(1,1) .

Definition of Aniline

Figure (1,1)

Aniline is found already formed in coal tar. M. Runge enumerated among the alkaline
products of coal tar, pyrrhol, aniline (called by him cyanol) and leukoline. Picoline,
naphthalin, and paranaphthalin were also found by MM. Anderson and Anders. The aniline
in tar is the product of the action of phenic acid on ammonia. At first these two substances
yield a compound phenate of ammonia NH 4O . C12H5O Ammonia. Phenic acid.which at a
high pressure is transformed into aniline and water,

NH4O + C12 + H2O CL2H7N + 2HO.I

Phenate of ammonia. Aniline. Water By treating the heavy hydrocarbons with dilute hydro
chloric acid aniline is dissolved from them in the form of hydroehlorate, which can be
obtained in the dry state by evaporating the solution. From this salt aniline may be easily
got by distillation with lime or potash. In the tar oils a small quantity of this substance
remains, but much too small to allow it to be extracted profitably. aniline must be produced
artificially. Analogous to the probable formation of aniline from the phonate of ammonia,

feedstock for polyurethanes

1.2 Aniline Properties[2]
1.2.1 physical properties of Aniline

Chemical formula C6H7N

Molar mass 93.13 g. mol-1

Appearance Colorless to yellow liquid

Density 1.0217 g/mL

Melting point -6.3 (20.7 0F,266.8 k)

3.6 g/100 mL at 20 0C
Solubility in water

Boiling point 184.13 0C ,363.43 0F ,457.28K)

Vapor pressure
0.6 mmHg(200C)

Acidity (pka ) 4.6 (for the conjugated

acid )

Freezing point -6.03

1.2.2 CHEMICAL PROPERTIES:

Aromatic amines are usually weaker bases than aliphatic amines by the difference in Pka of
the conjugate acids of aniline. Pka of Aniline is 4.63 and Pka of cyclo hexyl amine is 10.66.

This is due to resonance effect. Aniline is stabilized by sharing its lone-pair electrons with
the aromatic ring.

Aromatic amines form addition compounds and complexes with many inorganic
substances, such as Zinc chloride,copper chloride, Uranium Tetrachloride, or Boron
Trifloride.Various metals react with amino group to form metal anilides; Hydrochloric,
sulphuric, or Phosphoric acid salts of aniline are important intermediates in the dye
industry.

1.3. Uses[3]

Aniline is predominantly used as a chemical intermediate for the dye, agricultural,

polymer, and rubber industries.
It is also used as a solvent, and has been used as an antiknock compound for gasoline. .
Illustrative of the drugs prepared from aniline is paracetamol
(acetaminophen, Tylenol )
The principle use of aniline in dye industry is as a precursor to indigo ,the blue

1.4. Historical View[5]

Aniline was first isolated 1826 by Otto Unverdorben by destructive distillation of indigo. He
called it crystalline. In 1834, Friedlieb Runge isolated a substance from coal tar that turned
a beautiful blue color when treated with chloride of lime. He named it kyanol or cyanol. In
1840 , Carl Julius Fritsch (1808-1871) in indigo with caustic potash and obtained an oil that
he named aniline, after an andigo-yielding plant.
In 1842, Nicolay Nikolavich Zinin reduced nitrobenzene and obtained a base that he named
benzidam. In 1843, August Wilhelm von Hofmann showed that these were all the same
substance, known thereafter as phenyl amine or aniline.

1.5. production of aniline[1]

1.5.1 production of aniline from benzene
 nitration exothermic catalytic hydrogenation
benzene nitrobenzene aniline

C6H6 + HNO3 C6H5NO2 + H2O

C6H5NO2 + 3H2 C6H5NH2 + 2H2O

is the process of introducing the amino group (NH2) into an organic compound as, for
example, the production of aniline (C6H5NH2) by the reduction of nitrobenzene (C6H5NO2)
in the liquid phase or in the vapor phase in a fluidized bed reactor . For many decades, the
only method of putting an amino group on an aryl nucleus involved adding a nitro (NO2)
group, then reduction to the amino (NH2) group. Without high-pressure vessels and
catalysts, reduction had to be done by reagents that would function under atmospheric
pressure

