1

TABLE OF CONTENT

TITLE PAGE
Table of Content 1
1.0 Abstract 2
2.0 Introduction 3-4
3.0 Objectives 5
4.0 Theory 5-6
5.0 Apparatus and material 7
6.0 Experimental procedure 8
7.0 Results 9
8.0 Calculation 10-14
9.0 Discussion 15-16
10.0 Conclusion 16
11.0 Recommendations 16
References 17
Appendices 17









2

ABSTRACT
This simple experiment is conducted to determine the distribution of coefficient and
mass transfer coefficient with the aqueous phase as the continuous medium through liquid-
liquid extraction as the objectives of this experiment. Besides that, this experiment is also
based on the solubility of the solution used. In the experiment A, liquid-liquid extraction
column is used to obtain feed, raffinate and extract samples. The samples is taken for being
titrate with the different concentration of NaOH which is 0.1 M and 0.025 M. Moreover, the
value of mass transfer coefficient from liquid-liquid extraction are; 0.44 kg/min if titrated
with 0.1 M NaOH and -0.257 kg/min if titrated with 0.025 M NaOH. For the experiment B,
separators funnel is used to separate two solutions of different solubility and densities, and
then titration is done with different of NaOH concentration which is 0.1 M and 0.025 M. The
values for distribution coefficient by titration with 0.1 M are 7.78 in 1.0 ml of propionic acid,
2.30 in 3.0 ml of propionic acid and 1.80 in 5.0 ml of propionic acid. The experiment was
completely and successfully done.











3

INTRODUCTION
Liquid-liquid extraction, also known as solvent extraction and partitioning, is a
method to separate compounds based on their relative solubility in two different immiscible
liquids, which is water as usual and an organic solvent (propionic acid). It is an extraction of
a substance from one liquid phase into another liquid phase. Liquid-liquid extraction is a
basic technique in chemical laboratories, where it is performed using a separator funnel. This
type of process is commonly performed after a chemical reaction as part of the work-up.
Furthermore, this is the separation of a substance from a mixture by preferentially dissolving
that substance in a suitable solvent. By this process a soluble compound is usually separated
from an insoluble compound.
The basic principle behind extraction involves the contacting of a solution with
another solvent that is immiscible with the original. The solvent is also soluble with a specific
solute contained in a solution. Two phases are formed after the addition of solvent, due to the
differences in densities. The solvent is chosen so that the solute in the solution has more
affinity toward the added solvent. Therefore, mass transfer of the solute from the solution to
the solvent occurs. Further separation of the extracted solute and the solvent will be necessary.
However, these separation costs may be desirable in contrast to distillation and other
separation processes for situations where extraction is applicable.
A general extraction column has two input stream and two output streams. The input
streams consist of a solution feed at the top containing the solute to be extracted and a solvent
feed at the bottom which extracts the solute from the solution. The solvent containing the
extracted solute leaves the top of the column and is referred to as the extract stream. The
solution exits the bottom of the column containing only small amounts of solute and is known
as the raffinate. Further separation of the output streams may be required through other
separation process. Solvent extraction is used in nuclear reprocessing, ore processing, the
processing of perfumes and the production of vegetable oils and biodiesel.




4

Flow Sheet

Figure 1 : Liquid-liquid extraction column schematic diagram

Figure 2 : Extraction Flow sheet for an Extraction Column



5

OBJECTIVES
1. To conduct the simple experiments regarding liquid-liquid extraction.
2. To determine the distribution coefficient for the system organic solvent-propionic acid
water and show its dependence on concentration.
3. To demonstrate how a mass balance is performed on the extraction column and to
measure the mass transfer coefficient with the aqueous phase as the continuous
medium.

THEORY
In liquid-liquid extraction, two phases must be brought into contact to permit transfer
of material and then be separated. Extraction equipment may be operated batch wise or
continuous. The extract is the layer of solvent plus extracted solute and the raffinate is the
layer from which solute has been removed. The extract may be lighter or heavier than the
raffinate, and so the extract may be shown coming from top of the equipment in some cases
and from the bottom in others. The operation may of course be repeated if more than one
contact is required, but when the quantities involved are large and several contacts are needed,
continuous flow becomes economical.
In dilute solutions at equilibrium, the concentration of the solute in the two phases is
called the distribution coefficient or distribution constant K.
K=Y/X
Where the Y and X are the concentrations of the solute in the extract and the raffinate phases
respectively. The distribution coefficient can also be given as the weight fraction of the solute
in the two phases in equilibrium contact:
K =y*/x
Where y* is the weight fraction of the solute in the extract and x is the weight fraction of the
solute in the raffinate.
The rate at which a soluble component is transferred from one solvent to another will
be dependent, among other things, on the area of the interface between the two immiscible
6

