CHM 313: Organic Chemistry I Lab

Experiment 3: Extraction, separation and isolation

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 Extraction
• Extraction is the most common technique used to separate a desired organic
product from a reaction mixture or to isolate an organic substance from its
natural source.

• Extraction is the drawing or pulling out Organic phase

of something from something else Less polar, water-insoluble
substances

• It involves the partition (or separation)

of a compound between two
immiscible phases according to the
solubility Aqueous phase
Ionic or polar substances

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 Extraction

Conditions
➢ Two immiscible phases (not mixed, different densities): one phase is a water
(aqueous phase) and the other an organic solvent (organic phase)

➢ The compound to be extracted is more soluble in one of them more than

other

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 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.

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 Extraction

When an organic solvent is added to your aqueous mixture, a separation of the

two layers will be observed:

• 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)

Ether (org layer): higher layer Water (aq layer): higher layer

Water (aq layer): lower layer DCM (org layer): lower layer

Water (d=1 g/ml) / Ether (d= 0.71 g/ml) Water (d=1 g/ml) / DCM (d= 1.34 g/ml)

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 Extraction

The solutes distribute themselves between the aqueous and organic layers
according to their relative solubility:

KD = distribution coefficient
Sorg = solubility of solute in organic phase
Saq = solubility of solute in aqueous phase
Co = concentration of solute in organic phase
Cw = concentration of solute in aqueous phase

The larger the value of Kd → the more solute will be

transferred to the organic layer with each extraction 6
 Extraction
▪ Multiple, small volume extractions are more efficient than a single, large volume extraction
Example: If each extraction recovers 90 % of the compound
Doing two extractions: First extraction recovers 90 % of the compound, second
extraction recovers 90 % of the remaining 10 % ➔ 99 %

1g

0.9 g 0.1 g 0.09 g 0.01 g

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 Extraction

Example: suppose the solubility of compound A is 0.60 g/100 mL in ether and

0.12 g/100 mL in water.

✓ KD is then 0.60/0.12 = 5.

✓ Let us calculate the amount of A that is removed from a solution containing

60 mg of A in 60 mL of water by extracting with 100 mL of ether.
- If we let x be the number of milligrams of A extracted into the ether layer,
then 60 – x represents the milligrams of A remaining in the water.
- The equation for KD is, therefore,

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 Extraction

▪ Some common organic solvents:

- Highly flammable
upon standing in
petroleum ether air
(mixture of low- - Most organic
Diethyl ether compounds are
boiling alkanes)
= ether soluble in it
- Low BP

- Toxic and some are

dichloromethane,
carcinogenic.
chloroform, and
- Safely used if operations
carbon tetrachloride
are carried out in an
efficient hood
- Take care to avoid getting
them on the skin.

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 Extraction

▪ Acid-base extractions:

Used mostly for the isolation and purification of amines, carboxylic acids and
phenols

- Most phenols are less acidic than the carboxylic acids.

- Carboxylic acids and phenols can sometimes be separated by extraction first with
aqueous sodium bicarbonate (to remove carboxylic acids) and then with aqueous
sodium hydroxide (to remove phenols).

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 Extraction

▪ Acid-base extractions:

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 Extraction

Every liquid/liquid extraction is done using a separatory funnel

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 Extraction

✓ Support the funnel in an iron ring padded with plastic or rubber tubing.

✓ Close the stopcock, and add the liquids to be separated.

✓ Insert the stopper (which has been lightly greased if it is not Teflon)

✓ Grip the stopper with one hand and use the other hand to hold the stopcock

✓ Tip the separatory funnel upside down

✓ Gently shake or swirl to mix the layers

✓ Make sure to vent (relieve the pressure buildup) by opening the stopcock when the funnel is in the
inverted position

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 Extraction

✓ After mixing the layers and venting, place separatory funnel on ring stand

✓ Make sure to remove the stopper

✓ You can now proceed to separate your layers

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 Extraction

▪ How to identify the layers? ➔ Density

Non-halogenated organic solvents < 1 g/mL

Water = 1 g/mL
Halogenated organic solvents > 1 g/mL

✓ Sometimes a concentrated solute can reverse the order of layers

✓ The best method to make sure of the layers is a drop test

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 Extraction
• One significant problem with liquid-liquid extraction is that no solvent is
completely insoluble in another solvent
• Drying agents are added to remove traces of water and destroy emulsions
• Examples of common drying agents

• When ‘drying’ an organic solvent, the solution should go from cloudy to clear
• Always add an excess of drying agent to ensure that all the water is removed
(drying agent should be free floating in the beaker like snow)

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 Experimental part

Aim: Separate three organic compounds by extraction:

4-nitroaniline benzoic acid dichlorobenzene

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 Experimental part-1
1- Dissolve 1.5 g of the three-components mixture in 30 mL of ethyl acetate
and introduce into the separatory funnel

2- In a beaker, Add 5mL of HCl into 45mL of water

3- Divide into 3 (almost )equal portions
4Add the first portion of HCl into the separatory
funnel and shake
5 Do not forget to vent
6 Put the separatory funnel on the stand and
remove the stopper
7 Pour the Lower layer into a beaker
8Repeat two more times (Pour the lower layer in
the same beaker)

Benzoic acid and

4-nitroaniline
dichlorobenzene
LOWER LAYER in the beaker UPPER LAYER remains
in the separatory funnel 19
 Experimental part-2
The upper layer containing benzoic acid and dichlorobenzene is in the
separatory funnel
1In a beaker, take 50mL of of prepared 10%
NaOH
2Divide into 3 (almost )equal portions
3- Add the first portion of NaOH into the
separatory funnel and shake
4 Do not forget to vent
5 Put the separatory funnel on the stand and
remove the stopper
6 Pour the Lower layer into a beaker
7Repeat two more times (Pour the lower layer in
the same beaker)

Benzoic acid Dichlorobenzene

LOWER LAYER in the beaker UPPER LAYER remains

in the separatory funnel
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 Experimental part-3

Benzoic acid Dichlorobenzene

LOWER LAYER in the beaker UPPER LAYER remains

in the separatory funnel

1- Add concentrated HCl drop by

drop until the litmus paper turns red 1- Pour through the top of the
2- Keep in an ice bath seperatory funnel into a small beaker
3Perform a vacuum filtration to 2- Weigh a clean dry beaker
collect the crystals 3- Add anhydrous CaCl2, swirl and
4Allow the product to dry and decant in the preweighed beaker
weigh next day 5- Directly evaporate under hood
6- Weigh the residue

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 Post-Lab Questions

1. What are the important criteria one has to consider in selecting a

solvent for extraction?

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?

3. Why must the stopper at the top of the separatory funnel be removed before
liquid can be withdrawn through the stopcock?

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