CHEM 331L

Physical Chemistry Laboratory

Revision 1.0

The Liquid-Vapor Phase Diagram for Ethanol-Cyclohexane

In this laboratory exercise we will construct a liquid-vapor phase diagram for the EthanolCyclohexane system. This is basically a temperature-composition diagram for the mixture. To
do this, we will produce Ethanol-Cyclohexane mixtures, bring them to a boil and then determine
the composition of the liquid and vapor for each refluxing mixture. This data can then be used to
generate the desired phase diagram.

http://www.photoeverywhere.co.uk/britain/ukwild/slides/english_rain0254.htm

A typical liquid-vapor phase diagram that exhibits azeotrope formation is provided below for the
Propanol-Water system (J. Chem. Ed.). Note that a system of an overall Propanol composition
of 0.8 mole fraction at a boiling temperature of 365K produces a vapor of composition 0.7 mole
fraction and a liquid of composition 0.85.

Page |2

We would like to consider two things in this regard. First, how are the compositions of the liquid
and the vapor actually measured? Second, is there a theoretical construct that will allow us to
understand liquid-vapor equilibria? We will start with the second question first.
The compositions of the vapor and liquid are governed by Raoults and Daltons Laws; provided
the vapor and solution are both Ideal. Suppose we have a Binary mixture of components A
and B whose pure state vapor pressures are PAo and PBo. Further, we will suppose A is the
lower boiling component; so, PAo > PBo. According to Daltons Law:
PTot = PA + PB

(Eq. 1)

where the partial pressures of the components in the vapor above the mixture (Pi) are given by
Raoults Law:
PA = xA PAo

(Eq. 2)

PB = xB PBo = (1 xA) PBo

(Eq. 3)

xi represents the mole fraction of the component in the liquid:

xi =

 

 

(Eq. 4)

Inserting the Raoults Law expressions into Daltons Law, and rearranging, gives us:
PTot = PBo + (PAo - PBo) xA

(Eq. 5)

From this we can see there is a linear relationship between the total pressure and the composition
in the liquid.

Page |3

Now, what about the vapor? The composition variables are given by Daltons Law:
yA =

yB =

(Eq. 6)

Inserting the Raoults Law results and inverting to find the total pressure gives us:
PTot =

 
   
  

(Eq. 7)

We can add this inverse relationship between PTot & yA to our above Phase Diagram. Here we
plot PTot vs. xA and PTot vs. yA on the same diagram, letting zA represent both xA and yA.

Page |4

To understand this diagram, suppose we start with a piston filled with a liquid of composition zII
at Point 1. As we lower the total pressure by expanding the piston, we will reach a point where
the liquid begins to vaporize. At Point 2, we have established a liquid-vapor equilibrium; the
composition of the liquid is zI and that of the vapor is zIII. Notice that the vapor is enriched in
component A; zIII > zII. This is as we expect since A is the lower boiling component. As we
continue to expand the piston, the remaining liquid is converted entirely to vapor. At Point 3 all
the liquid has been converted to vapor with a composition again at zII.

Page |5

Unfortunately, this has provided us with a Pressure-Composition diagram. From a practical

point of view, Temperature-Composition diagrams are more useful because they lend themselves
easily to an analysis of distillation processes. It is much easier to vaporize a liquid in a Distilling
Pot by raising the temperature of the liquid and boiling it than it is to vaporize the liquid by
expanding a piston and lowering the pressure.
Our P vs. z Phase Diagram can be converted to a T vs. z Diagram via the use of a modified form
of the Clausius-Clapeyron Equation called the Antoine equation:
log    

(Eq. 8)



where A, B and C are empirical constants for a particular liquid i.

At intermediate compositions between xA = 1 (PAo) and xA = 0 (PBo), the vapor pressure for each
component Pio can be calculated at a given temperature t. This will allow us to determine the
liquid and vapor compositions using (Eq. 5) and (eq. 6):
 

 


 

 

(Eq. 9)

In conceptual terms, liquids with a high vapor pressure will have a low boiling point. So,
component A will have a lower boiling point TAo than will component B, which will boil at TBo
when pure. So, our P vs. z diagram will be inverted.

Page |6

Page |7

Of course, this assumes the liquid is behaving Ideally; i.e., follows Raoults Law. If it is not
behaving ideally, then a minimum boiling or a maximum boiling Azeotrope can form.

In this case, Raoults Law must be modified with an Activity Coefficient i:

Pi = i xi Pio

(Eq. 10)

Under the mild conditions we are working with, we will assume the vapor can still be treated as
Ideal and hence Daltons Law still holds:
Pi = yi P

(Eq. 11)

A good model for the non-Ideal behavior of the liquid is that of van Laar. Here, the activity
coefficients can be estimated from:
log A =

log B =

!
&
$

!
%
"#
$ !

!

&

$ 
"#  ! %
$

!

(Eq. 12)

(Eq. 13)

where AL and BL are van Laar constants that are relatively insensitive to Pressure and
Temperature. If the activity coefficients A and B are known, then the van Laar equations can be
inverted to determine AL and BL:

Page |8

AL

= log A '1 )

BL

= log B '1 )

 *+, - /
.

