Page |1

TABLE OF CONTENTS

4.0
5.0
6.0
7.0
8.0
9.0
10.0
11.0
12.0
13.0

1.0 Abstract
2.0 Introduction
3.0 Objectives
Theory
Materials and Apparatus
Procedures
Results
Calculation
Discussions
Conclusion
Recommendations
References
Appendices

2
3
3
5
6
7
8
9
13
14
15
15
16

1.0ABSTRACT

LIQUID LIQUID EXTRACTION

The purposes of the liquid-liquid extraction experiment is to separate two or more
components of a solution from one another and then to determine whether a certain
compound is present in an unknown reagent or not. There are three liquids used which
are propionic acid, oil and water. Oil and propionic acid are mixed together in the feed
tank, which is then mixed through the recycle system of the pump before it is sent to
be mixed with the water in the first stage. Out of each stage samples of propionic acid

Page |2
was taken, and titrated with sodium hydroxide to determine the amount of propionic
acid contained in the feed, extract and raffinite. For the first experiment, the data
shows that the propionic acid added lower will gives the concentration of sodium
hydroxide lower. The higher value is for 5.0 mL propionic acid added, which is 22.5 mL
of sodium hydroxide was titrated and have the concentration of 2.25 M. Next, the data
illustrates that the majority of the Propionic Acid was extracted from oil to the water in
the first stage, which is 0.350 M and 0.135 M after titrated with 35.0 mL of 0.1 M and
54.1 mL of 0.025 M of sodium hydroxide respectively. The amount of Propionic Acid in
water decreased in the next stage, which is at raffinite and then increase thereafter.
This means that the amount of Acetic Acid extracted into water not constant with each
stage. It was reliably assumed that the longer the mixing of the liquids the better the
molecules are able to partition into the preferred solvent.

3.0

OBJECTIVES
1. To separate two or more components of a solution from one another.
2. To determine whether or not a certain compound is present in an unknown
reagent.

2.1

2.1

INTRODUCTION

Definitions

Page |3

Liquid-liquid Extraction is a method of separation where an aqueous solution is usually

brought into contact with another immiscible organic solvent, so as to affect a transfer
of one or more solute from the aqueous solution into the organic solvent. This is a fast,
easy and convenient method of separation. It is usually performed by moderately
shaking the liquids inside a separating funnel for a few minute and can be used for
either large volume or trace level.
2.2

Properties of solvents

Solvent are selected based on, make sure both solvents must be immiscible to each
other. Then, solvent 1 can be aqueous / H 2O and solvent 2 can be Organic in nature. It
is because most targeted compound (or solute in solvent 1 ) are soluble in Organic
Solvents (if the solutes are organic ) and most organic solvent has lower boiling point
(Eg: Methanol, Chloroform, Carbon Tetrachloride has boiling point 50C, 61.2C and
76.8C respectively), and since, after extraction the solvent 2 is evaporated to collect
the targeted solute, there will be a less chance for the targeted solute to be degraded
at high temperature. Make sure, solvent 2 must be chosen accordingly. So that, the
Target Compound must have higher affinity toward Solvent 2, so that, during
extraction maximum amount of solute is transferred to Solvent 2. Density of both of
the solvents must be known. So, that in the separating funnel it is possible to know
which solvent is at the lower phase and which one is at the upper (Usually, the solvent
with higher density is at the lower phase). Then, make sure that density difference
between Solvent 1 and Solvent 2 should be high, so that there will be a less chance of
emulsion formation and even if emulsion forms, it will easy to breakdown. Then, K p
value / Partition Coefficient of immiscible solvent pair must be higher, since it is
important for the effectiveness of extraction.
2.3

Properties of Solute

Solute / Target Compound can be organic solute and inorganic solute.

