Statistical Physics A

winter term 2023-24

Prof. Krzysztof Meissner

Institute of Theoretical Physics, Faculty of Physics, University of Warsaw
Krzysztof.Meissner@fuw.edu.pl

Tutors:
dr Marta Waclawczyk, Marta.Waclawczyk@fuw.edu.pl, Wednesday 08:15-11:00
dr Jeffrey Everts, Jeffrey.Everts@fuw.edu.pl, Wednesday 14:15-17:00

Dates of colloquia and exams:

Colloquium I, 27th November 2023, room B0.14

Colloquium II, 22nd January 2024, room 1.40

Written exam, 6th February 2024, room 0.06

Rules:

• There are 2 colloquia. Each has 3 problems x 5 points=15 points (30 in

total).

• At the end of the semester the tutors give 0–10 points for activity.
• The classes are passed when a student has ≥ 20 points (maybe a little less
will be sufficient).
• Everybody can take the written exam - for those that have less than 20
points, passing the exam is a way to pass classes.
• If someone has < 20 points and does not pass the written exam he/she
will not be classified.
• The written exam has 4 problems x 5 points=20 points.

• Passing the exam requires ≥ 10 points (maybe a little less).

• If someone has ≥ 20 points from classes and does not pass the exam he/she
can still take the oral exam (and the correction exam).
• The grand sum consists of points for classes (40 points max) + 2x exam
= 80 points max.
• For those that passed both the classes and the written exam, a grade is
proposed based on the grand sum.

1
 • A student can accept the grade (and then doesn’t have to take the oral
exam) or take the oral exam (and then the grade cannot be lower than
proposed and can be upgraded by 1/2 if the oral exam goes well).

Tutorial
1 Week I
1. Equation of state - From an experiment it is known that
   
∂p 1 V
= − RT f ,
∂V T n n
 
∂p nR
= − 2nRT a,
∂T V V
where n - number of moles, a - a constant, f (V /n) - an arbitrary function.
Find the equation of state.
2. Exact and inexact differentials

(a) Show that dF ¯ (x, y) = xdx + xdy is inexact differential because the
integral from (0, 0) to (1, 1) depends on a path. Consider two paths
A: (0, 0) − (1, 0) − (1, 1) and B: (0, 0) − (0, 1) − (1, 1).
(b) Derive the condition for the differential dF (x, y) to be exact.
(c) Introduce an integrating factor dG(x, y) = r(x, y)dF
¯ (x, y). Consider
dF
¯ (x, y) = ydx + dy and find its integrating factor.
3. Thermodynamic potentials and Maxwell relations - For a gas described by
the fundamental relation dU = T dS − pdV derive corresponding thermo-
dynamic potentials: internal energy U (S, V ), entalpy H(S, p), Helmholtz
free energy F (T, V ), and Gibbs free energy G(T, p) by choosing proper in-
dependent variables. Derive all possible Maxwell relations. Discuss equiv-
alence and usefulness of different thermodynamic potentials in description
a system.
4. Engine efficiency - Find efficiency of an engine working in
(a) the Carnot cycle,
(b) the Otto cycle with an ideal gas as the working substance.
Remind students the heat capacity and specific heat at constant V and p.

2
1.1 Homework
AS 3
1. A gas is described by the fundamental relation U = nV , where A = const.
Find the equation of state p(T, V, n).
p
Answer: p = nT 3 /27AV
RT
2. A gas fulfills the van der Waals equation of state: p(T, v) = v−b − va2 ,
where a, b, R are positive constants, and v = V /n. Demonstrate that the
specific heat cv of this gas does not depend on volume V .

3. Evaluate cp − cv for a gas fulfilling the Clapeyron equation of state p =

nRT /V .
4. The internal energy of a certain one-component gas involving n = 2 moles
fulfills the equation U = ApV 2 , where A is a known constant. Find
U (p, V, n) for any n.
Answer: U (p, V, n) = 2ApV 2 /n

3
2 Week II
1. Show that      
∂p ∂T ∂V
· · = −1
∂T V ∂V p ∂p T

´∞ 2
2. Gaussian integrals - Compute the integral I = −∞ e−αx dx by first com-
puting I 2 using polar coordinates.
´∞ By taking a derivative of I over α
2
determine the integral J = −∞ x2 e−αx dx.
´∞ 2
3. Gamma function - Gaussian integrals in the form Im = 2 0 xm e−αx dx,
with m > −1, can be formulated in terms of the gamma function Γ(z) =
´ ∞ z−1
0
t e−t dt. Show the recursion relation Γ(n + 1) = nΓ(n) for n > 0.
Compute explicitly Γ(1/2), Γ(l + 1/2), Γ(1), Γ(l + 1), for l = 1, 2, 3, ....
4. Ball in n-dimensions - Find the volume of a ball and the area of a sphere
with radius r in n dimensions. Express the results in terms of the Gamma
function (generalized factorial function).

