Binary Phase Diagrams

Purpose
To construct a liquid/vapor temperature-composition (T-X) phase diagram for a binary mixture of
cyclohexane and ethanol.

Theory
Binary mixtures of two volatile liquids exhibit a range of boiling behavior from ideal, with a
simple continuous change in boiling point with composition, to nonideal, showing the presence
of an azeotrope and either a maximum or minimum boiling point. In this experiment, the
properties of a binary mixture of cyclohexane and methanol will be investigated by studying the
change in boiling point with composition. You will construct a boiling point diagram and
identify any nonideal behavior in the system.

For ideal mixtures of liquids, the composition of the vapor phase is always richer in the
component with the higher vapor pressure. According to Raoult's Law, the vapor pressure of
component A is given by

p A = x A p*A [1]

where xA is the mole fraction of A in solution and p ∗A is the vapor pressure of pure A. Actual
vapor pressures can be greater or less than those predicted by Raoult's Law, indicating negative
and positive deviations from ideality. In some cases, the deviations are large enough to produce
maxima or minima in the boiling point and vapor pressure curves. At the maximum or
minimum, the compositions of the liquid and vapor phases are the same, but the system is not a
pure substance. This results in an azeotrope, a mixture which boils with constant composition.
A distillation will not be able to completely separate the two components. Either the distillate or
the residue will eventually reach the azeotropic composition and no further separation will occur.

Simple distillation can be used to obtain a boiling point diagram so long as some method exists
to analyze both the distillate and the residue. In practice, several mixtures of differing
composition of the two liquids are distilled and samples of both the distillate and residue are
taken. The temperature (boiling point) of each distillation is recorded and the composition of
both the distillate and residue is determined. The analysis method should provide a measurement
which changes significantly and continuously over the entire range of concentration, from one
pure liquid to the other pure liquid. In many cases, the refractive index provides a suitable
measure of concentration. A calibration curve must be obtained using known mixtures. The
refractive index of an unknown mixture is then measured and the composition obtained using the
calibration curve.

Procedure
Calibration Curve
1. Make up 5 mL each of 0, 10, 20, 30, 40, 50, 60, 70, 80, 90, and 100 percent by volume ethanol
solutions using volumetric pipets.

2. Measure the refractive index for each of these solutions.

3. Convert the percent volume concentrations into mole fraction.

4. Construct a plot of mole fraction versus index of refraction.

Distillation
A simple distillation setup similar to that shown below is used. A two- or three-necked
roundbottom flask should be used. This equipment should be in a hood.

Have several Pasteur pipets available for taking samples of the distillate and residue. Also
prepare twenty sample vials labeled V1 to V10 and L1 to L10 as discussed below. The vials
marked V (for vapor) will be used to collect the distillate (the condensed vapor phase) and the
vials marked L will be used to collect the residue (the liquid phase). Graduated cylinders should
be used for measuring the pure liquids for the distillation.

1. Place 75 mL of ethanol and 25 mL of cyclohexane in the distillation flask. Start the

distillation with an Erlenmeyer flask or beaker as your receiving vessel and continue until
about 5 mL of distillate is collected and then discard. Now collect 5 more mL into sample
vial V1. Record the temperature during this collection period. Turn off the heater and allow
the boiling to stop, then transfer about 2 mL of the distillate into vial L1. Make sure that
you cap the vials and record their refractive index soon thereafter.

Repeat the process four more times, adding 25 mL of cyclohexane to the distillation flask
each time.

2. Start over with a mixture containing 95 mL of cyclohexane and 5 mL of ethanol. Distill and
collect samples of the distillate and residue as in part 1, labeling them V6 and L6,
respectively. Repeat four more times adding 10 mL of ethanol to the distillation flask each
time.

2
3. During the lab period, using the second distillation apparatus, the boiling points for pure
ethanol and pure cyclohexane should be obtained. Also, record the atmospheric pressure.

Calculations
Using the distillation data and your calibration curve, plot the temperatures against the mole
fraction of ethanol for both the liquid and vapor phases on the same plot. Make sure the data
from the pure liquid distillations are included. Draw (this means do not perform a fit in excel,
why?) two smooth curves, one through the liquid data (residue) and one through the vapor data
(distillate).

From your plot determine the azeotropic composition (as mass fraction and mole fraction) and
the azeotropic temperature. Compare to a literature value.

Questions

1. What type of deviation from ideality (if any) does this system show? Rationalize this
behavior in terms of the intermolecular forces expected for this system.

2. How could one separate the components in an azeotrope? One of the most important
azeotropes is that formed in the ethanol-water system. Find the composition of this
azeotrope (use the literature) and also find a method for "breaking" this azeotrope. It must
be possible since we can buy 100% ethanol and 100% water!

3. Use the literature to find a binary mixture whose azeotropic mole fraction is roughly 0.50

4. A similar experiment can be conducted to obtain a solid/liquid temperature-composition

phase diagram. For solid/liquid systems, eutectics may form rather than azeotropes as is the
case for liquid/vapor systems. Discuss the similarity between a eutectic and an azeotrope.