School of Science and Engineering page 1 of 4

ATENEO DE MANILA UNIVERSITY

CH 46 PHYSICAL CHEMISTRY LABORATORY I

Liquid-Vapor Equilibrium in an Azeotropic Mixture
1



In a homogeneous mixture of two liquids, the vapor pressures are quite different from the vapor
pressures of the pure components. Three different cases may be recognized: those that obey Raoults Law, and
those that deviate positively or negatively from Raoults Law (see Figure 1). For an ideal solution, Raoults Law
is written
0
i
i
i
P X P = (1)
where P
i
is the partial pressure of the ith component, P
i
is the vapor pressure of the pure ith component, and X
i

is the mole fraction of the ith component in the liquid phase.











(a) ideal (b) positive deviation (c) negative deviation
from Raoults Law from Raoults Law

Figure 1. Boiling point as a function of liquid and gas phase composition (mole fraction).


In this experiment, we will investigate the boiling point curve of a binary liquid mixture. Aside from
that determined experimentally, two other boiling curves will be constructed. One assumes that the mixture
behaves ideally, that is, it obeys Raoults Law. The other considers non-ideal solution behavior and includes
activity coefficients obtained from the van Laar equations. The three resulting boiling curves will then be
compared.

Ideal Solution Behavior
Daltons Law of Partial Pressures states that the total pressure P is just the sum of the partial pressures
of the components. For a system consisting of two gaseous components:

2 1
P P P + = (2)
If the mixture behaves ideally and does obey Raoults Law, Equation 2 may be rewritten as:


0
2 2
1
0
1
P X P X P + = (3)

For a two-components system, X
1
= 1-X
2
. Equation 3 may then be rewritten in terms of X
2
:

0
1
0
2
0
1
2
P P
P P
X

= (4)

1
Adapted from Sime, R. J. Physical Chemistry: Methods, Techniques, and Experiments (Saunders, 1990).
School of Science and Engineering page 2 of 4
Thus, the composition of the liquid phase, X
1
or X
2
, depends on the total pressure, usually atmospheric, and the
vapor pressures of each pure component at the equilibrium temperature.
From Daltonss Law, the composition of the gas phase is:
P Y P
2 2
= (5)
where Y
2
is the mole fraction of component 2 in the gas phase.
From Raoults Law,

P
P X
P
P
Y
0
2 2 2
2
= = (6)

To calculate the boiling point curve assuming ideal solution behavior, vapor pressure equations are
available such as the Antoine equation (Boublik et. al., 1973):

C T
B
A P
+
=
0
log (7)
where A, B, and C are the Antoine constants, P is in torr, and T is in C. The boiling point curve can then be
determined following these steps:
1. Determine the boiling points of pure components 1 and 2. The boiling point is the temperature
wherein the equilibrium between the vapor and liquid phases of a system is reached. This is calculated from the
Antoine equation by letting P equal the measured atmospheric pressure.
2. Choose a temperature between the calculated boiling points of the pure components.
3. At this temperature, calculate
0
1
P and
0
2
P using Equation 7.
4. Calculate X
2
and Y
2
using Equations 4 and 6.
5. Plot these points at the chosen temperature.
6. Repeat at several more equally spaced temperatures.

Nonideal Solution Behavior
When the solution deviates from the ideal, activity coefficients
1
and
2
are take into account in
Equations 1and 5. Thus,

0
i i i i
P X P = (8).
From Daltons Law:

0
2 2 2
0
1 1 1 2 1
P X P X P P P + = + = (9)

For the gaseous phase composition,

0
i i i i i
P X P Y P = = (10).

At the azeotropic point, the compositions of the liquid and gas phases are equal, i.e., X
1
= Y
1
and X
2
=
Y
2
. From Equation 9, it follows that the activity coefficients at thee azeotropic point are:


0
1
, 1
P
P
az
= (10) and
0
2
, 2
P
P
az
= (11)
To calculate for the activity coefficients at temperatures other than the azeotropic point, the van Laar
equations (Hala et. al., 1967) are used namely:


2
2
1
1
1
log
|
|
.
|

\
|
+
=
B
A
X
X
A
(12)
School of Science and Engineering page 3 of 4

2 2
2
1
log
1
B
X B
X A
=
| |
+
|
\ .
(13)
where A and B are the van Laar constants, calculated as follows:

2
2 2
1
1 1
2
1 1
2
2 2
log
log 1
log
log
log 1
log
X
A
X
X
B
X

| |
= +
|
\ .
| |
= +
|
\ .


