HYDROCARBONS KP

Hydrocarbons are simplest organic compounds which contain only carbon and hydrogen atoms.
Sources of hydrocarbons:
Cool, Petroleum, Natural gas
Uses of hydrocarbons:
 Hydrocarbons are used in the manufacture of polymers
 Higher hydrocarbons are used as solvents for paints
 They are used in the synthesis of dyes and drugs
Classification of hydrocarbons:
Depending on the type of carbon – carbon bonds present, hydrocarbons are classified in to three main categories.
i) Saturated hydrocarbons
ii) Unsaturated hydrocarbons
iii) Aromatic hydrocarbons
i) Saturated Hydrocarbons: These are the hydrocarbons which contain carbon-carbon and carbon hydrogen single
bonds. Eg: CH4, C2H6, C3H8
If carbon atoms are linked to give open chain struct then they are called ALKANES
H H H H

H C C C C H

H H H H
Butane
If carbon atoms are linked to give a closed chain or ring, they are called cycloalkanes.
CH2
H2
C H2 C CH2 H2 C CH2

H2C C H2 H2 C CH2 H2C CH2

Cyclopropane Cyclobutane Cyclopentae
ii) Unsaturated Hydrocarbons: These are the hydrocarbons which contain C C or – C ≡ C -

 The hydrocarbons which contain C C , they are called alkenes

 The hydrocarbons which contain –C≡C-, they are called alkynes

Eg: H-C≡C-H CH3-C≡C-CH3
Ethyne Butyne
iii) Aromatic hydrocarbons: These are the cyclic hydrocarbons which contain atleast one benzene ring and its
derivatives
CH3 OH
Eg:

Toluene Phenol Naphthalene

ALKANES:
Alkanes are saturated hydrocarbons which contain open chain structure of carbon atoms. The general formula of
alkane is CnH2n+2
Alkanes are also known as paraffins. [Little reactive]. They are inert under normal conditions and donot react with
acids, bases and solvents. In alkanes are carbon atoms are sp3 hybridised
No. of Carbon atoms CnH2n+2
n=1 CH4 Methane
n=2 C2H6 Ethane
n=3 C3H8 Propane
n=4 C4H10 Butane
n=5 C5H12 Pentane

Nomenclature and Isomerism:

There are two systems for naming,
a) Trivial or common system
b) IUPAC system
a) Trivial or common system: In this system, prefixes like normal [n], iso or neo are used for naming the parent
chain.
Eg.
H H H H H CH3

H C C C C C H H3C CH CH2 CH3 H3 C C CH3

H H H H H CH3 CH3

n - pentane iso - pentane neo - pentane

b) IUPAC system: IUPAC – International chion of pure and applied chemistry IUPAC name of an organic compound
consists of three parts.
* Root word [ Gives information regarding number of C-atoms
* Prefix – Gives information regarding substituents
* Suffix – It is of 2 types, primary suffix and secondary suffix
Primary suffix: It gives information regarding nature of C – C bond
Nature of C – C bond Primary suffix
C C ane

C C ene

C C yne

Secondary suffix: It is added to primary suffix to indicate the presence of functional group
Eg:
Functional group Secondary suffix
-OH Ol
-CHO Al
-C=O One
O
oic acid
C OH
-NH2 Amino

Rules:
1) The longest continuous chain of carbon atoms is slected and it is called the parent chain. The parent chain must
include the functional group. Give the root word.
2) Depending on the type of C-C linkage primary suffix is added to root word.
3) If any functional group is present then secondary suffix is added is primary suffix.
4) The carbon atoms of the parent chain are continuously numbered such that the subtituent gets least possible
number. If there are two or more substituents the sum of locants should be minimum.
5) Depending on the type of subtituent, prefix is attached to the root word.
6) If there are two or more different substituents present in the parent chain, then they are named according to
alphabetical order
7) If the same substituent is present more than once in a parent chain, then prefixes like di, tri and tetra are used.
NOTE:
→ Lovant is the number which indicates the position of the substituent.
→ The name of the substituent is separated from its lovant by a hypher [ - ]
→ The 2 numbers representing the positions of substiuents are seperated by commas [ , ]
For example:
H2C CH3

