PH2610A/34

Royal Holloway and Bedford New College 2002

UNIVERSITY OF LONDON
BSc and MSci EXAMINATION 2002
For Internal Students of
Royal Holloway
DO NOT TURN OVER UNTIL TOLD TO BEGIN
PH2610A: CLASSICAL AND STATISTICAL THERMODYNAMICS
Time Allowed: TWO hours
Answer QUESTION ONE and TWO other questions
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 are permitted
GENERAL PHYSICAL CONSTANTS
Permeability of vacuum
0
= 4 10
-7
H m
-1
Permittivity of vacuum
0
= 8.85 10
-12
F m
-1
1/4
0
= 9.0 10
9
m F
-1
Speed of light in vacuum c = 3.00 10
8
m s
-1
Elementary charge e = 1.60 10
-19
C
Electron (rest) mass m
e
= 9.11 10
-31
kg
Unified atomic mass constant m
u
= 1.66 10
-27
kg
Proton rest mass m
p
= 1.67 10
-27
kg
Neutron rest mass m
n
= 1.67 10
-27
kg
Ratio of electronic charge to mass e/m
e
= 1.76 10
11
C kg
-1
Planck constant h = 6.63 10
-34
J s
h = h/2
= 1.05 10
-34
J s
Boltzmann constant k = 1.38 10
-23
J K
-1
Stefan-Boltzmann constant

= 5.67 10
-8
W m
-2
K
-4
Gas constant R = 8.31 J mol
-1
K
-1
Avogadro constant N
A
= 6.02 10
23
mol
-1
Gravitational constant G = 6.67 10
-11
N m
2
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
m
3
One standard atmosphere P
0
= 1.01 10
5
N m
-2
MATHEMATICAL CONSTANTS
e 2.718 3.142 log
e
10 2.303
page 1 PH2610A
PART
MARKS
TURN OVER
ANSWER ONLY FIVE sections of Question One.
You are advised not to spend more than 40 minutes answering Question One.
1. (a) Calculate the change in entropy when 1 cm
3
of ice melts at 0 C. How is
this change understood microscopically?
[The latent heat of melting of water is 3.35 10
5
J kg
1
]
[4]
(b)
The equation of state of a solid is p V V T ( )
0
where V
0
is the volume
under zero external pressure and is a constant (a property of the solid).
Show that the work that must be done to compress the solid from volume
V
0
to volume V at constant temperature is
W T V V
1
2 0
2
( )
[4]
(c) Show that the fractional difference in the number of spin up and spin
down protons in a patients body when placed in the magnet of a
Magnetic Resonance Imaging scanner at magnetic field of 1 T is
7 10
6
.
[The magnetic moment of the proton = 14.1 10
27
J T
1
]
[4]
(d) Find the minimum power consumption of a heat pump, which maintains
the temperature of a building constant at 20C, against a heat loss of
10kW, when the outside temperature is 5C.
[4]
(e) Explain why the heat capacity of a degenerate Fermi gas is much less than
the value calculated for a gas the same density treated classically.
[4]
(f) Explain why the melting temperature of ice decreases with increasing
pressure.
[4]
page 2 PH2610A
PART
MARKS
TURN OVER
2. (a) Write down the Boltzmann distribution function for a system of N
identical localised particles, explaining the symbols used. [3]
(b) If each particle has three possible energy levels t , 0, write down the
single particle partition function, z.
[3]
(c)
If / k
B
1 K, determine the fraction of particles in the lowest energy
level at 0.5 K.
[3]
(d)
What are the populations of the energy levels when k T
B
>> ? Using the
Boltzmann-Planck definition of entropy, evaluate the entropy of the
system in this limit. [4]
(e) Show that in general the internal energy, E, is related to the single particle
partition function for a localised system, by the relation

z
z
N z
N E
n 1
Hence find an expression for the temperature dependence of the internal
energy in this case, and the value of E in the limits k T
B
<< and
k T
B
>> . Sketch the behaviour of E/N as a function of temperature.
[4]
(f) How can the theoretical heat capacity be determined from this expression
for the internal energy? Briefly discuss qualitatively the temperature
dependence you expect. Explain how experimental data for the heat
capacity should be processed in order to confirm the theoretical limiting
high temperature entropy discussed in (d) [3]
page 3 PH2610A
PART
MARKS
TURN OVER
3. (a) Discuss fully the distinguishing features of bosons and fermions, and give
examples of each.
[5]
(b) State the particle distribution function for bosons and fermions, defining
the symbols used.
[3]
(c) Describe the phenomenon of Bose-Einstein condensation (BEC) in a gas
of non-interacting massive bosons, outlining why it occurs. Include an
explanation of why, below the temperature for BEC, the chemical
potential is zero to a good approximation. [5]
(d) Discuss the conditions under which classical statistics break down and
quantum statistics must be used. [4]
(e) In the first observation of BEC in
87
Rb gas, a sample of order 10
3
atoms
was confined to a sphere of diameter 10 m. Make an order of magnitude
estimate of the required temperature. [3]
4. (a) State and briefly discuss the significance of the first, second and third
laws of thermodynamics. [5]
(b) The Helmholtz free energy F is defined as F E TS . Give one example
of its significance. [2]
(c) By taking the differential of F (T,V), prove the Maxwell relation
V T
T
p
V
S

,
_

,
_

[5]
(d) By considering entropy as a function of T and V, or otherwise, show that
the molar entropy difference of two states for an ideal gas is given by
S T V S T V C
T
T
R
V
V
V
( , ) ( , ) ln ln
1 1 2 2
1
2
1
2
+
[5]
(e) Hence show from the above expression for the entropy of an ideal gas, or
otherwise, that TV const

1
. in an adiabatic reversible expansion, where
C C
p V
/ . You may assume the result C C R
p V
, where C
v
and C
p
are the molar heat capacities at constant volume and constant pressure
respectively.
[3]
page 4 PH2610A
PART
MARKS
END JS
5. (a) Explain why the internal energy remains constant in the adiabatic free
expansion of a gas. Explain also why an ideal gas shows no cooling, but
that a real gas will cool. Why does an ideal gas cool when it expands
adiabatically pushing back a piston? [5]
(b) In a Joule-Kelvin expansion, a gas is expanded adiabatically from initial
pressure p
1
to final pressure p
2
through a porous plug. Prove that the
enthalpy pV E H + is constant in this process. What is meant by the
term inversion temperature applied to the Joule-Kelvin expansion of a
real gas. [5]
(c) Returning to the adiabatic free expansion show that
1
1
]
1

,
_

,
_

,
_

P
T
P
T
C V
E
C V
T
V
v
T
v
E
1 1
You may assume the Maxwell relation given in part (c) of question 4
without proof. [5]
(d) Assuming the equation of state one mole of a real gas to be given by the
simple virial expansion
2
) ( 1
V
T B
V RT
p
+
find an expression for . For argon at room temperature dB/dT = 0.25 cm
3
mol
1
K
1
. Calculate the temperature drop when the volume of one mole
at STP is doubled.
[5]