ABSTRACT

One of the main concerns of chemical engineering processes is the separation

of mixtures and the isolation of compounds in as pure a form as needed for
subsequent use. There are various ways of effecting such separation. However,
when the constituents of the mixture are liquids of varying solubility, then they
could be separated by liquid/-liquid extraction.

This report presents the experimental results and analysis of the liquid-liquid
extraction of propionic acid into two separate phases- aqueous and organic.
In the experiment, propionic acid of varying concentrations: 5ml, 2ml and 1ml
was introduced into the trichloroethylene-demineralized water mixture to
determine its distribution into the extract and raffinate phases. By titrating
10ml samples of each layer with 0.5M NaOH, the concentrations of propionic
acid in both phases were determined. With regards to the objectives of the
experiment, the distribution coefficient, as well as its dependence on the initial
concentration of propionic acid, was ascertained. The results of the
experiment showed that as the initial concentration decreased, the
distribution coefficient rather increased.

Moreover, in this experiment, considerations were also given to the theory of

liquid-liquid extraction, the method and calculations involved in the
experiment, and the discussion of the results of the experiment.

1
 TABLE OF CONTENTS
Title page
Abstract i
Table of contents ii

CHAPTER ONE- INTRODUCTION 1

1.1 Title of Experiment 1
1.2 Experiment Objectives 1
1.3 Justification of Experiment 2

CHAPTER TWO- THEORY 3

2.1. Definition of Keywords 3
2.2. The Liquid-Liquid Extraction Process 3
2.3. Principles of the Experiment 6
2.3.1. Liquid-Liquid Equilibria 6
2.3.2. The Distribution Law 7

CHAPTER THREE- EXPERIMENTATION AND RESULTS 8

3.1. Definition 8
3.2. Apparatuses Used 8
3.3. Reagents Used 9
3.4. Experimental Procedure 10
3.5. Results of the Experiment 11
3.6. Graphs 12

CHAPTER FOUR- DISCUSSION 14

4.1. Result Analysis 14
4.1.1. Result Comparison 14
4.2. Result Interpretation 16

CHAPTER FIVE- CONCLUSION/RECOMMENDATION 18

5.1. Conclusion 18
5.2. Recommendation 19

REFERENCES 20
APPENDIX 21

2
 CHAPTER ONE

INTRODUCTION

1.1 TITLE OF EXPERIMENT:

LIQUID-LIQUID EXTRACTION- Distribution Coefficient

Liquid-Liquid Extraction, also referred to as solvent extraction and partitioning,

is a method of separating compounds based on their relative solubility in two
different immiscible liquids which are usually water and organic solvents.
In this Liquid-Liquid Extraction experiment, molecules of propionic acid are
transferred across the aqueous and organic phases, until equilibrium is
established. However, the phase in which propionic acid is more soluble in will
have the higher concentration of the acid at equilibrium. Liquid-liquid
extraction is a basic technique in chemical laboratories, where it is performed
using a separating funnel.
Hence, the objective of the experiment is to ascertain the extent of solubility of
the acid in the extract layer with the help of the distribution coefficient, K.

1.2 EXPERIMENT OBJECTIVES:

The objectives of this experiment are as follows:

 To determine the distribution coefficient for the system:
trichloroethylene-propionic acid-demineralized water.
 To show the dependence of the distribution coefficient on the
concentration of propionic acid.

3
  To estimate the efficiency of the separation of propionic acid and
trichloroethylene using demineralized water as added solvent for
industrial applications.
 To demonstrate the working principles of industrial liquid-liquid
extraction equipment.

1.3 JUSTIFICATION OF THE EXPRIMENT

There are many industrial processes that involve the separation of liquids.
Some of these processes involve the separation of liquid mixtures of close
volatilities but different solubilities and mixtures of close solubilities but
varying volatilities. In chemical engineering, reaction products are usually
obtained as a solution or a suspension in water along other organic or
inorganic by-products and reagents. Hence, this experiment helps us to
understand the principles behind solvent extraction as well as be able to apply
the knowledge in the separation of such mixtures.
It is necessary to determine to what degree a particular constituent of a liquid
mixture is soluble in the extraction solvent, by experimentation. Also, the
selection of appropriate solvents that could be used to preferentially dissolve a
desired constituent over an undesired one is another benefit of this
experiment. Thus, the distribution coefficient is a property of the aqueous and
organic solvents which gives an idea of the relative extent of solubility of a
particular constituent in both solvents.
Consequently from this experiment, we can know how best to select the added
solvent so as to suit the required preferential extraction in industrial situations.

