Isomerism

It is possible for organic molecules with the same molecular formula to have different structures

Definition- Structural isomers: same molecular formula different structures (or structural formulae)

There are three types of structural isomerism

•Chain isomerism
•Position isomerism
•Functional group isomerism

Chain isomerism: Compounds with the same molecular formula but different structures of the carbon skeleton

These isomers arise because of the carbon chains can be branched. For example, there are two isomers
of butane, C4H10. In one of them, the carbon atoms lie in a "straight chain" whereas in the other the chain
is branched
H H H
H H H H
H C C C H
H C C C C H
H H
H C H
H H H H

H
butane
methyl propane
There are three isomers of pentane C5H12
H

H H H H H H H H H H C H
H H
H C C C C H
H C C C C C H
H C C C H
H H H
H H H H H H C H H H
H C H
H
pentane H
2-methylbutane 2,2-dimethylpropane

False isomers

Do not draw "false" isomers which are just twisted versions of the original molecule. Twisting
the molecule into a different shape does not make a different isomer. Isomers are only formed
if a bond would have to be broken and reassembled into the different structure

H H H H H
H H H
H C C C C H H C HH
H C C C H

H H H H
H H H C C H
H C H

H H
H C H

These are all exactly the same compound. H

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Number of Possible Chain Isomers for Selected Alkanes

Molecular Formula Number of possible isomers

C4H10 2
C5H12 3
C6H14 5
C7H16 9
C8H18 18
C9H20 35
C10H22 75
C15H32 4,347
C20H42 336,319
C30H62 4,111,846,763

Position isomers: Compounds with the same molecular formula but different structures due to
different positions of the same functional group on the same carbon skeleton

H H H H H H

H C C C H 1-bromopropane H C C C H 2-bromopropane

Br H H H Br H

Functional group isomers: Compounds with the same molecular formula but with atoms arranges to give different
functional groups

H H
H H

H C O C H Methoxymethane: an ether
H C C O H ethanol: an alcohol
H H
H H
H H
H H
C
H C C H

Cyclohexane- cyclo alkane CH3CH2CH2CH2CH=CH2 hexene- alkene

H C C H
C
H H
H H

Aldehydes and ketones of the same chain length would be classed as functional
group isomers- e.g. Propanal and propanone (both C3H6O)

H H O H O H

H C C C H C C C H

H H H
H H

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Structural Isomer Questions

1) a) Define what a structural isomer is.

b) Define what a molecular formula is.

2) Draw all the structural isomers of hexane and name them. What type of structural isomers are these isomers?

3) a) Draw the displayed formulae and name all the straight-chain isomers with the molecular formula C4H8Br2
b) Name the type of structural isomerism that these isomers show and explain why

4) a) Name and draw the displayed and skeletal formulae of a functional group isomer of pent -1-ene
b) Name and draw the displayed and skeletal formulae of a positional isomer of pent -1-ene
c) Name and draw the displayed and skeletal formulae of a chain isomer of pent -1-ene

5) The following is the structure of methoxyethane

H H H
H C C O C H
H H H
a) Draw the displayed formulae and name a functional group isomer of methoxyethane
b) Draw the displayed formulae and name a positional isomer of the compound you have
drawn in part 5a

6) Draw the skeletal formulas of the structural isomers of the different alcohols with the molecular formula
C4H10O. Name the isomers.
7) Deduce the number of structural isomers for Hexane C6H14

8) Name the compound on the right and draw its skeletal

formula. Deduce how many other position isomers of the
compound on the right can be formed.

9) Compound Y is shown below. It is a member of a homologous series of hydrocarbons.

H H H

H C C C C H
H H H
(a) Write the general formula of the homologous series that contains Y.
(b) Name a process used to obtain a sample of Y from a mixture containing other members of the same
homologous series.
(c) Name and draw the skeletal formula of a position isomer of Y.
(d) Name and draw the skeletal formula of a functional group isomer of Y.

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Stereoisomerism
There are two types of stereoisomerism:
Definition: Stereoisomers have the same structural formulae geometrical (E- Z isomerism) and optical
but have a different spatial arrangement of atoms isomerism

Isomerism

Structural isomerism Stereoisomerism

E-Z stereoisomerism Optical isomerism

E-Z stereoisomerism
Alkenes can exhibit a type of isomerism called E-Z stereoisomerism. This occurs because of
restricted rotation that occurs around a double bond

Single carbon-carbon covalent bonds can easily rotate

Cl Cl Cl H Cl H

H C C H H C C Cl H C C H

H H H H H Cl

All three of these structures are the same

C=C double bonds have restricted rotation, due to position

of the pi bond, so the groups on either end of the bond are
fixed in one position. It is not easy to flip between the two.

Cl H Cl Cl
C C C C
H Cl H H C-C
C-C pi
sigma
This produces two possibilities. The two structures cannot bond
bond
interchange easily so the atoms in the two molecules occupy
different positions in space.

E-Z stereoisomers arise when:

(a) There is restricted rotation around the C=C double bond.
(b) There are two different groups/atoms attached both ends of the restricted double bond

H H E-Z stereoisomers: Same structure NOT E-

H H H H H H
two different groups Z stereoisomers : two
C C C C
attached either end of C C C C identical groups attached
H H H H
the restricted double H H H H to one end of the
bond restricted double bond.

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 H H
two different groups H H
H C C H attached either end of
the restricted double H C C H But-1-ene
C C
bond- leads to EZ C C
H H H H isomers H H
H H
two identical groups attached to
Z- but-2-ene
H one end of the restricted double
H These are two bond – no E-Z isomers
C H isomers as the lack
H of rotation around But-1-ene is a structural isomer of But-2-
C C the double bonds
H ene but does not show E-Z isomerism
H C
means one cannot
H be switched to the
H other
E -but-2-ene

Naming E-Z stereoisomers

Cahn–Ingold–Prelog (CIP) priority rules.
On both sides of the double bond determine the priority group

1. Compare the atomic number (Ar) of the atoms

directly attached to each side of the double bond; the
priority
group having the atom of higher atomic number priority Cl Br
receives higher priority.

C C

H Cl

Priority Priority Cl H
group Cl Cl group
side 1 side 2 C C
C C
Z-1,2-dichloroethene
H H H Cl E-1,2-dichloroethene
If the priority atom is on the same side of the If the priority atom is on the opposite side of
double bond it is labelled Z from the german the double bond it is labelled E from the
zusammen (The Zame Zide!) german entgegen (The Epposite side!)

2. If there is are groups of atoms instead of

single atoms attached to the carbon of the
double bond then consider the sum of the H3C
atomic numbers of the entire group. The
CH3 priority
bigger group is the priority
C C
priority H
CH2
H3C
The CH3CH2 group is bigger
than the CH3 so it is the
priority group

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cis-trans isomerism

In some text books you will find this type of E-Z isomerism referred to as geometric isomerism and cis-
trans isomerism.
cis-trans isomerism can be considered as a special case of EIZ isomerism in which two of the substituent
groups are the same. It has been superseded by E/Z isomerism because the Cahn–Ingold–Prelog (CIP)
priority rules allow all alkenes to be considered and not just the ones where the groups are the same .

H
H H
H
H C C H C H
H
C C C C
H
H H H H H C
H
H
Z- but-2-ene E- but-2-ene
Can also be called Can also be called
Cis- but-2-ene trans- but-2-ene

Cis means “on this side of” in latin trans means “across” in latin

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 E-Z Isomerism Questions

1. State the meaning of the term stereoisomers

2. Identify the feature of the double bond in but-2-ene that causes it to form two EZ stereoisomers

3. Draw stuctural formulae of the E-Z isomers of the following compounds

a) 3-methylpent-2-ene.

b) but-2-ene

c) 3-methylpent-2-ene

d) pent-3-en-2-ol

e) hex-3-ene

f) pent-2-ene

4. Name the following including the correct E-Z letter at the start of the name

H3C CH3
C C
CH2 H
H3C

5. Compound A has the molecular formula C5H10O. It has a branched carbon chain and exists as a
pair of E-Z Stereoisomers. Draw the structures and name the two Isomers.

H H

6 Using the carbon skeleton like it is drawn on the right, H C C

Draw the 3 stereoisomers of 1,4-dichlorobuta-1,3-diene. C C H
H H

7. Draw the two E-Z stereoisomers of hex-4-en-2-one.

8. Explain why the following weak unsaturated acid CH3(CH)4COOH shows EZ isomerism. Draw the
structures of each of the E-Z isomers of this acid.

9. How many E-Z stereoisomers are there of the molecule shown below, including the molecule shown?

OH

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Optical Isomerism

Optical isomerism occurs in carbon compounds with 4 different groups of atoms attached to a carbon
(called an asymmetric carbon).

H H H H
A carbon atom that has four different groups attached is
H C C C C H called a chiral (asymmetric) carbon atom
H H O H

This causes two different isomers that are not superimposable to be formed. They are mirror images

H
H H

H
H H
H H H
H
H
H
H
H H
mirror
H
Mirror images
Non superimposable

H H

If the compound does not have 4 different

groups then when it is rotated it will be
H H H H superimposable
H H
not isomers (same compound)

Butan-2-ol has four different groups around a carbon and so forms optical isomers

OH OH

C C
H5 C2 CH3 H3C C 2 H5
H H

Two compounds that are optical isomers of each other are called enantiomers.

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Optical isomers have similar physical and chemical properties, but they rotate plane polarised light in different
directions.

One enantiomer rotates it in one direction and the other enantiomer

rotates it by the same amount in the opposite direction.

One optical isomer will rotate light clockwise (+)(called dextrorotatory).

-ve enantiomer +ve enantiomer
The other will rotate it anticlockwise(-)(called laevorotatory). clockwise
Anticlockwise
rotation rotation

Polarimeter
The rotation of light by a chiral compound can be observed by using a polarimeter.
The light source will produce unpolarised light which is light travelling in all planes. If this light is passed
through a polarising filter then plane polarised light will be formed, which is light that only travels in one plane.
When this passes through the sample of the chiral substance the plane polarised light will rotated in to a
different plane.

Polarising
Light filter
source Angle of rotation
of plane
polarised light

Unpolarised
light Plane
polarised
light Sample
solution of
chiral Plane
substance polarised light Analysing
after rotation filter

Method for using a polarimeter

•first put water in sample tube and rotate analysing filter to block out light
•replace water with sample. If the sample is chiral light will be seen
•rotate analysing filter again to block out light. The amount the analyser is rotated is the amount the light
has been rotated.

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R/S Nomenclature
Different systems of nomenclature are is existence for optical isomers. D/L or +/- are commonly
used, but both have been superseded by the more informative R/S system.

H4
1) Using the Cahn–Ingold–Prelog (CIP) priority rules, used in
EZ isomerism, assign a priority number for each of the four
groups. The ones with the higher atomic number Ar have 2
C
the higher priority. HOOC CH33
OH
1 (highest priority
O biggest Ar )

OH1
2) Redraw the molecule with the atom with the lowest H
priority pointing into the plane of the page (in this case H)
2 C 3
HOOC CH3

3) Imagine moving from substituent 1 to 2 to 3. If moving OH1

in a clockwise direction then assign the compound the R H
letter. If moving anticlockwise the assign the compound the
2 C 3 This is an S
S letter
CH3 enantiomer
HOOC

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Racemic mixtures

A mixture containing a 50/50 mixture of the two isomers (enantiomers) is described as being a racemate or
racemic mixture.

A racemic mixture (a mixture of equal amounts of the two optical isomers)

will not rotate plane-polarised light.
Racemate
no rotation

Chemical Reactions and Optical Isomers

Formation of a racemate
CH3
A racemate will be formed in a reaction
H
mechanism when a trigonal planar reactant or C
intermediate is approached from both sides by NC:
:CN
an attacking species
O

H
H H 3C CN
NC CH3

C There is an equal chance of C

either enantiomer forming so
a racemate forms. No OH
OH
optical activity is seen

Mechanism for the reaction (drawn the same for both enantiomers)
Nucleophilic addition of HCN to aldehydes
and ketones (unsymmetrical) when the O
δ-
O:
- H+ O H
trigonal planar carbonyl is approached from
+
both sides by the HCN attacking species: Cδ H3C C C 2H 5 H3C C C 2H 5
results in the formation of a racemate H 3C C2H5
:CN- CN CN

A racemate can also be formed in the reaction of the electrophilic addition of HBr to an unsymmetrical alkene

H
H :Br - The bromide can H
+ attack this planar
C CH2 C
δ+ δ- carbocation from C
H Br both sides leading to CH2 Br CH2
H3C CH3 H3C Br
a racemate CH3 CH3
CH3
H2C CH CH2 CH3
:Br - Major product s 90%
If the alkene is H H
unsymmetrical, addition of +
C C CH2 CH3
hydrogen bromide can CH2 CH2 CH2 CH3 Minor
lead to isomeric products. H H product
Br 10%

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Nucleophilic substitution reactions and optical activity

In the topic of reactions of halogenoalkanes we look at the nucleophilic substitution reactions of

halogenoalkanes with aqueous hydroxide ions to form alcohols. The reaction can occur via two different
mechanisms called SN1 and SN2. Primary halogenoalkanes tend to undergo the SN2 mechanism and
tertiary halogenoalkanes undergo the SN1 mechanism. Secondary halogenoalkanes can undergo either
mechanism. The two different mechanisms have a different effect on optical activity of chiral reactants. By
observing the differing effects it can give us evidence for which mechanism is occurring.

Nucleophilic substitution mechanism, SN1

H H
The OH- ion can then
δ+ δ- attack from either side
H3C C Br C + resulting in different
:OH- enantiomers and a
racemate forms
CH2CH3 CH3 C2H5
The Br breaks off leaving a
planar carbocation intermediate H H

C
C
H3C C 2H 5 H 5 C2 CH3
OH or HO

Nucleophilic substitution mechanism, SN2

H - H
δ+ δ- CH3 H

H3C C Br HO C Br HO C CH3
-HO:
CH 2CH3
CH2CH3 CH2CH3
In the SN2 mechanism no intermediates are formed and the reaction occurs via a transition state
If the reactant was chiral then during the reaction the opposite enantiomer would form
through inversion as shown below. H

H
HO C Br
H
HO C Br CH3
H3C H3CH2C
HO C Br
H3CH2C
H CH3 CH CH
2 3
H
H3C C Br
-HO: HO C
CH3
H3CH2C
CH2CH3

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 Drug action and optical isomers
Drug action may be determined by the stereochemistry of the molecule.
Different optical isomers may have very different effects

Ibuprofen
CH3
H3C HC CH CH CH3
CH2 C C HC
CH CH C O
HO

Thalidomide
H H O O H
H O
C H H H C C N
C C H C
C C C
C C H N C C O
C N
H C C C C H
C C C H C C C C
H C O H H
H N O H H
O H
O H
Chiral carbon
S thalidomide (effective
R thalidomide (dangerous drug) drug)

One enantiomer of thalidomide causes birth defects in unborn children whilst the other had useful
sedative problems. It was used as a drug for treat pregnant women with morning sickness. At the
time the side effect was not know. Unfortunately it was given in a racemic mixture when first used
and many babies were born with birth defects

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Introduction to Organic Chemistry
Organic chemistry is the study of carbon compounds. It is such a complex branch of chemistry because
carbon form a wide variety of compounds for the following reasons

1) Carbon atoms can form strong covalent bonds to each other.

Carbon is an unusual element in that it can form 4 covalent bonds per atom and can form strong covalent
bonds to other carbon atoms. This leads to the formation of a vast number of stable carbon compounds.
We used the word Catenation for the ability to form bonds between atoms of the same element. Other
Group 4 elements can also catenate but the stability of the compounds formed are limited due to weaker
bond strengths.

2) The carbon-carbon bonds can be single, double or triple which leads to the following bond patterns.

C C C C

2 double bonds 1 triple bond

4 single bonds 1 double bond 1 single bond
2 single bonds

3) Carbon atoms can be arranged in straight chains, branched chains and rings
H
H H H H H C H H H
H H HH H H H
C
H C C C C C H H C C H
H C C C C C H
H H H H H H C C H
HH C HH H H
C
straight chains H H
H H H
branched chains rings

4) Other atoms or groups of atoms can be placed on the carbon atoms.

H O H H H
H H H

H C C OH H C C C Cl
H C C C O H

H H H H H H H

5) Groups can be placed in different positions on a carbon skeleton.

H H H H H H
H C C C Cl H C C C H
H H H H Cl H

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Ways of Representing Organic Molecules

There are a number of different types of formulae that we use to represent organic molecules that
show varying degrees of information about the structure of the molecule.

Molecular formula: The formula which shows the actual number of each type of atom

e.g. C3H8 or C2H6O

This type of formula shows no detail about the structure and several different molecules
may have the same molecular formula.
C2H6O could be either ethanol or methoxymethane
H H H H

H C C OH H C O C H
H H H H
Condensed Structural formula shows the minimal detail that shows the arrangement of atoms
in a molecule,

eg for butane: CH3CH2CH2CH3

CH3CH2OH for ethanol CH3OCH3 for methoxymethane

Bonds are not drawn but it is possible to see what is attached to each carbon.

Displayed formula: show all the covalent bonds present in a molecule

H H H H
The displayed structural formula shows every bond and atom
H C C C C H in a 2D format. It is common to draw the single bonds at 90o.
H H H
This is done to simplify the representation of the molecule. It is
H C H not, however, a truthful representation of the 3D shape
H

Remember that the shape around the carbon atom in saturated

hydrocarbons is tetrahedral and the bond angle is 109.5o
We can represent the 3D shape by using stereochemical
formulae H H
• The solid line represent a bond on the plane of the paper H C C H
• The black triangular wedge represents a bond coming in
front of the paper
• The striped wedge represents a bond behind the plane of H H
the paper

Skeletal formula shows the simplified organic formula, shown by removing hydrogen atoms from alkyl chains,
leaving just a carbon skeleton and associated functional Groups.

OH

But-2-ene Butan-1-ol
2-methylbutane cyclohexane cyclohexene

Skeletal formulae are useful when the molecule is a large complex one

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Functional Groups

As organic chemistry is a vast subject with many millions of molecules we separate the molecules
into groups of molecules with similar chemical properties. This is usually done by studying
compounds which behave in a similar way because they have a particular atom, or group of atoms,
(functional group) in their structure.
Each functional group has its own distinctive properties

H H H These molecules have similar

H H H
properties due to the presence
H C O H H C C O H H C C C O H of the –O-H group of atoms.
H H H H H H We call this functional group a
alcohol
methanol ethanol propanol

We can use the term Homologous series to describe families of organic compounds
with the same functional group, (with varying carbon chain length) and the same general
formula.
•They show a gradual change in physical properties (e.g. boiling point).
• Each member differs by CH2 from the last.
• same chemical properties.

Some of the functional groups met at A-level are given in the table below and the next page.

prefix / suffix
homologous functional example
(* = usual use)
series group
Alkane
C C CH3CH2CH2CH3
-ane Butane

H H
Alkenes C C suffix -ene C C propene
H
H C
H
H

C OH suffix* -ol H H H Propan-1-ol

Alcohols prefix hydroxy- H C C C O H
OH
H H H

H H H
C halogen
Halogenoalkanes prefix chloro-
1-chloropropane
H C C C Cl
bromo- Cl
H H H
iodo-

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 prefix / suffix
homologous functional group example
(* = usual use)
series
O suffix -al H O
aldehydes O
C H prefix formyl- H C C H ethanal
H

suffix* -one H O H O
ketones O
prefix oxo-
C
H C C C H Propanone
H H

O suffix -oic acid H O

carboxylic acids O
C OH H C C OH
Ethanoic acid
H
OH
suffix -nitrile H H
nitriles
C N prefix cyano- H C C C N Propanenitrile
H H
suffix* -amine
amines prefix amino-
H H H
C NH2 Propylamine
H C C C NH2
Or propan-1-amine
H H H

H O H O
esters O methylethanoate
-yl –oate H C C O C H
C O
H H O
O
O
Acyl chloride CH 3 C ethanoylchloride
C -oyl chloride
Cl Cl

O
O
Amide ethanamide
C -amide CH3 C

NH2 NH2

-oic anhydride O
Acid Anhydrides O

R C CH3 C
O
Ethanoic anhydride
O

R C CH3 C
O O

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 General rules for naming carbon chains no of
code
carbons
•Count the longest carbon chain and name appropriately
meth 1
•Find any branched chains and count how many carbons they contain
eth 2
• Add the appropriate prefix for each branch chain
prop 3
Eg -CH3 methyl or -C2H5 ethyl –C3H7 propyl
1 CH but 4
3
pent 5
2 CH2 hex 6
5 3,5-dimethylheptane
hept 7
H3C CH CH2 CH CH3
3 oct 8
4
CH2 6 non 9

dec 10
CH3 7
Basic rules for naming functional groups

•When using a suffix, add in the following way :

If the suffix starts with a vowel- remove the –e from the stem alkane name
e.g. Propan-1-ol, butan-1-amine, ethanoic acid, ethanoylchloride, butanamide

If the suffix starts with a consonant or there are two or more of a functional group meaning di, or tri needs to be
used then do not remove the the –e from the stem alkane name
e.g. Propanenitrile, ethane-1,2-diol, propanedioic acid, propane-1,2,3-triol, Pentane-2,4-dione.

•The position of the functional group on the carbon

H H H O H
chain is given by a number – counting from the end of
the molecule that gives the functional group the lowest H C C3 C C1 H Butan-1-ol
4 2
number. For aldehydes, carboxylic acids & nitriles, the
functional group is always on carbon 1. H H H H
H H H
•We only include numbers, H C C C H
methylpropane CHCl3 trichloromethane
however, if they are needed to
H H
avoid ambiguity. H C H

•The functional groups take precedence over branched 3-methylbut-1-ene is correct and not 2-methylbut-3-ene
chains in giving the lowest number
H H H H H
•Where there are two or more of the same groups, di-, tri- or 2,3-dibromopentane.
H C C C C C H
tetra are used. Note the point made above about the addition of
‘e’ to the stem H H Br Br H

•Words are separated by numbers with dashes

CH2FCCl2CH2CH3 2,2-dichloro-1-fluorobutane.
• numbers are separated by commas
•If there is more than one functional group or side chain, the 3-bromo-1-fluoropentane
CH2FCH2CHBrCH2CH3
groups are listed in alphabetical order (ignoring any di, tri).

