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ABSTRACT

We know that liquid liquid extraction is crucial in our industry, where it


is used in washing acid, in extraction for valuable products from fermentation
broth, purification in heat sensitive materials and others. This Liquid-liquid
Extraction experiment is divided into two parts. The objective of the first
experiment is to determine the distribution coefficient for the system orgnic
solvent-propionic acid water and to show its dependence on concentration.
The objective of the second experiment is 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. In the
first experiment, we are required to titrate NaOH to two different layers
which are aqueous and organic layer with different volume of propionic acid
required. The first trial is with 5ml of propionic acid and then followed by 3ml
and 1ml of propionic acid. The results are then recorded and as the value of
distribution coefficient, K for 5ml, 3ml and 1ml of Propionic Acid are 0.70,
0.41, and 0.74 respectively. In the second experiment, liquid liquid extraction
column is used in order to collect feed, raffinate, and extract which all these
3 will be titrated with 0.1M and 0.025M of NaOH solution. The data of how
much of NaOH in mL needed the solution to turn light pink is recorded. The
value of the mass transfer coefficient calculated is 0.3556 kg/min for 0.1 M
NaOH, while 0.044 kg/min for concentration of 0.025 M of NaOH. The
experiment is considered succeed.

INTRODUCTION
Liquid-liquid extraction can be defined as transferring one or more
solute(s) contained in a feed solution to another immiscible liquid (solvent).
The solvent that is enriched in solute(s) is called extract. The feed solution
that is depleted in solute(s) is called raffinate. This experiment is about to
extract substance from liquid phase into another liquid phase performed
using a separator funnel.
In order to separate a substance from a mixture, we dissolve the
substance in a suitable solvent. By dissolving the substance, we can
separate the soluble compound from an insoluble compound.
As we know, the title of this experiment is liquid liquid extraction, thus
the main process involved is extraction. Extraction involves the contacting of
a solution with another solvent that is immiscible with the original. Due to
different densities, two phases are formed after the addition of the solvent.
Mass transfer will occur when the solute in the solution has more affinity
towards the added solvent.

Figure 1: Liquid liquid extraction unit

There are two types of streams exist in general extraction column


which are input stream and output stream. The solvent metering pump is
calibrated in percentage of maximum flow which varies slightly from pump to
pump. Initially, the pump should be calibrated by setting F2 to 100%, setting
valve V8 to the calibrate position and measuring the flow from the pump,
using a measuring cylinder and stopwatch. We need to calculate the flow
rate produced settings of 10% intervals (mL per minute), then plot a graph of
mL per minute against percentage of metering pump stroke to obtain any
selected flow using the graph.

OBJECTIVES

The objectives of this experiment are:

To conduct the experiments regarding liquid-liquid extraction.


To determine the distribution coefficient for the system of organic
solvent-propionic

acid-water

and

show

its

dependence

on

concentration.
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
Liquid-liquid extraction is a useful method to separate components or
compounds of a mixture. The extraction is based on the transfer of a solute
substance from a liquid phase into another liquid phase according to the
solubility.
At an equilibrium, in a dilute solution, the concentration of the solute in the
two phases are called the distribution coefficient or distribution constant, K
and describes in the following formula:
K = Y/X
Y: is the concentration of the solute in the extract phase
X: is the concentration of the solute in raffinate phase

The distribution coefficient can also be described as the weight fraction of


the solute in the two phases in equilibrium constant:
K= y/x
y: is the weight fraction of the solute in the extract
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, including on the interface between the two
immiscible liquids. Thus, the situation is an advantage for an interface
between two immiscible liquids.
For the system Trichloroethylene-Propionic Acid-Water is described as follows:
Mass Balance:
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Propionic acid extracted from the organic phase in raffinate,


V o ( X 1 X 2 )
Propionic acid extracted by the aqueous in the extractor,
V w (Y 10)
Thus, the theoretically,
V o ( X 1 X 2 )=V w (Y 10)
Mass transfer coefficient,

Rate of acid transfer


Volume of packing x Meandriving force

Let
V w:

Water flow rate, L/s

Vo:

Trichloroethylene flow rater, L/s

X:

Propionic acid concentration in the organic phase, kg/L

Y:

Propionic acid concentration in the aqueous phase, kg/L

Subscripts :

1: Top column
2: Bottom column

Log mean driving force is given as,

X1 :

X 1 X 2
ln ( X 1 X 2)

Driving force at the top of the column =


5

(X 20)

X 2:
X1

Driving force at the bottom of the column =

( X 1 X 1 )

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

with concentration

Y1

in the aqueous phase. The equilibrium values can be

found using the distribution coefficient found in the first experiment.

