Thermodynamics Assignment 4

Hatif Alam
November 11, 2024

Problem 1
A system consists of N noninteracting atoms. Each atom may be in two states: a low energy state with
energy E = 0 and an excited state with energy E = ϵ.
(a) How many atoms are in the excited state?
(b) What is the total energy U of this system as a function of N , ϵ, k (the Boltzmann constant), and T ?
Solution 1
(a) A system of N noninteracting particles with two possible states, either 0 or ϵ. A good rule is to
assume particles (e.g., atoms, electrons, etc.) are indistinguishable unless they are localized in a crystal or
on a surface. The number of atoms in the excited state can be determined using Boltzmann statistics under
the assumption that we are working at high temperature and/or low density.
Consider a system of noninteracting indistinguishable particles, for which

qN
Q(N, V, T ) =
N!
with X
q(V, T ) = e−ϵj /kT
j

This holds when Φ(ϵ) ≫ N .

For this system, the total energy is given by:
∂ ln Q
E = N · ϵ̄ = kT 2
∂T
Note that, according to the expression above,
X ϵj e−ϵj /kT
ϵ̄ =
j
q

The probability that a molecule is in the j-th state is

e−ϵj /kT
πj =
q
In this problem, the two available states are 0 and ϵ, and the total number of particles in the ϵ state is

Nϵ = N π ϵ

where πϵ is the probability an atom will be in state ϵ. This probability is determined using the single-particle
partition function and can be written as
ϵ


exp − kT
πϵ = ϵ


1 + exp − kT

1
Thus, Nϵ can be written as
ϵ


N exp − kT
Nϵ = N πϵ = ϵ


1 + exp − kT
N
Nϵ = ϵ


1 + exp kT

(b) The total energy is simply X

U = N ϵ̄ = N π i ϵi
i

Thus,
U = N (π1 ϵ1 + π2 ϵ2 ) = N [(1 − πϵ ) · 0 + πϵ · ϵ]
ϵ


N ϵ exp − kT Nϵ
U = N πϵ · ϵ = ϵ

= ϵ


1 + exp − kT 1 + exp kT

Problem 2
Consider a system of N distinguishable non-interacting spins in a magnetic field H. Each spin has a magnetic
moment of size µ and can point either parallel or anti-parallel to the field. The magnetic moment is given
by ni µ where ni = ±1.
(a) Determine the internal energy of this system as a function of β, H, and N by employing an appropriate
ensemble.
(b) Determine the entropy of this system as a function of β, H, and N .
(c) Determine the behavior of the energy and entropy of this system as T → 0.
2
(d) Determine the average magnetization
∂M

⟨M ⟩ and the variance of the fluctuations in magnetism ⟨δM ⟩.
Express in terms of the susceptibility ∂H T,N .
Solution 2
The magnetization is given by:
XN
M= µi
i=1

where µi is the magnetic moment at each site, which can either be up or down.
We need to determine the thermodynamic properties as a function of T , N , and H, assuming constant
volume. Thus, our controlling variables are T , N , V , and H.
Starting with the energy E, we can express the entropy S in terms of E:

E = T S − pV + HM + µN

Rearranging to get S in terms of E and performing a Legendre transform such that our controlling variables
are V , N , T , and H, we obtain:
S = βE + βpV − βHM − βµN
1
where β = kT is the inverse temperature.
We now introduce the characteristic potential for this ensemble, with V , N , T , and H constant. Let Z
be the partition function, which can be written as:
X
Z= exp[−β(Estate − Mstate H)]
states

where we sum over all possible energy states and magnetizations Mstate . Assuming non-interacting particles
and that E is independent of the arrangement of up versus down spins, we can set E = 0 when H = 0.
Thus: " N #
X X YN
Z= exp β µi H = (exp[βµi H] + exp[−βµi H])
n1 ,n2 ,...,nN i=1 i=1

2
Since µi = 1, we find:
Z = (exp[βH] + exp[−βH])N
Using properties of the hyperbolic functions, this simplifies to:
Z = (2 cosh(βH))N
The characteristic potential Φ for this ensemble is related to the partition function by:
Φ = −kT ln Z = −kT N ln[2 cosh(βH)]
From thermodynamics, we know:
dΦ = −SdT − pdV + µdN − M dH
which gives the following partial derivatives:
   
∂Φ ∂Φ
S=− , M =−
∂T V,N,H ∂H V,N,T

Answer (a): We have:

