LIQUID-LIQUID EXTRACTION

(EFFECT OF PHASE RATIO)

Abstract
A model is constructed in this work to separate acetic acid from aqueous solution using
liquidliquid extraction and to determine the optimum phase ratio (Solvent to Aqueous phase;
S/A) necessary for this separation. Different ratios of Ethyl Acetate and Aqueous Acetic
Acid are used in this procedure. This method will assist us in the design of a process that will
aid in the computation of flow rates for various streams in a continuous separation process.

Aim
o To study the effect of phase ratio on the extraction of Acetic acid (dispersed phase) by

Ethyl acetate (Continuous phase). o To establish equilibrium isotherm between the

concentration of Acetic acid and Ethyl acetate.

Theory
Liquid - liquid extraction, sometimes call solvent extraction, is the separation of the
constituents of a liquid solution by contact with another insoluble liquid. If the substances
constituting the original solution distributes themselves differently between the two liquid
phase a certain degree of separation will results and this can be enhances by use of multiple
contact or their equivalent in the manner of gas absorption and distillation.

Extraction equipment may be operated batch wise or continuously. A quantity oil feed liquid
may be mixed with a quantity of solvent in an agitated vessel (separating funnel), after which
a layer are settled and separated. 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 the top of the
equipment in some cases and from the bottom in others. The operation may 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. Figure shows the separating

1
funnel used in liquid - liquid extraction process to separate the components of a mixture into
two immiscible solvent phases of different densities.

Fig.1 Separating Funnel

Utilities Required
Beaker, Burette, Funnel, Separating funnel, Distilled Water, 15% Acetic Acid solution, Ethyl
Acetate, Phenolphthalein, 1 N NaOH solution, Stopwatch.

Experimental Procedure
o Experiments were performed for the extraction of acetic acid in toluene by using

ethyl acetate at different S/A ratio and extraction time was kept constant for 15min.

o Take a known amount (volume) of Ethyl Acetate having initial concentration C i and

keep it in the separating funnel. o Take same amount of ethyl acetate and mix it with

the acetic acid solution in the same separating funnel. o Mix it thoroughly for 2 min.

o Keep the separating funnel on the stand for the separation of two different layers.

2
 o Lower layer (extract) is separated from the raffinate and 10 ml of the sample is taken

for titration.
o Titrate the sample with 1N NaOH with phenolphthalein indicator.

o Repeat the experiment for different S/A ratio.

Extraction Isotherm
Extraction isotherm was plotted by assuming perfect equilibrium between the raffinate and
extract phase at each stage. Figure shows the systematic of the stage wise batch extraction
stream “S” (solvent) and “A” (aqueous) are mixed for the sufficient time with S/A ratio “r”.
Initial and final concentration of solvent is S1 and S2 and that of aqueous is A1 and A2.
Equilibrium concentration S2 and A2 are related as,

It can be noted that here A1 = 0.

Fig.2

3
Observation and Calculation

Observation:
Case-1: 100 mL Ethyl Acetate + 100 mL Acetic Acid solution

Case-2: 100 mL Ethyl Acetate + 200 mL Acetic Acid solution

Case-3: 200 mL Ethyl Acetate + 100 mL Acetic Acid solution

Observation Table

Volume Volume Volume

Volume Phase Burette
Sr. of Time of of Sample
of feed ratio Reading
No solvent (min) extract Raffinate (ml)
(ml) (S/A) (ml)
(ml) (ml) (ml)
19.8
1 100 100 1:1 110 90 20.7
21
20.8
2 200 100 1:2 15 92 208 10 20.5
20.8
14.1
3 100 200 2:1 235 65 13.3
13.9

Calculations
VR = Volume of Raffinate
S = Volume of Sample
V2 = Burette Reading
N1= Normality of Sample. N2=
Normality of NaOH = 1N
V1= Volume of sample.

