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Organic Chemistry – Alkanes
Hydrocarbons (compounds containing only C and H)
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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