Lecture 7: The Langmuir Isotherm and Ising Model

7.1 Recommended textbook chapters for this section

• Chandler - Ch. 4.6, 4.7, 5.1

7.2 Topics in this lecture

• The ideal gas partition function in the classical limit

• The Langmuir adsorption isotherm

• The Ising model

7.3 Announcements
• Pset 2 due today

• Pset 3 assigned, due next Thursday

• Exam 1 on Thursday, October 10

7.4 Ideal gas partition function in the classical limit

In the last lecture, we described the factorization of the partition function for independent, identical
subsystems, and defined the following approach for studying these systems:

• Determine a single-particle energy and corresponding single-particle partition function

• Write a partition function for the entire system using the single-particle partition function

• Derive thermodynamic quantities via derivatives of the partition function

We then used this approach to start analyzing the behavior of a monatomic ideal gas. Starting
from the expression for the energy of a quantum particle in a box and then assuming that energies
were continuous to solve for the degeneracy for each state, we arrived at the following single-particle
partition function:

 3/2 ∞
π 8m X
z= V ν1/2 e−βν dν (7.1)
4 h2 ν

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University of Wisconsin-Madison Lecture 7
CBE 710, Fall 2019 - Prof. R. C. Van Lehn September 26, 2019

Here, recall that h is Planck’s constant, V is the physical volume of the system, and m is the mass
of the particle. We then made an important assumption: if the difference between consecutive terms
in the sum is small (i.e., energy levels are nearly the same), then we can accurately approximate the
sum by a continuous integral. This assumption is equivalent to the method for deriving Stirling’s
approximation, and transforms a sum over discrete states to an integral over a continuum of states.
This assumption is also referred to as assuming that the system is at the classical limit: quantum
mechanics is defined by discrete states whereas the classical limit is defined by continuous states
because the difference in energy between states is extremely small. In the classical limit, the ideal
gas partition function becomes:
 3/2 Z ∞
π 8m
z= V ν1/2 e−βν dν (7.2)
4 h2 0
We
R ∞can analytically solve this expression by defining u = βν and recognizing the standard inte-
√
gral 0 u1/2 e−u du = π/2. Simplifying yields our final expression for the single-particle partition
function for the ideal gas:

 3/2 Z ∞
π 8m
z= V ν1/2 e−βν dν (7.3)
4 h2 0
 3/2 Z ∞
π 8m
= V (kB T ) 3/2
u1/2 e−u du (7.4)
4 h2 0
!
π 8mkB T 3/2 π 1/2
 
= V (7.5)
4 h2 2
2πmkB T 3/2
 
= V (7.6)
h2

We can then write the full partition function of the system, remembering that the particles are
indistinguishable, using the result for the factorization of the partition function:

zN
Z= (7.7)
N!
1 2πmkB T 3N/2 N
 
= V (7.8)
N! h2
 N
1 V
= (7.9)
N ! λ3

In the last line, we define:

s
h2
λ= (7.10)
2πmkB T
where λ is the thermal de Broglie wavelength which has units of length and is a function of T ;
this simplifies our notation and defines a characteristic length scale for treating a gas classically -
if V  λ3 , which we will generally assume to be the case, then the classical limit is reasonable.
We have now performed the first two steps in our approach by identifying an expression for
the energy of a microstate of our system and calculating the corresponding partition function (in

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University of Wisconsin-Madison Lecture 7
CBE 710, Fall 2019 - Prof. R. C. Van Lehn September 26, 2019

the classical limit) from the single-particle partition function. We can next derive thermodynamic
relationships using the connection between the canonical partition function and the Helmholtz free
energy. Let us first calculate the ensemble-average pressure of an ideal gas:

 
∂F
hP i = P = − (7.11)
∂V N,T
 
∂ ln Z
= kB T (7.12)
∂V N,T
" #
1 2πmkB T 3N/2
 
ln Z = N ln V + ln (7.13)
N! h2
1
P = N kB T (7.14)
V
∴ P V = N kB T (7.15)

This expression for the pressure is the familiar ideal gas equation of state, derived solely from
statistical mechanics. Note that R, the ideal gas constant, is related to kB by a constant factor of
Avogadro’s constant, NA , or R = NA kB . Basically, this is just a unit conversion. The only input
to obtain this relationship is an energy function from quantum mechanics - therefore this is entirely
a first-principles derivation that does not rely on empirical measurements. In the third line we
divided the partition function into a term that is a function of V and one that is not; the second
term does not contribute to the expression for P .
We can next calculate the average energy of an ideal gas. Recall that we can relate the energy
to the canonical partition function (from a previous lecture) via:

 
∂ ln Z
E=− (7.16)
∂β N,V
 
∂ ln Z
= kB T 2 (7.17)
∂T N,V

We apply this definition by writing out the partition function and separate into the temperature-
dependent and temperature-independent terms:

" #
2πmkB T 3N/2 N
 
1
ln Z = ln V (7.18)
N! h2
" #
1 2πmkB 3N/2 N
 
3N
= ln T + ln V (7.19)
2 N! h2

Taking the derivative gives:

3N
E = kB T 2 (7.20)
2T
3N kB T
= (7.21)
2

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University of Wisconsin-Madison Lecture 7
CBE 710, Fall 2019 - Prof. R. C. Van Lehn September 26, 2019

This again is a familiar expression - the internal energy of an ideal gas depends only on the
temperature, and we obtain the same prefactors as in thermodynamics. We can now easily also
calculate the heat capacity at constant volume, CV :

 
∂E
CV = (7.22)
∂T N,V
3
= N kB (7.23)
2
These last two results are manifestations of the equipartition theorem, which states that any
degree of freedom that appears quadratically in the energy of a system contributes 1/2kB T to the
internal energy and contributes 1/2kB to the heat capacity in the classical limit. Here, there are 3
translational degrees of freedom corresponding to the three quantum numbers that each contribute
a quadratic energy term (the kinetic energy) for each of the N atoms, leading to 3/2N kB for the
heat capacity as we found.
Finally, we can compute the chemical potential of an ideal gas using the ideal gas partition
function:

 
∂F
µ= (7.24)
∂N T,V
 
∂ ln Z
= −kB T (7.25)
∂N T,V
 N
z
ln Z = ln (7.26)
N!
= N ln z − ln N ! (7.27)
" #
2πmkB T 3/2

= N ln V − N ln N + N (7.28)
h2
"  #
2πmkB T 3/2

µ = −kB T ln V − ln N (7.29)
h2
2πmkB T 3/2
 
N
= −kB T ln + kB T ln (7.30)
h2 V
= µ0 (T ) + kB T ln ρ (7.31)

The last formula expresses the chemical potential in terms of a first term, which is temperature
dependent but concentration (ρ) independent, and then a second concentration-dependent term.
This form for the chemical potential is again exactly what is observed for ideal gases in classical
thermodynamics.

7.5 The Langmuir adsorption isotherm

The previous approach shows that statistical mechanics can reproduce classical thermodynamic
relationships from first-principles. We will now test a second example of the three-step approach
for studying independent particles by deriving the Langmuir adsorption isotherm.

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University of Wisconsin-Madison Lecture 7
CBE 710, Fall 2019 - Prof. R. C. Van Lehn September 26, 2019

Consider a system of N ideal gas particles that can adsorb onto a surface. Physically, this
system could represent the adsorption of reactants onto a catalytic surface, for example. We define
the number of adsorbed particles as Na and the remaining number of free gas particles as N − Na .
Particles adsorb favorably with an energy of −a per particle. To simplify our treatment, we assume
all particles adsorb onto a lattice of discrete with Ns possible binding sites, of which Na are occupied
assuming that only a single particle can bind to each site (with Ns > Na , allowing for all particles
to adsorb). All binding sites are assumed to be independent; that is, the arrangement of particles
does not affect the energy of the system. The quantity we will determine is the fraction of the
surface that is occupied as a function of the pressure of the surrounding gas, fa (P ).

We next have to consider what ensemble to use to solve this problem. We can think of particles
adsorbed to the surface and particles free in the bulk as two distinct sets of particles such that
particles are free to exchange between the surface and bulk. The number of particles adsorbed to
the surface, Na , is thus allowed to vary. hNA i will be determined at equilibrium which is reached
when each particle adsorbed to the surface has a constant chemical potential, µa , that is equal to
the chemical potential of each particle in the bulk, µb . Since the number of particles can vary on
the surface, the natural ensemble to consider is the grand canonical ensemble because the natural
variables of the ensemble, µV T , are the same variables that are constant at equilibrium. We thus
treat the surface as the system.
The surface has Ns potential binding sites; each binding site is either occupied or not, with the
number of occupied sites (Na ) fluctuating. We aim to find an expression for fa = N Ns . Since Na
a

can vary, we really seek the ensemble average value of Na , so that fa = hN ai

Ns . Since each binding
site is independent and identical, we can factorize the partition function by treating each site as a
subsystem that is either occupied or unoccupied, meaning that a single particle is adsorbed to the
site or not. Since the sites are spatially distinct, each subsystem is distinguishable. We then write
the grand canonical ensemble partition function for the whole surface as:

