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Alkenes

and
Electrophilic
Addition

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Preparation
of Alkenes

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A. Industrial preparation
Cracking

Prepared by the cracking of alkanes of


high molecular masses

Give alkenes of low molecular masses

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Cracking
e.g.
600 oC

2CH3CH3

CH2 = CH2 + 2CH4

2CH3CH2CH3
o
600
C

CH3CH = CH2 + CH2 = CH2 + CH4 + H2

New Way Chemistry for

New Way Chemistry for Hong Kong A-Level Book 3A

B. Synthetic preparation
Elimination Reactions

Involve removal of atoms or groups of


atoms from adjacent carbon atoms in
the reactant molecule

Formation of a double bond between


carbon atoms

New Way Chemistry for

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IntramolecularDehydration
Dehydrationof
ofAlcohols
Alcohols
1.1. Intramolecular

Removal of a water molecule from a


reactant molecule

By heating the alcohols in the


presence of a dehydrating agent.
E.g.

Alumina(Al2O3), conc. H2SO4,


conc. H3PO4

Give alkenes and water as the


products
New Way Chemistry for

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IntramolecularDehydration
Dehydrationof
ofAlcohols
Alcohols
1.1. Intramolecular
alumina
CH3CH2OH

350oC

conc. H2SO4
CH3CH2OH

H
C

H
C

H2O

up to 200oC

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H2O

IntramolecularDehydration
Dehydrationof
ofAlcohols
Alcohols
1.1. Intramolecular

Experimental conditions (i.e. temperature


and concentration of concentrated
sulphuric acid)
is closely related to the structure of the
individual alcohol.

New Way Chemistry for

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IntramolecularDehydration
Dehydrationof
ofAlcohols
Alcohols
1.1. Intramolecular

Primary alcohols generally required


concentrated sulphuric acid and a
relatively high temperature

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IntramolecularDehydration
Dehydrationof
ofAlcohols
Alcohols
1.1. Intramolecular

10

Secondary alcohols are intermediate in


reactivity

Tertiary alcohols dehydrate under mild


conditions (moderate temperature and
dilute sulphuric acid)

New Way Chemistry for

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IntramolecularDehydration
Dehydrationof
ofAlcohols
Alcohols
1.1. Intramolecular

The relative ease of dehydration of


alcohols generally decreases in the order:

>

>
Tertiary
alcohol
11

Secondary
alcohol
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Primary
alcohol

Intramolecular vs intermolecular

conc. H2SO4
H

OH

170 C

OH

H2O

Substitution
C2H5

12

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C2H5

H2O

Intramolecular dehydration is favoured at


higher temperatures because it involves
breaking of strong C H bonds.

13

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Q.29(a)
CH3
H3C

OH

CH3
H
H

H3C

OH

CH3

14

H3C

H
C

H3C

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C
H

H2O

Q.29(b)
OH

H
OH

15

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H2O

Q.29(c)

OH

OH

OH

CH3

C2H5
C

CH3
H

CH3
C

H3C

H
C

16

New Way Chemistry for

H2O

H3C
CH3

New Way Chemistry for Hong Kong A-Level Book 3A

H2O

C
CH3

IntramolecularDehydration
Dehydrationof
ofAlcohols
Alcohols
1.1. Intramolecular

Secondary and tertiary alcohols may


dehydrate to give a mixture of alkenes

The more highly substituted alkene is


formed as the major product

17

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Dehydrohalogenationof
ofhaloalkanes
haloalkanes
2.2. Dehydrohalogenation

Elimination of a hydrogen halide


molecule from a haloalkane

By heating the haloalkane in an


alcoholic solution of KOH

H
-

OH
H

C
H

18

C
X

H
C

C2H5OH, heat

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+ H2O + X-

C
H

H
-

OH
H

C
H

C
X

H
C

C2H5OH, heat

+ H2O + X-

C
H

C2H5OH is a co-solvent for both RX and OH

19

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Dehyhalogenationof
ofhaloalkanes
haloalkanes
2.2. Dehyhalogenation
e.g.

