Simple Mixtures

5A.2 The thermodynamics of mixing

The dependence of the Gibbs energy of a mixture on its composition is given by
eqn 5A.5, and we know that at constant temperature and pressure systems tend
towards lower Gibbs energy. This is the link we need in order to apply
thermodynamics to the discussion of spontaneous changes of composition, as in
the mixing of two substances. One simple example of a spontaneous mixing
process is that of two gases introduced into the same container. The mixing is
spontaneous, so it must correspond to a decrease in G. We shall now see how to
express this idea quantitatively.

G = nAμA + nBμB (5A.5)

 (a) The Gibbs energy of mixing of perfect gases
Let the amounts of two perfect gases in the two containers be nA
and nB; both are at a temperature T and a pressure p (Fig. 5A.6).
At this stage, the chemical potentials of the two gases
have their ‘pure’ values, which are obtained by applying the
definition
μ = Gm to eqn 3D.15 (Gm(p) = Gm 0+ RT ln(p/p#)):

Perfect gas Variation of chemical potential with pressure (5A.14a)

(a) The Gibbs energy of mixing of perfect gases
(5A.14a)
(a) The Gibbs energy of mixing of perfect gases
G = nAμA + nBμB (5A.5)

The Gibbs energy of the total system is then given by eqn 5A.5 as
 (a) The Gibbs energy of mixing of perfect gases

After mixing, the partial pressures of the gases are pA and pB, with pA+pB
= p. The total Gibbs energy changes to

The difference Gf − Gi, the Gibbs energy of mixing, ΔmixG, is therefore

(a) The Gibbs energy of mixing of perfect gases

At this point we may replace nJ by xJn, where n is the total amount of A and
B, and use the relation between partial pressure and mole fraction (Topic 1A,
pJ = xJp) to write pJ/p = xJ for each component, which gives
DmixG = xAnRTlnxA + xBnRTlnxB

DmixG = nRT(xAln xA + xBln xB )

(a) The Gibbs energy of mixing of perfect gases

Because mole fractions are never

greater than 1, the logarithms in this
equation are negative, and ΔmixG < 0
(Fig. 5A.7).
The conclusion that ΔmixG is
negative for all compositions confirms
that perfect gases mix spontaneously in
all proportions.
(b) Other thermodynamic mixing functions
It is shown that (∂G/∂T)p,n = –S. It follows
immediately from eqn 5A.16 that, for a
mixture of perfect gases initially at the same
pressure, the entropy of mixing, ΔmixS, is
 (b) Other thermodynamic mixing functions

Because ln x < 0, it follows that ΔmixS > 0

for all compositions (Fig. 5A.9).
(b) Other thermodynamic mixing functions
 (b) Other thermodynamic mixing functions

We can calculate the isothermal, isobaric (constant pressure) enthalpy of mixing, ΔmixH, the
enthalpy change accompanying mixing, of two perfect gases from ΔG = ΔH − TΔS. It
follows
from eqns 5A.16 and 5A.17 that

The enthalpy of mixing is zero, as we should expect for a system in which there
are no interactions between the molecules forming the gaseous mixture. It
follows that the whole of the driving force for mixing comes from the increase in
entropy of the system because the entropy of the surroundings is unchanged.
5A.3 The chemical potentials of liquids
To discuss the equilibrium properties of liquid mixtures we need to know
how the Gibbs energy of a liquid varies with composition. To calculate its
value, we use the fact that, as established in Topic 4A, at equilibrium the
chemical potential of a substance present as a vapour must be equal to its
chemical potential in the liquid.
 5A.3 The chemical potentials of liquids: (a) Ideal solutions:
(

We shall denote quantities relating to pure substances by a superscript *, so the chemical

potential of pure A is written μA*, and as μA * (l) when we need to emphasize that A is a liquid.
Because the vapour pressure of the pure liquid is pA* it follows from eqn 5A.14 that the
chemical potential of A in the vapour (treated as a perfect gas) is

i.e. μA *(g) =

μA *(l) = μA *(g) These two chemical potentials are

equal at equilibrium (Figure), so we can
write
(5A.19a)
5A.3 The chemical potentials of liquids (a) Ideal solutions
5A.3 The chemical potentials of liquids (a) Ideal solutions

(5A.19a)

If another substance, a solute, is also

present in the liquid, the chemical
potential of A in the liquid is changed to
μA and its vapour pressure is changed to
pA.
(5A.19b)

(in presence of solute)

5A.3 The chemical potentials of liquids (a) Ideal solutions

(5A.19a) (5A.19b)
5A.3 The chemical potentials of liquids (a) Ideal solutions

In the final step we draw on additional experimental information about the relation between
the ratio of vapour pressures and the composition of the liquid.
In a series of experiments on mixtures of closely related liquids (such as benzene and
methylbenzene), the French chemist Francois Raoult found that
the ratio of the partial vapour pressure of each component to its vapour pressure as a
pure liquid, pA/pA*, is approximately equal to the mole fraction of A in the liquid mixture.
That is, he established what we now call Raoult’s law:
 5A.3 The chemical potentials of liquids (a) Ideal solutions

This law is illustrated in Fig. 5A.11.

