2 Year O & A Chemistry 2019 - 2021 Study Pack 6A

2nd Year O & A Chemistry 2019 - 2021 Study Pack 6A
Contents
What you need to be able to do.........................................................2
References.....................................................................................4
Exercises .......................................................................................5
(1) How the structure of benzene was determined ..........................5
(2) The structure of benzene ..................................................... 14
(3) Naming aromatic compounds ............................................... 16
(4) The reactions of benzene..................................................... 20
(5) The mechanism of electrophilic substitution reactions .............. 24
(6) Phenol .............................................................................. 30
(7) Directing groups in aromatic compounds. ............................... 35
The directing effect of substituting groups in aromatic compounds ... 37
(8) Comparing reactions of benzene with alkenes and with phenol .. 44
Summary Exercises ....................................................................... 46
Review/ Exam style questions ......................................................... 50
Glossary ...................................................................................... 63
-1-
What you need to be able to do

This study pack relates to the following sections of the specification
Module 6: Organic Chemistry and Synthesis
6.1.1 Aromatic Chemistry
Learning Outcomes Additional Guidance

(a) the comparison of the Kekulé model of Learners may represent the
benzene with the subsequent delocalised structure of benzene as
models for benzene in terms of p-orbital
overlap forming a delocalised -system HSW1,7 Development of
model for benzene over time
(b) the experimental evidence for a HSW 11 Acceptance of the
delocalised, rather than Kekulé, model for delocalised benzene model by
benzene in terms of bond lengths, enthalpy the scientific community in
change of hydrogenation and resistance to the light of supporting
reaction (see also 6.1.1 f) evidence
(c) use of IUPAC rules of nomenclature for Use of locant numbers to

systematically naming substituted aromatic identify the positions of
compounds substitution e.g.
2,4-dinitomethyl benzene.
HSW 8 introduction of
systematic nomenclature
(d) the electrophilic substitution of aromatic Halogen carriers include iron,
compounds with: iron halides and aluminium
halides.
(i) concentrated nitric acid in the
presence of concentrated sulfuric
acid
(ii) a halogen in the presence of a
halogen carrier (iii) a haloalkane or
acyl chloride in the presence of a
halogen carrier (Friedel–Crafts
reaction) and its importance to
synthesis by formation of a C–C
bond to an aromatic ring (see also
6.2.4 d)
-2-
(e) the mechanism of electrophilic For the nitration mechanism

substitution in arenes for nitration learners should include equations
and halogenation (see also 4.1.1 h–i) for the formation of NO2+
Halogen carriers include iron, iron

halides and aluminium halides
For the halogenation mechanism

the electrophile can be assumed to
be X-
HSW 1,2,8 use of reaction

mechanisms to explain organic
reactions
(f) the explanation of the relative HSW2,5 Use of the delocalised
resistance to bromination of benzene model to explain reactivity
benzene, compared with alkenes, in
terms of the delocalised electron
density of the -system in benzene
compared with the localised electron
density of the -bond in alkenes (see
also 4.1.3 a, 6.1.1 a)
(g) the interpretation of unfamiliar Extra information may be provided

electrophilic substitution reactions of on exam papers
aromatic compounds, including
prediction of mechanisms
(h) the weak acidity of phenols

shown by the neutralisation reaction
with NaOH but absence of reaction
with carbonates (see also 5.1.3 b)
(i) the electrophilic substitution Note that nitration with phenol does
reactions of phenol: (i) with bromine not require concentrated HNO3 or
to form 2,4,6-tribromophenol (ii) the presence of a conc H2SO4
with dilute nitric acid to form 2- catalyst.
nitrophenol
(j) the relative ease of electrophilic Illustrated by the reactions with

substitution of phenol compared with bromine and nitric acid. Explanation
benzene, in terms of electron pair is only in terms of the susceptibility
donation to the -system from an of the ring to attack and not in
oxygen p-orbital in phenol (see also terms of intermediate stability.
4.1.3 a)
HSW2,5 Use of delocalised benzene
model to explain reactivity
(k) the 2- and 4-directing effect of Learners will not be expected to

electron-donating groups (OH, NH2) know further electron donating or
-3-
and the 3-directing effect of electron- electron withdrawing groups,

withdrawing groups (NO2) in additional relevant data will be
electrophilic substitution of aromatic supplied in examinations
compounds HSW 5 Correlation between the
substituted group and the position
of reaction.
(l) the prediction of substitution
products of aromatic compounds by
directing effects and the importance
to organic synthesis (see also 6.2.5
Organic Synthesis).
References
Course Textbook
The course is well covered by the following textbook, available in all
laboratories, the library, (reference only) and on the “Kerboodle” online
textbook system.
The topics covered in this study pack are found in p 432-450 of this
book:-
“A Level Chemistry for OCR A” by Rob Ritchie & Dave Gent,
published by Oxford University Press.
All references to “the textbook” and this symbol  within this pack
refer to the above book.
Student SharePoint.
You will also find many useful resources in the 6A Arenes folder on
SharePoint.
External resources.
The Chemguide website is designed for A level students and has many
clear explanations, and additional information.
Below is the link to the Arenes Menu
http://www.chemguide.co.uk/organicprops/arenesmenu.html
-4-
Exercises
(1) How the structure of benzene was determined

