1.

Abstract/summary

Regarding to the experiment objectives, which is to conduct the simple experiments

regarding liquid-liquid extraction and to determine the distribution of coefficient and mass
transfer coefficient with the aqueous phase as the continuous medium through liquid-liquid
extraction. This experiment is based on the solubility. First experiment, we used separators
funnel to separate two solutions of different solubility and densities, and then titrate with
different of NaOH concentration (0.1M and 0.025M). The values for distribution coefficient
by titration with 0.1M are 7.53 in 1.0 ml of propionic acid, 4.29 in 1.5 ml propionic acid and
3.64 in 2 ml propionic acid. While the value for distribution coefficients by titration with
0.025M are 4.41 in 1.0 ml of propionic acid, 1.825 in 1.5 ml propionic acid and 4.71 in 2 ml
propionic acid. Second experiment, we used liquid-liquid extraction column to obtain feed,
raffinate and extract samples. The samples were titrated with different of NaOH
concentration (0.1M and 0.025M). The value of mass transfer coefficient from liquid-liquid
extraction are; 0.0102 kg/min if titrated with 0.1M NaOH and 0.068 kg/min if titrated with
0.025M NaOH. The experiment was completely and successfully done.

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 2. Introduction

Liquid-liquid extraction, also known as solvent extraction and partitioning, is a method to

separate compounds based on their relative solubility in two different immiscible liquids,
usually water and an organic solvent(propionic acid). It is an extraction of a substance from one
liquid phase into another liquid phase. Liquid-liquid extraction is a basic technique
in chemical laboratories, where it is performed using a separator funnel. This type of process is
commonly performed after a chemical reaction as part of the work-up.

In other words, this is the separation of a substance from a mixture by preferentially

dissolving that substance in a suitable solvent. By this process a soluble compound is usually
separated from an insoluble compound.

The basic principle behind extraction involves the contacting of a solution with another
solvent that is immiscible with the original. The solvent is also soluble with a specific solute
contained in the solution. Two phases are formed after the addition of the solvent, due to the
differences in densities. The solvent is chosen so that the solute in the solution has more affinity
toward the added solvent. Therefore mass transfer of the solute from the solution to the solvent
occurs. Further separation of the extracted solute and the solvent will be necessary. However,
these separation costs may be desirable in contrast to distillation and other separation processes
for situations where extraction is applicable.
A general extraction column has two input stream and two output streams. The input
streams consist of a solution feed at the top containing the solute to be extracted and a solvent
feed at the bottom which extracts the solute from the solution. The solvent containing the
extracted solute leaves the top of the column and is referred to as the extract stream. The solution
exits the bottom of the column containing only small amounts of solute and is known as the
raffinate. Further separation of the output streams may be required through other separation
processes

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 Flow sheet

Figure 1. Extraction Flow sheet for an Extraction Column

Figure 2: Liquid-liquid extraction column schematic diagram

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 3. Aims/Objectives

The objectives of this experiment:

 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.
 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.

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 4. Theory

In liquid-liquid extraction, two phases must be brought into contact to permit transfer of
material and then be separated. Extraction equipment may be operated batch wise 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.
In dilute solutions at equilibrium, the concentration of the solute in the two phases is called
the distribution coefficient or distribution constant ‘K’.

K=Y/X

Where the Y and X are the concentrations of the solute in the extract and the raffinate phases
respectively. The distribution coefficient can also be given as the weight fraction of the solute in
the two phases in equilibrium contact:

K’=y*/x

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.

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The theory for the system Trichloroethylene-Propionic acid-Water is as follows:
Let Vw : Water flow rate, lt/s

Vo : Trichloroethylene flow rate, lt/s

X : Propionic acid concentration in the organic phase, kg/lt

Y : Propionic acid concentration in the aqueous phase, kg/lt
Subscripts: 1 : Top of column
2 : Bottom of column

Mass Balance:
Propionic acid extracted from the organic phase (raffinate).
= Vo (X1-X2) (8.1.1)

Propionic acid extracted by the aqueous phase (extract)

= Vw (Y1 -0) (8.1.2)

Therefore theoretically,
Vo (X1-X2) = Vw (Y1 -0) (8.1.3)

Mass transfer coefficient:

MTC=Rate of acid transfer/volume of packing × mean driving force (8.1.4)

Where Log mean driving force: (ΔX1-ΔX2) / ln (ΔX1/ΔX2)

ΔX1: Driving force at the top of the column = (X2-0)

*
ΔX2: Driving force at the bottom of the column = (X1-X1 )

Where X1* 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.