The suffix for alkenes can go in front of other suffixes. CH2OHCHBrCH=CH2 2-bromobut-3-en-1-ol

When compounds contain more than one functional group, the order of precedence determines which groups are
named with prefix or suffix forms. The highest precedence group takes the suffix, with all others taking the prefix
form. However, double and triple C-Cbonds only take suffix form.
Order of priority highest first:
Carboxylic acids >carboxylic acid derivative>nitriles>aldehydes>ketones>alcohols>amines

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Halogenoalkanes
H H Br H
Class the halogen as a substituent on the C chain and use the
suffix -fluoro, -chloro, -bromo, or –iodo. (Give the position H C C C C H 2-bromobutane
number if necessary)
H H H H

Cl
If there are two or more halogen groups then di, tri are
used and each one is numbered and the groups are
listed alphabetically 4-bromo-2,2-dichloropentane
Cl Br

Alcohols
OH
These have the ending -ol and if necessary the position
Butan-2-ol
number for the OH group is added between the name stem CH3 CH CH2 CH3
and the –ol 1 2 3 4

O
If the compound has an –OH group in addition to other H3C CH C 2-hydroxypropanoic acid
functional groups that need a suffix ending then the OH can be
named with the prefix hydroxy-):
OH OH

HO CH2 CH2 OH Ethane-1,2-diol

If there are two or more -OH groups then di, tri are used. H2C OH
Add the ‘e’ on to the stem name though
propane-1,2,3-triol
HC OH

H2C OH

Aldehydes H
O Ketones H O H
An aldehyde’s name ends in –al
It always has the C=O bond on the Ketones end in -one H C C C H
first carbon of the chain so it does H C C
When ketones have 5C’s or more
not need an extra number. It is by H H
in a chain then it needs a number
default number one on the chain Propanone
H
H to show the position of the double
bond. E.g. pentan-2-one
Ethanal H O H O H
If two ketone groups then
di is put before –one and H C C C C C H
an an e is added to the H H H
stem
Pentane-2,4-dione
O
The prefix oxo- should be
used for compounds that H3C C C
contain a ketone group in O OH
addition to a carboxylic acid
or aldehyde 2-oxopropanoic acid

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Carboxylic acids
These have the ending -
oic acid but no number is H H
O
If there are carboxylic acid groups on both ends of the
necessary for the acid chain then it is called a - dioic acid
group as it must always be H C C C O O
at the end of the chain. Ethanedioic acid
The numbering always C C
O H
H H Note the e in this name
starts from the carboxylic HO OH
acid end
Propanoic acid

Amines H H H
H2N O
These end in –amine.
There is, however, rather confusingly two H C C C NH2 If there is another priority
CH C
ways of using this suffix. functional group as well
H H H as the amine group then
The exam boards tend to use the H3C O H
common version where the name stem propylamine the prefix amino is used.
ends in -yl propylamine. Or propan-1-amine 2-aminopropanoic acid.
The IUPAC version of the same chemical
is propan-1-amine. (This is used in the
same way as naming alcohols)

If the amine is secondary and has two alkyl CH3CH2CH2NHCH3

groups attached to the nitrogen, then each chain N-methylpropylamine (common name)
is named and the smaller alkyl group is preceded N-methylpropan-1-amine (IUPAC name)
by an –N which plays the same role as a number
in positioning a side alkyl chain
CH2 CH2
H3C NH CH3
In the common naming version if the Diethylamine (common name- does not use N if chains are
chain lengths are the same an –N is not same length)
used N-ethylethanamine (IUPAC name does still use N)

If a tertiary amine similar rules apply, and CH3CH2 CH2 N CH3

each alkyl side group is given an N
CH3
N,N-dimethylpropylamine (common name)
N,N-dimethylpropan-1-amine (IUPAC name)

If there are two amine groups then it is H H

easiest to use amino prefix It could also be named
N (CH2)6 N
1,6-diaminohexane
H H
hexane-1,6-diamine

H H H OH
Nitriles H3C
These end in –nitrile, but the C of the C
H C C C CN
CN group counts as the first carbon of C
the chain. Note the stem of the name is H3C N
H H H
different : butanenitrile and not
2-hydroxy-2-methylpropanenitrile
butannitrile. butanenitrile

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Carboxylic acid derivatives

Esters H
H H O
Esters have two parts to their names
H C C C O C H
The bit ending in –yl comes from the alcohol that has
formed it and is next to the single bonded oxygen.
H H H
The bit ending in –anoate comes from the carboxylic acid.
(This is the chain including the C=O bond) methylpropanoate

Acid Anhydrides
O
O
If the alkyl groups are of
This is called ethanoic CH3 C different lengths then CH3 C
anhydride. It is ethanoic
O each one is named
because it is two ethanoate O
e.g. ethanoic propanoic
groups joined together. CH3 C anhydride CH3 CH2 C
.
O
O

Acyl Chlorides O H3C O

add –oyl chloride to the stem CH3 C CH C

name
Cl H3C Cl
ethanoyl chloride 2-methylpropanoyl chloride

O O
C (CH2)3 C
Cl Cl
Pentanedioyl dichloride

Amides

O Secondary and tertiary amides

Add –amide to the stem are named differently to show the O
name CH3 C
two (or three) carbon chains.
NH2 The smaller alkyl group is
H3C CH2 C NH CH3
preceded by an –N which plays
ethanamide the same role as a number in
N-methylpropanamide
positioning a side alkyl chain

O CH3
CH3 O CH3
H3C CH2 C N CH3
H3C CH C N CH3
N,N-dimethylpropanamide N,N,2-trimethylpropanamide

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 Naming Alkanes

1. Draw the displayed formula for 2,2-dimethylpropane

2. Draw the skeletal formula for 2,3-dimethylbutane

3. Draw the displayed formula for 3-ethylhexane

4. Draw the skeletal formula for (CH3)3CCH2CH3 and name the compound

5. Name the following compounds

a) b) CH3
CH3 CH3
CH3 H2C
H3C C CH2 C H
CH CH2 C H
H3C CH3
H3C CH3

c) d)
CH2CH3 CH3 CH3 CH3
H3C C CH2CH2CH3 H3C C C C CH3
CH2CH2CH3 CH3 CH3 CH3

e) f)

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 Naming Alkenes

1. Draw the displayed formula for but-2-ene

2. Draw the skeletal formula for pent-2-ene

3. Draw the skeletal formula for 2-methylpent-2-ene

4. Draw the skeletal and displayed formula for cyclopentene

5. Name the following compounds

a) CH3CH2CH=CH2 b) (CH3)2C=CHCH3

c) d) CH3
H CH3
C C H2C C C H
H3C H H CH3

e) f)
H3C H
H2C CH CH CH2
C C
H3C H

g) h)
CH3
H CH2
H CH3 C C
C C H3C CH2
H3C CH2 CH3 CH2

CH3

i) j)

k) l)

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 Naming Halogenoalkanes

1. Draw the displayed formula for 2,2-dichlorohexane

2. Draw the skeletal formula for 2,3,3,3-tetrafluoropropene

3. Draw the skeletal formula for 2,2-dichloro-3-methylpentane

4. Draw the displayed formula for 1,2-dichloro-2-methylpropane.

5. Draw the skeletal formula for 1,1,1-trichloro-2,2-difluoroethane

6. Draw the displayed formula for 5-chloro-2,2-dimethylhexane

7 Name the following compounds

a) CH3CH2CH2CH2Cl b) CH3CHICH3

c) H H d)

H C C H H3C CH CH3
Br
Cl Cl
e) Br CH3
f)

CH2 C CH2
H3C CH3
g) F h)
Cl C Cl
Cl

i) j)
CH3 CH3 Cl
H2C C C CH3
H Cl
k) l)

m)
n)
H Cl Cl H
H C C C C H
H H H
H C H

H C H
H

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 Naming Alcohols

1. Draw the displayed formula for Hexan-1-ol

2. Draw the displayed formula for prop-2-en-1-ol

3. Draw the skeletal formula for 3-methylpentan-2-ol

4. Draw the skeletal formula for 2,3-dimethylbutan-1-ol

5 Draw the displayed and skeletal formula for cyclohexanol

6 Name the following compounds

a) b)

c) d) HO

CH2

H3C C CH3
H

e) f)
CH3
H3C CH2
CH CH3 H3C C CH2
OH CH3 CH2 OH

g) h)
CH3 CH3
CH2 CH2
H C C CH3 HO CH OH
HO H
OH
i) j)
HO

OH

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 Naming Carbonyls

1) Draw the displayed formula for butanone

2) Draw the skeletal formula for hexan-3-one

3) Draw the displayed formula for propanal

4) Draw the skeletal formula for 2-methylbutanal

5) Name the following compounds

a) b) HCHO
O
H3C C
CH3

c) CH3CH(OH)CH2CHO d) CH3(CH2)2CHO

e) CH3 f) O O
C CH2 O C C
O CH2 C H CH H
CH3 CH3

g) H H h) CH3 O
O
H C C C H3C C C
H H H CH3 H

i) j) CH3 CH3

H2C C O
C
O H
CH3

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 Naming Carboxylic Acids

1) Draw the displayed formula for propanoic acid

2) Draw the skeletal formula for 3-methylpentanoic acid

3) Draw the displayed formula for 3-hydroxypropanoic acid

4) Draw the skeletal formula for 2,3-dichlorobutanoic acid

5) Name the following compounds

a) HCOOH b)
O O
C C
HO OH
c) CH3CH2CH2COOH d)
HOOC CH COOH
CH3

e) f)

H3C CH COOH
OH

g) h)
CH3 O OH O
H3C C C H2C C C
CH3 OH OH
OH CH3

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 Naming Carboxylic Acids Derivatives

1) Draw the displayed formula for methyl propanoate

2) Draw the skeletal formula for ethyl butanoate

3) Draw the displayed formula for Ethanoic anhydride

4) Draw the skeletal formula for Methyl pentanoate

5) Draw the skeletal formula for 2-methylpropanoyl chloride

6) Draw the displayed formula for Methyl-2-methylpropenoate

7) Name the following compounds

b) HCOOCH2CH3

a) CH3CH2COCl
d)

c) (CH3CH2CO)2O

e) O f) O
H3C C
C CH2
O O
Cl CH2
C
H3C CH2 C
O Cl
g) h)
HO O
CH3COOCH2CH2CH3
O

i) j) O

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 Naming Amines and ammonium salts

1) Draw the displayed formula for Methanamine or Methylamine

2) Draw the skeletal formula for butan-2-amine

3) Draw the displayed formula for 2,6-diaminohexanoic acid

4) Name the following compounds

a)
H3C CH2 NH2
b) (CH3CH2)2NH

c) d) NH2
H H H
CH CH3
H C C C NH2 H3C
HC
H H H
CH3
f) NH2

e) CH3CH2CH2NHCH3 CH CH3
H3C
CH2

g) NH2
h)
O H H
CH C N (CH2)6 N
H3C OH H H
CH2

i) j)
CH3 CH3
CH2 N CH3 CH2 N
H3C CH2 CH2 H3C CH2 CH3

a) l) CH3 CH3
CH N
H3C CH CH3
CH3

m) (CH3CH2)4N+ Br- ) CH3CH2NH3Cl

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 Naming Amides and Nitriles
1) Draw the displayed formula for Propanenitrile

2) Draw the skeletal formula for propanamide

3) Draw the displayed formula for N-ethylpropanamide

4) Draw the skeletal formula for 2-bromobutanenitrile

5) Name the following compounds

b) O
H3C C
a) CH3CN
NH2

c) H d) O
O
H3C C CN H3C C NH CH3

CH3

f)
O
CH2 CH3
e) CH3CH2CONH2 C
H3C NH CH2

g) h)
H3C CH2 CH3 CH2 CH3
CH C N N C C CH2
HO OH

i) O j)
O
H3C C
CH NH H3C CH2
C
CH2 NH CH3
CH3 CH3

k) O l) O CH3
H2N C NH2 H3C NH C NH
C CH2 C CH2
O O

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Alkanes

Alkanes are saturated hydrocarbons Saturated: Contain single carbon-carbon bonds only

General formula alkane CnH2n+2 Hydrocarbon is a compound consisting of

hydrogen and carbon only

Methane CH4

Ethane C2H6 Remember that the shape around the

carbon atom in saturated hydrocarbons is
Propane C3H8 tetrahedral and the bond angle is 109.5O
The shape is tetrahedral as a result of the
Butane C4H10 four bond pairs of electrons equally
repelling.
Pentane C5H12
H H
Hexane C6H14
H C C H
Heptane C7H16
H H
Octane C8H18

Nonane C9H20

Decane C10H22

Physical properties- boiling point

The increasing boiling points of the alkane homologous series can be explained by the increasing
number of electrons in the bigger molecules causing an increase in the size of the van der Waals
between molecules.

The shape of the molecule can also have an effect on the size of the van der Waals forces. Long chain
alkanes have a larger surface area of contact between molecules for van der waals to form than compared to
spherical shaped branched alkanes and so have stronger van der waals and higher boiling points.

H H C HH

H C C C H

H H
H C H

H
H H H H H Pentane B.p.36 oC
H C C C C C H 2,2 Dimethylpropane
H H H H H B.p.10 oC

Chemical Reactivity
Alkanes do not react with many reagents.
This is because the C-C bond and the C-H bond are relatively strong and so cannot form
stronger bonds with other elements that easily and there are no polar side groups .
There main reactions are combustion reactions in air although they can react with
halogens in the presence of UV light

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Fuels from crude oil
They are obtained from the crude oil in the order of fractional distillation, Alkanes are used as fuels
cracking and reformation of crude oil

Refining crude oil fuel gas (bottled)

20° C
Fractional Distillation: petrol/gasoline
40° C
Petroleum is a mixture consisting mainly of alkane naptha (chemicals)
hydrocarbons Crude 110° C
oil kerosene (jet fuel)
180° C
Fractional distillation of crude oil works because different diesel oil
components (fractions) of this mixture can be drawn off at 250° C
fuel oil
different levels in a fractionating column because of the 300° C
temperature gradient in the column. The The temperature of Furnace
column decreases upwards. lubricating oils
The crude oil is preheated in a furnace and then passed into 340° C
the column. The smaller molecules with lower boiling points
will evaporate in the column and move upwards in the column. bitumen
They will pass through the many bubble caps on the trays in
the column. As they move up to a colder part of the column
that is equal to their boiling point they will start to condense on
the trays. Similar molecules of similar size and boiling point will This is a physical process
condense at the same level. This fraction of similar molecules involving the splitting of weak
will be tapped off from the tray. Note that fractions are a London forces between
mixture of hydrocarbons with a similar chain length and boiling molecules
point range. The larger molecules with stronger London forces
and higher boiling points will condense at lower points in the
column where the temperature is higher

Vacuum distillation unit

The column show above is a simplification of the real process. The larger heavier fractions are tapped of
from the fractionating column and are distilled again under a lower pressure. Lowering the pressure over a
liquid will lower its boiling point.
Vacuum distillation allows heavier fractions to be further separated without high temperatures which could
break them down.

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Cracking

Cracking is the next process that occurs in a oil refinery after the initial fractional distillation of
the crude oil. Cracking is the conversion of large hydrocarbons to smaller molecules of by
breakage of C-C bonds. This is a chemical process involving the splitting of strong covalent
bonds so requires high temperatures .There are two mains types of cracking: thermal and
catalytic. The two processes are used to produce different types of useful products

Economic reasons for cracking

There is a general imbalance between the abundance of certain fractions in crude oil with their economic
demand
The petroleum fractions with shorter carbon chains such as petrol and naphtha are in more demand than the
larger fractions.
The larger hydrocarbons are abundant but have a lower demand. To make use of excess larger hydrocarbons
and to supply demand for shorter ones the longer hydrocarbons are cracked.
The products of cracking are more useful and valuable than the starting materials (e.g. ethene used to make
poly(ethene) and ethane-1,2-diol, and ethanol) The smaller alkanes are used for motor fuels which burn more
efficiently.

The two main types of cracking, thermal and catalytic, need different conditions and are used to produce
different products

Thermal Cracking

Conditions:
High Pressure (7000 kPa) The molecules only need to be exposed to the
High Temperature (400°C to 900°C) high temperature for a second for the reaction to
occur
The high temperatures involved in this process can break bonds anywhere in the molecule by
C-C bond fission and C-H bond fission. The fission of the bond is called homolytic and reactive
free radicals are formed.

H H H H H H H H H H H H H H H H
H C C C C C C C C H H C C C C C C C C H
H H H H H H H H H H H H H H H H

These radicals can then undergo a series of reaction to form more stable compounds. For
example they can lose a hydrogen to form a stable alkene plus a hydrogen radical
Hydrogen radicals can then react together to form hydrogen gas. There are several other
possible reactions that can occur and this process will always produce a mixture of products.
It does produce a high proportion of alkenes that can be useful for manufacturing polymers and
many other chemicals. The hydrogen gas produced can also be used in the Haber Process and
in margarine manufacture
Example Equations
Many different overall equations can be written for the process.
High Mr alkanes smaller Mr alkanes+ alkenes + (hydrogen)
C8H18 C6H14 + C2H4
C12H26 C10H22 + C2H4

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 Catalytic Cracking

Conditions: Catalytic cracking is cheaper than thermal cracking

Low pressure because it saves energy as lower temperatures and
High Temperature (450°C) pressures are used. It produces very different products.
Zeolite Catalyst

This type of cracking still involves breaking C-C bonds, but the bonds are broken heterolytically and
carbocations are produced instead of free radicals. In the process the large hydrocarbon chains can rearrange
to form branched chain alkanes, cyclic alkanes and aromatic hydrocarbons. These products are added to
motor fuels. Branched and cyclic hydrocarbons burn more cleanly and are used to give fuels a higher octane
number.

Reforming
Reforming is a similar process to catalytic cracking that is used in addition to cracking to turn straight chain
alkanes into branched and cyclic alkanes. Reforming is generally used to turn smaller straight chain
alkanes into branched or cyclic hydrocarbons of the same size. The products are added to motor fuels to
increase their octane number

H H H H H H CH2
H2C CH2
H C C C C C C H + H2
H2C CH2
H H H H H H CH2

Octane number

Knocking occurs in four stroke motor car engines when some hydrocarbons ignite too early. It causes a
knocking sound and reduces the engines performance.
We measure the problem using the octane number. The higher the number, the better the fuel.
The scale is based on the tendency to auto-ignite of two hydrocarbons:
2,2,4-trimethylpentane, which used to be called iso–octane is given an octane number of 100.
Heptane is given an octane number of zero.

For most of the 20th century pre-ignition in motor cars was reduced by the addition of a lead
compound, tetraethyl lead (CH3CH2)4Pb. The problem was the lead in the petrol was emitted into
the atmosphere via the exhaust gases. Lead is a toxic element and caused significant health
problems. Lead was phased out in petrol in the late 20th century but we still refer to lead free petrol.

To improve the octane number of petrol and lessen the need for lead additives, the products of the
reforming and catalytic cracking processes described above are now added to petrol.

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 Questions on Distillation and Cracking

1.a) Describe how fractional distillation of crude oil works. In your answer you should refer to the temperature
gradient in the column, the type and varying strength of the intermolecular forces between the molecules,
and why the fractions collect at different levels in the fractionating column

b) Why do fractions have a range of boiling points?

2. Catalytic cracking and thermal cracking of petroleum fractions produce different types of products, both
of which are valuable.

Discuss both catalytic cracking and thermal cracking of a petroleum fraction. In your answer you
should quote the conditions used for both cases. Identify the products formed and state their uses for both
cases.

3. a) Explain the economic reasons for the catalytic cracking of alkanes and why catalytic cracking is cheaper to
carry out than thermal cracking.

b) Explain why high temperatures are needed for thermal cracking

4) Thermal cracking of large hydrocarbon molecules is used to produce alkenes. Write an equation for the
thermal cracking of C21H44 in which ethene and propene are produced in a 3:2 molar ratio together with one
other product.

5) Cetane (C16H34) can be cracked to produce hexane, butene and ethene.

Write an equation to show how one molecule of cetane can be cracked to form hexane, butene and ethene.

6) The cracking of one molecule of compound X produces pent-1-ene, ethene and butane in a 1:2:1 mol ratio.
Deduce the molecular formula of X and write the equation for the reaction

7) One molecule of C9H20 can be cracked to form one molecule of pentane and one other
product.
Write an equation for this cracking reaction.

8) Find out some of the major uses of the alkene products from the thermal cracking reactions.

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 COMBUSTION
Alkanes readily burn in the presence of oxygen. This combustion of alkanes is highly exothermic,
explaining their use as fuels.

Complete Combustion
In excess oxygen alkanes will burn with complete combustion
The products of complete combustion are CO2 and H2O.
C8H18(g) + 12.5 O2(g) → 8CO2(g) + 9 H2O(l)

Incomplete Combustion Incomplete combustion produces

less energy per mole than
If there is a limited amount of oxygen then incomplete combustion
complete combustion
occurs, producing CO (which is very toxic) and/or C (producing a sooty
flame)
Carbon (soot) can cause global
CH4(g) + 3/2 O2(g) → CO(g) + 2 H2O(l)
dimming- reflection of the sun’s
CH4(g) + O2(g) → C(s) + 2 H2O(l)
light

Carbon monoxide is an highly toxic but odourless gas. It can cause death if it builds up in a enclosed space
due to faulty heating appliances.

