ADAMSON UNIVERSITY

College of Engineering
Chemical Engineering Department
M a n il a

Experiment no. 1

DISTILLATION OF BINARY LIQUIDS

Submitted by:
Lavilles, Francis Dominic
Lee Gee Hyun
Lojica, Kathlyn Joyce M.

Date performed: July 18, 2015

Date submitted: July 27, 2015

ABSTRACT:
The main objective of the experiment is to construct a boiling point composition diagram for a binary liquid
system. Distillation is a process in which two components are separated by boiling the component that has a lower
boiling point compared to the other. The researchers prepared a simple distillation set-up. 50-mL of glacial acetic acid
and 1-mL of distilled water were mixed and were used in the distillation of the binary liquids. After the distillates have
been collected, they were titrated with 1M NaOH and the mole percentages of acetic acid were computed. The results
showed that as the amount of water in the mixture increases, the boiling point and the concentration of acetic acid
decreases. The results were graphed in a temperature vs %mole acetic acid of the liquid and vapor mixture. The graph
showed that as the temperature increases, the %acetic acid also increases. The mixture is an example of an azeotropic
mixture since it cannot be separated using a simple distillation process.

INTRODUCTION:
The boiling point of a mixture is the temperature at which the vapor pressure of
the liquid mixture equals the pressure surrounding the liquid and the liquid changes into a
vapor. The vapor pressure of a binary liquid mixture is a sum of the partial vapor
pressures of the two liquids composing the mixture. During distillation, the boiling point
of the binary liquid mixture is equal to the vapor pressure. The total pressure can be
computed using Raoult's Law if the mixture forms an ideal solution.
PT = P01X1 +P02X2 +
In distilling binary mixture, liquids boil when their vapor pressure and external
pressure becomes equal. If a liquid has a high vapor pressure at some temperature, the
temperature does not need to be increased very much until vapor pressure reaches the
external pressure. If he vapor pressure is low, the mixture has to be heated up a lot more
to reach the external pressure. The liquid with higher vapor pressure a t a particular
temperature has the lower boiling point.
The boiling point composition diagram can be constructed for binary liquids. It
will show the mole fraction with the corresponding boiling points of the liquids
composing the mixture. This experiment aims to construct a boiling point composition
diagram for binary liquid system.

REVIEW OF RELATED LITERATURE:

In 1882, The French physicist Francois-Marie Raoult established Raoult's Law
which states that the partial vapor pressure of each component of an ideal mixture of
liquids is equal to the vapor pressure of the pure component multiplied by its mole
fraction in the mixture. Non-ideal mixture deviates from the Raoult's Law.There are many
mixtures that deviates from Raoult's Law (Preobrazhenskiin, Rudakov , 2015)
This experiment will examine the boiling composition diagram of a binary
system. Phase equilibrium in binary system are also being thoroughly examine (Bletskan,
2005) in many researches. The diagram is composed of concentrations and boiling points.
Some substances have known boiling points. There are also new methods of determining
the boiling point. One method is using ultrasonic investigation (Ramadoss and Vaidevi,
2010)
There are many factors that affects the boiling point of some binary mixture. The
boiling point of some of binary solution depends on the concentration (Marinichev, 2007)
The mixture used in this experiment is the binary system containing acetic acid and
water. The properties of the solution containing acetic acid and water are also being
investigated in various studies (Park, Laio, Lannuzzi, Parrinello M, 2006) The study of
acetic acid-water solution has various applications like in the recovery of acetic acid from
effluent. (Padhiyar, Thakore, 2013) Acetic acid and water also forms ternary mixture with
other compounds like methyl propyl ketone but the system is more complicated than the
binary system (Bianco, Correa , Arce, Correa, 2009). Acetic acid and water can also be
separated by other means according to recent researches. (Choi, Kim, 2012)
This experiment used the basic titration technique but there are also various recent
studies about titration (Baranauskien, Petrikait, Matulien, Matulis, 2009) The
experiment used the typical phenolphtalein indicator but there are recent studies
investigating other source of indicator for acid base titration. (Abugri, Apea, Pritchett,
2012)

