Chemistry

Aliphatic Hydrocarbons

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Table of Content

1. Sources of hydrocarbon.
2. Characteristics of hydrocarbon.
3. Alkanes (Paraffin’s).
4. Individual members of alkanes.
5. Alkenes.
6. Alkynes.
7. Separation of alkane, alkene and alkyne.
8. Distinction between alkanes, alkenes and alkynes.
9. Cycloalkanes.
10. Cycloalkenes.
11. Dienes.

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“Organic compounds composed of only carbon and hydrogen are called hydrocarbons. Hydrocarbons
are obtained mainly from petroleum, natural gas or coal. Petroleum is a major source of aliphatic
hydrocarbon. The important fuels like petrol, kerosene, coal gas, oil gas, compressed natural gas [CNG],
LPG etc., all are hydrocarbon and their mixtures”.

Hydrocarbons

Aliphatic or open chain Alicyclic or closed chain or cyclic Aromatic or arenes

Cyclo alkanes Cyclo alkenes

Saturated Unsaturated

Alkanes or paraffines Alkenes or olefins Alkynes or acetylenes

1. Sources of hydrocarbon.

Mineral oil or crude oil, petroleum [Petra  rock; oleum  oil] is the dark color oily liquid [do with offensive
odour found at various depths in many regions below the surface of the earth. It is generally found under
the rocks of earth’s crust and often floats over salted water.
(1) Composition
(i) Alkanes: found 30 to 70% contain up to 40 carbon atom. Alkanes are mostly straight chain but some
are branched chain isomers.
(ii) Cycloalkanes: Found 16 to 64% cycloalkanes present in petroleum are; cyclohexane, methyl
cyclopentane etc. cycloalkanes rich oil is called asphattic oil.
(iii) Aromatic hydrocarbon: found 8 to 15% compound present in petroleum are; Benzene, Toluene,
Xylene, Naphthalene etc.
(iv) Sulphur, nitrogen and oxygen compound: Sulphur compound present in the extent of 6% and
include mercaptans [R-SH] and sulphides [R-S-R]. The unpleasant smell of petroleum is due to sulphur
compounds. Nitrogen compounds are alkyl pyridines, quinolines and pyrroles. Oxygen compounds
present in petroleum are. Alcohols, Phenols and resins. Compounds like chlorophyll, haemin are also
present in it.

2
(v) Natural gas: It is a mixture of Methane (80%), Ethane (13%), Propane (3%), Butane (1%), Vapors of low
boiling pentanes and hexanes (0.5%) and Nitrogen (1.3%). L.P.G. Contain butanes and pentanes and used
as cooking gas. It is highly inflammable. This contain, methane, nitrogen and ethane.
(vi) C.N.G.: The natural gas compressed at very high pressure is called compressed natural gas (CNG).
Natural gas has octane rating of 130 it consists, mainly of methane and may contain, small amount of
ethane and propane.

(2) Theories of origin of petroleum: Theories must explain the following characteristics associated with
petroleum,
Its association with brine (sodium chloride solution). The presence of nitrogen and sulphur compounds in
it. The presence of chlorophyll and haemin in it. Its optically active nature. Three important theories are as
follows.
(i) Mendeleeff’s carbide theory or inorganic theory
(a) Molten metals in hot earth’s crust combine with coal deposits and formed carbides.
(b) Carbides reacted with steam or water under high temperature and pressure to form mixture of
saturated and unsaturated hydrocarbons.
(c) The unsaturated hydrocarbon in presence of metal catalyst, high pressure and high temperature,
undergoes reactions such as hydrogenation, isomerization and polymerization to form number of
hydrocarbons.
Reactions: Ca  2C  CaC 2 (Calcium carbide); Mg  2C  MgC 2 (Magnesium carbide)
4 Al  3C  Al 4 C 3 (Aluminum carbide); CaC 2  2 H 2 O  Ca(OH )2  C 2 H 2
(Acetylene)
Al 4 C 3  12 H 2 O  4 Al(OH )3  3CH 4 (Methane); C 2 H 2 
 C 2 H 4 
 C 2 H 6
H2 H2

(Ethane)

 C 6 H 6 ;
3[CH  CH ] 
Polymerisa tion

(Benzene)

CH 3  CH  CH  CH 3  CH 3  CH 2  CH  CH 2
Isomerisat ion

(1 -Butene)

Theory fails to account for, The presence of nitrogen and sulphur compounds. The presence of chlorophyll
and haemin derivatives. The presence of optically active compounds.
(ii) Engler’s theory or organic theory: Theory is supported by the following facts,
(a) The presence of brine with petroleum,
(b) The presence of optically active compounds,
(c) The presence of nitrogen and sulphur compounds
(d) The presence of fossils in the petroleum area.
The theory was further supported by the fact that when destructive distillation of fish oil and other animals
fats under high temperature and pressure was carried out, a petroleum like liquid was obtained.

3
Theory fails to account for, The presence of chlorophyll in the petroleum. The presence of coal deposits
found near the oil fields. The presence of resins in the oil.
(iii) Modern theory: This theory explain nearly all the facts about petroleum.
(a) The presence of chlorophyll and haemin in petroleum.
(b) The presence of coal deposits near oil fields suggesting its vegetable origin.
(c) The presence of nitrogen and sulphur compounds along with optically active compounds in
petroleum.
(d) The presence of resins also suggests that oil must have been formed from vegetable substances.
(e) The presence of helium gas in natural gas suggests that radioactive substances must have
helped in the decomposition of organic matter.

(3) Mining of petroleum: Petroleum deposits occurs at varying depth at different places ranging from
500 to 15000 feet. This is brought to the surface by artificial drilling.