20

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Dehyhalogenationof
ofhaloalkanes
haloalkanes
2.2. Dehyhalogenation

21

Dehydrohalogenation of secondary or
tertiary haloalkanes can take place in
more than one way

A mixture of alkenes is formed

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Q.30(a)

CH3

H3C

NaOH
H2C

Br

C2H5OH, heat
CH3

CH3

NaOH
H3C

Br

C2H5OH, heat
H

CH3

CH3

C
C
H

22

major

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H3C

CH3

H
C

C2H5

Br

C2H5OH, heat
H

CH3
C

NaOH
H3C

H3C

C
H

minor

Cl

Q.30(b)

NaOH
CH3

C2H5OH, heat
H
CH3

Cl

NaOH
major

CH3

C2H5OH, heat
H
Cl
H

NaOH

C2H5OH, heat

C
H

23

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C
H

minor

Dehyhalogenationof
ofhaloalkanes
haloalkanes
2.2. Dehyhalogenation

The ease of dehydrohalogenation of


haloalkanes decreases in the order:

>

>
Tertiary
haloalkane
24

Secondary
haloalkane
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Primary
haloalkane

25

The relative stabilities of alkenes


decrease in the order:

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Relative Stability of Alkenes in Terms


of Enthalpy Changes of Hydrogenation

Hydrogenation of alkenes is
exothermic

From enthalpy changes of


hydrogenation
predict the relative stabilities of
alkenes

26

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Enthalpy changes of hydrogenation of but-1-ene,


cis-but-2-ene and trans-but-2-ene

27

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Relative Stability of Alkenes in Terms


of Enthalpy Changes of Hydrogenation

28

The pattern of the relative stabilities


of alkenes determined from the
enthalpy changes of hydrogenation:

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Addition Reactions
Hydrogenationof
ofalkynes
alkynes
Hydrogenation

Alkenes can be prepared by


hydrogenation of alkynes
Depend on the conditions and the
catalyst employed

29

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Hydrogenation
Hydrogenation

30

Lindlars catalyst is metallic


palladium(Pd) deposited on calcium
carbonate
further hydrogenation of the alkenes
formed can be prevented
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Reactions of
Alkenes
An
Introduction
31

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Alkenes are more reactive than


alkanes

Undergoes addition reaction

rather than substitution

32

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Presence of C=C double bond

C=C double bond is made up of a bond


and a bond

Addition reactions only involve breaking


of weaker bonds of alkenes

33

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The electrons of the


bond are

diffuse in shape
less firmly held by the
bonding carbon
nuclei

Susceptible to the attack by electrophiles

34

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Electrophiles : Electron-deficient species


Attack electron-rich center e.g. C=C bond
Examples :
Cations : H+, Br+, R+, (lead to heterolysis)
Free radicals : H, Cl, R,(lead to homolysis)

35

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Nucleophiles : Electron-rich species


Attack electron-deficient site
e.g. carbonyl carbon, C=O
Examples :
anions : OH , Br , RO ,

molecules : H2O, ROH, NH3

All have lone pairs


for donating to
the reaction sites

All lead to heterolytic fissions


36

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Reactions of
Alkenes
Examples

37

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Catalytic Hydrogenation

Alkenes react with hydrogen in the


presence of metal catalysts (e.g. Ni,
Pd, Pt) to give alkanes

Lower temperatures can be used with Pd or Pt


38

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Catalytic Hydrogenation
e.g.

cis-addition, refer to notes on chemical


kinetics, pp.36-37)
39

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Catalytic Hydrogenation
O

H3C

CH2

CH3

H2 / Pt
25oC

CH3

H3C

CH3

Under mild conditions, C=O and benzene ring


are unaffected.

