EXPERIMENT NO.

11
PROPERTIES OF AMINES: ANILINE

PURPOSE OF THE EXPERIMENT

● The purpose of the aniline experiment is to demonstrate and investigate key chemical
reactions and appropriate qualitative observations involving aniline to achieve specific
learning objectives, including proving the basicity of amines and writing balanced
equations for diazotization, phenol formation, and coupling reactions.

MATERIALS
● Iron (III) chloride - FeCl3
● Aniline - ● Hydrochloric acid - HCl
● Sodium nitrite - NaNO2
● Sodium hydroxide - NaOH
● Phenol -
● Distilled water - H2O
● Bromine water - Br2

● Resorcinol -

APPARATUS
● Vials ● Wire gauze
● Vial brush ● Safety goggles
● Test tube holder ● Watch glass
● 100 mL beaker ● Stirring rod
● Thermometer

PROCEDURE AND OBSERVATIONS

A. Basicity

In a vial, a drop of aniline was added to 10 drops of distilled water and 2 drops of
universal indicator. It then resulted in a blue-green solution. Initially, the universal
indicator has a green color in neutral conditions. When subjected to acidic solutions, it
will turn from green to red.
 On the other hand, in basic solutions, it will turn from green to purple. In this
case, when aniline was mixed with a universal indicator, it formed a blue-green solution,
indicating that it is basic with a pH of 8.8.

Below illustrates the transition of the universal indicator’s color from a neutral pH
to an acidic and basic pH:

In a separate vial, a drop of aniline was mixed with 10 drops of distilled water and
2 drops of 15% ferric chloride solution, forming a reddish-brown precipitate of Fe(OH)3.
Since aniline readily accepts H+ ions due to its basic nature, the H2O that reacts with
aniline turns to OH- anion, which is an indicator of a basic compound as basic
compounds release OH- in water. The presence of OH- is then confirmed when it reacts
with FeCl3 to form the reddish-brown precipitate Fe(OH)3.
B. Salt Formation

In a vial, 2 drops of aniline were added with 6 drops of concentrated hydrochloric

acid. After which, a white precipitate was formed. As mentioned in the previous
experiment, aniline is a basic substance. Hence, when mixed with acid, it can neutralize
the acid and form a salt. In this case, aniline was mixed with hydrochloric acid, which is a
strong acid. The reaction between aniline and hydrochloric acid produced a white
precipitate, which is a salt called anilinium chloride. This reaction is called the
neutralization reaction. The formation of salt further confirms that aniline is indeed a
basic substance.

C. Diazotization

In a vial, 3 drops of aniline were added. It is then added with 15 drops of water
and 6 drops of concentrated hydrochloric acid. Then, it was cooled to 5°C in an ice bath.
After this, 2 drops of a cold 10% sodium nitrite solution were added. It then formed a
brown solution.

When aniline is treated with hydrochloric acid (HCl) and sodium nitrite (NaNO2)
under cold conditions, it undergoes a process called diazotization, forming nitrous acid
(HNO2). The brown solution indicates the formation of diazonium salt, which is
benzenediazonium chloride. These diazonium salts are unstable and require low
temperatures (0-5°C) to prevent it from decomposing. With that in mind, the acidic
conditions created by hydrochloric acid (HCl) and the cold temperate are essential for
the diazotization reaction to occur. Benzenediazonium chloride is a raw material used to
make dyes.
D. Formation of Phenol

One-fourth of the cold diazotized aniline from the previous step was warmed
gently in a water bath. It was then observed that the color changed to pinkish solution
and had an antiseptic-like odor. The observed color change and odor in this experiment
confirm the formation of phenol. When benzenediazonium chloride, the product of aniline
diazotization, is heated above 5°C, it decomposes to form phenol. This decomposition is
a result of the loss of nitrogen gas from the diazonium salt, leading to the formation of a
carbocation intermediate that is rapidly hydrolyzed to produce phenol.

E. Coupling and Formation of Dyes

In a vial, add 10 drops of phenol solutions. In another vial, add 10 drops of

resorcinol solutions. Then, 4 drops of NaOH were added to each vial. After which,
remaining diazotized aniline, which is benzenediazonium chloride, was divided into two,
with one half added to the phenol vial and the other half to the resorcinol vial. Shake the
solution well. Then, add 15 drops of water then shake it again. It was observed that the
vial with phenol formed a dark yellow-orange dye and the vial with resorcinol formed a
dark red dye.

The formation of the dark yellow-orange dye in the phenol vial indicates the
formation of benzeneazophenol, while the dark red dye in the resorcinol vial indicates
the formation of benzeneazoresorcinol. These azo dyes are produced through the
 coupling reaction between the previously diazotized aniline and the activated aromatic
compounds, which are phenol and resorcinol. The activation of the aromatic compounds
is achieved by adding NaOH, which facilitates the coupling reaction with the diazonium
salt. Azo dyes are the largest class of synthetic dyes, characterized by the presence of
the azo functional group (R-NN-R') or chromophore, which is responsible for their bright
colors.

