GROUP 5: VAPOUR LIQUID EQUILLIBRIUM.

STUDENT NAMES AND INITIALS STUDENT NUMBERS

MALINGA D.G 21721647
NKAMELA A 21721915
ZUNGU N.W 21722397
NAME OF THE MODULE CHEMICAL ENGINEERING LABORATORY 2A
NAME OF THE LECTURER REDDY G.K
DATE OF SUBMISSION 1 JULY 2021

1
Summary
Vapour liquid equilibrium (VLE) is commonly used in distillation to separate a combination
of different components with differing boiling points, with the light components vaporizing
fast and exiting the column as vapour, and the heavy components exiting through the
bottoms. This is true for both binary and multi-component mixtures, but the mixture must be
miscible and liquid. The major goal of this practical was to find the Vapour-Liquid
Equilibrium for a genuine system containing two miscible liquids. It was also to create the
isobaric and equilibrium diagrams for the two components. The other goal was to figure out
the Raoult’s activity coefficients.

All of the combinations in this experiment have an activity coefficient that is relatively close
to 1 or equal to 1 because 0.999 is the same as 1. From this, it may be concluded that all
mixes containing both ethyl acetate and ethanol obeyed Raoult's Law, which is believed to
apply to ideal systems. This is to illustrate that at atmospheric pressure, the system or mixture
normally boils, hence the activity coefficient is equal to 1. When a mixture is at equilibrium,
it forms an azeotrope at some point, as seen by the vapour-liquid diagram and the isobaric
diagram. The linear relationship between refractive index and volume fraction ensured that
the longer it took to collect the last dripping condensate from the condenser at boiling
temperature, the more we could determine the contaminants and how pure the mixture was.
In the vapour phase, this also increases the amount of desired product.

To read the solution that is more concentrated with the light component of the two, it is
recommended that the separation of two components through the boiling unit be done for a
longer duration. In order to visualize the equilibrium data, one must first know the
composition of the liquid and vapour phases of the two components.

2
Table of Contents
Summary ............................................................................................................................................. 2
Introduction ........................................................................................................................................ 4
Theory ................................................................................................................................................. 5
Experimental Procedure. .................................................................................................................... 7
Results and discussion. ....................................................................................................................... 8
Discussions of trends observed. ....................................................................................................... 10
Conclusion ......................................................................................................................................... 12
Recommendations. ........................................................................................................................... 12
References. ....................................................................................................................................... 13
Appendices........................................................................................................................................ 14

3
Introduction
Vapour Liquid Equilibrium is a technique or a procedure that is used to separate liquid
mixture depending on their boiling points. The driving force of the VLE is temperature
because substances that are separated are based on their boing point temperatures (wikipedia)
(wikipedia). The separated liquid combination is most likely a miscible liquid of homogenous
mixture. The ability of a liquid to entirely dissolve in another liquid solution is known as
miscibility. When you have a solution that is labeled miscible, a distinct layer between two
liquids will not form. Immiscibility occurs when a separate layer forms in a mixed solution
(Reid, 2003). A homogeneous mixture is one whose composition is consistent throughout the
entire mixture.

VLE is most commonly employed in distillation to separate a mixture of different

components with differing boiling points, with the light components vaporizing fast and
exiting the column as vapour, and the heavy components exiting through the bottoms.This
applies in both binary and multi-component mixture but the mixture has to be miscible, and I
must be in liquid form.

The main objective of this practical is to find the Vapour-Liquid Equilibrium for a genuine
system containing two miscible liquids. The isobaric diagram and the equilibrium diagram of
the two components must also be constructed. The other goal is to figure out what Raoult's
activity coefficients are.

4
Theory

= 𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝐶𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝐴

= 𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝐶𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝐵

𝜌𝑖 = 𝑚𝑖 𝑖

𝜌𝑖 = 𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝐶𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝐴 𝑜𝑟 𝐵

𝑚𝑖 = 𝑚𝑎𝑠𝑠 𝑜𝑓 𝐶𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝐴 𝑜𝑟 𝐵

𝑣𝑖 = 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝐶𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝐴 𝑜𝑟 𝐵

𝑛𝑖 = 𝑀𝑜𝑙𝑎𝑟 𝑀𝑎𝑠𝑠𝑖 × 𝑚𝑖

𝑛𝑖 = 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑐𝑜𝑚𝑝𝑜𝑝𝑛𝑒𝑛𝑡 𝐴 𝑜𝑟 𝐵

𝑀𝑜𝑙𝑎𝑟 𝑀𝑎𝑠𝑠𝑖 = 𝑀𝑜𝑙𝑎𝑟 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑐𝑜𝑚𝑝𝑜𝑝𝑛𝑒𝑛𝑡 𝐴 𝑜𝑟 𝐵