Independent study exercise
By the end of this exercise, you should be able to:
• Describe the structure of benzene in terms of delocalised
-electrons
• Show an understanding of how scientific models are arrived at over
time (HSW1,7)
Read the extracts (in boxes) and answer the questions below.
In 1823, Michael Faraday demonstrated the discovery of a new

hydrocarbon with the empirical formula CH. He christened it ‘bicarburet
of hydrogen’. Faraday proved, by combustion analysis, that it
contained 92.3% carbon by mass.
1. What is an empirical formula?
2. Show how the empirical formula CH was derived from Faraday’s

data.
C H
Percentage Mass 92% 100-86 = 8%
Moles 92/12 = 7.6mol 8/1 = 8mol
Molar Ratio 7.6/7.6 = 1 8/7.6 = 2
10 years later, benzene was extracted from benzoic acid by Eilhard

Mitscherlich (a German chemist whose early work lead to the first
calculations of relative atomic masses). Mitscherlich reacted benzoic
acid with soda lime, then distilled the products. He named the product
‘benzin’. By this point the formula of benzene was believed to be C6H6,
but its structure was still unknown.
-5-
Soda lime comprises essentially of solid sodium hydroxide. You may have
already noticed that benzene is not an expected product of the reaction
between sodium hydroxide and benzoic acid.
3. Write a chemical equation for the expected reaction of aqueous

benzoic acid with sodium hydroxide solution, including state symbols.
4. The reaction of benzoic acid with solid sodium hydroxide under

strong heat is known as a decarboxylation reaction. Benzene, water
and sodium carbonate are the products. Write a full chemical
equation for this reaction.
Friedrich August Kekulé published a paper outlining his proposed

structure of benzene in 1865. His model of a ring of 6 carbons
joined by alternating single and double bonds was rumoured to
have come to him in a dream, for which he received much ridicule!
5. Draw a displayed and a skeletal diagram of Kekulé’s benzene below.

Displayed Skeletal
-6-
6. Give the systematic name for Kekulé’s benzene.
Over the next few years, evidence came to light that did not support
Kekulé’s structure. The enthalpy of hydrogenation of benzene was
found to be much less exothermic than expected, calling into question
the presence of double bonds in the structure.
Alkenes undergo hydrogenation via an addition reaction.
7. Write an equation for the hydrogenation reaction of cyclohexene.

Give the systematic name of the product.
8. Why is this reaction classified as addition?

, where is accepts a
pair of form a new covalent bond.
The hydron is polari
sed by the highly electron- double bond in cyc
9. Write an equation for the full hydrogenation of Kekulé’s benzene.

C6H6 + 3H2 → C6H12
-7-
10. The standard molar enthalpy of hydrogenation of benzene

is -208.5 kJ mol-1. Using the standard molar bond enthalpy data
below, show that the enthalpy change of hydrogenation of Kekulé’s
benzene is more exothermic than this value.
Standard Bond Enthalpies

/ kJ mol-1
C–H +413
H–H +436
C–C +348
C=C +614
Bonds Broken 3 x H-H = +1308
Bonds Made 6 x C-H = -2478
Chan
ge Jmol-1
The relative lack of reactivity of benzene can also be demonstrated by

mixing it with bromine water. Alkenes such as cyclohexene react
readily with bromine water, however benzene does not.
An electrophile
11. Describe the observations you would expect to make if bromine
water were added to…
a. … Cyclohexene Bromine water decolourises
b. … Benzene Bromine water remains orange
-8-
12. Write a chemical equation for the expected reaction between

Kekulé’s benzene and bromine and give the systematic name of the
product.
13. In the reaction with cyclohexene, bromine acts as an electrophile.

Define the term electrophile.
14. Outline the mechanism for the reaction of cyclohexene with bromine,
with the aid of curly arrows and relevant dipoles and lone pairs.
15. Suggest why bromine does not react with benzene in a similar
manner.
-9-
In 1929, the crystallographer Kathleen Lonsdale showed benzene to

have a cyclical structure. At first this was believed to support Kekulé’s
model, however the cyclical structure was described as ‘regular’. Later
studies using scanning electron microscopy proved benzene has a
regular hexagonal shape.
16. What is the relationship between C-C bond length and strength?
Longer bonds are weaker ORA
17. Double bonds are stronger than single bonds. Using your answer to
Q16, draw a skeletal diagram of Kekulé’s benzene, paying particular
attention to bond length.
Benzene’s pleasant smell lead to the name ‘aromatic’ being applied to

its class of compounds by August Wilhelm Hofmann in the mid 1800’s.
Shockingly, benzene was used in after-shave lotion to improve its smell
for much of the 19th and early 20th century! Benzene was also the first
substance to be used to decaffeinate coffee, and was present in paint
strippers, spot removers and rubber cement products. It was only in
the late 1970s that it was discovered to be carcinogenic, until which
point you could have even used it in school! In 1997, benzene was
detected in deep space by the European Space agency’s Infra-red Space
Observatory.
Infra-red light is used to identify molecules by infra-red spectroscopy.
18. What effect does infra-red light have on the molecules absorbing it?
Bonds vibrate (different bonds absorb different frequencies)
- 10 -
19. Why might the use of infra-red spectroscopy prove ineffective for
identifying benzene in the classroom?
The bonds in benzene do not absorb infra-red within the region
shown on a traditional infra-red spect
rum
Benzene is now known to be made up of a ring of 6 carbons, each C–C

