Lebanese American University

School of Arts and Sciences

Department of Natural Sciences
Organic Chemistry I Lab-CHM313
Fall 2023

Experiment Three: Extraction, Separation and

Isolation: Acid-Base Liquid-Liquid Extraction
Done by:

Rayan Kanaan, Sara Al Ghadban, Chaza Al Haj Youssef

21/10/2023
A)Purpose:
The aim of this experiment is to separate a mixture of 4-nitroaniline, benzoic acid and
dichlorobenzene into its components through acid-base liquid-liquid extraction based on their
solubility.

B)Experimental procedure:
a) Equipment and chemicals used:
 Separatory funnel
 Erlenmeyer flask
 Graduated cylinder
 Beaker
 Watch glass
 Digital balance
 Hot plate
 Litmus paper
 Ice
 Buchner funnel
 Stand equipped with a ring clamp
 Filter paper
 1.5 g mixture of 4-nitroaniline, benzoic acid and dichlorobenzene.
 DCM
 Water
 CaCl2 as a drying agent
 10% NaOH
 HCl (concentrated)

b) Procedure:
 1.5 g of a 3 organic components (4-nitroaniline, benzoic acid and
dichlorobenzene) mixture is weighed using the digital balance.
 A separatory funnel with a closed stopcock is placed onto the ring clamp of
a stand.
 The weighed 1.5 g of the mixture are dissolved in 14 ml of DCM.
 The solution is transferred into a separatory funnel and mixed through gently
shaking the separatory funnel. Vent the separatory funnel (to remove any
pressure) through opening the stopcock. The stopper must be removed.
  15 ml of HCl are added to the separatory funnel to extract 4-nitroanaline
(base) in the lower organic layer. REPEAT THIS STEP 3 TIMES
 5 ml of water are used to extract the excess HCl dissolved in DCM.
 The extracted solution is neutralized with NaOH and placed in an ice bath to
cool.
 The precipitate is extracted by vacuum filtration through a Buchner funnel.
 14 ml of 10% NaOH are added to the 2 remaining components (benzoic acid
and dichlorobenzene) to extract benzoic acid in the lower layer. REPEAT
THIS STEP THREE TIMES.
 5ml of water are used to extract the excess NaOH.
 The extracted solution is neutralized with concentrated HCl (until the litmus
paper becomes red) and placed in an ice bath.
 Vacuum filtration is performed to collect the crystals.
 The product is kept to dry and weighed the next day.
 The upper layer containing dichlorobenzene and DCM is transferred into a
small beaker.
 A clean dry beaker is pre-weighed.
 Anhydrous CaCl2 is added to the solution.
 The solution is swirled and decanted into the pre-weighed beaker.
 The beaker is placed on a hot plate under the fume hood to evaporate the
solvent.
 The beaker is reweighed.

C) Data And Results:

Compound Mass Recovered
4-nitroaniline 0.43g
Benzoic acid 0.39g
Benzene 0.11g
4-Nitroaniline (1st beaker):
Mass of crystals= 0.43g
% 4-nitroaniline =0.43\1.5 ×100=28.7%
Benzoic Acid (2nd beaker):
Mass of crystals= 0.39g
% Benzoic Acid=0.39\1.5 ×100=26%

Dichlorobenzene (3rd beaker):

Empty beaker’s mass=31.68 g
Beaker + crystals mass= 31.79 g
Crystals’ mass= 31.79- 31.68 =0.11 g
% Dichlorobenzene= 0.11\ 1.5 =7.33%

D) Discussion:
Theory:
Extraction is a physical process used to isolate or purify a product (solute). The solute is
transferred from one phase to another to separate it from unreacted starting materials or
impurities based on difference in solubility by adding to it an immiscible solvent in which the
solute is more soluble. The conditions for a successful extraction requires first: two immiscible
phases (not mixed, different densities) in which one phase is a water (aqueous phase) and the
other an organic solvent (organic phase) and second the compound to be extracted is more
soluble in one of them more than other.
It is also extremely important to pay attention for the choice of a good solvent. Although it is
well known that water is ideally the most common solvents in such extractions, there is a wide
variety of good extraction solvents that can be used and must follow the following criteria:
-should not react with or be miscible with water (2 solvents with different densities)
-should easily be removed from the organic compound by evaporation by having a low boiling
point (volatile)
-should dissolve the substance to be extracted
-should not react with the substance to be extracted
Usually, a good extraction results in two clearly distinct layers. These layers are separated based
on their densities:
• The solvent with the lower density will be on the top (upper layer)
• The solvent with the higher density will be on at the bottom (lower layer)
Generally, there are three types of extractions: solid-liquid extraction , liquid-liquid
extraction, and chemically active extraction (acid-base extraction).
Acid–base extraction is a subclass of liquid–liquid extractions which involves the separation of
chemical species from other acidic or basic compounds and Used mostly for the isolation and
purification of amines, carboxylic acids and phenols. Acid-base extraction utilizes the
difference in solubility of a compound in its acid or base form to induce separation. Typically,
the desired compound transforms into its charged acid or base form by protonating or
deprotonating it. Generally, most organic compounds are neutral, and therefore more soluble in
organic solvents than they are in water. However, if the organic compound becomes ionic, then it
becomes more soluble in water. This is useful in extracting an organic acid or base compound
from an organic phase to an aqueous phase. For such extractions, there is a wide variety of
organic extraction solvents that can be used such as:
- petroleum ether (mixture of low-boiling alkanes)
- Diethyl ether= ether which is highly flammable upon standing in air, most organic
compounds are soluble in it and has a low boiling point.
- dichloromethane, chloroform, and carbon tetrachloride which are toxic and some are
carcinogenic. These should be safely used under an efficient hood and a deep care must be taken
to avoid their touch on skin.
Distribution Coefficient:
The Distribution Coefficient (constant), K: K= C2/C1
Where C2 and C1 are the concentrations at equilibrium in mass/volume [g/mL].
The solute will be distributed in the aqueous layer (water) and the organic solvent layer; it
depends on the solubilities in each solvent and the volume of each. K is the ratio of solute in the
2 solvent layers.

