Tests for Categorizing Carboxylic Acids and Their Derivatives

Authors: *Constantino, Faye R., Dagcuta, Arnoika P., Brillo, Paulo D.C., Calicaran,
Diane Jean P., Calumay, Marie Cris C., Chan, Jannelyn P.
Abstract
Carboxylic acid is a functional group containing a carbonyl and hydroxyl group,
which is also known as carboxyl group. It has derivatives namely acyl halides, acid
anhydrides, amides, and esters. These are functional groups which are derived from the
carboxylic acid. This experiment aims to perform the different classification tests to the
sample compounds, differentiate carboxylic acids and their derivatives through the
tests, and identify the chemical reactions involved in the tests which are responsible for
the observed results. The experiment was divided into 4 tests: A. Hydrolysis of Acid
Derivatives, B. Alcoholysis: Schotten-Baumann Reaction, C. Aminolysis: Anilide
Formation, and D. Hydroxamic Acid Test and performed to the sample compounds. The
sample compounds were acetyl chloride, acetic anhydride, ethyl acetate, acetamide,
and benzamide. The reaction in the first three tests involves nucleophilic acyl
substitution wherein the nucleophile attached to a carbonyl group is replaced by
another nucleophile. In the hydrolysis of acyl halides and acid anhydrides, acetyl
chloride produced a warming effect, and formed a white precipitate upon addition of
2%AgNO3. Evolution of gas is present in both samples upon addition of saturated
NaHCO3. A vinegar-like odor is observed in ethyl acetate, and a change of red litmus
paper to blue is observed in hydrolysis of benzamide. In the alcoholysis of acetic acid, a
plastic-like odor evolved which is explained by the CH3COOCH2CH3 product. The
alcoholysis of acetic anhydride and acetyl chloride both produced ethyl ethanoate which
is expressed in the plastic balloon-like/ fruity odor. In the aminolysis of acetyl chloride
and acetic anhydride, both samples formed a yellow oily layer, but the result is must be
the formation of a white precipitate which indicates an anilide formation. In
hydroxamine acid test, both the acetamide and ethyl acetate gave yellow solution and
brown
precipitate.
I. Introduction
Carboxylic acid is a functional group
containing a carbonyl and hydroxyl
group, which is also known as carboxyl
group. Their presence in nature is
abundant and they are important
building block of foodstuffs such as
vinegar, butter and vegetable oils.
Acyl halides, acid anhydrides, esters,
and amides are functional groups
derived from the carboxyl group. Acyl
halides is an acyl group (RCO--) bonded
to a halogen atom. Acid anhydrides are
two acyl group bonded to an oxygen

group which may be symmetrical or

mixed. Esters is an acyl group bonded
to OR or OAR. Amides are an acyl
group bonded to a trivalent nitrogen
atom.
Table 1: Carboxylic Acid Derivatives Examples

Functional
Group
Acyl
Halides

IUPAC
Name
Acetyl
chloride

Acid
Acetic
Anhydrides anhydride

Structural
Formula

Esters

Ethyl
acetate

Amides

Benzamide

The most common reaction of

carboxylic acid derivatives is the
addition of a nucleophile to the carbonyl
group to form a tetrahedral carbonyl
addition intermediate. This intermediate
breaks to remove the leaving group and

regenerate the carbonyl group. This

reaction is called nucleophilic acyl
substitution.
Figure 1. Nucleophilic Acyl Substitution

Acid halides are the most reactive

toward nucleophilic acyl substitution
because of the halide ion, which are the
weakest base and the best leaving
group. Amides are the least reactive
because of the amide ion which is the
strongest base and poorest leaving
group.
Hydrolysis is chemical process where
reaction with water breaks the bond/s in
a molecule. The water molecules are
also usually split into H+ and OH-.

