CHEM 210

Acid – Base Extraction

 Chemistry 210
Experiment 5 - Acid Base Extraction
Lecture Outline

1. Purpose of the Experiment

2. Theory of Extraction
3. Characteristics of a good extraction
solvent
4. Distribution Coefficient
5. Acid Base Extraction
6. Procedure
7. Drying Agents
8. Basic Tips Concerning Extraction
 Overview
Separatory funnel

• Compounds move from one liquid to another

depending on their relative solubility in each liquid.
• Can separate compounds of different polarities
 Purpose

1. To learn the principles of extraction.

2. To separate organic acids and bases from each

other using aqueous solutions of different pH

3. To separate and identify the components of an

unknown mixture of an acid compound, a base
compound.
 Theory
Extraction is a physical process by which a compound or a
mixture of compounds is transferred from one phase to another.

Extraction is used for the separation of an organic product from

a reaction mixture or for the isolation of a natural product from a
plant.

➢ Solid –liquid extraction: useful for separating natural

products which are composed of a complex mixture of
organic compounds
• Isolating specific compounds from the solid involves
repeated exposure of the solid to a solvent in which one or
more components are soluble. (Example: coffee or tea
preparation)
• A solvent is chosen that selectively dissolves the desired
component(s) but leaves behind the undesired insoluble solid.
• These components are dissolved in the solvent and heated
and are thus removed from the solid residue.
➢ Liquid–Liquid Extraction: useful
to separate compounds based
on their relative solubilities in
two different immiscible liquids,
usually water (polar) and an
organic solvent (non-polar).

• Most common organic solvents used in extraction:

methylene chloride CH2Cl2, or diethyl ether
CH3CH2OCH2CH3.
• The distribution of a solute between the two immiscible
solvents depend on its relative solubility in each.
• The solute will be more concentrated in the solvent in
which it is more soluble.
 The method consists of shaking (in a
separatory funnel) the aqueous solution
or suspension with a water immiscible
organic solvent and allowing the two
layers to separate.

➢ The organic compound is preferentially drawn into the

organic solvent in which it is more soluble.

➢ Other components particularly if ionic or very polar are

preferentially drawn into the water.

➢ When the two layers are separated the organic solvent

has been freed from most of the water soluble impurities.
Extraction Using a Separatory Funnel
 Characteristics of a Good
Extraction Solvent
The solvent should:
1. Readily dissolve the substance to be extracted.
2. Be immiscible with the other solvent (usually water).
3. Have a relatively low boiling point so as to be easily
removed from the compound after extraction.
4. Be unreactive with the solute or the other solvent.
5. Be nontoxic, readily available and inexpensive.

Common solvents used for extraction are hexane, methylene

chloride, diethyl ether and toluene.
 Distribution Coefficient
The efficiency of an extraction will depend upon the
solubility of the compound in the two solvents

➢ The ratio of solubility is called the distribution

coefficient KD

Solubility in organic solvent (g/100mL)

KD =
Solubility in water (g/100mL)
The magnitude of KD gives an indication of the efficiency of
the extraction
➢ The larger KD , the more efficient the extraction

➢ If KD = 1 equal amounts of the compound will dissolve in

each of the phases.

➢ If KD is much smaller than 1, the compound is more

soluble in water than in the organic phase.

➢ If KD is too low for a given extraction, it is better to search

for a different solvent in which the compound is more
soluble

➢ Multiple extractions can increase the amount of

compound extracted.
Example: The KD of methylene chloride/ water of an organic
compound is 2.50. A solution is made by dissolving 48 mg of
the compound in 10 mL of water. How many mg will be
extracted using:
1.One portion of 10 mL methylene chloride

SO
KD = = 2.50
Sw
Let x be the amount extracted
x/10
= 2.50
(48 − x) / 10

Solving for x X = 34.3mg

2.Two portions of 5 mL methylene chloride.
1st extraction
x1/5
= 2.50 X1 = 26.7 mg
( 48 − x1 ) / 10
Mass left = 48 - 26.7 = 21.3 mg
2nd extraction
x 2 /5
= 2.50 X2 = 11.8 mg
( 21.3 − x 2 ) / 10

Total mass extracted = X1 + X2

= 26.6 + 11.8 = 38.4 mg
 Acid Base Extraction
An acid-base extraction is a type of liquid-liquid extraction,
Typically used to separate organic compounds from each other
based on their acid-base properties.
Mixture of an organic acid (RCO2H) and an organic base (RNH2),
both are more soluble in organic solvents than in water.
How to separate?
Change polarity of one, Render it ionic!

CH2Cl2
 Acid Base Extraction
• If the organic compound is rendered ionic, it becomes more
soluble in water than in the organic solvent.
• These compounds can easily be made into ions either by
adding a proton (an H+ ion), making the compound into a
positive ion, or by removing a proton, making the compound
into a negative ion.

Dil. HCl

or Dil. NaOH
 Extraction of organic acids with aqueous NaOH

➢ Most organic acids (e.g., carboxylic acids) are insoluble

or slightly soluble in water, but these compounds are
highly soluble in dilute aqueous sodium hydroxide.

RCO2H (s) + NaOH (aq) RCO2-Na+ (aq) + H2O (l)

Water soluble salt
➢ The acid may be selectively removed from a mixture by
dissolving the mixture in an organic solvent like
dichloromethane (CH2Cl2) and then extracting the solution with
dilute sodium hydroxide.

➢ The organic acid may be recovered from the aqueous

solution by acidification which causes precipitation, followed
by filtration.
RCO2-Na+(aq) + HCl (aq) RCO2H (s) + NaCl (aq)
Extraction of organic bases with aqueous HCl
➢ Organic bases that are insoluble in water may be separated
by extraction with dilute hydrochloric acid. These bases (like
amines) are soluble in acid due to the formation of a soluble
salt.