liquids. Therefore it is very advantageous for this interface to be formed by droplets and films,
the situation being analogous to that existing in packed distillation columns. The theory for
the system Trichloroethylene-Propanoic acid-Water is as follows:
Let Vw : Water flow rate, lt/s
Vo : Trichloroethylene flow rate, lt/s
X : Propionic acid concentration in the organic phase, kg/lt
Y : Propionic acid concentration in the aqueous phase, kg/lt
Subscripts: 1: Top of column
2: Bottom of column
Mass Balance:
Propionic acid extracted from the organic phase (raffinate).
= Vo (

) (8.1.1)
Propionic acid extracted by the aqueous phase (extract)
= Vw (

-0) (8.1.2)
Therefore theoretically,
Vo (

) = Vw (

-0) (8.1.3)
Mass transfer coefficient:
MTC=Rate of acid transfer/volume of packing mean driving force (8.1.4)
Where Log mean driving force: (

) / ln (

: Driving force at the top of the column = (

-0)

: Driving force at the bottom of the column = (

*)
Where

* is the concentration in the organic phase which would be in equilibrium with

concentration

in the aqueous phase. The equilibrium values can be found using the
distribution coefficient found in the first experiment.
7

APPARATUS AND MATERIALS
Apparatus:
Liquid-liquid extraction column
Water pump
Separator funnel
Burette
Conical flask
Volumetric flask
Measuring cylinder
Materials:
0.1 M NaOH solution
0.025 M NaOH solution
Distillates product solution
Raffinate product solution
Feed solution
Propionic acid










8

PROCEDURES
Experiment A
1. Make sure valve V6 and V11 are closed.
2. Valve S1, C3 and S3 are switched on.
3. The feed flow rates (C1) are adjusted until maximum.
4. S4 is switched on.
5. When the water reaches the top column, C1 is set to 250 cc/min.
6. Wait for 20 minutes.
7. 150mL sample from raffinate, feed and extract is taken.
8. 15 mL from each sample is taken in Experiment A and 3 drops of phenolphthalein is
added.
9. Each sample is titrated with 0.1M NaOH.
10. Step 8 and 9 is repeated with 0.025 M NaOH.
11. For each moles of NaOH is titrated twice.
Experiment B
1. 50mL of water, 50mL of organic solvent and 1mL of propionic acid is added into a
conical flask and is shakes well.
2. Step 1 is repeated with 3 and 5 mL of propionic acid.
3. Two layers of solution is formed (immiscible) and 10mL from each upper and bottom
layer is taken.
4. 3 drops of phenolphthalein is added into each sample.
5. Each ample is titrated with 0.1 M of NaOH.






9

RESULT
Experiment A
Concentration of
NaOH (M)

Raffinate (mL)

Feed (mL)

Extract (mL)
0.1 M 2.1 35.5 14.7
0.025 M 2.9 114.3 48.5

Water flow rate : 0.20 L/min
Organic flow rate : 0.20 L/min
Packing dimension : Length = 1.2 m
Diameter = 50 mm
Experiment B


Volume of propionic
acid (mL)


Volume of NaOH(mL)



Concentration of
NaOH(M)

Upper Bottom
1.0 21.0 2.7

0.1 M
3.0 60.0 26.0
5.0 100.0 55.4







10

CALCULATIONS
Formula for finding distribution coefficient (Experiment B):
K = Y/X
Where Y: Concentration of solute in exact phase.
X: Concentration of solute in raffinate phase.
For 0.1M of NaOH
1. 1.0mL of propionic acid
Upper (Y) Bottom (X)
M
1
V
1
= M
2
V
2
(0.1M)(21.0 10
-3
L) = (M
2
)(1.0 10
-3
L)
M
2
= 2.10 M
M
1
V
1
= M
2
V
2
(0.1M)(2.70 10
-3
L) = (M
2
)(1.0 10
-3
L)
M
2
= 0.27 M
K = Y/X
= 2.10M / 0.27M
= 7.78
2. 3.0mL of propionic acid
Upper (Y) Bottom (X)
M
1
V
1
= M
2
V
2
(0.1M)(60.0 10
-3
L) = (M
2
)(3.0 10
-3
L)
M
2
= 2.00 M
M
1
V
1
= M
2
V
2
(0.1M)(26.0 10
-3
L) = (M
2
)(3.0 10
-3
L)
M
2
= 0.87 M
K = Y/X
= 2.00M / 0.87M
= 2.30
3. 5.0mL of propionic acid
Upper (Y) Bottom (X)
M
1
V
1
= M
2
V
2
(0.1M)(100 10
-3
L) = (M
2
)(5.0 10
-3
L)
M
2
= 2.00 M
M
1
V
1
= M
2
V
2
(0.1M)(55.4 10
-3
L) = (M
2
)(5.0 10
-3
L)
M
2
= 1.11 M
K = Y/X
=2.00M / 1.11M
= 1.80