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 5. Apparatus

Apparatus:
 Liquid-liquid extraction column
 Water pump
 Separator funnel
 Burette
 conical flask
 volumetric flask

Reagents:

 NaOH solution (0.1 M and 0.025 M)

 Distillates product solution
 raffinate product solution
 Feed solution
 Propionic acid

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 6. Procedure

Experiment A

1. Make sure valve V6 and V11 are closed.

2. Switch on valve S1, C3 and S3.
3. Adjust feed flow rate (C1) until maximum.
4. Switch on S4.
5. When the water reach the top column, set C1 to 300 cc/min.
6. Wait for 20 minutes.
7. Take 100mL sample from refinate, feed and extract.
8. Take 10mL from each sample in experiment A and add 3 drops of phenolphthalein.
9. Titrate each sample with 0.1 M NaOH.
10. Repeat step 1 and 2 with 0.025 M NaOH.
11. Titrate twice for each moles of NaOH.

Experiment B

1. Add 50mL of water, 50mL of organic solvent and 1mL of propanoic acid into a conical
flask and shake it well.
2. Repeat step 1 with 1.5 and 2 mL of propanoic acid.
3. It will form two layers and take 10mL from each upper and bottom layer.
4. Add 3 drops of phenophtalein into each sample.
5. Titrate each sample with 0.1 M and 0.025 M of naOH.

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 7. Result

EXPERIMENT A

Concentration of Raffinate Feed Extract

NaOH (M)
0.1 M NaOH 1.3 mL 0.1 mL 0.1 mL
0.025 M NaOH 1.0 mL 0.6 mL 0.4 mL

EXPERIMENT B

Volume of NaOH (mL) Concentration of

Volume of Propionic Upper Bottom NaOH (M)
acid (mL)
1.0 12.8 1.7
1.5 27.0 6.3 0.1 M
2.0 27.7 7.6
1.0 37.9 8.6
1.5 48.2 26.5 0.025 M
2.0 137.8 29.3

Water flow rate = 0.3 L/min

Organic flow rate = 0.3 L/min

Packing dimension: length = 1.2 m

Diameter = 50 mm

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 8. Calculations

Formula:

Finding distribution coefficient:

K = Y/X

Where Y: concentration of solute in extract phase.

X: concentration of solute in raffinate phase.

Finding mass transfer coefficient:

1. M1V1 = M2V2

Where; M1 – concentration of NaOH

M2 – concentration of propionic acid

V1 – volume of NaOH

V2 – volume of propionic acid

2. Rate of acid transfer = Vw (Y1- 0)

3. Vo (X1-X2) = Vw (Y1 -0)

4. K = Y1/X*

5. Log mean driving force= (ΔX1-ΔX2) / ln (ΔX1/ΔX2)

Where; ΔX1: Driving force at the top of the column = (X2-0)

ΔX2: Driving force at the bottom of the column = (X1-X*1)

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6. Packing dimension: length = 1.2 m

Diameter = 50 mm

Therefore, packing volume, V= πr2L

= (π) (0.025 m)2 (1.2m)

= 2.36×10-3 m3

= 2.36 L

7. Mass transfer coefficient = rate of acid transfer

Volumes of packing ×mean driving force

11
Finding the distribution coefficient:

For 0.1M of NaOH

1. 1.0 ml of propionic acid

Upper (Y): bottom (X)
M1V1 = M2V2 M1V1 = M2V2
(0.1) (0.0128) = M2 (0.001) (0.1) (0.0017) = M2 (0.001)
M2 = 1.28 M M2 = 0.17 M

K = Y/X
= 1.28 M/0.17 M
= 7.53
2. 1.5 ml of propionic acid
Upper (Y): bottom (X)
M1V1 = M2V2 M1V1 = M2V2
(0.1) (0.027) = M2 (0.0015) (0.1) (0.0063) = M2 (0.0015)
M2 = 1.80 M M2 = 0.42 M

K = Y/X
= 1.80 M/0.42 M
= 4.29
3. 2.0 ml of propionic acid
Upper (Y): bottom (X)
M1V1 = M2V2 M1V1 = M2V2
(0.1) (0.0277) = M2 (0.002) (0.1) (0.0076) = M2 (0.002)
M2 = 1.385 M M2 = 0.38 M

