CHEMISTRY FORM 6

ORGANIC CHEMISTRY
CHAPTER 2 : HYDROCARBON

Hydrocarbon which contain only

carbon-carbon single bond, CC

Hydrocarbon which contain at least

one carbon-carbon double bond, C=C
or triple bond, CC

2.1
Nomenclature of ALKANE

Alkane is a saturated hydrocarbon as it contain only single bond in
its molecule

General formula for homologous series of alkane is CnH2n+2

Table below shows the naming of straight chain of alkane

Name

Molecula
Molecular structure
r formula

Name

Molecula
Molecular structure
r formula

Methane

CH4

Ethane

C2H6

Propane

C3H8

Butane

C4H10

Pentane

C5H12

Hexane

C6H14

2.2

Naming alkane according IUPAC

Step 1
Step 2
Step 3
Step 4
Place a prefix
State the position
Find the longest
Identify the
upon the similar where the branch
chain of carbon
branched carbon
and name
(alkyl group) that alkyl group (if any). is located at which
If there is 2 similar carbon based on
accordingly. (it
attached to the
the numbering
does not has to be main chain. Then, alkyl, prefix di is
gave earlier.
a straight chain).
placed, if 3 similar
name the alkyl
accordingly
alkyl, prefix tri is
CH3
methyl
placed.
CH3CH2
ethyl
CH3CH2CH2-propyl

3-methylpentane

3,5-dimethylheptane 3-ethyl-4-methylhexane

3-ethyl-3,5dimethyloctane

CH3(CH2)5CH3

CH(CH3)2C(CH3)3

CH3CH(CH2CH3)2

C(CH3)3CH2C(CH3)3

n-heptane

2,2,3-trimethylbutane

3-methylpentane

2,2,4,4tetramethylpentane

2,3-dimethylpentane

3-ethyl-3methylhexane

2,2,3-trimethylpentane

3,3-diethylhexane

Step 3
Complete the structure by placing one hydrogen
(H) atom at each of single bonds.

Isomer of hexane, C6H14

2.4

Physical properties of alkane

Alkane

CH4

C2H6

C3H8

C4H10

C5H12

C6H14

C7H16

C8H18

Boiling
point oC

162

8.6

42.2

0.5

36.3

68.7

98.4

126

Boiling point
trend
Density
(g/cm3)
Density trend
Solubility

BOILING POINT INCREASE DOWN HOMOLOGOUS SERIES

--

--

0.50

0.58

0.63

0.66

0.68

DENSITY INCREASE DOWN HOMOLOGOUS SERIES

water
Not soluble in CCCCCCC..
organic solvent
Soluble in CCCCCCCCCCCC

0.70

A)
Boiling point of alkenes

The boiling point increase
CCCC when going down to homologous series
of alkane.

All alkane possessed the same intermolecular forces : weak
Van Der Waals
CCCCCCCCforces
molecular mass stronger the CCCCCCCCC
weak Van Der Waals

Greater the CCCCCCCC,
forces, increase
CCCC the boiling point

Boiling point of isomers of the same molecular formula varies with
the branched molecules
H

H
H

H
H

H
H

H
H

H
H

H
H

higher boiling point compared to branched chain

Straight chain has ..CC..
total surface area
as straight chain molecule has higher CCCCCCCCCC
compared to a branched chain. The positioning of alkyl and number
of alkyl also effect the boiling point of alkane. 2-methylpentane as a
higher boiling point than 3-methylpentane as it has a greater
exposure of intermolecular forced

B)
Solubility of alkane
non-polar

All alkanes are often consider as CCCCCCCCC
molecule as the dipole of moment created in molecule is
very small.
non-polar

Since alkane is CCCCCCC.
Molecule, it dissolve
easily in non-polar solvent such as benzene, and ether.
hydrogen

Alkane does not form CCCCC bond in water, so it is
insoluble in water. Thus, alkane is also described as
CCCCC
hydrophobic (waterhating).
CCCCCC.

The longer the alkane chain, the more insoluble it is in
water.

