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Unit I Molecular spectroscopy and Phase diagrams

Contents

Contents

1. Molecular Spectroscopy: Introduction

i) Electromagnetic spectrum

ii) Quantization of Energy

iii) Born-Oppenheimer approximation

2. Rotational Spectroscopy

3. IR Spectroscopy

4. Electronic spectroscopy

2. Phase Equilibria

1. Introduction and important terminology

a. Chemical potential (µ) in Phase equilibrium

b. Phase, Components, and Degrees of freedom

2. Statement and Derivation of Gibb’s phase rule

3. Phase diagram of one component system- e.g. : water system

4. Phase diagram of one component system- e.g. : carbon dioxide system

5. Phase diagram of two-component system- e.g. Pb-Ag system, Pattinson’s process

6. Construction of phase diagram using cooling curves , Fe-C system

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Unit I Molecular spectroscopy and Phase diagrams

1. Introduction to Molecular spectroscopy

Molecular spectroscopy refers to the field of looking at molecules using
electromagnetic radiation. This technique is used both to detect and to manipulate and
understand molecules. The information obtained from molecular spectroscopy relates to the
energy levels and the shapes and charge densities of molecules. There are a few generic
concepts and principles for all spectroscopy that we list below:
1. The energy of a molecule can be thought of as composed of different parts: Rotational
Energy, Vibrational Energy and Electronic Energy. The energy spacing between
rotational levels is smaller than that between vibrational levels which is smaller than
that between Electronic levels.
2. The Electromagnetic spectrum can be thought of as divided into different regions
based on the wavelength/frequency/energy of the light source used. The table below
lists these energies and the transitions that are probed by these energies.
3. When light of a certain wavelength falls on a molecule, then the molecule will absorb
light and go to an excited state such that the difference in energy between the ground
state and the excited state is hc/λ, where λ is the wavelength of the light used.
Alternatively, the molecule may emit light of a particular wavelength by going from
the higher energy state to the lower energy state.

This condition is used to predict the wavelength of absorption of light.

hc /  = E = hc = h

Where  and  are frequency and wave number respectively

In addition to the energy and frequency criterion, there are some other conditions that
are necessary in order for light to be absorbed. These refer to the symmetry of the molecule
and the wave functions involved. They are referred to as selection rules. There are two kinds
of selection rules - gross selection rules and specific selection rules for each type of transition.
These rules can be developed using quantum mechanics supplemented with the quantum
mechanical theory of interaction of radiation with matter.

The absorption spectrum refers to the absorption of light of different

energies/wavelengths/frequencies/wave numbers. Alternatively, there is also a possibility of
stimulated emission, wherein light of a certain energy stimulates a transition of the same
energy. We can think of a tunable light source which impinges on the sample and the
transmitted/scattered light is collected by a detector.
Name of light Frequency(Hz) Motions of the molecules
Microwave 109 -1013 Rotations
Infrared 1013-1014 Vibrations
Visible and Ultraviolet(UV-Vis) 1014 − 1016 Electronic Transitions

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Unit I Molecular spectroscopy and Phase diagrams

Electromagnetic radiation

Spectroscopy: Spectroscopy is that branch of science which deals with the study of
interaction of electromagnetic radiations with matter.

General Properties of all electromagnetic radiation: Electromagnetic radiation can travel

through empty space. Most other types of waves must travel through some sort of substance.
For example, sound waves need either a gas, solid, or liquid to pass through in order to be
heard. The speed of light is always a constant. (Speed of light : 2.99792458 x 10 8 m s-1).
Wavelengths are measured between the distances of either crests or troughs. It is usually
characterized by the Greek symbol λ. The term electromagnetic radiation represents the
radiant energy emitted from any source in the form of light, heat etc. Some important
characteristics of these electromagnetic radiations are given below:
1. They have dual character i.e. particle character as well as wave character. For
example, a beam of light is a stream of particles called photons moving through the space in
the form of waves.

2. These waves are associated with electric and magnetic fields oscillating
perpendicular to each other and also perpendicular to the direction of propagation.

All electromagnetic radiations travel with the velocity of light

Energy of electromagnetic radiation is given by E = hν where E is energy, h is Planck's

constant, (h = 6.625 x 10-34 Js), and ν is frequency

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Unit I Molecular spectroscopy and Phase diagrams

Wavelength is related to frequency by C = λν Where, c is the speed of light, λ is

wavelength, and ν is frequency. Wave number is related to wavelength by

1 
= , sin nce  = Therefore E = hc
 c

i) Electromagnetic spectrum:

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Unit I Molecular spectroscopy and Phase diagrams

Information obtained from different regions of electromagnetic spectrum

https://openstax.org/books/chemistry-2e/pages/6-1-electromagnetic-energy

ii) Quantization of Energy:

A molecule in space can have many sorts of energy, e.g., it may possess rotational energy
by virtue of bodily rotation about its center of gravity; it will have vibrational energy due
to the periodic displacement of its atoms from their equilibrium positions; it will have
electronic energy since the electrons associated with each atom or bond are in unceasing
motion, etc.
The chemist or physicist is early familiar with the electronic energy states of an atom or
molecule and accepts the idea that an electron can exist in one of several discrete energy
levels: he learns to speak of the energy as being quantized. In much the same way the
rotational, vibrational, and other energies of a molecule are also quantized - a particular
molecule can exist in variety of rotational, vibrational, etc., energy levels and can move
from one level to another only by sudden jump involving a finite amount of energy.
• The energy levels are quantized.

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Unit I Molecular spectroscopy and Phase diagrams

• The frequency of light absorbed when there is a transition between two energy levels
is the difference in energy between the two energy levels.
• When the molecule absorbs energy and moves from lower energy level to higher
energy level absorption spectrum is observed.
• Similarly emission spectrum arises when molecule comes from higher energy level to
lower energy level.

E = E2 − E1 = h

Difference between atomic spectra and molecular spectra

Sl.No. Atomic spectra Molecular spectra

1 The outer most electrons occupy one The outer most electrons occupy s, π or n
of the atomic orbitals and have its electronic energy levels in ground state.
energy levels [K, L, M, N]

2 Upon excitation electrons are Upon excitation electrons are raised to π, π*

promoted to the higher atomic energy or σ, σ* molecular orbital’s.
levels.

3 Since there are no bonds there are no Since there are bonds, there are vibrational
vibrational or rotational energy levels and rotational energy levels in both the
in either ground or excited state. ground and excited states.

4 The spectra are line spectra. The spectra are band spectra due to the
presence very close unresolved vibrational
and rotational energy levels in the excited
state.

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Unit I Molecular spectroscopy and Phase diagrams

iii) Born-Oppenheimer approximation:

According to Born-Oppenheimer approximation, the total energy of a molecule is the sum of

translational, rotational, vibrational and electronic energies, i.e.
Etotal = Etranslation + Erotation + Evibration + Eelectronic
It is found that the translational energy is negligibly small. Hence Born-Oppenheimer
approximation can be written as
Etotal = Erotation + Evibration + Eelectronic
This implies that the electronic, vibrational and rotational energies of a molecule are
completely independent of each other.

A change in the total energy of a molecule may then be written :

Etotal = Eelec. + Evib + Erot J
Or  total =  elec. +  vib +  rot cm −1

The approximate orders of magnitude of these changes are

 elec.   vib 10 3   rot 10 6

Energy level diagram for a diatomic molecule:

Types of Molecular Spectra

1. Pure rotational (Microwave) spectra.
2. Vibrational rotational spectra
3. Electronic Band Spectra.
4. Raman Spectra.
5. Nuclear Magnetic Resonance (NMR)
6. Electron Spin Resonance (ESR) Spectra.

