Tutorial 2
1) Diphenylethanedione is a pale yellow colour, which disappears
when it is reduced. The colour results from the arrangement of the
delocalised -bond electrons. Explain what is meant by the term
delocalised -bond electrons.
delocalised electrons
electrons are spread over more than two atoms
-bond
formed by overlap of p-orbitals/ diagram to show
2) The nitration of benzene is a very important industrial reaction.
(a) Name two types of commercially important material whose manufacture
involves the nitration of benzene.
any two of
fibres / dyes / explosives / pharmaceuticals etc
(b) State the conditions required for the nitration of benzene using nitric acid
and
sulphuric acid.
temp 50-60
concentrated (acids)
allow abbreviations for concentrated
(c) Write a balanced equation for the nitration of benzene.
C6H6 + HNO3 C6H5NO2 + H2O
Reactants
Products
allow a balanced equation for multiple nitration at any
positions
(d) The mechanism for the reaction is given below.
(i)
(ii)
(iii)
Explain what a curly arrow
mechanism.
represents in this type of
a pair of electrons
(electrons) move / transferred /
a (covalent) bond breaks/forms
State why the NO2+ is described as an electrophile in this
mechanism.
it accepts a pair of electrons (from the benzene)
NOT a lone pair
State why this mechanism is described as substitution.
H(+) (on the ring) is replaced by NO2(+)
allow substitutes
(iv)
ignore + charges
How does the mechanism show that the sulphuric acid is acting as a
catalyst?
it is not used up / reformed at the end
(e) The benzene ring and the ring in the intermediate formed after step 2 have
different structures shown below. Both structures have -bonds.
Deduce how many electrons are involved in the -bonding in each structure
and describe how their arrangements are different.
-bonding electrons are delocalised
six -electrons in benzene
four -electrons in the intermediate
-electrons are not over one carbon atom /
over five carbon atoms / p-orbitals in the intermediate
-electrons are over the complete ring / all around the ring
all six carbon atoms/ p-orbitals overlapping
3) Benzene reacts with chlorine in the presence of a halogen carrier,
such as AlCl3.
(a) (i) Write the equation for the reaction of benzene with chlorine.
(ii) How does the halogen carrier allow the reaction to take place?
Introduces a permanent dipole on Cl2 / forms Cl+/
AlCl3 + Cl2 AlCl4 + Cl+/
AlCl3 + Cl2 Cl+ AlCl3
(iii) Outline a mechanism for this reaction. Include curly arrows and relevant
dipoles.
correct dipole / Cl+
curly arrow from benzene ring to Cl+ / Cl+ intermediate
curly arrow from H to regenerate benzene ring in intermediate
H+ as other product
(iv) State the name of this mechanism.
electrophilic substitution
with electrophilic spelt correctly
(b) In contrast to benzene, the reaction of an alkene with bromine does not
need a halogen carrier. Compare the different reactivities of benzene and
alkenes towards chlorine.
In benzene, electrons are delocalised/spread out
In alkenes, electrons are concentrated between 2 carbons
Electrophiles attracted more to greater electron density in alkenes
4) In this question, one mark is available for the quality of spelling,
punctuation and grammar. Phenol reacts much more readily with
bromine than benzene does.
Describe, with the aid of a diagram, the bonding in benzene.
bonding in benzene
Overlap of p-orbitals / bonds/electrons (or labelled)
above and below the ring (or shown in a diagram)
Electrons are delocalised (or labelled)
CC bonds are: same length/strength / in between single and
Double / -bonded
Explain why electrophiles, such as bromine, react much more readily with
phenol than with benzene.
greater reactivity of phenol
(the ring is activated because )
lone pair from O is delocalised into the ring
so electron density (of the ring) is increased
so electrophiles are more attracted (to the ring) / dipole in
electrophile more easily induced
(NOT just more easily attacked or susceptible)
5) Salicylic acid is used in the manufacture of aspirin tablets. In the
UK around 3500 tonnes of salicylic acid are manufactured per year.
Salicylic acid is manufactured from phenol in three stages.
(a) Phenol is first converted to sodium phenoxide, C6H5ONa+.
(i) State a reagent that could be used for this reaction.
NaOH / Na
(ii) Write a balanced equation for this reaction.
C6H5OH + NaOH C6H5ONa+ + H2O /
C6H5OH + Na C6H5ONa+ + H2
(b) The phenoxide ion is then combined with carbon dioxide under high
pressure to form the salicylate ion.
(i) Add a partial charges + and to show the polarisation of the C=O
bonds in the carbon dioxide molecule above.
(ii) Complete the mechanism by adding curly arrows to show the movement
of electron pairs in step 1 to give the intermediate shown.
(iii) Carbon dioxide is normally a very poor electrophile. However, this
reaction does occur because the benzene ring in the phenoxide ion is
activated. Explain how the benzene ring in the phenoxide ion is activated.
lone/electron pair from oxygen is delocalised into the ring /interacts
with -electrons
increases -electron density / negative charge (around the ring)
attracts electrophiles more
(c) In the final stage of this process, the salicylate ion is acidified to give
salicylic acid. Assuming an overall yield by mass of 45% for this three stage
process, calculate the mass of phenol that is needed to produce the annual
UK output of 3500 tonnes of salicylic acid.
Mr of phenol = 94.0; 1 tonne = 106 g
Mass of phenol = ....................... tones
Mr salicylic acid = 138
Moles (in 1:1 reaction) = 3500 x 106/138 = 2.536 x 107
Mass of phenol needed = 2.536 107 94 = 2384 tonnes
Allowing for 45% yield = 2384 100/45 = 5298/5300 (tonnes)
6) Phenol reacts readily with dilute nitric acid at room temperature
in a nitration reaction to produce a mixture of products as shown
below.
(a) Suggest the structure of another organic product that is likely to be
formed in the nitration of phenol.
Correct structure of 3-nitrophenol or any multiple nitrated phenol
or
(b) Assuming a yield by mass of 27% for 4-nitrophenol, calculate the mass of
4-nitrophenol that would be produced from 100 g of phenol. Show your
working.
Give your answer to an appropriate number of significant figures.
Mass of 4-nitrophenol = g
Mr phenol (C6H6O) = 94.0
Mr 4-nitrophenol (C6H5NO3) = 139.0
Expected mass/moles of nitrophenol from 100 g = 148 g/1.06 mol (or ecf
from wrong Mrs)
At 27% yield gives 40 / 39.9 (g) (or ecf)
(last mark is for 0.27 expected mass to 2 or 3 sf)
(c) In this question, one mark is available for the quality of spelling,
punctuation and grammar.
Compare the reagents and conditions for the nitration of phenol with those
used for the nitration of benzene.
Conditions for nitration of benzene:
HNO3 is concentrated
conc H2SO4 is present
heating or stated temp above 50C
State and explain the effect of the OH group on the reactivity of the
benzene ring in phenol.
Explanation for greater reactivity of phenol
lone pair from O atom is delocalised into the ring
greater () electron density around the ring
(the benzene ring in phenol) is activated
attracts electrophiles/+NO2 more / makes it more susceptible to
electrophiles
7) 4-Nitrophenol can be converted into a range of useful organic
chemicals. Draw the structures of the organic products formed in
the following reactions.
Answers
