Organic chemistry

Organic chemistry
10.1 Introduction

20.1

10.2

10.3
Introduction (AHL)

Alkanes

Alkenes
10
10.4 Alcohols

10.5 Halogenoalkanes

10.6 Reaction pathways

20.5 Reaction pathways (AHL)

20.2 Nucleophilic substitution reactions (AHL)

20.3 Elimination reactions (AHL)

20.4 Condensation reactions (AHL)

20.6 Stereoisomerism (AHL)

10.1 intrOductiOn valence level (2,4 or 1s2 2s2 2p2) it forms four covalent
bonds. When these are all single bonds, they have a
10.1.1 Describe the features of a homologous tetrahedral arrangement. In organic molecules carbon
series. always forms four bonds, oxygen two, hydrogen and the
halogens one (refer Section 4.2)
10.1.2 Predict and explain the trends in boiling
points of members of a homologous Carbon atoms can combine with each other and with
series. other atoms (especially H and O) to form millions of
compounds. Compounds of this kind are the basis of
10.1.13 Discuss the volatility and solubility all known life, hence the term ‘organic’. he existence of
in water of compounds containing the such a large number of stable compounds is partly due to
functional groups listed in AS 10.1.9. the strength and stability of the C—C and C—H bonds
(348 and 412 kJ mol-1 respectively). he former ensure
©IBO 2007 that carbon can form long chains (a process known as
catenation) and rings of carbon atoms; the latter that these
Organic chemistry is the chemistry of carbon compounds structures are relatively stable and unreactive. Multiple
(excluding compounds such as metal carbonates bonds can also be formed between carbon atoms, but the
and oxides). Organic compounds constitute a major presence of these usually leads to an increase in chemical
component of energy sources (petroleum, coal, natural reactivity. Similarly functional groups containing other
gas), food (proteins, fats, carbohydrates, vitamins, enzymes, atoms, such as oxygen, nitrogen and the halogens, can be
hormones, steroids), drugs (anaesthetics, antiseptics, attached to the hydrocarbon chain and result in greater
antibiotics) and materials such as ibres, fabrics, plastics, reactivity. he reactions of these functional groups are
paints, dyes, soaps, detergents, explosives etc. the dominant feature of organic chemistry. Organic
compounds may therefore be usefully regarded as
Carbon is in group 4/14 of the periodic table and it always comprising a hydrocarbon skeleton to which functional
forms covalent bonds. As carbon has four electrons in its groups are inserted and/or attached:

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changes that occur in the strength of van der Waals’ forces

hydrocarbon skeleton with increasing molar mass and in some cases a change in
molecular polarity. he simplest illustration of the efect
functional groups of chain length on physical properties is the variation of
the boiling point of the alkanes with the number of carbon
atoms in the chain, as illustrated in Figure 1002.
FIGURE 1001 Diagrammatic representation of an organic
molecule his curve is initially quite steep because, for small
cOre

molecules, the addition of an extra carbon has a

he ability of carbon atoms to form chains leads to the proportionally larger efect on the molar mass (for
existence of a series of compounds that have the same example, from CH4 to C2H6 there is an increase of 97.5%)
functional group (and hence similar chemical properties) and hence on the strength of the van der Waals’ forces. As
and only difer from each other by the presence of an the length of the chain increases, the percentage change in
additional carbon atom and its two associated hydrogen molar mass becomes progressively smaller (there is a 10.9%
atoms in the molecule (which causes the physical properties increase in molar mass from C9H20 to C10H22) and so the
to change in a regular manner). A series of compounds curve lattens. Similar regular variation would be found in
related in this way is said to form an homologous series. graphs of other physical properties, such as density and
he alkanes are the simplest example of such a series, but viscosity, against the number of carbon atoms.
others include the alkenes, the alcohols and the carboxylic
acids. hese series can be thought of as diferent ‘families’ he physical properties, especially the melting and boiling
of organic compounds. In these homologous series: point of a compound, depend on the intermolecular forces
present. All other factors being unchanged, the greater the
• successive compounds difer from each other by a molar mass of a molecule the stronger the intermolecular
-CH2- unit (known as a methylene group) forces, hence the trend in the boiling points of the alkanes
illustrated below. Some functional groups (such as
• the compounds can all be represented by a general >δ+C=Oδ–, in aldehydes and ketones, and the presence
formula (in the case of the alkanes CnH2n+2; if n = 3, of halogens) give rise to polarity within molecules, and
then the formula is C3H8) this results in dipole-dipole forces and hence slightly
higher melting and boiling points than would otherwise
• the compounds have similar chemical properties be expected. Other functional groups, such as alcohol
(—OH), carboxylic acid (—COOH), amine (—NH2) and
• successive compounds have physical properties that amide (—CONH2) give rise to hydrogen bonding between
vary in a regular manner as the number of carbon the molecules. Compounds containing these tend to
atoms present increases. have signiicantly higher melting and boiling points than
non-polar or polar organic compounds of similar molar
he point about chemical properties is best illustrated by masses.
the sections that follow, on diferent homologous series.
he changes in physical properties are a result of the

100
Boiling point / °C

0
1 2 3 4 5 6 7 8 9 10

–100

–200

Figure 1002 Boiling points variations

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hese points are illustrated by the examples below: graphic formula and displayed formula) shows all the
atoms and bonds. For example the full structural formula
for butanoic acid is:
H H
H C C H
H H H O
H H
H C C C C OH

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H H H
Figure 1003 Ethane
Mr = 30 Non–polar b.p. = –89°C
Figure 1006 Structural formula for butanoic acid
O
A structural formula indicates in an unambiguous manner
H C H
how the atoms are arranged in the molecule. A condensed
structural formula, that can usually be written on a single
Figure 1004 Methanal line, is one in which the bonds are omitted, side chains
Mr = 30 Polar b.p. = –21°C put in brackets and repeated identical groups collected
together. Again using butanoic acid as the example:
H
CH3CH2CH2COOH or CH3(CH2)2COOH
H C O H condensed structural formula
H
As noted previously, the molecular formula gives the
actual number of each type of atom in the molecule and
Figure 1005 Methanol the empirical formula the simplest whole number ratio of
Mr = 32 Highly polar b.p. = 65°C these. For butanoic acid these are:

Most organic compounds are non–polar and hence tend to C4H8O2 molecular formula
be insoluble in water owing to the strong hydrogen bonds
between the water molecules. If however the functional C2H4O empirical formula
groups can hydrogen bond to the water (that is those that
hydrogen bond to themselves, plus those containing the Note that an alkyl group (CnH2n+1, like an alkane with one
>C=O group which can form hydrogen bonds to water), H removed) can be represented by R. hus alcohols (which
then the substance will be water soluble, as long as the contain the hydroxyl group —OH) can be represented as
hydrocarbon chain is relatively short. As the carbon chain ROH. Similarly the benzene ring can be represented as
increases there is a gradual decrease in the solubility as so that phenol (a benzene ring with an —OH attached) is
is the case with the alcohols. hus, ethanol, CH3CH2OH, represented as HO— .
is water miscible (mixes in all proportions), but hexan-1-
ol, CH3(CH2)5OH, dissolves only slightly in water. Some
functional groups interact with the water and hence
afect the pH of the resulting solution. Carboxylic acids, 10.1.4 Describe structural isomers as compounds
for example behave as weak acids and so reduce the pH. with the same molecular formula but with
Amines act as weak bases in a similar manner to ammonia different arrangements of atoms.
and so increase the pH. ©IBO 2007

Isomers are diferent compounds that have the same

10.1.3 Distinguish between empirical, molecular molecular formula. Diferent compounds have diferent
and structural formulas. physical properties (melting point, boiling point etc.).
©IBO 2007 hey may also have very diferent chemical properties
depending on the type of isomerism present. Isomers may
In organic chemistry it is particularly important to be divided into:
distinguish carefully between empirical formula,
molecular formula, structural formula and full structural
formula. he full structural formula (also referred to as

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 CHAPTER 10

Isomers

Structural Isomers Stereoisomers

Different bonding Different shapes
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Positional Hydrocarbon Functional Geometric Optical Isomers

Isomers Chain Isomers Group Isomers Isomers (Enantiomers)

Figure 1007 The relationship of different types of isomers

• structural isomers, in which the atoms are joined in

a diferent order so that they have diferent structural CH3 CH CH3
formulae.
CH3 CH2 CH2 CH3 CH3
and
Butane Methylpropane
• stereoisomers, in which the order that the atoms are
joined together is the same, but the molecules have Because of their nature, some functional groups will
a diferent arrangement of atoms in space and hence usually have isomers containing another functional
diferent three dimensional shapes. group. For example alcohols usually have an alkoxyalkane
that is isomeric to them, hence ethanol has an isomer
It is useful to subdivide structural isomers into positional methoxymethane:
isomers, hydrocarbon chain isomers and functional
CH3 CH2 OH CH3 O CH3
group isomers. Similarly stereoisomers can be divided
into geometrical isomers and optical isomers (also called Ethanol Methoxymethane
enantiomers) and these are dealt with in more detail later.
he relationship between the diferent types of isomerism Other common pairs of functional groups that display
is illustrated in Figure 1007. functional group isomerism with each other are:

Positional isomers have the same hydrocarbon skeleton Alkene and Cycloalkane
and the same functional group; it is just that the functional H5C2 C2H5 CH2
group is joined to a diferent part of the skeleton. A simple C C H2C CH2
example of this type of isomerism is propan–1–ol and
H H
propan–2–ol:
H2C CH2
CH CH CH OH CH3 CH CH3
3 2 2 CH2
OH
Propan-1-ol Propan-2-ol Hex-3-ene Cyclohexane

Hydrocarbon chain isomers have, as the name would Aldehyde and Ketone
imply, diferent hydrocarbon skeletons that the functional H
group is attached to. Butane and methylpropane illustrate O
H3C CH2 C
this type of isomerism: H3C C CH3
O

CH3 CH2 CH2 CH3

Propanal Propanone

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Carboxylic acid and Ester

O
O
H3C O C
H3C C OH H
Ethanoic Acid Methyl methanoate
ethoxide is obtained as a white solid if excess ethanol is
In the case of positional and hydrocarbon chain isomers evaporated.

cOre
the functional group, which usually dictates the reactivity
of the molecule, is unchanged therefore they have quite 2 C2H5OH (l) + 2 Na (s) 2C2H5O-Na+ (eth) + H2 (g)
similar chemical properties. With functional group
isomerism the change in the functional group can have Methoxymethane (at room temperature and pressure)
a profound efect on both the physical and chemical is a gas, since there is no hydrogen bonding, and it does
properties of the molecule. In the previous example not react with sodium because it has no hydroxyl group.
ethanol is a liquid (at room temperature and pressure) Similarly methyl methanoate is a sweet smelling liquid
that will react with sodium to release hydrogen. Sodium that forms neutral solutions, whereas ethanoic acid has a
sharp smell (vinegar) and forms acidic solutions.

