CHM 301

INTRODUCTION TO STATISTICAL THERMODYNAMICS

Statistical thermodynamics is based on the principle that thermodynamic observables
are averages of molecular properties, and it sets up a scheme for calculating these
averages.

Canonical ensemble
This is an imaginary collection of replication whereby every reproduction has exactly the
same temperature, and the system within each unit has exactly the same volume and
constitution.
Basically, two approaches can be applied to the calculation of the properties of an
ensemble:
The first view point: the role of reservoir
Let Et = total energy of isolated unit
Ei = energy of system
The energy of the reservoir, Er is Et – Ei
Supposing the reservoir can accommodate Er in W’ (Et – Ei) different ways, it follows
that the probability of the system being in a given state with energy Ei is

P(Ei) = CW’(Et – Ei) (1)

Where C is some constant

Equation (1) underlies much of statistical thermodynamics and is called the principle of
equal a priori probabilities, and asserts that, unless there is any information to the
contrary, all possibilities are assumed equally probable.
Since Ei << (Et – Ei), it follows that
In W’ (Et – Ei) = In W’ (Et) - ᵟIn W’ Ei + …………….. (2)
ᵟE Et
The other terms in the series (eqn.2) are higher powers of Ei and are negligible
because Ei is so small.

β= ᵟIn W’ (3)
ᵟE
Substituting eqn. (3) into eqn. (2)
In W’ (Et – Ei) = In W’ (Et) – β(Ei) (4a)

or
-β(E )
W’ (Et – Ei) = W’ (Et)e i (4b)

Substituting eqn. (4b) into eqn. (1)

P (Ei) = C W’ (Et)e --β(Ei)

The number W’ (Et), a property of the reservoir, is independent of the state of the
system, and so may be combined with C to give a new constant C’ = CW’ (Et)
C’ can be determined from the condition that the total probability of finding the system
in some state must be unity i.e.,
-β(E )
∑P(Ei) = C’∑e - i =I (6)
-β(E )
Therefore, C’ = 1 ∑ e i (7) {C’ = CW’ (Et)}
Putting the expression for C’ in eqn. (7) into eqn. (5)
-β(E ) / -β(E )
P (Ei) = e i ∑e i (8)
Eqn. (8) is called the canonical distribution.
The second view point: dominating distributions
Since the total number of members of the ensemble, Ne, is definite, the average energy
is also a constant with some value <E> i.e.,
<E> = Ee/Ne (10)
Where <E> = average energy of Ne members of an ensemble of total energy Ee.
Suppose the members can have some energy U(0) + Ei, where U (0) is some origin
from which all energies are measured, and supposed that ni members have that energy
at some instant. Then, the total energy of the ensemble is

Ee =∑ ni {U (0) + Ei}, Ne =∑ ni (12)

i i

hence,
<E> = (1/Ne) ∑ ni {U (0) + Ei},
i
Determining the most probable distribution for a given <E>
The number of ways of organizing a given type of distribution, its weight X is given by:
X (n1 n2……….) = N!/n1!n2!......... (12)
Where n1, n2 …… are the numbers with energies U (0), U (0) + E, ……etc.

Example
The distributions for a 3-member ensemble may be illustrated as follows:

2E ……………………… ………………………………… ………….*……………..

E………………………… …………….*………………… ………….*……………..
0………..***………… …………..**………………... ………..…*…………….
WA WB WC

XA (3,0,0) = 3!/3! = 1
XB (2,1,0) = 3!/2! = 3 x 2!/2! = 3
XC (1,1,1) = 3!/1! = 3 x 2x 1!/1! = 6

The numbers 6, 3 and 1 are known as the weights (X) of the distributions.