Examusthamsnthermo 2023

USTH Master 1 AMSN
Thermodynamics for physics and chemistry

Exam of March 2023 (2 h - inspired from U.Paris Saclay )
1. We consider an ideal classical gas of N atoms confined in a box of volume V.

(a) Remind the definition of the integrated density of states g(E) for the mono-atomic gas in three
dimensions
(b) Remind the definition of the micro-canonical entropy S. Explain why we can use the expression
S ≈ kB ln g(E)
and give its limits. Derive the Sackur-Tetrode formula .
" 3/2 !#
5 V mE
S(E,V, N) = NkB + ln
2 N 3πh̄2 N
(c) Show that S can be written as S = 3NkB ln(a∆x∆p/h) , where ∆x is a distance and ∆p a momen-
tum. Comment.
(d) Calculate the micro-canonical temperature T and pressure P. Derive an expressionq
of the entropy
2πh̄
as a function of the number density n = N/V and the de Broglie wavelength Λ = mkB T .
2. (a) Formulate the extensivity property that must be satisfied by the micro-canonical entropy S(E,V, N)
of the gas.
(b) Towards the end of the 19th century, there was no logical explanation for the factor 1/N! related
to indistinguishability of the atoms in the calculation of the integrated density of states.
i. From the integral g(E) for the density of states of a gas composed of N atoms calculate the
corresponding micro-canonical entropy S.
ii. We consider two identical volumes of the same gas separated by a wall. Calculate the dif-
ference between the entropy of this system and the entropy of the system with the wall
removed.
∆S = S(2E, 2V, 2N) − 2S(E,V, N)

Why do we say that this result is paradoxal ?
iii. Indistinguishability.– Compare S(E,V, N) to the Sackur-Tetrode formula Discuss the exten-
sivity in the two cases. Verify that if we calculate the entropy of mixing using the indiscerni-
bility factor N! we have ∆S = 0
(c) Grand Canonical ensemble (Systems in contact with a particle reservoir)
We consider an ideal gas at thermodynamic equilibrium in a volume V . We fix the temperature
T and chemical potential µ
i. Show that the grand potential may be written as J(T, µ,V ) = V j(T, µ). Discuss the physical
interpretation of the "volumetric density of the grand potential" j.
ii. We consider a dilute gas of monoatomic classical particles, for which we may assume that
the Maxwell-Boltzmann approximation is justified. For this question no supplementary hy-
pothesis (the number of the degrees of freedom, their relativistic or non-relativistic nature,
their dynamics, etc.) will be needed. We introduce z, the single particle partition fonction.
Justify that z α V . Show that the grand canonical partition fonction is
1
Ξ = exp(eβµ z)
.
Deduce the average number of particles N̄ and the pressure p . Show that, under this minimal
hypothesis, it is possible to derive the equation of state of the ideal gas, pV = NkB T
iii. Let us call ε̄ the average energy per particle. Show that the average total energy is
Ē = N̄ ε̄
iv. Using

∂ µ ∂
Var(E) = − + Ē
∂β β ∂µ
show that
Var(E) = N̄ ε¯2
Compare with the variance of the energy in the canonical ensemble.
v. Show that the entropy is

∂ ln z
S = N̄kB 1 − − µβ
∂ ln β
vi. Justify that z α V . With z(T,V ) = V /Λ3 express Λ (up to a dimensionlesss factor) for non
relativistic particles (ε = p2 /(2m)) and ultra-relativist particles (ε = pc). Recover the expres-
sion of µ(T, n). Deduce that the entropy coincides with the Sackur-Tétrode formula.
(d) We consider a container of volume V filled with a monatomic ideal gas of indistinguishable
atoms. This gas is in contact with a solid interface that may adsorb (trap) the gas atoms. We
model the interface as an ensemble of A adsorption sites. Each site can adsorb only one atom,
which then has an energy −εo
The system is in equilibrium at a temperature T and we model the adsorbed atoms, i.e. the
adsorbed phase, as a system with a fluctuating number of particles at fixed chemical potential µ
and temperature T . The gas acts as a reservoir.
i. Derive the grand-canonical partition function ξ for a single adsorption site. Deduce the grand-
canonical partition function Ξ(T, A, µ) for all atoms adsorbed on the surface.
ii. We will now explore an alternative route. Derive the canonical partition function Z(T, A, N)
of a collection of N adsorbed atoms (Note : the number of adsorbed atoms N is much smal-
ler than the number of sites A). Recover the results for Ξ(T, A, µ) obtained in the previous
question.
iii. Calculate the average number of adsorbed atoms N as a function of εo , µ, A, T . . From this,
derive the occupation probability θ = N/A of an adsorption site.
iv. The chemical potential µ is fixed by the ideal gas. This may be used to deduce an expression
for the site occupation probability θ as a function of the gas pressure P and temperature T
(note that the number of atoms N is much smaller than the number of gas atoms).
v. We define a parameter
23
2πmkB T ε0
P0 (T ) = kB T exp −
h2 kB T
Express θ as a function of P and P0 (T )
vi. How does the curve θ(P) behave for different temperatures ?

Examusthamsnthermo 2023

Uploaded by

Copyright:

Available Formats

Examusthamsnthermo 2023

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Examusthamsnthermo 2023

Uploaded by

Copyright:

Available Formats

USTH Master 1 AMSN

Thermodynamics for physics and chemistry

1. We consider an ideal classical gas of N atoms confined in a box of volume V.

∆S = S(2E, 2V, 2N) − 2S(E,V, N)

You might also like