University of Illinois at Chicago

Department of Physics

Thermodynamics and Statistical Physics

Qualifying Exam

January ?, 2012
9:00am-12:00pm

Full credit can be achieved from completely correct answers to

4 questions. If the student attempts all 5 questions, all of the
answers will be graded, and the top 4 scores will be counted
towards the exams total score.
 Mathematical Formulae

Notation:
1
kBT
z
erfz 2

0 dx expx 2 erf is known as the error function

erfcz 2

z dx expx 2 erfc is known as the complimentary error function

Integrals:
dx ln x x ln x x
dx ln x
x

b dx expax 2 1 erfc a b
2 a

0 dx erfcx 1 expa
a 2
a erfca

n
0 dx x 1/2 expx 2
erf n n expn
n
0 x 3/2 expx 3 erf n 1 n expn3 2n
4 2

Expansions:
1 1 x x 2 x 3 for x 1
1x
2 3
expx 1 x x x
2! 3!
erfcx expx 2 1 for x
x
sinhx x . . . for x 0
coshx 1 . . . for x 0
 Problem 1
Consider a system consisting of N non-interacting particles each with isospin I 3/2. The
energies of the states with different I z are given by
EI z 3/2 E 1 ; EI z 1/2 E 2
EI z 1/2 E 3 ; EI z 3/2 E 3
with E 1 E 2 E 3 and 12 E 2 E 1 23 E 3 E 2 .
a) Without using the partition function, give the value of the total energy, E, at
temperatures T 0, 12 T 23 , and 23 T. Provide a justification for your results.
Sketch E as a function of temperature.
b) What is the occupation of the I z -states for temperature T Without using the
partition function, give a value of the specific heat for temperature T ? Provide a
justification for your results.
c) Without using the partition function, give the value of the average isospin per particle,
I z , at temperatures T 0, 12 T 23 , and 23 T. Provide a justification for your
results. Sketch I z as a function of temperature.
d) Using the partition function, compute the average isospin per particle, I z , in the limit
T . How does you result relate to those in part c)?

Solutions:
a) At T 0, all particles are in the ground state, and hence E NE 1 . For
12 T 23 , the two lowest states are equally populated, while the two higher energy
states are empty, and thus E NE 1 E 2 /2. For 23 T, all states are equally populated,
and hence E NE 1 E 2 2E 3 /4.

b) For T , all I z -states are equally populated with N/4 particles being in each of these
four states. Hence, by increasing temperature, no more energy can be stored in the system, and
hence C 0 as T .

c) At T 0, all particles are in the ground state, and hence I z 3N/2. For
12 T 23 , the two lowest states are equally populated, while the two higher energy
states are empty, and thus I z N/23/2 1/2 N. For 23 T, all states are equally
populated, and hence I z 0.

d) The partition function is given by

Z e E 1 e E 2 2e E 3
and hence
I z N 3 e E 1 1 e E 2 1 e E 3 3 e E 3
Z 2 2 2 2
E 2 E 1
2 2 e
3 1
2 e E 3 E 1
1 3
e E 3 E 1
N 2
1 e E 2 E 1 2e E 3 E 1
0
since 0.This agrees with the result in c).
 Problem 2
Consider an ideal gas of N 0 non-interacting spin-less particles each with kinetic energy
mv
2
2
that is contained in a box. The temperature of the gas is T, and the particles are uniformly
distributed throughout the box.
a) What is the normalized velocity distribution of the gas?
b) What is the total energy, E 0 E of all particles in the box?
c) Instantaneously remove all particles from the gas that possess a kinetic energy larger
than nk B T (n is an arbitrary real, positive number). How many particles remain in terms of N 0 ?
What is the new total energy, E new in terms of E 0 ? After the remaining particles have returned
to equilibrium, what is the new temperature, T new of the gas in terms of T? For which n does
one obtain T new T/2?

Solutions:

a)
3/2 2
Pv m exp m v
2k B T 2k B T
b) Due to the equipartition theorem
m v 3 k B T
2
2 2
and hence
E 0 E 3 Nk B T
2

c)We instantaneously removed all particles with a kinetic energy

kin 1 mv 2 nk B T
2

The number of remaining particle, N new , is given by

3/2

2
N new N 0 m d 3 v exp mv
2k B T 2k B T
3/2 vc
4 dv v 2 exp mv
2
N0 m
2k B T 0 2k B T
where

vc 2nk B T
m
I next perform the variable transformation
 2 2k B Tx dv
x mv dx mv dv m m
2mx dv
2k B T kBT kBT kBT
and thus
3/2 n
N new N 0 m
2k B T
4 k B T
2m
0 dx 2kmB T x 1/2 expx
n
N0 2 dx x 1/2 expx
0

N0 2 erf n n expn
2

Next, we compute the remaining energy that is contained in the system after the particles
are removed.
3/2

