THE BRITISH UNIVERSITY IN EGYPT

Aromatic Compounds
Hydrocarbons and Phenols
Perihan Hussein El-Shafei

114932

This Paper discusses the Hydrocarbons types, their properties, and highlights of
their important reactions. The Experiment conducted was to identify and
differentiate between two Aromatic unknowns. Benzene and Anthracene, using
the class identification Tests Sulfonation and Nitration, and the specific test for
Anthracene the Picrate Test to determine which is which.

Table of Contents
Introduction: Aromatic Compounds.......................................................................3
Structures of Aromatic Compunds........................................................................3
Reactions of Aromatic Compounds..........................................................................4
Nitration............................................................................................................... 4
Sulfonation........................................................................................................... 5
Picrate.................................................................................................................. 5
Phenols....................................................................................................................... 5
Properties of Phenols.......................................................................................... 6
Acidity of Phenols................................................................................................ 6
Electrophilic reactions............................................................................................. 6
Azodye Formation.................................................................................................... 7
Methods and experimental set-up:.............................................................................8
Results........................................................................................................................ 9
Results of hydrocarbons.......................................................................................... 9
Unknown 1:............................................................................................................. 9
Unknown 2............................................................................................................ 12
Bibliography............................................................................................................. 19

Introduction:
Aromatic Compounds
An aromatic compound is a organic molecule containing a benzene ring.
(About.com)
Aromatic compound, are unsaturated chemical compounds characterised by
one or more planar rings of atoms attached together by covalent bonds. The
exceptional stability of these compounds is alluded by aromaticity. Despite
the fact that the name aromatic formerly concerned odour, nowadays its
utilization in chemistry is constrained to compounds that have certain
electronic, structural, or chemical properties. Aromaticity results from a
distinct bonding arrangement that induces certain (pi) electrons within a
molecule to be firmly held. Aromaticity is typically reflected in a scaled-down
heats of combustion and hydrogenation than the expected, and is associated
with low reactivity. (Britannica, aromatic compound)
Structures of Aromatic Compunds
Bellow you will find three different ways to draw the structure of the most
famous aromatic compound Benzene, and some examples of Aromatic
compounds and their structure:

Reactions of Aromatic Compounds

Unlike simple Alkenes Aromatic compounds do not undergo addition
reactions, instead they react using a substitution manner, For example a
simple Aromatic Bromination

In this reaction the bromine atom substituted a hydrogen. For this reason the
term aromatic substitution was given to this type of reaction. This occurs
because the benzene ring is quite electron-rich, it almost always behaves as
the nucleophile in a reaction - which means that the substitution on benzene
occurs by the addition of an electrophile -> electrophilic aromatic
substitution. (Chem) The Electrophilic substitution reaction will be discussed
later on in this paper.
Nitration
making a highly electrophilic form of NO2

reacting it with aromatic compounds via the standard mechanism to give

nitrated
aromatics.

Nitration could be done for two main reasons. The first reason is, nitration in
order to manufacture explosives highly nitrated organic molecules are
frequently used as explosives for example (trinitrotoluene(TNT),
nitroglycerine, etc.). The second reason is, nitration inorder to produce
amines. This occurs because of the fact of nitro-groups being generally easy
to reduce to amines. As well as the fact of making amine electrophilic is
nearly impossible. (inorder to add it to an aromatic ring under electrophilic
aromatic substitution conditions), aromatic nitro compounds are about the
only precursors to aromatic amines:

Sulfonation

But you should be aware that this reaction is reversible if you add it to hot
Aqueous acid the SO3 group will fall off. However, the aromatic sulfonic acids
were formerly used as antibiotics. They also could be used to make
detergents.
Picrate
We could use both the sulfonation reaction and the nitration reaction to
determine whether a sample is aromatic or not in the laboratory. The tests
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are done by adding conc.

