for Co. Therefore, cobalt catalysts are preferred for FT
synthesis of synthetic gas derived from natural gas, where the synthetic gas has relatively low
sulphur content and high hydrogen to carbon monoxide ratio. Iron catalysts are preferred
deriving synthetic gas from low quality feed stocks such as coal.
15.2 Fischer–Tropsch process
The Fischer–Tropsch process is a collection of chemical reactions that converts a mixture
of carbon monoxide and hydrogen into liquid hydrocarbons. It was first developed byFranz
Fischer and Hans Tropsch at the "Kaiser-Wilhelm-Institut für Kohlenforschung" in Mülheim an
der Ruhr, Germany, in 1925. The process, a key component of gas to liquidstechnology,
produces a synthetic lubrication oil and synthetic fuel, typically from coal, natural gas,
or biomass. The Fischer–Tropsch process has received intermittent attention as a source of low-
sulfur diesel fuel and to address the supply or cost of petroleum-derived hydrocarbons. A
Fischer–Tropsch-type process has also been suggested to have produced a few of the building
blocks of DNA and RNA within asteroids.
15.3 Fisher-Tropsch synthesis
The Fisher-Tropsch synthesis was discovered in Germany in the year 1920 and was used during
the Second World War to produce liquid hydrocarbon fuel from coal. The mixture of CO and H2
is pressed over certain transition metal surface. The basic reaction is given by the equations

This equation is an oversimplification because oxygen containing products such as alcohols,

acids, and esters are also formed apart from the hydrocarbons. The original process is used CO
and H2 with 100 atmosphere pressure and temperature of about 400 0C over an alkaline-doped
iron heterogeneous catalyst. The process from then on has undergone considerable refinement
and is currently being used in South Africa. The mechanism of Fisher-Tropsch synthesis is
complicated. Work has been carried out on heterogeneous and homogeneous system, using mono
and polynuclear metal complexes.
The rapid and at time drastic increase in the price of crude oil which has occurred over the last
few decades coupled with the realization that crude oil supplies whether limited by technical or
political factors, are likely to fall short of potential demand has rekindled interest in coal both as
a source of energy and as a feed-stock for the petrochemical industries. At the current rate of

Karnataka State Open University Page 279

Homogeneous and Heterogeneous catalysis Block 4.1.4

energy consumption, the known coal reserves are sufficient for more than 250 years. The most
direct method of using coal as a primary energy source is combustion, However if coal is to
replace crude oil in the production o fuels and organic chemicals, it is necessary to develop
efficient methods of converting coal into gas, liquid hydrocarbons and some organic chemicals.
One method of atleast partially accomplishing these goals is the Fischer- Tropsch synthesis,
where synthesis where synthesis gas namely a mixture of CO and H2 obtained by burning coal in
the presence of oxygen and steam is converted into a number of hydrocarbon product.
15.4 Mechanism of Fisher- Tropsch synthesis
The widely accepted mechanism for this process involves the generation of a methyl group on
the surface of the catalyst followed by a series of steps in which methylene groups are
successively inserted between the metal and the alkyl group thus building up a linear alkyl group.
Then the linear alkyl group is served form the metal in a hydrogenation step. Thus a product
hydrocarbon molecules is released. The methyl group is assumed to be formed by the reaction of
adsorbed hydrogen atoms formed by surface dissociation of H2 with adsorbed CO in a sequence
as shown below

Finally the production of hydrocarbon takes palce in a hydrogenation step as shown below,
where R is a long hydrocarbon chain and RH is the product hydrocarbon.

Karnataka State Open University Page 280

Homogeneous and Heterogeneous catalysis Block 4.1.4

15.5 Ziegler–Natta catalyst

A Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, is a catalyst used in the
synthesis of polymers of 1-alkenes (alpha-olefins). Two broad classes of Ziegler–Natta catalysts
are employed, distinguished by their solubility:
• Heterogeneous supported catalysts based on titanium compounds are used in polymerization
reactions in combination with cocatalysts, organoaluminum compounds such
astriethylaluminium, Al(C2H5)3. This class of catalyst dominates the industry.
• Homogeneous catalysts usually based on complexes of Ti, Zr or Hf. They are usually used in
combination with a different organoaluminum cocatalyst, methylaluminoxane (or
methylalumoxane, MAO). These catalysts traditionally include metallocenes but also feature
multidentate oxygen- and nitrogen-based ligands. Ziegler–Natta catalysts are used to
polymerize terminal 1-alkenes (ethylene and alkenes with the vinyl double bond):
n CH2=CHR → −[CH2−CHR]n−
The transfer of hydrogen atoms to form C-C bonds. These reactions are catalysed by transition
metal complexes. While investigation the multiple insertion of ethane into an Al-alkyl bond to
give long chain Al-alkyls. K.Ziegler and his co-workers discovered that small amounts of Ni
inhibit this polymerization reaction. This stimulated an extensive study of the effect of the
transition metals on the Al-alkyl polymerization system. In the early 1950s these studies led to
the discovery that certain transition metal complexes in the presence of Al-alkyl compounds will
catalyse the polymerization of ethane under mild reaction condition to give a material of
molecular weight in excess of 50,000. This discovery was of tremendous technical importance
because previously ethene had been considered a very difficult molecule to polymerise needing
pressure of over 1000 atmosphere and temperature of the order of 2000C.
G. Natta extended Ziegler’s work to the polymerization of propene and higher α- olefins using
Ziegler-type catalysts based on Ti. After these discoveries many metal combination have been
found to be capable of catalyzing alkene polymerisarion and the defiantion extended to include
any combination of alkyl hydride or halide of Groups I-III with a transition metal salt or complex
of Groups IV-VIII of the periodic table.