4
 CHAPTER TWO

THEORY

2.1 DEFINITION OF KEYWORDS

Extraction Solvent, Extract Phase, Raffinate Phase

I. Extraction Solvent: The extraction solvent, or just plain solvent, is the

immiscible liquid added to a process for the purpose of extracting a solute or
solutes from the feed.

II. Extract Phase: The extraction solvent phase leaving a liquid-liquid

contactor is called the extract. This is also the added solvent in an immiscible
liquid mixture that contains the required solute which has dissolved in it. The
required solute has a stronger affinity for the added solvent and forms a
solution with it, hence extracting it from its original solution.

III. Raffinate Phase: The raffinate is the liquid phase left from the feed after
being contacted by the second phase. The raffinate phase is the weaker
solution of the required solvent.

2.2 THE LIQUID–LIQUID EXTRACTION PROCESS

In this section, qualitative relationships for the extraction of a liquid solute

from a solvent using an added solvent are discussed. Attention is also given to
the effect of the distribution coefficient on the extraction process as well as its
dependence on the concentration of the solute.

Liquid-liquid extraction is a process for separating components in solution by

their distribution between two immiscible liquid phases. Such a process can

5
also be simply referred to as solvent extraction; however, this term may be
ambiguous because it also applies to the leaching of a soluble substance from a
solid.

Since liquid-liquid extraction involves the transfer of mass from one liquid
phase into a second immiscible liquid phase, the process can be carried out in
many different ways. The simplest example involves the transfer of one
component from a binary mixture into a second immiscible liquid phase. One
example is liquid-liquid extraction of an impurity from wastewater into an
organic solvent. This is analogous to stripping or absorption in which mass is
transferred from one phase to another. Or in some instances a chemical
reaction can be used to enhance the transfer, an example being the use of an
aqueous caustic solution to remove phenolics from a hydrocarbon stream. A
more sophisticated concept of liquid-liquid fractionation can be used in a
process to separate two solutes completely. A primary extraction solvent is
used to extract one of the solutes from a mixture (similar to stripping in
distillation), and a wash solvent is used to scrub the extract free from the
second solute (similar to rectification in distillation)

Liquid-liquid extraction which is used, for example, in the processing of coal tar
liquids and in the production of fuels in the nuclear industry has been applied
extensively to the separation of hydrocarbons in the petroleum industry, as
well as other mixtures. Primarily, this operation is used when distillation is
impracticable or very costly. It is more practical than distillation when the
relative volatility of the liquids falls between 1.0 and 1.2. Extraction in many
ways could complement distillation and is preferable in the following cases:

(a) Where distillation would require excessive amounts of heat, such as, for
example, when the relative volatility is near unity.

6
(b) When the formation of azeotropes limits the degree of separation
obtainable in distillation.

(c) When heating must be avoided.

(d) When the components to be separated are quite different in nature.

In this operation, it is essential that the liquid-mixture feed and solvent are at
least partially if not completely immiscible. There are three stages which are
involved:

I. Bringing the feed mixture and the solvent into intimate contact,

II. Separation of the resulting two phases,

III. Removal and recovery of the solvent, and

IV. Desolventizing of the raffinate.

It is possible to combine stages I and II into a single piece of equipment such as

a column which is then operated continuously. Such an operation is known as
differential contacting. Liquid-liquid extraction could also be carried out in
stage wise equipment, a good example is a mixer–settler unit in which the
main features are the mixing of the two liquid phases by agitation, followed by
settling in a separate vessel by gravity. Also, stages III and IV can be combined
too.

