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1.

0- ABSTRACT

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. 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 using a variety of apparatus,
from separatory funnels to counter current distribution equipment. This type of process is
commonly performed after a chemical reaction as part of the work-up, often including an
acidic work up.
In this experiment, we were doing two parts of that. Firstly, to determine the
distribution coefficient for the system organic solvent-Propionic acid-water and to show it
dependence on the concentration and the second to demonstrate how a mass balance is
performed on the extraction column and to measure the mass transfer coefficient with
aqueous phase as the continuous medium. In the first experiment, mixture of organic
solvent with de-mineralised water that mixture has been separated to the organic and
aqueous layer. The separated components then were titrated by with different
concentration of NaOH which were 0.1M and 0.025M.

The values for distribution coefficient by titration with 0.1M NaOH are 7.53 (1.0
ml of propionic acid), 4.29 (1.5 ml propionic acid) and 3.64 (2 ml propionic acid). While
the value for distribution coefficients by titration with 0.025M are 4.41, 1.83 and 4.71 in
1.0 ml, 1.5 ml, 2 ml of propionic acid respectively. Second experiment, we used liquid-
liquid extraction column to obtain feed, raffinate and extract samples. The samples were
titrated with 0.1M and 0.025M NaOH. The values of mass transfer coefficient from
liquid-liquid extraction are 0.066 kg/min and 0.072 kg/min with the titration of 0.1 and
0.025 NaOH respectively. We were able to complete the experiment with some errors
occurred.

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2.0- INTRODUCTION

Liquidliquid 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. 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 using a variety of apparatus, from separatory
funnels to countercurrent distribution equipment. This type of process is commonly
performed after a chemical reaction as part of the work-up, often including an acidic
work up. The term partitioning is commonly used to refer to the underlying chemical and
physical processes involved in liquidliquid extraction, but on another reading may be
fully synonymous with it. The term solvent extraction can also refer to the separation of a
substance from a mixture by preferentially dissolving that substance in a suitable solvent.
In that case, a soluble compound is separated from an insoluble compound or a complex
matrix.
In other words, liquid-liquid extraction involves the separation of the constituents
(solutes) of a liquid solution by contact with another insoluble liquid. Solutes are
separated based on their different solubilities in different liquids. Separation is achieved
when the substances constituting the original solution is transferred from the original
solution to the other liquid solution. This can be presented in the figure below:

Figure 1 Solvent extraction

A general extraction column has two input streams 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 feed can be
considered as comprising the solute A and the "carrier" liquid C. Solvent S is a pure
liquid. During contact, mass transfer of A from the feed to the solvent S occurs, with little
transfer of C to S. The solvent (with the solute) is then permitted to separate from the

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carrier liquid. The solvent-rich product of the operation is called the extract, and the
residual liquid from which solutes has been removed is the raffinate.

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3.0- OBJECTIVES

The liquid-liquid extraction experiment is carried to:

A. Determine the distribution coefficient for the system organic solvent-Propionic


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

B. Demonstrate how a mass balance is performed on the extraction column and to


measure the mass transfer coefficient with aqueous phase as the continuous
medium.

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4.0- THEORY

Liquid-Liquid Extraction is the process of extracting a solute from a feed by use of a solvent to
produce an extract and a raffinate. In its simplest form, it may take the guise of a single stage mixing and
separation unit analogous to a single stage flash in distillation. The choice of solvent is critical in effecting
a liquid-liquid extraction. Factors affecting the choice are summarized below. It is usually necessary to
compromise in one area or another. As in distillation it is frequently impossible to achieve the separation
required by use of a single stage unit, and a multistage unit is required.

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. A single-stage extractor can
be represented as:

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Where;

F = Feed quantity / rate, mass


R = Raffinate quantity / rate, mass
S = Solvent quantity / rate, mass
E = Extract quantity / rate, mass

Xf, Xr, Ys, and Ye are the weight fractions of solute in the feed, raffinate, solvent and extract,
respectively.

Partition coefficient m is defined as the ratio of Ye to Xr at equilibrium conditions.

The flowsand concentrations are represented in solute-free, basis as such are presentation leads to
simplification of equations. For example, for a 100 kg/hr feed containing 30% weight sulfuric acid, F =
100-30 = 70 kg/hr, Xr = 0.3/ (1-0.3) = 0.4286.

The component mass balance can be represented as:

F Xf + S Ys = R Xr + E Ye.

Assuming (i) immiscibility of feed and solvent and (ii) the initial solvent is free of solute, i.e., F =
R, S = E and Ys = 0 and using the equilibrium relation of Ye = m Xr, this equation simplifies to S = F/m
(Xf /Xr 1) or reduction ratio, Xf /Xr = 1+ m S/F.