Karnataka State Open University Page 281

Homogeneous and Heterogeneous catalysis Block 4.1.4

The most familiar example is the original Ziegler catalyst formed from TiCl4 and AlR3
In the inert hydrocarbon solvent used an insoluble mixed halide-alkyl complex of Al and Ti is
formed. This material is the active catalyst for the polymerization of ethylene, presumably acting
as a heterogeneous catalyst.
Note: In recent years, the utility of homogeneous hydrogenation, isomerization, oligomerization,
carbonylation reactions etc…. have expanded enormously. commercial process based on
homogeneously-catalized routes are becoming increasingly important as evidenced by the
Wacker’s process and others. However homogeneous catalyst can exhibit the problems of
product contamination and catalyst loss, where the products are not readily separated from the
catalyst. Anchoring homogeneous catalyst to polymers or other compounds effectively
heterogenises them, allowing their use in fixed beds and simplifying catalyst recovery. Thus
anchoring of homogeneous catalyst has assumed importance.
15.6 Importance of Ziegler-Natta catalyst
The Ziegeler-Natta catalysis of alkene polymerization which operates at modest temperatures
and pressure leads to the formation of stereoregular polymers. this is in direct contrast to the high
temperature nad pressure polymerization of alkenes. Stereoregularity often introduceds some
very desirable properties into yield long linear head-to-tail chains consisting of sequences of
monomeric units having the same steric arrangement. These polymers are called isotactic
polymers. The advantages of stereoregularity are that it conveys greater mechanical strength to
the polymer enabling it to be used in making string and rope as well as more rigid articles such
as industrial buckets. They possess higher melting and are stronger than nylon.
One of the features of organometallic polymerization catalyst is that they produce stereoregular
polymers. For example, propelene forms two stereoregular polymers namely isotatic and
syndiotactic polymers and one non-regular polymer namely attactic polymer. in isotactic
polymer. In isotactic polymer, they methyl groups always lie on the same side of the chain.

In syndiotactic polymers methyl groups alternate along the chain

Karnataka State Open University Page 282

Homogeneous and Heterogeneous catalysis Block 4.1.4

In atactic polymer, the methyl groups have no regularity along the chain.

When the double bond of the propylene attaches itself to Ti, the methyl group must always point
away from the surface of the crystal simply because the reaction occurs on the surface. Thus
when the molecule migrates and is increased into the Ti-C bond, it always has the same
orientation. This is called cis-insertion of the alkene and explains why the polymers produced are
steroregular.
15.7 Mechanism of Ziegular-Natta catalysis
The most familiar example of Ziegler-Natta catalyst is the one formed from TiCl4 and Al(C2H5)3.
These components react in a way that is not completely understood but may involve the
following steps.

Thus, if inert hydrocarbon solvent is used, an insoluble mixed halide-alkyl complex of Al and Ti
of variable composition is formed. This is the active catalyst for the polymerization of ethylene,
presumably acting as a heterogeneous catalyst.
Several similar mechanisms have been proposed for this catalytic process. The most widely
accepted of these is outlined below. To understand how the catalyst works, we must look at the
crystal structure of TiCl3. In solid TiCl3, a Ti atom in the centre of the crystal is surrounded
octahedrally by six chlorine atoms. Each Cl atom is further bound to a Ti atom (otherwise the
formula would be TiCl6 but not TiCl3). However if such bonding is carried on indefinitely, it is
apparent that in order to make the crystal electrically neutral (i.e., to have the formula TiCl3),
some of the Ti atoms at the surface should have only 5 Cl atoms around them and so possess a
vacant site. On treating such crystal of TiCl3 with Al(C2H5)3, this vacant site is alkylated. The

Karnataka State Open University Page 283

Homogeneous and Heterogeneous catalysis Block 4.1.4

starred Cl (Cl*) indicates a Cl bound to a second Ti and an unsaturated Cl atoms lie on the
surface of the crystal.

