Chem Factsheet

www.curriculum-press.co.uk Number 187

Avoidable Errors in Reaction Mechanism

Questions
The aim of this Factsheet is to enable you to score full marks when answering AS questions on reaction mechanisms.
Mechanisms must be written with care: curly arrows, lone pairs, electrical charges and covalent bonds have to be placed correctly to be
certain that full marks will be gained. There are usually alternative answers that will gain (full) credit but these are not given since often they
are less precise.
We will consider the correct mechanism and then the same mechanism with typical errors.
However, first of all, here are the meanings of some important terms:

1. Types of Reaction
(a) Addition
a chemical reaction in which two (or more) molecules chemically combine to form a single molecule.
e.g. H2C=CH2 + H2 → C2H6 (Also a redox reaction.)
(b) Elimination
A chemical reaction involving the removal of a small molecule (e.g. H2O, HBr) from an organic molecule to leave an unsaturated molecule.
e.g. CH3CH2Br + KOH → H2C=CH2 + KBr + H2O
(HBr has been removed from CH3CH2Br)
(c) Substitution
A chemical reaction where one atom or group of atoms is replaced by another atom or group of atoms.
e.g. CH3Br + KOH → CH3OH + KBr

2. Attacking species
(a) Electrophile
An electron pair acceptor. e.g. +CH3. An electrophile attacks an electron rich centre and forms a new covalent bond by accepting a pair of
electrons.
(b) Nucleophile
An electron pair donor. e.g. –:CN / :NH3. A nucleophile donates a lone pair of electrons to an electron deficient atom (δ+) so forming a co-
ordinate bond with that centre.
(c) Free radical
An atom or group of atoms with a single unpaired electron. e.g. •CH3
(d) Base
a proton acceptor. e.g. –OH

3. Reaction Mechanisms
A reaction mechanism is a theoretical stepwise description of how a chemical reaction occurs. A mechanism shows what happens to
bonding electrons and sometimes, lone pair electrons. It shows which bonds break and which bonds form and often involves an intermediate
species.

A curly arrow ( ) shows the movement of an electron pair. The tail is placed at the electron pair (a covalent bond or a lone pair) and the
head shows where the electron pair is to be moved (forming a new covalent bond or new lone pair).

A curly half-arrow (“fishhook”) ( ) shows the movement of a single electron. A dot (•) shows a single unpaired electron. The dot
should be on the atom which has the missing electron.

The type of reaction mechanism is obtained by combining the type of attacking species with the type of reaction.

As you work through the following examples you will be presented with the “correct” mechanism along with one containing common
errors. Try to spot the errors.

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187. Avoidable Errors in Reaction Mechanism Questions Chem Factsheet

(a) Free Radical Substitution

This is involved when halogens, (e.g. Cl2 and Br2) react with alkanes in the presence of UV light.
The UV supplies the energy for the homolytic fission of the non-polar halogen covalent bond.
Mechanism: e.g. Monochlorination of Ethane

Step 1. Initiation: Cl2 → 2Cl• (production of free radicals.) Cl Cl → 2Cl•

Step 2. Propagation (i) CH3CH3 + Cl• → HCl + •CH2CH3 (i) CH3CH3 + Cl• → HCl + CH2CH3•
(ii) Cl2 + •CH2CH3 → CH3CH2Cl + Cl• (ii) Cl2 + CH2CH3• → C2H5Cl + Cl•
(Propagation: molecule + free radical → molecule + free radical.)
Step 3. Termination e.g. 2•CH2CH3 → CH3CH2CH2CH3 2CH2CH3 → CH3CH2CH2CH3

(Combination of two free radicals: stops propagation continuing.) Free radical substitution with errors

Spot the errors and check them at the end of this FactSheet.

(b) Electrophilic Addition

Alkenes have double bonds (>C=C<) and hence, are sites of high electron density. Thus alkenes react with electrophiles provided by such
reagents as halogens, (not F2), hydrogen halides and concentrated sulfuric acid. Addition reactions occur in a two step mechanisms.
• Step 1: The pi bond of the double bond breaks with both electrons forming a dative bond with a cation from the attacking electrophile.
A carbocation is formed and at the same time an anion.