2.5
Chemical Properties of Alkane
2.5.1 Preparation of Alkane

Alkane can be prepared using the following methods :

Decarboxylation of sodium salt of a carboxylic acid
RCOOH + NaOH RH + Na2CO3
Example : CH3COOH + 2 NaOH
CH4 + H2O + Na2CO3

Kolbes method : electrolysing concentrated sodium ethanoate

Cathode : 2 H2O + 2 e-
H2 + 2 OH
Anode : 2 CH3COO-
C2H6 + 2 CO2 + 2 e
Wurtz reaction : reaction of sodium on alkyl halide in ether.

2 RX + 2 Na
R R + 2 NaX
Example

2 CH3CH2Cl + 2 Na
CH3CH2CH2CH3 + 2 NaCl

2.5.2 Reaction of Alkane

saturated hydrocarbon, so alkane is inert to

Since alkane is a CCCCC.
most of the chemical reaction

Table below shows the description of reaction of ethane with other
substances.
Reagents

Effect on ethane

Sodium hydroxide aqueous

No effect on hot or cold condition

Concentrated hydrochloric acid

No effect on hot or cold condition

Acidified potassium manganate (VII)

No effect on hot or cold condition

Air (oxygen)

No effect under room condition. Burns when heated

Bromine water

No effect on dark. Decolourised slowly under sunlight

Chlorine gas

No effect on dark. Reaction occur under sunlight

From the series of reaction above it can be conclude that

Ethane does no react with polar or ionic substances
Ethane react with non-polar substances such as Cl2 , Br2 and O2
and energies are required for reaction to occur.

1.

Combustion of alkanes
All hydrocarbon react with oxygen to form carbon dioxide and water.
The equation for a complete combustion for all hydrocarbons can be
represented by the equation
y

C X H y + x + O 2 x CO 2 +
4

C2H6

y
H 2O
2

H = m kJ / mol

C2H6 + 7/2 O2
2 CO2 + 3 H2O

C5H12 C5H12 + 8 O2
5 CO2 + 6 H2O

C8H18 C8H18 + 25/2 O2
8 CO2 + 9 H2O

Note that the reaction is exothermic for all hydrocarbons. Equation

above is also known for Hc. Higher the number of carbon, the more
exothermic the reaction.
Under limited supply of air (oxygen), sometimes, carbon monoxide
(CO) is produced instead of CO2.

2. Halogenation of alkanes

When alkane is run together with chlorine gas under the presence of
ultraviolet ray (which comes naturally from sunlight)
Example : CH4 (g) +
Cl2 (g)
CH3Cl (g) + HCl (g)
C2H6 (g) + Cl2 (g)

The mechanism for the reaction of chlorination of alkane can be
explained using the following steps
Step 1 : Initiation

Step 2 : Propagation

Since chlorine radical are highly

reactive, when it collide with
Cl Cl
2 Cl H = +242 kJ/mol methane molecule forming HCl
H3CH
CH3 + H
and methyl radical
H = + 433 kJ/mol H CH + Cl
H C + HCl

chlorine required lower

Since ......................
energy to form radical, so the
initiation will start off with

chlorine Gas
CCCCC..

Methyl radical will propagate with

other chlorine molecule and
forming back chlorine radical
H3C + ClCl
H3CCl + Cl
Under such propagation reaction
thousands of methane and chlorine
molecules will react continuously

Step 3 : Termination

When 2 free radicals collide with

each other and combined, the
reaction stops. This reaction is highly
exothermic, where
H3C + Cl
H3CCl
H = -349 kJ/mol
H3C + CH3
H3CCH3
(H = -368 kJ/mol
Usually, termination will occur when
[radical] > [molecule], which is after
thousands of propagation.
The presence of small amount of
ethane may also present due to the
collision between 2 methyl radicals

2.1.1 Sources of hydrocarbon

The main sources of hydrocarbons are :

a) crude oil
b) coal
c) natural gas
Since all these main sources are made up from dead animals and
fossil fuel
plants, so they are also known as CCCCCCCC
Coal is complex mixture consisting mainly hydrocarbons, which is
mainly made up from dead plaints in swamp.
Petroleum is a mixture of hydrocarbons (alkanes, alkenes, alkyne),
ethane
while natural gas contain mainly methane
C.CCC and some CCCCC
The mixture in petroleum can be separated by using
fractional distillation in oil refinery. Diagram below shows the
CCCCCCCCCC.
chamber and oil refinery used to separate the mixture of petroleum.

