Classification Tests for Carboxylic Acids and Their Derivatives

Danika Ligores, Patrick Lopez, Santi Macadangdang, Louise Magbanua, Alyssa Malixi, Thea Mallari
Group 5, 2F-PH, Department of Pharmacy, Faculty of Pharmacy

Abstract
In this experiment, the objectives are to differentiate the reactivities of carboxylic acids and their
derivatives, distinguish carboxylic acids and their derivatives using classification tests and to explain
through chemical equations and mechanisms the reaction involved in each test. The tests may yield
positive or negative results and will determine the presence of carboxylic acids and its derivatives.
Hydrolysis of Acid Derivatives using acyl halides and acid anhydrides, esters (ethyl acetate) and amides
was the first test performed to find out if the sample has gone under hydrolysis by comparing the
temperatures, formation of precipitates upon addition of 2% silver nitrate and the reactions upon
addition of saturated sodium bicarbonate, the odor and color change in litmus paper. Second,
Alcoholysis: Schotten-Baumann Reaction using acetic acid and acyl halides and acid anhydrides was
done to test for hydrolysis by comparing the odor and the formation of layers. Aminolysis: Anilide
Formation was the third test undergone by comparing the appearance of the precipitates. Lastly, the
Hydroxamic Acid Test was done by comparing the preliminary tests and the color of the solution upon
adding 5% Ferric Chloride.
Introduction
Generally, carboxylic acids are weak
acids which contain a carbonyl group and
attached to it is a carboxyl group. Carboxylic
acid derivatives have a carbonyl group
attached to either an electronegative element
or a substituent which would determine the
reactivity of the compound. Like alcohols,
carboxylic acids form strong intermolecular
hydrogen bonds.
Most carboxylic acids exist as dimmers
which are held together by two hydrogen
bonds which causes the significant higher
boiling points than other compounds. Low
molecular weight and solubility in water are
some of the properties of carboxylic acids.
The most common carboxylic acid derivatives
are acyl halide, acid anhydride, ester and
amide with acyl halide being the most
reactive and amide being the least.
Acyl halides are commonly used as a
starting material for synthesis due to its high
reactivity. Acid anhydrides are mostly used in
the preparation of acetate esters, aspirin, and a
precursor to various resins.
Esters, which are found in essential oils
and fruits, are typically used in making
perfumes, artificial flavorings, varnishes and
paints. Amides are frequently found in nylon,
proteins and drugs like LSD and penicillin.

Figure 1 Structural formula of

acetamide

Figure 2 Structural formula of acetic acid

Figure 3 Structural formula of

benzamide

Figure 4 Structural formula of ethyl

acetate

Figure 5 Structural formula of acetic

anhydride

Figure 6 Structural formula of acetyl

chloride
All carboxylic derivatives yield the parent

carboxylic acid upon reaction with water. One

derivative can be converted to another, provided the
first is more reactive than the second. The reaction
mechanism is the same for each of its derivatives in
which
the
nucleophile attacks
the carbonyl group
forming an unstable
intermediate.
A
way of stabilizing
the newly formed
organic compound
is the removal of
the weakest base in
the compound. The
mechanism
involved in this
experiment
is
nucleophilic acyl
substitution which involves the leaving group by a
nucleophile resulting the formation of carboxylic acid
derivatives.
Methodology
In the first test, under acyl halides and acid
anhydrides, we first placed 1 mL of water in a test
tube then we cautiously added dropwise 10 drops of
the sample. The warming effect was noted. Second,
we divided the resulting mixture in the first part into
two portions. To the first, we added 1 mL of 2%
silver nitrate. The precipitation was observed. To the
second portion, we added 1 mL of saturated sodium
bicarbonate. The evolution of gas was then noted.
Under esters, we first addded 2 mL of 25% sodium
hydroxide solution to 1 mL of ethyl acetate. The
mouth of the test tube was covered with a marble and
the test tube was heated in a boiling water bath for 5
minutes. After boiling it in a water bath, it was cooled
down and the mixture was neutralized with 10%
hydrochloric solution. The odor was taken note of by
wafting motion.
Under amides, we treated 1 mL of benzamide
with 5 mL of 10% sodium hydroxide solution. It was
then heated until boiling. During heating, the reaction
of gas evolved was tested by holding a piece of moist
red litmus paper over the test tube. Color change in
the litmus paper was noted.
In the second test, Alcoholysis or the SchottenBaumann Reaction, under acetic acid, we warmed a

