AS Chemistry

Bonding in methane,
ethane and ethene
and bonds

Learning Objectives
Candidates should be able to:
describe covalent bonding in terms of orbital overlap,
giving and bonds.
explain the shape of, and bond angles in, ethane and
ethene molecules in terms of and bonds.

Starter activity

Alkenes
pent-2-ene

CH3CH=CHCH2CH3

hex-3-ene

CH3CH2CH=CHCH3

2,3-dimethylpent-2-ene

cyclopenta-1,3-diene
3-ethylhept-1-ene

CH2=CHCH2CH(CH2CH3)CH2CH2CH3

Hybridisation of orbitals
The electronic configuration of a carbon atom is
1s22s22p2
2p
2
2s

1s

HYBRIDISATION OF ORBITALS
If you provide a bit of energy you can promote (lift)
one of the s electrons into a p orbital.
The
configuration is now 1s22s12p3
2p
2
2s

1s

The extra energy released when the bonds form more than
compensates for the initial input.

Hybridisation of orbitals in alkanes

The four orbitals (an s and three ps) combine or
HYBRIDISE to give four new orbitals. All four orbitals are
equivalent.
Because one s and three p orbitals are used, it is called sp3
hybridisation.
2s22p2

2s12p3

4 x sp3

Hybridisation of orbitals in alkanes

In ALKANES, the four sp3
orbitals repel each other
into
a
tetrahedral
arrangement.

sp3 orbitals

Bonding in methane

Bonding in ethane

Bonding in ethene
Alternatively, only three orbitals (an s and two ps)
combine or HYBRIDISE to give three new orbitals. All
three orbitals are equivalent. The remaining 2p orbital is
unchanged.
2s22p2

2s12p3

3 x sp2

2p

What about ethene?

sp2 hybrids

 - bonds

AS Chemistry

Geometric Isomerism

Learning Objectives
Candidates should be able to:
describe cis-trans isomerism in alkenes, and explain
its origin in terms of restricted rotation due to the
presence of bonds.
deduce the possible isomers for an organic
molecule of known molecular formula.
identify cis-trans isomerism in a molecule of given
structural formula.

Starter activity

What is stereoisomerism?
In stereoisomerism, the atoms making up the isomers
are joined up in the same order, but still manage to have
a different arrangement in space
ISOMERISM

STRUCTURAL ISOMERISM

STEREOISOMERISM

GEOMETRIC
ISOMERISM

OPTICAL ISOMERISM

Geometric Isomerism?

GEOMETRIC ISOMERISM
RESTRICTED ROTATION OF C=C BONDS
Single covalent bonds can easily rotate. What appears
to be a different structure in an alkane is not. Due to
the way structures are written out, they are the
same.

ALL THESE STRUCTURES ARE THE SAME BECAUSE C-C BONDS HAVE FREE
ROTATION

Animation doesnt
work in old
versions of
Powerpoint

Geometric Isomerism?

Geometric isomers of but-2-ene

Geometric Isomerism?

GEOMETRIC ISOMERISM
How to tell if it exists
Two
different
atoms/groups
attached

Two
different
atoms/groups
attached

Two similar
atoms/groups
attached

Two similar
atoms/groups
attached

Two similar
atoms/groups
attached

Two
different
atoms/groups
attached

Two
different
atoms/groups
attached

Two
different
atoms/groups
attached

GEOMETRICAL ISOMERISM

Once you get two similar

atoms/groups
attached
to one end of a C=C,
you
cannot
have
geometrical isomerism

GEOMETRICAL ISOMERISM

GEOMETRIC ISOMERISM
Isomerism in butene
There are 3 structural isomers of C4H8 that are alkenes*. Of these
ONLY ONE exhibits geometrical isomerism.

