Identification of organic compound laboratory
Identification of carboxylic acids
UNKNOWN: 24
Ali Hussein Sabr, Mustafa Abd-Alsalam|
Pharmaceutical Chemistry| 27/3/2024
Supervised by: Assist. Prof. Dr. Karima Fadhil Ali
Introduction
Carboxylic acids; are organic compounds that have a carboxyl group attached to an alkyl
group (RCOOH) or an aryl group (ArCOOH). The 'R' may be hydrogen and the result is
formic acid. They may be mono-carboxylated, multi-carboxylated, substituted (e.g.,
hydroxyl groups), or they may be aromatic.
Carboxylic acids occur widely in nature. The fatty acids are components of glycerides,
which in turn are components of fat. Hydroxyl acids, such as lactic acid (found in sour
milk products) and citric acid (found in citrus fruits), and many keto acids are important
metabolic products that exist in most living cells. Proteins are made up of amino acids,
which also contain carboxyl groups.
PAGE 1
Compounds in which the ―OH of the carboxyl group is replaced by certain other groups
are called carboxylic acid derivatives, the most important of which are acyl halides, acid
anhydrides, esters, and amides. Carboxylic acid derivatives have varied applications. For
example, in addition to its use as a disinfectant, formic acid, the simplest carboxylic acid,
is employed in textile treatment and as an acid-reducing agent. Acetic acid is extensively
used in the production of cellulose plastics and esters. Aspirin, the ester of salicylic acid,
is prepared from acetic acid. Palmitic acid and stearic acid are important in the
manufacture of soaps, cosmetics, pharmaceuticals, candles, and protective coatings.
Stearic acid also is used in rubber manufacture. Acrylic acid is employed as an ester in
the production of polymers (long-chain molecules) known as acrylates. Methacrylic acid
serves as an ester and is polymerized to form Lucite. Oleic acid is used in the
manufacture of soaps and detergents and of textiles.
Physical properties
• Only formic acid, acetic acid, and lactic acid are liquids at room temperature. The
others are solids.
• Low molecular weight carboxylic acids are soluble in water. Water-insoluble acids
dissolve in both sodium hydroxide solution and sodium bicarbonate solution. When
they react with sodium bicarbonate, they evolve carbon dioxide gas. This is considered
as a good simple indication of them.
• Their boiling points are generally high due to the association through hydrogen bonds:
two molecules of the carboxylic acid are held together by two hydrogen bonds rather
than one.
• Aromatic carboxylic acids burn with a yellow smoky flame whereas aliphatic ones burn
with a blue flame without smoke.
Chemical properties
The acidic properties of carboxylic acids are attributed to the proton of the carboxyl
group. Mono carboxylic acids are weak acids except formic acid, which is the strongest.
The tendency of the alkyl group to release electrons weakens the acid; thus formic acid is
the strongest. On the other hand presence of electron-withdrawing groups (such as
halogens) especially on the alpha carbon increases the acidity.
Reactions of carboxylic acids are related to:
• The proton as in salt formation reactions.
• Removal of the hydroxyl group as in conversion to derivatives such as esters, amides,
or acid chlorides.
• Substitution either in the alpha position of aliphatic acids or in the meta position of
aromatic ones.
PAGE 2
General test (Ferric chloride test).
The acid solution should be neutral before performing the test with ferric chloride
solution. This is achieved by adding dilute ammonia solution drop by drop with shaking
to a solution of about 0.5 gm of the acid in water until the medium becomes basic as
indicated by changing the color of litmus paper to blue or changing the color of the
phenolphthalein indicator from colorless to pink, in which case the characteristic odor
of ammonia is predominant. As mentioned above the solution should be neutral and the
excess ammonia should be removed by heating the test tube until the odor of ammonia
disappears. (Note: In the case of oxalic acid keep part of its neutral solution to be used in
its special test as will be seen later).
Cool the solution, and then add a few drops of ferric chloride solution to get different
colors of solutions or precipitates as follows: Formic acid and acetic acid give a red-
colored solution.
Succinic acid and benzoic acid give a light brown precipitate.
To distinguish between these two acids add to the precipitate a few drops of dilute
sulfuric acid to liberate the free carboxylic acid again. In one case the liberated acid is
water soluble and it is succinic acid which is aliphatic. On the other hand, benzoic acid is
liberated as a white precipitate because it is insoluble in water since it is aromatic.
PAGE 3
Salicylic acid gives a violet color.
Oxalic, tartaric, citric, and lactic acids don't give a special change. Again the details of
the general reaction are:
PAGE 4
Special tests for formic acid: Formic acid has the group (HC=O) so it can reduce
certain compounds while being oxidized:
A. HgCl2 test.
Formic acid reduces mercuric chloride to mercurous chloride (white precipitate) and, in
the presence of excess acid, to mercury element (gray precipitate).
To a few drops of the acid add a few drops of mercuric chloride solution, and Then heat
to get a white precipitate. Add an excess of the acid with heating to get the gray
precipitate of elemental mercury.
B. Tollen's test.
C. Alkaline KMnO4 test.
Formic acid reacts with potassium permanganate solution, a strong oxidizing agent, in an
alkaline medium causing de-colourization of the reagent. Mix 2 - 3 drops of the acid with
5 ml of sodium bicarbonate solution, and then add 1% potassium permanganate solution
drop by drop and observe the disappearance of a brown precipitate of manganese oxide.
PAGE 5
Special tests for oxalic acid.
