Organic Chemistry Chapter 14

Hydrocarbons

14.2 – ALKENES (Part 1)

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 LEARNING OUTCOMES
]

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 Structure & Physical Properties
]
• Unsaturated and also known as olefin
• Contain C=C double bond.

• Most basic alkene: ethene

• Non-polar

• General formula: CnH2n

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 Preparation of Alkenes

Preparation of
alkenes

Dehydration of
Removal of HX Cracking
alcohol

Elimination reaction
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 Elimination Reaction
 Small molecule is removed from larger molecule producing double bond/ triple
bond.
 Reverse of addition reactions.
 Examples:
i) dehydration (removal of H2O) of alcohol to form alkene by concentrated
H2SO4. Conc. H SO
2 4

C C OR C C H2O
H OH Al2O3
alcohol alkene

Example:

H H Conc. H2SO4 H H
H C C H H C C H H2O
H OH
ethanol ethene
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 Elimination Reaction

ii) Removal of HX (removal of hydrogen and a halogen atom) of alkyl halide to form
alkene.

C C C C HX
H X
alkyl halide alkene
HX = HCl or HBr or Hl

Example: Ethanolic
NaOH
H H Heat
H H
CH3 C C H CH3 C C H HCl
H Cl
chloropropane propene
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 Cracking Reaction

 Large hydrocarbons can be broken up into smaller molecule using heat

and a catalyst.
 The reaction is an example of thermal decomposition

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 Cracking Reaction
 Example,
Decane Ethene + Propene + Pentane
800oC
Catalyst
C10H22 C2H4 + C3H6 + C5H12
Used in petrol

Used to make plastics

(polyethylene and
polypropylene)

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REACTION OF ALKENES
(A) Electrophilic Addition of Alkenes

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 Electrophilic Addition of Alkenes

Reaction where unsaturated molecule becomes saturated by

addition of a molecule across multiple bond (C=C in alkenes, -
C≡C- in alkynes, C=O in aldehydes and ketones)

Addition reactions to double bonds have these 3 characteristics:

i) π bond of double bond broken and single bonds formed
ii) only one product obtained
iii) product is saturated

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 Electrophilic Addition of Alkenes
• Undergo addition with: -
o Halogens, X2 (aq)
o Hydrogen halides, HX (aq)
o Hydrogen, H2(g)
o Water (in the form of steam)
• C=C broken, new single bond form

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 Electrophilic Addition with HYDROGEN
• Alkenes undergo hydrogenation when they react with hydrogen.
• The C=C double bond breaks up to form C-C single covalent bonds with the
new hydrogen atoms.
• The reaction requires excess hydrogen, a temperature of around
150oC and a nickel/platinum catalyst.
Pt, Pd or Ni
C C + H2 C C
H H

H2, Ni
HCH3C CH2 CH3CH2CH3
propene(propylene) propane
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 Electrophilic Addition with STEAM
• Alkenes are hydrated when they react with steam to form alcohols.
• This requires an acid catalyst such as conc. H3PO4 or conc. H2SO4 or hot
Al2O3.

• Ethanol found in alcoholic drinks is always produced by the fermentation

of glucose

ETHENE ETHANOL
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 Electrophilic Addition with HYDROGEN HALIDES
 Halogenoalkane formed when alkene is bubbled through a
concentrated solution of hydrogen halide (HF, HCl, HBr or HI) at room
temperature.
 For symmetric alkene, there is only one product formed

 For asymmetric alkene, two products could be expected:

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 Electrophilic Addition with HYDROGEN HALIDES
 General mechanism electrophilic addition with hydrogen halide

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 Electrophilic Addition with HYDROGEN HALIDES
 Mechanism for electrophilic addition of symmetrical alkene

δ+ δ-

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 Electrophilic Addition with HYDROGEN HALIDES
Mechanism for electrophilic addition of asymmetrical alkene

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Electrophilic Addition with HYDROGEN HALIDES

The addition of H-X across a

double bond results in the more
highly substituted alkyl halide
as the major product.

Consider the stability of

carbocation

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 Electrophilic Addition with HYDROGEN HALIDES

Stability of carbocations The more alkyl groups that are

depends on the number of alkyl bonded to carbocation, the
groups attached to positively more stable it is.
charged carbon atom
H H R R
H CH R C H R CH R C R

primary secondary tertiary

carbocation carbocation carbocation

stability of the carbocation increases

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 Carbocation Stability
• Alkyl groups tend to "push" electrons away.

• The alkyl group has a positive inductive effect.

• The arrow shows the electrons being "pushed" away from the CH3 group. The plus sign
on the left-hand end of it shows that the CH3 group is becoming positive.
• The general rule-of-thumb is that if a charge is very localised (all concentrated on one
atom) the ion is much less stable than if the charge is spread out over several atoms.

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 Carbocation Stability

• The electron pushing effect of the CH3 group is placing more and more negative charge
on the positive carbon as you go from primary to secondary to tertiary carbocations

• At the same time, the region around the various CH3 groups is becoming somewhat
positive.
• The net effect, then, is that the positive charge is being spread out over more and more
atoms as you go from primary to secondary to tertiary ions.
• The more you can spread the charge around, the more stable the ion becomes.
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 Carbocation Stability
• The more alkyl groups bonded to the positive carbon in the carbocation, the more stable
it is.
• It is the stability of these carbocations which determines which is made in preference to
the other.

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 Carbocation Stability
Primary carbocation
• When a compound HX is added to an unsymmetrical alkene, the hydrogen becomes
attached to the carbon with the most hydrogens attached to it already.

Minor

bromopropane
1o carbocation

Major

2 - bromopropane
2o carbocation 23
 Electrophilic Addition with HALOGENS
?”C?&Y^|||||||||||||||||||||||||||||\\\
Addition of Halogen (Br2, Cl2)
• When alkenes react with halogens, covalent bonds form between the
halogen atoms and the carbons on either side of the double bond,
producing a dihalogenoalkane.

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 Electrophilic Addition with HALOGEN
?”C?&Y^|||||||||||||||||||||||||||||\\\
Mechanism Addition of Halogen
 Nucleophile (C═C) bond attack one of Br atom.
 Br-Br covalent bond break
 New bond between C and Br atom forms
 Br− ion formed attacks carbocation intermediate.

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 Electrophilic Addition with HALOGENS
?”C?&Y^|||||||||||||||||||||||||||||\\\
Testing the presence of alkene

Bromine water, Br2(aq), is

orange or yellow. Alkene
decolourised Bromine water.

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 Addition of Asymmetrical Alkenes
• When steam reacts with propene, according to the stability of
carbocations, the OH group joins to the carbon atom in the double
bond which is directly bonded to the most carbons atoms. (H atom
join to C with more H)

• Propan-2-ol is the major product and propan-1-ol is the minor

product due to the stability of carbocation.
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THE
END

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