3.

EXPERIMENTAL SECTION
The direct experimental determination of vapour – liquid equilibrium means
analyzing the concentration of both liquid and vapour phase which are in equilibrium which
each other. There are some systems for which equilibrium relation can be calculated from
Raoult’s and Dalton’s laws from the known dependences of the vapour pressure of the pure
compounds on temperature, but there are a large number of industrially important systems
whose equilibrium relations can’t be predicted from purely theoretical considerations. Vapour
liquid equilibrium data can be generated either at constant temperature or at constant pressure.
For distillation calculations the isobaric data are more important and their determination is also
simpler. Classification of the methods that can use to find equilibrium relation experimentally
(Hala et al. 1967).

 Distillation method,

 Static method,

 Flow method,

 Circulation method,

The distillation method is the oldest method in which small amount of liquid is
distil off from boiling flask. It is very simple method. Major disadvantage is that large amount
of liquid is required and major error can be obtain due to condensation of boiling liquid on the
cold surface of the distillation flask at the beginning of the experiment(Hala et al. 1967).

In static method, binary mixture is charged to a closed, heated chamber and mixes
until equilibrium is established. Major disadvantage is that, small change in pressure and
volume can have significant effect on the system due to that it is very difficult to take a sample
for analysis without disturbing the equilibrium. This method is generally use for high pressure
because for low and moderate pressure other easier methods are available (Scholten 1997).

In flow method, mixture of known composition is continuously feed to an

equilibrium chamber where it is heated to boiling. After the vapour and liquid reach steady
state and equilibrium is confirmed by constant temperature and pressure in the system, samples
are taken and analyzed. This method may give very accurate results, but it requires fairly
complicated equipment. Further drawback include the possibility of long time to achieve
equilibrium and large quantity of liquid sample.

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 The circulation method is the most common and widely accepted method. In
circulation method vapors coming off from the boiling mixture are condensed in condenser and
this condensate is returned to liquid chamber, creating a continuous cycle. Constant pressure
and temperature in the system indicate that pseudo – equilibrium steady state is achieved.

3.1 Equipment and Setup details

Setup 1:

Differential ebulliometer is used to generate vapour – liquid equilibrium data that

is shown briefly in figure 3.1. The name ebulliometer is comes from Latin word “EBULLIO”
– meaning boil or bubble up. The primary components in the ebulliometer are the boiler,
Cottrell pump, thermowell and condenser. Entire experimental setup is shown in Figure 3.2.

Figure 3.1 Detail diagram of differential ebulliometer (Walas, 1985)

For the VLE data generation chemicals (pure component as well as binary mixture)
were fed into the modified ebulliometer. Ebulliometer has provision of drop counter to ensure
equilibrium conditions more over data can be generated with minimum quantity of chemical
requirement. The drop counter facility is very unique and provides additional resource to ensure
equilibrium condition along with the temperature. The bottom section of the ebulliometer was
wound with external heating element. The detail of the experimental setup given in Table 3.1.

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 Figure 3.2 Schematic Experimental Setup 1.

1. Ebulliometer, 1 a. Feed outlet, 1 b. Boiling chamber, 1 c. Cottrell Pump, 1 d. Drop counter, 1 e. Thermowell,
1 f. Feed inlet 2. Mercury in glass thermometer, 3. External belt heater, 4. U – Tube Mercury manometer, 5.
Jacketed internal coil condenser, 5 a. Cooling water inlet, 5 b. Cooling water outlet, 6. SS Ballast tank, 7. Bypass
line, 8. Belt Driven oil ring Vacuum pump, 9. Nitrogen cylinder, 10. Dimmer stat.

Table 3.1 Details of experimental setup 1.

Temperature Measurement Mercury Thermometer (0 – 250 0C), Accuracy:- 0.1/0.1 0C

Pressure Measurement Mercury manometer (400 to 760 mmHg), Accuracy:- 1 mmHg

Vacuum Pump Belt Driven oil ring Vacuum pump

Cooling media water (40 – 60 0C)

Condenser 24 inch Jacketed internal coil condenser

Ballast 10 lit. SS – 316 setup

Heater 0.5 KW External belt heater

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Setup 2:

Setup 1 was failed due to high temperature gradient between condensed vapor and
boiling chamber create an crack in setup so that new setup of stainless steel – 316 was prepared
as shown in figure 3.3. Design parameter of SS-316 ebulliometer is unchanged and as same as
mention in figure 3.1. The detail of the experimental setup given in Table 3.2. Experimental
procedure for this setup is also same as setup 1. Small but thick glass tube is provided as drop
counter.