CO is toxic to humans as CO can from a strong bond with haemoglobin in red blood cells. This is a stronger
bond than that made with oxygen and so it prevents the oxygen attaching to the haemoglobin.

Sulphur dioxide

Sulphur containing impurities are found in petroleum fractions which produce SO2 when they are burned.
One impurity found in fuels is methanethiol CH3SH. It combusts
according to the following equation
CH3SH+ 3O2 SO2 + CO2 + 2H2O
Coal is high in sulphur content, and large amounts of sulphur oxides are emitted from power stations.
S+ O2 SO2

SO2 will dissolve in atmospheric water and can produce acid rain by the following two reactions

Reaction with oxygen in the atmosphere form SO3

2SO2 + O2 → 2 SO3 Acid Rain can acidify lakes resulting in
problems for aquatic creatures. It can also
The SO3 dissolves in atmospheric water to form acid destroy forests and corrode buildings and
statues made from limestone
SO3 + H2O → H2SO4 sulphuric acid

SO2 can be removed from the waste gases from furnaces (e.g. coal fired
power stations) by flue gas desulphurisation. The gases pass through a The calcium sulphite which is
scrubber containing basic calcium oxide which reacts with the acidic formed can be used to make
sulphur dioxide in a neutralisation reaction calcium sulphate for
plasterboard.
SO2 + CaO CaSO3

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 Nitrogen Oxides NOx
Nitrogen oxides form from the reaction between N2 and O2 inside the car engine.
The high temperature and spark in the engine provides sufficient energy to break strong N2 bond

N2 + O 2 2NO N2 + 2O2 2NO2

Pollutant Environmental consequence

Nitrogen oxides (formed when N2 in the air NO is toxic and can form acidic gas NO2
reacts at the high temperatures and spark in NO2 is toxic and acidic and forms acid rain
the engine)
Carbon monoxide toxic
Carbon dioxide Contributes towards global warming
Unburnt hydrocarbons (not all fuel burns in the Contributes towards formation of smog
engine)
soot Global dimming and respiratory problems

Catalytic converters
These remove CO, NOx and unburned hydrocarbons (e.g. octane,
C8H18) from the exhaust gases, turning them into ‘harmless’ CO2, N2 Converters have a ceramic
and H2O. honeycomb coated with a thin
layer of catalyst metals
2 CO + 2 NO → 2 CO2 + N2 Platinum, Palladium, Rhodium
– to give a large surface area.
C8H18 + 25 NO → 8 CO2 + 12½ N2 + 9 H2O
Catalytic converter

CO CO2
NOx N2
C8H18 H2O

How Catalytic converter works Bonding to the catalyst surface

• CO and NO are adsorbed onto surface of catalyst must be weak enough for
• This weaken bonds in the CO and NO, thereby adsorption and desorption to
lowering activation energy take place but strong enough
• Reaction occurs to weaken bonds and allow
• CO2 and N2 desorbs from the surface reaction to take place.

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The ‘Greenhouse Effect’ and Global Warming

•Carbon dioxide (CO2), methane (CH4) and water vapour (H2O) are all greenhouse gases. (They trap
the Earth’s radiated infra red energy in the atmosphere).
•Water is the main greenhouse gas (but is natural), followed by carbon dioxide and methane.

The Greenhouse Effect

Ultraviolet radiation from the sun comes and heats up the earth. The earth like all hot objects then
emits infra red radiation. Some of the infra red radiation is absorbed by greenhouse gases such as
CO2. Infrared radiation is absorbed by C=O, O–H and C–H bonds in H2O, CO2 and CH4.
The greenhouse gases then radiates infra red radiation back to the earth’s surface. This makes the
atmosphere warmer

The ‘Greenhouse Effect’ of a given gas is dependent both on its atmospheric concentration and
its ability to absorb infrared radiation and also its residence time. (Time it stays in
atmosphere)

Concentrations of Carbon dioxide in the atmosphere have risen The Earth is thought to be getting
significantly in recent years due to increasing burning of fossil fuels. warmer, and many scientists
Carbon dioxide is a particularly effective greenhouse gas and its believe it is due to increasing
increase is thought to be largely responsible for global warming. amounts of greenhouse gases in
the atmosphere.

Role of chemists in minimising climate change resulting from global warming

Chemists provide scientific evidence to governments to

Carbon Capture and Storage, CCS
verify that global warming is taking place such as
Carbon dioxide could potentially be stored in a
monitoring atmospheric changes
number of different ways
• removal of waste carbon dioxide as a liquid
Chemists are investigating solutions to environmental
injected deep in the oceans or on the sea-
problems, such as developing carbon capture and
bed.
storage, CCS.
• storage in geological formations or under
the sea-bed by the reaction of carbon
Chemists can monitor progress against initiatives dioxide with metal oxides to form stable
such as the Kyoto protocol solid carbonates, which can be stored

Chemists can also develop

• alternative energy sources such as developing fuel cells or developing solar power or fuels
that do not produce CO2
• Develop more efficient engines for transport or lean burn engines
• Develop uses for carbon dioxide e.g. dry cleaning or making decaffeinated coffee OR
blowing agent in polymer or making fizzy drinks.

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Questions on Combustion and Pollution

Complete Combustion:
1. Cetane (C16H34) is a major component of diesel fuel.
a) Write an equation to show the complete combustion of cetane.
b) Cetane has a melting point of 18oC and a boiling point of 287oC . In polar regions vehicles that use diesel
fuel may have ignition problems. Suggest one possible cause of this problem with the diesel fuel.
c) What are the environmental consequences of this combustion reaction?
d) How can complete combustion of a fuel be maximised?
e) Another fuel, propane has a boiling point of –42 °C, it is usually supplied as a liquid for use in camping
stoves. Why is it supplied as a liquid?

2)Write equations to shows how the following compounds burns completely in air
a) pentane
b) ethanol C2H5OH

Incomplete combustion
3) a) Write an equation to show the incomplete combustion of ethanol to form only carbon monoxide
b) What are the environmental and economic problems of incomplete combustion forming carbon
monoxide

4) a) Give the name of a solid pollutant which may form when pentane burns incompletely in air. Write
an equation for the combustion of pentane for the formation of this solid pollutant
b) What are the environmental problems caused by the formation of this solid pollutant?

Nitrogen Oxides
5a) The pollutant gas NO is found in the exhaust gases from petrol engines. Explain why NO is formed in
petrol engines but is not readily formed when petrol burns in the open air.
b) Write an equation to show how NO is formed in the combustion engine and give a condition needed for
its formation.
c) The oxide NO reacts with oxygen to form nitrogen dioxide. Write an equation for this reaction. Then
deduce an equation to show how NO2 reacts with water and oxygen to form nitric acid (HNO3)
d) What are the environmental consequences of the formation of nitrogen oxides.

Sulphur dioxide
6a) There are sometimes sulphur-containing impurities naturally found in crude. One impurity
is called methanethiol (CH3SH). This impurity causes environmental problems when
burned. Write an equation to show the complete combustion of methanethiol, and explain what are the
environmental consequences of this reaction?
b) Describe how the sulfur dioxide can be removed from the waste gases produced when sulphur
containing fuels are burnt on a large scale in industry by reacting with calcium oxide on a mesh. As part of
your answer include the following
• Write an equation to show how the SO2 is removed and explain what type of reaction this is.
• Why is CaO placed on a mesh?
• Give a use for the product formed.
• Give reasons why the method you have described may not be 100% efficient.

N Goalby chemrevise.org 9
Catalytic Convertors

7)a) What is the main role of a catalytic convertor in a car?

b) What metals is a catalytic convertor made from and explain why these metals are coated on an inert
ceramic honeycomb structure.
c) Outline, with an equation, how a catalytic converter removes CO and NO from the exhaust gases of the
engine.
d) Catalytic convertors can also remove unburnt hydrocarbons. Write an equation to show how inside
a catalytic converter the unburnt octane reacts with nitrogen monoxide to form carbon dioxide, water and
nitrogen only . What are the environmental consequences of unburnt hydrocarbons escaping into the
atmosphere?
*e) The combustion of diesel is less efficient than that of petrol. Despite an excess of oxygen,
unburnt hydrocarbons, CO and even solid carbon are produced. Whilst the first two pollutants may be
removed as before in the catalytic converter, the carbon formed would simply block it up were it not
removed. At the operating temperatures within the catalyst, very little of the carbon reacts with oxygen; it
is, however, oxidised by nitrogen dioxide, NO2 , forming CO2 and NO. Write an equation for the reaction
between carbon and NO2 .

*8) a) The catalysts in a catalytic converter work by a process called heterogeneous catalysis. Explain this
term, and describe (with the help of diagrams) the adsorption and desorption mechanism by which
heterogeneous catalysts work.
b) Explain why the adsorption strength of the catalyst is an important factor in determining its success.

Pre-ignition
*9) In petrol engines, the vaporised petrol–air mixture is compressed before it is sparked. Some
hydrocarbons with a low octane rating, however, ignite under pressure before sparking so that
pre-ignition, called knocking, occurs which causes the engine to run unevenly. The octane
rating is based on a scale on which 2,2,4-trimethylpentane has an octane rating of 100.

One way to reduce knocking and improve the octane rating is to add tetraethyllead, Pb(C2H5)4
(TEL), and 1,2-dibromoethane. During the combustion, TEL reacts with oxygen and
1,2-dibromoethane to form a mixture of products including lead(II) bromide. Use of TEL is banned in Britain
because of the danger to health of lead compounds in the exhaust gases being released into the atmosphere.
a)Using molecular formulae, write equations for
(i) the complete combustion of 2,2,4-trimethylpentane;
(ii) the complete combustion of TEL in the presence of 1,2-dibromoethane to form a mixture of products.
Assume that all the bromine and lead combine to form lead(II) bromide.

b) Find out what types of hydrocarbons have a large octane numbers and how petrol is stopped from pre-
igniting now TEL cannot be used
c) Another way to improve the octane rating of petrol is to add compounds such as ethers or
alcohols. The ether functional group is R-O-R. The most commonly used ether is methyl tertiary butyl ether
(MTBE)

Explain why the ether MTBE is more volatile than its isomeric alcohols

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 Free Radical Substitution Reactions of Alkanes
Reaction of alkanes with bromine / chlorine in UV light
In general, alkanes do not react
In the presence of UV light alkanes react with chlorine to form a with many reagents.
mixture of products with the halogens substituting hydrogen atoms. This is because the C-C bond
and the C-H bond are relatively
Overall Reaction strong
This is the overall reaction, but
CH4 + Cl2 CH3Cl + HCl a more complex mixture of
products is actually formed
methane chloromethane
It proceeds via a series of steps:
The MECHANISM for this reaction is called a FREE RADICAL STEP ONE: Initiation
SUBSTITUTION STEP TWO: Propagation
STEP THREE: Termination

STEP ONE Initiation The UV light supplies the energy to break the Cl-Cl bond. It is
Essential condition: UV light broken in preference to the others as it is the weakest.

Cl2 2Cl
.
UV light does not have enough energy to break the C-H bond

The bond has broken in a process called homolytic fission.

Cl Cl Cl each atom gets one electron from the covalent bond

Cl

DEFINITION
When a bond breaks by homolytic fission it forms Free Radicals.
A Free Radical is a reactive species which
Free Radicals do not have a charge and are represented by a
possess an unpaired electron

STEP TWO Propagation

The chlorine free radicals are very reactive and remove
CH4 + Cl. HCl + .CH3
an H from the methane leaving a methyl free radical

.CH + Cl CH3Cl + Cl. The methyl free radical reacts with a Cl2 molecule to
3 2
produce the main product and another Cl free radical

All propagation steps have a free radical in the reactants and in the products.

As the Cl free radical is regenerated, it can react with several more

alkane molecules in a CHAIN REACTION

STEP THREE Termination Collision of two free radicals does not generate further free radicals:
the chain is TERMINATED.
.CH + Cl . CH Cl
3 3
.CH + .CH CH3CH3
Minor step leading to impurities of ethane in product.
3 3 Write this step using structural formulae and
Cl . + Cl . Cl2 don’t use molecular formulae

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Applying the mechanism to other alkanes
The same mechanism is used: Learn
Example: Write mechanism of Br2 and Propane the patterns in the mechanism

STEP ONE Initiation

Essential condition: UV light
Br2 2Br
. Br2 splits in the same way as Cl2

STEP TWO Propagation

CH3CH2CH3 + Br
. HBr + CH3CH2CH2
.
Remove one H from the alkane to produce a radical
.
CH3CH2CH2 + Br2 CH3CH2CH2Br + Br
.
To the radical produced in the previous step add a Br
STEP THREE Termination
.
CH3CH2CH2 + Br
. CH3CH2CH2Br
.
CH3CH2CH2 + CH3CH2CH2
. CH3CH2CH2CH2CH2CH3

Further substitution
Excess Cl2 present will promote further substitution and could produce CH2Cl2, CHCl3 and CCl4

These reactions could occur Example propagation steps that would lead to
further substitution
CH3Cl + Cl2 CH2Cl2 + HCl
CH2Cl2 + Cl2 CHCl3 + HCl CH3Cl + Cl. HCl + .CH2Cl
CHCl3 + Cl2 CCl4 + HCl . CH Cl + Cl CH2Cl2 + Cl .
2 2

You should be able to write overall reaction equations for various reactions
Example 1. Write the overall reaction equation for the formation of CCl4 from CH4 + Cl2

CH4 + 4 Cl2 CCl4 + 4 HCl

Example 2. Write the overall reaction equation for the formation of CFCl3 from CH3F + Cl2
CH3F + 3 Cl2 CFCl3 + 3 HCl

Note HCl is always the side product – never H2

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Free Radical Substitution questions
1a) Explain what is meant by homolytic bond fission. Draw a dot and cross diagram to show the outer electrons in
CH3Cl. Then draw dot and cross diagrams of the two species formed when the C-Cl bond in CH3Cl undergoes
homolytic fission.
b) Explain what a free radical is. Use the species formed in 1a) to illustrate your answer.

2) a) Name and outline a mechanism for the reaction of chlorine with methane to form chloromethane (CH3Cl).

Include:Initiation step, First propagation step, Second propagation step, 2 different termination steps
b) What is the essential condition needed for the initiation step? Explain why it is the Cl-Cl bond that breaks in this
step rather than the C-H bond in the methane
c) Write an overall equation for the reaction of chlorine with methane to form trichloromethane (CHCl3).

3. The mechanism for the reaction of methane with fluorine is a free-radical substitution similar to the chlorination of
methane.

(a) Outline the following steps in the mechanism for the reaction of methane with fluorine to form fluoromethane,
CH3F

Include:Initiation step, First propagation step, Second propagation step, 2 different termination steps

(b) Write an overall equation for the reaction of fluorine with fluoromethane to form tetrafluoromethane.

4. When chlorine reacts with trichloromethane, tetrachloromethane, CCl4, is formed.

(a) Write the overall equation for this reaction and state the essential condition for this reaction.

(b) The mechanism for the chlorination of trichloromethane is free-radical substitution, which proceeds by a series of
steps. Write equations for the steps named below in this chlorination.

Include: Initiation step, First propagation step, Second propagation step, 2 different termination steps

5. a) Outline the following steps in the mechanism for the reaction of bromine with ethane to form 1-Bromoethane

Include:Initiation step, First propagation step, Second propagation step, 2 different termination steps

b) Further substitution in the reaction of bromine with ethane produces a mixture of liquid organic compounds.
(i) Name a technique which could be used to separate the different compounds in this mixture.
(ii) Write an overall equation for the reaction between bromine and ethane which produces hexabromoethane,
C2Br6, by this substitution reaction.

6. When bromine reacts with methane. The main product will be CH3Br. A mixture of other halogenoalkane products
are also formed due to further propagation and termination steps.

a) Work out the formulae of the other 3 halogenoalkanes formed with 1 carbon atom and explain how they are
formed.

b) Work out the formulae of at least four of the halogenoalkanes formed with 2 carbon atom and explain how they
are formed

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Alkenes
Alkenes contain a carbon-
Alkenes are unsaturated hydrocarbons General formula is CnH2n
carbon double bond
somewhere in their structure
H H H H

C C C C C H
Ethene Propene
H H H
H H

H H H H
Numbers need to be H
added to the name when C C C C H H C C C C H But-2-ene
But-1-ene
positional isomers can
H H H H H H H H
occur

π bonds are exposed and have high

C=C double covalent bond electron density.
consists of one sigma (σ)
bond and one pi (π) bond. They are therefore vulnerable to attack
by species which ‘like’ electrons: these
C-C sigma bond C-C pi bond species are called electrophiles.

Formation of σ bond

C C

One sp2 orbital from each carbon overlap to

form a single C-C bond called a sigma σ bond sigma σ bond

Rotation can occur around a sigma bond

Formation of π bond
p orbitals

The π bond is formed by

sideways overlap of two p
orbitals on each carbon atom
forming a π-bond above and
below the plane of molecule

C-C sigma bond The π bond is weaker than

C-C pi bond the σ bond

The pi bond leads to resultant high electron density above

There is Restricted rotation about a pi bond and below the line between the two nuclei

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Stereoisomerism
There are two types of stereoisomerism:
Definition: Stereoisomers have the same structural formulae geometrical (E- Z isomerism) and optical
but have a different spatial arrangement of atoms isomerism

E-Z stereoisomerism
Alkenes can exhibit a type of isomerism called E-Z stereoisomerism. This occurs because of
restricted rotation that occurs around a double bond

Single carbon-carbon covalent bonds can easily rotate

Cl Cl Cl H Cl H

H C C H H C C Cl H C C H

H H H H H Cl

All three of these structures are the same

C=C double bonds have restricted rotation, due to position

of the pi bond, so the groups on either end of the bond are
fixed in one position. It is not easy to flip between the two.

Cl H Cl Cl
C C C C
H Cl H H C-C
C-C pi
sigma
This produces two possibilities. The two structures cannot bond
bond
interchange easily so the atoms in the two molecules occupy
different positions in space.

E-Z stereoisomers arise when:

(a) There is restricted rotation around the C=C double bond.
(b) There are two different groups/atoms attached both ends of the restricted double bond

H H E-Z stereoisomers: Same structure NOT E-

H H H H H H
two different groups Z stereoisomers : two
C C C C
attached either end of C C C C identical groups attached
H H H H
the restricted double H H H H to one end of the
bond restricted double bond.

H H
two different groups H H
H C C H attached either end of
the restricted double H C C H But-1-ene
C C
bond- leads to EZ C C
H H H H isomers H H
H H
Z- but-2-ene two identical groups attached to
H one end of the restricted double
H These are two isomers bond – no E-Z isomers
C H as the lack of rotation
H around the double bonds
C C
But-1-ene is a structural isomer of But-2-
means one cannot be
H ene but does not show E-Z isomerism
switched to the other
H C
H
H E -but-2-ene

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Naming E-Z stereoisomers
Cahn–Ingold–Prelog (CIP) priority rules.
On both sides of the double bond determine the priority group

1. Compare the atomic number (Ar) of the atoms priority

directly attached to each side of the double bond; the priority Cl Br
group having the atom of higher atomic number
receives higher priority.
C C

H Cl

Priority Priority Cl H
group Cl Cl group
side 1 side 2 C C
C C
Z-1,2-dichloroethene
H H H Cl E-1,2-dichloroethene
If the priority atom is on the same side of the If the priority atom is on the opposite side of
double bond it is labelled Z from the german the double bond it is labelled E from the
zusammen (The Zame Zide!) german entgegen (The Epposite side!)

2. If there is are groups of atoms instead of

single atoms attached to the carbon of the
double bond then consider the sum of the H3C
atomic numbers of the entire group. The
CH3 priority
bigger group is the priority
C C
priority H
CH2
H3C
The CH3CH2 group is bigger
than the CH3 so it is the
priority group

cis-trans isomerism
In some text books you will find this type of E-Z isomerism referred to as geometric isomerism and cis-
trans isomerism.
cis-trans isomerism can be considered as a special case of EIZ isomerism in which two of the substituent
groups are the same. It has been superseded by E/Z isomerism because the Cahn–Ingold–Prelog (CIP)
priority rules allow all alkenes to be considered and not just the ones where the groups are the same .

H
H H
H
H C C H C H
H
C C C C
H
H H H H H C
H
H
Z- but-2-ene E- but-2-ene
Can also be called Can also be called
Cis- but-2-ene trans- but-2-ene
Cis means “on this side of” in latin
trans means “across” in latin

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Reactions of Alkenes
Combustion
Alkenes will combust in air readily. They do burn with a smokier flame than alkanes. In general the lower the
carbon to hydrogen ratio in a hydrocarbon the sootier the flame.
CH3CH=CH2 + 4 ½ O2 3CO2 + 3H2O
Alkenes are not used as fuels though because there reactivity makes them more valuable for making other
chemicals

Reactivity of alkenes
Alkenes are more reactive than alkanes, because of the double bond.
E(C=C) = +610 kJ mol-1.
E(C-C) = +346 kJ mol-1.

Although the double bond is stronger than a single bond, it is energetically more favourable to form two single
bonds than one double bond. The C=C bond energy is less than two times the value of most single bonds.
This leads to the double bond undergoing addition reactions

Addition reactions of alkenes

The double bond in the alkene makes it much

H H X
more reactive than alkanes. Alkenes undergo H Y
H
a variety of addition reactions where the C C + X-Y
double bond breaks and a reactant molecule C C
will split and add to the carbons at both ends of H H
H H
the double bond

There are a number of different mechanisms by which addition reactions can occur with alkenes.
The most common one is called electrophilic addition.

Electrophilic Addition
The π (pi)bonds in alkenes are exposed and have high
electron density. They are therefore vulnerable to attack
by species which are attracted to high electron density.
These species are called electrophiles.