K = Y/X
= 1.385 M/0.38 M
= 3.64

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For 0.025 M of NaOH

1. 1.0 ml of propionic acid

Upper (Y): bottom (X)
M1V1 = M2V2 M1V1 = M2V2
(0.025) (0.0379) = M2 (0.001) (0.1) (0.0086) = M2 (0.001)
M2 = 0.9475 M M2 = 0.215 M

K = Y/X
= 0.9475 M/0.215 M
= 4.41
2. 1.5 ml of propionic acid
Upper (Y): bottom (X)
M1V1 = M2V2 M1V1 = M2V2
(0.025) (0.0482) = M2 (0.0015) (0.1) (0.00265) = M2 (0.0015)
M2 = 0.803 M M2 = 0.44 M

K = Y/X
= 0.803 M/0.44 M
= 1.825
3. 2.0 ml of propionic acid
Upper (Y): bottom (X)
M1V1 = M2V2 M1V1 = M2V2
(0.025) (0.1378) = M2 (0.002) (0.1) (0.0293) = M2 (0.002)
M2 = 1.723 M M2 = 0.366 M

K = Y/X
= 1.723 M/0.366 M
= 4.71

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Finding the mass transfer coefficient:

For 0.1 M of NaOH

Raffinate:

M1V1 = M2V2

(0.1)(0.0013) = M2 (0.01)

M2 = 0.013M of propionic acid X1

Feed:

M1V1 = M2V2

(0.1)(0.0001) = M2 (0.01)

M2 = 0.001M of propionic acid

Extract:

M1V1 = M2V2

(0.1)(0.0001) = M2 (0.01)

M2 = 0.001M of propionic acid Y1

Rate of acid transfer = Vw (Y1- 0)

= 0.3 L/min (0.001 mol/L)

= 0.0003 mol/min

Vo (X1-X2) = Vw (Y1 -0)

0.3 L/min (0.013 mol/min – X2) = 0.003 mol /min

X2 = 0.012 M

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Log mean driving force= (ΔX1-ΔX2) / ln (ΔX1/ΔX2)

ΔX1 = (X2-0)

= 0.012 M

K = Y1/X* at equilibrium, assume R = 7.53 (from experiment A)

X* = Y1/K

= 0.001/7.53

= 0.000133 M

ΔX2= (X1-X*1)

= ( 0.013 M - 0.000133M)

= 0.0129

Log mean driving force= (0.012 – 0.0129) / ln (0.012/0.0129)

= 0.0124

Mass transfer coefficient = rate of acid transfer

Volumes of packing ×mean driving force

= 0.0003 mol/min
2.36 L × 0.0124
= 0.0102 mol/L.min

= 0.0102M/min

= 0.0102 kg/min

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For 0.025 M of NaOH

Raffinate:

M1V1 = M2V2

(0.025)(0.001) = M2 (0.01)

M2 = 0.0025M of propionic acid X1

Feed:

M1V1 = M2V2

(0.025)(0.0006) = M2 (0.01)

M2 = 0.0015M of propionic acid

Extract:

M1V1 = M2V2

(0.025)(0.0004) = M2 (0.01)

M2 = 0.001M of propionic acid Y1

Rate of acid transfer = Vw (Y1- 0)

= 0.3 L/min (0.001 mol/L)

= 0.0003 mol/min

Vo (X1-X2) = Vw (Y1 -0)

0.3 L/min (= 0.0025mol/min – X2) = 0.003 mol /min

X2 = 0.0015 M

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Log mean driving force= (ΔX1-ΔX2) / ln (ΔX1/ΔX2)

ΔX1 = (X2-0)

= 0.0015 M

K = Y1/X* at equilibrium, assume R = 4.41 (from experiment A)

X* = Y1/K

= 0.001/4.41

= 0.000227 M

ΔX2= (X1-X*1)

= (0.0025M - 0.000227M)

= 0.002273

Log mean driving force= (0.0015– 0.002273) / ln (0.0015/0.002273)

= 0.00186

Mass transfer coefficient = rate of acid transfer

Volumes of packing ×mean driving force

= 0.0003 mol/min
2.36 L × 0.00186
= 0.068 mol/L.min

= 0.068 M/min

= 0.068 kg/min

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 9. Discussions

In this experiment, we want to determine the distribution of coefficient and to determine the
mass transfer coefficient. This experiment is based on the solubility, the solvent is also soluble
with a specific solute contained in the solution, and this is the separation of a substance from a
mixture by preferentially dissolving the substance in a suitable solvent.

