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PHYSICAL PROPERTIES OF
HYDROCARBONS
 The table below lists the melting and boiling point of some
straight chain alkanes
Alkanes (also known as paraffins) are saturated hydrocarbons
The general formula of alkanes is CnH2n+2
All the bond angles in molecule are ≈109.5◦
Compound Structure Atom Mr State Bp (˚C) Mp(˚C)
C

Methane CH4 1 16 Gas -164 -184

Ethane CH3 – CH3 2 30 Gas -89 -172
Propane CH3 – CH2 – CH3 3 44 Gas -42 -187
n-butane CH3 – CH2 –CH2 - CH3 4 58 Gas 1 -135
n-pentane CH3 – CH2 –CH2 - CH2 - CH3 5 72 Liquid 36 -130
n-heksane CH3 – CH2 –CH2 - CH2 –CH2 - 6 86 Liquid 69 -96
CH3
n-heptane CH3 – CH2 –CH2 - CH2 –CH2 - 7 100 Liquid 97 -91
CH3
Alkanes from C5H12 to C17H36 are liquids. Alkanes from C18H38 onwards are solid
 Melting and Boiling Points

1. Melting and boiling point is a measure of the strength of

the intermolecular forces between the molecules
2. The stronger the intermolecular force, the higher the
melting and boiling point
3. The intermolecular forces between alkane molecules
are the Van der Waals forces.
4. The strength of the van der waals forces increases with
the size of the molecule and the total number of
electrons in the molecule
5. The increases in the melting point is not uniform. This is
because the melting point of a solid depends on how
the molecules are packed in the solid.

Evi Elfrida | SLHS | Organic chemistry

 Melting and Boiling Points
1. The boiling point of the branched chain isomers is lower than linear chain
isomer.
2. The greater the degree of branching of an isomer, the lower the boiling point
3. Branched-chain isomers are more spherical. This decreases the total
surface area of contact between the molecules

Alkane Structural formula Skeletal Structure Bp (Celcius)

Pentene 309
2-methylbutane 301

2,2-dimethylprop 283
ane

Van der waals forces

Evi Elfrida | SLHS | Organic chemistry

 Density

1. All alkanes are less dense than water.

2. The density increases with the molar mass of the molecule
3. Branched-chain isomers are less dens than the straight-chain
isomers because they cannot be as compactly packed as their
straight-chain counterparts

alkanes Density
Methane 0.424
Ethane 0.446
Less Compact packing
Propane 0.502
Butane 0.600
Pentane 0.626
Hexane 0.658
Compact packing
heptane 0.684
 Density
• For example:
Molecule Density
2,2-dimethylpropane 0.591
2-methylbutane 0.620
Pentane 0.626

Solubility
• All alkanes are non-polar. This is due to the very small
difference between the electronegativity of carbon and
hydrocarbon
• Alkanes are insoluble in water (polar solvent) as they cant
form hydrogen bonds with water molecules
• Alkanes are soluble in non-polar solvents such as benzene
and tetrachloromethane
Evi Elfrida | SLHS | Organic chemistry
 CRACKING oil fraction
HYDROCARBONS to produce more
useful products

Evi Elfrida | SLHS | Organic chemistry

 CRACKING

• Cracking is a thermal decomposition process by which

large alkane hydrocarbon molecules are broken down
by passing them over a heated catalyst at high
pressure.
• The products are smaller alkanes used for fuels (e.g.
petrol or diesel) and alkenes which are used to make
polymers–plastics and other important compounds.
• There are two good economic reasons for cracking oil
fractions
1. there isn't enough of fuels like petrol or diesel in the
original crude oil
2. alkenes are NOT found in oil, so must be
manufactured from oil.
Evi Elfrida | SLHS | Organic chemistry
There are lots of possibilities for cracking ! These are examples below show in each case
the formation of a shorter alkane and an alkene from a cracking reaction ...

Cracking reaction (1) butane 🡪 ethane + ethene

C4H10 🡪 C2H6 + C2H4

Cracking reaction (2) butane 🡪 methane + propene

C4H10 🡪 CH4 + C3H6

Cracking reaction (3) octane 🡪 hexane + ethene

C8H18 C6H14 + C2H4
 Types of organic reaction

HOMOLYTIC AND HETEROLYTIC FISSION

Evi Elfrida | SLHS | Organic chemistry

A. Organic reaction involve breaking and formation of covalent bonds
1. Homolytic Fission
2. Heterolytic Fission

B. The three main types of reagents usually encountered in organic reactions are :
1. Free Radicals
2. Electrophiles
3. Nucleophiles