Electrophiles tend to be molecules where part of the C-C

molecules has a slight positive charge. They could be C-C π
sigma
called electron deficient. They attack electron rich parts bond
bond
of molecules. The usual definition of an electrophile is
an acceptor of an electron pair. This is because
during the reaction they will accept the pair of electrons
from the double bond to form a bond between the
alkene and the electrophile. δ+ δ-
H-Br is common electrophile. The molecule has a
dipole. The H has a partial positive charge because of H-Br
the electronegativity difference between the hydrogen
and the bromine.

On the next page we will look at the mechanism in

detail

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Reaction of hydrogen halide with alkenes

Change in functional group: H H H H H H

alkene halogenoalkane
H C C C C H + HBr H C C C C H
Reagent: HCl or HBr
Conditions: Room temperature H H H H H H Br H

Mechanism: Electrophilic Addition But-2-ene 2-bromobutane

Type of reagent: Electrophile, Hδ+
Type of Bond Fission: Heterolytic

H H H
HBr is a polar molecule because Br is more electronegative H
+
than H. The H δ + is attracted to the electron-rich pi bond. H3C C C CH3
H3C C C CH3
The two electrons in the π bond come out to make a covalent
bond with the positive hydrogen of the HBr. The H-Br bond δ+ H
H
breaks heterolytically. The H attaches to one of the carbon -
atoms and a bromide ion is formed Brδ :Br -

An intermediate species is formed, which has a positive H H H H

charge on a carbon atom. This is called a carbocation. +
H3C C C CH3 H3C C C CH3
The bromide ion contains a lone pair. It acts as a H H
Br
nucleophile and is attracted to the positive carbon on the
carbocation, forming a new covalent bond. :Br -
Overall, there is addition of HBr across the alkene.

Reaction of Alkenes with bromine/chlorine

The reaction of alkenes with bromine and chlorine is very similar to the one with hydrogen halides. The
difference is the Bromine and chlorine molecules are non-polar because of the zero electronegativity difference
between the halogen atoms. It may seem unusual how they can act as electrophile. The mechanism below
explains how.

Change in functional group: H H

alkene dihalogenoalkane H H

Reagent: Bromine (dissolved in organic solvent) H C C H

C C + Br2
Conditions: Room temperature (not in UV light)
Mechanism: Electrophilic Addition H H Br Br
Type of reagent: Electrophile, Brδ+ 1,2-dibromoethane
Type of Bond Fission: Heterolytic

As the Br2 molecule approaches the alkene, the π bond electrons H H H H

repel the electron pair in the Br-Br bond. this induces a dipole.
+
Br2 becomes polar and electrophilic (Brδ+). C C H C C H
The Br δ+ is attracted to the electron-rich pi bond. H δ+ H :Br - Br
The two electrons in the π bond come out to make a covalent Br
bond with the positive bromine of the Br2 . The Br-Br bond
breaks heterolytically. One Br attaches to one of the carbon Brδ-
atoms and a bromide ion is formed with the other H H
H H
The bromide ion contains a lone pair. It acts as a nucleophile + H C C H
and is attracted to the positive carbon on the carbocation, H C C H
forming a new covalent bond.
Overall, there is addition of Br2 across the alkene.
Br Br Br
:Br -

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Markownikoff’s Addition
If the alkene is unsymmetrical, addition of hydrogen bromide can lead to two isomeric products because there
are two different possibilities where the bromine could attach to the alkene- either side of the double bond.

But-1-ene will form a mixture of 1-bromobutane and 2-bromobutane on reaction with hydrogen bromide

CH2 CH2 CH2 CH3 H H H H

H2C CH CH2 CH3
or
Br H C C C C H
H Br H H
The two products do not, however, form in equal amounts. The 2-Bromobutane forms much more often
(90%) and is called the major product. The other possibility 1-bromobutane is called the minor
product and forms much less (10%)

We can use Markownikoff’s rule to identify which is the ‘Markownikoff’s Rule’

major product but it is not an explanation about why it In most cases, bromine will be added to the
happens. We need to look at the mechanism to carbon with the fewest hydrogens attached to it
understand why.

H :Br -
H H H H
+
C CH2
H C C C C H Major
product
H3C CH3 H Br H H 90%
δ+ δ-
H Br
:Br -
H2C CH CH2 CH3 H
H
C
+
C CH2 CH3 CH2 CH2 CH2 CH3 Minor
product
H Br 10%
H

If we look at the mechanism, the major product forms via a secondary H H H

carbocation and the minor product forms via a primary carbocation. The
secondary carbocation is much more stable than a primary carbocation. H C C C H
+
This is because in a secondary carbocation the alkyl (e.g.methyl, ethyl)
groups on either side of the positive carbon are electron releasing and H H
reduce the charge on the positive carbon which stabilises it. In a primary
carbocation there is only one electron releasing alkyl group so the A secondary carbocation
carbocation is less stabilised and less likely to form. has two carbons
attached to the carbon
with a positive charge
The overall rule is in electrophilic addition to alkenes, the major
product is formed via the more stable carbocation intermediate.
H H
The order of stability for carbocations is +
C C CH2 CH3
tertiary > secondary >primary
H H

A primary carbocation
It is possible for an unsymmetrical alkene (e.g. pent-2-ene) to react with has one carbon attached
HBr and give two secondary carbocations. In this case then both will be to the carbon with a
equally stable and a 50/50 split will be achieved (2-bromopentane and positive charge
3-bromopentane)

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Reaction of Sulphuric acid with Alkenes
Concentrated sulphuric acid can also react with alkenes in an electrophilic addition reaction. This reaction is
usually done as the first part of a 2 stage reaction to product an alcohol from an alkene. Only the first stage is
an electrophilic addition. It produces an alkyl hydrogensulphate molecule. In the second stage the
hydrogensulphate is warmed with water to produce the alcohol in a hydrolysis reaction.

Stage 1
Stage 2
Change in functional group
Change in functional group
alkene alkyl hydrogensulphate alkyl hydrogensulphate alcohol
Reagents: concentrated H2SO4 Reagents: water
Conditions: room temperature Conditions: warm mixture
Mechanism: Electrophilic Addition Type of reaction: hydrolysis
Type of reagent: Electrophile, H2SO4
CH3CH2OSO2OH + H2O CH3CH2OH + H2SO4
CH2=CH2 + H2SO4 CH3CH2OSO2OH

Definition: Hydrolysis – a reaction where the

molecule is split by the addition of water

Stage 1: electrophilic addition

H H With
H H H H unsymmetrical
H3C C C H alkenes a minor
H3C C C H +
H3C C C H and major product
O H
δ+ δ- O O can also be
H O H
- O S formed similar to
S :O HO
O
the addition of
O
H O S HBr. The same
O explanation
H O applies
Stage 2: hydrolysis
H H The sulphuric acid is
H O regenerated in the
H3C C C H H O second stage of the
+ H2O H3C C CH3 + S reaction. The overall
O H O
O role of sulphuric acid
OH H O
S is that of a catalyst
HO as it is regenerated
O

This reaction is a laboratory method for making an alcohol from an alkene. It does not work well on
large industrial scale

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industrial formation from of ethanol from ethene

Ethanol can be made by reacting Ethene with steam at high temperatures in the presence of an acid catalyst. This
process is used industrially to produce ethanol. It is an addition reaction but is not the same sort of electrophilic
addition reaction as the previous cases. The mechanism is a different because of the role of a phosphoric acid
catalyst

This reaction is sometimes called a Hydration reaction CH2=CH2 (g) + H2O (g) CH3CH2OH (l)

Ethene ethanol Definition: Hydration is the addition

Reagents: steam of water to a molecule

Conditions: high temperature 300 °C, high

pressure 70 atm and strong acidic catalyst
of conc H3PO4
Mechanism: acid catalysed addition

Mechanism for acid catalysed addition of steam to ethene

H H
H H -
C C O
Step 1: A pair of electrons from + O
H C C H H P
the double bond in the alkene H H
O
forms a bond with a proton from H O
the phosphoric acid forming a H
O H
carbocation intermediate O
H P
O
O
H
H H H H
Step 2: The lone pair of electrons on + H C C H
H C C H
the water form a bond to the
carbocation forming a protonated H +
H H O H
alcohol
O H
H

H H
Step 3: The protonated H H
H C C H O H
alcohol loses a proton to the O
+ H C C H
phosphate ion regenerating H O H H P
the phosphoric acid catalyst H O O
in the process H O
H H
-
O
O
H P
O
O
H

A high pressure is used to push the position of equilibrium to the right as two moles of gas will go to one.
The high pressures needed mean this cannot be done in the laboratory.

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Reaction of alkenes with hydrogen

Another addition reaction of alkenes is that with hydrogen gas using a nickel catalyst. This reaction is used
industrially to add hydrogen to unsaturated vegetable oils to increase their melting points and make them
margarine in a process called hardening, This is another type or mechanism involving a solid heterogeneous
nickel catalyst. The diagrams below illustrate how the reaction occurs.
H H
Change in functional group: alkene alkane H H
Reagent: hydrogen
C C + H2 H C C H
Conditions: Nickel Catalyst
Type of reaction: Addition/Reduction
H H H H
ethene ethane

Ethene and hydrogen adsorb on to atoms on The bonds within the hydrogen molecules
the surface of the catalyst by donating electron break and produce hydrogen radicals. A
density into empty d-orbitals in the nickel hydrogen radical interacts with the electron
atoms. density in the ethene double bond producing
an ethyl radical

The second hydrogen radical forms The ethane desorbs from the
a bond with the ethyl radical surface of the catalyst

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 Testing for alkenes

The following two reactions can be used as functional group tests for alkene double bonds.

Reaction of Bromine Water with Alkenes

Reagent: Bromine dissolved in water H H H H

Conditions: Room temperature
Type of reaction: Addition C C + BrOH H C C H
Observation: Orange colour of bromine water H H Br OH
will decolourise to colourless

This reaction with its colour change is used as a test for the
alkene functional group.

Reaction of Potassium Manganate(VII) with Alkenes

Change in functional group: alkene diol H H

H H H
Reagent: KMnO4 in an acidified solution KMnO4
C C C H H C C C H
Conditions: Room temperature
Type of reaction: Oxidation
H H H OH OH H
Observation: purple colour of MnO4- ion will propene Propane-1,2-diol
decolourise to colourless
This reaction with its colour change can be used as a test
for the alkene functional group. It would not change colour
with alkanes

Addition polymerisation

An important reaction industrially for alkenes is their conversion to addition polymers. This is dealt in
detail in the polymer chapter

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 Alkene Questions
1. a) State what is meant by the term unsaturated as applied to an alkene.
b) Draw the skeletal formulae and name all the chain and position isomers of C5H10
c) Draw a functional group isomer of C5H10
d) But-2-ene can exist as a pair of stereoisomers.
(i) State what is meant by the term stereoisomers.
(ii) Draw the structure of (E)-but-2-ene.
e) Draw and name the geometrical EZ isomers of pent-2-ene

2) What are the molecular formulae of the following molecules and calculate the Mr of them?

a)

b)

3) Draw the displayed formulae of the products of the following reactions

a) But-2-ene + HBr
b) Propene + Br2
c) cyclohexene + HCl
d) 2-methylbut-1-ene + Cl2

4) Organic reaction mechanisms help to develop an understanding of how and why reactions occur.
Name the mechanism for the reaction of bromine with but-2-ene. Draw the mechanism out with curly arrows.
Add a written description to your mechanism covering the following points.
• Describe what happens initially to a bromine molecule as it approaches an ethene double bond.
• Describe the interaction in an electrophilic attack between electrons of the double bond and bromine.
• Describe the species formed when a bromine atom has been added to ethene and a bromide ion has
formed.
• Describe how the bromide ion then reacts with the electron-deficient carbon atom.

5) Propene reacts with hydrogen bromide by an electrophilic addition mechanism forming 2-

bromopropane as the major product.

(a)Outline the mechanism for this reaction using curly arrows, showing clearly the structure of the intermediate
carbocation formed.

(b)Give the structure of the alternative carbocation which could be formed in the reaction between propene
and hydrogen bromide. Explain why this carbocation leads to the minor product compared to the carbocation
drawn in part a)

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6) Choose an alkene with molecular formula C4H8 which reacts with HBr to form two structural isomers.
Give the structures of these two isomers and name the type of structural isomerism shown. Identify which of
the isomers would be the major and minor product.
Outline a mechanism for the formation of the major product

Explain why the major product forms in preference to the minor product.

7) Alkenes can be converted into alcohols in a two stage reaction.

Stage 1 CH3CH=CH2 + H2SO4 CH3CH(OSO2OH)CH3

Stage 2 CH3CH(OSO2OH)CH3 + H2O CH3CH(OH)CH3 + H2SO4

(a) Name and outline a mechanism using curly arrows for Stage 1 using concentrated sulphuric acid.

(b) Stage 2 can be called a hydrolysis reaction. What does this mean?

(c) State the overall role of the sulphuric acid for overall reaction of the two stages.

8) Compound A has the molecular formula C4H8. It shows E-Z Stereoisomerism. Compound A reacts with
Br2 to form compound B. Compound B is then reacted with aqueous KOH to form compound C.
Draw skeletal formulae of compound A, B and C.

9) Propene can undergo an electrophilic addition reaction with a molecule of I-Br to form two isomeric
products.
• Deduce what the dipole would be on a molecule of I-Br.
• Draw the structures of the two products and say which would be the major and minor product.
• Draw out the mechanism for the formation of the major product
• Explain why the major product forms in preference to the minor product.

10) Cyclohexa-1,3-diene also displays reactivity typical of alkenes. Its structure is shown.

Draw the skeletal formulae of all possible products of the reaction when one molecule of
cyclohexa-1,3-diene completely reacts with two molecules of hydrogen bromide. Ignore
any stereochemistry

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 Halogenoalkanes
Naming Halogenoalkanes H H H
H

H C H
H H H
Based on original alkane, with a prefix indicating halogen atom: H C C C H
H C C C C H
Fluoro for F; Chloro for Cl; Bromo for Br; Iodo for I.
Br H H H Cl H H
Substituents are listed alphabetically
1-bromopropane 2-chloro-2-methylbutane
Cl
If there are two or more halogen groups then di, tri are
used and each one is numbered and the groups are
listed alphabetically 4-bromo-2,2-dichloropentane
Cl Br

Classifying Halogenoalkanes

Halogenoalkanes can be classified as primary, secondary or tertiary depending

on the number of carbon atoms attached to the C-X functional group.
H
H H H H H H
H C H
H H H
H C C C H H C C C H
H C C C C H
Br H H H Br H
H Cl H H

Primary halogenoalkane Secondary halogenoalkane Tertiary halogenoalkane

One carbon attached to the Two carbons attached to the Three carbons attached to the
carbon atom adjoining the carbon atom adjoining the carbon atom adjoining the
halogen halogen halogen

Reactions of Halogenoalkanes
Halogenoalkanes undergo either substitution or elimination reactions
Nucleophilic substitution reactions
Most halogens are more electronegative than carbon and so a dipole is induced and the C-X bond is polar.

Cδ+– Fδ- > Cδ+– Clδ- > Cδ+– Brδ-

The positive dipole on the carbon attracts nucleophiles, and the halogen Nucleophile: electron
atom is swapped atom for another atom or groups of atoms in a substitution pair donator e.g. :OH-,
reaction. The generalised mechanism shows the general mechanism for :NH3, CN-
nucleophilic substitution although there are variations in the mechanism
depending on whether the halogenoalkane is primary, secondary or tertiary.

Nu:-
The nucleophiles
H H The carbon has a small
attack the positive H H positive charge because
carbon atom
of the electronegativity
H C C X H C C Nu + X- difference between the
δ+ δ-
H H carbon and the halogen
H H

:Nu represents any nucleophile – they always have a lone

pair and act as electron pair donators

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Rate of Nucleophilic Substitution Reactions
Comparing the rate of hydrolysis reactions
The different halogenoalkanes react at different rates. This can be Hydrolysis is defined as the
observed by observing the hydrolysis reaction of the splitting of a molecule ( in
halogenoalkanes with water in a silver nitrate solution. this case a halogenoalkane)
by a reaction with water
Water is a poor nucleophile but it can react slowly with
halogenoalkanes in a substitution reaction
CH3CH2X + H2O CH3CH2OH + X- + H+

Aqueous silver nitrate is added to a halogenoalkane and the

halide leaving group combines with a silver ion to form a
CH3CH2I + H2O CH3CH2OH + I- + H+
SILVER HALIDE PRECIPITATE.
The precipitate only forms when the halide ion has left the
halogenoalkane and so the rate of formation of the precipitate Ag+ (aq) + I-(aq) AgI (s) - yellow precipitate
can be used to compare the reactivity of the different
halogenoalkanes.

The quicker the precipitate is formed, the faster the AgI (s) - yellow precipitate
substitution reaction and the more reactive the AgBr(s) – cream precipitate forms faster
halogenoalkane AgCl(s) – white precipitate

One might consider that the different strength of the dipoles on the C-Halogen bond might play a role in
the rate of the hydrolysis reaction. The evidence does not hold up though as the one with the weakest
dipole (iodine) forms fastest. So the limiting factor cannot be how well the halogenoalkane attracts the
nucleophile. The factor that actually seems to explain the results if the strength of the C-Halogen bond.

The rate of these substitution reactions depends on the strength Bond enthalpy /
of the C-X bond . The weaker the bond, the easier it is to break kJmol-1
and the faster the reaction. C-I 238
C-Br 276
The iodoalkanes are the fastest to substitute and the fluoroalkanes
are the slowest. The strength of the C-F bond is such that C-Cl 338
fluoroalkanes are very unreactive
C-F 484
The iodoalkane forms a precipitate with the silver nitrate first as the C-
I bond is weakest and so it hydrolyses the quickest

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Nucleophilic substitution with aqueous hydroxide ions
This is a similar reaction to the hydrolysis reaction with water but the OH– is a stronger nucleophile than water as it has
a full negative charge and so is more strongly attracted to the Cδ+ so the reaction occurs more readily

Change in functional group: halogenoalkane H H H

H H H
alcohol
Reagent: potassium (or sodium) hydroxide H C C C Br + KOH H C C C OH + KBr
Conditions: In aqueous solution; Heat under reflux
H H H H H H
Mechanism: Nucleophilic Substitution
Role of reagent: Nucleophile, OH- 1-bromopropane propan-1-ol

The aqueous conditions needed is an important point. If the solvent is changed to ethanol an elimination reaction occurs

SN2 nucleophilic substitution mechanism for halogenoalkanes

SN2 The S means substation, the N means nucleophile and 2 is for two molecules in the rate determining step.
This will be explained more in the reaction kinetics chapter but the slow step is the first step here.

H CH3 H - H
δ+ δ-
H3C C Br HO C Br H3C C OH + :Br -
-HO:
H H
H
transition state.
The attacking OH- group is a nucleophile. It is attracted to the slightly positive carbon atom and
has a lone pair of electrons which can form a new covalent bond to the carbon.
This mechanism goes through a transition state: the C-OH bond is forming at the same time as the
C-Br bond is breaking
This mechanism occurs with primary halogenoalkanes

SN1 nucleophilic substitution mechanism for tertiary halogenoalkanes

The 1 in SN1 is for one molecules in the rate determining step. This will be explained more in the reaction kinetics
chapter but the slow step is the first step here and there is only one molecule in it

CH3 CH3 Tertiary halogenoalkanes

CH3
undergo this mechanism as the
+
H3C C Br H3C C H3C C OH tertiary carbocation is made
:OH- stabilised by the electron
CH3 CH3 CH3 releasing methyl groups around it.
(see alkenes topic for another
The Br first breaks example of this).
The hydroxide Also the bulky methyl groups
away from the
nucleophile then
halogenoalkane to prevent the hydroxide ion from
attacks the positive
form a carbocation attacking the halogenoalkane in
carbon
intermediate the same way as the mechanism
above

Primary halogenoalkanes don’t do the SN1 mechanism because they would only form an unstable primary
carbocation.

See chapter 6.15 Isomerism for a discussion how these mechanism can affect optical activity in chiral
compounds

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Nucleophilic substitution with ammonia
This is a similar reaction to the one with hydroxide ions and converts the halogenoalkane into an amine. The
conditions reflect the need to keep a high concentration of Ammonia in the reaction which is not so easy
because ammonia is a gas.

Change in functional group: halogenoalkane

amine H H H
H H H

Reagent: NH3 dissolved in ethanol H C C C NH2

H C C C Br + 2NH3 + NH4Br
Conditions: Heating under pressure in a sealed
tube H H H
H H H

Mechanism: Nucleophilic Substitution propylamine

Type of reagent: Nucleophile, :NH3
Naming amines:
In the above example propylamine, the propyl shows
the 3 C’s of the carbon chain.
Sometimes it is easier to use the IUPAC naming for
amines e.g. Propan-1-amine

H H H H
δ+ δ- + :Br -
CH3 CH2 C Br CH3 CH2 C N H CH3 CH2 C NH2
3HN:
H H H + NH4Br
H
:NH3

The reaction needs two molecules of ammonia. The first acts as a nucleophile in the first step.
The second ammonia molecule acts as a base and removes a proton from the intermediate
formed in step 1

Further substitution reactions can occur between the halogenoalkane and the amines formed leading to
a lower yield of the amine. Each H on the amine can be successively removed. Using excess ammonia
helps minimise this but this method will give a mixture of products.