(4) Petroleum refining: Separation of useful fractions by fractional distillation is called petroleum refining.
Fraction Boiling range Approximate Uses
(oC) composition

Uncondensed gases Up to room C1 – C4 Fuel gases: refrigerants; production of

temperature carbon black, hydrogen; synthesis of
organic chemicals.

Crude naphtha on 30 – 150o C5 – C10

refractionation yields,
(i) Petroleum ether 30 – 70o C5 – C6 Solvent

(ii) Petrol or gasoline 70 – 120o C6 – C8 Motor fuel; dry-cleaning; petrol gas.

(iii) Benzene derivatives 120 – 150o C8 – C10 Solvent; dry-cleaning
Kerosene oil 150 – 250o C11 – C16 Fuel; illuminant; oil gas

Heavy oil 250 – 400o C15 – C18 As fuel for diesel engines; converted to
gasoline by cracking.

Refractionation gives,
(i) Gas oil

(ii) Fuel oil

(iii) Diesel oil

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 Residual oil on Above 400o C17 – C40
fractionation by vacuum
distillation gives,

(i) Lubricating oil C17 – C20 Lubrication

(ii) Paraffin wax C20 – C30 Candles; boot polish; wax paper; etc.

(iii) Vaseline C20 – C30 Toilets; ointments; lubrication.

(iv) Pitch C30 – C40 Paints, road surfacing
Petroleum coke As fuel.
(on redistilling tar)

(5) Purification
(i) Treatment with concentrated sulphuric acid: The gasoline or kerosene oil fraction is shaken with
sulphuric acid to remove aromatic compounds like thiophene and other sulphur compound with impart
offensive odour to gasoline and kerosene and also make them corrosive.
(ii) Doctor sweetening process: 2 RSH  Na 2 PbO2  S  RSSR  PbS  2 NaOH
Mercaptan Disulphides

(iii) Treatment with adsorbents: Various fractions are passed over adsorbents like alumina, silica or clay
etc., when the undesirable compounds get adsorbed.

(6) Artificial method for manufacture of Petrol or gasoline

(i) Cracking, (ii) Synthesis

(i) Cracking: It is a process in which high boiling fractions consisting of higher hydrocarbons are heated
strongly to decompose them into lower hydrocarbons with low boiling pts. Cracking is carried out in two
different ways.
(a) Liquid phase cracking: In this process, the heavy oil or residual oil is cracked at a high temperature
(475 – 530oC) under high pressure (7 to 70 atmospheric pressure). The high pressure keeps the reaction
product in liquid state. The conversion is approximately 70% and the resulting petrol has the octane
number in the range 65 to 70.
The cracking can be done in presence of some catalysts like silica, zinc oxide, titanium oxide, ferric oxide
and alumina. The yields of petrol are generally higher when catalyst is used.

(b) Vapor phase cracking: In this process, kerosene oil or gas oil is cracked in vapor phase. The temperature
is kept 600 – 800oC and the pressure is about 3.5 to 10.5 atmospheres. The cracking is facilitated by use of
a suitable catalyst. The yields are about 70%.

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(ii) Synthesis: Two methods are applicable for synthesis.
(a) Bergius process: This method was invented by Bergius in Germany during First World War.
Coal  H 2  o Mix. Of hydrocarbons or crude oil
Fe 2 O3
450  500 C
250 atm

(b) Fischer- tropsch process: The overall yield of this method is slightly higher than Bergius process.
o
H 2 O  C   CO  H 2
1200 C

Water gas

xCO  yH 2  Mix. Of hydrocarbon  H 2 O .

The best catalyst for this process is a mixture of cobalt (100 parts), thoria, (5 parts), magnesia (8 parts) and
kieselguhr (200 parts).

2. Characteristics of hydrocarbons.

(1) Knocking: The metallic sound due to irregular burning of the fuel is termed as knocking.

“The greater the compression greater will be efficiency of engine.” The fuel which has minimum knocking
property is always preferred.

The tendency to knock falls off in the following order: Straight chain alkanes > branched chain alkanes
> olefins > cyclo alkanes > aromatic hydrocarbons.

(2) Octane number: It is used for measuring the knocking character of fuel used in petrol engine. The
octane number of a given sample may be defined as the percentage by volume of iso-octane present in a
mixture of iso-octane and heptane which has the same knocking performance as the fuel itself.
CH 3  CH 2  CH 2  CH 2  CH 2  CH 2  CH 3 n-heptane; octane no. = 0
CH 3
CH 3
| |
CH 3 — C — CH 2 — CH — CH 3 ; Octane no. = 100
|
CH 3
2, 2, 4-Trimethyl pentane or Iso-octane.

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For example: a given sample has the knocking performance equivalent to a mixture containing 60% iso-
octane and 40% heptane. The octane number of the gasoline is, therefore, 60.
Presence of following types of compounds increases the octane number of gasoline.
(i) In case of straight chain hydrocarbons octane number decreases with increase in the length of the
chain.
(ii) Branching of chain increases the value of octane number
(iii) Introduction of double bond or triple bond increases the value of octane number.
(iv) Cyclic alkanes have relatively higher value of octane number.
(v) The octane number of aromatic hydrocarbons are exceptionally high
(vi) By adding gasoline additives (eg TEL)

(3) Antiknock compounds: To reduce the knocking property or to improve the octane number of a fuel
certain chemicals are added to it. These are called antiknock compounds. One such compound, which is
extensively used, is tetraethyl lead (TEL). TEL is used in the form of following mixture,
TEL = 63%, Ethylene bromide = 26%, Ethylene chloride = 9% and a dye = 2%.
However, there is a disadvantage that the lead is deposited in the engine. To remove the free lead,
the ethylene halides are added which combine with lead to form volatile lead halides.
Pb  Br  CH 2  CH 2  Br  PbBr2  CH 2  CH 2
Ethylene bromide Volatile Ethylene

However, use of TEL in petrol is facing a serious problem of Lead pollution, to avoid this a new compound
cyclopenta dienyl manganese carbonyl (called as AK-33-X) is used in developed countries as antiknocking
compound.