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Unit I Molecular spectroscopy and Phase diagrams

2. Rotational spectroscopy
Free atoms do not rotate or vibrate. For an oscillatory or a rotational motion of a
pendulum, one end has to be tied or fixed to some point. In molecules such a fixed point is the
center of mass. The atoms in a molecule are held together by chemical bonds. The rotational
and vibrational energies are usually much smaller than the energies required breaking
chemical bonds. The rotational energies correspond to the microwave region of
electromagnetic radiation (3x1010 to 3x1012 Hz; energy range around 10 to100 J/mol) and
the vibrational energies are in the infrared region (3x10 12 to 3x1014 Hz; energy range around
10kJ/mol) of the electromagnetic radiation. For rigid rotors (no vibration during rotation)
and harmonic oscillators (wherein there are equal displacements of atoms on either side of
the center of mass) there are simple formulae characterizing the molecular energy levels. In
real life, molecules rotate and vibrate simultaneously and high speed rotations affect
vibrations and vice versa. However, in our introductory view of spectroscopy we will simplify
the picture as much as possible. We will first take up rotational spectroscopy of diatomic
molecules.
A molecule undergoing rotation absorbs in the MW region.
➢ For a molecule to be rotationally active (MW active) the molecule has to possess a
dipole moment.
➢ As a dipolar molecule rotates, the rotating dipole constitutes the transition dipole
operator μ.
➢ Rotations of a molecule having permanent dipole moment will cause changes in
electric dipoles that will interact with the electrical component of the electromagnetic
radiation.
➢ When the frequencies match, resonance occurs and the molecule absorbs energy and
goes to the higher rotational levels and exhibits rotational spectrum.
➢ Molecules such as HCl and CO will show rotational spectra while H 2, Cl2 and CO2 will
not.

The rotation of a polar diatomic molecule HCl, showing the fluctuation in the dipole
moment measured in a particular direction
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Unit I Molecular spectroscopy and Phase diagrams

An electromagnetic wave is an oscillating electrical field and interacts only with molecules
that can undergo a change in dipole moment. The oscillating dipole can be provided by the
rotation of a permanent dipole like for example HCl. This type of interaction leads to
microwave spectra.

Changes in the y-component of the dipole moment due to rotation of water

molecule

The asymmetric stretching vibration of the CO 2 molecule, showing the fluctuation in

the dipole moment

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Unit I Molecular spectroscopy and Phase diagrams

The bending motion of the carbon dioxide molecule and its associated dipole
fluctuation
In the above diagrams, one bond stretches while other is compressed and vice versa. As the
figure shows, there is a periodic alteration in the dipole moment, and the vibration is infrared
active. Further vibration is allowed to this molecule is known as the bending mode is also
infra-red active. In both the cases during motions center of gravity does not move.

Derivation of Moment of Inertia for a diatomic molecule-rigid rotor model:

A rigid diatomic with masses m 1 and m2 joined by a thin rod of length r o = r1 + r2 .The centre
of mass is at C.
The two independent rotations of this molecule are with respect to the two axes which pass
though C and are perpendicular to the “bond length” r. The rotation with respect to the bond
axis is possible only for “classical” objects with large masses. For quantum objects, a
“rotation” with respect to the molecular axis does not correspond to any change in the
molecule as the new configuration is indistinguishable from the old one. The center of mass is
defined by equating the moments on both segments of the molecular axis.

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The center of mass is defined by equating the moments on both segments of the molecular
axis
m1r1 = m2r2
The moment of inertial about C is defined by:

I = m1r1 + m2 r2
2 2

I = m2 r2 r1 + m1r1r2

I = r1 r2 (m1 + m2 )

m1 r1 + m2 r2 = m2 (ro − r1 )

m2 ro m1 ro
Therefore, r1 = and r2 =
m1 + m2 m1 + m2

m1 m2 2
I= ro = ro
2

m1 + m2

m1 m2
Where  = and  is called reduced mass of the system.
m1 + m2

The rotation of a diatomic is equivalent to a “rotation” of a mass μ at a distance of r from

the origin C. The kinetic energy of this rotational motion is K.E. = L 2/2I where L is the angular
momentum, Iω where ω is the angular (rotational) velocity in radians/sec.

𝐼𝜔2 𝐿2
Rotational energy 𝐸𝑟 = = 𝑆𝑖𝑛𝑐𝑒 𝐿 = 𝐼𝜔
2 2𝐼

Solving the Schrodinger equation for a rigid rotor shows that angular momentum is
quantized and is given by, L=√𝐽(𝐽 + 1) where J is the rotational quantum number. The
quantity J which can take integral values from zero upwards J=0,1,2,3...... Hence the rotational
energy levels are quantized and given by the expression,

ℎ2
𝐸𝐽 = 𝐽(𝐽 + 1) 𝐽𝑜𝑢𝑙𝑒𝑠
8𝜋 2 𝐼

ℎ = 𝑃𝑙𝑎𝑛𝑐𝑘𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 = 6.626𝑥10−34 𝐽 𝑎𝑛𝑑 𝐼 𝑖𝑠 𝑚𝑜𝑚𝑒𝑛𝑡 𝑜𝑓 𝑖𝑛𝑒𝑟𝑡𝑖𝑎

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Unit I Molecular spectroscopy and Phase diagrams

The energy differences between two rotational levels are usually expressed in cm -1. The wave
number corresponding to a given ∆E is given by ν = ∆E /hc, cm -1. The energy levels in cm-1 are
therefore

E J
J = = BJ ( J + 1) cm-1
hc

ℎ
𝑊ℎ𝑒𝑟𝑒 𝐵 = 2
𝐶𝑚−1
8𝜋 𝐼𝑐

The selection rule for rotational transitions for a rigid rotor is, Δ J = ± 1.

For rotational transition of molecule from level J to J+1 the energy absorbed is given by (in
cm-1),
 J →J +1 = = 2B( J + 1) cm−1

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Unit I Molecular spectroscopy and Phase diagrams

The first line in the spectrum appears at 2B cm -1 and the distance between any two
consecutive lines is constant and is equals to 2B cm -1

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Unit I Molecular spectroscopy and Phase diagrams

ROTATIONAL SELECTION RULES ∆J = ±1

➢ A molecule must have a transitional dipole moment that is in resonance with an
electromagnetic field for rotational spectroscopy to be used. Polar molecules have a
dipole moment.
➢ A transitional dipole moment not equal to zero is possible.
➢ Only transitions are permitted in which there is an increase or decrease by unity in the
rotational quantum number. It means that J=0 to J=2 transitions are not possible.
➢ In contrast, no rotational spectra are displayed by homonuclear diatomics; the same is
true for spherical tops.
➢ Nevertheless, certain states of a such molecules allow unexpected interactions with
the electromagnetic field; i.e. some vibrations, that introduce a time-dependent dipole
moment high rotational speeds that cause some distortion of an originally spherical
symmetry.
➢ A (weak) dipole moment emerges.
➢ The conservation of the angular momentum is fundamental for the selection rules that
allow or prohibit transitions of a linear molecule:
➢ In addition to this requirement, the molecule has to possess a dipole moment. As a
dipolar molecule rotates, the rotating dipole constitutes a transition dipole operator μ.
Molecules such as HCl and CO will show rotational spectra while H 2, Cl2 & CO2 will not.

➢ Let us apply the equation to the observed microwave spectrum of the molecule to
calculate its moment of inertia and hence the bond length. The first line corresponding
to J=0 appears in the rotational spectrum of Carbon monoxide at 3.84235 cm -1
C=12.0000 amu, O= 15.9949amu.

➢ Calculate the value of I and r of CO. B = 1.92118 cm-1.

h 6.626 10 −34
I = 2 =
8 Bc 8  ( 3.1415) 2  1.92118  31010 (Solution)
I =1.45579 10 −46 kgm 2

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Unit I Molecular spectroscopy and Phase diagrams

Since the value of B is in cm-1, the velocity of light c is taken in cm/s. I = r . the atomic mass
2

of C= 12.000 amu, O= 15.9994 amu. 1mu = 1.6604 x 10 -27kg. The reduced mass of CO can be
calculated to be 1.13836 x 10-27kg.