Applications of Liquid-Liquid Extraction

Important applications of liquid–liquid extraction include the separation of

aromatics from kerosene-based fuel oils to improve their burning qualities and
the separation of aromatics from paraffin and naphthenic compounds to
improve the temperature-viscosity characteristics of lubricating oils. It may

7
also be used to obtain, for example, relatively pure compounds such as
benzene, toluene, and xylene from catalytically produced reformates in the oil
industry, in the production of anhydrous acetic acid, in the extraction of phenol
from coal tar liquors, and in the metallurgical and biotechnology industries.
Several examples of cost-effective liquid-liquid extraction processes include
the recovery of acetic acid from water (Fig. 15-1), using ethyl ether or ethyl
acetate, or the recovery of phenolics from water with butyl acetate, or with
isopropyl ether, or with methyl isobutyl ketone. Another example of a cost-
effective liquid-liquid extraction process is the one used for recovery of
uranium from ore leach liquors. In this case the solvents, alkyl phosphates in
kerosene, are recovered by liquid-liquid extraction using a strip solution, and
the raffinate requires practically no desolventizing because the solubility of the
solvents in water is extremely low. However, most of the solvent loss occurs
because of the entrainment of small droplets in the water. Hence, the
economic utility of a liquid-liquid extraction process depends strongly on the
solvent selected and on the procedures used for solvent recovery and raffinate
desolventizing.

After these matters have been considered, the principles behind the liquid-
liquid extraction experiment can be considered in proper perspective.

2.3 PRINCIPLES OF THE EXPERIMENT

2.3.1. Liquid-Liquid Equilibria

Many chemical liquid species do not mix to form one single liquid phase,
rather; they split into two liquid phases of different compositions. If the phases
are at thermodynamic equilibrium, the phenomenon is an example of liquid-
liquid equilibrium, which is important for industrial operations such as solvent
8
extraction. For equilibrium to occur, there must be a uniformity of
temperature, of pressure and of fugacity, for each of the chemical species
existing in both phases.

At equilibrium the molecules naturally distribute themselves in the solvent

where they are more soluble. Inorganic and water soluble materials will stay in
the water layer and more organic molecules will remain in the organic layer.

2.3.2. The Distribution Law

The extraction of a compound from one liquid phase to another is an

equilibrium process governed by the solubilities of a substance in the two
solvents. The ratio of the solubilities is called the distribution coefficient K=Y/X
and it is essentially an equilibrium constant with a characteristic value for any
compound and pair of solvents at a given temperature. The constant K is
essentially the ratio of the concentrations of the solute in the two different
solvents once the system reaches equilibrium.

The terms Y and X are the concentrations at equilibrium, in moles per dm 3, of

the solute in the extract and raffinate layers, respectively. This relationship is a
ratio of the two concentrations and is independent of the actual amounts of
solvents mixed.

9
 CHAPTER THREE

EXPERIMENTATION AND RESULTS

3.1 DEFINITION

This is a liquid-liquid extraction experiment to determine the distribution

coefficient for the system: Trichloroethylene-Propionic Acid-Demineralized
Water, and how the distribution coefficient depends on the initial
concentration of propionic acid. This experiment entails the study of the
dependence of the distribution coefficient to the concentration of the solute
(propionic acid).

3.2 APPARATUSES USED

The apparatuses used in this experiment are:

3 Conical Flasks, 2 Beakers, Measuring Cylinder, Separating Funnel, Pipette,

Burette, Retort Stand, Funnel

The description of the apparatuses used in the experiment is given below:

I. Separating Funnel:
II. Conical Flask: this is a conical glass vessel that was used to collect the
extract and raffinate layers from the separating funnel.
III. Beaker: A beaker is a flat-bottomed glass container used to hold the liquid
sample solutions. It contained the demineralized water used in the
experiment.
IV. Measuring Cylinder: a graduated glass vessel used to measure 50ml of
trichloroethylene and demineralized water for separation. It was also used
to measure 10ml of the extract and raffinate layers for titration

10
 V. Pipette: a small glass tube that liquid is drawn into so that it can be
measured, often before it is delivered to another container. It was used to
collect 5ml of propionic acid.
VI. Burette: a glass tube with measurements marked on the side and a stopcock
at the bottom. It is used in laboratories to release an accurately measured
quantity of liquid.
VII. Retort Stand: this is the stand that was used to hold the separating funnel
and the burette upright while the separation and titration processes took
place, respectively.
VIII. Funnel: a cone-shaped apparatus with a large opening at the top and a small
narrow tube at the bottom. It was used to guide the NaOH solution into the
burette for titration.

