Chem Factsheet

www.curriculum-press.co.uk Number 131

Why Students Lose Marks – Reaction Mechanisms
Try out the following questions to assess your current knowledge 4. The delocalized electron systems of organic compounds are
in this area. less susceptible to electrophilic attack than would be expected in
terms of charge density alone. The delocalization energy contributes
Statement True False to stability and makes bond breaking much more endothermic. For
example, benzene needs a catalyst to react with electrophiles,
Heterolytic bond cleavage gives movement
whereas alkenes do not.
of single electrons
Nucleophiles are always negatively charged 5. Bond polarization can be caused by:
(a) Electronegative atoms in molecules, as they withdraw some of
Nucleophiles are attracted to the nuclei
the negative charge. This can leave a positive centre (or δ+)
of atoms
which is a possible target for nucleophilic attack.
Curly arrows always begin on a bond
(b) Induction of a molecule moving close to a region of high electron
Electrophiles have a lone pair of electrons
density, such as a π bond. This can result in the molecule
to donate to form a dative bond
having a temporary positive end, which can then act as an
The p-bond in a carbonyl group electrophile. However, the charge is not a full charge and should
does not react readily with electrophiles not be shown as such.
The movement of single electrons produces
6. Intermediates, such as carbocations, and ions such as the
free radicals
chloride ion carry a full charge, and this should be shown as + or -
Nucleophiles need electrophiles for reaction .
An intermediate may be formed, for Criticism from an examiners’ report: “the bromine molecule
example a carbocation was sometimes shown with a full charge or the intermediate/
bromide ion with partial charge”
Energy must be provided to initiate
homolytic bond cleavage
7. Curly arrows must always begin on the electron pair which is
If you answered false to the first five statements and true to the going to move, that is a bond or lone pair, and end on the atom to
rest, then you have clearly grasped the fundamental ideas and are which the new bond will form or on a single bond which is going to
well on your way to an A for this topic! become a double bond.

However, if you are struggling to learn lots of reactions and their 8. If a lone pair is involved in the electron movement, then this
mechanisms, the following basic ideas might help you to make sense must be in the answer showing the mechanism. The mark is for the
of the topic, organize your knowledge, and avoid some of the arrow and the lone pair together.
common errors.
Extracts from examiners’ reports:
Key Facts (a) “The arrow shows movement of a pair of electrons and
1. Nucleophiles have either non-bonded pairs of electrons (lone must start at a bond or a lone pair and not at a minus sign or
pairs) or π electrons, which they can provide to form a dative covalent atom” (b) “Curly arrows moving in the wrong direction were
bond. not uncommon”

2. Electrophiles are molecules or ions which are prepared to form a 9. Equations must be balanced.
new dative covalent bond using a pair of electrons provided by
another atom or molecule (i.e. they have an empty bonding orbital, Extract from examiners’ report: “Candidates should be
as in a positive ion, or are ready to undergo heterolytic bond cleavage reminded that the use of [H] for a reducing agent does not
to make the empty orbital available) remove the need to balance an equation”

Criticism from an examiners’ report: "A substantial number 10. Ambiguous representation of parts of molecules (even if the
of candidates described electrophiles as having a surplus of part is not directly involved in the mechanism) is penalized.
electrons or as being positive ions”
Example from examiners’ report: “The propyl group should
3. Nucleophiles need electrophiles in order to react, that is a not be drawn as C3H7 as this could represent either CH3CH2CH2
molecule or ion prepared to accept the electron pair and form a or (CH3)2CH”
dative covalent bond.

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131. Why Students Lose Marks – Reaction Mechanisms Chem Factsheet

11. Clear diagrams are essential. No marks are given for any part Actual Mark Scheme
of a diagram which could be right or wrong. Conditions: u.v. light or high temperature (1 mark)
Initiation (1 mark)
Example from examiners’ report: “When drawing electrophilic .
Br2 → 2Br (1 mark)
substitution mechanisms of benzene, the benzene rings should Propagation (1 mark)
be drawn large enough so the placing of the positive charge in . .
CH Br + Br → CH2Br + HBr (1 mark)
the intermediate and of the curly arrows is clear” . 3 .
CH2Br + Br2 → CH2Br2 + Br (1 mark)
.
Termination : 2 CH2Br → CH2BrCH2Br (1 mark)
12. Problems can also arise from ‘incorrect structures’:
Student’s Worked Example Number 2
Ethanol can undergo a dehydration reaction to form ethene. State
a ) Sticks, that is bonds,without hydrogen atoms on their ends,
a suitable catalyst for use in this reaction and name and draw the
e.g.
C mechanism (7 marks)

b) Incorrectly bonded functional groups, e.g. − HO or OH− and Student’s Answer:

NH2− are incorrect, although alkyl groups may be written as catalyst is NaBH4
CH3− etc. the mechanism is dehydration
c) The position of a charge must be correct, e.g. − NH3+ is incorrect
as the charge is actually on the nitrogen
d) Cyclohexane drawn for benzene is also penalized.