1- Acidic KMnO4 test
Oxalic acid doesn't react with an alkaline potassium permanganate solution. With acidic
potassium permanganate solution, it reacts causing de-colourization of the reagent:
Dissolve 0.5 gm of the acid in 2 - 3 ml of distilled water and add 2 - 3 ml of dilute sulfuric
acid. Heat gently (water bath), and then add potassium permanganate solution drop by
drop and observe the disappearance of the violet color of the reagent.
2- CaCl2 test.
To the neutral solution of the acid (see the general test) add a few drops of calcium
chloride solution; a white precipitate of calcium oxalate is formed. This precipitate
dissolves in dilute hydrochloric acid and not in dilute acetic acid.
Special test for lactic acid.
1. H2SO4 test.
Add 1 ml of concentrated sulfuric acid to 0.5 ml of the acid and heat slowly to get
bubbles of carbon dioxide and then a black color is produced
2. Iodoform test.
Lactic acid can undergo an Iodoform formation reaction since it contains a terminal
methyl group;
PAGE 6
Fluorescence test for succinic acid.
In a test tube mix equal quantities of succinic acid and resorcinol with 2 drops of
concentrated sulfuric acid. Heat the mixture on direct flame for 1 minute until the
mixture melts. Cool and add an excess of 10% sodium hydroxide solution to get a red
color with green fluorescence. If the color is not so clear dilute with water.
Aim of experiment
To identify the presence of carboxylic acids in a given sample.
Procedure
Specific test (KMno4)
1- Mix 0.5 gm of the acid (dissolved in water) with 1 ml of sodium bicarbonate
solution, bubbles will form (CO2 gas) indicating a positive test (presence of
carboxylic acid)
PAGE 7
2- Repeat the test using a few drops of NH4OH and the litmus paper as an
indicator watching the color to be Blue (basic medium).
PAGE 8
3- Heating in a water bath for 2-3 min. to remove the excess ammonia and
neutralize the solution
4- Cool the solution, then add 1% potassium permanganate solution drop by drop
and observe the disappearance of color.
5- The violet color (color of the reagent) disappeared, then it’s a Negative test (
not a benzoic acid)
General test (ferric chloride test)
1- Dissolve 0.5 gm of the unknown in 1 ml of water
2- Add a few drops of NH4OH and the litmus paper as indicator watching the color
to be Blue (basic medium).
3- Heating in a water bath for 2-3 min. to remove the excess ammonia and neutralize
the solution
4- Cool the solution then add a few drops of FeCl3, a light brown precipitate will be
formed means that the unknown is succinic acid
PAGE 9
Discussion
Carboxylic acids are a class of organic compounds that contain a carboxyl group (-
COOH) attached to a hydrocarbon chain. Identification of carboxylic acids is
important in various fields such as organic chemistry, biochemistry, and forensic
science. Several tests can be used to identify carboxylic acids. Identification of
carboxylic acids can be done using different chemical tests, each with its unique
properties and advantages. The choice of test depends on the purpose of
identification, the type of sample, and the availability of reagents and equipment.
The Ferric chloride test is a widely used chemical test to identify the presence of
carboxylic acids. It is a simple and reliable test that can be carried out easily in the
laboratory.
The test works by adding a few drops of Ferric chloride solution to a sample of the
carboxylic acid. If the carboxylic acid is present, it will react with the Ferric
chloride to form a colored complex. The color of the complex depends on the
particular carboxylic acid present, but generally, it is a deep violet or purple color.
PAGE 10
The reaction between the carboxylic acid and the Ferric chloride involves the
coordination of the carboxylate anion to the iron(III) cation. The resulting
complex has a characteristic color due to the ligand field splitting of the iron(III)
cation in the complex.
The Ferric chloride test is highly specific to carboxylic acids and does not generally
react with other functional groups, such as alcohols, aldehydes, or ketones.
However, some phenols and amines may also give a positive result with this test.
It is important to note that the Ferric chloride test may not be suitable for all
carboxylic acids. Some carboxylic acids may form weak or unstable complexes with
Ferric chloride, leading to false-negative results. In such cases, it is necessary to
use other tests in conjunction with the Ferric chloride test to confirm the presence
of carboxylic acids.
In conclusion, the Ferric chloride test is a useful tool in the identification of
carboxylic acids, and its simplicity and reliability make it a popular choice in the
laboratory. It is important to use this test in combination with other tests to
ensure the accuracy of the identification.
The Alkaline KMnO4 test, also known as Baeyer's test, is another commonly used
chemical test for the identification of carboxylic acids. This test involves the
reaction of the carboxylic acid with a solution of potassium permanganate
(KMnO4) in the presence of a strong base, such as sodium hydroxide (NaOH).
The reaction between the carboxylic acid and the KMnO4 in the presence of the
strong base leads to the oxidation of the carboxylic acid to carbon dioxide (CO2)
and the salt of the carboxylic acid. The purple color of the KMnO4 solution
disappears, indicating that the reaction has occurred. The reaction can also be
monitored by observing the evolution of gas bubbles, which indicate the release of
carbon dioxide.
The Alkaline KMnO4 test is specific to carboxylic acids and does not generally
react with other functional groups. However, some other organic compounds, such
as aldehydes and alcohols, may also give a positive result with this test.
It is important to note that some carboxylic acids may not give a positive result
with this test, especially if they are highly branched or contain multiple carbon-
carbon double bonds. Additionally, some compounds that are not carboxylic acids,
such as some phenols and ketones, may also react with KMnO4 under alkaline
conditions.
In conclusion, the Alkaline KMnO4 test is a useful tool in the identification of
carboxylic acids, and its simplicity and specificity make it a popular choice in the
laboratory. However, it is important to use this test in combination with other
tests to ensure the accuracy of the identification, especially if the carboxylic acid is
a complex or unusual compound.
PAGE 11