(4) Other methods of improving octane number of gasoline

(i) Isomerization [Reforming]: By passing gasoline over AlCl 3 at 200 o C .
CH 3
|
CH 3 CH 2 CH 2 CH 2 CH 3  
AlCl 3
o
 CH 3 CHC H 2 CH 3
Pentane 200 C Isopentane
(Octane number  62) (Octane number  90 )

CH 3 CH 3 CH 3 CH 3
| | | |
(ii) Alkylation: CH 3 CH  CH 2  C CH 3   CH 3 CCH 2 CHCH
H 2 SO 4
3
| Isobutylene |
CH 3 CH 3
Isobutane Iso- octane
(Octane number  100)

CH 3
(iii) Aromatization: CH 3 (CH 2 )5 CH 3  o 
  4 H2
Pt / Al 2 O 3

Heptane 500 C

Toluene

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The octane no. of petrol can thus be improved.
 By increasing the proportion of branched chain or cyclic alkanes.
 By addition of aromatic hydrocarbons (BTX)
 By addition of methanol or ethanol.
 By addition of tetraethyl lead (C2 H 5 )4 Pb

(5) Cetane number: It is used for grading the diesel oils.

CH 3  (CH 2 )14  CH 3 Cetane  cetane no. = 100
CH2

Cetane no. = 0

-Methyl naphthalene

The cetane number of a diesel oil is the percentage of cetane (hexadecane) by volume in a mixture of
cetane and  -methyl naphthalene which has the same ignition property as the fuel oil

(6) Flash point: The lowest temperature at which an oil gives sufficient vapors to form an explosive mixture
with air is referred to as flash point of the oil.
The flash point in India is fixed at 44 o C , in France it is fixed at 35oC, and in England at 22.8oC. The flash
point of an oil is usually determined by means of “Abel’s apparatus”.
Chemists have prepared some hydrocarbons with octane number even less than zero (e.g., n-nonane has
octane number – 45) as well as hydrocarbon with octane number greater than 100 (e.g., 2, 2, 3 trimethyl-
butane. has octane number of 124).

(7) Petrochemicals: All such chemicals which are derived from petroleum or natural gas called
petrochemicals. Some chemicals which are obtained from petroleum are:

Hydrocarbons Compounds derived

Methane Methyl chloride, chloroform, methanol, formaldehyde, formic acid, freon, hydrogen
for synthesis of ammonia.
Ethane Ethyl chloride, ethyl bromide, acetic acid, acetaldehyde, ethylene, ethyl acetate,
nitroethane, acetic anhydride.

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 Ethylene Ethanol, ethylene oxide, glycol, vinyl chloride, glyoxal, polyethene, styrene,
butadiene, acetic acid.

Propane Propanol, propionic acid, isopropyl ether, acetone, nitromethane, nitroethane,

nitropropane.
Propylene Glycerol, allyl alcohol, isopropyl alcohol, acrolein, nitroglycerine, dodecylbenzene,
cumene, bakelite.
Hexane Benzene, DDT, gammexane.

Heptane Toluene

Cycloalkanes Benzene, toluene, xylenes, adipic acid.

Benzene Ethyl benzene, styrene, phenol, BHC (insecticide), adipic acid, nylon, cyclohexane,
ABS detergents.

Toluene Benzoic acid, TNT benzaldehyde, saccharin, chloramine-T, benzyl chloride, benzal
chloride.

3. Alkanes [Paraffines].

“Alkanes are saturated hydrocarbon containing only carbon-carbon single bond in their molecules.”
Alkanes are less reactive so called paraffins; because under normal conditions alkanes do not react with
acids, bases, oxidizing agents and reducing agent.
General formula: Cn H 2n 2
Examples are: CH 4 , C 2 H 6 , C 3 H 8
Methane Ethane Propane

(1) Structure:
(i) Every carbon atom is sp 3 hybridized. H H
H
(ii) The bond length between carbon-carbon
and carbon-hydrogen are 1.54 Å and 1.112 Å
109o28’
respectively. 109o28’ 1.54Å
(iii) Bond angle in alkanes are tetrahedral 1.112Å C H 1.112Å C C
H
angles having a value of 109.5 o (109 o .28 ) .
H H H
(iv) Alkanes have 3  D , rather than planer Methane H H
structure. Ethane

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(v) C  C bond dissociation energy is 83 k cal / mol .
(vi) C  H bond dissociation energy is 99k cal / mol .

(2) Isomerism: Only chain and structural Isomerism found.

No. of carbon atom in molecule  no. of chain Isomers
Alkanes : C 4 H 10 C 5 H 12 C 6 H 14 C 7 H 16 C 8 H 18 C10 H 22
No. of possible Isomer : 2 3 5 9 18 75

(3) General Methods of preparation

(i) By catalytic hydrogenation of alkenes and alkynes (Sabateir and sanderen’s reaction)
C n H 2n  H 2 
Ni
C n H 2n 2 ; C n H 2 n  2  2 H 2 
Ni
C n H 2n 2
Alkene heat Alkane Alkyne heat Alkane

Note: Methane is not prepared by this method

(ii) Birch reduction: R  CH  CH 2    R  CH 2  CH 3

1. Na / NH 3
2. CH 3 OH

(iii) From alkyl halide

(a) By reduction: RX  H 2   RH  HX

Zn / HCl

(b) With hydrogen in presence of pt/pd: RX  H 2    RH  HX

Pd orPt.

