Identification of Phenols

Phenols are organic compounds with a hydroxyl group attached directly to benzene
or substituted benzene. They have the general formula Ar OH. Examples of them
include phenol (also known as carbolic acid), hydroquinone, resorcinol, o-cresol,
m-cresol, p-cresol, β-naphthol, and α-naphthol.

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Physical properties
 Phenols are liquids (o.- and m-cresol) or solid crystalline
compounds (phenol and resorcinol)
 They are coloured due to air oxidation and have a special odour
Pure compounds are colorless
 They have high boiling points because of intermolecular hydrogen
bonding
 Phenol itself is soluble in water due to its ability to form hydrogen
bonding with water For other phenols the solubility in water
decreases by increasing the molecular weight (cresols and
naphthols are insoluble in water)
 Phenols burn with a yellow smoky flame due to the presence of
aromatic ring

Chemical properties
Phenols are weak acidic compounds, so they are soluble in strong
alkaline solutions only (sodium hydroxide solution) For this
reason they fall into solubility class A2 Presence of electron
withdrawing group at the phenyl ring strengthens the acidity of the
phenol making it of solubility class A1 ( nitrophenol) However,
phenol itself is of solubility class S1 since it is water soluble.

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Types of phenols reactions
1. Reactions at the phenolic hydroxyl group OH) ether formation and salt
formation
 phenol r e acts with sodium hydroxide to form sodium phenoxide.

2. Substitution at the aromatic ring; bromination and nitration reactions:


 reaction with bromine water.

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  reaction with dilute nitric acid.

Chemical reactions
1. Reaction with ferric chloride
Phenols react with ferric chloride to give coloured compounds due
to the presence of the enol group Actually this reaction is
considered as a test for any compound with enol group

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Procedure

To a very dilute aqueous solution of the phenol (30-50 mg in 1-2 mL water) or to a

few crystals of the solid phenol (50-100 mg) dissolved in water add 1 drop of ferric
chloride solution and observe the resulting color :

Hydroquinone undergoes oxidation in the presence of ferric chloride resulting in a

deep green solution (crystals may separate) and, on further addition of ferric
chloride solution, a yellow solution of p benzoquinone is produced :

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2. Reaction with bromine water

This reaction is an example of substitution reaction at the phenyl ring (mentioned

earlier).

Procedure

To a concentrated aqueous solution of the phenol or to the phenol itself,

add bromine water gradually At first the bromine is decolourized and
then, on adding an excess, a white or yellowish-white precipitate of a
poly bromo-derivative is produced with all except hydroquinone and
α-and β-naphthol On gradually adding bromine water to a solution of
hydroquinone, a deep red coloration is produced, followed by the
separation of deep green crystals which then dissolv giving a yellow
solution The naphthols decolourize bromine water, but usually no
precipitate of the bromo compound can be obtained.

This test is not very satisfactory with those phenols which are insoluble
in water, owing to the difficulty of distinguishing the bromo compound
from the original phenol

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3. Phthalein test

Many phenols yield phthaleins which give special colours (sometimes with
fluorescence) in alkaline solutions when reacted with phthalic anhydride and a
little amount of concentrated sulphuric acid Phenol and resorcinol are examples .

The fluorescence of resorcinol is due to the presence of an oxygen linkage between

the two phenolic nuclei (in basic medium).

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Procedure

In a dry test tube put about 0 1 g of the phenol and an equal amount of phthalic
anhydride or phthalic acid, mix well, and add 1 2 drops of concentrated sulphuric
acid Heat gently on a direct flame for 1 minute until the crystals of the mixture
melt and fuse Then cool the test tube and add excess of 10 sodium hydroxide
solution Results should be as follows

If the resultant colour is not so clear you can dilute with water.

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4. Reimer-Tiemann reaction
Treatment of phenol with chloroform and aqueous sodium hydroxide solution
introduces an aldehyd roup CHO) into the aromatic ring at the ortho or para
positions.

Procedure
To about 0 2 g of the phenol add 1 mL of 30 sodium hydroxide solution and 1 mL
of chloroform, heat on water bath, and observe the colour of the aqueous layer :

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5. Reduction of potassium permanganate
Phenols reduce potassium permanganate solutions and undergo oxidation to
quinones The manganese is reduced from 7 which gives a purple solution, to 4
which is brown This test is highly successful with dihydroxylated phenols than
phenol itself

Procedure:
Add (0,1 g or 0,2 mL 3-4 drops) of the compound to 2 mL of water or ethanol Add
2 aqueous potassium permanganate solution drop by drop with shaking until the
purple colour of the permanganate persists If the permanganate color is not
changed in 0,5-1 minutes, allow the mixture to stand for 5 minutes with occasional
vigorous shaking. The disappearance of the purple color and the formation of a
brown suspension, which is manganese ( oxide, at the bottom of the test tube is a
positive result for the presence of phenols.

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