I.

EXPERIMENT TITLE : Aldehyde, ketone and Carboxylic Acid

Identification
II. EXPERIMENT DATE : Tuesday, February 27th 2018 at 10.20 a.m.
– 16.20 p.m.
III. EXPERIMENT PURPOSE :
1. To identify organic compound that contain aldehyde group.
2. To identify organic compound that contain ketone group.
3. To identify organic compound that contain carboxylic group.
4. To differentiate between aldehyde, ketone, and carboxylic acid in the
organic compound.
IV. BASIC THEORY
A. Definition of Aldehyde, Ketone and Carboxylic Acid
Everyone has at least some first hand sensory knowledge of
aldehydes and ketones. Some aldehydes are responsible for very pleasant
tastes and odors, such as vanillin from vanilla beans, benzaldehyde from
almonds, and cinnamaldehyde from cinnamon. On the other hand,
acetaldehyde causes unpleasant hangover feeling that can result from
consuming alcoholic beverages, and formaldehyde (methanal) is highly
toxic and has a very pungent odor, as do many other aldehydes.

Structurally, the difference between the chemical causes of

hangovers and the taste of vanilla ice cream is simply a methyl group
versus a substituted phenyl group. But, what a difference this switch
makes ice cream would not be pleased in their dessert were replaced
replaced by acetaldehyde.

An aldehyde is an organic compound. It contains a formyl group.

A formyl group is a part of a molecule with the structure R-CHO. It is
made of a carbon double bonded to oxygen. The oxygen is also bonded
to hydrogen and an R group. A side chain is the rest of the molecule. The
group without the side chain is called the aldehyde group or formyl group.
Aldehydes are different from ketones because the formyl group is at the
end of the molecule in an aldehyde. Ketones have the formyl group in the
middle of the molecule. Aldehydes are common in organic chemistry.
Many fragrances (smell producing compounds) are aldehydes. Aldehydes
have a carbon double bonded to an oxygen. Because of this, they are
slightly polar. This causes aldehydes to have a number of properties. One
of the most important of these is solubility in water.

Aldehydes can be subjected to a number of reactions. In fact, the

Virtual Organic Chemistry Book lists over 10 common reactions of
aldehydes. A key similarity in the reactions of aldehydes is that the
carbonyl is the site of reactivity. The carbonyl carbon of aldehyde is
slightly positive because it is double bonded to an electronegative oxygen.
Due to the positive nature of the carbonyl carbon, aldehydes are
considered electrophiles. Electrophiles, or electron 'loving' molecules,
attract the electrons from molecules called nucleophiles. A nucleophile is a
molecule capable of donating a pair of electrons to form a new covalent
bond. You can think of electrophiles and nucleophiles like magnets. The
positive magnet (electrophile) attracts the negative magnet (nucleophile).
When aldehydes react with nucleophiles, the nucleophile forms a
new bond with the carbonyl carbon. This action is called a nucleophilic
attack. Molecules that act as nucleophiles typically have oxygens, such as
H2O, or nitrogen's, as in NH3, with lone pairs of electron free to 'attack'
the carbonyl carbon. In organic chemistry, the nucleophilic attack of
aldehydes is classified as an addition reaction. Often in reactions of
aldehydes, nucleophilic attack is followed by loss of water. This process is
called condensation.
Ketone, any of a class of organic compounds characterized by the
presence of a carbonyl group in which the carbonatom is covalently
bonded to an oxygenatom. The remaining two bonds are to other carbon
atoms or hydrocarbon radicals.

