LUMS School of Science and Engineering

PH-202 Ideal Gas and Microcanonical Ensemble Feb,

25,2010

1 Micro-Canonical Ensemble
We will write the micro-canonical ensemble using the notation which matches that of Greiner.
Micro-canonical ensemble describes a system which is isolated and hence has a fixed energy.
(However, in principle it can be used to describe systems in interaction with other systems
by considering the combined system as isolated).
Writing the probability density for microcanonical ensemble again ( using Greiner’s nota-
tion)
1
ρM C (p, q) = δ (H(q, p) − E)
σ(E)
here σ(E) is a constant and apart from energy also depends on N and V and given by
normalization ∫ ∫
dqdpρM C = 1, ⇒ σ(E) = dqdpδ(H(q, p) − E)

1.1 The Accessible Phase Space Volume Ω(E)

As we described in the last set of notes, for calculational purposes, we write the microcanonical
probability density as
1
ρM C (q, p) = = E ≤ H(q, p) ≤ E + ∆
Ω(E)
=0 otherwise
effectively broadening the energy surface with energy E to an energy shell with energy between
E and E + ∆. Now Ω(E) is again given by normalization
∫
Ω(E) = d3N qd3N p = Volume in phase space of the region having energy b/w E and E + ∆
(1)

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 The Ω(E) as it stands has units of

(momentum)3N × (length)3N

. It is desirable to convert Ω into a dimensionless quantity by multiplying the right-hand

side of eq 1. by a constant which makes Ω(E) dimensionless. The reasons for doing this is
that we will soon be needing logarithms of Ω(E). Now one can not write logarithms of a
dimensionfull quantity. The argument of logarithm must be a pure number. If one writes
logarithm of a dimensionfull quantity, say pressure or volume, the argument of logarithm
must be understood as a pure number, stripped of its units. Hence, if we use, say log(V ) in
our equation, we must be able to understand beforehand that in which units this quantity
should be calculated, as the units themselves can not be taken into the argument. Otherwise,
our equations will not make sense as we will not be aware of which system of units they
are written in. For example, one can say that the value of volume is 6 in the logarithm,
but then one does not know in which units the value is 6 as volume is not a dimensionless
quantity.Therefore, in our expressions, we can only have things of the sort log( vV0 ) where v0
is some constant with dimensions of volume. It serves to define the units of volume. Hence,
for example, it now makes sense to say that the argument of log is 6, as we understand it to
be 6 numbers of v0 .

Consider the following example. We can have an equation

T = PV (2)

where T ,P and V are temperature, pressure and volume, as whatever units we put in for P
and V , we will get an answer for T in corresponding units. However, consider the following
equation
T = T0 log(P V ) (3)
where TO has dimensions of temperature. Now, we can only put pure numbers in the argument
of log for P V . Which units we use for these numbers?

In the light of above discussion, we want to use a constant v which makes Ω(E) dimen-
sionless. But which one we use? It turns out that using any constant whatsoever is equivalent
as we measure only the ratios of probabilities, and the constant will only change the normal-
ization for Ω(E). However, we still do need some constant, to be able to take the logarithm,
but anyone will do. Hence we write for Ω(E)
∫
1
Ω(E) = d3N qd3N p
v0
The dimensions of phase-space volume are

(momentum)3N × (length)3N

therefore v0 also has the same dimensions so that Ω is a dimension-less number. This will
now change our expression for ρM C to
1
ρM C =
v0 Ω(E)
But we could decide to keep
1
ρM C =
Ω(E)
∫
and chose to always integrate on v10 d3N qd3N p. This will make ρ also dimensionless. Then
∫
we have Ω, ρM C and the volume element v10 d3N qd3N p all dimensionless.
This has the added advantage that our formulas for classical case can be easily connected
to those in case of quantum mechanical ones ( where we will be counting states instead