Case: 1

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(PR = 1:1)

N1 V1 = N2 V2

N1= (1*20.5)/10 = 2.05 N

Mass of Acetic acid in Raffinate = (N1*VR*mol. Wt.)/1000

= (2.05*90*60)/1000 = 11.07 gm.

Mass of Acetic acid in Extract = 15.75 – 11.07 = 4.68 gm.

Case: 2

(PR = 1:2)

N1 V1 = N2 V2

N1= (1*20.7)/10 = 2.07 N

Mass of Acetic acid in Raffinate = (N1*VR*mol. Wt.)/1000

=
(2.07*208*60)/1000 = 25.83 gm.

Mass of Acetic acid in Extract = 31.5 – 25.83 = 5.67 gm.

Case: 3

(PR = 2:1)

N1 V1 = N2 V2

N1= (1*13.77)/10 = 1.377 N

Mass of Acetic acid in Raffinate = (N1*VR*mol. Wt.)/1000

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= (1.377*65*60)/1000 = 5.34 gm.

Mass of Acetic acid in Extract = 15.75 – 5.34 = 10.41 gm.

Result and Discussion

Sr. no. Phase ratio % Extraction

1 1:1 29.71
2 1:2 18
3 2:1 66.1

From the above observations we may conclude that, the percentage extraction increases with
the increase in the value of phase ratio.

Precautions
o Do not keep the stopper inserted in after shaking the mixture inside separating funnel.

Stopper might shoot open because of the generated vapor pressure of Ethyl acetate.
o Handle all glassware carefully.

6
7
 LIQUID-LIQUID EXTRACTION
(EFFECT OF TIME)

Abstract
Liquid-Liquid Extraction (LLE) is an important method to separate constituents (solutes) of
homogeneous liquid solutions. In this separation process, second liquid solvent is added
which is immiscible or partially miscible with the feed and the solutes of the mixture are
distributed between the two phases. A quantitative measure of the how a component will
distribute between the two phases is called the distribution or partition coefficient.
Distribution coefficient is the ratio of the concentrations of the solute in the two different
solvents when the system reaches equilibrium.

Aim
To determine the effect of time on extraction efficiency and find out the optimum time for
maximum percentage extraction.

Theory
Liquid - liquid extraction, sometimes call solvent extraction, is the separation of the
constituents of a liquid solution by contact with another insoluble liquid. If the substances
constituting the original solution distributes themselves differently between the two liquid
phase a certain degree of separation will results and this can be enhances by use of multiple
contact or their equivalent in the manner of gas absorption and distillation.

Extraction equipment may be operated batch wise or continuously. A quantity oil feed liquid
may be mixed with a quantity of solvent in an agitated vessel (separating funnel), after which
a layer are settled and separated. 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 the top of the
equipment in some cases and from the bottom in others. The operation may be repeated if
more than one contact is required but when the quantities involved are large and several

8
contacts are needed, continuous flow becomes economical. Figure shows the separating
funnel used in liquid - liquid extraction process to separate the components of a mixture into
two immiscible solvent phases of different densities.

Utilities Required
Beaker, Burette, Funnel, Separating funnel, Distilled Water, 15% Acetic Acid solution, Ethyl
Acetate, Phenolphthalein, 1 N NaOH solution, Stopwatch.

Experimental Procedure o Experiments were performed to find out optimum time

required for maximum extraction percentage in extraction of acetic acid by using ethyl
acetate at equal volume ratio.
o Take a known amount (volume) of Ethyl Acetate having initial concentration Ci and

keep it in the separating funnel. o Take same amount of ethyl acetate and mix it with

the acetic acid solution in the same separating funnel. o Mix it thoroughly for 2 min.

o Keep the separating funnel on the stand for the separation of two different layers. o

Lower layer (extract) is separated from the raffinate and 10 ml of the sample is taken
for titration.
o Titrate the sample with 1N NaOH with phenolphthalein indicator.

9
 o Repeat the experiment for different mixing time.