In outline form, the calculation for the non-ideal solution boiling point curve is as follows:
1. Calculate the activity coefficients
1
and
2
at the azeotropic point using Equations 10 and 11.
2. From Equations 11 and 12, derive the van Laar constants A and B for the system given the liquid
phase composition and activity coefficients at the azeotropic point.
3. Divide the composition, for instance, X
2
into several parts from 0.1 to 0.9 by increments of 0.1.
4. For a certain X
2
, determine X
1
. With the van Laar constants A and B, compute the corresponding
activity coefficients.
5. Insert the calculated mole fractions and activity coefficients in Equation 9. This results to an
equation with two unknowns (
0
1
P and
0
2
P ). Using the Antoine equation (Equation 7), vary the
temperature T to determine
0
1
P and
0
2
P that will satisfy the equality represented by Equation 9.
6. Repeat steps 4 and 5 for the other X
2
values.


Apparatus
The distilling apparatus shown in Figure 2 is constructed from a 50-mL distilling flask from which the
side arm is removed. A small water-cooled condenser is sealed to the neck of the flask near the junction of the
neck and the flask.


















Procedure
Figure 2. Apparatus for measuring boiling points as a
function of composition. The liquid refluxing into the
small glass bulb below the condenser has the
composition of the gas phase. The liquid in the main
boiler has the composition of the liquid in equilibrium
with that gas phase.
School of Science and Engineering page 4 of 4

Prepare a series of solutions by weight of known mole fractions approximately equal to 0.25, 0.50, and
0.75 acetone and cylcohexane. The total volume need only be 5 or 10 mL. Weigh to 0.5 mg. Keep the solutions
tightly stoppered when storing or the composition may change due to evaporation. Measure the refractive
indices of these solutions as well as of pure acetone and pure cyclohexane. Prepare a calibration curve of
refractive index versus mole fraction. The curve is not generally linear. The measurements of refractive index
for the calibration curve and the azeotrope should be done at exactly the same temperature, preferably with the
same refractometer.
With a graduated cylinder, place about 25 mL acetone in the reflux apparatus and measure the boiling
point. With a measuring pipet, add about 2 mL cyclohexane and let the system reflux until the small sample tube
below the reflux condenser has been thoroughly rinsed out and contains liquid with the composition of the gas
phase (several minutes). Let the apparatus cool somewhat; then remove a sample from the sample tube (gas
phase composition) and from the reflux flask (liquid phase composition). Analyze the samples with a
refractometer.
Repeat this procedure with subsequent additions of 4, 6, 8, and 12 mL cyclohexane. Then discard the
mixture, rinse the flask with pure cyclohexane, and fill it with about 25 mL cyclohexane. As above, determine
the boiling point of pure cyclohexane, and mixtures of cyclohexane with 2, 4, 6, 8, and 12 mL acetone added.

Results and Calculations
Tabulate and plot a calibration curve of refractive index versus mole fraction for your system. Draw a
smooth curve through the points. Use this curve to determine the composition of the liquid and gas phases at the
recorded boiling temperatures.
Tabulate and plot boiling point versus mole fraction for the experimental, ideal, and van Laar case. The
Antoine constants A, B, and C for acetone and cylohexane are listed in Table 1. Take note of the tie linesthese
are horizontal lines that connect the liquid and vapor composition at equilibrium at a particular boiling
temperature. Draw a smooth curve through the points using the tie lines as a guide. Compare the three boiling
point curves.

Table 1. Antoine Constants for acetone and cyclohexane
Component A B C
acetone 7.11714 1210.595 229.664
cyclohexane 6.84941 1206.001 223.148
Source: T Boublik,, V Fried, and E Hala. 11973. The Vapor Pressures of Pure Substances. Amsterdam: Elsevier.

In addition, determine the azeotropic composition and compare it with the literature value, if available.



References:
Main: RJ Sime. 1990. Physical Chemistry: Methods, Techniques, and Experiments. Saunders Publishing.
1. TV Boublik, V Fried, and E Hala. 1973. The Vapor Pressures of Pure Substances. Amsterdam: Elsevier.
2. HC Carlson and AP Coburn. 1942. Vapor-Liquid Equilibria of Nonideal Solutions. Ind. Eng. Chem. 34: 581.
3. JM Grow. 1983. Display of Vapor Pressure Data with a Theoretical Fit. J.Chem Educ. 60: 1062.
4. EJ Hala, V Fried, & O Vilim. 1967. Vapor-Liquid Equilibrium, 2/e. NY: Pergamon Press.
5. GN Lewis, & M Randall, revised by K Pitzer & L Brewer. 1961. Thermodynamics. NY: McGraw-Hill.
6. JM Prausnitz, CA Eckert, RV Orye, & JP OConnell. 1967. Computer Calculations for Multicomponent
Vapor-Liquid Equilibria. Englewood Cliffs, NJ: Prentice-Hall.
7. RD Rossini, et. al., 1953. Selected Values of Physical and Thermodynamic Properties of Hydrocarbons and
Related Compounds. Pittsburgh, Pennsylvania: API Project 44, Carnegie Press.
8. J Timmermans. 1959. Physico-chemical Constants of Binary Systems. NY: Interscience.