Each of the above is only penalized once per paper. Comments on this answer:
NaBH4 is not a suitable catalyst.
13. When the names of mechanisms are asked for, these must be
correct. Note NaBH4 is used (similarly to LiAlH4) as a hydride ion, :H-,
donor in the reduction of carbonyl compounds and should be
Example from examiners report: “reduction is a type of reaction remembered in this context.
not a mechanism” Dehydration is not a mechanism.
You can also do some revision by reading fact sheets 40 and 73. 1 mark for correct arrow from lone pair onto the H+ ion.
Then try the following exercises.
In the next step a structure mark is lost, as there is no + on the
When you read through the following examples, work out whether oxygen atom.
the student’s response is correct before reading the comments.
One mark is given for the correct arrow from the C – O bond onto
the oxygen.
Student’s Worked Example No 1
Bromomethane reacts with bromine by a free-radical substitution In the last step, one mark is gained for the correct formula of the
mechanism to form dibromomethane. Give the conditions and carbocation including + on correct carbon atom.
outline the mechanism for the reaction, naming each step. Write The mark for the arrow is lost as it is in the wrong direction and
an equation for the termination step in which 1,2-dibromoethane also is on the hydrogen atom rather than the C – H bond (two
could be formed in this reaction. (7 marks) mistakes but only one mark lost).

Student’s Answer: Note When a double bond is being formed there must be an arrow
Suitable conditions are heat and light onto the new position of that bond and also, when a bond is being
Initiation broken the arrow must come from the bond.
Br2 → Br. Total awarded is only three marks out of seven!
.
CH3Br + Br → CH2Br + HBr
.
CH2Br + Br2 → CH2Br2 + Br. Actual Mark Scheme
Termination Suitable catalysts are conc. H2SO4 or conc. H3PO4 or Al2O3 (1 mark)
.
CH2Br + Br. → CH2Br2
The reaction mechanism is elimination (1 mark)
Comments on this answer:
The conditions are too vague
One mark for ‘Initiation’
The initiation equation is not balanced
Propagation is not stated
1st propagation equation has a dot missing
The dot should be on the C, not the Br, in the propagation steps
Termination is given in the question so there is no mark available
Termination step is not the one asked for in the question and cannot
gain credit.
Two out of a possible seven marks.
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131. Why Students Lose Marks – Reaction Mechanisms Chem Factsheet

Student’s Worked Example Number 3 Student’s Worked Example Number 4

Name the compound shown below Ethyl benzene can be prepared by the reaction of benzene with
Cl ethene.
CH2CH2 C Give the two catalysts required for this reaction, and the equation
O
for the reaction of the catalysts with ethene to form the reactive
Name and outline the reaction mechanism for the reaction of this
intermediate. (3 marks)
compound with CH3OH. (5 marks)
Name the mechanism. (1 mark)
Student’s answer
The name of the compound is ethanoyl chloride. Student’s Answer
The mechanism is electrophilic addition-elimination. Aluminium chloride and Iron chloride
H2C=CH 2 + AlCl3 + FeBr3 ! H2C=CH3+ + AlCl4¯
Friedel Crafts or acylation