40

New Way Chemistry for

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Q.31
C5H10

H2 / Pt
C5H12

A
C5H10

B
H2 / Pt

no reaction

41

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A / B

42

New Way Chemistry for

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A / B

43

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*
*

44

*
*

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*
*

Application : - hardening of plant oils


Plant oil (polyunsaturated liquid with low m.p.)

Partial hydrogenation
Margarine (soft unsatd solid with higher m.p.)

Complete hydrogenation
Animal fat (hard satd solid with still higher
m.p.)

45

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Catalytic Hydrogenation

Fats and oils are organic compounds


called triglycerides
triesters formed from glycerol and
carboxylic acids of long carbon chains

46

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Catalytic Hydrogenation

Saturated fats
solids at room temp
usually come from animal sources
long carbon chains are zig-zag and
easily packed

47

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Catalytic Hydrogenation

Unsaturated oils
liquids at room temp
usually come from plant sources
lower m.p. due to cis-arrangement
(kinked shape)

48

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Catalytic Hydrogenation

49

Fats are stable towards oxidation by air

More convenient to handle and store

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Catalytic Hydrogenation

Advantages:
higher m.p. ideal for baking
turning rancid much less readily than
unsaturated oils

50

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New Way Chemistry for Hong Kong A-Level Book 3A

Application : - hardening of plant oils


Plant oil (polyunsaturated liquid with low m.p.)

Partial hydrogenation
Margarine (soft unsatd solid with higher m.p.)

Complete hydrogenation
Animal fat (hard satd solid with still higher
m.p.)

51

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O
H2C
O
O
HC
O
O
H2C
O

O
H2C
CH

H2C

150C
,
5 atm

H2 / Ni

O O
O

trans-fat coronary heart disease


52

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Catalytic Hydrogenation

Hydrogenation of vegetable oils


produces margarine
53

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Catalytic Hydrogenation

54

Margarine and butter do not have sharp


m.p. because they are NOT pure
substances.

They are mixtures containing different


triesters.

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Electrophilic Addition Reactions(AdE)

55

Addition of electrophiles to the C=C


double bond of alkenes

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Electrophiles that attack the C=C double


bond include
protons (H+)
neutral species in which the molecule
is polarized, e.g. bromine

56

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(a) Addition
Additionof
ofhalogens
halogensin
innon-aqueous
non-aqueoussolvents
solvents
(a)
CH3CCl3

X = Cl, Br or I
Occurs with or without light
Addition is preferred to substitution
Reaction mechanism is not required
57

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+ Br

Br

+ Br
Br

58

bromonium
ion

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BrC

Br

Br

Br
C

59

Br
-

Br

C
Br

Br

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transaddition

(a) Addition
Additionof
ofhalogens
halogensin
innon-aqueous
non-aqueoussolvents
solvents
(a)

60

New Way Chemistry for

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(a) Addition
Additionof
ofhalogens
halogensin
innon-aqueous
non-aqueoussolvents
solvents
(a)
e.g.

61

New Way Chemistry for

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(a) Addition
Additionof
ofhalogens
halogensin
innon-aqueous
non-aqueoussolvents
solvents
(a)
The decolourization of bromine in 1,1,1trichloroethane is a useful test for unsaturation

The reddish
brown colour
of bromine
is
decolourized

A drop of
bromine
dissolved in
1,1,1trichloroethane
is added to an
alkene

62

New Way Chemistry for

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(b) Addition
Additionof
ofhalogens
halogensin
inaqueous
aqueoussolutions
solutions
(b)
OH
C

(major)

X
C

X2(aq)

X
C

(minor)

-OH comes from H-OH which is in excess.


Reaction mechanism is not required.
63

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(b) Addition
Additionof
ofhalogens
halogensin
inaqueous
aqueoussolutions
solutions
(b)
e.g.