Φ = −kT N ln[2 cosh(βH)]
The internal energy E is then:
E = T S + HM
Alternatively, defining the internal magnetic energy EH (analogous to enthalpy in the T, p, N ensemble):
EH = E − HM
we find:
EH = −N H tanh(βH)
Answer (b): For entropy S, we calculate:
sinh(βH)
S = kN ln(2 cosh(βH)) + kT N
cosh(βH)
which simplifies to:
S = kN {ln(2 cosh(βH)) − βH tanh(βH)}
Answer (c): As T → 0, the energy EH approaches:
EH (T → 0) = −N µH
and the entropy S becomes:
lim S = kN {ln(2 cosh(βH)) − βH tanh(βH)} = 0
T →0

which is consistent with the third law of thermodynamics.

Answer (d): The average magnetization M is given by:
N
X
M= µi
i=1

Now, we compute the magnetization M by taking the derivative of the characteristic potential Φ with respect
to H:  
∂Φ
M =−
∂H V,N,T
Given that:
Φ = −kT N ln(exp(βH) + exp(−βH))
we find:
M = N tanh(βH)
1
where β = kT .

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Problem 3
Consider a one-component gas of non-interacting structureless particles of mass m at temperature T .
(a) Calculate the grand canonical partition function Ξ for this system as a function of V , T , and µ. Show
that it is in the form: Ξ = ezV where z is a function of T and µ.
 2 1/2
(b) Calculate the density fluctuations for 1 cc of gas at 298 K and 1 atm ⟨δρ ρ2
⟩
.

Solution
The grand partition function Ξ for a one-component gas of non-interacting particles can be written as:
 
X∞ X ∞
X
Ξ=  e−βEj  eβµN = Q(N, V, T )eβµN
N =0 j N =0

where Q(N, V, T ) is the canonical partition function for N particles.

For non-interacting particles, we can write:
qN
Q(N, V, T ) =
N!
where q is given by:
V 3/2
q= (2πmkT )
h3
Thus, Ξ can be expressed as:
∞
X (qeβµ )N
Ξ=
N!
N =0
βµ
Letting a = qe , we have:
∞
X aN
Ξ= = ea
N!
N =0
Substituting for q, we get:
Ξ = ezV
1 3/2 βµ
where z = h3 (2πmkT ) e .

Answer (a)
Thus, the grand partition function Ξ can be written as:
Ξ = ezV
 3/2
1 3/2 βµ eβµ 2πm
where z = h3 (2πmkT ) e = h3 β .

Answer (b)
We need to compute the variance ⟨N 2 ⟩ − ⟨N ⟩2 .
Starting with the relation for ⟨N ⟩:
1 3/2
⟨N ⟩ = zV where z= (2πmkT ) eβµ
h3
we find:
⟨N ⟩
⟨N 2 ⟩ − ⟨N ⟩2 = kT
V
Thus,
⟨δρ2 ⟩ 1
2
=p
ρ ⟨N ⟩

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Calculation of ⟨N ⟩ and Density Fluctuation
Given: V = 1 cm3 = 10−6 m3 , T = 298 K, P = 1 atm = 1.013 × 105 Pa.
Using the ideal gas law, we find the average number of particles ⟨N ⟩:

PV
⟨N ⟩ =
kB T

where kB = 1.38 × 10−23 J/K is the Boltzmann constant.

Substituting the values:
(1.013 × 105 Pa)(10−6 m3 )
⟨N ⟩ =
(1.38 × 10−23 J/K)(298 K)
After performing the calculation:
⟨N ⟩ ≈ 2.46 × 1019
The density fluctuation can then be found as:
s
⟨δρ2 ⟩ 1
=p
ρ2 ⟨N ⟩

Substituting ⟨N ⟩ ≈ 2.46 × 1019 : s

⟨δρ2 ⟩
≈ 2 × 10−10
ρ2

Problem 4
An iron rod of length l and made up of N iron atoms is held in vacuum (P = 0) under uniaxial tension with
a constant force F at constant temperature T .
(a) What is the characteristic potential for this set of thermodynamic boundary conditions?
(b) Write down the appropriate partition function for this ensemble and express the characteristic potential
in terms of this partition function.
(c) Express the thermodynamic variables l, S, µ, and E as a function of the partition function.
(d) What are the fluctuations in length, expressed in terms of the Hookean spring constant of the bar?