Ketone compounds have important physiological properties. They

are found in several sugars and in compounds for medicinal use, including
natural andsynthetic steroid hormones. Molecules of the anti-inflammatory
agent cortisonecontain three ketone groups.
Only a small number of ketones are manufactured on a large scale
in industry. They can be synthesized by a wide variety of methods, and
because of their ease of preparation, relative stability, and high reactivity,
they are nearly ideal chemical intermediates. Many complex organic
compounds are synthesized using ketones as building blocks. They are
most widely used as solvents, especially in industries
manufacturing explosives, lacquers, paints, and textiles. Ketones are also
used in tanning, as preservatives, and in hydraulic fluids.
The most important ketone is acetone (CH3COCH3), a liquid with a
sweetish odour. Acetone is one of the few organic compounds that is
infinitely soluble inwater (i.e., soluble in all proportions); it also dissolves
many organic compounds. For this reason—and because of its low boiling
point (56 °C [132.8 °F]), which makes it easy to remove by evaporation
when no longer wanted—it is one of the most important industrial
solvents, being used in such products as paints, varnishes, resins, coatings,
and nail-polish removers.
Carboxylic acid, any of a class of organic compounds in which
a carbon (C) atom is bonded to an oxygen (O) atom by a double bond and
to a hydroxyl group (−OH) by a single bond. A fourth bond links the
carbon atom to a hydrogen (H) atom or to some other univalent combining
group. The carboxyl (COOH) group is so-named because of the carbonyl
group (C=O) and hydroxyl group.

The chief chemical characteristic of the carboxylic acids is their

acidity. They are generally more acidic than other
organiccompounds containing hydroxyl groups but are generally weaker
than the familiar mineral acids (e.g., hydrochloric acid, HCl,sulfuric acid,
H2SO4, etc.).
Carboxylic acids occur widely in nature. Thefatty 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 ofamino
acids, which also contain carboxyl groups.
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 intextile 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 rubbermanufacture. 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.
B. Reaction of Aldehyde. Ketone and Carboxylic Acid
Tollens’ test, also known as silver-mirror test, is a qualitative
laboratory test used to distinguish between an aldehyde and a ketone. It
exploits the fact that aldehydes are readily oxidized (see oxidation),
whereas ketones are not. Tollens’ test uses a reagent known as Tollens’
reagent, which is a colorless, basic, aqueous solution containing silver ions
coordinated to ammonia [Ag(NH3)2+][Ag(NH3)2+]. It is prepared using a
two-step procedure.
Step 1: Aqueous silver nitrate is mixed with aqueous sodium hydroxide.

AgNO3+NaOH2AgOH→AgOH+NHO3→Ag2O+H2OAgNO3+NaOH→
AgOH+NHO32AgOH→Ag2O+H2O

Step 2: Aqueous ammonia is added drop-wise until the precipitated silver

oxide completely dissolves.

Ag2O+4NH3+H2O→2Ag(NH3)+2+2OH−Ag2O+4NH3+H2O→2Ag(NH
3)2++2OH−

Tollens’ reagent oxidizes an aldehyde into the corresponding carboxylic

acid.

The reaction is accompanied by the reduction of silver ions in Tollens’

reagent into metallic silver, which, if the test is carried out in a clean glass
test tube, forms a mirror on the test tube.

Fehling's reagent, a blue colored basic solution of

bistartratocuprate(II) complex, is added to three different aqueous sugar
solutions immersed in beakers of warm water. A brick-red precipitate
forms in the solutions containing glucose and fructose. There is no
reaction in the test tube containing sucrose solution.

Fehling's solution is used as a chemical test used to differentiate

between water-soluble aldehyde and ketone functional groups, and as a
test for monosaccharides. The test was developed by German
chemist Hermann von Fehling in 1849.[1]

Fehling's solution is always prepared fresh in the laboratory. It is

made initially as two separate solutions, known as Fehling's A and
Fehling's B. Fehling's A is a blue aqueous solution of copper(II)
sulfate pentahydrate crystals, while Fehling's B is a clear solution of
aqueous potassium sodium tartrate (also known as Rochelle salt) and a
strong alkali (commonly sodium hydroxide).

Equal volumes of the two mixtures are mixed together to get the
final Fehling's solution, which is a deep blue colour. In this final mixture,
aqueous tartrate ions from the dissolved Rochelle salt chelate to Cu2+ (aq)
ions from the dissolved copper sulfate crystals, as bidentate ligands giving
the bistartratocuprate(II)complex as shown in the accompanying
illustration.