3.3 REAGENTS USED:

I. Trichloroethylene
II. Propionic Acid
III. Demineralized Water
IV. 0.5M Sodium Hydroxide Solution
V. Phenolphthalein Indicator

11
 3.4 EXPERIMENTAL PROCEDURE:

We were enlightened on the liquid-liquid extraction operation and the procedure

for the experimentation.
The experimental procedure is as follows:
I. Using the measuring cylinder, we measured 50ml each of trichloroethylene and
demineralized water, respectively.
II. Then, we poured the measured trichloroethylene and demineralized water into
a conical flask.
III. 5ml of propionic acid was pipetted into the flask containing the mixture.
IV. After adding propionic acid, we shook the flask vigorously so that the
constituents of the mixture mixed properly. This was done for about 5 minutes.
V. The burette was dismounted from the retort stand and the separating funnel
was mounted on the retort stand using paper cushioning. The separating
funnel was checked to ensure that there was no leakage at all.
VI. Furthermore, the mixed mixture was poured into the separating funnel and
allowed to settle for 3-5 minutes.
VII. Once a distinct separation of the extract phase from the raffinate phase was
observed, we collected the raffinate (lower aqueous layer) and the extract into
separate clean conical flasks.
VIII. We measured 10ml of each layer and titrated against 0.5M NaOH solution,
using 2-3 drops of phenolphthalein as indicator. This was done three times for
each layer.
IX. The titres for each titration was measured and recorded for the extract and the
raffinate layers.
X. The average values for each layer were also calculated and recorded.
XI. The entire experiment was repeated with two new volumes of propionic acid
as 2ml and 1ml. The appropriate readings for each layer were made.

12
 3.5 RESULTS OF THE EXPERIMENT

GIVEN:

Also,

RESULTS:

The results of the Liquid-Liquid Extraction Experiment are tabulated below.

READINGS

Propionic Acid Titre of 0.5M NaOH (ml)

Added (ml) Extract Raffinate
5ml 20.04 11.53
2ml 12.70 4.53
1ml 5.70 1.10

TABLE 3.1

CALCULATIONS

Titre of 0.5M NaOH Propionic Acid Concentration Distribution

Propionic Acid
(ml) (mol/dm3) Coefficient
Added K=Y/X
Aqueous Layer, Organic Layer,
(ml) Extract Raffinate
Y X
5ml 20.04 11.53 1.0020 0.5765 1.7380

2ml 12.70 4.53 0.6350 0.2265 2.8034

1ml 5.70 1.10 0.2850 0.0550 5.1818

TABLE 3.2

13
 3.6. GRAPHS

EQUILIBRIUM CURVE FOR THE EXTRACTION OF PROPIONIC ACID

1.2

y = 1.9064x
1.1

1
Propionic Acid Concentration in the Aqueous Layer, Y (mol/dm 3)

0.9

0.8

0.7

0.6

0.5

0.4

0.3

0.2

0.1

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Propionic Acid Concentration in the Raffinate Layer, X (mol/dm 3)

GRAPH 3.1 A Graph of the Concentration of Propionic Acid in the Aqueous Layer, Y, against the
Concentration in the Organic Layer, X

14
 DISTRIBUTION COEFFICIENT FOR PROPIONIC ACID
5.5

4.5

4
Distribution Coefficientof Propionic Acid, K=Y/X

3.5

2.5

1.5

0.5

0
0 1 2 3 4 5 6
Volume of Propionic Acid Added (ml)

GRAPH 3.2 A Graph of the Distribution Coefficient of the System, K, against the Volume of
Propionic Acid Added

15
 CHAPTER FOUR

DISCUSSION

4.1 RESULT ANALYSIS

This experiment was carried out to describe the relationship between the
distribution coefficient and concentration of propionic acid in trichloroethylene
and demineralized water. Having performed this experiment on liquid-liquid
extraction and calculated the concentrations of propionic acid in the aqueous
and raffinate layers, the following analysis is made. The results of the
experiment are shown on Table 3.2.

4.1.1 RESULT COMPARISON

Regarding the aim of the experiment which is to determine the effect of the
distribution coefficient on the concentration of the added acid, the following
comparisons could be made. It was observed that for an initial volume of 5ml
of propionic acid, more NaOH solution was used to neutralize the acid (that is,
20.04ml NaOH for the extract and 11.53ml NaOH for the raffinate) compared
with the lesser volumes of 12.70 and 4.53ml NaOH for 2ml of acid. This
relationship was also observed to be consistent with the third volume of the
acid, 1ml.

