Experiment 3: Liquid-Liquid Extraction of Benzoic Acid

Group 3
Chem 31.1, MEJ1
March 27, 2017

I. Abstract
Liquid-liquid extraction is a type of extraction technique that uses the application of chemical properties of
compounds. The desired solute, which is benzoic acid, was separated from the solvent using liquid extracting
solvent. The solute and solvent were agitated in the separatory funnel and made to settle until a clear distinction
between the two was observed. The organic layer which contained the benzoic acid was taken and evaporated. In
this experiment, among diethyl ether, hexane and methylene chloride, ether has the highest benzoic acid recovery.
For the multiple extraction of benzoic acid, it was discovered that doing more extractions using small amount of
solvent is more effective than doing one extraction using a large amount of solvent.

II. Keywords: Benzoic acid, Density, Extracting solvent, Multiple extraction, Polarity, Volatility

III. Introduction type of extraction has four principal steps involved:

Extraction is an old and common technique
employed by chemists to isolate and purify specific
substances from a solid or liquid mixture by means
of a solvent. It is the type of physical process that
involves transferring of a solute compound from one
phase to either the same or opposite phase as the
solute. However, in this method, it is unattainable to
completely extract a compound from a given solvent
and in an ideal set-up, a small amount of impurity
still remains. A crucial factor is involved for this
procedure to happen and that is to have at least two
phases present. There are two classifications of
extraction depending on the phases involved. It can
be classified as solid-liquid extraction and liquid-
liquid extraction.
Solid-liquid extraction involves the removal of
compounds from a solid mixture or natural product.
A Soxhlet extractor is often used in this type of
extraction. Also, brewing beverages is the most
common example for this kind of extraction.
Liquid-liquid extraction also known as solvent
extraction is the separation of compounds by means
of two solvents with immiscible phases due to their
relative solubility differences. It is usually used to
isolate organic compounds from aqueous solutions.
Also, in solvent extraction process, the properties of
the extracting solvent must always be considered.
Firstly, it must be immiscible with the original
solution. It should have a different density from the
mixture, a low boiling point, and not highly
flammable or toxic. These are some of the
characteristics that extracting solvents have. This
(1) Mixing or shaking the solvents, (2) Separation of
organic and aqueous layers depending on their
densities, (3) Heating and drying the organic layer,
and (4) Removal of the solvent. In most cases,
liquid-liquid extraction is used to isolate and purify
reaction products. There are two types of liquid-
liquid extraction namely, neutral and acid-base. In
simple reactions containing acidic, basic, and neutral
mixtures, it can be separated based on their acid-base
properties.
The Distribution coefficient constant (KD), also
known as the partition coefficient is a quantitative
way to determine the ratio of the aqueous and
organic layers in liquid-liquid extraction at
equilibrium. This is a constant with definite values
depending on the temperature and solvents used.
There is a measurable way to determine the
efficiency of the liquid-liquid extraction by solving
for the fraction remaining in the original solvent.
!
!!
!! =
!! !! + !!
In the equation above, FO is the fraction
remaining in the original solute; Vo is the volume of
the original solvent; KD is the distribution coefficient

