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 ?

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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)

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