5. Find the Legendre transform of the function g(x) = exp(x − 1).

Internal energy can be expressed in terms of its natural variables S and
∂U
V : U = U (S, V ). Find the Legendre transform Ũ (S, ∂V ). Which thermo-
dynamic potential does it define?

2.1 Homework
1. n-dimensional ball - Volume of n-dimensional ball is expressed by the
formula
π n/2 rn
Vn =
Γ(n/2 + 1)
(n > 0 is a natural number). Prove that the non-dimensional parameter
Vn /rn attains its maximum value for n = 5.
2. Gamma function - Express the following integral in terms of the Gamma
function ˆ 1  3
2 1
I= dxx ln .
0 x

Answer: Γ(4)/81
3. Find the Legendre transform of f (x) = x2 + x − 3.

4. Find the Legendre transform of the internal energy: Ũ ( ∂U

∂S , V ). Identify
which thermodynamic potential is defined in this way.

4
3 Week III
1. A gas expanded adiabatically from state 1, in which it had volume V1
and pressure p1 , to volume V2 and pressure p2 (state 2) passing on the
way through a sequence of states satisfying the relation pV γ = const with
some exponent γ > 1. The gas has been next isobarically and reversibly
compressed to the volume V1 (state 3). From the state 3 the gas has been
finally brought back to the initial state 1 by enclosing it adiathermally
and performing on it isochorically a work W (e.g. by placing in it a Joule
paddle-wheel device or by passing a controlled current through a resistor
immersed in it) which has been measured. How much heat has the gas
absorbed in the first two processes? Would it be possible to bring the gas to
the state 2 by performing on it some work while it remained adiathermally
isolated, if it were first isobarically (at the pressure p1 ) and reversibly
expanded to the volume V2 ?
2. A very large mass M of porous hot rock is to be utilized to generate
electricity by injecting water and utilizing the resulting hot steam to drive
a turbine. As a result of heat extraction, the temperature of the rock
drops, according to d̄Qh = −M CdTh where C is the specific heat of the
rock, assumed to be temperature independent. If the plant operates at the
Carnot limit, calculate the total amount W of electrical energy extractable
from the rock, if the temperature of the rock was initially Th = Ti , and
if the plant is to be shut down when the temperature has dropped to
Th = Tf . Assume that the lower reservoir temperature Tl stays constant.
3. Magnetic work - Derive the expression for work in magnetic systems

dW
¯ = µ0 HdM.

4. Electric work - Derive the expression for work in electric systems

dW
¯ = EdP.

5. (a) Let f be a homogeneous function of degree 1. That is

f (u1 , ..., un ) = λf (x1 , ..., xn ),

for all λ ∈ R and ui = λxi . Prove Euler’s theorem
n  
X ∂f
f (x1 , ..., xn ) = xi .
i=1
∂xi {xj }̸=xi

(b) Consider the internal energy U (S, V, N ) with dU = T dS−pdV +µdN .

Use the result in (a) to find the Euler form of the internal energy

U (S, V, N ) = T S − pV + µN.

5
 (c) Derive the Gibbs-Duhem relation

dµ = −sdT + vdp,

where s = S/N and v = V /N .

3.1 Homework
1. Using the First Law of Thermodynamics calculate the heat absorbed by an
ideal gas (with the equation of state pV = nRT and with cv = const) going
through a process from an equilibrium state 1 characterized by the pressure
p1 and volume V1 to the equilibrium state 2, characterized by p2 and V2 ,
where V2 < V1 and p2 > p1 . The gas was first heated isochorically (V =
const) and next isothermally (at T = const) and reversibly compressed.
Moreover, p1 V1γ = p2 V2γ , where γ = 5/3, that is the initial and final states
are on the same adiabath.
Answer: Q = 3/2nR(T2 − T1 ) − nRT2 ln(V1 /V2 )
2. Consider a magnetic system subject to a magnetic field H. Its fundamental
thermodynamic relation is given by

dU = T dS + µ0 HdM, (1)

where µ0 is the vacuum magnetic permeability and M is the total magnetic

moment of such a system. Derive the respective thermodynamic potentials
for such a system, as well as the heat capacities at constant magnetic
moment and constant magnetic field.
3. Consider an electric system subject to an electric field E. ts fundamental
thermodynamic relation is given by

dU = T dS + EdP, (2)

where P is the dipole moment. Redo problem 2 for such a system.

4. A magnetic compound behaves according to the Curie law, m = CH/T ,
where C is a constant, H is the applied magnetic field, m is the magne-
tization per particle, and T is temperature. In a quasi-static process, we
have
du = T ds + Hdm, (3)
where u = u(s, m) plays the role of an internal energy. For an infinitesimal
adiabatic process, show that we can write
CH
∆T = ∆H, (4)
cH T
where cH is the specific heat at constant magnetic field.