H 2 SO 4

and conc. Nitric acid . However in

Aromatic compounds we have single rings and fused rings. A Single ring is
like the Benzene Ring, the fused Ring is like Anthracene.

In order to differentiate between single rings and fused rings we apply the
Picrate test. This test is applied by adding picric acid to Anthracene solvent
in a test tube where the sample was already been added, then keeping it on
water bath, after that it is added in a watch glass, if crystals are formed then
the sample is fused rings. If it doesnt for crystals then the sample is a single
ring compound.

Phenols
phenols, are known to be any organic compound that contains the hydroxyl
(OH) functional group attached to a carbon atom that is part of an aromatic
ring. Phenols are similar to alcohols but form stronger hydrogen bonds. Thus,
they are more soluble in water than alcohols are, and have higher boiling
points. Phenols are either colourless liquids or white solids at room
temperature, and may be highly toxic and caustic. (Britannica, Phenols)

Structure of Phenols.
Properties of Phenols
Pure phenol is a white crystalline solid, smelling of disinfectant. It has to be
handled with great care because it causes immediate white blistering to the
skin. The crystals are often rather wet and discoloured. The reasons behind
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the melting and boiling point being what it is is due to permanent dipoledipole attractions due to the electronegativity of the oxygen - but is mainly
due to hydrogen bonding. Hydrogen bonds can form between a lone pair on
an oxygen on one molecule and the hydrogen on the -OH group of one of its
neighbors. (ChemGuide, Introducing Phenols)
Acidity of Phenols
Phenols are more acidic than aliphatic alcohols. As illustrated in the below
figure.

There are two main factors affecting the acidity of Phenols. First, is the
inductive effect.
A benzene ring is generally considered electron withdrawing and stabilizes
the negative charge through inductive effects. The second reason is the
resonance effect. The benzene ring stabilizes the the phenoxide ion by
resonance delocalization of the negative charge. (Vanderbilt)
Electrophilic reactions
Because the benzene rings electrons were acting as the nucleophile in the
previously mentioned reactions, rings substituted with strong electrondonating groups (particularly -electron
donating) are considered activated - they will often even react without a
catalyst! Some
examples of activating groups are: OH, OR, NH2, NR2, Alkyl. The oxygen and
nitrogen-based activating groups increase reactivity by a resonance effect:

As you can see, the very nature of the activation requires ortho-para
direction!
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Alkyl groups work somewhat differently. They are not as strong at activating
the ring,
and their main function is stabilizing the positive charge formed after the
attack on the
electrophile.
Azodye Formation
Azo dye compounds contain
. Due to the N double N in the compound the
R- is much more stable than it wouldve been in the form of alkyl, this occurs
because - N = N becomes part of an extended delocalised system. The Azo
compounds are highly colored and are used as Dyes. (ChemGuide, REACTIONS OF
DIAZONIUM SALTS) Below is the reaction of Azos with Phenols.

(4college.com)

Methods and experimental set-up:

Procedure: (for benzene and toluene)

In a dry test tube add equal volumes of 1mL of conc. HNO3 and conc.
H2SO4. To this mixture slowly add 1mL of hydrocarbon drop wise with
shaking. Cool the reaction mixture, stand for 2 min. Carefully pour the
reaction mixture into 20 mL cold water.
Procedures:
In a dry test tube add 1mL of benzene or toluene then slowly add 1 ml
of conc. H2SO4. Shake the reaction mixture well till a homogenous
solution is obtained. Heat the reaction mixture for 10 minutes in a
water bath at 90 oC. Cool, then carefully pour the reaction mixture into
20 mL ice cold water.
Freezing Test (to differentiate between Toluene and benzene)
In a dry test tube place 1mL of liquid hydrocarbon (benzene and
toluene) put the tube in an ice path for 5 min. Benzene will solidify to
colorless crystals at 5 oC, while toluene will remain liquid.
Nitration (Naphthalene)
Dissolve 0.5 gm of naphthalene in 2 mL glacial acetic acid and cool the
solution. Slowly add 1 mL of nitric acid to reaction mixture. Heat the
reaction mixture for 3 min. in a water bath at 90

C. Cool, then

carefully pour the reaction mixture into 20 mL ice cold water.

