STEM HYDROCARBONS

HYDROCARBONS

OPEN CHAIN CLOSED CHAIN

or or
ACYCLIC CYCLIC

SATURATED

ALICYCLIC
ALKANES Ex: Cycloalkanes

UNSATURATED

AROMATIC
ALKENES ALKYNES Ex:Arenes

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INTRODUCTION
1. The simplest organic compounds are hydrocarbons.
2. Compounds formed by the combination of carbon and hydrogen only.
3. Petrol, diesel, kerosene, liquid petroleum gas (LPG) and condensed natural gas (CNG) etc. are all
hydrocarbons or their mixtures.
4. All organic compounds can be considered as the derivatives of hydrocarbons which are obtained by
substituting hydrogen with an appropriate functional group.
5. Hydrocarbons are broadly classified as
a) Acyclic (Open Chain) b) Cyclic (Closed Chain)
6. Acyclic compounds are further classified into two types based on the saturation of Carbon atom.
a) Saturated - All the four valencies of carbon are sigma bonds i.e., Carbon is bonded to 4 different
atoms.
Ex: Alkanes : Saturated compounds containing only single bonds around carbon.

b) Unsaturated - Compounds in which there is atleast one double bond or triple bond between two
carbons.
Ex: Alkenes : Unsaturated due to presence of a double bond.

C C

Alkynes : Unsaturated due to presence of a triple bond.

C C
7. Alkanes are quite stable compounds and gives mainly substitution reactions.
Alkenes and Alkynes are more reactive and give addition reactions.
8. Cyclic hydrocarbons are further classified into two types.
a) Alicyclic compounds : Compounds which behave as acyclic compounds except they are closed
chain compounds.
Ex: Cycloalkanes, Cycloalkenes, Cycloalkynes.

Cyclo Cyclo Cyclo Cyclo Cyclo Cyclo

propane butane pentane hexane butene octyne
b) Aromatic compounds : Ex: Arenes (Benzene and its compounds)

B enzene N a p h th a le n e

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Introduction:
1. Saturated hydrocarbons are known as alkanes or paraffins (Less reactive).
2. General formula is CnH2n+2, where n is the no. of carbon atom.
3. All the carbon atoms in alkanes are in sp3 state of hybridization.
4. All the bond angles are tetrahedral angles i.e., H – C – H or H – C – C bond angle is 109º28' .
5. Alkanes are insoluble in water because water molecules are polar whereas alkanes are non-polar
(C – C and C – H bonds are nearly purely covalent).
6. Alkane molecules are non planar because all the carbon atoms possess sp3 hybridisation.
7. C–C C–H
(i) Overlapping sp3 – sp3 sp3 – s
(ii) Bond length 1.54 Å 1.112 Å
(iii) Bond energy 80 – 85 kcal 98.6 kcal
8. Alkanes exhibit chain isomerism (minimum 4 Carbons) and conformational isomerism.
METHODS OF PREPARATION :
1. From Alkenes and Alkynes : (Sabatier Senderen's reaction) :
H2
R – CH = CH – R' + H2   R – CH2 – CH2 – R'
Ni / 300º
When the catalyst are Pt or Pd, the hydrogenation proceeds smoothly at ordinary temperature and
pressure. With Nickel catalyst, higher temperature (250º – 300ºC) and pressure are needed.
2. From Alkyl Halides
a) Reduction of Alkyl Halides :–
Reductant
R – X  R – H + HX
Alkyl halide Alkane
Reductants :
Zn–Cu couple/EtOH, Na–EtOH, Zn–HCl, Pt or Pd or Ni/H2, Al–Hg/EtOH, LiAlH4 etc.
Zn Cu / alcohol
CH 3 I   CH 4  HI
b) Wurtz Reaction :
R – Br + 2Na + Br – R Na / dry Ether
  R – R + 2NaBr
CH3 – I + 2Na + I – CH3  Na / dry Ether
 CH3 – CH3 + 2NaI
Methyl iodide Ethane
i) Methane cannot be prepared by this method.
ii) The higher alkane produced is symmetrical i.e., it contains double the number of carbon
atoms present in the alkyl halide used.
iii) When the two reacting alkyl halides are different, a mixture of three different alkanes is
obtained. Hence the wurtz reaction is not useful for preparing unsymmetrical alkanes.
Ex: C2H5I + CH3I  Na / dry Ether
 C2H6 + C3H8 + C4H10
Mechanism :
Wurtz reaction may take place by the formation of organometallic compound or alkyl free radical.
Ex: 2C2H5Br + 2Na  Dry ether C2H5 – C2H5 + 2NaBr