BUT-1-ENE

cis BUT-2-ENE

trans BUT-2-ENE

2-METHYLPROPENE

* YOU CAN GET ALKANES WITH FORMULA C4H8 IF THE CARBON ATOMS ARE IN A
RING

Summary
To get geometric isomers you must have:
restricted rotation (involving a carbon-carbon double
bond for A-level purposes);
two different groups on the left-hand end of the bond
and two different groups on the right-hand end. It
doesn't matter whether the left-hand groups are the
same as the right-hand ones or not.

The effect of geometric isomerism on

physical properties
isomer

melting
(C)

point boiling
(C)

cis

-80

60

trans

-50

48

point

You will notice that:

the trans isomer has the higher melting point;
the cis isomer has the higher boiling point.

Why is the boiling point of the cis

isomers higher?

The difference between the two is that the cis isomer is

a polar molecule whereas the trans isomer is non-polar.

Why is the melting point of the cis

isomers lower?
In order for the intermolecular forces to work well, the
molecules must be able to pack together efficiently in the
solid.
Trans isomers pack better than cis isomers. The "U" shape
of the cis isomer doesn't pack as well as the straighter
shape of the trans isomer.

AS Chemistry

Optical Isomerism

Learning Objectives
Candidates should be able to:
explain what is meant by a chiral centre and that
such a centre gives rise to optical isomerism.
deduce the possible isomers for an organic
molecule of known molecular formula.

identify chiral centres in a molecule of given

structural formula.

Starter activity

Optical isomerism
Chiral centre
Chiral molecule

When four different atoms or groups are attached to a

carbon atom, the molecules can exist in two isomeric forms
known as optical isomers. These are non-superimposable
mirror images.

Optical Isomerism
What is a non-superimposable mirror image?

Animation doesnt
work in old
versions of
Powerpoint

Optical isomerism

Amino acids (the building blocks of proteins) are optically

active. They affect plane polarised light differently.

Butan-2-ol

Optical Isomerism
The polarimeter
A

B
C

A
B
C
D
E
F

Light source produces light vibrating in all directions

Polarising filter only allows through light vibrating in one direction
Plane polarised light passes through sample
If substance is optically active it rotates the plane polarised light
Analysing filter is turned so that light reaches a maximum
Direction of rotation is measured coming towards the observer

If the light appears to have

turned to the right
turned to the left
DEXTROROTATORY
LAEVOROTATORY

Enantiomers how do they differ?

Usually have the same chemical and

physical properties but behave
differently in presence of other
chiral compounds.

Enantiomers how do they differ?

TYPES OF ISOMERISM
CHAIN ISOMERISM

STRUCTURAL ISOMERISM
Same molecular formula but
different structural
formulae

POSITION ISOMERISM

FUNCTIONAL
GROUP ISOMERISM

GEOMETRICAL ISOMERISM

STEREOISOMERISM
Same molecular
formula but atoms
occupy different
positions in space.

Occurs due to the restricted

rotation of C=C double
bonds... two forms - CIS and
TRANS
OPTICAL ISOMERISM
Occurs when molecules have a
chiral centre. Get two nonsuperimposable mirror images.

AS Chemistry

Electrophilic
Addition to Alkenes

Learning Objectives
Candidates should be able to:
describe the mechanism of electrophilic addition in
alkenes, using bromine/ethene as an example.
describe the chemistry of alkenes as exemplified,
where relevant, by the following reactions of ethene:
addition of hydrogen, steam, hydrogen halides and
halogens.

Starter activity

Electrophilic addition

CH2=CH2

Br2

CH2BrCH2Br

Electrophilic addition
bromine with ethene
CH2=CH2

+ Br2

CH2BrCH2Br
1,2-dibromoethane

hydrogen bromide with ethene

CH2=CH2

+ HBr

CH3CH2Br
bromoethane

Electrophilic addition mechanism

bromine with ethene
H

H
C
H

C
H

Br

Br-

carbocation

C
+

Br-

Br

Br
Br 1,2-dibromoethane

Br

Br

Electrophilic addition mechanism

hydrogen bromide with ethene
H

H
C

C
H

H
+

Br-

carbocation

C
+

Br-

H
H

Br

bromoethane

Electron flow during electrophilic addition

EQUATION

TEMPERATURE
(OC)

hydrogen

CH2=CH2 + H2 CH3CH3

~150

steam

CH2=CH2 + H2O

330

CH3CH2OH

hydrogen
halides
(e.g. HBr)
halogens

CH2=CH2 + HBr
CH3CH2Br

CH2=CH2 +Br2
CH2BrCH2Br

PRESSURE

CATALYST
Finely divided
nickel
on
support
material

6MPa

Phosphoric (V)
acid
(H3PO4)