H3C CH CH CH CH3
5 4 3 2 1
CH3 Br

* Parent chain has 5 carbon atoms, root word – ‘pent’

* Primary suffix – ‘ane’
* Sum of lovcants is 9, the substituent which comes first in the alphabetical order gets the lower number
* Bromo, ethyl and methyl are the prefixes Hence the IUPAC name of the compound is
2-bromo-3-ethyl-4-methyl pentane
Give IUPAC names for the following organic compounds
1) H3C CH CH2 CH2 CH3
CH3
Ans: 2-methyl pentane
2) H3C CH2 CH CH2 CH2 CH3

CH3
Ans: 3-methyl hexane
CH3

3) H3C C CH2 CH3

CH3

Ans: 2, 2-dimethyl butane

CH3

4) H3C C CH2 OH

CH3

Ans: 2, 2 – dimethyl – 1 – propanol

5) H3C CH CH2 CH CH2 CH3

CH3 H2 C CH3

Ans: 4 – ethyl – 2 – methyl hexane

6) H3C CH CH C2H5

CH3 C2H5
Ans: 3-ethyl-2methyl pentane
CH3 CH3

7) H3C C CH2 C CH3

CH3 CH2

Ans: 2, 2, 4, 4-tetramethyl pentane

ISOMERISM:
Compounds having same molecular formula but different properties are called iosmers and the phenomenon in
known as isomerism.
Types of Isomerism
a) Structural isomerism b) Stereo isomerism
a) Structural isomerism: Compounds having same molecular formula but different structures are called structural
isomers and the phenomenon is called structural isomerism
Eg: C5H12 can be written in 3 ways
CH3

H3C CH2 CH2 CH2 CH3 H3C CH CH2 CH3 H3C C CH3

CH3 CH3
n - pentane 2 - methyl butane 2, 2 - dimethyl propane
I II III
I, II and III are three structural isomers of pentane.
Stuctural isomer which differ in the number of carbon atoms in the parent chain are called chain isomers.
Eg:
CH3

H3C CH CH2 CH3 H3C C CH3

1 2 3 4 1 2 3
CH3 CH3
I II
 Both I and II are chain isomers of pentane structure I has 4 carbon atoms in parent chain but structure II has 3
carbon atoms in parent chain but both I and II has same molecular formula C5H12
NOTE:
1. Primary carbon: [10]
Carbon atom attatched to no other atom or to only one carbon atom is called primary carbon.
Eg: CH4, CH3-CH3
2. Secondary carbon: [20]
Carbon atom attached to 2 other carbon atoms are called secondary carbon.
Eg: CH3-CH-CH2-CH3
3. Tertiary carbon;
Carbon atom attached to other three carbon atoms are called 30 carbon
Eg:
H3C CH CH2 CH3

CH3

4. Quanternary carbon:
Carbon atom attached of other 4 carbon atom is called quanternary carbon.
Eg:
CH3

H3C C CH3

CH3

Q Write different structural isomers for alkane with molecular formula C6H14
i) CH3-CH2-CH2-CH2-CH2-CH3
n-hexane
ii) H3C CH CH2 CH2 CH3

CH3
2-methyl pentane
iii) H3C CH CH CH3

CH3 CH3
2, 3-dimethyl butane
CH3

iv) H3C C CH2 CH3

CH3
2, 2-dimethyl butane
v) H3C CH2 CH CH2 CH3

CH3
3-methyl pentane
Totally there are 5 structural isomers for C6H14
Note:
1) Removal of one H-atom from CH4 gives methyl group
-H -H
CH4 CH3 C2 H6 C 2 H5
atom atom
Methyl group Ethyl group
2) General formula of alkyl group is CnH2n+1
3) To write the structure of any organic compound following steps should be followed.
→ Draw the chain of C-atoms based on root word
→ Give number to carbon atoms in the parent chain
→ Attatch the substituents to carbon atoms depending on the locant
→ Satisfy the valency of each carbon atom by putting hydrogen atoms as required
Q Write the structure for following organic compounds
1) 3 – ethyl – 2, 2 – elimethyl pentane
 CH3