I1.45579 10 −46

r = =
2

Therefore  1.13826 10 −27


or r =1.131 

3. Vibrational-Rotational (IR) spectroscopy

When system’s molecular vibrations involve dipole moment changes, dipole-
oscillators are going to form. These oscillators send EM waves to the space with certain
frequency. External EM radiation with identical frequency supply system enough energy to
generate a vibrational quantum jump of the system.
When a molecule undergoes vibrational changes it absorbs IR radiation. For a
molecule to be vibrationally active (IR active) the vibration of a molecule must be associated
with change in dipole moment. Vibrations of molecules can result in changes in electric
dipoles that could interact with the electrical component of the electromagnetic radiation.
When the frequencies match, resonance occurs and the molecule absorbs energy and goes to
the higher vibrational levels and exhibits vibrational spectrum. Molecules such as HCl, CO and
H2O will show vibrational spectra while H2, Cl2 will not.
CO2 molecule although does not possess permanent dipole moment is IR active because
some of its vibrational modes are IR active: Symmetric stretch is IR inactive

CO2 asymmetric stretch

is IR active

The asymmetric stretching vibration of the CO 2 molecule, showing the fluctuation in

the dipole moment

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Unit I Molecular spectroscopy and Phase diagrams

CO2 Bending mode is IR active

Bending motion of the carbon dioxide molecule and its associated dipole fluctuation.

CO2 molecule although does not possess permanent dipole moment is IR active because some
of its vibrational modes are IR active:

Vibrational modes of CO2

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H2O

Changes in the y-component of the dipole moment due to vibration of the water
molecule

In water molecule symmetric, asymmetric and bending vibrations are IR active

Energy of a diatomic molecule

Vibrational spectroscopy of diatomic molecule considered as simple harmonic oscillator.

(SHO Model). Every type of bond in a molecule has a unique natural vibrational frequency.
Therefore the IR spectrum of every molecule is unique as much as the finger print of human
beings.

Spring analogy of a bond vibration

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Unit I Molecular spectroscopy and Phase diagrams

We have seen that the bonds are not static but vibrating in different ways. A vibrating bond
can therefore be considered a spring with its ends tethered to two atoms as shown in the
above figure and obeys Hooke’s law., F = − k (r − req ) 2 Where F is restoring force, k is a force
constant, r is bond length and req is equilibrium internuclear distance.

1
Hence the energy curve is parabolic E = k (r − req ) 2
2
You have noticed in your earlier studies that simple pendulums or stretched strings exhibit
simple harmonic motion about their equilibrium positions. Molecules also exhibit oscillatory
motions. A diatomic oscillates about its equilibrium geometry. The quantized vibration
1
energies Eν of a harmonic oscillator are Ev = (v + )hv
2

The oscillation frequency is given by,

1 k
vosc = Hz
2 
Where μ is reduced mass. Expressing frequency of oscillation in terms of wave number
1 k
vosc = cm−1
2c 
Solving Schrodinger equation for harmonic oscillator shows vibrational energy levels are
quantized and are given by the expression
1
Ev = (v + )hvosc Joules
2
Where v= vibrational quantum number which can take up values zero upwards; v=0,1, 2, 3....
Vibrational energy expressed in terms of wave number is given by,
1
 v = (v + )vosc cm−1
2
The energy levels will appear at, v = 0

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Unit I Molecular spectroscopy and Phase diagrams

1
 o = vosc cm−1
2
This is called zero point energy v = 1
3
1 = vosc cm−1
2
5
v=2,  2 = vosc cm−1
2
The difference between any two consecutive energy levels is equal to
 osc cm−1
Hence the energy levels are equally spaced.
The selection rule for vibrational transition is Δv = ± 1
Therefore transition between any two vibrational levels corresponds to absorption of
frequency
 osc cm−1
Hence only one line is observed in the spectrum at
 osc cm−1
• Why only 1 line is seen in the vibration spectrum of a diatomic molecule?
All Transitions from any V to V+1 are the same. Therefore, the resulting spectrum contains
only one line and its featureless.

Vibrational energy levels diagram for a diatomic molecule executing simple harmonic
oscillation.

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Unit I Molecular spectroscopy and Phase diagrams

1. Anharmonic oscillator model

We have seen several equally spaced lines in SHM (spacing hν) corresponding to the
transitions 0→1, 1→2, 2→3 and so on. The first transition will be the most intense as the
state with v = 0 is the most populated.

In actual diatomics, the potential is an anharmonic in actual diatomics, the potential is

anharmonic because the bond when stretched beyond a point breaks and the molecule
dissociates. Hence anharmonic oscillator model should be used. A good description of an
anharmonic oscillator is given by the Morse function.

P.E. = Deq [1 – exp {a(ro-r }]2

Deq is the depth of the PE curve r0 is the bond length. Solving the Schrodinger equation for
anharmonic oscillator the vibrational energy levels are given by the expression;

Ev 1 1
v = = (v + ) e − (v + ) 2 e xe cm−1
hc 2 2

Here xe , is called the anharmonicity constant whose value is near 0.01.

The spacing between energy levels decreases for larger values of v, the vibrational
quantum number

The selection rule for vibrational transition of anharmonic oscillator is Δv = ± 1, ±2, ±3.........

All transitions start from v = 0 level because this state is most populated.

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2. Vibrational spectrum

First line in the spectrum is called fundamental frequency and corresponds to transition
from v = 0 to v = 1. The energy absorbed is given by,

1→0 = ve (1 − 2 xe ) cm−1

Second line is called first overtone and corresponds to transition from v=0 to v=2. The
energy absorbed is given by,

 2→0 = 2ve (1 − 3xe ) cm−1

Third line is called second overtone and corresponds to transition from v=0 to v=3. The
energy absorbed is given by,

 3→0 = 3ve (1 − 4 xe ) cm−1

The spacing between the lines in the spectrum decreases as we go to higher values of v. At
higher temperatures additional lines are visible in the spectrum as higher vibrational levels
may also get populated and these lines originating from the higher vibrational levels are
called hot bands. Ex: Energy absorbed for the transition from v=1 to v=2 is given by

 2→1 = ve (1 − 4 xe ) cm−1

Vibrational transitions for diatomic molecule undergoing anharmonic oscillations

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Unit I Molecular spectroscopy and Phase diagrams

4. Electronic spectroscopy

According to Born-Oppenheimer approximation, the total energy of a molecule is the sum of

translational, rotational, vibrational and electronic energies, i.e.

Etotal = Etranslation + Erotation + Evibration + Eelectronic

Which implies that the electronic, vibrational and rotational energies of a molecules are
completely independent of each other. The change in total energy of the molecule is given by

ETotal = ERot + EVib + EElec

ERot  EVib  EElec

Hence vibrational changes will produce “coarse structure” and rotational changes will
produce “fine structure” in the electronic spectra of molecules. Information about vibrational
and rotational structure of homonuclear molecule can be obtained from their electronic
spectra.

The ground state energy levels are denoted by Ɛ” and v”, while the excited state energy levels
are denoted by Ɛ’ and v’. There are no selection rules for vibrational transitions during
electronic transition. Most of the transitions start from v”= 0 as It is most populated level.
The lines in the resulting spectrum are denoted by (v’,v”). The resulting spectrum is called
progression. The lines converge at higher energy levels showing anharmonicity in the excited
electronic state.

