Live Sahab20

Hydrocarbon
By Singh Sahab
 Hydrocarbons
Compounds containing carbon and hydrogen.

Example

C6H6, C2H6, C2H4, C2H2

Classification
Hydrocarbons

Saturated Unsaturated Aromatic

H H H H Benzene
―

―
―
H―C―C― H H― C = C ― H
―

H H H― C  C ― H
 Saturated Hydrocarbon

The hydrocarbons containing single bonds between two carbon atoms.

e.g : Alkanes & cycloalkanes

Unsaturated Hydrocarbon

The hydrocarbons which contain Double bonds or triple bonds between two
adjacent carbon atoms .

e.g: Ethene , Ethyne

 Cycloalkanes

The saturated compounds which contains carbon atoms in a closed chain or

a ring.

e.g: Cyclopropane, Cyclobutane etc.

C H2 CH2 CH2

H2 C CH2 CH2 CH2

Alkanes
Saturated open chain hydrocarbons containing carbon - carbon
single bonds.

General Formula → CnH2n+2

n=1 → CH4

n=2 → C2H6
.
.
.
.
 Structure of Alkanes

✓ C-C bond length = 154 pm (1.54 A0)

✓ C-H bond length = 112 pm (1.12 A0)

✓ All H-C-H bond angles are of 109.5°.

Classification of carbon atoms

Tertiary carbon (3) Quaternary carbon (4)

CH3

― ―
H3C ― CH ― CH2 ― C ― CH2 ― CH3
―

CH3 CH3

Primary carbon (1)

Secondary carbon (2)

Preparation
1. From unsaturated hydrocarbons
This process is called
hydrogenation
2. From alkyl halides

i) Alkyl halides (except fluorides) on reduction with zinc and dilute

hydrochloric acid give alkanes.

ii) Alkyl halides with sodium metal in dry ether give higher alkanes.

This reaction is known as Wurtz reaction

Which of the following alkane can’t be prepared by Wurtz reaction…
( NEET 2020 )
1) n-hexane

2) 2,3-Dimethylbutane

3) n-heptane

4) n-butane
 3. From carboxylic acids

i) Sodium salts of carboxylic acids on heating with soda lime give alkanes
containing one carbon atom less than the carboxylic acid.

This process of elimination of CO2from a carboxylic acid is known as

decarboxylation.
ii) Kolbe’s electrolytic method

An aqueous solution of Na or K salt of a carboxylic acid on

electrolysis gives alkane containing even number of carbon atoms
at the anode.

Electrolysis
Complete Process
What is Z in the following reactions..

−
NaOH / CaO
CH3 – CH2 – 𝑪𝑶𝑶 Na+ Z
∆

1) n - butane 2) ethane 3) ethyne 4) propane

Sodium butyrate is subjected to decarboxylation and Kolbe’s
electrolysis to give compounds A and B respectively. A and B
Are..

1) C3H8 2) C3H8 & C6H14

3) C6H14 & C3H8 4) C3H4 & C3H8

 Physical properties of alkanes

• Non-polar due to covalent nature of C-C and C-H bonds.

• Possess only weak vander Waal’s force of attractions.

• As the molecular weight increases, force of attractions also will increase.

• The first four members of alkanes (C1 to C4 ) are gases.

• Next, (C5 to C17) are liquids & remaining alkanes are solids.
 Boiling Point
• As the molecular weight increases, boiling point also increases.

• In case of chain isomers, the isomer with more branches has less
boiling points. (due to less surface area)

In case of chain isomers of pentane, the order of boiling point is

n-pentane > Isopentane > Neopentane

Melting Point

Alkanes with even number of C atoms have more melting point than their
preceeding and succeeding odd ‘C’ alkanes.

Reason- alkanes with even number of carbon atoms pull closely and have
greater intermolecular attractions.
Solubility

• Alkanes are insoluble in water and hydrophobic in nature.

• Alkanes are soluble in organic solvents.

• As the molecular weight increases, solubility decreases.

Chemical properties

Substitution Reactions

One or more hydrogen atoms of alkanes can be replaced by halogens,

nitro group and sulphonic acid group at high temperature (or) in the
presence of light.
Halogenation
Mechanism

Halogenation of alkanes is free radical substitution reaction.