bond being of equal length, somewhere between that of a single and
double bond. The 6 electrons (1 from each carbon) that are not
involved in sigma bonds are delocalised, forming 2 rings above and
below the plane of the molecule. The model supports all the evidence
described above and is the currently accepted structure. Beware that
diagrams that appear to show Kekulé’s model are still widely used to
represent this delocalised structure.
20. Draw the skeletal diagram normally used to represent current model
of benzene below.
Full Structural Skeletal
The unusual C to C bonds in benzene are also stronger than single C-C
bonds, but weaker than C=C bonds. They are formed in a similar way to
pi (π) bonds in alkenes.
21. With the aid of a diagram, show how pi bonds form in alkenes.
- 11 -
22. In benzene, the electrons in the π bonds are described as being

‘delocalised, found in 2 rings above and below the plane of the
molecule’. Draw a diagram similar to that in question 21 to show the
formation of these rings in benzene.
TIP: You will be expected to recognise benzene drawn in both the

Kekulé style and delocalised style, but when drawing you should
use the delocalised model.
In this pack you will see both styles used. This is not intended to be
confusing, but to prepare you for the questions you will encounter in your
course!
You will still see this

You should draw this used in some
questions
- 12 -
Summary: Evidence against the Kekulé model of benzene

1. Benzene has equal C to C bond lengths, forming a regular hexagonal
structure.
• Evidence from x-ray crystallography and scanning electron microscopy.
• Kekule’s structure would have 3 long single C to C bonds and 3 shorter

C to C double bonds.
2. Benzene does not undergo electrophilic addition reactions with

bromine as its electron density is insufficient to polarise Br2
molecules.
• When bromine water is added to benzene, it does not decolourise.
3. Benzene has a less exothermic enthalpy change of hydrogenation

than expected.
Summary: The Structure of Benzene

• Benzene is a cyclic hydrocarbon of 6 Cs and 6 Hs.
• The Cs are arranged in a planar hexagonal ring with bond angles of

120°.
• Each C has 4 bonding electrons, it uses 3 to form sigma (σ) bonds to

2 other Cs and 1 H.
• The 4th electron from each C is found in a 2p orbital which extends

above and below the plane of the molecule.
• These p orbitals overlap sideways with those of neighbouring C

atoms, creating a delocalised ring of electron density above and
below the plane of the molecule.
• This overlap produces a system of pi (π) bonds which spread over all
6 C atoms. The p electrons are no longer held by an individual C
atom and are spread over the ring (delocalised).
- 13 -
(2) The structure of benzene

• State the evidence supporting the delocalised model of the
structure of benzene.
• Explain why this evidence supports this model of the structure.
 Read pages 432- 436 of your text book.
➢ Summarise the three main pieces of evidence that pointed towards the
delocalised structure of benzene below:
Evidence (give examples) Explanation

i) Bond lengths
ii) Enthalpy of hydrogenation data
iii) Types of reactions of benzene
- 14 -
1. Describe the bonding in benzene.
In answering this question, you should discuss the following:

• The formula and shape of the benzene molecule
• How the main framework of the molecule is held together
• The position and nature of the -bonding in the molecule and
how it is formed – using technical words as appropriate
• The relative lengths of the carbon-carbon bonds in the
molecule
(This is one of the most common types of exam question on this topic,
although the examiner does not generally give the bullet points – you are
expected to know what you should say!)
Stretch and Challenge! (answer on file paper)

2. How many different structures exist for dimethylbenzene for
a) the Kekulé structure?
b) the delocalised structure?
Draw them all.
3. How might you expect an infra-red spectrum of benzene to support

the delocalised view of the structure of benzene rather than the
Kekulé structure?
- 15 -
(3) Naming aromatic compounds

Read the notes below and refer to textbook pages 434-436.
At the end of this exercise you should be able to
• use IUPAC nomenclature for systematically naming substituted
aromatic compounds. HSW 8
➢ Read the information in the four boxes below
Aromatic compounds are often named as derivatives of benzene, so

benzene forms the root of the name. Some aromatic compounds have old
non-systematic names (some of these are shown underneath) However,
chemists seem to deviate and break the rules when it comes to naming
aromatic compounds, and at A level the crucial thing is to be able to work
out the structure from the name.
CH3 Cl NO 2 COOH
methylbenzene chlorobenzene nitrobenzene benzoic acid

