HYDROCARBONS

Hydrocarbons are the organic compounds containing carbon and hydrogen only.
Depending upon the types of carbon-carbon bonds present, hydrocarbons can be
classified into three categories- (i) Saturated (ii) Unsaturated (iii) Aromatic
hydrocarbons.
Saturated hydrocarbons contain carbon-carbon muiltiple bonds–double bonds, triple
bonds or both.
ALKANES : Saturated open chain hydrocarbons containing carbon-carbon single
bonds. These are inert under normal conditions i.e. do not react with acids, bases and
other reagents. Alkanes exhibit Chain isomerism, Position isomerism and
conformational isomerism.
General methods of preparation of alkanes :
1. From Unsaturated hydrocarbons : By hydrogenation in the presence of
platinium, palladium or nickel as catalyst.
General Chemical Equation :

2. From alkyl halides : On reduction with Zinc and dilute hydrochloric acid.
3. From alkyl halides by Wurtz reaction : Reaction of alkyl halide with sodium in
dry ether, useful only for the preparation of symmetrical alkanes.
Dry Ether
CH3CH2Br + 2Na + Br CH2CH3 CH3CH2CH2CH3
Bromoethane Butane
Dry Ether
CH3CH2CH2 Br + 2Na + Br CH2CH2CH3 CH3CH2CH2CH2CH2CH3
1-Bromopropane n–Hexane

4. From Carboxylic acids : By decarboxylation with soda lime

5. By Kolbe's electrolytic method : Electrolysis of an aqueous solution sodium or

potassium salt of carboxylic acid. Alkane containing even number of carbon atoms is
formed at anode.
Electrolysis
2CH3COO Na + 2H2O → CH3 – CH3 + 2CO2 + H2 + 2NaOH

At Anode : (Oxidation)

At Cathode : (Reduction)

2H2O —→ 2OH– + 2H+

2H+ + 2e– —→ H2

Physical Properties of alkanes :

1. Boiling point of alkanes decreases on branching due to decrease in surface ara of
molecule with branching which decreases magnitude of van der Waal's forces of
attraction.
2. Alkanes being non-polar in nature are soluble in non-polar solvents.
Chemical properties of Alkanes :
• Alkanes undergo substitution reactions.
e.g., Halogenation, Nitration, Sulphonation.
Halogenation : For example Chlorination of methane
CH4 + Cl2 → CH3Cl + HCl
Chloromethane

CH3Cl + Cl2 → CH2Cl2 + HCl

Dichloromethane

CH2Cl2 + Cl2 → CHCl3 + HCl

Trichloromethane

CHCl3 + Cl2 → CCl4 + HCl

Tetrachloromethane

Rate of reaction of alkanes with halogens is F2 > Cl2 > Br2 > I2. Rate of
replacement of hydrogen in alkanes is 3° > 2° > 1°. Fluorination is too violent to
be controlled. Iodination is reversible and it is therefore carried out in the
presence of oxidising agent like HNO3.

Mechanism of halogenation : Free radical mechanism

Cl – Cl → Cl• + •Cl Initiation

Cl• + CH4 → H – Cl + •CH3 Propagation

•CH3 + Cl – Cl → CH3 Cl + •Cl Propagation

. Cl• + •CH3 → CH3 Cl Termination

Combustion : Complete combustion gives carbon dioxide and water.

CH4 + 2O2 → CO2 + 2H2O

Isomerisation :

Aromatisation :
CH3 Cr2O3 or V2O5
CH2 CH2 or Mo2O3
CH2 CH2 773 K
CH 10–20 atm
2

(vi) Reaction with steam

Ni
CH4 + H2O CO + 3H2
Pyrolysis : Decomposition of higher alkanes to lower alkanes on heating.