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By Organometallic compound formation:

C2H5Br + 2Na – +
  C2H5 Na + NaBr
Ethyl sodium(organo metallic)
C2H5–Na+ + C2H5Br   C2H5 – C2H5 + NaBr
Free radical Mechanism :
C2H5Br + Na   C2H5
· + NaBr
Ethyl free radical
C2H5· + C2H5·  Dimerisation
 C2H5 – C2H5 (n-Butane)
iii) Corey-House Synthesis :
R – Br + 2Li  Ether
 R – Li + LiBr
Alkyl bromide Alkyl lithium
2R – Li + CuI  R2LiCu + LiI
Lithium dialkyl cuprate
R2LiCu + R' – X  R – R' + RCu + LiX
Alkane
Alkyl halide which is used to react with dialkyl lithium cuprate should be a primary (R – CH2 – X) or
secondary alkyl halide (R – CH(X) – R). If Tertiary alkyl halides is used alkenes are formed.
iv) Frankland's reaction : Alkyl iodides when heated with zinc produces alkanes.

RI + Zn + RI  R – R + ZnI2
v) From Grignard reagent (RMgX) :
R-X + Mg  Ether
 RMgX  Z H
 RH + Mg(Z)X
ZH [compound containing active hydrogen]
HOH, NH3, RC  CH, C6H5OH, CH3COOH, RNH2, R2NH, Pyrrole, C2H5OH etc.
C2H5MgI  HOH
 C2H6 + MgI(OH)
C2H5MgI  RCOOH
 C2H6 + MgI (OOCR)
3. Reduction : HI / Red P used as reducing agent at elevated temperature.
a) Reduction of Alcohols :
Re d P
R – OH + HI 
150ºC
RI + H2O
b) Reduction of alkyl halides
Re d P
R – I + HI 
150ºC
R – H + I2
c) Reduction of Aldehydes, Ketones:
R R
Red P R'=Alkyl or H
C O + 4 HI CH2 + H2O + 2I2
1500C
R' R'
d) Reduction of Carboxylic acids:
Re d P
RCOOH + 6HI  RCH3 + 3I2 + 2H2O
150ºC
4. From Aldehydes, Ketones:
a) Wolff-Kishner reduction : Both aldehydes and ketones are reduced to alkanes by reacting with
hydrazine in presence of sodium ethoxide.(NH2 – NH2 / C2H5ONa)
R H N.NH R C2 H5ONa R
2 2
C O  C = N.NH2   C H2 + N2
(Hydrazine) 160ºC
H H H
R1 R1 R1
H 2 N.NH2 C2 H5ONa CH 2 + N2
C O   C = N.NH2  
R2 (Hydrazine) R2 160ºC R2

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b) Clemmensen's reduction : Only ketones are reduced to alkanes by treatment with zinc
amalgam and conc. HCl
R1 Zn  Hg R1
C O + 4HI 
 CH2 + H2O + 2I2
conc. HCl
R2 R2

