Introduction

Phase Transitions” is a topic which has grown up with as early as science. Though the coverage of on
this topic had been associated with transitions between solid, liquid and gas till the mid-20 the
Century, with the development of solid state physics and crystal growth, phase transitions got
predominance. All of the matter that one encounters in daily life is found in one of the three
phases, which are Solid, liquid, or gas. They are important in multiple ways, as to understand why an
ice cube melts , how a refrigerator works, etc. Phase transitions are crucial to understand . It is vital
to gain better knowledge of what phase transitions actually are and why these every day events
occur. Changes in state are called phase transitions. Each of the phase transitions has a technical
name and many have common names. The change from solid to liquid is fusion (or melting).The
change from liquid to solid is solidification (or freezing). The change from liquid to gases
vaporization (or boiling). The change from gas to liquid is condensation. The change from solid to
gas is sublimation. The change from gas to solid is deposition. Temperature T and pressure P
changes cause substances to change state. We can use kinetic molecular theory to understand what
happens on a molecular level when substances undergo phase transitions .

For example, a liquid normally becomes gas upon heating to its Boiling Point physically resulting in
an abrupt change in its VOLUME. In the diagram below are changes taking place in matter.

The figure shows the phase transition of solid to liquid to gas.

 What is Phase

It is the state in which the matter can exist . In physical sense , phase is a set of a macroscopic
physical system that have relatively uniform chemical composition and physical properties ( like
density, crystal structure, refractive index etc). Most familiar examples of phases are : solid , liquid,
and gases and less familiar phases include plasmas .Phases are sometimes called as “states of
matter”.

What is phase transition

Phase transition is a qualitative change in the state of a system under continuous change in
parameters.

From thermodyanamical point of view, phase transition is change in the state from one phase to
another phase of matter where the defining characteristic of phase transition is change in one or
more physical properties with an infinitesimal change in temperature and pressure .A simple
example is the water changing from liquid to solid when the temperature drops below the freezing
point, water changing from liquid to gas above boiling point and likewise the different phase
transitions in matter is shown schematically in figure.

Thi
s diagram shows the nomenclature for the different phase
transitions.
, Similarly, dry ice to liquid co2 gas, graphite transforming to diamond .

Phase transition can occur in exotic forms that are very similar to liquid - solid transitions but do not
occur as obviously. for example, above curie temperature , a magnetic field ceases to remain
magnetic . The substance changes from ferromagnetic to paramagnetic substance above the critical
temperature i.e. above curie temperature

In crystallography, phase transitions are the transitions between two different solid phases of same
material . for example, SiO2 , it is the mineral beta- cristobalite, on reducing temperature slowly
and allowing it to stay in equilibrium , the material changes its structure forming beta-tridymite .

Classification of phase transitions

The classification of general types of transition between phases of matter , introduced by Paul
Ehrenfest in 1993 , lies at a crossroads in the thermodynamically study of critical phenomena . It
arose following the discovery in 1932 of a surprising new phase transition in liquid Helium, the
lambda transition . when “ W.H .Keesom and co-workers in lieden , Holland observed a lambda
shaped( jump) discontinuity in the curve giving the temperature dependence of the specific heat of
helium at a critical value. This apparent jump led Ehrenfest to introduce a classification of phase
transitions on the basis of derivatives of the free energy function.
Ehrenfest classification
Paul Ehrenfest classified phase transitions based on the behaviour of the thermodynamic free
energy as a function of other thermodynamic variables .Under this scheme, phase transitions
were labeled by the lowest derivative of the free energy that is discontinuous at the
transition. First-order phase transitions exhibit a discontinuity in the first derivative of the free
energy with respect to some thermodynamic variables .The various solid/liquid/gas transitions
are classified as first-order transitions because they involve a discontinuous change in density,
which is the (inverse of the) first derivative of the free energy with respect to pressure. Second-
order phase transitions are continuous in the first derivative (the order parameter, which is the
first derivative of the free energy with respect to the external field, is continuous across the
transition) but exhibit discontinuity in a second derivative of the free energy .These include the
ferromagnetic phase transition in materials such as iron, where the magnetization, which is the
first derivative of the free energy with respect to the applied magnetic field strength, increases
continuously from zero as the temperature is lowered below the Curie temperature.
The magnetic susceptibility, the second derivative of the free energy with the field, changes
discontinuously. Under the Ehrenfest classification scheme, there could in principle be third,
fourth, and higher-order phase transitions.
The Ehrenfest classification implicitly allows for continuous phase transformations, where the
bonding character of a material changes, but there is no discontinuity in any free energy
derivative. An example of this occurs at the supercritical liquid–gas boundaries.

