4.

4 Extraction
Extraction method is often used to purify substances from impurities and to separate
mixtures of substances. The basis of extraction, as a method of separation and purification of
substances, is the difference in solubility of the extracted components in two immiscible phases.
Depending on the characteristics of the process, the following varieties are distinguished:
1) liquid-liquid extraction
2) liquid-solids extraction.
4.4.1 Liquid extraction
The simplest device for liquid-liquid extraction is a separating funnel into which a solution
containing the extracted substance and the extracting liquid is poured – the extractant, i.e. a
solvent in which the substance is highly soluble.
Separating funnels are used to separate immiscible liquids (for example, water and oil).
They are conical or pear-shaped, and in most cases are equipped with a ground glass stopper
(Fig. 48). At the bottom of the funnel there is a ground glass tap. Separating funnels can be of
different sizes. Depending on the volume, the wall thickness varies.
Before working with a separating or dropping funnel, the glass joint of the tap must be
lubricated with Vaseline or a special lubricant, then check the operation of the tap for leaks. This
will allow you to open the tap easily and effortlessly, which is very important, otherwise, when
opening, you can break the tap or damage the entire device.
Choice of solvent
Knowledge of the factors influencing the solubility of a given chemical compound greatly
facilitates the selection of the optimal extractant.

Fig. 48. Conical (a) and pear-shaped (b) separatory funnels

The extraction solvent must comply with the following conditions:

• mutual solubility of phases. The most effective solvents are those that are only limitedly
soluble in each other (for example, benzene-water, chloroform-water, petroleum ether-
methanol);
• the solubility of a given substance and the selectivity of the solvent. As a rule, substances
in which hydrophobic groups predominate (long aliphatic chains, benzene rings, etc.) are better
soluble in non-polar solvents with low dielectric constant. On the contrary, substances with
hydrophilic groups (hydroxyl group, carboxyl group, sulfo group, etc.) are usually highly soluble
in polar solvents with high dielectric constant (Table 5);
• ease of use and safety. It should be remembered that solvents such as ether, carbon
disulfide and hydrocarbons are very flammable;
• ease of solvent removal from the extract.
Table 5
Eluotropic series of solvents
Solvent *Dielectric Solvent *Dielectric
constant, ξ r constant,
 ξr
Water 78.30 Chloroform 4.81
DMSO 46.45 Ethyl ether 4.20
Methanol 32.66 Trichlorethylene 3.42
Ethanol 24.55 Toluene 2.38
Acetone 20.70 Benzene 2.27
n-Propyl alcohol 20.45 Carbon tetrachloride 2.23
Amyl alcohol 13.90 Dioxane 2.21
Pyridine 12.91 Methylene chloride 2.20
Methyl acetate 6.68 Cyclohexane 2.02
Acetic acid 6.17 Hexane 1.88
N o t e : * values taken from source 1

The most common extraction solvents are:

a) lighter than water ‒ diethyl ether (low boiling point, flammable, slightly soluble in water),
benzene (toxic), petroleum ether (flammable), etc.;
b) heavier than water ‒ methylene chloride (low boiling point: +41°C), chloroform, carbon
tetrachloride.
Since solvents with low boiling points are used as solvents for extraction, distillation of the
solvent after extraction is carried out quickly and does not cause difficulties.
For extraction, the two immiscible liquids are transferred to a separatory funnel (Fig. 49).

Fig. 49. Method of working with separatory funnel: a) method of holding the funnel
with hands; b) shaking; c) venting

Do not vigorously shake the contents of the funnel, as the resulting excess pressure may
cause the stopper to be squeezed out; in addition, persistent emulsions may form, which are
usually difficult to separate. After shaking is complete, the separating funnel is placed on a stand
and the liquid is allowed to completely separate into two transparent layers.
Then, open the stopper and carefully turn the tap, allowing the bottom layer to slowly flow
into the receiver or beaker, while being careful not to drain part of the top layer along with the
bottom layer (Fig. 50).

1
Никольский Б. Н. Справочник химика. – Л.: Химия, 1966. ‒ 6760 с
 Fig. 50. Separation of liquids using a separating funnel

To more completely extract the extracted substance, the aqueous layer is again transferred to
a separating funnel and the substance is extracted with a new portion of the extractant,
proceeding in exactly the same way as the first time. Substances that are poorly soluble in water
are extracted with two portions of the solvent; for compounds that are highly soluble in water,
the extraction is carried out at least four times. It should be taken into account that when carrying
out extraction, it is more expedient to extract the substance several times in small portions of the
solvent than to immediately treat the solution with a large amount of it.
The extract is dried with a suitable drying agent (according to the point 3.5). After drying,
the extract is decanted or filtered through a folded filter, the solvent is distilled off in a water
bath, and the resulting product is purified by crystallization, sublimation or distillation.
Often, when extracted from liquids, especially from aqueous solutions, emulsions that are
difficult to separate are formed. The resulting emulsion can be destroyed:
a) adding a few drops of ethyl alcohol, which reduces surface tension;
b) by filtration of the mixture;
c) by standing the mixture for a long time;
d) adding salts;
e) adding acids or bases.
Typically, sodium chloride is used as a salting out agent for neutral or basic substances and
ammonium sulfate for acidic substances.