𝑛𝑡𝑜𝑡𝑎𝑙 = 𝑛𝐴 + 𝑛𝐵

𝑛𝐴 = 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝐴

𝑛𝐵 = 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝐵

𝑛𝑡𝑜𝑡𝑎𝑙 = 𝑡𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠

𝑖 = 𝑙𝑖𝑞𝑢𝑖𝑑 𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛 𝑜𝑓 𝐴 𝑜𝑟 𝐵

( )

𝑝𝑖 = 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑜𝑓 𝑃𝑢𝑟𝑒 𝐶𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝐴 𝑜𝑟 𝐵

𝑃 = 𝑇𝑜𝑡𝑎𝑙 𝑠𝑦𝑠𝑡𝑒𝑚 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒

𝑅 = 𝑔𝑎𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

= 𝑚𝑜𝑙𝑎𝑟 𝑒𝑣𝑎𝑝𝑜𝑟𝑎𝑡𝑖𝑜𝑛 𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑦

𝑇 = 𝑃𝑢𝑟𝑒 𝐶𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝐵𝑜𝑖𝑙𝑖𝑛𝑔 𝑃𝑜𝑖𝑛𝑡 𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡ure

𝑇𝑖 = 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝐵𝑜𝑖𝑙𝑖𝑛𝑔 𝑃𝑜𝑖𝑛𝑡 𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢re

5
𝑃 𝑝

𝑃𝑖 = 𝑃𝑎𝑟𝑡𝑖𝑎𝑙 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒

𝑝𝑖 = 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑜𝑓 𝑃𝑢𝑟𝑒 𝐶𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝐴 𝑜𝑟 𝐵

𝑖 = 𝑙𝑖𝑞𝑢𝑖𝑑 𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛 𝑜𝑓 𝐴 𝑜𝑟 𝐵

𝑖 = 𝑣𝑎𝑝𝑜𝑢𝑟 𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛 𝑜𝑓 𝐴 𝑜𝑟 𝐵

𝑃𝑖 = 𝑃𝑎𝑟𝑡𝑖𝑎𝑙 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒

𝑃 = 𝑇𝑜𝑡𝑎𝑙 𝑠𝑦𝑠𝑡𝑒𝑚 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒

𝑃 𝑃 𝑃

𝑃𝐴 = 𝑃𝑎𝑟𝑡𝑖𝑎𝑙 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑜𝑓 𝐴

𝑃𝐵 = 𝑃𝑎𝑟𝑡𝑖𝑎𝑙 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑜𝑓 𝐵

𝑃 = 𝑇𝑜𝑡𝑎𝑙 𝑠𝑦𝑠𝑡𝑒𝑚 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒

𝛾𝑖 = 𝐴𝑐𝑡𝑖𝑣𝑖𝑡𝑦 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡 𝑜𝑓 𝐶𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝐴 𝑜𝑟 𝐵

𝑃𝑖 = 𝑃𝑎𝑟𝑡𝑖𝑎𝑙 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑜𝑓 𝐴 𝑜𝑟 𝐵

𝑝 = 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑜𝑓 𝑃𝑢𝑟𝑒 𝐶𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝐴 𝑜𝑟 𝐵 𝑖 = 𝑙𝑖𝑞𝑢𝑖𝑑 𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛 𝑜𝑓 𝐴 𝑜𝑟 B.

𝑖 = 𝑙𝑖𝑞𝑢𝑖𝑑 𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛 𝑜𝑓 𝐴 𝑜𝑟 B.

6
Experimental Procedure.
 6 solutions of ethyl acetate and ethanol which each has the total volume of 40mL
 Refractometer was used to read the refractive index of each solution, by first dropping few
drops and face the refractometer towards light to read the refractive index.
 Record each concentration with the corresponding refractive index.
 First solution was put in a round bottom flask then heated.
 The boiling unit was already set up.
 The solution will boil or see bubbles once heating start and the vapour will travel up the flask
to the condenser.
 The first few droplets of condensate we taken and the refractive index of the condensate were
determined.
 The temp at which the solution was boiling at was recorded.
 This was done for all the six solutions.

Apparatus.