The Schotten-Baumann reaction is

an organic reaction that reacts an acyl
halide or anhydride with an amine and
base to produce an amide, or with an
alcohol and base to produce an ester.
The conversion to amide begins with
nitrogen, from the amine, attacking the
carbonyl carbon of the acyl halide which
rearranges to kick out the halide.
Deprotonation with the base then
provides the final amide product. The
reaction with the alcohol happens in the
same manner. It forms an ester RCOOR where R is an alkyl or aryl group
while R is usually an aryl group.
Aminolysis is chemical reaction
whereby a reaction with amine produces
an amide.
Hydroxamic Acid Test is a
confirmation test of the formation of
hyroxamic acid.
This experiment aims to perform
the different classification tests to the
sample
compounds,
differentiate
carboxylic acids and their derivatives
through the tests, and identify the
chemical reactions involved in the tests
which are responsible for the observed
results.
II.
Methodology
A. Hydrolysis of Acid Derivatives
Acyl halides and Acid anhydrides:
One milliliter of water was placed in
a test tube, and ten drops of the sample
was added dropwise. The warming
effect was observed. The mixture was
divided into two portions. One milliliter
of 2%AgNO3 was added to the first
portion, and the precipitate was
observed. To the second portion, one
milliliter of saturated NaHCO3 was
added, and the evolution of gas was
observed.

Esters:
Two milliliters of 25%NaOH solution
was added to one milliliter of ethyl
acetate. The test tube mouth was
covered with marble, and it was heated
in boiling water bath for five minutes.
The mixture was neutralized with
10%HCl solution, and with wafting
motion, the odor was noted.
Amides:
One milliliter of benzamide was
treated with five milliliters of 10%NaOH
solution, and it was heated to boiling.
During heating, the reaction of gas
evolved was tested by holding a piece of
moist red litmus paper over the test
tube. The change in the color of the
litmus paper is observed.
B. Alcoholysis:Schotten-Baumann
Reaction
Acetic Acid:
A mixture of 10 drops of acetic acid, 1
mL
ethanol,
and
5
drops
of
concentrated H2So4 was heated through
water bath. The odor of the ester
formed was noted.
Acyl Halides and Acid Anhydrides:

In a clean and dry test tube, 0.5 mL

ethanol, 1 mL water and 0.2 mL of
acetyl chloride was mixed. 2 mL of 20%
NaOH solution was added and the test
tube was covered with parafilm and was
shaken for several minutes. The odor
and the layers of esters were observed.
In a separate test tube, a similar
reaction was done with 0.2 mL of acetic
anhydride instead of acetyl chloride.
C. Aminolysis
Acyl halides and Acid anhydrides:
Few drops of acetyl chloride are
added to 0.5mL of aniline. The mixture
is transferred to a new test tube
containing five milliliters of water. The
precipitate formed was described.
D. Hydroxamic Acid Test
Preliminary Test: 2 drops of ethyl
acetate, 1 mL of 95% ethanol, and 1 M
HCl were mixed. A drop of 5% FeCl was
then added. The mixture was assured to
be yellow, otherwise it was discarded.
2 drops of the yellow mixture was
added to 2 mL of alcoholic NH2OHHCl
and 1 mL 1M KOH. The mixture was
heated in boiling water for 2 minutes.
The mixture was cooled and added 1 mL
of 5% FeCl3. The same procedure was
done
to
acetamide.

III. Results
Table 3: Hydrolysis Results

Hydrolysis of Acid
Derivatives
Acyl halides and Acid
anhydrides

Observations

1. Acetyl chloride
Acetic anhydride

Warming Effect

Upon addition
of 2% AgNO3

With warming
effect

Presence of a
white
precipitate
No precipitate

Upon addition
of saturated
NaHCO3
Evolution of
gas

No warming
effect
Odor: Vinegar-like odor
Litmus paper: Red to Blue

2. Ester: Ethyl acetate

3. Amide

Evolution of
gas

Table 4: Alcoholysis Results

Alcoholysis: SchottenObservations
Baumann Reaction
Acetic acid
Odor: plastic balloon-like
Acyl Halides and Acid
Odor
Formation of Layers
anhydrides
Acetyl chloride
Plastic balloon-like
None
Acetic anhydrides
Fruity
None
Table 5: Aminolysis Results

Aminolysis: Anilide formation

Acyl halides and Acid anhydrides
Acetyl Chloride
Acetic Anhydride

Observations
White precipitate
White precipitate

Table 6: Hydroxamic Acid Test Results

Hydroxamic Acid Test

Ethyl Acetate
Acetamide

Observations
Preliminary Test
Upon addition of 5% FeCl3
Yellow
Yellow-orange w/ brown ppt
Yellow
Yellow-orange w/ brown ppt

IV.