Modern classifications
In the modern classification scheme, phase transitions are divided into two broad categories,
named similarly to the Ehrenfest classes

 FIRST ORDER PHASE TRANSITION

 SECOND ORDER PHASE TRANSITION

FIRST ORDER PHASE TRANSITION :

First order phase transition is the phase transition in which the free energy is continuous(but can have
kinks ) , 1st order derivative of free energy is discontinuous as shown in figure below and the 2 nd
order derivative of free energy diverges at transition point. Typically we say that the first order phase
transition is associated with the discontinuity in the entropy as in figure. So, first order transitions
have discontinuities in the first derivatives of G:

(∂G/ ∂T) p = −S ; (∂G/ ∂p) T = V.

First order transitions are therefore discontinuous.

For example, entropy of liquid is greater than that of solid. The latent heat is proportional to

this entropy( L = T ∆S).

During such a transition, a system either absorbs or releases a fixed (and typically large) amount
of energy per volume. During this process, the temperature of the system will stay constant as
heat is added: the system is in a "mixed-phase regime" in which some parts of the system have
completed the transition and others have not.  Familiar examples are the melting of ice or the
boiling of water (the water does not instantly turn into vapour, but forms a turbulent mixture of
liquid water and vapour bubbles).

The figure shows the continuity of free energy and discontinuity of the first order derivative of free
energy at the transition point.
SECOND ORDER PHASE TRANSITION:

The phase transition in which the free energy is continuous (without kinks) and the first order
derivative of free energy is also continuous (can have some kinks) and second order derivative is
discontinuous.

(∂ 2G/ ∂T2) p = − cp T , ( ∂ 2G/ ∂p2 ) T = −V κT

, ( ∂ 2G /∂T ∂p) = V βp
Second order transitions are examples of continuous transitions.  Second order phase transitions are
also called "continuous phase transitions". They are characterized by a divergent susceptibility.
Examples of second-order phase transitions are the ferromagnetic transition, superconducting
transition (for a Type-I superconductor the phase transition is second-order at zero external field
and for a Type-II superconductor the phase transition is second-order for both normal-state–
mixed-state and mixed-state–superconducting-state transitions) and the super fluid transition.
The liquid–glass transition is observed in many polymers and other liquids that can be super
cooled far below the melting point of the crystalline phase. This is a typical in several respects. It
is not a transition between thermodynamic ground states: it is widely believed that the true
ground state is always crystalline. Glass is a quenched disorder state, and its entropy, density,
and so on, depend on the thermal history. Therefore, the glass transition is primarily a dynamic
phenomenon: on cooling a liquid, internal degrees of freedom successively fall out of equilibrium.
Some theoretical methods predict an underlying phase transition in the hypothetical limit of
infinitely long relaxation times. No direct experimental evidence supports the existence of these
transitions.
The gelation transition of colloidal particles has been shown to be a second-order phase
transition under non equilibrium conditions .
Unlike 1st order phase transition where entropy is discontinuous the 2 nd order phase transition is
associated with the continuity in the entropy with discontinuity in the specific heat as shown in
figure:
So 2nd in order phase transition

1) G (T, P) continuous;
2) S (T, P) and V (T, P) continuous;
3) The discontinuities in the second order derivative of G(T, P, N) leads to discontinuities of the
response functions
CP = T (∂S/ ∂T) P = −T (∂2G/ ∂T2) P

κT = − 1/ V (∂V/ ∂P ) T = − 1 /V (∂2G /∂P2 ) T

α = 1 V (∂V/ ∂T) = 1 V (∂2G/ ∂T∂P)

(Susceptibilities) across the transition, CP is specific heat at constant pressure. κT is the isothermal
compressibility, α the thermal expansion coefficient, and dG = −SdT + V dP + µdN.

Specific heat jump: Phase transitions of the second order show a finite discontinuity in the
specific heat CH termed as specific heat jump. An example is the transition to a superconducting
state at zero magnetic fields H.
The entropy for a continuous transition. In this case we find:
(i) S continuous ⇒ no latent heat

(ii) ∃ critical point Tc;

(iii) singularities in CV , κT , Χt

Now,

The Ehrenfest classification has proven to be useful for the classification of the first observed phase
transitions such as the magnetic transitions, and the solid/liquid/gas ones. However, this
classification is not powerful enough to account for more complicated transitions such as the
superconducting, BKT, or topological phase transitions which show more subtle features (non-trivial
behaviour of correlation length, phase stiffness, robust ground state degeneracy...), hence the need
for a new classification method.