Thermodynamics of Mixing

Dependence of Gibbs energy on mixture composition is

G = n A µA + n B µB
and at constant T and p, systems tend towards a lower Gibbs energy

The simplest example of mixing: What is the Gibbs free energy if we

take two pure ideal gases and mix them together? Consider gas A and
gas B, both in separate containers at pressure p at temperature T.
The chemical potentials are at their “pure
values” at this point. Gibbs energy is
G = n A µA + n B µ B
⎛ ⎛ p ⎞⎞ ⎛ ⎛ p ⎞⎞
= n A ⎜µAo + RT ln⎜ o ⎟⎟ + n B ⎜µBo + RT ln⎜ o ⎟⎟
⎝ ⎝ p ⎠⎠ ⎝ ⎝ p ⎠⎠
We can simplify things by letting p denote the
pressure relative to po, writing

G = n A (µAo + RT ln p)+ n B (µBo + RT ln p)

Prof. Mueller Chemistry 451 - Fall 2003 Lecture 16 - 1

 Gibbs Energy of Mixing
After mixing, the partial pressures of the gases are pA and pB, where the
total pressure is p = pA + pB. The total Gibbs energy is then
G = n A (µAo + RT ln pA )+ n B (µBo + RT ln pB )
The difference in Gibbs energies, Gf - Gi, is the Gibbs energy of mixing
⎛ pA ⎞ ⎛ pB ⎞
∆ mix G = n A RT ln⎜ ⎟ + n B RT ln⎜ ⎟
⎝ p⎠ ⎝ p⎠
We use mole fractions, replacing nJ with xJ n :

∆ mix G = nRT (x A ln x A + x B ln x B )
Since the mole fractions are never greater than 1,
the ln terms are negative, and ∆mixG < 0

This allows is to conclude that mixing processes

are spontaneous, and gases mix spontaneously in
all proportions

Prof. Mueller Chemistry 451 - Fall 2003 Lecture 16 - 2

 Calculating Gibbs Energy of Mixing
Two containers of equal volume are partitioned from one another, with one
containing 3.0 mol H2 and the other 1.0 mol N2 at 25oC. Calculate the Gibbs energy
of mixing when the partition is removed

We assume ideal gas behavior, with pressure of N2 being p, pressure of H2 being 3p.
Volume of each gas will double, and therefore partial pressures fall by a factor of 2

Prof. Mueller Chemistry 451 - Fall 2003 Lecture 16 - 3

 Calculating Gibbs Energy of Mixing
Two containers of equal volume are partitioned from one another, with one
containing 3.0 mol H2 and the other 1.0 mol N2 at 25oC. Calculate the Gibbs energy
of mixing when the partition is removed
Gi = (3.0 mol)(µ oH 2 + RT ln 3p)+ (1.0 mol)(µNo 2 + RT ln p)
⎛ o 3p ⎞ ⎛ o p⎞
G f = (3.0 mol)⎜ µ H 2 + RT ln ⎟ + (1.0 mol)⎜µN 2 + RT ln ⎟
⎝ 2⎠ ⎝ 2⎠
Gibbs energy of mixing is the difference
between the above quantities

⎛ 3p ⎞ ⎛ p⎞
⎜ ⎟ ⎜ ⎟
∆ mixG = (3.0 mol)⎜ RT ln 2 ⎟ + (1.0 mol)⎜ RT ln 2 ⎟
⎜ 3p ⎟ ⎜ p⎟
⎝ ⎠ ⎝ ⎠
= −(3.0 mol)RT ln2 − (1.0 mol)RT ln2
= −(4.0 mol)RT ln2 = −6.9 kJ

Prof. Mueller Chemistry 451 - Fall 2003 Lecture 16 - 4

 Other Thermodynamic Mixing Functions
Since ⎛ ∂G ⎞
⎜ ⎟ = −S, and ∆ mix G = nRT (x A ln x A + x B ln x B )
⎝ ∂T ⎠ p,n
it follows that for a mixture of perfect gases, the entropy of mixing is
⎛ ∂∆ G ⎞
∆ mix S = −⎜ mix ⎟ = −nR(x A ln x A + x B ln x B )
⎝ ∂T ⎠ p,n A ,n B
Since ln x < 0, then ∆mixS > 0 for mixtures of all compositions

We expect this increase IF WE SPEAK ABOUT DISORDER,

since dispersal of one gas into another implies greater
disorder in the system. What is the preferred interpretation ?

Example: ∆ mixG = −(4.0 mol)RT ln2 = −6.9 kJ

∆ mix S = (4.0 mol)Rln2 = +23 J K -1
The isothermal isobaric enthalpy of mixing of two
gases is found from ∆G = ∆H – T ∆S, and we find
∆ mix H = 0
This is expected for a system in which there are no
interactions between the molecules in the mixture.
Prof. Mueller Chemistry 451 - Fall 2003 Lecture 16 - 5
 Chemical Potentials of Liquids
Some nomenclature: Quantities relating to pure substances will be denoted with
asterisks, so the chemical potential of pure liquid A is µA*(l). Since the vapor
pressure of pure liquid A is pA*, the chemical potential of A in the vapor is
µo + RT ln pA* (pA* as relative pressure pA*/po).