Picrates Test (for naphthalene and anthrracene)
In a dry test tube make a saturated solution of the hydrocarbon in
benzene or acetone (according to in which picric acid is dissolved). To
this solution add the solution of picric acid and shake well, concentrate
by boiling on a water bath (not on direct flame). Colored red or yellow
crystals will be obtained on pouring on porcelain or a glass.

Results
Results of hydrocarbons
Benzene
Anthracene

Nitration
Forms a
coloured ppt
Forms an oily
ppt

Sulphonation
Forms a
coloured ppt
Forms an oily
ppt

Picrate test
No result
Red crystals
are formed

Unknown 1:
Physical Characteristics:

Appearance: clear liquid

Color : colorless liquid
Odor: aromatic odur
Solubility in water: insoluble
Boiling point: 80 oC
Melting point: 5.5 oC

Chemical reactions:
Test

Observation

Result

Nitration Test

Yellow oil

Nitrobenzene is
formed.

Sulfonation test

Clear Solution

Benzene Sulphonic
acid is formed.

Pictrate test

-ve

Not Anthracene.

Unkown is: Benzene,

write the structure: C 6H6

Comment using chemical equations:

First and second tests indicate the aromaticity of this compound.

Nitration Test:

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Mechanism:

(1)

Sufonation Test:
OR

The product is benzenesulphonic acid.

The electrophile is actually sulphur trioxide, SO3, accordingly we may write
the equation for the sulphonation reaction as follows:

Mechanism :

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Stage one:

Stage Two:

(2)

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Last test indicate that the unknown is benzene, because it would only react
with Anthracene, therefor since it gave a negative result with this unknown it
means that this is not Anthracene, So it is Benzene.

Unknown 1:
Physical Characteristics:

Appearance: clear liquid

Color : colorless liquid
Odor: aromatic odur
Solubility in water: insoluble
Boiling point: 80 oC
Melting point: 5.5 oC

Chemical reactions:
Test

Observation

Result

Nitration Test

Yellow oil

Nitrobenzene is
formed.
(Aromatic compound.)

Sulfonation test

Clear Solution

Benzene Sulphonic
acid is formed.
(Aromatic compound.)

Pictrate test

-ve

Not Anthracene.

Unkown is: Benzene,

write the structure: C 6H6

Comment using chemical equations:

13

Nitration and sulfonation tests were used to identify whether the unknown is
aromatic or not, since it gave a +ve result then the unknown is aromatic.
Next the Picrate test was done to determine whether the unknown is
Anthracene or not, since it gave a ve result then the compound is Benzene.

Unknown 2
Physical Characteristics:

Appearance: colorless crystals

Color : colorless
Odor:
Solubility in water: insoluble
Boiling point: 340 oC
Melting point: 218 oC

Chemical reactions:
Test

Observation

Result

Nitration Test

+ve result (Yellow oil)

Aromatic compound.

Sulfonation test

+ve result (Clear

Solution)

Aromatic compound.

Pictrate test

Red picrate

Anthracene is formed.

Unkown is: Anthracene

write the structure: C 14H10

Comment using chemical equations

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Nitration and sulfonation tests were used to identify whether the unknown is
aromatic or not, since it gave a +ve result then the unknown is aromatic.
Next the Picrate test was done to determine whether the unknown is
Anthracene or not, since it gave +ve result then it shows that the product is
anthracene.