(c) With HI in presence of Red phosphorus: RBr  2 HI  RH  HBr  I 2

Purpose of Red P is to remove I

(iv) By Zn-Cu couple: 2CH 3 CH 2 OH  Zn 

 (CH 3 CH 2 O)2 Zn  2 H
Cu
Zn -Cu couple Zinc ethoxide

RX  2 H  RH  HX

(v) Wurtz reaction: R X  2 Na  X R    R  R  2 NaX

Dry ether

Alkylhalide Alkylhalide Alkane

Note: R  Br or RI preferred in this reaction. The net result in this reaction is the formation of even no. of carbon
atoms in molecules.

(vi) Frankland’s reaction: 2 RX  Zn  R  R  ZnX 2

(vii) Corey-house synthesis

CH 3 CH 2 Cl
CH 3  CH 2  Cl  (CH 3  CH 2 )2 LiCu 
1. Li
  CH 3  CH 2  CH 2  CH 3
2. CuI

10
Note: Reaction is suitable for odd number of Alkanes.

(viii) From Grignard reagent

(a) By action of acidic ‘H’: RMgX  HOH  RH  Mg(OH )X

Alkylmagnesium Water Alkane
halide

(b) By reaction with alkyl halide: R  X  R MgX  R  R   MgX 2

(ix) From carboxylic acids

(a) Laboratory method [Decarboxylation reaction or Duma reaction]

R COONa  NaOH  R  H  Na 2 CO 3

heat
CaO Alkane

Note: NaOH and CaO is in the ratio of 3: 1.

O
||
(b) Kolbe’s synthesis: R  C  O  Na  Electrolysis
R  C  O   Na 
|| Ionization
O
 
At anode [Oxidation]: 2 R  C  O   2e   2 R  C  O  2 R  2CO 2
|| ||
O O

2 R  R  R (alkane)

At cathode [Reduction]: 2 Na   2e   2 Na   2 NaOH  H 2 (  )

2H 2O

Note: Both ionic and free radical mechanism are involved in this reaction.

(c) Reduction of carboxylic acid: CH 3 COOH  6 HI   CH 3 CH 3  2 H 2 O  3 I2

Re duction

Acetic acid p Ethane

(x) By reduction of alcohols, aldehyde, ketones or acid derivatives

CH 3 OH  2 HI    CH 4  H 2 O  I2 ; CH 3 CHO  4 HI    C 2 H 6  H 2 O  2 I2
Red P Red P
o o
Methanol 150 C Methane Acetaldehy de 150 C Ethane
(Methyl alcohol) (Ethanal)

11
 CH 3 COCH 3  4 HI  
Red P
o
 CH 3 CH 2 CH 3  H 2 O  2 I2 ;
Acetone 150 C Propane
(Propanone )

O
||
CH 3  C  Cl  6 HI  
Red P
o
 CH 3  CH 3  H 2 O  HCl  3 I 2
Acetyl chloride 200 C Ethane
(Ethanoyl chloride)

O
||
CH 3  C  NH 2  6 HI  
Red P
o
 CH 3  CH 3  H 2 O  NH 3  3 I 2
Acetamide 200 C Ethane
(Ethanamid e)

Note: Aldehyde and ketones when reduced with amalgamated zinc and conc. HCl also yield alkanes.

Zn  Hg
Clemmensen reduction: CH 3 CHO  2 H 2    CH 3  CH 3  H 2 O
Acetaldehy de HCl Ethane
(Ethanal)

Zn  Hg
CH 3 COCH 3  2 H 2    CH 3 CH 2 CH 3  H 2 O
Acetone HCl Propane
(Propanone )

Note: Aldehydes and ketones ( C  O) can be reduced to hydrocarbon in presence of excess of hydrazine and
sodium alkoxide on heating.

R R R
Wolff-kishner reduction: C  O  
H 2 NNH 2
C  NNH 2  o 

C 2 H 5 ONa
CH 2
H 2O 180 C
R R R

(xi) Hydroboration of alkenes

(a) On treatment with acetic acid
R  CH  CH 2   (R  CH 2  CH 2 )3 B 
B2 H 6
  R  CH 2  CH 3
CH 3 COOH

Alkene Trialkyl borane Alkane

(b) Coupling of alkyl boranes by means of silver nitrate

o
6[R  CH  CH 2 ]  [2 R  CH 2  CH 2 ]3 B 
2 B2 H 6
 3[RCH 2 CH 2  CH 2 CH 2 R]
AgNO3 25 C
NaOH

(4) Physical Properties

(i) Physical state: Alkanes are colorless, odorless and tasteless.
Alkanes State
C1  C 4 Gaseous state
C5  C17 Liquid state [Except neo pentane] [gas]
12
 C18 & above Solid like waxes

(ii) Density: Alkanes are lighter than water.

1
(iii) Solubility: Insoluble in water, soluble in organic solvents, solubility 
Molecular mass
1
(iv) Boiling pts and Melting pts: Melting pt. and boiling pts.  Molecular mass 
No. of branches
Alkane : C3 H 8 C 4 H 10 C5 H 12 C6 H 14 C7 H 16 C8 H 18
M.P. (K) : 85.9 138 143.3 179 182.5 216.2
C C C C C C

C C C C C C C
Odd no. of Carbons Even no. of carbons

600 – 300
Melting point oC

200
Temperature (K)

400 – 100
 
Boiling Pt. 
0     
increases 
 
200 – – 100  
  
– 200
4 8 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
12 16 20
50 Number of carbon atoms
No. of C atoms per molecule

Note: Melting points of even > Odd no. of carbon atoms, this is because, the alkanes with even number of carbon
atoms have more symmetrical structure and result in closer packing in the crystal structure as compared to alkanes
with odd number of carbon atoms.

