1

EXPERIMENT 4 - BOILING POINT COMPOSITION DIAGRAMS OF BINARY

SYSTEMS

THEORY:

According to Raoult’s law, ideal solutions consisting of one volatile component A,

and a non-volatile component B, show the following dependence:

PT = PA = x A PAo (1)

where PT is the total pressure above the solution. Since A is the only volatile
component, the total pressure is the same as the partial pressure of A, i.e. PA. xA
is the mole fraction of A in the solution and P0A is the vapor pressure of pure liquid
A at the same temperature as the solution. If the solution consists of two volatile
components, A and B, then the same equation can be written as:

PT = x A PAo + x B PBo (2)

As before, xB is the mole fraction of B in the solution and P0B is the vapor pressure
of pure liquid B at the same temperature as the solution. xA and xB represent the
composition of A and B in the solution, respectively.

You can see the temperature-composition diagram of a binary mixture of A and B

in Figure 1. The lower line is the liquid line below which liquid and above which
vapor phases exist. Similarly the top line is the vapor line. Above this line exists
the vapor phase, and below it the liquid.

T↑

TA0

TB0

0 xB 1

Figure 1

The composition of any point in between these lines can be given by a tie-line (see
the line between the two curves in Figure 1). The point on the liquid curve of this
line is used to determine the composition of the liquid at equilibrium with the
vapor above it. The point on the vapor curve shows the composition of the vapor
phase. The composition of the vapor above the solution, however, is not the same
as that in the solution. The vapor is richer in the more volatile component. This
simply means the mole fraction of the more volatile component (let us say A) in
the vapor, yA, is higher than xA. When distilling a binary solution, the vapor (i.e.
the distillate) will be richer in e.g. A. If the distillation is repeated a few times,
2

eventually the vapor is expected to consist of pure A. This way, all A and B can be
separated from one another. The “boiling-condensation” cycle is known as
“fractional distillation”.

In the case of non-ideal solutions, it might not be possible to separate A and B

completely. The systems which are impossible to separate completely are known
as azeotropes (azeotrope = not changing composition when boiling). When the
azeotropic composition is reached the condensate retains the composition of the
boiling liquid. A maximum boiling point observed in the azeotropic mixtures (i.e.
the boiling point of the azeotrope is higher than the boiling point of either
component (A or B) if the interactions between A and B are stronger than those
betweens A and A, and between B and B; A-B > A-A ~ B-B. Figure 2 is an example
to high-boiling azeotropes. Similarly a minimum is observed if the vapor pressure
of the binary mixture is lower than the vapor pressure of either pure A or pure B;
A-B < A-A ~ B-B. Again, Figure 3 is an example to low boiling azeotropes.

T
T
TA0
0 0
TA TB TB0

0 xB 1 0 xB 1

Figure 2 Figure 3

In this experiment you will be asked to distil and separate out an azeotropic
mixture and determine the azeotropic composition.

PROCEDURE

It is very important that the glassware is not rinsed with H2O!!

• Place CONDENSED VAPOR samples taken from the CONDENSER into vials
labeled with V.
• Place LIQUID SAMPLES taken from the DISTILLATION FLASK into vials
labeled with L.
• For the cooling 10 0C decrease in temperature would be enough.
• During collecting the sample, you will take a few drops from the flask.

1. Put 90 ml of acetone into the distillation flask. Determine its boiling point by
carrying out the distillation close to 560C. Collect sample 1V. Then cool the
flask and collect sample 1L.
2. Return the distillate from step 1 into the distillation flask. Add 10 ml of
chloroform and start distillation. When the temperature reaches about 580C,
collect sample 2V. Then cool the flask and collect sample 2L.
3

3. Resume the distillation procedure. Collect sample 3V at around 600C. Cool the
flask and collect sample 3L.
4. Resume the distillation and continue to about 610C. Cool the flask somewhat,
and then add 17.5 ml chloroform and 32.5 ml acetone. Collect sample 4V at
around 620C. Cool the flask and collect sample 4L.
5. Resume the distillation and continue to about 630C. Cool the flask somewhat,
and then add 25 ml chloroform and 25 ml acetone.
6. DISCARD THE DISTILLATE (from the condenser). Then save the new one to use
later.
7. Resume distillation, and collect sample 5V at around 63.50C. Cool the flask and
collect sample 5L.
8. Resume distillation, continue until the boiling point ceases to change
significantly (at around 640C), and then collect sample 6V at around 640C. Cool
the flask and collect sample 6L.
9. Combine the RESIDUE (in distillation flask) with the DISTILLATE OF STEPS 7 AND
8 in another flask, and set aside. DO NOT DISCARD! You will use it in Step 11.
10. Rinse the distillation flask with a little chloroform. Then put 40 ml chloroform
into the flask. Resume the distillation and collect sample 7V at around 610C.
Cool the flask and collect sample 7L.
11. Add 10 ml of the “combined distillate and residue of steps 7 and 8” into the
flask containing the distillate of step 10. Continue with this mixture as
distillate.
12. Resume distillation and collect sample 8V at around 62.50C. Cool the flask and
collect sample 8L.
13. Return the distillate of step 12, and then add approximately 25 mL of the
"combined distillate of steps 7 and 8".
14. Resume distillation and collect sample 9V at around 63.50C. Cool the flask and
collect sample 9L.
15. Resume distillation and collect sample 10V at around 640C. Cool the flask and
collect sample 10L.
16. After the samples are collected, their refractive indices must be measured and
recorded. This can be done at any convenient time.

CALCULATIONS

1. Using the refractive index values given in Table 1 for conversion, determine
the mole fractions of chloroform, and hence of acetone.
2. Plot T versus x (mole fraction) using your results. Draw smooth curves a)
through the points obtained for the distillate (V) and b) through the points
obtained for the residue (L).
3. Label all the phases present on the graph.
4. State what kind of an azeotrope this mixture is. What is the nature of the
interactions between molecules?
5. Determine the azeotropic composition and its boiling point from your graph.
4

6. Compare your results with those given in literature. Determine the error in
your results.

TABLE 1

REFRACTIVE INDEX COMPOSITION FOR ACETONE-CHLOROFORM MIXTURES

nD25 mass % nD25 mass % nD25 mass % nD25 mass %

CHCl3 CHCl3 CHCl3 CHCl3
1.3562 0.00 1.3780 23.50 1.4000 47.55 1.4220 72.85
1.3570 0.75 1.3790 24.60 1.4010 48.70 1.4230 74.10
1.3580 1.75 1.3800 25.65 1.4020 49.80 1.4240 75.30
1.3590 2.75 1.3810 26.70 1.4030 50.90 1.4250 76.50
1.3600 3.80 1.3820 27.80 1.4040 52.00 1.4260 77.70
1.3610 4.85 1.3830 28.85 1.4050 53.10 1.4270 78.95
1.3620 5.90 1.3840 29.95 1.4060 54.20 1.4280 80.20
1.3630 7.00 1.3850 31.00 1.4070 55.30 1.4290 81.40
1.3640 8.10 1.3860 32.05 1.4080 56.45 1.4300 82.65
1.3650 9.20 1.3870 33.15 1.4090 57.60 1.4310 83.90
1.3660 10.30 1.3880 34.25 1.4100 58.75 1.4320 85.15
1.3670 11.40 1.3890 35.30 1.4110 59.90 1.4330 86.40
1.3680 12.50 1.3900 36.40 1.4120 61.05 1.4340 87.70
1.3690 13.60 1.3910 37.50 1.4130 62.25 1.4350 89.00
1.3700 14.70 1.3920 38.60 1.4140 63.40 1.4360 90.35
1.3710 15.80 1.3930 39.75 1.4150 64.55 1.4370 91.65
1.3720 16.90 1.3940 40.85 1.4160 65.75 1.4380 93.00
1.3730 18.00 1.3950 42.00 1.4170 66.90 1.4390 94.35
1.3740 19.10 1.3960 43.10 1.4180 68.10 1.4400 95.75
1.3750 20.20 1.3970 44.25 1.4190 69.30 1.4410 97.20
1.3760 21.30 1.3980 45.35 1.4200 70.50 1.4420 98.55
1.3770 22.40 1.3990 46.45 1.4210 71.70 1.4430 100.00

DATA SHEET:

1L 2L 3L 4L 5L 6L 7L 8L 9L 10L
nD25
1V 2V 3V 4V 5V 6V 7V 8V 9V 10V
nD25