APPARATUS

250 ml conical flask stoppered flask


250 ml measuring cylinder
250 ml separating funnel
Pipette with rubber bulb
Burette
Sodium Hydroxide solution (0.1M)
Phenolphthalein
Propionic acid

PROCEDURE
Experiment A:
1 A mixture of 50 ml organic solvent and 50 ml of demineralised are
made up in a conical flask.
2 5 ml of propionic acid is added. 5ml can be pipette into the flask using
a pipette with a rubber bulb.
3 A stopper is placed into a flask and it is shaken for a minimum of 5
minutes.
4 It is then poured into a separating funnel and it is left for 5 minutes.
Later, the lower aqueous later is removed.
5 A 10 ml of sample of the layer is taken and titrated against 0.1M
sodium hydroxide solution using phenolphthalein as indicator.
6 The experiment is repeated for two further concentration of propionic
acid. For example, for initial additions of 3 ml and 1 ml of propionic
acid.
Experiment B:
1 100 ml of propionic acid is added to 10 litres of organic phase. The
mixture is mixed well to ensure an even concentration then the organic
phase feed tank (bottom tank) is filled with the 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 litres of clean demineralised water,
the water feed pump is started and the column is filled with water at a
high flow rate.
4 As soon as the water is above the top of the packing, the flow rate is
reduced to 0.21 litre per minute.
5 The metering pump is started and a flow rate is set to 0.2 litre per
minute.
6 The unit is ran for 15 to 20 minutes until steady conditions are
achieved, the flow rates are monitored during this period to ensure
that they remain constant.

7 15ml of sample from the feed, raffinate and extract streams are taken.
It is ensured to not use the calibration valve V8 for taking feed
samples.
8 10 ml of

each

sample

is

titrated

against

0.1M

NaOH

using

phenolphthalein as the indicator.


Note: To titrate the feed and raffinate they need continuous stirring using
magnetic stirrer. As an alternative, 0.025 M NaOH may be used which lead to
phase inversion of raffinate and feed streams so that the aqueous is the
continuous phase.

RESULT AND CALCULATIONS

EXPERIMENT A
DETERMINATION OF DISTRIBUTION COEFFICIENT OF SOLUTION WITH WATER
AND ITS DEPENDENCE ON CONCENTRATION
PROPANOIC
ACID
ADDED (Ml)

AQUEOUS LAYER

ORGANIC LAYER

TITRE OF
M/10 NaOH
(mL)

50

PROPIIONIC
CONCENTRA
TION
(Y)
1.00

TITRE OF
M/10
NaOH
(mL)
71

PROPIIONIC
CONCENTRA
TION
(X)
1.43
0.70

15

0.50

36.8

1.23

0.41

13

1.30

17.5

1.75

0.74

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K=Y/X

EXPERIMENT B :
DEMONSTRATING A MASS BALANCE IN THE EXTRACTION COLUMN AND
MEASURING THE MASS COEFFICIENT, K, WITH AUQEOUS PHASE AS THE
CONTINOUS MEDIUM
FLOW RATE OF
AQUEOUS
PHASE
(L/ min)
FLOW RATE OF
ORGANIC PHASE
(L/ min)
SODIUM
HYDROXIDE
CONCENTRATIO
N (M)
FEED (mL)
RAFFINATE (mL)
EXTRACT (mL)
PROPIONIC ACID
EXTRACTED
FROM THE
ORGANIC PHASE
(mol/min)
PROPIONIC ACID
EXTRACTED
FROM THE
AQUEOUS
PHASE (mol/min)
MASS TRANSFER
COEFFICIENT
(kg/min )

0.2

0.2
0.1 M

0.025 M

17.0
10.0
6.0
0.04

54.1
15.0
23.2
0.03

CONCENTRATION OF
PROPIONIC ACID (M)
0.1 M
0.025 M
0.17
0.10
0.06

0.14
0.04
0.06

PACKING DIMENSIONS :
LENGTH: 1.2 m
DIAMETER : 50 mm
0.012

0.0025

0.3556

0.044

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SAMPLE CALCULATIONS:
Experiment A
1 Calculation of concentration (Aqueous)
( 5 m l P r o p i o n i c Ac i d )
Fo rm u l a : M 1 V 1 = M 2 V 2
M1 =

Concentration of NaOH (moles)

V1 =

Vo l u m e o f N a O H ( m l )

M2 =

C o n c e n t r a t i o n o f P ro p i o n i c a c i d ( m o l e s )

V2

Vo l u m e o f P ro p i o n i c a c i d ( m l )

(0.1)(50 ml) = M2(5ml)