(5) Chemical properties

(i) Substitution reactions of Alkanes
(a) Halogenation: R  H  X  X  R  X  HX
The reactivity of halogen is: F2  Cl 2  Br2  I2

Note: Fluorine can react in dark Cl 2 , Br2 require light energy. I2 does not show any reaction at room temperature,
but on heating it shows iodination.
Iodination of methane is done in presence of oxidizing agent such as HNO 3 / HIO3 / HgO which neutralizes HI .

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  HCl
Chlorination of methane: CH 4  Cl  Cl   CH 2  Cl 2 
u . v . light
 CHCl 3 
u. v . light
 CCl 4
 HCl  HCl

(ii) Reaction based on free radical mechanism

(a) Nitration: R  H  HONO 2  R  NO 2  H 2 O
High
Alkane temp . Nitroalkan e

Nitrating mixture: (i) (Con . HNO 3  Con . H 2 SO 4 ) at 250 o C

(ii) (HNO 3 vapour at 400 o  500 o C) .

(b) Sulphonation: Free radical mechanism R  H  HOSO 3 H SO

3 R  SO 3 H  H 2 O
Prolonged heating

Note: Lower alkanes particularly methane, ethane, do not give this reaction.

(iii) Oxidation
 3n  1 
(a) Complete Oxidation or combustion: Cn H 2 n  2   O2  nCO 2  (n  1)H 2 O  Q
 2 
Note: This is exothermic reaction.

(b) Incomplete combustion or oxidation

2CH 4  3O 2   2CO  4 H 2 O
Burn

CH 4  O2  C 2 H 2 O

Cu  tube
(c) Catalytic Oxidation: CH 4  [O]   o
CH 3 OH
100 atm / 200 C

This is the industrial method for the manufacture of methyl alcohol.

Note: Higher alkanes are oxidized to fatty acids in presence of manganese stearate.

CH 3 (CH 2 )n CH 3 
 
O
2
CH 3 (CH 2 )n COOH
100 160 C
o

(d) Chemical oxidation: (CH 3 )3 CH   (CH 3 )3 .C.OH

KMnO4

Isobutane Tertiary butyl alcohol

(iv) Thermal decomposition or cracking or pyrolysis or fragmentation

o
 C  2H 2 ; C 2 H 6 
o
CH 4  
1000 C

 CH 2  CH 2  H 2
500 C

Methane Ethane Cr2O3  Al 2O3 Ethylene

C3 H 8  C2 H 4  CH 4 or C3 H 6  H 2

14
Note: This reaction is of great importance to petroleum industry.
CH 3
|
AlCl3  HCl
(v) Isomerization: CH 3 CH 2 CH 2 CH 3     CH 3 CHCH 3 ;
n - Butane
o
200 C , 35 atm Isobutane 2-Methyl pentane
2,3 Dimethyl
butane

(vi) Aromatization:
CH3
H2C CH3
+4H2
H2C CH2
CH2 Benzene
n-Hexane

n-Heptane Methyl cyclo Toluene

Hexane

(vii) Step up reaction

(a) Reaction with CH 2 N 2 : R  CH 2  H  CH 2 N 2 

hv
R  CH 2  CH 2  H

(b) Reaction with CHCl 3 / NaOH : R  CH 2  H   R  CH 2  CHCl 2
CHCl 3 / OH
: CCl2

O
||
CH 2 C/ 
(c) Reaction with CH 2  C : R  CH 2  H    R  CH 2  CH 3
:CH 2 / CO
||
O

(viii) HCN formation: 2CH 4    2 HCN  3 H 2 or CH 4  NH 3 

N 2 / electric arc

Al 2O3
o
 HCN  3 H 2
700 C

(ix) Chloro sulphonation/Reaction with SO2+Cl2

CH 3  CH 2  CH 3  SO 2  Cl 2    CH 3  CH 2  CH 2 SO 2 Cl  HCl
u.v light

This reaction is known as reed’s reaction.

Note: This is used in the commercial formation of detergent.

(x) Action of steam: CH 4  H 2 O  o  CO  3 H 2

Ni / Al 2O3
800 C

15
4. Individual members of alkanes.

(1) Methane: Known as marsh gas.

(i) Industrial method of preparation: Methane gas is obtained on a large scale from natural gas by
liquefaction. It can also be obtained by the application of following methods,
(a) From carbon monoxide: A mixture of carbon monoxide and hydrogen is passed over a catalyst
containing nickel and carbon at 250 o C when methane is formed.
Ni  C
CO  3 H 2  o
 CH 4  H 2 O
250 C

(b) Bacterial decomposition of cellulose material present in sewage water: This method is being used in
England for production of methane.
(C6 H10 O5 )n  nH 2 O  3nCH 4  3nCO 2
Cellulose

(c) Synthesis: By striking an electric arc between carbon electrodes in an atmosphere of hydrogen at
1200oC, methane is formed.
o
C  2 H 2   CH 4
1200 C

By passing a mixture of hydrogen sulphide and carbon disulphide vapor through red hot copper, methane
is formed.
CS 2  2 H 2 S  8 Cu   CH 4  4 Cu 2 S
High temperature

(ii) Physical properties

(a) It is a colorless, odorless, tasteless and non-poisonous gas.

(b) It is lighter than air. Its density at NTP is 0.71 g/L.

(c) It is slightly soluble in water but is fairly soluble in ether, alcohol and acetone.

(d) Its melting point is  182.5 o C and boiling point is  161.5 o C .

16
(iii) Uses

(a) In the manufacture of compounds like methyl alcohol, formaldehyde, methyl chloride, chloroform,
carbon tetrachloride, etc.
(b) In the manufacture of hydrogen, used for making ammonia.
(c) In the preparation of carbon black which is used for making printing ink, black paints and as a filler in
rubber vulcanization.
(d) As a fuel and illuminant.