Organic Solute :
Most Organic Solutes are soluble in Organic Solvents, which can be extracted with any
organic solvents ( Eg: Extraction Caffeine by Chloroform ). However, for both
pharmaceutical and therapeutic purpose, some organic solutes are introduced as salts
in order to increase their solubility in Water ( Eg : Promethazine hydrochloride, a
hydrochloric salts of Promethazine). So, before performing liquid-liquid extraction of
such organic solutes, they are converted into their original organic forms by means of

Page |4
a chemical reaction, so that they can be extracted by any organic solvents ( E.g.
Promethazine Hydrochloride is converted into Promethazine before they are extracted
with organic solvents like n-hexane or Chloroform ). However, it is to say that upon
chemical reaction the concentration of original compound does not changes.
Inorganic Solute :
Inorganic solutes are frequently encountered in aqueous solvents either as impurities
or as Pharmaceutical Ingredients. And before their extraction, it is absolutely
necessary to form ion-association complexes or metal-chelates (by using organicligands), so that they may be extracted by an appropriate organic solvent. For
example, Cu (2) can be extracted by acetyl acetone by forming Cu(2) - acetyl acetone
complex.
2.4

Different principle of Liquid-Liquid Extraction

Feed phase:
Feed phase is the initial solution containing the target compound / Solute and Solvent
1. In the feed phase, the solvent 2 added to perform the extraction. So,
Feed Phase = Solute + Solvent 1
Extractant and Extract :
Extractant is the Solvent 2 that is added to the Feed Phase for extraction. After
extraction, the Extractant is called Extract which contains the target compound. The
Extract is evaporated to collect and measure the amount of the solute. So before
extraction,
Extractant = Solvent 2
And after extraction,
Extractant

= Extract
= Solvent 2 + Solute

Raffinate :
Raffinate is generally, termed for the Feed Phase after extraction. And if the extraction
process is repeated, the Raffinate becomes the feed phase to which the Solvent 2 is
added again. So,
Raffinate

= Feed phase after Extraction

= Solvent 1 + Remaining Solute

And if the extraction process is repeated, then

Page |5
Raffinate

4.0

= Feed phase
= Solvent 1 + Remaining Solute

THEORY

Liquid-liquid extraction is a separation process in which substances or compounds are

separated based on their properties, usually their solubility or polarity. In general, two
streams, one consisting of solution+solute and the other consisting of the extracting
solvent shall come in contact, and the solvent shall extract the solutes from the
solution. This solubility and polarity characteristic is the most important for the
extraction process, as this characteristic determines the solvent that needs to be
used, and the effectiveness of the solvent. The feed solution is the solution that
contains solute plus the solution, where this is the solution that needs to be separated
from the solutes. The raffinate solution is the product stream, where this stream is
the one that contains low composition of solutes, as the solutes have been extracted
out from the feed solution stream by the solvent. The extract solution is the second
product stream, where this stream is the one that contains a high amount of solute.
The extract stream is basically solvent+solute.

Extract stream
Solvent stream

Feed

Raffinate stream

Example Flowchart: Extraction of CH3COOH using C6H13OH as

solvent
There are a few ways to determine the effectiveness of the extraction process. The
term distribution coefficient is used as a quantitative measure for the effectiveness
of the solvent extraction. This coefficient is usually denoted with K. The formula is
given as below:

sol ub ili t y o f s olu t e di s s ol v e d i n sol v ent (

K=

g
)
ml

solubi li t y o f so l ut e di s sol v e d i n aque o us sol ut i o n(

g
)
ml

In other words, the distribution coefficient K is simply the ratio of amount of solute in

Page |6
solvent (extract) to the amount of solute in aqueous solution (raffinate) once the
process has achieved equilibrium. In certain cases, there are multiple solvents used in
the extraction process. Some solvents are more effective than others. This defines in
multiple solvent extraction, certain solvents will extract more solute than the other
solvent. Thus, to determine the total amount of solutes that has been extracted by a
certain solvent in multiple solvent system, the following formula can be used:
n

F r a c t i o n s ol u t e d i s s ol v e d i n s o l v e n t A=(

1
)
VB
1+
K
VA
n

Where VA and VB are volumes of solvents, K is the distribution coefficient and n is the
number of extractions performed. However, in this experiment, only one solvent is
used, therefore this formula shall not be applied in the calculations.