5. From Carboxylic acids :

a) By de-carboxylation of a fatty acid :
NaOH / CaO(Sodalime)
R-COOH + NaOH  RCOONa  
 R – H + Na2CO3
Sodium carboxylate Alkane
NaOH / CaO(Sodalime)
CH3COONa  
 CH4 + Na2CO3
NaOH / CaO(Sodalime)
CH3CH2COONa  
 C2H6 + Na2CO3
The – COOH present in the original acid is removed in the process (in the form of carbonate) hence
the name decarboxylation.
b) Kolbe's electrolytic synthesis :
2RCOONa + 2H2O Electrolysis
 R – R + 2CO2 + H2 + 2NaOH
Methane cannot be prepared by this method.
Mechanism : Involves Ion and Free Radical intermediates
2CH3COONa + 2H2O   CH3–CH3 + 2CO2 + 2NaOH + H2
2CH3COONa  – +
 2CH3COO + 2Na
At anode : 2CH3COO–  ·
 2CH3COO + 2e
2CH3COO·  ·
 2CH3 + 2CO2
CH3· + CH3· 
 C2H6
At cathode : +
2Na + 2e   2Na
2Na + 2H2O 
 2NaOH + H2 A
6. Other methods
a) From dialkyl zinc :
R2Zn 
R ' X
 R–R' + RZnX
b) Hydrolysis of trialkyl borane
H
(RCH2)3B + 3H2O   3RCH + B(OH)3(H3BO3)
3
c) Increasing chain length of Alkane by insertion of CH2 (methylene) group.
Decomposition of diazomethane give singlet methylene (odd electrons with opp.spins) which
inserts between C-H bond in an alkane.

CH2N2 h CH2 + N2
Singlet
Methylene

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at C1 6 4 2

5 3 1
Hexane
2 4
at C2
1 5
3
H 2-Methylpentane
H 2 4
4 H H CH2 at C3 3
H 5 3 2 1 1 5
H H insertion
H H H H 3-Methylpentane
H at C4 (3 Products are formed.)
Pentane 2-Methylpentane
Same as C2
at C5
Hexane
Same as C1
d) Bergius Process: Heating the paste of powdered coke in heavy oil at 750K and 200-250 atm in
the presence of FeO Catalyst gives mixture of Hydrocarbons.
This on refining gives petroleum like material.
FeO , 750 K
C  H 2 
200  250 atm
Mixture of Hydrocarbons
f) Fischer-Tropsch Process: Heating red hot coke with steam to get water gas. Water gas is
mixed with half of its volume of hydrogen at 473K and 1-10atm in
presence of catalyst to give mixture of hydrocarbons. This on
refining gives petroleum like material.
H 2 ,473 K ,110 atm
C  H 2 O 
Catalyst Co 100,Thoria 5,

 Mixture of Hydrocarbons
Re d Hot Steam
Coke Magnesia 8, Keise lg uhr  200 parts

METHANE (CH4)
1. Methane is also called marsh gas or damp fire.
2. Methane is one of the constituents of different fuel gases.
Natural gas = 80% CH4 + 20% C2 to C6
Coal gas = 40% CH4
CNG (Compressed natural gas) = CH4(84%) + propane + butane + Higher alkane.
LPG (Liquefied petroleum gas) or kitchen gas or domestic gas.
Methods of preparation:
1. Hydrolysis of aluminum and beryllium carbides give methane.
These carbides are referred as Methanides as they produce methane on hydrolysis.
These carbideds contains C4- ion.
12H2 O
Al4C3   3CH4 + 4Al(OH)3
4H 2O
Be2C   CH4 + 2Be(OH)2
2. Decarboxylation of acids:
NaOH / CaO
CH 3COONa 

CH 4  Na2 CO3
PHYSICAL PROPERTIES
1. Alkanes from C1 – C4 are colourless, odourless gases.
C5 – C17 are colourless liquids,
C18 – onwards are waxy, white solids.
2. Boiling points : Boiling points of alkanes are the lowest of all the groups of organic compounds. The
forces of attraction among the alkane molecules are the weakest vander Waal's forces
of attraction.
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Among isomeric alkanes, the boiling point decreases with branching.

n-Pentane > iso-Pentane > neo-Pentane
B.P  mol. wt. (for homologous)
1
B.P  (for Isomers)
Lateral chain
3. Melting point : Unbranched alkanes containing even number of carbon atoms have higher melting
points than the unbranched alkanes containing odd number of carbon atoms.
C C C C C C

