ABSTRACT

Liquid-liquid extraction is a very important separation technology for a wide range of

applications in the chemical process industries (CPI). Liquid-liquid extraction is the process
when the two phases are liquid, where a solute or solutes are being removed from one liquid
phase to another liquid phase. The objectives of this experiment are to conduct the simple
experiments regarding liquid-liquid extraction, to determine the distribution coefficient for the
system organic solvent-propionic acid water and show its dependence on concentration and 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. This experiment is
divided into two parts. For the first part, water and organic solvent is mixed with different
volume of propionic acid. Two layers are formed. Sample from each layers are taken and added
with phenolphthalein. After that, it is titrated with NaOH. For the second part, sample is taken
from Liquid-liquid extraction unit UOP5 for feed, raffinate and extract. Phenolphthalein is added
to the samples. After that, it is titrated with different molarity of NaOH. For both parts, the
volume of NaOH needed for the mixture to turns pinkish-purple colour is recorded for further
calculation.

INTRODUCTION
Liquid-liquid extraction is a very important separation technology for a wide range of
applications in the chemical process industries (CPI). Unlike distillation, which is based on
boiling point differences, extraction separates components based on their relative solubilities in
two immiscible liquids. Extraction is typically chosen over distillation for separation applications
that would not be cost-effective, or even possible, with distillation.
Liquid-liquid extraction is the process when the two phases are liquid, where a solute or
solutes are being removed from one liquid phase to another liquid phase. Liquidliquid
extraction also known as solvent extraction and partitioning, is a method to separate compounds
based on their relative solubilities in two different immiscible liquids, usually water and an
organic solvent. It is an extraction of a substance from one liquid into another liquid phase.
Liquidliquid extraction is a basic technique in chemical laboratories, where it is performed
1

using a variety of apparatus, from separatory funnels to countercurrent distribution equipment.

Liquidliquid extraction (LLE) consists in 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.
In a liquid-liquid extraction unit, a liquid stream (carrier) containing the component(s) to
be recovered (solute) is fed into an extractor, where it contacts a solvent. The two liquids must be
immiscible or only slightly miscible; this allows them to form a dispersion, with one liquid
dispersed as droplets in the other.
Mass transfer occurs between the droplets (dispersed phase) and the surrounding liquid
(continuous phase). In order for the two liquids to be subsequently separated, they must have
different densities. The droplets then accumulate above or below the continuous phase,
depending on the liquids relative densities. The boundary between the continuous phase and the
droplet dispersion is referred to as the interface, and can be at the top or bottom of the extraction
column.

Figure 1: Illustrates the general concept of liquid-liquid extraction.

Extraction is typically carried out in continuous, staged units, which can be operated in
either of two modes: with co-current mixing or with counter-current mixing. The co-current
2

mixing mode is generally limited to one theoretical stage per extraction unit, whereas countercurrent mixing is amenable to multiple stages per unit. For this reason, counter-current mixing is
usually preferred over co-current mixing.
Counter-current extractors can be arranged in one of two ways (Figure 2), the choice of
which depends on the density of the solvent relative to that of the solute carrier. If the solvent is
less-dense than the carrier liquid, the solvent is fed into the bottom of the column, the solute is
carried upward to the top of the extractor, and the carrier liquid is removed from the bottom of
the unit (Figure 2, left). If the solvent is more-dense than the carrier liquid, the solvent is fed into
the top of the column, the solute is carried downward to the bottom of the extractor, and the
carrier stream is removed from the top (Figure 2, right).

Figure 2: Counter-current extraction units can be set up in one of two ways. Left: When the solvent
is lighter than the carrier liquid, the solvent is introduced at the bottom of the column and the solute
is carried up toward the top of the extractor. Right: When the solvent is heavier than the carrier, the
solvent is introduced at the top of the column and the solute is carried downward by the solvent toward
the bottom of the column.