Table 3.2 Details of experimental setup

Temperature Measurement Mercury Thermometer (0 – 250 0C), Accuracy:- 0.1/0.1 0C

Pressure Measurement Mercury manometer (400 to 760 mmHg), Accuracy:- 1 mmHg

Vacuum Pump Belt Driven oil ring Vacuum pump

Cooling media Chilled water (15 – 25 0C) for Secondary condenser,

Water (30 – 50 0C) for Primary Condenser

Condenser 4 inch secondary Annulus condenser, SS-316

12 inch Primary Annulus Condenser with 5 Baffles, SS-316

Ballast 10 lit. SS – 316 setup

Heater 4 External bend heater of 1.5 KW each

Figure 3.3 Schematic Experimental Setup 2.

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Setup 3:

Pure component data for n-butanol was successfully generated in Setup 2 but it
failed to generate data for butyl glycolate as due to high wall temperature effect leading to
decomposition of butyl glycolate. To resolve this issue third setup was build based on indirect
heating concept. A cylindrical glass vessel with provision of tilted thermowell was connected
to double coiled glass condenser with O ring vacuum trap joint. System assembly is shown in
figure 3.4. Change detail of the experimental setup given in Table 3.2. Steps for experimental
procedure are mention below.

 Pure or mixture solution and magnetic stirrer was initially taken in the glass vessel.
 Vessel was deep in oil bath,
 Condenser was then connected using O ring connector,
 Start cooling water supply and magnetic stirrer,
 Oil bath temperature was set at specific temperature,
 Wait till thermometer shows constant temperature,

Table 3.3 Details of experimental setup 1.

Cooling media water (40 – 60 0C)

Condenser Double coil condenser

Heater 6 KW External bend heater

Figure 3.4 Schematic Experimental Setup 3.

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Setup 4:

In step up 3 there was drastic drop in temperature due to sub-cooling of vapour. To

avoid this problem temperature of cooling water supplied was increased and due to that
problem of vapor losses was observed. Due to all this difficulty occurring in isobaric system
because of sub-cooling of vapor of butyl glycolate a very simple setup is built to generate
isothermal data. Schematic diagram of experimental set up is shown in figure 3.5.

Figure 3.5 Schematic Experimental Setup 4

3.2 CHEMICALS
Pure component vapor pressure data as well as partial vapor – liquid equilibrium data was
generated for n-butanol – butyl glycolate system. The details about chemicals used for this
work is given in Table 3.4. The GC analysis of all these species showed absence of any
additional peak hence they were used directly without any purification.

Table 3.4: Details of the chemicals used

Chemicals Source Purity Analysis method

N – Butanol Suvidhinath 99% GC

Laboratories

Cyclopentanol LOBA chemicals 99% GC

Ltd.

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 Butly Glycolate Sigma – Aldrich > 90% GC
Chemie Gmbh

GC- Gas Liquid Chromatography

3.3 Experimental Procedure

To generate data feed sample and magnetic needle are inserted from feed point and
then sonication was done to remove dissolved gases in the system then manometer was
connected with the inlet point and seal with PTFE tape. Desired temperature was set in
controller. Result was taken after manometer and thermometer gives constant reading.

After completion of experiment vessel was flushed with acetone followed by

Drying. After the completion of experiment all the initial and the final liquid composition were
analyzed by gas chromatography (CHEMITO 1000).

3.4 Analysis
The mixture of ethylene dichloride and n-butanol was analyzed on Chemito Gas
Chromatograph using 1.8 m Chromatopak column. The parameters set for the analysis are
given in Table 3.3.

Table 3.3: G.C parameters

GC PARAMETERS CONDITIONS GC PARAMETERS CONDITIONS

Column Packed Oven Temperature (0C) 80 – 190 @ 9 0C / min

Range 0-0 Carrier Gas (N2) Pressure 0.8 bar

Injection Port Temperature 200 0C FID (+Ve)

Detector Temperature 210 0C Injection Quantity 0.1 μ liter

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 Figure 3.3 Calibration plot for Ethylene Dichloride (EDC) and n-Butanol (BuOH)

Synthetic samples were prepared using external standard for calibration.

Cyclopentanol (CP) was used as an external standard for the analysis. Calibration plots are
shown in Figures 3.2. The data obtained from gas chromatography analysis is given in
Appendix C and the chromatograms are shown in Appendix D.

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