Chapter 4 Phase Transitions

4.1 Phenomenology
4.1.1 Basic ideas

Partition function ?!?!

Thermodynamic limit

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4.1.2 Phase diagrams

p
p
critical

S+G
point
solid
G
S
liquid
L
S+L

L+G triple
point
G
gas
S+G T
T
V is the extensive variable
V
P V T system

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 B

critical point
up
T
down
phase boundary

M is the extensive variable

magnetic system

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4.1.3 Symmetry

• Crystal Translational symmetry

• Ferromagnet Rotational (time reversal) symmetry
• Ferroelectric Inversion symmetry
• Superfluid Gauge symmetry

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4.1.4 Order of phase transitions (1st use of the word "order")

G phase 1

kink in G at transition

phase 2
actual state:
minimum G

1/T
Fig. 4.5 Variation of Gibbs free energy for two phases

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4.1.5 The order parameter (2nd use of the word "order")

System Order parameter

● Ferromagnet magnetisation M vector
● Ferroelectric polarisation along P Scalar !!!
displacement axis
● Fluid density difference (n – nc) real scalar
● Superfluid 4He ground state Ψ0 complex scalar
wavefunction
● Superconductor pair wavefunction Ψs complex scalar
● Ising Ising ‘magnetisation’ m real scalar
● Binary alloy species concentration x real scalar

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In terms of the order parameter . . . . . order order!

Order parameter in first and second order transitions

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4.1.6 Conserved and non-conserved order parameters

System Order Section

parameter
● Ferromagnet magnetisation M non-cons. 4.3
● Ferroelectric polarisation P non-cons. 4.6
● Fluid density (n – nc) conserved 4.2
difference
● Superfluid 4He ground state Ψ0 non-cons.
wavefunction
● Superconductor pair Ψs non-cons.
wavefunction
● Ising Ising m non-cons. 4.4
‘magnetisation’
● Binary alloy species x conserved 4.7
concentration

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4.1.7 Critical exponents
In terms of the reduced temperature
T − Tc
t=
Tc
they are defined (using the ferromagnet variables for example) through
−α
heat capacity C~ t
β
order parameter M ~ t
−γ
susceptibility χ ~ t
1δ
equation of state at Tc M~ B
There are two more critical exponents, which are connected with the
spatial variation of fluctuations in the order as the critical point is
approached…………

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The spatial correlation function for the order parameter is written as
M ( r ) M ( 0 ) ~ r − p e− r l
where M (in the ferromagnetic case) is the magnetisation per unit
volume. From this we obtain two more exponents, ν and η. These
describe the divergence in the correlation length l and the power law
decay p that remains at t = 0, when l has diverged. The exponents are
defined through

−ν
correlation length l~ t
power law decay at Tc p = d − 2 + η

where d is the dimensionality of the system.

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4.1.8 Scaling theory

γ = ν ( 2 −η ) Fisher law
α + 2β + γ = 2 Rushbrooke law
γ = β (δ −1) Widom law
ν d = 2 −α Josephson law

The experimental verification of these results is strong evidence in

favour of the scaling hypothesis. Thus it would appear that the
correlation length is the only length of importance in the vicinity of the
critical point. A consequence of the hypothesis is that only two critical
exponents need be calculated for a specific system. Note the Josephson
law is the only one to make explicit mention of the spatial
dimensionality d.

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4.2 First order transition – an example
4.2.1 Coexistence
p

critical
point

liquid - gas
coexistence gas
liquid

V
Coexistence region, showing p-V isotherms for liquid–gas system

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 F

F1
phase 1
F0 (liquid)
F′

F2

phase 2
(gas)

v1 v0 v2 v
volume per particle
Helmholtz free energy curve

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Thus if a fraction α1 of the particles is in regions of specific volume v1
and a fraction α2 = 1 – α1 in regions of specific volume v2 then

v1α1 + v2α 2 = v0
so that the fractions are given by

v2 − v0 v0 − v1
α1 = , α2 =
v2 − v1 v2 − v1 .