Conformations : Different spatial arrangement of atoms arising due to rotation

around C-C single bond.
Conformation of ethane, CH3CH3
Two conformational isomers or conformers.
Eclipsed form = all hydrogen atoms nearest to each other.
Staggered form = all hydrogen atoms are farthest apart.
 Stability of eclipsed conformation is least while staggered conformation is most
stable. The energy difference between two extreme forms is 12.5kJmol-1. Due to
this small energy difference the two forms are easily inter-convertible at ordinary
temperature and cannot be separated and isolated.
ALKENES
These are unsaturated non-cyclic hydrocarbons which have.sp2 -hybridisation with 120°
bond angle.
Alkenes are also called olefins [oil.forming] which indicates their high reactive nature.
Alkenes have general formula C n H2n, where n = 2, 3, 4, .......
C2H4 (ethene), C3H6 (propene), etc.

 Methods of Preparation of Alkenes

 (i) From alkynes
Pd/C
R — C ≡ C — R' + H2
cis-alkene

(ii) From alkyl halide [Dehydrohalogenational]

H H H H
Alc. KOH
H—C—C—H C= C
∆
H X H H
[X = Cl, Br, I] [β-Elimination product]

(iii) From vicinal dihalides

CH2Br—CH2Br + Zn —∆→ CH2 = CH2 + ZnBr 2

CH3—CH—CH2 + Zn —∆→ CH3—CH = CH2 + ZnBr2

Br Br

(iv) From alcohols by acidic dehydrogenation

H H Conc. H2SO4

H—C—C—H CH2 = CH2 + H2

∆
Ethene
H OH
Ethanol

 Chemical Properties of Alkenes :

1. Addition of Halogens :
2. Addition of hydrogen halides HCl, HBr, Hl : Add up to alkenes to form alkyl
halides as per their reactivity order in HI>HBr>HCl.
Addition reaction of HBr to unsymmetrical alkenes (Markownikov's rule)
According to Markownikovs' rule, the negative part of the addendum (adding
molecule) gets attached to that carbon atom which possesses lesser number of
hydrogen atoms.
H—CH2—CH=CH2 + HBr → H3C—HCBr—CH3
Anti Markownikov addition or peroxide effect or Kharasch effect in the presence
of organic peroxide, addition of only HBr molecule on unsymmetrical alkene takes
place contrary to the Markownikov's rule. Peroxide effect is not observed in case
of HF, HCl and HI.

CH3—CH=CH2 + HBr (C6H5CO)2O2 CH3CH2CH2Br

→ 1-bromopropane

3.Addition of sulphuric acid

CH3—CH=CH2 + HOSO2OH → CH3CH(OSO3H) CH3

[cold and conc.] propyl hydrogen sulphate

4.Addition of water

5.Oxidation : Alkenes decolourise cold dilute aqueous solution potassium

permanganate (Baeyer's reagent). It is used as a test for unsaturation.
Dil.KMnO4
CH2=CH2 + H2O + [O] CH2—CH2
273K
OH OH
Ethane–1,2-diol or glycol

Acidic KMnO4 or acidic K2 Cr2O7 oxidises alkenes to ketones and/or acids

depending upon the nature of alkene and the experimental conditions.
 (CH3)2C=CH2 (CH3)2CO + CO2 + H2O
2-Methyl propene Propane-2-one
KMnO4/H+
CH —CH= CH—CH3 2CH3COOH
But-2-ene Ethanoic acid

Ozonolysis : Reaction of ozone with alkene to form ozonide which on

subsequent reductive cleavage with zinc dust and water give carbonyl
compounds (aldehydes & ketones).

H3C
Zn/H2O
CH3-C(CH3) = CH2 + O2 C= O + HCHO + H2 O2
H3C

Zn + H2O2 ZnO + H2O

Polymerization

ALKYNES
H e.g., C H
These are unsaturated hydrocarbons with general formula Cn 2n-2 2 2 (ethyne),
C3H4 (propyne).

Alkynes also exhibit electrophilic addition reaction but less reactive than alkenes
because the dissociation of π-electron cloud requires more energy.

H–C≡C–H contins 3σ and 2π -bonds and bond length is 120 pm. In acetylene.
H–C–C bond angle is 180°.