C. Types of organic reaction

Most organic reaction (other than redox) can be classified as :
1. Substitution
2. Addition
3. Elimination

Evi Elfrida | SLHS | Organic chemistry

A. Organic reaction involve breaking and formation of covalent bonds
1. Homolytic Fission
Breaking of covalent bond
•One electron goes to each of the atom
•Form free radical (very reactive)

2. Heterolytic Fission
• Breaking of a covalent bond such as that both e- go to same atom
• Form positive and negative ions

Evi Elfrida | SLHS | Organic chemistry

A. The three main types of reagents usually encountered in organic reactions are :
1. Free Radicals
a. A free radical is any chemical species (atoms, molecules or ions) that has unpaired
electron in its structure
b. Free radicals are usually formed via the homolytic fission of a covalent bond.

c. The relative stability of a free radical depends on the electron density of the radical.
The higher the electron density, the less reactive it is (because the degree of 'electron
deficiency' is reduced) and the more stable it is.
d. The stability of the free radicals decreases in the order :
30 > 20 > 10 > methyl free radical
e. The reactivity of the free radicals increases in the order :
methyl free radical >10 > 20> 30

Evi Elfrida | SLHS | Organic chemistry

2. Electrophiles
a. An electrophiles (literally, electron loving) is a reagent that accepts an electron pair from another
substance to form a co-ordinate bond.
b. Most electrophiles are either positively charged or have an atom which carries a partial positive charge
or have an atom which does not have an octet of electrons
c. Electrophiles attack species which are electron-rich by accepting a lone pair electron from the
electron-rich species to form a co-ordinate bond. They are lewis acids.

d. An electrophile can be formed by the heterolytic fission of a covalent bond.

e. Examples of electrophiles are : H+ , NO2+, Cl+ etc and carbonium ions

f. Carbonium ions (or carbocations) are electrophiles where the positive charge is localized on a carbon
atom

g. The more alkyl groups (electron releasing) that are attached to the positive charge carrying carbon atom,
the more stable is the carbonium ion

h. The stability of the carbonium ion increases in the order :

Methyl carbonium ion <10 < 20<30

i. the reactivity of the carbonium ion increases in the order :\

30 < 20 < 10 < Methyl carbonium ion Evi Elfrida | SLHS | Organic chemistry
3. Nucleophiles
a. A nucleophile (literally, nucleus-loving) is a reagent which donates a lone pair electrons to
another substance to form a co-ordinate bond.
b. Nucleophiles are lone-pair electron donors. They are Lewis base.
c. The reactivity of nucleophiles depends on the electron density of the lone-pair electrons.
The higher the electron density, the more reactive is the nucleophile and hence less stable
d. As a result, electron-withdrawing groups stabilizes nucleophiles by reducing the electron
density of the lone pair electrons.

e. Examples are OH- , RCOO-, Cl- , Br-, I-, F-, H2O and carbanions.
f. Carbanions are nucleophiles where the negative charge is localized on a carbon atom

Evi Elfrida | SLHS | Organic chemistry

 Types of organic reaction
1. Substitution Reaction
a. In substitution reaction, an atom or a group of atom in a particular molecule is
replaced by another atom or a group of atoms
b. Substitution usually involves saturated molecules
c. Example of substitution are :
(i) Halogenation by alkane and halogen

(ii) Hydrolysis of 1-iodobutane by aqueous sodium hydroxide

CH3CH2CH2CH2I + NaOH 🡪 CH3CH2CH2CH2OH + NaI

Evi Elfrida | SLHS | Organic chemistry

 2. Addition Reaction
1. In an addition reaction, two or more molecules combined to form a larger one.
2. Addition reaction usually occurs in unsaturated molecules.

Examples are :
(a) Reaction between alkene and halogen
2. Addition Reaction
(b) Reaction between alkene and HCl

(c ) Reaction between alkene and hydrogen

(d) Polymerisation of alkene

 Chemical Reaction of Alkanes

1. FREE RADICAL SUBSTITUTION

Evi Elfrida | SLHS | Organic chemistry

Chemical Reaction of Alkanes

1. FREE RADICAL SUBSTITUTION

Uv light

Evi Elfrida | SLHS | Organic chemistry

 Halogenation
(Substitution with halogens)

• Reactivity : F > Cl > Br > I

a. Alkanes with Fluorin
Explosive

b. Alkanes with chlorin and bromine

Evi Elfrida | SLHS | Organic chemistry

8/24/2021
2. Combustion of Alkanes

ΔH◦= -2220 kJ/mol

In limited supply of Oxygen, incomplete combustion occurs to produce carbon monoxide.