TOK The importance of chemical models

The different types of formulas referred to in this chapter are certainly employed for different purposes. “Empirical”
means “by experiment” and that’s exactly what the empirical formula is – the result of a microanalysis experiment
in which all of the carbon in the compound is converted into carbon dioxide and all the hydrogen into water, so
the relative amounts of carbon, hydrogen and oxygen can be calculated, but on its own it is not of much further
use. Combine it however with some information about how heavy each molecule is and we can then deduce some
much more interesting information; how many atoms of each element are present in every molecule. That then
allows us to test our theories of chemical bonding to work out the structural formulae showing how atoms can join
together. Sometimes this can really stretch the mind and require creative thought, like Kekulé’s dream.

This question also started me thinking about the words “formula” and “model” – do they mean the same thing
and if not how do they differ? Both transfer information, but models (like the Bohr model of the atom) are also
used to help with our “understanding” (whatever exactly that is) of the world and maybe that is a facet we do not
seek in a formula. When I look, even at a full structural formula, I do not think that it helps my “understanding”, it
just conveys “information” about how the atoms are joined in the molecule and hence its probable shape. Now
that leads us back to “models”, though perhaps a slightly different use of the word – I’ll leave you to judge. We get
an even better idea of the shape using molecular models of different types. These are rather like different maps,
each show some things clearly and other things less well, “Ball and stick” models for example give a clear idea of
shape and what bonds are present, but the atoms always seem to be a long way apart. “Space filling” models more
accurately reflect bond lengths as well as the different sizes of the atoms involved. Actually the concept of atomic
size is an interesting one considering that we envisage the outer regions of an atom as just a cloud of electron
density. How do we know where it ends? It’s a bit like asking where does the Earth’s atmosphere end; it doesn’t
really it just sort of fades away to nothing.

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10.1.9 Deduce structural formulas for compounds 4 but Butyl

containing up to six carbon atoms with one
of the following functional groups: alcohol, 5 pent Pentyl
aldehyde, ketone, carboxylic acid and
halide. 6 hex Hexyl

Benzene ring benz Phenyl

10.1.10 Apply IUPAC rules for naming
compounds containing up to six carbon
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atoms with one of the following functional Figure 1008 The naming of hydrocarbon chains
groups: alcohol, aldehyde, ketone,
carboxylic acid and halide. Note that it pays to inspect the formula carefully as the
most obvious carbon chain is not always the longest one;
10.1.11 Identify the following functional groups CH3—CH(C2H5)—CH=CH2 has a principal chain 5
when present in structural formulas: amino carbons long, not 4 carbons long as shown below:
(NH2), benzene ring ( ), esters (RCOOR).
H
10.1.12 Identify primary, secondary and H3C C CH CH2
tertiary carbon atoms in alcohols and
halogenoalkanes. CH2
CH3
©IBO 2007
which is the same as

the IUPAC SYSTEM CH3

here is a systematic scheme for naming organic H3C CH CH CH2
CH2
compounds known as the IUPAC (International Union of
Pure and Applied Chemists) system, but many compounds
also have ‘trivial’ names used before the introduction of he preix ‘cyclo’ can also be added to indicate that the
this system, hence a large number of organic compounds carbon atoms are arranged in a ring. Hydrocarbon side
have two names. In this book IUPAC names will be used chains may be attached to this longest chain and they are
consistent with the names used in the IB syllabus. named in a similar manner. Another cyclic hydrocarbon
structure that is oten found in organic compounds is the
From the point of view of IUPAC naming, organic benzene ring, C6H6, which in condensed formulas may be
compounds are considered to comprise a hydrocarbon abbreviated to
‘backbone’ to which side chains and functional groups
are attached. he backbone is considered to be the longest If the compound is an alkane where no functional groups
continuous chain of carbon atoms in the molecule and are present, the ending ‘-ane’ is added to the stem. Hence:
this supplies the stem of the name. he irst six of these are CH2
given in Figure 1008: H2C
H3C CH2 CH3 CH2
H2C
No. of C atoms Stem Side chain CH2

1 meth Methyl Propane Cyclopentane

2 eth Ethyl CH3

3 prop Propyl H3C CH2 CH CH3

Methylbutane

Figure 1009

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 Organic chemistry

20.1 intrOductiOn (ahL)

20.1.1 Deduce structural formulas for compounds he functional groups present in the molecule are indicated
containing up to six carbon atoms with one by preixes or suixes attached to the stem. hese and
of the following functional groups: amine, a speciic example of each class of compound are given
amide, ester, nitrile. in Figure 1010. In some cases a preix is used if another
functional group is already providing the ending; these
20.1.2 Apply IUPAC rules for naming compounds alternatives are shown in brackets. here are also, in many
containing up to six carbon atoms with one cases, two ways of writing the functional group depending
of the following functional groups: amine, on whether a full structural formula or a condensed
amide, ester, nitrile. structural formula is being written. In formulas written
©IBO 2007

Name Functional group Preix/suix Example

Alkane None -ane CH4; methane

Alkene C=C -ene CH2=CH2; ethene

ahL
Alcohol —O—H or —OH -anol (or hydroxy-) CH3CH2OH; ethanol

O
Aldehyde
C H -anal CH3CHO; ethanal
or

—CHO

Ketone O -anone CH3COCH3; propanone

C or CO

O CH3COOH;
Carboxylic acid -anoic acid
C O H or COOH ethanoic acid
Halogenoalkane
Halogeno-
(chloro, bromo, or X (i.e. Cl, Br, I) CH3CH2Cl; chloroethane
(luoro-, chloro-, bromo-, or iodo-)
iodoalkane)
-ylamine
H
Amine CH3CH2NH2; ethylamine
N H or NH2 (or amino-)
O
Amide H -anamide CH3CONH2; ethanamide
C N
H or CONH2
O he naming of esters is covered in CH3—CO—O—CH3
Ester
R C OR’ or CO—O— section 20.4, Methyl ethanoate
CH3—CN
—C≡N -anenitrile
Nitrile Ethanenitrile
or-CN (or cyano-)
(cyanomethane)

Figure 1010 The naming of functional groups table

(Note that the shaded groups are only required by Higher Level students).

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this latter way, brackets are used to denote side chains, for the name ‘propanol’ is ambiguous as it could be referring
example methylbutane would be CH3CH(CH3)CH2CH3. to propan-1-ol or propan-2-ol.

he naming of esters is slightly diferent in that they Comprehensive IUPAC nomenclature is a very complex
are named as if they were salts of the carboxylic acid, as subject, but this brief summary should enable you to cope
explained in Section 20.4. with most of the compounds commonly encountered.

• If there is more than one functional group or side Organic compounds oten contain functional groups
chain present then a principal functional group bonded on to diferent types of carbon chains. hese can
deines the ending and the other functional groups oten be usefully distinguished using the terms primary,
and side chains are indicated as preixes, arranged in secondary and tertiary. Primary means that the carbon
alphabetical order: that the functional group is joined to is bonded to only
one other carbon atom, secondary means that it is bonded
e.g. HO—CH2—CH(CH3)—CHO is to two other carbon atoms and tertiary three other carbon
3-hydroxy-2-methylpropanal (“h” comes before “m”; atoms. his is illustrated in Figure 1011 where X represents
note CHO must be a terminal group and the COOH the functional group.
group is the same)

• A double or triple bond may be indicated by changing

X
the irst vowel in the ending.
ahL

e.g. HO–CH2–C(CH3)=CH–COOH is
C H
4-hydroxy-3-methylbut-2-enoic acid C H
• If there are a number of identical side chains or
Primary
substituents, then this is indicated by placing the
preixes di– (2), tri– (3), tetra– (4) immediately in
e.g. CH3CH2CH2 CH2Cl
front of the preix/suix.

e.g. Cl3C—COOH is trichloroethanoic acid

X
• If there is more than one possible position for the side
chain or functional group to attach itself, then this is
indicated by numbers identifying the carbon atoms
C C
in the principal chain. If there is a functional group C
which must occur at the end of a carbon chain (such as H
COOH), then the carbon in this group is taken as the
Secondary
irst carbon in the chain.

e.g. CH3—CH2—CHCl—COOH is 2–chlorobutanoic e.g. CH3CH2CHCl CH3

acid

In other cases, the numbering starts from the end of X

the chain which gives the lowest sum of numbers for
the substituents present.
C C
e.g. CH3—CH2—CHC—CH2—OH is
C
2–chlorobutan–1–ol, not 3–chlorobutan–4–ol C
Note that numbering of a side chain or functional group is Tertiary
ignored when there are no alternatives. For example as the
aldehyde CH3CHO is propanal, not propan-1-al, similarly e.g. (CH3)3CCl
(CH3)3CH is just methylpropane (the 2- numbering for
methyl can be ignored as it can only be in the 2-position; Figure 1011 Illustrating primary, secondary and tertiary
if it were in the 1-position it would be butane). However, structures

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6. Which one of the following formulae could represent

Exercise 20.1 more than one compound?

A C3H8
1. Which of the following is correct about the number B CH3CH=CH2
of bonds formed by atoms of diferent elements in C CH3(CH2)3CH3
organic compounds? D C4H10

Carbon Hydrogen Oxygen 7. How many isomers are there of the molecular formula
A 4 2 2 C3H7Cl?
B 4 1 2
C 4 1 3 A 2
D 3 2 3 B 3
C 4
2. he alcohols, methanol, ethanol, propanol, butanol D 8
etc., form a homologous series. his means that
they: 8. To which series of compounds does the molecule
belong?
A have similar chemical properties, but O
gradually changing physical properties. CH3 CH2 C CH3

ahL
B have similar physical properties, but
gradually changing chemical properties. A Ketone
C have the same molecular formula, but B Alcohol
diferent physical properties. C Carboxylic acid
D have similar physical properties and the D Aldehyde
same structural formula.
9. Which of the following is the structure of
hese structural formulae are required for questions 3 & 4: but–1–ylamine?

H3C CH2 CH3 A CH3—CH2—CH2—CH2—CH2—NH2

a B CH3—CH2—CH2—CH2—NH2
C CH3—CH2—CH2—CO—NH2
H3C CH2 CH2 CH2 CH3 D CH3—CH2—CH2—CH2—CO—NH2
B
10. What is the correct name of
H3C CH2 CH2 CH2 Br CH3CHClCH2CH2CHO?
c
A 2-chlorobutanal
H3C CH2 CH2 NH2 B 4-chlorobutanal
d C 2-chloropentanal
D 4-chloropentanal

3. Which one of the above compounds would have the 11. he molecular formulae of a group of closely related
lowest boiling point? molecules are given below.

