Índice

1. Free Energies 2
1.1. The Canonical Ensemble . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2. Uncoupled Systems and Canonical Ensembles . . . . . . . . . . . . . . . . . . . . . . . . 4
1.3. Grand Canonical Ensemble . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.4. Chemical Equilibrium and Reaction Rates . . . . . . . . . . . . . . . . . . . . . . . . . . 7

1
1. Free Energies
If this chapter we explain how to study parts of statistical mechanical systems. If we ignore most of
our system-agreeing not to ask questions about certain degrees of freedom-the statistical mechanical
predictions about the remaining parts are embodied in a new statistical ensemble and its associated
free energy.

1.1. The Canonical Ensemble

This ensemble governs the equilibrium behavior of a system at fixed temperature. It is appropriate
for calculating properties of systems which can exchange energy with an external world at tempera-
ture T . We defined temperature by considering a total system comprised of two weakly-coupled parts
(P1 , Q1 ) and (P1 , Q1 ) that can exchange energy. We focus on the first of these (the system) and assume
that the second (the heat bath) is large.

The probability that our system is in a state s depends upon its energy Es , more specific on the
volume of the energy shell for the heat bath at bath energy E − Es

ρ(s) ∝ Ω2 (E − Es )
S2 (E−Es )
=e kB
.

Let us compare the probability of two states A and B of our equilibrium system. The energy
∂S2
fluctuations are small and the heat bath is large, therefore it is assumed that T12 = ∂E 2
is constant in
the range (E − EA , E − EB ). Hence

ρ(sB ) Ω(EEB )
=
ρ(sA ) Ω(E − EA )
S2 (E−EB )−S2 (E−EA )
=e kB

∂S2
(EA −EB )
∂E
=e kB

EA −EB
=e kB T2
.

This is the general derivation of the Boltzmann distribution. The probability of a particular system
state of energy Es is

− kEsT
ρ(s) ∝ e B .

The probability is normalized so

− kEsT
e B
ρ(s) = R H
dP1 Q1 − kB1T
h3N1
e
− kEsT
e B
=P
− kEnT
ne
B

1 − kEsT
= e B ,
Z
where

dP1 Q1 − kH1T
Z
− kEnT
X
Z= e B = e B
n
h3N1

2
 is the partition function.

It is a surprise that the normalization factor is actually a crucial quantity in the theory. Most
quantities can be calculates from its derivatives.
1
Internal energy. Using β = kB T ,

1 X
⟨E⟩ = En e−βEn
Z n
1 ∂Z
=−
Z ∂β
∂ ln Z
=− .
∂β

Specific heat. Let cv be the specific heat per particle at constant volume

∂⟨E⟩
N cv =
∂T
1 ∂⟨E⟩
=−
kB T 2 ∂β
1 ∂ 2 ln Z
= .
kB T 2 ∂β 2

It can be also written as

1 ∂⟨E⟩
N cv = −
kB T 2 ∂β
En e−βEn
P 
1 ∂ n
=− P −βE
kB T 2 ∂β e n
" P n
−βEn 2
2 −βEn
P
#
1 E e E n e
=− − n n + n
kB T 2 Z Z2
−⟨E 2 ⟩ + ⟨E⟩2
=−
kB T 2
2
σE
= .
kB T 2

Are results calculated using the canonical ensemble the same as those computed using the original
microcanonical ensemble? The energy fluctuations per particle are

p
σE (kB T )(cv T )
= √
N N

are tiny. This will not change the properties of a macroscopic system; the constant energy (mi-
crocanonical) and constant temperature (canonical) ensembles predict the same behavior.
Entropy. Calculate

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 X
S = −kB Pn ln Pn
X e−βEn 
e−βEn

= −kB ln
Z Z
X e−βEn [−βEn − ln Z]
= −kB
Z
1 X En e−βEn X e−βEn
= + kB ln Z
T Z Z
⟨E⟩
= + kB ln Z.
T

All the results involve ln Z and its derivatives. This motivates a free energy for the canonical
ensemble called the Helmholtz free energy

A = −kB T ln Z = ⟨E⟩ − T S.

The entropy is calculated as

∂A ⟨E⟩
= −kB ln Z − kB T
∂T N,V kB T 2
⟨E⟩
= −kB ln Z −
T
= −S.

It is called free energy because it has units of energy and it is the energy available to do work.
A = E − T S is the energy free to do useful work.

1.2. Uncoupled Systems and Canonical Ensembles

Suppose we have a system with two weakly-interacting subsystems L and R, both connected to a
heat bath at β = 1/kB T . The partition function for the whole system is

X L R
Z= e−β(Ei +Ej
ij
! 
−βEiL R
X X
= e  e−βEj 
i j
L R
=Z Z .

Partition functions factor for uncoupled subsystems. The Helmholtz free energy adds

A = −kB T ln Z
= −kB T ln(Z L Z R )
= AL + AR ,

as does the entropy, average energy, and other extensive properties that scale with the size of the
system. We can now solve several important examples of uncoupled systems.

Ideal gas. The partition function for N distinguishable ideal gas atoms of mass m in a cube of
volume V = L3 factors into a product over each degree of freedom

4
 3N Z ∞
1 L p2
Z
α
Y
Z= dqα dpα e−β 2mα
α=1
h 0 −∞
 r 3N
L 2πm
=
h β
 3N
L
= ,
α

where

s
2πh̄2
λ=
mkB T

is again the thermal de Broglie wavelength. The mean internal energy is

∂ ln Z
⟨E⟩ = −
∂β
3 ∂
= N ln beta
2 ∂β
3
= N kB T,
2

giving us the equipartition theorem. For N distinguishable particles the partition function must
be divided by N !