(toluene)
If two or more substituents are present on the benzene ring, their

positions must be indicated by the use of numbers. This should be done to
give the lowest possible numbers to the substituents. When two or more
different substituents are present, they are listed in alphabetical order.
Cl
CH3 COOH COOH
OH
CH3 O 2N NO 2
CH3
1,3- 4-methyl- 2-hydroxybenzoic 3,5-dinitrobenzoic
dimethylbenzene 1-chlorobenzene acid acid
- 16 -
The benzene ring can be regarded as a substituent of a larger molecule, like

alkyl groups are. The C6H5- group is called the phenyl group.
NH2 CH2 O CH3

HC C
phenylamine phenylethene 2-phenylbutane phenylethanone

(aniline)
O
C O O
O CH3 C CH3
phenyl ethanoate methyl benzoate
There are some other compounds to be aware of, such as phenol. When
an –OH group is directly attached to a benzene ring, that molecule and its
functional group is known as “phenol”.
OH OH OH OH
Cl Cl NO 2 OH
Cl
phenol 2,4,6- 2-nitrophenol benzene-1,2-diol
trichlorophenol
(TCP)
- 17 -
1. Name the following compounds using IUPAC rules:
a) b)
Cl Cl
d)
c)
Br
Br
OH f)
e)
Br Br
Br
h) COOH
g) O O
OH
j) Cl
i)
NO 2
O O l) OH
k)
Cl F
Br NH2
- 18 -
2. Draw the structures of the following compounds
a) 2, 4-dibromomethylbenzene
b) 1,3-dinitrobenzene
c) 2-phenyloctane
d) 3-phenylbutan-1-ol
- 19 -
(4) The reactions of benzene

• State the reagents and conditions required to carry out the
following substitution reactions of benzene and its derivatives
o Nitration
o Halogenation
o Alkylation
o Acylation
• Write balanced equations for the above reactions.
 Read pages 437-441 of your text book
1. For each of the reactions below:

• State any necessary reaction conditions
• Write the balanced equation
• Name the organic product(s)
a) Benzene and chlorine
b) Benzene and bromine
2. Benzene can be nitrated to form nitrobenzene.
a) State the reagents needed and write the equation for the
reaction.
- 20 -
It is necessary to make sure the mixture does not get too hot, is because
it is likely that if it does then another nitro- group may substitute into the
benzene ring, producing 1,3-dinitrobenzene.
b) Write an equation for the nitration of nitrobenzene to produce

1,3-dinitrobenzene.
c) Methylbenzene (which is still often called toluene) can also be

nitrated in the same way, and it is actually easier to nitrate
methylbenzene than benzene. For methylbenzene, the nitro- groups
will tend to go into the 2, 4 or 6 positions on the benzene ring.
a) Write an equation for the single nitration of methylbenzene and

name the organic product formed.
b) Under forcing conditions, it is possible to add 3 nitro- groups to

a methylbenzene molecule. Write an equation for the formation
of trinitromethylbenzene and give the full, systematic name of
the molecule formed.
c) What is the abbreviation often used for trinitrotoluene, and

what is the compound used for?
- 21 -
d) Iodine is too unreactive to substitute benzene even in the presence

of a catalyst. However, iodobenzene can be made by treating
benzene with iodine chloride (ICl).
a) Write a balanced equation for this reaction.
b) Explain why a catalyst is not needed.
c) Why is chlorobenzene not formed in this reaction?
e) The hydrogen atoms in benzene can be substituted by alkyl groups in

a process known as alkylation, this is a very useful reaction as it
forms new carbon-carbon bonds increasing the number of carbon
atoms in the structure.
a) Write an equation for the reaction of benzene with

chloromethane.
b) What reagents and conditions are required for this reaction?
- 22 -
c) Write an equation for the reaction of 1-bromopropane with

benzene, and name the product formed.
f) Acylation is the formation of an aromatic ketone via the substitution

of an acylchloride onto the aromatic ring. It is also a very useful
reaction on organic synthesis
a) Draw the structure of propanoyl chloride.
b) Write an equation for the reaction between propanoyl chloride

and benzene and name the product.
c) What reagents and conditions are required for this reaction?
- 23 -
(5) The mechanism of electrophilic substitution

reactions
• Show the mechanism for the nitration of benzene.
• Show the mechanism for the halogenation of benzene.
• State the name of these mechanisms.
 Read pages 438 and 439 of the text book.

1. Define the term electrophile.
Text
Definition of electrophile
An atom or group of atoms which is attracted to an electron-rich centre where it accepts
a pair of electrons to form a new covalent bond
2. 1,4-dimethylbenzene was reacted with a mixture of concentrated

nitric and concentrated sulfuricText
acids, and the temperature was
carefully controlled. A product with molecular formula C8H9NO2 was
obtained.
a) What type of reaction has taken place?
Electrophilic substitution
b) What type of attacking species is involved?

Electrophilies
c) Write an equation for the formation of the electrophile using

concentrated nitric and concentrated sulfuric acid.
Text
- 24 -
d) Show the mechanism of the reaction, between the electrophile

and 1,4-dimethylbenzene using curly arrows to show the
movement of electrons.
e) Write an equation to show how sulfuric acid is regenerated, and

hence state the role of the sulfuric acid.
3. Aluminium chloride can be used as a halogen carrier catalyst.
a) Draw a dot and cross diagram of an aluminium chloride

molecule (AlCl3), showing outermost electrons only.
b) What is unusual about the aluminium atom in this molecule?
- 25 -
c) Draw a dot and cross diagram for a chlorine molecule.
d) Suggest how the aluminium chloride might catalyse the reaction

between chlorine and benzene.
e) Treating the attacking species as if it were Cl+, construct a

