Aim:

To study the vapor-liquid equilibrium curve.

Objective:
To plot the Vapor-Liquid Equilibrium Curve for Ethyl-Acetate and Acetonitrile system.

Introduction:
The design of distillation and other contacting equipment requires reliable VLE data. It
shows the relationship between the composition of the vapor and that of liquid in
equilibrium with the vapor for a binary mixture at constant pressure or constant
temperature. Although relatively few ideal solutions are known whose equilibrium relations
can be calculated from vapor pressure–temperature data of the pure components, by far
the larger numbers of systems of industrial importance are non-ideal; and attempts to
predict the equilibrium compositions of such mixtures from theoretical considerations alone
have not proved to be successful. It has been the practice to determine such data
experimentally under various conditions.

Theory:
Knowledge of the vapor-liquid equilibrium is helpful in predicting how liquid mixtures may
separate. Because of the distinct boiling points of the two liquids, one will boil into a vapor
and ascend in the column, while the other will remain liquid and drain through the device. A
steady state is reached when the rate of condensation (from vapor to liquid) equals the rate
of evaporation (from liquid to vapor). The link between the composition of the vapor and
the composition of the liquid in equilibrium with the vapor for a binary mixture at constant
pressure or constant temperature is shown by the vapor-liquid diagram. The equilibrium
between the liquid and vapor phases of the system undergoing distillation is the
fundamental data for every distillation issue. Therefore, understanding the Vapour-liquid
equilibrium is crucial.
A calibration curve is used to calculate the limit of detection and the limit
of quantitation, as well as the concentration of an unknown material. The instrument
response to a series of standard samples at various concentrations is used to produce the
curve. To enable the prediction of unknown concentrations, the data are then fitted using a
function. For this experiment calibration curve of refractive index is plotted. Temperature,
the light source's wavelength, and the substance being studied all affect the refractive
index. The refractometer employs a suitable light source and is thermostated. For the target
binary system, known concentration mixtures are created, and their refractive indices are
measured alongside those of the pure constituents.
Description:
The set-up consists of distillation still with a heating element. An electrical Dimmer stat is
connected to the heating element for varying heat input. The vapor from the top of the
column is condensed in the concentric tube-type condenser by circulating cooling water.
The condensate is feedback to the column as reflux. A tank with a pump is provided to
circulate cold water to the condenser. Flow rates can be regulated through a control valve
fitted. Instrumentation is done to measure the temperatures at different points.

Materials Required:
1. Electrical supply: Single Phase, 220 V AC, 50 Hz, 5-15 Amps socket with earth connection.
2. Water Supply (Initial Fill).
3. Drain required.
4. Floor Area Required: 1 m x 0.5 m.
5. Refractometer for analysis.
6. Chemicals Required: Ethyl-Acetate, Acetonitrile

Line Diagram:
Procedure:

1. Three samples of a mixture of Ethyl Acetate & Acetonitrile were prepared.

2. The feed solution was charged in the vessel from the funnel provided at the top of the
vessel.
3. The switches provided on the panel were put at OFF position.
4. First the supply was switched ON and then the heater.
5. The dimmer stat was gradually increased and T2 temperature was observed.
6. The pump was switched ON when temperature T2 started increasing and allows cooling
water to pass through the condenser.
7. T2 was maintained between 70 and 100 °Celsius by adjusting the heat input from the
dimmer stat.
8. After observing constant temperatures T1 and T2 we took a sample of distillate and
residue from the valve provided at the bottom of the condenser and still respectively.
9. The dimmer stat was set to zero and the still was recharged with another feed mixture.
10. Above steps were repeated for the other set of compositions.

Formulas used:
If liquid and vapor behave ideally, such curves are calculated as follows:
P1=P°1x1
P2=P°2x2
Where P1 and P2 are partial pressures of components 1 and 2 in the mixture, P°1, and P°2 are
the vapor pressure of pure components at the same temperature as the mixture.
P1 = PTy1
P2 = PTy2
x1 and x2 are the mole fractions of components in the liquid phase whereas y1 and y2 are the
mole fractions of components in the vapor phase.
PT = P°1x1 + P°2x2
From these equations we get
P T −P2 P 1 x1
x1 = P −P ; y1 =
1 2 P

The theoretical VLE curve can thus be calculated by choosing various boiling points of the
mixture and calculating x and y as shown above.