(2) Ethane

(i) Methods of preparation

Zn  Cu couple
(a) Laboratory method of preparation: C 2 H 5 I  2 H    C 2 H 6  HI
Ethyl iodide C2 H 5 OH Ethane

(b) Industrial method of preparation: CH 2  CH 2  H 2 

Ni
o
CH 3  CH 3
Ethylene 300 C Ethane
(ethene)

(iii) Physical properties

(a) It is a colorless, odorless, tasteless and non-poisonous gas.

(b) It is very slightly soluble in water but fairly soluble in alcohol, acetone, ether, etc.
(c) Its density at NTP is 1.34 g/L
(d) It boils at – 89oC. Its melting point is –172oC.

(ii) Uses
(a) As a fuel. (b) For making hexachloroethane which is an artificial camphor.

(3) Interconversion of Alkanes

Ascent of alkane series,

(i) Methane to ethane: CH 4 

 CH 3 Cl 
Cl2
  CH 3  CH 3
Wurtz reaction

Methane UV Heat with Na in ether Ethane

(ii) Butane from ethane: C 2 H 6 

 C 2 H 5 Cl 
Cl2
 C 2 H 5  C 2 H 5
Wurtz reaction

Ethane UV Ethyl chloride Heat with Na in ether Butane

(excess)

17
Descent of alkane series: Use of decarboxylation reaction is made. It is a multistep conversion.
Ethane to methane

C 2 H 6 
 C 2 H 5 Cl 
Cl2
 C 2 H 5 OH 
Aq . KOH
 CH 3 CHO 
[O ]
 CH 3 COOH 
[O ]
 CH 3 COONa 
NaOH
 CH 4
NaOH / CaO

Ethane UV Ethyl chloride Ethyl alcohol Acetaldehy de Acetic acid Sodium acetate heat Methane
(excess)

Higher 
 Alkyl 
Cl2
 Alcohol 
Aq .
 Aldehyde 
[O ]
 Acid 
[O ]
 Sodium salt of 
NaOH
 Lower alkane
NaOH / CaO

alkane UV halide KOH the acid heat

5. Alkenes.

These are the acyclic hydrocarbon in which carbon-carbon contain double bond. These are also known as
olefins, because lower alkene react with halogens to form oily substances. General formula is Cn H 2n .
Ex: Ethene C 2 H 4 , Propene C 3 H 6 , Butene C 4 H 8

(1) Structure
(i) Hybridization of unsaturated ‘C’ atom is sp 2
Unhybridised orbital
(ii) Geometry of unsaturated ‘c’ atom is trigonal planer  bond

(iii) C  H Bond length is 1.34 Å H

sp2
sp2
H
(iv) C  C Bond energy is 143.1 K cal/mol sp2 sp2
sp2
(v) C  H Bond length is 1.10 Å H sp2
H
(vi) C  C Bond energy is 108 Kcal/mol

(2) Isomerism
(i) Chain Isomerism: CH 3  CH 2  CH  CH 2 and (CH 3 )2  C  CH 2
(Ii) Position Isomerism: CH 2  CH  CH 2  CH 3 and CH 3  CH  CH  CH 3
(iii) Functional Isomerism: [Ring chain] CH 3  CH 2  CH  CH 2 and CH 2  CH 2
1  butene
| |
CH 2  CH 2
Cyclo butene

(iv) Geometrical Isomerism: CH 3  C  H and CH 3  C  H

|| ||
CH 3  C  H H  C  CH 3
cis  2 butene Trans 2  butene

18
 CH  CH 2
|
(v) Optical Isomerism: H  C  CH 3
|
CH 2 CH 3
a
Note: Cumulated polythene having even no. of double bonds. Which has  C system at the both end can exhibit
b
optical isomerism but cannot exhibit geometrical isomerism.
a
Cumulated polythene having odd no. of double bonds which have  C system at both end can exhibit
b
geometrical isomerism but cannot exhibit optical isomerism.

(3) Preparation methods

H
|
(i) From Alkynes: R  C  C  H  H 2     R  C  C  H
Lindlar' s Catalyst
Pd . BaSO 4
|
H
Note: Poison’s catalyst such as BaSO 4 , CaCO 3 are used to stop the reaction after the formation of alkene.
H H H
| | |
(ii) From mono halides: R  C  C  H  Alc. KOH  
 HX
 R  C  C H
| | |
H X H
Alkene

Note: If we use alc. NaOH in place of KOH then trans product is formed in majority because of its stability.
According to saytzeff rule.

(iii) From dihalides

(a) From Gem dihalides
X Zn X
R – CH + + CH – R R – CH = CH – R
X Zn X

Note: If we take two different types of gemdihalides then we get three different types of alkenes.
Above reaction is used in the formation of symmetrical alkenes only.

19
 H H H H
| | | |

(b) From vicinal dihalides: R  C  C  H  Zn dust  R  C  C  H  ZnX 2
| | 300 o C

X X

Note: Alkene is not formed from 1, 3 dihalides. Cycloalkanes are formed by dehalogenation of it.
C H 2  CH 2  C H 2  
Zn dust
CH 2
| |
X X H 2C CH 2
Br Br I I
| | | |
(iv) By action of NaI on vic dihalide: C C 
NaI
C C  C C
acetone
unstable

(v) From alcohols [Laboratory method]: CH 3 CH 2 OH    CH 2  CH 2  H 2 O

H 2 SO 4 or H 3 PO 4

Ethyl alcohol 443 K Ethene

CH 2 COOK CH 2
(vi) Kolbe’s reaction: |  2 H 2 O   
| |  2CO 2  H 2  2 KOH
Electrolysis

CH 2 COOK CH 2
Potassium succinate Ethene

(vii) From esters [Pyrolysis of ester]: CH 3  CO  O H Glass wool 450 o

CH 3  COOH
| |      
CH 2  CH 2
liq. N 2
CH 2  CH 2

 
(viii) Pyrolysis of quaternary ammonium compounds: (C 2 H 5 )4 N OH  (C 2 H 5 )3 N  C 2 H 4  H 2 O
heat

