CHM 215

Study Themes 1.1 - 1.3, 1.4 (partially), 1.5 & 2.1

(CHM 181 Self study - No lectures!)

Study Theme 2.2 ALKENES

[See Study Guide for Textbook References (updated version on
ClickUP under ‘Study Guides’!)]
• Stability of Alkenes (Smith par 8.2A - C) (Revision)
i) Trans isomer (more stable) more favoured than cis
isomer (less stable)

Reason: Steric (spatial) interaction (strain) between bulky

substituents on the same side of the double bond
Exercise: Draw line structures to show that trans-2-hexene
(no steric strain) is more stable than cis-2-hexene
(steric strain)

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ii) Alkenes become more stable with increasing substitution:

tetrasubstituted trisubstituted disubstituted mono-

substituted

Reason: Increasing alkyl substitution stabilizes alkene by an

e− donating inductive effect

Exercise:

i)

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ii) 1-methylcyclohexene vs 3-methylcyclohexene

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• Physical Properties of Alkenes (Smith par 10.4)
(Revise Smith par 3.3 & 3.4 (CHM 181 Self study))

Weak van der Waals interactions (CHM 181)

i) Solubility
ii) Melting and boiling points

Which isomer boils higher, the trans isomer or the cis isomer?

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Exercise: Match a high, low or intermediate b.p. with the following
alkene isomers and give a reason for your choice:

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• Addition Reactions of Alkenes (Revise CHM 181)
Markovnikov’s Rule! (Smith par 10.10) & all reactions
covered in CHM 181!
Exercise:
Complete the following reactions. Include stereochemistry
where appropriate:
1) NBS

DMSO (aq)

Br2

H2O

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2)

H3O+
or
+
H2 O / H

HBr Br2

H2 O

1. BH3, THF
_
2. H2O2, HO

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• Alkene Polymers (Smith par 15.1; 15.2; 15.14A, B;
par 30.1 - 30.2A)
• Polymer: A large molecule composed of repeating units of
smaller molecules (monomers) covalently bonded to each other
• Natural polymers
– DNA (many linked nucleic acids)
– Starch or cellulose (many linked sugar molecules)
– Proteins (many linked amino acids)
• Synthetic polymers (1/3 of SA’s chemical industry)
– Polyethylene (plastics) − Polypropylene
– PVC (polyvinylchloride) − Teflon
– PVA (polyvinylacetate) − Polystyrene

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Polymer definitions
 Monomer = starting unit from which a polymer is made

 Polymer = A large molecule made of repeating smaller

units (monomers)
 Vinyl group = ethylene without 1 H (like an alkyl group)
H H

Ethylene H H
H Vinyl group
H H
 Repeating Unit = the basic structure of a monomer after it
has polymerised
General formula
for most polymers
repeating unit R n
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• Radicals: Highly reactive!
Contain odd number of electrons (usually 7 rather
than 8) in valence shell
Can achieve a valence shell octet in several ways
in Radical Reactions:
i) Radical substitution reactions
(To be discussed in Theme 2.3 Alkyl halides)

Rad . + A:B Rad .. A + .B

new product
A B or Rad A
radical

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ii) Radical addition reactions

Rad

Rad . + C C C C .

Polymerization usually occurs at high temperatures (100 -

250°C) and/or pressures (1000 - 3000 atm) in presence of
a radical catalyst (initiation step)

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• Line structures for substituted ethylene (vinyl) polymers
(Chain-growth polymers)

R R R R R R
polymerize
Rad . Rad .
Catalyst
Substituted ethylene R
or
Initiator (vinyl) monomers or Rad
In . n
n = 3 monomers
Polymer segment
R = H, CH3, Ph, Cl with n = 3 repeating units
(General formula)

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6 common polymers and their uses

Monomer Polymer Uses

Ethylene Polyethylene Packaging,
bottles, cable
insulation
Propylene Polypropylene Car moldings,
rope, carpet
fibres
Cl Cl
Vinyl chloride PVC (polyvinylchloride) Insulation, films,
Cl pipes

Styrene Polystyrene Foam and

moulded articles
Tetrafluoroethylene Teflon Valves, gaskets
F F and coatings

F F
Vinyl acetate O PVA (polyvinylacetate) Paints, adhesives
O
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• Exercise:
1) Draw representative segments of polymers made from the
following monomers:

a) Polyethylene from ethylene (ethene)

b) Polypropylene from propylene (propene)

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c) Polystyrene (styron) from styrene

d) Poly(vinyl chloride) from chloroethylene (vinyl chloride)

(PVC)

Cl Cl Cl Cl
polymerize
x 3

Cl
or
n

Polymer segment
with n = 3 repeating units

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 e) Teflon from tetrafluoroethylene

2) Show the monomer units you would use to prepare the

following polymer:

Cl Cl Cl

Cl Cl Cl

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• Radical polymerisation (addition) mechanism
3 Kinds of steps involved in the overall polymerization process:

1) Initiation
2) Propagation
3) Termination

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• Mechanism:

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