H3C C HC CH2 CH3

C2H5
CH3
2) 3, 4, 4, 5 – tetramethyl heptane
CH3

H3C CH2 CH C CH CH2 CH3

CH3 CH3 CH3

3) 2-methyl – 2 – butanol
CH3

H3C C CH2 CH3

OH
4) 3-ethyl – 5 – methyl heptane
H H

H3C CH2 C CH2 C CH2 CH3

C2H5 CH3
Methods of preparation of alkanes:
1) Frame unsaturated hydrocarbons:
Alkenes and alkynes react with hydrogen in the presence of finely divided Ni|Pt|pd catalyst at higher temperature
to give alkanes
H 2C  CH 2  H 2   CH 3  CH 3
pt pd Ni


Ethene Ethane
H3C  CH 2  CH 2  H 2   CH3  CH 2  CH3
pt pd Ni


Propene Propane
CH3  C  C  H  H 2   CH3  CH  CH 2   CH3  CH 2  CH3
Ni pt pd Ni pt pd
 

Propyne Propene Propane

From alkyl halides:
i) Alkyl halides when treated with Zn and dilute HCl undergoes reduction to give alkanes.
CH3  Cl  H2 Zn
dil HCl
 CH4  HCl
Chloromethane Methane
C2H5Cl  H 2 Zn
dil HCl
 C2H 6  HCl
Chloro ethane Ethane
CH3  CH 2  CH 2  Br  H 2 Zn
dil HCl
 CH3  CH 2  CH3  HBr
Bromopropane Propane
ii) Alkyl halides react with sodium in the presence of dry ether to give alkanes. This reaction is called wurtz reaction.
CH3  Br  2Na  Br  CH3 
dry
ether
 CH3  CH3  2NaBr
Brmomethane Ethane
C2H5  Br  2Na  Br  C2H5 
 C6H5  C2H5  2NaBr dry
ether

Brmoethane Butane
Q What will happen if 2different alkyl halides react in wurtz reaction
CH 3  Br  2Na  Br  C 2H 5 
dry
ether
 CH 3  C 2H 5  2NaBr
Brmomethane Bromoethane Propane
Alkanes with add number of carbon atoms are obtained when 2 different alkyl halides react in wurtz reaction.
3) From carboxylic acids:
i) Decarboxylation:
 Sodium salts of carboxylic acids on heating with soda lime [NaOH + CaO] gives alkanes having one C-atom
lesser than carboxylic acid.
[The process of removal of CO2 from carboxylic acid is called decarboxylation]
CH3COONa  NaOH 
CaO

 Na 2CO3  CH4
Q In oreder to prepare butane sodium salt of which carboxylic acid is required? Give equation
Ans; Pentanoic acid
CH3  CH2  CH2  CH2  COONa  NaOH 
CaO

CH3  CH2  CH2  CH3  Na 2CO3
ii) Kolbe’s electrolytic method:
When an agneous solution of sodium or potassium salt of carboxylic acid is electrolysed, alkane is formed. This
method is suitable for preparation of alkanes that have even number of carbon atoms.
2CH3COONa  2H 2O 
Electrolysis
 CH3  CH3  2CO2  NaOH  H 2
Sodium acitate
Anode cathode