The vibrational coarse structure of the bond formed during electronic absorption from
the ground (ν"=0) state to a higher state
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Unit I Molecular spectroscopy and Phase diagrams

Franck-Condon principle:

All lines in the spectra are not of the same intensity though no selection rule for vibrational
transitions exists. The excited state usually has longer internuclear distance because of
antibonding character. The transitions arise from the centre of v’=0 because the maximum
probability of finding the nuclei is at the centre of v”=0.

“An electronic transition takes place so rapidly that a vibrating molecule does not
change its internuclear distance appreciably during the transition” This implies that the
electronic transitions are always vertical transitions

Probability distribution for a diatomic molecule according to quantum theory

Intensity of vibrational-electronic spectra:

Three possibilities of vibrational - electronic

transitions exist- ( re” and re’ are internuclear
distances of the ground and excited states
respectively)
No change in internuclear distance r”e = r’e The
spectrum shows maximum intensity for (0,0) line
and intensity falls for the remaining lines as in fig.

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Unit I Molecular spectroscopy and Phase diagrams

Internuclear distance of excited state is more than that of ground state re” < re’

The spectrum shows maximum intensity for (v’,0)

line where v’ is the vibrational level in the excited
state to which electronic transition takes place.

Internuclear distance of excited state is considerably greater than that of ground state re”<<
re’ .

The spectrum shows continuum since the

transition results in the molecule going
beyond dissociation energy. The molecule
dissociates into atoms which gain kinetic
energy. Since this energy is not quantized a
continuum is seen in the spectrum.

• After studying molecular spectroscopy, you will be able to Calculate the bond lengths
of diatomics from the value of their rotational constant.
• Outline the selection rules for rotational and vibrational spectra and rationalize the
role of the molecular dipole moment in the selection rules.
• Distinguish between the energy levels of a rigid and a non rigid rotor.
• Distinguish between harmonic and anharmonic vibrations.
• Sketch qualitatively rotational-vibrational spectrum of a diatomic.
• Calculate the relative populations of rotational and vibrational energy levels.
• Identify the IR frequencies where simple functional groups absorb light.

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Raman Spectroscopy:

• scattering of light
• When monochromatic radiation is passed through a transparent medium:
• Most of the scattered radiation consists of radiation of incident wavelength –
Rayleigh scattering
• Some of the scattered radiation consists of radiation with different wavelength
from incident wavelength – Raman scattering
• When the wavelength of scattered radiation is more than that of incident radiation
– Stokes lines
• When the wavelength of scattered radiation is less than that of incident radiation –
anti -Stokes lines

• Exchange of energy between the molecules and radiation

• Homonuclear diatomic molecules which are microwave and Infra-red inactive are Raman
active.

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2. Phase Equilibria
Introduction and important terminology:
Statement:

The Gibb’s phase rule

The phase rule states that, provided the equilibrium in a heterogeneous system phase is
not influenced by gravity, or electrical, or magnetic forces, or by surface action but are
influenced only by temperature, pressure and concentration, then the number of
degrees of freedom (F) of the system is related to the number of components (C ) and
number of phases (P) by the following phase rule equation

F=C –P+2

Explanation of terms:

Phase (P): A phase is defined as “any homogeneous, physically distinct and mechanically
separable portion of the system, which is separated from other such parts of the system
by definite boundary surfaces”.

Examples

1. Liquid phase: The number of liquid phases depends on the number of liquids present
andtheir miscibility.
i) If two liquids are immiscible, they will form two separate liquid phases. Example:
benzeneand water
ii)If two liquids are miscible they will form one liquid phase
only.Example: alcohol and water
2. Solid phase: Each solid forms a separate phase. The number of solid phases depends on
the number of solids present in it. Example: Many forms of sulphur can exist together,
but these are all separate phases.
3. Gaseous phase: Since gaseous mixtures are thoroughly miscible in all proportions, it
will form one phase only.
i) Example: a mixture of N2 and H2 forms one phase only.
ii) A solution of a substance in a solvent consists of one phase only, e.g. glucose solution.
iii)A heterogeneous mixture like: CaO(s)+CO2(g) CaO(s)+CO2(g)
It consists of three phases ( i.e., two solids and one gaseous).
iv) At freezing point, water consists of three phases:
Ice (s) Water (l) Water
vapour(g)
v)A homogeneous solid solution of a salt forms a single phase. Example: Mohr’s salt
[ FeSO4. (NH4)2SO4.6H2O] solution has a single phase.

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Component (C): Component is defined as “the smallest number of independently variable

constituents, by means of which the composition of each phase can be expressed in the
form of a chemical equation”.

Example: i) In the water system,

Ice(s) Water(l) Water vapour(g)

The chemical component of all the three phases is H2O and therefore it is one
component system.
ii) Sulphur exists in four phases namely rhombic, monoclinic, liquid and vapour, but the
chemical composition of all phases is S. Thus is a one component system.
iii) A system of saturated solution of NaCl consists of solid salt, salt solution and water
vapour. The chemical composition of all the three phases can be expressed in terms of
NaCl and H2O. Therefore it is a two component system.
iv) In the thermal decomposition of
CaCO3(s) CaO(s)+ CO2(g)
The composition of each of the three phases can be expressed in terms of at least any two
of the independent variable constituents, CaCO3, CaO and CO2. Suppose CaCO3 and CaO are
chosen as the two components, then the composition of different phases is represented as
follows:

Phase : CaCO3= CaCO3 + 0CaO

Phase : CaO = 0CaCO3 + CaO
Phase: CO2= CaCO3– CaO

Thus, it is a two component system.

v) In the dissociation of NH4Cl, the following equilibrium occurs:

NH4Cl(s) NH3(g) + HCl(g)

The system consists of two phases namely solid NH4Cl and the gaseous mixture containing
NH3 + HCl. When NH3 and HCl are present in equivalent quantities the composition of
both the phases can be represented by the same chemical compound NH4Cl and hence
the system will be a one component system. If excess NH3 and HCl are introduced in to the
system, then system will be two component systems

Degree of Freedom:

Degree of freedom is defined as the minimum number of independent variable factors such
as temperature, pressure and concentration of the phases, which must be fixed in order to
define the condition of a system completely.

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A system having 1,2,3 or 0 degrees of freedom is called univariant, bivariant, trivariant

andnonvariant respectively.

Example : i) Consider the water system,

Ice(s) Water(l) Water vapour(g)
The three phases can be in equilibrium only at particular temperature and pressure.
Therefore, when all the three phases are present in equilibrium, then no conditions need
to be specified. The system is therefore zero variant or invariant or has no degree of
freedom.

In this system if pressure or temperature is altered, three phases will not remain in
equilibrium and one of the phases disappears.

ii)Consider a system consisting of water in contact with its vapour,

Water(l) Water vapour(g)

To define this system completely, we must state either the temperature or pressure. Thus
degree of freedom is one and the system is univariant.

iii) For a system consisting of water vapour phase only, we must state the values of both
the temperature and pressure in order to define the system completely. Hence the system
is bivariant or has two degrees of freedom.
iv) For a gaseous mixture of N2 and H2, we must state both the pressure and temperature,
because if pressure and temperature are fixed, the volume automatically becomes definite.
Hence, for a gaseous system, two factors must be stated in order to define it completely and
thus, it has two degrees of freedom or bivariant system.

v)Consider a system consisting of

NaCl(s) NaCl-water(aq) Water vapour(g)

we must state either the temperature or pressure, because the saturation solubility is
fixed at a particular temperature or pressure. Hence the system is univariant.

Merits of the Phase Rule:

1. It is applicable to both physical and chemical equilibria.

2. It requires no information regarding molecular/micro-structure, since it is applicable
to macroscopic systems.
3. It is a convenient method of classifying equilibrium states in terms of phases,
components and degrees of freedom.
4. It helps us to predict the behavior of a system, under different sets of variables.
5. It indicates that different systems with same degree of freedom behave similarly.
6. It helps in deciding whether under a given set of conditions:

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a) Various substances would exist together in equilibrium (or)

b) Some of the substances present would be inter converted (or)
c) Some of the substances present would be eliminated.

