ABSTRACT / SUMMARY

The goal of this experiment is to understand the behavior of solubility, mass transfer and
diffusion of the solute from one liquid phase to another liquid phase through
liquid-liquid extraction in a packed column. This experiment are separated into
two parts, which is part A and part B. Part A is to determine the distribution
coefficient for the system organic solvent-Propionic acid-water and to show it
dependence on concentration and part B 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 part, mixture of
organic solvent with de-mineralised water that mixture has been separated to the
organic and aqueous layer. Then 10 mL of the organic and aqueous layer has been
titrated with 0.1 M of NaOH with the addition of different amount of propionic
acid which are 1 mL 2 mL and 5 mL. In experiment B, 50 mL sample from feed
(V13), raffinate (V11) and extract (V1) stream are taken. Then 10 mL of feed,
raffinate and extract has been titrated with different amount of NaOH. Which are
0.1 M and 0.025 M . After the calculation, the value of mass

transfer coefficient is 144561. The experiment is conducted and

completed successfully.

INTRODUCTION
Liquid-liquid extraction can be defined as a separation process that requires the removal
of desired solute component using two immiscible liquids of different density. The feed mixture
contains two components which is the solute and the diluent. Solute is the component needed to
be extracted and diluent is its carrier. As the feed enters, the solute will diffuse into another liquid
known as solvent. Later, the solvent carrying the solute comes out as an extract. In the other hand,
the feed without the solute is withdrawn as raffinate. The three major steps involved in this
liquid-liquid extraction process is mixing, phase seperation and withdrawal of phase form the
process unit.
Furthermore, appropriate solvent is required to increase the efficiency of separation
process. Examples of two common immiscible solvents are water-ether and water-hexane. Water

as a non-polar compound plays a vital role in extraction by not mixing with most of the organic
solvents. Furthermore, the extracted solute should not be soluble in water but must be soluble in
organic solvent. For instance, benzene has low solubility in water thus, it it easier to extract it
from water. There are several criterias to be considered before chosing a solvent for liquid-liquid
extraction process. Solvent needs to have high density differences so that it can be seperated
rapidly by gravity. Solvents with low viscosity will help to increase overall mass transfer in the
process. It is also important that the solvent is highly compatible with the solute and carrier. This
is to prevent contamination or any formation of foreign matters, emulsions, and scum layers.
Besides, solvents that are non-toxic, non-flammable and with high flash point promotes a safe
separation system.
Liquid-liquid extraction is widely used in many industries. In general, this process will be
aided by distillation as the extracted product still contain some amount of solvent. Besides, liquidliquid extraction is highly preferred for temperature sensitive products, components with close
boiling point but high solubility differences, seperation based on species type and azeotropeforming mixtures. There are several types of units for this seperation process such as tray column,
packed column, pulsating and agitation. In addition, some of the application of liquid-liquid
extraction process in industries are uranium recovery in nuclear industry, extraction of bitumen
from water in effluent treatmment, extraction of essential oils in pharmeceutical industry and
copper/iron seperation in mining.
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 l e a c h i n g , but there are two major differences which are the carrier phase is a liquid, not a
solid, so the physical 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
In experiment Part A, the objectives are to determine the distribution coefficient for
the system organic solvent propionic acid water as well as to its dependence on
concentration.

Meanwhile, the objectives of experiment Part B are 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 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.[1]
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.

The theory for the system Trichloroethylene-Propionic acid-Water is as follows:

Let;
Vw

: Water flow rate, L/s

Vo

: Trichloroethylene flow rate, L/s

: Propionic acid concentration in the organic phase, kg/L

: Propionic acid concentration in the aqueous phase, kg/L

Subscripts

: 1 : Top of column
: 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)
Therefore theoretically,
Vo(X1X2) = Vw(Y10) ...................(5)

Mass transfer coefficient:

MTC = ......................(6)

( Rate, of , acid , transfer )

(vol.of , packing meandriving , force )

where Log mean driving force : (X1-X2) / ln (X1/X2)

X1 : Driving force at the top of the column = (X2 - 0)
X2 : Driving force at the bottom of the column = (X1-X1*)
where X1* and X2* are the concentrations in the organic phase which would be in equilibrium with
concentrations Y1 and Y2 ( = 0.0) in the aqueous phase, respectively. The
equilibrium values can be found using the distribution coefficient for the chemicals
used (Assume that Y = K X 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 phases, respectively. [2]

APPRATUS
Experiment A

conical flask
measuring

cylinder

separating funnel

Burette

Sodium Hydroxide solution ( 0.1M and

0.025M)

Phenolphthalein
Propionic acid

Experiment B

Extraction
column

Control panel

Product
tank

Feed
tank

PROCEDURE
Experiment Part A
1.

50 ml of trichloroethylene was mixed with 50ml water in conical flask. Then 2ml of
propionic acid was 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.

4.

Each of the bottom and upper samples is titrated against 0.1M NaOH using different amount
of phenolphthalein as the indicator. (5 mL, 3 mL, 1 mL)

Experiment Part B

1.

100mL of propionic acid was 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 was filled with 15 litres of clean demineralised water (the 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 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.

7.

Two or three batches of 30 ml sample are taken from the feed, 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).

REFERENCE
[1]

G e a n k o p l i s , C . J . ( 2 0 0 3 ) . Tra n s p o r t P r o c e s s e s a n d S e p a r a t i o n

Process Principles. (4th edition). Pearson Prentice Hall.

[2]

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

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 .