Organic Chemistry 2 Laboratory

Carboxylic Acids and their Derivatives

ABSTRACT
Carboxylic acid contains the COOH group. Carboxylic acids have their derivatives. These derivatives are acid halide, acid
anhydride, ester, amide, and nitrile. Esterification, acid and base hydrolysis, anilide formation, hydroxamic acid test, alcoholic
silver nitrate test, and sodium bicarbonate test are used to classify carboxylic acids. In this experiment, these tests are used
to classify and characterized some carboxylic acids and their derivatives. These tests are also used to differentiate organic
compound as carboxylic acid, acid halide, acid anhydride, ester, or amide based on their reactivity and characterization.
Glacial acetic acid, acetic anhydride, acetyl chloride, acetamide, and ethyl acetate are used to illustrate the positive result for
each test. The reagents used in the experiment were concentrated sulphuric acid, absolute ethanol, saturated sodium
bicarbonate, methanol, 6 M NaOH 10% CuSO4, 6 M HCl, 20 % NaOH, 5% FeCl 3 solution, 1 M HCl, 95 % ethanol, propylene
glycol, 1 M KOH, 5% nitric acid, silver nitrate in ethanol solution 1.0 M hydroxylamine hydrochloride in 95% ethanol, and
hydroxylamine hydrochloride solution in propylene glycol. All of these tests include nucleophilic addition-elimination
mechanism. To summarize some of these tests, the nucleophile attacks the carbonyl group forming tetrahedral intermediate.
The pi bond between the acyl carbon and the oxygen formed again forcing the leaving group to leave. These tests can also be
used to identify unknown compounds, when the unknown compound has identified to contain a carbonyl group based on
preliminary test and solubility classification test.

Keywords: Carboxylic Acids, Acid Halide, Acid Anhydride, Ester, Amide, and Nitrile.
INTRODUCTION

Carboxilyc acids are organic compounds which contain the O O O O

COOH group.
R X R O R R OR
O
Acid Halide Acid Anhydride Ester
C
R OH
O
Carboxylic acids are prepared by oxidative cleavage of alkynes, R C N
oxidation of primary alcohols, oxidation of alkyl benzenes R NH2
andhydrolysis of nitriles. Amide Nitrile
Carboxylic acids and their derivatives have many reactions.
Carboxylic acid exhibits hydrogen-bonding causing it to have a These reactions involve nucleophilic addition-elimination
relative high boiling point. Also, carboxylic acid is considered as mechanism. The nucleophile attacks the carbon in carbonyl and
acidic because the proton connected to the oxygen in the it forms a tetrahedral intermediate. Then the double bond in the
hydroxyl group is easily deprotonated. And the conjugate base of carbonyl is again formed and the leaving group will leave the
a carboxylic acid is relative stable because of resonance and compound.
induction. The reactions of carboxylic are used to characterize acyl
compounds. These tests include esterification, acid and base
Carboxylic acid has many derivatives. Carboxylic acid derivatives hydrolysis, anilide formation, hydroxamic acid test, alcoholic
exhibit the same oxidation state as carboxylic acids. These silver nitrate test, and sodium bicarbonate test.
carboxylic derivatives are acid halide, acid anhydride, ester,
amide, and nitrile. Esterification using ethanol is used to classify carboxylic acid,
acid halide, and acid anhydride. The evolution of pleasant smell
is an indicator of formation of ester. Esters naturally exhibits
pleasant odor.

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O O NH2
O O
O O
+ + H2O + -+
H3C OH R O CH3 + 2 R O H 3N
R OH R O R
R NHC 6H6

Carboxylic Acid Ethanol Ester

NH2
O O
Na OH O O
O O + - +
+ H3C OH R O CH3
+ R OH R X
+ 2 R NHC 6H6
X H 3N
R O R

Acid Anhydride Ethanol Ester Carboxylic Acid

Another test involves conversion of the compound to hydroxamic

O O
acid. This test is called hydroxamic test. The hydroxamic acid
R X
+ H3C OH R O CH3
+ H X
conversion to ferric hydroxamate forms burgundy to magenta
Acid
color. The formation of burgundy to magenta is a positive result
Acid Halide Ethanol Ester
for the test. For amides, the evidence of positive result is the
formation of red to orange color.
Another reaction to classify carboxylic acid derivatives is acid
hydrolysis. Acid anhydride and acid halide is hydrolyzed to form O
O
O O H
carboxylic acid with an evolution of heat. Then to confirm the +
+ N OH R NH
R OH
reaction, sodium bicarbonate is added to form carboxylic salt and R O R H OH
CO2, which is liberated. Acid Anhydride Hydroxamic Acid
O
O H
O O O +
+ N OH R NH
H X