4. Which one of the above compounds would be the

most soluble in water? CH3NO2; C2H5NO2; C3H7NO2; C4H9NO2; C5H11NO2

5. Which one of the following lists the alkanes in order a) What name is given to a group of compounds
of decreasing boiling point? related in this way?

A Octane, Methane, Butane, Ethane b) Write a general formula for this group of
B Methane, Ethane, Propane, Butane compounds.
C Hexane, Octane, Propane, Methane
D Hexane, Pentane, Propane, Ethane

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c) How would you expect the boiling points of 10.1.5 Deduce structural formulas for the
these compounds to change with increasing isomers of the non-cyclic alkanes up to C6.
numbers of carbon atoms? Explain.
10.1.6 Apply IUPAC rules for naming the isomers
d) Compared to alkanes of a similar molar mass, of the non-cyclic alkanes up to C6.
would you expect these compounds to be
i) more or less soluble in water. ©IBO 2007
ii) more or less volatile.
Explain your answers.

e) CH3NO2 can be reduced to CH3NH2 by Hydrocarbons are compounds containing only carbon
reacting it with hydrogen over a nickel and hydrogen. he simplest homologous series of this
catalyst. What product would you expect type is that comprising the straight chain alkanes. he
when C5H11NO2 was treated in the same irst six members of this series, along with their names and
way? On what do you base your prediction? structural formulae are given in Figure 1014.

12. Draw structural formulae of the following No. of Molecular Structural

compounds: Name
C atoms Formula formula
a) Pentane
ahL

b) 3–ethylhexane 1 CH4 Methane H

H C H
c) Bromoethane H

d) 2–methylbut–1–ene
e) 3.3–dichloro–2–methylbutanoic acid
2 C2H6 Ethane H H
H C C H
13. he structural formula of 1–methoxybutane is H H

CH3—O—CH2—CH2—CH2—CH3
3 C3H8 Propane H H H
H C C C H
Draw structural isomers of this compound that H H H

illustrate:

a) positional isomerism 4 C4H10 Butane H H H H

H C C C C H
H H H H

b) hydrocarbon chain isomerism

c) functional group isomerism 5 C5H12 Pentane H H H H H

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

14. Write abbreviated structural formulae and name

all the structural isomers of the compound with
molecular formula C6H14. 6 C6H14 Hexane H H H H H H
H C C C C C C H
H H H H H H

15. Name the following compounds:

CH3 C CH2
a) Figure 1014 The straight chain alkanes
CH3
he compounds shown in Figure 1014 are known as the
CH3 CH2 CH Cl straight chain alkanes because isomers of these compounds
b) exist in which the carbon atoms are not joined in a single
CH2 CH3
chain. he simplest example of such isomerism is butane
c) CH3—CHI—CH2—CH2—OH and methylpropane which both have the molecular
formula C4H10. Similarly three isomers exist with the
d) HO—C(CH3)2—CH2—CH2—COOH formula C5H12. he names and structural formulae of
these compounds are shown in Figure 1015 below (Note
that C6H14 has 5 isomers).

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c 4 h10 3. he number of oxygen molecules on the let must be

H
adjusted to balance the oxygen
H H H H H C H
H H Consider applying this to the complete combustion of
H C C C C H octane (C8H18), a major component of gasoline:
H C C C H
H H H H
H H H C8H18 + O2 CO2 + H2O
Butane

cOre
Methylpropane
1. here are 8 carbon atoms so these must form 8 carbon
c 5h12 dioxide molecules.
H H H H H
2. here are 18 hydrogen atoms so these must form 9
H C C C C C H water molecules.
H H H H H
3. here are now 25 oxygen atoms on the right hand side,
Pentane H
requiring 12½ O2 molecules.
H H C H
H H he inal equation is therefore:
H C H
H H H H C C C H
C8H18 + 12½ O2 8 CO2 + 9 H2O
H C C C C H H H
H C H his form is acceptable, but the ‘½’ can be eliminated by
H H H H doubling all the coeicients.
H
Methylbutane Dimethylpropane Gasoline and many other fuels very rarely burn in this
way. If the supply of air/oxygen is limited, as is the case
Figure 1015 Isomers of C4H10 and C5H12 in an automobile engine, then incomplete combustion
occurs, so some of the carbon in the fuel, rather than
forming carbon dioxide, is converted to carbon monoxide
10.2 aLkanes (CO, a colourless, odourless, highly toxic gas) or the
element carbon itself (hence black smoke). Note that the
10.2.1 Explain the low reactivity of alkanes hydrogen is still converted to water. hese products, along
in terms of bond enthalpies and bond with other minor products of hydrocarbon combustion
polarity. and the residue of the lead compounds still added to some
gasolines, are a major source of air pollution in large cities.
10.2.2 Describe, using equations, the complete Many countries now require the installation of catalytic
and incomplete combustion of alkanes. converters which ensure that the combustion process is
©IBO 2007 more nearly complete. For more details of these pollution
problems, refer to Option D.

he most familiar reaction of the alkanes is combustion. 10.2.3 Describe, using equations, the reactions
Like almost all organic compounds, the alkanes are of methane and ethane with chlorine and
lammable and oxidise when burnt in the air to form bromine.
carbon dioxide and water if suicient oxygen is present. he
combustion of organic compounds is a highly exothermic 10.2.4 Explain the reactions of methane and
process and is one of the most common sources of energy ethane with chlorine and bromine in terms
in society. Equations for these reactions oten involve quite of a free-radical mechanism.
large coeicients, but balancing them is easy provided the ©IBO 2007
following procedure is adopted:
Alkanes can also react with chlorine or bromine in a
1. All carbon atoms are converted to carbon dioxide substitution reaction, to give an initial product in which
ixing this coeicient one hydrogen atom is replaced by the halogen. Usually
these reactions are brought about by exposure to ultraviolet
2. All hydrogen atoms are converted to water, ixing a light or sunlight, though they will also occur without light
second coeicient

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 CHAPTER 10

TOK The importance of IUPAC names

Communicating what exactly we are talking about few cases it might be quicker (compare HOOC-COOH
quickly and effectively is important in any subject, with ethanedioic acid, 9:15 characters), but in most
hence names. It also depend on who you are talking cases the reverse would be true and complex ring
to. For example when you are talking to other people structures are really difficult to do in the middle of
in your class “Charlie” is an effective way to refer to a text! Nevertheless alanine is a lot simpler to write than
particular individual. It is however not very specific. 2-aminopropanoic acid and p-xylene is simpler than
cOre

If you said “Charlie” to your mother for example she 1.4-dimethylbenzene, which is probably why IUPAC
probably wouldn’t know who you were talking about. names have never really caught on with biochemists
To her “Charlie” is probably the name of the security and industrial chemists.
guard at the hospital where she works. You would
then have to go into a longer explanation – joined the An IUPAC equivalent with humans might be to have
school from Finland last term / has ginger hair / did a a system that looks at facial characteristics so you
solo in the school concert / father drives a Ferrari etc. can draw somebody from their name? For example:
It’s useful not to have to go through all of that each {gender / hair colour / hair length / eye colour / nose /
time you want to tell a friend about something that chin} - I’m sure my children used to have a game that
took place during the last lesson, so names have their was based on this idea – what was it called? Anyway,
uses and pitfalls. Chemistry has the same problems; on this system I might be {male-brown-neck length-
names that are unique and universal. For example brown-medium-bearded} - though it would be
in one research group TCP might be trichlorophenol strange to have to change your name if you altered
and in another it might be tetrachloropropyne. your hairstyle! The advantage is you now have
The IUPAC system tries to tidy this and goes one some idea what I look like, but it requires a lot more
step further because it should allow us to draw the writing than “John” and it’s hardly unique. How many
structure of an organic compound from its name. Is it characteristics would I have to list until my name was
worth it? Why don’t we just draw the structure? In a unique?

at very high temperatures. Taking ethane and chlorine as up but another formed) and termination which consumes
an example: radicals. As a result the initiation stage occurring once can
cause the propagation steps to occur many times before
CH3–CH3 (g) + Cl2 (g) CH3–CH2–Cl (g) + HCl (g) the radicals are consumed in a termination step. he
details of such a process are given below using the reaction
Note that the inorganic product is the hydrogen halide of methane with chlorine as an example.
(in the above case HCl) and not hydrogen (H2). hese
Cl Cl Cl + Cl
substitution reactions can replace more than one hydrogen,
so that some of the chloroethane produced above will react
with more chlorine to produce dichloroethanes. hese Figure 1016 - Initiation
substitutions also occur in a random manner so that the
product will be a mixture of both 1.1-dichloroethane and Cl + H CH3 Cl H + CH3
1.2-dichloroethane:
CH3 + Cl Cl CH3 Cl + Cl
C2H5Cl (g) + Cl2 (g) HCl (g) + C2H5Cl2 (g)
(both ClCH2CH2Cl and CH3CHCl2)
Figure 1017 - Propagation
Further substitution of hydrogen atoms by chlorine can
take place eventually yielding, with a large excess of
Cl + Cl Cl Cl
chlorine, hexachloroethane (C2Cl6)

he reaction of an alkane, such as methane, with a halogen Cl + CH3 CH3 Cl

is a free radical chain reaction. his process can be split
up into three distinct stages, initiation which produces
CH3 + CH3 CH3 CH3
the radicals (reactive species with unpaired electrons),
propagation which forms most of the product and in
which the radicals are reformed (that is one radical is used Figure 1018 - Termination

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 Organic chemistry

It is traces of this inal product, ethane that give a clue as hydrocarbons. he simplest compounds of this type
to the nature of the reaction mechanism. Note that the are the alkenes, which contain a carbon–carbon double
hydrogen atom (H•) does not occur at any stage in the bond. he alkynes, containing C≡C triple bonds, are also
mechanism. he mechanism of the reaction with ethane unsaturated hydrocarbons. he general formula for the
is very similar except that it involves the ethyl radical alkene homologous series is CnH2n (note that this is also
(CH3CH2•) rather than the methyl radical and traces the general formula of the cycloalkanes) and the structural
of butane (C4H10) are found in the product from the formulae and names of the simplest isomers of the irst
combination of these in a termination step. ive members of the series are given in Figure 1019.

