Naming, Properties and Reactions

of Aliphatic hydrocarbons
RECAP!

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 Isomers
The organic compounds having the same molecular
formula but different arrangements of carbon atoms in
them, are known as Isomers.
ISOMERISM
 STRUCTURAL ISOMERISM

 This type of Isomerism is classified into 6:

a) Chain Isomerism.
b) Positional Isomerism.
c) Functional Isomerism.
d) Ring Chain Isomerism.
e) Metamerism Isomerism.
 CHAIN ISOMERISM

 The same molecular formula represents two or more

compounds.
 It differs in the nature of carbon chain(straight or
branched)
 Example, C4H10 (Butane) has two isomers namely butane and 2-
methylpropane.

BUTANE
2-METHYLPROPANE
 POSITIONAL ISOMERISM

 The same molecular formula represents two or more

compounds.
 It differs in the position of the same functional
group
 Example, Butene has two isomers namely But-1-ene and
But-2-ene.

BUT-1-ENE BUT-2-ENE
 FUNCTIONAL ISOMERISM

 The same molecular formula represents two or more

compounds.
 It differs in the nature of the functional group.
 Example, C3H602 has two isomers namely Propanoic acid and
Methyl ethanoate.

PROPANOIC ACD
METHYL ETHANOATE
 METAMERISM ISOMERISM

 The same molecular formula represents two or more compounds.

 It differs in the nature of the alkyl groups attached to the
same functional group.
 Example, Diethyl ether and Methyl propyl ether are metamerical
isomers.

METHYL PROPYL
DIETHYL
ETHER
ETHER
 RING CHAIN ISOMERISM

 The same molecular formula represents two or more compounds.

 It differs in the mode of linkage of carbon atoms.
 The isomers have either open chain or closed chain.
 Example, Propene and cyclopropane are ring chain isomers.

PROPENE
CYCLOPROPANE
 STEREOISOMERISM

This type of Isomerism differs in the spatial arrangement of

atoms or groups. It is of two types –
1. Geometrical Isomerism.
2. Optical Isomerism.
 GEOMETRICAL ISOMERISM

The same molecular formula represents two or more compounds.

It differs in the spatial arrangement of atoms or groups around carbon- carbon
double bond.
It is of two types:
If same group are on same side then,
it is called ‘cis’ isomers

if it is on opposite sides, then

it is called ‘trans’ isomers.
Example, cis-2-butene and trans-2-butene are ‘cis’ and ‘trans’ isomers.

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 OPTICAL ISOMERISM

 Optical Isomers are named like this because of their effect on

plane polarized light.
 Optical Isomers, which are non-superimposable mirror images
of each other, are called Enantiomers.
 Example, d-Alanine and l-Alanine, lactic acid etc.

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 Sigma and pi bonds are types of covalent bonds that differ in the overlapping of atomic
orbitals.
 Covalent bonds are formed by the overlapping of atomic orbitals.
 Sigma bonds are a result of the head-to-head overlapping of atomic orbitals whereas
 pi bonds are formed by the lateral overlap of two atomic orbitals.
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 Practice
1) Draw structures for the five isomers of C6H14
2) Draw an alkane that meet the following description:
i. An alkane with two tertiary carbons.
ii. An alkane that has one quaternary and one secondary carbon.
3) Identify the carbon atoms in the following molecules as 10ry, 20ry
30ry or quaternary.

(ii) (iii)
(i)

(iv) (iv

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 Naming of Organic Compounds

 Systematic nomenclature can be used to name organic compounds and

therefore make it easier to refer to them.

 The alkanes provide the basis of the naming system.

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Quick Check

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Answers

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 Practice Questions
(Assignment)
Name the following molecules using the IUPAC nomenclature system

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Alkyl groups

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 Practice Questions

1. What is the IUPAC name of the following alkane?

CH2CH3 CH3

CH3CHCH2CH2CH2CHCH3

2. Draw the structures corresponding to the following IUPAC

names:
a) 3,4-Dimethylnonane b) 3-Ethyl-4,4-dimethylheptane
c) 2,2-Dimethyl-4-propyloctane d) 2,2,4-Trimethylpentane

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 Physical properties of alkanes

1. Generally, at room temperature,

i. C1 – C4 Gases
ii. C5 – C17 Liquid
iii. Higher alkanes Solids

2. Alkanes have low melting and boiling points due to the weak intermolecular forces
of attraction (van der Waals forces) which can be overcome by a small amount of
heat energy.
 As the number of carbon atoms increases, the intermolecular forces of
attraction become stronger
 More heat is needed to overcome those forces of attraction and to separate
the molecules hence increase in melting and boiling point as the number of
atoms increases.

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 Physical properties of alkanes

 The melting and boiling points of alkanes depend on both the relative
molecular mass and on the structure of the molecules.
 Hence,
 For straight chain alkanes, the b.pt increases with increasing
molar mass.
 For branched chain alkanes, the more the branching in the
molecule, the lower the b.pt.
 The unbranched alkanes have greater van der Waals forces of attraction
because of their greater surface areas.

