VAPOUR LIQUID EQILIBRIUM

Dt: 16-05-2016

OBJECTIVE: To experimentally determine the vapor-liquid equilibrium conditions for the

binary ACETONE-WATER system and correlate the results for the use in the analysis of the
distillation column.

THEORY:

Vapor-liquid equilibrium (VLE) is a condition in which a liquid and its vapor (gas phase) are
in equilibrium with each other & in this condition the rate evaporation equals to the rate of
condensation on a molecular level such that there is no net vapor-liquid interconversion.

THERMODYNAMIC DESCRIPTION OF VLE:

PURE (Single-component) SYSTEMS:

If the liquid and vapor are pure i.e; they consist only one molecular component and no
impurities, then the equilibrium state between the two phases is described as follow:

Pliq=Pvap ;

Tliq=Tvap ; and

Gliq=Gvap

Where Pliq, Pvap, Tliq, Tvap, Gliq, Gvap are the pressures, temperatures, Gibbs free energies within
the liquid and vapor respectively.

MULTICOMPONENT SYSTEMS:

In a multicomponent system, vapour and liquid consist of more than one type of molecule. For
all components i in the system, the equilibrium between the two phases is described by:

Pliq=Pvap ;

Tliq=Tvap ; and

Giliq=Givap

Where P and T are the temperature and pressure for each phase, and Giliq and Givap are the partial
molar Gibbs free energy also called chemical potential within the liquid and vapor, respectively,
for each phase. The partial molar Gibbs free energy is defined by:

Gi =

1
Where G is the (Extensive) Gibbs free energy, and is the amount of substance of component .

BOILING-POINT DIAGRAMS:

Binary mixture VLE data at a certain overall pressure showing mole fraction vapor and liquid
concentrations when boiling at various temperatures can be shown as a two-dimensional graph
called a Boiling-point diagram. The mole fraction of components 1,2 in the mixture be X1,X2
respectively. Then:

X1 + X2 = 1

In multi-component mixtures in general with n components, this becomes:

X1 + X2 + + Xn = 1

The preceding equilibrium equations are typically applied for each phase (liquid or vapor)
individually.

In a binary boiling-point diagram, temperature (T) is graphed vs. X1. At any given temperature
where both phases are present, vapor with a certain mole fraction is in equilibrium with liquid
with a certain mole fraction. These vapor and liquid mole fractions are represented by two points
on the same horizontal isotherm line.

When an entire range of temperatures vs. vapor and liquid mole fractions is graphed, two lines
result. The lower one, representing the mole fraction of the boiling liquid at various
temperatures, is called the bubble point curve. The upper one, representing the mole fraction of
the vapor at various temperatures, is called the dew point curve.

These two lines (or curves) necessarily meet where the mixture becomes purely one component,
namely where X1 = 0 (and X2 = 1, pure component 2) or X1 = 1 (and X2 = 0, pure component 1).
The temperatures at those points correspond to the boiling point of the two pure components.

Fig.1.1

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Azeotropic mixtures:

For azeotropic pairs of substances, the two curves also coincide at some point strictly between X1
= 0 and X1 = 1. When they meet, they meet tangentially; the dew-point temperature always lies
above the boiling-point temperature for a given composition when they are not equal. The
meeting point is called an azeotrope for that particular pair of substances. It is characterized by
an azeotrope temperature and an azeotropic composition. There can be maximum-boiling
azeotropes, where the azeotrope temperature is at maximum in the boiling curves, or minimum-
boiling azetropes, where the azeotrope temperature is at a minimum in the boiling curves.

Fig.1.2

VLE diagrams:

These diagrams would graph liquid mole fraction on a horizontal axis and vapor mole fraction on
a vertical axis. Here also:

X1 + X2 = 1 and Y1 + Y2 = 1

Fig.1.3

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Raoults law:

Raoults law states that for components 1, 2, etc. in a mixture:

P1 = X1P01 , P2 = X2P02 ,.. etc.

Where P01 , P02 ,etc. are the vapor pressures of components 1,2,etc. when they are pure, and x1 ,
x2, etc. are mole fractions of the corresponding component in the liquid.