Material balance
Figure shows the systematic of the stage wise batch extraction stream “S” (solvent) and “A”
(aqueous) are mixed for the sufficient time with S/A ratio “r”. Initial and final concentration
of solvent is S1 and S2 and that of aqueous is A1 and A2. Equilibrium concentration S2 and A2
are related as,

It can be noted that here A1 = 0.

Fig.2

Observation and Calculation

Observation Table

Sr. Volume Volume Phase Time Volume Volume of Sample Burette

No of feed of ratio (min) of Raffinate (ml) Reading
(ml) solvent (S/A) extract (ml) (ml)
(ml) (ml)
1 100 100 1:1 5 105 95 10 22.5

10
 2 100 100 15 110 90 18.5
3 100 100 60 112 88 19.5

Calculations
VR = Volume of Raffinate
S = Volume of Sample
V2 = Burette Reading
N1= Normality of Sample.
N2= Normality of NaOH =
1N
V1= Volume of sample.

Case: 1

(t = 5 min)

N1 V1 = N2 V2

N1= (1*22.5)/10 = 2.25 N

Mass of Acetic acid in Raffinate = (N1*VR*mol. Wt.)/1000

= (2.25*95*60)/1000 = 12.82 gm.

Mass of Acetic acid in Extract = 15.75 – 12.82 = 2.93 gm.

Case: 2

(t = 15 min)

N1 V1 = N2 V2

N1= (1*18.5)/10 = 1.85 N

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Mass of Acetic acid in Raffinate = (N1*VR*mol. Wt.)/1000

= (1.85*90*60)/1000 = 9.99 gm.

Mass of Acetic acid in Extract = 15.75 – 9.99 = 5.76 gm.

Case: 3

(t = 60 min)

N1 V1 = N2 V2

N1= (1*19.5)/10 = 1.95 N

Mass of Acetic acid in Raffinate = (N1*VR*mol. Wt.)/1000

= (1.95*88*60)/1000 = 10.29 gm.

Mass of Acetic acid in Extract = 15.75 – 10.29 = 5.46 gm.

Result and Discussion

Sr. no. Time (min) % Extraction

1 5 18.61
2 15 36.57
3 60 34.66

From the above observations we may conclude that, the percentage extraction increases with
the increase in the settling time.

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Precautions
o Do not keep the stopper inserted in after shaking the mixture inside separating funnel.

Stopper might shoot open because of the generated vapor pressure of Ethyl acetate.
o Handle all glassware carefully.

SOLID-LIQUID EXTRACTION

13
Aim
To study solid liquid extraction in batch process and hence find out the effect of solvent
temperature on the percentage recovery of oil from oil seeds.

Theory
Leaching is method of extraction a desired chemical that is dispersed or dissolved in a solid.
The solid is ground up into small pieces and wasted with a solvent in which the desired
chemical is soluble. Sometimes the solid and solvent from slurry that can be conveyed easily.
In any event the desired chemical is transferred from the solid to the liquid phase. The
resultant liquid, which is rich in the desired chemical is filtered to remove fine suspended
grains of the solid. The liquid can then be distilled of otherwise purified.
The laboratory experiment uses simple equipment to explore a leaching operation that is
familiar to all of us the extraction of oil from seeds using hexane as the leaching solvent.
Some of the parameters affecting the leaching efficiency

are o Extraction time o Extraction temperature o Size

of the solid particles o Type and amount of solvent

used

Utilities Required

Hot plate, Beaker, Thermometer, Hexane, Oilseed, Oven, Weighing balance.

Experimental Procedure
o Leaching process was studied for the extraction of oil from the cotton seed

oil using hexane as the solvent. o 500ml of Hexane is taken in a beaker and

raised to predetermined temperature.

o Note down the temperature o Add known weight of cotton seed oil in a

beaker. Mix the sample for 30 min.

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 o Filter the mixture and keep the solid material for drying in an oven. o After

drying sample was weighted. o Repeat the experiment for different

temperature.