The consequent decolourization of the


reddish brown colour of bromine water
is also a test for unsaturation
64

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+ Br

Br

+ Br
Br

65

bromonium
ion

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H
O

H
O

H
O

Br

Br

OH
C

bromohydrin

H3O+

Br

66

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Q.32
C

Br2

NaCl(aq)
Br
C

OH
C
Br

67

Cl
C

Br

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C
Br

Cl
C

C
Br

68

Cl
C
Br

New Way Chemistry for

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Q.32
C

Br2

NaI(aq)
Br
C

OH
C
Br

69

Br

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C
Br

I
C

C
Br

70

I
C
Br

New Way Chemistry for

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Q.32
C

Br2

NaNO3(aq)
Br
C

OH
C
Br

71

ONO2

Br

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C
Br

NO3
C

ONO2
C

Br

Br

72

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(c) Addition
Additionof
ofHHXX
(c)
X = Br, Cl, OSO3H, OH, etc.
H

Br

H-Br
H

H
C

conc. H-OSO3H

C
H

H-OH

H3O

73

Mechanism
required

OSO3H

OH

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Acid-catalyzed
hydration

Additionof
ofHydrogen
HydrogenBromide
Bromide
Addition

74

A molecule of HBr adds to the C=C


double bond of an alkene

Give a bromoalkane

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Reaction Mechanism: Electrophilic Addition


Reactions of Hydrogen Bromide to Alkenes
rate-determining step

sp2 hybridized
carbonium ion
H
H

Br

fast

Br

Br

Br is a nucleophile
75

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sp2 hybridized
trigonal planar
50%

H
H

C
H

racemic mixture
-

Br

fast

Br

50%

Br

50%

If the resulting C is chiral

76

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50%

Q.33

77

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Q.33
(a) one bond and one bond are broken
(b) two bonds are formed
(c) Heat evolved during bond formation >
Heat required during bond breaking
Addition reactions are usually exothermic
view movie
78

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Regioselectivity of Hydrogen Halide Addition:


Markovnikovs Rule
CH2=CH2 & CH3CH=CHCH3 are
symmetrical alkenes.
CH3CH=CH2 is an asymmetrical alkene.

79

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Regioselectivity of Hydrogen Halide Addition:


Markovnikovs Rule

A hydrogen halide can add to an


asymmetrical alkene in either of the
two ways

The reaction proceeds to give a major


product preferentially
the reaction is said to exhibit
regioselectivity

80

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Regioselectivity of Hydrogen Halide Addition:


Markovnikovs Rule
the addition of HBr to ethene
produces bromoethane as the only
product

81

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Regioselectivity of Hydrogen Halide Addition:


Markovnikovs Rule

When but-2-ene reacts with HBr


2-bromobutane is formed as the only
product

82

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Regioselectivity of Hydrogen Halide Addition:


Markovnikovs Rule

When propene reacts with HBr


the major product is 2-bromopropane
the minor product is 1-bromopropane

83

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Regioselectivity of Hydrogen Halide Addition:


Markovnikovs Rule

H is given to the rich


84

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Regioselectivity of Hydrogen Halide Addition:


Markovnikovs Rule
Markovnikovs rule states that in the
addition of HX to an asymmetrical
alkene, the hydrogen atom adds to the
carbon atom of the carbon-carbon
double bond that already has the
greater number of hydrogen atoms

85

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Regioselectivity of Hydrogen Halide Addition:


Markovnikovs Rule

86

The products formed according to this


rule are known as Markovnikov products

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Stability of Carbocation and Mechanistic


Explanation of the Markovnikovs Rule

Carbocations are a chemical species that


contains a positively charged carbon

Very unstable

Exist transiently during the reaction

Classified as primary, secondary or tertiary


according to the number of alkyl groups
that are directly attached to the
positively charged carbon

87

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Stability of Carbocation and Mechanistic


Explanation of the Markovnikovs Rule
The more stable the carbocation
the more stable the transition state
the lower the activation energy
the faster its formation

88

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Stability of Carbocation and Mechanistic


Explanation of the Markovnikovs Rule

89

The stability of the carbocations


increases in the order:

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Alkyl groups stabilize the positively charged


carbocation by positive inductive effect

90

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A greater number of alkyl groups


release more electrons to the
positively charged carbon
increase the stability of the carbocation

91

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Stability of Carbocation and Mechanistic


Explanation of the Markovnikovs Rule

92

Consider the addition of HBr to propene:

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Stability of Carbocation and Mechanistic


Explanation of the Markovnikovs Rule

93

The hydrobromination of propene involves


two competing reactions:

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Since the formation of carbocation is the


rate-determining step,
the overall reaction is faster if it involves
the formation of a more stable
carbocation.
94

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Q.34(a)

X = Cl, Br, or I

H3C

H
C

HX
H3C

H3C

CH3

CH3

H3C
CH2H

>

H3C

H3C

95

C
H

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H
C
H

Q.34(b)
H3C
C
H

OH

heat

cold

H3C

H
C

CH3

CH3

CH3

OSO3H

96

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> C2H5

C
H

97

On heating, alkyl hydrogensulphates


form alkenes and sulphuric acid

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Separation of a mixture containing an alkane


and an alkene.
Alkane / Alkene
conc. H2SO4 / cold
no reaction

addition

Alkane
insoluble in
conc. H2SO4
Separated by separating
funnel
98

New Way Chemistry for

OSO3H

dissolved in
conc. H2SO4

New Way Chemistry for Hong Kong A-Level Book 3A

Separation of a mixture containing an alkane


and an alkene.
Alkane / Alkene
conc. H2SO4 / cold
no reaction

Alkane
insoluble in
conc. H2SO4

addition

heat

Alkene
99

New Way Chemistry for

OSO3H

dissolved in
conc. H2SO4

New Way Chemistry for Hong Kong A-Level Book 3A

Alkyl hydrogensulphates can be easily


hydrolyzed to alcohols by heating with
water

conc. H2SO4 + H2O dilute H2SO4


acid-catalyzed hydration
100

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(c) Addition
Additionof
ofHHXX
(c)
X = Br, Cl, OSO3H, OH, etc.
H

Br

H-Br
H

H
C

conc. H-OSO3H

C
H

H-OH

H3O

101

Mechanism
required

OSO3H

OH

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Acid-catalyzed
hydration

Acid-catalyzed hydration
H3C

H
C

O
H

102

OH

H3C

C
H

CH3

CH3

O
H

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C
H

CH3

Acid-catalyzed hydration
H

H
O

CH3

H
O
H

CH3

CH3

HO

C
H

The acid catalyst is + H3O+


regenerated
103

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CH3

Q.34(d)
OH

H2O / H+

(d)

>

3
104

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Q.34(c)
H3C

H
C

I Cl

H3C

H3C

H
H3C

electron-donating
C

CH2I

>

H3C

H3C

3
EN : C = I = 2.5
105

CH3

Cl

CH3
C

H
C
H

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Q.34(e)
F3C

(e)
H

H HCl
Cl

CF3

Cl

CF3

F3C
C

CH3

<

C
H

More destabilized by negative


inductive effect
106

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H
C
H

Q.34(f)
Cl

(f)
H

Cl

Cl

CH3

CH3

>

The resonance effect more than compensates the


negative inductive effect of Cl
107

Cl

Cl

Cl

H HCl
Cl

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H
C
H

Q.34(g)
H

(g)
H

H HBr
Br

Br

>

CH3

108

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H
C
H

C
H

CH3

C
H

The +ve charge is shared by the


benzene ring by resonance effect.
Stabilized by resonance effect as
well as inductive effect(2)
109

CH3

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CH3

C
H

CH3

benzylic carbocation

CH3

More stable than 3 carbocation

110

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Q.34(h)
H2C

C
H

C
H

CH2

excess H F

111

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CH2H
H2C

C
H

H2C

CH2H
C

>

H2C

C
H

C
H

Allylic carbocation is stabilized by


resonance effect.
Stabilized by resonance effect as well as
inductive effect
Stability : Benzylic > allylic > 3 > 2 > 1 > CH3+
112