Ξs = ξsNs (7.32)
where ξs is the single-site grand canonical partition function given as:

X
ξs = e−Ej β eµa Nj β (7.33)
j

For a single site, there are only two possible values of Nj : either the site is occupied, for which
Nj = 1, or the site is unoccupied, for which Nj = 0. Similarly, there are only two possible energies:
if Nj = 1, Ej = −a , and if Nj = 0, Ej = 0. Therefore the single-site partition function is:

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University of Wisconsin-Madison Lecture 7
CBE 710, Fall 2019 - Prof. R. C. Van Lehn September 26, 2019

ξs = e0β e0β + e−a β eµa β (7.34)

a β µa β
=1+e e (7.35)
Ξs = ξsNs (7.36)
 N s
= 1 + ea β eµa β (7.37)

Note that we do not include a factor of 1/Ns ! for the partition function, because here we write
the partition function for lattice sites, which themselves are distinguishable (as opposed to the
particles adsorbing onto them). Next, we write an expression for the grand potential:

ΣG = −kB T ln Ξs (7.38)
 
= −Ns kB T ln 1 + ea β eµa β (7.39)

We need to relate this thermodynamic potential to the quantity of interest, hNa i. Recall that
we can write an expression for ΣG , which is a function of the natural variables µa V T , as:

ΣG (µa , V, T ) = E(N, V, S) − T S − µa Na (7.40)

dΣG = dE − T dS − SdT − µa dNa − Na dµa (7.41)
= T dS − P dV + µa dNa − T dS − SdT − µa dNa − Na dµa (7.42)
= −SdT − P dV − Na dµa (7.43)
 
Therefore, we recognize that ∂Σ G
∂µa = −Na , so:
V,T
 
∂ΣG
Na = − (7.44)
∂µa V,T
Ns e e β
a β µa
= (7.45)
1 + ea β eµa β
Na
fa = (7.46)
Ns
ea β eµa β
= (7.47)
1 + ea β eµa β
We now have an expression in terms of the chemical potential of the particles adsorbed to the
bulk, but we’d like an expression in terms of the pressure of the bulk gas. At equilibrium, we
know that µa = µb , so we can calculate the chemical potential for particles in the bulk and relate
this to the pressure. Since the gas molecules are ideal, non-interacting particles, these particles
are described as an ideal gas. As a result, we can substitute in the expression for the chemical
potential derived from the ideal gas (canonical) partition function defined earlier and use this for
the chemical potential of particles in the bulk:

2πmkB T 3/2
 
N − Na
µb = −kB T ln 2
+ kB T ln (7.48)
h V
 
V
= −kB T ln (7.49)
(N − Na )λ3

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University of Wisconsin-Madison Lecture 7
CBE 710, Fall 2019 - Prof. R. C. Van Lehn September 26, 2019

Note that we use λ (the thermal de Broglie wavelength) to simplify the notation. We use the
ideal gas equation of state (V = (N −NPa )kB T ) to obtain a pressure dependence:

 
(N − Na )kB T
µb = −kB T ln (7.50)
P (N − Na )λ3
P λ3
 
= kB T ln (7.51)
kB T

Finally, we now require the condition µa = µb to find an expression for fa . Substituting in the
expression for µb to our prior expression for fa yields:

 
P λ3
ea β
kB T
fa = 
3
 (7.52)
1 + kPBλT ea β
P/P0
= (7.53)
1 + P/P0
 
Here, we define P0 = kλB3T e−a /kB T as a constant (equal to the pressure for which fa = 0.5)
that does not depend on fa or on P . This expression is our goal - we relate the pressure to the
fraction of occupied sites, fa . We can rearrange this to equivalently write:

P
fa = (7.54)
P + P0
This last expression is referred to as the Langmuir adsorption isotherm. It shows that
as the pressure of the system increases, the surface coverage increases until eventually plateauing.
Similar isotherm behavior is observed in a number of experimental systems. Note also that by
solving for the value P0 , which is equivalent to the pressure where the surface is half-occupied,
we can find a value for a or the binding energy if the thermal de Broglie wavelength is known.
Thus, statistical mechanics provides a valuable connection between microscopic and macroscopic
observables relevant to surface occupancy.