UNIVERSITY OF LONDON

MSci EXAMINATION 2008

For Students of the

University of London

DO NOT TURN OVER UNTIL TOLD TO BEGIN

PH4211A: STATISTICAL MECHANICS

Time Allowed: TWO AND A HALF hours

Answer THREE questions only.

No credit will be given for attempting any further questions.

Approximate part-marks for questions are given in the right-hand margin

Only CASIO fx85WA Calculators or CASIO fx85MS Calculators are permitted

PH4211A/100

© Royal Holloway and Bedford New College 2008

2007 - 08
GENERAL PHYSICAL CONSTANTS

Permeability of vacuum µ0 = 4π × 10-7 H m-1

Permittivity of vacuum ε0 = 8.85 × 10-12 F m-1
1/4πε0 = 9.0 × 109 m F-1
Speed of light in vacuum c = 3.00 × 108 m s-1
Elementary charge e = 1.60 × 10-19 C
Electron (rest) mass me = 9.11 × 10-31 kg
Unified atomic mass constant mu = 1.66 × 10-27 kg
Proton rest mass mp = 1.67 × 10-27 kg
Neutron rest mass mn = 1.67 × 10-27 kg
Ratio of electronic charge to mass e/me = 1.76 × 1011 C kg-1
Planck constant h = 6.63 × 10-34 Js
! = h/2π = 1.05 × 10-34 Js
Boltzmann constant k = 1.38 × 10-23 J K-1
Stefan-Boltzmann constant σ = 5.67 × 10-8 W m-2 K-4
Gas constant R = 8.31 J mol-1 K-1
Avogadro constant NA = 6.02 × 1023 mol-1
Gravitational constant G = 6.67 × 10-11 N m2 kg-2
Acceleration due to gravity g = 9.81 m s-2
Volume of one mole of an ideal gas at STP = 2.24 × 10-2 m3
One standard atmosphere P0 = 1.01 × 105 N m-2

MATHEMATICAL CONSTANTS

e ≅ 2.718 π ≅ 3.142 loge10 ≅ 2.303

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PART
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1. The Helmholtz free energy F for a binary alloy of two atomic species A
and B with relative proportions x and 1 − x is shown in the figure, at low
temperatures.

0 x 1
(a) The equilibrium state in this case is found by the double tangent
construction. In other systems the equilibrium state is found at the
minimum of the free energy curve. Explain the distinction and the [4]
circumstances in which each procedure is used.

(b) The free energy of mixing Fm for this system is given by

Fm = Nk ⎡⎣2Tc x (1 − x ) + T {x ln x + (1 − x ) ln (1 − x )}⎤⎦ .

Identify the energy and the entropy terms and explain the structure of this
equation. What is Tc?

Sketch the form of Fm as a function of x for high and low temperatures.

[4]
Why is Fm more convenient than F for the double tangent construction?

(c) Show that the phase separation, or binodal, curve is given by

2 (1 − 2 x )
Tps = Tc .
ln ( (1 − x ) x )
[4]
Sketch and label this curve.

(d) By reference to the phase separation curve, explain what happens as one
cools through the phase separation transition. [4]

(e) How would one determine the order parameter critical exponent β from
the phase separation curve? What value is predicted by the result in (c),
and what value is found experimentally? Discuss the difference. [4]

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2. (a) Write down the virial expansion for the equation of state of a non-ideal
gas. Under what circumstances would an expansion up to only the second
virial coefficient be appropriate? [3]

(b) A gas of particles interacts with a square-well potential

U (r ) = ∞ 0< r <σ
= −ε σ < r < ασ
=0 ασ < r < ∞.

Sketch this and explain the significance of the parameter σ, ε and α. [3]

(c) The second virial coefficient for a gas interacting with a potential U(r) is
given by
∞

( )
B2 (T ) = −2π ∫ r 2 e −U ( r ) kT − 1 dr .
0

Show that for a square-well gas B2 is given by

2
{ (
B2 (t) = πσ 3 1− α 3 − 1 eε
3
)( kT
−1 .)} [6]

In the limit that the range of the interaction becomes very large, while the
depth of the attractive potential becomes very small, show that B2 takes
the form

2 ⎛ α 3ε ⎞
B2 (T ) = πσ 3 ⎜1 − ⎟.
3 ⎝ kT ⎠ [3]

Continued over

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Measurements of B2(T) for argon are plotted (as a function of inverse

temperature) in the figure below.
8.0
6.0
4.0
B2(T ) × 1029 in m3
2.0

0.0
–2.0

–4.0
–6.0

–8.0

–10.0

–12.0
0.000 0.001 0.002 0.003 0.004 0.005 0.006
–1
1/T in K
What can you deduce, from this, about the inter-atomic interaction
potential of argon? [5]

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3. (a) Give a statement of the Third Law of Thermodynamics. [3]

Discuss the microscopic origin of this law, paying particular attention to

the question of the degeneracy of the ground state. [4]

(b) Show that the Third Law requires the heat capacity of bodies to go to zero
as temperature T → 0. The equipartition theorem implies a constant heat
capacity. Explain the reason for this contradiction. [3]

(c) By writing the heat capacity (at constant volume) as CV = TdS/dT, where S
is the entropy, show that a constant heat capacity implies S varying as the
logarithm of T. What would this imply about the T → 0 entropy? [3]

Explain how this result may be understood in terms of the accessible

regions of phase space. Then show how the incorporation of Quantum
Mechanics recovers the Third Law of Thermodynamics. [3]

(d) It is sometimes stated that the Third Law of Thermodynamics implies the
un-attainability of Absolute Zero. Show how a hypothetical system,
violating the Third Law, can be used to reduce the temperature to T = 0 in
a finite number of steps. Show how this is no longer possible if the system [4]
obeys the Third Law.

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4. (a) The Ising model and the Heisenberg model are both models of
ferromagnetism. In one case the transition corresponds to the breaking of
a discrete symmetry, while in the other it corresponds to the breaking of a
continuous symmetry. Explain this distinction, with particular reference to
the nature of the order parameter of each model. [4]

(b) The essential qualitative features of these transitions are accounted for by
the free energy

⎧⎪⎛ T ⎞ 1 ⎫⎪
F = const × ⎨⎜ − 1⎟ ϕ 2 + ϕ 4 ⎬ .
⎪⎩⎝ Tc ⎠ 6 ⎪⎭

(i) Sketch this free energy for different values of T/Tc, indicating how the
system evolves as the transition proceeds.

(ii) What is the significance of Tc? [4]

(c) How is the free energy expression above modified in the presence of an
applied magnetic field? [2]

(d) In the presence of an applied magnetic field one model exhibits hysteretic
behaviour and the other does not. Explain this difference, particularly
considering the fact that the free energy expression is formally the same
for the two cases. [6]

(e) Explain, in principle, with the aid of diagrams, how one determines the
limits of stability or the spinodal points in the hysteretic case. [4]

5. Write an essay on the Landau theory of phase transitions. You should

include a discussion of: how this provides a common description of phase
transition phenomena; the central assumptions of the theory; the
application to both second order and first order transitions; and the [20]
limitations of the theory.

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