Experiment B

Separating a Mixture by Solvent Extraction

Objectives

- To separate a mixture consisting of a carboxylic acid, a phenol and a neutral compound.

- To calculate the percentage recovery of extracted compounds.
- To determine the purity of extracted compounds.
- To acquire skills and techniques for solvent extraction, vacuum filtration, and melting
point determination.

Introduction

Solvent Extraction: Principles and Applications

Solvent extraction, or liquid-liquid extraction, is a method to separate compounds based on

their relative solubilities in two immiscible liquids (solvents). It is a common technique in
chemistry laboratory to separate or purify a compound from its mixture or impurities.
Extraction is a process that selectively dissolves one or more of the mixture compounds into
an appropriate solvent in which the target compound(s) is/are more soluble. In this case, the
second solvent will contain the target compound(s) while the original solvent retains other
compounds (or impurities). During a solvent extraction, the two layers are mixed thoroughly
in a separatory funnel to maximize the surface area between them. This mixing facilitates the
transfer of a dissolved compound from one layer to another. Then the layers are allowed to
separate to complete the transfer process.

Fig. 1a Extraction Fig. 1b Washing

The same principle can also be applied to remove the unwanted impurities to a second
solvent, leaving the desired compound in the original solvent. This reverse process to
extraction is called washing.

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Extraction Solvent

The most critical step in the extraction process is the selection of appropriate solvents. One
solvent, usually water, should be polar in nature. The second solvent should be non-polar and
can be a hydrocarbon (e.g. hexane), an ether (e.g. diethyl ether), or a chlorinated solvent (e.g.
chloroform). The polar solvent dissolves polar substances such as charged molecules and
inorganic salts while the non-polar solvent dissolves non-polar substances such as neutral
organic compounds. When the two immiscible solvents are placed into a container, two
distinct layers are resulted. The more dense solvent is the bottom layer; the less dense one is
the top layer.

Non-polar layer Polar layer

Polar layer chloroform Non-polar layer

Fig. 2a Ethers and hydrocarbons: Fig. 2b Chloroform:

less dense than water denser than water

It is important to identify the solvent in each layer. Although the identity of each layer can be
established from the density of each solvent, their identities should be confirmed. It is
because dissolved substances in a solvent can sometimes significantly increase the density of
the solution and therefore its actual density is not the same as the density of the pure solvent.
As such, it is necessary to do a solubility test. For example, if one of the two solvents used is
water, and to find out which layer is the aqueous layer, you can add two or three drops of
water just below the surface of the top layer. If the drops of water mix with the top layer, then
the top layer is the aqueous layer; if the drops of water fall through the top layer to the layer
below, the water layer is the bottom one. It is a good practice to save all layers in labeled
containers (e.g. beakers) until the experiment is complete and the desired product is
obtained.

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Properties of Some Commonly Used Extraction Solvents

Solvent B.p. (°C) Density (g/ml) Remarks

For extracting polar compounds (NaOH or HCl
Water 100 1.00
may be added as appropriate)
Good general solvent; absorbs some water; very
Diethyl ether 35 0.71
flammable
Dichloromethane 40 1.34 Good general solvent; suspected carcinogen
Chloroform 61 1.48 For extracting fats, oils, grease; carcinogen
For extracting aromatic and non-polar
Toluene 111 0.87
compounds; difficult to remove
For extracting non-polar compounds; very
Petroleum ether 35-60 ~0.64
flammable
Hexane 69 0.66 For extracting non-polar compounds; flammable

Extraction Method

Solvent extraction separates a compound from the mixture by the “like dissolves like”
principle. For an aqueous/organic phase solvent extraction system, the highly polar and ionic
compounds will dissolve in the aqueous phase while the neutral organic compounds will
dissolve in the non-polar organic phase. Separation of organic compounds in a mixture
containing two or more components can be achieved if one compound in the mixture can be
chemically converted to an ionic form. The ionic form is soluble in an aqueous layer and
can then be extracted into it. Other non-ionized components in the mixture will remain
dissolved in the organic layer. Separation of the two layers results in the separation of the
dissolved compounds (in case a layer containing more than one component can be further
treated to separate the compounds).

Ionic forms of some organic compounds can be produced by reacting them with aqueous
acids or bases. Reacting organic acids with bases such as sodium hydroxide (NaOH)
converts these acids to water-soluble anions. Reacting basic amines with dilute aqueous acid
solutions such as hydrochloric acid (HCl) converts the amines to water-soluble cations. The
extent to which an acid-base reaction proceeds to complete depends upon the relative acidity
and basicity of the reactants and products. By adjusting the pH of the aqueous layer, only
the particular species (with suitable pKa value) in the mixture will be ionized and hence
selectively extracted to the aqueous layer. This is called acid-base extraction.

