September 18, 2001

Reading: Chapter Four

Homework: 4.1,4.2,4.3,4.4

Boltzmann Equation:
Consider adding a small amount of heat to a system of fixed V and T, So, w = 0.
First law:

So,

dU = q w = q
q dU
dS =
=
T
T
dU dS
d (ln ) =
=
k BT k B
dS = k B d (ln )
S = k B (ln ) --- Boltzmann equation.

Configurational Entropy:

Consider two crystalline materials that are completely miscible in each other in
physical contact, such as Au(A) and Ag(B).
Suppose there are nA number of A atoms and nB number of B atoms. Initially, two
crystals are completely separately. Number of ways of distributing nA atoms on nA
n !
sites is A = A = 1 ; similarly, number of ways of distributing nB atoms on nB
n A!
n !
sites is B = B = 1 .
nB !
nA
A atoms

nB
B atoms

Thus, initial = A B = 1
Now, let two crystals completely mixing up, i.e. distributing nA A atoms and nB B
atoms on (nA+nB) sites.
The number of ways in doing so is
(n + n B )!
final = A
n A ! nb !

Thus, the entropy of mixing (configurational entropy), i.e., the increase of entropy
due to mixing is
S = S f S i = k B ln f k B ln i = k B ln f = S f

S = k B ln f = k B ln

(n A + n B )!
n A ! nb !

Using Stirlings relation:

S = k B [(n A + n B ) ln(n A + n B ) (n A + n B ) n A ln n A + n A n B ln n B + n B ]
= k B [n A ln(n A + n B ) n A ln n A + n B ln(n A + n B ) n B ln n B ]
nA
nB
= k B n A ln
k B n B ln
n A + nB
n A + nB
So, S = k B N ( A ln A + B ln B )
Where A =

nA
nB
,B =
, is the mole fraction, i.e., concentration.
n A + nB
n A + nB

N = n A + n B = total number of particles.

For 1 mole, N = N 0 = Avogadros number
S = R( A ln A + B ln B )
This is known as configurational entropy. It corresponds to maximum entropy of
mixing with uniform composition. Since U and V are fixed (no heat, no work), the
criterion for equilibrium is to maximize entropy.
Example: Prove that the configurational entropy is indeed the maximum in a twocomponent system if the composition is uniform.

Solution: Starting with the uniform composition, suppose we move a few atoms
from one side to another to create a compositional inhomogeneity. So, lets say
we shift n0 A atoms from left to right, and n0 B atoms from right to left.

AnA - n0
A atoms

AnB + n0
A atoms

BnA + n0
B atoms

BnB - n0
B atoms

nA sites

nB sites

The new can be calculated as

nA!
nB !
=

( A n A n0 )!( B n A + n0 )! ( A n B + n0 )!( B n B n0 )!
Thus,
ln = n A ln n A ( A n A n0 ) ln( A n A n0 ) ( B n A + n0 ) ln( B n A + n0 )
+ n B ln n B ( A n B + n0 ) ln( A n B + n0 ) ( B n B n0 ) ln( B n B n0 )
The objective is to determine n0 for which ln is a maximum.
0

d (ln )
= ln( A n A n0 ) + 1 ln( B n A + n0 ) 1 ln( A n B + n0 ) 1 + ln( B n B n0 ) + 1
dn0

ln( A n A n 0 ) + ln( B n B n0 ) = ln( A n B + n0 ) + ln( B n A + n0 )

( A n A n0 )( B n B n0 ) = ( A n B + n0 )( B n A + n0 )

A B n A n B + n02 n0 ( A n A + B n B ) = A B n A n B + n02 + n0 ( A n B + B n A )
n0 ( A n A + B n B + A n B + B n A ) = 0
n0 {n A + n B } = 0
Since {n A + n B } 0, n0 = 0
Furthermore,
d 2 ln()
dn02

n0 = 0

1
1
1
1
=

A n A n0 B n A + n0 A n B + n0 B n B n0 n0 =0
=

1
1
1
1

<0
A n A B n A A nB B nB

Thus, ln is a maximum when n0=0, i.e., when the composition is uniform.