H R
Further reactions H H
RX RX
RX R N:
H N: H N: R N:

H R R R

We will look at these further reactions in more detail in the chapter 6.10 amines

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Nucleophilic substitution with cyanide ions
This is another similar substitution reaction swapping the halogenoalkane for a nitrile groups. This is an
important reaction in organic synthesis because it can be used to increase the length of the carbon chain.
The nitrile group can be hydrolysed to carboxylic acid group or reduced to an amine group so adding a
nitrile group on to a chain can be an important step in building up new organic molecules

Change in functional group: halogenoalkane H H H H H H

nitrile
Reagent: KCN dissolved in ethanol/water mixture H C C C Br + :CN- H C C C CN + Br-
Conditions: Heating under reflux H H H H H H
Mechanism: Nucleophilic Substitution
1-bromopropane butanenitrile
Type of reagent: Nucleophile, :CN-

H H This reaction increases the length of

the carbon chain (which is reflected in
δ+ δ-
H3C C Br H3C C CN + :Br - the name) In the above example
-NC:
butanenitrile includes the C in the
H H nitrile group

Note: the mechanism is identical to hydroxide ion one

Naming Nitriles

Nitrile groups have to be at the end of a chain. Start

numbering the chain from the C in the CN Note the naming: butanenitrile and not
butannitrile.
CH3CH2CN : propanenitrile
H3C CH CH2 C N 3-methylbutanenitrile
CH3

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Elimination reaction of halogenoalkanes

Halogenoalkanes can also be converted to alkenes by an elimination reaction which can be defined as the
removal of small molecule (often water) from the organic molecule. The reagent of potassium hydroxide is
the same one as used for the substitution reaction. The conditions here are vital. Using ethanol as a solvent
for the KOH instead of water will promote the elimination reaction. Often though a mixture of products from
both elimination and substitution occurs

Elimination with alcoholic hydroxide ions

Change in functional group: halogenoalkane H H H H H H
alkene
H C C C H + KOH H C C C + KBr + H2O
Reagents: Potassium (or sodium) hydroxide
H H Br H H
Conditions: In ethanol ; Heat
Mechanism: Elimination 1-bromopropane propene
Type of reagent: Base, OH-

H H H H
Note the importance of
CH3 C C H + Br - + H2O the solvent to the type of
CH3 C C H
reaction here.
Br H Aqueous: substitution
:OH- Alcoholic: elimination
The hydroxide ion, OH-,
acts as a base and removes a proton from
a carbon atom adjacent to the one bonded to the bromine. The two
electrons in the C-H bond move to form the Pi bond to make the
alkene, and the C-Br bond breaks.

2-methyl -2- H
chlorobutane can give
H H C H
With unsymmetrical secondary 2-methylbut-1-ene and H H
H
and tertiary halogenoalkanes H C H 2-methylbut-2-ene
H H H C C C C H
two (or sometimes three)
different structural isomers can H C C C C H H H H
H
be formed because there is H Cl H H
more than one different H C H
H H
H
hydrogen atoms on adjacent
carbon atoms H C C C C H

H H

The structure of the halogenoalkane also has an effect on the

degree to which substitution or elimination occurs in this reaction.
Primary tends towards substitution
Tertiary tends towards elimination

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 Questions on halogenoalkanes
1) a)C4H9Cl has 4 structural isomers. Draw using skeletal formulae the 4 isomers and name each one

b) Give the molecular formula and calculate the Mr of the following compound
Br

Br

2) Draw displayed formulae the organic product of the following reactions. Also name the products
a) bromoethane + aqueous KOH
b) 2-chorobutane + aqueous KOH
c) 1-bromopropane + NH3
d) 2-chloro-2-methylbutane + KCN
e) 1,2-dibromopropane + aqueous KOH

3) Explain what the following terms mean

a) nucleophile
b) substitution
c) elimination
d) hydrolysis
e) Base

4) A substitution reaction occurs when 2-bromopropane reacts with aqueous sodium hydroxide.
a)Draw the skeletal formula of the organic product of this reaction and give its name.
b) Name the mechanism for this reaction. Draw the mechanism out with curly arrows. Explain what each of
the arrows represents.
c) Explain the role of the hydroxide ion in this reaction
d)Explain why halogenoalkanes can undergo substitution reactions with hydroxide ions whereas alkanes do
not undergo this reaction

5) In an experiment, some 1-chlorobutane, 1-bromobutane and 1-iodobutane were placed in separate test
tubes containing silver nitrate solution. The test tubes were put in a water bath. The halogenoalkanes reacted
with the water in the silver nitrate solution. The student timed how long it took for the first appearance of the
silver halide precipitate in each tube at a constant temperature. This time was used to provide a measure of
the initial rate of reaction.
a) Describe the likely observations – include colour of precipitate and order of appearance of precipitates.
Write ionic equations for the formation of the precipitates
b) Explain in terms of bond enthalpies the observations
c) What is the name of the organic product formed in these reactions?
d) In this reaction the nucleophile is water. Explain why using sodium hydroxide as the reagent would lead to
a faster reaction than using water
e) In this experiment, explain why a water bath was used rather than heating the test tube containing the
reaction mixture directly over a Bunsen flame

6) Ethanenitrile can be made by reacting chloromethane with potassium cyanide.

a) Write an overall equation using structural formulae for this reaction.
b) Name and the outline the mechanism for this reaction.
c) Explain, in terms of bond enthalpies, why bromomethane reacts faster than chloromethane with potassium
cyanide.

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7) a) Write an overall equation and outline the mechanism for the reaction of chloromethane with an
excess of ammonia.

b) Explain why an excess of ammonia is needed in this reaction to produce a high yield of the amine

8) When potassium hydroxide reacts with bromoethane, ethene can also be formed as well as ethanol.
a) What conditions are used to maximise the formation of the ethanol.
b) Explain why, other than safety, this method is not used in industry to make ethanol.
c) What conditions are used to maximise the formation of the ethene.
d) Name the mechanism for the reaction where the bromomethane forms ethene. Draw the mechanism
out with curly arrows. Explain what each of the arrows represents
e) Explain the role of the hydroxide ion in the reaction where the bromomethane forms ethene.

9) Consider the following reaction in which an alkene is formed from a halogenoalkane.

CH3CHBrCH2CH3 + KOH CH3CH=CHCH3 + KBr + H2O

a) Name the halogenoalkane used in this reaction.

b) What essential conditions must have been used for this reaction to occur?
c) Name and outline a mechanism for this reaction.
d) Draw structures for the E and Z stereoisomers of but-2-ene.
e) Another alkene, which is a structural isomer of but-2-ene, is also formed during this reaction.
(i) State what is meant by the term structural isomers.
(ii) State the type of structural isomerism shown by these two alkenes
(ii)Draw the structure of this other alkene.

10) Hot concentrated ethanolic potassium hydroxide reacts with 2-bromo-3-methylbutane to form two
alkenes that are structural isomers of each other. The major product is 2-methylbut-2-ene.

a) Name and outline a mechanism for the conversion of 2-bromo-3-methylbutane into 2-methylbut-2-
ene according to the equation.

(CH3)2CHCHBrCH3 + KOH (CH3)2C =CHCH3 + KBr + H2O

b) Draw and name the displayed formula for the other isomer that is formed.
c) State the type of structural isomerism shown by these two alkenes
d) A small amount of the Halogenoalkane undergoes the substitution reaction to form an alcohol. Draw
the skeletal formula of the alcohol and name it

11)* Nucleophilic substitution of halogenoalkanes can undergo two different mechanisms SN1 and SN2.
Outline the two different mechanisms and explain how the different mechanisms are favoured by
different types of halogenoalkanes

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Uses of halogenoalkanes

The halogenoalkanes have many uses although some have been phased out for environmental and safety
reasons

Solvents
Chloroalkanes and chlorofluoroalkanes can be used as solvents. Tetrachloromethane CCl4 was
a common non-polar solvent for use in the laboratory
CH3CCl3 was used as the solvent in dry cleaning. These have now largely
been phased out due to the toxicity of these compounds

Anaesthetics
Trichloromethane (Chloroform) CHCl3 was one of the first anaesthetics used in Victorian times but its
toxicity often result in patient death. Another anaesthetic used at the time was ether
(CH3CH2OCH2CH3). This was much less toxic but had a very high flammability. In the mid 20th century
another halogenoalkane ‘Halothane’ CF3CHBrCl was developed. This was much less flammable and
much less toxic than the previous anaesthetics used. Today Isoflurane CF3CHClOCHF2 and
Sevoflurane (CF3)2CHOCHF2 are used

CFC’s
Chlorofluorocarbons were used extensively in the late 20th century. They were non-toxic, non-
reactive liquids with low flammability. They had many uses including refrigerants, aerosol
propellants, and foaming agents for making expanded plastics such as those used in insulation and
packaging. The stability of the CFC’s caused an environmental problem because they once
released they lingered in the atmosphere. Eventually they diffused into the upper atmosphere. In
the upper atmosphere the were exposed to high levels of ultra-violet radiation which caused the
C–Cl bonds in chlorofluorocarbons (CFCs) to break and form reactive free radicals. (The C-F bond
is much harder to break than the C-Cl bond.) The chlorine free radicals then destroyed the ozone
layer. This process is explored more on the next page.

Legislation to ban the use of CFCs was supported by chemists and they developed alternative
chlorine-free compounds. HFCs (Hydro fluoro carbons) were developed e.g. CH2FCF3 to replace
CFC’s. These are now used for refrigerators and air-conditioners. These are safer as they do not
contain the C-Cl bond so break down much more easily in the lower atmosphere where they do not
cause the same problem

CFC’s still concern us because CFCs are still entering the atmosphere from disused items and are still used
for some purposes and by some countries.CFCs have a long lifetime in the atmosphere and it takes a long
time for CFCs to reach upper atmosphere.

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The Ozone Layer

The naturally occurring ozone (O3) layer in the upper Ozone in the lower atmosphere
atmosphere is beneficial as it filters out much of the sun’s is a pollutant and contributes
harmful UV radiation towards the formation of smog

Ozone is continuously being formed and broken down

in the stratosphere by the action of ultraviolet radiation O + O2 O3
Ozone formation Ozone depletion
UV light causes an O2 molecule to split into free radicals This is the reverse of the formation reaction..
O2 + UV-light → O + O The energy is supplied by ultraviolet light
When the free radical hits another O2 molecule ozone O3 + ultraviolet light O2 + O
forms
O + O2 → O3 There is a continuous cycle of formation
and depletion of ozone
The frequency of ultra-violet light absorbed equals the rate of ozone formation = rate of ozone removal
frequency of biologically damaging ultra-violet radiation.
These reactions therefore filter out harmful UV from
So there is a constant amount of ozone in
reaching the Earth’s surface and allow life to survive on
earth.
the atmosphere
UV light can increase risk of skin cancer and increase
crop mutation.
Chlorine radicals are formed in the upper
Destruction of Ozone Layer atmosphere when energy from ultra-violet
radiation causes C–Cl bonds in
Radicals from CFCs, and NOx from thunderstorms or chlorofluorocarbons (CFCs) to break. The
aircraft, may catalyse the breakdown of ozone C-F bond is much harder to break than
the C-Cl bond.

The chlorine free radical atoms catalyse the CF2Cl2 → CF2Cl + Cl

decomposition of ozone due to these reactions
because they are regenerated. (They provide an
alternative route with a lower activation energy)
.
Cl + O3
.
ClO + O2
.
ClO + O3 2O2 + Cl
.
They contributed to the formation of a hole in the
ozone layer. Overall equation
2 O3 3 O2

The regenerated Cl radical means

that one Cl radical could destroy
many thousands of ozone molecules

N Goalby chemrevise.org 10
 Ozone Layer.

1) a) What is the formula of Ozone?

b) Explain how ozone is formed in the atmosphere

c) What beneficial role does the Ozone layer provide for life on Earth?
2)a) Explain how chlorine atoms are formed from chlorine-containing organic compounds in the upper
atmosphere. Write an equation to show this process for a molecule of CF3Cl
b) Why does the C-Cl bond break rather than the C-F bond in the stratosphere?
3) What is a free radical?

4) a) Write two equations that show how chlorine atoms catalyse the decomposition of ozone into oxygen.

b) Explain why the chlorine atoms can be classed as a catalyst in the decomposition of ozone into oxygen.

c) Write the overall equation for the change specified in question 4a)

d) Explain why a small amount of CFC molecules can destroy many ozone molecules

5) One of the first substances used as an anaesthetic in medicine was chloroform (trichloromethane, CHCl3).
By 1950, halothane was in common use but by 1990 this had been replaced by more acceptable
anaesthetics such as desflurane.

CF3CHBrCl CF3CHFOCHF2
halothane desflurane
a) Give the IUPAC name for halothane
b) Calculate the Mr of halothane.
c) Calculate the percentage by mass of fluorine in halothane.
d) Give the types of intermolecular force present between molecules of liquid halothane
e) Show by using an equation how halothane could decompose to form free radicals in the atmosphere
f) Use the formulae of the two anaesthetics, halothane and desflurane, to help to explain why desflurane is
considered to be a more environmentally acceptable anaesthetic than halothane.

6) 3O2(g) 2O3(g) ΔH = +284 kJ mol–1

a) Use Le Chatelier’s principle to explain how an increase in temperature causes an increase in the
equilibrium yield of ozone.

b) Nitrogen monoxide (NO) catalyses the decomposition of ozone into oxygen.

Deduce Step 3 in the following mechanism that shows how nitrogen monoxide catalyses this
decomposition.
Step 1 O3 O + O2
Step 2 NO + O3 NO2 + O2
Step 3 ...................................................................................................................................

7) Chemists supported the legislation to ban the use of CFCs. Modern refrigerators use pentane rather
than CFCs as refrigerants. These belong to the class of refrigerants that cool by change of state (typically
by boiling).
(a) Suggest how these refrigerants cool by change of state.
(b) Describe characteristics or properties desirable in a refrigerant
(c) With reference to its formula, state why pentane is a more environmentally acceptable refrigerant.

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6.5 Alcohols

General formula alcohols CnH2n+1OH

Naming Alcohols
OH
These have the ending -ol and if necessary the position
Butan-2-ol
number for the OH group is added between the name stem CH3 CH CH2 CH3
and the –ol 1 2 3 4

O
If the compound has an –OH group in addition to other H3C CH C 2-hydroxypropanoic acid
functional groups that need a suffix ending then the OH can be
named with the prefix hydroxy-):
OH OH

HO CH2 CH2 OH Ethane-1,2-diol

If there are two or more -OH groups then di, tri are used. H2C OH
Add the ‘e’ on to the stem name though
propane-1,2,3-triol
HC OH

H2C OH

Bond angles in Alcohols

H The H-O- C bond is 104.5o (bent line
All the H-C-H bonds and C- H
shape), because there are 2 bond
C-O are 109.5o (tetrahedral O H
109.5O C pairs of electrons and 2 lone pairs
shape), because there are 4 104.5O
H C repelling to a position of minimum
bond pairs of electrons
repulsion. Lone pairs repel more than
repelling to a position of H bond pairs so the bond angle is
minimum repulsion. H reduced.

Different types of alcohols

H

H H H
H H H O
H H

H C C C H
H C C C O H H C C C H

H H H H O H H H
H C H
Propan-1-ol H
H
Primary Propan-2-ol
Secondary methylpropan-2-ol
Tertiary
Primary alcohols are alcohols Secondary alcohols are alcohols Tertiary alcohols are alcohols
where 1 carbon is attached to where 2 carbon are attached to where 3 carbon are attached to
the carbon adjoining the the carbon adjoining the oxygen the carbon adjoining the oxygen
oxygen

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 Solubility of simple alcohols
δ- δ+ δ- +
O H O H δ
H
The smaller alcohols are soluble in water
because they can form hydrogen bonds
C H
H δ+
with water. The longer the hydrocarbon H
chain the less soluble the alcohol. C
H
H
Reactions of Alcohols

Combustion of Alcohols
Alcohols combust with a clean flame

CH3CH2OH + 3O2 2CO2 + 3H2O

Reaction of Alcohols with Sodium Observations:

• effervescence,
Sodium reacts with alcohols • the mixture gets hot,
• sodium dissolves,
2CH3CH2OH + 2Na 2CH3CH2O-Na+ + H2 • a white solid is produced.
This reaction can be used as a test for alcohols

Substitution reactions of Alcohols to form Halogenoalkanes

Various halogenating compounds can be used to
substitute the –OH group for a halogen PCl5 / PCl3 / conc HCl / SOCl2 /
mixture of NaCl + H2SO4 can all be
Reaction with phosphorous (V) halide uses for substituting a Cl

CH3CH2OH + PCl5 CH3CH2Cl + POCl3 + HCl For Br and I it is best to use PI5, PI3
and Br equivalents. It is not suitable
This reaction with PCl5 (phosphorous(v)chloride) can be to use NaBr, or NaI + H2SO4 to
used as a test for alcohols. You would observe misty produce HBr or HI because the
fumes of HCl produced. sulphuric acid with oxidise the
hydrogen halides to other products
Reaction with phosphorous (III) halide
The phosphorous (III) halide can also be produced
PI3 + 3 CH3CH2OH 3CH3CH2I + H3PO3 in situ by reacting red phosphorus and the halogen.

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Oxidation and Reduction in organic chemistry
Oxidation and reduction reactions are common in organic chemistry. Whilst it is possible to assign individual atoms in
an organic molecule an oxidation state/number, it can be quite complicated to work them out. Instead some chemists
use the concept of functional group level to scaffold their ideas about oxidation and reduction.

The functional group level of a carbon atom can be worked out by counting the number of bonds to
electronegative atoms on the carbon.
• No such bonds is called the Hydrocarbon level
• one bond is called the Alcohol level
• two bonds is the Carbonyl level
• three bonds the Carboxylic Acid level
• four bonds the Carbon Dioxide level

Alcohol level

C OH C NH2 C halogen common examples within the Alcohol level include

alcohols, amines, halogenoalkanes

Carbonyl level
O O

C H C
examples in the Carbonyl level: aldehydes, ketones

Carboxylic Acid level

O O O O
Examples in the Carboxylic Acid
C C C N
C OH C O level: carboxylic acids, esters,
Cl
NH2 acyl chlorides, amides, nitriles;

Moving a carbon atom up a level is oxidation and requires an oxidizing agent. Moving a carbon
atom down a level is reduction and requires a reducing agent

Oxidation reactions of the alcohols

Potassium dichromate K2Cr2O7 is an oxidising agent that causes alcohols to oxidise.
The exact reaction, however, depends on the type of alcohol, i.e. whether it is primary, secondary, or tertiary,
and on the conditions.

Primary alcohols can be oxidised up one level to an aldehyde, or two levels to a carboxylic acid
H H H H H
H H O
O K2Cr2O7
K2Cr2O7
H C C C O H H C C C H C C C
H H H H H O H
H H H

Propan-1-ol (a Propanal (an Propanoic acid (a

primary alcohol) aldehyde) carboxylic acid)
-alcohol level -carbonyl level -carboxylic acid level

Secondary alcohols can only be oxidised up one level to a ketone

H H H
K2Cr2O7 H O H
H C C C H
H C C C H
H O H H H
H
Propanone (a ketone) -
Propan-2-ol (a secondary carbonyl level
alcohol) -alcohol level
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Partial Oxidation of Primary Alcohols

H An aldehyde’s name ends

Reaction: primary alcohol aldehyde O
in –al
Reagent: potassium dichromate (VI) solution and dilute
H C C It always has the C=O bond
sulphuric acid.
on the first carbon of the
Conditions: (use a limited amount of dichromate) warm H H
chain so it does not need
gently and distil out the aldehyde as it forms:
Ethanal an extra number

Primary alcohols can be oxidised to aldehydes or up an extra level to carboxylic acids. If we just want to oxidise
the alcohol up to an aldehyde and no further then we need to choose the conditions carefully. The main
condition is to conduct the reaction in a distillation set up, as shown below, and by application of gentle heat
distil off the aldehyde as it forms, which will prevent it from reacting with more dichromate to produce a
carboxylic acid. Using a limited amount of the oxidising agent will also help prevent further oxidation

H H O Observation: the
H H H
orange dichromate ion
+ [O] H C C C + H2O
H C C C O H (Cr2O72-) reduces to
H H H the green Cr 3+ ion
H H H
OH + [O]
O + H2O

CH3CH2CH2OH + [O] CH3CH2CHO + H2O

propan-1-ol
propanal

Generally we write the oxidation equations in a simplified form using [O] which represents O from the
oxidising agent rather than a full balanced equation with the dichromate ion as shown below.

K2Cr2O7 + 3CH3CH2CH2OH + 4H2SO4 K2SO4 + Cr2(SO4)3 + 3 CH3CH2CHO + 7H2O

When writing the formulae of aldehydes in a condensed way write CHO and not COH e.g.CH3CH2CHO

Distillation
In general used as separation technique to thermometer
separate an organic product from its reacting
mixture. Need to collect the distillate of the
approximate boiling point range of the desired
liquid.

Note the bulb of the thermometer should Liebig condenser

be at the T junction connecting to the
condenser to measure the correct boiling
point

Note the water goes in the bottom of the Water

condenser to go against gravity. This allows out
more efficient cooling and prevents back flow
of water. Water in

Heat

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Full Oxidation of Primary Alcohols
H H
O
Reaction: primary alcohol carboxylic acid
Reagent: potassium dichromate(VI) solution and dilute H C C C
sulphuric acid
Conditions: use an excess of dichromate, and heat H H
O H
under reflux: (distil off product after the reaction
has finished) Propanoic acid

If we want to oxidise the primary alcohol up two levels to a carboxylic acid then we need to use more
vigorous conditions. Heating under reflux allows the reaction to happen quicker.

H H H H H O
+ 2 [O] H C C C + H2O Observation: the
H C C C O H
O H orange dichromate
H H H H H ion (Cr2O72-)
OH OH reduces to the
+ 2[O] + H2O green Cr 3+ ion
O
CH3CH2CH2OH + 2[O] CH3CH2COOH + H2O
propan-1-ol Propanoic acid

Reflux
Reflux is used when heating organic reaction mixtures for long Water out
periods. The condenser prevents organic vapours from escaping
by condensing them back to liquids.

Never seal the end of the condenser as the build up of gas

pressure could cause the apparatus to explode. This is true of any
apparatus where volatile liquids are heated including the distillation
set up

Water in
Anti-bumping granules are added to the flask in both distillation and
reflux to prevent vigorous, uneven boiling.