Results of Phenols
Phenol

Resorcinol

FeCl3

Violet

violet

NaOH
Azo-dye
Phthalei
ne

Green-blue
Red-dye
Pink

Brown
Red ppt
Fluorescent
green

OH

OH

Alphanaphthol
Green to
violet
No reaction
Brown red
Green

OH

OH

OH

Reagent

H2 O
NaOH

15

-naphthol

violet

greenish
turns to
violet

green or
blue

deep
green

FeCl3

Liebermann
H2 S O4

No reaction
Scarlet red
Faint green

OH

OH
OH

phenol
soln. +

Betanaphthol
Green

OH
quinol

naphthol

catechol resorcinol

green
color
slowly

green
violet color red, green
turns red discharged then
by NaOH by sodium yellow
acetate

brownish
black

deep
green
brown

red
green or blue

red

Azo-Dye

red ppt.

brownish
red color

scarlet red

Phthalin

red

green

faint green

deep blue
red
brownish
red ppt.

blue

green
fluoresence

purple

Unknown 1

Physical Characteristics:

Appearance: crystalline solid

Color : white
Solubility in water: soluble

Chemical reactions
Test

Observation

Result

Reaction with NaOH

Green

Phenol

FeCl3 Test

Violet color

Phenol

Phthalein Test

Pink color

Phenol

Azodye Test

-ve

Phenol

Unknown is: Catechol

Red

write the structure: C 6H6O2

Comment using chemical equations:

All tests which is done show that the product is phenol.

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Unknown 2

Physical Characteristics:

Appearance: needles
Color : colorless
Solubility in water: soluble

Chemical reactions
Test

Observation

Result

Reaction with NaOH

Brown color

Resorcinol

FeCl3 Test

Violet color

Resorcinol

Phthalein Test

Fluorescent green

Resorcinol

Azodye Test

Red

Resorcinol

Unkown is: Resorcinol

structure: C6H6O2

17

write the

Unknown 3
Physical Characteristics:

Appearance: solid
Color : white
Solubility in Water: soluble in water

Chemical reactions
Test

Observation

Reaction with NaOH

-ve result

FeCl3 Test

green

-naphthol

Phthalein Test

Green color

-naphthol

Azodye Test

Brown red ppt.

-naphthol

Unkown is: -naphthol

Result

write the structure: C 10H7 OH

Comment using chemical equations:

The(-ve) result with NaOH indicates that the unknown is a phenol, and then
three tests are carried out, and accordingly to their observation it was
deduced that the unknown is -naphthol.

18

Unknown 4
Physical Characteristics:
Appearance: crystalline solid
Color : colorless
Solubility in Water: slightly soluble in water
Chemical reactions

Test

Observation

Reaction with NaOH

-ve result

FeCl3 Test

Green slowly color

-naphthol

Phthalein Test

Faint green color

-naphthol

Azodye Test

Scarlet red color

-naphthol

Unknown is: -naphthol

C10H7OH

Result

write the structure:

Comment using chemical equations:

The(-ve) result with NaOH indicates that the unknown is a phenol, and then
three tests are carried out, and accordingly to their observation it was
deduced that the unknown is -naphthol.

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Bibliography
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http://www.chemguide.co.uk/mechanisms/elsub/nitrationtt.html
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http://www.chemguide.co.uk/mechanisms/elsub/nitrationtt.html
4college.com. (n.d.). Azo Compounds. Retrieved from 4college:
http://www.4college.co.uk/a/Cd/azo.php
About.com. (n.d.). Aromatic Compound Definition. Retrieved November 11, 2013,
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http://chemistry.about.com/od/chemistryglossary/a/aromaticcmpndef.htm
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Encyclopedia Britannica:
http://www.britannica.com/EBchecked/topic/35891/aromatic-compound
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%20Chemistry.pdf
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ChemGuide: http://www.chemguide.co.uk/organicprops/phenol/background.html
ChemGuide. (n.d.). REACTIONS OF DIAZONIUM SALTS. Retrieved from ChemGuide:
http://www.chemguide.co.uk/organicprops/aniline/propsdiazo.html
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http://www.vanderbilt.edu/AnS/Chemistry/Rizzo/Chem220b/Ch24.pdf

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