Discussion

Hydrolysis of Acid Derivatives

Hydrolysis of acetyl chloride gave
off a warming effect because of its
exothermic reaction. It also produced
effervescence upon addition of acetyl
chloride
to
water.

Figure 2. Hydrolysis of Acetyl Chloride

Whereas hydrogen chloride gas

was liberated in the reaction and
ethanoic acid (also known as acetic
acid) was formed.
There was no warming effect
observed in the hydrolysis of acetic
anhydride.

saturated NaHCO3, evolution of gas is

present.

Figure 4. Addition of NaHCO3 to Acetic

Acid

Carbon dioxide gas was liberated

in the reaction and formation of a
carboxylate ion, sodium acetate is also
present.
Hydrolysis of ethyl acetate with
25% NaOH, a dilute base was preferred
because of its irreversible reaction.

Figure 5. Hydrolysis of Ethyl Acetate

Sodium acetate was formed, and

upon neutralizing with 10%HCl, it
produced ethanoic acid which gave a
vinegar-like odor.

Figure 3. Hydrolysis of Acetic Anhydride

Heating of benzamide with

10%NaOH produced sodium benzoate
and ammonia.

There was formation of ethanoic

acid but no liberation of gas.
Upon addition of 2% AgNO3, a
white precipitate was formed only in the
first portion of acetyl chloride because
of the presence of chloride ion with
silver nitrate will produce silver chloride,
a white precipitate. The reaction also
produced a carboxylate ion, silver
acetate.
The second portion of both acetyl
chloride and acetic anhydride contains
ethanoic acid, and upon addition of

Figure 6. Hydrolysis of Benzamide

Ammonia gas turns red litmus

paper to blue because of its basicity.
Alcoholysis: Schotten-Baumann
Reaction
The reaction of acetic acid, ethanol
and concentrated H2SO4 was

which shows that the reaction was

reversible. It shows that the reaction
produced CH3COOCH2CH3.
The second reaction of alcoholysis
took place in a fashion similar to the
figure
below.

Aminolysis: Anilide Formation

White precipitate is the correct
result in the reaction of aniline with both
acetyl chloride and acetic anhydride.
The product formed in the reaction of
both samples is acetanilide which is a
white precipitate. The other product
formed is hydrogen chloride gas in
acetyl chloride and acetic acid in acetic
anhydride.

Figure 7. Schotten-Baumann Reaction

In this experiment, the acetyl

chloride was used as a representative
for Acyl Halides. In the reaction
the acetyl chloride (CH3COCl) is reacted
through nucleophilic attack by the
alcohol molecules and substituting the
chlorine, a very good leaving group, as
the stable chloride ion. The ester formed
in the reaction of acetyl chloride
(CH3COCl) was ethyl ethanoate or ethyl
acetate (C4H8O2)

Figure 8. Ethyl ethanoate structure

The
acetic
anhydride,
a
representative of acid anhydrides,
reacted with the alcohol and base in a
similar way as the acetyl chloride. The
resulting ester was still ethyl ethanoate
(C4H8O2).
The
reaction
was

Figure 9. Aminolysis of Acetic Anhydride

The results showed a yellow oily

layer only, but no precipitation occurred.
This error might be caused by
insufficient amount of sample in
performing the, or lack of agitation to
form the precipitate.
Hydroxamic Acid Test
Preliminary test was done to remove
those phenols and enols that would give
colors with ferric chloride in acidic
solution and give a false-positive result
in the hydroxamic test.
Esters react with hydroxylamines to
yield hydroxamic acids which in turn
should form a wine red ferric
hydroxamate with ferric ions. The
results shown are different from the
theoretical outcome of the experiment.
Amides are converted to hydroxamic
acid through hydroxylamine but more
slowly than the others. Hydroxamine
acid should give a violet color with ferric
ion.

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