This mechanism involves 3 steps namely

i) Initiation

ii) Propagation

iii) Termination.
Initiation

The reaction is initiated by homolysis of chlorine molecule in the

presence of light or heat.

h
Cl – Cl Cl + Cl
homolysis
Chlorine free
radicals
Propagation

(a) When chlorine free radical attacks the methane molecule it

breaks the C-H bond to methyl free radical.

h
CH4 + Cl CH3 + HCl
Methyl free
radical

The reaction between a molecule and free radical is known as

chain propagation reaction.
(b) The methyl free radical attacks the 2nd molecule of chlorine to
form CH3Cl & chlorine free radical.

CH3 + Cl − Cl CH3−Cl + Cl

Both a & b steps repeat many number of times before

obtaining the main products.
Termination

The possible chain termination steps are:

(a) Cl+Cl Cl2

(b) CH3+CH3 CH3-CH3

(c) CH3+Cl CH3-Cl

 Important Points

• Rate of the replacement of hydrogens of alkanes is

30 > 20 > 10.

• Rate of the reaction of alkanes with halogens is

F2 > Cl2 > Br2 > I2.

• Iodination can be carried out in the presence of oxidising agents

like HIO3 or HNO3

HIO3
CH4 + I2 CH3 I + HI
Which branched chain isomer of the hydrocarbon with molecular
mass 72U gives only one isomer of mono substituted alkyl halide….
(Jee Mains 2012)

1) Isohexane

2) Neohexane
3) Tertiary butyl chloride
4) Neopentane
A hydrocarbon with molecular formula C 8H18 gives only one
monochloro derivatives the compound is ….
1) n-octane

2) 2-methyl heptane

3) 2, 2, 4 – trimethyl pentane

4) 2, 2, 3, 3 – tetramethyl butane
Combustion

• When alkanes are heated in the presence of air or O2, it oxidises to

carbon dioxide and water.

• This is highly exothermic reaction.

 Incomplete combustion:

CH4 + O2 C + 2H2O (l)

Controlled oxidation
 Isomerisation

Anhydrous
AlCl3/HCl
CH3 – (CH2)4CH3 CH3 – CH – CH2 -CH2 – CH3
|
n-hexane CH3

CH3─CH2 – CH – CH2 – CH3

|
CH3
 Aromatization

n- alkanes having six or more carbon atoms on heating to 773 K at 10 _ 20 atm

pressure in the presence of V2O5 or Cr2O3 or Mo2O3 over alumina, produce benzene
or its homologues.
 Reaction with steam

Methane reacts with steam at 1273 K in the presence of nickel catalyst to

form carbon monoxide and dihydrogen.

 Pyrolysis
Higher alkanes on heating to high temperature decompose into lower
alkanes, alkenes etc.

This reaction takes place through the free radical mechanism.

Some Other Reactions
 Conformations

• Free rotation can occur about C–C single bond.

• This rotation results into different spatial arrangements of atoms in space

which can change into one another.

• Conformations or conformers or rotamers- spatial arrangements of

atoms which can be converted into one another by rotation around a C-
C single bond.
• Alkanes can have infinite number of conformations.

• The rotation around a C – C single bond is not completely free.

• It is hindered by a small energy barrier of 1-20 kJ/mole, due to weak

repulsive interaction between the adjacent bonds.

• This repulsive interaction is called torsional strain.

Conformations of ethane:

• Ethane (C2H6) molecule contains a C – C single bond with each carbon

atom attached to three hydrogen atoms.

• Keep one carbon atom stationary and rotate the other carbon atom
around the C – C axis.

• This rotation results into infinite number of conformations.

Cases

• Eclipsed conformation - hydrogen atoms attached to two carbons are

closest to each other.

• Staggered conformation - hydrogen atoms are farthest to each other.

 Sawhorse projections

• In this projection, the molecules are viewed along the molecular axis.

• A long straight line, projected on paper represent C – C bond.

• Upper end of the line is tilted towards right or left hand side.
The front carbon → lower end of the line
The rear carbon → upper end.

Rear carbon

front carbon

Each carbon has three lines attached to it corresponding to three

hydrogen atoms.
These three lines are inclined at an angle of 1200.

H
H H
H
H
H

H H

H
H H
H

Eclipsed Staggered
Newmann projections

• The molecule is viewed at the C – C bond head on.