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 Physical properties of alkanes

Solid alkanes are normally soft, with low melting points

 due to strong repulsive forces generated between electrons on
neighbouring atoms, which are in close proximity in crystalline solids.

 The strong repulsive forces counterbalance the weak van der Waals
forces of attraction.

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Physical properties of alkanes

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Physical properties of alkanes

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Physical properties of alkanes

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Physical properties of alkanes

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Physical properties of alkanes

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Physical properties of alkanes

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 Reactions/Chemical Properties of alkanes

Reactions
Halogenation
Combustion
Cracking

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 Chemical Properties of alkanes

Alkanes are sometimes referred to as paraffins which means

‘slight affinity’
 They show little chemical affinity for other substances and
are inert to laboratory reagents.
They do not usually react with strong acids or bases or
with most oxidizing (halogens, KNO3, HNO3) or reducing
agents (H2, Li, Fe).
They’re least reactive among other organic compounds.
Alkanes, however, react under appropriate conditions with
oxygen (combustion), chlorine (halogenation) and a few
other substances.

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 Reactions of alkanes

1. Halogenation – Substitution Reaction

Halogenation of alkanes is only useful with Cl2 or Br2. Reaction
with F2 is too violent, and reaction with I2 is too slow to be
useful.
With an alkane that has more than one type of hydrogen
atom, a mixture of alkyl halides may result

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 Reactions of alkanes

 Alkanes undergo substitution reaction with halogens.

 The hydrogen atom of the alkane is substituted with a halogen
atom to give an alkyl halide in the presence of light or heating
at 250oC – 400oC

Depending on the relative amounts of the two reactants and

the time allowed for the reaction, sequential replacement of
the alkane hydrogen atoms by chlorine occurs
 leading to a mixture of chlorinated compounds.

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Reactions of alkanes

hv

hv

hv

hv

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 Reactions of alkanes

• Radical halogenation has three distinct parts.

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 Reactions of alkanes

The previous reaction proceeds via a free radical mechanism

hv
Cl-Cl 2Cl. initiation step
Cl. + CH4 CH3. + HCl propagation step

CH3. + Cl. CH3Cl termination step

 The free radical reaction is less vigorous in bromine. Bromine radical will prefer
secondary carbon to the primary as shown below:

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Reactions of alkanes

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 Reactions of alkanes

 A mechanism such as radical halogenation that involves two or

more repeating steps is called a chain mechanism.

 The most important steps of radical halogenation are those that

lead to product formation—the propagation steps .

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 Reactions of alkanes

2. Combustion of alkanes
The reaction of alkanes and oxygen occurs during combustion in an
engine or furnace when alkane is used as a fuel. E.g. methane (natural
gas) reacts with oxygen and a large amount of heat is released.

+890kJ/mol

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 Reactions of Alkanes

CO is highly poisonous
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 Reactions of alkanes

3. Cracking
Cracking is the most important process for the commercial production of gasoline
and diesel fuel.
It is the process in petroleum refining by which heavy hydrocarbon molecules are
broken up into lighter molecules by means of heat, pressure and sometimes catalysts.

 The demand for the shorter hydrocarbons (refinery gases and petrol) is greater
than for the longer hydrocarbons.

 There is a large supply of long hydrocarbons but a low demand and there is a
short supply of short hydrocarbons but a high demand.
 To solve this problem the long hydrocarbons are normally ‘cracked’ into
shorter hydrocarbons.

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 Reactions of alkanes

There are two different types of cracking:

Thermal cracking
happens at high temperatures (between 450°C - 900°C) and high pressures (7000 kPa).
Ethene, C2H4 is a valuable product of cracking. It can be used to make polymers such as
poly(ethene) which is used to make plastics.

Catalytic cracking
takes place at a slight pressure (100 kPa), high temperature (450 °C) and in the presence of a
zeolite catalyst.
mainly used to produce motor fuels and aromatic hydrocarbons
Catalytic cracking produces branched, cyclic and aromatic hydrocarbons.
Branched hydrocarbons are used as motor car fuels as they burn more smoothly than
unbranched hydrocarbons.

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Reactions of alkanes

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 Reactions of alkanes

Pt = Platinium
Pd = Palladium
Ni = Nickel
 Note that the sum of carbon and hydrogen atoms on ethane and alkane
equals the number of carbon and hydrogen atoms on the long
hydrocarbon.
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Reactions of alkanes

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 Reactions of alkanes

Branched chain hydrocarbons are more desirable than straight chain

hydrocarbons in petrol.
The straight chain hydrocarbons cause "knocking" - undesirable small explosions
that cause power loss.
Branched chain hydrocarbons burn smoothly.
The ability to burn smoothly or the quality of the petrol is indicated by its octane
number.