OBJECTIVES
The objectives of this experiment:
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) 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
A mixture was brought into contact with another phase in order to separate one or more
of the components in the mixture. Liquid-liquid extraction was considered as one of the
separation method. By taking advantage of a solubility differential of the substance in different
solvents, liquid-liquid extraction technique was used to purify impure substances. Two different
solvent were mixed together with the impure sample and one of them was referred to as the
extracting solvent. There would be partition between the solvents since the sample was soluble in
both solvent. The final ratio of the concentrations of the sample in the two solvents was
determined by its distribution (or partition) coefficient K.
A quantitative measure of the how an organic compound would be distributed between
aqueous and organic phases was called the distribution coefficient or distribution constant, K
described as:
K=

Y
X

where Y was the concentration of the solute in the extract phase (extracting solvent) whereas X
was the concentration of the solute in raffinate phase (original solvent). The greater the
concentration of sample in the extracting solvent, the higher the distribution coefficient would be
that lead to more efficient of extraction. The molecules would naturally distribute themselves in
4

the solvent where they were more soluble once the system reached equilibrium. Inorganic and
water soluble materials would stay in the water layer and more organic molecules would remain
in the organic layer.
As for trichloroethylene-propionic acid-water system using the liquid-liquid extraction
unit UOP5, their mass balances were as followed:
Propionic acid extracted from organic phase (raffinate) = V0(X1 X2)
Propionic acid extracted by aqueous phase (extract) = Vw(Y1 0)
Theoretically,

V0(X1 X2) = Vw(Y1 0)

where Vw: water flow rate, L/s, V0: trichloroethylene flow rate, L/s, X: propionic acid
concentration in the organic phase, kg/L, Y: propionic acid concentration in the aqueous phase,
kg/L, and the subscript 1 for top of column while 2 for bottom of column.

Mass transfer coefficient:

MTC=

Rate of acid transfer

volume of packing mean driving force

where log mean driving force, x 1 : driving force at top of column = (X2 - 0)
x 2 : driving force at bottom of column = (X X *)
1
1

x 1 x 2
x1
(
)
x2

X1* and X2* were the concentrations in the organic phase that would be in equilibrium with
concentrations Y1 and Y2 in the aqueous phase.

APPARATUS AND MATERIAL

1. 250 mL conical flask

2. 50 mL measuring cylinder
3. 10 mL measuring cylinder

4. 250 mL separating funnel

5. 50 mL burette

6. Liquid-liquid extraction unit UOP5

7. Trichloroethylene
8. Sodium Hydroxide solution ( 0.1 M and 0.025 M)
9. Phenolphthalein
10. Propionic acid
11. Water

PROCEDURE
Experiment Part A
1.
2.
3.
4.
5.

50 mL of trichloroethylene and 50 mL of water were added and mixed in a conical flask.

5 mL of propionic acid was then added to the mixture.
A stopper was placed and the mixture was shake for 5 minutes.
The mixture was then poured into a separating funnel and was let to form layer of liquid.
Each of the bottom and upper samples were titrated against 0.1 M NaOH using three

drops of phenolphthalein as the indicator.

6. Record the value of titration needed to change the colour of mixture to light pink.
7. Steps 1 to 6 were repeated for 3 mL and 1 mL of propionic acid added into the mixture.
Experiment Part B
1. 100 mL of propionic acid was added to 10 L of trichloroethylene. The mixture was then
filled into the organic phase tank (bottom tank).
2. The level control was switched to the bottom of the column by keeping the bottom
electrodes on (S2 valve was switched on).
3. The water feed tank was filled with 15 L of clean demineralized water (V13 valve was
open). The water feed pump was started (valve S3) and the flow rate of water was
regulated to the maximum by opening valve C1.
4. The flow rate was reduced to 0.5 L/min as the water reached the top packing.
5. The metering pump (S4) was started.
6. A steady condition was achieved by running the set up for 15-20 minutes. The flow rate
was monitored during the period to ensure that it remain constant.
7. Two or three batches of 30 mL sample were taken from the feed, raffinate and extract
stream (valve V1).
8. 10 mL of each sample was titrated against 0.025 M NaOH using phenolphthalein as the
indicator (to titrate the feed and raffinate, continuous stirring using magnetic stirrer would
be needed).