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Bromine reacts in an almost identical manner to chlorine. hough double bonds are stronger than single bonds, they
Because of its brown colour the speed of reaction with are not twice as strong (C=C 612 kJ mol–1, C—C 348 kJ
bromine is easily followed and if a mixture of an alkane mol–1). his means that it is energetically favourable for a
and bromine is placed in sunlight the brown colour slowly double bond to be converted into two single bonds. he
fades, but there is no reaction in the dark. activation energy for these reactions is also relatively low,
owing to the high electron density in the double bond.
his means that alkenes are considerably more reactive
10.3 aLkenes than alkanes and are an important starting point in the
synthesis of other organic compounds. As a result alkenes,
10.1.7 Deduce structural formulas for the usually formed by the cracking of fractions of petroleum,
isomers of the straight-chain alkenes up are very important intermediates in the economically
to C6. important petrochemicals industry.

10.1.8 Apply IUPAC rules for naming the isomers

of the straight-chain alkenes up to C6.

©IBO 2007

he alkanes are said to be saturated hydrocarbons

because they contain only single carbon-carbon bonds,
those with multiple bonds are called unsaturated

No. of C atoms Molecular formula Name Structural formula

H H
C C
2 C2H4 Ethene
H H

H H H
C C C H
3 C3H6 Propene
H H

H H H H
C C C C H
4 C4H8 But-1-ene
H H H

H H H H H
C C C C C H
5 C5H10 Pent-1-ene
H H H H

H H H H H H
C C C C C C H
6 C6H12 Hex-1-ene
H H H H H

Figure 1019 Straight chain terminal alkenes

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 CHAPTER 10

10.3.1 Describe, using equations, the reactions of the basis of the conversion of vegetable oils, which contain
alkenes with hydrogen and halogens. a number of C=C double bonds, into margarine, which
has fewer double bonds and hence a higher melting
10.3.2 Describe, using equations, the reactions of point.
symmetrical alkenes with hydrogen halides
and water. With water (in the form of superheated steam), the addition
reaction is reversible. At a temperature of ~ 300°C and a
10.3.3 Distinguish between alkanes and alkenes high pressure (~7 atm) the equilibrium shown is driven to
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using bromine water. the right (Le Chatelier’s principle) and this provides the
basis for the industrial manufacture of ethanol. Ethanol is
10.3.4 Outline the polymerization of alkenes. used in large quantities by industry both as a solvent and as
an intermediate in the manufacture of other compounds,
10.3.5 Outline the economic importance of the hence this is a very commercially important process. At
reactions of alkenes. atmospheric pressure the equilibrium lies to the let and
©IBO 2007 alkenes are formed by the dehydration of alcohols. he
reaction in both directions is catalysed by either acids
A reaction in which the double bond of an alkene is (usually H2SO4 or H3PO4) or heated aluminium oxide,
converted to a single bond and two new bonds are formed Al2O3.
to the species it reacts with is known as an addition
reaction and they are typical of alkenes and alkynes. A
C C + H2O C C
number of important addition reactions are illustrated in
Figure 1020: H OH

Polymers are long chain molecules that are formed by the

C C + Br 2 C C joining together of a large number of repeating units, called
Br Br monomers, by a process of polymerisation. Polymers,
can be made artiicially and these are usually referred to
as plastics, but there are also a great number of naturally
occurring polymers.

C C + HCl C C One type of polymerisation reaction is known as addition

polymerisation. In this the monomers contain double
H Cl bonds and in the addition reaction new bonds (shown
coloured below) form between these monomer units. he
simplest polymerisation reaction of this type is that of
ethene when heated under pressure with a catalyst to form
Nickel polyethene, commonly known as ‘polythene’.
C C + H2 C C
Catalyst H H H H H H
H H C C C C C C
H H H H H H
Figure 1020 Common addition reactions
Ethene monomers
he usual test for the presence of a carbon–carbon double
or triple bond is to add bromine water to the compound.
If a double or triple bond is present, the bromine water
changes colour from yellow–brown to colourless. his
reaction, shown in Figure 1020a, which also occurs with
H H H H H H
chlorine and iodine, takes place spontaneously at room
temperature and pressure. A similar spontaneous reaction C C C C C C
occurs between alkenes and hydrogen halides such as H H H H H H
hydrogen chloride and this is shown in Figure 1020b. With
hydrogen, the activation energy is slightly higher, but if a Polyethene polymer
gaseous mixture of an alkene and hydrogen is passed over
a heated nickel catalyst, an addition reaction to form an Figure 1021 The addition polymerisation of ethene to
alkane occurs as shown in Figure 1020c. his reaction is form polyethene

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 Organic chemistry

his may also be represented by the equation below in All of these polymers are produced in very high tonnages
which the repeating unit is shown in square brackets. for the manufacture of a wide variety of products, hence
these polymerisation reactions are economically very
n CH2=CH2 [–CH2–CH2–]n important. Polymers are discussed in greater detail in
the Chemistry in Industry and Technology Option,
Two other common addition polymers are Chapter 14.
poly(chloroethene), better known as PVC (short for
its old name of PolyVinyl Chloride), formed by the

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polymerisation of chloroethene
Exercise 10.3

n CH2=CHCl [–CH2—CHCl–]n
1. It is found that natural gas from a particular source
decolourises bromine water. From this it can be
concluded that

H Cl H Cl H Cl A the gas contains some unsaturated

C C C C C C hydrocarbons.
H H H H H H B the gas contains only unsaturated
hydrocarbons.
C the gas is an alkene.
Chloroethene monomers
D the gas contains some saturated
hydrocarbons.

2. What is the formula of the organic product of the

reaction between propene and bromine?
H Cl H Cl H Cl
A Br—CH2—CH=CH2
C C C C C C
B CH3—CH2—CHBr2
H H H H H H C CH3—CHBr—CH2Br
D Br—CH2—CBr=CH2

Figure 1022 Polymerisation of chloroethene to form 3. Which one of the following molecular formulae does
poly(chloroethene) not represent an alkane?

and polypropene, formed by the polymerisation of propene: A C3H6

B C6H14
n CH2=CHCH3 [–CH2—CHCH3–]n C C8H18
H H CH3 H CH3 D C12H26
CH3
C C C C C C
H H H H H H 4. When propane underoes complete combustion in air,
for each mole of propane burnt, how many moles of
oxygen are consumed and how many moles of water
Propene monomers
are formed?

Moles of oxygen Moles of water

A 3 8
H CH3 H CH3 H CH3 B 5 8
C 3 4
C C C C C C
D 5 4
H H H H H H

Polypropene polymer

Figure 1023 Polymerisation of propene to form

polypropene

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 CHAPTER 10

5. Which one of the following would you not expect to 8. a) Name and write the structural formula of the
ind in the exhaust gases of a normal car? organic product formed when ethene reacts
with hydrogen bromide.
A Nitrogen
B Hydrogen b) To what class of reactions does this belong?
C Water vapour
D Carbon monoxide c) What reagents and conditions are required
for the conversion shown below?
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6. A free radical is any chemical species that:

CH3—CH=CH2 CH3—CH2—CH3
A is very reactive.
B results from the breaking of a covalent d) What test could you carry out on both the
bond. starting material and the product that would
C is formed by the action of UV light on a show that this reaction had occurred?
molecule.
D contains unpaired electrons. e) What conditions are required for an alkene to
react with steam?
7. a) Draw the structural formula of pent–2–ene.
f) Name the alkene CH3—CH=CH—CH3.
b) Write a balanced chemical equation for the
complete combustion of pent–2–ene. g) Write the structural formula of the product
formed when this alkene reacts with steam.
c) What is produced during the reaction, other
than the chemical products? 9. Most plastics are polymers formed from monomers
produced from crude oil.
d) If the supply of oxygen was reduced, what
other chemical product might result from the a) Explain what is meant by the terms in italics.
combustion?
b) Polythene, which may be produced by
e) Give one reason why the production of this heating ethene (CH2=CH2) at a very
substance is undesirable. high pressure, can be represented by the
formula [–CH2CH2–]n. Give the equivalent
f) Draw a structural isomer, other than formulae for P.V.C. (polyvinyl chloride;
pent-1-ene, and name the compound. polychloroethene) and also give the formula
of the monomer that it is made from.

c) Propene too can be polymerised to form the

polymer “Polypropylene”, used in ropes and
knitwear. Write the structural formula of a
section of “Polypropylene” containing three
propene units.

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 Organic chemistry

10.4 aLcOhOLs 10.4.2 Describe, using equations, the oxidation

reactions of alcohols.
he simplest group of organic compounds containing 10.4.3 Determine the products formed by the
oxygen are the alcohols, which contain the hydroxyl oxidation of primary and secondary
(—OH) group. he best known of this group of compounds alcohols.
is ethanol (C2H5OH), the ‘alcohol’ in alcoholic drinks. For ©IBO 2007
the production of alcoholic drinks ethanol is formed by

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the fermentation of sugars such as glucose, a slow process Alcohols may be subdivided into three classes according to
requiring warm, anaerobic (meaning in the absence of the number of carbon atoms attached to the same carbon
oxygen) conditions: atom as the the hydroxyl group, -OH, group:

C6H12O6 (aq) 2 C2H5OH (aq) + 2 CO2 (g) H

C C O H
his reaction is brought about by enzymes (biochemical
catalysts) produced by yeast (a microorganism) that H (One C atom
grows in the fermenting liquid. his produces only ~15% Primary on –OH carbon)
ethanol, but pure ethanol may be produced by distillation.
Ethanol for industrial purposes is usually produced by the
H
addition reaction of ethene with steam over a phosphoric
acid catalyst at high pressure. If an alcohol is passed over C C O H
the acid catalyst or a heated aluminium oxide catalyst at
C (Two C atoms
atmospheric pressure it is dehydrated to an alkene:
Secondary on –OH carbon)
H3PO4 or Al2O3
C2H4 (g) + H2O (g) C2H5OH (g)
catalyst
C
In the laboratory the dehydration reaction is more usually
C C O H
performed by heating the alcohol with a dehydrating agent
such as concentrated sulfuric or phosphoric acid. Using C (Three C atoms
ethanol as the example: Tertiary on –OH carbon)
excess H2SO4 ≈ 170 oC
C2H5OH (l) C2H4 (g) + H2O (l) Figure 1024 Groups of alcohols (page 383)

he mechanism of this dehydration is discussed in more he hydrogen atoms attached to the same carbon as the —
detail later on. OH group are readily oxidised and so these three classes
of alcohols behave in rather diferent ways when they
react with oxidising agents such as acidiied potassium
10.4.1 Describe, using equations, the complete dichromate(VI). Tertiary alcohols do not have any reactive
combustion of alcohols. hydrogen atoms and are not readily oxidised. Secondary
alcohols have one reactive hydrogen and so undergo one
©IBO 2007 stage of oxidation to yield ketones. Primary alcohols have
two readily oxidised hydrogen atoms and so the oxidation
Alcohols, like most other organic compounds, burn readily occurs in two stages producing irstly aldehydes and then,
in air to form carbon dioxide and water, hence they are on further oxidation, carboxylic acids.his is summarised
useful fuels. An equation for this reaction is given below, in Figure 1025.
using ethanol as the example:
Both aldehydes and alcohols are polar, however, alcohols
C2H5OH (l) + 3 O2 (g) 2 CO2 (g) + 3 H2O (g) have higher boiling points as these experience hydrogen
bonding in addition to dipole-dipole forces. hus, in
As with all such combustion reactions, carbon monoxide practice to obtain the aldehyde, the alcohol is added to the
or even carbon can be produced if the supply of air boiling oxidising agent so that as soon as the more volatile
is restricted, hydrogen however is never a product of aldehyde is formed, it distils of (see Figure 1026a) before
combustion. it can be further oxidised. In order to obtain the carboxylic
acid a more concentrated solution of the oxidising agent
is used and the mixture is reluxed so that the aldehyde