In the alkylated product, the vacancy in the coordination shell of the Ti atom is still present but
in a fresh position. This vacant site is potentially capable of coordinating an alkene such as C2H4.
The alkene coordinates to the Ti atom as a π-donor in its vacant coordination site. The
electropositive nature of the Ti atom allows the electrons in the Ti-C2H4 bond to flow towards
the C2H5 group. This weakens the bond which is labile and is cis to the newly arrived alkene π-
bond. When am alkene and an alkyl group are bound to adjacent sites on a metal atom, they react
to give what is known as an insertion product through a concerted four centre rearrangement.
This step is assumed to be the rate determining step. The alkyl group shifts to one carbon of the
alkene double bond, while the other carbon develops a sigma bond to the Ti atom. When the
arrangement of the alkayl on to the alkene carbon is complete, a new coordination site is opened
up on the Ti atom cis to the new longer alkyl group. This regeneration of the vacant site enables
the process to be repeated. For the sake of clarity, the starred chlorine atoms have been omitted.

Karnataka State Open University Page 284

Homogeneous and Heterogeneous catalysis Block 4.1.4

The presence of vacant site enables the chain to continue growing by switching back and forth
between the two sites.

Termination would occur by a reverse insertion reaction in which a hydride ion shifts to the
metal.
Polyethylene produced by Ziegle-Natta catalysis is superior to that produced by free radical
polymerization. A comparative account of these two polymers is given in below table.
Polyethylene produced by Ziegler-Natta Polyethylene produce by free radical
catalysis polymerization
Produced under severe conditions of about
1 Produced under milder reaction conditions
190 - 210 oC and 1500 atm pressture
2 Has high density, 0.95-0.97 g/cc Has lower density, 0.91-0.94 g/cc
3 Has higher melting point, 135 oC Has lower melting point 115 oC
Contains straight chains with very little
4 Consist of branched chains
branch
5 Relatively hard and stiff Relatively softer
Has higher molecular weight 20,000-
6 Has relatively lower molecular weight
30,000
15.8 Summary of the unit
The Fischer-Tropsch (F-T) reaction converts a mixture of hydrogen and carbon monoxide
derived from coal, methane or biomass—to liquid fuels. The F-T process was discovered by
German scientists and used to make fuels during World War II. There has been continued
interest of varying intensity in F-T technology ever since. Both iron-based and cobalt-based
catalysts have been examined.
In Ziegler-Natta polymerisation, monomers are treated with a catalyst, such as a mixture of
titanium chloride (or related compounds, like oxovanadium chloride) with triethylaluminum (or
trimethylaluminum). Other components are often added, such as magnesium chloride, to modify
the catalyst and improve performance. Ziegler-Natta polymerization is a method of vinyl

Karnataka State Open University Page 285

Homogeneous and Heterogeneous catalysis Block 4.1.4

polymerization. It's important because it allows one to make polymers of specific tacticity. It was
discovered by two scientists, and I think we can all figure out what their names were. Ziegler-
Natta is especially useful, because it can make polymers that can't be made any other way, such
as linear unbranched polyethylene and isotactic polypropylene. Free radical vinyl polymerization
can only give branched polyethylene, and propylene won't polymerize at all by free radical
polymerization. So this is a pretty important polymerization reaction, this Zieglar-Natta stuff.
15.9 Key Words
Fischer–Tropsch process; Fisher-Tropsch synthesi; Mechanism of Fisher- Tropsch synthesis;
Ziegler–Natta catalyst; Importance of Ziegler-Natta catalyst; Mechanism of Ziegular-Natta
catalysis
15.10 References for further studies
1) Homogeneous Catalysis: Mechanisms and Industrial Applications; Sumit Bhaduri, Doble
Mukesh; John Wiley & Sons, 2014.
2) Homogeneous Catalysis with Metal Complexes: Fundamentals and Applications; Gheorghe
Duca; Springer Science & Business Media, 2012.
3) Industrial Catalysis: A Practical Approach; Jens Hagen; John Wiley & Sons, 2015.
4) Handbook of Asymmetric Heterogeneous Catalysis; Kuiling Ding, Yasuhiro Uozumi; John
Wiley & Sons, 2008.
5) Principles and Practice of Heterogeneous Catalysis; John Meurig Thomas, J. M. Thomas, W.
John Thomas; John Wiley & Sons, 2015.
6) Organometallic Chemistry and Catalysis; Didier Astruc; Springer Science & Business Media,
2007.
15.11 Questions for self understanding
1) What is Fischer–Tropsch process?
2) Explain the Fisher-Tropsch synthesis.
3) Discuss the Mechanism of Fisher- Tropsch synthesis
4) What is Ziegler–Natta catalyst?
5) Discuss the importance of Ziegler-Natta catalyst.
6) Explain the mechanism of Ziegular-Natta catalysis

Karnataka State Open University Page 286

Homogeneous and Heterogeneous catalysis Block 4.1.4

UNIT-16
Structure
16.0 Objectives of the unit
16.1 Introduction
16.2 Zeolites as shape selective catalysts
16.3 Zeolites
16.4 Clays used as catalysts.
16.5 Pillared Clays
16.6 Advantages
16.7 Decomposition of isopropanol using oxide catalyst
16.8 Catalytic converter
16.9 Summary of the unit
16.10 Key words
16.11 References for further studies
16.12 Questions for self understanding

Karnataka State Open University Page 287

Homogeneous and Heterogeneous catalysis Block 4.1.4

16.0 Objectives of the unit

After studying this unit you are able to

Explains the structure and preparation procedure of zeolites

Explain the use of zeolites as shape selective catalysts

Explain the use of clays as catalysts.