mechanism for the reaction with benzene, using curly arrows.
- 26 -
4. Methylbenzene reacts with bromine, forming 4-bromomethylbenzene
a) Write an equation for the substitution reaction of

methylbenzene with bromine, forming 4-bromomethylbenzene
b) State any essential conditions for this reaction.
c) Draw out the mechanism for this reaction, using curly arrows.
You should include equations to show the generation of the
electrophile and the regeneration of the catalyst.
- 27 -
5. The alkylation and acylation reactions of arenes are known

collectively as Friedel-Crafts reactions. The catalysts work as
“halogen carriers” in exactly the same way as they do in the
halogenation reactions of benzene outlined above.
a) Write an equation to show how AlBr3 might react with

bromoethane, to produce a species which will act as an
electrophile.
b) Assuming the electrophile is CH3CH2+, show, using curly arrows,

the mechanism for how this would react with benzene.
c) Write an equation to show how the catalyst would be

regenerated.
d) Write the overall equation for this reaction and name the
aromatic product.
- 28 -
6. Ethanoyl chloride (CH3COCl) reacts with benzene in the presence of

anhydrous AlCl3.
a) Write an equation for the reaction of ethanoyl chloride

(CH3COCl) with benzene in the presence of anhydrous AlCl3.
b) Suggest a mechanism for this reaction.
For help and further information on the above see:

http://www.chemguide.co.uk/mechanisms/elsub/fcacyl.html
- 29 -
(6) Phenol
• State how the structure of phenols differs from that of alcohols.
• Show how phenols can behave as weak acids.
• Write equations for the reactions of phenols with sodium hydroxide.
• Explain the lack of reaction of phenol with carbonates.
• Describe electrophilic substitution reactions of phenol.
 Read pages 442- 445 of the textbook
1. The compounds below are all aromatic hydroxy-compounds, yet not

all of them are phenols.
a) Identify the phenols.
b) Give the systematic names of all the compounds.
OH OH CH 2OH OH
CH3
OH
- 30 -
Demonstration
Your teacher will show you some phenol, and then carry out some tests
on phenol as a demonstration, complete the table below as this
demonstration is carried out.
Alternatively, watch this video:
https://www.youtube.com/watch?v=NOVkLMrw2ls
Demo Observations and equation if

appropriate
Phenol appearance at
room temperature.
Reaction with water
Add sodium hydroxide

solution to phenol in
water.
Add solid sodium

carbonate to phenol in
water.
Add bromine water to

solid phenol.
- 31 -
1. Phenol is a weak acid.
a) What is meant by the term weak acid?
b) Write an equation showing how phenol behaves as a weak acid

when placed in water.
c) Phenol undergoes a typical reaction of acids with sodium

hydroxide – write an equation for this reaction.
d) Explain why the product of this reaction is highly soluble

whereas phenol is not.
e) Why does phenol not react with carbonates?
- 32 -
2. 4-methylphenol (also known as paracresol) is a component of both

human and pig sweat, it has a low solubility in water. It can however
be dissolved in aqueous sodium hydroxide to give a colourless
solution, A. On adding dilute hydrochloric acid, this solution
becomes cloudy at first and then separates to give a solid, B.
Identify A and B, and write equations for the reactions involved.
Identity of A
Identity of B
Equations
3. Give two reasons, which together explain the fact that phenols are
acidic, although alcohols have almost no acidic properties.
- 33 -
4. Phenol undergoes electrophilic substitution reactions
a) State what is observed when bromine water is added to an

aqueous solution of phenol at room temperature.
b) Write an equation for the reaction.
5. Write an equation for the reaction of nitric acid with phenol at room
temperature.
6. How can the relative ease of bromination, and nitration of phenol

compared with benzene be explained?
- 34 -
(7) Directing groups in aromatic compounds.

By the end of this section, you should be able to:
• Explain the activating and deactivating effect of groups attached to
the benzene ring.
• Explain the effect of these groups on reaction conditions for
electrophilic substitution.
• Describe the directing effect of different groups attached to the
benzene ring.
• Predict the products of reactions involving these compounds.
 Read pages 446-449 of the textbook
Activation and deactivation of the ring

From the previous section, we have seen that benzene requires the use of
catalysts to undergo electrophilic substitution reactions whereas phenol
does not, this is the result of the phenol group activating the ring.
Other groups have a similar effect to the phenol group, in other words
they make the ring more susceptible to electrophilic substitution.
1. The reaction of phenylamine with bromine at room temperature and

pressure is shown below:
a) Draw dot and cross diagrams of the –OH group and the –NH2
group.
b) Both of the above groups have the effect of activating the

aromatic ring – what feature found on both of these groups
causes this activation?
- 35 -
c) How does this reaction compare with that of phenol and

bromine, and that of benzene and bromine?
d) The NH2 group, like the OH group, is an example of an

activating group – what does this term mean with regards to
the electron density of the benzene ring?
e) Draw a dot cross diagram of an –NO2 group.
f) What feature is missing from the –NO2 group compared with -

NH2 and –OH?
g) The NO2 group is an example of a de-activating group – what

does this term mean in terms of electron density of the benzene
ring?
h) Write an equation using skeletal formula for the organic species

for the reaction of nitrobenzene with bromine and give the
reagents and conditions for this reaction.
- 36 -
The directing effect of substituting groups in aromatic

compounds
In addition to activating or de-activating the ring, different groups also
have the effect of directing further substitutions to specific positions
within the ring.
2,4,6 directing 3,5 directing