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 CHAPTER 10

Tertiary
Alcohol C
C C O H Not easily oxidised
C

Secondary
Alcohol H Ketone
C C O H C C O No further oxidation
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C C

Primary
Alcohol H Aldehyde Carboxylic acid
C C O H C C O C C O
H H O H

Figure 1025 The oxidation of alcohols

cannot escape further oxidation (see Figure 11.8b). square brackets. Hence the oxidation of ethanol to its inal
Heating under relux allows us to carry out a reaction at product, ethanoic acid, can be written as:
the boiling point of the solvent without any loss of the
solvent. he vapour from the boiling solvent turns back to CH3—CH2—OH + 2 [O]
a liquid in the vertical condenser and drips back into the ethanol Cr2O72–/H+
lask (see Figure 1026b).
Intermediate stage
If dichromate(VI) is used as the oxidising agent, then CH3—CHO + H2O + [O]
the orange dichromate(VI) ion (Cr2O72–) undergoes a ethanal
colour change to the green chromium(III) ion (Cr3+). he CH3—COOH + H2O
balanced equation is rather complex (though writing one ethanoic acid
is a good test of understanding of half equations) and so
in such reactions the convention has arisen to indicate Other oxidising agents, such as the permanganate(VII) ion
the oxygen from the oxidising agent as an oxygen atom in in acidiied solution, may also be used, but care must be

(a) distillation (b) reflux

Water out
Alcohol

Water out Water in

Water in

Aldehyde
Reaction mixture
Reaction mixture Heat

Heat
Figure 1026 Apparatus for distillation and reflux

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 Organic chemistry

taken as this more powerful reagent can also oxidise other

functional groups (e.g. >C=C<). Ethanoic acid is also 10.5
produced by bacterial oxidation when alcoholic drinks
are let exposed to the air, producing vinegar. Carboxylic haLOgenOaLkanes
acids, as their name suggests, act as weak acids in aqueous
solution. 10.5.1 Describe, using equations, the
substitution reactions of halogenoalkanes
O O with sodium hydroxide.

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R C R C + H+
– (aq)
O H O 10.5.2 Explain the substitution reactions of
(aq) (aq)
halogenoalkanes with sodium hydroxide
in terms of SN1 and SN2 mechanisms.
FIgure 1027
©IBO2007

Exercise 10.4 In halogenoalkanes, the polarity of the carbon–halogen

bond means that the carbon atom carries a slight positive
1. When ethanol is oxidised to ethanoic acid by heating charge. Because of this it is susceptible to attack by
with acidiied potassium dichromate(VI): nucleophiles (reagents that attack at a centre of positive
charge by donating an electron pair), and this means that
A the ethanol is reduced and the colour halogenoalkanes are considerably more reactive than the
changes from orange to green. alkanes, undergoing nucleophilic substitution reactions,
B the ethanol is reduced and the colour in which the halogen atom is readily replaced by other
changes from green to orange. atoms or groups of atoms. For example when they are
C the ethanol is oxidised and the colour warmed with an aqueous alkali halogenoalkanes undergo
changes from green to orange. hydrolysis to form an alcohol:
D the ethanol is oxidised and the colour
changes from orange to green. R—X (l) + OH– (aq) R—OH (aq) + X– (aq)

2. When propan-1-ol is burnt in a plentiful supply of Warming 1-bromobutane with aqueous sodium hydroxide
air, how many molecules of oxygen are consumed for will therefore produce butan-1-ol:
each molecule of propanol?
C4H9—Br (l) + OH– (aq) C4H9—OH (aq) + Br– (aq)
A 4½
B 5 here are two distinct mechanisms by which nucleophilic
C 9 substitution reactions occur. A mechanism is a model
D 10 of how a reaction occurs through series of steps). he
irst of these is known as SN1. In this mechanism there
3. Propan-1-ol can be oxidised to propanoic acid in the is a slow, rate determining, unimolecular (hence the 1),
same way as ethanol to ethanoic acid. heterolytic ission of the carbon–halogen bond to yield
an intermediate electron deicient carbocation. his then
a) What reagents would you use for this reacts rapidly with the hydroxide ion to yield the inal
oxidation? product.
b) What colour change would you expect to
observe during the reaction?
c) How would you expect the product to react C X C+ + X- (slow)
with sodium carbonate? Carbocation
intermediate

-
C+ + OH C OH (fast)

Figure 1028 Nucleophilic substitution by an SN1

mechanism

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 CHAPTER 10

Experimentally, the rate expression for this reaction is With primary halogenoalkanes (for example
found to be: CH3CH2CH2CH2Cl) reaction with nucleophiles, such as
the hydroxide ion, usually occurs by the SN2 mechanism,
rate = k •[R—X] whereas with tertiary halogenoalkanes (for example
(CH3)3CCl) it usually occurs by the SN1 mechanism. With
that is it is irst order with respect to halogenoalkane and secondary halogenoalkanes (such as CH3CH2CHClCH3)
independent of (zero order in) the concentration of the both mechanisms can occur.
hydroxide ion.
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he second mechanism is known as SN2. In this Exercise 10.5

mechanism, the bimolecular (hence the 2) attack of the
hydroxide ion on the halogenoalkane molecule is rate
determining. he reaction passes through a transition 1. When 2-iodopropane (CH3CHICH3) is warmed with
state (or activated complex) in which the bond to the aqueous potassium hydroxide the major organic
hydroxide ion is starting to form at the same time as the product is:
bond to the halogen breaks, hence the substitution occurs
in one concerted step: A CH3COCH3
B CH3CH2CH2I
C CH3CH2CH2OH
–
OH C X D CH3CH(OH)CH3

2. Which one of the following compounds would be

most likely to react with aqueous sodium hydroxide
by an SN2 mechanism?
–

[
HO C X

Transition state
] A
B
C
D
CH3CH2CHBrCH2CH3
CH3CH2CH2CH2CH2Br
CH3C(CH3)BrCH2CH3
CH3CH2CH2CHBrCH3

3. Which one of the following is not true about a reaction

between an aqueous alkali and a halogenoalkane that
– occurs by an SN1 mechanism?
HO C + X

A he product will be an alcohol

Figure 1029 Nucleophilic substitution by a sn2 B he hydroxide ion bonds to the carbon
mechanism at the same time as the halogen breaks
free
Reactions that occur by this mechanism are found to C he reaction occurs through the
be irst order with respect to both [RX] & [OH], hence formation of a carbocation intermediate.
second order overall: D he mechanism involves the heterolytic
ission of the carbon-halogen bond.
rate = k[R-X]1[OH]1
4. Write a balanced equation for the reaction between
Like alcohols, halogenoalkanes can be divided into iodoethane and aqueous sodium hydroxide, then
primary, secondary and tertiary according to the number describe the mechanism of the reaction indicating
of groups bonded to the same carbon as the halogen: the movements of the valence electrons.
H H C
5. Write the mechanism for the alkaline hydrolysis
C C X C C X C C X of 3-chloro-3-ethylpentane and use this to explain
the meaning of the terms heterolyic ission and
H C C
carbocation intermediate.
Primary Secondary Tertiary
Figure 1030 Classes of halogenoalkanes

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 Organic chemistry

It is also important to know the conditions required to

10.6 reactiOn bring these reactions about and this can be found either
from the relevant sections of this chapter or from the
pathways summary table at the end of this section.

10.6.1 Deduce reaction pathways given the Another example of a conversion that cannot be directly
starting materials and the product. carried out is be the preparation of butanone from but-
2-ene. In the scheme in Figure 1031 the only reaction to

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©IBO2007 produce a ketone is the oxidation of an alcohol. In fact it
must be a secondary alcohol, as a primary alcohol gives an
Oten in organic chemistry the desired product cannot be aldehyde then a carboxylic acid. Butanone must therefore
produced from the available starting material in a single be produced by the oxidation of butan-2-ol. his reaction
step. In these cases the reaction must be carried out in a can be brought about by heating the alcohol with acidiied
number of steps, referred to as the reaction pathway. For potassium dichromate(VI):
example if you wanted to convert 1-iodopropane into Cr2O72-/H+
propanal you could not achieve this in a single step, so you CH3—CH2—CH(OH)—CH3 (aq) + [O]
must consider what substances can be easily converted to CH3—CH2—CO—CH3 (aq) + H2O (l)
aldehydes (alcohols can) and whether you can form such a
compound directly from the available starting material (in he scheme in Figure 1031 shows that it is possible to
this case “yes”; if the answer is “no” then the pathway would convert an alkene to an alcohol. his can be brought about
involve more than 2 steps. he conversion can therefore by reacting the alkene with water in the presence of an
be brought about by irstly hydrolysing 1-iodopropane to acid catalyst, so that the reaction with but-2-ene will be:
propan-1-ol and then oxidising this to propanal: H+ cat
CH3—CH=CH—CH3 (g) + H2O (l)
CH3—CH2—CH2—I + OH– CH3—CH2—CH(OH)—CH3 (aq)
CH3—CH2—CH2—OH + I–
Note that it is important to use but-2-ene as but-1-ene could
CH3—CH2—CH2—OH + [O] also produce some of the primary alcohol (butan-1-ol),
CH3—CH2—CHO + H2O which would oxidise to the aldehyde, not the ketone.

alkane dihalogenoalkane trihalogenoalkane

tetrahalogenoalkane

halogenoalkane alkene poly(alkene)

alcohol aldehyde carboxylic acid

M = mechanism required

ketone
Figure 1031 Standard Level Reaction Pathways

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 CHAPTER 10

M M
alkene halogenoalkane nitrile

alcohol amine

ester carboxylic acid amide

M = mechanism required
ahL

Figure 1032 Higher Level Reaction Pathways

higher LeVeL Exercise 10.5

(* indicates hL question)
20.5 reactiOn
1. Which one of the following would be a suitable
pathways (ahL) intermediate in the conversion of methane to
methanol?
20.5.1 Deduce reaction pathways given the
starting materials and the product. A CH3Cl
B CH2Cl2
©IBO2007 C CHCl3
D CCl4
An example of a more advanced conversion of this type
would be the formation of ethylamine from ethene. 2. An alkene can be converted to a ketone via
Here the alkene could be converted to a halogenoalkane,
which could then be converted to an amine, (refer to A an aldehyde.
Figure 1032) B an alcohol.
C a halogenoalkane.
CH2=CH2 (g) + HBr (g) CH3—CH2—Br (g) D an alkane.