RESULT AND CALCULATION

EXPERIMENT A
Concentration of
NaOH (M)
Concentration
of
NaOH0.1
(M)

Volume of propionic
Numbers acid (mL)
of titration
1
2
3
Average
1
2
3
Average

0.025

0.1

5.0
3.0
1.0

Feed
8.5
8.6
9.0
8.7
3.5
2.5
3.0
3.0

Volume of NaOH titrated (mL)

Volume of NaOH titrated (mL)
Upper
Bottom
80
42.5
Extract
Raffinate
50
21
36 3.4
65
10.9
3.0
11.5
3.5
10.6
3.3
11.0
0.6
5.6
0.8
5.4
0.7
4.5
0.7
5.17

EXPERIMENT B

CALCULATIONS
Formula:
Finding distribution coefficient:
K = Y/X
Where Y: concentration of solute in extract phase
9

X: concentration of solute in raffinate phase

Finding mass transfer coefficient:
1

2
3
4
5
6

M1V1 = M2V2
Where; M1 concentration of NaOH
M2 concentration of propionic acid
V1 volume of NaOH
V2 volume of propionic acid
Rate of acid transfer = VW (Y1 - 0)
V0 (X1 - X2) = VW (Y1 - 0)
K = Y1 / X*
Log mean drive force = (X1 - X2) / ln (X1 / X2)
Where; X1 driving force at the top of the column = (X2 - 0)
X2 driving force at the bottom of the column = (X1 - X*1)
Packing dimension: Length = 1.2m
Diameter = 0.05m
Therefore, packing volume, V = r2L
= 2.36 10-3m3
= 2.36L

Mass transfer coefficient =

Rate of acid transfer

(Volume of packing mean driving force)

Finding the distribution coefficient:

For 0.1M of NaOH
1

1.0 ml of propionic acid

Upper (Y):
M1V1 = M2V2
(0.1)(0.036) = M2 (0.001)
M2 = 3.6 M

Bottom (X):
M1V1 = M2V2
(0.1)(0.065) = M2 (0.001)
M2 = 6.5 M

K = Y/X
= 3.6 M / 6.5 M
= 0.55
2

3.0 ml of propionic acid

Upper (Y):
M1V1 = M2V2

Bottom (X):
M1V1 = M2V2
10

(0.1)(0.05) = M2 (0.003)
M2 = 1.667 M

(0.1)(0.021) = M2 (0.003)
M2 = 0.7 M

K = Y/X
= 1.667 M / 0.7 M
= 2.38
3

5.0 ml of propionic acid

Upper (Y):
M1V1 = M2V2
(0.1)(0.08) = M2 (0.005)
M2 = 1.6 M

Bottom (X):
M1V1 = M2V2
(0.1)(0.0425) = M2 (0.005)
M2 = 0.85 M

K = Y/X
= 1.6 M / 0.85 M
= 1.88

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Finding the mass transfer coefficient:

For 0.1M of NaOH
Raffinate:
M1V1 = M2V2
(0.1)(0.00517) = M2 (0.01)
M2 = 0.0517 M of propionic acid . (X1)
Feed:
M1V1 = M2V2
(0.1)(0.003) = M2 (0.01)
M2 = 0.03 M of propionic acid
Extract:
M1V1 = M2V2
(0.1)(0.0007) = M2 (0.01)
M2 = 0.007 M of propionic acid . (Y1)

Rate of acid transfer = VW (Y1 - 0)

= 0.2 L/min (0.007 mol/L)
= 0.0014 mol/min

V0 (X1 - X2) = VW (Y1 - 0)

0.2 L/min (0.0517 mol/min X2) = 0.0014 mol/min
X2 = 0.0447 M
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Log mean drive force = (X1 - X2) / ln (X1 / X2)

X1 = (X2 0)
= 0.0447 M
K = Y1 / X*

at equilibrium, assume R = 1.47 (from experiment A)

X* = Y1 / K
= 0.007 / 0.55
= 0.0127 M
X2 = (X1 X*1)
= (0.0517 M 0.0127 M)
= 0.039
Log mean drive force = (0.0447 0.039) / ln (0.0447 / 0.039)
= 0.0419
Mass transfer coefficient =