Reaction Path:
2CH3COO Na  2CH3COO  Na 
aqueous

At anode
2e
2CH3  COO :   2CH3CO : 
 2CH3  2CO2 
acetate free radical Methyl free radical
CH3  CH3 
 C2H6 
At cathode
H2O  e 
OH  H
H  H 
 H2 
Physical properties:
1) Alkanes are non-polar because of covalent C-C and C-H bonds
2) Alkanes posses weak van der Waal’s forces. Due to weak forces C1-C4 members are gases, C5-C17 are liquids and
C18 and more are solids.
3) Alkanes are insoluble in water, but soluble in organic solvents like ether
4) Boiling point of alkanes increases with the increase in the molecular mass.
Chemical properties:
Alkanes are saturated hydrocarbons, generally they are inert towards acids, bases and other solvents but under
certain conditions they undergo following rens.
1) Substitution ren:
It is type of organic reaction in which the hydrogen atom of an alkane is replaced by other atom
Halogenation: It involves substitution of one or more hydrogen atoms of an alkane by halogens.
Example: Chlorination
When alkane is treated with diffused sunlight mixture of 4 derivatives are obtained.
h
CH4  Cl2   CH3Cl  HCl
Chloromethane
h
CH3  Cl2  CH3Cl2  HCl
Dichloromethane
h
CH2Cl2  Cl2  CH3Cl3  HCl
Trichloromethane
h
CHCl3  Cl2 CCl4  HCl
Tetrachloromethane
NOTE:
Rate of reaction of alkanes with halogens F2>Cl2>Br2>I2 reactivity of alkanes 30>20>10
→ Iodination is very slow and reversible, Hence it is carried out in the presence of oxidising agents like HIO 3 or
HNO3
CH 4  I 2 CH3I  HI
 5HI  HIO3 3I 2  3H 2O
Mechanism of chlorination of methane [Free radical mechanism]
Chlorination is a halogenation reaction in which one or more hydrogen atoms of alkane is replaced by chlorine
atoms.
It proceeds in three steps
I Initiation: In the presence of light or heat Cl2 molecule undergoes homolysis to give chlorine free radicals
h
Cl  Cl   Cl  Cl
II Propogation: Chlorine free radical attacks CH4 molecule and takes the reaction in the forward direction and
generated methyl free radical
CH4  Cl 
CH3  HCl
methyl free radical [CH3 ] thus formed attack second molecule of Cl2 giving methyl chloride and again chlorine free
radical
CH3  Cl2 
CH3  Cl  Cl
III Termination:
The free radicals thus formed in the propogation step combine to give products
Cl  Cl 
 Cl2
CH3  CH3 
 C2H6
CH3  Cl 
 CH3Cl
Thus during chlorination of methane, ethane is formed as a byproduct
2) Combustion: When alkanes are heated in the presence of air or O2 undergoes complete oxidation to give CO2 and
H2O with the elimination of excess of heat.
CH4(g) + 2O2(g) → CO2(g) + 2H2O(e)
ΔHc = -890 KJ/mol
NOTE:
→ General combustion equation for any alkane
 3n  1 
Cn H2n 2    O2 
 nCO2  (n  1)H2O
 2 
Alkanes are used as fuels due to liberation of excess amount of heat during combustion
→ When alkanes undergoes incomplete combustion with insufficient amount of air, carbon black is formed which is
used in the manufacture of ink, printer ink etc.
Incomplete
CH 4(g)  O 2(g) C(s)  2H 2O ( l )
combustion
3) Controlled oxidation: Alkanes when treated with regulated supply of O2 or air at high pressure and in the
presence of suitable catalysts give variety of products
i) 2CH 4  O 2   2CH 3OH
Cu
523K/100atm
methanol

ii) CH 4  O 2  HCHO H 2O

MO2O3
 methanal

iii) 2C2H6  3O2  HCHO  H2O

(CH3COO)2 Mn
 Ethanoic acid

Alkanes having tertiary H-atoms can be easily oxidised by KMnO4

CH3 CH3
KMnO 4
H3C C H H3C C OH

CH3 CH3
2-methyl propane 2 - methyl propan - 2 - ol

4) Isomerisation: When n-alkanes are treated with anhydrous AlCl3 and HCl gas it isomerises to give branched chain
alkanes
 anhydrous
H3C CH2 CH2 CH2 CH2 CH3
AlCl 3/HCl
H3C CH CH2 CH2 CH3 + H3C CH2 CH CH2 CH3
n - hexane
CH3 CH3
2-methylpentane 3-methylpentane

