CHEMISTRY FORM 6

ORGANIC CHEMISTRY
CHAPTER 2 : HYDROCARBON
Hydrocarbon which contain only Hydrocarbon which contain at least one
carbon-carbon single bond, CC 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
 Molecular Molecular
Name Molecular structure Name Molecular structure
formula 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 upon State the position
chain of carbon and branched carbon the similar alkyl where the branch is
name accordingly. (it (alkyl group) that group (if any). If located at which
does not has to be a attached to the there is 2 similar carbon based on the
straight chain). main chain. Then, alkyl, prefix di is numbering gave
name the alkyl placed, if 3 similar earlier.
accordingly alkyl, prefix tri is
CH3 methyl placed.
CH3CH2 ethyl
CH3CH2CH2-propyl
 3-ethyl-3,5-
3-methylpentane 3,5-dimethylheptane 3-ethyl-4-methylhexane
dimethyloctane

CH3(CH2)5CH3 CH(CH3)2C(CH3)3 CH3CH(CH2CH3)2 C(CH3)3CH2C(CH3)3

n-heptane 2,2,3-trimethylbutane 3-methylpentane 2,2,4,4-

tetramethylpentane

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

methylhexane

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
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

water
Not soluble in AAAAAAA..
Solubility
organic solvent
Soluble in AAAAAAAAAAAA
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

Greater the AAAAAAAA, weak Van Der Waals
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..
straight chain molecule has higher AAAAAAAAAAtotal surface areacompared 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 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
y y
CXH y + x + O2 x CO 2 + H 2O H = m kJ / mol
4 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

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 Step 3 : Termination

Since chlorine radical are highly
reactive, when it collide with methane
molecule forming HCl
Cl Cl
2 Cl H = +242 kJ/mol and methyl radical
H3CH
CH3 + H
H3CH + Cl
H3C + HCl
H = + 433 kJ/mol
chlorine Methyl radical will propagate with other
Since ...................... required lower chlorine molecule and
energy to form radical, so the initiation forming back chlorine radical
will start off with AAAAA.. Gas H3C + ClCl
H3CCl + Cl
chlorine
Under such propagation reaction
thousands of methane and chlorine
molecules will react continuously
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,
so they are also known as AAAAAAAA fossil fuel

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
natural gas contain mainly A.AAA methane
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
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 and

Bitumen (asphalt) 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
(homolytic fission) take place and form
various products of unbranched alkane
and alkene
 Example, when breaking decane, C10H22
C10H22 C3H6 + C7H16
C10H22 C4H8 + C6H14
 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 Molecular formula Displayed formula Skeletal formula

Cyclopropane
C3H6

Cyclobutane
C4H8

Cyclopentane
C5H10

Cyclohexane
C6H12
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-2-methyl-1-
propylcyclobutane

3-ethyl-1-methylcyclopentane 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
Molecular Molecular
Name Molecular structure Name Molecular structure
formula formula

Ethene C2H4 Propene C3H6

Butene C4H8
But-2-ene But-1-ene

Pentene C5H10

pent-2-ene pent-1-ene
Hex-1-ene Hex-2-ene Hex-3-ene
Hexene C6H12

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 2,3-dimethylpent-2-ene 3,5-dimethylhept-3-ene

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

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

2,5-dimethylhex-1,3-diene oct-2,5-diene
2-methylbut-1,3-diene

3,4,5-trimethylcyclopentene
3-ethyl-2-methylcyclohexene
3-methylcyclopropene
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
164 12.0 5.8 0.5 38.0 72.07 96.5 117
point oC
Boiling
point trend Boiling point increase
Solubility in
Insoluble in water (solubulity decrease)
water
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

Greater the AAAAAA.., weak Van Der Waals
molecular massstronger the AAAAAAAAA forces,
higher the boiling point
AAAA
2.11 Preparation of Alkene

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 (Al2O3)
alcohol
at 350oC
2.12 Chemical reaction of alkene
Name of Reagent used and
Equation
reaction condition

CH3CH=CH2 + H2 (g) Ni CH3CH2CH3 (g)

Hydrogen gas under
-------------- propene propane
Nickel (Ni) at 180oC
Hydrogenation
@
Platinum (Pt) at
room temperature
cyclohexene cyclohexane

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

Addition of Hydrogen halide

Hydrogen (HX)
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)

Oxidation
(under hot,
concentrated KMnO4 (aq) / H+
acidified (hot &
potassium concentrated)
manganate
(VII)
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) (major)
2-methylpropene 2-methylpropan-1-ol 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 Methanoic acid

methanal
a. CH3CH2CH=CHCH3 + H2 (g) CH3CH2CH2CH2CH3

b. CH3CH2CH=CH2 + Cl2 (g) CH3CH2CHClCH2Cl

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