XII Chemistry | Coaching Classes 2024 Batch 01

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Alkanes
Introduction:
 Alkanes are simplest organic compounds having carbon and hydrogen only.
 Their general formula is CnH2n+2.
 In these compounds all carbon atoms form four single covalent bonds.
 All C-C and C-H bonds are sigma covalent bonds.
 Alkanes are saturated hydrocarbons because all four valencies of C-atoms are fully satisfied
by four single covalent bonds.
 Alkanes do not have any functional group even though they have difference in their reactivity.
(30>20>10).
 Each C-atom is sp3 hybridized and tetrahedral.
 The C-C bond distance is 1.54A0 and C-H bond distance is 1.09A0.
 The C-C bond energy is 347 K.J.mol-1.
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 XII Chemistry | Coaching Classes 2024 Batch 01
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 Alkanes are nonpolar molecules, the operating IMFs in alkanes are LDFs.
 LDFs are weakest IMFs. Hence they have low melting and boiling points.
 The first four members are gases (C1-C4) next thirteen members (C5 – C17) are liquids while
higher members from C18 are wax like soft solids at room temperature.
 Alkanes being nonpolar insoluble in water but soluble in non-polar solvents like benzene, ether,
carbon tetra chloride etc.
 Their physical properties like boiling points, melting points, densities etc increase with
increases in number of carbon atoms.
 The boiling points of branched chain alkanes are lower than their straight chain isomers.
 Increase in branching decrease surface area and IMFs. Hence boiling point decrease.
 The increase in boiling point is in between 20-30 oC for each addition of CH2 group.
 The densities of alkanes increase as their molecular mass increase and become constant at
0.76g/ml.
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 XII Chemistry | Coaching Classes 2024 Batch 01
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 Their solubility decreases with increase in number of C-atoms.

 Their melting points increases with increases in molecular mass or number of C-atoms but in
irregular manner.
 Methane is the 1st member of alkane family. It is also known as marsh gas.
 Methane is colourless, odourless, tasteless and non-poisonous gas.
 It is sparingly soluble in water. (5ml/100ml @ 200C).
 It is lighter than air, when liquefied less dense than water.
 Methane is used as a domestic fuel, in the manufacture of methanol, carbon black, polishes etc.
 Ethane is 2nd member of alkane family with molecular formula C2H6.
 It occours along with methane in natural gas and gases from oil-wells.
 Very small amount of ethane is also present in coal gas.
 It is colourless gas and it burns with non-luminous (dull) flame.

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 XII Chemistry | Coaching Classes 2024 Batch 01
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Relative stability:
 Branched chain alkanes are more stable than their straight chain isomers. The heats of
formation of
n-pentane is -147 K.J.mol-1
iso-pentane is -1547.1 K.J.mol-1
neo-pentane is -168 K.J.mol-1

Reactivity:
 Alkanes are called paraffins (Latin Parum = little and affins = ability).
 They are less reactive and inert towards acids, bases (Alkalis), oxidizing agents and reducing
agents at normal conditions.
 They are called paraffins because of their low reactivity and high stability.
 Their low reactivity is due to
By Rajesh Jemlani M.Sc Chemistry M.Phil Nanotechnology
 XII Chemistry | Coaching Classes 2024 Batch 01
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i. Inertness of C-C and C-H sigma bonds

ii. Non-polarity of C-C and C-H sigma bond.
 Alkanes undergoes four type of rxns however their principle or characteristic rxns are free
radical substitution rxns.
1. Thermal or cracking rxns
2. Catalytical oxidation rxns
3. Substitution rxns
4. Combustion rxns

By Rajesh Jemlani M.Sc Chemistry M.Phil Nanotechnology

 XII Chemistry | Coaching Classes 2024 Batch 01
@ DUA ACADEMY MIRPUR

1. Thermal or cracking reactions

 These rxns occour at high temperature in the presence of or absence of catalyst.
 These rxns are used to increase the production of gasoline and some useful small side
products.
 The catalyst used for these rxns is mixture of Al 2O3 & SiO2 or Zeolite.
CH4(g)/7000C  C(s) + 2H2(g)
2C3H(8)/700-8000C  CH4(g) + CH2=CH-CH3(g) + CH2=CH2(g) + H2(g)
C16H34/7000C  C7H16(g) + 3CH2=CH-CH3(g) + CH2=CH2(g)

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 XII Chemistry | Coaching Classes 2024 Batch 01
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2. Combustion
 The burning of hydrocarbons in oxygen or oxygen of air is called combustion.
 The combustion may be incomplete, partial or complete depending upon availability of
concentration of oxygen.
 In excess of oxygen complete combustion occours and all C-atoms and H-toms of alkanes are
converted into CO2 & H2O.
 The rxn is highly exothermic requires high temperature, flame or spark to initiate.

CH4(g) + 2O2  CO2(g) + 2HO2(g)

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 XII Chemistry | Coaching Classes 2024 Batch 01
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3. Catalytical oxidation
 Lower alkanes when burnt in the presence of metallic catalyst such as copper, at high
temperature and pressure (4000C & 200atm), produces some useful products.

By Rajesh Jemlani M.Sc Chemistry M.Phil Nanotechnology

 XII Chemistry | Coaching Classes 2024 Batch 01
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4. Substitution rxns
 The free radical substitution rxns are principle rxns of alkanes.
 Every homologous have some characteristic chemical rxns by which it is identified. These rxns
occours at normal conditions. These common rxns of each family are called principle or
characteristic rxns.
For example:
i. The principle rxns of alkanes are free radical substitution
ii. The principle rxns od of unsaturated compounds (Alkenes, alkynes, cycloalenes etc) are
electrophilic addition rxns.
iii. The principle rxns of aromatic compounds are electrophilic substitution rxns.
 Alkanes undergo two substitution rxns
i. Nitration at 4500C
ii. Halogenation at room temperature

By Rajesh Jemlani M.Sc Chemistry M.Phil Nanotechnology

 XII Chemistry | Coaching Classes 2024 Batch 01
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i. Nitration of alkanes
 The introduction of –NO2 group with replacement of H from alkanes to produce nitro alkane is
called nitration of alkanes.
 It is type of substitution rxn and it occours at 4500C.

By Rajesh Jemlani M.Sc Chemistry M.Phil Nanotechnology

 XII Chemistry | Coaching Classes 2024 Batch 01
@ DUA ACADEMY MIRPUR

ii. Halogenation of alkanes

 The introduction of halogen (–X group) with replacement of H from alkanes to produce halo
alkane is called nitration of alkanes.
 Alkanes react with chlorine and bromine in the presence of sunlight or UV light or at high
temperature resulting in the successive replacement of hydrogen atoms with halogens called
halogenation.
 Extent of halogenation depends upon the amount of halogen used.
 Reaction of alkanes with fluorine is highly violent and results in a mixture of carbon, fluorinated
alkanes and hydrofluoriq acid.
 Iodine does not substitute directly because the reaction is too slow and reversible.
 The order of reactivity of halogens is F2>Cl2>Br2>I2.
 Halogenation is believed to proceed through free radical mechanism. It involves the following
three steps.
By Rajesh Jemlani M.Sc Chemistry M.Phil Nanotechnology
 XII Chemistry | Coaching Classes 2024 Batch 01
@ DUA ACADEMY MIRPUR

By Rajesh Jemlani M.Sc Chemistry M.Phil Nanotechnology

 XII Chemistry | Coaching Classes 2024 Batch 01
@ DUA ACADEMY MIRPUR

By Rajesh Jemlani M.Sc Chemistry M.Phil Nanotechnology