Required for -NH2 or -NHR
-NO2
exam. -OH
If provided -COOR
-OR
must be able -SO3H
-R or -C6H5
to use to -CHO
-F
predict -COR
-Cl
products of -COOH
-Br
an unfamiliar -CN
-I
reaction. -NR3+
Rule of Thumb!
• Activating groups or electron donating groups are 2, 4, 6 directing.
• De-activating groups or electron withdrawing groups are 3, 5
directing.
This can be a useful rule of thumb for your A-level exams, but be careful
at university as there are exceptions. For example, Halogens are in fact
slightly deactivating, but are 2, 4, 6 directing.
- 37 -
2. Write equations for the following single step reactions. Draw all
likely products.
a) Reaction between phenylamine with concentrated nitric acid and

concentrated sulfuric acid at 50oC.
b) Reaction between nitrobenzene and chlorine in the presence of

AlCl3.
c) Reaction between chlorobenzene with concentrated nitric acid

and concentrated sulfuric acid at 50oC.
d) Reaction between benzoic acid and bromine presence of FeBr3.
- 38 -
3. Write equations for the following two-step reactions, commenting on

the potential percentage yield of the overall reaction.
a) Benzene to 1-(3-bromophenyl)ethan-1-one
i) The bromo and ethanoyl groups are substituted into the ring
in separate steps. Write the equations and give the reagents
and conditions for each step.
ii) Does the order in which these reactions takes place affect
the product of the reaction?
- 39 -
b) Benzoic acid to ethyl(2-methyl)benzoate
i) Write the equations and give the reagents and conditions for
each of the two steps in this preparation.
ii) Does the order in which these reactions takes place affect
the product of the reaction?
- 40 -
c) Benzene to 1-chloro-4-ethylbenzene
i) Write the equations and give the reagents and conditions for
each of the two steps in this preparation.
ii) Does the order in which these reactions takes place affect the
product of the reaction?
iii) Comment if the order of the steps of the reaction affects the
rate of reaction.
- 41 -
4. A chemist wants to prepare a sample of this compound.
a) Name the compound
b) Outline how, starting with benzene, to synthesize this product,

• Clearly state the order in which you would carry out the
reactions,
• Give equations for each step,
• Give the reagents and conditions, which would be
required for each step.
- 42 -
5. A chemist wants to prepare a sample of this compound.
a) Name the compound.
b) Outline how, starting with benzene, to synthesize this product,

• Clearly state the order in which you would carry out the
reactions,
• Give equations for each step,
• Give the reagents and conditions which would be
required for each step,
• Clearly indicate if more than one product is expected at
any stage and suggest how you would separate the
desired product.
- 43 -
(8) Comparing reactions of benzene with alkenes

and with phenol
• Explain the difference in reactivity with electrophiles of cyclohexene
and benzene.
• Explain the difference in reactivity with electrophiles of phenol and
benzene.
 Read pages 437 - 441 and pages 444 - 445 of the textbook.
Cyclohexene Benzene
Bromination-formula of
product
Type of attacking species electrophile
electrophile
Type of reaction
undergone Electrophilic addition Electrophilic substitution
Conditions required for

bromination RTP Catalyst – halogen carrier
Mechanism
Electrophilic substitution
Electrophilic addition
Explanation for the Higher electron density as the pi Lower electron density as the pi
difference in reactivity: bond is localised between two electrons are delocalised across the
carbons. This higher electron whole ring, so insufficient electron
density can induce a dipole in the density to induce a dipole in the Br2. A
Br2. halogen carrier catalyst is required to
produce the Br+ electrophile.
- 44 -
Benzene Phenol
Bromination – formula(e)
of product(s)
Nitration – formula(e) of
product(s)
Type of attacking species

electrophile electrophile

bromination

nitration
Mechanism name
Higher electron density as one of

Explanation for the Lower electron density as the pi
the lone pairs from the O in the
difference in reactivity: electrons are delocalised across the
phenol joins the delocalised pi
whole ring, so insufficient electron
density to induce a dipole in the cloud increasing its electron
attacking species. density and making it able to
induce a dipole in the attacking
species without a catalyst.
- 45 -
Summary Exercises
Structure and bonding in benzene
Fill in the following gaps:
• Benzene has the formula ______.