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CH2H

CH2H
H2C

C
H

H2C

C
H

HF
H

H
C
H

> H

less destabilized by ve I-effect of F


113

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Effect of substituents on the reactivity of AdE

1.
Electron-donating groups increase the
reactivity by
(a) the electron density of C=C bond,
thus making it more susceptible to
electrophilic attack.
(b) Stabilizing the carbocation
intermediate/T.S. by +ve I-effect and/or
resonance effect, thus lowering the Ea for
the rate-determining step.
114

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Effect of substituents on the reactivity of AdE

2.

Resonance effect > inductive effect

3.
Electron-withdrawing groups lower the
reactivity by working in the opposite
ways.

115

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Q.35
H

H3C

116

H3C

>

CH3

C
CH3

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CF3
C

>

H
C

>

CH3
C

>
H

CH3

Oxidation of alkenes
(a)
C

Combustion
C

O2

CO2 + CO + C + H2O

More sooty and luminous than that of


corresponding alkanes due to higher carbon
contents

117

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(b)

Reaction with KMnO4

R1

R3
C

R2

R4

KMnO4, H+ or OH

R2

cold

R1

R3

OH

OH

R4

Used as a test for alkenes


R1

R3
C

R2

118

C
R4

KMnO4, H+ or OH
heat

R1

R3
C

R2

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C
R4

R1

R3
C

R2

KMnO4, H+ or OH
heat

R4

R1

R3
C

R2

R4

If all R groups are alkyl groups,


ketones will be the final products.
H3C

CH3
C

H3C

119

C
CH3

H3C

KMnO4, H+ or OH

heat

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H3C

New Way Chemistry for Hong Kong A-Level Book 3A

H3C
C
H3C

120

KMnO4, H+ or OH
heat

No reaction

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R1

R3
C

R2

KMnO4, H+ or OH
heat

R4

R1

R3
C

R2

C
R4

If either R1 or R2 is H / either R3 or R4 is H,
further oxidation of aldehydes to carboxylic
acid will occur.
H3C
C
H

121

H3C

CH3

KMnO4, H+ or OH

C
H

heat
H

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H3C

H3C

KMnO4, H+ or OH

heat

HO

carboxylic
acid

aldehyde

122

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R1

R3
C

R2

R4

KMnO4, H+ or OH
heat

R1

R3
C

R2

R4

If both R1 & R2 are H / both R3 & R4 are H,


further oxidation to first methanoic acid
and then CO2 will occur.
H
C
H

123

KMnO4, H+ or OH

C
H

heat

2
H

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H
C

KMnO4, H+ or OH
heat

2CO2 + 2H2O

HO

methanoic acid
124

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(c)

Ozonolysis
O

CH3CCl3

O3

< 20oC

unstable ozonide
O

+
O

H 2O

Zn dust
CH3COOH

H2O2

Further oxidation of aldehyde to carboxylic


acid by H2O2 is inhibited using Zn dust and
CH3COOH
125

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(c)

Ozonolysis

H3C

CH3
C

H3C

H
C

H3C

126

C
H

1. O3
2. Zn dust / H2O
1. O3
2. Zn dust / H2O

CH3

H3C
C

+ O

H3C

H
C

H3C

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+ O

C
H

Oxidative cleavage can be used to locate C=C


bond in an unknown sample

127

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Q.36

CH3
H2C

CH3
C

(3Z)-2-methylpenta-1,3-diene
CH3
H2C

H
C

C
CH3

(3E)-2-methylpenta-1,3-diene
128

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Q.36

H3C

CH3

CH2
H

(3E)-3-methylpenta-1,3-diene
H
H3C

CH2

CH3

(3Z)-3-methylpenta-1,3-diene
129

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Q.37

130

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Q.37

131

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Q.37

132

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The END

133

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28.4 Preparation of Alkenes (SB p.173)

Classify the following alcohols as primary,


secondary or tertiary alcohols.
(a) CH3CHOHCH2CH3
(b) CH3CH2CH2OH
(c) (CH3)2COHCH2CH2CH3
(a) It is a secondary alcohol.
(b) It is a primary alcohol.
(c) It is a tertiary alcohol.

