Liquid Liquid Extraction Experiment

LIQUID LIQUID EXTRACTION
CHE523
ABSTRACT / SUMMARY
I n l i q u i d - l i q u i d e x t r a c t i o n e x p e r i m e n t , i t c o n s i s t s o f t w o p a r t s . F i r s t l y,
to deter mine
the distribution coefficient for the s yste m organic solvent-
Propionic acid-water and to show it dependence on concentration and the

second is to demonstrate how a mass balance is performed on the extraction
column, and to me asure the ma ss transfer coefficient with the aqueous phase as
the continuous medium. In the first part, mixture of organic solvent with demineralised water that mixture has been separated to the organic and aqueous
la yer. Then 10 mL of the organic and aqueous la yer has been titrated with 0.1
M of NaOH. When 5 mL of propionic acid added to the mixture of organic
solvent with de-mi neralised water and titrated with 0.1 M of NaOH, the a mount
o f N a O H u s e d i s 0 . 3 m L f o r o r g a n i c l a ye r a n d 1 . 7 m L f o r a q u e o u s l a y e r . F r o m
the calculation we obtained the value of K is 5.67. When 3mL of propionic acid
is added to the mixture and titrated with 0.1 M NaOH, 2.5mL of NaOH is used
for organic la yer while 14 mL of NaOH is used for aqueous la yer and after
c a l c u l a t i o n w e g e t t h e v a l u e o f K i s 5 . 6 3 . L a s t l y, w h e n 1 m L m L o f p r o p i o n i c
acid added to the mixture and the solution has been titrated with 0.1 M of
NaO H, the a mount of NaO H used is 22.6 mL for organic la yer and 7.9 mL for
aqueous la yer. Then the value of K is 0.35. In experi ment B, 50 mL sa mp le
fro m feed (V13), raffinate (V11) and extract (V1) strea m are taken. Then 10 mL
of feed, raffinate and extract has been titrated with 0.1 M NaOH, the amount of
NaOH that used is 7.2 mL for feed, 3.1 mL for raffinate and 17 mL for extract.
After the calculation, the value of mass transfer coefficient is 144561. The
e x p e r i m e n t i s c o n d u c t e d a n d c o m p l e t e d s u c c e s s f u l l y.
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INTRODUCTION
Liquid-liquid
extraction
(LLE)
is
widely
used
in
chemical,
p e t r o l e u m r e f i n e r y, p h a r m a c e u t i c a l , m i n i n g , a n d t h e n u c l e a r i n d u s t r i e s t o
separate chemicals in liquid mixtures by treating the mixture with an
immiscible solvent in which these components are preferentially soluble.
In some cases purification of a liquid may be the function of the process,
in
others
the
extraction
of
dissolved
component
for
subsequent
p r o c e s s e s m a y b e t h e i m p o r t a n t a s p e c t . An e x a m p l e i s t h e p r e p a r a t i o n o f
t h e p u r e o r g a n i c l i q u i d s f r o m p r o d u c t s o f t h e o i l i n d u s t r y. L i q u i d - l i q u i d
e x t r a c t i o n s m a y a l s o b e u s e d a s e n e r g y s a v i n g p r o c e s s e s b y, f o r e x a m p l e ,
eliminating distillation stages. It is possible, of course that the substance
of
interest
may
be
heat-sensitive
a n yw a y
and
that
distillation
is
accordingly an unacceptable process.
There are a few characteristics that are required in choosing the

solvent for LLE process. First, solvent would preferably completely
dissolve both compounds in the mixture. Second, the solvent selected
must be immiscible with the first solvent. Third, second solvent should
preferentially dissolve only one component of the original mixture.
In liquid-liquid extraction, mixture is dissolved or suspended in the
first solvent and then this solution is introduced to the second solvent. By
shaking the solvent together in an apparatus called a separator funnel, one
component of the mixture will be transferred into the second solvent. This
would leave the other component in the first solvent. Final separation of
two
solvents
is
accomplished
using
separator
funnel,
followed
by
evaporation of solvents, produces the separated components.
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In liquid-liquid extraction, as in gas absorption and distillation, two

phases must be brought into contact to permit transfer of material and
then be separated. Extraction equipment may be operated batchwise 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.
If the components of the original solution distribute differently
between the two liquids, separation will result. The component balances
will be essentially identical to those for leaching, but there are two major
differences which are the carrier phase is a liquid, not a solid, so the
p h ys i c a l
separation
technique
will
change
and
two
distinct
phases
develop, so the simplicity of uniform solution is lost.