Heat

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Oxidation of Secondary Alcohols
Ketones end in -one
H O H
Reaction: secondary alcohol ketone When ketones have 5C’s
Reagent: potassium dichromate(VI) solution and H C C C H
or more in a chain then it
dilute sulphuric acid. H H needs a number to show
Conditions: heat under reflux the position of the double
Propanone bond. E.g. pentan-2-one

H H H
H O H
H C C C H + [O] Observation: the
H C C C H orange dichromate
+ H2O
H O H H H ion (Cr2O72-) reduces
H to the green Cr 3+ ion

propan-2-ol Propanone

There is no further oxidation of the ketone under these conditions.

Tertiary alcohols cannot be oxidised at all by potassium dichromate: This is because there is no hydrogen
atom bonded to the carbon with the OH group

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Distinguishing between Aldehydes and Ketones

The fact that aldehydes can be further oxidised to carboxylic acids whereas ketones cannot be further oxidised
is the chemical basis for two tests that are commonly used to distinguish between aldehydes and ketones

Tollen’s Reagent

Reagent: Tollen’s Reagent formed by mixing

aqueous ammonia and silver nitrate. The
active substance is the complex ion of
[Ag(NH3)2]+ .
Conditions: heat gently
Reaction: aldehydes only are oxidised by
Tollen’s reagent into a carboxylic acid and
the silver(I) ions are reduced to silver
atoms
Observation: with aldehydes, a silver mirror
forms coating the inside of the test tube.
Ketones result in no visible change
CH3CHO + 2Ag+ + H2O CH3COOH + 2Ag + 2H+

Fehling’s solution
Reagent: Fehling’s Solution containing blue Cu 2+
ions.
Conditions: heat gently
Reaction: aldehydes only are oxidised by
Fehling’s solution into a carboxylic acid and
the copper ions are reduced to copper(I)
oxide .
Observation: Aldehydes :Blue Cu 2+ ions in
solution change to a red precipitate of Cu2O.
Ketones do not react

CH3CHO + 2Cu2+ + 2H2O CH3COOH + Cu2O + 4H+

The presence of a carboxylic acid can be tested by addition of sodium carbonate. It will fizz and produce
carbon dioxide

2CH3COOH + Na2CO3 2CH3COO-Na+ +H2O + CO2

Ethanoic Acid Sodium Ethanoate

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 Elimination Reaction of Alcohols with Dehydrating Agents

Reaction: Alcohol Alkene

Dehydration Reaction: removal of a
water molecule from a molecule
Reagents: Concentrated Sulphuric or Phosphoric acids
Conditions: warm (under reflux)
Role of reagent: dehydrating agent/catalyst
Type of reaction: acid catalysed elimination
H
H H H H

H C

H C C C O H H
C C
+ H2O
H H H
H H
propan-1-ol Propene

E1 Elimination Reaction
H
H
Step 1: The oxygen on the alcohol with H3C C CH3
its lone pair accepts a proton from the H3C C CH3
sulphuric acid O H +
O O H
:

H O
S H
O
H O

H H H
Step 2: The protonated
H3C C CH3 +
alcohol loses water H C C CH3
forming a carbocation +
O H H
H

Step 3: The carbocation loses a H H H H

proton and forms a double bond, +
H C C CH3
regenerating the sulphuric acid H C C CH3
catalyst in the process
H O
H O
- O S
:O O
S H O
O
H O
The Elimination reaction is called an E1 reaction. It is most likely to occur with tertiary alcohols
because the carbocation formed in step 2 is stabilised by the electron releasing alkyl groups
around it. Secondary alcohols will react by this reaction less readily. This mechanism is unlikely
for primary alcohols because it would result in the formation of a unstable primary carbocation

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E2 Elimination Reaction – primary alcohols

H H
H H
H C C H O
H C C H :O -

H O: H O
O
+
+ S
O
S H O H H O
H
O
H O H

H H
H H O
H C C H H O

+
C C + S
+ H2O
H O H O
H H H O
H O
: O- This E2 mechanism is more likely with primary alcohols because no
S carbocations are formed
O
H O

Some 2o and 3o H
alcohols can give
H C H H
more than one Butan-2-ol But-1-ene
product, when the H H H H C C C H
double bond
forms between H C C C C H
H H H
different carbon
atoms H H O H
H H
HH
H
C C
H H
Butan-2-ol can form both alkenes C C
although more but-2-ene would be But-2-ene
H H
formed
But-2-ene could also exist as E and Z
isomers

Producing alkenes from alcohols provides a possible route to polymers without using monomers derived from oil

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 Questions on Alcohols

1. Draw skeletal formula of the four structurally isomeric alcohols of molecular formula C4H10O.

Name each isomer and identify whether they are primary, secondary or tertiary alcohols
2) Draw displayed formulae of compound formed by the following oxidations
a) propan-1-ol + acidified K2Cr2O7 (heated under reflux with excess oxidising agent)
b) propan-1-ol + acidified K2Cr2O7 (gently heated and product distilled off with limited oxidising
agent)
c) propan-2-ol + acidified K2Cr2O7 (heated under reflux with excess oxidising agent)
d) cyclohexanol + acidified K2Cr2O7 (heated under reflux with excess oxidising agent)
e) 2-methylpropan-1-ol + acidified K2Cr2O7 (gently heated and product distilled off with limited
oxidising agent)

3 a)Butan-1-ol, CH3CH2CH2CH2OH, was oxidised by adding it dropwise to acidified potassium

dichromate(VI) and distilling off the organic product immediately. Write an equation for this
reaction showing the skeletal formula of the organic substances. You may use [O] to represent the
oxidising agent.

b) Butan-2-ol, CH3CH2CH(OH)CH3, was oxidised by heating it under reflux with acidified

potassium dichromate(VI). Write an equation for this reaction the skeletal formula of the organic
substances. You may use [O] to represent the oxidising agent.

c) Fehling’s solution could be used to distinguish between the products formed in 3a and 3b.
Describe the observations that would be made with both products. The product that reacts with
Fehling’s solution turns into another organic substance. Draw the displayed formula of the organic
product that is formed from the reaction of Fehling’s solution with the substance that reacts. What
type of reaction is this?

4 Ethanol can be oxidised to an aldehyde and to a carboxylic acid.

a) Draw the structure of this aldehyde and of this carboxylic acid.
b) Give a suitable reagent and reaction conditions for the oxidation of ethanol to form the
carboxylic acid as the major product. Explain what colour change would be observed in this
reaction and identify which species is responsible for each colour.
c) Draw the structure of an alcohol containing four carbon atoms which is resistant to
oxidation. Explain why this compound cannot be oxidised.
d) Draw the structure of an alcohol containing four carbon atoms which can be oxidised to a
ketone.

5 a) Describe two chemical tests that could be done to distinguish between a sample of
propanal and a sample of propanone. Describe the relevant colour changes for each test

b) Describe a chemical test that could be done to distinguish between a sample of propanone
and a sample of propanoic acid. Describe the relevant observations.

c) Describe a chemical test that could be done to distinguish between a sample of propan-1-ol
and a sample of 2-methylpropan-2-ol acid. Describe the relevant observations.

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 6. Methanol is the first member of the homologous series of alcohols
(a) Write the general formula for this homologous series.
(b) Methanol can be oxidised to methanoic acid. State the reagent(s) which you would use to
perform this oxidation and give any colour change which might be seen during the reaction.
(c) Write an equation for the oxidation of methanol to methanoic acid, using displayed
formulae to show the structures of the organic substances. You may use the symbol [0] for the
oxidising agent.
(d) By considering the structure of methanoic acid, explain why it can easily be oxidised
further and suggest the product(s) formed by further oxidation.

7. Most alcohols can be readily dehydrated.

(a) Explain what is meant by the term dehydration.
(b) State the type of compound formed by dehydration of alcohols.
(c) What are the reagent(s) and condition(s) necessary for the dehydration of alcohols.
(d) Draw the displayed formula of the product that would be formed if propan-2-ol was dehydrated.
(e) Choose an alcohol with the formula C4H9OH which, on dehydration, would give a single
product. Draw the displayed formula of the alcohol and the displayed formula of the product.
(f) Choose an alcohol with the formula C4H9OH which, on dehydration, would give three products,
A,B and C which are isomeric. A and B are E-Z stereoisomers of each other and C is a structural
isomer of A and B. Draw skeletal formulae for the alcohol and for these three isomers and explain
why the formation of these isomers is possible in this case.

8. Outline the mechanism for the reaction for the reaction where water is eliminated from a
molecule of propan-1-ol
9. Outline the mechanism for the reaction for the reaction where water is eliminated from a
molecule of butan-2-ol to form but-2-ene

10. Draw the products that would be formed by reacting

the cyclic alcohol shown on the right with:
a) Acidified potassium dichromate (heat under reflux)
b) concentrated sulphuric acid

11a) Draw the skeletal formula of an alcohol with 7 carbon atoms that could be dehydrated to form 3
different structurally isomeric organic products
b) Draw the skeletal formula of an alcohol with 7 carbon atoms that could be dehydrated to form 2
different structurally isomeric organic products
c) Draw the skeletal formula of an alcohol with 7 carbon atoms that could be dehydrated to form 1 organic
products
d) Draw the skeletal formula of an alcohol with 7 carbon atoms that could not be dehydrated

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Formation of Ethanol

Ethanol can be produced in two main ways. One way is from the fermentation of sugars. The other way is by
reacting ethene with Steam

Fermentation The conditions needed are:

glucose ethanol + carbon dioxide •Yeast
C6H12O6 2 CH3CH2OH + 2 CO2 •No air
•temperatures 30 –40oC
Type of reaction: Fermentation
The optimum temperature for fermentation is around 38oC
At lower temperatures the rate of reaction is too slow.
At higher temperatures the yeast dies and the enzymes denature.
Fermentation is done in an absence of air because the presence of air can cause extra reactions to occur.
Air oxidises the ethanol produced to ethanoic acid (vinegar).
The solution produced by fermentation will only contain around 15% ethanol. Above this concentration of
ethanol the yeast will not survive. Therefore to get pure ethanol it is necessary to fractionally distil the
solution made by fermentation

Advantages of producing ethanol from fermentation

•Sugar is a renewable resource so producing ethanol by this method would not use up non-renewable crude oil
•Production by this method uses low level technology and cheap equipment and will have low energy costs.

Disadvantages of producing ethanol from fermentation

• This is a batch process which has a slow rate of reaction. The need to be refilling and emptying batch
containers will require labour and this will lead to higher production costs.
• The ethanol made by this process is not pure and will need purifying by fractional distillation which is an extra
stage in the process with extra costs.
•Using land to produce sugar for fermentation will potentially deplete the land bank used for growing food crops
which could have a knock on effect on food prices. If the land came from destruction of rain forests this would
obviously be a disadvantage too

Ethanol as a carbon neutral biofuel

A biofuel is a fuel produced from plants Ethanol produced from fermentation is a biofuel.
It can be argued that ethanol produced from this method is classed as carbon–neutral as any carbon dioxide
given off when the biofuel is burnt would have been extracted from the air by photosynthesis when the plant
grew so there is not net annual addition to carbon dioxide levels in the atmosphere

Equations to show no net contribution to CO2

Removal of CO2 by photosynthesis 6CO2 molecules are removed from the atmosphere when
the plants grow by photosynthesis to produce one
6CO2 + 6H2O C6H12O6 + 6O2 molecule of glucose

Production of CO2 by fermentation and combustion

When 1 molecule of glucose is fermented 2 molecules of CO2 is
C6H12O6 2 CH3CH2OH + 2 CO2 emitted. The two ethanol molecules produced will then produce
2 CH3CH2OH + 6O2 4CO2 + 6H2O 4 molecules of CO2 when they are combusted
Overall for every 6 molecules of CO2 absorbed , 6 molecules of CO2 are emitted

This does not take into account any energy needed to irrigate plants, transport the crops, fractionally distil
the ethanol from the reaction mixture or process the fuel. If the energy required for these processes come
from fossil fuels then the ethanol produced is not carbon neutral

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Forming ethanol industrial formation from ethene
Essential Conditions
Ethene - from cracking of fractions from distilled crude oil
high temperature 300 °C
is reacted with steam at high temperatures in the
presence of an acid catalyst high pressure 70 atm
strong acidic catalyst of conc H3PO4
CH2=CH2 (g) + H2O (g) CH3CH2OH (l)

Type of reaction: Hydration/addition Definition: Hydration is the addition

of water to a molecule

Advantages of producing ethanol from ethene

This is a large scale industrial process that will have a faster rate of reaction and will produce a
purer product. It is suitable for making large amounts of pure ethanol quickly. It is a continuous
process which means cheaper manpower costs.

Disadvantages of producing ethanol from ethene

High technology equipment is needed so there are expensive initial capital costs. Ethene is non-
renewable resource and will become more expensive when the raw material crude oil run out.
The process will also have high energy costs for pumping to produce the high pressures needed.

Mechanism for acid catalysed addition of steam to ethene

H H
H H -
C C O
Step 1: A pair of electrons from + O
H C C H H P
the double bond in the alkene H H
O
forms a bond with a proton from H O
the phosphoric acid forming a H
O H
carbocation intermediate O
H P
O
O
H
H H H H
Step 2: The lone pair of electrons on + H C C H
the water form a bond to the H C C H
carbocation forming a protonated H +
H H O H
alcohol
O H
H

H H
Step 3: The protonated H H
H C C H O H
alcohol loses a proton to the O
+ H C C H
phosphate ion regenerating H O H H P
the phosphoric acid catalyst H O O
in the process H O
H H
-
O
O
H P
O
O
H

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 Questions Making Ethanol: Fermentation or Hydration?
1. Ethanol can be manufactured by the direct hydration of ethene
1.1) State what is meant by the term hydration.
1.2) What are the reactants and essential conditions necessary for the hydration of ethene?
1.3) Write an equation using skeletal formulae for this reaction
1.4) Outline the mechanism for this reaction using curly arrows for this reaction
1.5) By referring to the mechanism explain why it is classed as ‘acid -catalysed addition’
1.6) What are the advantages and disadvantages of making ethene by this method?

2. Ethanol can also be produced commercially by fermentation of aqueous glucose, C6H12O6

2.1) Write an equation for the production of ethanol by fermentation

2.2) State all the conditions which are necessary for fermentation.
2.3) Explain why neither a low temperature nor a high temperature is suitable for this reaction.

2.4) Describe the process used to separate ethanol from the dilute aqueous solution made by the
fermentation process.
2.5) Give advantages of this method of production over that by the direct hydration of ethene.

2.6) Give disadvantages of this process when it is used to make ethanol on a large scale

3. In aqueous solution, some glucose molecules have the structure shown below.
OH OH

OH OH OH
3.1) Give the empirical formula of glucose and name the two different types of functional
group in this form of glucose.
Scientists have used bacteria to ferment glucose and the produce the biofuel butan-1-ol
3.2) Write an equation for the fermentation of glucose C6H12O6 to form butan-1-ol, carbon dioxide and
water only.
3.3) State one condition necessary to ensure complete combustion of a fuel in air.
3.4) Write an equation for the complete combustion of butan-1-ol.
3.5) Explain why butan-1-ol made in this way can be classed as a biofuel. Discuss some of the
advantages and disadvantages of using biofuels.

4 Ethanol produced by fermentation can be classed as a carbon neutral biofuel

4.1) Define the term carbon neutral.
4.2) Write an equation for the complete combustion of ethanol.
4.3) Write an equation for the formation of ethanol from glucose by fermentation
4.4) Write an equation for the formation of glucose from CO2 by photosynthesis
4.5) By considering the 3 equations written in 4.2, 4.3, 4.4, show how this process could be classed as
carbon neutral
4.6) In reality it is not valid to say producing ethanol from fermentation is carbon neutral. Give reasons
why this is the case.

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Purifying an organic liquid
• Put the distillate of impure product into a separating funnel
Sodium hydrogencarbonate will
• wash product by adding either neutralise any remaining reactant acid.
• sodium hydrogencarbonate solution , shaking and
releasing the pressure from CO2 produced. Sodium chloride will help separate the
• Saturated sodium chloride solution organic layer from the aqueous layer

•Allow the layers to separate in the funnel, and then run and
discard the aqueous layer.
The drying agent should
•Run the organic layer into a clean, dry conical flask and add •be insoluble in the organic liquid
three spatula loads of drying agent (anhydrous sodium • not react with the organic liquid
sulphate) to dry the organic liquid.

• Carefully decant the liquid into the distillation flask

•Distil to collect pure product

Separating funnel

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Carbonyls: Aldehydes and Ketones
Carbonyls are compounds with a C=O bond.
They can be either aldehydes or ketones

H O H O H If the C=O is in the middle of

If the C=O is on the end of the
H. C C chain with an H attached it is an H C C C H the chain it is a ketone
The name will end in -one
aldehyde. H H
H H The name will end in –al
CH3COCH3 propanone
CH3CHO ethanal

Solubility in water
CH3
The smaller carbonyls are soluble Pure carbonyls cannot hydrogen bond, but
in water because they can form O H O C bond instead by permanent dipole bonding.
hydrogen bonds with water.
H CH3

δ-
Reactions of carbonyls O
In comparison to the C=C bond in
The C=O bond is polarised because alkenes, the C=O is stronger and does
O is more electronegative than δ+ not undergo addition reactions easily.
C
carbon. The positive carbon atom
attracts nucleophiles. H3C CH3
This is in contrast to the electrophiles
that are attracted to the C=C .

nucleophile

Oxidation Reactions

Potassium dichromate K2Cr2O7 is Key point: Aldehydes

Primary alcohol  aldehydes  carboxylic acid
an oxidising agent that causes can be oxidised to
alcohols and aldehydes to Secondary alcohol  ketones carboxylic acids, but
oxidise. Tertiary alcohols do not oxidise ketones cannot be
oxidised.

Oxidation of Aldehydes

Reaction: aldehyde  carboxylic acid H H O H H O

Reagent: potassium dichromate (VI) solution and H C C C + [O]  H C C C
dilute sulphuric acid.
Conditions: heat under reflux H H H H H O H

Full Equation for oxidation RCHO + [O]  RCO2H

3CH3CHO + Cr2O72- + 8H+  3 CH3CO2H + 4H2O + 2Cr3+
Aldehydes can also be oxidised using Fehling’s
Observation: the orange dichromate ion solution or Tollen’s Reagent. These are used
(Cr2O72-) reduces to the green Cr 3+ ion as tests for the presence of aldehyde groups

1
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Reduction of carbonyls
Reducing agents such as NaBH4 (sodium tetrahydridoborate)
Reagents: NaBH4 In aqueous ethanol or LiAlH4 (lithium tetrahydridoaluminate) will reduce carbonyls
Conditions: Room temperature and pressure to alcohols.

Aldehydes will be reduced to primary alcohols Ketones will be reduced to secondary alcohols.
H H O H H H H O H H H H

H C C C + 2[H] H C C C O H H C C C H + 2[H]  H C C C H

H H H H H H H O H
H H
propanal Propan-1-ol propanone H
Propan-2-ol

Nucleophilic Addition Mechanism H+ from water or weak acid

δ-
O
O:
- H+
O H
NaBH4 contain a source of
nucleophilic hydride ions (H-)
δ+ which are attracted to the positive
C H3C C CH3 H3C C CH3 carbon in the C=O bond.
H3C CH3
H H
:H-

Catalytic Hydrogenation
Carbonyls can also be reduced using catalytic hydrogenation Example Equations
Reagent: hydrogen and nickel catalyst CH3CHO + H2  CH3CH2OH
Conditions: high pressure CH3COCH3 + H2  CH3CH(OH)CH3

Addition of hydrogen cyanide to carbonyls to form hydroxynitriles

R
Reaction: carbonyl  hydroxynitrile The NaCN supplies the
Reagent: sodium cyanide (NaCN) and dilute nucleophilic CN- ions. The NC C OH
sulphuric acid. H2SO4 acid supplies H+ ions
Conditions: Room temperature and pressure needed in second step of the
H
Mechanism: nucleophilic addition mechanism hydroxynitrile

CH3 When naming hydroxy

CH3COCH3+ HCN  CH3C(OH)(CN)CH3
nitriles the CN becomes
NC C OH part of the main chain
2-hydroxy-2-methylpropanenitrile
CH3
We could use HCN for this reaction but it
CH3CHO + HCN  CH3CH(OH)CN CH3 is a toxic gas that is difficult to contain.
The KCN/NaCN are still, however, toxic,
2-hydroxypropanenitrile NC C OH
because of the cyanide ion.
H

Nucleophilic Addition Mechanism

H+ from sulphuric acid
δ-
O
O:
- H+ O H
δ+ H3C C CH3
C H3C C CH3
H3C CH3
CN CN
:CN-

2
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Nucleophilic addition of HCN to aldehydes and ketones (unsymmetrical) when the trigonal planar carbonyl is
approached from both sides by the HCN attacking species: results in the formation of a racemate

Mechanism for the reaction (drawn the same for both enantiomers)
δ-
O O:
- H+
O H
δ+
C
H3C C H H3C C H
H3C H
:CN- CN CN

CH3
H
C
NC:
:CN

O
H
H3 C CN
H There is an equal
NC CH3 chance of either
enantiomer forming C
C so a racemate forms.
No optical activity is OH
OH seen

Reaction with 2,4-dinitro phenylhydrazine

2,4-DNP reacts with both aldehydes and ketones. The Use 2,4-DNP to identify if the compound is a
product is an orange precipitate, It can be used as a test carbonyl. Then to differentiate an aldehyde
for a carbonyl group in a compound. from a ketone use Tollen’s reagent.