Fractional
distillation

Products

Uses

Petrol gas

Use for house cooking gas

Gasoline

Use as fuel for automobile vehicle

Naphtha

Use to synthesis different petrochemical

Kerosene

Use as fuel for jet engine and oil stove

Diesel oil

Use as fuel of heavy vehicle such as

bus or lorry

Lubricant Oil

Use for lubrication, making wax and

polish

Fuel Oil

Fuel for ship and power station

Bitumen (asphalt)

Use as tar for paving road surface

and coating underground water pipe

The separation does not end with fractional distillation. They are then
treated with various ways to improve the quality and quantity of
useful hydrocarbon. One of the major treatments gives after
fractional distillation is cracking process.
Cracking of hydrocarbon

Thermal cracking (Pyrolysis)

Catalytic cracking
 Using high temperature, bond breaking  With the aid of zeolite as catalyst,
(homolytic fission) take place and form
carbon cracking can occur at lower
various products of unbranched alkane
temperature compare to thermal
and alkene
cracking.
 Example, when breaking decane, C10H22  Products using catalytic cracking usually
C10H22 C3H6 + C7H16
contain branched alkane and alkene.
C10H22 C4H8 + C6H14
C10H22

2.7
Cycloalkane (alicyclic compound)

Cycloalkane has a general formula of CnH2n

Some examples of cycloalkane
Cycloalkane

Molecular
formula

Cyclopropane

C3H6

Cyclobutane

C4H8

Cyclopentane

C5H10

Cyclohexane

C6H12

Displayed formula

Skeletal formula

2.7.1 Naming cycloalkane

The way of naming cyclolalkane is more or less the same with
naming alkane. If theirs is one alkyl attached to the cycle, it will be
automatically become 1 by itself. E.g. methylcyclobutane
(not 1-methylcyclobutane)

If theres more than one group attaching the cycle, only then
numbering will be given to the particular number of C that it is
attached.

methylcyclopropane
1,2,4-trimethylcyclohexane

3-ethyl-1-methylcyclopentane

3-ethyl-2-methyl-1propylcyclobutane

1,2,3-trimethylcyclooctane

2.7.2
Preparation and Reaction of Cycloalkane

Cycloalkane can be prepared by catalytic hydrogenation of benzene
at 200oC

Reaction of cycloalkane is similar to alkane. When react with chlorine

/ bromine gas under sunlight, substitution reaction take place

Mechanism :

Initiation

Propagation

Termination

2.8
Alkene Nomenclature of alkenes and cycloalkenes

The homologous series of alkenes has general formula of CnH2n.

The significance of alkene is all of them have C=C in their molecules
with its name end with ene
Name

Molecular
formula

Ethene

C2H4

Butene

C4H8

Molecular structure

Propene

But-2-ene
Pentene

Molecular
Molecular structure
formula
C3H6

But-1-ene

C5H10
pent-2-ene
Hex-1-ene

Hexene

Name

C6H12

pent-1-ene
Hex-2-ene

Hex-3-ene

In naming alkene, the following steps are given

Step 1 : Find the longest C C chain which contain double bond
in it (parent chain) and name them
Step 2 : Find and name the alkyls attached to the parent chain.
Step 3 : If there are more than 2 of the same type alkyls, prefix
are put accordingly.
Step 4 : Put the number of the alkyl that attached to the
particular carbon atom.
Example : Name the following alkenes accordingly

2-methylpropene
2-methylbut-2-ene

2,3-dimethylpent-2-ene
2-ethyl-3-methylpent-1-ene

3,5-dimethylhept-3-ene
3,4-dimethylhex-3-ene

2.8.1 Naming alkene with more than one single bond & cycloalkene

A diene (alkene with 2 C=C bond) and cycloalkene has general
formula of CnH2n2.

