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Alkenes

(chapter 31)
Preparation

Industrial - cracking

Laboratory

1. Elimination
a. Dehydrohalogenation of haloalkanes
RX => alkene
b. Dehydration of alkanols
ROH => alkene

4. Hydrogenation of alkynes
Physical properties
Alkene m.p. oC b.p. oC density
CH2=CH2 -169.4 -102.4 0.610
CH2=CHCH3 -185.0 -47.7 0.610
CH2=CHCH2CH3 -185.0 -6.5 0.643
Cis-CH3CH=CHCH3 -139.0 3.7 0.621
Trans-CH3CH=CHCH3 -106.0 2.9 0.604
CH2CH=C(CH3)2 -140.7 -6.6 0.627
CH2=CH(CH2)2CH3 -138.0 30.1 0.643
Chemical properties

Weaker π bond (Bond energy: C=C 611


C-C 346)

More reactive than alkanes.

π electrons in C=C bond are easily


polarized, acts as a source of electrons,
Eσ+---Nσ-
attacked by electrophiles.
Electrophilic Additions of Alkenes

δ+ δ-
C=C + E-N C C
δ+ δ-
E N

δ+ δ-
E-N = H-Cl, H-Br, H-I, H-OSO3H ,
H-OH (H3O+), Cl-Cl, Br-Br,
Br-OH, Cl-OH
Electrophilic Additions of Alkenes

C=C + H-X C C Hydrohalogenation


H X
+ H-OSO3H C C Hydrogensulphate
H OSO3H
H
+
+ H2O C C Hydration
H OH
+ X2 C C Halogenation
X X
+ X-OH C C Halohydrin
X OH formation
Mechanism of Addition reactions

Carbonium ion as intermediate (H-X, acidic reagents)

Two
steps:
δ+ δ-
C=C + H-X C C + X-
δ+ δ- +
H

C C + X- C C
+
H H X
Orientation of Addition reactions

CH3CH=CH2 + H-X => CH3CHXCH3 + CH3CH2CH2X


(major)

Markovnikov’s rule: In addition of HX to alkenes,


hydrogen adds to the doubly-bonded carbon that
has the greater number of hydrogen already attached
to it.
Orientation of Addition reactions
CH3CH=CH2 + H-X

CH3-CH-CH3 CH3-CH2-CH2
+ +
(more stable) (less stable)
X- X-

CH3CHXCH3 CH3CH2CH2X
(major product) (minor product)

(-R group has +inductive effect, stabilizes the carbocation.)


Orientation of Addition reactions

H
CH3-CH2-CH2
+

CH3-CH-CH3
+
CH3CH2CH2X
CH3CH=CH2 + H-X
CH3CHXCH3
Reaction coordinate
Electrophilic Additions of Alkenes

C=C + c. H2SO4 C C
H OSO3H
(Alkyl Hydrogensulphate)

H2O

Uses:
C C Produce alkanol
H OH Separate alkenes from alkanes
(Alkanol)
Catalytic Hydrogenation
Pt/Pd/Ni
CH3CH=CHCH3 + H2 CH3CH2CH2CH3
heat, pressure

Transition metals are able to adsorb


hydrogen on to their surface to form
metal-hydrogen bond.
H C
The alkene molecule then reacts
H C with these adsorbed hydrogen.
Nickel
The lowered activation energy makes
the reaction goes faster.
Catalytic Hydrogenation

Heterolytic catalyst

Exothermic

Stereochemistry:
The two H atoms are added from the same
side of the π-bond of the alkene molecule.
(syn or cis-addition)
Hardening of oils - Margarine

Margarine is made from vegetable oils by


the hydrogenation of double bonds in the oil.
Hydrogenation converts liquid oils (polyunsaturated
fats) into semi-solid fats (partially saturated fats).
Hardening of oils - Margarine

CH2-OOC(CH2)14CH3
CH-OO(CH2)7CH=CH(CH2)7CH3 + 3 H2
CH2-OO(CH2)6(CH2CH=CH)3CH2CH3
vegetable oil
Powdered
Ni catalyst,
420K and 5 atm. pressure
CH2-OOC(CH2)14CH3
CH-OO(CH2)7CH=CH(CH2)7CH3
CH2-OO(CH2)16CH3
margarine
Link

Check point 31-2


Ozonolysis

1. O3
CH2=CH2 2 HCH=O
2. Zn,H2O

Step 1: Oxidation
Step 2: Hydrolysis by adding water, zinc is used
to prevent H2O2 from oxidizing the aldehydes.
Ozonolysis

By analysing the products from ozonolysis,


the position of the C=C bond in the alkene
molecule, and hence the structure can be
determined.