Limitations of Phase Rule:

1. It can be applied only for system in equilibrium. Consequently, it is of little value in
caseof very slow equilibrium state attaining system.
2. It applies only to a single equilibrium system; and provides no information regarding
any other possible equilibria in the system.
3. It requires at most care in deciding the number of phases existing in an equilibrium
state, since it considers only the number of phases, rather than their amounts. Thus
even if a trace of phase is present, it accounts towards the total number of phases.
4. It conditions that all phases of the system must be present simultaneously under the
identical conditions of temperature and pressure.
5. It conditions that solid and liquid phases must not be in finely-divided state;
otherwise deviations occurs.

2. Statement and Derivation of Phase Rule:

• The phase rule was given by Williard Gibb's in 1876 is based on the principles of
thermodynamics. It is a mathematical equation that relates the number of degrees
of freedom, components and phases.
• It describes the mathematical relationship for determining the stability of the
phases present in material at equilibrium condition.
• Degrees of the freedom of the system=Total number of independent variables.
• Mathematically it is stated as “for a heterogeneous system in equilibrium, the
number of phases (P) plus the number of degrees of freedom (F) is equal to the
number of components plus 2”
• We know that in a given phase involving C components at temperature T and
pressure P, the chemical potential is determined by the molar mole fraction of the
component present.
• However, for each phase the sum of mole fraction of all components is unity,
implying that at most C-1 mole fraction can be independent. Therefore, for P phases,
there are atP(C-1) independently variable mole fraction.

.
.

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• However, for each phase the sum of mole fraction of all components is unity,
implying that at most C-1 mole fraction can be independent. Therefore, for P phases,
there are atP(C-1) independently variable mole fraction.

Where μ = Chemical potential

• For the first component chemical potential must be same in every phase

• For the second component chemical potential must be same in every phase

• For the third component chemical potential must be same in every phase

• For the Cth component chemical potential must be same in every phase

Therefore, for C components the total number of equations relating chemical

•
potentials = C(P-1)
• In addition, the temperature and pressure are two intensive variables of the system
• Hence, the total number of independent variable properties of the system =P(C-
1)+2
• However, these P(C-1)+2 variables are related to each other through C(P-1)
equations
Total number of independent intensive variables F
= Total Number of variables – Total Number of equations connecting to the variables
𝐹 = 𝑃(𝐶 − 1) + 2 − 𝐶(𝑃 − 1)
𝐹 =𝐶−𝑃+2
This is the Gibb's phase rule
Uses of Phase diagram

1. From the phase diagram, it is possible to predict whether an eutectic alloy or a

solid solution is formed on cooling a homogeneous liquid containing mixture of two
metals.
2. The phase diagrams are useful in understanding the properties of materials in
theheterogeneous equilibrium system.
3. The study of low melting eutectic alloys, used in soldering, can be carried out
using phase diagrams.

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3. Phase diagram of one component system – e.g. : water system

The water system is a one component system

Ice(s) water(l) water vapour(g)

Since water exists in three possible phases such as solid, liquid and vapour, there are three
forms of equilibria:
➢ Liquid – vapour
➢ solid - vapour
➢ solid - liquid
➢ Each equilibrium involves two phases. The nature of these phases which
exist inequilibrium at any time depends on the conditions of temperature and
pressure.

1. Curves : There are three curves

OA, OB and OC.
2. Areas : Three curves OA , OB and
OCdivide the diagram into three
areas AOB, AOC and BOC.
3. Triple point : The above three
curvesmeet at the point O and is
known as triple point.
4. Metastable equilibrium : The
curve OA’ represents the
metastable equilibrium.

1)Curve OA
• The curve OA is called vaporization curve, it represents the equilibrium
betweenwater and vapour. At any point on the curve the following equilibrium
will exist.
water(l) water vapour(g)
• The degree of freedom of the system is one, i.e. univariant. Thus applying phase
rule equation,
F=C–P+2=1–2+2;F=1
• This equilibrium (i.e, line OA) will extend up to the critical temperature (374 0C).
Beyond the critical temperature the equilibrium will disappear only water
vapour willexist at 218.3 atmospheric pressure.
2) Curve OB
• The curve OB is called sublimation curve of ice, it represents the equilibrium
between ice and vapour. At any point on the curve the following equilibrium will
exist.
Ice(s) water vapour(g)

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• The degree of freedom of the system is one, i.e., univariant.

• This is predicted by the phase rule.
F=C–P+2;F=1–2+2;F=1

• This equilibrium line will extend up to the absolute zero (– 2730C ) where no
vapourcan be present and only ice will exist.
2) Curve OC
• The curve OC is called melting point curve of ice, it represents the equilibrium
between ice and water. At any point on the curve the following equilibrium will
exist.

Ice(s) water(l)

• The curve OC is slightly inclined towards pressure axis. This shows that melting
pointof ice decreases with increase of pressure.
• The degree of freedom of the system is one. i.e., univariant.
3) Triple point (Point ‘O’)
• At triple point all the three phases namely ice, water and vapour coexist. Thus the
value of P is 3. Applying phase rule equation, the degree of freedom at this point is
zero. It means that three phases can coexist in equilibrium only at a definite
temperature and pressure. The values are 0.00750C and 4.58 mm respectively.
F=C-P+2; F=1-3+2=0

• At this triple point, neither pressure nor temperature can be altered even slightly
without causing the disappearance of one of the phases. The triple point is not the
same as the ordinary melting point of ice ( i.e, 00C). It’s value has been increased due
to the fact that 00C is the melting point of ice at 760mm of mercury and a decrease of
4.58 mm will rise the melting point to 0.00750C.
4) Curve OA’ (Metastable equilibrium)
• The curve OA’ is called vapour pressure curve of the super-cool water or
metastableequilibrium.
• Where the following equilibrium will exist.

• Sometimes water can be cooled below 0 0C without the formation of ice, this
water is called super-cooled water. Super-cooled water is unstable and it can be
converted into solid by ‘seeding’ or by slight disturbance.
5) Areas
• Area AOC, BOC, AOB represents water, ice and vapour respectively. In order to
define the system at any point in the areas, it is essential to specify both
temperature and pressure. The degree of freedom of the system is two. i.e.,
bivariant.
• This is predicted by the phase rule

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F = C – P + 2; F = 1 – 1 +2 ; F = 2
Clapeyron-Clausius Equation
For fusion of ice, ΔH is +ve, ΔV is –ve [ΔH Enthalpy of fusion is endothermic]

The change in volume is –ve when ice is converting into water, so is –ve, so
melting curve has –ve slope.