C C C C C
n-pentane n-hexane
M.P of Even no. of carbon atoms HC > M.P of Odd no. of carbon atoms HC
CHEMICAL PROPERTIES
1. Stability : Alkanes are chemically unreactive under ordinary conditions due to the presence of
strong C – C and C – H sigma (s) bonds.
But they undergo reactions under special conditions.
2. Substitution Reaction :
a) Halogenation:
h
R – H + X2   R – X + HX
i) Reactivity order of hydrogen atoms in alkanes is 3ºH > 2ºH > 1ºH
ii) Reactivity order of halogens is F2 > > Cl2 > Br2 > I2
iii) F2 can react in dark.
Cl2 and Br2 require light energy.
I2 does not shown any reaction at R.T but on heating it reacts reversibly.
Fluorination : Direct-fluorination of alkanes is usually explosive . It is carried out successfully by
diluting fluorine with nitrogen.
The reaction is performed in a metal tube packed with copper gauze at a
temperature of 150ºC–350ºC.
Product of fluorination is usually a complex mixture.
CH4 + F2  C + HF
CH4 + F2  CH3F + HF
Chlorination :
R – H + Cl2  R – Cl + HCl
Alkyl chloride
The monochloro derivative of alkane is obtained by taking alkane in large excess.
C2H6 + Cl2  u
 C2H5Cl + HCl
Ethane (Excess) Ethyl chloride
When chlorine is in excess, a mixture of mono, di tri, tetra and perchloro derivatives is obtained.
h,Cl2 Cl2 Cl2 Cl2
CH4   CH Cl 
3  CH2Cl2   CHCl3   CCl4
Chlorination of alkanes takes place in the following conditions.
At 300ºC in darkness,
100ºC in the presence of organic peroxides and
150ºC in the presence of Tetra ethyl lead.
Mechanism: Chlorination of alkanes is based on free radical mechanism.
It undergo the reaction in the following three steps :

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i) Chain intiating (first) step : Homolytic cleavage results free radicals of Chlorine.
Cl2  · ·
 Cl + Cl
ii) Chain propagating (second) step : Generation of alkyl free radical and Chlorine free radical
Cl· + CH4  ·
 CH3 + HCl
CH3· + Cl2   CH3Cl + Cl
·

iii) Chain terminating (third) step : Removal of Free radicals by combination.

CH3· + ·Cl   CH3Cl
· ·
CH3 + CH3   CH3 – CH3
· ·
Cl + Cl   Cl2
Bromination : Bromination of alkanes is similar to chlorination but not so vigorous.
iv) Chlorination is more reactive, less selective whereas bromination is less reactive and more
selective. This fact can be indicated by the reactivity ratio of different types of hydrogens.
Chlorination : 30H : 20H : 10H = 5 : 3.8 : 1
Bromination : 30H : 20H : 10H = 1600 : 82 : 1
Iodination : Iodination of alkanes is reversible.
CH4 + I2  

CH3 – I + HI
Iodination is carried out in the presence of an oxidising agent such as HIO3, HNO3, HgO, etc.
which destroys the HI thus facilitating shift of equilibrium in forward direction as it is formed and
so drives the reaction to the right.
5HI + HIO3   3I2 + 3H2O
Solved Problem: Chlorination of n-Butane at 400K gives two isomeric monochlorobutanes.
Calculate the percentage of two isomers. Relative rate of abstaction of 30,20,10
hydrogens is 5 : 3.8 : 1.
Solution: n-Butane has two types of Hydrogens.(6-10 and 4-20 hydrogens) hence forms two
isomers n-Butyl chloride and sec-butyl chloride.