M1 = 1.00 M
( 3 m l P ro p i o n i c Ac i d )
(0.1)(15 ml) = M2(3ml)
M2 = 0.50 M

( 1 m l P ro p i o n i c Ac i d )
(0.1)(13 ml) = M2(1ml)
M2 = 1.3 M
C a l c u l a t i o n o f c o n c e n t r a t i o n ( 0 rg a n i c )
( 5 m l P ro p i o n i c Ac i d )
(0.1)(71 ml) = M2(5ml)

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M1 = 1.42 M

( 3 m l P ro p i o n i c Ac i d )
(0.1)(36.8 ml) = M2(3ml)
M2 = 1.23 M
( 1 m l P ro p i o n i c Ac i d )
(0.1)(17.5 ml) = M2(1ml)
M1 = 1.75 M

2 C a l c u l a t i o n o f D i s t r i b u t i o n C o e ffi c i e n t , K :
D i s t r i b u t i o n c o e ffi c i e n t ( 5 m l P ro p i o n i c Ac i d )
Fo r m u l a :

K = Concentration of the solute in the ext ract

phase, Y
C o n c e n t r a t i o n o f t h e s o l u t e i n t h e r a ffi n a t e
phase, X
K = 1.00 M
1.43M
K

= 0.70

D i s t r i b u t i o n c o e ffi c i e n t ( 3 m l P ro p i o n i c Ac i d )
K = 0.50 M
1.23 M
K

= 0.41
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D i s t r i b u t i o n c o e ffi c i e n t ( 1 m l P ro p i o n i c Ac i d )
K = 1.30 M
1.75 M
K

= 0.74

Experiment B
1 C o n c e n t r a t i o n o f P r o p i o n i c Ac i d a t f e e d :
Fo rm u l a : M 1 V 1 = M 2 V 2
(0.1)(17.0 ml) = M2(10ml)
M2

= 0.17M

C o n c e n t r a t i o n o f P ro p i o n i c Ac i d a t Ra ffi n a t e ( X 1 )
(0.1)(10.0 ml) = M2(10ml)
M2 = 0.1M
Concentration of Propionic Acid at Extract (Y1)
(0.1)(6.0 ml) = M2(10ml)
M2 = 0.06 M
2 T h e fl o w r a t e o f a q u e o u s a n d o r g a n i c p h a s e = 0 . 2 L / m i n
3 Ra t e o f a c i d t r a n s f e r = V w ( Y 1 - 0 )
= 0.2 (0.06 - 0)
= 0.012 mol/min
0 . 0 1 2 k g / s = Vo ( X 1 - X 2 )
= 0.2 (0.1 X2)
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X2 = 0.04 mol/min = 0.04 M

To

L o g m e a n d r i v i n g f o rc e =

calculate

the

X1*,

X1 - X 2
X1
ln
X 2

calculate

the

average

c o e ffi c i e n t f r o m e x p e r i m e n t A
K

=0.70 +0.41+0.74
3
K = 0.62
Y1 = 0.06 M
K = Y1
X1*
X1* = 0.097M
X1= ( X2-0)= 0.04 M
X 2 = ( X 1 -X 1 * ) = 0 . 1 - 0 . 0 9 7 = 0 . 0 0 3

Lo g m e a n d r i v i n g f o rc e =
=

(0.04)-(0.003)
ln

0.04
(0.003
)

= 0.0143
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X 1 - X 2
X 1
ln
X 2

distribution

5 M a s s t r a n s f e r c o e ffi c i e n t ( b a s e d o n t h e r a ffi n a t e p h a s e )

Rate of Acid Transfer


Volume of Packing Mean Driving Force
=

0.012

2.36 x0.0143
= 0.3556 kg/min

*using the same way calculate for 0.025 M NaOH

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DISCUSSION

The experiment liquid-liquid extraction was conducted in the purpose


of determining the coefficient distribution, K as well as the mass transfer
coefficient. For that, the experiment was divided into two parts with each
carrying a different objective. The extraction method that was used is based
on the relative principle of solubility where a solution can be separated and
extracted into its individual component.
For first part of the experiment, which is to determine the distribution
of coefficient, titration method is carried out between a solution against 0.1M
Sodium Hydroxide (NaOH). The solution is made up of 50 mL organic solvent
and another 50 mL de-mineralized water that is also added with 5 mL of
propionic acid. The mixture was then shaken for 5 minutes in a stopperenclosed beaker. This step is repeated with an addition of 3 mL and 1 mL of
propionic acid. Due to the immiscibility of both liquids, a two-layer solution
was formed and titration was carried out for both layers. The bottom part is
known the aqueous layer whereas the upper is called as the organic layer.
Titration was carried out until the colour changed from colourless to light
pink where the amount of NaOH used was recorded.
Based on the results, it is shown that with the addition of 5 mL
propionic acid, it took 50 mL and 71 mL of NaOH for the aqueous and organic
layer to change colour respectively. Based on these, the distribution
coefficient, K was calculated to be 0.70. Next, for the addition of 3 mL
propanoic acid, it took 15 mL and 36.8 mL of NaOH for the aqueous and
organic layer respectively with the K calculated to be 0.41. Finally, with 1 mL
addition of propionic acid, the amount of NaOH that was needed was 13 mL
and 17.5 mL for aqueous and organic layer respectively. The mass transfer
coefficient for this trial is 0.74.
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Based on the calculations done for the distribution coefficients, it can