PHASE

Gas

Gas

adsorbed onto
the surface of
silica.

Room
temperature

Room
temperature

Aqueous
solution
Liquid bromine
or
solution
(both aqueous
and non-polar
solvent.

NOTES
Never carried
out
industrially.
Analogous
reaction used
to
produce
some
margarines
from oils (see
later).
Major
industrial
process
for
the
manufacture of
ethanol.
Reactivity
increases from
HF to HI.
Chlorine
and
iodine produce
similar addition
products.
Fluorine is too
powerful
an
oxidizing agent.

Addition reactions of alkenes

Addition to unsymmetrical alkenes

Electrophilic addition to propene

2-bromopropane

1-bromopropane

Addition to unsymmetrical alkenes

In the electrophilic addition to alkenes the major
product is formed via the more stable carbocation
(carbonium ion)
least stable
methyl

<

primary (1)

most stable
< secondary (2) < tertiary (3)

Addition to unsymmetrical alkenes

SECONDARY
CARBOCATION
PATH A

MAJOR PRODUCT
PRIMARY
CARBOCATION
PATH B

MINOR PRODUCT

AS Chemistry

Polymerisation

Learning Objectives
Candidates should be able to:
describe the
polymerisation.

chemistry

of

alkenes

including

describe
the
characteristics
of
addition
polymerisation as exemplified by poly(ethene) and
PVC.
Recognize the difficulty of the disposal of
poly(alkene)s, i.e. non-biodegradability and harmful
combustion products.

Starter activity

Poly(ethene)

Conditions
Temperature:

about 200C

Pressure:

about 2000 atmospheres

Initiator:

often a small amount of oxygen

as an impurity

Free radical addition

Initiation
Propagation

Propagation

Termination

LDPE or HDPE

LDPE or HDPE

Sandwich bags, cling wrap, car covers, squeeze bottles,

liners for tanks and ponds, moisture barriers in
construction

Freezer bags, water pipes, wire and cable insulation,

extrusion coating

Polymerisation of alkenes
ETHENE

CHLOROETHENE

PROPENE

TETRAFLUOROETHENE

POLY(ETHENE)

POLY(CHLOROETHENE)
POLYVINYLCHLORIDE

PVC

POLY(PROPENE)

POLY(TETRAFLUOROETHENE)
PTFE

Teflon

Disposal of polymers
Method
Landfill

Incineration

Recycling
Feedstock
recycling

Comments
Emissions to the atmosphere and water;
vermin; unsightly. Can make use of old
quarries.
Saves on landfill sites and produces
energy. May also release toxic and
greenhouse gases.
high cost of collection and reprocessing.
Use the waste for the production of
useful
organic
compounds.
New
technology can convert waste into
hydrocarbons which can then be turned

AS Chemistry

Oxidation of
alkenes

Learning Objectives
Candidates should be able to describe the oxidation
of alkenes by:
cold, dilute, acidified manganate(VII) ions to form
the diol, and
hot, concentrated, acidified manganate(VII) ions
leading to the rupture of the carbon-to-carbon
double bond in order to determine the position of
alkene linkages in larger molecules.