Comparing the titre values for both the extract and the raffinate phases, it was
also observed that the amount of base required to neutralize the acid in the
extract phase was always larger than that required to neutralize the acid left in
the raffinate layer, for all three initial concentrations of acid.

16
Furthermore, it was also noticed that there was a consistent increase in the
values of the distribution coefficients as the volume of acid was increased. At
an initial propionic acid volume of 5ml, the distribution coefficient (1.738) was
relatively smaller and closer to unity as compared with other values: 2.8034
and 5.1818, for acid volumes of 2ml and 1ml respectively.

A graph of the concentration of propionic acid in the extract against the

concentration in the raffinate was plotted to show the relationship between
the concentrations of the acid in both phases. The graph obtained was a linear
one and had a positive slope of 1.9064 which is also greater than one. Hence,
this agrees with the Distribution Law which states that the concentration of the
acid in the extract phase is proportional to that in the raffinate phase and the
constant of proportionality is the distribution coefficient, K. This means that,
by implication, the slope of Graph 3.1 gives the distribution coefficient of the
propionic acid in the aqueous layer relative to the organic layer.

Another graph, Graph 3.2, was plotted to reveal the effect of a change in the
initial volume of the added acid on the distribution coefficient. A non-linear
relationship was found to exist between the two parameters. According to the
graph, for minute volumes of the acid, the distribution coefficient of the acid
will tend towards infinity, since in this region the curve is asymptotic to the
distribution coefficient axis. Also, for very large volumes of acid added, it could
be predicted that the distribution coefficient will tend towards zero for this
same extraction solvent, since the curve is asymptotic to the acid volume axis
as well.

17
4.2. RESULT INTERPRETATION
Having compared the hitherto obtained results and calculations of the
experiment, the following interpretation is made.
Firstly, from the observed titre values, we can conclude that most of the
propionic acid was found in the extract phase since a larger volume of NaOH
was required to neutralize it than was required for the raffinate phase. Hence,
the added solvent (demineralized water) was an appropriate solvent for the
extraction of propionic acid from trichloroethylene. Another reason why
demineralized water served well as an extraction solvent is that its density is
distinctly different from that of trichloroethylene. Therefore, with a lesser
density, the aqueous layer which was the extract floated on the organic layer,
the raffinate, and the required separation was effected.
Considering the effect of initial volume of added acid on the distribution
coefficients, and as shown on Graph 3.2, a more efficient extraction of
propionic acid will occur when the initial volume of the acid is small. However,
in industrial applications, the volume of the required solute is usually very
large and cannot be manipulated at will. Hence, a more effective extraction
could be effected when the relative volume of the added solvent is very large
compared to that of the solute as well as its original solvent.
Having concluded that the distribution coefficient is dependent on the
concentration of the solute, the overall distribution coefficient was calculated.
The value for the overall distribution coefficient was 1.9064. We can infer that
for the range of acid volumes used for this experiment, an effective extraction
will always be achieved. Considering the table in the appendix, this distribution
coefficient approximately equals that obtained from the literature. Also, this
means that the selection of demineralized water as the extraction solvent was
a right choice.

18
Since the distribution coefficient was greater than 1, there was a greater
amount of the acid found in the extract phase more than there was in the
raffinate phase. This implies that for a continuous extraction process, the
amount of propionic acid in the raffinate could be continually reduced until it
gets down to a limiting value. This is the principle that governs fractional liquid-
liquid extract. However, it is almost impossible to completely extract the solute
from its original solvent and get a pure raffinate without any loss of solute. This
also can be explained as the reason why the curve on Graph 3.2 never touches
the vertical axis. That is, K is never equal to infinity or zero (except when the
solute is completely insoluble in the added solvent) for any volume of solute in
the entire mixture. For a perfect extraction, the distribution coefficient would
have been infinity only that it is not obtainable.

