CLASSIFICATION TESTS FOR CARBOXLYIC ACIDS AND THEIR DERIVATIVES

Jon Ellis G. Datu, Athina Darla B. Deala, Alan Nathaniel D. Derige, Mary Kimberly L. Espaldon,
Ma. Theresa Angeli M. Estabillo, and Jemielle Patricia A. Estrada
Group 3 2F Medical Technology Organic Chemistry Laboratory
ABSTRACT
Different classification tests were done in order to distinguish and differentiate carboxylic acids and its
derivatives. Carboxylic acids, which are strong organic acids, were made to react with silver nitrate and
sodium bicarbonate in order to form its corresponding carboxylate salts. For the hydrolysis of acid
derivatives, in the test about acyl halides and acid anhydrides, warming effect and an evolution of gas was
observed. In the test about esters, the odor was taken note of, and for the test about amides, the change
in the color of the litmus paper was observed. For alcoholysis; in the test about acetic acid, the odor of the
ester formed was observed while in the test about acyl halides and acid anhydrides, the odor formed and
the layers of ester that were visible were the ones taken note of. For aminolysis, the precipitate formed
was taken note of and for the hydroxamic test, the color produced when a drop of 5% FeCl3 was added
was recorded.

INTRODUCTION
Carboxylic
acids
are
homologous
series
containing functional groups. It is an organic
compound that has a carboxylic acid as functional
group with it an oxygen double bond and an OH
group also attached to the same carbon atom.
When the following functional groups are
attached to the acyl group (RCO) consisting of
alcohols, phenols, ethers, amines and halides
consist of alkyl and/or aryl groups bonded to
hydroxyl, alkoxyl, amino and halo substituents in
that order, they will be called a carboxylic acid
derivative. The group attached to the acyl group
will act as a leaving group in a nucleophilic acyl
substitution, giving a mechanism involving
hydrolysis, alcoholysis, and aminolysis reactions.
The experiment aims to be able to differentiate
the reactivities, distinguish through classification
tests the carboxylic acids and their derivatives
and the mechanisms involved.

EXPERIMENTAL
A. COMPOUNDS TESTED
Acetyl chloride, Acetic anhydride, Ethyl
acetate, Acetamide, and Benzamide are
carboxylic acids that contains acyl core
which are the most reactive.

B. PROCEDURE
1. HYDROLYSIS
DERIVATIVE

OF

ACIDIC

The test tube was filled with 1 mL of

water and 10 drops of the sample was

cautiously added. The warming effect

was noted. The resulting mixture from
the test tube was divided into two
portions. The first portion was added
with 1 mL of 2% AgNO3 and the
second portion was added with 1 mL of
saturated NaHCO3.

2. ALCOHOLYSIS:
SCHOTTENBAUMANN REACTION
A warm mixture of 10 drops of acetic
acid, 1 mL ethanol, and 5 drops of
concentrated H2SO4 were put in a
water bath for two minutes. 0.5 mL of
ethanol, 1 mL water, and 0.2 of acyl
halide or acid anhydride were placed in
a test tube. In the same test tube, 2
mL of 20% NaOH solution was added
and all the mixtures were mixed. The
odor and the layers of the ester
formed were taken note of.

3. AMINOLYSIS:
FORMATION

ANILIDE

Few drops of Acetyl chloride or acetic

anhydride was added to 0.5 mL aniline
and transferred the mixture to a new
test tube containing 5 mL of water.

4. HYDROXAMIC ACID TEST

2 drops of the sample, 1 mL of 95%
ethanol, and 1 M HCl were mixed. The
color was noted after the addition of

FeCl3. When yellow was not the color

produced, the test was not used.
When yellow was proceeded was the
result, 2 drops of the sample was
added to a 2 mL of alcoholic NH2OH

HCl and 1 mL of 1 M KOH. The

mixture was heated in the boiling
water for 2 minutes and was cooled
afterwards. 1 mL of 5% FeCl3 was then
added and the color of the solution
was taken note of.

RESULTS AND DISCUSSION

1 HYDROLYSIS OF ACID
DERIVATIVES
Hydrolysis of Acid
Derivative

Observations

Acetyl Chloride

Warming effect
White cloudy precipitate
Evol. Of CO2
No warming effect
No precipitate
Evolution of CO2
Fruity plastic balloon
like odor

Acetic Anhydride

Ethyl Acetate
Benzamide

Red litmus paper turned

blue(basic) (presence of
Ammonia) with amine
like odor
Table 1: Hydrolysis of Acid Derivatives
The acid halides and the anhydrides,
acetyl alcohol and acetic anhydride has both
shown evolution of CO2 with addition of NaHCO3
and with the addition of water and AgNO3, Acetyl
chloride exhibited a warming effect and a white
cloudy precipitate, respectively; however acetic
anhydride did not exhibit both the warming and
precipitate.
The Ester, Ethyl acetate, after neutralizing
with 10% HCL and water bathing, expressed a
Plastic balloon like odor
The Amide, Benzamide, upon heating
turned basic, indicating presence of ammonia
with an amine-like odor.