Chem 31.1, Liquid-liquid Extraction of Benzoic Acid 1 of 5

constant; VX is the volume of the extracting solvent;
n is the number of extractions. After solving for the
FO multiply it by 100 in order to find the percentage
of the remaining original solvent.
In this experiment, there are five main
objectives, namely, understanding and applying the
theory of liquid-liquid extraction; identifying the
properties an extracting solvent should have;
determining the ideal solvent to use when extracting
a solute; analyzing how the number of extractions
and volume of the original solvent affect each other;
and learning how to compute for the percent
recovery and percentage of the remaining original
solvent.
IV. Methodology
To prepare the filtrate to be used in the
extraction, 100 mL distilled water and 0.5 g of
benzoic acid was placed in a 250 mL beaker. Then,
the mixture was continuously stirred until all of the
benzoic acid was dissolved. While stirring the
mixture, if the benzoic acid did not dissolve more
distilled water was added. The filtrate was set aside
for the next part.
Four set-ups were
prepared (See Figure 1). In
each set-up, an aliquot of 50
mL from the filtrate that was
set aside earlier was taken and
was transferred to a separatory
funnel. Before transferring the
aliquot to the separatory
funnel, the stopcock of the
funnel was made sure to be
horizontal or perpendicular.
For the first three set-ups, A, B,
Figure 1: Set-up
and C, 20 ml of each kind of
organic solvents, ether, hexane, and dichloromethane
was used in each system respectively.
In set-ups A, B and C, after adding the 20 mL
organic solvent, a stopper was inserted to the funnel.
The funnel was shaken not too vigorously for a few
times; then, the stopcock was opened to release the
pressure build-up by producing a slightly hissing
sound, and was closed once again. While shaking the
funnel, the dominant hand should hold the area near
the stopcock and the bottom of the funnel should be
facing upwards or away from anyone. The repeated
cycle of shaking, opening and closing should only be
stopped if there appeared to have no more excess
Chem 31.1, Liquid-liquid Extraction of Benzoic Acid
pressure or sound heard. Then, the funnel was
positioned upright in the ring support and the stopper
on the funnel was removed allowing the separation
of the mixture into 2 distinct layers without any
bubble formation. For set-up C, to determine the
aqueous and organic layer, a drop of distilled water
was added at the side of the funnel. The layer in
which the water was dissolved was considered to be
the aqueous layer. When the layers were formed, the
organic layer was drained into a pre-weighed 100
mL beaker and was placed on an electric stove until
the organic solvent has evaporated. The benzoic acid
retained in the beaker was weighed and the percent
recovery was calculated.
For the last set-up, 10 mL of hexane was used in
the first and second extractions and the aqueous
layer for the first extraction was re-used for the
second extraction. In the first extraction, when the
10 mL hexane was added to the aliquot, a stopper
was then inserted into the funnel. Afterward, the
repeated cycle of shaking the funnel, closing and
opening of the stopcock happened until there is no
more pressure build-up. Then, it was placed in the
iron ring and the stopper was removed to allow the
formation of layers. After the layers were formed,
the first organic layer was drained and was
evaporated then the percent recovery of benzoic acid
retained was calculated. Then, the second extraction
proceeded, by adding another 10 mL hexane to the
used aliquot. For the second extraction, the whole
procedure from the first extraction starting from the
repeated shaking of the funnel until the calculation
of percent recovery was again repeated.
V. Results and Discussion
Not all solvents are suitable for use in all liquid-
liquid extraction experiments. There are certain
factors that can determine whether a solvent is ideal
to be used in an experiment or not. First, the solute
that was used must have greater solubility in the
extracting solvent than in the original solvent
because the molecules of a compound naturally
disperse into the solvent where they are more soluble
with. This can be predicted by computing for the
distribution coefficient constant or KD. A KD value
of 1 implies a 50%-50% solubility of a compound in
the two solvents that were used. In other words, the
compound is equally dissolved and distributed
between the two solvents. Thus, the KD value must
be higher than 1 in order to have a greater amount of
recovery. Another way to predict the solubility of a
2 of 5
solute in a solvent is to look at their
polarity. Second, the extracting solvent must be
immiscible with the original solvent. This can be
determined by comparing the polarity, just like
