Topic 18 WEB LINKS

18A1 p
Web links:
Arenes = aromatics = 1/+ benzene ring

Phenyl C6H5 = iGCSE 19.2

Styrene = Phenylethene (CH2CHC6H5) = iGCSE 19.2

19.2 Poly(phenylethene) = Polystyrene

TO DO.....
Make-up:
- a Board for each of these sub-topics within Topic 18,
each with 'models' of the reaction on them!
- laminated terms for each: "Reaction name", reactant,
products, catalyst, conditions.
 Benzene C6H6 = Topic 18A.1 to 18A.3 p222-5- APPARATUS:
Toluene C6H5CH3 = Topic 18A.2 & 3
PhenylEthanone C6H5COCH3 = Topic 18A.2 & 3 Yellow tray: Models of electron orbitals (esp benzene), +
BenzeneSulfonic Acid C6H5SO3H = Topic 18A.3
and 4x Benzene models
Phenol C6H6O / C6H5OH = Topic 18A.4
Phenyl C6H5 = iGCSE Unit 19.2
Phenylamine C6H5NH2 = 19A.1 & 19A.3 SPECIFICATION
REFERENCE
18A 1 BENZENE:
Styrene
A MOLECULE 18.1 18.2 18.3

WITHTWOMODELS
=Phenylethene (CH2CHC6H5) =iGCSE 19.2
Poly(phenylethene) = Polystyrene

LEARNING
OBJECTIVES
■ Be able to use thermochemical, X-ray diffraction and infrared data as evidence for the structure and stab ility of the ben zen e ring.
"a system"
■ Understand that the delocalised model for the structure of benzene involves overlap of p-orbitals to fo rm n- bonds with
. a 'doughnut shaped
"a electron cloud' above and
■ Understand why benzene is resistant to bromination , compared to alkenes , in terms of delocalisation of n -bonds in ben zene below the
system" plane of
compared to the localised electron density of the n- bond in alkenes . Carbon
atoms, all
containing
6 electons.
WHATAREAROMATIC
COMPOUNDS? PHYSICAL
PROPERTIES
OFBENZENE
The sections in Topic 18 dea l with compounds contain ing a Benzene is a colourless liquid with a boiling temperature of
benzene ring. You have already seen benzene rings in previous 80 °C, and it is insoluble in wate[ It is present in crude oil and
sections . However, no detail was given about them. For example , the fuels obtained from it, so the petrol tank of a car contains
in the section of Topic 15 on carbonyl compounds, there was a some benzene. The one place you will not find it is in a school or
reaction involving 2,4-dinitrophenylhydrazine , which contains a college laboratory, because of its toxic nature; in particular, it is
benzene ring. In the section of Topic 15 on carboxylic acids, one a carcinogen (i.e. it can cause cancer). It was first isolated by the
of the monomers used to make polyesters was terephthalic acid, English chemist Michael Faraday in 1825. Within a few years, the
which also contains a benzene ring. compound became known as benzene and its molecular formula
was established.
Its molecular formula is C6 H6 , which suggests that it is highly
hexane
unsaturated, because the alkane with six carbon atoms has 14
hydrogen atoms. Finding a structura l formula to fit the molecular
perhaps suggesting that there was formu la, and which was supported by studies of its chemical
a lot of potential for 8 more H
atoms to be incorporated... reactions, was a challenge for chemists .

THEKEKULE
STRUCTURE
.A. fig A Many brightly coloured dyes are made from aromatic compounds. ,
One of the better -known stories in the history of chemistry is how
ORIGIN
OFTHETERM the German chemist Friedrich August Kekule came to suggest the
!Structure of benzene that still bears his name. The story goes like
The word 'aromatic ' in everyday language refers to smells,
this ... Kekule was sleeping in an armchair in front of a fire. In the
usually pleasant. Some herbs used in cooking are often described
flames he imagined some snake-like molecules dancing, one of
as aromatic .
which held its own tail and whirled around in the flames. Inspired
ALIPHATIC
ANDAROMATIC by this dream about snakes, in 1865 he proposed a cyclic or ring
structure for benzene. Fig B shows the displayed and skeletal forms
With a few exceptions , almost all the organic compounds you
of this structure.
have seen so far in this course could have been described as
'aliphatic', although this is a term we did not use to describe them
because there was no point. You can regard aliphatic cqmpounds
as all those that are not aromat ic! '

