A9.1 A Statistical Mechanical Interpretation of the Entropy of Mixing in an Ideal Mixture CDA9.

1-1

Appendix A9.1 A Statistical Mechanical Interpretation of the Entropy of Mixing

in an Ideal Mixture
The entropy change of mixing for an ideal binary gaseous or liquid mixture,



mix S IM = −R x i ln x i
= −R(x 1 ln x 1 + x 2 ln x 2 ) (A9.1-1)
(cf. Eq. 9.1-8 and the appropriate entry in Table 9.3-1) has a very simple statistical
mechanical interpretation.
To demonstrate this, we consider a collection of N1 molecules of species 1 and N2
molecules of species 2 maintained at constant total internal energy U and constant
volume V . Furthermore, it is assumed either that the molecules do not interact (this is
the case for an ideal gas mixture) or that the molecules do interact, but the interaction
energy function is the same for all species; that is, the species 1–species 1, species 2–
species 2, and species 1–species 2 interactions are all alike (this is the assumption that
underlies the ideal mixture model).
In courses on advanced physical chemistry and statistical mechanics, it is shown
that the entropy function for a binary mixture at constant internal energy, volume, and
number of particles is
S = N1 S1,intra + N2 S2,intra + Sconf (A9.1-2)
Here Si,intra is the entropy of one molecule of species i due to its intramolecular struc-
ture (which can be calculated from detailed structural and spectroscopic information
on the species), and Sconf is the entropy contribution due to the configuration of the
system, that is, the way species 1 and 2 are distributed in the mixture. The statistical
mechanical expression for the configurational entropy for a specific macroscopic state
of the mixtures being considered here is

Sconf = k ln  (A9.1-3)
where  is the number of different arrangements of the molecules that result in the
desired macroscopic state and k is the Boltzmann constant. Our interest here is in
computing the value of Sconf for different distributions of the two species within the
system.
To compute Sconf we will imagine that within the volume V there is a three-dimen-
sional lattice with N = N1 + N2 equally spaced lattice points. Different macroscopic
states for this model system correspond to different arrangements of the N1 molecules
of species 1 and the N2 molecules of species 2 among the N lattice points. By the ideal
mixture assumption, each distribution of molecules among the lattice points has the
same energy as any other.
The number of ways of distributing the N1 identical molecules of species 1 and the
N2 identical molecules of species 2 among the N1 + N2 lattice sites in a completely
random fashion is, from simple probability theory, equal to
(N1 + N2 )!
N1 !N2 !
Therefore, the configurational entropy of the completely random mixture is
 
random (N1 + N2 )!
Sconf = k ln (A9.1-4)
mixture N1 !N2 !
CDA9.1-2 Chapter 9: Estimation of the Gibbs Energy and Fugacity of a Component in a Mixture

This equation can be simplified by using Stirling’s approximation for the logarithm of
a factorial number,
ln M! = M ln M − M (A9.1-5)
which is valid for large M. Using Eq. A9.1-5 in Eq. A9.1-4 yields
 
random
Sconf = k[ln(N1 + N2 )! − ln N1 ! − ln N2 !]
mixture
= k[(N1 + N2 ) ln(N1 + N2 ) − (N1 + N2 )
− N1 ln N1 + N1 − N2 ln N2 + N2 ] (A9.1-6)
 
N1 N2
= −k N1 ln + N2 ln
N1 + N2 N1 + N2
= −k(N1 + N2 )[x 1 ln x 1 + x 2 ln x 2 ]
Now dividing by the sum of N1 and N2 and multiplying by Avogadro’s number Ñ
( = 6.022 × 1023 ), we obtain an expression for the configurational entropy per mole
of mixture
 
random
S conf = − Ñ k[x 1 ln x 1 + x 2 ln x 2 ] (A9.1-7)
mixture
= −R[x 1 ln x 1 + x 2 ln x 2 ]
where R = Ñ k is the gas constant of Table 1.4-1.
Now consider the completely ordered configuration in which the molecules of species
1 are restricted to the first N1 lattice sites and the molecules of species 2 to the remain-
ing N2 lattice sites; that is, the two species are not mixed. The number of different ways
in which this can be accomplished is
N1 !N2 !
=1 (A9.1-8)
N1 !N2 !
so that
 
completely
S conf = R ln 1 = 0 (A9.1-9)
ordered
Therefore, the entropy change on going from the completely ordered (unmixed) state
to the randomly ordered (completely mixed) state is
   
random completely

mix S = S conf − S conf
mixture ordered (A9.1-10)
= −R[x 1 ln x 1 + x 2 ln x 2 ]
which is in agreement with Eq. A9.1-1.
One can easily establish, though we will not do so here, that any partially ordered
state will have a molar configurational entropy intermediate to the randomly mixed and
completely ordered states. Therefore, the randomly mixed state is the state of highest
entropy. Since the criterion for equilibrium at constant internal energy and volume is
that the entropy of the system achieve a maximum, the randomly mixed or completely
disordered state is the equilibrium state in an ideal mixture.
It is tempting to try to generalize this result by suggesting that the completely disor-
dered state is always the equilibrium state. However, this is not correct! In a mixture
A9.1 A Statistical Mechanical Interpretation of the Entropy of Mixing in an Ideal Mixture CDA9.1-3

in which not all interactions are alike, different distributions of molecules among the
lattice sites will result in different total energies of the system. In this case, energetic,
as well as entropic, effects are important in determining the equilibrium state. Thus,
in a system at constant internal energy and volume, the equilibrium state will be the
state of maximum entropy (or maximum randomness) among only those states that
have the required internal energy. For systems at constant temperature and volume, the
equilibrium state is a state of minimum Helmholtz energy. Since A = U − T S, it is
evident that increasing the entropy (or disorder) in the system decreases the Helmholtz
energy only if it does not simultaneously increase the internal energy of the system.
For example, consider the lattice model used here, but now let u ii be the interaction
energy of a species i–species i interaction, where u 11
= u 12
= u 22 , so the mixture is
not ideal. Clearly, if u 12 is greater than the arithmetic average of u 11 and u 22 , that is, if

u 12 > 12 (u 11 + u 22 )
increasing the randomness of the mixture (and the number of 1–2 interactions at the
expense of 1–1 and 2–2 interactions) increases both the entropy and the internal energy
of the system. Therefore, the equilibrium state for this system will be that compromise
between energetic and entropic effects for which the Helmholtz energy is a minimum.
In real mixtures this balance between energetic and entropic effects is illustrated, for
example, in liquid-liquid phase equilibrium (to be discussed in Chapter 11), in which
the equilibrium state of some liquid mixtures is as two coexisting phases of different
composition, a distinctly ordered rather than random state. The equilibrium state is not
a single phase of uniform composition, since the increase in randomness (and hence
decrease in −T S) of producing such a state from the two-phase mixture would be less
than the increase in the internal energy of the system. Consequently, the random single-
phase mixture would have a higher Helmholtz energy than the more ordered two-phase
mixture, and therefore would not be a stable equilibrium state.