4. Phase diagram of one component system., e.g. Carbon dioxide (CO2)

A phase diagram of a substance is a plot of pressure versus temperature for transition
equilibria, viz. solid-liquid, liquid-gas and solid-gas transitions.
The typical phase diagram of CO2 is displayed below:

AB: Sublimation curve

BD: Melting point curve

BC: Vaporization curve

B: Triple Point

C: Critical point

Beyond C: Supercritical Fluid

Sublimation curve AB
• The curve AB is called the sublimation curve. It shows the equilibrium between gaseous
CO2 and solid CO2.
solid CO2 ⇌ gaseous CO2
• variation of sublimation temperature of solid CO 2 with pressure
• Here, the degree of freedom of the system (variance), F=1 (mono variant or univariant
system)
• This is predicted by the phase rule. F = C – P + 2; F = 1 – 2 + 2; F = 1

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•Clausius Clapeyron equation: 𝑑𝑃/𝑑𝑇=∆𝐻𝑠𝑢𝑏/𝑇∆𝑉

•slope is positive
∆𝑉= Increase in volume as solid CO2 sublimes, +𝑣𝑒;
𝛥𝐻𝑠𝑢𝑏𝑙𝑖𝑚𝑎𝑡𝑖𝑜𝑛 = endothermic reaction, +𝑣𝑒

Melting/fusion curve BD
• The curve BD is called melting point curve. It shows the equilibrium between solid CO 2
and liquid CO2
solid CO2 ⇌ liquid CO2
• Here, the degree of freedom of the system (variance), F=1 (mono variant or univariant
system)
•variation of melting/fusion temperature of solid CO 2 with pressure
𝑑𝑃 ∆𝐻𝑓𝑢𝑠𝑖𝑜𝑛
•Clausius Clapeyron equation: 𝑑𝑇
= 𝑇∆𝑉
•slope is positive
∆𝑉= Increase in volume as solid CO2 liquefies, +𝑣𝑒;
𝛥𝐻fusion = endothermic reaction,+𝑣𝑒

Vaporization curve BC
The curve BC is called the vaporization curve. It shows the equilibrium between liquid CO 2
and gaseous CO2
• liquid CO2 ⇌ gaseous CO2
•Here, the degree of freedom of the system (variance), F=1 (mono variant or univariant
system)
•variation of boiling temperature of liquid CO 2 with pressure
𝑑𝑃 ∆𝐻𝑣𝑎𝑝
•Clausius Clapeyron equation: =
𝑑𝑇 𝑇∆𝑉
•slope is positive
Δ𝑉= Increase in volume as liquid CO2 vaporizes, +𝑣𝑒;
𝛥𝐻vaporization = endothermic reaction,+𝑣𝑒

Triple Point (B)

•It represents equilibrium between liquid, vapor and solid CO 2 (dry ice)
•All three phases co-exist simultaneously
• Here, the degree of freedom (variance), F=0, invariant system
•Triple point for CO2 lies at −56.6° C and 5.11 atm i.e. liquid CO 2 cannot exist at pressures
lower than 5.11 atm.

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Note:
• At 1 atm, solid CO2 sublimes directly to vapor instead of melting into a liquid, whilst
preserving a temperature of −78.5°C.
• Thus, solid CO2 is also called “dry ice”. It is a cold solid with no liquid phase observed
when it is warmed.
• This property makes it a useful coolant without using water (generally required for
chilling purposes).

Critical Point (C)

• Represents the maximum temperature and pressure beyond which liquid and vapor
phases
become indistinguishable, i.e. the interface between liquid CO 2 and CO2 (gas) vanishes.
• At such high temperatures, the gas cannot condense back to liquid, no matter how much
pressure is applied.
• Critical point lies at 30.98 0C and 72.79 atm.
• Beyond the critical point, the substance becomes a supercritical fluid.

Supercritical fluid
A supercritical fluid (SCF) is a state of matter of a substance in which the temperature and
pressure are above the critical point, resulting in properties between those of a gas and a
liquid. When applied to the fluid, supercritical refers to a temperature and pressure above
the critical point.
Uses
• Supercritical carbon dioxide is widely used as a solvent for industrial extraction
processes.
• It is widely used for decaffeinating coffee.
• It is widely used as a dry-cleaning solvent.
• It is also used as a natural refrigerant, making it a low carbon (more environmentally
friendly) solution for domestic heat pumps.

5. Condensed Phase rule for two-component system, Phase diagram of two-

component system- e.g. Pb-Ag system, Pattinson’s process:

We know the phase-rule equation,

F=C-P+2 ……… (1)
Two component system
• For a two component system, C = 2 and hence the above equation becomes,
• F = 2 – P + 2 = 4 – P ……… (2)
• The minimum number of phases in any system at equilibrium is one. It is clear
from the equation (2), the maximum number of degree of freedom is three.

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• Thus, three variables – pressure, temperature and composition of one of the

components must be specified to describe the system. This will lead to three
dimensional figures which cannot be conveniently represented on a paper. To
make this simple, one of the three variables is kept constant.
• In solid-liquid equilibrium of an alloy, practically there is no gaseous phase and
the pressure will not have much influence. In the case of solid-liquid equilibrium,
the experiments are generally carried out at constant pressure.
• Thus the system in which only the solid and liquid phases are considered and the
gas phase is ignored is called a condensed system. This reduces the degree of
freedom ofthe system by one. The phase rule equation is then written as
F’ = C – P + 1

• This equation is called reduced phase rule or condensed phase rule. For a two
component system the phase rule equation is written as
F’ = C – P + 1 = 2 – P +1 = 3 – P ……… (4)

• The above equation is known as the reduced form of phase rule for two
component system.
• There are various types of solid-liquid equilibria of which only two of them are
taken here. Those equlibria in which the components are completely miscible
with one another in liquid state. They do not form any compound on
solidification. They give rise to merely an intimate mixture known as eutectic.
• Some examples of this system are
1) lead-silver system
2) Lead-Antimony system
3) Zinc-cadmium system
4) Potassium iodide- water system

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Classification of two component system:

The two component systems are classified into the following three types:

i) Simple eutectic formation

ii) a) Formation of compound with congruent melting point.
b) Formation of compound with incongruent melting point.

iii) Formation of solid solution.

i) Simple eutectic formation:

• A system with two substances which are completely miscible in the liquid state,
but completely immiscible in the solid state is known as eutectic system. In this
system thesubstances do not react chemically.
• Among the mixtures of different proportions of two substances, the mixture which
hasthe lowest melting point is known as the eutectic mixture.
• The temperature and composition corresponding to the eutectic point is called
eutectic temperature and eutectic composition respectively.

Simple eutectic systems:

• The general phase diagram for binary alloy systems is shown in Fig. Here the
pressure does not have the considerable effect. Hence, the other two variables
viz, temperature and compositions are taken into account.
• Components A and B.
When small quantities of B are added to A gradually, the melting point of A falls along
the curve AC. In the same way when small quantities of A are added to B gradually,
the melting point B falls along the curve BC. Hence, AC and BC are the freezing point

curves of A and B respectively

• The curves AC and BC meet at the point C. At this point the three phases solid A,

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solid B and their solution coexist. The degree of freedom is zero here and the
system is therefore invariant. Also only at this point C, the liquid can exist at the
lowest temperature. Since the mixture of components A and B of composition
corresponding to the point C has the lowest melting point, the point C is called
the eutectic point.
• The temperature and composition corresponding to the point C is called eutectic
temperature and eutectic composition respectively.
• Consider a liquid mixture of composition represented by a point alpha cooled at
constant pressure. The temperature falls without any change of composition
until the point beeta on the curve AC is reached. At this temperature t 1, the solid
A will separate out. The system now consists of two phases and hence
monovariant. As cooling continues, the component A keeps on separating out
and the solution becomes relatively richer in B. The temperature and the
solution composition both change along AC.
• Thus at the temperature t1, solid A is in equilibrium with solution of composition
X and at temperature t2, it is in equilibrium with solution of composition Y. It is
clear therefore, in the area ACD, solid A is in equilibrium with solutions of
varying composition given by the curve AC depending upon the temperature.
• When the temperature reaches a point delta represented by, the solid B also
begins to separate out. On further cooling the system, solid A and B separate
out together in constant ratio so that the composition of the solution remains
constant. The temperature also remains constant for some time.
• When the liquid solution has been completely solidified and the system consists
only of a mixture of solid A and B, it becomes monovariant. Further cooling will
result in the fall of temperature below the line DD into the area in which only the
two solids coexist as shown.
• In the same way, if the composition of liquid mixture is on the right of the
eutectic point C, as represented by point beeta, similar series of changes will be
obtained on cooling.
• In the same way, if the composition of liquid mixture is on the right of the
eutectic point C, as represented by point ‘alpha’, similar series of changes will be
obtained oncooling.