Then the free energy of the inhomogeneous system will be given by

F = α1F1 + α 2 F2
v2 F1 − v1F2 F1 − F2
= − v0 .
v2 − v1 v2 − v1

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 F fraction fraction
α2 α1

phase 1 this would be the

single-phase state
(liquid)

this is a point of
lower F made up
from fraction α1 of
phase 1 and fraction phase 2
α2 = 1 - α1 of phase 2 (gas)

v1 v0 v2 v
volume per particle

Double tangent construction for phase coexistence

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 dF = − SdT − pdV

so that

∂F
p=−
∂V T ;

equality of pressure.

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4.2.2 Van der Waals fluid

⎛ aN 2 ⎞ critical
⎜ p + 2 ⎟ (V − Nb ) = NkT point
⎝ V ⎠
liquid

gas
forbidden
region
superheated supercooled V
liquid gas

Isotherms of the van der Waals equation

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4.2.3 The Maxwell construction
Vb
∂F
Fb = Fa + ∫ dV
Va
∂V T
Vb

= Fa − ∫ p dV.
Va

Integral independent
of path:
Vb Vb

∫ p dV = ∫ p dV.
Va Va

so that
Vb Vb

∫ p dV = 0,
Va
∴ ∫ p dV = 0.
Va

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4.2.4 The critical point

∂p ∂2 p
=0 and =0
∂V T ∂V T
2 .

a 8a
Vc = 3Nb, pc = , kTc =
27b 2
27b .

-- Elegant derivation of Stanley.

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4.2.5 Corresponding states

V p T
v= , π= , t=
Vc pc Tc

then the van der Waals equation takes on the universal form:

⎛ 3 ⎞⎛ 1 ⎞ 8t
⎜ π + 2 ⎟⎜ v − ⎟ = .
⎝ v ⎠⎝ 3⎠ 3

‘Critical compressibility ratio’ zc = pcVc / NkTc is predicted to have the

universal value 3/8 = 0.375 for all liquid–gas systems.

4
He Ne A Kr Xe N2 O2 CO CH4
pcVc/NkTc 0.308 0.305 0.290 0.291 0.290 0.291 0.292 0.294 0.290

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 1.00
gas liquid
T/Tc

0.90

0.80
Ne
A
Kr
0.70 Xe
N2
O2
CO
CH4
0.60

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6
c

Liquid - gas coexistence

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Guggenheim’s formula
Solid line
1/3

4( Tc ) 4( Tc )
ρl − ρc 7 T 3 T
= 1− + 1−
ρc Order parameter
1/3

critical exponent

ρc − ρg
4( Tc ) 4( Tc )
7 T 3 T β = 1/3
= 1− − 1−
ρc

From van der Waals equation (Maxwell construction)

Dashed line
1/2

( Tc ) 5( Tc )
ρl − ρc T 2 T
= 2 1− + 1− +…
ρc
Order parameter
1/2 critical exponent

ρc − ρg
( Tc ) 5( Tc )
T 2 T
= 2 1− − 1− +… β = 1/2
ρc

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4.2.7 Quantum mechanical effects
1.00
gas liquid
T/Tc

0.90

0.80 3
He
4
He
Ne
A
Kr
0.70 Xe
N2
O2
CO
CH4
0.60

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6
c

Liquid - gas coexistence including data for helium

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 2π
Λ=!
mkT .
Here m is the mass of the particles. This shows how Λ increases when m
is small. At the critical temperature we can write Λ as
3 6π
Λc = !
4 mε
where ε is the energy parameter of the Lennard Jones potential, since
16
kTc = ε .
27
Then the ratio Λc/σ compares the thermal deBroglie wavelength with
the interparticle spacing; σ is the length parameter of the Lennard Jones
potential. We tabulate values of this ratio:
3
He 4He Ne A Kr Xe N2 O2
Λc/σ 1.595 1.388 0.307 0.096 0.053 0.033 0.119 0.103

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