RNO2 + 3H2 RNH2 + 2H2O

reducing agents available under these restrictions are:

1. Iron and acid
2. Zinc and alkali
3. Sodium sulfide or polysulfide
4. Sodium hydrosulfite
5. Electrolytic hydrogen
6. Metal hydride

1.5.2. production of aniline from phenol

Amination is also achieved by the use of ammonia (NH3), in a process referred to as

ammonolysis. An example is the production of aniline (C6H5NH2) from chlorobenzene
(C6H5Cl) with ammonia (NH3). The reaction
proceeds only under high pressure.The replacement of a nuclear substituent such as
hydroxyl (OH), chloro, (Cl), or sulfonic acid (SO3H) with amino (NH2) by the use of
ammonia (ammonolysis) has been practiced for some time with feedstocks that have
reaction-inducing groups present thereby making replacement easier. For example, 1,4-
dichloro-2-nitrobenzene can be changed readily to 4-chloro-2-nitroaniline by treatment
with aqueous ammonia. Other molecules offer more processing difficulty, and pressure
vessels are required for the production of aniline from chlorobenzene or from phenol
C6H5NH2 + H2O
C6H5OH + NH3 C6H5NH2 + H2O

Ammonia is a comparatively low cost reagent, and the process can be balanced to produce
the desired amine. Phenol Ammonia

Catalytic
reactor
Ammonia recovery column
Dehydrating column
Purification column
Bottoms removal column
Ammonia recycle Water Aniline Azeotrope Azeotrope recycle Diphenylamine.

1.6. Selection process

The first method is the most widely used in industrial chemical processes for the following
reasons [6] :

Dealing with phenol is not easy ,so gasoline is best used to produce aniline
Phenol requires an acidic medium while the stimulating medium causes erosion
Gasoline freezes at 5 and evaporates at 40

Phenol is more dangerous and causes burns and wounds of user .

1.8. PROCESS DESCRIPTION

Rayer and Allied work with nickel sulphide catalysts at 300-475 C in a fixed bed. The
activation of the hydrogenation catalysts with Cu or Cr, and the use of different supports
and catalyst sulfidization methods with sulphate, H2S or CS2 all belong to the expertise of
the corresponding firms. The selectivity to aniline is more than 99%. The catalytic activity
slowly decreases due to carbon deposition. However, the catalyst can be regenerated with
air at 250-350C and subsequent H2 treatment. Similar processes are operated by Lonza
with Cu on pumice, by ICI with Cu, Mn, or Fe catalysts with various modifications involving
other metals, and by Sumitomo with a Cu-Cr system.

1.9. Flow sheet

1.10.1 Hazard Summery

Exposure to aniline may occur from breathing contaminated outdoor air, smoking tobacco,
or working or
being near industries where it is produced or used. The acute (short-term) and chronic
(long-term) effects
of aniline in humans consist mainly of effects on the lung, such as upper respiratory tract
irritation and
congestion. Chronic exposure may also result in effects on the blood. Human cancer data
are insufficient
to conclude that aniline is a cause of bladder tumors while animal studies indicate that
aniline causes
tumors of the spleen. EPA has classified aniline as a Group B2, probable human carcinogen

1.10.2 Health Hazard Information

- Acute Effects:
Acute inhalation exposure to high levels of aniline in humans has resulted in effects on the
lung, such as
upper respiratory tract irritation and congestion.
Aniline has been classified as very toxic in humans, with a probable oral lethal dose in
humans at 50 to 500 milligrams per kilogram body weight (mg/kg).
milligrams per kilogram body weight (mg/kg).
Aniline is considered to have high acute toxicity, based on short-term animal tests in rats.
- Chronic Effects (Non cancer):
The major effects from chronic inhalation exposure to aniline in humans is the formation
of
methemoglobin, which can cause cyanosis (interference with the oxygen-carrying capacity
of the blood).
Aniline is severely irritating to mucous membranes and affects the eyes, skin, and upper.
Significant amounts of aniline can be absorbed through the skin.