For example :
2C3H8 + 7O2 🡪 3CO + 4H2OEvi Elfrida | SLHS | Organic chemistry
 Alkenes
•

Evi Elfrida | SLHS | Organic chemistry

 PHYSICAL PROPERTIES OF
ALKENES
1. Alkenes are non-polar molecules with weak van der Waals forces
between the molecule
2. The alkenes have lower melting point and lower boiling point than
alkanes. This is due to the smaller number of hydogen atoms in
the molecule.
3. The first three numbers of the alkenes, ethene, propene and
butene are colourless gases.
4. Linear alkene of approximately five to sixteen carbon are liquids,
and higher alkenes are solids
5. Boiling point cis > trans
6. Melting point trans>cis
7. Alkenes insoluble in water but dissolved in non-polar solvents
8. All alkenes are less dense than water
Evi Elfrida | SLHS | Organic chemistry
ADDITION REACTION OF
ALKENES

Evi Elfrida | SLHS | Organic chemistry

Evi Elfrida | SLHS | Organic chemistry
 ELECTROPHILIC ADDITION

HYDROGENATION
1. Addition of hydrogen (Hydrogenation) or Catalytic Hydrogenation
• the reaction is carried out under pressure in the presence of a metallic catalyst
such as platinum, nickel or palladium.

Evi Elfrida | SLHS | Organic chemistry

 ELECTROPHILIC ADDITION

HYDROGENATION
1. Addition of hydrogen (Hydrogenation) or Catalytic Hydrogenation

•Example :
1. Propene + H2 🡪 propane
2. 2-methyl-2-hexene + H2 🡪.................
3. 1,3-butadiene + H2 🡪 ..........................
4. 4-methylcyclohexene + H2 🡪............... Evi Elfrida | SLHS | Organic chemistry
 Manufacture of Margarine
Addition of hydrogen (Hydrogenation) or Catalytic Hydrogenation

• Naturally occurring vegetable oils are

unsaturated and so contain C=C double
bonds. When these react with
hydrogen, some of the C=C double
bonds become C-C single bonds.
• This process changes the properties of
the vegetable oil and conver it into a
solid : margarine
• Monosaturated fats
(one C=C double bond per molecule)
and polyunsaturated fats (two or more
C=C double bonds per molecule) are
better than saturated fats (no C=C
double bonds)
Evi Elfrida | SLHS | Organic chemistry
1. Addition of hydrogen (Hydrogenation) or Catalytic Hydrogenation

● Oleic acid (C18H34O2) is a

cis-unsaturated fatty acid found
most abudantly in olive oil.
● Complete hydrogention of oleic
acid produce a saturated fatty
acid called stearic acid which is
found naturally in animal fats.
● Elaidic acid (trans-fat) = isomer of
Oleic acid
● Trans-fat increases the risk of
coronary heart disease by lowering
the level of HDL cholesterol (the
good cholesterol)
● HDL : High Density Lipoprotein

Evi Elfrida | SLHS | Organic chemistry

 ELECTROPHILIC ADDITION

HALOGENATION
2. Addition of X2 (Halogenation)
Examples
Reaction 1

The test for a C=C double

bond. The tube on the left
shows coloured bromine
water with a layer of an
organic compound on top

The tube on the right shows

the mixture after shaking and
leaving to settle. The bromine
has been decolorised by the
C=C double bond

Reaction 2

Evi Elfrida | SLHS | Organic chemistry

 ELECTROPHILIC ADDITION

HALOGENATION

• Step 2 : the intermediate in the addition reaction is a carbonium ion

• Step 3: Reaction of the carbonium ion with a negative species completes

the reaction

Evi Elfrida | SLHS | Organic chemistry

 ELECTROPHILIC ADDITION

ADDITION OF HYDROGEN HALIDES

• This reaction cannot be used as a test for C=C because the
reactants and the product are all colourless, so there is no colour
change to observe

Evi Elfrida | SLHS | Organic chemistry

 reactions of alkenes
3. Addition of Hidrogen Halides HX (Hydrohalogenation)
The H-X bond gets weaker with the increasing size of the halogen atom. As a result,
the reactivity of the H-X : HCl < HBr < HI
(Markovnikov’s rule)
• The H from HX will attach itself to the unsaturated carbon atom with the least
alkyl substituents and the X will attach itself to the unsaturated carbon atom
with the most alkyl substituents.