4.4.3 Practical work No. 4 Purification of organic substances by extraction

The extraction method is used to purify substances from impurities and separate mixtures of
substances based on the difference in solubility of the extracted components in two immiscible
phases. As part of this practical work, two experiments are carried out.

Objective:
• to get acquainted with the method of purification of organic substances by extraction;
• to study the method of separation of organic substances (alcohol, hexane, iodine, benzene)
by extraction, become familiar with laboratory equipment;
• to calculate the mass fraction of hexane solution in the initial solution and the yield of the
product;
 • to calculate the volume of extractant required for complete iodine extraction.
Experiment technique
1) It is necessary to study from the reference literature the properties of an organic
substances – hexane, benzene (or tetrachlorocarbon), ethyl alcohol and iodine (write down the
chemical formula, molar mass, density, dielectric constant, boiling and melting points, solubility
and insolubility in substances) before the experiment.

Properties of starting, intermediate and final substances

Formula Mol. Mass, Тm.p., Тb.p., Density,
No name Notes
g/mol °С. °С. g/ cm3
1
2
3
4

2) Before starting work, lubricate the upper round glass stopper and the lower tap with
Vaseline and check the operation of the tap and the tightness of the stopper.
3.1) Measure 20 mL of the mixture to be analyzed (hexane and ethyl alcohol) with a
cylinder and pour into a separatory funnel mounted in a stand. Measure 10 mL of solvent
(distilled water) with a cylinder and pour into the funnel with the mixture to be separated. Close
the separatory funnel with the stopper, remove it from the stand, shake gently while holding the
stopper. Open the tap to release the resulting vapors. The collected vapors exit through the open
tap, and the pressure is equalized to atmospheric pressure. The process is repeated several times
(Fig. 49–50).
3.2) Place the separatory funnel on the stand. When the solvent interacts with the solution
being purified, the extractant absorbs ethyl alcohol, and hexane does not dissolve in water. It
takes time for the liquids to separate (Fig. 52).

Fig. 52. Separating layers using a separating funnel

3.3) Separate the bottom and top layers into separate containers. Measure the volume of
hexane produced. Calculate the volume fraction of hexane in the initial mixture and possible
losses.
3.4) Do calculations and draw conclusions about the work.
Processing analysis results
Determine the volume fraction of hexane (ω h exane) using formula (10) and the yield (φ ) of
hexane using formula (11):
v h exane
ω h exane = ∙100 % (10)
v sample
 v h exane
φ= ∙100 % (11)
v solv
where v sample ‒ volume of the analyzed solution, mL; v h exane – volume of hexane produced, mL;
v solv . – volume of solvent, mL.
4.1) Prepare an aqueous solution of iodine in advance by adding 3 drops of a 5%
pharmaceutical alcohol solution of iodine in 20 mL of distilled water. The aqueous solution will
turn light brown.
4.2) Aqueous solution of iodine 20 mL pour into a separatory funnel mounted in a stand.
Measure 5 mL of benzene (or tetrachlorocarbon), with a cylinder and pour into the funnel with
the mixture to be separated. Close the separatory funnel with the stopper, remove it from the
stand, shake gently while holding the stopper. Open the tap to release the resulting vapors. The
collected vapors exit through the open tap, and the pressure is equalized to atmospheric pressure.
The process is repeated several times (Fig. 40–50).
4.3) Place the separating funnel on the stand. When the solvent interacts with the solution
being purified, the extractant will absorb iodine and will turn purple and the aqueous solution
will become discolored. Liquid separation occurs times (Fig. 52).
4.4) Repeat the extraction 2‒3 more times with new portions of 5 mL of benzene (or
tetrachlorocarbon) until the color of the extractant stops changing.
4.5) Calculate the amount of required extractant that was required before complete
extraction.
Processing analysis results
Determine the amount of required extractant that was required before complete extraction
using formula (12).
v total=v 1 + v 2+ …+v n (12)
where v n. ‒ extractant portion volume, mL; v total. ‒ total volume of extractant used, mL;
At the end of the work you should make a conclusion!
Additional questions.
1. What is the basis of the extraction process?
2. How should a solvent be selected, and what are the basic requirements for it?
3. What are the main equipment used for the extraction process?
4. Why does liquid stratification occur?
5. Describe the extraction procedure?
6. Where is the extraction method used?