CHEMISTRY FORM 6

ORGANIC CHEMISTRY
CHAPTER 2 : HYDROCARBON
Hydrocarbon which contain only Hydrocarbon which contain at least
carbon-carbon single bond, C–C one carbon-carbon double bond, C=C
or triple bond, C≡C

2.1 Nomenclature of ALKANE

C Alkane is a saturated hydrocarbon as it contain only single bond in
its molecule
C General formula for homologous series of alkane is CnH2n+2
C Table below shows the naming of straight chain of alkane
 Molecula Molecula Molecular structure
Name Molecular structure Name
r formula 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
Find the longest Identify the Place a prefix State the position
chain of carbon ‘branched’ carbon upon the similar where the ‘branch’
and name (alkyl group) that alkyl group (if any). is located at which
accordingly. (it attached to the If there is 2 similar carbon based on
does not has to be ‘main’ chain. Then, alkyl, prefix di is the numbering
a straight chain). name the alkyl placed, if 3 similar gave earlier.
accordingly alkyl, prefix tri is
CH3– methyl placed.
CH3CH2– ethyl
CH3CH2CH2-propyl
 CH3(CH2)5CH3 CH(CH3)2C(CH3)3 CH3CH(CH2CH3)2 C(CH3)3CH2C(CH3)3

2,3-dimethylpentane 3-ethyl-3- 2,2,3-trimethylpentane 3,3-diethylhexane

methylhexane
Isomer of hexane, C6H14
2.4 Physical properties of alkane
Alkane CH4 C2H6 C3H8 C4H10 C5H12 C6H14 C7H16 C8H18

Boiling
– 162 – 8.6 – 42.2 – 0.5 36.3 68.7 98.4 126
point oC
Boiling point
trend BOILING POINT INCREASE DOWN HOMOLOGOUS SERIES

Density
-- -- 0.50 0.58 0.63 0.66 0.68 0.70
(g/cm3)

Density trend DENSITY INCREASE DOWN HOMOLOGOUS SERIES

Not soluble in …………..

Solubility
Soluble in ………….
A) Boiling point of alkenes
C The boiling point .................when going down to homologous
series of alkane.
C All alkane possessed the same intermolecular forces : weak
……………… . forces
C Greater the ……………s. tronger the …………………forces, ..................the
boiling point
C Boiling point of isomers of the same molecular formula varies with
the branched molecules
H H
H C H
H C H
H H H
H H H H
H C C C C H
H C C C C C H
H H H
H C H H H H H H
H

C Straight chain has……………...boiling point compared to branched

chain as straight chain molecule has higher ……………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
C All alkanes are often consider as …………………….molecule
as the dipole of moment created in molecule is very
small.
C Since alkane is ……… . …. Molecule, it dissolve easily in
non-polar solvent such as benzene, and ether.
C Alkane does not form ……………bond in water, so it is
…………………in water. Thus, alkane is also described as
…………………. (water–hating).
C The longer the alkane chain, the more insoluble it is in
water.
2.5 Chemical Properties of Alkane
2.5.1 Preparation of Alkane
C Alkane can be prepared using the following methods :
C Decarboxylation of sodium salt of a carboxylic acid R–
COOH + NaOH → R–H + Na2CO3
Example : CH3COOH + 2 NaOH € CH4 + H2O + Na2CO3
C Kolbe’s method : electrolysing concentrated sodium ethanoate
C Cathode : 2 H2O + 2 e- € H2 + 2 OH-
C Anode : 2 CH3COO- € C2H6 + 2 CO2 + 2 e-
C Wurtz reaction : reaction of sodium on alkyl halide in ether.
2 R–X + 2 Na € R – R + 2 NaX
Example
2 CH3CH2–Cl + 2 Na € CH3CH2CH2CH3 + 2 NaCl
2.5.2 Reaction of Alkane
C Since alkane is a ………. hydrocarbon, so alkane is inert to most of
the chemical reaction
C 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

C From the series of reaction above it can be conclude that

C Ethane does no react with polar or ionic substances
C Ethane react with non-polar substances such as Cl2 , Br2 and O2
and energies are required for reaction to occur.
1. Combustion of alkanes
C All hydrocarbon react with oxygen to form carbon dioxide and water.
C The equation for a complete combustion for all hydrocarbons can be
represented by the equation