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of calculating volumes of phase space regions). Now we can think of Ω(E) as “number of
microstates”, instead of a volume, as it becomes a dimensionless number. The constant v
divides the volume in phase space into small cells and Ω(E) just counts those cells. So, for
example, one could say that there is one state for each cell, then Ω is a measure of number of
microstates.
Notice however, that the actual number of microstates are not of any relevance in classical
case, as v is completely arbitrary. We could make it as small as we like to get a larger number
of states. Or put many states in each cell. It is only the ratio of number of states for different
energies which is of physical importance.
But again, to make connection with quantum mechanical formulas, there is a natural
choice for v, chosen to respect the quantum to classical limit, and that is an appropriate
power of Planck’s constant. Planck’s constant has same dimensions as the product of one
conjugate pair of position and momenta. So for N particles, we will have v = h3N . Now, in
quantum mechanical case, we should have

∆q∆p ∼ h

where ∆q and ∆p are uncertainties in position and momenta, so that the volume of each cell
can not be smaller than h3N . For classical case, h goes to zero, or in other words our volume
elements d3N qd3N p are much bigger than h. In any case, we will make this choice for v but
keep in mind that it is just a convention at this level.

2 Ideal Gas in Canonical Ensemble

Now in order to get a feel for what we have discussed so far for microcanonical ensemble,
we will consider a specific system in this ensemble, which can be exactly solved. The system
consists of N non interacting particles with mass m, which are confined to a container of
volume V . This is a model for ideal gas. Now, the energy function ( Hamiltonian) of the
system is simply given by

∑
N
p2i
H=
i
2m
We want to calculate the volume of an energy shell which is bounded by surfaces of energy
E and E + ∆. Our strategy will be to first calculate the volume of all states with energy

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up to E,denoted by w(E), the volume of the solid region bounded by energy surface E, and
subtract it from the volume of all states with energy up to E + ∆. This gives us volume of
our desired thin shell. We will find out that the thickness of the shell is not really important.

Let us first calculate the volume of the full energy ball w(E) The volume of the small shell
will be then
w(E + ∆) − w(E)
But this can be written as,

w(E + ∆) − w(E)
Ω(E) = ×∆
∆
dw(E)
Ω(E) = ×∆
dE
Here we do not need to take the limit ∆ → 0 as the errors introduced will be very small.
Now ∫ ∫ ∫
1
w(E) = 3N d3 x1 · · · d3 xN d3 p1 · · · d3 pN
h H≤E

where we have to integrate the momenta with the limits so that the energy does not exceed
E. Now, since the energy does not depend on the position coordinates, they are totally free
to be integrated with the limits that integration over each particle should be limited to the
“physical volume” it can move around in. Each integration gives us a V , giving us a total
contribution of V N for the coordinate integrations.
∫
VN
w(E) = 3N d3 p1 · · · d3 pN
h H≤E

Now the condition on total energy implies

H ≤ E ⇒ p21 + p22 + · · · + p2N ≤ 2mE

Hence the integration over momenta can be written as
∫ ∫
d3 p1 · · · d3 pN = √ √ d3 p1 · · · d3 pN
H≤E p21 +p22 +···+p2N ≤ 2mE=R

This suggests that there is spherical symmetry in N dimensions formed by the p′ s and we
can go to spherical coordinates. The integral only depends on the radial coordinate. Using
the symmetry, it will be quite easy to evaluate this integral, without computing
√ the Jacobians.
This integral is simply area of a 3N -dimensional sphere with radius R = 2mE

Now let us see how the volume of a general d-dimensional sphere can be calculated.

2.1 Volume of a d-sphere

Consider a sphere in d dimensions. It is given by

x21 + x22 + · · · + x2d = R2

where x′i s are the cartesian coordinates in d-dimensions and R is a radius, a constant. First
of all, because the integral for volume of a d-sphere only depends on the radius R, we have
for the volume

V (R) = Cd Rd
where Cd is a constant and the power of R has been determined by matching the dimensions,
as R has the same dimensions as each xi and the volume integral has dimensions of dim[x]d .