F. Effect of NH2 Group on Substitution in the Benzene Ring

In a vial, add 2 drops of aniline and 15 drops of water. Then, add 1 drop of
bromine water and shake the mixture. Upon shaking the vial, a white precipitate was
formed.

The observed white precipitate is due to the formation of 2,4,6-tribromoaniline

upon reaction with bromine water. This indicates the occurrence of an electrophilic
aromatic substitution reaction. This reaction is characteristic of aniline due to the
presence of the electron-donating amino (NH2) group attached to the benzene ring.

Like aniline, phenol also undergoes electrophilic aromatic substitution reactions

with bromine water, forming a white precipitate of 2,4,6-tribromophenol. This similarity in
reactivity is due to the presence of an activating group (-OH) attached to the benzene
ring.
 In contrast to aniline and phenol, toluene exhibits lower reactivity towards
electrophilic aromatic substitution with bromine water. Toluene requires more vigorous
conditions, such as the presence of iron filings, to undergo bromination. The methyl
group in toluene is a weaker activating group compared to the amino and hydroxyl
groups in aniline and phenol, respectively.

CONCLUSION

Aniline, an aromatic amine, exhibits basicity, allowing it to dissolve in strong acids and
form salts due to its weak base nature. This basicity is attributed to the presence of the amino
group (NH2) attached to the benzene ring. Furthermore, aniline's reactivity is evident in its ability
to undergo diazotization reactions, forming diazonium salts like benzenediazonium chloride
under specific conditions. However, these diazonium salts are highly reactive and can
decompose at higher temperatures, resulting in the formation of phenol and nitrogen gas. This
decomposition was observed in the experiments as a color change to pink and the formation of
an antiseptic-like odor. Aniline's participation in coupling reactions, such as with phenol and
resorcinol, results in the formation of azo dyes, showcasing its versatility in organic synthesis.
Additionally, the reaction of aniline with bromine water demonstrates the high reactivity of the
benzene ring due to the presence of the NH2 group, forming 2,4,6-tribromoaniline.

In essence, aniline's diverse chemical properties, including basicity, salt formation,

diazotization reactivity, phenol formation, coupling versatility, and bromine reactivity, highlight its
significance in organic chemistry and its potential for various industrial applications, such as the
production of dyes, pharmaceuticals, and rubber chemicals.
THEORETICAL DISCUSSION

The experiment involves the following concepts, principles, and theories:

A. Electrophilic Aromatic Substitution (EAS)

Electrophilic Aromatic Substitution (EAS) is a fundamental concept in organic chemistry

that explains the substitution reactions of aromatic compounds with electrophiles. It is an
essential organic reaction where an atom attached to an aromatic system, typically
hydrogen, is replaced by an electrophile. This reaction proceeds through a two-step
mechanism. In the first step, the aromatic ring, acting as a nucleophile, attacks an
electrophile, which is the slow, rate-determining step. This attack disrupts aromaticity,
forming a carbocation intermediate. The second step involves the deprotonation of a C-H
bond to restore aromaticity by re-forming a C-C pi bond.

B. Arrhenius Acid and Base Theory

The Arrhenius acid and base theory, proposed by Swedish chemist Svante
Arrhenius in 1884, defines acids as compounds that increase the concentration of
hydrogen ions (H+) in aqueous solutions and bases as compounds that increase the
concentration of hydroxide ions (OH-) in aqueous solutions. Arrhenius acids dissociate to
form H+ ions, while Arrhenius bases dissociate to form OH- ions. This theory is limited to
reactions in aqueous solutions and does not account for reactions in other solvents or
gas phases. Acids, like hydrochloric acid (HCl), increase the concentration of H+ ions,
while bases, such as sodium hydroxide (NaOH), increase the concentration of OH- ions
in solution.

C. Diazotization

Diazotization is a chemical reaction that involves transforming a primary aromatic

amine into its corresponding diazonium salt. This reaction typically utilizes nitrous acid
and a mineral acid like hydrochloric acid to react with aromatic amines, resulting in the
formation of diazonium salts. These diazonium salts are crucial in synthesizing various
organic compounds, such as dyes and pigments. Diazotization plays a significant role in
 organic chemistry and has various applications in industries like dye production and
organic synthesis.

D. Coupling Reactions

Coupling reactions are a fundamental concept in organic chemistry where two

reactant molecules are bonded together, often with the aid of a metal catalyst. The
mechanism of coupling reactions involves the formation of a common intermediate and
the transfer of energy from one side of the reaction to the other. This process begins with
the formation of a common intermediate, typically a metal-carbon bond, which is the key
to the reaction. The energy from the reactants is then transferred to the intermediate,
allowing it to react with another reactant molecule to form a new carbon-carbon bond.
This reaction is the result of the transfer of energy from one side of the reaction to the
other, enabling the formation of a new bond between the two reactant molecules.
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