 Beakers
 Refractometer
 Boiling Unit
 Round Bottom Flask
 Ethyl Acetate
 Ethanol

7
Results and discussion.
XA YA
0,13 0,12
0,31 0,25
0,43 0,43
0,57 0,44
1,00 0,72
1,00

XB YB Temp(oC)
0,87 0,88 74
0,69 0,75 71
0,57 0,57 77
0,42 0,56 69,9
68
1,00 0,28 67

X-y diagram
1,00
0,90
0,80
0,70
0,60
Ya

0,50 Series1
0,40
0,30
0,20
0,10
0,00
0,00 0,10 0,20 0,30 0,40 0,50 0,60 0,70 0,80 0,90 1,00
Xa

Figure 1.1: shows the Vapour Liquid Equilibrium of ethyl acetate and ethanol.

8
 80
Txy diagram
78

76
Tempeature

74
xa Boiling Point
72
ya Dew Point
70

68

66
0,00 0,20 0,40 0,60 0,80 1,00
Xa,Ya

Figure 1.2 a: shows the azeotrope graph of ethyl acetate.

78
Txy diagram
76

74
Temperature

72 Xb, boiling point

70 Yb, dew point

68

66
0,00 0,20 0,40 0,60 0,80 1,00
Xb,Yb

Figure 1.2b: shows the azeotope graph of ethanol.

9
 Refractive index vs Volume fraction
of A
1,374
1,373
1,372
1,371
1,37
Refractive index vs
1,369
Volume fraction of A
1,368
1,367
1,366
1,365
0 0,2 0,4 0,6 0,8 1 1,2

Figure 1.3: show the trend between refractive index and volume fraction of ethyl acetate.

Discussions of trends observed.

The equilibrium curve of the real system of two miscible mixtures, ethyl acetate and ethanol, is shown
in Figure 1.1. They are considered to be miscible because ethyl acetate dissolves completely when
mixed with ethanol, resulting in no distinguishable layer forming when the two components are
blended. The equilibrium curve has that shape because the mixture is a genuine system, and it is
believed that separating these two components using equilibrium distillation is difficult due to their
close boiling points.

According to the VLE theory, a component with a lower boiling point should vaporize faster than one
with a higher boiling point (Rui, Xianboa, Ying, Tianyang, & Cai, 2012), and in this mixture, ethyl
acetate is the light key component and ethanol is the heavy key component (Rui, Xianboa, Ying,
Tianyang, & Cai, 2012). (Cicero Sena Moreira, Humberto Neves Maria, Osvaldo, & Edson Luiz,
2014). Because it has a lower boiling point than ethanol, ethyl acetate is considered a light essential
component. Because ethanol has a boiling point of 78°C and ethyl acetate has a boiling point of
77.1°C, it's tough to tell the two apart. The pinch point on the curve is the azeotrope, azeotrope is
defined as the point where the mixture boiled and the vapour has the proportions of constituents as the
unboiled mixture (wikipedia).

Figures 1.2a and 1.2b show the isobaric Txy diagrams of ethyl acetate and ethanol, respectively. The
boiling point and dew point temperatures of both components are shown in both figures and graphs
for various compositions corresponding to various temperatures. The trend in both graphs is the same,
but in opposite directions; figure 1.2a is for ethyl acetate, and because it is considered a light
component, the trend will first drop in temperature as the composition of vapour and liquid increases.
Till they met at the point where both boiling and dew point are equal, at this point which in this case
is at 77 and the azeotrope occurs. Figure 1.2b the same trend is followed but this curve increases the
compositions of vapour and liquids increases too. At 77 the azeotrope occurs. Because ethanol is a
heavy component that requires a high temperature to evaporate as the composition increases, the
graph on figure 1.2b is increasing before the azeotrope point.

The linear relationship between the refractive index and the volume fraction of ethyl acetate is shown
in Figure 1.3. As the value of a variable rises, the trend rises with it. The graph depicts the relationship

10
between refractive index and volume fraction. The refractive index is the ratio of the speed of light
passing through a sample to the speed of light passing through a vacuum (Tim). The refractive index
is an important fluid characterisation measure with a wide range of uses in industry. Many pure liquid
values are well-known or readily available in the literature. When experimental data is unavailable,
the refractive indices of binary and multi-component liquids are frequently calculated by mixing the
pure components (Sunday, 2015). This demonstrates that as the volume of the solution increases, the
solution becomes more pure.