Discuss the advantages of pillared plays

Explains the procedure of decomposition of isopropanol using oxide catalyst

Explain the catalytic converter
16.1 Introduction
The industrial uses of clay minerals as catalysts date from the early 'thirties. The application of
catalysis to the thermal cracking of oil started in about 1931; pre-heated oil was passed
downwards through fixed beds of granular catalyst, often attapulgite, under pressure (80 lb. per
sq. in.) and at about 900~ as in the Houdry and Hydroforming systems. The catalyst had to be
periodically burned off to regenrrate it, and was reintroduced at the top of the reaction column.
An improvement on this static process came when the granulated catalyst was kept moving
counter current to the pre-heated oil. This led about 1939 to the fluid-flow method of catalysis in
which powdered catalysts are used in a fluid, free-flowing condition, circulated by the air-rift
method well-known in the movement of liquids. The motive power for the circulation of the fluid
is obtained from the static head of gas-solid columns and by the introduction under pressure of
oil vapours to the oil-cracking reactor, and of air to the catalyst reactivator. An up-flow system
has recently given way to a down-flow technique, which gives greater efficiency and accuracy of
control. Clay minerals have played an important part in these petroleum techniques, and it is with
this astonishingly rapid development of new catalytic techniques in our minds that we may
review this morning the part which clay minerals have played and may play in catalysis.
16.2 Zeolites as shape selective catalysts
Shape selective catalysis differentiates between reactants, products, or reaction intermediates
according to their shape and size. If almost all of the catalytic sites are confined within the pore
structure of a zeolite and if the pores are small, the fate of reactant molecules and the probability
of forming product molecules are determined by molecular dimensions and configurations as
well as by the types of catalytically active sites present. Only molecules whose dimensions are

Karnataka State Open University Page 288

Homogeneous and Heterogeneous catalysis Block 4.1.4

less than a critical size can enter the pores, have access to internal catalytic sites, and react there.
Furthermore, only molecules that can leave appear in the final product.
Shape selective catalysis can be used to increase yields of preferred products or to hinder
undesirable reactions. It has been 25 years since Weisz and Frilette first described the concept of
shape selectivity. The significance of this phenomenon was recognized immediately. Scientific
experimentation went hand-in-hand with the exploration of commercial possibilities. Desktop
laboratory experiments were soon followed by development work, and pilot plant demonstrations
soon led to the construction and start—up of commercial units.
16.3 Zeolites
Most shape selective catalysts today are molecular sieve zeolites. Zeolites are porous crystalline
aluminosilicates possessing intracrystalline channels with reproducible morphology. They are
built up from Si04 and Al04 tetrahedral elements, cross—linked to each other through the
oxygens. In natural zeolites, aluminum or silicon occupy all the tetrahedra but in some synthetic
zeolites gallium, germanium, boron, and phosphorus have been also incorporated into the
framework. Natural zeolites are frequently found in rocks of volcanic origin (e.g.,glassy tuffs
near alkaline lakes).
Synthetic zeolites are made by precipitation from supersaturated alkaline solutions of various
inorganic or organic bases. The organic cations (often various tetraalkylammonium hydroxyls)
serve as templates to direct crystallization toward the desired structure.
Zeolites have four properties which make them interesting and valuable for heterogeneous
catalysis:
1) They have exchangeable cations, allowing the introduction of different cations with arious
catalytic properties;
2) If these cationic sites are exchanged to H, they can have a very high number of very strong
acid sites;
3) They have pore diameters with one or more discrete sizes; and
4) They have pore diameters that are in the order of molecular imensions, i.e., less than 1 nm.
Properties 1 and 2 account for catalytic activity and properties 3 and 4 are responsible for the
molecular sieving action.