• Step 2. The carbocation combines with the anion by C+ accepting an electron pair to give the product.

Symmetrical alkenes form only one carbocation and hence only one addition product.
Unsymmetrical alkenes can form two carbocations and hence two products are possible with reagents of the form H-X. The order of
stability of carbocations is primary < secondary < tertiary and the more stable the carbocation, the greater yield of the product derived from
that carbocation.
Mechanism: e.g. HBr Addition to Propene to Produce 2-bromopropane, the Major Product

CH3CH CH2 → CH3CHCH

+ 3
→ CH3CH(Br)CH3 CH3CH CH2 → CH3CHCH3 → CH3CH(Br)CH3
Hδ+ :Br- Hδ+ :Br-
:

Brδ- Brδ-
mechanism with some errors

Spot the errors and check them at the end of this FactSheet.

(c) Nucleophilic Substitution

Halogenoalkanes (haloalkanes) have polar bonds (Cδ+⎯Xδ-). Hence they react with nucleophiles such –:OH, –:CN, and :NH3.
(i) Primary halogenoalkanes react by a one step process. Nucleophilic attack on the electron deficient carbon atom (Cδ+) and the
heterolytic fission of the C-X bond are simultaneous.
Mechanism: e.g. (Sodium) Cyanide in Ethanol with 1-Bromopropane

H H H H
CH 3CH2 Cδ+ Brδ- → :Br− + CH 3CH2 C CN CH3CH2 Cδ+ Brδ- → Br− + CH 3CH2 C CN
NC−: H H NC : −
H H
Note: anion + molecule → anion + molecule mechanism with some errors

Spot the errors and check them at the end of this FactSheet.

Note The product is butanenitrile. This reaction increases the length of the carbon chain by one carbon atom.

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187. Avoidable Errors in Reaction Mechanism Questions Chem Factsheet

(ii) Tertiary halogenoalkanes react by a two step process. Step 1 is the heterolytic fission of the C-X bond producing a carbocation. Step
2 is the rapid combination of the carbocation with the nucleophile.
Mechanism: e.g. (Sodium) Cyanide in Ethanol with 1-Bromo-2-Methylpropane

CH3 CH3 CH3 CH3

Br → :Br
δ+ δ- − +
CH 3 C + CH3 C CH 3 C+ :−CN → CH3 C CN
CH3 CH3 CH3 CH3
Step 1 Step 2

Note: Tertiary carbocations are able to form because there are three electron donating alkyl groups so spreading this positive charge over the whole
ion and so stabilising the ion

CH3 CH3 CH3 CH3

Br → :Br +
δ+ δ- +
CH 3 C CH3 C CH 3 C +
:CN → CH3 C CN
CH3 CH3 CH3 CH3
Step 1 Step 2

mechanism with some errors

Spot the errors and check them at the end of this FactSheet.
(d) Elimination
Halogenoalkanes (haloalkanes), as well as undergoing nucleophilic substitution reactions with strong alkalis (e.g. KOH and NaOH), can
also undergo elimination reactions. The hydroxide ion acts as a Bronsted-Lowry base because it accepts a proton from a carbon atom
adjacent to the carbon atom bonded to the halogen atom. Primary halogenoalkanes produce only one alkene.

Some secondary and tertiary halogenoalkanes can produces more than one alkene since the hydrogen atoms on the adjacent carbon atoms
are not all equivalent. Elimination is favoured over substitution by using a concentrated ethanolic solution of e.g. KOH. To favour
substitution the alkali would be dissolved in water. In both cases heat is usually required.

Mechanism: (Potassium) Hydroxide in Ethanol with 1-Bromopropane

HO −: HO −

H H H H

H C C C Br → CH3 CH CH2 + H2O + :Br− C C C Br → CH3 CH CH2 + H2O + :Br−

H H H
mechanism with some errors

Spot the errors and check them at the end of this FactSheet.

Wrong C-H bond moves. 4.