2
E new N 0 m d 3 v 1 mv 2 exp mv
2k B T 2 2k B T
3/2
N0 m m 4 v c dv v 4 exp mv 2
2k B T 2 0 2k B T
I next perform the variable transformation
2 2k B Tx dv
x mv dx mv dv m m
2mx dv
2k B T kBT kBT kBT
and thus
3/2 2
E new N 0 m m 4 k B T n dx 2k B T x 3/2 expx
2k B T 2 2m 0 m
n
N 0 2k B T dx x 3/2 expx
0

N 0 k B T 3 erf n 6 n expn 4n 3/2 expn

2

After equilibration, the new temperature is given by

E new 3 N new k B T new
2
or
kBT
N0 3 erf n 6 n expn 4n 3/2 expn
T new n 2 E new 2
2
3 k B N new 3
kBN0 2
2
erf n n expn
3 erf n 6 n expn 4n 3/2 expn
1
T
6 erf n n expn
2
and thus
T new T/2
requires
1 3 erf n 6 n expn 4n expn 1
3/2

6 2
2
erf n n expn
and thus
n 1. 527
 Problem 3

Suppose one mole of an ideal gas is subjected to the cyclic process shown below (with
temperature V 1 , V 2 and V 3 in states 1, 2 and 3, respectively)
p
1
p1

p2 = p3 2
3

V1 = V 3 V2 V

1 2 is an isothermal expansion.
2 3 is an isobaric expansion.
3 1 is an isochoric heating step.
All steps are reversible
a) What is the change in internal energy, U, for the entire cyclic process 1 2 3 1.
b) Use the First Law of Thermodynamics to calculate U, Q, and W for the process
1 2.
c) Use the First Law of Thermodynamics to calculate U, Q, and W for the process
2 3.
d) Use the First Law of Thermodynamics to calculate U, Q, and W for the process
3 1.
e) Is the total work done in a cycle positive or negative? What is the efficiency, , of this
cycle? In which limit does one obtain 1.

Solutions:

a) Since we have carried out a cyclic process, namely 1 2 3 1 we must have

U 0, or
Q 12 W 12 Q 23 W 23 Q 31 W 31 0

b) Since this is an isothermal expansion, we have

U 12 Q 12 W 12 0
and thus
 Q 12 W 12 Nk B T 1 ln V 2
V1

c)
T3
Q 23 T C p dT C p T 3 T 2 0
2
V3
W 23 p 2 dV p 2 V 2 V 3 Nk B T 2 V 2 V 1 Nk B T 1 1 V 1
V2 V2 V2
U 23 Q 23 W 23

d) We have W 31 0 since there is no change in volume, but

T1
Q 31 T C V dT C V T 1 T 3
3

U 31 Q 31

Let us check that

U tot 0
I have
U 12 0
U 23 C p T 3 T 2 Nk B T 1 1 V 1
V2
U 31 C V T 1 T 3
and thus
U tot C p T 3 T 2 Nk B T 1 1 V 1 C V T 1 T 3
V2
5 Nk B T 3 T 1 Nk B T 1 1 V 1 3 Nk B T 1 T 3
2 V2 2
Nk B T 3 Nk B T 1 V 1 Nk B T 3 Nk B T 2 V 3
V2 V2
Nk B T 3 T 2 V 3 p 3 p 2 V 3 0
V3 V2
e) The total work done is
W tot W 12 W 23 W 31 Nk B T 1 ln V 2 Nk B T 1 1 V 1
V1 V2
Nk B T 1 1 V 1 ln V 2 0
V2 V1
Thus the system is performing work.
 The efficiency is defined via
|W tot | Nk B T 1 ln VV 21 1 V1
V2
1 V1
V2
1
Q in Nk B T 1 ln VV 21 ln V2
V1
V1
One obtains 1 for V2
0.
 Problem 4
Consider a system consisting of M non-interacting molecules at temperature T. Each of
these molecules possesses vibrations with energies
En 0 n 1 where n 0, 1, 2, 3, . . . , N 0
2
Let us first consider the case N 0
a) Using the partition function, compute the total energy, E, of the system for temperature
T 0 and T . Explain your results. At what temperature occurs the crossover from the
T 0 to the T behavior of E?
b) Compute n for T . What is the physical interpretation of n? What is the relation
of n to the partition function and to E?
c) Consider next the case where N 0 is a finite, integer number (i.e., N 0 ). What is now
the form of E for temperature T ?
d) Compute the specific heat, C V , of the system in the limit T for the two cases
N 0 and N 0 . Explain the difference in C V between these two cases.