5.0

MATERIALS/APPARATUS

The apparatus used in this experiment:

50 mL burette-for titration process
250 mL Conical flask-for titration process
50 mL beakers-to measure the feed, raffinate and extract solutions
Measuring cylinders
Phenolphthalein as indicator
0.025 M and 0.1 M NaOH as titrate

6.0

PROCEDURE

6.1

Determination of Distribution Coefficient

1. A mixture of 50 mL organic solvent and 50 mL of de-mineralised water is
made up in a conical flask.
2. 5 mL of propionic acid is added to the mixture in the flask by using a
pipette.

Page |7
3. A stopper is placed into the flask and the mixture is well shaken for 5
minutes.
4. The mixture is then poured into a separating funnel and left for 5
minutes.
5. After 5 minutes, the lower aqueous layer is removed.
6. 10 mL sample of this payer is taken and is titrated with 0.1 M NaOH
solution, where phenolphthalein is used as indicator.
7. Steps 2 to 6 are repeated, by manipulating the amount of propionic acid
added to the mixture from 5 mL to 3 mL and 1 mL
8. All data is recorded.

6.2

Determination of Mass Transfer Coefficient

1. 100 mL of propionic acid is added to 10 L of the organic phase. The
mixture is mixed well and the organic feed tank is filled with the organic
mixture.
2. The level control is switched to the bottom of the column (electrode
switch S2)
3. The water feed tank is filled with 15 L of de-mineralised water, by starting
the water feed pump and is operated at high flowrate. Once the water is
above the packing, the flowrate is reduced.
4. The metering pump is started and is set at a flowrate of 0.2 L/min
5. The system is left to operate for 15 to 20 minutes to achieve steady state
conditions.
6. Two 15 mL samples of feed, raffinate and extract are taken, using 50 mL
beakers.
7. One set of the three samples are titrated using 0.1 M NaOH solution,
while the other set of three samples are titrated using 0.025 M NaOH.
Phenolphthalein is used as indicator for all six titration processes.

7.0

RESULTS

7.1

Determination of Distribution Coefficient

Page |8

Table 7.0: Propionic acid added with sodium hydroxide titration

Propionic
acid

Aqueous layer (Y)

Titre of
Concentra

added
(mL)
5.0
3.0
1.0

7.2

M/10

Organic layer (X)

Titre of
Concentra

tion (M)

NaOH

M/10

K = Y/X

tion (M)

NaOH

(mL)
22.5
20.5
16.3

(mL)
78.2
51.0
17.5

2.25
2.05
1.63

7.82
5.10
1.75

0.29
0.40
0.93

Determination of Mass Transfer Coefficient

Table 7.1: Titration of 0.1 M and 0.025 M of sodium hydroxide in propionic acid

Flow rate of

0.2

aqueous phase
(L/min)
Flow rate of

0.2

organic
phase (L/min)
Sodium

0.1

0.025

hydroxide

Concentration of Propionic
acid (kg/L)

concentration
(M)
Feed (mL)

35.0

54.1

0.350

0.135

Raffinite (mL)

12.5

1.5

0.125

0.004

Extract (mL)

20.0

23.2

0.200

0.058

0.15

0.077

Propionic acid
extracted from
the organic
phase (mL)
Propionic acid
extracted from

0.04

0.0116

the aqueous
phase (mL)
Mass transfer
coefficient
(kg/min)
8.0 CALCULATIONS

0.0223

0.024

Page |9

8.1

Determination of Distribution Coefficient

Finding the distribution coefficient, K

where ,
K= Y
X
Y = Aqueous layer concentration
X = Organic layer concentration

8.1.1 For 1.0 mL of Propionic acid added

Aqueous Layer , Y:

Organic Layer , X:

M1V1 = M2V2
where
M1 = Concentration of NaOH
V1 =Volume of NaOH added
M2 = Concentration of Propionic
acid
V2 = Volume of Propionic acid

M1V1 = M2V2
(0.1M) (17.5mL) = M2 (1 mL)
X = 1.75 M

K= Y
X
K = 16.3
1.75
= 0.93

(0.1M) (16.3 mL) = M2(1 mL)

Y = 1.63 M

8.1.2 For 3.0 mL of Propionic acid added

Aqueous Layer , Y:

Organic Layer , X:

M1V1 = M2V2
where
M1 = Concentration of NaOH
V1 =Volume of NaOH added
M2 = Concentration of Propionic
acid
V2 = Volume of Propionic acid

M1V1 = M2V2
(0.1M) (51.0mL) = M2 (1 mL)
X = 5.10 M

K= Y
X
K = 20.5
51.0
= 0.40

(0.1M) (20.5 mL) = M2(1 mL)

Y = 2.05 M
8.1.3 For 5.0 mL of Propionic acid added
Aqueous Layer , Y:

Organic Layer , X:

K= Y
X

P a g e | 10
M1V1 = M2V2
where
M1 = Concentration of NaOH
V1 =Volume of NaOH added
M2 = Concentration of Propionic
acid
V2 = Volume of Propionic acid

M1V1 = M2V2
(0.1M) (78.2mL) = M2 (1 mL)
X = 7.82 M

K = 22.5
78.2
= 0.29

(0.1M) (22.5 mL) = M2(1 mL)

Y = 2.25 M

8.2

Determination of Mass Transfer Coefficient

Finding the mass transfer coefficient,

where,
Mass transfer coefficient =

Rate of propionic acid transfer

Volume of packing x mean

driving force

8.2.1 For titration with 0.1 M of NaOH

Feed:

Raffinite:

Extract:

M1V1 = M2V2
(0.1M) (35.0mL) = M2 (10
mL)
M2 = 0.350 M (X1)

M1V1 = M2V2
(0.1M) (12.5mL) = M2 (10
mL)
M2 = 0.125 M

M1V1 = M2V2
(0.1M) (20.0mL) = M2 (10
mL)
M2 = 0.200 M (Y1)

i. Propionic acid extracted from aqueous phase

Rate of acid transfer = Vw (Y1 0)
Where Vw is flowrate of aqueous phase is equal to 0.2 L/min
So ,
Rate of acid transfer =( 0.2 L/min ) (0.200 mol/L 0)
=0.04 mol/min
ii. Propionic acid extracted from the organic phase
Rate of acid transfer = Vo (X1 X2)
Where Vo is flowrate of aqueous phase is equal to 0.2 L/min
So ,
Rate of acid transfer =( 0.2 L/min ) (0.350 mol/L X2)
By mass balance:
Vo ( X1 X2 ) = Vw ( Y1 0)
(0.2 L/min)(0.350 mol/L - X2) = (0.2 L/min)(0.200 mol/L - 0)
X 2 = 0.15 mol/L

P a g e | 11

Next , the driving force ,

Log mean driving force = X'1 - X2
ln (X1 /X2)
Where X1 is the Driving Force at the top of column = (X 2 0)
X1 = 0.15 mol/L
And X2 is the Driving Force at the bottom of column = (X 1 X'1)

Then by coefficient, K = Y1
X' 1
By assuming the K is 0.93 ( from Experiment A )
The , X'1 = 0.215 mol/min
So, X2 = 0.135 mol/min
And log mean driving force is , = (0.215 - 0.135)
ln (0.15/0.135)
= 0.759
Lastly to find mass transfer coefficient =

Rate of propionic acid transfer

Volume of packing x mean driving force
=
0.04
2.36 x 0.759
= 0.0223

8.2.2 For titration with 0.025 M of NaOH

Feed:

Raffinite:

Extract:

M1V1 = M2V2
(0.025M)(54.1mL)=M2 (10
mL)
M2 = 0.135 M (X1)

M1V1 = M2V2
(0.025M)(1.5mL) = M2 (10
mL)
M2 =0.004 M

M1V1 = M2V2
(0.025M)(23.2mL) = M2 (10
mL)
M2 = 0.058 M (Y1)

i. Propionic acid extracted from aqueous phase

Rate of acid transfer = Vw ( Y1 0)
Where Vw is flowrate of aqueous phase is equal to 0.2 L/min
So ,
Rate of acid transfer =( 0.2 L/min ) (0.058 mol/L 0)
=0.0116 mol/min
ii.Propionic acid extracted from the organic phase
Rate of acid transfer = Vo ( X1 X2 )
Where Vo is flowrate of aqueous phase is equal to 0.2 L/min
So ,
Rate of acid transfer =( 0.2 L/min ) (0.135 mol/L X2)