Raoults law approximately valid for mixtures of components between which there is little
interaction other than the effect of dilution by the other components. Example: mixtures of
alkanes , which are non-polar, relatively inert compounds in many ways, so there is little
attraction or repulsion between the molecules.

Daltons law:

At boiling and higher temperatures the sum of the individual component partial pressures
becomes equal to the overall pressure ,Ptot.

Ptot = P1 + P2 + ..

Then for each component in the vapor phase:

Y1 = P1 Ptot , Y2 = P2 Ptot , . Etc.

Where P1 = partial pressure of component 1 ,

P2 = partial pressure of component 2, etc.

K value:

The tendency of a chemical species to partition itself preferentially between liquid and vapor
phases is the Henrys law constant. for multi-component mixtures, the VLE data are represented
in terms of K values (vapor-liquid distribution ratios) defined by :

Ki =

Where Xi,Yi are the mole fractions of the species i in the liquid and vapor phases, respectively.

Assuming ideal conditions near ambient temperature and pressure, the K-value may be described
according to Henrys and Raoults laws for dilute and concentrated solutions respectively:

Henrys Law: Ki = Hi

Raoults Law: Ki = Pis/P

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Where Hi is an empirical constant, Pis is the saturation vapor pressure of pure component i, and P
is the total pressure of the equilibrium vapor mixture assuming Daltons Law:

P =

Where Pi is the partial pressure of species i in the vapor phase.

For binary mixtures, the ratio of the K values for the two components is called the relative
volatility denoted by .
(/)
= Ki/Kj =
(Yj/Xj)

Which is a measure of relative ease or difficulty of separating the two components. Large-scale
industrial distillation is rarely taken if the relative volatility is less than 1.05 with the volatile
component being i and the less volatile component being j.

EXPERIMENTAL SETUP:

EQUIPMENT:

1. Equilibrium still
2. Gas chromatography instrument
3. 10 ml volumetric flask
4. 2 ml Clip lock tubes OR Sample vials
5. Digital thermometer
6. Beakers
7. Syringe

CHEMICALS:

1. Acetone Fig.1.4
2. Water

DESCRIPTION:

A vapor-equilibrium still consists of:

A. A boiling pot
B. Central and outlet vapor tubes
C. Thermocouple
D. Condenser

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 E. Pot sampling cock
F. Interchangeable receiver with liquid sampling cock which can hold approx. 15 ml of
distillate.

EXPERIMENTAL PROCEDURE:

1. Prepare a mixture of 250 ml acetone and 60 ml water in a 500 ml beaker.

2. Feed the mixture in to the boiling pot.
3. Switch on the heater and the digital thermometer.
4. Switch on the cooling water supply to the condenser.
5. Note down the top temperature and bottom temperature for every 5 minutes of interval.
6. Note down the temperature at which condensation begins.
7. Take samples of the vapor distillate and liquid in the clip lock tubes at different time
intervals, when sufficient amount of distillate is collected in the distillate receiver.
8. The remaining distillate obtained is kept separately and add 40 ml of water in to the
boiling pot for every sample collected.
9. The procedure is repeated until the temperature is reached up to the boiling point
temperature of water, i.e; 100 c.
10. The samples taken are analyzed in a gas chromatography instrument and the
compositions of water and acetone in different sample are noted down.
11. Draw a Temperature (T) vs. X, Y graph by plotting T on the vertical axis and X, Y on the
horizontal axis.
12. Draw another graph showing Y on the vertical axis and X on the horizontal axis.

OBSERVATIONS:

TABULAR FORM:

S.NO TIME TEMPERATURE (C) REMARKS

TOP BOTTOM
1 10:38 34 34 HEATER ON
2 10:43 35 36
3 10:48 49 43
4 10:53 53 47 CONDENSATION
START
5 10:58 57 50 CUT 1
6 11:03 59 56
7 11:07 61 57 CUT 2
8 11:12 60 58
9 11:17 60 58
10 11:20 62 59 CUT 3
11 11:28 60 61