mixture of 10 drops of acetic acid, 1 mL

ethanol, and 5 drops of concentrated sulfuric
acid over a water bath for two minutes. The
odor of the ester found was noted.
Under acyl halides and acid anhydrides,
we placed 0.5 mL of ethanol, 1 mL water and
0.2 mL of acyl halide or acid anhydride
sample in a separate test tube. Then we added
2 mL of 20% sodium hydroxide solution. The
test tube was plugged with a cork stopper then
the mixture was agitated for several minutes.
The odor and the layers of the ester formed
was noted.
During the third test, known as
Aminolysis or Anilide Formation, under acyl
halides and acid anhydrides, a few drops of
acetyl chloride or acetic anhydride was added
to 0.5 mL of aniline. The mixture was then
transfered to a separate test tube containing 5
mL of water. The precipitate formed was
noted then described.
The last test, which is the Hydroxamic
Acid Test, we mixed 2 drops of the sample
(ethyl acetate & acetamide), 1 mL of 95%
ethanol and 1M hydrochloric acid during the
preliminary test. Upon addition of 5% ferric
chloride, the mixture should yield a yellow
solution otherwise the test continues with the
addition of two drops of the sample to 2 mL
of alcoholic NH2OH.HCl and 1 mL of 1M
potassium hydroxide. It was then heated in a
boiling water bath for two minutes. The
mixture was cooled then 5% ferric chloride
was added. The color of the solution was
noted.
Results and Discussion
Observations
Acyl
Warmin Upon
halides
g effect addition
and acid
of 2%
anhydrid
silver
es
nitrate
Acetyl
chloride

Very
warm

White
ppt.

Upon
addition
of
saturated
sodium
bicarbon
ate
Bubble
formatio
n

Acetic
anhydrid
e
Ethyl
acetate
Amide

Slightly
warm

No
reaction

warmer

Odor: plastic balloon-like odor

Litmus paper: red-blue, blueblue

Table 1 Hydrolysis of Acid Derivatives and

Observations
Acetyl chloride and acetic anhydride both exhibited
warming effects and upon adddition of 2% silver
nitrate, acetyl chloride formed white precipitates
while acetic anhydride had no reaction. Upon
addition of saturated sodium bicarbonate, acetyl
chloride and acetic anhydride both showed evolution
of gas. Ethyl acetate had a fruity, plastic balloon-like
odor and amide turned the red litmus paper into blue
and the blue one to blue.
Alcoholysis
Acetic acid
Acyl halides
and acid
anhydrides:
Acetyl
chloride
Acetic
anhydride

Observations
Odor: plastic balloon odor
Odor
Formation
of layers
Fruity odor

none

Plastic
baloon odor

none

Table 2 Schotten-Baumann Reaction and

Observations
After two minutes of water bath, fruity odor and
plastic balloon odor was exhibited by acetyl chloride
and acetic anhydride respectively but no layer was
formed in both.

Observations
Acyl halides Appearance of precipitate
and
acid
anhydrides:

Acetyl
chloride

experiments for advanced organic laboratory. USA:

John Wiley & Sons. Inc.

White,
W/ water, no
mushy ppt. ; ppt. , w/
w/o water
brownorange
globules
W/o water, W/
water,
no ppt.
white
crystalline
ppt., brownorage ppt.

Acetic
anhydride

Bettelheim, F.A., Brown, W.H., Campbell, M.K.,

Farrell, S.O. (2007). Introduction to General,
Organic, Biochemistry. 8th Ed. Singapore: Thomson
Learning Asia.
McMurry, J. (2011). Fundamentals of Organic
Chemistry. 7th Ed. Belmonte, CA: Brooks/Cole,
Cengage Learning.

Table 3 Aminolysis: Anilide Formation

Acetyl chloride formed a white
precipitate upon the addition of 0.5 mL
aniline.
Observations
Preliminary Upon
test
addition of
5%
ferric
chloride
Clear,
Yellow
colorless
solution
solution
Clear,
Yellow
colorless
solution
solution

Ethyl
acetate
acetamide

Table 4 Hydroxamic Acid Test and

Observations
A preliminary test was performed to
eliminate phenols that give color with ferric
chloride in acidic solution. Ethyl acetate and
acetamide both exhibited a clear, colorless
solution during the preliminary test a yellow
solution upon addition of 5% ferric chloride.
References
Pavia, D., Lampman, G., Kriz, G., & Engel,
R. (1998). Introduction to organic laboratory
techniques: a microscale approach. 3rd Ed.
USA: Saunders Publishing Company.
Garner,

CM.

(1997).

Techniques

&