134

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Answer
Back

New Way Chemistry for Hong Kong A-Level Book 3A

28.4 Preparation of Alkenes (SB p.173)

Back

Classify the following haloalkanes as primary,


secondary or tertiary haloalkanes.
(a)

(b)

(c)

(a) A secondary haloalkane


(b) A primary haloalkane
(c) A tertiary haloalkane

Answer
135

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28.5 Reactions of Alkenes (SB p.177)

Of the isomeric C5H11+ carbocations, which one


is the most stable?
The more stable C5H

+
11

carbocation is the tertiary

carbocation as shown below:

Back

136

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Answer

28.5 Reactions of Alkenes (SB p.179)

Back

Both alkanes and alkenes undergo halogenation. The


halogenation of alkanes is a free radical substitution
reaction while the reaction of alkenes with halogens is
an electrophilic addition reaction. Can you tell two
differences between the products formed by the two
different types of halogenation?

Answer

Alkenes give dihalogenated products while alkanes usually give


polysubstituted products. Another difference is the position of the
attachment of the halogen atom. For alkenes, the halogen atom is
fixed to the carbon atom of the carbon=carbon double bond. In the
substitution reaction of alkanes, the position of the halogen atom
varies.
137
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Chemistry
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Chemistry
for Hong
Kong A-Level
Book 3A

28.5 Reactions of Alkenes (SB p.183)

(a) What chemical tests would you use to


distinguish between two unlabelled
bottles containing hexane and hex-1-ene
respectively?
Answer
(a)

138

We can perform either one of the following tests:


Hex-1-ene can decolourize bromine water or chlorine water in
the dark while hexane cannot.
Hex-1-ene can decolourize acidified potassium manganate(VII)
solution while hexane cannot.

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28.5 Reactions of Alkenes (SB p.183)

(b) What is the major product of each of the


following reactions?
(i)

(ii)

Answer
139

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28.5 Reactions of Alkenes (SB p.183)

(b)

(i)

(ii)

140

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28.5 Reactions of Alkenes (SB p.183)

(c) Give the products for the following


Ni
reactions:
conc.
(i) CH3CH = CH2 +
H2 H2SO4
(ii) CH3CH = CHCH3
(iii)

141

CH3CH = CHCH3 + Br2

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Answer

28.5 Reactions of Alkenes (SB p.183)

Back
(c)

(i)

CH3CH2CH3

(ii)

(iii)

142

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28.5 Reactions of Alkenes (SB p.184)

(a) Arrange the following carbocations in


increasing order of stability. Explain your
answer briefly.

Answer
143

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28.5 Reactions of Alkenes (SB p.184)

(a)

The increasing order of the stability of carbocations is:

Tertiary carbocations are the most stable because the three alkyl
groups release electrons to the positive carbon atom and thereby
disperse its charge. Primary carbocations are the least stable as
there is only one alkyl group releasing electrons to the positive
carbon atom.

144

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28.5 Reactions of Alkenes (SB p.184)

(b) Based on your answer in (a), arrange the


following molecules in the order of
increasing rates of reaction with hydrogen
chloride.

Answer
145

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28.5 Reactions of Alkenes (SB p.184)

Back
(b)

The reaction of these compounds with hydrogen chloride involves


the formation of carbocations. Therefore, the order of reaction
rates follows the order of the ease of the formation of
carbocations, i.e. the stability of carbocations:

Therefore, the rates of reactions of the three compounds with


hydrogen chloride increase in the order:

146

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