1. Symmetrical Alkene • Another way : In

the addition of HX
to an
unsymmetrical
alkene, H from HX
will attach itself to
the unsaturated
carbon having the
greatest number of
hydrogen
 reactions of alkenes
3. Addition of Hidrogen Halides HX (Hydrohalogenation)
(Markovnikov’s rule)
• The H from HX will attach itself to the unsaturated carbon atom with the least
alkyl substituents and the X will attach itself to the unsaturated carbon atom
with the most alkyl substituents.

Evi Elfrida | SLHS | Organic chemistry

reactions of alkenes

3. Addition of HX (Hydrohalogenation)

Evi Elfrida | SLHS | Organic chemistry

 reactions of alkenes

3. Addition of HX (Hydrohalogenation)
2. An unsymmetrical alkene
• The reaction between HBr is highly regioselective. It was noted by a Russian chemist,
Vladimir V. Markovnikove, who purposed the Markovnikove’s rule in 1869
• When a hydrogen halide adds to an Unsymetrical alkene, two possible products will be
formed

Evi Elfrida | SLHS | Organic chemistry

 reactions of alkenes
Initiation Steps

Anti Markovnikov

Propagation Steps

Termination Steps

There are also Termination Steps, but we do not concern about the termination steps as they are just the radicals
combining to create waste products.
Evi Elfrida | SLHS | Organic chemistry
 reactions of alkenes

Anti Markovnikov

secondary free radical

A secondary free radical is more stable than a primary ion or

primary radical

Peroxides

Evi Elfrida | SLHS | Organic chemistry

 reactions of alkenes

c. Addition of Bromine Water

• The addition follows Markovnikov’s rule.

• Treatment of alkene with aqueous bromine or chlorine produces a halohydrin
• A halohydrin contains a halogen atom & a hydroxyl group

C=C + X-OH 🡪 -CX—COH-

• Addition with water follows the Markovnikov’s rule
Evi Elfrida | SLHS | Organic chemistry
 ELECTROPHILIC ADDITION

HYDRATION
• Hydration should not be confused with hydrogenation
• Hydration mean adding water, but we should consider it as adding H and OH
to the two atoms in a C=C double bond
• This reaction is usually done by heating the alkene with steam and passing
the mixture over a catalyst of phosphoric acid
• The hydration of ethene forms ethanol

Evi Elfrida | SLHS | Organic chemistry

 reactions of alkenes

4. Addition with water (Hydration)

• Under normal conditions, alkenes dont react with water. However, they react
with steam under high temperature and pressure and in the present catalyst to
form alcohol
• The catalyst used is ussually concentrated phosphoric acid (H3PO4) adsorbed
on the surface of an inert solid such as silica

H3PO4, 300OC, 70 atm

2-hydroxy butane or 2-butanol

• Addition with water follows the Markovnikov’s rule

Evi Elfrida | SLHS | Organic chemistry
 ELECTROPHILIC ADDITION

OXIDATION TO DIOLS
• A diol is a compound containing two OH (alcohol) groups
• The oxidising agent is potassium manganate(VII) in acid conditions
(usually dilute sulfuric acid).
a. Potassium manganate(VII) provides and oxygen atom (oxidation)
b. The water in the solution provides another oxygen atom and two
hydrogen atoms, so there is the addition of two OH groups across the
double bond KMnO4
+ MnO2
Cold

• The colour of the potassium manganate(VII) solution changes from purple to brown (MnO 2)
• This colour change means that this reaction can be used to distinguish alkenes from alkanes
• Alkanes don’t have double bond and so are not oxidised in this way
 reactions of alkenes

D. Reaction with concentrated sulphuric acid

• The addition follows Markovnikov’s rule.

• Alkenes react with cold, concentrated sulphuric acid to produce alkyl
hydrogen sulphate

Evi Elfrida | SLHS | Organic chemistry

 reactions of alkenes
E. Oxidation of alkenes
Using Cold, KMnO4 or K2Cr2O7
• Unlike the alkanes, alkenes can be oxidised by KMnO4 or K2Cr2O7

(Ethane-1,2-diol)

• A diol is an organic compound that has two –OH GROUPS in its molecule

Evi Elfrida | SLHS | Organic chemistry

 reactions of alkenes
E. Oxidation of alkenes
Using heat, KMnO4 or K2Cr2O7 🡪 ketone + aldehyde (aldehyde 🡪 carboxylic acid)
• If the unsaturated C atom is bonded to a hydrogen atom and an alkyl group, the group will be oxidised
to a carboxylic acid

• If the unsaturated C atom is bonded to 2 alkyl group, the double bond will break and the groups are
oxidised to produce a ketone

This portion is oxidised to ketone

This portion is oxidised to carboxylic acid