+ H2O 2 + Heat R X
H
OH
R O R R OH
Acid Halide Hydroxamic Acid
Acid Anhydride Carboxylic Acid
O
O H

O O + N OH R NH
+ R' OH
R OR' H

+ H2O + H X + Heat
Ester
OH

R X R OH Hydroxamic Acid

Acid Halide Carboxylic Acid

O O
3 + FeCl 3 Fe + 3 HCl
O R NH R NHO
O 3
+ NaHCO 3 Na + H2O + CO 2 OH
R OH R O

Carboxylic Acid Alcoholic silver nitrate test is also used to classify carboxylic acid
and their derivatives. This test is used to determine if the
Amides can undergo hydrolysis in a presence of a base. The unknown compound is an acid halide or a carboxylic acid.
blue color on the filter paper and an odor of ammonia is a Formation of solid is an evidence of a positive result for this test.
positive result of the test.
O
O
+ H2O
R OH
+ HCl
R X

O O
O O R
+ AgNO 3 + HNO 3
+ Na OH Na + N H
R OH R O Ag
- +
R NR 2 R O R
Amide
O Sodium bicarbonate is used to identify carboxylic acid. Evolution
O
+ + + Na
+
of gas or bubbles is the positive result for this test.
Na H R OH
R O
O O
+ H2O + CO 2
+ NaHCO 3
Anilide formation is another chemical test. Acid anhydrides and R OH R OH

acid halide react with aniline to form an anilide precipitate.