Propionic acid is an important commercial product and extracting it
out of aqueous solution is a growing requirement in fermentation based
industries and recovery from waste streams.
OBJECTIVES
1) I n e xper i me nt Par t A, we ne e d to de t er mi ne t he di s tr i but i on c oeffi ci e nt
for the s yste m organic solvent propionic acid water as well as to its
2)
dependence on concentration.
For experi ment in Part B we need to de monstrate how a mass balance is
performed on the extraction column

3) To measure t he mass transfer coeffici ent wi t h t he aqueous phase as t he
continuous mediu m.
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THEORY
In dilute solution at equilibrium, the concentrations of the solute in

the two phases are called the distribution coefficient or distribution
constant K, as describe in the followings:
K = Y/X ..............(1)
where Y is the concentration of the solute in the extract phase whereas X
is the concentration of the solute in raffinate phase. The distribution
coefficient can also be expressed as the weight fraction of the solute in
the two phases in equilibrium contact:
K = y/x ................(2)
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
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.
T h e t h e o r y f o r t h e s y s t e m Tr i c h l o r o e t h y l e n e - P r o p i o n i c a c i d - Wat e r i s a s
follows:
Let
Vw
: Wat e r f l o w r a t e , l t / s
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CHE523
Vo
: Tr i c h l o r o e t h y l e n e f l o w r a t e , l t / s
: Propionic acid concentration in the organic phase, kg/lt
: Propionic acid concentration in the aqueous phase, kg/lt
S u b s c r i p t s : 1 : Top o f c o l u m n
: 2 : Bottom of column
Mass Balance :
Propionic acid extracted from the organic phase (raffinate).
=Vo(X1X2) .................(3)
Propionic acid extracted by the aqueous phase (extract)
=Vw(Y10) ..................(4)
T h e r e f o r e t h e o r e t i c a l l y,
Vo(X1X2) = Vw(Y10) ...................(5)
Mass transfer coefficient:
( Rate of acid transfer ) / (Volume of packing Meandriving force )

......................(6)
MTC =
where Log mean driving force : (X 1-X2) / ln (X1/X2)

X1 : Driving force at the top of the column = (X 2 - 0)
X2 : Driving force at the bottom of the column = (X 1-X1*)
where X1* and X2* are the concentrations in the organic phase which
would be in equilibrium with concentrations Y 1 and Y2 ( = 0.0) in the
a q u e o u s p h a s e , r e s p e c t i v e l y. T h e e q u i l i b r i u m v a l u e s c a n b e f o u n d u s i n g
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CHE523
the distribution coefficient for the chemicals used (Assume that Y=KX
relation holds at equilibrium for a constant K). Rate of acid transfer may
be calculated using Equation (3) or (4) based on raffinate or extract
p h a s e s , r e s p e c t i v e l y.
A P P R A TU S
Experiment A
250 ml conical flask
250 ml measuring cylinder
250 ml separating funnel
Pipette with rubber bulb
S o d i u m H yd r o x i d e s o l u t i o n ( 0 . 1 M a n d 0 . 0 2 5 M )
Phenolphthalein
Propionic acid
Experiment B
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E X P E R I M E N TAL P R O C E D U R E
Experiment Part A
1. 50ml of trichloroethylene is being mixed with 50ml water in conical
flask. Then 2ml of propionic acid is added to the mixture.
2. A stopper is placed and the mixture is shaken for 5 minutes.
3. The mixture is then separated using the separation funnel.
Each of the bottom and upper samples is titrated against 0.1M NaOH
u s i n g p h e n o l p h t h a l e i n a s t h e i n d i c a t o r.
Experiment Part B
1. 100mL of propionic acid are added to 10 litres of trichloroethylene.
The mixture is then filled into the organic phase tank (bottom tank).
2. The level control is switched to the bottom of the column by keeping
the bottom electrodes on (the S2 valve is switched on).
3. The water feed tank is filled with 15 litres of clean demineralised
water (the V13 valve was open). The water feed pump is started
(valve S3) and the flow rate of water is regulated to the maximum
by opening valve C1.
4. The flow rate is reduced to 0.5 litre/min as soon as the water
reaches the top packing.
5. The metering pump (S4) is started.
6. Steady conditions must be achieved by running the set up for 15-20
minutes. The flow rate is monitored during the period to ensure that
they remain constant.
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7 . Two o r t h r e e b a t c h e s o f 3 0 m l s a m p l e a r e t a k e n f r o m t h e f e e d ,
raffinate and extract streams (valve V1).
8. 10 ml of each sample is titrated against 0.025M NaOH using
phenolphthalein as the indicator (to titrate the feed and raffinate
continuous stirring using magnetic stirrer may be needed).
RESULTS
Experi ment A
Titre of M/10
NaOH
Titre of M/10
NaOH
added
(Organic)
(Aqueous)
(mL)
(mL)
(mL)
45.8
Propioni
c acid
Propionic acid
concentration in
organic layer, X
Propionic acid
concentration in
aqueous layer, Y
K = Y/X
87.5
0.916
1.750
1.910
23.2
55.7
0.773
1.857
2.402
1.9
14.8
0.190
1.480
7.789
Experi ment B
Compounds
Volume NaOH needed for titration (ml)

