86

Chapter 3 Second and Third Laws of Thermodynamics

As a second illustration we will consider the spontaneous (irreversible)

freezing of water below its freezing point (see Fig. 3.6). The freezing of a mole
of supercooled water at 10 !C is an irreversible change, but it can be carried
out reversibly by means of the three steps for which the entropy changes are
indicated:
H2O(l)

H2 O(l, 0 ! C)

S H /T

H2 O(s, 0 ! C)

273 Cliq
S  263 T dT

Heat reservoir
at 10 C

H2 O(l,

263 C ice
S  273 T dT

"

10 ! C)

H2 O(s,

(3.37)

10 ! C)

For the crystallization of liquid water at 0 !C, H  6004 J mol 1 . The heat
capacity of water may be taken to be 75.3 J K 1 mol 1 , and that of ice may be
taken to be 36.8 J K 1 mol 1 over this range. Then the total entropy change
of the water when 1 mol of liquid water at 10 !C changes to ice at 10 !C is
simply the sum of the three entropy changes:
H2O(s)

S  (75.3 J K

Heat reservoir
at 10 C

Figure 3.6 When a mole of liquid

water freezes at 10 !C, its entropy
changes by 20.54 J K 1 mol 1 ,
corresponding to the increase
in structural order. The entropy
of the reservoir increases by
21.37 J K 1 mol 1 because of the
heat transferred to it. The system
as a whole increases in entropy, as
expected for an irreversible process
in an isolated system.

(36.8 J K


20.54 J K

mol 1 ) ln
1
1

mol 1 ) ln
mol

( 6004 J mol 1 )
273 K

273
263
263
273

(3.38)

The decrease in entropy corresponds to the increase in structural order when water freezes.
The statement that the entropy of an isolated system increases in a spontaneous process may be illustrated by considering supercooled water at 10 !C
in contact with a large heat reservoir at this temperature. The entropy change
for the isolated system upon freezing includes the entropy change of the reservoir as well as the entropy change of the water. Since the heat reservoir is large,
the heat evolved by the water on freezing is absorbed by the reservoir with
only an infinitesimal change in temperature. The transfer of heat to a reservoir at the same temperature is a reversible process. Since the heat of fusion of
water at 10 !C is H (263 K)  (75.3 J K 1 mol 1 )(10 K) 6004 J mol 1
(36.8 J K 1 mol 1 )(10 K)  5619 J mol 1 , the entropy change of the reservoir
in the transfer of heat is
S 

(5619 J mol 1 )
 21.37 J K
263 K

The entropy change of the water is 20.54 J K

change of the system water plus reservoir is
S  (21.37

20.54) J K

mol

mol

(3.39)

mol 1 , and the total entropy

 0.83 J K

mol

(3.40)

Thus, the total entropy of the isolated system, including water and reservoir, increases, as required by inequality 3.24.

3.5 Entropy of Mixing Ideal Gases

ENTROPY OF MIXING IDEAL GASES

Figure 3.7 shows that amount n1 of gas 1 at P and T is separated from amount n2
of gas 2 at the same pressure and temperature. When the partition is withdrawn
the gases will diffuse into each other at constant temperature and pressure if they
are ideal gases. To calculate the change in entropy in this irreversible process we
need to find a way to carry it out reversibly. This can be done in two steps. First,
we expand each gas isothermally and reversibly to the final volume V  V1 V2 .
These volumes are not molar volumes, but are actual volumes. When extensive
volumes are used, the ideal gas law is written PV  nRT .
Using equation 3.35, the entropy changes for the two gases are
n1 R ln

S2 

V2
n2 R ln

V

n1 R ln
n2 R ln

n1
n1

n2
n2

n1

n2

n1 R ln y1

n2 R ln y2

n1 R ln y1

n2 R ln y2

ni ln yi 

nt R

 11.526 J K

mol

n1 + n2

(3.43)

yi ln yi

Gas 1

Gas 2

Gas 1

Gas 2

(3.44)
Gases
1 and 2

Vacuum

What is the entropy of mixing of 1 mol of oxygen with 1 mol of nitrogen at 25 !C, assuming
that they are ideal gases?
Equation 3.44 becomes
1

P, T, V1 + V2

(3.42)

Example 3.10 Entropy of mixing ideal gases

(2 mol)(8.3145 J K

Initial state

Figure 3.7 Mixing of ideal gases.

The partition between n1 mol of gas
1 at P and T and n2 mol of gas 2 at
P and T is withdrawn so that the
gases can mix.

Since yi " 1, ln yi " 0, and mix S is always positive. A plot of the entropy of
mixing two ideal gases is shown in Fig. 3.9.

mix S 

n2

Final state

In the second step the expanded gases are mixed reversibly at constant volume.
To see how this might be done we have to imagine two semipermeable membranes,
arranged as shown in Fig. 3.8, one of which (represented by dashes) is permeable
only to gas 1, and the other (represented by dots) is permeable only to gas 2. The
membrane that is permeable to gas 1 and an impermeable membrane, which is separated from it by volume V, are moved at the same infinitesimally slow rate to the
left. As shown by the diagram for the intermediate stage in the reversible mixing
process, the
membrane combination has to be moved to the left against a pressure of P1 (to the left of
) plus P2 (to the left of ). But the pressure on the
right-hand side of is also P1 P2 . Therefore, no work is required to move the
membrane in this frictionless device. The internal energies of the two ideal gases
are functions only of T (Section 2.6), and so according to the first law no heat is absorbed by the gas in this step. Consequently, there is no entropy change associated
with the second step, and so equation 3.43 gives the total entropy change for the
isothermal mixing of the two ideal gases.
Equation 3.43 can be generalized to
mix S 

n1

(3.41)

where yi is the mole fraction. The entropy of mixing mix S is the sum of the entropy changes for the two gases:
mix S 

P, T, V2

Vacuum

V1

V

S1 

P, T, V1

Gases
1 and 2

3.5

87

You might try other proportions and see what happens.

)  12 ln 12

1
2

ln 12 

Figure 3.8 Reversible isothermal

mixing of ideal gases 1 and 2 using a
membrane permeable only to gas 1
(shown by dashes), a membrane
permeable to gas 2 (shown by dots),
and an impermeable membrane
(shown by the solid line).

Chapter 3 Second and Third Laws of Thermodynamics

0.7
0.6
0.5

Smix /R

88

0.4
0.3
0.2
0.1
0

0.2

0.4

0.6

0.8

y2

Figure 3.9 Plot of the entropy of mixing of two ideal gases to produce one mole of an
ideal mixture. (See Computer Problem 3.C.)

Example 3.11

The Gibbs paradox

For the mixing of two gases that have the same temperature and pressure, equation 3.43
can be written in the form
mix S  n1 R ln

Vf
V1

n2 R ln

Vf
V2

where V1 and V2 are the volumes of the two gases and Vf  V1 V2 . Suppose that two
equal volumes of the same gas are mixed. What is the change in entropy?
If we apply this equation to the mixing of two equal volumes of the same gas, we obtain
mix S  (n1

n2 )R ln 2

This answer is wrong because there is no change of state in this process, and so S  0.
This is known as the Gibbs paradox. The answer to this paradox was not properly understood until the development of quantum mechanics. According to quantum mechanics, the
molecules of a single species are indistinguishable; therefore, equation 3.44 does not apply.
If two different species have properties that are very nearly the same, they are still different
from a quantum mechanical point of view, and equation 3.44 does apply.

(a)

3.6

(b)

Figure 3.10 (a) Equilibrium

gaseous system after a hole is
punched in the diaphragm.
(b) Highly improbable state of
the gaseous system after the
hole has been punched.

ENTROPY AND STATISTICAL PROBABILITY

Using the macroscopic approach of thermodynamics, we have found that the

equilibrium state of an isolated system is that state in which the entropy has its
maximum value. From a microscopic point of view, we might expect that the
equilibrium state of an isolated system would be the state with the maximum statistical probability. For simple systems we can use the molecular point of view to
calculate the statistical probabilities of different final states. For example, assume
that one mole of an ideal gas is in a container that is connected to a container of
equal volume through a stopcock; this expansion has already been discussed in
Example 3.3. Actually, it is a little easier to think about the reverse process, and so
we will do that. As shown in Fig. 3.10, we will start with an opening between the
two chambers and ask, what is the statistical probability that all of the molecules
will be in the original chamber? The probability that a particular molecule will be
in the original chamber is 1/2. The probability that two particular molecules will
be in the original chamber is (1/2)2 , and the probability that all the molecules

3.6 Entropy and Statistical Probability

will be in the original chamber is (1/2)N , where N is the number of molecules in

the system. If the system contains a mole of gas molecules, the statistical probability that all the molecules will be in the original chamber is
(1/2)6.022

1023

 e!4.174

1023

(3.45)

Boltzmann postulated that

S  k ln 

(3.46)

where k is Boltzmanns constant (R /NA ) and  is the number of equally probable

microscopic arrangements for the system. This relation can be used to calculate
S for the transformation from an initial state with entropy S and  equally
probable arrangements to a final state with entropy S " and  " equally probable
arrangements:
S  S " ! S  k ln( "/)

(3.47)

It is often difficult to count the number of equally probable arrangements in the

final state and in the initial state, but the ratio  "/ in this case is equal to the ratio
of the probability that all the molecules are in one chamber to the probability that
they are all in one chamber or the other. The probability that all the molecules
are in the original chamber or the other chamber is, of course, unity. Thus, for
the system in the preceding paragraph, we have already calculated the ratio
of the probabilities that is equal to  "/ . The change in entropy in going from
the state with the gas distributed between the two chambers to the state with
all the molecules in the original chamber is
S  k ln e!4.174
 (1.381

1023

10!23 J K!1 )(!4.174

 !5.76 J K!1

1023 )
(3.48)

Since we are considering one mole of an ideal gas, the change in entropy for the
expansion process in Example 3.3 is S  5.76 J K!1 mol!1 , in agreement with
the result using Boltzmanns hypothesis. This confirms that the Boltzmann constant is indeed given by k  R /NA .
If the gas molecules were all to be found in one chamber after having been
distributed between the two chambers, we would say that the second law had been
violated. We have just seen that the probability that such a thing might happen is
not zero. It is, however, so small that we could never expect to be able to observe
all the molecules in one chamber, even for systems containing much, much less
than one mole of gas. If, however, we considered a system of only two molecules,
then we could find both molecules in one chamber with reasonable probability.
This shows that the laws of thermodynamics are based on the fact that macroscopic systems contain very large numbers of molecules.
The equation S  k ln  embodies an important concept, but it is not used
very often because it is difficult to calculate  . In Chapter 16 on statistical mechanics we will use other equations to calculate the entropy.
The collision of two gas molecules is reversible in the sense that the reverse
process can also happen. If, after the molecules are moving away from each other,
we could simply reverse the direction of the velocity vectors, the molecules would
move along the same trajectories in the reverse direction. In short, the movie of
the reverse process is just as reasonable as the movie of the forward process. This is
true for both classical mechanics and quantum mechanics. If molecular collisions

89

90

Chapter 3 Second and Third Laws of Thermodynamics

are reversible, then why is the expansion of a gas into a vacuum, or the mixing of
two gases, irreversible? If we could take a movie of the expansion of a gas into a
vacuum that would show the locations of all the molecules, we could tell whether
the movie was being run forward or backward. However, if we were to look at
each molecular collision we would find that each followed the laws of mechanics,
and was reversible. If we were to look at the movie being run backward, we would
feel that it was depicting something that could not happen. But why couldnt it
happen? As a matter of fact, it could, but only if we could give all the molecules
the positions they have at the end of the movie but then reverse their velocity
vectors. If we then looked at the individual collisions, we would find that they
would take all the molecules to the region from which they had expanded. The
reason this does not happen in real life is that it takes an extraordinarily special
set of molecular coordinates and velocities. This set of coordinates and velocity
vectors is so unlikely that thermodynamics says that the reverse process can never
happen.
Since dS
dq /T , the entropy is a measure of the flow of heat between a system and its environment. When heat is absorbed by the system from its surroundings, q is positive and the entropy of the system increases. The energy flowing into
the sysem is dispersed in the sense that it goes into increasing the energy of various molecular motions in the system. This concept of the dispersal of energy also
applies to the expansion of an ideal gas into a vacuum. In this case q is zero, but
the total energy of the gas is dispersed over a larger volume. Thus entropy is a
measure of the dispersal of energy among the possible microstates of molecules
in a system.
Sometimes entropy is referred to as disorder, and a messy desk is referred
to as a state of high entropy. Or shuffling a deck of playing cards is said to result
in an increase in entropy of the cards. But this is misleading from a scientific viewpoint because moving macroscopic objects around does not involve an increase in
entropy.* Another source of confusion about entropy comes from the use of this
term in information theory, which was introduced by Shannon in 1948. The quantity entropy in information theory is not the entropy of thermodynamics because
it does not deal with the transfer of heat and the dispersal of energy among the
microstates of a system.
The concept of temperature is necessarily involved in understanding thermodynamic entropy because it indicates the thermal environment of the particles in a system. These particles are involved in the ever-present thermal
motion that makes spontaneous change possible because it is the mechanism
by which molecules can occupy new microstates when the external conditions are
altered.

Comment:
The entropy of mixing of ideal gases brings up a very important idea, namely, that
some processes happen spontaneously even though they do not reduce the energy
of a system. Our experience with mechanics leads us to expect that if something
happens spontaneously, there is necessarily a decrease in energy. Now we know
that is not true, and we can expect to find chemical reactions that occur because of
the contribution of a positive S .
*F. L. Lambert, J. Chem. Educ. 79:187192 (2002).