11

Formula for finding mass transfer coefficient (Experiment A):
M
1
V
1
= M
2
V
2

Where:
M
1
= concentration of NaOH
M
2
= concentration of propionic acid
V
1
= volume of NaOH
V
2
= volume of propionic acid
Rate of acid transfer = Vw (Y
1
0)
Vo (X
1
X
2
) = Vw (Y
1
0)
K = Y
1
/X*
Log mean driving force = (X
1
-X
2
) / ln (X
1
/X
2
)
Where:
X
1
: Driving force at the top of the column = (X
2
0)
X
2
: Driving force at the bottom of the column = (X
1
- X
1
*)
Packing dimension : Length = 1.2m
Diameter = 50mm
Radius = (

) = 0.025m
Therefore, packing volume, V = r
2
L
= ( 0.025m)
2
(1.2m)
= 2.36 10
-3
m
3

= 2.36 L

For 0.1M of NaOH
Raffinate:
M
1
V
1
= M
2
V
2

(0.1)(2.110
-3
) = M
2
(0.015)
M
2
= 0.014M of propionic acid X
1
Feed:
M
1
V
1
= M
2
V
2
(0.1)(35.510
-3
) = M
2
(0.015)
M
2
= 0.237M of propoinic acid
Extract:
M
1
V
1
= M
2
V
2

(0.1)(14.710
-3
) = M
2
(0.015)
M
2
= 0.098M of propoinic acid Y
1


Rate of acid transfer = Vw (Y
1
- 0)
= (0.20 L/min)(0.098 mol/L)
= 0.0196 mol/min
12

Finding the value of X
2
:

Vo (X
1
-X
2
) = Vw (Y
1
-0)
(0.20 L/min)(0.014 mol/L - X
2
) = 0.0196 mol/min
X
2
= 0.084 mol/L @ M

Finding the log mean driving force:
X
1
= (X
2
-0)
= 0.084 M

K = Y
1
/ X*
X* = Y
1
/ K At equilibrium, assume K = 7.78 (from experiment B)
= 0.098 / 7.78
= 0.013 M
X
2
= (X
1
-X
1
*)
= 0.014 M 0.013M
= 0.001M
Log mean driving force = (X
1
-X
2
) / ln (X
1
/X
2
)
= ( 0.084 0.001)M / ln (0.084 / 0.001)
= 0.019
Finding the mass transfer coefficient:
Mass transfer coefficient =



=



= 0.44 mol/L.min
= 0.44 M/min
= 0.44 kg/min




13

For 0.025M of NaOH
Raffinate:
M
1
V
1
= M
2
V
2

(0.025)(2.910
-3
) = M
2
(0.015)
M
2
= 0.00483 M of propionic acid X
1
Feed:
M
1
V
1
= M
2
V
2
(0.025)(114.310
-3
) = M
2
(0.015)
M
2
= 0.1905 M of propoinic acid
Extract:
M
1
V
1
= M
2
V
2

(0.025)(48.510
-3
) = M
2
(0.015)
M
2
= 0.0808 M of propoinic acid Y
1


Rate of acid transfer = Vw (Y
1
- 0)
= (0.20 L/min)(0.0808 mol/L)
= 0.0162 mol/min
Finding the value of X
2
:

Vo (X
1
-X
2
) = Vw (Y
1
-0)
(0.20 L/min)(0.00483 mol/L - X
2
) = 0.0162 mol/min
X
2
= - 0.0762 mol/L @ M

Finding the log mean driving force:
X
1
= (X
2
-0)
= - 0.0762 M

K = Y
1
/ X*
X* = Y
1
/ K At equilibrium, assume K = 7.78 (from experiment B)
= 0.323 / 7.78
= 0.0104 M
X
2
= (X
1
-X
1
*)
= 0.00483 M 0.0104 M
= -0.00557 M
Log mean driving force = (X
1
-X
2
) / ln (X
1
/X
2
)
= ( -0.0762+ 0.00557)M / ln (-0.0762 / -0.00557)
= -0.02670
14

