Qualitative Organic Analysis 1

Course 222: Exp No-02

Name of the experiment:

Test of Carboxylic Acids and Phenols

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 Objectives 2

This experiment is designed for this course to make the students able-
Course 222: Exp No-02

 To identify carboxylic acids and phenols functional group in organic samples.

 To use reagent grade chemicals for wet test of carboxylic acid and phenols in the
laboratory.
 To use simple apparatus for the confirmatory test of carboxylic acids and phenols.
 To understand the reaction of carboxylic acids and phenols with other chemicals.
 To observe change of colour for different reactions related with carboxylic acids and
phenols.

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 Theory 3

Carboxylic acid contains –COOH group with aliphatic or aromatic carbon chain.
Course 222: Exp No-02

OH

O
Structure of carboxylic
acid group

Phenol contains –OH group with aromatic carbon chain.

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 Physical Properties of Carboxylic Acids 4
Course 222: Exp No-02

 Some carboxylic acids are colorless liquids with disagreeable odors.

 The carboxylic acids with 5 to 10 carbon atoms all have “goaty” odors (explaining the
odor of Limburger cheese).
 These acids are produced by the action of skin bacteria on human sebum (skin oils),
which accounts for the odor of poorly ventilated locker rooms.
 The acids with more than 10 carbon atoms are waxlike solids, and their odor diminishes
with increasing molar mass and resultant decreasing volatility.

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 Solubility 5
Course 222: Exp No-02

 The carboxyl group readily engages in hydrogen bonding with water molecules. The acids
with one to four carbon atoms are completely miscible with water. Solubility decreases as
the carbon chain length increases because dipole forces become less important and
dispersion forces become more predominant.

 Hexanoic acid [CH3(CH2)4COOH] is barely soluble in water (about 1.0 g/100 g of water).
Palmitic acid [CH3(CH2)14COOH], with its large nonpolar hydrocarbon component, is
essentially insoluble in water.

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 Solubility 6
Course 222: Exp No-02

The carboxylic acids generally are soluble in such organic solvents as ethanol, toluene, and
diethyl ether.

Hydrogen bond of carboxylic

acid in water
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 Solubility Test (in water) 7

Procedure:
Course 222: Exp No-02

 Add small amount of sample to water in a test tube,

 Observe the solubility of the sample in water.
 If it is soluble in water add a piece of litmus paper in to the solution
 Observe colour changes of litmus paper

Litmus paper Benzoic acid Phenol

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 Experiment for solubility test in water 8
Course 222: Exp No-02

Figure : a) Reaction of carboxylic acid with water to produce a slightly acidic solution, b) Results
of a negative pH test, c) Results of a positive pH test.
Inference:
If colour of blue litmus paper turns red then the supplied sample is carboxylic acid. If colour
remain unchanged then it is neutral.
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 Solubility Test (in NaOH) 9
Course 222: Exp No-02

Procedure:
 Take about 2 cm3 or 50 mg sample in a test tube.
 Add 3-4 drops of 5% NaOH solution to the test tube
 Observe the changes
Solid NaOH

Inference:

 If the unknown sample is soluble in 5% NaOH solution then it indicates sample is

acidic in nature. It may be carboxylic acid or phenol.

©Department of Chemistry, BUET

 Experiment for NaHCO3 Test 10
Course 222: Exp No-02

Procedure:
 Take about 2 cm3 or 50 mg sample in a test tube.
 Add 3-4 drops of 5% NaHCO3 solution to the test tube
 Observe for any gas evolved

Inference:

 If the unknown sample create bubbles after adding NaHCO3, it will be carboxylic
acid.

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 Experiment for NaHCO3 Test 11
Course 222: Exp No-02

Figure: a) Negative result (Acetone), b) Positive result (Lactic acid), c) Positive result (Octanoic
acid).
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 Esterification Test 12

Procedure:
Course 222: Exp No-02

 Take about 2 cm3 or 50 mg of the sample

 Add 2 cm3 of ethanol
 Add few drops of conc. H2SO4.
 Heat the mixture in hot water bath. Water Bath

 Pour the resulting mixture into a beaker containing

Na2CO3 solution about 10 cm3.

Sulphuric Acid Solid Na2CO3

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 Esterification Test 13

Reaction:
Course 222: Exp No-02

Observation and inference:

A pleasant smell of ester in the test tube is indicative
of the presence of carboxylic acid group in the sample

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 Ferric Chloride Test of Phenol 14
Course 222: Exp No-02

Procedure:
 Take about 2 cm3 or 50 mg of the supplied sample
 add neutral FeCl3 solution dropwise
 Boil gently.
FeCl3 solid

Reaction:

Violet colour
FeCl3 solution
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 Ferric Chloride Test 15
Course 222: Exp No-02

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 Unsaturation Test by KMnO4 16

Procedure:
Course 222: Exp No-02

 Take small amount of the test sample in test tube

 Add acidified KMnO4 solution dropwise
 Shake slowly

Solid KMnO4 Concentrated and dilute KMnO4 solution

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 Unsaturation Test by KMnO4 17

Reaction:
Course 222: Exp No-02

OH R
R
+ KMnO4 solution OH
OH
OH
Purple colour Colourless

Figure: Colour change of KMnO4

by unsaturated sample

Observation and inference:

After adding purple KMnO4 solution to the sample, if it turns colourless then the supplied
sample might contain unsaturation
©Department of Chemistry, BUET
 Unsaturation Test by Bromine Water 18

Procedure:
Course 222: Exp No-02

 Take a small amount of the test sample in a test tube

 Add Bromine solution dropwise.
 Shake slowly and observe colour change

Picture of Bromine Water

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 Unsaturation Test by Bromine Water 19
Course 222: Exp No-02

Reaction:

O Br O
H2O
+ Br2
OH OH
Br
Brown solution Colourless solution

Fig. Test of bromine water for

unsaturated carboxylic acids
Observation: Brown solution of bromine turns colourless after
adding the supplied sample
Inference: Supplied acid sample might contain unsaturation.
©Department of Chemistry, BUET
 Bromine Water Test of Phenol 20
Course 222: Exp No-02

Procedure:
 Take small amount of the test sample
 Add Bromine solution dropwise.
 Shake slowly and observe any changes.

Picture of Bromine Water

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 Bromine Water Test of Phenol 21

Reaction:
Course 222: Exp No-02

OH OH
Br Br
H2O
+ 3 Br2 + 3 HBr

Br

White ppt of 2,4,6-tribromophenol

Observation and inference:

A white precipitate formed with Br2 solution is indicative to the
presence of phenolic group in the sample
White ppt of 2,4,6
tribromophenol

©Department of Chemistry, BUET