Observation and Calculation

Observation:
Density of seed oil: 0.933 g/cm3
Oil extracted: 17.43 ml (1st run)
18 ml (2nd run)

Observation Table

Initial Volume Initial Final

of Solvent (ml) wt. of oilseed wt. of oilseed
Sr. No. T (º C)
(g) (g)
1 65 150 50 31.2
2 68 150 50 30.7

Calculations

For T=65°C

For T=68°C

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Result and Discussion
SI. No T (º C) % extraction
1 65 37.6
2 68 38.6

From the above obtained results we can conclude that the percentage extraction increases
with the increase in temperature.

Precautions
o Always use the fresh oilseed.

o Hexane should be oil free or not used. o Proper cleaning should be

necessary for the set up.

ADSORPTION

16
Aim
The aim of this experiment is to study the adsorption of acetic acid by solid adsorbent
activated carbon and then test the validity of certain adsorption isotherm.

Theory
Adsorption is a process that uses special solids to remove substances from either gaseous or
liquid mixtures. It is an industrially important process occurs with the attachment of the gas
particles onto a solid surface. The special solids that gas or liquid particles attached are
called adsorbent. The substances adsorbed are called adsorbate. Adsorption is a
phenomenon occurs at the surface; the molecules are taken up by the surface. It should not
be confused with absorption. Adsorption and absorption are two different processes: the
molecules are taken up by the volume in absorption, not by surface i.e. the solute is dissolved
in the bulk material in absorption. Adsorption can be classified into two different groups
depending on the type interaction between the adsorbed molecule and the solid surface.

o Physisorption: Physisorption is caused mainly by intermolecular forces (Van der

Waals) and electrostatic forces between adsorbate molecule and the atoms which
compose adsorbent surface. It will occur when the intermolecular attractive forces
between and adsorbent and adsorbate are greater than those existing between
molecules of the adsorbate itself.

o Chemisorption: Chemisorption is the result of chemical interaction between

adsorbate and adsorbent. The adsorbate sticks to the solid by the formation of a
chemical with the surface. This interaction is much stronger than Physisorption.
Unlike in Physisorption only monolayer adsorption is observed.

Activated carbon is basically amorphous carbon based material exhibiting a high degree of
porosity and inter-particulate surface area. Large surface area of activated carbon provides
excellent adsorbent characteristics. The surface area per gram of material can range 500 to
2000 m2. Because of its good adsorption properties they are useful in many industrial

17
processes. Filtration, purification, deodorization, decolourization and separations are the
examples of processes.

Adsorption Equilibrium

A large majority of adsorption operate through equilibrium adsorption of mixture. The

amount of gas or liquid adsorbed, na by mass, per gram of solid, ms, depends on the
specific surface area of the solid, the equilibrium solute concentration in the solution on,
Ceq (pressure for gas phase adsorption), the temperature, and the nature of the molecules
involved. For the given system at constant temperature it is possible to write the adsorption
isotherm equation as follows
q eq= na / ms = f (Ceq)
(1)
Where qeq is the amount of adsorbate per unit mass of adsorbent.
The most common way of getting information about a given system is to take experimental
measurements, at constant temperature, of the amount of adsorbate on the surface as a
function of concentration(or pressure) and then draw a plot of q eq (the amount of adsorbate
per unit mass of adsorbent) versus Ceq(the equilibrium solute concentration in adsorption
from solution). Such a graph is called an adsorption isotherm.
The Freundlich isotherm
It applies over a limited range of concentrations and is somewhat better for liquid –solid
systems. It has the form of
qeq= na / ms K. (Ceq)a (2)
where, na Amount of the adsorbate(grams) & ms = Amount of the adsorbent
In Eqn. (2) K and a are constants.