In diene, the position of both C=C in parent chain has to be stated in
alkan-x,y-diene, whereas in cycloalkene, C=C is always place as
C1=C2. So the numbering is fixed for naming.

Example, name the following diene / cycloalkene below

2-methylbut-1,3-diene

3-methylcyclopropene

2,5-dimethylhex-1,3-diene

3-ethyl-2-methylcyclohexene

oct-2,5-diene

3,4,5-trimethylcyclopentene

2.9
Isomerism in alkene.

Alkenes which contain at least 4 Carbon atoms may exhibit 2
isomerism, structural and stereoisomerism.

For example, butane (C4H8) contain 5 isomers.

CH3

Isomers of pentene

CH2CH3

CH3

CH3

CH3

CH3

2.10

Physical Properties of Alkene

Alkene

C2H4

C3H6

C4H8

C5H10

C6H12

C7H14

C8H16

C9H18

Boiling
point oC

164

12.0

5.8

0.5

38.0

72.07

96.5

117

Boiling
point trend
Solubility
in water

Boiling point increase

Insoluble in water (solubulity decrease)

A)
Boiling Point of Alkene
increase when going down to homologous series

The boiling point CCCC
of alkane.

All alkane possessed the same intermolecular forces : weak
Van Der Waals
CCCCCCCforces
weak Van Der Waals forces,
molecular mass stronger the CCCCCCCCC

Greater the CCCCCC..,
higher
CCCC
the boiling point

2.11 Preparation of Alkene

Alkene can be prepared in a few ways
Name of
reaction

Reagent used
and condition

Ethanolic
Dehydrohalogenation
sodium
from
hydroxide (heat
haloalkane
& reflux)

Dehydration
(removal of
water)
from
alcohol

Excess conc.
H2SO4
at 1800C
or
Alumina
(Al2O3) at
350oC

Equation

2.12

Chemical reaction of alkene

Name of
reaction

Reagent used and

condition

Hydrogen gas
CH3CH=CH2 + H2 (g)
under
propene
-------------Nickel (Ni) at
Hydrogenation
180oC
@
Platinum (Pt) at
room temperature
cyclohexene
Halogenation

Halogen gas, X2
(X2 = Cl2 ; Br2 ; I-2)

Addition of
Hydrogen
halide

Hydrogen halide
(HX)
(X = Cl ; Br ; I)

Equation
Ni

CH3CH2CH3 (g)
propane

cyclohexane

Name of
reaction

Reagent used and

condition

Hydration

Steam (H2O)
--------Phosphoric acid,
(H3PO4 )
At 300oC ; 60 atm

Equation

Hydroxylation
(cold, diluted KMnO4 (aq) / H+
(cold and diluted)
acidified
KMnO4)
ethanal
H

methanal
H

Oxidation
(under hot,
concentrated
acidified
potassium
manganate
(VII)

C
H

H+

KMnO4 (aq) /
(hot &
concentrated)

C + 2 [O]

KMnO4 / H

hot, concentrate

+ O

propene

[O]

[O]

OH

ethanoic acid

CO2
+
H2O

2.12 Chemical reaction

(1)
Hydrogenation of alkene

Carry out under mixture of alkene and hydrogen over a finely
divided transition metal as a catalyst.

2 catalysts can be used in hydrogenation
i) Platinum : ~ can react even under room condition. Longer alkene
required some heat
ii) Nickel : ~ required high temperature to allow hydrogenation to occur
(180oC)

Hydrogenation is an exothermic reaction and its H is about 120
kJ / mol

CH3CH=CH2 (g) + H2 (g)
CH3CH2CH3 H = 124 kJ / mol

Catalytic hydrogenation is important in food industries especially in
hardening unsaturated fats and oil to make margarine. Unsaturated
hydrocarbon makes them too soft for commercial use.

CH3(CH2)7CH=CH(CH2)7COOH + H2 (g)
CH3(CH2)16COOH

In industries, a special Raney Catalyst is used to replace platinum
as it is EXPENSIVE!!!