• The carbon atom nearer to the eye is represented by a point.

• The rear carbon atom(the carbon atom away from the eye) is
represented by a circle.

• The lines radiating from the center of the circle denotes the bonds of the
carbon closest to us.
• Those lines radiating from the circumference (out side) denote the

bonds of the carbon farthest form us.

Rear carbon
Near carbon
• Dihedral angle in
staggered form = 1800
Dihedral angle in eclipsed form = 00.

Remaining conformations are called skew or Gauche conformations.

 Relative stability of conformations

• Staggered conformation > skew conformation > eclipsed conformation.

• In eclipsed conformation, bonds are very close & have maximum

repulsions.

• In staggered conformation, bonds are at maximum distance & have

minimum repulsions.
Which one is most stable…. [Jee Mains 2010]
 Alkenes
Aliphatic unsaturated hydrocarbons containing – C = C –
| |
Also known as olefins.

General molecular formula → CnH2n.

H3C – CH = CH2
Alkadienes

H2C CH CH CH2

Alkatrienes

H2C CH CH CH CH CH2
Structure of Double Bond

C-C double bond in alkenes = 1 strong σ bond + 1 weak π bond .

head-on lateral or
overlapping sideways
of sp2 overlapping
hybridised of the two 2p
orbitals orbitals

Bond Length => C=C < C – C

134 pm 154 pm
pi (π) bond → weaker bond

Reason- poor sideways overlapping between the two 2p orbitals.

Alkenes are easily attacked by electrophile.

Reason- pi (π) bond makes alkenes behave as sources of loosely held mobile
electrons.

Therefore, alkenes are also unstable molecules in comparison to alkanes.

Sigma Bond
pi Bond
Isomers

Compounds with same general formula or molecular formula but different

physical and chemical property
 Isomers

Structural Stereoisomers
Isomers
Same M.F. and different Same M.F., same structural
structural formula formula but different
arrangement of
1. Chain atoms/groups in space.
2. Position
3. Functional 1. Optical
4. Metamers 2. Geometrical
5. Tautomers 3. Conformational
Different size of main chain

Different size of side chain

Example

C—C—C—C & C—C—C

|
C
Chain Isomers of C5H12
Different position of F.G./M.B./Substituents in same skeleton of C-atoms.

Nature of F.G. and M.B. should not change.

Example

C—C—C—C—C—C & C—C—C—C—C—C

| |
C C
C—C—C—C & C—C—C—C
| |
OH OH
Different nature of F.G.

Chain and positional isomers is ignored.

Example

C—CC—C & C=C—C=C

C—C—C & C—C—O—C
|
OH
C—C—C & C—C—C
|| ||
O O
CH3—CN & CH3—NC
Same F.G. ( containing – O,N,S )

Different nature of alkyl or aryl group attached to the hetero atom

Following F.G. shows metamerism

R1—O—R2
2/3 amines

R1—S—R2

Esters, anhydrides, sulphonate esters.

C—C—N—C —C & C—N—C—C—C
O—C—C—C

O—C

O—C
Rule

Determine type of isomer by FMCP

Que. An isomer of ethanol is:

1. Methanol
2. Diethyl ether
3. Acetone
4. Dimethyl ether
Que. The number of isomers of C 6H14 is:

1. 4
2. 5
3. 6
4. 7
Que. Isomers of a substance must have the same….

1. Structural formula
2. Physical formula
3. Chemical formula
4. Molecular formula
 Stereoisomers
Isomers having same molecular formula but differing in 3 dimensional
orientation of their atoms in a space.

Stereoisomers

Geometrical Conformers Optical

Diastereomers Enantiomers
 Geometrical isomers
The restricted rotation of atoms or groups around the doubly bonded

carbon atoms gives rise to different geometries of compounds.

These stereoisomers are called geometrical isomers.

Cis-isomer = in which two identical atoms or groups lie on the same side
of the double bond

Trans-isomer = in which identical atoms or groups lie on the opposite

sides of the double bond

• Cis and trans

isomers have the
same structure
but have different
arrangement of
atoms or groups in
space.
The number of stereoisomers possible for a compound of the
molecular formula..

CH3 – CH = CH – CH(OH) – Me (Jee Mains -2009)

1) 2
2) 4
3) 6
4) 3
Physical Properties based on cis-trans

Boiling Point:
Dipole Moment:

Cis form of alkene is more polar than trans form.