Chemical potentials are at equilibrium:

µ∗A = µAo + RT ln p∗A
If another substance is present (e.g., a solute in
the liquid), chemical potential of A in the liquid
is µA and vapor pressure is pA
µA = µAo + RT ln pA
Combine to eliminate the standard potential:
⎛ pA ⎞
µA = µ + RT ln⎜ ∗ ⎟
∗
A
⎝ pA ⎠
The chemical potential of A depends on its partial vapor pressure. It
follows that chemical potential of liquid A is related to its partial pressure

Prof. Mueller Chemistry 451 - Fall 2003 Lecture 16 - 6

 Raoult’s Law
After experimenting with mixtures of similar liquids, the French chemist Francois
Raoult found that the ratio of the partial vapor pressure of each component to its
vapor pressure as a pure liquid, pA/pA*, is approximately equal to the mole fraction
of A in the liquid mixture
pA = x A p∗A

Some mixtures obey

Raoult’s law very
closely, especially
when they are
structurally similar –
these are called ideal
solutions, and they
obey

µA = µ∗A + RT ln x A

Prof. Mueller Chemistry 451 - Fall 2003 Lecture 16 - 7

 Molecular Interpretation of Raoult’s Law
We have to consider the rate at which molecules leave and enter solution to
understand Raoult’s law
The presence of a second component actually hinders molecules from leaving the
solution, but does not inhibit the rate at which they return
The rate at which A molecules leave the surface is
proportional to the number of them at the surface,
which is proportional to their mole fraction
rate of vaporization = k xA

where k is a proportionality constant. The rate at

which molecules return is proportional to their gas
phase concentration, which is proportional to their
partial pressure
rate of condensation = k’ pA

At equilibrium, rates of vaporization and condensation are equal, so

kx A
kx A = k ′pA pA =
k′
k
For a pure liquid, xA = 1, so p∗A =
k′
Prof. Mueller Chemistry 451 - Fall 2003 Lecture 16 - 8
 Departure from Raoult’s Law, Dilute Solutions

Some solution mixtures behave very differently from Raoult’s law,

notably with mixtures of structurally and chemically dissimilar liquids

Mixture of When the

CS2 and solute is dilute,
acetone: and solvent
obeys Raoult’s
Law very
closely

• When the solvent is nearly pure, it has a vapor pressure proportional

to the mole fraction with slope pB*
• When it is the minor component (the solute) the vapor pressure has a
different constant of proportionality

Prof. Mueller Chemistry 451 - Fall 2003 Lecture 16 - 9

 Henry’s Law
The English chemist William Henry found that for real solutions at low
concentrations, although the vapor pressure of the solute is proportional to the
mole fraction, the constant of proportionality is not the vapor pressure of the pure
substance
pB = xBKB

Here xB is the mole fraction of the solute B, and KB is an empirically determined

constant with pressure dimensions. KB is chosen so that a plot of vapor pressure of
B against mole fraction is tangent to the experimental curve at xB = 0

Such solutions are called ideal-dilute solutions

Solvent behaves like a slightly modified pure

liquid

Solute behaves entirely differently from its pure

state (since its molecules are surrounded by
solvent molecules), unless the molecules of the
two components are very similar

Prof. Mueller Chemistry 451 - Fall 2003 Lecture 16 - 10

 The Validity of Raoult’s & Henry’s Laws
Consider an acetone (A) and chloroform (C) mixture at 35 oC
xC 0.00 0.20 0.40 0.60 0 80 1.00
pC (Torr) 0 35 82 142 200 273
pA (Torr) 347 250 175 92 37 0

K = 175 Torr for (A) and K = 165 Torr for (C)

When mole fractions of (A) or (C) are near 1,

Raoult’s Law predicts the partial pressures

When mole fractions of (A) or (C) are near 0,

Henry’s Law predicts the partial pressures

In both cases, there are some deviations from

this predicted behavior

Prof. Mueller Chemistry 451 - Fall 2003 Lecture 16 - 11

 Using Henry’s Law
Estimate the molar solubility of oxygen in water at 25oC and partial
pressure of 120 Torr, its partial pressure at sea level

The amount of O2 dissolved is very small, and xJ = pJ/KJ, so

n (O 2 ) n (O 2 )
x (O 2 ) = ≈
n (O 2 ) + n (H 2O) n (H 2O )
p(O 2 )n (H 2O) (160 Torr) × (55.5 mol kg )
-1

n (O 2 ) = x (O 2 )n (H 2O ) = = = 2.69 × 10 -4 mol kg -1
K 3.33 × 10 Torr
7

So the molar solubility of oxygen is 2.69 x 10-4 mol kg-1 corresponding to

concentration 2.7 x 10-4 mol L-1
Henry’s law constants are very well known by biochemists for treatment of
gas behavior in fats and lipids - very important in understanding
respiration processes: especially when partial pressure of O2 is abnormal,
such as in mountaineering, scuba diving, and in the use of gaseous
anaesthetics.

Prof. Mueller Chemistry 451 - Fall 2003 Lecture 16 - 12