HO- accepts the wrong proton. 3.
Curly arrow from the negative charge – should be from lone pair. 2. 2. The intermediate has no + charge on the central carbon atom.
All H atoms should be shown 1. not both. This would indicate 4 electrons between H and Br!
Elimination (d) 1. The H-Br bond should be shown as a line only or electron pair only,
(b) Electrophilic addition
2. The charge is missing from the cyanide nucleophile.
(ii) 1. The charge is missing from the bromide product of step 1. 4. Dot is missing from line 4 – should be 2•CH2CH3.
the C-Br bond. 3. In (ii), the dot is at wrong end (C2H5•) – electron should be on C of CH2.
3. The lone pair on Br- should be shown – these electrons derive from CH2.
centre of the bond. 2. In (i), the dot is at wrong end (CH2CH3•) – electron should be on C of
2. The tail of the curly arrow from the C-Br bond must be near the originate from the bond.
Cä+, not the C-C bond. 1. Should be “fishhook” arrows (if used at all) in step 1. Also they should
(i) 1. The head of the curly arrow from the cyanide ion should go to the (a) Free radical substitution
(c) Nucleophilic substitution Spotting the Errors in Mechanisms

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187. Avoidable Errors in Reaction Mechanism Questions Chem Factsheet

Practice Questions
1. (a) Chloroethane reacts with chlorine in the presence of UV light to form a mixture of products. Write the propagation steps for the
conversion of chloroethane into 1,2-dichloroethane.
(b) A little 1,4-dichlorobutane and also a substance with the empirical formula CH2Cl are also formed. Write equations for the formation
of these products.
2. Write the mechanism for the reaction of concentrated sulfuric acid with propene to produce CH3CH(OSO2OH)CH3.
3. Name and outline the mechanism for the conversion of 1-chloropropane into 1-aminopropane by reaction with ammonia.
4. Examine each of the following mechanisms and identify the errors in each.
(a) Mechanism of electrophilic addition of Br2 to ethene
H H H H H
H
C C → H C
− C H → H C C H Note: Br2 is induced by e- being repelled by e- of C=C
H H
Brδ− :Br+ Br Br Br
1, 2 - bromoethane
Brδ+
(b) Nucleophilic substitution of 1-bromopropane by aqueous hydroxide
H H

CH 3CH2 Cδ- Brδ+ → Br− + CH 3CH2 C CN

OH −: H H

Answers
1. (a) (i) CH3CH2Cl + Cl• → HCl + •CH2CH2Cl
(ii) Cl2 + •CH2CH2Cl → ClCH2CH2Cl + Cl•
(b) 2•CH2CH2Cl → ClCH2CH2CH2CH2Cl.
(c) •Cl + •CH2CH2Cl → ClCH2CH2Cl
2. H3C H H 3C H
+ CH3CHCH3
C C → C C H →
OSO2OH
H Hδ+ H H H
:O− SO2OH
Oδ− SO2OH

Note: More stable secondary carbocation intermediate is preferred.

3. Nucleophilic substitution
H H H H H
CH 3CH2 Cδ+ Clδ− → :Cl− + CH 3CH2 C N+ H → CH3CH 2 C N: + NH4+
H3N : H H H :NH3 H H
Note: Molecule + molecule → anion + cation (charges must balance). Do not use the :Cl- to act as the base to remove the proton from
the cation. Only use NH3.
4 (a) The induced dipole in bromine is the wrong way round. The intermediate is a carbocation, not a carbanion. The Br is released as a
negative ion in the first stage. The cleavage of the Br-Br bond is in the wrong direction. The correct mechanism follows:
H H H H H
H
C C → H C C H → H C C H
+ NB: Br2 dipole is induced by bond e- being repelled by e- of C=C
H H
Brδ+ :Br- Br Br Br
1, 2 - bromoethane
Brδ-
(b) The lone pair should be on the O of the OH ion. The polarity of the C-Br bond is the wrong way round. A lone pair is missing from
the bromide ion product. The correct mechanism follows:
H H Acknowledgements: This Factsheet was researched and written by Bob Adam.
Curriculum Press, Bank House, 105 King Street, Wellington, Shropshire, TF1
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