Tetraethyl ammonium Triethylam ine Ethene

hydroxide (Tert. amine)

(ix) Action of copper alkyl on vinyl chloride: H 2 C  CHCl   H 2 C  CHR

CuR 2

Vinylchloride

R
(x) By Grignard reagents: Mg  X  CH  CH 2  MgX 2  R  CH  CH 2
X

(xi) The Wittig reaction: (Ph)3 P  CH 2  CH  R (Ph)3 P  O  R  CH

|| ||
O CH 2

O
||
(Ph)3 P  CH  R  CH  R (Ph)3 P  O  R  CH  CH  R

20
(xii) From  bromo ether [Boord synthesis]

Br O  C 2 H 5
| | Br
R  CH  CH  Zn
 R  CH  CH  R   Zn
C4 HgOH
| O  C2 H 5
R

(4) Physical Properties

(i) Alkenes are colorless and odorless.

(ii) These are insoluble in water and soluble in organic solvents.

(iii) Physical state

C1  C 4  Gas
C5  C16  Liquid
 C16  Solid wax
(iv) B.P. and M.P. decreases with increasing branches in alkene.

(v) The melting points of cis isomers are lower than trans isomers because cis isomer is less symmetrical
than trans. Thus trans packs more tightly in the crystal lattice and hence has a higher melting point.

(vi) The boiling points of cis isomers are higher than trans isomers because cis-alkenes has greater polarity
(Dipole moment) than trans one.

(vii) These are lighter than water.

(viii) Dipole moment: Alkenes are weakly polar. The, -electrons of the double bond. Can be easily
polarized. Therefore, their dipole moments are higher than those of alkanes.

The symmetrical trans alkenes are non-polar and hence have zero dipole moments in these alkene the
dipole moment of individual bonds are equal in opposite direction. Therefore these get cancelled
resulting zero dipole moment for the molecule.
CH3 H CH3 CH3
C=C C=C
H CH3 H H
Trans-2-Butene Cis –2-Butene

=0  = 0.25 D 21
Thus symmetrical and unsymmetrical cis alkene are polar and hence have finite dipole moments

CH3 H CH3 – CH2 H

C=C C=C
H H H H
Propene Bute 1-ene

 = 0.35 D  = 0.37 D

(5) Chemical properties

(i) Francis experiment: According to Francis electrophile first attacks on olefinic bond.
CH2 = CH2 + Br – Br CH2 – CH2
| |

Br Br
CH2 – CH2 + CH2 – CH2
| | | |

Br Br Br Cl
H H H H
| | | |
(ii) Reaction with hydrogen: R  C  C  R  H 2 
Ni
R  C  C R
| |
H H

(iii) Reduction of alkene via hydroboration: Alkene can be converted into alkane by protolysis

H  BH 2
RCH  CH 2   (R  CH 2  CH 2 )3 B   R  CH 2  CH 3
H / H 2O

Hydroboration: Alkene give addition reaction with diborane which called hydroboration. In this reaction
formed trialkylborane, which is very important and used for synthesis of different organic compound
3 R  CH  CH 2  BH 3 (R  CH 2  CH 2 )3 B

CH3COOH/Zn Trialkyl borane

HI/H2O2
NaOH
H2O2
R – CH2 –CH3
R – CH2 –CH2OH R – CH2 –CH3
The overall result of the above reaction appears to be antimarkownikoff’s addition of water to a double
bond.

22
(iv) By treatment with AgNO3 + NaOH: This reaction gives coupling
CH 3 CH 3
| |
6 CH 3  CH 2  CH 2  C  CH 2  2[CH 3  (CH 2 )2  C  CH 2 ]3 B 
B2 H 6
 
Ag / NO3 NaOH

|
H
CH 3 CH 3
| |
CH 3  CH 2  CH 2  C  CH 2  CH 2  C  CH 2  CH 2  CH 3
| |
H H

(v) Birch reduction: This reaction is believed to proceed via anionic free radical mechanism.

  
Et  O  H Et .  O  H
R  CH  CH 2 

Na

R  C H  C H 2   R  CH  CH 3 

Na

R  C H  CH 3   R  CH 2  CH 3
e e

(vi) Halogenation
o
CH 3 CH  CH 2  Cl 2  
 ClCH 2  CH  CH 2  HCl
500 C

Propene Allylchloride
or 3 - Chloro -1 - propene

Note: If NBS [N-bromo succinimide] is a reagent used for the specific purpose of brominating alkenes at the allylic
position.
CH2 – CO CH2 – CO
CH3 CH=CH2 + N – Br CH2 – CH = CH2+ N–H
| |
CH2 – CO | CH2 – CO
Propene NBS BrAllyl bromide Succinimide
In presence of polar medium alkene form vicinal dihalide with halogen.
H H H H
| | | |
R  C  C  H  X  X   R  C  C  H
CCl4

| |
X X
Vicinal dihalide

Reactivity of halogen is F2  Cl 2  Br2  I 2

(vii) Reaction with HX [Hydrohalogenation]

23
 H
|
CC  HX  C C
|
alkene X
Alkylhalide

According to markownikoff’s rule and kharasch effect.

H H
| |
CH 3  CH  CH 2  HBr  CH 3  C  C  H Markownikoff rule
| |
Br H
H H H H
| | | |
(Based on F.R.M.) CH 3  CH  CH 2  HBr   CH 3  C  C  H  CH 3  C  C  H
Peroxide

| | | |
Br H H Br
(minor) (major)

 
(viii) Reaction with hypohalous acids: CH 2  CH 2  H O Cl  CH 2 OH .CH 2 Cl
Ethylene Ethylene chlorohydrin

Note: In case of unsymmetrical alkenes markownikoff rule is followed.