The melting point of the crystal formed can be used to help identify which carbonyl was used. Take the melting
point of orange crystals product from 2,4-DNP. Compare melting point with known values in database

H O 2N You don’t need to

learn these equations

H3C C
..
H2N NH NO2
for the exam

+
O 2,4-DNP
addition

O 2N H O 2N
H
elimination of
water
H3C C NH NH NO2 H3C C N NH NO2

orange precipitate
OH

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Functional group tests for an Aldehyde

Tollen’s Reagent
Reagent: Tollen’s Reagent formed by mixing aqueous ammonia and silver
nitrate. The active substance is the complex ion of [Ag(NH 3)2]+ .
Conditions: heat gently
Reaction: aldehydes only are oxidised by Tollen’s reagent into a carboxylic
acid and the silver(I) ions are reduced to silver atoms
Observation: with aldehydes, a silver mirror forms coating the inside of the
test tube. Ketones result in no change.

CH3CHO + 2Ag+ + H2O  CH3COOH + 2Ag + 2H+

Tollen's reagent method

Place 1 cm3 of silver nitrate solution in each of two clean boiling tubes.
Then add one drop of sodium hydroxide solution to form a precipitate of
silver oxide. Add ammonia solution dropwise until a clear, colourless
solution is formed. Add a few drops of the unknown and leave in the
water bath for a few minutes.

Fehling’s solution
Reagent: Fehling’s Solution containing blue Cu 2+ ions. Fehling's solution method
Conditions: heat gently Place 1 cm3 of Fehling's A into each of
two boiling tubes, and then add Fehling's
Reaction: aldehydes only are oxidised by Fehling’s Solution
into a carboxylic acid and the copper (II) ions are B until the blue precipitate redissolves.
reduced to copper(I) oxide . Add a few drops of the unknown and
Observation: Aldehydes :Blue Cu 2+ ions in solution change leave in the water bath for a few
to a red precipitate of Cu2O. Ketones do not react minutes.

CH3CHO + 2Cu2+ + 2H2O  CH3COOH + Cu2O + 4H+

Reaction of carbonyls with iodine in presence of alkali

Reagents: Iodine and sodium hydroxide Only carbonyls with a methyl group next to O
Conditions: warm very gently the C=O bond will do this reaction. Ethanal
is the only aldehyde that reacts. More H3C C H
The product CHI3 is a yellow crystalline commonly is methyl ketones.
precipitate with an antiseptic smell

This reaction is called the Iodoform test

CH3COCH3 + 3I2 + 4NaOH → CHI3 + CH3COONa + 3NaI +3H2O

CH3COCH2CH3+ 3I2 + 4NaOH → CHI3 + CH3CH2COONa + 3NaI +3H2O

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Carboxylic Acids

Carboxylic acids
These have the ending -
oic acid but no number is H H
O
If there are carboxylic acid groups on both ends of the
necessary for the acid chain then it is called a - dioic acid
group as it must always be H C C C O O
at the end of the chain. Ethanedioic acid
The numbering always C C
O H
H H Note the e in this name
starts from the carboxylic HO OH
acid end
Propanoic acid

Solubility in Water

The smaller carboxylic (up to C4) H
 
acids dissolve in water in all O H O
proportions but after this the solubility 
H3C C
rapidly reduces. They dissolve   H
because they can hydrogen bond to 

O H O
the water molecules.
H

Hydrogen bonding in solid ethanoic acid

δ- Hydrogen bonding
δ- between dimer in
δ+
solid ethanoic acid
O H O
C CH3
H3C C - + δ- Solid Ethanoic
δ δ
O H O appears to have Mr
of 120

IR Spectrum for Carboxylic acids

Carboxylic acids have distinct IR spectra with a broad -O-H absorption around (2500-
3000) and a sharp –C=O absorption (around 1680-1750)

Butanoic acid
O-H
absorption

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 Acidity
The carboxylic acid are only weak acids in water and only slightly dissociate, but
they are strong enough to displace carbon dioxide from carbonates.

CH3CO2H(aq) CH3CO2-(aq)+ H+(aq)

Delocalisation
The delocalised ion has equal C-O bond lengths. If
The carboxylic acid salts are stabilised by delocalisation, delocalisation did not occur, the C=O bond would be
which makes the dissociation more likely. shorter than the C-O bond.

O O The pi charge cloud has O

delocalised H3C C delocalised and spread out. The
H3C C delocalisation makes the ion C
H3C
OH O more stable and therefore more
likely to form.
O

Relative acidities of carboxylic acids, phenols and alcohols

Carboxylic acids are acidic enough to react with sodium, sodium hydroxide, and O
sodium carbonate. As mentioned earlier the carboxylic acid salts are stabilised by
delocalisation, which makes the formation of the salts more likely. Delocalisation H3C C
spreads out the negative charge which makes it more stable
O
2CH3CO2H + 2Na  2CH3CO2-Na+ + H2
CH3CO2H + Na  CH3CO2-Na+ + H2

Phenols are very weakly acidic. They are weaker acids than carboxylic acids.
Phenols will react with sodium metal and sodium hydroxide, but are not strong
enough an acid to react with sodium carbonate. In phenol the lone pair of
electrons on the oxygen is delocalised with the electron charge cloud of the
arene ring. The delocalised bonding stabilises the formation of the phenoxide
ion. The delocalisation is less effective than that in a carboxylate ion

-
OH + Na O Na+ + ½ H2

-
OH + NaOH O Na+ + H2O

sodium phenoxide

Alcohols have almost no acidity. The do not react with sodium hydroxide or sodium
carbonate. They can react with sodium metal.
There is no delocalisation within an alcohol so the formation of a stable ethoxide
ion from ethanol is not possible except with the reaction with sodium. The negative
charge stays on the oxygen atom which makes it very unstable

2CH3CH2OH + 2Na  2CH3CH2O -Na+ + H2

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Strength of carboxylic acids

O O Increasing chain length pushes

delocalised electron density on to the COO-
H3C CH2 C H3C CH2 C
ion, making it more negative and
OH O less stable. This make the acid
less strong.
Alkyl groups electron releasing
Propanoic acid less acidic than ethanoic acid

Cl O Cl O Electronegative chlorine atoms

H C C delocalised withdraw electron density from
H C C the COO- ion, making it less
OH negative and more stable. This
H O
H make the acid more strong.
Chlorine electron withdrawing
chloroethanoic acid more acidic than ethanoic acid

O H H
O O OH In a dibasic acid the second HO2C- group
C C C C C C - withdraws electron density from the
COO- ion, making it less negative and
H O H O H H O OH
H more stable and weakens the O-H bond.
This make the acid more strong.
HO2C- group electron withdrawing

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Revisiting Functional group level
This idea was met in my chapter on alcohols. Although it is only tested explicitly on Pre-U courses it is a good
scaffolding exercise to see how the functional groups relate to each other, and is particularly useful for carboxylic acid
and related compounds.

The functional group level of a carbon atom can be worked out by counting the number of bonds to
electronegative atoms on the carbon.
• No such bonds is called the Hydrocarbon level
• one bond is called the Alcohol level
• two bonds is the Carbonyl level
• three bonds the Carboxylic Acid level
• four bonds the Carbon Dioxide level

Alcohol level

C OH C NH2 C halogen common examples within the Alcohol level include

alcohols, amines, halogenoalkanes

Carbonyl level
O O

C
C H examples in the Carbonyl level: aldehydes, ketones

Carboxylic Acid level O

Examples in the Carboxylic Acid
O level: carboxylic acids, esters,
O O O O acyl chlorides, amides, nitriles;
C OH C C C N
C O
Cl NH2
O
carboxylic acids , esters, acyl chlorides, amides, nitriles, anhydrides

The functional groups in the carboxylic acid level are often called carboxylic acid derivatives. The
carbon in the functional group has the same oxidation state in all these compounds. Conversions
between functional groups within this level are therefore not redox reactions.
One reaction they all have in common is the hydrolysis reaction.
All functional groups within a carboxylic acid level will on reaction with acid produce a carboxylic acid.
O

Ethanoic anhydride
O
O
Ethanoyl chloride
N O Cl
Ethanenitrile
O

HO O

O Ethanoic acid Ethanamide

H 2N

O
Heating all these substance with a dilute acid will
Ethylethanoate produce ethanoic acid. (ethanoic anhydride and
ethanoyl chloride will undergo the reaction in milder
conditions with just water)

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Moving a carbon atom up a level is oxidation and requires an oxidizing agent. Moving a carbon
atom down a level is reduction and requires a reducing agent

Alcohol level

C OH Primary alcohol

Carbonyl level reducing agent

Oxidising agent LiAlH4
K2Cr2O7 O
aldehyde
C H

A less powerful reducing agent

Carboxylic Acid level
NaBH4 will reduce carbonyls to alcohols but
is not strong enough to reduce carboxylic
O acid level substances
Carboxylic acid
C OH

Alcohol level

C NH2

reducing agent
LiAlH4

The same LiAlH4 reducing agent will

reduce nitriles and amide to amines
Carboxylic Acid level
O

C C N
NH2

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Methods of preparing carboxylic acids
As the previous pages show there are many ways carboxylic acids can be produced either by oxidation or
hydrolysis. There follows some more detail on some of the more useful reactions of this type.
Full Oxidation of Primary Alcohols

Reaction: primary alcohol  carboxylic acid Observation: the

Reagent: potassium dichromate(VI) solution and dilute sulphuric acid orange dichromate ion
Conditions: use an excess of dichromate, and heat under reflux: (distill off product after (Cr2O72-) reduces to
the reaction has finished) the green Cr 3+ ion

H H H H H
O

H C C C O H + 2 [O] H C C C + H2O

H H H O H
H H

CH3CH2CH2OH + 2[O]  CH3CH2COOH + H2O

propan-1-ol Propanoic acid

Oxidation of Aldehydes

Reaction: aldehyde  carboxylic acid H H O H H O

Reagent: potassium dichromate (VI) solution and dilute
H C C C + [O]  H C C C
sulphuric acid.
Conditions: heat under reflux H H H H H O H

Full Equation for oxidation RCHO + [O]  RCOOH

3CH3CHO + Cr2O72- + 8H+  3 CH3COOH + 4H2O + 2Cr3+

Amide hydrolysis
primary amides can be hydrolysed by aqueous acids
With HCl an amide will be hydrolysed and split up in to a carboxylic acid and an ammonium salt

O O
CH3 C + H2O + HCl  CH 3 C + NH4+Cl-
NH2
OH
Secondary amides can be hydrolysed by aqueous acids
With HCl an amide will be hydrolysed and split up in to a carboxylic acid and an amine salt

O O
CH3 C NH CH3 + H2O + HCl  CH 3 C + CH3NH3+Cl-

OH

Hydrolysis of Nitriles
Reaction: Nitrile  carboxylic acid
Reagent: dilute hydrochloric/ sulphuric acid.
Conditions: heat under reflux

CH3CH2CN + H+ + 2H2O  CH3CH2COOH + NH4+

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 The Reactions of Carboxylic Acids

Salt formation reactions of carboxylic acids

Carboxylic acids can form salts with metals, alkalis and
carbonates.
acid + metal (Na)  salt + hydrogen The effervescence caused by production of CO2
2CH3CO2H + 2Na  2CH3CO2-Na+ + H2 with carboxylic acids with solid Na2CO3 or
aqueous NaHCO3 can be used as a functional
acid + alkali (NaOH)  salt + water group test for carboxylic acids
CH3CO2H + NaOH  CH3CO2-Na+ + H2O

acid + carbonate (Na2CO3)  salt + water + CO2

2CH3CO2H + Na2CO3  2CH3CO2-Na+ + H2O + CO2

Reaction of carboxylic acid with phosphorous (V) chloride

Reaction: carboxylic acid  acyl chloride This reaction with PCl5 (phosphorous(v)chloride)
Reagent: PCl5 phosphorous(v)chloride can be used as a test for carboxylic acids. You would
Conditions: room temp observe misty fumes of HCl produced.

CH3COOH + PCl5  CH3COCl + POCl3 + HCl

O O
+ PCl5  + POCl3 + HCl
H3C C H3C C
OH Cl

Reduction of carboxylic acids to alcohols

Lithium tetrahydridoaluminate (LiAlH4) is a
Carboxylic acids will be reduced to primary alcohols
strong reducing agent
H H O H H H
Reagents: LiAlH4 In dry ether
Conditions: Room temperature and pressure H C C C + 4[H] H C C C O H + H2O

Type of reaction: Reduction H H O H H H H

Propanoic acid Propan-1-ol
Role of reagent: Reducing agent

LiAlH4
CO2H CH2OH + H2O

benzoic acid phenylmethanol

The LiAlH4 acts as a nucleophile since H- ions are present.

LiAlH4 can also be used to reduce carbonyls to alcohols

It is not possible to partially reduce a carboxylic acid to an aldehyde.

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 Oxidation of carboxylic acids

Most carboxylic acids cannot be oxidised but the are a couple of very specific examples

Oxidation of methanoic acid O O It forms carbonic acid

Carboxylic acids cannot be oxidised by using (H2 CO3 ) which can
oxidising agents but methanoic acid is an H C + [O]  H O C decompose to give
exception as its structure has effectively an O H O H CO2
aldehyde group

Oxidation of ethanedioic acid

Ethanedioic acid can be oxidised by potassium manganate (VII). The
The reaction between MnO4- and
ethanedioic acid is oxidised to carbon dioxide gas. This reaction can be
C2O42- is slow to begin with (as
done as a quantitative titration.
the reaction is between two
negative ions). To do as a titration
Ox H2C2O42-  2CO2 + 2H+ + 2e- the conical flask can be heated to
Red MnO4-(aq) + 8H+(aq) + 5e-  Mn2+ (aq) + 4H2O 60o C to speed up the initial
Overall 2MnO4-(aq) + 6H+(aq) + 5C2O42-(aq)  10CO2(g) + 2Mn2+(aq) + 8H2O(l) reaction.

8
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Esterification
H H O H Esters have two parts
Carboxylic acids react with alcohols, in the to their names, eg
presence of a strong acid catalyst, to form H C C C O C H methyl propanoate.
esters and water. H H H

The bit ending in –anoate The bit ending in –yl comes from
H+ comes from the carboxylic the alcohol that has formed it
Carboxylic Acid + Alcohol Ester + water acid and includes the C in and is next to the single bonded
the C=O bond. oxygen.

H H H O H H
O The reaction is reversible. The
H+ reaction is quite slow and needs
+ H C C O H H C C O C C H + H2O
H3C C heating under reflux, (often for
OH H H H H H several hours or days). Low yields
(50% ish) are achieved. An acid
CH3CO2H + CH3CH2OH CH3CO2CH2CH3 + H2O catalyst (H2SO4) is needed.
Ethanoic acid Ethanol Ethyl Ethanoate

Detailed Method for Preparing and Purifying an Ester

Propyl ethanoate can be made in the laboratory from propan-
1-ol and ethanoic acid.
The equation for the reaction is
CH3COOH + CH3CH2CH2OH  CH3COOCH2CH2CH3 + H2O
Procedure
1. Propan-1-ol (50 cm3) and ethanoic acid (50 cm3) are mixed
thoroughly in a 250 cm3 round-bottomed flask.
2. Concentrated sulfuric acid (10 cm3) is added drop by drop Sulfuric acid is a catalyst
Adding conc H2SO4 is an exothermic reaction- to
to the mixture, keeping the contents of the flask well-shaken
prevent uncontrolled boiling over add drop by drop
and cooled in an ice-water bath. and cool

3. When the acid has all been added, a reflux condenser is In reflux the reactant vapours of volatile compound
fitted to the flask and the mixture gently boiled over an are condensed and returned to the reaction mixture.
electric heating mantle for about 30 minutes. The reaction is slow so it is heated for 30 minutes
The electric heating mantle allows for controlled
heating and stops flammable vapour lighting
4. The mixture is cooled, and the apparatus rearranged for
distillation. The crude ester (about 60 cm3) is distilled off. Sodium carbonate reacts with unreacted acid and
5. The distillate is placed in a separating funnel and shaken remaining catalyst still present after distillation.
with about half its volume of 30% sodium carbonate solution, The reaction produces CO2 so the pressure of gas
with the pressure being released at intervals. The lower needs to be released.
The upper layer is organic because it has a lower
aqueous layer is then discarded.
density than water

6. The crude ester is shaken in a separating funnel with about

half its volume of 50% calcium chloride solution, which
removes unreacted alcohol. The lower layer is discarded.
Calcium chloride is a drying agent. The liquid will
7. The ester is run into a clean, dry flask containing some appear clear when dry.
anhydrous calcium chloride and swirled.

8. The ester is filtered into a clean, dry flask, with a few anti- Anti-bumping granules are added to the prevent
bumping granules, and distilled. The fraction boiling between vigorous, uneven boiling by making small bubbles
100°C and 103°C is collected. form instead of large bubbles

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Mechanism for Esterification
There are two possibilities for the mechanism. Does the single bonded oxygen come from the alcohol or
the carboxylic acid?
Experiments were done where a radioactive isotope of oxygen O18 was inserted in an alcohol that was used
to make an ester.
O

C OH + CH318OH

There are two possible results and esters

Result 1 Result 2
O O
18
C O CH3 + H2O C O CH3 + H218O

A mass spectrometer showed that the oxygen was found in the ester and not in the water. Result 1 occurs
These bonds must therefore be broken.

O H

H C O H
C OH

Acid catalysed Addition - Elimination

CH3
O OH O
H+
+
C OH C H
protonation
OH

Addition of
Alcohol

+
OH

C O CH3

OH H

-H2O
elimination

- H+
O
deprotonation OH
C O CH3
C O CH3
+

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N Goalby chemrevise.org 11
 Uses of Esters
Esters can have pleasant smells
Esters are sweet smelling
compounds that can be used in CH2 CH2 O O
perfumes and flavourings. H3C CH2 CH2 C
Pentylethanoate – banana smell
CH3
For use in perfumes they need to
be non toxic, soluble in solvent O
such as ethanol, volatile (turns
into gas easily), and not react with CH2 C Ethylbutanoate – pineapple smell
water. H3C CH2 O

H2C
CH3

Esters can be used as solvents Although polar, they do not form hydrogen bonds (reason: there is no
for polar organic substances hydrogen bonded to a highly electronegative atom)
thus, they have much lower b.p. than the hydrogen-bonded carboxylic
Ethyl ethanoate is used as a acids they came from. They are also almost insoluble in water
solvent in glues and printing inks

Esters can be used as Often pure polymers have limited flexibility because the polymer chains
plasticisers for polymers cannot move over each other.
Incorporating some plasticiser into the polymer allows the chains to move
more easily and the polymer can become more flexible.

O
H2C CH3
To make PVC ‘mock leather’ material up to
CH C
50% by weight plasticiser must be added.
HC C O CH2 CH CH2 CH2 CH2 CH3

The plasticiser may evaporate over time making HC C O CH2 CH CH2 CH2 CH2 CH3
CH C
the plastic more brittle as it ages.

O H2C CH3

A common ester plasticiser

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Hydrolysis of esters Esters can be hydrolysed and split up by either heating with acid or with sodium hydroxide.

i) with acid
This reaction is the reverse reaction of ester formation. When an ester
reagents: dilute acid (HCl)
is hydrolysed a carboxylic acid and an alcohol are formed.
conditions: heat under reflux
H+
This reaction is reversible and does not
CH3CH2CO2CH2CH3 + H2O CH3CH2CO2H + CH3CH2OH
give a good yield of the products.
ethyl propanoate

ii) with sodium hydroxide

reagents: dilute sodium hydroxide CH3CH2CO2CH3 + NaOH  CH3CH2CO2- Na+ + CH3OH
conditions: heat under reflux methyl propanoate sodium propanoate methanol

The carboxylic acid salt product is the anion of the carboxylic acid.
This reaction goes to completion. The anion is resistant to attack by weak nucleophiles such as alcohols, so the
reaction is not reversible.

Fats and soaps

Fats and oils are ESTERS of glycerol and long Vegetable oils and animal fats can be hydrolysed to give
chain carboxylic acids (fatty acids) soap, glycerol and long chain carboxylic (fatty) acids

O
H2C OH
CH2 O C (CH2)16CH3
O HC OH + 3 CH3(CH2)16 CO2–K+
+ 3 KOH 
HC O C (CH2)16CH3
O H2C OH long chain carboxylic (fatty) acids

CH2 O C (CH2)16CH3 Propane-1,2,3-triol

Glycerol (propane-1,2,3-triol) forms hydrogen bonds very easily and is readily soluble in water. It is used in cosmetics,
food and in glues.

Soap
Long chain carboxylic (fatty) acids, produced by the hydrolysis of fats, act as soaps. The polar CO 2- end is hydrophilic and
mixes with water.
O
Sodium palmitate
CH2 CH2 CH2 CH2 CH2 CH2 CH2 C -
H3C CH2 CH2 CH2 CH2 CH2 CH2 CH2 O Na+
Non polar polar

The long non-polar hydrocarbon chain is hydrophobic and

mixes with grease. The soap molecules surround a droplet of
oil with the hydrophobic ends pointing towards the oil and the
hydrophilic ends towards the water. The droplet is then
washed away.

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 H3C
unsaturated fatty acids

Cis-octadec-9-enoic acid,
Prority groups on same side
of double bond
O

OH

H3C O

trans-octadec-9-enoic acid, OH

trans fatty acids are thought to possibly cause an

increase in ‘bad’ cholesterol and the resultant increased
risk of coronary heart disease
and strokes

Biodiesel
Biodiesel is a mixture of methyl Vegetable oils can be converted into biodiesel by reaction
esters of long chain carboxylic acids with methanol in the presence of a (strong alkali) catalyst
O
H2C OH
CH2 O C (CH2)14CH3
O
+ 3 CH3OH  HC OH + 3 CH3(CH2)14CO2CH3
HC O C (CH2)14CH3
O biodiesel
H2C OH
CH2 O C (CH2)14CH3
Propane-1,2,3-triol
It can be argued that the biodiesel produced from this method is classed as carbon–neutral as any carbon
dioxide given off when the biofuel is burnt would have been extracted from the air by photosynthesis when
the plant grew.
This does not take into account any energy needed to irrigate plants, extract the oil, heat the reaction with
methanol mixture or process the fuel. If the energy for this process comes from fossil fuels then the biofuel
produced is not carbon neutral.
It also does not take into account the effect on land available for food production.