Solution
(a) Characteristic Potential
The differential form of energy is given by:

dE = T dS + pdV + F dl + µdN
The energy expression is:

E = T S + pV + F l + µN
Since we are working under a vacuum (p = 0), we can simplify this to:

E = T S + F l + µN
The characteristic potential, denoted by Φ, is:

Φ = E − TS − Fl

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 Therefore, the differential of the characteristic potential is:

dΦ = −SdT − ldF + µdN

This can also be written as a Legendre transform of the entropy:

S − Φ = k − µE + µF l

(b) Partition Function

The partition function Z for this ensemble is:
 
X Ej + F lj
Z= exp −
j
kT

The characteristic potential Φ is related to the partition function by:

Φ = −kT ln Z

(c) Thermodynamic Variables

Now, we express the thermodynamic variables l, S, µ, and E as functions of the partition function Z.
For the length l:
   
∂Φ ∂ ln Z
l=− = kT
∂F T,N ∂F T,N

For the entropy S:

   
∂Φ ∂ ln Z
S=− = k ln Z + kT
∂T F,N ∂T F,N

For the chemical potential µ:

 
∂ ln Z
µ = −kT
∂N T,F

For the energy E, we use the following relation:

E = TS + Fl
Rewriting this in terms of the partition function:
   
∂ ln Z ∂ ln Z
E = −kT ln Z + kT 2 + kT F
∂T F,N ∂F T,N

(d) Fluctuations in Length

To find the fluctuations in length ∆l, we use the relation to the Hookean spring constant k of the bar. The
fluctuations in length are given by the second derivative of the partition function with respect to the force
F:
kB T
(∆l)2 = ⟨l2 ⟩ − ⟨l⟩2 =
k
where k is the effective Hookean spring constant that characterizes the stiffness of the bar under tension.
This relation shows that the fluctuations in length are inversely proportional to the stiffness of the material
and directly proportional to the temperature.

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Problem 5
Consider a surface with M potential adsorption sites, of which N < M are occupied by Argon atoms. The
Ar atoms do not interact with each other on this surface, but there is an energy −ϵ associated with each
adsorbed atom. There is also the possibility that the adsorbed Ar atoms can be in an excited state with an
increased energy δϵ.

(a) What is the entropy of this system if N and M are fixed?

(b) If the surface is open to Ar gas with a chemical potential µ = kT ln(CPAr ) (a partial pressure of PAr
N
and constant C), write the expression for the surface coverage M as a function of PAr .

(c) What if there are now NA and NB atoms of type A and B, which bind with energies −ϵA and −ϵB (no
excited states)? Assume they have different values of CA and CB . What is the surface coverage of A
and B as a function of the two partial pressures?

Solution 5
(a) Entropy of the System
The entropy S of the system is determined by the number of ways to arrange N adsorbed Argon atoms
on M sites. The number of microstates Ω is given by the binomial coefficient:
 
M M!
Ω= =
N N !(M − N )!

The entropy S can be expressed using Boltzmann’s entropy formula:

 
M!
S = k ln Ω = k ln
N !(M − N )!

This is the entropy of the system when M and N are fixed.

N
(b) Surface Coverage M as a Function of PAr
When the surface is in contact with an Argon gas reservoir, the equilibrium surface coverage can be
determined by considering the adsorption-desorption equilibrium. For each Argon atom, the probability
of adsorption depends on the chemical potential µ and the energy associated with adsorption.
The adsorption equilibrium is:
N µ+ϵ
= e kT
M −N
Substituting µ = kT ln(CPAr ), we get:

N kT ln(CPAr )+ϵ ϵ
=e kT = CPAr e kT
M −N
N
Rearranging to solve for M, we get:
ϵ
N CPAr e kT
= ϵ
M 1 + CPAr e kT
(c) Surface Coverage with Two Types of Atoms
If there are two types of atoms, A and B, with NA and NB atoms adsorbed on the surface, each with
different adsorption energies −ϵA and −ϵB , and different constants CA and CB , we can extend the
analysis from part (b).
For type A, the adsorption equilibrium is:
NA ϵA
= CA PA e kT
M − NA − NB

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For type B, the adsorption equilibrium is:
NB ϵB
= CB PB e kT
M − NA − NB
NA NB
Solving for M and M , we obtain:
ϵA
NA CA PA e kT
= ϵA ϵB
M 1 + CA PA e kT + CB PB e kT
ϵB
NB CB PB e kT
= ϵA ϵB
M 1 + CA PA e kT + CB PB e kT
These expressions give the surface coverage for types A and B as functions of their respective partial
pressures.