P a g e | 12

By mass balance:
Vo ( X1 X2 ) = Vw ( Y1 0)
(0.2 L/min)(0.135 mol/L - X2) = (0.2 L/min)(0.058 mol/L - 0)
X 2 = 0.077 mol/L
Next, the driving force ,
Log mean driving force = X'1 - X2
ln (X1 /X2)
Where X1 is the Driving Force at the top of column = (X 2 0)
X1 = 0.077 mol/L
And X2 is the Driving Force at the bottom of column = (X 1 X'1)

Then by coefficient, K = Y1
X'1
By assuming the K is 0.93 ( from Experiment A )
Then , X'1 = 0.062 mol/min
So, X2 = 0.073 mol/min
And log mean driving force is =

(0.062- 0.073)
ln (0.077 / 0.073)
= 0.206

Lastly to find mass transfer coefficient =

9.0

Rate of propionic acid transfer

Volume of packing x mean driving force
=
0.0116
2.36 x 0.206
=0.024

DISCUSSIONS

The purposes of the liquid-liquid extraction experiment is to separate two or more

components of a solution from one another and then to determine whether a certain
compound is present in an unknown reagent or not. The system works off the premise
that the components involved are immiscible with one another. In this case of this lab
there are three liquids used which are propionic acid, oil and water. Oil and propionic
acid are mixed together in the feed tank, which is then mixed through the recycle
system of the pump before it is sent to be mixed with the water in the first stage.
When it is properly mixed it is then sent to the first stage and allowed to interact with

P a g e | 13
the water which is flowing countercurrent to the feed of the acid-oil mix. Throughout
the three stages the acetic acid will transfer from theoil, which is the raffinate, to the
extract, water in this case. Out of each stage samples of propionic acid was taken, and
titrated with sodium hydroxide to determine the amount of propionic acid contained in
the feed, extract and raffinite. For the first experiment, the data was collected in Table
7.0. it shows that the propionic acid added lower will gives the concentration of
sodium hydroxide lower. The higher value is for 5.0 mL propionic acid added, which is
22.5 mL of sodium hydroxide was titrated and have the concentration of 2.25 M.
Next, from Table 7.1, the data illustrates that the majority of the Propionic Acid was
extracted from oil to the water in the first stage, which is 0.350 M and 0.135 M after
titrated with 35.0 mL of 0.1 M and 54.1 mL of 0.025 M of sodium hydroxide
respectively. The amount of Propionic Acid in water decreased in the next stage, which
is at raffinite and then increase thereafter. This means that the amount of Acetic Acid
extracted into water not constant with each stage. It was reliably assumed that the
longer the mixing of the liquids the better the molecules are able to partition into the
preferred solvent. As stated, the data does not agree with this for the simple fact that
the majority of Propionic Acid used is evaporated. It should be noted that almost 95%
of the Propionic Acid used in this experiment evaporated to the air. This explains the
trend seen in the data, because the majority of the Propionic Acid that was extracted
into the water occurred in the first stage shortly after the Propionic Acid Oil mixture
was added to the system. Once the liquids were allowed to mix and settle throughout
the other two stages all the mixing and time to settle out allowed the Propionic Acid to
evaporate out due to uncovered tanks. With so much Propionic Acid evaporating out it
is clear that with time the amount of Acetic Acid extracting into the water decreased
with increasing evaporation as seen in the data.
Furthermore, the data should show that the amount of Propionic Acid in the oil is
decreasing between each stage (meaning that the Propionic is partitioning into the
water), which it does for the most part but there are a few discrepancies most likely
due to the fact that the oil was not standardized and that the tank covers were
removed for a significant portion of both trials. There are a few causes for this. One
major complication of this experiment was the fact that the system kept clogging. This
not only affected the mixing between the two liquids but also required the tank covers
to be removed in order to manually fix the clogging as stated before. The drain valves
of the settling compartments were very tiny and prone to clogging. This could have
been avoided if the drain valves were increased in size to avoid clogging from all the
debris that enters in from the dirty holding tanks. Also, the rotameter for the Propionic

P a g e | 14
Acid Oil mixture did not indicate any oil flow rate, and it also had a large clog in it.
Without knowing the flowrate of the Oil-Acid mixture, or whether its flow was steady, it
was difficult to determine the water flowrate required for the 2:1 countercurrent flow
necessary to achieve steady state.