CH3—CH2—Br (l) + NH3 (aq) 3. Which one of the following cannot be produced by
CH3—CH2—NH2 (aq) + HBr (aq) the oxidation of an alcohol?

Again the conditions required to bring these reactions A An aldehyde.

about and this can be found either from the relevant B A ketone.
sections of this chapter or from the summary table C A carboxylic acid.
provided. D An alkane.

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 Organic chemistry

4*. Which one two compounds can react to form an

amide? higher LeVeL
A An alcohol and a carboxylic acid.
B An amine and an alcohol. 20.2 nucLeOphiLic
C A halogenoalkane and an amine.
D An amine and a carboxylic acid. suBstitutiOn
5*. Which of the following reactions does not require a reactiOns (ahL)
catalyst?
20.2.1 Explain why the hydroxide ion is a better
A A nitrile reacting with hydrogen nucleophile than water.
B An alcohol reacting with a carboxylic
acid 20.2.2 Describe and explain how the rate
C A halogenoalkane reacting with aqueous of nucleophilic substitution in
sodium hydroxide halogenoalkanes by the hydroxide ion
D An alkene reacting with water. depends on the identity of the halogen.

6. Indicate by means of balanced equations how you 20.2.3 Describe and explain how the rate
could convert 2-chlorobutane to butanone. Give the of nucleophilic substitution in

ahL
reagents and conditions for the reactions that you halogenoalkanes by the hydroxide ion
give. depends on whether the halogenoalkane
is primary, secondary or tertiary.
7*. Given just ethanol, how could you produce an
ester? Name the ester and outline the reagents and ©IBO2007
conditions required for all of the reactions you
describe.
he reaction of halogenoalkanes with the hydroxide
ion is just one example of a class of reactions known as
nucleophilic substitution reactions. As outlined above
these can occur by two diferent mechanisms, SN1 and SN2.
In the SN1 mechanism, the slow heterolytic ission of the
carbon-halogen bond to form a carbocation intermediate
is the rate determining step. he intermediate then reacts
rapidly with the nucleophile (Nu–) to form the inal
product. Note that the intermediate has a inite existence
and occurs at a potential energy minimum on Figure
1033.

Intermediate
Energy

R3C+

Reactants
R3C-X

Products
R3C-X---Nu

Extent of reaction

Figure 1033 Energy profile of a SN1 reaction

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 CHAPTER 10

In the SN2 mechanism the breaking of the carbon-halogen Tertiary halogenoalkanes (R3C—X) usually react by
bond occurs simultaneously with the formation of the new an SN1 mechanism, whereas primary halogenoalkanes
bond to the nucleophile. he point at which both are half (RCH2—X) usually react by an SN2 mechanism. his is a
completed is known as the transition state and it occurs at result of a number of factors:
a potential energy maximum on the energy level diagram
in Figure 1034. • Tertiary carbocations are relatively stable because of
the inductive efect of the alkyl groups, which reduces
Transition state the charge on the central carbon, so stabilising the
carbocation intermediate required for SN1.
C -- X: ½ broken
Ea { C -- Nu: ½ made • he change from tetrahedral to trigonal planar geometry
when the carbocation is formed increases the bond
Energy

angle from 109o to 120o. In tertiary halogenoalkanes

CH3CH2X this allows the alkyl groups to move further apart, so
stabilising the carbocation by reducing steric stress.
CH3CH2Nu
• In the SN2 mechanism, the nucleophile usually attacks
the central carbon from the direction opposite to the
Progress of reaction halogen. In tertiary compounds bulky alkyl groups
hinder such an attack.
ahL

Figure 1034 Energy profile of a SN2 reaction Secondary halogenoalkanes (R2CH—X) can react by
either or both mechanisms. Because SN1 reactions
he rate at which these reactions occur depends on the generally occur faster than SN2 reactions it is found that,
nature of both the nucleophile and the halogenoalkanes. all other factors being equal, the rate of hydrolysis of
For example some species are described as being stronger halogenoalkanes decreases in the order
nucleophiles because they more readily attack a carbon with
a partial positive charge. he hydroxide ion, for example, tertiary > secondary > primary.
is a stronger nucleophile than the water molecule because
it is negatively charged and hence attracted to the partial Note that halogenated aromatic compounds, in which
positive charge on the carbon attached to the halogen. As the halogen is bonded directly on to the benzene ring, are
a result SN2 hydrolysis reactions occur far more rapidly in much less reactive than other halogenoalkanes. he main
aqueous alkali than in neutral solution. reasons for this are:

he nature of the halogen also afects the rate of reaction. • the carbon-halogen bond is stronger and more diicult
here are two factors. Firstly, as the halogen changes from to break because one of the lone electron pairs on the
chlorine to iodine, the polarity of the carbon–halogen halogen atom interacts with the delocalised σ-bond
bond decreases and this would be expected to decrease of the benzene ring giving the carbon-halogen bond
the rate of reaction going from chlorine to iodine because partial double bond characteristics.
the partial positive charge on the carbon would become
smaller. Secondly, the strength of the carbon–halogen bond • attack from the opposite side to the carbon-halogen
decreases going from chlorine to iodine and it would be bond is blocked by the electron rich benzene ring.
expected to have the opposite efect. In practice it is found
that the rate of hydrolysis is greater for iodoalkanes than it • the partial charge on the carbon bonded to the halogen
is for chloroalkanes, implying that the bond strength is the is reduced because of adjustments in the mobile
dominant factor: see Figure 1035. electrons of the delocalised σ-bond.

C—Cl C—Br C—I

Decreasing polarity of C—X bond

Decreasing strength of C—X bond
Increasing rate of reaction

Figure 1035 Effect of the halogen on the rate of

nucleophilic substitution

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 Organic chemistry

20.2.4 Describe, using equations, the substitution

reactions of halogenoalkanes with
–
ammonia and potassium cyanide. NC C X

20.2.5 Explain the reactions of primary

halogenoalkanes with ammonia and
potassium cyanide in terms of the SN2
–

[ ]
mechanism.
NC C X
20.2.6 Describe, using equations, the reduction
of nitriles using hydrogen and a nickel
catalyst. Transition state
©IBO2007

–
Besides the hydroxide ion, a variety of other molecules NC C + X
and ions can behave as nucleophiles and participate in
nucleophilic substitution reactions with halogenoalkanes.
Two examples of these are the reaction with ammonia to Figure 1037 The SN2 mechanism for the formation of a
form a primary amine and reaction with the cyanide ion nitrile from a halogenoalkane

ahL
to form a nitrile:
In forming this product a new carbon-carbon bond has
R—X (l) + NH3 (l) R—NH2 (l) + HX (l) been formed and hence it is a useful way to lengthen the
hydrocarbon chain of a molecule. he triple bond in the
With a primary halogenoalkane this will occur by an SN2 nitrile may be readily reduced, using hydrogen and a nickel
mechanism as shown in Figure 1036. catalyst to form a primary amine, but note that this amine
contains one more carbon atom than the one formed by
direct reaction with ammonia.

H3N C X R—C≡N (l) + 2 H2 (g) R—CH2—NH2 (l)

Exercise 20.2

[
H3N C X

Transition state
] 1. When a halogenoalkane reacts with ammonia, the
product is:

A a nitrile
B an amine
C a carboxylic acid
–
H+ + H2N C + X D an amide

2. Which one of the following isomers would hydrolyse

Figure 1036 The SN2 mechanism for the formation of a the most rapidly with aqueous sodium hydroxide?
primary amine from a halogenoalkane
A CH3—CH(CH3)—CH2—Br
Note that the product above is the cation formed from the B (CH3)3C—Br
amine and it must lose a hydrogen ion to form the amine C CH3—CH2—CH2—CH2—Br
itself. Similarly the reaction of a primary halogenoalkane D CH3—CHBr—CH2—CH3
with the cyanide ion to form a nitrile will occur by an SN2
mechanism as shown in Figure 1037. 3. Which one of the following does not undergo
a nucleophilic substitution reaction with
R—X (l) + C≡N– (aq) R—C≡N (l) + X– (aq) iodomethane?

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 CHAPTER 10

A Ammonia When a bromoalkane is warmed with dilute aqueous

B Water alkali it undergoes a substitution reaction to produce the
C Bromide corresponding alcohol. If however it is added to a hot,
D Hydroxide concentrated solution of an alkali in ethanol it undergoes
an elimination reaction to form an alkene as shown in
4. a) Write a balanced equation for the conversion Figure 1038.
of 1-chlorobutane to but-1-ylamine.
In the case of the elimination reaction, the hydroxide ion
b) What mechanism would this occur by? reacts with the ethanol to produce the ethoxide ion as
c) Draw this mechanism and use it to explain follows:
what is meant by the terms nucleophile and a
transition state. C2H5OH + OH– C2H5O– + H2O
d) Would you expect the reaction using
1-bromobutane to be more rapid or less his is a stronger base and weaker nucleophile than the
rapid? Explain your reasoning. hydroxide ion and so favours the elimination reaction,
as does the higher temperature and concentration. he
5. a) Draw the structural formula of ethanenitrile ethoxide ion acts as a base and removes the hydrogen ion
and give the hybridisation of the two carbon from the carbon next to the halogen as shown in Figure
atoms involved. 1039.
ahL

b) Write a balanced equation for the formation H H

of this compound from bromomethane and –
C2H5O H C C Br
draw the mechanism for this reaction so as to
show the movement of electrons. H H
c) Ethanenitrile will react with hydrogen
under suitable conditions. Write a balanced
H H
equation for this reaction, naming both the
C2H5O H C C Br -
catalyst required and the product.
H H

Figure 1039 Mechanism of the elimination reaction of a

20.3 eLiminatiOn bromoalkane

reactiOns (ahL) he overall reaction is therefore the elimination of

hydrogen bromide from the bromoalkane. Note that if
the halogen is in the middle, rather than at the end of
20.3.1 Describe, using equations, the the hydrocarbon chain then the elimination can occur in
elimination of HBr from bromoalkanes. more than one direction, hence a mixture of products may
result. Hence, as shown in Figure 1040 below, two diferent
20.3.2 Describe and explain the mechanism alkenes are produced when 2-bromobutane is heated with
for the elimination of HBr from alcoholic solution of potassium hydroxide:
bromoalkanes.