Melting Point:

In the case of solids → trans isomer has higher melting point than the
cis form.
Which of the following compounds will show cis-trans
isomerism…

(iv) CH2 = CH2

 Preparation
1. From alkynes:

Alkynes on partial reduction gives alkenes.

Alkyne Reduction with H2 + Lindlar Catalyst => cis geometry alkene

Lindlar Catalyst
Alkyne reduction with Na in liquid NH3 => trans alkenes
The hydrocarbon which can react with sodium in liquid ammonia is… [Jee Mains 2008]

(1) CH3CH2C ≡ CCH2CH3

(2) CH3CH2CH2C ≡ CCH2CH2CH3

(3) CH3CH2C ≡ CH

(4) CH3CH ≡ CHCH3

2. From alkyl halides:

(β-elimination reaction)

This reaction is known as dehydrohalogenation i.e. removal of halogen acid.

 Rate of the reaction depends upon-

Nature of Halogen-

I > Br > Cl,

Type of alkyl groups –

tert > secondary > primary.

3. From vicinal dihalides:

This reaction is known as dehalogenation.

4. From alcohols by acidic dehydration:

(β-elimination reaction)

A H2O molecule is eliminated from the alcohol molecule in the presence

of an acid.
Thus it is acidic dehydration of alcohols.
Physical properties

First three members => gases

Next fourteen => liquids
higher ones => solids

Ethene => colourless gas (faint sweet smell).

All other alkenes are

• Colourless
• Odourless
• Insoluble in water
• Fairly soluble in nonpolar solvents like benzene, petroleum ether.
Boiling Point

• Increase in size => increase in boiling point

• With every – CH2 group added increases boiling point by 20–30 K.

• Straight chain alkenes have higher boiling point than isomeric

branched chain compounds.
Chemical properties

1. Addition of dihydrogen:

C3H6 + H2 Ni/Pt
C3H8
2. Addition of halogens :

(electrophilic addition reaction)

• Only Br, Cl shows this.

• Iodine does not show addition reaction under normal conditions.

Test of Unsaturation-

The reddish orange colour of bromine solution in CCl4 is discharged when

bromine adds up to an unsaturation site.
3. Addition of hydrogen halides:

The order of reactivity –

HI > HBr > HCl.

It is electrophilic addition reaction.

CH3 – CH2Cl alcoholic KOH Br2 Zn
A B  C

C is ..

1) acetylene

2) ethylene

3) ethyne

4) methane
Addition reaction of HBr to symmetrical alkenes
Addition reaction of HBr to unsymmetrical alkenes

Markovnikov Rule- In unsymmetrical alkene, negative part of the reagent

gets added to the carbon atom containing the less number of H - atoms
across the C = C bond.

By rule-
2-bromopropane
is expected and
is the principal
product of the
reaction.
Mechanism
The carbocation (b) is attacked by Br– ion
Anti Markovnikov addition or peroxide effect or Kharash effect

Rule- Opposite of Markovinikov.

• Reaction only with HBr;

• not with HCl and Hl.

Mechanism:
->free radical chain mechanism
 Homolysis

Homolysis
 4. Addition of sulphuric acid :

Follow Markovnikov rule and is electrophilic addition reaction.

 5. Addition of water

Follow Markovnikov rule

Which of the following alkene on acid catalyzed hydration form
2 – methyl propan – 2 – ol .

CH3 CH3
1) CH3 – CH = CH2 2)
CH3 – C = C – CH3

CH3
3) H2C = CH2 4) C = CH2
H3C
 6. Oxidation:

Decolorisation of KMnO4 solution is used as a test for unsaturation.

• Acidic KMnO4 / K2Cr2O7 oxidises alkenes to ketones
and/or acids depending upon the nature of the alkene
and the experimental conditions
7. Ozonolysis

Zn + H2O

Zn + H2O
Ozonolysis of an organic compound gives formaldehyde as one
of the products. This confirms the presence of…
Jee Mains 2010

1) an acetylenic triple bond

2) two ethylenic double bonds

3) a vinyl group
4) an isopropyl group
8. Polymerisation

Polythene is obtained by the combination of large number of ethene

molecules at high temperature, high pressure and in the presence of
a catalyst.
Which compound would give 5 – keto – 2- methyl hexanal upon
Ozonolysis.. ( JEE MAINS – 2015)

CH3 CH3
1) CH3 2)

CH3
CH3
CH3
3) H3C
4)
CH3
 Alkynes
Hydrocarbons containing atleast one triple bond between two carbon
atoms

– C C –
General formula of Alkynes is- CnH2n-2

The first stable member of it is ethyne (acetylene)

 Structure of Triple Bond

• Each carbon atom of ethyne undergoes ‘sp’ hybridization.