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 12 11:33 61 62
13 11:37 64 63 CUT 4
14 12:00 64 66 CUT 5
15 12:13 64 69
16 12:23 69 77 CUT 6
17 12:27 68 75
18 12:32 67 73
19 12:42 73 81 CUT 7
20 12:47 68 80
21 12:53 72 81
22 13:42 80 92
23 13:49 78 88 CUT 8
24 13:54 84 90
25 14:01 86 94 CUT 9
26 14:08 84 92
27 14:13 87 94 CUT 10
28 14:20 84 93
29 14:25 81 91
30 14:31 87 94
31 14:39 89 99 CUT 11
32 14:46 88 94
33 14:51 89 100
34 14:56 90 100 CUT 12
35 15:02 96 97 CUT 13

Analysis from Gas chromatography:

Gas Chromatography is used in analytical chemistry for separating and analyzing compounds

Fig.1.5

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that can be vaporized without decomposition. Typical uses of GC include testing the purity of a
particular substance, or separating the different components of mixture or relative amount of
compounds present can also be determined.

In gas chromatography the mobile phase is a carrier gas, usually an inert gas such as Helium or
Nitrogen. The stationary phase is a microscopic layer of liquid or polymer on an inert solid
support, inside a piece of glass or metal tubing called a column. The instrument used to perform
gas chromatography is called a gas chromatograph.

The gaseous compounds being analyzed interact with the walls of the column, which is coated
with stationary phase. This causes each compound to rise at a different time of the compound.
The comparison of the retention times is what gives GC its analytical usefulness.

S.NO. TEMPEARTURE DISTILLATE COMPOSITION RESIDUE COMPOSITION

(C) (%) (%)
WATER ACETONE WATER ACETONE
1 57 18.9841 80.6359 26.3796 73.0140
2 61 8.4750 91.4310 26.8845 72.3245
3 62 8.0901 91.8180 25.6440 74.0382
4 63 8.7885 91.0941 27.5207 72.2709
5 66 10..2121 89.7174
6 69 13.1921 86.6813
7 74 19.8444 80.0890 34.1312 65.8120
8 76 23.9594 75.9805
9 86 51.6227 48.3229 55.1580 44.8421
10 87 68.5985 31.3665 62.4705 37.5295
11 89 84.7303 15.2696 66.2088 33.7912
12 91 90.5451 8.3151 72.1778 27.1413
13 95 73.7435 25.5217

CALCULATIONS:

Antoine parameters:

A B C
Water 8.07131 1730.63 233.7912
Acetone 7.6313 15566.69 273.419

Total pressure Ptot = 760 mm of Hg

Partial pressure at saturation temperature T from Antoine equation:

8

logP = +

Using Raoults law , the acetone mole fraction in the liquid residue (Xacetone) can be calculated
from the acetone mole fraction in the distillate (Yacetone) as:
Yacetone Ptot
Xacetone =

The obtained results are tabulated as:

S.NO. TEMPERATURE (C) Pacetone (mm of Hg) Yacetone Xacetone

1 57 775.845 0.806359 0.78980
2 61 884.074 0.914310 0.78599
3 62 912.968 0.918180 0.76433
4 63 942.626 0.910941 0.73445
5 66 1036.34 0.897174 0.65794
6 69 1137.47 0.866813 0.57916
7 74 1323.70 0.800890 0.45982
8 76 1404.75 0.759805 0.41107
9 86 1872.18 0.483229 0.19616
10 87 1925.05 0.313665 0.12366
11 89 2034.37 0.152696 0.05700
12 91 2148.60 0.831510 0.02941
13 95 2392.39 0.255217 0.08100

Graphical representation of:

1. T vs. Yacetone , Xacetone :

100
90
80
70
60
50
T

40 T-x
30
20 T-y
10
0
0 1
x and y

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 2. Yacetone vs. Xacetone:

1
0.9
0.8
0.7 vapor- liquid
0.6 equilibrium
y 0.5 curve
0.4 x=y line
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5
x 0.6 0.7 0.8 0.9 1

RESULT:

The behavior of the ACETONE-WATER system is studied at various temperatures with various
feed compositions and VLE graph is plotted showing the liquid and vapor compositions of
acetone in the binary water-acetone mixture at various isothermal conditions.

APPLICATIONS:

1. VLE diagrams are used in the McCabe-Thiele method to determine the equilibrium
stages (or theoretical plates) needed to distill a given composition binary feed mixture in
to one distillate and one bottom fraction.
2. In the determination of activity coefficient for the low pressure systems containing an
ideal gas phase, but a non-ideal liquid phase.

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