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Hydrocarbons
Part-01

Hydrocarbons

Alkane

Alkene

Alkyne

Aromatic Hydrocarbon

Alkane
everyda
Methods of preparation of alkane
1. Reduction
Addition of hydrogen or removal of N, O, X

(i) From Alkenes and Alkynes (Reduction)

When alkenes and alkynes are completely hydrogenated in the presence of a metal catalyst, alkane is formed
and addition of hydrogen is syn (same side)

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Hydrocarbons Part-01

Catalyst :
(a) Pd/Pt at ordinary temperature and pressure.
(b) Ni, 200–300° C (Sabatier and Senderens reaction)
(c) Raney Nickel (Fine grains of Ni–Al) at room temp.

Example

(ii) By Reduction with Red P + HI / 150°C

HI removes all oxygen and adds hydrogen.

In these reactions, red P is used to remove I2.

(iii) By Reduction of Aldehyde/ Ketone

(A) Clemmensen Reduction
Reagent : Zn-Hg/Conc. HCl
Function : Aldehyde/Ketone to Alkane

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Hydrocarbons Part-01

In this reaction is converted into —CH2— (Methylene).

(B) Wolff-Kishner Reduction

Reagent :

Function : Aldehyde/Ketone to Alkane

In this reaction is converted into —CH2— (Methylene).

(iv) By Reduction of Halide

Reducing agents may be

Example

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Hydrocarbons
Part-02

2. Reaction of Haloalkanes with Na

(i) By Wurtz Reaction

Example

(1)

(2)

Note

(1) Reactivity order of alkyl halide:- R–I > R–Br > R–Cl > R–F
(2) We can form only symmetrical alkanes having even number of carbon atoms.

Mixed-Wurtz reaction

 If two different alkyl halides are used, then it is known as mixed-wurtz reaction.
 Methane cannot be prepared.

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Hydrocarbons Part-02

Note

Wurtz reaction is not suitable for preparation of unsymmetrical alkane because in preparation of unsymmetrical
alkane mixture of products is obtained which cannot be easily separated.

(ii) Fittig Reaction

(iii) Wurtz–fittig reaction

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Hydrocarbons
Part-03

3. From Carboxylic Acids

(i) Kolbe's Electrolysis
On electrolysis of sodium/potassium salt of carboxylic acid, generally alkane is obtained as a product.

Note

 Due to increase in concentration of OH, the pH of solution increases with time during electrolysis.
 CH4 cannot be prepared.
 H2 gas is released at cathode and CO2 gas is released at anode.

(ii) Soda–lime Decarboxylation

Carboxylic acid or sodium salts of carboxylic acids are heated with soda-lime. (NaOH and CaO in 3 : 1 ratio)
Removal of CO2 from carboxylic acid is known as decarboxylation.

Note

 In this reaction carbanion intermediate is formed.

 Rate of decarboxylation  stability of carbanion.

 Product contains 1C atom less than reactant that’s why this reaction is used for stepping down in homologous
series.

 CaO is used to keep NaOH dry because it is quite hygroscopic in nature.

 -keto acid can be easily decarboxylated by heating only (no need of soda-lime)

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Hydrocarbons Part-03

4. From Grignard Reagent

Preparation of Grignard Reagent

Note

Grignard reagent behaves like a base and reacts with compounds containing acidic H.

5. From Metal Carbide (By Hydrolysis)

CH4 can be obtained by the hydrolysis of Be or Al carbides.

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Hydrocarbons
Part-04

Physical properties of alkane

1. Solubility
Alkanes being non-polar are insoluble in water but soluble in non-polar solvents like C6H6, CCl4 etc.

2. Boiling Point
Boiling point  Molecular weight
1
 (If molecular weight is same)
Branching

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Hydrocarbons
Part-05

Chemical Properties of alkane

The characteristic reaction of alkanes is Free Radical Substitution Reaction (FRSR)
1. Substitution reaction (Halogenation)