For the first experiment, which is to determine the distribution coefficient, we used
titration method from the upper (Y) and bottom (X) layer sample. By titration with 0.1M, the
values are 7.53 in 1.0 ml of propionic acid, 4.29 in 1.5 ml propionic acid and 3.64 in 2 ml
propionic acid. While the value for distribution coefficients by titration with 0.025M are 4.41 in
1.0 ml of propionic acid, 1.825 in 1.5 ml propionic acid and 4.71 in 2 ml propionic acid.

For the second experiment, which is to determine the mass transfer coefficient, we used
the liquid-liquid extraction column to get the feed, raffinate and extract solution. The samples
then were titrated with 0.1M NaOH and 0.025M NaOH. The mass transfer coefficient value
when titrated with 0.1M NaOH is 0.0102 kg/min while the mass transfer coefficient value when
titrated with 0.025M NaOH is 0.068 kg/min.

From the result in the first experiment, if titrated with 0.1M NaOH, it shows that the
value of distribution coefficient decrease as the volume of propionic acid increase. Meanwhile, if
titrated with 0.024M NaOH, the value of distribution coefficient firstly decrease then increase
back, this might be of the errors during titration. The value of distribution coefficient should
decrease as the volume of propionic acid increase.

Result for the second experiment shows the increase of mass transfer rate as the
concentration of NaOH decrease. So, here we say that the mass transfer rate will differ as the
concentration of NaOH increase.

The value from this experiment might be different with the actual. This maybe because of
several error occur during the experiment progress. The most common error is the position of the
eye during taking the volume value at the burette, the eye position should be straight to the scale
and must be perpendicular to the meniscus.

18
 We choose pinkish-purple color for the color indicator during titration, but to get all the
same color might be hard enough to identify. As the color is not constant, the value of mass
transfer coefficient and distribution coefficient will be different from the actual. The color
indicates that the NaOH is at equilibrium with the sample solution.

The differences of the experiment result from the actual result might also caused by the
oil emission and impurities at the beaker, conical flask or burette. To avoid the error, the
equipment or apparatus we use must be in clean condition.

The concentration of propionic acid in raffinate is more than in extract. The concentration
of propionic acid should more in extract than in raffinate, this might be the extraction process
does not occur efficiently. More time needed to extract the solution.

Moreover, the experiment should be repeated at least 3 times to get the accurate values
and the mistake during the experiment progress can be identified.

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 10. Conclusion

As a conclusion:
 The value for distribution coefficient can be determine by titration with 0.1M and the
values are, 7.53 in 1.0ml of propionic acid, 4.29 in 1.5ml propionic acid and 3.64 in 2ml
propionic acid. While the value for distribution coefficients by titration with 0.025M are
4.41 in 1.0 ml of propionic acid, 1.825 in 1.5 ml propionic acid and 4.71 in 2 ml
propionic acid.
 The value of mass transfer coefficient from liquid-liquid extraction are; 0.0102 kg/min if
titrated with 0.1M NaOH and 0.068 kg/min if titrated with 0.025M NaOH.

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 11. Recommendations

 Use clean apparatus, if not clean the apparatus using distilled water
 The eye position should be perpendicular to the meniscus and the scale.
 Repeat the experiment at least 3 times to get accurate values and to make comparisons.
 Titration should be repeat several times to get the average values.
 Used magnetic stirrer during titration.
 Make sure the changes of color should be constant in every titration.

12. References

 http://en.wikipedia.org/wiki/Liquid-liquid_extraction
 http://rothfus.cheme.cmu.edu/uolab/lle/projects/t8_f00/t8_f00.pdf
 http://www.scribd.com/doc/5552507/3-Liquid-Liquid-Extraction
 http://www.scribd.com/doc/7009722/Liquid-Liquid-Extraction
 Perry, R.H., and D. Green, Perry’s Chemical Engineering Handbook, 6th edition,
McGraw-Hill, 1984.
 Bennett, C. O., and J. E. Myers, Momentum, Heat and Mass Transfer, 3rd edition,
McGraw-Hill, 1983.
 Sinnott, R.K., J. M. Coulson, and J. F. Richardson, An Introduction to Chemical
Engineering Design, 1st edition, Pergamon Press, 1983.

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13. Appendices

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