The choice of Solvent is influenced by many factors some of which are listed below:

Distribution or Partition Coefficient: The ratio of the solubility of the solute in the solvent
compared to the feed. This factor will affect the selectivity and the amount of solvent phase
required.
High Selectivity: The ability of a solvent to extract a component or class of components in
preference to others. This factor will determine the number of extraction stages required.
Viscosity: A high viscosity will inhibit both mass transfer and separation of the phases. A low
viscosity (say less than 10 cP) is desirable.
Density: The greater the density difference between the feed and the solvent the easier it will be
to obtain phase separation.
Stability: The solvent should be stable at process conditions in order to minimize losses by
degradation and generation of further impurities.

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Volatility: The solvent is likely to need to be separated from the solute and/or the feed. If this is
to be done by distillation the volatility should, where possible, be chosen to allow this separation
to be easily effected.
Interfacial Tension: This affects the settling, coalescence and mass transfer coefficient of a
system. Coalescence and settling are generally aided by high interfacial tension whilst mass
transfer is hindered.
Cost: The extraction process may only be a small part in the overall process and solvent losses
should not greatly affect process economics.
Corrosivity: If possible, there is a strong incentive to use a component that is already in the
process, such as a reactant feed stream, as the solvent. This may avoid additional materials
handling, environmental and corrosion penalties later in the process.
Toxicity: The advantages of a non-toxic solvent are self-evident in considering inherent process
safety and capital cost. Some solvents now appear on the "Environmental Red List" and should be
avoided.

No solvent is likely to meet all the above criteria and the list is not claimed to be exhaustive. A
compromise will be necessary based on overall process economics.

It has already been indicated that it may require more than one stage of liquid-liquid extraction
in order to achieve the degree of separation required. It is possible to achieve this by removing the
extract and making the raffinate the feed to another liquid-liquid extraction unit using fresh solvent.
This requires a considerable amount of solvent to be used and as in distillation it is more usual to
employ equipment where a counter-current flow of one phase against the other occurs. In this
experiment, a single stage extraction is used. Below are the liquid-liquid extraction column used in
this experiment.

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5.0- APPARATUS

Liquid-liquid extraction unit


Burette clamp
Conical flask
Burette
Beaker

Reagents:

NaOH solution (0.1 M and 0.025 M)


Distillates product solution
raffinate product solution
Feed solution
Propionic acid

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6.0- METHODOLOGY

1. Make sure valve V6 and V11 are closed.


2. S1, C3 and S3 valve was switch on.
3. Feed flow rate (C1) has been adjusted until maximum.
4. S4 was switch on.
5. C1 has been set to 300 cc/min when the water reach the top column,
6. Wait for 20 minutes.
7. 100mL sample has been take from refinate, feed and extract.
8. 10mL from each sample was take and add 3 drops of phenolphthalein.
9. Each sample was titrated with 0.1 M NaOH.
10. Step 8 and 9 was repeated with 0.025 M NaOH.
11. 3 times titrated for each moles of NaOH.

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Concentration Of NaOH Volume of 0.1 M NaOH Volume of 0.025M 7.0- RE
(M) (mL) NaOH (mL) SU
1st 32.0 111.4 LT
2nd 34.0 110.0 S
Feed
3rd 31.0 111.3
Average 32.33 110.90 A)
1st 0.4 1.0
2nd 0.5 1.2
Raffinate
3rd 0.7 1.2
Average 0.53 1.13
1st 13.5 45.7
2nd 12.5 46.3
Extract
3rd 12.5 46.2
Average 12.83 46.07
EXPERIMENT A

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

Water flow rate = 0.3 L/min


Organic flow rate = 0.3 L/min
Packing dimension length = 1.2 m
Diameter = 50 mm

8.0- CALCULATIONS

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Distribution coefficient,

Where Y = concentration of solute in exact phase


X = concentration of solute in raffinate phase

Where M1 = concentration of NaOH


M2 = concentration of propionic acid
V1 = volume of NaOH
V2 = volume of propionic acid

Rate of acid transfer,

where

X1 driving force at the top of the column (X 2 - 0)


X 2 driving force at the bottom of the column (X1 - X *1 )

Packing dimension,
Length = 1.2 m
Diameter = 50mm

Packing volume,

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Mass transfer coefficient =

Calculation for distribution coefficient

0.1M of NaOH

1. 1.0 mL of Propionic Acid

Upper (Y) Bottom (X) Distribution coefficient

2. 1.5 mL of Propionic Acid

Upper (Y) Bottom (X) Distribution coefficient

3. 2.0 mL of Propionic Acid

Upper (Y) Bottom (X) Distribution coefficient

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0.025M of NaOH

1. 1.0 mL of Propionic Acid

Upper (Y) Bottom (X) Distribution coefficient

2. 1.5 mL of Propionic Acid

Upper (Y) Bottom (X) Distribution coefficient

3. 2.0 mL of Propionic Acid

Upper (Y) Bottom (X) Distribution coefficient

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Calculation for mass transfer coefficient

0.1M of NaOH

Feed

Raffinate

Extract

Rate of acid transfer

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0.025M of NaOH

Feed

Raffinate

Extract

Rate of acid transfer

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9.0- DISCUSSION

The purpose of conducting this experiment is to determine the distribution of


coefficient and to determine the mass transfer coefficient. The solvent in the solution is
soluble with the solute and hence, preferentially dissolving the substance in a suitable
solvent is known as the separation of a substance from a mixture.