In this experiment, esterification, acid and base hydrolysis,
anilide formation, hydroxamic acid test, alcoholic silver nitrate
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 Organic Chemistry 2 Laboratory
test, and sodium bicarbonate test are used to classify and
characterized some carboxylic acids and their derivatives. These
tests are also used to differentiate organic compound as
carboxylic acid, acid halide, acid anhydride, ester, or amide
based on their reactivity and characterization. Glacial acetic acid,
acetic anhydride, acetyl chloride, acetamide, and ethyl acetate
are used to illustrate the positive result for each test.
MATERIALS AND METHODS
Esterification, acid and base hydrolysis, anilide formation,
hydroxamic acid test, alcoholic silver nitrate test, and sodium
bicarbonate test were visualized using glacial acetic acid, acetic
anhydride, acetyl chloride, acetamide, and ethyl acetate. Figure 1
illustrates the chemical structure of the test compounds used in
the experiment.
O O O O
H3C OH H3C O CH3 H3C
acetic acid acetic anhydride acetyl chloride
O O
H3C NH2 H3C O CH3
acetamide ethyl acetate
Figure 1. Chemical Structure of Test Compounds
The reagents used in the experiment were concentrated
sulphuric acid, absolute ethanol, saturated sodium bicarbonate,
methanol, 6 M NaOH 10% CuSO4, 6 M HCl, 20 % NaOH, 5%
FeCl3 solution, 1 M HCl, 95 % ethanol, propylene glycol, 1 M
KOH, 5% nitric acid, silver nitrate in ethanol solution 1.0 M
hydroxylamine hydrochloride in 95% ethanol, and hydroxylamine
hydrochloride solution in propylene glycol. The materials used in
the reaction for the experiments were pipettes, micro test tube
with cork stopper, test tube reck, condenser, Erlenmeyer flask,
hot plate, iron stand warm water bath, thermometer, dropper, and
filter paper.
Esterification reaction involved the formation of esters. Glacial
acetic acid, acetic anhydride, and acetyl chloride were used as
the test compounds. Ten drops of each compound were added to
5 drops of concentrated sulphuric acid with 1 ml of ethanol in
separate micro test tubes. Each micro test tube was heated for 3
minutes in a steam bath.
Acid hydrolysis reaction involved the formation of carboxylic acid
from the carboxylic acid derivatives and the carboxylic acids
formed were identified. Three drops acetyl chloride and acetic
anhydride were placed in 1 ml of water in separate micro test
tubes. One ml of ethanol and 1 ml of saturated sodium
bicarbonate were added to the solution.
Base hydrolysis involved also the formation of carboxylic acid
from the carboxylic acid derivatives. Approximately 0.20 ml
acetamide was added to the 4 ml of 6 M NaOH. A filter paper
with 2 drops of 10% copper sulfate was placed on the top of the
beaker. The mixture was boiledfor few minutes. The solution is
acidified by adding 2 ml of 6 M HCl solution. In separate micro
test tube, ethyl acetate was also hydrolyzed. Four ml of ethyl
acetate and 5 ml of 20 % NaOH were placed on the Erlenmeyer
flask. The mixture was refluxed for five minutes. The solution was
neutralized with dilute HCl. FeCl3 was added to the solution
produced.
Cl Anilide formation involved the reaction of the carboxylic
derivatives to aniline. Approximately 0.20 ml of acetyl chloride
and acetic anhydride were placed in separate micro test tubes.
One ml of aniline and 4 ml of distilled water were added to the
micro test tubes.
Hydroxamic acid test involved the conversion of hydroxamic acid
with aid of base or basic salt. About 0.10 ml of Acetyl chloride,
acetic anhydride, and ethyl acetate was placed in separate micro
test tube with 1.0 M hydroxylamine hydrochloride in 95% ethanol
and 0.20 ml of 6 M NaOH. The solution produced was boiled and
allowed to cool for few minutes. Two ml of HCl was added. Five
percent ferric chloride was added to the solution. For amides,
0.10 ml of acetamide was dissolved in propylene glycol and 1.50
ml hydroxylamine hydrochloride solution in propylene glycol was
added. After all, 0.75 ml of 1 M KOH was added to the solution
produced. The mixture was boiled for two minutes. The mixture
was allowed to cool down. Five percent of ferric chloride was
added.
Alcoholic silver nitrate test involved the formation of silver
carboxylate salt. Approximately 0.20 ml of acetic acid and acetyl
anhydride was placed in separate micro test tubes. Two ml of
silver nitrate in ethanol solution was added to each micro test
tube. The solution was boiled for few minutes and 3 drops of 5%
nitric acid wass added.
Sodium bicarbonate test involved the evolution of carbon dioxide.
In 1 ml of of methanol in a micro test tube, 0.20 ml acetic acid
was dissolved. One ml of saturated sodium bicarbonate was to
the solution.
The reactions involved in the tests were written. All the odor and
color observed during and after the reactions were recorded.
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Also, other observations in the experiment were recorded and Clear and red layers were
noted. formed

RESULTS The solution was sparingly

soluble
Table 1. Esterification Reactions Acetyl Chloride
Cloudy layer and red layer
were formed
Test Compounds Observations

The solution was clear

Glacial Acetic Acid
It smells like plastic balloon Table 4. Hydroxamic Acid Test

The solution was clear Test Compounds Observations

Acetic Anhydride
It smells like plastic balloon
The solution was clear
Acetyl Chloride
It smells like plastic balloon
No change in color after mixing
and boiling
Acetic Anhydride
After adding FeCl3, the color
changed to purple

No change in color after mixing

Table 2. Hydrolysis and boiling
Acetyl Chloride
After adding FeCl3, the color
Test Compounds Observations changed to dark purple

Heat was evolved After adding FeCl3, the color

Acetamide
Acetic Anhydride Gas was evolved changed to red orange
It was a clear solution
After adding FeCl3, the color
Ethyl Acetate
Heat was evolved changed to purple
Acetyl Chloride Gas was evolved
It was a clear solution

Big blue spot was formed on Table 5. Alcoholic Silver Nitrate Test
Acetamide the filter paper
It gave strong foul odor Test Compounds Observations

Ethyl Acetate Red flakes was formed Formation of small particles

upon addition of silver nitrate
Acetic Anhydride
Particles were dissolved after
addinf HNO3

White precipitate formed when

silver nitrate was added
Evolution of heat was
Acetyl Chloride
Table 3. Anilide Formation observed
Particles were not dissolved in
addition of HNO3
Test Compounds Observations

Acetic Anhydride The solution is immiscible

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 Organic Chemistry 2 Laboratory

O O O

+ H2O 2
H3C OH
+ Heat
H3C O CH3
Table 6. Sodium Bicarbonate Test
O O
Test Compounds Observations + +
H3C Cl + H2O
H3C OH
HCl Heat