Construction of Phase Diagram by Thermal Analysis (or) cooling curve:

• Thermal analysis is a method involving a study of the cooling curves of various
compositions of a system during solidification. The shape of the freezing point
curves for any system, especially those involving metals can be determined by
thermal analysis.
• The data obtained from thermal analysis along with recorded curves are called
as thermogram.
• These thermograms are characteristic of a particular system composed of either
single or multi component materials.
• Thermograms indicate the system in terms of temperature, dependencies of
its thermodynamic properties.

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• Let us discuss in detail the cooling curves or time-temperature curves of some

simple systems.

Example 1 :
a
• If a pure substance say x, in molten state is cooled
slowly and the temperature is noted at different
time interval. The graph plotted between
temperature and time (the cooling curve) will be of
the form shown in Fig.

• In this diagram ‘ab’ denotes the rate of cooling of

molten liquid and the liquid starts solidifying at the
freezing point ‘b’. Now the temperature remains
constant until the liquid melt is completely
solidified. Solidification completes at the point ‘c’.

• The horizontal line ‘bc’ represents the equilibrium

between the solid and liquid melt. After the point
‘c’,the temperature of the solid begins to decrease
alongthe curve ‘cd’.
Example 2 :

• When a molten liquid containing two components

(say A and B) is cooled slowly then the cooling
curve isdifferent and one such curve is shown in
Fig.

• As before, initially the rate of cooling is continuous.

When it reaches the point ‘b’ one substance (either
A or B) begins to solidify out of the melt, which is
Fig shows the cooling curve
indicated by a break and the rate of cooling is
ofa mixture A+B
different.

• On further cooling at the break point ‘c’ the second

compound also begins to solidify. Now the
temperature remains constant until the liquid melt
is completely solidified, which forms the eutectic
mixture (line cd) .

• After the break point ‘d’ cooling of solid mass

begins. The temperature of horizontal line ‘cd’ gives
the eutectic temperature.

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• A number of mixtures of A and B are taken with different composition.

• Each mixture is heated to the molten state and their cooling curves are drawn
separately for each mixture.
• From the cooling curves of various compositions, the main phase diagram can be
drawn by taking the composition in X-axis and temperature in Y-axis.
• Any point on this line indicates the appearance of the solid phase from the liquid.
Thearea above this curve is only liquid phase.

Uses of cooling curves:

• Cooling curves are used to find the percentage purity of the compounds.
• It is used to find the melting point of the compounds
• Thermal analysis is useful in derivation of phase diagram of any two component
system
• Used to find the composition of the alloy.
• Used to analyse the behaviour of the compounds.

Lead-Silver system:
It is a two component system. The two metals are completely miscible in liquid state and do
not form any compound. There is almost no effect of pressure on this system. The
temperature- composition phase diagram is shown in Figure. It contains lines, areas and the
eutectic point.

The curve AC:

• The curve AC is the freezing point curve of pure lead. The melting point of
leaddecreases gradually along the curve AC, with the continuous addition of
silver.
• Thus the curve AC is showing the effect of addition of silver on the melting
point ofpure lead.
• All along the curve AC two phases –solid lead and liquid are in equilibrium.
• According to reduced phase rule equation
F’ = C – P + 1 ; = 2 – 2 + 1 ; = 1 i.e, F’ = 1 i.e., the system is univariant.

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The curve BC:

• Curve BC is the freezing point curve of pure silver and represents the effect of
addition of pure lead on the melting point of pure silver. All along the curve BC
two phases –solid silver and liquid are in equilibrium.

• According to reduced phase rule equation.

• F’ = C – P + 1 ; = 2 – 2 + 1 ; = 1, i.e. F’ = 1 ( The system is univariant )

Point C (Eutectic point):

• Point C is the eutectic point where solid silver, solid lead and their solution
coexist. The curves AC and BC meet at point C. Since the experiment is carried
out at constant pressure, the number of degree of freedom for the system at the
eutectic point C is zero on the basis of reduced phase rule.
F’ = C – P + 1 ; = 2 – 3 + 1 = 0 ; i.e., F’ = 0

• The system is non-variant or invariant. The point C, as can be seen, is the lowest
temperature, at which liquid can exist in equilibrium with the solids, silver and
lead. Since the mixture of silver and lead of composition corresponding to point
C, has the lowest melting point, the point C is known as the eutectic point.
Eutectic composition is 2.6%, silver and 97.4% lead and the corresponding
temperature is 576K.

Areas:

• The area above the line ACB has a single phase (molten Pb + Ag).
• According to reduced phase rule equation,
F’ = C – P + 1 ; = 2 – 1 + 1 = 2 ; i.e., F’ = 2

• The system is bivariant. Both the temperature and composition have to be

specifiedto define the system completely.
• The area below the line AC (solid Ag + liquid melt), below the line BC (solid Pb
+liquidmelt) and below the eutectic point ‘C’ have two phases and the system is
univariant.
• According to reduced phase rule
equation,
F’ = C – P + 1 ; = 2 – 2 + 1 = 1 i.e., F’ = 1

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Application of Pattinson’s process:

• The phase diagram of lead-silver is useful in the extraction of silver from the
argentiferous lead ore which has a very small percentage of silver. This process is
known as Pattinson’s process.
• Let x represent the molten argentiferous (Pb + Ag alloy) lead containing very small
amount of silver in it. It is a homogeneous liquid and on cooling, the temperature falls
but without change in concentration till any point y on the curve AC is reached.
• On further cooling, lead begins to separate out and the solution becomes richer in
silver. Further cooling will shift the system along the line ‘yc’. More of lead separates as
solid till the point C is reached when the percentage of Ag rises to 2.6%. This process of
increasing the relative proportion of silver in the alloy is known as Pattinson’s process
of desilvering of lead.

4. Construction of phase diagram using cooling curves , Fe-C system Uses of Eutectic
system:

1. Eutectic systems are useful in predicting the suitable alloy composition.

2. It is used in the preparation of solders which are used for joining two metal pieces
together.

Iron-Carbon System:

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Unit I Molecular spectroscopy and Phase diagrams

• Allotropy of Iron: Iron exists in three allotropic forms namely, alpha iron (α-Fe), gamma
iron (γ-Fe) and delta iron (δ-Fe).
α-Fe: It is stable below 9100 C and has a bcc structure. It is ferromagnetic but loses this
property at 7230C which is called as curie temperature. It dissolves very little carbon
(0.001%) at room temperature and 0.02% at 7230C.

• The solid solution of carbon in α-Fe is called ferrite.

γ-Fe: At 9100C, changes into another allotrope γ-Fe which is stable up to 14730C. It has a fcc
structure.

• It dissolves relatively high amount of carbon, 0.8% at 723 0C and 1.7% at 11300C. The
solidsolution of carbon in γ-Fe is called austenite. δ-Fe: At 14730C, γ-Fe changes to δ-Fe.
This isstable up to 15500C. It has bcc structure which is similar to that of α-Fe.

• The Fe-C is a two component system involving solid-solid phase transition.

• The phase diagram is a plot of temperature against the amount of C dissolved in

Fe(composition)

• It consists of several areas, lines and points.

Areas: ACB = Liquid only From condensed phase rule these two are
bivariant systems
ADOF = only austenite
• ACD ( liquid and austenite) From condensed phase rule these two are univariant
systems
• BCE (liquid and cementite) two phase system.

Lines:
• Consider the lines AC and BC. Along the line AC, on cooling, the solubility of carbon
increases indicating the transformation δ-Fe into austenite. Along the line BC, the
solubility of carbon decreases.
• The excess carbon that separates combines with iron forming Fe3C. The iron carbide
formed is called cementite.
• Below the lines DCE, the Fe-C system will be in the solid state. As the austenite
phasecools, the structure of iron changes to ferrite.
• Simultaneously the excess carbon is precipitated as cementite. This occurs along the
line DO. Ferrite and cementite crystals grow side by side to give structure of
pearlite; pearlite consists of alternate layers of ferrite and cementite.