Table 1.4: shows the Raoult’s Activity Coefficient for all the runs.

activity
Coefficient Run 1 Run 2 Run 3 Run 4 Run 5
ɤi 0,999 0,999 0,999 0,999 1

The activity coefficient for all of the runs is shown in the table above, and the component utilized for
this was ethyl acetate. For liquids and solids, the activity coefficient is used to indicate non-ideal
systems. The activity coefficient for an ideal system is 1. This demonstrates that the system adheres to
Raoult's Law, which was created for an ideal system. Because the system is claimed to be isobaric,
with system pressure equal to that of the atmosphere, it will obey this law. The chart does not indicate
Run 6 since it was said to be undefined because there was no ethyl acetate and it was exclusively
made up of ethanol, or we can be certain that solution 6 was pure ethanol.

11
Conclusion
All of the combinations in this experiment have an activity coefficient that is relatively close
to 1 or equal to 1 because 0.999 is the same as 1. From this, it may be concluded that all
mixes containing both ethyl acetate and ethanol obeyed Raoult's Law, which is believed to
apply to ideal systems. This is to illustrate that at atmospheric pressure, the system or mixture
normally boils, hence the activity coefficient is equal to 1. When a mixture is at equilibrium,
it forms an azeotrope at some point, as seen by the vapour-liquid diagram and the isobaric
diagram.

The linear relationship between refractive index and volume fraction ensured that the longer
it took to collect the last dripping condensate from the condenser at boiling temperature, the
more we could determine the contaminants and how pure the mixture was. This also
increases the amount of desired product at the vapour phase.

Recommendations.
It is suggested that the boiling unit be used to separate two components for a
longer period of time in order to read the solution that is more concentrated with
the light component of the two. In order to visualize the equilibrium data, one
must first know the composition of the liquid and vapour phases of the two
components.

12
References.
Anon. (n.d.). Lumen. Retrieved July 27, 2020, from Chemistry for non-Majors:
https://courses.lumenlearning.com/cheminter/chapter/homogenous-and-
heterogenous mixtures/

Cicero Sena Moreira, G., Humberto Neves Maria, d. O., Osvaldo, C. F., & Edson Luiz, F.
(2014). Vapor Liquid Equilibria for ethyl acetate+methanol and ethyl acetate+ ethanol
Mixtures: experimental verification and prediction. Chemical Engineering Research and
esign.

Miguel, I., Rafael, G.-O., Goenaga, J. M., & Resa, J. M. (2010, July 14). Phase behaviour of
ethanol + water + ethyl acetate at 1013kPa. An Internetional Journal, 48(4), 461-576.

Reid, D. (2003). Study.Com. Retrieved June 27, 2021, from

https://study.com/academy/lesson/miscible-liquids-definition-examples.html

Rui, L., Xianboa, C., Ying, Z., Tianyang, F., & Cai, J. (2012, February 13). Vapor Liquid
equilibrium and Liquid Liquid Equilibrium of ethyl acetate+ Ehanol + Ethyl-3-
methylimidazolium Acetate. Chemical Engineering Data, 57(3), 911-917.

Sunday. (2015, April). Researchgates. Retrieved June 27, 2021, from

https://www.researchgate.net/figure/Refractive-index-versus-volume-fraction-of-
heptane hexane-at-20C_fig2_290475688

Tim, M. (n.d.). Enotes. Retrieved June 27, 2021, from Science Questions and Answers:
https://www.enotes.com/homework-help/what-purpose-boiling-point-refractive-
index 606942

wikipedia. (n.d.). Retrieved June 27, 2021, from https://en.wikipedia.org

13
Appendices.
Sample calculations

Converting density from kg/m3 to g/ml

𝜌 𝑔 𝑚𝑙

𝜌 𝑔 𝑚𝑙

The molar mass of ethyl acetate = 88.11 g/mol

Molar mass of ethanol = 46.07 g/mol

The total volume = 40 ml

Run 1

10 ml + 30 ml = 40 ml

𝑚 𝑔

The number of moles of ethyl acetate

𝑛 𝑚𝑜𝑙𝑒𝑠

𝑚 𝑔

The moles of ethanol

𝑛 𝑚𝑜𝑙𝑒𝑠

The total moles = 𝑛 𝑛 𝑚𝑜𝑙𝑒𝑠

Determining the composition ethyl acetate and ethanol

Ethyl acetate =

Ethanol =

The pressure of pure components

14
 ( ) = ( )

= 𝑝

Using Raoult’s law: 𝑃 𝑃 ( ) 𝑝𝑎

Using Dolton’s law = 𝑝 𝑝 𝑝

𝑝 𝑝 𝑃 𝑝𝑎

15