Heat was evolved

Bubbles were formed upon Figure 3. Acid Hydrolysis of Acetic Anhydride and Acetyl
Acetic Acid Chloride
adding saturated sodium
bicarbonate solution
The presence of the carboxylic acid formed in the acid hydrolysis
is identified by the sodium bicarbonate. The reaction between
DISCUSSION
carboxylic acid and sodium bicarbonate forms sodium salt of the
acid and water and liberates carbon dioxide gas. The formation
Carboxylic acid and their derivatives can be classified using of bubbles is the evidence of evolution of carbon dioxide gas.
different test. These tests are esterification, acid and base This formation of bubbles is the positive result for sodium
hydrolysis, anilide formation, hydroxamic acid test, alcoholic bicarbonate test. Figure 4 illustrates the reaction between sodium
silver nitrate test, and sodium bicarbonate test. bicarbonate and carboxylic acid.
Esterification reaction produces esters. Esters are derived O O
NaHCO 3
carboxylic acid that contains COOR group. In a presence of an + H2O + CO 2
- +
acid catalyst, esters are produced when carboxylic acids or their H3C OH H3C O Na
derivatives and alcohol are heated together. This reaction is slow
and reversible. In this case, the acid catalyst is the sulphuric
Figure 4. Carboxylic Aacid and Sodium Bicarbonate Reaction
acid. The acid catalyst is used to activate the carbonyl group
because the nucleophile used in the reaction is neutral or weak.
Base hydrolysis is used for the amides and esters. It involved the
The alcohol acts as the nucleophile attacking the carbonyl group
use of an alkaline solution. In this case, sodium hydroxide is
forming the ester. Glacial acetic acid with ethyl alcohol is heated
used to hydrolyzed acetamide and ester forming sodium salt of
to form ester and water. Acetic anhydride with ethyl alcohol is
the carboxylic acid. The sodium hydroxide is the nucleophile
heated to form ester and acetic acid. A fruity smell or pleasant
attacking the carbonyl group forcing the leaving group to leave.
odor shows the formation of esters and is an evidence of a
The hydrolysis of acetamide produced the sodium salt and
positive result. Figure 2 illustrates the reaction involved in
ammonia. The smell of ammonia after the heating of the solution
esterification reaction.
proves the reaction shows a positive result. Addition of the acid
O O forms precipitates. The hydrolysis of ester forms alcohol and
+
H2SO4
+ H2O sodium salt. The sweet smell of the ester will vanish after the
H3C OH H3C OH H3C O CH3
reaction is complete. Again, the addition of the acid gives
O O O O
precipitates. In ethyl acetate, red flakes were produced. Figure 5
H2SO4 shows the reaction involved in the base hydrolysis.
H3C O CH3 + H3C OH H3C O CH3 + H3C OH

O
O
O
H2SO 4
O
+ NaOH - +
+ NH3
H3C Cl + H3C OH H3C O CH3 + HCl
H3C NH2
H3C O Na

O O
Figure 2. Esterification of Carboxylic Acid, Acid Anhydride and +
Acetyl Chloride H3C O CH3
+ NaOH
H3C
-
O Na
+
H3C OH

Acid hydrolysis involves the reaction of a compound with water or
a dilute acid. This reaction forms carboxylic acid and heat. Acid
anhydride is mixed with water forming acetic acid and evolving
heat. Acetyl chloride is also mixed with water forming acetic acid
and hydrochloric acid and evolving heat. The evolution of heat is
the evidence of the positive result of the reaction. Figure 3 shows
the acid hydrolysis of acetic anhydride and acetyl chloride.
Figure 5. Base Hydrolysis of Acetamide and Ethyl Acetate
Addition of the acid forms precipitates. Addition of acid and FeCl 3
in the hydrolysis ethyl acetate produces red. Figure 6 shows the
formation of the precipitate.
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 Organic Chemistry 2 Laboratory

O O shows the positive result for the test. Acetic anhydride with silver
+
+ H nitrate forms carboxylic salt and nitric acid. Acetyl chloride first
- + H3C OH form carboxylic acid and the carboxylic acid forms carboxylate.
H3C O Na
Figure 9 shows the reaction involved in silver nitrate test.
O O

