CHEE 311 Lecture 24 1

Azeotropic Mixtures SVNA 10.5

Large deviations from ideal liquid
solution behaviour relative to the
difference between the pure component
vapour pressures result in azeotrope
formation.
In CHEE 311, we are interested in:
1. Describing azeotropic mixtures
both physically and in
thermodynamic terms.
2. Detecting azeotropic conditions
and calculating their composition.
CHEE 311 Lecture 24 2
Azeotropic Mixtures
Water / Hydrazine, P=1atm Water / Pyridine, P=1atm
CHEE 311 Lecture 24 3
Azeotropes - Impact on Separation Processes
Separation processes that exploit
VLE behaviour (flash operations,
distillation) are influenced greatly
by azeotropic behaviour.
An azeotropic mixture boils
to evolve a vapour of the
same composition and,
conversely,condenses to
generate a liquid of the
same composition.
Ethanol(1)/Toluene(2) at P=1 atm
CHEE 311 Lecture 24 4
Predicting Whether an Azeotrope Exists
To determine whether an azeotrope will be encountered at a given
pressure and temperature, we define the relative volatility. For a
binary system,
12
is
10.8
where x
i
and y
i
are the mole fractions of component i in the liquid
and vapour fractions, respectively.
At an azeotrope, the composition of the vapour and liquid are
identical. Since, y
1
=x
1
and y
2
=x
2
at this condition,
To determine whether an azeotropic mixture exists, we need to
determine whether at some composition,
12
can equal 1.
2 2
1 1
12
x y
x y
=
1
12
=
CHEE 311 Lecture 24 5
Predicting Whether an Azeotrope Exists
We can derive an expression for
12
using modified Raoults Law
as our phase equilibrium relationship,
which when substituted into the relative volatility, yields
10.9

12
is therefore a function of T (P
i
sat
,
i
) and the composition of the
liquid phase. Calculation of
12
therefore requires:
Antoines equation
an activity coefficient model (Margules, Wilsons, )
a liquid composition
Our goal is to determine whether an azeotrope exists.
At some composition, can
12
=1?
sat
i i i i
P x P y =
sat
2 2
sat
1 1
12
P
P

=
CHEE 311 Lecture 24 6
Ethanol(1)/Toluene(2) at 78C
0
5
10
15
20
0.0 0.2 0.4 0.6 0.8 1.0
x1
1
2
Predicting Whether an Azeotrope Exists
One means of determining
whether
12
=1 is possible
is to evaluate the function
(Eqn10.9) over the entire
composition range.
This is plotted for the
ethanol(1)/toluene(2)
system using Wilsons
equation to describe liquid
phase non-ideality.
According to this plot,

12
=1 at x
1
= 0.82,
meaning that an azeotrope
exists at this composition.
CHEE 311 Lecture 24 7
Predicting Whether an Azeotrope Exists
Because equation 12.22 is continuous and monotonic, we do not
need to evaluate
12
over the whole range of x
1
.
It is sufficient to calculate
12
at the endpoints, x
1
=0 and x
1
=1
At x
1
= 0, we have
and at x
1
= 1, we have
If one of these limits has a value greater than one, and the other
less than one, at some intermediate composition we know
12
=1.
This is a simple means of determining whether an azeotrope
exists.
sat
2
sat
1 1
0 x
12
P
P
1

=

=
sat
2 2
sat
1
1 x
12
P
P
1
=

=
CHEE 311 Lecture 24 8
Determining the Composition of an Azeotrope
For an azeotropic mixture, the relative volatility equals one:
at an azeotrope.
To find the azeotropic composition, two methods are available:
trial and error (spreadsheet)
analytical solution
Rearranging 12.22 as above yields:
The azeotropic composition is that which satisfies this equation.
Substitute an activity coefficient model for
1
, and
2
.
Solve for x
1
.
1
P
P
sat
2 2
sat
1 1
12
=

=
sat
1
sat
2
2
1
P
P
=

CHEE 311 Lecture 24 9

Example
While azeotropes are undesirable from a processing point of view,
we can still benefit from this phenomenon in obtaining parameters
for GE models.
For example, the binary mixture of 1,4-dioxane (1)/water (2)
exhibits an azeotrope at x1=0.554 at T= 50
o
C and P=0.223 bar.
How can we use this information in the estimation of the Margules
parameters A
12
and A
21
for the mixture?
Given: P
1
sat
(50
o
C)=0.156 bar; P
2
sat
(50
o
C)=0.124 bar.
Set all fugacity coefficients equal to 1.00.