Finding Binary Azeotropes Using Thermodynamic Relationships

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Finding Binary Azeotropes

Technical Note: MKS 06160
Updated: 2013-07-16
1.0 Summary
This technical note explains the thermodynamic relationships used to identify binary azeotropes. A video is
available from Molecular Knowledge Systems website that describes the step-by-step procedure for using
Cranium to search for binary azeotropes. The video is available at:
www.molecularknowledge.com/casestudies/azeotropes.htm
2.0 Azeotropic Behavior

Figure 1 shows a qualitative depiction of a typical binary azeotrope consisting of components A and B. At
low concentrations of component A the mole fraction of A in the vapor phase is greater than the mole
fraction of A in the liquid phase. At high concentrations of A the mole fraction of A in the vapor phase is
less than the mole fraction of A in the liquid phase. The composition at which the mole fraction of A in the
vapor is equal to the mole fraction of A in the liquid is the azeotropic point.
yA
xA
Figure 1: Typical Behavior of a Binary Azeotrope
Quantitatively we can model the phase behavior of components A and B using our standard, low pressure,
vapor-liquid equilibrium relationships:

= (1)

= (2)
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The slope of the curve in Figure 1 is given by:

= + (3)

As the concentration xA approaches 0 the slope approaches:

= (4)

=0
Using the relationships:
= 1 (5)

= 1 (6)

= (7)

+ = 0 (8)
We obtain:

= + (9)

As the concentration xA approaches 1 the slope approaches:

= (10)

=1
Figure 1 shows that when an azeotrope is present the slopes at each concentration limit must both be either
greater than 1 or less than 1. We can thus use this observation with the slopes calculated by Equations 4 and
10 to identify binary azeotropic systems.
3.0 Temperature Values

The infinite dilution activity coefficients and vapor pressures in Equations 4 and 10 are both temperature
dependent properties. Equation 4 represents the slope of the equilibrium curve for a mixture containing
almost pure B. Thus the properties used in Equation 4 should be evaluated at the boiling point of pure B.
Similarly, Equation 10 represents the slope of the equilibrium curve for a mixture containing almost pure A.
Thus the properties used in Equation 10 should be evaluated at the boiling point of pure A.
4.0 Modeling Activity Coefficients

To evaluate Equations 4 and 10 we need pure component vapor pressures and infinite dilution activity
coefficients. Numerous models are available for both properties. The MOSCED model [1] is one of the
easier to use infinite dilution activity coefficient models. Similar in concept to the solubility parameter
model, the MOSCED model tabulates six parameters for each pure chemical:
v q
These parameters are then inserted into the following equations to generate an estimate for the infinite
dilution activity coefficient.
[ 3.4
Note that Equation 6 has been corrected from the original reference.
For example, to calculate the infinite dilution activity coefficient of aniline in cyclohexane at 300 K we
begin by compiling the pure component parameters.
Parameter Cyclohexane (1) Aniline (2)

v 108.9 91.6
16.74 16.51
0.00 9.41
q 1.00 0.90
0.00 6.51
0.00 6.34
Inserting these values into Equations 11 through 20 we obtain:
Parameter Aniline (2)

6.388

6.221

9.322
POL 1.641
2.578
1.745
aa 0.953
d12 -0.01287
which gives us a final estimate of:
2 = 56.455 (11)
5.0 Examples
We use this approach to find a chemical that has an azeotrope with methanol at a pressure of 1.0 bar. We
chose benzene as our first candidate. Table 1 shows the parameters for methanol and benzene taken from
Reference 1.
Table 1: MOSCED Model Parameters

Parameter Methanol Benzene
v 40.6 89.5
14.43 16.71
3.77 3.95
q 1.00 0.90
17.43 0.63
14.49 2.24
The boiling points of our components were taken from the NIST website [2]:
Methanol: Tb = 337.8 K
Benzene: Tb = 353.3 K
We next calculate the infinite dilution activity coefficient of methanol in benzene at 353.3 K, the boiling
point of benzene. Inserting the values for methanol and benzene from Table 1 into Equations 11 through 20
we obtain:
Parameter Methanol (2) Benzene (1)