19
 CHAPTER FIVE

CONCLUSION/RECOMMENDATION

5.1. CONCLUSION

From our experiments, the value for distribution coefficient was determined by
titration of the samples with 0.5M NaOH and the values are: 5.1818 for 1.0ml
of propionic acid, 2.8034 for 2ml propionic acid and 1.7380 for 5ml propionic
acid. While the overall distribution coefficient for the three concentrations was
1.9064.
It was observed that the distribution coefficients of propionic acid in the
extract and raffinate layers increased as the initial concentration of the acid
decreased in the entire mixture. In comparison with data from the literature, it
was also discovered that the results gotten from this experiment corresponded
appropriately.
In conclusion, the use of demineralized water to extract propionic acid from
trichloroethylene was proven to be of high efficiency, considering the high
value of the distribution coefficient for the system. By in large, this experiment
illustrated accurately the behaviour of the distribution coefficient with respect
to varying solute concentrations and it showed the apparent connection
between the values obtained experimentally and theoretically through
correlations.

20
5.2 RECOMMENDATION

For future experimentation on liquid-liquid extraction of propionic acid, there

are a few recommendations and precautions that should to be considered so
that better results can be obtained with fewer errors.

More extraction solvents (apart from water) should be used so that the results
obtained could be compared with themselves and also with the results
obtained from the experiment using demineralized water as extraction solvent.
The comparison of the results gotten from the above suggestion would help
provide and understanding of propionic acid’s affinity for the different
solvents. It could also help in extraction solvent choice for industrial processes.

Aside from the above, the report gives an acceptable description of the
experiment and thus can be adopted for further analysis.

21
REFERENCES

James A. M., David L. D., “Experimental Methods in Organic Chemistry”, 3rd

Edition, Holt-Saunders International Editions, pp. 5-7.

John D. T., “Science and Practice of Liquid-Liquid Extraction, Volume 2”,

Clarendon Press Oxford 1992 pp. 3-27.

McCabe S. H., “Unit Operations of Chemical Engineering”, 6th Edition,

McGraw-Hill International, pp. 747-752.

Obibuenyi J. I., “Laboratory Manual on CHE 310: Chemical Engineering Lab 2-

Liquid-Liquid Extraction”, FUT Owerri, pp. 22-24.

Richardson J. F., Harker J.H., “Coulson and Richardson’s Chemical Engineering

Volume 2: Particle Technology & Separation Processes”, 5th
Edition, ButtterWorth-Heinemann, pp. 721-728.
Robert H. P., Don W. G., “Perry’s Chemical Engineers’ Handbook- Liquid-Liquid
Extraction”,7th Edition, McGraw-Hill Publishers, 2007, 15-4.

22
 APPENDICES
Titration Reaction:

Where, concentration of C2H5COOH, CA

concentration of NaOH, CB = 0.5M

volume of C2H5COOH, VB = 10 ml

volume of NaOH, VB = titre value

Calculation of the Concentration of Propionic Acid, Y, in the Extract Layer

For 5ml;

For 2ml;

For 1ml;

Calculation of the Concentration of Propionic Acid, X, in the Raffinate Layer

For 5ml;

For 2ml;

For 1ml;

Calculation of the Distribution Coefficient, K

Where,
23
Y is the concentration of Propionic Acid in the Extract Layer

X is the concentration of Propionic Acid in the Raffinate Layer

For 5ml;

For 2ml;

For 1ml;

Overall Distribution Coefficient, KOVERALL= slope of Graph 3.1 = 1.9064

Selected List of Ternary Systems

Extraction solvent = demineralized water

SOLUTE FEED SOLVENT TEMP.,OC K

Propionic acid Benzene 30 1.6722
Propionic acid Cyclohexane 31 5.1151
Propionic acid Cyclohexene 31 3.3003
Propionic acid Ethyl acetate 30 0.3610
Propionic acid Ethyl butyrate 26 0.6803
Propionic acid Ethyl propionate 28 1.9608
Propionic acid Hexanes (mixed) 31 5.3763
Propionic acid Methyl butyrate 30 0.4651
Propionic acid Methylisobutyl carbinol 30 0.2841
Propionic acid Methylisobutyl ketone 26.7 0.5131
Propionic acid Monochlorobenzene 30 1.9493
Propionic acid Tetrachloroethylene 31 5.9880
Propionic acid Toluene 31 1.9417
Propionic acid Trichloroethylene 30 2.0161

24