Karnataka State Open University Page 289

Homogeneous and Heterogeneous catalysis Block 4.1.4

16.4 Clays used as catalysts.

Although the clay mineralogist is bringing some order out of chaos in the classification of clays
we are faced with rather a large number of trade names when we come to study the literature of
clay catalysts. I shall name some of the better known ones, beginning with the kaolinitic group,
The clays of this group have not been much used in catalysis and are not cursed with strange
nomenclature. Dickite, nacrite, and halloysite are not worked commercially, so we are left with
the familiar china clays and ball clays of commerce. These are clays with a 7 Angstrom unit
basal spacing of the lattice.
The 10 Angstrom unit clays or illite group includes attapulgite, which is the clay mineral of
Florida fuller's earth, Floridin, Florex, and Florigel, the products of Florida and Georgia in the
United States. (I should add that Florite is a bauxite catalyst made by the same company). These
clays in granulated and powder form are the most important clay catalysts in the world. They are
not known to exist in Britain in commercial quantities; some Russian clays seem to be similar.
The montmorillonite group tend to lose activity on heating above 500~ ; certainly they lose their
adsorptive power. There may be catalytic reactions in which tl~e kilned material is more active.
But for low temperature catalytic reactions where regeneration of the catalyst does not involve
the use of high temperatures, drying of the montmorillonite to the optimal moisture content is an
obvious suggestion. This precaution is necessary in the essential oil reactions to be described
later.
16.5 Pillared Clays
Pillared clays (PILCs) are one of the promising porous materials which can be utilized as
catalysts in a number of reactions. More than thirty years have passed since the first
announcement of pillared interlayered clay. The preparative techniques have progressed
remarkably with a wide variety of pillared solids being made. Recent advances in the synthesis
of PILCs have expanded considerably the scope of their potential catalytic applications. PILCs
are formed by intercalation of polymeric metal hydroxides or oligomerichydroxycations into the
interlamellar space of the cationic clays, followed by thermal treatment, allows pillaringof the
clays, with a modification of the interlayer distance and typically also an increase of the thermal
stability.
The catalytic behaviour of PILCs is usually associated to the modification of the acidity (by
substituting tetrahedral and octahedral sites), by active sites introduced during the pillaring

Karnataka State Open University Page 290

Homogeneous and Heterogeneous catalysis Block 4.1.4

process and by intercalation with organometallic complexes. The method of pillaring could
largely affect the final characteristics and performances. Also anionic clays could be pillared.
These materials, particularly those having isopoly- and heteropoly-anions intercalated between
the layers, show a quite interesting catalytic behavior. Moreover, the transition metal oxide
pillars can be modified by oxidation/reduction to become catalytically active and the pillars of
the clay create specific and stable active sites. In these contexts first row transition metals like
iron, titanium, vanadium and chromium-pillared materials are mostly studied. So there is enough
scope of developing new catalytic materials for different applications by varying the transition
metal oxide pillars only.
This area of research is still growing and need further exploration as potential catalyst which is
very limited in the literature. Generally, it is also claimed that the pillaring procedure
significantly improves the performances with respect to the starting clays. As a result there is
now a renewed interest in the pillared material as polyfunctional catalysts and catalyst supports.
Several research groups have investigated the characteristics of PILCs and their use as catalysts
or catalytic materials The general conclusion which may be derived from thesestudies that
pillared clays are very interesting and promising catalysts in a broad range of applications, for
example in acid-catalyzed reaction catalytic hydrotreating of heavy vacuum gas oilalkylation of
aromatics , the synthesis of bulk and fine chemicals (a broad range of reactions such as
dehydrogenation, hydroxylation, disproportionation, esterification, epoxidation, alkylation,
isomerization, Fischer-Tropsch, methane reforming, hydrogenation, aromatization, etc.),
upgrading of lubricant oils and for the reduction of pollutants (selective catalytic reduction of
NOx and catalytic removal of organic volatile compounds).
The best clay base for pillaring is a high-swelling Na-montmorillonite.It is mineral clay that can
hold guest molecules between its layers. Many different cations, including hydroxy-aluminium,
hydroxy-chromium, hydroxy-titanium and hydroxy-zirconium polycations have been used for
2
the preparation of pillared montmorillonite characterised by surface area of 200-400m /g, pore
3
volume of 0.15-0.30 cm /g and interlayer spacing of 1-2 nm. Vaughan and Lussier demonstrated
that montmorillonite interlayered with hydroxy-aluminium pillars will promote catalytic
16.6 Advantages
The main groups of uses for clay catalysis are in the essential oil, glyceride oil and petroleum oil
fields, as well as in general organic synthesis or pyrolysis, not covered by these fields. A very

Karnataka State Open University Page 291

Homogeneous and Heterogeneous catalysis Block 4.1.4

great number of reactions have been studied not only to throw light on the nature of the reactions
themselves and of the role of the catalyst, but as part of the huge research programme which has
revolutionised the oil industry converting it from a fuel-producing to a chemical-producing
industry.
• Glyceride oils.Clay catalysts have been used, experimentally at any rate, for dehydrating
castor and fish oils to produce drying oils to eke out limited supplies of linseed and tung oils;
and contrariwise, in China, where petroleum products were unobtainable, tung oil and other
glyceride oils were cracked with a clay catalyst to yield hydrocarbon products.
• Petroleum oil. The original aim of using clay and other catalysts in the petroleum industry
was to reduce the temperatures required for cracking crude residual oil to increase the yield
of motor spirit and light gas oil. The emphasis later passed to the production of high octane
fractions by catalytic isomerisation or "reforming," as well as to desulphurisation. And more
recently catalytic processes have been developed so highly that a considerable range of pure
chemicals can be produced. Most of this development has been carried out, of course, in the
United States by all the larger companies, but in Britain big developments are on the way,
notably the Shell Chemicals processes and the Catarole process of Petrochemicals Ltd.
• General organic synthesis.This leads us imperceptibly towards the wide field of general
organic synthesis. A few reactions will be mentioned.
• Dehydrations.--Resin alcohols produced from colophony or abietic acid by hydrogenation
can be dehydrated by Tonsil activated clay to produce unsaturated hydrocarbons utilisable in
the textile industry. Simple reactions have been studied with the production of unsaturated
hydrocarbons and ethers from primary aliphatic alcohols over Japanese acid clay.
Cyclohexanol can be converted to cyclohexene. Under severer conditions, that is to say, at
higher temperatures, the reactions are called pyrolytic, and are akin to the cracking of
petroleum crudes in heterogeneous catalysis. Many single chemicals have been pyrolysed
over clays.
• Condensations. An enormous number of condensation reactions have been catalysed by
clays. Aldehydes and ketones passed over kaolin with ammonia yield pyridine bases. Nitriles
are formed over clays with ammonia acting on acetic acid, adipic acid, fatty acids, and so on.
Alcohols and amines from paratoluidine and other compounds. Members of the
anthraquinone series condense with phthalic anhydride over clay catalysts.