RNH2 (s) + HCl(aq) RNH3+ Cl- (aq)

Water soluble salt

➢ After the amine has been removed, it may be recovered from

the aqueous solution by treatment with base

RNH3+ Cl- (aq) + NaOH (aq) RNH2 (s) + NaCl (aq)

Separation Scheme
RCO2H (A), RNH2 (B), Neutral (N)
Dissolve in organic solvent
Extract with NaOH

Aqueous layer Organic layer

RCOO- Na+ RNH2 (B) , Neutral (N)
(Salt of acid A)
Extract with HCl

Add HCl

RCO2H (Acid A) Aqueous layer Organic layer

RNH3+Cl- Neutral (N)
(Salt of base B)
Add NaOH
RNH2 (Base B)
Four different classes of compounds can be separated from a
mixture based on differing solubility properties. The four classes are:
1. Amines (organic base)
2. Carboxylic acids (strong acid)
3. Phenols (weak acid)
4. Neutral compounds.
 Procedure
1. Clean your 100 mL separatory funnel with soap and water, then rinse
with acetone, followed by water, 6 M HCl, water, 6 M NaOH and then
water again. The cleanliness of the separatory funnel is very crucial

2. Obtain an unknown from your instructor and record its number in the
report form. The unknown contains an acid compound and a base
compound.
Unknown acid Melting point Unknown base Melting point

o-Toluic acid 104 p-Chloroaniline 72

Benzoic acid 122 Ethyl p-aminobenzoate 89

Trans-Cinnamic acid 133 2-aminobenzophenone 106

2-chlorobenzoic acid 142 p-Phenylenediamine 140

p-Toluic acid 180 4-Aminoacetanilide 162

Salicylic acid 159

Extraction of the Acid with dilute NaOH

1. Dissolve the solid mixture in 10 mL of dichloromethane

a 50 mL Erlenmeyer flask

2. Transfer the solution to a 100 mL separatory funnel

and extract with 10 mL of 6 M NaOH.

3. Remove the lower organic layer from the lower part

of the separatory funnel and transfer it to a separate clean flask;

4. Transfer the upper layer through the mouth (upper part) of the separatory funnel
into a clean Erlenmeyer flask labeled aqueous base extract (AB).

5. Return the organic layer back into the separatory funnel.

6. Rinse the flask that was holding the organic later with 1 mL dichloromethane and
add the rinse to the separatory funnel.

7. Extract the organic layer one more time with 10 mL of 6 M NaOH

8. Combine the two aqueous base layers and place the flask in ice.
Extraction of the base with dilute HCl
1. Transfer the organic layer back to the separatory funnel and extract with
10 mL of 6 M HCl (The organic layer might turn milky, or three layers
(organic layer, a milky layer and aq. layer) might be observed).

2. Remove the organic layer into a clean Erlenmeyer flask (together with the
milky layer) and keep it for last step

3. Transfer the aqueous acid into a new clean Erlenmeyer flask labeled
aqueous acid extract (AA).

4. Repeat the extraction procedure with a second 10 mL of acid.

5. Combine the two aqueous acid layers and place the flask in ice.

You should now have three separate solutions:

(1) aqueous base extract containing organic acid (AB)
(2) aqueous acid extract containing organic base (AA)
(3) organic solution of dichloromethane.

Note: Discard the dichloromethane layer in the provided waste bottle.

 Recovering the Acid
1. Neutralize the aqueous base extract by adding 6 M HCl gradually with
stirring until it is just acidic with litmus paper
2. An insoluble solid confirms the presence of an acidic compound in your
unknown.
3. Isolate the solid by vacuum filtration and wash the solid with a small
amount of cold water.
4. Leave the solid dry for around 15 minutes in the oven and then determine
its melting point and identity.

Recovering the Base

1. Neutralize the aqueous acid extract by adding 6 M NaOH gradually with
stirring until it is just basic with litmus paper
2. An insoluble solid confirms the presence of a base in your unknown.
3. Isolate the solid by vacuum filtration and wash the solid with a small
amount of cold water.
4. Leave the solid dry for around 15 minutes in the oven and then determine
its melting point and identity.

Note: The aqueous acid and base layers can be discarded in the sink.
 Drying and Drying Agents
Drying agents are anhydrous salts that are used to remove water from
“wet” organic liquids.

➢ During extraction, the organic layer becomes saturated with water, a

drying agent must be used to remove the water from the organic
solvent.
➢ The salts bond to water molecules to form hydrated salts that can easily
be removed by gravity filtration or decantation.
Drying agent + xH2O → Drying agent.xH2O

Characteristics of a good drying agent:

▪ Should be fast acting

▪ Should have a high capacity for reacting with water.
▪ Some common drying agents are:
Calcium chloride (CaCl2),
Magnesium sulfate (MgSO4)
Sodium sulfate (Na2SO4).
 Basic Tips Concerning Extraction

➢ Never discard any layer until the experiment has been completed!
➢ Make certain that the phases are thoroughly mixed by vigorously
shaking the funnel.
➢ Vent frequently especially with very volatile solvents such as
diethyl ether and methylene chloride.
➢ To determine which layer is the organic and which layer is the
aqueous add a few drops of water and see in which layer they
dissolve.
➢ Always drain the lower layer out through the stem and pour the
upper layer out of the top of the separatory funnel.
➢ Break emulsions, if encountered, by any of the following
techniques:
• Swirling the separatory funnel
• Stirring the mixture with a stirring rod
• Adding a salt (usually sodium chloride), it increases the ionic strength of
the aqueous layer, thus, renders the aqueous and the organic layers less
compatible.
• Gravity filtration.