The Langmuir Isotherm

The theory of Langmuir is restricted to cases where only one layer of molecule can be
adsorbed on the surface. As mentioned before, in the case of chemisorption monolayer
adsorption is usually observed. The monolayer adsorption is distinguished by the fact that

18
amount adsorbed reaches a maximum value at moderate concentrations (corresponding a
complete coverage of the surface of the adsorbent by a layer of adsorbed molecules which is
one molecule thick only), and remains constant with further increase in concentration. The
equation of Langmuir as derived for the chemisorption of gases is:

𝜃 = K (Ceq) /(1+K . Ceq) (3)

Where,
𝜃 : Fraction of the solid surface covered by the adsorbed molecules
K: Adsorption equilibrium constant
Ceq: Equilibrium concentration
Langmuir isotherm equation can be written for the gas adsorption by replacing C by P, also
note that

∅ = qeq / qmeq (4)

Where qmeq is the amount of adsorbate per unit mass of adsorbent required to form a
monolayer.
Hence Eqn. 3 takes the form of

qeq / qmeq = K.( Ceq) /(1+K . Ceq) (5)

Ceq / q = Ceq / qmeq + 1/(K . qmeq ) (6)

Utilities Required
Activated carbon, Acetic acid, Sodium Hydroxide, Phenolphthalein, Hydrochloric acid,
Potassium Hydrogen phthalate.

Experimental Procedure

In this experiment it is important to measure the acetic acid concentration accurately. To this
end the NaOH solution must be titrated with standard 0.1M HCL solution and then titrated
with the acetic acid solution.
1. Weight out 0.3 g of activated into each of 5 clean stoppered 125ml conical flasks

19
 2. Add 40 ml of 0.20M acetic acid (Stock Solution) to the first flask and shake. Then
add 40mL to each of the other flasks at concentration of 0.15M, 0.10M and 0.05M
3. Shake each loosely stoppered flask periodically over 30 minutes noting the room
temperature. Then filter each solution through a filter paper ( to completely remove
charcoal particles). It is important that the equilibrium acetic acid concentration be
accurately determined
4. Pipet two 10mL potion of each filtrate add a few drops of phenolphthalein indicator
and titrate with 0.1 M/N NaOH. Record the volume of NaOH used.

Data Analysis

Calculate the no. of acetic acid molecules adsorbed per gram of charcoal (q meq) and
the corresponding equilibrium acid concentration (Ceq) plot qmeq against Ceq and Ceq /
qmeq against Ceq .
Determine the surface area per gram of charcoal assuming that one adsorbed acetic
acid molecule occupies an area of 21x 10-10 m2.

Estimate the value of the equilibrium constant K with the correct units.

Observation and Calculation

Observation Table

Volume Volume q
of NaOH of sample Ceq (molecules/gm.
Sr. No. C0 (M) Ceq/q
used (ml) (M) of adsorbent)
(ml)
1 0.05 3.9 10 0.039 8.83227E+20 4.41563E-23
2 0.1 7.1 0.071 2.32851E+21 3.04916E-23
3 0.15 12.1 0.121 2.32851E+21 5.19646E-23
4 0.2 16.9 0.169 2.48909E+21 6.78962E-23

20
Sample Calculation

Ceq = Equilibrium concentration of acetic acid

M2 = Concentration of NaOH (0.1M)
V1 = Volume of sample (10ml)
V2 = Volume of NaOH

Ceq

Ceq

Ceq = 0.039 M

Co = 0.05 M V = 40 ml m =

mass of adsorbent = 0.3g

q=

q=

q = 8.83 × 1020 molecules/g

Plot q against Ceq and Ceq / q against Ceq.

From Graph-1,

Slope = 2E-22

Therefore the value of qm = 5*1021 (molecules/gm. of adsorbent)

Intercept = 3E-23

Therefore the value of K = 6.67 M-1

Also the Maximum surface area provided per gram of charcoal is given as,
= 5*1021 (molecules/gm. of adsorbent) * (21x 10-10 m2/molecule)
= 1.05 * 1013 (m2/ gm. of adsorbent)

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