• Its basic structure is six _____ atoms in a hexagonal ring, with one H
atom bonded to each C atom.
• The molecule is planar, and the six C-C bonds are the same length –
intermediate between ______ and ________.
• Each C atom is bonded to two other C atoms and one H atom by single
covalent  bonds.
• This leaves one unused electron on each C atom in a ____orbital,
perpendicular to the plane of the ring.
• Each p orbital overlaps with the neighbouring p orbitals to form a
 bond.
• The overall result is a ring of negative charge ("electron cloud")
________ and _______ the plane of the ring.
the six p orbitals before overlap The six orbitals after overlap
• The electrons in the ring of negative charge do not belong to any

particular C atom (or to a bond between two C atoms) - they are free to
move throughout the whole  system - they are __________.
• Due to this, the structure of benzene is

represented by:
• There are three key pieces of evidence to support this structure, in

particular how they fit this structure and not a structure with three C=C
bonds and three C-C bonds, that of a "triene" - 1,3,5-cyclohexatriene.
- 46 -
Explain how the following factors led to the Kekulē

structure being discredited.
1) C-C bond length.
2) Addition reactions.
3) Enthalpy of hydrogenation.
Enthalpy
kJ/mol
152
-360
-208
- 47 -
Reactions of benzene and directing effects.
Then react with…….
On separate file paper, draw a mechanism for the reaction between

benzene and concentrated nitric acid in the presence of concentrated
sulfuric acid at 50oC.
- 48 -
Reactions of phenol
Complete the reaction map below stating any expected obervsations.
Dilute
HNO3
NaOH Br2, RTP
NaCO3
Explain why does phenol react more readily with electrophiles than
benzene?
- 49 -
Review/ Exam style questions

Multiple Choice Questions.
1. Chemists often use two different structures to represent a

molecule of benzene, as shown below.
i. Describe, with the aid of suitable diagrams showing orbital

overlap, the difference in bonding between structure A and
structure B.
In your answer, you should use appropriate technical

terms, spelled correctly.
[4]
- 50 -
The table below shows the enthalpy changes for the reactions of
cyclohexene, C6H10, and benzene, C6H6, with hydrogen.
reaction enthalpy change / kJ mol−1

C6H10 + H2 → C6H12 −119
C6H6 + 3H2 → C6H12 −208
Using this information, suggest and explain whether

structure A or structure B is a better representation of
benzene.
[2]
- 51 -
2. A student investigates the relative ease of nitration of phenol,

benzene, and benzoic acid.
The student finds that the conditions required for the nitration of
each compound are different, as shown in Table 17.1.
Compound phenol benzene benzoic acid
Concentrated Concentrated
Conditions Dilute HNO3
HNO3 HNO3
required for 20oC
55oC 100oC
nitration No catalyst
H2SO4 catalyst H2SO4 catalyst
Table 17.1
i. State the trend in the relative ease of nitration of phenol,

benzene, and benzoic acid.
[1]
ii. Apply your knowledge of the bonding in arenes to explain the

trend in part (b)(i).
[3]
- 52 -
3. a) Salicylic acid is a naturally occurring carboxylic acid, widely used

in organic synthesis.
The flowchart below shows some reactions of salicylic acid.

i. In the box below, draw the structure of the organic compound
formed by reaction 1.
[1]
ii. Describe what would be observed during reaction 2.
[1]
iii. Write a chemical equation to represent reaction 2.
[1]
iv. State the reagents and conditions in reaction 3.
[1]
- 53 -
c) Bromine reacts more readily with salicylic acid than with benzene.
Outline the mechanism for the bromination of salicylic acid shown

in reaction 2 in the flowchart.
A halogen carrier is not required for this reaction.
The electrophile is Br2.
[4]
i. Explain why bromine reacts more readily with salicylic acid than
with benzene.
In your answer, you should use appropriate technical

terms, spelled correctly.
[3]
- 54 -
4. * Many organic reactions use electrophiles as reagents.
Explain the role of electrophiles in organic chemistry.
Your answer should include one reaction of an aliphatic compound

and one reaction of an aromatic compound, including relevant
mechanisms.
[6]
- 55 -
5. a) A chemist investigates the chlorination of methylbenzene and

finds that the methyl group has a 2– and 4– directing effect.
4-Chloromethylbenzene is one of the products of the chlorination of

methylbenzene.
Outline the mechanism for the formation of 4-chloromethylbenzene

from methylbenzene and chlorine in the presence of the catalyst, AlCl3.
Show how AlCl3 behaves as a catalyst.
[5]
- 56 -
b) The A chemist carries out further investigations into the reactions of

substituted benzene compounds.
The table below shows the directing effects of different groups attached
to a benzene ring.
Position to which new substituent is

Group
directed
−NO2 3
−OH 2, 4
−COCH3 3
−N(CH3)2 2, 4
−NHCOCH3 2, 4
−CN 3
i. Draw all of the organic products from monosubstitution reactions
of the substituted benzene compounds shown below.
[3]
ii. The reactions of C6H5N(CH3)2 are similar to the reactions of
phenol.
Draw the organic product that is formed from the tri-substitution

of C6H5N(CH3)2 with chlorine.
[1]
- 57 -
iii. Explain why chlorine reacts much more readily with C6H5N(CH3)2
than with benzene.
[3]
- 58 -
6. This question is about the chemistry of aromatic compounds.
Benzoic acid can be nitrated by concentrated nitric acid in the

presence of concentrated sulfuric acid as a catalyst, as shown in
Equation 17.1.
The organic product of this reaction is 3-nitrobenzoic acid.
Outline the mechanism for this nitration of benzoic acid.
Show how H2SO4 behaves as a catalyst.
[5]
- 59 -
7. This question is about medical compounds made from salicylic acid.
Salicylic acid can be made from the reaction of phenol with carbon
dioxide as shown below.
i. Stage 2 takes place by electrophilic substitution and part of the

mechanism is shown below.
Complete the mechanism by showing relevant dipoles, curly

arrows and the structure of the intermediate.
[3]
- 60 -
What type of reaction takes place during Stage 1 and Stage 3?
Explain your answer.
Type of reaction
Explanation
[2]
ii. A chemist prepares 4.83 g of salicylic acid from phenol. The
percentage yield of this reaction is 45.0%.
Calculate the mass of phenol that the chemist uses.
Give your answer to three significant figures.
mass of phenol = .......................................................... g
[3]
- 61 -
8. Methylbenzene reacts with sulfur trioxide, SO3, to form D, shown

below.
The electrophile in this reaction is SO3.
Complete the mechanism for the formation of D.