Comments on this answer

The two catalysts given are either/or and so only one mark is
given
Comments on this answer
The name is incorrect as the carbonyl carbon must be included, The equation is wrong.
thus there are three carbons in the chain. The names Friedel Crafts and acylation are not names of
The mechanism is an addition- elimination but not electrophilic mechanisms. [Note: Friedel Crafts refers to the catalyst, which
which is penalised. functions as a Lewis acid as the central atom can accept a pair of
electrons. Acylation is the result of the reaction, not the mechanism
Step 1 of mechanism loses two marks because: or how it occurs.]
(a) the first arrow should not come from the hydrogen of the OH Actual Mark Scheme
(also the lone pair on the oxygen is omitted!) Catalysts are:
Anhydrous aluminium chloride, AlCl3 (or AlBr3, FeCl3, FeBr3)
(b) the second arrow is in the wrong direction and should not be (1 mark)
onto the carbon. Hydrogen chloride, HCl (or HBr ) (1 mark)
Step 2 of the mechanism has the correct structure and gains one
H2C=CH 2 + AlCl3 + HCl ! +
CH2-CH3 + AlCl4¯ (1 mark)
mark. (The C H is allowed as the full structure has already been
2 5
shown and also it is not ambiguous) However the arrow from the The mechanism is electrophilic substitution. (1 mark)
oxygen comes from the minus sign and the lone pair is omitted,
and so the candidate loses the fourth mark, as all the arrows must Student’s Worked Example Number 5
be correct. ‘The commonest reactions of benzene involve electrophilic
substitution.’ Explain why this statement is true. (2 marks)
Actual Mark Scheme
Propanoyl chloride (1 mark) Student’s Answer
(nucleophilic) addition-elimination (1 mark) Benzene reacts with electrophiles, although in general it needs a
catalyst to do so. For example in the nitration of benzene, the
reaction will occur without a catalyst but takes hours to do so.

Comments on this answer

Although the student’s answer is true it restates the question rather
than answering it. The question is basically asking: ‘what it is
about benzene’s structure which makes it react with electrophiles,
Step One: and when it does so, why is substitution the resulting mechanism?‘
Correct arrow and lone pair (1 mark) Thus the student does not score any marks.
Correct arrow from double bond to oxygen atom (1 mark)
Actual Mark Scheme
Step Two: The following points score one mark each:
Intermediate structure correct (including charges) (1 mark) (a) Benzene has a delocalised π electron system. The energy of the
Three arrows correct and lone pair (1 mark) system is lower (by the delocalisation energy) and so, in order
to maintain this low energy advantage and to retain the
delocalised π electron system, substitution is favoured.
(b) The π cloud is electron rich, and so susceptible to attack by
electrophilic species.

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131. Why Students Lose Marks – Reaction Mechanisms Chem Factsheet

Practice Questions
1. Name and outline the mechanism for the reaction between ethanoyl chloride and methylamine, and draw the structure of the organic
product. (6 marks)
2. Using [H] as the reductant, write an equation to show the reduction of butan-2-one by aqueous NaBH4 to form butan-2-ol.
Name and outline the mechanism for this reaction.
Why is the butan-2-ol produced in this reaction not optically active?(7 marks)
3. Ethene can undergo electrophilic addition with hydrogen bromide. State what is meant by the term electrophile and outline a mechanism
for this reaction. (5 marks)
4. Explain what is meant by the term nucleophile. Outline a mechanism for the reaction of ammonia with chloromethane and name the
organic product produced. (6 marks)

Answers
1. (Nucleophilic) addition elimination (1 mark)

Step One (one mark each): Step Two:

(a) Arrow from lone pair on N to carbonyl C (d) One mark for 3 arrows correct and lone pair on oxygen
(b) Arrow from double bond to oxygen
(c) Structures correct
Note + on the carbon of C=O loses a mark but δ+ is ignored (providing it is in the correct position). (4 marks)
NHCH3
CH 3 C (1 mark)
O
Note the use of the key for “G” – this saves time and space!

2. C4H8O + 2[H] ! C4H9OH (1 mark) 4. A nucleophile is an electron pair donor or a species with an
Nucleophilic addition (1 mark) electron pair able to form a covalent bond. (1 mark)

One mark for each correct arrow with associated charges and lone Step one: one mark for arrow showing correct breakage of C-Cl and
pairs and one mark for correct structure shown in second step. one mark for the arrow from the lone pair on N to form a bond with
(4 marks) C.

A racemic mixture is formed or 2 enantiomers are formed in equal Step two: one mark for the correct structure and one mark for the
amounts. (1 mark) correct arrow from the N-H bond to N atom. (4 marks)
Note again the use of a key to save time and space!
Organic product is methylamine (aminomethane). (1 mark)
3. An electrophile is an electron pair acceptor or lone pair acceptor.
(1 mark)

Acknowledgements: This Factsheet was researched and written by Christine

Collier. Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire,
TF1 1NU. ChemistryFactsheets may be copied free of charge by teaching
Step One has one mark for each correct arrow (2 marks) staff or students, provided that their school is a registered subscriber. No part
of these Factsheets may be reproduced, stored in a retrieval system, or
Step Two has one mark for the correct carbocation structure and transmitted, in any other form or by any other means, without the prior
one mark for the correct arrow, lone pair and charge on the carbon permission of the publisher. ISSN 1351-5136
and the bromide ion. (2 marks)