Karnataka State Open University Page 292

Homogeneous and Heterogeneous catalysis Block 4.1.4

• Dechlorinations.A chloride atom is removed in other condensations, as when benzylchloride

and benzene form diphenylmethane over clay. Chlorbenzol, chlortoluol and chlorinated
paraffins have been dechlorinated with clays. Some examples of chlorination are mentioned.
lsomeri~ation and cyclisation.--Aldehydes may be converted to ketoncs over clay catalysts,
and cyclisation is by no means confined to the hydrocarbons already mentioned. Thus
unsaturated aliphatic acids yield cyclopentenones. Some elegant examples have been given
of such reactions among the essential oils.
• OxMations and reductions. Natural gas has been oxidised to alcohols, mainly, over
silicates. Silica gel helps to form phenols from benzol and water, but I have no record of
clays being used in this reaction.
16.7 Decomposition of isopropanol using oxide catalyst
The adsorption and reaction of alcohols on metaloxide catalysts has been used as a chemical
probe reactionfor many years. Alcohol reactions have been studied extensively using temperature
programmed decomposition (TPD), steady-state kinetic studies, in situ spectroscopy,
microcalorimetry and many ultra-high vacuum surface science studies as cited by Rekoske and
Barteau. Isopropanol decomposition has long been considered as a chemical probe reaction for
surface acid–base properties. Isopropanol undergoes dehydration to give propylene on acidic
surface sites and dehydrogenation via a concerted mechanism on adjacent acidic and basic
surface sites to give acetone.
Ai and Suzuki were the first to correlate various acidic and basic properties of metal oxide
catalysts with their rates of dehydration and dehydrogenation of isopropanol. Isopropanol
adsorption has also been employed as a method of measuring the surface titania content in mixed
titania-silica catalysts. Zaki and coworkers have done in situ IR spectroscopy studies of
isopropanol adsorption on Al2O3, CeO2, TiO2, ZrO2 and HfO2. Other metal oxides that have been
extensively studied are ZnO and MoO3.
All these investigations adsorbed isopropanol at room temperature and found that isopropanol
adsorbs both dissociatively as a surface isopropoxide intermediate and as physisorbed
isopropanol at room temperature. In some cases, also intact isopropanol was chemisorbed via
coordinative bonding to the metal oxide surface. This coordinatively bonded isopropanol was
also found on Y2O3 at up to 250 ◦C. Upon evacuation most of the physisorbed isopropanol
desorbed leaving only the surface isopropoxide species and the coordinatively bonded

Karnataka State Open University Page 293

Homogeneous and Heterogeneous catalysis Block 4.1.4

isopropanol. Dehydroxylated surfaces dissociated isopropanol to give isopropoxide species and

surface hydroxyls. The hydroxyl species desorbed as water upon heating to sufficiently high
temperatures. The surface isopropoxide species underwent further C–H bond scission at higher
temperatures to give acetone. Two kinds of surface isopropoxide species were observed on metal
oxide catalysts. One of the surface alkoxides is terminally bonded to a single cation and the other
is bridge bonded to two cations. Hussein and Gates propose that the bridge bonded species yield
propylene and the terminal species give acetone. The surface reactions to the acetone and
propylene are shown below:
(CH3)2CHOH + Mn+(s) + O2 (s)→ (CH3)2CHO− · · ·Mn+(s)+ OH−(s)……….. (1)
(CH3)2CHO− · · ·Mn+(s) + OH−(s)→ (CH3)2C=O + H2 + O2(s)+Mn+(s)…… (2)
O2 +HCH2–(CH3)CH–HO + Mn+(s)→ CH3CH=CH2 +Mn + OH(s) + H−(s)..(3)
where Mn+ is the positive metal cation to which the surface isopropoxide species are bonded.
One of the objectives of the present investigation is to determine the number of active surface
sites per m2 (Ns) and also the isopropanol oxidation turnover frequencies on the various metal
oxide catalysts. Isopropanol can distinguish between acidic and redox surface sites.
16.8 Catalytic converter
A catalytic converter is a vehicle emissions control device that converts
toxic pollutants in exhaust gas to less toxic pollutants by catalyzing a redox reaction (oxidation
or reduction). Catalytic converters are used with internal combustion engines fueled by
either petrol (gasoline) or diesel—including lean-burn engines.
The first widespread introduction of catalytic converters was in the United
States automobile market. To comply with the U.S. Environmental Protection Agency's stricter
regulation of exhaust emissions, gasoline-powered vehicles starting with the 1975 model
year must be equipped with catalytic converters. These "two-way" converters
combined oxygen with carbon monoxide (CO) and unburned hydrocarbons (HC) to
produce carbon dioxide (CO2) and water (H2O). In 1981, two-way catalytic converters were
rendered obsolete by "three-way" converters that also reduce oxides of nitrogen (NOx); however,
two-way converters are still used for lean-burn engines.

Karnataka State Open University Page 294

Homogeneous and Heterogeneous catalysis Block 4.1.4

Although catalytic converters are most commonly applied to exhaust systems in automobiles,
they are also used on electrical generators,forklifts, mining
equipment, trucks, buses, locomotives and motorcycles. They are also used on some wood stoves
to control emissions. This usually in response to government regulation, either through direct
environmental regulation or through health and safety regulations.
The catalytic converter's construction is as follows:
1. The catalyst support or substrate. For automotive catalytic converters, the core is usually
a ceramic monolith with a honeycomb structure. Metallic foil monoliths made
of Kanthal (FeCrAl) are used in applications where particularly high heat resistance is
required. Either material is designed to provide a large surface area. The cordierite ceramic
substrate used in most catalytic converters was invented by Rodney Bagley, Irwin
Lachman and Ronald Lewis at Corning Glass, for which they were inducted into the National
Inventors Hall of Fame in 2002.
2. The washcoat. A washcoat is a carrier for the catalytic materials and is used to disperse the
materials over a large surface area.Aluminum oxide, titanium dioxide, silicon dioxide, or a
mixture of silica and alumina can be used. The catalytic materials are suspended in the
washcoat prior to applying to the core. Washcoat materials are selected to form a rough,
irregular surface, which greatly increases the surface area compared to the smooth surface of
the bare substrate. This in turn maximizes the catalytically active surface available to react

Karnataka State Open University Page 295

Homogeneous and Heterogeneous catalysis Block 4.1.4

with the engine exhaust. The coat must retain its surface area and prevent sintering of the
catalytic metal particles even at high temperatures (1000 °C).
3. The catalyst itself is most often a mix of precious metals. Platinum is the most active catalyst
and is widely used, but is not suitable for all applications because of unwanted additional
reactions and high cost. Palladium and rhodium are two other precious metals used. Rhodium
is used as a reduction catalyst, palladium is used as an oxidation catalyst, and platinum is
used both for reduction and oxidation. Cerium, iron, manganese and nickel are also used,
although each has limitations. Nickel is not legal for use in the European Union because of
its reaction with carbon monoxide into toxic nickel tetracarbonyl. Copper can be used
everywhere except North America, where its use is illegal because of the formation
of dibenzodioxins.
Upon failure, a catalytic converter can be recycled into scrap. The precious metals inside the
converter, including platinum, palladium and rhodium, are extracted. Prices paid for converters
vary depending on the type and market prices.
Environmental impact Catalytic converters have proven to be reliable and effective in reducing
noxious tailpipe emissions. However, they also have some shortcomings in use, and also adverse
environmental impacts in production:
• An engine equipped with a three-way catalyst must run at the stoichiometric point, which
means more fuel is consumed than in a lean-burn engine. This means approximately 10%
more CO2 emissions from the vehicle.
• Catalytic converter production requires palladium or platinum; part of the world supply of
these precious metals is produced near Norilsk, Russia, where the industry (among others)
has caused Norilsk to be added to Time magazine's list of most-polluted places.[32]
A two-way (or "oxidation") catalytic converter has two simultaneous tasks:
1. Oxidation of carbon monoxide to carbon dioxide: 2CO + O2 → 2CO2
2. Oxidation of hydrocarbons (unburned and partially burned fuel) to carbon dioxide
and water: CxH2x+2 + [(3x+1)/2] O2 → xCO2 + (x+1) H2O (a combustion reaction)
This type of catalytic converter is widely used on diesel engines to reduce hydrocarbon and
carbon monoxide emissions. They were also used on gasoline engines in American- and
Canadian-market automobiles until 1981. Because of their inability to control oxides of nitrogen,
they were superseded by three-way converters.

Karnataka State Open University Page 296

Homogeneous and Heterogeneous catalysis Block 4.1.4

Three-way
Three-way catalytic converters (TWC) have the additional advantage of controlling the emission
of nitrogen oxides (NOx), particularly nitrous oxide, a greenhouse gas over three hundred times
more potent than carbon dioxide, a precursor to acid rain and currently the most ozone-depleting
substance.[ Technological improvements including three-way catalytic converters have led to
motor vehicle nitrous oxide emissions in the US falling to 8.2% of anthropogenic nitrous oxide
emissions in 2008, from a high of 17.77% in 1998.