Mechanism
Step-I Chain initiation step

Step-II Chain propagation step

Step-III Chain termination step

Note

1. Reactivity order of halogen : F2 > Cl2 > Br2 > I2

2. In this reaction, intermediate is carbon free radical.
3. RDS of this reaction is the 1st step of chain propagating step (Abstraction of H).
Rate of halogenation  stability of free radical

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Hydrocarbons Part-05

4. The order of reactivity of hydrogens towards free radical halogenation is

5. To avoid Polyhalogenation, alkanes should be taken in excess.

6. Fluorination is explosive in nature, should be carried out in the presence of inert gas like N2 (inhibitor).
7. Fluorination can take place in dark also.
8. Bromine is less reactive than chlorine so generally requires high temperature.
9. Iodination is reversible so carried out forward in the presence of oxidizing agents like HIO3, HNO3, etc.

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Hydrocarbons
Part-06

Allylic and Benzylic Substitution Reactions (FRSR)

Allylic and Benzylic Hydrogens
The sp2 carbons of an alkene are called vinylic carbons. An sp3 carbon that is adjacent to vinylic carbon is
called an allylic carbon. A hydrogen bonded to a vinylic carbon is called a vinylic hydrogen, and a hydrogen
bonded to an allylic carbon is called an allylic hydrogen.

Reagents used for halogenation at allylic and benzylic position.

1. NBS (N-Bromosuccinimide)
2. NCS (N-Chlorosuccinimide)

It is an example of free radical substitution reaction.

2. Combustion reaction
 Alkanes on heating in the presence of excess air or dioxygen are completely oxidized to carbon dioxide and
water with the evolution of large amount of heat.

 During incomplete combustion of alkanes with insufficient amount of air or dioxygen, carbon black is formed.

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Hydrocarbons Part-06

3. Controlled Oxidation

4. Oxidation by KMnO4 or K2Cr2O7 (Strong oxidising agent)

Alkanes having 3°H are oxidised in Alcohol

5. Isomerisation
Unbranched chain alkanes on heating with AlCl3 + HCl are converted into branched chain alkanes.

6. Aromatization
n-Alkanes having six or more carbon atoms on heating to 500°C at 10-20 atmospheric pressure in the presence
of oxides of vanadium, molybdenum or chromium supported over alumina (Al2O3) results in the formation of
aromatic hydrocarbons.

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Hydrocarbons Part-06

7. Pyrolysis
 When alkanes are heated to 500-700°C then they are decomposed into lower hydrocarbon.
(liquid hydrocarbon is converted in gaseous hydrocarbon)
 This decomposition is known as pyrolysis/cracking.
 It involves free radical elimination.

8. Reaction with steam

Methane reacts with steam at 1273K in the presence of nickel catalyst to form carbon monoxide and dihydrogen.
This method is used for industrial preparation of hydrogen gas.

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Hydrocarbons
Part-07

Alkene
everyda
Methods of preparation of alkene
1. From Alkynes (By Partial Hydrogenation)

 Alkynes on reduction in the presence of palladised charcoal partially deactivated with poisons like quinoline etc.
give alkenes. (partial hydrogenation)

 Partially deactivated palladised charcoal is known as Lindlar’s catalyst.

For partial hydrogenation Birch catalyst (Na + Liq. NH3) is also used.

Birch reduction

Note

Terminal alkynes do not give Birch reduction.

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Hydrocarbons Part-07

2. From Alcohols (By Dehydration)

Alcohols on heating with conc. H2SO4 give alkenes with the elimination of water molecule. This is known as acid
catalysed dehydration of alcohols.
Reagents used: (1) Conc. H2SO4/ (2) Conc. H3PO4/
(3) KHSO4/ (4) H/

3. From Alkyl Halide (By Dehydrohalogenation)

 Dehydrohalogenation of alkyl halide to form alkene is an example of ,  Elimination reaction because H
removes from -carbon.
 Alkyl halides (R—X) on heating with alcoholic potash eliminate one molecule of halogen acid to form alkenes.

4. Dehalogenation of Vicinal Dihalide

Dihalides in which two halogen atoms are attached to two adjacent carbon atoms are known as vicinal dihalides.

Vicinal dihalides on treatment with zinc metal eliminate a molecule of ZnX 2 to form an alkene. This reaction is
known as dehalogenation.