 5A.3 The chemical potentials of liquids (a) Ideal solutions

Some mixtures obey Raoult’s law very well,

especially when the components are structurally
similar (Fig. 5A.12).
Mixtures that obey the law throughout
the composition range from pure A to
pure B are called ideal solutions.
5A.3 The chemical potentials of liquids (a) Ideal solutions:
5A.3 The chemical potentials of liquids (a) Ideal solutions

For an ideal solution, it follows from eqns 5A.19a and 5A.21 that

μA = μA* +RT lnxA Ideal solution Chemical potential (5A.22)

This important equation can be used as the definition of an ideal

solution (so that it implies Raoult’s law rather than stemming from it). It
is in fact a better definition than eqn 5A.21 because it does not assume
that the vapour is a perfect gas. The molecular origin of Raoult’s law is
the effect of the solute on the entropy of the solution. In the pure
solvent, the molecules have a certain disorder and a corresponding
entropy; the vapour pressure then represents the tendency of the
system and its surroundings to reach a higher entropy.
 (a) Ideal solutions
5A.3 The chemical potentials of liquids

For an ideal solution, it follows from eqns 5A.19a and 5A.21 that
μA = μA* +RT lnxA

Ideal solution Chemical potential (5A.22)

When a solute is present, the solution has a greater disorder than the
pure solvent because we cannot be sure that a molecule chosen at
random will be a solvent molecule. Because the entropy of the
solution is higher than that of the pure solvent, the solution has
a lower tendency to acquire an even higher entropy by the
solvent vaporizing. In other words, the vapour pressure of the solvent
in the solution is lower than that of the pure solvent.
5A.3 The chemical potentials of liquids: (a) Ideal solutions
Some solutions depart significantly from
Raoult’s law (Fig. 5A.13). Nevertheless,
even in these cases the law is obeyed
increasingly closely for the component in
excess (the solvent) as it approaches purity.
The law is another example of a limiting
law (in this case, achieving reliability as xA
→ 1) and is a good approximation for the
properties of the solvent if the solution
is dilute.

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(b) Ideal–dilute solutions
In ideal solutions the solute, as
well as the solvent, obeys Raoult’s
law.
(b) Ideal–dilute solutions
English chemist William Henry found experimentally
that, for real solutions at low concentrations, although
the vapour pressure of the solute is proportional to its
mole fraction, the constant of proportionality is not the
vapour pressure of the pure substance (Fig. 5A.14).
Henry’s law is:
pB =xBKB
Ideal–dilute solution Henry’s law (5A.23)
In this expression, xB is the mole fraction of the solute
K is an empirical constant (with the dimensions of
and B
pressure) chosen so that the plot of the vapour
pressure of B against its mole fraction is tangent to
the experimental curve at xB = 0. Henry’s law is
therefore also a limiting law, achieving reliability as
xB → 0.
(b) Ideal–dilute solutions
Mixtures for which the solute B obeys Henry’s law
and the solvent A obeys Raoult’s law are called
ideal–dilute solutions.
(b) Ideal–dilute solutions (Molecular interpretation)
The difference in behaviour of the solute and solvent at low
concentrations (as expressed by Henry’s and Raoult’s laws,
respectively) arises from the fact that

in a dilute solution the solvent molecules are in an

environment very much like the one they have in the
pure liquid (Fig. 5A.15).
In contrast, the solute molecules are surrounded
by solvent molecules, which is entirely different
from their environment when pure.
(b) Ideal–dilute solutions (Molecular interpretation)

Thus, the solvent behaves like a slightly

modified pure liquid, but the solute behaves
entirely differently from its pure state unless
the solvent and solute molecules happen to
be very similar. In the latter case, the solute
also obeys Raoult’s law.
(b) Ideal–dilute solutions
For practical applications, Henry’s law is
expressed in terms of the molality, b, of
the solute, pB = bBKB.
Some Henry’s law data for this convention are
listed in Table 5A.1. As well as providing a link
between the mole fraction of solute and its
partial pressure, the data in the table may also
be used to calculate gas solubilities. A
knowledge of Henry’s law constants for gases
in blood and fats is important for the discussion
of respiration, especially when the partial
pressure of oxygen is abnormal, as in diving
and mountaineering, and for the discussion of
the action of gaseous anaesthetics.
(b) Ideal–dilute solutions