0
Aromatic: - years ago... described smelly organic compounds
- now describes the bonding in a compound... of delocalised
BENZENE electrons forming pi (π) bonding in a hydrocarbon ring.
The compound benzene is at the heart of every aromatic
compound. So, the first thing we must do is understand what is
special about benzene.
Benzene can be described as an arene, as can many of its derivatives. Skeletal
You already know that -eneindicates the presence of a C = C double fig B Kekulestructureof benzene.
bond in a molecule (as in ethene). Therefore, you would expect that Perhaps Kekule was also influenced by Josef Loschmidt , who
an arene also contains C=C double bonds . The answer is -yes and had suggested a ring structure for benzene a few years earlie[
no. This obviously needs careful explanation! Loschmidt's role in developing the structure of benzene is not well
remembered. However; you may remember his name from Book 1
as the source of the symbol L for the Avogadro constant.
 TOPIC18 1BA.1BENZENE:
A MOLECULE
WITHTWOMODELS 223

PROBLEMS
WITHTHEKEKULE
STRUCTURE BOND I BONDLENGTH/pm
We still use the original skeletal structure to represent benzene C-C in cyclohexene 154
today. However, since it was first used, there has been mounting C=C in cyclohexene 134
experimental evidence that does not fit with the structure. Several ·-
C-C in benzene 139
problems arose in the 19th century, although more became
apparent in the 20th century. table A

This evidence suggests that the carbon-carbon bonds in benzene

PROBLEM
1 are all the same, and perhaps also intermediate in character
If benzene contains three C=C double bonds, it should readily between C-C and C=C bonds.
decolourise bromine water in an addition reaction. However, it
does not decolourise bromine water. When bromine does react PROBLEM
4
with benzene, a subst itution reaction occurs (see Section 18A.2). When thermochemical data about enthalpy changes of hydrogenation
This evidence suggests that there are no C=C double bonds . became available, there was yet another problem. Table B shows
Fig C shows the results of shaking bromine water with a liquid these enthalpy changes for three relevant compounds.
alkane, benzene and a liquid alkene in separate test tubes .
COMPOUND ENTHALPY
CHANGE
OF
I mo1-1
HYDROGENATION/kJ
(p226: substitution =
heated under Reflux cyclohexene -120
with a Halogen carrier -
catalyst,
[for Bromination [by
cyclohexa-1 ,4-diene -239
substitution], this is
l J Fe filings that react
cyclohexa-1,3,5-triene (theoretical) -360
with the Bromine to
form Fe(III)Br ]) benzene (actual) -208
·-
table B 3x 120 = 360 - 208 = 152kJ/mol
All of these hydrogenation reactions form the cyclic alkane
cyclohexane. This evidence suggests the following.
• The first two values indicate that the entha lpy change for adding
1 mol of H 2 to 1 mol of C= C bonds is around-120kJ mo1-1
alkane benzene alkene
(the value for cyclohexa -1,4-diene is double that of cyclohexene
fig C The yellow colour is caused by unreacted bromine.
because there are twice as many C= C bonds).
2
PROBLEM • The Kekule structure cou ld be named cyclohexa-1,3,5-triene,
for which the value should be treble that of cyclohexene .
As more compou nds containing the benzene ring were discovered,
including those such as dibromobenzene (C4H4 Br2), another • The actual benzene has a value very much lower ( 152 kJ moJ- 1
problem arose. If the Kekule structure is correct, there should be lower) than a theoret ical structure with three C=C double
3x 120 = 360 - 208 = 152kJ/mol
four isomers with this molecular formula: bonds would have .
The values for cyclohexa-1,3,5-triene (theoretical) and benzene
Br Br Br Br

~Br(¾
(actual) can be represented on an enthalpy level diagram, as
shown in fig E.

u 0
Br~

V ~Br

Br
Kek,t;"sbemene

fig D These are the four isomers of C6 H4 Br2, assuming that the Kekule
structure is correct.
Enthalpy
Real benzene
However, only three were known to exist. So, the two isomers with
Expected:
bromine on adjacent carbon atoms are identical. It is not the case
l:!..H= -360kJmoJ - 1
that adjacent atoms in one isomer are joined by C-C and in the l:!..H= -208 kJ moJ- 1
other by C = C. This suggests that the bonds between the carbon
atoms in the benzene ring are the same, not different.

PROBLEM
3 A fig E This diagram shows the enthalpy changes for Kekule's benzene and
real benzene.
When data from X-ray diffraction about the lengths of covalent
bonds in molecules became available, there was another problem.
Table A shows the bond lengths in benzene and cyclohexene
When writing an equation for the complete hydrogenation of
(a cyclic alkene with five C-C single bonds and one C=C
benzene , make sure you include 3H 2 to balance the equation (see
double bond) in picometres.
Section 1SA.2).
 224 18A.1BENZENE:
A MOLECULE
WITHTWOMODELS TOPIC18
PROBLEM 5
Fig F shows a comparison of the infrared spectra of cyclohexene and benzene .
(a) 1.0

a, 0 .8
0
C:

-~ 0.6
E
(/)

~ 0 .4
F
0.2

0.0+--~---~-~-~-~-~
2000 1750 1500 1250 1000 750 500 250
Wavenumbers / cm - 1

(b) 1.0

a, 0.8
0
C:

-~ 0.6
E
(/)

~ 0.4
F
0.2

0.0+--~---~-~-~~~-~
2000 1750 1500 1250 1000 750 500 250
Wavenumbers / cm - 1

fig F Comparison of the infrared spectra of (a) cyclohexene and (b) benzene.
(NON-aromatic / not ring-structured)
Cyclohexene has an absorption at around 1650 cm- 1, which is typical of an isolated alkene C=C
stretch (normally between 1680 and 1645 cm- 1).
Benzene has a strong absorption at around 1500cm - 1, and also absorpt ions at 1580cm - 1 and
1450 cm - 1, which arealltypical of an aromatic C=C stretch.
Aromatic
= "delocalised electrons forming pi (π) bondING in a hydrocarbon ring"
[ "a pi (π) bond system" ]
A NEWMODEL
FORBENZENE
The weaknesses of the Kekule structure and growing evidence from other areas of chemistry led
to a new mode l of benzene. In Book 1, we explained the C=C double bond in ethene in terms of
single sigma C-C bonds and pi bonds formed by the sideways overlap of orbitals .
H H
Now consider the situation in benzene after all the sigma (a-)bonds have formed. Each carbon atom
C C has one electron in a p-orbital. You can imagine the formation of three individual 1r-bonds, but instead
system"
imagine the formation of one large "1r-bond made up of all six electrons. Three are in a doughnut
shape above the atoms and three are in another doughnut shape below the atoms. Together, these six
system"
H C C H electrons form a delocalised "1r-bond , as shown in Fig G.

C C
H H

=> so say: "a pi (π) system" / "a pi (π) bond system" fig G The delocalised structure of benzene forms when the p-orbitals overlap sideways forming a rr-electron cloud
above and below the plane of the carbon atoms. Each carbon atom contributes one electron to the cloud , giving a
delocal ised system of six electrons in total.
 TOPIC18 1BA.1BENZENE:
A MOLECULE
WITHTWOMODELS 225

PROBLEMS
SOLVED? A NEWMEANING
OF'AROMATIC'
Let us see how this new model overcomes the problem s Now we can use the old word 'aromatic ' in a new way - it refers
associated with the Kekule structure . to a hydrocarbon ring containing delocalised electrons. The
Problem 1 There are no individual C= C bond s, so there is no traditional skeletal formula for benzene can now be replaced
addition reaction with bromine. by this:

0
Problem 2 There are three , not four, isomer s of C6H 4Br2 becau se
when the bromine atoms are on adjacent carbon
atoms there is no difference in the arrangement of
electron s between these atom s.
Problem 3 The carbon-carbon bond s are all the same length system"
fig H The circle representsthe delocalised"pi bonds with six electrons in
because they are identical and are not individual C-C total.
and C=C bonds.
Problem 4 When charge is spread around in a species, there is
increased stability, which explains the 152 kJ mo1- 1 When explaining the bonding in a benzene molecule, be careful to
greater stab ility of benzene compared with cyclohexa- avoid confusion between electrons in p-orbitals and delocalised
3x 120 = 360 - 208 = 152 electrons in 1r-bonds., or in a pi (π) bond system".
1,3,5-triene.
(3xC=C bond)
Problem 5 The infrared spectrum of benzene has a very strong
absorption at around 1500 cm- 1, which is typical of CHECKPOINT
C=C in an aromatic compound. Absorptions for C=C
in non -aromatic compounds are between 1680 and 1. Using the Kekule stru cture fo r benzene, dr aw th e isomers of
Since Benzene does not have any significant IR absorption at 1680-1645 t ribrom obenzene, C6 H3 Br3 .
1645cm - 1. /cm we can't expect the standard type of C=C bonds as in non-ring
structured alkenes. 2. How many electro ns in a benzene mo lecule are invo lved in:
The fact that benzene undergoes a substitut ion reaction with
(a) a- bonding
bromine to form C6H 5Br, rather than add ition to form C6H 4 Br2 ,
can be explained because substitu tion preserves the stab ility of (b) 1r-bo ndin g?
the deloca lised electrons in the pi bond. The addit ion reaction
would instead produce a compound with two C= C double
SUBJECT
VOCABULARY
bonds , and that would lack the extra stability of the product of the
substitutio n react ion. aromatic the original meaning was a description of the smell of
certain organic compounds . The new meaning is a description of the
(p226: substitution = heated under Reflux with a Halogen carrier catalyst, bonding in a compound - delocalised electrons forming pi (1r)
[for Bromination [by substitution], this is Fe filings that react with the Bromine ,< • bonding in a hydrocarbon ring
to form Fe(III)Br ])

Aromatic
= "delocalised electrons forming pi (π) bondING in a hydrocarbon ring"
[ "a pi (π) system" / "a pi (π) bond system" ]

Change
modify NO2

and
delete
as
required
fro
duplicati