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Unit I Molecular spectroscopy and Phase diagrams

Points:

• Point C is called eutectic point. It is a point where austenite, cementite and liquid
are in equilibrium to each other.
• At this point temperature and composition are fixed at 11300C and 95.7% Fe
and 4.3%C respectively.
• From phase rule, system at point C is invariant.
F+P = 3, F= 3-3 =0
• Point O is called the eutectoid point. It is the point where austenite, ferrite and
cementite are in equilibrium with each other.
• At this point temperature and composition are fixed at 7230C and 99.17% Fe
and0.83% C respectively.
• From phase rule, system at point O is invariant.
F+P = 3, F= 3-3 =0
• Point D indicates the maximum solubility of carbon in solid Fe (1.7%).
• Eutectoid point refers to a separation of a solid with a fixed composition at a
fixedtemperature from another solid.

Peritectic point:

Peritectic point: at 0.16% C and 14730 C δ(0.11% C) + L(0.51%C) ↔ γ (0.16%C) at

peritectic point, the liquid and δ iron transforms into austenite (containing 0.16% C). The
peritectic point occurs at a constant temperature. This is known as peritectic
temperature and is 1473°C.

Significance of Iron carbon system:

• It is used tailor properties of steel and to heat treat them.

• It is also used for comparison of crystal structures for metallurgists in case of
ruptureor fatigue

Phase Crystal structure Characteristics

Ferrite BCC Soft, ductile, magnetic

Soft, moderate strength,

non-magnetic
Austenite FCC

Cementite Compound of Iron & Carbon Fe3C Hard &brittle

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Unit I Molecular spectroscopy and Phase diagrams

REFERENCES:

1) Nptel https://nptel.ac.in/content/storage2/courses/122101001/downloads/lec-
22.pdf
2) Banwell C N “Fundamentals of Molecular spectroscopy “4th edition, McGraw Hill
Education (India) 2016.
3) Engineering Chemistry, Chapter 9, by Nityananda Shetty and R V Gadag, Edn 3rd 2014.

45 Department of Science & Humanities (Chemistry) PESU

Phase diagram of one component system., e.g. Carbon dioxide (CO2)
A phase diagram of a substance is a plot of pressure versus temperature for transition equilibria,
viz. solid-liquid, liquid-gas and solid-gas transitions.
The typical phase diagram of CO2 is displayed below:

AB: Sublimation curve

BD: Melting point curve

BC: Vaporization curve

B: Triple Point

C: Critical point

Beyond C: Supercritical Fluid

Sublimation curve AB
• The curve AB is called the sublimation curve. It shows the equilibrium between gaseous CO2 and
solid CO2.
solid CO2 ⇌ gaseous CO2
• variation of sublimation temperature of solid CO2 with pressure
• Here, the degree of freedom of the system (variance), F=1 (mono variant or univariant system)
• This is predicted by the phase rule.
F = C – P + 2; F = 1 – 2 + 2; F = 1
•Clausius Clapeyron equation: 𝑑𝑃/𝑑𝑇=∆𝐻𝑠𝑢𝑏/𝑇∆𝑉
•slope is positive
∆𝑉= Increase in volume as solid CO2 sublimes, +𝑣𝑒;
𝛥𝐻𝑠𝑢𝑏𝑙𝑖𝑚𝑎𝑡𝑖𝑜𝑛 = endothermic reaction, +𝑣𝑒
Melting/fusion curve BD
• The curve BD is called melting point curve. It shows the equilibrium between solid CO2 and
liquid CO2
solid CO2 ⇌ liquid CO2
• Here, the degree of freedom of the system (variance), F=1 (mono variant or univariant system)
•variation of melting/fusion temperature of solid CO2 with pressure
𝑑𝑃 ∆𝐻𝑓𝑢𝑠𝑖𝑜𝑛
•Clausius Clapeyron equation: =
𝑑𝑇 𝑇∆𝑉

•slope is positive
∆𝑉= Increase in volume as solid CO2 liquefies, +𝑣𝑒
𝛥𝐻fusion = endothermic reaction, +𝑣𝑒

Vaporization curve BC
The curve BC is called the vaporization curve. It shows the equilibrium between liquid CO 2 and
gaseous CO2
• liquid CO2 ⇌ gaseous CO2
•Here, the degree of freedom of the system (variance), F=1 (mono variant or univariant system)
•variation of boiling temperature of liquid CO2 with pressure
𝑑𝑃 ∆𝐻𝑣𝑎𝑝
•Clausius Clapeyron equation: =
𝑑𝑇 𝑇∆𝑉

•slope is positive
Δ𝑉= Increase in volume as liquid CO2 vaporizes, +𝑣𝑒
𝛥𝐻vaporization = endothermic reaction, +𝑣𝑒

Triple Point (B)

•It represents equilibrium between liquid, vapor and solid CO2 (dry ice)
•All three phases co-exist simultaneously
• Here, the degree of freedom (variance), F=0, invariant system
•Triple point for CO2 lies at −56.6° C and 5.11 atm i.e. liquid CO2 cannot exist at pressures lower
than 5.11 atm.
Note:
• At 1 atm, solid CO2 sublimes directly to vapor instead of melting into a liquid, whilst preserving
a temperature of −78.5°C.
• Thus, solid CO2 is also called “dry ice”. It is a cold solid with no liquid phase observed when it
is warmed.
• This property makes it a useful coolant without using water (generally required for chilling
purposes).

Critical Point (C)

• Represents the maximum temperature and pressure beyond which liquid and vapor phases
become indistinguishable, i.e. the interface between liquid CO2 and CO2 (gas) vanishes.
• At such high temperatures, the gas cannot condense back to liquid, no matter how much pressure
is applied.
• Critical point lies at 30.98 0C and 72.79 atm.
• Beyond the critical point, the substance becomes a supercritical fluid.

Supercritical fluid
A supercritical fluid (SCF) is a state of matter of a substance in which the temperature and pressure
are above the critical point, resulting in properties between those of a gas and a liquid. When
applied to the fluid, supercritical refers to a temperature and pressure above the critical point.
Uses
• Supercritical carbon dioxide is widely used as a solvent for industrial extraction processes.
• It is widely used for decaffeinating coffee.
• It is widely used as a dry-cleaning solvent.
• It is also used as a natural refrigerant, making it a low carbon (more environmentally friendly)
solution for domestic heat pumps.
Phase diagram of a two-component system
The phase rule equation is F = C – P + 2……… (1)
For a 2- component system, the ordinary phase rule cannot be used.
Two component system
• For a two-component system, C = 2 and hence the above equation becomes,
F = 2 – P + 2 = 4 – P ……… (2)
• The minimum number of phases in any system at equilibrium is one. It is clear from the equation
(2), the maximum number of degrees of freedom is three.
• Thus, three variables – pressure, temperature, and composition of one of the components must
be specified to describe the system. This will lead to three dimensional figures which cannot be
conveniently represented on paper. To make this simple, one of the three variables is kept constant.
• In solid-liquid equilibrium of an alloy, there is practically no gaseous phase, and the pressure will
not have much influence. In the case of solid-liquid equilibrium, experiments are generally carried
out at constant pressure.
• Thus, the system in which only the solid and liquid phases are considered, and the gas phase is
ignored is called a condensed system. This reduces the degree of freedom of the system by one.
The phase rule equation is then written as
F’ = C – P + 1
• This equation is called reduced phase rule or condensed phase rule. For a two-component system
the phase rule equation is written as
F’ = C – P + 1
= 2 – P +1 = 3 – P ……… (3)
•The above equation is known as the reduced form of phase rule for two component system.