C2H6

C5H12

C8H18
C 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.
C Under limited supply of air (oxygen), sometimes, carbon monoxide
(CO) is produced instead of CO2.
2. Halogenation of alkanes
C 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)
C The mechanism for the reaction of chlorination of alkane can be
explained using the following steps
Step 1 : Initiation Step 2 : Propagation Step 3 : Termination
2.1.1 Sources of hydrocarbon
C The main sources of hydrocarbons are :
a) crude oil b) coal
c) natural gas
C Since all these main sources are made up from dead animals and
plants, so they are also known as ……………….
C Coal is complex mixture consisting mainly hydrocarbons, which is
mainly made up from dead plaints in swamp.
C Petroleum is a mixture of hydrocarbons (alkanes, alkenes, alkyne),
while natural gas contain mainly …………and some ………………
C The mixture in petroleum can be separated by using
………………… . .in oil refinery. Diagram below shows the chamber and
oil refinery used to separate the mixture of petroleum.
Fractional
Products Uses
distillation
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

Use as tar for paving road surface

Bitumen (asphalt) and coating underground water pipe
 C 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)
C Cycloalkane has a general formula of CnH2n
C Some examples of cycloalkane
Molecular
Cycloalkane Displayed formula Skeletal formula
formula

Cyclopropane C3H6

Cyclobutane C4H8

Cyclopentane C5H10

Cyclohexane C6H12
2.7.1 Naming cycloalkane
C 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)
C If there’s more than one “group” attaching the cycle, only then
numbering will be given to the particular number of C that it is
attached.
2.7.2 Preparation and Reaction of Cycloalkane
C Cycloalkane can be prepared by catalytic hydrogenation of benzene
at 200oC

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

/ bromine gas under sunlight, substitution reaction take place

Mechanism :
C Initiation
C Propagation

C Termination
2.8 Alkene – Nomenclature of alkenes and cycloalkenes
C The homologous series of alkenes has general formula of CnH2n.
C The significance of alkene is all of them have C=C in their molecules
with its name end with –ene
Molecular Molecular
Name Molecular structure Name Molecular structure
formula formula

Ethene C2H4 Propene C3H6

Butene C4H8

Pentene C5H10

Hexene C6H12
C 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-methylbut-2-ene 2-ethyl-3-methylpent-1-ene 3,4-dimethylhex-3-ene
2.8.1 Naming alkene with more than one single bond & cycloalkene
C A “diene” (alkene with 2 C=C bond) and cycloalkene has general
formula of CnH2n–2.
C 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.
C Example, name the following diene / cycloalkene below
2.9 Isomerism in alkene.
C Alkenes which contain at least 4 Carbon atoms may exhibit 2
isomerism, structural and stereoisomerism.
C For example, butane (C4H8) contain 5 isomers.
C Isomers of pentene
2.10Physical Properties of Alkene
Alkene C2H4 C3H6 C4H8 C5H10 C6H12 C7H14 C8H16 C9H18

Boiling
– 164 – 12.0 – 5.8 – 0.5 38.0 72.07 96.5 117
point oC
Boiling
point trend Boiling point increase
Solubility
Insoluble in water (solubulity decrease)
in water
A) Boiling Point of Alkene
C The boiling point ……………when going down to homologous series
of alkane.
C All alkane possessed the same intermolecular forces : weak
………………….
C Greater the ………………s . tronger the …..........….forces,
………………….the boiling point
2.11 Preparation of Alkene
C Alkene can be prepared in a few ways
Name of Reagent used
Equation
reaction and condition

Dehydro- Ethanolic
halogenation sodium
from hydroxide (heat
haloalkane & reflux)

Excess conc.
Dehydration H2SO4
(removal of at 1800C
water) or
from Alumina
alcohol (Al2O3) at
350oC
2.12Chemical reaction of alkene
Name of Reagent used and
Equation
reaction condition
Hydrogen gas CH3CH=CH2 + H2 (g) Ni
under
--------------
propene
Nickel (Ni) at
Hydrogenation
180oC
@
Platinum (Pt) at
room temperature cyclohexene

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

Addition of Hydrogen halide

Hydrogen (H–X)
halide (X = Cl ; Br ; I)
 Name of Reagent used and
Equation
reaction condition