5) Aromatisation: n – Alkanes having six or more carbon atoms when heated with V2O5/Mo2O3/Cr2O3 at 773K and
10 – 20 atm undergoes cyclisation to give benzene and its derivatives. This rxn is called aromatization.
CH3
H2C Cr2O3
CH3 V 2O 5
H2C 773K
CH2
CH2 10-20atm
n-hexane
6) Rxn with steam: Alkanes react with steam at 1.273K in the presence of Ni catalyst to give Co and H2
CH4  H2O 
Ni

CO  3H2
Pyrolsis: Higher alkanes when heated to higher temperature decomposes to give lower alkanes, alkenes etc. This
process decomposition of higher alkanes to lower alkanes/alkenes by heating is called pyrolysis or cracking.
C6H12 + H2

773K
C6H14
C6H12 + C2H6

C6H12 + C3H6 + CH4

Conformations:
Alkanes contain carbon – carbon ‘a’ bonds. Electron distribution will be cylindrically symmetrical around the
internuclear axis. Therefore rotation about C-C single bond is not disturbed and there is a free notation about C-C
single bond.
Different arrangement of atoms which can be converted in to one another by rotation about carbon – carbon single
bond are called
CONFORMERS ON CONFORMATIONS OR ROTAMERS
NOTE: Rotation about C-C bond is not completely free. It is hindered by a small energy barrier of 1-20 KJ/mol due to
repulsive interaction between adjacent bonds. Such type of repulsive interaction is called Torsional strain. Rotation
about C-C bond will not alter bond length and bond angle.
Conformations of Ethane: Ethane contains 2 carbon atoms each carbon atom is bonded to three hydrogen atoms. In
ethane rotation about C-C single bond results in number of arrangement of hydrogen atoms of one carbon atom with
respect to another. These are called conformational isomers.
There are two types of conformations of ethane
a) Eclipsed conformation
b) Staggered conformation
a) Eclipsed conformation: In this type, the hydrogen atoms attached to two carbon are close to each other
b) Staggered conformations: In this type, the hydrogen attoms attached to two carbon atoms are as far as possible
Eclipsed and staggered conformations can be separated by sawhorse and Newman projections
Sawhorse projection: The molecule is viewed along molecular axis. The C-C bond is written is a straight line. The
front carbon is at lower end and rear carbon at upper end. Each carbon has 3lines attached to it corresponding to 3
hydrogens with a bond angle of 1200.
H
H H

C C
H
H H

H
H
C
H C
H
H
H
Eclipsed Staggered
Newman Projection: In this type molecule is viewed at C-C head on. The C-atom nearer to eye is represented by a
point. Three lines which joins the point at 1200 to each other corresponds to 3hydrogens. The near carbon atom is
represented by a circle and the 3 hydrogens one attatched by shorter lines at 1200 to each other.
HH H H Angle of rotation/Angle of Torsinal Dihedral angle

H H H
H

HH H H

Eclipsed Staggered
Relative stability of conformations of ethane
Ethane has 2 conformations, Eclipsed and staggered . In eclipsed form the electron clouds of carbon – hydrogen
bonds are closer to each other. Thus there occurs repulsion between the electron clouds. In order to overcome this
repulsion ethane molecule posses more energy and hence possess lesser stability where as in staggered form the
electron clouds of carbon – hydrogen bonds are for from each other. Thus there is minimum repulsive forces,
molecule possess minimum energy and hence maximum stability. Thus staggered form is more stable than Eclipsed
form.
Note: The angle of rotation about C-C bond is called dihedral angle or torsional angle.
ALKENES:
These are unsaturated hydrocarbons which contain atleast one double bond. The general formula of alkenes is
CnH2n alkenes are also known as olefins (oil forming)
Structure of double bond:
→ A hydrocarbon with a double bond between the 2 carbon atoms is an alkene. The carbon atoms are sp2 hybridised
with a trigonal planar geometry
→ Among 2 double bonds, one is strong sigma (σ) bond which is formed due to head on overlapping of sp 2 hybrid
orbitals of two carbon atoms.
→ Other one is a pi bond (π), which is weaker formed due to side wise overlapping of two 2p orbitals of 2carbon
atoms.
→ The presence of π bond makes alkenes reactive and unstable. It shows number of addition reactions