(2)
Halogenation of alkene

Chlorine and bromine react readily with alkene and form
dichloroalkane and dibromoalkane respectively. Cl2 and Br2 gas are
add across double bond.

CH3CH=CH2 (g) + Cl2 (g)
CH3CH(Cl)CH2Cl

The mechanism of halogenation can be explained by a few steps
describe below :

Step 1 : Formation of carbocation propene has region of high
electron density because of the electron. When Cl2 approaches,
molecule is strongly polarised by region and consequently formed
an induce dipole. The positive charge end of Cl2 molecule act as
electrophile and bond to C=C via electroplilic addition and caused
Cl+Cl repelled. As a result, carbocation & chloride ion are
formed.

Step 2 : Nucleophilic attack to form addition product carbocation

formed is very unstable. It quickly combines with Cl ion to produce
by heterolytic fission of Cl2 molecule to give 1,2-dichloropropane.

However, if bromine water is used instead of bromine gas, the

results of products are not as same as in bromine gas. When
bromine water is reacted with propene

(3)
Addition of hydrogen halide

Unlike addition of halogen, addition of hydrogen halide produced 2
products. For example, when propene react with hydrogen bromide
(HBr)
CH3CH=CH2 + HBr
CH3CH2CH2Br + CH3CH(Br)CH3
Propene
1-bromopropane
2-bromopropane
(minor)
(major)

The major / minor product of the reaction can be predicted using
Markovnikoffs Rule where it stated when an unsymmetrically
substituted alkene reacts with a hydrogen halide, the hydrogen adds
to the carbon that has the greater number of hydrogen substituents,
and the halogen adds to the carbon having fewer hydrogen
substituents.

Step 1 : Electrophilic attack when the polar hydrogen bromide

approaches propene, the positively charged hydrogen ion is
polarising C=C, and caused Br to form

Step 2 : Nucleophilic attack the negative bromide ion react fast

with the unstable carbocation.

Relative stability of carbocation can be explained using

Markovnikoffs Rule. According to the rule, a tertiary (30) carbocation
is more stable than a secondary (20) carbocation than a primary (10)
carbocation. this is due to the inductive effect of the electrondonating alkyl group.
In the example above, there are 2 methyl group donating electron to
positive charged carbon electron at 20 carbocation whereas there
are 1 ethyl group in 10 carbocation donating electron to the
positively charged electron.
As a result, 20 carbocation are more stable as the 2 alkyl group tend
to decrease the charge density of C, making the cation more stable.

stability of carbocation increase.

(4)
Hydration (addition of water) in alkene

Using phosphoric acid as acidic medium, hydration of alkene can be
represent by equation :
CH3C(CH3)=CH2 + HOH

CH3CH(CH3)CH2OH + CH3C(CH3)(OH)CH3

(minor)
2-methylpropene

2-methylpropan-1-ol

(major)
2-methylpropan-2-ol

Similar to hydrogen halide, hydration of alkene follows

Markovnikoffs Rule.
The mechanism of hydration of alkene is slightly different from
addition of hydrogen halide

Step 1 : Protonation of the carboncarbon double bond in the

direction that leads to the more stable carbocation

Step 2 : Water acts as a nucleophile to capture carbocation

Step 3 : Deprotonation of tert-butyloxonium ion. Water acts as a

Brnsted Lowry base:

Other than using diluted acid medium, sometimes, hydration of

alcohol is prepared by adding concentrated sulphuric acid to
alkene.
When H2SO4 (conc) is added to alkene under room condition, it give
an alkyl hydrogensulphate

Hydrolysis of alkyl hydrogensulphate will convert into alcohol

(5)
Oxidation of alkene using acidified potassium manganate (VII)

Alkene are readily oxidised by acidified KMnO4 (decolourised the
purple colour of KMnO4) and give different products under different
condition

If cold diluted acidified KMnO4 is used, a diol is given as a
product.

If hot concentrated acidified KMnO4 is used, a ketone or an
aldehyde is formed which will further oxidised to become a
carboxylic acid or into carbon dioxide and water depend on alkene.
a) Hydroxylation of alkene (react under cold dilute acidified KMnO4)

The product of this reaction is a diol (di-alcohol) which contain 2
hydroxyl group.