Reagent used: Zn dust/

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Hydrocarbons
Part-08

Physical properties of Alkenes

Physical State
The first three members of alkene are gases, next fourteen are liquids and the higher ones are solids.
Ethene is a colourless gas with a faint sweet smell and all other alkenes are colourless and odourless.

Solubility
Alkenes are insoluble in water but fairly soluble in non-polar solvents like benzene, petroleum ether.

Boiling Point
Alkenes show a regular increase in boiling point with increase in size.

Chemical properties of Alkenes

Electrophilic Addition Reactions (EAR)
Characteristic reaction of alkene is EAR

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Hydrocarbons
Part-09

Carbocation Rearrangement
Observed in those reactions in which carbocation is formed as an intermediate.
Less stable carbocation rearranges itself to more stable carbocation via transition state.

(1)

(2)

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Hydrocarbons
Part-10

1. Reaction with Conc. H—X (Halogen Acid)

Mechanism

Note

1. Carbocation intermediate is formed, so make more stable carbocation.

2. Rate of reaction- HI > HBr > HCl > HF

Markovnikov's Rule
The rule states that negative part of the reagent gets attached to that carbon of double bond which possesses
lesser number of hydrogen atoms.

Note

1. Markovnikov’s rule is not applicable if alkene is symmetrical.

2. Markovnikov’s rule is not applicable in the cases where double bonded carbon is directly attached to strong
⨁
electron withdrawing group like (–NO2, –CHO, –CCl3, –NH3)

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Hydrocarbons
Part-11

2. Reaction with Dilute H2SO4 Or H+/H2O Or H3O+

Mechanism

Note

1. Reaction is reversible.
2. Forward reaction is acidic hydration of alkene and backward reaction is acidic dehydration of alcohol
(Elimination reaction).

3. Reaction with Conc. H2SO4

Cold concentrated sulphuric acid adds to alkenes in accordance with Markovnikov rule to form alkyl hydrogen
sulphate by the electrophilic addition reaction.

4. Reaction with X2/CCl4

Mechanism
(Electrophile has lone pair)

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Hydrocarbons Part-11

Note

1. Electrophile contains lone pair.

2. No carbocation intermediate is formed so no rearrangement is possible.
3. Reaction intermediate : Cyclic halonium ion.
4. Reactivity of halogens: F2 > Cl2 > Br2 > I2
5. Reaction with F2 is explosive.
6. Reaction with I2 is reversible.

7. Test of Unsaturation
Br
Unknown organic compound ⎯⎯⎯
2
→ Reddish brown colour disappears ⎯⎯→ Unsaturation may be present
CCl4

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Hydrocarbons
Part-12

5. Reaction with X2/H2O or HOX (Hypohalous Acid)

Mechanism

Note

1. No carbocation intermediate is formed so no rearrangement is possible.

2. Reaction intermediate – cyclic halonium ion.

6. Reaction with NOCl (Tilden’s Reagent)

7. Oxymercuration Demercuration (OMDM)

Reagent :
(i) (CH3COO)2 Hg, H2O or Hg(OAc)2, H2O
Θ
(ii) NaBH4/OH

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Hydrocarbons Part-12

Note

1. In this reaction addition of water takes place and alcohol is formed as a product.
2. No carbocation intermediate is formed so no rearrangement takes place.
3. Markovnikov addition of water.

8. Hydroboration Oxidation (HBO)

Mechanism

Note

1. In this reaction addition of water takes place by Anti markovnikov addition of water and alcohol is formed.
2. No carbocation intermediate is formed so no rearrangement takes place.

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Hydrocarbons
Part-13

Free Radical Addition Reaction (FRAR)

Peroxide effect / Kharasch effect

“Reaction of alkene with HBr in the presence of peroxide takes place through free radical mechanism and this is
an example of Free Radical Addition Reaction (FRAR)”

Mechanism
(i)

(ii)

(iii)

(iv)

Note

It may be noted that the peroxide effect is not observed in addition of HCl and HI. This is due to the fact that
the H—Cl bond being stronger than H—Br bond is not cleaved by the free radical, whereas the H—I bond is
weaker and iodine free radicals combine to form iodine molecules instead of adding to the double bond.

