THERMODYNAMICS CHEE-220

Laboratory
Winter 2022 Professor Girard-Lauriault

Vapour - Liquid Equilibrium in a Binary System

The objective of this laboratory exercise is to obtain empirical information about a typical
binary mixture and then fit these data to an appropriate model. An ebulliometric apparatus will be
used to determine equilibrium data for binary mixtures of different overall compositions at
atmospheric pressure. The normal boiling point and the compositions of the vapour and liquid phases
in equilibrium will be determined. The system to be studied will be 1-propanol and water.

Safety Regulations

• Eating and drinking are not permitted in the laboratory at any time.
• Lab coats and safety glasses and gloves must be worn.
• The alcohols are relatively safe organic liquids but are flammable and should be
handled with care.
• DO NOT wear contact lenses in the lab.
• All students must have gone through WHMIS training and successfully passed the
exam prior to working in the laboratory.
• All students are required to consult the MSDS for the potentially dangerous chemicals
that will be used in the laboratory. MSDS can easily be found on the web or through
the myLab inventory (https://myLab.mcgill.ca, username:chemenglab, password:
msds, you must login using a McGill computer or through the McGill VPN).
o 1-propanol
• Any student who chooses to ignore these rules will be asked to leave.
.
General Method

The main apparatus is a simple isobaric ebulliometer shown in figure 1. The liquid in the
boiler is heated until it refluxes at atmospheric pressure. The saturated vapour condenses in the
condenser and flows to the tap and boiler. When a steady state (equilibrium) is achieved, samples are
taken of both the boiling liquid and the vapour condensate. The samples are allowed to cool to room
temperature and their compositions are determined using the gas chromatograph shown in figure 2.

Important note: You will be provided with one alcohol stock solutions for preparing GC
calibrations: 12000 mg/L solution of 1-propanol. You will also be provided with one alcohol solution
for the ebulliometer.
Figure 1. Laboratory set up of a simple ebulliometer

Figure 2. Gas chromatograph

 Experimental Procedure

1. Fill the boiler of the ebulliometer:

- The required masses of 1-alcohol and water required to fill the boiler will be provided to you
by the TA.
- Subsequent data for spiking the mixture to desired concentrations will also be made available.

2. Chiller will be turned on prior to the lab.

- The TA will verify the chiller temperature is set to 6 deg. C.

3. Turn on the main power on the setup.

4. The TA will control the heater. Monitor the temperature until the system reaches steady state.
Within 15-30 minutes the temperature should remain fairly constant for at least 5 minutes.

5. While waiting for the system to reach steady state, prepare samples for calibration of the gas
chromatograph data:
- Assume that the volume change of mixing is negligible.

a. Please note the exact concentration of the stock solution that is provided to you
(approximately 12000 mg/L).
b. Using a 1-5 mL pipette, perform successive ½ serial dilutions in the provided capped
glass vials. Each vial should be mixed before pipetting. Prepare the calibration samples
by successive dilutions (TA will tell you the conc.), for example, see table below:

Table 1. Dilution volumes for preparation of calibration samples.

n Nominal Volume of solution n-1 Volume of RO Water
Concentration*
1 6000 mg/L 5 ml 5 ml
2 3000 mg/L 5 ml 5 ml
3 1500 mg/L 5 ml 5 ml
4 750 mg/L 5 ml 5 ml

c. Run the calibration samples through the gas chromatograph (GC). For each injection 2
!L of the solution will be used.
d. In the lab, plot Area vs. Concentration (mg/L) for 1-Propanol from the chromatogram.
*Note: Use the correct concentrations based on the provided stock solution and not the
nominal concentrations.
e. Fit the data to a linear model and check that R2 > 0.98. If it is not, repeat the injections
for the calibration curve (step 5c).

The data will be provided for you in an excel sheet.

6. When the temperature on the ebulliometer reaches steady state, collect samples of both the
 condensed vapour and the boiling liquid phases.
a. Use the lower stop-cock to take a liquid sample and the condensate valve to collect
a sample of the vapour that has condensed.
b. Record the equilibrium temperature when sampling.
c. Record the atmospheric pressure (barometer on the wall).

7. Dilute the samples to prepare for injection in the GC.

d. Tare an empty vial (with cap) on an analytical balance (4 decimal balance).
e. With the 1 -10 ml pipette, pipette 10 ml RO water and cap. Record mass of water.
f. Tare balance with this vial.
g. With the 20 -200 !L pipette, pipette 100 !L of the sample into vial. The TA may
advise to use a different volume of sample fraction to make the dilution factor fit
within the GC cal. curve range. Record mass of sample
h. Label this vial appropriately and place it in the provided rack.