solubility, of the two solvents (like dissolves like)
or by mixing the two solvents in a test tube to see if
they would mix or form distinct layers. Using two
miscible solvents in a liquid-liquid extraction is not
ideal as it is more difficult to separate them from
each other. Following this principle, the two
solvents must also have different densities to be able
to properly form distinct layers for easier
separation. The extracting solvent must also be
more volatile than the component to be isolated so as
to prevent the latter from evaporating with the
former. The extracting solvent must also dissolve
only the desired component in order to prevent
impurities from contaminating the pure
compound. Lastly, for health and safety purposes,
the extracting solvent should be nontoxic.
Table 1. Materials used and their recorded weight
Material Weight (g)
Benzoic acid 0.5 g
Beaker for DCM 51.1 g
Beaker for Hexane1 54.1 g
Beaker for Hexane2 46.9 g
Table 1 shows a list of some of the materials
that were used in Experiment 3 along with the
recorded weight of each. These data are important
to be able to accurately compute for the amount of
recovery of the benzoic acid in each extracting
solvent that was used in this experiment. The
amount of pure benzoic acid recovered from each
extraction was determined by subtracting the weight
of the empty beaker from the combined weight of
the beaker and the pure benzoic acid crystals that
were left after the solvent evaporated. The given
amount of benzoic acid that was used in this
experiment was 0.5 g. Each beaker that was used
during the process of evaporation weighed
differently. The empty beaker that was used for
Dichloromethane or DCM weighed 51.1 g while the
empty beaker used for the first extraction of hexane
Chem 31.1, Liquid-liquid Extraction of Benzoic Acid
weighed 54.1 g. Lastly, the empty beaker that was
used for the second extraction weighed 46.9 g.
Table 2. Organic solvents miscibility with and
ability to dissolve water and benzoic acid,
respectively
Extracting Miscibility with Solubility of
Solvent Water Benzoic Acid
Ether Immiscible Soluble
Hexane Immiscible Moderately
soluble
DCM Slightly miscible Soluble
Table 2 provides a summary of the miscibility
of the three extracting solvents used in this
experiment with water as well as their ability to
dissolve benzoic acid. In this experiment, 0.5 grams
of the benzoic acid sample was partially dissolved in
about 250 mL of water. Water is a highly polar
molecule due to its shape and uneven distribution of
electron density, possessing a partial negative charge
near the highly electronegative oxygen atom and a
partial positive charge near the hydrogen atoms,
while benzoic acid is a slightly polar molecule. Its
carboxyl group is polar and therefore soluble in
water while the benzene ring is nonpolar and
therefore insoluble in water.
Meanwhile, DCM is a moderately polar
molecule. Despite having a symmetrical
arrangement around the carbon atom, it is slightly
more negative at the side of the chlorine atoms due
to their electronegativity. Because of this, DCM is
slightly miscible with water although it cannot form
hydrogen bonds. It is also denser than water at
1.325 g/mL. Hexane, which consists of only
nonpolar C-H bonds, is a highly nonpolar molecule
so it is immiscible with water. It is also less dense
than water at 0.6548 g/mL. On the other hand, ether
is very slightly polar. It is not as polar as other
functional groups with similar structure, although it
is more polar than alkanes due to the lone pairs in
the oxygen atom, and is practically immiscible with
water. Ether in general is also less dense than water
(e.g. Ethyl ether has a 0.7133 g/mL density). Thus,
in theory, ether is the most ideal extracting solvent in
this experiment as it can dissolve benzoic acid while
also being immiscible with water.
3 of 5
 partial miscibility with water. Comparing the two
Table 3. Amount of organic solvent used, amount of trials performed using hexane, the amount recovered
recovered compound, and the percentage of recovery from the first trial using more solvent and only a
of benzoic acid in different extracting solvents single extraction is larger than that of the second trial
which used less amount of solvent in a double
extraction process. Theoretically, when performing
Extracting Amount Amount %
a series of n identical extractions, performing more
Solvent of Solvent Recovered Recovery
extractions while using smaller portions of solvent is
(mL) (g)
more effective than performing a single extraction
Ether 20 mL 0.4 g 80 % using a larger amount of solvent. Unfortunately, this
principle cannot be proven using this experiment due
Hexane 20 mL 0.44 g 88 % to the inaccuracy of the results that were obtained
from the single extraction that had been performed
DCM 20 mL 0.1 g 20 % using hexane.