The first experiment which is Experiment A, it is conducted to determine the mass


transfer coefficient by using the liquid-liquid extraction column in order to obtain the
feed, raffinate and the extract of the solution. Each of the sample were taken 15 mL for
three of the conical flasks for titration all of the samples. The samples were titrated for
0.025 M of NaOH and 1.0 M of NaOH.The mass transfer coefficient value when is has
been titrated with 1.0M NaOH is 0.0492 kg/min while the mass transfer coefficient when
titrated with 0.025M NaOH is 0.0720 kg/min.

The results show that the lower the concentration of NaOH, the higher the mass
transfer rate. Generally, the value of mass transfer rate change when the concentration
differs.

Experiment B is conducted to determine the distribution coefficient by titration


method from the upper (Y) and the bottom (X) layer sample. However, we did not
conduct the experiment. Data obtained are from others group data. From the titration of
0.1M, in 1.0 mL of propionic the value in 7.53, in 1.5 mL propionic acid the value is 4.29
and in 2 mL of propionic, it is 3.64.

From experiment B, we can see that as the volume of propionic increases, the lower
the value of distribution coefficient. The value for titration of 0.025M NaOH has slightly
different with the assumption that we have made just now. This may cause by the error
done while conducting the experiment.

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The amount of NaOH needed in titration of 0.025M NaOH is very high maybe due to
the presence of impurities at the wall of the conical flask. The apparatus may not be
cleaned thoroughly with distilled water. The function of distilled water is to remove the
impurities that may have been situated at the wall of the apparatus.

The tip of the burette may have been contaminated while titrating the NaOH solution.
The conical flask was swirled and the tip of the burette may trip over the neck of the
conical flask and thus affecting the volume of the NaOH titrated.

The rate of titration also affects the volume of titration. When it has been done too
fast, the colour of the solution may has changed but we did not realise as the colour has
turned to colourless again. That is why it is important to do the titration drop by drop in
order to prevent this kind of problem occur again. We also can get ready to stop the
titration when the solution has already turn to pink in colour.

The value of the data attain from the experiment is not very accurate like the
theoretical value. This may cause by the way of taking the reading. The eyes should be in
place at the level of meniscus and perpendicular to it.

The volume of NaOH needed in titration of the feed is too high and surely there is
some errors occur during the extraction. The extraction may have not occur efficiently
because more time is needed in order to extract the solution.

The colour change in the solution is hardly to be recognize to be the same for all of
the solutions. It is hard to get the same colour for each of the solution as the colour has
varies of intensities of pinkish colour. The value of mass transfer coefficient and the
distribution coefficient will be different from the actual reading because of different in
indicating the colour.

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10.0- 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; 0.066
kg/min if titrated with 0.1M NaOH and 0.0720 kg/min if titrated with 0.025M NaOH.

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11.0- RECOMMENDATIONS

In order to get the best results, some precautions should be considered and apply
when conducting the experiment. Here are some recommendations need to take into
account when the experiment is being carried out.
Before we start the experiment, make sure all the apparatus are clean from any
impurities, if not rinse the apparatus by using the distilled water. Secondly, the eye
position should be perpendicular to the meniscus and the scale when pouring the solution
into the burette. It is crucial to take the reading at the meniscus level because it will affect
the accuracy of conducting the experiment.
.Next, the experiment need to be repeated for 3 times and take the average reading
as it is more accurate especially when plotting the graph and to make comparison
between the results. Make sure the changes of colour after the titration should
approximately about the same colour on each other because it will affect the calculations
of the results.
Besides, the titration should be done in the fume hood and repeat the titration
several times to get the average values. Last but not least, always wear safety equipment
such as gloves and goggle because we are dealing with the chemical reagents that might
be harmful to ourselves.

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12.0- REFERENCE

1. https://en.wikipedia.org/wiki/Liquid%E2%80%93liquid_extraction
2. http://www.separationprocesses.com/Extraction/SE_Chp01.htm
3. Paul, A. (2007). Liquid-liquid extraction principles [Power point presentation].
Retrieved from http://eleceng.dit.ie/gavin/Bioprocess%20SC/Liquid-liquid
%20extraction%20principles.ppt
4. Christie J.Geankoplis, Transport Processes and Unit Operations, 3rd Edition,
Prentice-Hall PTR, (1993).
5. Mc Cabe, W.L, Smith, J.C & Harriot, P., Unit Operations of Chemical Engineering,
5th Edition, Mc Graw-Hill International, (1993).

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13.0- APENDIX

Figure 3 Titration setup

Figure 2 Liquid-liquid extraction unit

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Figure 4 Results of experiment B

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