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Polymers There are two types of polymerisation: addition and condensation

Addition Polymers
Addition polymers are formed from alkenes. The alkene molecules add to themselves to form long chain molecules.
The original alkene molecule is called the monomer. The double bond in the alkene opens to bond to next monomer
molecule. Chains form when the same basic unit is repeated over and over.

The simplest addition polymer is made from ethene and is called poly(ethene). Modern naming of polymers is to put the
name of the monomer in brackets after the word poly.
e.g. poly(ethene) , poly(chloroethene). Most polymers are still known by their original names or trade names.

Polymer chains can be of various lengths. There are usually between 10 4 to 106 repeating units in a chain

Poly(alkenes) like alkanes are unreactive due to the strong C-C and C-H bonds

be able to recognise the repeating unit in a poly(alkene)

n
H H H H H H

Monomer Polymer C C C C C C
Ethene Poly(ethene)
CH3 H CH3 H CH3 H
Polymerisation equations are written in the form
above showing the formula or one monomer and one
repeating unit. The letter n is used to represent the
number of repeating units.
H H
If asked to draw one
The polymer chains consist of strong covalent bonds. repeating unit, don’t add the
Between different polymer chains there are weaker n on to your diagram, C C
intermolecular forces which can be a mixture of because n represents a large
London forces and permanent dipole forces. number H CH3
Increased chain length leads to increasing density,
melting point and hardness.

Poly(ethene) -polythene
Poly(ethene): is used to make plastics bags, buckets, bottles. It is a flexible, easily moulded, waterproof,
chemical proof, and a low density plastic.

Poly(ethene) is chemically inert due to the strong C-C and C-H bonds and non-polar nature of the bonds and
therefore is non-biodegradable.

This shows three repeating units of poly(ethene)

H H H H H H
C C C C C C
H H H H H H

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Different forms of poly(ethene)
Low density (LD) and high density (HD) poly(ethene) are produced from ethene, using different catalysts and
reaction conditions.
In HDPE the polymer chains are single strands and can closely line up in parallel (called a crystalline structure). In
LDPE, the chains are irregularly packed, branched chain polymers therefore they cannot get as close together.
The polymer chains in HDPE can form stronger van der waals forces between them.

Low Density poly(ethene) LDPE High Density poly(ethene) HDPE

Conditions for polymerisation: high pressure, 1500 Condition for polymerisation : low pressure (2-6 atm),
atm, 200oC and a free radical organic peroxide 60oC. Ziegler-Natta Catalyst.
initiator.
The structure consists of regularly packed, linear
The high pressure compresses the gas molecules
polymers chains . This is called a highly crystalline
together which increases the rate of the reaction
structure. The polymer chains fit closer together.
The Structure consists of irregularly packed, branched
chain polymers- a more amorphous structure Uses: Rigid articles such as ice trays, buckets,
Properties: flexible, low tensile strength and low bottle crates.
melting point
Uses: plastic bags, wrappers, bottles.

Free radical Polymerisation mechanism

Chain Initiation
RO-OR  2RO· (organic peroxide)

RO· + CH2=CH2  RO-CH2-CH2·

Chain Propagation
RO-CH2-CH2· + CH2=CH2  RO-CH2CH2-CH2-CH2·
Chain Termination
2 RO-(CH2CH2)n-CH2-CH2· 
RO-(CH2CH2)n-CH2-CH2-CH2-CH2-(CH2CH2)n-OR

The mechanism for the formation of HDPE using the Ziegler-Natta catalyst is different from the free radical
mechanism above.

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 A poly(propene)
Poly(propene) is a stiffer polymer, used in utensils and
container
containers and fibres in rope and carpets.

H H H H

n C C C C

H CH3
H CH3 n
propene
poly(propene) H H H H H H
Poly(propene) is recycled
C C C C C C
Add the n’s if writing an equation showing the reaction
where ‘n’ monomers become ‘n’ repeating units CH3 H CH3 H CH3 H
This shows three repeating units of
poly(propene)

Poly(propene) has stronger London

intermolecular forces between
chains than poly(ethene) because it
has more electrons in its structures.

Poly(chloroethene) also known as PVC

Poly(chloroethene) is a polymer that is water proof, an electrical insulator and doesn’t

H H react with acids.
In its pure form it is a rigid plastic. The strong permanent-dipole intermolecular
C C bonding between polymer chains prevents them moving over each other. In this un-
plasticised form it is used make uPVC window frame coverings and guttering.
H Cl
If a plasticiser is added the intermolecular forces are weakened which allows the
chains to move more easily resulting in more flexibility in the polymer. In this form
PVC is used to make insulation on electrical wires, and waterproof clothing.

O
H2C CH3
To make PVC ‘mock leather’ material up to 50%
by weight plasticiser may be added. CH C
HC C O CH2 CH CH2 CH2 CH2 CH3

The plasticiser may evaporate over time making the HC C O CH2 CH CH2 CH2 CH2 CH3
CH
plastic more brittle as it ages. There are health C
concerns over the use of some phthalate plasticisers
H2C CH3
as some with lower molecular weights are O
potentially toxic.
A common ester phthalate plasticiser

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 Poly(phenylethene) also known as polystyrene

H H
H H

n C C H3C C C CH3

H H

phenylethene n

The phenyl group is -C6H5

See chapter 6.9 on benzene for more detail on its structure

Polystyrene in its unexpanded form is a clear, relatively stiff and brittle plastic
used in toys, plastic cups, CD cases, and moulded electronic equipment.

Expanded polystyrene
Expanded or extruded polystyrene foams are produced by mixing blowing agents
with the polymer during its production. The blowing agents evaporate to form
bubbles and expand the foam. The blowing agents are usually volatile organic
liquids such as pentane or hydrofluorocarbons.
In its expanded form it is commonly used in packaging, and for heat insulation. It
has good insulating properties and is a good shock absorber

Isotatic, syndiotatic and atactic forms of polymer chains

The properties of polymers can also be affected by the positioning of the substituent side group (eg –Cl, -CH3 or
phenyl group)

In the isotactic form the substituent groups H H H H H H H H H H H H H H

are all on the same side of the polymer chain
in a regular arrangement. H3C CH2 CH2 CH 2 CH 2 CH2 CH 2 CH3

In the syndiotactic form the substituent H H H H H H H H H H H H H H

groups are regularly alternate from one side
of the polymer chain to the other. H3C CH2 CH2 CH 2 CH 2 CH2 CH 2 CH3

In the atactic form the substituent groups H H H H H H H H H

are randomly arranged on alternate sides. H H H H H
H 3C CH2 CH2 CH 2 CH 2 CH2 CH 2 CH 3

These different forms can have different properties. Often the isotactic form can fit closer together and
have stronger intermolecular forces between chains so have higher melting points.
The isotatic form of polystyrene is produced using a Ziegler-Natta catalyst and the atactic form is produced
using the free radical mechanism

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Polytetrafluoroethene
F F F F
Polytetrafluoroethene (PTFE, or “Teflon”) is very resistant to heat n C C C C
and chemical corrosion. It is used on nonstick cookware and
F F
coatings on bearings. F F n
Tetrafluorethene
Poly(tetrafluorethene)

How is it non stick?

Sticking is caused by chemical bonds forming between the food and the metal pan These bonds may be relatively weak
London forces or covalent bonds. Protein-rich foods are particularly sticky because they can form complexes with the iron
atoms in the steel pan

PTFE
The PTFE is applied as a liquid and covers the
surface of the pan going into the pores in the
rough surface. When it solidifies, it is fixed in
place .

Metal surface of pan

The PTFE has a high melting point so will not melt when the pan is heated. Food can not bond with the smooth
inert surface of the PTFE. It has a high melting point because it has strong London forces and permanent
dipole forces between chains.

Poly(ethenol)

H OH H OH
The addition polymer poly(ethenol) has good solubility in
n C C H C C H water because it can form many strong hydrogen bonds with
water. The makes it a useful polymer for uses such as soluble
H H H H n laundry bags and liquid detergent capsules .
poly(ethenol)

It is best to first draw out H CH3

You should be able e.g. For but-2-ene the monomer with groups H CH3
to draw the polymer of atoms arranged around
H3C CH CH CH3 C C C C
repeating unit for any the double bond
alkene H3C H
CH3 H

O O O
C H C NH2 H C NH2
H2C CH NH2
C C H C C H
e.g. For propenamide n
H H H H
poly(propenamide)

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Condensation Polymerisation
In condensation polymerisation there are two different monomers that
The two most common types of add together and a small molecule is usually given off as a side-product
condensation polymers are polyesters e.g. H2O or HCl.
and polyamides which involve the
formation of an ester linkage or an The monomers usually have the same functional group on both ends of the
amide linkage. molecule e.g. di-amine, di carboxylic acid, diol, diacyl chloride.

Forming polyesters and polyamide uses these reactions we met earlier in the course

Carboxylic Acid + Alcohol  Ester + water Carboxylic Acid + Amine  amide + water
Acyl chloride + Alcohol  Ester + HCl Acyl chloride + Amine  amide + HCl

If we have the same functional group on each end of molecule we can make polymers so we have the analogous
equations:
dicarboxylic acid + diol  poly(ester) + water dicarboxylic acid + diamine  poly(amide) + water
diacyl dichloride + diol  poly(ester) + HCl diacyl dichloride + diamine  poly(amide) + HCl

Using the carboxylic acid to make the ester or amide would need an acid catalyst and would only give an equilibrium
mixture. The more reactive acyl chloride goes to completion and does not need a catalyst but does produce hazardous HCl
fumes.

PET- Terylene- a common polyester

O O
O O
n C C +n HO CH2 CH2 OH C C O CH2 CH2 O + 2n-1 H2O
n
Ethane-1,2-diol
HO OH
The -1 here is because at each
Benzene-1,4-dicarboxylic acid
end of the chain the H and OH
are still present
This condensation polymer is commonly known as PET or PETE (short for polyethylene terephthalate). It is the most
widely used polyester. It is often used to produce fizzy drink bottles. It can also be drawn into filaments and blown
into films. In its fibre form, known as Terylene in the UK, it can be used to produce textiles.
Terylene fabric is used in clothing, tire cords

O O O O
n
C (CH2)3 C + n HO OH + 2n-1 HCl
C (CH2)3 C O O
Cl Cl n

Pentanedioyl dichloride Benzene-1,4-diol

Polyesters have permanent dipole bonding between the C δ+=Oδ- groups in the different chains in addition
to the London forces between the chains.
The stronger intermolecular forces in polyesters mean they can form strong fibres that can be woven into
clothes

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Nylon 6,6 - a common polyamide
O O
O O H H
N (CH2)6 N
n C (CH2)4 C +n C (CH2)4 C N (CH2)6 N + 2n-1 H2O
H H
HO OH
hexanedioic acid Hexane-1,6-diamine H H
n
The 6,6 stands for 6 carbons in each of the monomers. Different length carbon chains produce different polyamides

Polyamides (and proteins) have hydrogen bonding between the lone pairs on oxygen in Cδ+=Oδ-
groups and the H in the Nδ- —Hδ+ groups in the different chains.
There are also Permanent dipole-permanent dipole forces because the polar C=O bond and polar
C-N bond
There are also London forces which are large because there are many electrons in the molecule
Polyamides will therefore have higher melting points than polyesters.

Kevlar- a common polyamide

O O
n HO2C CO2H + n H2N NH2 N N C C
+ 2n-1 H2O
H n
H

δ-
Kevlar is a polyamide with a strong and
:

O Oδ- O
δ-
N C N C Nδ- C ordered structure.
H
δ+
H δ+
δ+
H δ+
It is used to make bullet proof clothing and
reinforcing tyres.
:

O δ- Oδ- O
Kevlar is insoluble in most solvents except
δ- δ-
N δ+
C N C N C concentrated sulfuric acid
δ+
H H Hδ+ The hydrogen bonds between O and N can
δ+
be broken with the use of concentrated
Hydrogen bonding between Kevlar chains causes chains to sulfuric acid.
line up into very strong sheets.

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It is also possible for polyamides and polyesters to form from one monomer, if that monomer contains both
the functional groups needed to react

O O O O
HO (CH2)3 C O (CH2)3 C O (CH2)3 C O (CH2)3 C
Cl
4-hydroxybutanoyl chloride 3 repeating units

O O O
O
H2N C N C N C N C
OH H H H
3 repeating units
H O H O H O
HO O
CH C HO C C O C C O C C OH

H 3C OH CH3 CH3 CH3

2-hydroxypropanoic acid (lactic acid) 3 repeating units poly(lactic acid)

O
2 lactic acid molecules
O O can also form a ring
diester

OH
O O

O
OH 1 repeating unit
4-hydroxypentanoic acid
O
O

It is possible for some of these compounds to form

various cyclic esters under different conditions from
forming the polymer.
You do not need to learn these but may be asked to
deduce structures from information given

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Thermoplastic/Thermosoftening polymers
Thermoplastic polymers soften on heating and can be re-shaped. In general they have low melting points. Most
polymers met in this chapter are classed as thermoplastic polymers.

There are weak inter-molecular forces between the chains

holding them together.
The chains can slide over each other and this creates the
flexibility often found in polymers.
On heating the weak forces between the chains are broken
and the object can be reshaped.

overlapping chains of polymers in thermoplastic polymers with

only intermolecular forces between chains
Thermosetting polymers

The chains are held together by strong covalent bonds called crosslinks. These
bonds cannot be broken easily; this makes the polymers rigid because the
polymer chains are fixed.
The cross-links do not break on heating and so the polymer cannot be reshaped
once it is made.
Thermosetting polymers include epoxy glues and bakelite ( which is used in light
fittings and saucepan handles because they do not soften on heating.)

Polymer chains held together by cross links. The amount of

crosslinks and regularity of the structure may vary between
different thermosetting polymers

Elastomers
Elastomers can be stretched to many times their original length, and then return to their original shape
without permanent deformation

This is what the polymer chains look like in a piece of

stretched rubber. The chains are stretched out and have
This is what the polymer chains look like in a piece of lower entropy as they have a more ordered arrangement.
un-stretched rubber. It has high entropy
When released the elastomer returns to the original point of high entropy and the polymer reforms its original shape.
Limited cross linking of chains can help the Elastomer ‘remember’ its original state and return to it.
Vulcanising Rubber with Sulfur is an example of this cross linking in an elastomer

H3C H
H 2C CH 2 S
CH2 CH2 C C CH2 CH2
C C S
H3C C C CH2 CH2 C C
H3C CH3
H
H3C H H3C H
Monomer unit for rubber Polymer chain for rubber
2-methybuta-1,2-diene Poly(2-methybuta-1,2-diene)
Sulfur cross links between polymer
chains.
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Non-solvent based adhesives
Most adhesives are solvent based. They harden when the solvent evaporates. The following harden in a different way.

Epoxy resin glues

The glues have two components: one containing O CH 3 O
polymers chains and the other a hardener (which is a H 2C CH CH 2 O C O CH2 HC CH 2
cross-linking agent). They are mixed together when CH 3
the glue is applied. As the glue sets the hardener forms
cross links between the polymer chains forming a pre-polymer with epoxy group
strong thermosetting structure.

O O
HC CH 2 H 2C CH OH OH
H H
CH CH 2 CH 2 H C
N
Diamine is N
polymer chains cross linked
crosslinking R
R into a strong thermosetting
hardener N
structure
H
N
H
HC CH2 H2C CH HC CH 2 CH 2 CH
O O OH OH

Ends of polymer chains

You don’t need to remember the details of
the substances here- just the process of
Cross links in thermosetting polymers tend to be
crosslinking.
covalent bonds which are strong and not easy to break.
Once formed the polymer cannot be melted

Superglue N
N N N

The monomer in superglue

polymerises on exposure to
moisture in the atmosphere to O
O O O
form a strong addition polymer O O O
O

monomer
ethyl 2-cyanoprop-2-enoate You don’t need to remember the details of
the substances here

Conducting polymers –poly(ethyne)

Ethyne has a triple bond. It can form an
addition polymer that has alternate CH CH CH CH3
H C C H
double single bonds. H3C CH CH CH
Ethyne
Poly(ethyne) also known
as polyacetylene

Poly(ethyne) conducts electricity. It conducts through its long chain of delocalised electrons. It
can delocalise because the polymer chain is planar so the π bonds overlap with each other.

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Chemical reactivity of condensation polymers The reactivity can be explained by the presence of polar
polyesters and polyamides can be broken down by bonds which can attract attacking species such as
hydrolysis and are, therefore, biodegradable nucleophiles and acids

Hydrolysis
Polyesters and polyamides can be hydrolysed by acid and alkali
The hydrolysis will result in the original monomers forming- although the carboxylic acid or amine group
will be in salt form depending on whether the conditions are alkaline or acidic

O O
O
+
HCl OH H 3N +
C (CH2)4 C N (CH2)6 N
HO
+ NH 3
H H O
n

NaOH O
-
-CO(CH2)4CONHC(CH3)2CH2O- - O
O + H2N
This polymer has both an amide and O
OH
ester link

Dealing with waste polymers Waste polymers can be processed in several ways.

Landfill
The most common method of disposal of waste in UK. Many are now reaching capacity.
European regulations will mean councils are charged much more for using landfill.
Most polymers (polyalkenes) are non-biodegradable and take many years to break down. One solution to this problem is
to more biodegradable plastics, e.g. Polyamides and cellulose and starch based polymers to improve rates of
decomposition

Incineration
Rubbish is burnt and energy produced is used to generate electricity.
This will result in large amounts of greenhouse gases such as carbon dioxide being produced. They can also
produce the products of incomplete combustions such as toxic carbon monoxide.
Combustion of halogenated plastics (ie PVC) can lead to the formation of toxic and acidic waste products such
as HCl and various dioxins.

O Cl O Cl

O Cl O Cl
dibenzodioxin
A PCDD tetrachlorodibenzodioxin

Dioxins are highly toxic compounds that consist of two benzene rings connected by two oxygen atoms. They
are often carcinogenic. Burning PVC has a potential risk of producing dioxins such as a polychlorinated
dibenzodioxins. Dioxins do not decompose in the environment and can be passed on in the food chain.

Modern incinerators can burn more efficiently and most toxins and pollutants can be removed.
Greenhouse gases will still be emitted though. The volume of rubbish is greatly reduced.

House fires can release many toxins due to plastics in things like shower curtains burning.
Low smoke zero halogen cabling is now often used in wiring to prevent these hazards.

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Polychlorinated biphenyls, PCBs are a group of manufactured
organic chemicals containing carbon, hydrogen and chlorine
atoms
Cl n

PCBs were manufactured in the twentieth century but are

now banned. They are often hightly toxic.
Cl n
Their properties include non-flammability, chemical stability,
high boiling point and electrical insulating properties.
General structure of PCB’s can be shown like
PCBs were therefore used in many applications including:
this. The hydrogens on the benzene rings are
•Electrical and heat transfer equipment
replaced with chlorine atoms. Different
•Plasticisers in paints and plastics.
PCB’s have different numbers of chlorine
atoms. One example below.
Disposal of old products containing PCB’s can still be an issue
as they are stable and do not break down in the environment.
Cl Cl
Burning of plastics containing PCB’s can be a problem.

Cl Cl

Cl Cl Cl

Recycling
Plastics require more processing to be recycled than other materials.
The waste is sorted into each different type of polymer (ie PTFE, PVC, PET) based on different resin types
codes. Then each type of thermoplastic polymers can be recycled by melting and remoulding.
Recycling saves raw materials. Nearly all polymers are formed from compounds sourced or produced
from crude oil. Recycling saves precious resources.
The collecting and sorting can be an expensive process in terms of energy and manpower.
Polymers can only be recycled into the same type, so careful separation needs to be done.

Resin identification codes

polyvinyl chloride polypropylene other

polyethylene terephthalate
OTHER
PETE PVC PP

high-density polyethylene low-density polyethylene polystyrene

HDPE LDPE PS

Feedstock for Cracking

Waste polymers can be used as a feedstock for the cracking process allowing for the new
production of plastics and other chemicals.

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 Addition Polymers

1. Propene polymerises to form poly(propene). Draw 3 repeating units of poly(propene)

2. Write an equation, using displayed formulae, for the formation of poly(tetrafluorethene) from its monomer.
3. Compound chloroethene, CH2=CHCl, forms an addition polymer.
a) Draw the repeating unit of the polymer formed and name the polymer
b) This polymer is rigid. Explain why in terms of intermolecular bonding
c) The use of plasticisers can be used to modify the properties of this polymer and make the polymer more
flexible. Explain how this works in terms of intermolecular forces.
H3C H
4. The monomer can be used to make a polymer. Name the monomer (including appropriate E-Z
C C
terminology) Draw one repeating unit of the polymer formed.
H CN

H H
5. Draw two repeating units of the polymer formed from phenylethene.
C C
H

CH3 H CH3 H
6 .The following diagram shows a portion of a polymer chain
Draw and name the monomer that forms this polymer. H3C C C C C CH3

H CH3 H CH3

7. Draw and name the momomer that makes poly(ethenol) OH H OH H

.Why does this polymer dissolve in water? H C C C C H

H H H H

8. Draw one repeating unit of the polymer formed from but-1-ene.

9. 2-methylbut-2-ene forms an addition polymer. Draw one repeating unit of the polymer formed.

10. Pent-2-ene forms an addition polymer. Draw two repeating units of the polymer formed.

11. Cyclopentene can be polymerised to form poly(cyclopentene). Draw two repeating units of this polymer.

12.The following figure shows one repeating unit of a polymer made from two H F F CH3
monomers by addition polymerisation.
H3C C C C C CH3
Draw and name the two monomers.
H F F F

13.The compound ethyl 2-cyanoprop-2-enoate

can polymerise by addition polymerisation to
form a strong glue. Draw 3 repeating units of
the polymer formed.

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