Starter activity

Oxidation of alkenes
In the presence of dilute (acidified or alkaline) potassium
manganate (VII).
Alkenes react readily at room temperature (i.e. in the
cold).
The purple colour disappears and a diol is formed.
CH2=CH2

H 2O

[O]
HOCH2CH2OH
ethane 1,2-diol

Oxidation of alkenes
In the presence of a hot, concentrated solution of
acidified potassium manganate (VII), any diol formed is
split into two fragments which are oxidized further to
carbon dioxide, a ketone or a carboxylic acid.
Fragment
=CH2

Product

CO2

R-CH=
Aldehyde

R2C=
Ketone

carboxylic acid

Oxidation of alkenes
1. CH2=CH2
2. CH3CH=CH2
3. (CH3)2C=CH2

2 products both
contain ketone

1 product only

2 products one contains

2 ketone groups and one
contains 2 acid groups.

AS Chemistry

Halogenoalkanes

Learning Objectives
Candidates should be able to recall the chemistry of
halogenoalkanes as exemplified by the following
nucleophilic substitution reactions of bromoethane:
hydrolysis;
formation of nitriles;
formation of primary amines by reaction with
ammonia.

Starter activity

Naming Halogenoalkanes
a. CHCl3
trichloromethane
b. CH3CHClCH3 2-chloropropane
c. CF3CCl3
1,1,1-trichloro-2,2,2-trifluoroethane

Cl

Cl
F

Cl

Physical Properties
a. 1-chloropropane is polar and has permanent dipoledipole intermolecular forces that are stronger than
the temporary dipole-induced dipole forces in nonpolar butane.

b. 1-chloropropane is polar and has permanent dipoledipole intermolecular forces that are stronger than
the temporary dipole-induced dipole forces in nonpolar butane.

Nucleophilic substitution
negotiate clever

electronegative

alp or

polar

cadet tart

attracted

eat given

negative

enticed if

deficient

chenille soup

nucleophiles

had lie

halide

stubs tuition

substitution

Nucleophilic substitution

This is known as an SN2 reaction.

S stands for substitution,
N for nucleophilic, and
2 because the initial stage of
the reaction involves two species.

Nucleophilic substitution - mechanism

Attack by nucleophile is to the back of the molecule

away from the negatively charged halogen atom.
ANIMATION SHOWING THE SN2 MECHANISM

Rate of reaction
Halogen
Electronegativity

F
4.0

Cl
3.0

Br
2.8

I
2.5

Bond strength (C-X)

kJ mol-1

484

338

276

238

You may expect the fluoroalkane to react more quickly as the C-F bond is the
most polar and therefore more susceptible to attack by nucleophiles. However,
the C-F bond is the strongest. A nucleophile may be more attracted more
strongly to the carbon atom but, unless it forms a stronger bond to carbon, it
will not displace the halogen.
Actually the reaction with the iodoalkane is the most rapid. This suggests that
the strength of the C-X bond is more important than its polarity. Note that
the C-I bond is not polar. However, it is easily polarisable.

Measuring the rate of reaction

Experiment
Water is a poor nucleophile but it can slowly displace halide
ions
C2H5Br(l)

H2O(l)

C2H5OH(l)

H+(aq) + Br(aq)

If aqueous silver nitrate is shaken with a halogenoalkane

(they are immiscible) the displaced halide combines with a
silver ion to form a precipitate of a silver halide. The
weaker the C-X bond the quicker the precipitate appears.

Nucleophilic substitution
hydroxide ion with bromoethane
CH3CH2Br + OH

warm
(aqueous)

CH3CH2OH + Brethanol

Water with bromoethane

CH3CH2Br + H2O

warm
(aqueous)

CH3CH2OH + HBr
ethanol

This is a slower reaction water is not such a good nucleophile.