©IBO2007

Conc. alcoholic OH-at ~100˚C C2H4 + H+ + Br- (elimination)

C2H5Br

Dilute aqueous OH - at ~60˚C C2H5OH + Br- (substitution)

Figure 1038 The competition of elimination and substitution reactions in bromoalkanes

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 Organic chemistry

Exercise 20.3 20.4 cOndensatiOn

reactiOns (ahL)
1. When 1-bromobutane is added to the following
solutions of potassium hydroxide, which would give 20.4.1 Describe, using equations, the reactions
the greatest yield of but-1-ene? of alcohols with carboxylic acids to form
esters, and state the uses of esters.
Solvent Concentration Temperature
©IBO2007
A Ethanol 5 mol dm-3 70˚C

B Ethanol 0.5 mol dm-3 40˚C When alcohols are heated with carboxylic acids in the
presence of concentrated sulfuric acid, they produce sweet
C Water 5 mol dm-3 40˚C smelling compounds called esters. Because of their aroma
and taste, esters are oten incorporated into artiicial
D Water 0.5 mol dm-3 70˚C perfumes and lavours. hey are also used as solvents and
plasticisers. A simple reaction of this type is that of ethanol
with ethanoic acid to form ethyl ethanoate:
2. In the elimination reaction of 1-bromoethane to
produce ethene, the hydroxide ion acts as: CH3 CO OH + CH3 CH2 OH

ahL
ethanoic acid ethanol
A a nucleophile.
H2 SO 4
B an oxidising agent.
C a reducing agent. catalyst
D a base.
CH3 CO O CH2 CH3 + H2O
3. When 3-bromopentane undergoes an elimination
reaction the product will be In these reactions, known as esteriication reactions, the
small amount of sulfuric acid has two functions. Firstly,
A pent-1-ene only. and most importantly, the hydrogen ions act as a catalyst to
B pent-2-ene only. increase the rate of the reaction and secondly it reacts with
C a mixture of pent-1-ene and pent-2-ene. the water formed to shit the position of the equilibrium
D a mixture of pent-1-ene and pentan-3- to the right hand side (Le Chatelier’s principle) ensuring
ol. a good yield of product. Note that unlike the acid and
alcohol, an ester does not contain an –OH group and so is
4. Explain how varying the reaction conditions can afect much more limited in its ability to hydrogen bond to water
the product of the reaction between 1-bromopropane molecules, hence esters tend to be insoluble in water.
and sodium hydroxide.
It can be seen that the naming of esters is rather diferent
5. 2-bromohexane is added to a concentrated boiling from that of other organic compounds. hey are named as
solution of potassium hydroxide in ethanol. if they were salts of the alcohol and the acid; the alcohol
provides the irst half of the name (alkyl) and the organic
a) What class of reactions does this belong to? acid provides the second half of the name (alkanoate). In
naming an ester it is important to remember that the –CO–
b) Draw the mechanism by which this reaction group is part of the carboxylic acid. he molecule below
occurs. is therefore methyl propanoate (not propyl methanoate),
because it can be considered as being formed from
c) Explain why two diferent products can be methanol and propanoic acid.
obtained and name these products. This bond is part This bond is part
of the alcohol of the acid
d) How would the product change if the
halogenoalkane were warmed with dilute CH 3 O CO CH2 CH3
aqueous alkali? methanol/propanoic acid

Figure 1041 Naming of an ester

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 CHAPTER 10

20.4.2 Describe, using equations, the reactions of polymers, two diferent functional groups are required
amines with carboxylic acids. and for each new bond between the monomer units
©IBO2007 (shown coloured below), a small molecule (oten water) is
produced. Each monomer must also have two functional
Ammonia and primary amines initially react with groups. his can involve two diferent functional groups on
carboxylic acids to form a salt of the acid, but if this is the same monomer or more frequently, as in the examples
heated it dehydrates to form an amide. If ethanoic below, two diferent monomers which have two identical
acid is reacted with methylamine, and the initially groups on them. One group of condensation polymers are
formed methylammonium ethanoate is heated, then the polyesters, so called because the bonding depends on
N-methylethanamide is formed: the reaction of an alcohol with a carboxylic acid to form an
ester. he best known example of this polymer is Terylene,
CH3—CO—OH (aq) + CH3—NH2 (aq) formed by the reaction of benzene–1.4–dicarboxylic acid
Ethanoic acid Methylamine with ethane–1.2–diol. as shown in Figure 1042(a)

[CH3—CO—O– CH3—NH3+ (s)] he repeating unit in Terylene is therefore

methylammonium ethanoate
[—O—CH2—CH2—O—CO— —CO—].
CH3—CO—NH—CH3 (s) + H2O (g)
N-methylethanamide Another group of condensation polymers is the polyamides,
so called because the bonding depends on the reaction of
ahL

20.4.3 Deduce the structures of the polymers an amine group with a carboxylic acid to form an amide.
formed in the reactions of alcohols with hese polymers are better known as nylon, though there are
carboxylic acids. actually a whole range of nylons. One of the most common
is nylon 6.6, formed by the polymerisation of hexanedioic
20.4.4 Deduce the structures of the polymers acid with hexane–1.6–diamine (See Figure 1042[b]).
formed in the reactions of amines with
carboxylic acids. he repeating unit in this is therefore

20.4.5 Outline the economic importance of [HN–(CH2)6–NH–CO–(CH2)4–CO].

condensation reactions.
©IBO2007 Both polyesters and nylons are used in large quantities for
the production of ibres to convert into cloth for garments,
he two reactions discussed above are made use of in hence the above reactions are of major economic
polymers known as condensation polymers. In these importance in most developed countries.

... HO CH2CH2 OH + HOOC COOH + HO CH2CH2 OH + HOOC COOH ...

ethane–1.2–diol benzene–1.4–dicarboxylic acid

... OCH2CH2O CO CO OCH2CH2O CO CO ... + 3 H2O

Terylene
Figure 1042(a) The polymerisation reaction forming a polyester - Terylene

—H2N—(CH2)6—NH2 + HO—CO—(CH2)4—CO—OH + H2N—(CH2)6—NH2 + HO—CO—(CH2)4—CO—OH—

hexane–1.6–diamine hexanedioic acid

…—HN—(CH2)6—NH—CO—(CH2)4—CO—HN—(CH2)6—NH—CO—(CH2)4—CO—…

+ H2O + H2O + H2O

Figure 1042(b) The polymerisation reaction forming Nylon 6.6

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 Organic chemistry

Exercise 20.4 20.6

stereOisOmerism
1. Which one of the following is not necessarily a
characteristic of condensation polymers? (ahL)
A It involves two diferent monomers. 20.6.1 Describe stereoisomers as compounds
B A small molecule is formed for each with the same structural formula but with
new bond between the monomers. different arrangements of atoms in space.
C Each monomer must have two
functional groups. 20.6.2 Describe and explain geometrical
D he reaction to form the bond between isomerism in non-cyclic alkenes.
the monomers involves two diferent
functional groups. 20.6.3 Describe and explain geometrical
isomerism in C3 and C4 cycloalkanes.
2. he molecule CH3-CH2-CH2-O-CO-CH3 is called
20.6.4 Explain the difference in the physical
A prop-1-yl methanoate. and chemical properties of geometrical
B prop-1-yl ethanoate. isomers.

ahL
C ethyl propanoate.
©IBO2007
D methyl butanoate.

3. Which one of the following could not be a monomer Stereoisomers are molecules, in which the order that the
for a condensation polymer? atoms are joined in is the same (hence they are isomers
with the same structural formula), but the molecules
A HO–CO–CH2–CH2–CH2–CO–OH have a diferent arrangement of atoms in space and hence
diferent three dimensional shapes. Stereoisomers can be
B HO– –CO–OH sub-divided into geometrical isomers and optical isomers
(or enantiomers).
C HO–CO–CH2–CH2–CH2–NH2
D CH3–CH2–CH2–CO–NH2
geOmetric isOmerism
4. Write a balanced equation for the reaction that you It is possible for a molecule to rotate freely around a single
would expect to occur when the initial product (σ-)bond so that, for example, the two CH3 groups in
formed between butanoic acid and ethylamine is ethane can rotate relative to each other. Atoms joined by a
strongly heated and give the full structural formula double bond are however not free to rotate. his is because
of the organic product. the π-bond in the double bond involves two regions of
high electron density on opposite sides of σ–the bond,
5. a) What reagents would you require to prepare a hence rotation would involve breaking this π–bond. As
sample of methyl butanoate? a consequence in a molecule containing a double bond,
if the form produced by rotating one end of the bond by
b) Write a balanced equation for the reaction 180° is not identical to the original, then there can be two
that occurs giving structural formulae for all separate forms of the molecule. See Figure 1043.
organic compounds.

c) Apart from the reactants what else would be Cl Cl Cl H

required if the reaction were to produce a
C C C C
good yield of the product?
H H H Cl
d) Predict one property of methyl butanoate.
cis–1.2–dichloroethene trans–1.2–dichloroethene

Figure 1043 Geometric isomerism in alkenes

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 CHAPTER 10

hese isomers are known as geometric isomers and the cis–1.2 dichlorocyclopropane
forms of 1.2-dichloroethene (ClCH=CHCl) is a typical Cl
example. he isomer in which the groups or substituents C
are on the same side of the double bond is known as the
cis–isomer, the one with them on opposite sides is the H H Cl
trans–isomer. C C

Frequently, as in this case, the cis–isomer will be polar H H

whilst the more symmetrical trans–isomer will not. his
afects physical properties such as the boiling points,
trans–1.2 dichlorocyclopropane
the cis–isomer above for example boils at 60°C, whereas
Cl
the trans–isomer boils at 48°C. hus, geometric isomers
have diferent physical properties such as polarity (dipole C
moment), boiling point, melting point, and solubility, H H
H
etc. hey can therefore be separated by methods such as
fractional distillation, chromatography, etc. C C
H Cl
Usually the chemical properties are similar, but in some
cases the proximity of the functional groups allows
interaction in the cis–isomer more easily than in the trans– Figure 1045 Geometric isomerism in cycloalkanes
ahL

isomer. For example cis–butenedioic acid dehydrates at

under 200°C to form the anhydride (see below), whilst the
trans–isomer sublimes unchanged at ~200°C. Dehydration OpticaL isOmerism
of the trans–isomer requires a much higher temperature
so as to achieve the activation energy required for rotation 20.6.5 Describe and explain optical isomerism in
about the double bond and hence the product has the simple organic molecules.
same form as the cis–isomer as shown in Figure 1044
20.6.6 Outline the use of a polarimeter in
distinguishing between optical isomers.