Solutions:
a) Since the molecules do not interact with each other, the partition function of a single
molecule is

0
Z1 exp 0 n 1
2
exp
2 exp 0 n
n0 n0
0 1 1
exp
2 1 exp 0 exp
0
exp 2 0
2

1
0
2 sinh 2
The partition function of the entire system is then
ZM ZM M 1
1 2 M 0
sinh 2
The average energy is given by
0
cosh
E ln Z M M 1 M 0 2
Z 1 2 sinh 0 2Z 1 2 sinh 2 0
2 2
0 0
M 2 sinh
0 0 cosh 2
M 0
cosh 2
2 2 2 sinh 2 0 2 sinh 0
2 2

M 0 1
2 tanh 0
2
For T 0, we expand E in the limit which yields
1 M 0
E M 0
2 tanh 0 2
2
 Hence each molecule has the energy 2 0 associated with the zero-point fluctuations.
For T , we expand E in the limit 0 which yields

1 cosh 2 0 exp 2 0 exp 2 0
E M 0
M 0
M 0
2 tanh 0 2 sinh 0 2 exp 0 exp 0
2 2 2 2

M 0
2 M Mk B T
2 2 0
2
This is the classical result expected from the equipartition theorem. The crossover between

these two limits occurs at 2 0 1.

b) We have
E M 0 n 1 M kBT
2
and thus
k T
n 1 B
2 0
kBT
and hence for 0
1, I obtain
k T
n B
0
The excitation of each quantum n of oscillation requires the energy 0 .

c)
In this case, we have
n0
N0
0 n 12 exp 0 n 1
n0
N0
0 n 12 exp 0 n
E 2

n0
N0
exp 0 n 12 n0
N0
exp 0 n
n0
N0
0 n 1
0 1 N 0 1 N 0 N 0 1
2

n0
N0
1 N0 1 2 2

0 1 N 0
2

Or Alternatively,
 N0 N0
0
Z1 exp 0 n 1
2
exp
2
exp 0 n
n0 n0

0
exp
2
exp 0 n
exp 0 n
n0 nN 0 1

0
exp 1 exp 0 nN 0 1
2 1 exp 0 n0
0 1 exp 0 N 0 1 1 expN 0 1 0
exp
2 1 exp 0 2 sinh
0
2
The partition function of the entire system is then
ZM ZM 1
The average energy is given by
1 expN 0 1 0
E ln Z M M
Z 1
2 sinh 2 0
0 0
M N 0 1 0 expN 0 1 0 sinh 2 0 1 expN 0 1 0 cosh

2 2
2Z 1 sinh 2 2 0
0
M N 0 1 0 expN 0 1 0 sinh 1 expN 0 1 0 cosh
1expN 0 1 0
2
2 0
2 0
sinh 2
2 sinh 2

0
M 0 N 0 1 expN 0 1 0 sinh 1 expN 0 1 0 cos
2
1 expN 0 1 0 sinh
0
2
0 N 1 expN 0 1 0
M 0 coth 2 0
2 2 1 expN 0 1 0
0 N 0 1
M 0 1 coth
2 2 1 expN 0 1 0
and for 0 I obtain
1 N 0 1
E M 0
0 1 1 N 0 1 0 12 N 0 1 2 0 2

1 N 0 1
M 0
0 1 1 N 0 1 0 12 N 0 1 2 0 2

M 0 1 1 1
0 1 1
N 0 1 0
2

M 0 1 N 0 1
2
 d) N 0
E
CV Mk B T Mk B
T T

N0
E
CV 0
T

For N 0 the number of quanta one can excite is not bounded, and one can therefore
increase the energy of the system with increasing temperature. For N 0 this is not possible,
hence there is an upper bound for the energy stored in the system, and hence C V has to go to
zero for T
 Problem 5

Consider a monoatomic ideal gas.

a) What is the internal energy and the equation of state of an ideal gas?
b) Compute the entropy of an ideal gas as a function of T and V for constant particle
number N starting from
dU TdS pdV
c) Compute the chemical potential of the ideal gas as a function of p and T starting from
the Gibbs-Duhem relation
SdT Vdp Nd 0

Solutions:

a) What is the internal energy and the equation of state of an ideal gas?
U 3 Nk B T; pV Nk B T
2
b) Compute the entropy of an ideal gas as a function of T and V for constant particle
number N starting from
dU TdS pdV
We start from
p
dS dU dV 3 Nk B dT Nk B dV
T T 2 T V
We can now integrate the above expression from a state with entropy S 0 at T 0 and V 0 to obtain
3/2
ST, V S 0 T 0 , V 0 3 Nk B ln T Nk B ln V Nk B ln T V
2 T0 V0 T0 V0
c) Compute the chemical potential of the ideal gas as a function of p and T starting from
the Gibbs-Duhem relation
SdT Vdp Nd 0
Thus
d S dT V dp
N N
Using next
ST, V S 0 T 0 , V 0 3 Nk B ln T Nk B ln V
2 T0 V0
5/2 3/2
T V T p0
Nk B ln Nk B ln p
T0 V0 T0
and
V NkpB T
I obtain
 5/2
1 S T , V k B ln T p0 dp
d dT k B T p
N 0 0 0 T0 p
and by integrating
T p dp
T, p T 0 , p 0 dT 1 S 0 T 0 , V 0 k B 5 ln T p0 k B T
T0 N 2 T0 p p0
p

T T 0 S 0 T 0 , V 0 5 k B T ln T T T 0 ln T 0 T 0 T T 0 ln T 0 k B T ln p 0
p
N 2
T T 0 S 0 T 0 , V 0 5 k B T ln T 5 k B T T 0 k B T ln p 0
p
N 2 T0 2