Nomenclature:
IUPAC System
a) The longest continuous chain of carbon atoms containing double bond is selected
b) The parent chain is numbered in such a way that the carbon atoms containing double bond gets lower number
c) the suffix ‘one’ is replaced by ‘ene’
Example:
1) H3C CH CH2 Propene

2) H2C CH CH3 2 - Methyl - prop - 1 - ene

CH3
3) H2C CH CH CH3 3 - methyl but - 1 - ene

CH3
4) H3C CH CH CH CH2 3 CH
7 6 5 4

2 C CH3
8 CH3
1 CH3
2, 7 - dimethyl - 2, 5 - octadiene
Isomerism:
 Alkenes show both structural and stereo isomerism
a) Structural isomerisms: Consider Butene which can have following structures C4H8
H2C CH CH2 CH3 H3C CH CH CH3 H2C CH CH3

CH3
But-1-ene But-2-ene
II 2 - methyl prop - 1 - ene
I III
Structure I and III are example for chain isomers
II and III
Compounds having same molecular formula but differ in the number of carbon atoms in the parent chain are called
chain isomers.
Structure I and II are position isomers
Compounds having same molecular formula but differ in the position of double bond (functional group) are called
position isomers.
b) Geometrical isomerism: Geometrical isomerism arises due to restricted rotation about carbon – carbon double
bond
“Compounds having same molecular formula and structural formula but differ in the spatial arrangement of atoms or
groups about carbon – carbon double bond are called geometrical isomers and the phenomenon is called geometrical
isomerism consider the molecule of type Y X C = C X Y, It can be represented in space in 2 ways
X Y X Y
C C

C C
X Y Y X
+
cis rans
(a) (b)
X and Y are 2 different substituent’s
In structure (a) , the 2 identical substituents lie on the same side of double bond, it is called is isomer.
In structure (b), the two identical subtituent lie on the opposite side of the C=C, it is called trams isomer.
Eg: But – 2 – ene CH3-CH=CH-CH3
In But-2-ene, each one of the C-atom is linked together by double bond and contain two different substituent’s [H1 and
CH3]. Hence it exhibits geometrical isomerisme
H3C CH3 H3C CH3

C C C C

H H H CH3
cis - But - 2 - ene trans - but - 2 - ene
  0.33 Debye OD
In cis – But – 2 – ene, the two –CH3 group are present on the same side of C = C bond.
In trans – But – 2 – ene the two –CH3 groups are present on the opposite sides of C = C bond.
cis – but – 1 – ene is polar and possess dipole moment of 0.33D where as in trans – but – 2ene the dipole moments
are equal and in equal directions therefore cancers making trans form non-polar.
Preparation of alkenes
1. From alkynes: Alkenes on partial reduction with hydrogen in the presence of charcoal partially deactivated with
quinoline [lindlar’s catalpt] give cis – alkenes. However alkeynes on reduction with sodium in liquid ammonia forms
trans – alkenes
1
R R
1 pd/C
RC CR + H2 C C

H H
cis - alkene
R H
1 Na/liq NH 3
RC CR + H2 C C

H R1
Eg:
pd/C
HC CH + H2 H2C CH2
pd/C
H3C C CH + H2 H3C CH CH2
2) From alkyl halides: [Removed of hydrogen and halogen simultaneously] is called dehydropalogenation when
alkyl halides are heated with alcoholic potash (KOH) dehydrohalogenation takes place giving alkenes [x = cl, Br, I, F]
H H H H
alc
H C C H KOH
H C C H + KX + H2O
heat
H X