H C CO OH 20.6.7 Compare the physical and chemical

H C CO OH properties of enantiomers.
©IBO2007

If a carbon atom has four diferent groups attached to it

H C CO then there are two diferent ways in which these groups
O + H2O
H C CO can be arranged around this carbon atom, which is known
as an asymmetric carbon atom, or a chiral centre (from
the Greek word for ‘hand’). he two forms of such a chiral
Figure 1044 The dehydration reaction of butenedioic molecule, known as optical isomers (or enantiomers), are
acid mirror images of each other, but cannot be superimposed
on each other (like a pair of gloves). his is illustrated
Cycloalkanes also display geometrical isomerism below using butan-2-ol as an example. he asymmetric
because being part of a ring prevents rotation of carbon atom is marked with * in Figure 1046.
carbon–carbon single bonds as well, so for example, 1.2
dichlorocyclopropane can exist as both cis– and trans– Note that all four groups must be diferent for this to occur
isomers: so that propan-2-ol (CH3-CHOH-CH3) does not exist as
a pair of optical isomers. Because these molecules are
so similar, there is very little diference in their physical
and chemical properties. In fact the only diference in the
properties of these compounds is in their interaction with
plane polarised light.

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 Organic chemistry

OH OH OH

Rotate by 180°
*C *C *C
CH3 C5H5 C5H5 CH3 CH3 H
H H C5H5

Mirror images

Figure 1046 Optical isomerism

Optically inactive

Vertical Horizontal
Incident Vertical Second Light maximum none
normal polarising polarising passing
light filter filter through
Optically active

ahL
Maximum light at an angle

Figure 1047 Illustrating the effect of optically active compounds

TOK Belief or truth?

‘The existence of optical isomers provided indirect evidence of a tetrahedrally bonded carbon atom. This is an
example of the power of reasoning in allowing us access to the molecular scale. Do we know or believe those
carbon atoms are tetrahedrally coordinated?’ ©IBO2007

Knowledge and belief; the relationship between I suppose that the strength of a justification lies in
these is the basis of so many issues in TOK. One of whether we can think of any alternatives to explain
the most common definitions of knowledge (though observations that we agree upon. In this case that
strongly challenged about 50 years ago by Edmund there are two substances, identical in every way
Gettier) is that knowledge is “Justified True Belief”. except for the effect they have on the plane of
Taking this as a starting point, the difference between polarisation of polarised light. One explanation
knowledge and belief therefore lies in Truth and for this is the familiar one given in this chapter.
Justification. How do we know what is true? On truth The real test is to come up with an alternative
test is “correspondence”; that something is true if it explanation, which preferably also explains a few
corresponds with reality, but can we consider atoms other phenomena as well (the way that relativity
and molecules part of reality in the way that this book did), and does not contradict other evidence relating
is? A second test is “coherence”; that something is to the tetrahedral arrangement of bonds in carbon,
true if it fits in, and does not contradict, other ideas such as x-ray diffraction data about the structure of
we consider true. Now this might be a little more diamond. In other words it’s back to Popper again
hopeful. What of justification? This is a far more – our confidence in any theory depends only on our
personal thing. Even before the days of space flight, attempts to refute it (see TOK Box in Chapter 5). It
most people still accepted that the world was a sphere probably follows that our knowledge of the universe
in spite of our observations, especially when in the is constrained only by our inability to imagine better
middle of the ocean, that it looks pretty flat. This was theories than the ones we currently have.
because we accepted the many justifications for this,
though inevitably there were still those who were not
convinced.

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 CHAPTER 10

Plane polarised light can be considered to be light in which Apart from this the physical properties of optical isomers
the oscillation of the wave is restricted to one plane, say the are identical. Chemically, the behaviour of the optical
vertical. his can be achieved by passing the light through a isomers is identical unless the reaction also involves another
polarising ilter. If the light is now passed through a second pure optical isomer. Chemical reactions that produce an
polarising ilter orientated in the same direction (vertical) asymmetric (chiral) carbon atom in a molecule usually
then there is virtually 100% transmission (see Figure 1045). give rise to a mixture containing exactly equal amounts
If the second polarising ilter has its axis at right angles to of the two optical isomers. Such a mixture is known as a
the irst (horizontal) then no light will pass. A pure optical racemic mixture. he efects of the two optical isomers in
isomer placed between the two ilters will rotate the plane a racemic mixture cancel each other out and so it is not
of polarisation in one direction (say clockwise) so that optically active. In contrast almost all natural products,
maximum transmission is no longer when the second produced by enzyme catalysed biochemical processes,
ilter is aligned with the irst one. he second optical result in just one pure optical isomer and hence produce
isomer will rotate the plane of polarisation by exactly the optically active material. Natural turpentine (produced
same amount (assuming equal concentration), but in the from pine tree resin) can, for example, be diferentiated
opposite direction (anticlockwise). Substances that afect from white spirit (a substitute produced by the chemical
polarised light in this way are said to be optically active. industry) because turpentine is optically active and will
An instrument containing two polarising ilters that can be rotate the plane of polarised light, whereas white spirit will
rotated relative to each other, separated by a compartment not.
in which the plane polarise light passes through a liquid,
allowing the angle through which the plane of polarisation
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is rotated is called a polarimeter. See Figure 1047.

tOk The use of conventions in representing three-dimensional molecules in two dimensions

Conventions, and the extent that they are a result of appears to be smaller the further away from us it goes,
cultural conditioning, is a fascinating subject. The hence as it disappears towards the horizon the sides
diagrams in this book have to attempt to represent of the road appear to get closer together, meeting at
three-dimensional molecules through the two- the horizon (in theory an infinite distance away!). We
dimensional medium of the page of the book. This have grown up with these tricks of the graphic artist
is a problem that graphic artists also have to contend and find it difficult when viewing a scene drawn using
with and as a result they developed the technique of perspective, to imagine in any other way.
perspective. Our drawings have attempted to draw
on some of these techniques, but added a few other It is reported that when drawings incorporating
little conventions, such as things with dotted lines perspective are shown to people of more ‘primitive’
being below the plane of the book and wedge shaped cultures, they do not realise that some of the objects
lines coming out of the page. Like so many things, the are supposed to be further away than others, in other
concept of perspective was well known to the Greeks, words the appreciation of perspective is something
but was then lost to be rediscovered and thoroughly that we develop by growing up in a culture where it
developed in the Renaissance period. It depends on is widely employed. Others however contest this say
the apparent diminution of size with distance and the that the appreciation of perspective, even though not
resulting convergence of lines. If we show two human developed by all societies, is innate to humans rather
figures in a drawing, but one is much smaller than the than something that is culturally developed. Anyway
other we can either assume the smaller one is further I hope that you have all been exposed to enough
away from us, or that it represents a leprechaun or Escher “impossible geometries” to be able to pick up
some other kind of diminutive human. Usually for the three-dimensional shapes that we are trying to
us the former explanation is more convincing. A represent.
consequence of this is that the constant width of a road

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070810 Chem Chap 10-3.indd 287
Cl2 or Br 2 & UV light R/H-C 2 H4 X Cl2 or Br 2 & UV light R/H-C 2 H3 X2 Cl2 or Br 2 & UV light Polyhalogenated
R/H-CH2 -CH3 isomers isomers isomers
H2 & Ni
catalyst R/H-CH2 -CH2 -X X 2 at R/H-CHX-CH2 X
room
Heat with dil. T&P
R/H-CHX-CH3
aq. alkali
[-CH2 -CH2 -]n and
HX at High T &
R/H-CH2 -CH2 -OH room conc. alc. other addition
H2O & acid T&P alkali polymers
catalyst
R/H-CH(OH)-CH3 R/H-CH=CH 2
Very high P and
trace of O 2 catalyst Heat with KCN

Heat with Distil with Heat with R/H-CH2 -CH2 -CN

acidified acidified trace of
Cr2O72- Cr2O72- c. H2SO 4
R/H-CH2 -CH2 -O-CO-CH2 -R

and polyester, e.g. terylene Heat with NH3

R/H-CO-CH3 R/H-CH2 -CO-H

Reflux with
acidified R/H-CH2 -CO-OH React then heat to R/H-CH2 -CH2 -NH2
Cr2O72- dehydrate salt

R/H-CH2 -CH2 -NH-CO-CH2 -R

Summary table for the interconversion and polyamides, e.g. nylons
of organic compounds

Figure 1048 A summary table for the interconversion of organic compounds

Colour shaded - HL only
Bold arrow - Mechanism needed

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Organic chemistry

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7/12/2007 8:53:21 AM
 CHAPTER 10

Exercise 20.6

1. Which one of the following compounds will exhibit 6. a) Samples of 2–bromobutane may exhibit
geometrical isomerism? optical activity. Explain why.

A CH3CH=CH2 b) 2–bromobutane may be produced by

B CH3CCl=CH2 the reaction of hydrogen bromide with
C CH3CH=CHCl but–2–ene. Would you expect a sample
D CH3CH=CCl2 prepared in this way to be optically active?
Explain why.
2. Counting from the let hand end of the principal
chain, which carbon atom in the following molecule
is an asymmetric one?
ClCH2—C(CH3)2—CHCl—CHCl2
A he irst
B he second
C he third
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D he fourth

3. Which one of the following isomeric alcohols can

exist as a pair of optical isomers?

A CH3—CH2—CH2—CH2—OH
B (CH3)2CH—CH2—OH
C CH3—CH2—CH(OH)—CH3
D (CH3)3C—OH

4. 3–bromopent–1–ene can exist in many isomeric

forms. Draw a full structural formula of the molecule
and then draw structural formulae of isomers that
only difer from it in the manner given:

a) A hydrocarbon chain isomer.

b) An optical isomer (enantiomer).
c) A positional isomer.
d) An isomer which displays geometric
isomerism.
e) An isomer not containing a double bond.

5. Lactic acid [CH3CH(OH)COOH] can either be

extracted from sour milk, or it may be produced
synthetically by the addition of water to propenoic
acid (CH2=CHCOOH).

a) Explain what is meant by the terms ‘optically

active’ and ‘racemic mixture’.
b) How would you expect samples from these
two sources to difer.
c) In practice, how could you determine
whether a sample of lactic acid was of natural
or synthetic origin?

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