• Ethyne has one C-C sigma bond, two C-H sigma bonds and two C-C Pi () bonds
Strength

C≡C bond > C=C bond > C–C bond.

Bond Length

C≡C < C=C < C–C

Preparation
1. From calcium carbide
2. From vicinal dihalides

NaBr

NH3
 Physical Properties
First three members => gases
Next eight => liquids
Higher ones => solids.

• All alkynes are colourless.

• Ethyene has characteristic odour.

• Other members are odourless.

Alkynes are

• weakly polar
• lighter than water
• immiscible with water
• soluble in organic solvents like ethers, carbon tetrachloride and benzene.

Their melting point, boiling point and density increase with increase in molar
mass.
Chemical properties
(a) Acidic character of alkyne

In alkynes, the triply bonded carbon atoms undergo ‘ sp’ hybridisation.

Due to the presence of 50% s-character, these carbon atoms have more
electronegativity which attract shared pair of electrons (C-H) towards themselves.

Hence hydrogen atoms of ethyne attached to triply bonded carbon atoms are
acidic in nature.
2H – C  C – H+ 2Na 2H – C  C– Na++ H2
Monosodium acetylide

2H – C  C– Na++ 2Na 2Na+ –C  C– Na+ + H2

Disodium acetylide

These reactions are not shown by alkenes and alkanes.

 (b) Addition reactions:

• The addition product formed depends upon stability of vinylic cation.

• Addition in unsymmetrical alkynes => Markovnikov rule.

• Majority reactions of alkynes are electrophilic addition reactions.

(i) Addition of dihydrogen
(ii) Addition of halogens
The compounds 1 – butyne and 2 – butyne can be distingushed by
using …

1) Bromine water

2) KMnO4 solution

3) Tollen’s reagent

4) Chlorine gas
Test for Unsaturation
Reddish orange colour of the solution of bromine in carbon
tetrachloride is decolourised.

This is used as a test for unsaturation.

 (iii) Addition of hydrogen halides

Two molecules of hydrogen halides (HCl, HBr, HI) add to alkynes to

form gem dihalides
Markovnikov Rule
In the following sequence of reactions the product (D) is..
HBr HBr alc KOH NaNH2
HC  CH A B C. D.

1) ethanol 2) ethane 3) ethene 4) ethyne

(iv) Addition of water

1%HgSO4
HC  CH + H2O [CH2 = CHOH]
Acetylene 20-40%H2SO4
(Unstable)

Tautomerism
[CH2 = CHOH] CH3CHO
Propyne on hydration in presence of HgSO4 and H2SO4 gives acetone.

1%HgSO4
CH3-C  CH + H2O [CH3-CH = CHOH]
Propyne 20-40%H2SO4
(Unstable)

[CH3-CH = CHOH] Tautomerism

CH3COCH3
(Unstable)
 HgSO4 + dil.H2SO4
Hydrolysis
CaC2 A B . B is..

1) Acetylene 2) Propene

3) Acetone 4) Acetic acid

 C≡ C - CH3

In the given reaction H+/Hg2+ A the product ‘A’ is….

H2O
OH-C=CHCH3 OH
1) HC=C-CH3
2)

O
CH2-C-CH3 O=C-CH2CH3
4)
3)
(v) Polymerisation

(a) Linear polymerisation:

(b) Cyclic polymerisation:
Aromatic Hydrocarbon

These hydrocarbons are also known as ‘arenes’.

Most of them possess pleasant odour

Aroma => pleasant smelling

Most of Aromatic compounds contain benzene ring.

Benzenoids - Aromatic compounds containing benzene ring

Non-benzenoids- Aromatic compounds not containing a benzene ring
Structure of Benzene
Cyclic structure with 3 conjugated double bonds

Also called 1,3,5-cyclohexatriene

All carbons in benzene => sp 2 hybridized.