Rate of acid transfer

(Volume of packing mean driving force)
=

0.0014 mol/min
2.36 L 0.0419

= 0.014 mol/L.min
= 0.014 M/min
= 0.014 kg/min

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DISCUSSION
Liquid-liquid extraction is process which is used to separate chemicals in liquid mixture by
adding immiscible solvent. The aim of this experiment is to determine the distribution coefficient
and the mass transfer coefficient. In the first experiment, the mixture of trichloroethylenepropionic acid-water is separated by using separator funnel. Most extractions will involve water
because it is highly polar and immiscible with most organic solvent. The chemicals is shake for 5
minutes to make sure the two solutions is in contact which each other to allow solute to be
extracted into the second layer. After the mixing is done, the mixture will be pour into separator
funnel and split into two layers. The densities of the solvent will predict which solvent is the
upper or lower layer (Lewis, 2007). Since water is denser than propionic acid, it forms two layers
which the upper layer contains propionic acid meanwhile the bottom layer contains water.
From the experiment, the value of upper layer concentration when 5.0 ml and 3.0 ml of
propionic acid is added is larger than the value of lower layer concentration except for 1.0 ml of
propionic acid. The distribution coefficient, K is calculated by divided the concentration solute in
extract phase with concentration solute in raffinate phase. The concentration of sodium
hydroxide used to titrate the upper and lower layer is 0.1M. The distribution coefficient when 5.0
ml, 3,0 ml and 1.0ml of propionic acid is added is 1.88, 2.38 and 0.55 respectively. It can be said
that the distribution coefficient from 5.0 ml to 1.0 ml of propionic acid is not consistent; it
increased at 3.0 ml of propionic acid and then decreased. 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
(Lewis, 2007). Which in this experiment, from the calculated distribution coefficient and for
volume of propionic acid of 5.0 ml and 3.0 ml, the solute is mostly in organic solvent meanwhile
for volume of 1.0 ml, the solute is mostly in water.
In experiment B, the feed, extract and raffinate are obtained from liquid-liquid extraction
column. From this information, we can calculate the mass transfer coefficient. The sample then is
titrated with 0.1 M and 0.025M NaOH. The mass transfer coefficient value when titrated with
0.1M is 0.014kg/min meanwhile for 0.025 M NaOH, the value cannot be calculated as the
distribution coefficient for 0.025M cannot be obtained because experiment A is not repeat using
0.025M of NaOH.
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CONCLUSION
From the experiment A, the distribution coefficient calculated from the concentration solute in
extract and raffinate for each different value of propionic acid; 5.0 ml, 3.0ml and 1.0 ml is 1.88,
2.38 and 0.55 respectively. The solute is mostly in organic solvent for value of propionic acid;
5.0 ml, 3.0ml meanwhile for volume of 1.0 ml, the solute is mostly in water. The mass transfer
coefficient for 0.1M is 0.014kg/min. The mass transfer coefficient will differ according to the
concentration of NaOH used. In conclusion, the main objective of this experiment to determine
the distribution coefficient and mass transfer coefficient are achieved successfully.
RECOMMENDATION:
1

Make sure the colour change after the titration should approximately about the same

colour on each other.

Make sure the eyes are perpendicular with the meniscus of the burrete when taking

3
4
5
6

reading.
Make sure to rinse all the apparatus before used it repeatly with another substance.
Make sure to use the correct concentration of sodium hydroxide when titrate.
Repeat the experiment at least 3 times to get an accurate value.
Make sure to wear appropriate personal protective equipment (PPE) when conducting the
experiment.

REFERENCES
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Lewis, R. J. (2007). Liquid-liquid Extraction. PreLab, 7392.

doi:10.1002/9780470114735.hawley09899
Anonymous (2012). Liquid/ Liquid Extraction Unit (UOP5). Retrieved April 26, 2016 from
https://eng.najah.edu/apparatus/2381
Design

principles

of

liquid-liquid

extractions.

Retrieved

April

28,

2016

from

http://www.aiche.org/resources/publications/cep/2015/november/design-principles-liquid-liquidextraction.
Geankoplis, C.J. (2014). Transport Processes & Separation Process Principle (includes unit
operations). Pearson Education Limited.

APPENDIX
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