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

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

H H H
KMnO4 / H+
Oxidation H C C C + 2 [O]
hot, concentrate
(under hot, H H
concentrated KMnO4 (aq) / H+ propene
acidified (hot &
potassium concentrated)
manganate
(VII)
2.12 Chemical reaction
(1) Hydrogenation of alkene
C Carry out under mixture of alkene and hydrogen over a finely
divided transition metal as a catalyst.
C 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)
C Hydrogenation is an exothermic reaction and its ∆H is about –120
kJ / mol
C CH3CH=CH2 (g) + H2 (g) € CH3CH2CH3 ∆H = –124 kJ / mol
C 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.
C CH3(CH2)7CH=CH(CH2)7COOH + H2 (g) € CH3(CH2)16COOH
C In industries, a special “Raney Catalyst” is used to replace platinum
as it is EXPENSIVE!!!
(2) Halogenation of alkene
C Chlorine and bromine react readily with alkene and form
dichloroalkane and dibromoalkane respectively. Cl2 and Br 2 gas are
add across double bond.
C CH3CH=CH2 (g) + Cl2 (g) € CH3CH(Cl)CH2Cl
C The mechanism of halogenation can be explained by a few steps
describe below :
C Step 1 : Formation of carbocation – propene has region of high
electron density because of the π 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
Clδ+–Clδ− repelled. As a result, carbocation & chloride ion are
formed.
C 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.

C 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
C Unlike addition of halogen, addition of hydrogen halide produced 2
products. For example, when propene react with hydrogen bromide
(H–Br)

C The major / minor product of the reaction can be predicted using

Markovnikoff’s 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.
C 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
−

C Step 2 : Nucleophilic attack – the negative bromide ion react fast

with the unstable carbocation.
C Relative stability of carbocation can be explained using
Markovnikoff’s 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.
C 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.
C 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
C Using phosphoric acid as acidic medium, hydration of alkene can be
represent by equation :
CH3C(CH3)=CH2 + H–OH CH3CH(CH3)CH2OH + CH3C(CH3)(OH)CH3

C Similar to hydrogen halide, hydration of alkene follows

Markovnikoff’s Rule.
C The mechanism of hydration of alkene is slightly different from
addition of hydrogen halide
Step 1 : Protonation of the carbon–carbon 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

Brønsted – Lowry base:

C Other than using diluted acid medium, sometimes, hydration of

alcohol is prepared by adding concentrated sulphuric acid to
alkene.
C When H2SO4 (conc) is added to alkene under room condition, it give
an alkyl hydrogensulphate
C Hydrolysis of alkyl hydrogensulphate will convert into alcohol
(5) Oxidation of alkene using acidified potassium manganate (VII)
C Alkene are readily oxidised by acidified KMnO4 (decolourised the
purple colour of KMnO4) and give different products under different
condition
C If cold diluted acidified KMnO4 is used, a diol is given as a
product.
C 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)
C The product of this reaction is a diol (di-alcohol) – which contain 2
hydroxyl group.

C This reaction is often used to distinguish between saturat ed

hydrocarbon and unsaturated hydrocarbon (alkane and alkene)
b) Oxidation of alkene using hot, concentrated acidified potassium
manganate (VII)
C 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
C 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
a. CH3CH2CH=CHCH3 + H2 (g)

b. CH3CH2CH=CH2 + Cl2 (g)

c. CH3CH=C(CH3)CH3 + Br2 (l)

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

C Isomers of pentene
Practice : Write the chemical equation for the following reaction
1. Butane react with chlorine under the presence of sunlight

1. Pentane burned with excess air

3. Octane burned with excess air

4. Propene reacts with hydrogen gas using platinum as catalyst

5. 1-hexene burned with excess air

6. 2-heptene reacts with bromine water

7. Propene reacts with hydrogen chloride

8. 1-Butene react with excessoxygen

9. 2-Pentene reacts with steam catalysed by sulphuric acid

10. 3-Hexene reacts with cold dilute acidified KMnO4

11. 2-methylhex-2-ene reacts with cold dilute acidified KMnO4

12.Propane react with fluorine under the presence of sunlight

13.Propene is polymerized at 2000C and 1200 atm

14. 2-methylbut-2-ene eac with bromine wat r under the presence of

sunlight.
4. Proposed the mechanism for the following reaction below
H
H C H
H H
H C C C H + Cl Cl

H H H