The Water Rotameter was constantly being

changed by operators of the apparatus (leading to a nonsteady state operation) and

it is likely that these complications lead to some of the discrepancies observed.
There were many errors in the performance of the lab which yielded improper data.
Therefore it is very difficult to make any definite conclusions on how the speeds of the
agitators affected the overall efficiency of removing Propionic acid from the oil. The
most significant error was that the Propionic acid was lost, and because of this fact the
rest of the data cannot definitively draw any conclusions. From data collected for the
concentrations of the Propionic acid found in each stage it can be seen that most of
the acid was lost between the first and third stage. Concentration of acetic acid stayed
relatively constant in the oil samples indicating that it was indeed transferred from the
oil to the water in the mixing stages. It is recommended that covers for all of the tanks
should be kept on at all times while the process is in operation to ensure there is no
loss of the acetic acid through evaporation. Another recommendation is to understand
early on how exactly the system works because it is difficult to get the countercurrent
flows to perform properly and to ensure that the mixing is successful in transferring
the acetic acid.

10.0 CONCLUSION
The experiment was conducted to separate the mixture using two immiscible solvent.
From experiment A, table 7.0 shows that in aqueous and organic layer, both are
decreasing in concentration due to decreasing volume of propanoic acid titrate with
sodium hydroxide. The differences in degree of extraction of propanoic acid by these
diluents were explained in terms of relative permittivity and dipole moment. The
higher the volume of propanoic acid much stronger the dipole moment hence the
concentration will increase. From table 7.1 in experiment B, the volume of feed titrate
with 0.025M of sodium hydroxide is higher compare to 0.1M of sodium hydroxide
similar with extract but different for raffinite. From calculation, the concentration of
propanoic acid in each sample was higher when the sample was titrated with 0.1M
sodium hydroxide. The volume of propanoic acid extracted from the organic and
aqueous phase, both higher in 0.1M sodium hydroxide. This shows that, the higher the
concentration of sodium hydroxide titrated with the sample, much easier for propanoic

P a g e | 15
acid to be extracted.
11.0 RECOMMENDATIONS
1. The component mixture must dissolve in a suitable solvent.
2. The mixture is thoroughly mixed (shaking) to make sure that the entire
components are well mixed.
3. Gloves and goggles are used in order to prevent any unexpected contact
with the reagents as well as lab coat is used when conducting an
experiment.
4. Do not use any crack glassware as well as used glove when handling sodium
hydroxide solid or solution as it can cause corrosive effect.
5. When transferring the solutions, make sure all of the solutions was
transferred completely to avoid inaccurate volume of the solution transferred
resulting in slightly different value in the molarity.

12.0 REFERENCES
1. Dr. Pahlavan, Extraction Determination of Distribution Coefficient
2. Liquid extraction is an operation used to separate the component. (n.d.).
Retrieved from Solution Inn: http://www.solutioninn.com/engineering/chemicalengineering/chemical-processes/liquid-extraction-is-an-operation-used-toseparate-the-components
3. Liquid-Liquid

Extraction.

(n.d.).

Retrieved

from

Wikipedia:

http://en.wikipedia.org/wiki/Liquid%E2%80%93liquid_extraction
4.

Liquid-Liquid

Extraction.

(n.d.).

Retrieved

from

Chemistry

Courses:

http://courses.chem.psu.edu/chem36/Experiments/PDF's_for_techniques/Liquid_
Liquid.pdf
5. Techniques in Organic Chemistry 2nd ed pages 75-99, 3rd ed pages 113-140.

P a g e | 16

13.0

APPENDICES

Figure 13.0: sample from raffinite

Figure 13.2: Liquid Liquid extraction unit

Figure 13.1: Sample for feed