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 Some examples illustrating how acid-base reaction can be used to extract the desired
compound into the aqueous layer in aqueous/organic phase solvent extraction system are
given below.

E.g.1) By reacting with NaOH (aq),

benzoic acid is converted to
benzoate.
E.g.2) By reacting with NaOH (aq),
p-tert-butylphenol is converted to
p-tert-butylphenoxide.
E.g.3) By reacting with HCl (aq),
p-methylaniline is converted to
p-methylaniline cation.

These ions are soluble

in the aqueous layer.

Acid-Base Extraction

pKa is a measure of the acidity of an acid, as shown in the following equation:

p = − log

Stronger acids have smaller pKa values and their conjugate bases are inherently weaker. The
position of an acid-base equilibrium is determined by the relative acidity of the reactant acid
and the product acid. The following examples illustrate this idea.

E.g. 4)

p-toluic acid (pKa=4.2) p-toluate anion pKa=16

E.g. 5)
p-tert-butylphenol (pKa=10.2) p-tert-butylphenoxide anion pKa=16

E.g. 6)
p-tert-butylphenol (pKa=10.2)

E.g. 7)

p-toluic acid (pKa=4.2) p-toluate anion pKa=6.4

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With reference to E.g. 4–7, consider a mixture containing p-toluic acid and p-tert-butylphenol,
you could separate them by making use of the difference in acidity of these two weak acids.
You could first add to the organic layer containing p-toluic acid and p-tert-butylphenol an
adequate amount of NaHCO3(aq) to perform the extraction, only p-toluic acid is strong
enough to react with NaHCO3(aq) and therefore p-toluate anion will be formed and extracted
to the aqueous layer, p-tert-butylphenol will remain in the organic phase.

If the organic layer contains only p-tert-butylphenol, you could evaporate the solvent and
obtain the compound. But if the organic layer contains other impurities that do not react with
base, then you could add NaOH (aq) to the organic phase to perform the extraction, because
NaOH is a stronger base, p-tert-butylphenol can react with it and be turned to
p-tert-butylphenoxide anion, dissolving in the aqueous phase. By using this sequence of
extraction (adding a weaker base and then a stronger base), you could isolate compounds
with different acidities from a mixture.

In this experiment, a mixture of p-toluic acid, 2-naphthol and naphthalene is dissolved in

diethyl ether and the compounds will be extracted by NaHCO3(aq) and then washed by
NaOH(aq). p-toluic acid will be extracted by NaHCO3 (aq) first because of its higher acidity
(pKa = 4.36). Then after the unwanted component 2-naphthol (pKa = 9.51) is washed off by
NaOH (aq), unreacted naphthalene will be left in the ether layer.

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Recovery and Isolation

The target solutes extracted in acid-base extraction are in ionic form. They can be recovered
by precipitation. To recover an organic acid, HCl (aq) can be added to convert its conjugate
base back to acid form. Because of the low polarity of organic acid, the acid is not water
soluble and will precipitate in aqueous medium. Hence the solid acid can be isolated from the
solution by vacuum filtration. The same principle can also be applied on organic bases by
using NaOH (aq) to precipitate the target solutes out.

For the organic phase containing the neutral solute, water should be removed before
evaporation to avoid wet residue. Drying agents like anhydrous salts are added to dry the
organic solvent through the formation of hydrates to consume water molecules present:

salt + nH O ⇌ salt ∙ (H O)

As hydrate is formed, the drying agent added will be clumped together at the flask bottom.
More drying agent should be added until free flowing powder (excess drying agent) is
observed when the flask is swirled to ensure complete removal of water.

Followed by the removal of moisture, the solution is heated to distill off the solvent. A rotary
evaporator is used to remove the organic solvent in an efficient and safe manner. The rotary
evaporator provides a reduced pressure environment (by vacuum pump), increased heating
surface area (through rotation) and uniform heat source (water bath) to remove organic
solvent efficiently. As the solute is crystallized on the flask wall, isolation is complete.

Extraction Products Analysis

After the isolation of all target solutes, the melting points of these isolated products need to
be checked to confirm their identities as well as to access their purities. Percentage recovery
is calculated for the estimation of extraction efficiency.