This reaction is often used to distinguish between saturated

hydrocarbon and unsaturated hydrocarbon (alkane and alkene)

b) Oxidation of alkene using hot, concentrated acidified potassium

manganate (VII)

When alkene react with hot concentrated acidified potassium
manganate (VII), it will oxidise immediately to form aldehyde or
ketone, depend on the type of alkene

Using this method, the position of C=C in alkene can be deduced.
If the alkene is a 10 alkene, it will turn lime water chalky when the
particular alkene is reacted with hot concentrated acidified
potassium manganate (VII)

Alkene

Products

methanal

Methanoic acid

a. CH3CH2CH=CHCH3 + H2 (g)
b. CH3CH2CH=CH2 + Cl2 (g)
c. CH3CH=C(CH3)CH3 + Br2 (l)

CH3CH2CH2CH2CH3
CH3CH2CHClCH2Cl
CH3CHBrC(CH3)(OH)CH3 major
CH3CHBrCBr(CH3)CH3 minor

d. CH3CH(CH3)CH=CH2 + HCl (g)

CH3CH(CH3)CHClCH3 major
CH3CH(CH3)CH2CH2Cl minor

4-ethyl-2,2,4-trimethylhexane
2,2,4,5-tetramethylhexane
5-ethyl-3,4-dimethyloctane

2,3,4,6,6-pentamethyl-3-heptene

7-ethyl-1,3-dimethylcyloheptene

C(CH3)2=C(CH2CH3)CH(CH3)CH(CH3)2

CH2=CHC(CH3)(CH2CH3)C(CH3)=CH2

Isomers of pentene

CH2CH3

CH3

CH3

CH3

CH3

Practice :
Write the chemical equation for the following reaction
1. Butane react with chlorine under the presence of sunlight
CH3CH2CH2CH3 + Cl2 CH3CH2CH2CH2Cl + HCl
2. Pentane burned with excess air
C5H12 + 8 O2 5 CO2 + 6 H2O
3. Octane burned with excess air
C8H18 + 25 / 2 O2 8 CO2 + 9 H2O
4. Propene reacts with hydrogen gas using platinum as catalyst
CH3CH=CH2 + H2 CH3CH2CH3
5. 1-hexene burned with excess air
C6H12 + 9 O2 6 CO2 + 6 H2O
6. 2-heptene reacts with bromine water
CH3CH2CH2CH2CH2CH=CH2 + Br2 + H2O
CH3CH2CH2CH2CH2CH(OH)CH2Br + CH3CH2CH2CH2CH2CHBrCH2Br

7. Propene reacts with hydrogen chloride

CH3CH=CH2 + HCl CH3CH2CH2Cl (min) + CH3CHClCH3 (maj)

8. 1-Butene react with excess oxygen

C4H8 + 6 O2 4 CO2 + 4 H2O
9. 2-Pentene reacts with steam catalysed by sulphuric acid
CH3CH=CHCH2CH3 + H2O CH3CH(OH)CH2CH2CH3 CH3CH2CH(OH)CH2CH3

10. 3-Hexene reacts with cold dilute acidified KMnO4

CH3CH2CH=CHCH2CH3 + KMnO4/H+ CH3CH2CH(OH)CH(OH)CH2CH3
11. 2-methylhex-2-ene reacts with cold dilute acidified KMnO4

CH3C(CH3)=CHCH2CH2CH3 + KMnO4/H+
CH3C(CH3)(OH)CH(OH)CH2CH2CH3
12. Propane react with fluorine under the presence of sunlight
CH3CH2CH3 + F2 CH3CH2CH2F + HF
13. Propene is polymerized at 2000C and 1200 atm

14. 2-methylbut-2-ene react with bromine water under the presence of

sunlight.

4. Proposed the mechanism for the following reaction below

H

H
H C
H
H

H
H

C H

Cl

Cl

H C
H

H
H

C H

Cl

+ H

Cl