Show curly arrows and the structure of the intermediate.
[3]
- 62 -
Glossary
Ensure you understand the meaning of these terms
(Use your textbook glossary to help you)
∏ bond
Acylation
Addition reaction
Alkylation
Aromatic
Benzene
Bromination
Delocalisation
Electrophile
Friedel-Crafts
reaction.
Kekulé structure
Nitration
Phenol
Substitution
reaction
- 63 -

2 Year O & A Chemistry 2019 - 2021 Study Pack 6A

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2 Year O & A Chemistry 2019 - 2021 Study Pack 6A

Uploaded by

2nd Year O & A Chemistry 2019 - 2021 Study Pack 6A

What you need to be able to do

Learning Outcomes Additional Guidance

(c) use of IUPAC rules of nomenclature for Use of locant numbers to

(e) the mechanism of electrophilic For the nitration mechanism

Halogen carriers include iron, iron

For the halogenation mechanism

HSW 1,2,8 use of reaction

(g) the interpretation of unfamiliar Extra information may be provided

(h) the weak acidity of phenols

(j) the relative ease of electrophilic Illustrated by the reactions with

(k) the 2- and 4-directing effect of Learners will not be expected to

and the 3-directing effect of electron- electron withdrawing groups,

(1) How the structure of benzene was determined

In 1823, Michael Faraday demonstrated the discovery of a new

1. What is an empirical formula?

2. Show how the empirical formula CH was derived from Faraday’s

10 years later, benzene was extracted from benzoic acid by Eilhard

3. Write a chemical equation for the expected reaction of aqueous

4. The reaction of benzoic acid with solid sodium hydroxide under

Friedrich August Kekulé published a paper outlining his proposed

5. Draw a displayed and a skeletal diagram of Kekulé’s benzene below.

6. Give the systematic name for Kekulé’s benzene.

Alkenes undergo hydrogenation via an addition reaction.

7. Write an equation for the hydrogenation reaction of cyclohexene.

8. Why is this reaction classified as addition?

sed by the highly electron- double bond in cyc

9. Write an equation for the full hydrogenation of Kekulé’s benzene.

10. The standard molar enthalpy of hydrogenation of benzene

Standard Bond Enthalpies

Bonds Broken 3 x H-H = +1308

Bonds Made 6 x C-H = -2478

The relative lack of reactivity of benzene can also be demonstrated by

b. … Benzene Bromine water remains orange

12. Write a chemical equation for the expected reaction between

13. In the reaction with cyclohexene, bromine acts as an electrophile.

In 1929, the crystallographer Kathleen Lonsdale showed benzene to

Longer bonds are weaker ORA

Benzene’s pleasant smell lead to the name ‘aromatic’ being applied to

Infra-red light is used to identify molecules by infra-red spectroscopy.

Bonds vibrate (different bonds absorb different frequencies)

Benzene is now known to be made up of a ring of 6 carbons, each C–C

22. In benzene, the electrons in the π bonds are described as being

TIP: You will be expected to recognise benzene drawn in both the

You will still see this

Summary: Evidence against the Kekulé model of benzene

• Evidence from x-ray crystallography and scanning electron microscopy.

• Kekule’s structure would have 3 long single C to C bonds and 3 shorter

2. Benzene does not undergo electrophilic addition reactions with

• When bromine water is added to benzene, it does not decolourise.

3. Benzene has a less exothermic enthalpy change of hydrogenation

Summary: The Structure of Benzene

• The Cs are arranged in a planar hexagonal ring with bond angles of

• Each C has 4 bonding electrons, it uses 3 to form sigma (σ) bonds to

• The 4th electron from each C is found in a 2p orbital which extends

• These p orbitals overlap sideways with those of neighbouring C

(2) The structure of benzene

 Read pages 432- 436 of your text book.

Evidence (give examples) Explanation

ii) Enthalpy of hydrogenation data

iii) Types of reactions of benzene

1. Describe the bonding in benzene.

In answering this question, you should discuss the following:

Stretch and Challenge! (answer on file paper)

Draw them all.

3. How might you expect an infra-red spectrum of benzene to support

(3) Naming aromatic compounds

➢ Read the information in the four boxes below

Aromatic compounds are often named as derivatives of benzene, so

methylbenzene chlorobenzene nitrobenzene benzoic acid

If two or more substituents are present on the benzene ring, their

The benzene ring can be regarded as a substituent of a larger molecule, like

NH2 CH2 O CH3

phenylamine phenylethene 2-phenylbutane phenylethanone

phenyl ethanoate methyl benzoate

1. Name the following compounds using IUPAC rules: