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CHEM 254

EXPERIMENT 8

Phase Diagrams - Liquid Vapour Equilibrium
for two component solutions

The partial pressures of the components of an ideal solution of two volatile liquids are related to the
composition of the liquid by Raoults Law

and

where P
A
0
and P
B
0
are the vapour pressures of pure A and B
respectively and x
A
and x
B
are the mole fractions of A and B in the
liquid phase respectively

The total vapour pressure of the mixture is

(1)

The partial pressures of each component can also be calculated using Daltons Law which gives the
relation between the mole fractions in the vapour phase (y
A
and y
B
) and the partial pressures.

and

(2)

(3)


The dependence of total vapour pressure of an ideal solution on the mole fraction of A in the entire
system is shown in Figure 1.















Figure 1. Pressure versus composition diagram for a two component ideal solution

The composition of solutions can be determined by various techniques. One of these techniques is
refractormetry. A refractometer device is for the measurement of refractive index. The refractive index,
n, of a medium is defined as the ratio of the velocity of a wave in a vacuum to the phase velocity, v
p
in
the medium itself: n = c / v
p

p
r
e
s
s
u
r
e
mole fraction of A
0.0 1.0
p
A
*
p
B
*
x
A
y
A
liquid
vapour
a
b
Liquid +vapour
p
r
e
s
s
u
r
e
mole fraction of A
0.0 1.0
p
A
*
p
B
*
x
A
y
A
liquid
vapour
a
b
Liquid +vapour


Figure 2. Scheme for Abbe Refractometry.


When the interface between the two mediums of different light speed (u) is flat, the angles of incidence
(
i
, in medium 1) and refracted (
r,
in medium 2), angle between the ray and a surface normal are
related through Snell's law:

sin
i
/ sin
r
=n
2
/n
1




Figure 3. Refraction and Reflection


Purpose: In this experiment liquid - vapor equilibrium of a two component system will be studied.


angle of
reflection
angle of
incidence
angle of
refraction
incident ray
refracted ray
Sample
medium
air

i
angle of
reflection
angle of
incidence
angle of
refraction
incident ray
refracted ray
Sample
medium
air

i
Surface
normal
Interfa
ce
n

n

Apparatus and Chemicals

Apparatus: Refractometer, boiling point apparatus with electrical resistance and condenser, variac,
labeled stoppered test tubes, thermometer, graduated cylinder, soft absorbent paper
Chemicals: Benzene, acetone.

Procedure

1. Place 15 mL of pure benzene into the distillation flask and set up the apparatus.

2. Open the condenser. Heat the sample very slowly. Adjust the transformer so that liquid boils
vigorously at a constant rate (3-4 mV AC). Continue to the boiling with the same rate until the
thermometer reading becomes constant.

3. Record the boiling point (Report Sheet-Table 1).

4. Turn off the heater. After waiting for about one minute take about 1 mL of samples from the distillate
and the residue.

5. Transfer the samples into labeled test tubes for refractive index measurements.

6. Measure refractive index of both solutions. Caution: Do not touch the surface of the prism of Abbe
refractrometer with any glass or metal object. Do not scratch the prism surface. Clean the surface
of the prism using soft absorbent paper to keep it always free from dust and dirt.

7. Repeat the steps 2-6 after successive additions of 1.0, 3.0, 5.0 and 7.0 mL of acetone to the
residue in the distillation flask through the sampling port.

8. Repeat the experiment using acetone instead of benzene and benzene instead of acetone.


Treatment of data
1. a. Using the calibration curve given in Figure 2, find mole fractions of acetone and benzene in the
residue and distillate



Figure 4. Calibration curve. Variation of refractive index as a function of mole fraction of acetone in
acetone-benzene mixtures.


y = -0.1794x + 1.5341
R = 0.9979
1.35
1.36
1.37
1.38
1.39
1.4
1.41
1.42
1.43
1.44
0.5 0.6 0.7 0.8 0.9 1 1.1
R
e
f
r
a
c
t
i
v
e


I
n
d
e
x

Mole Fraction of Acetone
b. Plot temperature versus composition graphs for both distillate and residue on the same graph.


2.a. Calculate theoretical vapour pressures using the following equations
(Report Sheet, Table 2).

log p
A
0
= 7.02447 - [ 1161 / (224 + T(C)) ] for acetone

log p
B
0
= 6.090565 - [ 1211 / (220.79 + T(C)) ] for benzene

b. Calculate mole fractions in the liquid and vapor phases using Raoults Law.

c. Plot temperature versus composition graphs for both distillate and residue on the same graph.



QUESTIONS

1. Define Raoults Law and Daltons Law.
2. What is the purpose of using Refractive index in this experiment?
3. What is the reason of seperating residue and distillate in this experiment?
DATA SHEET Experiment 6- Liquid Vapour Equilibrium for Two Component Solutions

Group Number:
Student Name:
Date: Assistant name and signature:



Table1. Experimental data and mole fractions determined from the calibration curve
T(C) n
R
n
D
x
A
(D) x
A
(R) p
A
0
p
B
0

15 mL benzene
+ 1 mL acetone
+ 3 mL acetone
+ 5 mL acetone
+ 7 mL acetone

15 mL acetone
+ 1 mL benzene
+ 3 mL benzene
+ 5 mL benzene
+ 7 mL benzene


1.b. Plot temperature-composition graph.


2.a. Calculate theoretical vapour pressures at each temperature and fill Table 1


log p
A
0
= 7.02447 - [ 1161 / (224 + T(C)) ] for acetone

log p
B
0
= 6.090565 - [ 1211 / (220.79 + T(C)) ] for benzene



2.b. Calculate mole fractions in the liquid and vapour phases using Raoults law and fill the following
Table 2.





Table 2. Theoretical mole fractions
T(C) p
A

p
B
x
A
y
A

15 mL benzene
+ 1 mL acetone
+ 3 mL acetone
+ 5 mL acetone
+ 7 mL acetone

15 mL acetone
+ 1 mL benzene
+ 3 mL benzene
+ 5 mL benzene
+ 7 mL benzene

2.c. Plot temperature versus composition diagram.