1. O3
e.g. X CH3CHO + CH3COCH3
2. Zn,H2O

X: CH3CH=C(CH3)2
Ozonolysis

Predict the structures of the following hydrocarbons


using the information:

• OHC-(CH2)4-CHO (C6H10)
• CH3CHO, OHC-CH2-CHO (C10H16)

Check Point 31-3


Polymerization

O2,200-400oC
n CH2=CH2 → (-CH2CH2-)n Poly(ethene)
1500 atm
n = 700 – 800
Molar mass 20000 - 25000
Polymerization
Free radical mechanism:

Chain Initiation
RO-OR → 2RO· (organic peroxide)
RO· + CH2=CH2 → RO-CH2-CH2·
Chain Propagation
RO-CH2-CH2· + CH2=CH2 →
RO-CH2CH2-CH2-CH2·
Chain Termination
2 RO-(CH2CH2)m-CH2-CH2· →
RO-(CH2CH2)m-CH2-CH2-CH2-CH2-(CH2CH2)m-OR
Low Density poly(ethene) LDPE

Condition: high pressure,


1500 atm, 200oC.

Consists of mainly
irregularly packed, branched
chain polymers.

Properties: highly deformable, low tensile strength


and low m.p. (105oC)

Uses: plastic bags, wrappers, squeeze bottles.


High Density poly(ethene)
HDPE

Condition: lower pressure


(2-6 atm), 60oC. Ziegler-
Natta Catalyst (ionic
mechanism).

Consists of regularly
packed, linear
polymers with extensive
crystalline region. Uses: Rigid articles
such as refrigerator ice trays,
buckets, crates.
Poly(propene)

Ziegler-Natta Catalyst
nCH3-CH=CH2 → (-CH-CH2-)n poly(propene)
CH3

More rigid than HDPE.


Regular structure, -CH3 group arranged on one
side (isotactic) of the polymer chain.

Uses: Crakes, kitchenware food containers,


fibres for making hard-wearing carpets.
Isotactic (Me all on same side)
CH3 H CH3 H CH3 H CH3 H CH3 H

Syndiotactic (Me on alternate sides)


CH3 H H CH3 CH3 H H CH3 CH3 H

Atactic (Me randomly distributed)


CH3 H CH3 H H CH3 CH3 H H CH3
Poly(phenylethene) or Polystyrene

peroxides
nC6H5-CH=CH2 → (-CH-CH2-)n
reflux in kerosene C6H5

Stiffer than poly(ethene), greater Van der Waals’


force due to the benzene rings.

Uses: Toys, cups, refrigerator parts.


Expanded polystyrene for packaging, heat
and sound insulation.
Past AL papers
Markovnikov’s rule and Mechanism of
Electrophilic addition:
90II Q.8 (4b)
91 I Q.1 (6a)
93II Q.9 (20b)
94 I Q.3 (21b)
96II Q.9 (37b)
Polymerisation of alkenes
93I (17)
94II Q.9 (26b)
95I (29)
97I Q.4 (38c)
Practice questions

CH3 CH3
• ?(Alkene) + ?(reagent) => CH3-C-CH2-C-CH3
H OH

CH3 CH3 CH3 CH3


Ans. CH3-C-CH=C-CH3 or CH3-C-CH2C=CH2
H H
Practice questions

2. (CH3)2C=CHCH3 + I-Cl => ?

Ans. (CH3)2C-CH (CH3)


Cl I
Practice questions

3. H2C=CHCF3 + HCl => ?

Ans. CH2ClCH2CH3