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Reagents and Properties

M.W. melting boiling density

Substance pKa pH
(g/mol) point (°C) point (°C) (g/cm3)

diethyl ether (l) 74.12 – 34.6 0.7134 – –

NaHCO3 (aq) – – – ~1 – 8.5

NaOH (aq) – – – ~1 – 14.5

p-toluic acid (s) 136.15 180.5 – – 4.36 –

2-naphthol (s) 144.17 – – – 9.51 –

naphthalene (s) 128.19 80.2 – – neutral –

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Experimental Procedure

Part I) Preparing the Extraction Mixture

1. Weigh 0.30 g (±0.05 g) each of p-toluic acid, 2-naphthol and naphthalene. Record the
exact weight on the Data Sheet.
2. Measure 25 mL of diethyl ether with a 25-mL measuring cylinder. Pour it into a 100-mL
beaker.
3. Add all the samples weighed to the beaker, stir for 10 mins to mix and dissolve the
samples.
4. Pour the solution into a 250-mL separatory funnel.
5. Rinse the used 100-mL beaker with two portions of 5 mL diethyl ether. Pour the rinses
into the separatory funnel.

Part II) Extracting p-Toluic Acid

1. Measure 10 mL of 0.5 M NaHCO3 (aq) with a 10-mL measuring cylinder. Pour it into the
separatory funnel.
2. Mix the contents well by inverting and rotating the separartory funnel for 3-4 times (while
holding the stopper in place).
3. During extraction, invert the funnel and open the stopcock to release the CO2 produced.
Repeat until no further CO2 gas is produced.
4. Let the mixture stand for a few minutes to allow the two layers to separate.
5. If an emulsion is formed, add ~5 drops of saturated NaCl (aq) to facilitate the separation.
(Suggestion: Consult your demonstrator for advice if an emulsion is formed.)
6. Remove the stopper and open the stopcock to allow the lower aqueous layer to drain into
a 100-mL beaker (beaker A).
7. Repeat steps 1-6 twice and transfer the aqueous layer to the same beaker (beaker A).
8. Repeat steps 1-6 with another 5 mL of deionized water and transfer the aqueous layer to
the same beaker (beaker A).
9. Discard any residual aqueous layer remained in the separatory funnel by draining it out.

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Part III) Washing off 2-Naphthol

1. Measure 10 mL of 3.0 M NaOH (aq) with a 10-mL measuring cylinder. Pour it into the
separatory funnel containing the organic layer.
2. Mix the contents well by inverting and rotating the separatory funnel for 3-4 times (while
holding the stopper in place).
3. During extraction, frequently vent the vapour produced.
4. Let the mixture stand for a few minutes to allow the two layers to separate.
5. If an emulsion is formed, add ~5 drops of saturated NaCl (aq) to facilitate the separation.
(Suggestion: Consult your demonstrator for advice if an emulsion is formed.)
6. Remove the stopper and open the stopcock to allow the lower aqueous layer to drain into
a 100-mL beaker (beaker B).
7. Repeat steps 1-6 twice and transfer the aqueous layer to the same beaker (beaker B).
8. Repeat steps 1-6 with another 5 mL of deionized water and transfer the aqueous layer to
the same beaker (beaker B).
9. Discard any residual aqueous layer remained in the separatory funnel by draining it out.
10. Transfer the organic layer in the separatory funnel to a clean 250-mL conical flask.

Part IV) Isolating p-Toluic Acid

1. Add 3.0 M HCl (aq) dropwise to beaker A with stirring, until no more precipitate forms.
2. Use pH paper to confirm that the solution is acidic.
3. Filter and separate the precipitates from the solution by vacuum filtration.
4. Wash the crystals by deionized water. Let it air dry for at least 10 mins.
5. Collect and weigh the crystals. Record results on the Data Sheet.
6. Determine the melting point of the crystals by a melting point apparatus.

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Part V) Isolating Naphthalene

1. Weigh ~1.5 g of anhydrous MgSO4.

2. Add the anhydrous MgSO4 incrementally into the conical flask containing the organic
layer. Swirl the flask gently after each addition. When there is flowing powder (not
clumped together) in the layer, this indicates the water present is all adsorbed and no
more drying agent is needed.
3. Allow the flask to stand for 5 mins.
4. Weigh an empty 100-mL round bottom flask (flask C).
5. Filter the mixture and collect the filtrate into flask C.
6. Use a rotary evaporator to evaporate the ether.
7. Weigh flask C with the crystals. Record results on the Data Sheet.
8. Determine the melting point of the crystals by a melting point apparatus.

Data Treatment

Calculation of the Percentage Recovery

weight of sample extracted

Recovery = × 100%
weight of sample used

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