0.1 M
0.025 M
Feed
94.4
33.0
Extract
10.5
39.2
Raffinate
6.2
5.0
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SAMPL E CALC ULATI ON

Experi ment Part A
Calculation of concentration (Organic)
1) Conc e ntr a ti on in Orga ni c La ye r, Y ( 5 ml Pr opi oni c Ac i d)
For mula: M1V1 = M2V2
M1 = Concentration of NaOH ( moles)

V1 =
Vol u m e o f N a O H ( m l )
M2 =
Concentration of Propionic acid ( moles)
V 2 = Vol u m e o f P r o p i o n i c a c i d ( m l )
(0.1)(0.3ml) = M2(5ml)
M1 = 0.006M
(0.1)(2.5ml) = M2(3ml)
M2 = 0.083M

(0.1)(22.6ml) = M2(1ml)
M2 = 2.26M
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CHE523
Calculation of concentration (Aqueous)
1) Conc e nt r at i on i n Aque ous La ye r, X (5 ml Pr opi oni c Ac i d)

(0.1)(1.7ml) = M2(5ml)
M1 = 0.034M
(0.1)(14ml) = M2(3ml)
M2 = 0.467M
(0.1)(7.9ml) = M2(1ml)
M1 = 0.79M
Calculation of Distribution Coefficient, K :
1) Di s t ri buti on c oe ffic i e nt ( 5 ml Pr opi oni c Ac i d)
For mula:
K = Concentration of the solute in the extract phase, Y

Concentration of the solute in the raffinate phase, X
K = 0.034M
0.006M
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CHE523
K = 5.67
For mula:

K = 0.467M
0.083M
K = 5.63
For mula:

K = 0.79M
2.26M
K = 0.35
Experi ment Part B
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Conc e nt ra t i on of Pr opi oni c Aci d at fe e d:
Formula: M1V1 = M2V2
M1 = Concentration of NaOH (moles)

V1 =
Vol u m e o f N a O H ( m L )
M2 =
Concentration of propionic acid ( moles)
V 2 = Vol u m e o f p r o p i o n i c a c i d ( m l )
(0.1)(7.2ml) = M2(10ml)
M2 = 0.072M
Conc e nt ra t i on of Pr opi oni c Aci d at Ra ffi nat e

Formula: M1V1 = M2V2
(0.1)(3.1ml) = M2(10ml)
M2 = 0.031M
Conc e nt ra t i on of Pr opi oni c Aci d at Ext r a ct

(0.1)(17ml) = M2(10ml)
M2 = 0.17M
The flow rate of aqueous and organic phase = 0.0033 L/s
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CHE523
Mass Balance:
Pr opi oni c Aci d e xt r a ct e d f r o m the orga ni c pha s e ( ra ffi na t e)
= Vo ( X 1 - X 2 )
= 0.0033 (0.072 0.0031)
= 0.000135 kg/s
Pr opi oni c Aci d e xt r a ct e d b y t he a que ous pha s e ( e xt r ac t )

= Vw (Y1 - 0)
= 0.0033 (0.17 - 0)
= 0.000561 kg/s
To cal cul at e
the
X1*,
calculate
the
average
distribution
coefficient
from
experiment A
K = 5.67 + 5.63 + 0.35