Fehling's can be used to determine whether a carbonyl-

containing compound is an aldehyde or a ketone. The bistartratocuprate(II)
complex in Fehling's solution is anoxidizingagent and the active reagent in
the test. The compound to be tested is added to the Fehling's solution and
the mixture is heated. Aldehydes are oxidized, giving a positive result, but
ketones do not react, unless they are alpha-hydroxy-ketones. The
bistartratocuprate(II) complex oxidizes the aldehyde to a carboxylateanion,
and in the process the copper(II) ions of the complex are reduced to
copper(I) ions. Red copper(I) oxide then precipitates out of the reaction
mixture, which indicates a positive result i.e. that redox has taken place
(this is the same positive result as with Benedict's solution. A negative
result is the absence of the red precipitate; it is important to note that
Fehling's will not work with aromaticaldehydes; in this case Tollens'
reagent should be used. Aldehydes are oxidised to corresponding
carboxylate anion. Aromatic aldehydes do not respond to this test.

Sodium bisulfite (NaHSO3) adds to aldehydes and some ketones to

give what is usually known as a bisulfite addition compound. The reaction
occurs by nucleophilic attack of a lone pair on the carbonyl group. This
leaves a positively charged sulfur atom but a simple proton transfer leads
to the product.

The products are useful for two reasons. They are usually crystalline and
so can be used to purify liquid aldehydes by recrystallization. This is of
value only because this reaction, like is reversible. The bisulfite
compounds are made by mixing the aldehyde or ketone with saturated
aqueous sodium bisulfite in an ice bath, shaking, and crystallizing. After
purifi cation the bisulfite addition compound can be hydrolysed back to the
aldehyde in dilute aqueous acid or base.

2,4-Dinitrophenylhydrazine (2,4-DNP or 2,4-DNPH) reacts readily

with aldehydes and ketones viaa condensation reaction (the lone pair of
electrons on the terminal amino group in 2,4-DNPH makes it a strong
nucleophile and the condensation starts by the nucleophilic 2,4-DNPH
attacking the electrophilic carbonyl carbon) to produce the corresponding
hydrazone. The hydrazine is usually a brightly colored yellow, orange or
red compound, so the reaction is often used to test for the presences of an
aldehyde or ketone.
2,4-DNPH does not react with amides, esters or carboxylic acids. As
shown below for the case of an ester, an extra resonance structure can be
drawn for these 3 types of compounds as compared to a ketone. This extra
resonance structure delocalizes some of the positive charge away from the
carbonyl carbon onto the adjacent hetero-atom (oxygen in the case of the
ester or carboxylic acid, nitrogen in the case of an amide). This makes the
carbonyl carbon less electrophilic in these compounds, and consequently
attack by the nucleophilic 2,4-DNPH is less favored.

Ketones having an α - hydrogen atom react readily with halogens

and β- haloketones are obtained as the product. The reaction is promoted
both by acids and bases.

In presence of the base, multiple halogenation occurs to give the

trihalo product.
The trihalo group is a good leaving group and the trihalo ketone
reacts with OH– which finally gives a carboxylate ion and a haloform.
This reaction is called the haloform reaction after the name of the product.
If iodine is used as the halogen, then we getiodoform( CHI3 ) as the
product. The iodoform is a bright yellow solid having a characterstic
melting point. This reaction, thus, forms the basis of the iodoform test.
Thus, methyl ketones give a positive iodoform test.
Aldehydes and ketones having at least one α-hydrogen undergo a
reaction in the presence of dilute alkali as catalyst to form β-hydroxy
aldehydes (aldol) or β-hydroxy ketones (ketol), respectively. This is
known as Aldol reaction.

The name aldol is derived from the names of the two functional groups,
aldehyde and alcohol, present in the products. The aldol and ketol
readily lose water to give α,β-unsaturated carbonyl compounds which
are aldol condensation products and the reaction is called Aldol
condensation. Though ketones give ketols (compounds containing a
keto and alcohol groups), the general name aldol condensation still
applies to the reactions of ketones due to their similarity with
aldehydes.
Carbon compounds containing a carboxyl functional group, –
COOH are called carboxylic acids. The carboxyl group, consists of a
carbonyl group attached to a hydroxyl group, hence its name carboxyl.
Carboxylic acids may be aliphatic (RCOOH) or aromatic (ArCOOH)
depending on the group, alkyl or aryl, attached to carboxylic carbon.
Large number of carboxylic acids are found in nature. Some higher
members of aliphatic carboxylic acids (C12 – C18) known as fatty
acids, occur in natural fats as esters of glycerol. Carboxylic acids serve
as starting material for several other important organic compounds such
as anhydrides, esters, acid chlorides, amides, etc.