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Organic Chemistry – Alkanes

Hydrocarbons (compounds containing only C and H)
.............................................|.....................................................

Aliphatic Hydrocarbon Alicylic Hydrocarbon Aromatic Hydrocarbon or

Arenes
1. Alkanes 1. Cycloalkanes 1. Benzene
2. Alkenes 2. Cycloalkenes 2. Benzene and its
derivatives
3. Naphthalene and
others

 Alkanes belong to the homologous series of saturated aliphatic hydrocarbons, with general
formula CnH2n+2

 Structural isomerism exists in alkanes containing more than 3 C atoms due to branching of
chains

Nomenclature of branched chain isomers

Step 1 Identify the parent chain (largest continuous C chain) and name the compound
after it

Step 2 Identify substituents of parent chain which are alkyl groups (general formula of
CnH2n+1)

Step 3 Determine the position of alkyl group by numbering the C atoms consecutively
from one end of the parent chain to the other

 The number is such that a smaller digit is given to the C attached to the substituent
 If some alkyl groups occur more than once as substituents, indicate prefix di-, tri-, tetra-,
etc
 Arrange substituents in alphabetical order or increasing size, ignoring the prefixes
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Cycloalkanes

 The chemical behavior of cycloalkanes is similar to the open-chain alkanes

Physical Properties

 Insoluble in water but soluble in benzene, ether and other non-polar solvents (e.g. CCl4)

 Less dense than water

 Viscosity of liquid alkanes increase with increasing molecular mass as long molecules have
higher tendency to become ‘tangled up’ with one another (or less likely to slide over each
other)
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 Boiling point of straight chain alkanes increases with no of C atoms due to increasing
strength of dispersion forces

 Melting point of straight chain alkanes increases in a zig-zag pattern due to intermolecular
forces in a crystal, which depend not only on size of molecules but also how well they pack
into a crystal lattice

 At room temperature and atmospheric pressure, the first 4 alkanes (C1 – C4) are gases; the
next 13 alkanes (C5 – C17) are liquids and the C18 or more are solids

 Branched chain isomers have a lower boiling point than straight chain isomers
 Reason: Branched molecules are more spherical and hence packed less closely with the
resultant decrease in dispersion forces

 Effect of branching on packing and on melting point is irregular

Preparation

Hydrogenation of Alkenes

 Alkene is reacted with hydrogen gas at 140oC using Ni catalyst

 No heat is needed if Pt or Pd are used at catalyst (i.e. reaction can occur at r.t.p.)

Reactions

Combustion

 In limited supply of oxygen, incomplete combustion takes place to produce CO or C and

H2O

 In unlimited supply of oxygen, complete combustion takes place to produce CO2 and H2O

Note:

 Reaction is exothermic

 The ease of burning accounts for the use of many alkanes as fuels

 Methane (natural gas or cooking gas) burns with a clean blue flame tinged with a little
yellow. Very little ‘soot’ (carbon) is formed

 Burning of higher alkanes produce sooty flames

 Complete combustion of hydrocarbons provides the basis for quantitative analysis

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( 4y )O → xC O +( 2y ) H O
C x H y+ x + 2 2 2

Halogenoalkanes

R-H + X2 200−400 ° C∨UV

→
light R-X + H-X where X = Cl, Br, I

Free Radical Substitution

 UV light or high temperature is needed to generate the free radical

 It is a chain reaction involving 3 basic steps: initiation, propagation and termination

Example: chlorination of methane via free radical substitution mechanism

Initiation

Heat or light provides energy for the homolytic cleavage of Cl–Cl bond to generate free radicals

Cl – Cl UV →
light 2Cl•

Propagation

Each step consumes a radical and generates another. Together, 2 propagation steps consume
one CH4 molecule and one Cl2 molecule and produce one HCl molecule and one CH3Cl
molecule, giving the net reaction

Cl• + CH4  •CH3 + HCl

•CH3 + Cl2  Cl• + CH3Cl

Termination

Free radicals are consumed but not generated

2Cl•  Cl2
•CH3 + •CH3  CH3CH3 (when [•CH3] is high)
•CH3 + •Cl  CH3Cl

Overall, C l 2 +C H 4 UV light HCl+C H 3 Cl

→

Note:

 A single free radical (once formed) can produce a large number of molecules of product by
chain reaction sequence
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 The reaction does not stop at this step (monosubstitution). More than one H atom in the
alkane can be replaced by Cl with elimination of Cl  reaction is not clean as it does not
give a single organic product
Specif
 Monosubstituted alkane, CH3Cl, predominates if excess of alkane is used y the
exces
 Fully substituted alkane, CCl4, predominates with an excess of Cl2 s
reage
nt

 Unlike CH4, C2H6 and higher alkanes give rise to isomeric halogen derivatives when more
than one H atom is substituted. Reactions tend to be indiscriminate due to little difference
between the strengths of the differently situated C-H bonds

Reactivity

 F2 > Cl2 > Br2 > I2

 F2: reaction proceeds with explosive violence and cannot be used in the lab
 Cl2 and Br2: reaction at 250 - 400oC or UV light
 I2: least reactive as I atoms do not react with alkanes

Environmental Pollutants

 Car exhausts emissions contain:

 Unburnt hydrocarbons due to incomplete combustion of fuel. In strong sunlight it becomes

smog and can cause lung damage

 Carbon monoxide due to incomplete combustion of fuel. CO combines with haemoglobin in

blood and reduces the oxygen-carrying ability of the haemoglobin and can lead to death

 Nitrogen oxides from the reaction of N2 and O2 in the car’s engines can cause acid rain

Catalytic Converters

 In many countries, pollution from motor cars is being reduced by fitting a platinum catalyst
converter onto the motor car exhausts

 It oxidizes CO and unburnt hydrocarbons to CO2 and H2O, and it reduces NOx to N2 and O2

 The catalytic converter can be poisoned by lead, which can explains why lead-free petrol is
used

Note:
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 In accounting for the probability of theoretical yield of where H is substituted, count the
number of positions on the C atom which the H can be substituted and divide it by the total
number of positions

 Radical stability will determine the products. The more stable the radical, the more likely to
form a product due to the more stable radical.

Most stable Least stable