3
K = 3.883
K = Y1
X1*
3.883 = 0.17
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X1*
X1* = 0.0438
X1 - X 2
X1
ln
X 2
Log mean driving force =
= (0.0031)-(0.072 0.0438)
ln
0.0031
(0.0720.0438
)
= 0.0114
Mass transfer coefficient (based on the raffinate phase)
Rate of Acid Transfer

Volume of Packing Mean Driving Force
=
=
3.883
( 50 x 103 ) x 1.2
4
x 0.0114
= 144561
DISCUSSION
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CHE523
This experiment is conducted basically to achieve the main objectives
which are to determine the distribution coefficient and therefore the mass
transfer coefficient, which is based on the concentration of the solvent.
As
what
has
been
practised
in
the
experiment,
the
mixture
of
t r i c h l o r o e t h yl e n e - p r o p a n o i c a c i d - w a t e r i s s e p a r a t e d b y u s i n g s e p a r a t o r f u n n e l .
When a compound is shaken in a separator funnel with two i mmiscible
solvents, the compound will distribute itself between the two solvents. The
upper la yer contains mo re water and the botto m la yer contains more propanoic
acid as water is denser than the solvent.
Regarding the result, we can see the decrease in distribution coefficient
when the a mount of solvent added is decreasing. This shows that the greater
the amount of solvent added, the higher the increase in distribution coefficient.
Nevertheless, there mi ght be some errors that happened during the
experiment. First, errors might be done while taking the reading of the burette.
S u p p o s e d l y, t h e e ye o f t h e o b s e r v e r s h o u l d b e p a r a l l e l t o t h e m e n i s c u s l e v e l .
Likewise, it is preferable to put a white paper just behind the level in order to
aid in reading the meniscus. Therefore, a different reading will lead to
different values of calculation from the correct one.
Second, all of the instrume nts used during this experi ment mi ght not be
h a n d l e d p r o p e r l y. S i n c e t h e q u a n t i t y o f t h e m e a s u r i n g i n s t r u m e n t s i s l i m i t e d ,
the me mbers of the group needed to wash all the me asuring c ylinders required
to perform the titration. Therefore, the added solutions are inevitably mixed
with the water left after being washed. This ma y also lead to some errors in the
calculations.
CONCLUSION
T h e m a i n o b j e c t i v e s o f t h i s e x p e r i m e n t a r e a c h i e v e d s u c c e s s f u l l y, w h e r e
the distribution coefficient for solution with 5mL, 3mL and 1mL of propanoic
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a c i d a d d e d a r e 5 . 6 7 , 5 . 6 3 a n d 0 . 3 5 r e s p e c t i v e l y. L i k e w i s e , t h e m a s s t r a n s f e r
coefficient is 144561. From experiment B, the concentration of propanoic acid
a ppe ar s to be t he hi ghes t i n ext ra c t pha s e. Fr o m e xpe r i me nt A, t he di st ri but i on
coefficient value increases as the volume of propanoic acid added as an
extracting solvent is increased.
R E C O M M E N D ATI O N S
There are some recommendations to make sure this experiment
would attain more accurate and precise results in the future:
Make sure the apparatus are in good condition before conducting the
experiment.
All the color change after the titration should approximately about
t h e s a m e c o l o r o n e a c h o t h e r.
Be concerned with the eyes should always be at the same level when
taking the reading of pipette and burette.
For Experiment A and B can be repeated on titration with 0.025M

NaOH.
References
http://en.wikipedia.org/wiki/Liquid-liquid_extraction
h t t p : / / w w w.c h e r e s o u r c e s . c o m / e x t r a c t i o n . s h t m l
G e a n k o p l i s , C . J . ( 2 0 0 3 ) . T ra n s p o r t P r o c e s s e s a n d
Process Principles. (4th edition). Pearson Prentice Hall.

M c C a b e , W. L . , a n d J . C . S m i t h , ( 1 9 5 6 ) . U n i t O p e r a t i o n s o f
Separation
C h e m i c a l E n g i n e e r i n g . N e w Yor k : M c G r a w - H i l l C o m p a n i e s .
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APPENDICES
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Liquid Liquid Extraction Experiment

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LIQUID LIQUID EXTRACTION

the distribution coefficient for the s yste m organic solvent-

Propionic acid-water and to show it dependence on concentration and the