Notations/ Nomenclature:
EA - Ethyl Acetate
ACN - Acetonitrile
R.Itop = Refractive index of residue
R.Ibottom = Refractive index of distillate
Ttop = Temperature of the vapor, oC
Tbottom = Temperature of the vapor, oC
x,y = Mole fraction of component

Observations :
Given:
Density(ACN) 0.786 g/cm3
Density(EA) 0.902 g/cm3
Molar Mass(ACN) 41.05 g/mol
Molar Mass(EA) 88.1 g/mol
Boiling Point of Acetonitrile: 82 oC
Boiling Point of Ethyl-Acetate: 77.2 oC
 Calibration Data
Volume (in ml) Volume Fraction(V/V) Weight Fraction(w/w) Mole Fraction
ACN EA R.I ACN EA ACN EA ACN EA
0 10 1.3698 0 1 0 1 0 1
1.3649 0.82128240
2 8 4 0.2 0.8 0.178717599 1 0.31834707 0.68165293
1.3591 0.63279607
4 6 2 0.4 0.6 0.367203924 6 0.554643586 0.445356414
1.3532 0.43371757
6 4 8 0.6 0.4 0.566282421 9 0.736989763 0.263010237
0.22312824
8 2 1.347 0.8 0.2 0.776871757 3 0.881969072 0.118030928
1.3414
10 0 6 1 0 1 0 1 0

Actual Data
Volume (in ml)
ACN EA R.I
0 10 1.36979
1 9 1.36729
2 8 1.36488
3 7 1.36221
4 6 1.3595
5 5 1.35658
6 4 1.35382
7 3 1.35065
8 2 1.3498
9 1 1.34464
10 0 1.3415

Calibration Data
1.2
Mole Fraction Of Ethyle Acetate

0.8 f(x) = 33.9259521620497 x − 45.5833209833388

0.6

0.4

0.2

0
1.34 1.345 1.35 1.355 1.36 1.365 1.37 1.375

R.I

Calibration Data Linear (Calibration Data) Linear (Calibration Data)

 Data for different concentrations of Ethyle-Acetate and Acetonitrile
1.

Feed Composition (Acetonitrile 55.64% + Ethyle Acetate 44.36%)

Feed Sample R.I : 1.35461, 1.35462 Feed Volume : 680 ml
S.No Ttop( °C) T bottom( °C) R.I top R.I bottom Y-EA X-EA Y-ACN X-ACN
1 75 77.9 1.35773 1.3547 0.47934798 0.3765522 0.52065202 0.6234478
2 75 77.9 1.35764 1.35448 0.47629464 0.36908848 0.52370536 0.63091152

2.

Feed Composition (Acetonitrile 21.63% + Ethyl Acetate 78.37%)

Feed Sample R.I : 1.36428, 1.36428 Feed Volume : 680 ml
S.No Ttop( °C) T bottom( °C) R.I top R.I bottom Y-EA X-EA Y-ACN X-ACN
1 74.3 75.7 1.36438 1.36279 0.70495588 0.65101354 0.29504412 0.34898646
2 74.3 75.7 1.36449 1.36438 0.70868774 0.70495588 0.29131226 0.29504412
3 74.3 75.7 1.36449 1.36408 0.70868774 0.69477808 0.29131226 0.30522192

3.

Feed Composition (Acetonitrile 37.28% + Ethyl Acetate 62.72%)

Feed Sample R.I : 1.35986, 1.35981 Feed Volume : 720 ml
S.No Ttop( °C) T bottom( °C) R.I top R.I bottom Y-EA X-EA Y-ACN X-ACN
1 74.3 76.1 1.36144 1.3601 0.60521344 0.5597526 0.39478656 0.4402474
2 74.3 76.1 1.36135 1.35984 0.6021601 0.55093184 0.3978399 0.44906816
3 74.3 76.1 1.36135 1.35979 0.6021601 0.54923554 0.3978399 0.45076446

Result:
 The calibration data between the mole fraction and refractive index is lof linear
relationship.
 The solution is of minimum boiling azeotrope from which we can see that repulsive
forces exist between the components and solution is not ideal.
 The graph y vs x shows the vapour liquid equilibrium relation between the
components of the feed.

Discussions :
 The y vs x curve is referred to as the equilibrium curve for the given components.
 The solution is non ideal because it is evident form the above graphs and data that
repulsive forces exist between the components.
 Due to the repulsive forces, Raoult’s law is violated as the solution is no more ideal.
  Solution’s heat of mixing and change in mixing both are non-zero as the solution is
not ideal.

Conclusions :
 The mixture given is not perfectly ideal solution.
 Raoult’s Law applies only to those ideal solutions which have no intermolecular
attraction.
 Azeotrope for the given mixture is minimum boiling azeotrope, which gives the idea
that repulsive forces exist between the components.
 The relation between refractive index and molar composition is linear.

Applications:
The McCabe-Thiele approach uses these kinds of VLE diagrams to calculate the number of
equilibrium stages (or theoretical plates) required to separate a binary feed mixture with a
specified composition into a distillate fraction and a bottoms fraction.

Precautions:
1. Fill the still at least half of the capacity.
2. Drain the still and water tank after completion of the experiment.
3. Do not run the pump before filling the tank with water.
4. Do not start the heater before fill the chemical into the still.
5. While putting drops of distillate and residue mixture in the refractometer, use different
droppers.
6. Put on gloves and safety goggles while handling the chemicals.

References:
 https://www.jove.com/v/10425/vapor-liquid-equilibrium
 Coulson & Richardson, “Chemical Engineering Vol-2”, 4th ed, Asian Books Pvt.Lt, ND,
1991, Page 428-429.
 Treybal, R.E, “Mass-Transfer Operations”, 3rd ed, McGraw-Hill, NY, 1981, Page 343-
348.