 3N
1 L
Z= .
N! λ

This does not change the internal energy but does affect the Helmholtz free energy

"  3N #
1 L
A = −kB T ln
N! λ
 
V
= −N kB T ln + kB T ln N !
λ3
 
V
≃ −N kB T ln + kB T (N ln N − N )
λ3
   
V
= −N kB T ln + 1
N λ3
= N kB T ln ρλ3 − 1 ,



where ρ is the average density. Finally, the entropy of N undistinguished particles is

∂A
S=−
∂T  
5 3
= N kB − ln(ρλ ) .
2

5
 Classical harmonic oscillator. Using the canonical ensemble, the statistical mechanics of these
systems decomposes into calculation for each mode separately. The Hamiltonian of the system is

p2 1
H= + mω 2 q 2 .
2m 2

The partition function for one such oscillator is

Z ∞ Z ∞ p2
1
 
1 2 2
−β 2m + 2 mω q
Z= dq e
h −∞ −∞
r r
1 2π 2πm
=
h βmω 2 β
1
= .
βh̄ω

The Helmholtz free energy is

 
h̄ω
A = kB T ln .
kB T

The internal energy is

∂ ln Z
⟨E⟩ = −
∂β
= kB T,

and hence

∂⟨E⟩
cv =
∂T
= kB .

1.3. Grand Canonical Ensemble

This ensemble allows one to decouple calculations of systems which can exchange both energy and
particles with their environment. Consider the system in a state s with energy Es and number Ns ,
together with a bath with energy E2 = E − Es and number N2 = N − Ns . In analogy,

ρ(s) ∝ Ω2 (E − Es , N − Ns )
S2 (E−Es ,N −Ns )
=e kB

∂S2 ∂S2
Es +Ns
− ∂E ∂N
∝e kB

− Esk−µNs
=e T
B ,

where

µ ∂S
=−
T ∂N

6
 ∂E
is the chemical potential. From dE = T dS − P dV + µdN we see that µ = ∂N is the energy
S,V
change needed to add an additional particle adiabatically and keep the (N + 1)-system in equilibrium.
At low temperatures a given system will fill with particles until the energy needed to jam in another
particles reaches µ, and the exhibit thermal number fluctuations around that filling.

There is a normalization factor called the grand partition function

− Enk−µN n
X
Ξ= e BT
.
n

There is a grand free energy

ϕ = −kB T ln(Ξ)
= ⟨E⟩ − T S − µN.

From Euler’s relation E = T S − P V + µN it is clear that ϕ = −P V .

The expected number of particles is

1X − Enk−µNn
⟨N ⟩ = Nn e BT
Ξ n
kB T ∂Ξ
=
Ξ ∂µ
∂ϕ
=− .
∂µ
The number fluctuations are related to the rate of change of particle number with chemical potential

∂⟨N ⟩ ⟨N 2 ⟩ − ⟨N ⟩2
=
∂µ kB T
2
σ
= N .
kB T

1.4. Chemical Equilibrium and Reaction Rates

As an example, take the ammonia molecule NH3 that can be produced through the reaction

3H2 + N2 ⇀
↽ 2N H2 .

In chemical equilibrium the concentrations satisfy the law of mass-action

[N H3 ]2
.
[N2 ][H2 ]3

Since we are uninterested in the positions and moments, at fixed volume and temperature our
system is described by a Helmholtz free energy A(T, V, NH2 , NN2 , NN H3 ). When the reaction takes
place, it changes the number of the three molecules and changes the free energy

∂A ∂A ∂A
∆A = ∆NH2 + ∆NN2 + ∆NN H3
∂NH2 ∂NN2 ∂NN H3
= −µH2 ∆NH2 − µN2 ∆NN2 − µN H3 ∆NN H3 .

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 In equilibrium ∆A = 0

0 = −µH2 ∆NH2 − µN2 ∆NN2 − µN H3 ∆NN H3

∆NH2 ∆NN2
−→ 0 = −µH2 − µN2 − µN H3
∆NN H3 ∆NN H3
3 1
= µH2 + µN2 − µN H3
2 2
−→ 0 = −3µH2 − µN2 + 2µN H3 .

To derive the law of mass-action, we must now make the assumption that molecules are uncorrelated
in space. This makes each molecular species into a separate ideal gas. The Helmholtz free energy of a
gas X is

A = N kB T ln [X]λ3 − 1 + N F0 ,



where the term N F0 comes from the internal free energy of the molecules that includes the ground
state energy of the molecules and possible rotational motion contributions. The chemical potential of
the gas is

∂A
µ=
∂N
= kB T ln([X]λ3 ) + F0 .

Then

0 = −3µH2 − µN2 + 2µN H3

−→ 3F0H2 + F0N2 − 2F0N H3 = −3kB T ln([H2 ]λ3H2 ) − kB T ln([N2 ]λ3N2 ) + 2kB T ln([N H3 ]λ3N H3 )
[N H3 ]3
−→ Keq = ,
[H2 ]2 [N2 ]

with

∆Fnet
−
Keq = K0 e kB T
,

and

∆Fnet = −3F0H2 − F0N2 + 2F0N H3 ,

λ9H2 λ3N2
K0 = ∼ T −3 .
λ6N H3
∆F
−
The factor ∼ e kB T represents the Boltzmann factor favoring a final state with molecular free
energy lower than the initial state.