METHODOLOGY:
Firstly, a simple distillation set-up was prepared. Then, 50-mL of glacial acetic
acid and 1-mL of distilled water were mixed in a 100-mL beaker. Next, 1-mL of the
mixture was pipetted into each of the two 125-mL Erlenmeyer flasks and both flasks
were labeled L-1 to make two trials. Afterwards, the rest of the solution of the distilled
water and glacial acetic acid were transferred into the distilling flask in the set up and the
boiling chips were added.
Secondly, the mixture was slowly distilled and the distillate was collected in a
clean, dry 10-mL graduated cylinder. The temperature was read and was recorded when
3-mL of the distillate has been collected. The distillation was stopped when 6-mL of the
distillate has been collected.
Thirdly, 1-mL of the remaining solution was pippeted in the distilling flask into
each of the Erlenmeyer flasks that were previously labeled L-1. Then 2-mL of the
distillate was pipetted into each of the two Erlenmeyer flasks and both flasks were
labeled V-1. Next, 5-mL of the distilled water was added to the remaining solution in the
distilling flask. 1 to 2-mL was distilled to wash out the condenser. Afterwards, heating
was then stopped and 1-mL of the solution was pippeted into each of the two Erlenmeyer
flasks that were labeled L-2. The steps were repeated by labeling the distillate fractions
as V-2.
Fourthly, the steps were repeated using 10, 20, and 30-mL of distilled water. The
flasks were labeled L-3 and V-3, L-4 and V-4, and L-5 and V-5, respectively. All of the
solutions were titrated in the flasks with 1M NaOH using phenolphthalein as indicator.
Finally, the data were recorded on the report sheet and the mole% of acetic acid
was calculated by assuming that the density of all solutions is 1.05 g/mL.

RESULTS:
Table 1. Average Mole % HC2H3O2 in the Liquid and Vapor of the Mixture
Ru

Boiling

point

No.

(0C)

118

mL NaOH
2
1

1
L

33.

31.

4
12.

2
14.

Mole % HC2H3O2
1
2

Average

33.

86.2

71.1

76.1

83.9

78.67

80.06

1
26.

3
14.1

2
18.1

4
47.1

25.

9
14.

5
20.

2
21.

3
13.5

9
17.1

16.16

45.89

1
12.

13

6.4

6.75

6.5

5.19

5.73

114

112

12

110

6.5

6.8

108

5.4

5.9

32

7
6.8

44.6
28.8

8
32.0

14.5

7
15.0

9
6.75

6
6.4

15.35
6.575
5.46

120
118
116
114
112
Temperature (C) 110

108

106
104
102
0

10 20 30 40 50 60 70 80 90
%mole acetic acid

30.43
5
14.82
5
6.575

Fig 1. Temperature (0C) vs. % Mole of HC2H3O2 of Liquid and Vapor of Mixture

DISCUSSION:
From table no.1, the recorded boiling points of the mixture from run 1 to 5 are
118 , 114 , 112 , 110 , and 108

respectively. From the

Perrys Chemical Engineers Handbook, the boiling point of acetic acid is 118

and

the boiling point of water is 100 . The results showed that as the amount of water
increases, the boiling point of the mixture decreases.
Also from table no.1, the average mole percentages of acetic acid for the liquid
phase are 78.675%, 16.16%, 15.35%, 6.575%, and 5.46% consecutively from run 1 to 5.
For the vapor phase, the average mole percentages of acetic acid are 80.065%, 45.89%,
30.435%, 14.825% and 6.575% respectively. The %mole composition of the acetic acid
in both the liquid and vapor phase showed a decreasing trend. As the amount of water
increases, the concentration of the acetic acid decreases. Figure 1 shows the temperature
(0C) vs. % mole of acetic acid of liquid and vapor of the mixture.

In the acid-water system, the attractive forces between similar molecules are
greater in comparison to unlike molecules. Since there is a greater attraction between
similar molecules, they tend to have a higher boiling point since it is harder two separate
the two. On the contrary, unlike molecules have weaker attraction and therefore tend to
have a lower boiling point. When the cohesive forces between like molecules are greater
than the adhesive forces between dissimilar molecules, the dissimilarities of polarity
leads both components to escape solution more easily.
At equilibrium, the composition of the vapour above the solution of a mixture of
acetic acid and water would be closer to the azeotropic mixture than that of the original.
No number of distillations will ever result in a distillate that exceeds the azeotropic ratio.
Azeotropes are a mixture of at least two different liquids. Their mixture can either have a
higher boiling point than either of the components or they can have a lower boiling point.
Azeotropes occur when fraction of the liquids cannot be altered by distillation (Petrucci,
2007). Thus, the glacial acetic acid and water mixture is an azeotropic mixture.