The mixture we aimed to separate contained three components: a base (m-nitroanaline), an

acid (benzoic acid), and neutral substance (dichlorobenzene). These are all organic products
that will be separated into their individual components through extraction procedure. The
procedure involved a series of steps and techniques to achieve the isolation and purification of
these compounds.
We started our experiment by dissolving 1.5 g of the three-components mixture in 30 mL of
ethyl acetate and introduce into the separatory funnel which is a standard piece of equipment
used in liquid-liquid extraction to separate two immiscible solvents with different densities.
The first step of the procedure is to extract the nitroanaline from the mixture. To do this, we
diluted 5mL of HCl into 45mL of water through adding water first followed by the addition of
HCl to avoid vigorous exothermic reactions and the harmful effects of HCl splashing and then
we added them to the mixture in three equal proportions for a more efficient extraction. This will
react with nitroanaline to from water soluble alkyl ammonium salts forming two layers in the
separatory funnel, where the upper layer is the organic solvents while the lower layer is the
aqueous solution. During this step, it is essential to vent the solution by closing the stopper and
the stopper cock and flipping the separatory funnel carefully to shake the solution without any
loss and danger. Then, the excess pressure produced by HCl is released several times after
shaking, by opening the stopcock with the funnel still inverted. Then the solution is allowed
some time to settle and form the interface between the two layers. After the layers are clearly
formed, we extracted the lower layer after making sure that the stopper is removed. This
procedure is done 3 times to ensure all the nitrobenzene are reacted completely. We end up with
an aqueous solution containing the acidic extract, alkyl ammonium salts, thus separating the
nitroaniline from the mixture. Then, the solution was cooled to facilitate the crystallization of
nitroaniline followed by vacuum filtration using a Büchner funnel. The precipitate obtained
through this process was the purified nitroaniline.
The second step is to extract the benzoic acid by the addition of NaOH which will react with the
benzoic acid to produce its sodium salts which dissolve in the aqueous layer, and the neutral
compound (chlorobenzene) remains in the organic layer. We reintroduced the remaining two
components of the initial mixture into the separatory funnel. Then, in a beaker, we took 50mL of
prepared 10% NaOH and divided it into three equal proportions for efficient extraction then
added it to the mixture in the separatory funnel. We made sure to vent the mixture every time we
add NaOH the same way we did in the first part to release pressure. This step was repeated three
times as well to have maximum separation. Finally, water is also added to the mixture in the
funnel to get rid of the excess NaOH. All of the aqueous solutions (bottom layer) are put in the
same flask. To neutralize the benzoate salt in the combined solution, we gradually added
concentrated hydrochloric acid (HCl) until the litmus paper indicated an acidic pH. We end up
with an aqueous solution containing the basic extract, sodium salts of benzoic acid, thus
separating the benzoic acid from the mixture. Just as we did in the first part, the solution was
cooled to encourage benzoic acid to crystallize. The precipitate was separated using vacuum
filtration with a Büchner funnel to obtain benzoic acid.
In the third step of the experiment, we poured chlorobenzene which is left in the separatory
funnel into a beaker. We added anhydrous calcium chloride (CaCl2) as a drying agent to get rid
of the residual water in the organic solvent and thoroughly mixed the contents. The, we decanted
the chlorobenzene into a previously weighed flask leaving behind any remaining water and
CaCl2 in the flask. The obtained mixture was introduced under hood to extract chlorobenzene
and evaporate excess ethyl acetate which is volatile and can be easily removed by evaporation.
We left the obtained masses in the lab for a while to remove any excess water and to obtain a
better yield. The following values were obtained :

E) Sources of errors:
 Poor calibration of the digital balance
 Loss of the compound on the filter paper
 Loss of crystals while transferring them from the Buchner funnel for weighing
 Wet crystals affecting the mass
  Insufficient cooling prior to weighing
 Insufficient drying
 Leakages from the stopcock
 Any impurities in the chemicals used
 Temperature fluctuations

F) Questions:
1 What are the important criteria one has to consider in
selecting a solvent for extraction?
An Extraction solvent must:
 readily dissolve the substance to be extracted,
 Be immiscible with the other solvent from which the
desired compound is to be extracted
 Extract only the desired substance or as small an amount as
possible of any other substance present;
 not react chemically with the solute in an undesirable way,
be easily separated from the desired solute after extraction =
Having a low- boiling point and easily removable by distillation
2\A mixture of a carboxylic acid and a phenol can often be separated
by extracting with aqueous sodium bicarbonate and a suitable
organic solvent. What difference in the chemical properties of the
carboxylic acid and the phenol makes this separation possible?
The Phenols are less acidic than the carboxylic acids. Aqueous
sodium bicarbonate can convert carboxylic acids to their salts because
it is alkaline, but not so alkaline to convert phenols to their salts. This
means carboxylic acids and phenols can sometimes be separated by
extraction with aqueous sodium bicarbonate which removes carboxylic
 acids and then with aqueous sodium hydroxide which removes
phenols.

3\ Why must the stopper at the top of the separatory funnel

be removed before liquid can be withdrawn through the
stopcock?
The Removing of stopper can :
1\ release the pressure from the funnel
2\enhances the liquid's ability to flow smoothly
3\ keeps you safe from an unexpected pressure