Since 1981, "three-way" (oxidation-reduction) catalytic converters have been used in vehicle
emission control systems in the United States and Canada; many other countries have also
adopted stringent vehicle emission regulations that in effect require three-way converters on
gasoline-powered vehicles. The reduction and oxidation catalysts are typically contained in a
common housing; however, in some instances, they may be housed separately. A three-way
catalytic converter has three simultaneous tasks:
1. Reduction of nitrogen oxides to nitrogen and oxygen: 2NOx → xO2 + N2
2. Oxidation of carbon monoxide to carbon dioxide: 2CO + O2 → 2CO2
3. Oxidation of unburnt hydrocarbons (HC) to carbon dioxide and water:
CxH2x+2 + [(3x+1)/2]O2 → xCO2 + (x+1)H2O.
These three reactions occur most efficiently when the catalytic converter receives exhaust
from an engine running slightly above the stoichiometric point. For gasoline combustion, this is
between 14.6 and 14.8 parts air to one part fuel, by weight. The ratio for Autogas (or liquefied
petroleum gas (LPG)), natural gas and ethanol fuels is each slightly different, requiring modified
fuel system settings when using those fuels. In general, engines fitted with 3-way catalytic
converters are equipped with a computerized closed-loop feedbackfuel injection system using

Karnataka State Open University Page 297

Homogeneous and Heterogeneous catalysis Block 4.1.4

one or more oxygen sensors, though early in the deployment of three-way

converters, carburetors equipped for feedback mixture control were used.
Three-way converters are effective when the engine is operated within a narrow band of air-fuel
ratios near the stoichiometric point, such that the exhaust gas composition oscillates between rich
(excess fuel) and lean (excess oxygen). Conversion efficiency falls very rapidly when the engine
is operated outside of this band. Under lean engine operation, the exhaust contains excess
oxygen, and the reduction of NOx is not favored. Under rich conditions, the excess fuel
consumes all of the available oxygen prior to the catalyst, leaving only stored oxygen available
for the oxidation function.
Closed-loop engine control systems are necessary for effective operation of three-way catalytic
converters because of the continuous balancing required for effective NOxreduction and HC
oxidation. The control system must prevent the NOx reduction catalyst from becoming fully
oxidized, yet replenish the oxygen storage material so that its function as an oxidation catalyst is
maintained.
Three-way catalytic converters can store oxygen from the exhaust gas stream, usually when
the air–fuel ratio goes lean. When sufficient oxygen is not available from the exhaust stream, the
stored oxygen is released and consumed (see cerium(IV) oxide). A lack of sufficient oxygen
occurs either when oxygen derived from NOx reduction is unavailable or when certain
maneuvers such as hard acceleration enrich the mixture beyond the ability of the converter to
supply oxygen.
16.9 Summary of the unit
Zeolites are hydrated aluminosilicates of the alkaline and alkaline-earth metals. About 40 natural
zeolites have been identified during the past 200 years; the most common are analcime,
chabazite, clinoptilolite, erionite, ferrierite, heulandite, laumontite, mordenite, and phillipsite.
More than 150 zeolites have been synthesized; the most common are zeolites A, X, Y, and ZMS-
5. Natural and synthetic zeolites are used commercially because of their unique adsorption, ion-
exchange, molecular sieve, and catalytic properties.
16.10 Key words
Zeolites as shape selective catalysts; Zeolites; Clays used as catalysts. ; Pillared Clays ;
Decomposition of isopropanol using oxide catalyst; Catalytic converter

Karnataka State Open University Page 298

Homogeneous and Heterogeneous catalysis Block 4.1.4

16.11 References for further studies

1) Homogeneous Catalysis: Mechanisms and Industrial Applications; Sumit Bhaduri, Doble
Mukesh; John Wiley & Sons, 2014.
2) Homogeneous Catalysis with Metal Complexes: Fundamentals and Applications; Gheorghe
Duca; Springer Science & Business Media, 2012.
3) Industrial Catalysis: A Practical Approach; Jens Hagen; John Wiley & Sons, 2015.
4) Handbook of Asymmetric Heterogeneous Catalysis; Kuiling Ding, Yasuhiro Uozumi; John
Wiley & Sons, 2008.
5) Principles and Practice of Heterogeneous Catalysis; John Meurig Thomas, J. M. Thomas, W.
John Thomas; John Wiley & Sons, 2015.
6) Organometallic Chemistry and Catalysis; Didier Astruc; Springer Science & Business Media,
2007.
16.12 Questions for self understanding
1) What are zeolites?
2) Write a note on zeolites as shape selective catalysts
3) Discuss about use of clays as catalysts.
4) What are pillared clays? Explain their uses.
5) Discuss the advantages of pillared clays
6) Explain the process decomposition of isopropanol using oxide catalyst
7) Write a note on catalytic converter

Karnataka State Open University Page 299