*+, -

(Eq. 14)


*+, -
/
 *+, -

(Eq. 15)

Once our phase diagram has been constructed and the azeotropic point determined, we can
calculate the activity coefficients using equations (10) and (11) because at this point xi = yi, hence:
i,az = P/Pio

(Eq. 16)

Once A,za and B,az have been determined, AL and BL can be calculated from equations (14) and
(15). Now equations (12) and (13) can be used to calculate A and B at any other system
composition. These can then be used to construct the entire phase diagram.
Now, onto how to generate the phase diagram experimentally. To do this, we will need a method to

sample and measure the composition of both the vapor and liquid once equilibrium has been
established between them. We
will establish our Liquid-Vapor
equilibrium in a standard
distilling apparatus operated
under reflux. The Claissen Head
will be modified so that as the
vapor condenses it can be
trapped and collected.
Our method of determining the
composition of the liquid and
trapped vapor will be to
determine the Refractive Index of
these mixtures and to compare
this measurement with an
appropriate calibration curve.
During the first week of the lab,
we will prepare the calibration
curve. During the second week
we will generate the phase
diagram.

Page |9

Procedure
Week 1
To obtain data for the calibration curve, you will need a series of 10 samples approximately
evenly spaced over the full range of mole fractions from 0 to 1. Prepare the calibration samples
by weight, using two burets to deliver approximate amounts into 25 mL Erlenmeyer flasks.
Weigh the flasks empty and after the addition of each component. The volumes to be used in
preparing these samples should be computed from density and molecular weight data. The total
volume should be 5 10 mL. Stopper the flasks promptly to prevent evaporation, which can
cause serious errors. Be sure each sample is thoroughly mixed, then measure the refractive
index. Include measurements for the two pure liquids. Your always helpful laboratory instructor
will demonstrate the use of the Abbe Refractometer.

Week 2
Set-up the Still as pictured in the background material above. Use a heating block on a hot plate
as a heat source. To begin the equilibrium measurements, introduce about 50 mL of Ethanol into
the clean, dry distilling flask. Add a boiling stone to the liquid. Adjust the heat source so that
the liquid boils vigorously, with the vapor condensing well below the top of the reflux
condenser. Continue boiling until the temperature has become stable, that is, until it fluctuates
about a mean value rather than showing an upward trend. It is quite useful to record temperature
readings periodically as the system approaches a steady state, as this makes it easier to decide
when this condition has been reached.
For the first series of measurements on mixtures, make successive additions of Cyclohexane of,
for example, 4, 8, 14, 20 and 20 mL. Do not empty the flask between additions.
With pure liquids, the steady state is reached within a few minutes, but with mixtures a much
longer time is required because a steady-state composition difference must be established
between the Claissen Head and the distilling flask. To expedite reaching a steady state with
mixtures, flush out the distillate collected in the Claissen Head several times by inserting a
disposable pipet with a squeeze bulb attached and forcing Air through it.
After a steady temperature has been reached, record the temperature. Withdraw a sample of
about 1 mL from the condenser pocket and another from the distilling flask. Use a dry pipet for
each sample, and stopper the samples promptly.
After the first series of measurements has been completed, drain and dry the flask and introduce
about 50 mL of Cyclohexane for a boiling point determination. Additions of Ethanol (0.4, 1, 2,
10, 10 and 10 mL) may then be made for the remaining series of measurements.
Be sure and make a measurement of the atmospheric pressure for the day.

P a g e | 10

Data Analysis
1.

Construct your Refractive Index calibration curve.

2.

Determine the composition of the Liquid and Vapor at each recorded boiling temperature
using your calibration curve results.

3.

Construct a T-Z Phase Diagram for the Ethanol-Cyclohexane system at the recorded
atmospheric pressure. Use a French Curve to smoothly connect your data points.
Determine the temperature and composition of the azeotrope for this system. Include an
error estimate for each determination. Compare this with literature values.

4.

Calculate the van Laar constants AL and BL. Include appropriate error estimates.

5.

Compute the activity coefficients EtOH and Cyc at 0.1 mole fraction intervals over the
entire composition range. Include appropriate error estimates. Plot your results on a single
graph.

6.

Use the van Laar model to reconstruct the T-Z phase diagram. For each composition used
above (Calc. 5), use the determined activity coefficients and the atmospheric pressure to
determine the temperature at which the system should boil via Daltons Law:
P = PEtOH + PCyc = EtOH xEtOH PEtOHo + Cyc xCyc PCyco

(Eq. 17)

The Pios can be determined using the Antoine equation. Equation parameters for our
system are:
Substance
A
Ethanol
8.11220
Cyclohexane 6.84941

B
1592.864
1206.001

C
226.184
223.148

Some numeric technique will be require to determined the desired temperatures. The vapor
composition can be determined using (Eq. 11).
7.

Include a phase diagram which compares the van Laar model results with the experimental
results.

P a g e | 11

References
Hala, E., Pick, J., Fried, V., and Vilim, O. (1967) Vapor-Liquid Equilibrium, 2nd Ed.
Pergamon Press, New York.
Sime, Rodney J. (1990). Physical Chemistry: Methods, Techniques and Experiments.
Saunders College Publishing, Philadelphia.
Vaughan, Worth and Turner, Ed. Liquid-Vapor Equilibrium Laboratory. University of
Wisconsin-Madison. Personal Communication.