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Hydrocarbons Part-13

Oxidation
Reactions involving oxidation of carbon-carbon double bond may be classified into two general groups :
1. Oxidation of  bond without cleavage of sigma bond.
2. Oxidation of  bond with cleavage of sigma bond.

1. Oxidation of  bond without cleavage of sigma bond.

Hydroxylation using Baeyer’s reagent (cold dilute alkaline KMnO 4)

Note

1. This reaction is also used as test of unsaturation.

2. Baeyer’s reagent is purple in colour. As the reaction proceeds, the purple colour disappears and brown
precipitate of MnO2 is observed.

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Hydrocarbons
Part-14

2. Oxidation of  bond with cleavage of sigma bond.

(a) Ozonolysis

In oxidative ozonolysis further oxidation of aldehyde takes place while oxidation of ketones does not take place.
If formic acid is formed in oxidative ozonolysis then it further oxidises into CO 2.

(b) Strong oxidising agent (KMnO4/H+ or K2Cr2O7 /H+)

Acidic KMnO4 or acidic potassium dichromate oxidises alkenes to ketones and acids depending upon the nature
of the alkene and the experimental conditions.

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Hydrocarbons Part-14

Polymerisation
Polythene is obtained by the polymerisation of ethene molecules at high temperature, high pressure in the
presence of a catalyst.

The large molecules thus obtained are called polymers and simple compounds from which polymers are formed
are called monomers.

Use of Polymers
Polymers are used for the manufacture of plastic bags, squeeze bottles, refrigerator dishes, toys, pipes, radio
and T .V. cabinets etc.

Polypropene is used for the manufacture of milk crates, plastic buckets and other moulded articles.

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Hydrocarbons
Part-15

Alkyne

Preparation methods of Alkynes

1. From Vicinal Dihalides
Vicinal dihalides on treatment with alcoholic KOH undergo dehydrohalogenation to form alkenyl halide which
on further treatment with sodamide give alkyne.

2. From Geminal Dihalides

3. From Calcium Carbide

On industrial scale, ethyne is prepared by treating calcium carbide with water.

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Hydrocarbons Part-15

4. From CHCl3/CHI3 (Preparation of acetylene)

Physical Properties of Alkynes

(A) First three members are gases, the next eight are liquids and the higher ones are solids.
(B) Ethyne has characteristic odour, other members are odourless.
(C) Alkynes are weakly polar in nature so insoluble with water but soluble in organic solvents like ethers, carbon
tetrachloride and benzene.
(D) Their melting point, boiling point and density increase with increase in molar mass.

Chemical Properties of Alkynes

Addition Reaction R—CC—R
1. Addition of hydrogen halides
Two molecules of hydrogen halides (HCl, HBr, HI) add to alkynes to form gem dihalides (in which two halogens
are attached to the same carbon atom).

Note

“In the addition of HX to vinyl halide, the halogen attached itself to the carbon atom, on which the halogen
atom is already present.”

2. Addition of halogens

Reddish brown colour of the solution of bromine in carbon tetrachloride is decolourised so this reaction is used
as a test for unsaturation.

3. Addition of water
Like alkanes and alkenes, alkynes are also immiscible and do not react with water. However, one molecule of
water adds to alkynes on warming with mercuric sulphate and dilute sulphuric acid at 333K to form carbonyl
compounds.

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Hydrocarbons Part-15

Reaction of terminal alkynes R—CC—H

1. Reaction with sodium (Na)

Example

2. Reaction with Tollen’s reagent (ammoniacal silver nitrate solution)

AgNO3 + NH4OH

3. Reaction with ammoniacal cuprous chloride solution.

(Cu2Cl2 + NH4OH)

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Hydrocarbons Part-15

1. Polymerisation
(a) Linear polymerisation :
Under suitable conditions, linear polymerisation of ethyne takes place to produce polyacetylene or polyethyne
which is a high molecular weight polyene.