Nucleophilic substitution mechanism

hydroxide ion with bromoethane

CH3

H
C
H

OH-

Br

H
CH3

C
H

ethanol

OH

Br

Nucleophilic substitution mechanism

water with bromoethane
H

+
CH3 C

Br

H
CH3

+
OH

Br

H2O
H
ethanol

CH3

C
H

OH

HBr

Nucleophilic substitution
cyanide ion with bromoethane
CH3CH2Br

+ CN

(ethanol)

reflux

CH3CH2CN + Brpropanenitrile

ammonia with bromoethane

CH3CH2Br + NH3(ethanol)

CH3CH2Br + 2 NH3(ethanol)

Heat /
pressure
Heat /
pressure

CH3CH2NH2 + HBr
aminoethane
CH3CH2NH2 + NH4+Br-

Nucleophilic substitution mechanism

cyanide ion with bromoethane

CH3

H
C
H

CN-

Br

H
CH3

CN

H
propanenitrile

Br

Nucleophilic substitution mechanism

ammonia with bromoethane
H

+
CH3 C

Br

H
CH3

+
NH2

Br

NH3

NH3
H
CH3
aminoethane

C
H

NH2

NH3+Br -

Past paper question

Cl2
U.V. /sunlight
Ethanolic
KCN
reflux
Br2
U.V. /sunlight

AS Chemistry

Substitution vs.
Elimination

Learning Objectives
Candidates should be able to:
recall the chemistry of halogenoalkanes as
exemplified by the elimination of hydrogen bromide
from 2-bromopropane.
describe the mechanism of nucleophilic substitution
(by both SN1 and SN2 mechanisms) in halogenoalkanes.

Starter activity

Type of
halogenoalkane

Position of
halogeno- group

Example

primary

at end of chain:

bromoethane

secondary

in middle of chain:

2-bromopropane

tertiary

attached to a carbon atom which 2-bromo-2-methylpropane

carries no H atoms:

SN1 tertiary halogenoalkanes

Nucleophilic attack at the back of the molecule is

hindered by bulky CH3 groups. Tertiary carbocation is
stabilised by electron donating effect of CH3 groups.

SN1 or SN2 ?
Halogenoalkane
Primary
Secondary
Tertiary

Mechanism
SN2
SN1 and SN2
SN1

Elimination
You need to be aware that the hydroxide ion can act as a
strong base as well as a nucleophile.
An alternative reaction can take place in which HBr is
removed and an alkene is formed. This is known as
elimination.
CH3CH2Br + NaOH CH2=CH2 + NaBr

+ H 2O

Elimination of HX from haloalkanes

Elimination of HBr from 2-bromopropane
CH3CHBrCH3 + OH(in ethanol)

CH3

Br

CH3CH=CH2 + H2O + Br-

H
H

CH3
OH acting as a base

propene

H
Br

H OH

Substitution or Elimination?
nucleophilic substitution
+ OH- (aqueous)

alcohol
RCH3CH2OH + Brhydroxide acts as a nucleophile

RCH2CH2X
+ OH- (ethanol)
elimination

hydroxide acts as a base

RCH=CH2 + H2O + Xalkene

92

AS Chemistry

Pros and Cons

Learning Objectives
Candidates should be able to:
interpret
the
different
reactivities
of
halogenoalkanes e.g. CFCs; anaesthetics; flame
retardants; plastics with particular reference to
hydrolysis and to the relative strengths of the C-Hal
bonds;
explain
the
uses
hydrofluorooalkanes in
chemical inertness;

of
fluoroalkanes
and
terms of their relative

recognise the concern about the

chlorofluoroalkanes on the ozone layer.

effect

of

Starter activity

Chlorofluorocarbons - CFCs
Properties:

Non-flammable

Low toxicity

Unreactive

Liquefy easily when compressed

Refrigerants

Propellants for aerosols

Uses
Solvents (including dry-cleaning)

Degreasers

The ozone layer

Natural ozone layer

Replacements
Hydrochlorofluorocarbons, HCFCs: shorter life in the
atmosphere.
Hydrofluorocarbons, HFCs: dont contain chlorine so
zero affect on ozone layer.
Hydrocarbons: zero effect on ozone layer but
flammable and lead to photochemical smog.

C. Why is BCF good at extinguishing fires?

The presence of a bromine confers flame retarding qualities on the
product.
The high temperature in fires break this compound down, producing free
radicals such as Br. These react with other free radicals produced
during combustion, quenching the flames.