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 Now we will find the constant Cd by a trick.
Now the change in volume, due to a small change in radius only, keeping the angular
coordinates fixed is

dV (R) = Cd dRd−1 dR
For a function f (R) which depends only on R,
∫ ∫
dx1 · · · dxd f (R) = Cd d dR Rd−1 f (R)

As the function does not change along other directions other than R, we only need to look
at its variation with R and hence the above equation holds. Now consider the gaussian
∫ ∞
dx1 · · · dxd e−x1 −x2 −···−xd = π 2
2 2 2 d

−∞

Going to the radial coordinate, this can be written as

∫ ∞
dR Cd d Rd−1 e−R = π 2
2 d

Now substituting R2 = y, we get

∫ ∞
1
e−y y 2 −1 dy = π 2
d d
Cd d
2 0

d
π2
Cd = d d
2 Γ( 2 )
Therefore Volume of a d-sphere is
d
π 2 Rd
Vd = d d
2 Γ( 2 )

Now we can come back to our original

√ integral, i.e., the phase space volume up to energy
E. There we have a sphere of radius R and dimension d = 3N , which gives
3N
V N π 2 Rd
w(E) =
h3N 3N 3N
2 Γ( 2 )
3N
V N (2πmE) 2
w(E) =
h3N ( 3N
2 )!

Now Ω(E) can be found from here by taking the derivative with respect to E and multi-
plying by ∆
3N
−1
V N 2πm(2πmE) 2
Ω(E) = ∆
2 − 1)!
h3N ( 3N
This is our final result for the phase space volume.

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3 Entropy and Equation of State
The Ω(E) derived above contains all the statistical and hence thermodynamic information
about the system, as it defines the probability distribution. However, as we discussed before, in
order to make contact with macroscopic measurements, one not only has to give a probability
distribution, but also give a prescription about which microscopic quantities are those whose
ensemble average coincides with a particular macroscopic measurement.
It was Boltzmann who guessed how the entropy from the probability density can be de-
rived. All the other thermodynamic information is derived from this connection. Entropy
is the bridge between microscopic averages and macroscopic measurements. We will discuss
this in detail later, right now our intention is to take this guess of Boltzmann ass granted and
see what other information we can get from our ensemble. In the end, the justification for
Boltzmann’s guess comes from the fact, that starting from just his definition of Boltzmann,
one can derive all of thermodynamical laws.

For now we will assume the thermodynamic laws to hold, and staring from our calculated
Ω(E), derive equations of state for the ideal gas.
Now Boltzmann’s definition for entropy in terms of probability density is

S = k log Ω =< −k log ρ >

which for microcanonical case becomes

S = k log Ω

here k is Boltzmann’s constant.

Now putting in our Ω(E), we get for entropy
3N
S =N k ln V + ( − 1)k ln(2πmE) + k ln(2mπ)
2
3N
+ k ln ∆ − 3N ln h − ln(( − 1)!)
2
Now N is a very very large number. Therefore, we can drop all terms which are not
multiplied by N as they are extremely small compared to the ones which have N . Also using
Sterling’s approximation for log x! = x ln x − x for large x, we have
3N 3N 3N 3N
S = N k ln V + k ln(2πmE) − 3N k ln h − k ln( ) + k ln( )
2 2 2 2
Now from the first law of thermodynamics

dE = dQ − pdV
Considering a reversible process, we can replace dQ by T dS.

dE = T dS − pdV
However, one we have this equation, everything in here is a state quantity. Therefore, the
above equation always holds for the states functions it contains. Now from this equation, we
find ( )
1 dS
=
T dE V
Using our formula for entropy, this gives
3N
1 k
= 2
T E
3N
E= kT
2

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which is just one of the equations of state for ideal gas i.e., its energy is a constant times
temperature.
Now we also have from T dS form of first law ( also sometimes called combined first and
second law)
( )
P dS
=
T dV E
Again using our entropy formula to calculate the derivative, we get
P Nk
=
T V

P V = N kT
which is just the ideal gas law.
Now these are extremely interesting results. The two equations of state were an extra
input in case of thermodynamics. In fact we always need to give an equation of state from
outside to apply laws of thermodynamics to a system. But here, starting from a simple
model Hamiltonian, and our machinery of Micro-canonical Ensemble, we have “derived” the
equations of state. The complicate integrals gave simple beautiful result in the form of
equation of state.