1

Gibbs Paradox


Consider the following scenariosuppose we have a box divided into two equal halves.
The entire box is thermally isolated, but the partition separating the two parts allows the
exchange of energy. In the left half, we place helium gas; in the right half, an equal
quantity of argon gas.




Now suppose we remove the barrier. Both gases will diffuse to fill the entire container;
and intuitively, it seems reasonable to expect the total entropy of the system to increase.
Its not so hard to calculate the increase in entropy. If we use the microcanonical
ensemble, we have
( )
3 / 2
3
( , , ) 2
!
N
N
N
B
E V N V mE
N h
=
We will absorb the mass term into B, and so obtain
3 / 2
3
( , , )
!
N N
N
B
E V N V E
N h
=
The entropy is given by
3
ln ( , , )
3
ln ln ln
! 2
3
const ln ln
2
N
S k E V N
B Nk
k Nk V E
N h
Nk
Nk V E
=
| |
= + +
|
\ .
= + +

Notice that we could get the same result from purely thermodynamic reasoningfrom
the first TdS equation, for example.
We pretend we can neglect the constant term involving ! N Then, assume that the final
volume for both gases is just twice the initial volume (that is,
1 2
V V V = = , and hence
1 2
2
f f f
V V V V = = = ). We also assume that the energy remains constant. Under these
circumstances,

helium argon

N
1
, V
1
N
2
,V
2

2
final initial
1 1 2 2 1 1 2 2
ln ln ln ln
ln2 ln2 ln ln
ln2 ln2
2 ln2
f f i i
S S S
N k V N k V N k V N k V
Nk V Nk V Nk V Nk V
Nk Nk
Nk
=
= +
= +
= +
=

This result seems reasonable. And in fact, it is identical to the result we found earlier
when we calculated the entropy change involved in an adiabatic free expansion, if we
assume that 2
f i
V V = . (Recall that we calculated the entropy by doing a quasi-static
compression to return the gas to its original state.)
Now, suppose we have exactly the same process, except that both halves of the insulated
container initially contain helium. For this case, one expects intuitively that 0 S = . But
when we do the calculation, we find
( )
final initial
(2 ) ln 2 ln
(2 ) ln(2 ) 2( ln )
2 ln2
f i
S S S
N k V Nk V
N k V Nk V
Nk
=
=
=
=

which is exactly the same result we got in the first casesomething must be wrong!!
Strange as it may seem, the problem lies in the neglect of the N! term. To see why, return
to our original expression for entropy; this time, we will be more careful.
3
ln ( , , )
3
ln ln ln
! 2
3
ln ln ln ! 3 ln ln
2
N
S k E V N
B Nk
k Nk V E
N h
Nk
Nk V E k N Nk h k B
=
| |
= + +
|
\ .
= +

Using the Stirling approximation, ln ! ln N N N N , we obtain
3
ln ln ln 3 ln ln
2
Nk
S Nk V E Nk N Nk Nk h k B = + + +
Now we combine the first and third terms to obtain
3
ln ln 3 ln ln
2
V
S Nk Nk E Nk Nk h k B
N
= + +
The last three terms will still make no contribution when we calculate the entropy change
S . But replacing V by V/N will make a difference. We use this new expression to
calculate S for the two cases discussed above. We assume that
1 2
N N N = = .
3
case 1helium and argon
final initial
1 2
1 2
1 2 1 2
1 2 1 2
ln ln ln ln
2 2
ln ln ln ln
ln2 ln2
2 ln2
f f
i i
S S S
V V
V V
N k N k N k N k
N N N N
V V V V
Nk Nk Nk Nk
N N N N
Nk Nk
Nk
=
= +
= +
= +
=

This result is exactly the same as the one we obtained above.
case 2helium on both sides
final initial
(2 ) ln 2 ln
2
2
(2 ) ln( ) 2( ln )
2
2 ln 2 ln 0
f
i
S S S
V
V
N k Nk
N N
V V
N k Nk
N N
V V
Nk Nk
N N
=
| |
=
|
\ .
=
= =

This result is quite different from the result we obtained above, and agrees with our
intuitive expectation. Strangely enough, keeping the N! term leads to the correct result,
even in a system that does not seem in the least quantum-mechanical.

Connection to the canonical ensemble and Baierleins result
It is worth noting that the same result follows from the canonical ensemble. Take
Baierlein Eq. (5.39) as a starting point:
( )
3 / 2
3
2 3
ln
2 !
N
N
N
V mkT
S Nk k
h N

= + .
First note that
( )
3 3
ln ln ln 2 ln ! 3 ln
2 2
S Nk e Nk V Nk mkT k N Nk h = + +
where I have used the identity ln 1 e = to put the equations into Baierleins form. Using
the Stirling approximation,
( )
ln ! ln
(ln 1)
ln ln
ln
N N N N
N N
N N e
N
N
e
=
=
=
=

4
we have, on substituting,
( )
( )
3 3
ln ln ln 2 ( ln ln ) 3 ln
2 2
5 3
ln ln ln 2 3 ln
2 2
S Nk e Nk V Nk mkT k N N N e Nk h
V
Nk e Nk Nk mkT Nk h
N

= + +
= + +

To make a connection to our earlier results, note that we could rewrite this equation in the
form
3
ln ln constant
2
V
S Nk Nk T
N
= + + .
Thus, if we recall that we measure entropy changes, it should be evident that the
canonical ensemble, the microcanonical ensemble, and macroscopic thermodynamics (for
example, the first TdS equation all lead us to the same result!
This form is also identical to Baierleins Eq. (5.41), which if we write it out in full, reads
3/ 2
5/ 2 5/ 2
3 2
/ 2
ln ln
th
V N V mkT
S Nk e Nk e
N h

| |
= =
` ` |
\ .
)
)
.
Writing out the log terms leads us back to Eq. 5.39, and to the intermediate result given
above.