Resonance and stability of benzene
 Aromaticity
Criteria for aromaticity

a) Cyclic
b) Planar (i.e., all atoms should be sp 2 hybridized)
c) Completely Conjugated
d) Huckel’s Rule :
Compounds must contain (4n+2) π electrons
where, n = 0,1,2,3,4…
Cyclobutadiene is said to be ….

1) Aromatic

2) Aliphatic
3) Nonaromatic

4) Anti aromatic
Preparation of Benzene
(i) Cyclic polymerisation of ethyne:
(ii) Decarboxylation of aromatic acids:
(iii) Reduction of phenol:
 Physical properties

• non- polar molecules

• usually colourless liquids or solids
• have characteristic aroma (Ex. naphthalene balls )
• immiscible with water
• readily miscible with organic solvents.
• burn with sooty flame.
When acetylene is passed through red hot iron tube, compound X is
formed. Which one of the following reactions will yield “X” as the
major product.

Distillation
1) C6H5OH + Zn

2) C6H5SO3H + NaHCO3
Ni
3) C6H12+ 3H2
Δ
4) C6H5Cl + H2O
 Chemical properties
Electrophilic substitution reactions

(i) Nitration:
(ii) Halogenation:
(iii) Sulphonation:
(iv) Friedel-Crafts alkylation reaction:
(v) Friedel-Crafts acylation reaction:
If excess of electrophilic reagent is used
The major product obtained by the Friedel –Craft’s reaction of n
butylbromide with benzene in the presence of anhydrous AlCl 3 ..

1) CH2CH2CH2CH3 2) CH3-CH-CH2-CH3

CH3

CH3-C-CH3
3) 4) None of these
Mechanism of electrophilic substitution
reactions:

S = substitution; E = electrophilic

Three steps:
(a) Generation of the electrophile
(b) Formation of carbocation intermediate
(c) Removal of proton from the carbocation
intermediate
(a) Generation of electrophile E⊕ :
In the case of nitration
Note that in the process of generation of nitronium ion-

• sulphuric acid serves as an acid and

• nitric acid as a base.

Thus, it is a simple acid-base equilibrium.

(b) Formation of Carbocation (arenium ion):
The arenium ion gets stabilised by resonance:
(c) Removal of proton:

in case of halogenation, alkylation and acylation

in case of nitration
Addition reactions

At high temperature and/ or pressure in the presence of nickel

catalyst, hydrogenation of benzene gives cyclohexane.
Under utra-violet light, three chlorine molecules add to benzene to
produce benzene hexachloride ( C6H6Cl6 )

Benzene hexachloride is also called gammaxane.

Combustion:

When heated in air, benzene burns with sooty flame producing CO 2

and H2O
Directive influence of a functional group in
mono substituted benzene

1.) Activating ortho and para directing groups.

Ring activation groups- The substituents that make the ring more reactive than
benzene

–NH2, –NHR, –NR2, –OH, –OR, –NHCOR, –C6H5, –R.

e.g.

Note-

Halogens are deactivating but ortho, para directing groups.

Directive influence of phenolic (–OH) group
2.) Deactivating and meta directing groups.

Ring deactivating groups - The group that makes the ring less reactive than
benzene.

e.g.

–NO2, –CN, –COOH, –COOR, –SO3H, –CHO, –COR

Nitro group reduces the electron density in the benzene ring due to
its strong –I effect.
The major product obtained in the reaction ..
COOH
HNO3
is
H2SO4
COOH

COOH
1) 𝑵𝑶𝟐 2)

O2N COOH

COOH COOH
3)
NO2
4)
COOH COOH
NO2 NO2
Which form of xylene has only one monobromo derivative..

a) Ortho-

b) Para-
3) Meta-

4) Both 1 and 2
The compound that is most reactive towards nucleophilic
substitution is ….
1) Toluene

2) Benzene

3) Benzoic acid

4) Nitrobenzene
In the below mentioned compounds the decreasing order of
reactivity towards electrophilic substitution is .

OCH3 CH3 CF3

(i) (ii) (iii) (iv)

1) (i) >(ii)>(iii)>(iv) 2) (ii) >(iii)>(i)>(iv)

3) (iii) >(i)>(iv)>(ii) 4) (iv) >(i)>(ii)>(iii)