Figure 6.Formation of Precipitates 3 + FeCl 3 Fe + 3 HCl

H3C NH H3C NHO
3
OH
Anilide formation is another chemical test involving nucleophilic
addition-elimination. This reaction involves the reaction between Figure 9. Alcoholic Silver Nitrate Test
the carboxylic derivatives with aniline forming anilide precipitates.
Acetic anhydride and acetyl chloride react with aniline forming Sodium bicarbonate is used to identify the presence of carboxylic
anilide and ammonium salt. The aniline acts as the nucleophile in acid. The positive result shows an evolution of gas or formation
the reaction attacking the carbonyl group in the carboxylic of bubbles. The carboxylic acid and sodium bicarbonate reaction
derivative. Figure 7 illustrates the reaction between anilide and forms sodium salt of the carboxylic acid and gaseous carbon
carboxylic derivatives. dioxide.
NH2
O O O O O O
+ NaHCO 3
+
H3C O CH3
2
H3C NHC 6H6 H3C O
- +
H3 N
- + + H2O + CO 2
H3C OH H3C O Na
NH2
O
O
+
Figure 10. Sodium Bicarbonate Test.
- +

H3C Cl
+ 2 H3C NHC 6H6
Cl H3 N

All of these tests include nucleophilic addition-elimination

Figure 7. Anilide Formation mechanism. To summarize some of these test, the nucleophile
attacks the carbonyl group forming tetrahedral intermediate. The
Hydroxamic acid test involves the formation of hydroxamic acid. pi bond between the acyl carbon and the oxygen formed again
Ferric chloride converts hydroxamic acid to ferric hydroxamate forcing the leaving group to leave.
complex. The solution will turn to burgundy to orange showing an
positive result to the reaction. Acetic anhydride, acetyl chloride These tests can also be used to identify unknown compounds.
and ethyl acetate forms burgundy to magenta color after the test When the unknown compound has identified to contain a
is complete. Amide forms red to orange color. The formation of carbonyl group based on preliminary test and solubility
these colors shows the positive result for the test or the reaction. classification test, esterification, acid and base hydrolysis, anilide
Figure 8 shows the reaction involved in the test. formation, hydroxamic acid test, alcoholic silver nitrate test, or
O
sodium bicarbonate test can be used to further classify it and to
O
O O H
determine the identity of the unknown compound.
+ N OH H3C NH + H3C OH
H3C O CH3 H OH
CONCLUSION AND RECOMMENDATION
O
O H
+ N OH H3C NH + H Cl Carboxylic group contains the COOH group. It has derivatives.
H3C Cl
H OH These derivatives are acid halide, acid anhydride, ester, amide,
and nitrile. It can be classified by preliminary tests and solubility
O H
O classification test. After identifying that the unknown is a
+ N OH H3C NH
+ NH3
carboxylic acid or a carboxylic acid derivative, esterification, acid
H3C NH2 H OH and base hydrolysis, anilide formation, hydroxamic acid test,
alcoholic silver nitrate test, or sodium bicarbonate test can be
O H
O use to classify it. Almost all of these tests are used to identify the
H3C O CH3
+ N OH H3C NH + H3C OH presence of carboxylic acid and carboxylic acid derivative.
H OH Sodium bicarbonate test is used to identify the presence of
carboxylic acid.
Figure 8. Hydroxamic Acid Test
To have better result of the experiment, enough amounts of each
Alcoholic silver nitrate test is used to determine the possibility to reagents and test compounds should be used. Accuracy will help
have a halide or a carboxylic acid. Formation of precipitates in determining the actual identity of the unknown compound. To
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be more accurate of identifying the true identity and nature of the
unknown compound, one should be familiar of the evidences of
the positive result of these tests.The tests for carboxylic acids
and their derivatives are recommended to use if the compounds
belong to Class Sn, Class Sa, Class A1, or Class N or the
compound has found to contain a carbonyl group.
2. Klein, D. (2012) Organic Chemistry, John Wiley & Sons,
Inc.
3. Whitten, K. W., Dvis, R. E., Peck, M. L., & Stanley G.
G., (2010). Chemistry, Ninth Edition, International
Edition. Brooks/Cole, Cengage Learning.

REFERENCES

1. Carey, F. A. (2000) Organic Chemistry Fourth Edition.

United State of America: The McGraw-Hill Companies,
Inc.

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