be seen that as the volume of propionic acid added increases, the value of K
decreases. However, for the case of 1 mL propionic acid addition, the value
of K had been gotten as 0.74, which is higher than the other two values. This
is possibly due an error that had occurred during the titration process when
the amount of NaOH titrated was not stopped when the solution turned pink.
This is because the colour change was a sudden process and to get the exact
amount on that point was quite difficult to achieve. Theoretically, the
distribution coefficient K should be inversely proportional to the volume of
the propionic acid whereby the addition of propionic acid will decrease the
value of K.
In the second part of the experiment, which is to determine the mass
transfer coefficient, the liquid-liquid extraction column is used to obtain the
feed, raffinate and extract solution. The flow rate used for the whole
experiment is 0.2 L/min. 15 mL of feed, raffinate and extract solution is
obtained from the liquid extraction column after 15 to 20 minutes the system
is at the steady condition. The samples used in the titration process are 0.1
M and 0.025M of Sodium Hydroxide, NaOH solution. Calculations where then
done based on the data collected to obtain the mass transfer coefficient. For
the sample of 0.1 M NaOH, the propionic acid extracted from organic phase
is 0.04 mol/min and the aqueous phase is 0.012 mol/min. On the other hand,
for the sample of 0.025 M of NaOH, the propionic acid extracted from organic
phase and aqueous phase are 0.03 mol/min and 0.025 mol/min respectively.
Finally, the mass transfer by titration of 0.1M NaOH is calculated to be
0.3556 kg/min meanwhile for the 0.025M NaOH is 0.044 kg/min.

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CONCLUSION

The objective of this experiments are to conduct the experiments regarding


liquid-liquid extraction and to determine the distribution coefficient for the system of organic
solvent-propionic acid-water and show its dependence on concentration. Besides, we are also
demonstrated 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. Based on the
experiment 1, the distribution coefficient for the system recorded is 0.74. It can be seen that as the
volume of propionic acid added increases, the value of K decreases. However, the results does not follow
theoretically which is the distribution coefficient K should be inversely proportional to the volume of the
propionic acid whereby the addition of propionic acid will decrease the value of K. For the second
experiment, the mass transfer by titration of 0.1M NaOH is calculated to be 0.3556 kg/min meanwhile for
the 0.025M NaOH is 0.044 kg/min. In conclusion, both experiments were conducted safely and
successfully except for the some errors during the experiments.

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RECOMMENDATION

From the experiment that we have conducted, there are several recommendations that can
be taken to obtain more accurate results which do not differ much from the theoretical values and
observations. Before starting the experiment, we need to make sure that we have our safety attire
such as lab coat, safety helmet, and fully covered shoes to handle the experiment. We also need
to make sure the unit is checked properly where it is in a good conditions and follow the
procedures properly. If needed, use the medical gloves to avoid any solution in contact with our
hands. During titration, it needs to be made in the fume chamber to avoid us inhaling any toxic
gases and so the gaseous produced is sucked immediately when there is a gas released in a
chemical reaction. Also during titration, make sure the titration is stopped until a light pink
solution is formed to get the accurate result. When taking the reading of the volume of sodium
hydroxide titrated, avoid parallax error by making sure that eyes level is perpendicular with the
scale of the burette.

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REFERENCES

Thermopedia. (2011). Extraction, Liquid-liquid. Retrieved 7 November 2014, from

http://www.thermopedia.com/content/752/
M. Lovric. (2000). Liquid-liquid extraction. Retrieved 7 November 2014, from

http://en.wikipedia.org/wiki/Liquid%E2%80%93liquid_extraction
Chemwiki (2001). Liquid liquid extraction. Retrieved 7 November 2014, from

http://chemwiki.ucdavis.edu/Reference/Lab_Techniques/Liquid-Liquid_Extraction
Organic Chemistry. (2014). Extraction. Retrieved 7 November 2014, from
http://orgchem.colorado.edu/Technique/Procedures/Extraction/Extraction.html

Liquid-Liquid Extraction Theory, Julie Lawson, 2007, Department of Chemical


Engineering Units.

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APPENDIX

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