3N os H H
H H H
10
10 2 0
H
H 20 H
3N os
H H

2N os +2N os

The relative ratio of two isomeric butanes is calculated as

n-Butylchloride No.of 10 H Reactity of 10 H
= x
sec-Butylchloride No.of 20 H Reactity of 20 H

n-Butylchloride 6 1 6
= x 
sec-Butylchloride 4 3.8 15.2
Sum of ratios = 6 + 15.2 = 21.2
6 15.2
% of n-Butyl chloride = x100  28% % of sec-Butyl chloride = x100  72%
21.2 21.2

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b) Nitration : When a mixture of alkane and vapours of fuming nitric acid is heated between
150ºC and 475ºC, a complex mixture of nitroalkanes is obtained.
high temp.
R – H  HO – NO2 
 R – NO2 + H2O

CH3CH2CH3NO2 (25%)

NO2

CH3CHCH3 (40%)
450°C
CH3CH2CH3 + HNO3
Vapour
CH3CH2NO2 (10%)

CH3NO2 (25%)
c) Sulphonation : Hydrogen atom of the C – H bond is replaced by – SO3H group.
R – H  HO – SO3 H   R – SO3H + H2O
Fuming H2SO4 Alkane sulphonic acid
Fuming H2SO4 = mixture of SO3 + Conc. H2SO4 = H2S2O7 (Oleum).
Lower alkanes are not sulphonated,
Branched or higher alkane if heated with highly concentrated sulphuric acid at about 100ºC alkane
sulphonic acid is formed.
CH3 CH3
| 100o C
|
CH3 – C – H + HO–SO3H  CH3 – C – SO3H

| |
CH3 CH3

(tert. butyl sulphonic acid)

d) Reed reaction (Chlorosulphonation)
When propane reacts with SO2 and Cl2 in presence of ultraviolet light then propyl sulphonyl
chloride is formed.
CH3 – CH2 – CH3 + SO2 + Cl2  U.V.Light
  CH3 – CH2 – CH2SO2Cl + HCl
This process is used in the commercial preperation of detergents.
O O
|| alkaline 
CH3–CH2–CH2– S – Cl + NaOH   CH –CH –CH – S – O–Na
3 2 2
hydrolysis ||

O O
Sodium salt of Sulphonic acid (Detergent)
3. Oxidation :
a) Combustion : All alkanes readily burn in excess of air or oxygen to form CO2 and H2O.
 3n  1
CnH2n+2 +  2  O2 
 nCO2 + (n + 1) H2O + heat
Volume of alkane 2

Volume of oxygen 3n  1
CH4(g) + 2O2(g) 
Burns
 CO2(g) + 2H2O

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b) Incomplete combustion : Alkanes when burnt in a limited supply of oxygen, partial combustion
takes place to give CO or carbon (carbon black).
2CH4 + 3O2   2CO + 4H2O + heat
CH4 + O2   C + 2H2O + heat
carbon black
c) Catalytic oxidation : For the same given alkane different products are obtained by change in
catalyst.
1 Cu
RCH3 + O2 250º C 100 atm.pressure RCH2OH (Alcohol)
2
MoO
RCH3 + O2  RCHO (Aldehyde)
270º C 100 atm. pressure
3 (CH3 COO)2 Mn
RCH3 + O  RCOOH (Carboxylic acid)
2 2 high temp.
d) By strong oxidant : Oxidising agents such as KMnO4 readily oxidise a 3ºH atom to a hydroxy
group.
CH3 CH3
| |
Alk. KMnO 4
CH3 – C – H  [O]  CH3 – C – OH
| |
CH3 CH3

Isobutane t-Butanol
4. Pyrolysis/Cracking or Thermal Decomposition :
The decomposition of a compound by heat is called pyrolysis.
Thermal decomposition of alkanes is known as cracking. It leads to the formation of lower alkanes,
alkenes and hydrogen.
CH4  1000ºC
 C + 2H2
Methane carbon black (used for printing)
CH3–CH3  
 CH 2 = CH2 + H2
Ethane Ethene
CH 3 -C H =C H 2 + H 2
400-600 0 C
C H 3 -C H 2 -C H 3

C H 2 = CH 2 + CH 4
5. Isomerisation : Straight chain alkanes are converted into their branched chain isomers when
heated in the presence of AlCl3 at 300ºC.
CH3
AlCl3  HCl |
CH3 – CH2 – CH2 – CH3   CH3  CH  CH3
300ºC
n-heptane converts into most stable form triptane.
CH3
|

 CH3 – C –– CH – CH3
CH3–(CH2)4–CH3
| |
CH3 CH 3
n-heptane Triptane

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n-octane converts into most stable iso-octane.