Eg: H H H H
alc
H C C H KOH
H C C H + KBr + H2O
Ethene
H Br
Ethyl bromide
3) From vicinal dihalides: Vicinal dihalides on treating with Zn metal gives alkene
H2C CH2 + Zn H2C CH2 + ZnBr 2

Br Br
1, 2 - dibromo ethane Ethene

NOTE: When 2 halogen atomes attatched to adjacent carbon atoms, it is called vicinal dihalide [Eg CH2 – CH2]
From alcohols:
When alcohols are treated with concentrated H2SO4 elimination of water [dehydration] takes place giving alkenes
since water molecule is eliminated from the alcohol in the presence of acid is called ‘Acidic dehydration of alcohols’
H H H H
conc H2SO 4
H C C H H C C H + H2O
Ethene
H OH
Ethanol
H H
conc H2SO 4
H C C H H3C CH CH2 + H2O
Propene
H OH
Propanol
Physical properties
→ Insoluble in water
→ They are colourless are odorless [except ethane which is having sweet small]
→ Soluble in organic solvents like ether, benzene
→ Boiling point increases with increase in molecular mass
Chemical properties
Electrophilic addition reaction:
1) Addition of H2: Alkenes react with hydrogen in the presence of Ni/pallodium gives alkanes
Ni/pd/pt
H2C CH2 + H2 H3C CH3
Ethene Ethane

Ni
H3C CH CH2 + H2 H3C CH2 CH3
Propene Propane
2) Addition of halogens: When alkenes are treated with halogens they form vicinal dihalides

CCl 4
H2C CH2 + Br Br H2C CH2

Ethene Br Br
1,2-dibromoethane

Ethene when treated with Br2 water in CCl4, addition reaction takes place carbon – carbon bond giving 1, 2
dibromo ethane. The orange color of Br=2 water discharged
CCl 4
H3C CH CH2 + Br 2 H3C CH CH2
Propene
Br Br
1,2-dibromoethane
3) Addition of hydrogen halides: [HX = HCl, HBr, HI]
Addition of HBr to symmetrical alkenes
When H-Br is treated with symmetrical alkenes, electrophilic addition reaction takes place giving addition product.

H2C CH2 + H Br H2C CH2 Br

bromoethane
Ethene

H3C CH CH CH3 + H Br H3C CH2 CH CH3

2-Butene Br
2 - bromo propane
NOTE: Similar group attached to double bond are called symmetrical alkenes. Eg: CH2=CH2
Addition of HBr to unsymmetrical alkenes
When HBr adds to propene either 1-bromo propane or 2 – bromo propane is formed. But experimentally it was
found that 2-bromo propane is formed.
H3C CH2 CH2 1-bromopropane
H3C CH CH2 + HBr
Br
H3C CH CH3 2-bromopropane

Br
In 1869 markovnikov a russian chemist predicted the formation of 2-bromo propane experimentally and put formed a
rule called Markonikov’s rule. Markovnikov’s rule states that, when hydrogen halide adds to unsymmetrical alkene,
the negative part of the adding molecule adds to that carbon atom which has lener number of hydrogens
Mechanism:
→ Hydrogen bromide undergoes heterolytic fission to give electrophile H+
H X H+ + Br-

→ Electrophile, H+ attacks propene to give carbocation


H3C CH2 CH3
H3C CH CH2 + H+ 10 carbocation

H3C CH2 CH3
0
2 carbocation
Since secondary carbocation is more stable than primary carbocation, it is readily formed.
→ Br- attacks, the 20 carbocation, to form 2-bromo propane
 
H3C CH CH3 + Br H3C CH CH3

Br
2 - bromo propane

Antimarkovnikov’s addition
When propene is treated with HBr in presence of peroxide, addition of HBr to propane takes place against to
markonikov’s rule, and 1 – Bromo propane is formed but not 2 – bromo propane. This reaction is called
antimarkovnikov’s addition or peroxide effect or kharasch effect.
(C6H5CO) 2O2
H3C CH CH2 + HBr H3C CH2 CH2

Br
1 - bromo propane
Mechanism: [Free radical mechanism)