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

Molecular
formula

Methane

CH4

Ethane

C2H6

Propane

C3H8

Butane

C4H10

Pentane

C5H12

Hexane

C6H14

Molecular structure

Name

Molecular
Molecular structure
formula

2.2

Naming alkane according IUPAC

Step 1
Step 2
Find the longest
Identify the
chain of carbon and branched carbon
name accordingly. (it (alkyl group) that
does not has to be a
attached to the
straight chain).
main chain. Then,
name the alkyl
accordingly
CH3
methyl
CH3CH2
ethyl
CH3CH2CH2-propyl

Step 3
Step 4
State the position
Place a prefix upon
where the branch is
the similar alkyl
located at which
group (if any). If
carbon based on the
there is 2 similar
numbering gave
alkyl, prefix di is
earlier.
placed, if 3 similar
alkyl, prefix tri is
placed.

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 AAAAAAA..
organic solvent
Soluble in AAAAAAAAAAAA

0.70

A)
Boiling point of alkenes
increasewhen going down to homologous series of

The boiling point AAAA
alkane.

All alkane possessed the same intermolecular forces : weak
Van Der Waals
AAAAAAAAforces
molecular mass stronger the AAAAAAAAA
weak Van Der Waals

Greater the AAAAAAAA,
forces,
AAAAincrease
the boiling point

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

higherboiling point compared to branched chain as

Straight chain has ..AA..
total surface areacompared to a
straight chain molecule has higher AAAAAAAAAA
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 AAAAAAAAA
molecule as the dipole of moment created in molecule is very
small.
non-polar

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

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

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 most of

Since alkane is a AAAAA.
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
CXH y

+ x + O2
4

x CO 2 +

y
H 2O
2

C2H6

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

H = m kJ / mol

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 methane
molecule forming HCl
Cl Cl
2 Cl H = +242 kJ/mol
H3CH
CH3 + H

and methyl radical

Since ...................... required lower

H3CH + Cl
H3C + HCl

Methyl radical will propagate with other
chlorine molecule and

energy to form radical, so the initiation

forming back chlorine radical

will start off with AAAAA.. Gas

H3C + ClCl
H3CCl + Cl

Under such propagation reaction
thousands of methane and chlorine
molecules will react continuously

H = + 433 kJ/mol

chlorine
chlorine

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 plants,
fossil fuel
so they are also known as AAAAAAAA
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), while
methane
natural gas contain mainly A.AAA
and some AAAAAethane
The mixture in petroleum can be separated by using
fractional distillation in oil refinery. Diagram below shows the chamber
AAAAAAAAAA.
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)

 Using high temperature, bond breaking
(homolytic fission) take place and form
various products of unbranched alkane
and alkene
 Example, when breaking decane, C10H22
C10H22 C3H6 + C7H16
C10H22 C4H8 + C6H14

Catalytic cracking
 With the aid of zeolite as catalyst, carbon
cracking can occur at lower temperature
compare to thermal cracking.
 Products using catalytic cracking usually
contain branched alkane and alkene.
C10H22

2.7
Cycloalkane (alicyclic compound)

Cycloalkane has a general formula of CnH2n

Some examples of cycloalkane
Cycloalkane
Cyclopropane

Cyclobutane

Cyclopentane

Cyclohexane

Molecular formula

C3H6

C4H8

C5H10

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

But-2-ene
Pentene

Molecular
formula

Propene

C3H6

Molecular structure

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 alkanx,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.

Isomers of pentene

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
increasewhen going down to homologous series of

The boiling point AAAA
alkane.

All alkane possessed the same intermolecular forces : weak
Van Der Waals
AAAAAAAforces
weak Van Der Waals
molecular massstronger the AAAAAAAAA

Greater the AAAAAA..,
forces,
higher the boiling point
AAAA

2.11 Preparation of Alkene

Alkene can be prepared in a few ways
Name of
reaction

Reagent used
and condition

Dehydrohalogenation
from
haloalkane

Ethanolic
sodium
hydroxide (heat
& 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 under

-------------Nickel (Ni) at 180oC
Hydrogenation
@
Platinum (Pt) at
room temperature

Equation

CH3CH=CH2 + H2 (g)
propene

cyclohexene
Halogenation

Halogen gas, X2
(X2 = Cl2 ; Br2 ; I2)

Addition of
Hydrogen
halide

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

Ni CH3CH2CH3 (g)

propane

cyclohexane

Name of
reaction

Reagent used and

condition

Hydration

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

Hydroxylation
(cold, diluted
acidified
KMnO4)

KMnO4 (aq) / H+
(cold and diluted)

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

KMnO4 (aq) / H+
(hot &
concentrated)

Equation

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 electron-donating 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

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