CH3 CH
| |
 CH3 C| CH2 – CH3 – CH3
CH3 – (CH2)5 – CH3 
CH3
n-octane iso-octane
6. Aromatization, hydroforming or catalytic reforming :
The conversion of aliphatic compounds into aromatic compound is referred to as aromatization.
Alkanes having six or more carbon atoms are heated at 600ºC in the presence of a catalyst such as
Cr2O3 supported over alumina or Pt which results an aromatic hydrocarbon.
CH 3
CH 2
H 2C CH 2 CH 3 Cr O / Al O or
2 3 2 3
+ 4H 2
Pt Catalyst)
H 2C CH 3 600 0 C
CH 2
n-Heptane Toulene
Aromatization involves cyclization and dehydrogenation.
7. Dehydrogenation : Removal of hydrogen molecule from the Hydrocarbon is dehydrogenation.
Cr2O3 / Al2 O3
CH3 – CH2 – CH3 
600ºC
 CH – CH = CH + H
3 2 2
Propane Propene

Chemical properties of Methane (CH4)

1. CH4 + O3  HCHO + O2 + H2O
2. CH4 + H2O (Steam)  CO + 3H2
Synthesis gas (Water gas)
3. CH4 + O2 
1500ºC
 C2H2 + H2 + CO
acetylene
4. CH4 + N2  Electric arc
  HCN + H2
Al2O3
5. CH4 + NH3   HCN + H2
High temp.

Determination of Quality of Fuel

Knocking: The pre-ignition of fuel-air mixture in the cylinder ahead of the flame.
It reduces the efficiency of the engine and also causes damage to the cylinder and piston
of the engine.
Quality of Fuel: A fuel that produces minimum knocking is considered as a good-quality fuel.
The extent of knocking depends on the quality of the fuel used.
The anti-knocking property is the measure of the quality of a fuel
It is usually expressed in terms of the octane number.
Octane Number: The percentage of isooctane by volume in a mixture of isooctane and n-heptane
that has the same anti-knocking properties as the fuel under examination.
Two pure hydrocarbons have been selected as standards :
1. n-Heptane has poor anti-knocking property, therefore, arbitrarily it has been assigned an octane
number of zero.
2. 2,2,4- Trimethylpentane (isooctane), a branched-chain hydrocarbon, has the highest anti-
knocking property. Therefore, it has been given the octane number of 100.

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The tendency of knocking decreases in the order :

Straight-chain alkane > branched-chain alkane > alkenes > cycloalkanes > aromatic hydrocarbon.
Anti Knocking agents: Compounds that are added to reduce knoking .
Ex: Tetraethyl Lead (TEL) or Pb(C2H5)4 - TEL decomposes to produce ethyl radicals that combine
with the radicals produced due to irregular combustion. As a result, reaction chains are broken
and smooth burning of the fuel occurs and thus knocking is prevented.

Heat
Pb  C2 H5 4   Pb+4 C2 H5  Ethyl radical 
Cetane Number
Cetane number is a scale that is used to determine the quality of a diesel fuel.
Cetane number is the percentage of cetane by volume in a mixture of cetane and α -methylnaphthalene
that has the same ignition properties as the diesel under examination in a test engine.
Following Hydrocarbons are selected as Standards :
1. Cetane number of C16H34 (n-hexadecane) which ignites spontaneously = 100
2 4 6 8 10 12 14 16

1 3 5 7 9 11 13 15
n - H ex a d e ca n e o r C e ta n e
(ig n ites sp o n tan e o u sly )
C et a n e n u m b e r = 1 0 0

2. Cetane number of 1-Methylnaphthalene which ignites slowly = 0

CH 3

-M ethylnaphthalene or 1-Methylnaphthalene

(ignites slowly)
cetane number = 0

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