6
4 Week IV
1. Entropy change - A system with n mole of water at temperature T1 is in
thermal contact with a very large environment at temperature T2 . Find
changes of entropy: a) in the water, b) in the environment, and c) in the
whole system, when the temperature of both gets equal. Mole specific
heat is given cV . Discuss the importance of the assumption that the
environment must be infinitely large.
2. Heat capacity - Show that the heat capacities are expressed by the two
state functions    2 
∂S ∂ F
CV = T = −T
∂T V ∂T 2 V
and
∂2G
   
∂S
Cp = T = −T .
∂T p ∂T 2 p

3. Thermodynamics of a rubber band - Consider a rubber band of length L

at tension f . The total differential of the internal energy U is given by
dU = T dS +f dL+µdn. As usual, here T is temperature, S is the entropy,
µ is the chemical potential, and n is the mole number of the rubber band.
(a) An equation of state for the rubber band is given by either
"   #
2
1/2 1 L L0 3
S = L0 γ(θU/L0 ) − L0 γ + −
2 L0 L 2

or "   #
2
θnU/L0 1 L L0 3
S = L0 γe − L0 γ + − ,
2 L0 L 2
with L0 = nl0 . Here l0 > 0, θ > 0, and γ are constants. Explicitly
demonstrate which one of these entropy functions is physical. Can γ
be negative? For the proper choice of S determine the equation of
state for the tension f (T, l) with l = L/n.
(b) Compute for the correct equation of state (∂cl /∂l)T with cl being the
heat capacity per mole at constant length.
(c) Derive the analogue of the Gibbs-Duhem relation (see week III prob-
lem 5c) for a rubber band.
(d) Suppose you have two pieces of rubber band satisfying the equation
of state in (a). Each of these rubber bands is characterized by a
temperature T (α) , length per mole l(α) , and mole number n(α) with
α = 1, 2. Determine as a function of these state variables the final
energies and temperatures of the two rubber bands if they are held at
constant length and placed in thermal contact with one another. You
may neglect thermal convection and mass flow to the surroundings.

7
 4. Thermodynamic inequalities.
(a) Let Φ stand for a general thermodynamic potential, which is a natural
function of the extensive variables X1 , X2 , ..., Xr and the intensive
variables Ir+1 , ..., In . The total differential is given by
r
X n
X
dΦ = Ii dXi − Xj dIj .
i=1 j=r+1

Note that a pair Xi and Ii are thermodynamically conjugate with

each other. Prove the thermodynamic stability criteria
 
∂Ii
0≤ .
∂Xi X1 ,...,Xi−1 ,Xi+1 ,...,Xr ,Ir+1 ,...,In

(b) An experimentalist claims to have found that a certain gaseous ma-

terial obeys the conditions (i) (∂p/∂v)T < 0, (ii) (∂p/∂T )v > 0,
(iii) (∂µ/∂v)T < 0, (iv) (∂T /∂v)s > 0. Here v = V /n, and s = S/n.
Which one of these inequalities is determined by thermodynamic sta-
bility? Which pairs of inequalities are inconsistent with each other?

4.1 Homework
1. Entropy change in an ideal gas - Find the entropy change of an n mole of
ideal gas in a reversible process from a state A (pA , VA , TA ) to a state B
(pB ,VB ,TB ). Specific heats cV and cp are given.
2. Response functions - Show that

κT (Cp − CV ) = T V α2

and
Cp (κT − κS ) = T V α2 .
Here the compressibility is given by κx = −(1/V )(∂V /∂p)x and the coef-
ficient of thermal expansion is α = −(1/V )(∂V /∂T )p .
3. Thermodynamic stability of rubber bands and Gibbs-Duhem - One can
experimentally verify quite easily that a rubber band heats up when it is
stretched adiabatically.
(a) Given this fact, will a rubber band contract or expand when it is
cooled at constant tension?
(b) The same amount of heat flows into two identical rubber bands, but
one is held at constant tension, and the other one at constant length.
Which one has the largest increase in temperature?

8
 (c) Suppose the rubber band satisfies the equation of state U = θS 2 L/n2 ,
with θ being a constant. Determine the chemical potential of the
system µ(T, l) and show explicitly that the equation of state satisfies
the relevant Gibbs-Duhem relation from the tutorials.

4. Stability of magnetic systems - Consider a magnet with magnetization M

in the direction of the magnetic field strength H. In appropropriate units
the work is given by HdM .
(a) Determine the signs of the isothermal and adiabatic susceptibilities,
   
∂M ∂M
χT = , χS = .
∂H T,n,V ∂H S,n,V

Furthermore, determine the sign of χT − χS .

(b) Suppose a paramagnetic substance has a decreasing magnetization as
function of temperate at constant H. Will the temperature increase
or decrease when the material is adiabatically demagnetized?

5. Generalised Euler theorem - Given the generalised homogeneous function

f (λθ1 x1 , ..., λθn xn ) = λf (x1 , ..., xn ),

with θi a real number for i = 1, ..., n. Show that

   
∂f ∂f
θ 1 x1 + ... + θn xn = f (x1 , ..., xn ).
∂x1 x2 ,...,xn ∂xn x1 ,...,xn−1

This generalisation of Euler’s theorem plays an important role in the the-

ory of phase transitions close to the critical point.