(b) Cyclic polymerisation :

Ethyne on passing through red hot iron tube at 873K undergoes cyclic polymerisation.

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Hydrocarbons
Part-16

Aromatic Hydrocarbon

Preparation methods of Benzene

1. Cyclic polymerisation of ethyne

2. Decarboxylation of aromatic acids (Soda lime reaction)

Sodium salt of benzoic acid on heating with sodalime gives benzene.

3. Reduction of phenol
Phenol is reduced to benzene by passing its vapours over heated zinc dust.

Physical properties of Benzene

(A) Aromatic hydrocarbons are non- polar molecules and are usually colourless liquids or solids with a characteristic
aroma.
(B) Naphthalene balls are used in toilets and for preservation of clothes.
(C) Aromatic hydrocarbons are immiscible with water but are readily miscible with organic solvents.
(D) They burn with sooty flame.

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Hydrocarbons
Part-17

Chemical properties of Benzene

Electrophilic Substitution Reaction (ESR)
ESR is the characteristic reaction of benzene and its derivatives.

Mechanism

Note

1. Rate towards ESR  Nucleophilicity of benzene ring

 stability of  complex

Activating Groups
Substituents which make ring more reactive than benzene are activating groups
(rate towards ESR is more than benzene).

Example

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Hydrocarbons Part-17

Note

All activating groups are ortho-para directing.

(Directs the incoming electrophile at ortho-para position)

Deactivating Groups
Substituents which make ring less reactive than benzene are deactivating groups
(rate towards ESR is less than benzene).

Example

Note

Generally, deactivating groups are meta directing.

(Directs the incoming electrophile at meta position)

Exception
Halogens are weakly deactivating but ortho para directing.
Reactivity is controlled by inductive effect but orientation is controlled by mesomeric effect.

Rate towards ESR

Attack of electrophile

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Hydrocarbons Part-17

1. Halogenation reaction

Mechanism

Electrophile:– Chloronium ion (Halonium ion)

2. Friedel crafts alkylation

When benzene is treated with an alkyl halide in the presence of anhydrous aluminium chloride, alkylbenene is
formed.

Carbocation forms, So rearrangement occurs (if possible) before attack on benzene or derivatives.

3. Friedel crafts acylation

The reaction of benzene with an acyl halide or acid anhydride in the presence of Lewis acids (AlCl 3) yields acyl
benzene.

4. Nitration reaction
In nitration reaction, -NO2 group is introduced in an aromatic ring.

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Hydrocarbons Part-17

Mechanism

⨁
Electrophile :- Nitronium ion (NO2)
Note: If KHSO4 is added to the reaction mixture rate of reaction decreases, due to common ion effect.

5. Sulphonation reaction (By conc. H2SO4 or oleum)

Mechanism

Electrophile:

6. Alkylation (By alcohol)

Mechanism

Carbocation forms, So rearrangement occurs (if possible) before attack on benzene or derivatives.

Important Points
1. Vinyl halide and aryl halide cannot be used as halide component in Friedel Crafts alkylation.

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Hydrocarbons Part-17

2. Polyalkylation is a major problem in Friedel Crafts Alkylation as the formed product is more reactive compared
to reactant.

⊕
3. In presence of strongly deactivating groups (meta directing groups –NO2, –COOH, –CHO, –NH3 etc.) Friedel
Crafts reaction (alkylation and acylation) does not take place.

Example

Nitrobenzene can be used as solvent in Friedel Crafts reaction.

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Hydrocarbons
Part-18

7. Gattermann Koch Reaction

8. Oxidation using
⨁
1. KMnO4 /H
⊖
2. KMnO4/OH/
⨁
3. K2Cr2O7/H

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Hydrocarbons Part-18

9. Oxidation using V2O5

Carcinogenicity and toxicity

 Benzene and polynuclear hydrocarbons containing more than two benzene rings fused together are toxic and
said to possess cancer producing (carcinogenic) property.
 Such polynuclear hydrocarbons are formed on incomplete combustion of organic materials like tobacco, coal
and petroleum.
 They enter into human body and undergo various biochemical reactions and finally damage DNA and cause
cancer.

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