Finding the mass transfer coefficient:
Mass transfer coefficient =



=



= -0.257 mol/L.min
= -0.257 M/min
= -0.257 kg/min

















15

DISCUSSION
In this experiment, we want to identify the distribution of coefficient and to identify
the mass transfer coefficient. This experiment is referred to the solubility which is the solvent
is also soluble with a specific solute contained in the solution and also about the separation of
a substance from a mixture by preferentially dissolving the substance in a suitable solvent.
For the first experiment, which is to determine the mass transfer coefficient, we used
the liquid-liquid extraction column to get the feed, raffinate and extract solution to be the
samples. The samples then are titrated with 0.1 M NaOH and 0.025 M NaOH. The value of
mass transfer coefficient when titrated with 0.1 M NaOH is 0.44 kg/min while titrated with
0.025 M, the value of mass transfer coefficient is -0.257 kg/min. Result for this experiment
shows that the experiment is failed because the values of mass transfer coefficient supposedly
in positive. Besides that, we cannot show that the relation between mass transfer rate with the
concentration of NaOH. For the actual result, this experiment can shows the increment of
mass transfer rate when the concentration of NaOH is decreasing.
For the second experiment, which is to determine the distribution coefficient, we used
the titration method from the upper (Y) and bottom (X) layer sample. By titration with 0.1 M,
the values are 7.78 in 1.0 ml of propionic acid, 2.30 in 3.0 ml of propionic acid and 1.80 in
5.0 ml of propionic acid. From the result in this experiment, if titrated with 0.1 M NaOH, it
shows that the value of distribution coefficient decrease as the volume of propionic acid
increase. This experiment is totally successful because those results followed the actual
results which is the value of distribution coefficient must be decrease when the volume of
propionic acid is increasing.
Several error occurred during this experiment progress that totally effect the result of
first experiment which is for finding the mass transfer coefficient. The most common error is
the position of the eye during taking the volume value at the burette. As the solution, the eye
position should be straight to the scale and must be perpendicular to the meniscus. Besides
that, the error also occurred while using the apparatus that is not properly clean. We should
used the clean apparatus to avoid the oil emission and impurities at the beaker, conical flask
or burette. If the apparatus not clean, we should used the distilled water to clean up those
apparatus.
16

Besides that, the experiment should be repeated at least 2 or 3 times to get the
accurate values and the mistake during the experiment progress can be identified. However,
the first experiment only done with one trial that cause the experiment being failed.
Furthermore, we choose light pink color for the color indicator during titration, but to get all
the same color might be hard enough to identify. As the color is not same in each titration, the
value of mass transfer coefficient will be different from the actual and made the experiment
failed. This is because the color indicates that the NaOH is at equilibrium with the sample
solution.
CONCLUSIONS
As the conclusion, the values for distribution coefficient by titration with 0.1 M are
7.78 in 1.0 ml of propionic acid, 2.30 in 3.0 ml of propionic acid and 1.80 in 5.0 ml of
propionic acid. This experiment is only done for 0.1 M of NaOH and the results for this
experiment is totally successful. The value of mass transfer coefficient from liquid-liquid
extraction are; 0.44 kg/min if titrated with 0.1 M NaOH and -0.257 kg/min if titrated with
0.025 M NaOH. However, in this experiment, the value of mass coefficient must be positive
not negative. Therefore, this experiment is recognized as failed.
RECOMMENDATIONS
These are some recommendations must be followed during the experiment. Before
starting the experiment, we must made sure the apparatus is clean. However, if the apparatus
is not clean, we must cleaned up those apparatus using distilled water. Furthermore, the eye
position should be perpendicular to the meniscus and the scale. In addition, the experiment
must repeated at least 2 or 3 times. Those ways is done to make sure the values is accurate.
Besides that, titration process should be repeat several times to get the average values. Then,
we must used magnetic stirrer during the titration process. Finally, we needed to make sure
the changes of color is constant in every titration.




17

REFERENCES
W. McCabe, J. Smith, and P. Harriot, (2005). Unit Operations of Chemical
Engineering, 7
th
ed. McGraw-Hill.
Bennett, C. O., and J. E. Myers, Momentum, Heat and Mass Transfer, 3rd
Edition,McGraw-Hill, 1983.
Perry, R.H., and D. Green, Perrys Chemical Engineering Handbook, 6th
Edition,McGraw-Hill, 1984.
http://en.wikipedia.org/wiki/Liquid-liquid_extraction
http://rothfus.cheme.cmu.edu/uolab/lle/projects/t8_foo.pdf
http://www.scribd.com/doc/5552507/3-Liquid-liquid-extraction

APPENDICES

Liquid-liquid extraction column Separator funnel