15.006 0.542

12.475 1.929

3.498 3.665
POL 1.082
1.063
1.085
aa 0.491
d12 -0.06657
which gives us an estimate of:
Methanol in benzene:
2 = 7.307
We next calculate the infinite dilution activity coefficient of benzene in methanol at 337.8 K, the boiling
point of methanol. Inserting the values for benzene and methanol from Table 1 into Equations 11 through
20 we obtain:
Parameter Benzene (2) Methanol (1)

0.562 15.555
1.999 12.931
3.731 3.561
POL 1.115
2.589
1.644
aa 0.918
d12 -0.34058
which gives us an estimate of:
Benzene in methanol:
2 = 6.314
The vapor pressures of our components are calculated using Antoines equation. The Antoine parameters
were taken from the NIST website:
Methanol: log10(Pvp) = 5.20409 1581.341 / (T 33.50)

Benzene: log10(Pvp) = 4.72583 1660.652 / (T 1.461)
where Pvp is in units of bar and T is in units of K. Evaluating the vapor pressure for each component at the
boiling point of the other component we obtain:
Methanol: Pvp(353.3) = 1.816 bar

Benzene: Pvp(337.8) = 0.614 bar
The slope, calculated by Equations 4 and 10, at each side of the graph is calculated to be:
vp

A PA
Pure methanol: = 3.879
P
vp

B PB
Pure benzene: = 13.275
P
Since both slopes are greater than 1.0 an azeotrope is predicted.
Data from Husdon and Van Winkle [3] confirm that methanol and benzene form an azeotrope at 1 bar.
1.00
0.88
Benzene, mol fraction vapor
0.75
0.63
0.50
0.38
0.25
0.13
0.00
0.00 0.13 0.25 0.38 0.50 0.63 0.75 0.88 1.00
Benzene, mol fraction liquid
To verify our approach we can compute the slope of the curve using the first and last data points. The first
point is:
x: 0.027 y: 0.093
which gives us a slope of
0.093
Pure methanol: = 3.44
0.027
The last point is:

x: 0.974 y: 0.733
which gives us a slope of
1.00.733
Pure benzene: = 10.26
1.00.974
Our calculated slopes are in good agreement with the experimental slopes.
6.0 References
1. Michael J. Lazzaroni, David Bush, Charles A. Eckert, Timothy C. Frank, Sumnesh Gupta and James D.
Olson. "Revision of MOSCED Parameters and Extension to Solid Solubility Calculations." Industrial
and Engineering Chemistry Research. Volume 44, number 11, page 4075-4083, 2005.
2. NIST Chemistry WebBook. http://webbook.nist.gov. Accessed November 2010.
3. John W. Hudson and Matthew Van Winkle. "Multicomponent Vapor-Liquid Equilibriums in Systems
of Mixed Positive and Negative Deviations." Journal of Chemical and Engineering Data. Volume 14,
number 3, page 310-318, 1969.

Finding Binary Azeotropes Using Thermodynamic Relationships

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Molecular Knowledge Systems, Inc.

Finding Binary Azeotropes

2.0 Azeotropic Behavior

The slope of the curve in Figure 1 is given by:

As the concentration xA approaches 0 the slope approaches:

Using the relationships:

As the concentration xA approaches 1 the slope approaches:

3.0 Temperature Values

4.0 Modeling Activity Coefficients

Parameter Cyclohexane (1) Aniline (2)

Inserting these values into Equations 11 through 20 we obtain:

Parameter Aniline (2)

which gives us a final estimate of:

Table 1: MOSCED Model Parameters

Parameter Methanol (2) Benzene (1)

which gives us an estimate of:

Parameter Benzene (2) Methanol (1)

which gives us an estimate of:

Methanol: log10(Pvp) = 5.20409 1581.341 / (T 33.50)

Methanol: Pvp(353.3) = 1.816 bar

Since both slopes are greater than 1.0 an azeotrope is predicted.

which gives us a slope of

The last point is:

which gives us a slope of

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