Hexane1 10 mL 0.2 g 40 % 0.5 ! !!

Hexane2 10 mL 0.1 g 20 %
Table 3 shows a list of the extracting solvents
that were used in this experiment along with the
computed amount of benzoic acid (in grams and in
percentage) recovered in each. Three different
solvents were used, namely, Ether, Hexane, and
DCM. In the case of ether and DCM, 20 mL
samples were used in each trial. Meanwhile, two
trials had been conducted using hexane as extracting
agent. In the first trial, a 20 mL sample of hexane
underwent only one extraction while in the second
trial, two samples of the mentioned solvent, each
weighing 10 mL, were used in a double
extraction. Using the formula for getting the Percent
Recovery,
% !"#$%"&'
!"#$%& !" !"#$%&'()$ !"#$%"&"'
= 100
!"#$%& !" !"#$%& !"#$%&
results from the extraction using ether show a high
value of recovered solute at 80%, which is equal to a
total of 0.4 g of extracted pure benzoic acid. As for
the extraction using DCM, only 20% or 0.1 g was
recovered. These results correspond with the
predicted results after an analysis of their
polarity. As expected, using ether resulted to a large
amount of the recovered pure compound due to its
effectiveness in dissolving benzoic acid as well as its
immiscibility with water. Using DCM produced
only a small amount of the pure compound despite
its effectiveness in dissolving benzoic acid due to its
=
250 !" 50 !"
! = 0.1 !
According to the result of the computation
above, if 0.5 g of benzoic acid sample was dissolved
in 250 mL of distilled water, then a maximum of 0.1
g of the solute can be extracted from each 50 mL of
aliquot taken from the solution. However, the
results above indicate that 0.44 g of benzoic acid (or
more than 90% of the initial mass of the solute) had
been dissolved in the 50 mL aliquot that had been
used for the single extraction and only 0.06 g had
been dissolved in the remaining 200 mL of the
solution despite constant stirring. This result did not
coincide with the concept of diffusion, which
explains how the components of a solution will
eventually distribute themselves in a completely
random manner even without external interference,
given enough time, until equilibrium is
achieved. Moreover, the results also show that the
extraction using hexane as the extracting solvent
yielded a higher amount of recovery than when ether
was used, which also did not agree with the expected
results. This discrepancy may have been caused by
an inaccurate recording and/or computation of the
weight of certain equipment that had been utilized,
particularly the beakers.
VI. Conclusions and Recommendations
The liquid-liquid extraction is a good technique
in separating solutes from solvents. In this type of
extraction, the chemical properties of substances are
being considered instead of their physical properties.
Also, the properties of the extracting solvent are

Chem 31.1, Liquid-liquid Extraction of Benzoic Acid 4 of 5

carefully accounted in order to get the best amount
of the desired substance or solute. In the experiment,
the best extracting solvent was hexane with one
extraction but theoretically, it should be ether.
Lastly, in performing multiple extractions,
performing more extractions using a smaller amount
of solvent is more effective than performing a single
extraction using a larger amount of solvent.
Future studies may investigate furthermore on
extracting solvents that are immiscible with water.
Since not all organic solvents used are extracted only
once, conducting multiple extractions of the other
organic solvents is recommended in order to yield a
higher percent recovery and to understand more
about the relationship between the volume of solvent
and number of extraction. Furthermore, the
characteristics of the solvent used should be taken
into account so that the expected value would be
near the theoretical answer. Before conducting this
experiment, it is also advisable for the participants to
learn and understand the concepts of intermolecular
forces of attraction, solubility, and density of
compounds. Proper weighing of materials and
products, and careful transferring of solvents should
be done to attain better results.
VII. References
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Unit, Department of Physical Sciences and
Mathematics, College of Arts and Sciences,
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Masters, Katherine, and Williamson, Kenneth.
Extraction. In Macroscale and microscale
organic experiments (6th ed., pp. 131-
163). USA: Brooks/Cole, Cengage
Learning, 2011.
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from
http://courses.chem.psu.edu/chem36/Experi
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Volatility of a Liquid The Alcohol Pharmacology
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March 19, 2017, from
https://sites.duke.edu/apep/module-4-
alcohol-and-the-breathalyzer-test/biology-
and-chemistry-connections/volatility-of-a-
liquid/
Whitten, K. W., Davis, R. E., Peck, M. L., &
Stanley, G. G. (2004). General chemistry.

Extraction. (n.d.). Retrieved March 15, 2017, from

http://personal.tcu.edu/jmontchamp/files%2
0for%20lab%20F2016/Extraction%20hando
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Gilbert, J. C., & Martin, S. F. (2011). Extraction. In
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Kolthoff, I. M., Sandell, E. B., Meehan, E. J., &
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Laboratory Manual in Organic Chemistry (2010

Ed.): Committee on Organic Chemistry

Chem 31.1, Liquid-liquid Extraction of Benzoic Acid 5 of 5