The possible sources of error are instrumental errors and personal errors. The
burette pipe that was used resulted into the over titration of the solutions. The researchers
were unable to use a half-drop method during the titration process thus resulting to a dark
color of the solution.

CONCLUSION AND RECOMMENDATION:

As the amount of water in the mixture increases, the boiling points of the mixture
and the concentration of the acetic acid both decreases. The glacial acetic acid and water
mixture is an azeotropic mixture since it cannot be separated using a simple distillation.
The composition of the liquid phase and the vapor phase are almost similar and shows a
same trend in the decrease of the percent composition of acetic acid.

The researchers recommended the use of a burette pipe that has a smaller opening
to prevent the solutions from over titrating and for the researchers to perform a half-drop
method during the titration procedure.

APPENDIX:
SAMPLE CALCULATIONS:

C2 H 3 O2(aq )+ H 2 O( L )
Na+
(aq)+
NaOH (aq )+H C 2 H 3 O2(aq)
moles NaOH =moles acetic acid

[ MV ] NaOH =

mass acetic acid

MW acetic acid

33.4 mL

=33.4 mmol acetic acid

( 1 mmol
1 ml )

mass solution= 1.05

g
( 2 ml )=21 g2100 mg
ml

33.4 mmol acetic acid

mg
( 60mmol
)=2004 mgof acetic acid

mass solutionmass of acetic acid=mass of water

2100 mg2004 mg =96 mg of water

mole of acetic acid=

mole of acetic acid=

moles of acetic acid

x 100
total moles of solution
33.4
x 100 =86.23
96
33.4+
18

ave . mole of acetic acid=

mole acetic acid L 1+mole acetic acid L 2

2

REFERENCES:
Ramadoss P., Vaidevi A. 2010. Boiling point of binary liquid mixture using ultrasonic
investigation Rec. Res. Sci. Tech. 2010; 2(1): pp 101-109.

Preobrazhenskiin M.P ., Rudakov O.B. 2015. Dependences between the boiling point of
Aqueous-Organic Mixtures and their composition. Russian Journal of Physical
Chemistry. Vol 89, No. 1, pp.69-72

Marinichev, A.N. 2007. Concetration dependence of the boiling point of binary

equidistant solutions. Russian Journal of Applied Chemistry. Vol 80, No. 2, pp 209-212

Park J.M., Laio A., Lannuzzi M., Parrinello M., 2006. Dissociation Mechanism of Acetic
Acid in Water. J. Am. Chem. Soc., 2006, 128 (35), pp 1131811319

Padhiyar T.C., Thakore S.B. 2013. Recovery of Acetic Acid from Effluent via Freeze
Crystallization. International Journal of Scientific Engineering and Technology. Vol 2,
Issue 4, pp 212-215

Bianco A., Correa J.M., Arce A., Correa A. 2009. Liquid-liquid equilibria of system water
+ acetic acid + methyl propyl keton. The Canadian Journal of Chemical Engineering. Vol
66, Issue 1, pp 136-140

Bletskan D.I., 2005. Phase equilibrium in binary system. Journal of Ovonic Research. Vol
1, No.5, pp 61-69

Baranauskien L., Petrikait V., Matulien J., Matulis., D, 2009. Tiration Calorimetery
standards and the precision of Isothermal Titration Calorimetery Data. Int. J. Mol. Sci.
2009

Abugri D.A., Apea O.B., Pritchett G., 2012. Investigation of a simple and cheap source of
a Natural indicatior for Acid-Base Titration: Effects of system conditions on Natural
Indicatiors. Green and Sustainable Chemistry. 2012, Vol 2, pp 117-122

Choi W.S., Kim K.J., 2012. Separation of Acetic acid from Acetic Acid-Water Mixture by
Crystallization. Separation Science and Technology. Vol 48, Issue 7, pp 1056-1061