Hydrolysis of Acid
Derivatives

Observations

Acyl Halides and acid anhydrides

White precipitate
Acetyl chloride
with evolution of gas
No precipitate with
Acetic anhydride
evolution of gas
Esters
Plastic balloon-like
Ethyl acetate
odor
Amides
Red to Blue litmus
Benzamide
paper (Base)
Table 1. Results observed from the
hydrolysis of acid derivatives.
In the hydrolysis of acyl halides and acid
anhydrides, a warming effect was observed due
to exothermal reaction and formation of the
acetic acid, the parent carboxylic acid. The gas
that evolved during effervescence caused by the
addition of 2% AgNO3 and saturated NaHCO3 in
acetyl chloride was because of the evolution of
CO2 gas.
An aqueous base, 25 % NaOH was used
to hydrolyze ethyl acetate yielding acetic acid
with alcohol which gives a plastic balloon-like
odor to the sample.
Benzamide yields ethanoic acid and
amine when heated in 5 mL of 10% NaOH
solution. The resulting vapor from the reaction
upon testing with moist litmus paper was basic
due to the basic nature of amine (NH3)
RCONH2 + NaOH ---> RCOO-Na+ + NH3.

2 ALCOHOLYSIS: SCHOTTEN
BAUMA REACTION
Alcoholysis
Acetic Acid
Acetyl Chloride

Observations
Plastic balloon like odor
No layer formed
Plastic balloon like odor
No layer formed

Table 2: Alcoholysis
The carboxylic acid, acetic acid, while
being in water for 2 minutes had plastic balloon
like odor although no layer was formed
Acyl halide, Acetyl chloride with the
addition of 20% NaOH solution and agitation also
had a plastic balloon like odor and formation of
no layers.

Alcoholysis

Observations

Acetic acid

Plastic balloon-like
odor
Acetyl chloride
Fruity odor
Table 2. Results observed from alcoholysis
of acetic acid and acetyl chloride.
In alcoholysis, acetyl chloride and acetic
anhydride upon reaction with ethanol and H2SO4
has formed an ester which gave the agreeable
odor of the mixture.
3. AMINOLYSIS: ANILIDE FORMATION
Aminolysis
Observation
Formation of white
Acetyl Chloride
precipitate
Without precipitate
Acetic anhydride
Formation of layers
Table 3: of Aminolysis
Acetyl Chloride had formation of white
precipitate with the addition of 0.5ml anilline.
Acetic Anhydride however did not form any
precipitate, but formed a layer.
Aminolysis

Observations

Acetyl chloride

Yellow oily layer

Figure 4.1 of Ethyl Acetate and Acetamide

Acetic anhydride

Whitish-yellow
precipitate
Table 3. Results observed from the
aminolysis of acetyl chloride and acetic
anhydride.
In aminolysis, the formation of the oily
layer was the result of the difference in density
and solubility of the compounds. White
precipitate was also formed due to the presence
of anilide in the mixture which was yield upon
addition of water.

Fig. 4.1 Ethyl Acetate and Acetamide

Hydroxamic Acid
Test

Observations

Yellow Solution is
obtained
Ethyl Acetate
Deep burgundy color
Acetamide
Orange-red color
Table 4: Hydroxamic Acid Test
Preliminary Test

HYDROXAMIC ACID TEST

A Preliminary test was done to eliminate

the phenols and enols that gave colors with
ferric chloride in acidic solution that would
give false positive results in the ferric
hydroxamic test.
Ethyl acetate yielded deep burgundy color
which was a positive result. Acetamide gave
an orange-red color which is also a positive
result.
Hydroxamic Acid
Test

Observations

Ethyl acetate and

acetamide turned
into a yellow solution
Deep burgundy
Ethyl acetate
discoloration
Deep burgundy
Acetamide
discoloration
Table 4. Results observed from the
Hydroxamic acid test of ethyl acetate and
acetamide.
Preliminary Test

In the hydroxamic acid test, a yellow

color of the resulting mixture during the
preliminary test proves the enolic character of
the mixture. Ethyl acetate and acetamide were
converted to hydroxamic acid upon heating with
NH2OHCl. The deep burgundy discoloration of
ethyl acetate and acetamide was due to the
reaction of hydroxamic acid with FeCl3.

Carboxylic acid and derivatives can be

classified by different classification tests. The
types of nucleophilic acyl substitution that a
carboxylic
acid
derivative
undergoes
are
hydrolysis, aminolysis and alcoholysis and using
the gathered positive result, the presence of the
particular carboxylic acid derivatives may be
determined.

REFERENCES
[1] Chapter 20: Carboxylic Acid Derivatives and
Nucleophilic Acyl Substitution.
http://www.mhhe.com/physsci/chemistry/carey/s
tudent/olc/ch20carboxylic.html 11/17/15
[2] Reusch, William. Carboxylic Acid Derivatives.
https://www2.chemistry.msu.edu/faculty/reusch/
VirtTxtJml/crbacid2.htm 11/19/15
[3] Goyal, R.N. Carboxylic Acids and their
Derivatives.
http://nsdl.niscair.res.in/jspui/bitstream/1234567
89/190/1/PDF%20carboxylic%20acids.pdf
11/19/15
[4] Haynes, William M. Organic Compounds. CRC
Handbook of Chemistry and Physics 92
(2011) 94-98.
[5] Milligan, D.E, Jacox, M.E. Infared Spectrum
and Structure of Intermediates of OH with CO.
Journal of Chemical Physics 54 (1971) 927942.