Methods of Preparation of Alkynes

1. From calcium carbide
CaCO3 CaO + CO2
CaO + C CaC2 + CO
CaC2 + 2H2O Ca(OH)2 + C2H2
2. From vicinal dihalides
H
KOH
H C—CH2 C= C
Alcohol
Br Br - KBr H Br
- H2O
NaNH2 – NaBr, – NH3
HC≡ CH
3. From tetrahalides
CH3 OH
Br2CH—CHBr2 + 2Zn H—C≡ C—H + 2ZnBr2
∆ 2

Physical Properties of Alkynes :

1. The first two members are gases next eight members (C5 – C12) are liquids and
higher members are solids.
2. They are all colourless and odourless with the exception of acetylene which has
slightly garlic odour due to the presence of PH3 and H2S as impurities.
3. Alkynes are insoluble in water but soluble in organic solvents like ethers, carbon
tetrachloride and benzene.
4. Melting point, boiling point and density increase with increase in molar mass.
Chemical properties of Alkynes
Alkynes show electrophilic as well as nucleophilic addition reactions.

Acetylenic hydrogens are acidic in nature due to 50% s-character in sp-hybridised

orbitals. Acidity of alkynes is lesser than water.

Acidic behaviour order

(i) HC≡CH > CH2 = CH2 > CH3 —CH3

sp sp2 sp3
 (ii) HC≡CH > CH3—C≡CH >> CH3—C≡C—CH3

AROMATIC HYDROCARBONS
These hydrocarbon are also known as arenes. The parent member of the family aromatic
hydrocarbons is benzene.
Aromatic compounds containing benzene ring are known as benzenoids.
Structure of benzene : Hexagonal ring of carbon atoms with alternate single and double
bonds. Each carbon atom is sp2 hybridised. Planar ring, bond angle 120°. All C-C bond
lengths are equal due to complete delocalisation of π electrons.
H H

H H

H H

Formation of C-C and C-H Sigma skeleton of

sigma bonds benzene molecule

Sideways Sideways
overlap overlap

HUCKEL'S RULE
• Huckel's rule, (based on calculations) : a planar cyclic molecule with
alternating double and single bonds has aromatic stability if it has (4n +2π)
electrons (n is 0, 1, 2, 3, 4)

• For n = 1 : 4n+2 = 6; benzene is stable and electrons are delocalized.

 Benzene
Three double bonds; six π
electrons
METHODS OF PREPARATION

1. Cyclic polymerisation of ethyne

Red hot fe tube

3C2H2 873K

2. Decarboxylation of aromatic acids

COONa

CaO
+ NaOH + Na2CO3
∆

Reduction of phenol
OH

Zn
+ ZnO
∆

Physical Properties of Benzene :

(i) Aromatic hydrocarbons are non-polar molecules and are usually
colourless liquids or solids with a characteristic aroma.
(ii) Aromatic hydrocarbons are immiscible with water but readily miscible
with organic solvents.
(iii) Aromatic compounds burn with sooty flame.

Chemical Reactions of Benzene :

(i) Benzene gives electrophile substitution reactions.

(ii) According to experimental evidences, electrophile substitution reaction
involve following three steps :
• Generation of electrophilie
 • Formation of carbocation intermediate.
• Removal of proton from the carbocation intermediate.
(i) Nitration

(ii) Halogenation

(iii) Sulphonation

Friedel-Craft's alkylation reaction (iv)

(v) Friedel-Crafts acylation reaction

 Benzene also undergoes addition reactions e.g.

benzene bexachloride or 666

(BHC or Gammexane or lindane)
 COMBUSTION
2C6H6 + 15O2 12CO2 + 6H2O

Directing influence of substituents in monosubstituted benzene

(i) Ortho and para directing groups : Ring activating groups
e.g., NH2, – CH3, – C2H5, – OCH3 etc. ( + R effect) (ii) Meta
directing groups : Ring deactivating groups

e.g. - NO2, – CN, – CHO, – COOH, – SO3H ( – R effect).