8. Repeat steps 6 to dilute the samples. Do not forget to gently mix the liquid fraction vial by
tilting upward and downward several times. The small volume should be homogenous
because vapour will recondense on the walls when hot sample is taken.

9. The TA will provide you with a known volume of water to be added to the boiler. After
spiking the solution in the boiler, repeat steps 6 and 8 to obtain the composition of the new
solution. You will collect data for 4 different mole fractions of 1- propanol.

The data will be provided for you in an excel sheet.

10. Turn off the heater to stop the experiment.

11. When the liquid stops boiling, shut-off the tap to the condenser hose and drain the boiler.
Dispose of the liquid in the container provided.

Operational Notes

Proper use of the pipette:

Fill the pipette slowly to avoid contaminating the filter inside. Likewise, empty the pipette slowly to
avoid errors.

In order not to contaminate the pipette, it is extremely important to always keep the pipette in the
vertical position, with the piston on top. The solvent that you are pipetting should never touch the
pipette. When you are not using the pipette, place the pipette on the stands provided and not on the
bench.
 Experimental Report

The report must be typed and presented in a technical format. Each group of 4 is to prepare a single
report. The data will be provided for you in an excel sheet.
The report should include the objectives of the experiment, an outline of the methodology, the
experimental results, and most important, a discussion of the results and errors in your particular
experiment.

Please follow the general guidelines found in the document titled “2017_Guidelines for Assignment
and report writing”. The following is EXTRA information specific to this lab report.

Calculations: Using the data provided:

1. Setup the calibration curve; this will give you a line: Area vs. mg of alcohol/L of solution. For
the y-axis of the calibration curve, the area ratios are the values that you obtained directly from
the GC. For the x-axis, the concentrations used are dependent on the initial concentration of the
solution provided to you. Remember (where n refers to the solutions in Table 1):

"!"# #!"# = "!"$ #!"$

2. Use the calibration curve to convert the GC data (areas) for the vapor and liquid samples from
the ebulliometer, to mg/L and then to mg of alcohol/kg of solution.
2.1. To go from mg/L to mg of alcohol/kg of solution assume that the diluted sample solution
has the density of water. Therefore, if you have 600 mg/L as the concentration of a diluted
sample, this is equivalent to:

() 0.998 /) ()
600 ÷ = 599 .
* 1* /)

3. The concentrations you have now correspond to that of the diluted samples. You must find the
concentrations of the original samples. The concentrations in mg/kg that you have must be
multiplied by their dilution factor which is 23456 789)h4⁄:5(;68 789)h4. This will give you
the actual concentration of your sample in mg/kg. Therefore, if you get 599 mg/kg for your
diluted sample, and your original sample weight was 0.0300 g and your total weight was 10.0000
%& #(.(((( & %&
g, this means the actual concentration you had was 599 '& × (.(+(( & = 200000 '& .

4. You then use the density of 1-propanol, density of water and the molecular weights to convert
these values to mole fractions.
5. The ebulliometer was open to the atmosphere at the top of the condenser, therefore the
equilibrium pressure was equal the atmospheric pressure.
Data Analysis:

The following four graphs should appear in the report.

(1) Plot T vs x,y using literature data for 1-propanol.

(2) In one graph plot all of the following: lng1, lng2, GE/RT and GE/RTx1x2 vs x1 using the literature
data for 1-propanol. Use this plot to determine both the Margules and (with the inverse) the van Laar
constants.
(3) On the same graph plot GE/RTx1x2 vs x1 for both the literature data and the student data using two
different symbols.

(4) The final graph demonstrates the fit between the models and the actual data. You will end up with
three pairs of lines on a single graph with axes g1 and x, y for your alcohol.

For the first plot use the literature data. The other two sets of data will be generated from the Margules
and van Laar constants calculated in part (2) above. For example, you could use the Margules to calculate
a value of y for a particular value of x. (It is necessary to assume that these constants do not vary for the
small temperature changes involved.)

Discussion:

The following are several points to be discussed in the report:

- Differences between literature and class data

- Validity of the curve fitting
- The differences between the models.
- Assumptions made when calculating constants

Some questions to consider:

What is going on while the apparatus is being heated to equilibrium?
When the system reaches equilibrium, why does it still need constant energy input?