 This is the percentage by volume of isooctane in a mixture

of isooctane and heptane (a straight chain hydrocarbon), which gives the same
knocking characteristics as petrol under test.

A poor fuel has a zero octane number, whereas a good fuel has an octane number
of 100.
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 Preparation of alkanes

Homologous series members resemble each other and so can be

prepared by similar general methods from:
1. Unsaturated Hydrocarbons
2. Alkyl halide
a) Reduction
b) Wurtz reaction
c) Frankland method
3. Grignard reagents
4. Alcohols, ketones and fatty acids
5. Alkanoic acids
a) Decarboxylation
b) Kolbe’s Electronic Method
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 Preparation of alkanes

1) From Unsaturated Hydrocarbons - Hydrogenation

Alkane can be prepared from alkene and alkyne through the
process of hydrogenation.
Alkenes or alkynes, in the presence of nickel or platinium catalyst,
can be hydrogenated to give alkanes. Examples
catalyst i)
a) R-CH=CH-R + H2 RCH2CH2R
ethene ethane

ii)

cyclohexene cyclohexane
b) RC≡CR + 2H2 RCH2CH2R
Pt Pt
Example: CH3-C≡C-CH3 + 2H2 CH3CH=CHCH3 CH3CH2CH2CH3
butyne butene butane
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 Reactions of alkanes

The use of Pt and Pd catalysts for hydrogenation only takes place

at room temperature.
 Ni catalyst needs higher temperature of about 200oC to 300oC.

The hydrogenation method cannot be used to prepare methane.

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 Preparation of Alkanes

2. From Alkyl Halides

i) Reduction
Alkyl halides (except alkyl fluorides) on reduction with zinc and dilute
hydrochloric acid produce alkanes.
Zn/H+
R-X + 2H RH + HX
Zn/H+
CH3Cl + 2H CH4 + HCl
Zn/H+
C3H7Cl + 2HCl C3H8 + HCl

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 Reactions of alkanes

ii) Wurtz reaction

 The formation of the higher alkane proceeds through the free radical mechanism
C2H5I + 2Na. C2H5. + NaI
2C2H5. C2H5-C2H5
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 Reactions of alkanes

iii) Frankland reaction

This is similar to Wurtz reaction. The only difference is the use of
Zn in place of Na. This method is used for the preparation of higher
alkanes
RX + Zn + XR’ R-R’ + ZnX2
C3H7I + Zn + C3H7I C3H7-C3H7 + ZnX2
 The above reaction involves the formation of organozinc compound:
RX + Zn RZnX (alkyl zinc halide)
2RZnX R2Zn + ZnX2
R2Zn + 2RX 2R-R’ + ZnX2

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 Reactions of alkanes

3. From Grignard Reagents

 Haloalkanes (alkyl halides) and aryl and vinyl halides react with magnesium metal
to yield organomagnesium halides called Grignard reagents.
 Important reagents employed in organic chemistry for a variety of purposes. Their general
formula:
R-MgX where R = an alkyl group
Mg = magnesium
X = halogen
They are obtained by adding a solution of an alkyl/aryl/vinyl halides in dry
ether(solvent) and metallic magnesium. The metal dissolves to form a cloudy
solution of the Grignard reagent.
RX + Mg RMgX

Eg. C2H5Br + Mg C2H5MgBr

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 Reactions of alkanes

Grignard reagents when treated with compounds containing

active hydrogen (e.g. water, alcohols, amines, etc.) gives pure
alkane.
a) C2H5MgBr + H2O C2H6 + Mg(OH)Br
water

b) C2H5MgBr + HOCH
methanol3 C2H6 + Mg(OCH3)Br

c) C2H5MgBr +methyl
H2NCH amine
3 C2H6 + Mg(Br)NHCH3

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 Reactions of alkanes

4. From Alcohols, Ketones and Fatty Acids

 The reduction of alcohols, ketones and fatty acids with

hydroiodic acids and red phosphorus (150 – 200 oC) in a sealed

tube yields alkanes.
i. C2H5OH + 2HI C2H6 + H2O + I2

ii. CH3COCH3 + 4HI CH3CH2CH3 + H2O + 2I2

iii. CH3COOH + 6HI CH3CH3 + 2H2O + 3I2

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 Reactions of alkanes

5. From Alkanoic acids

Preparation of alkanes from carboxylic acids mainly happens via
two means:
i) Decarboxylation
Sodium salts of carboxylic acids on heating with soda lime (mixture
of NaOH and CaO) gives alkanes containing one carbon atom less
than the carboxylic acid.
RCOONa + NaOH RH + Na2CO3
NaOH(CaO)
heat

NaOH(CaO)
C2H5COONa + NaOH heat
C H6 + Na2C03
2
Sodium propanoate ethane

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 Reactions of alkanes

ii) Kolbe’s Electronic Method

 In this process, the alkane is produced through electrolysis of
sodium or potassium salt of carboxylic acid.

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