(ix) Reaction with sulphuric acid: CH 2  CH 2  H  HSO 4  CH 3 CH 2 HSO 4

Ethylene Ethyl hydrogen sulphate

CH 3 CH 2 HSO 4  CH 2  CH 2  H 2 SO 4
Note: This reaction is used in the separation of alkene from a gaseous mixture of alkanes and alkenes.

(x) Reaction with nitrosyl chloride

NO
|
CC  NOCl  C  C ( NOCl is called Tillden reagent)
|
Cl
Note: If hydrogen is attached to the carbon atom of product, the product changes to more stable oxime.
NO
| H C C
C C ⇌ C  C  NOH ; CC  NOCl  C  C (Blue
| | | | |
C C
Cl Cl NO Cl
Oxime

color)

24
(xi) Oxidation: With alkaline KMnO 4 [Bayer’s reagent]: This reaction is used as a test of unsaturation.
H H H H
| | | |
R  C  C  H  [O]  H  OH    R  C  C  H
Alk KMnO4
 OH
| |
HO OH
glycol

H H O
| | ||
With acidic KMnO 4 : R  C  C  H  [O]   R  C  O  H  CO 2  H 2 O
acidic
KMnO4

(xii) Hydroxylation
CH 3 CH 3
| |
(a) Using per oxy acid: H  C    
H 2 O 2 , HCOOH
H  C  OH
|| or HCO 3 H
|
H C OH  C  H
| |
CH 3 CH 3
2-Butene Trans (racemic)

R H
C R
(b) Hydroxylation by OsO4: | |  OsO 4  
I
H OH
C HO H
H R R
Trans ()

Note: If per benzoic acid or peroxy acetic acid is used then oxirane are formed.
H 2O
R  CH  CH  R   R  CH  CH  R   R  CH  CH  R
C 6 H 5 CO 3 H
or CH 3 CO 3 H
| |
OH OH O
[Oxirane]

3n
(xiii) Combustion: C n H 2n  O 2  nCO 2  nH 2 O
2
They burn with luminous flame and form explosive mixture with air or oxygen.
(xiv) Ozonolysis

O O O
CC 

O
3

I C C
C+C
O O
Ozonide

Application of Ozonolysis: This process is quite useful to locate the position of double bond in an alkene
molecule. The double bond is obtained by joining the carbon atoms. of the two carbonyl compounds.
25
 Ex.
H H
| |
CH 3  C  O  O  C  CH 3  CH 3  CH  CH  CH 3
Bute- 2-ene
Ethanal

H CH 3 H
| | |
CH 3  C  O  O  C  CH 3  CH 3  C  C  CH 3
|
CH 3
2 - methyl, but- 2 - ene

(xv) Oxy – mercuration demercuration: With mercuric acetate (in THF), followed by reduction with
NaBH 4 / NaOH is also an example of hydration of alkene according to markownikoff’s rule.

(CH 3 )3 C  CH  CH 2  (CH 3 COO ) 2 Hg (CH 3 )3 C  CH  CH 2  Hg   (CH 3 )3 C  CH  CH 3

NaBH 4 / NaOH
THF
| |
OCOCH 3 OH
3 , 3  Dimethyl  2  butanol

Ex.
HOOH/OH – (CH2)2OH
CH = CH2 BH3 (CH2 – CH2)3 B
Antimarkowni -
koff rule

Hg (CH3COO)2 CH CH2 H2O/H+ CH CH3

Mercuration OH
OCOCH3 HgOCOCH3
markowni -koff rule

H   CH2 –CH3
CH2 CH3 H2O/H +
H+/H2O CH CH3 ⇌ OH

More stable alcohol

Less stable
carbocation
Carbocation

26
(xvi) Epoxidation
O O
1
(a) By O 2 / Ag : CH 2  CH 2  O 2 
 CH 2  CH 2
Ag ||
2
C–O–O–H
O

(b) Epoxidation by performic acid or perbenzoic acid: CH 2  CH 2  CH 2  CH 2

O
O
||
H  C O O  H
CH 3  CH  CH 2    CH 3  CH  CH 2

(xvii) Hydroboration

3 R  CH  CH 2  BH 3 (R  CH 2  CH 2 )3 B   R  CH 2  CH 2  OH  B(OH )3
H 2 O2 / OH

Tri alkyl borane

(Anti markownikoff’s rule)

H H
| |
(xviii) Hydroformylation: R  CH  CH 2  CO  H 2    R  C  C  H
CoH (CO )4

| |
H C O
|
H

Note: If CO  H 2 O is taken then respective acid is formed.

R  CH  CH 2  CO  H 2 O    R  CH 2  CH 2
CoH (CO )4

|
COOH

(xix) Addition of formaldehyde

   
R  CH  CH 2 HOH
H 2 C  O  H [H 2 C  O H  H 2 C  OH ]   R  C H  CH 2  CH 2  OH 
 H
CH2

R – CH CH2 

    R  CH  CH 2  CH 2
HCHO / H

O O | |
OH OH
CH2
Cyclic acetal 1, 3 diol

27
(xx) Polymerization
H H  H H H H
| |  | | | | 

Trace O 2  Catalyst
C  C    C  C  C  C 
1500o / high pressure  
| |  | | | | 
H H  H H H H 
n

Note: If in polymerization zeigler- natta catalyst [(R)3 Al  TiCl 4 ] is used then polymerization is known as zeigler-
natta polymerization.

AlCl3

(xxi) Isomerization: CH 3  CH 2  CH 2  CH  CH 2 CH 3  CH 2  CH  CH  CH 3
The mechanism proceeds via carbocation.
(xxii) Addition of HNO3 : CH 2  CH 2  HO  NO 2  CH 2 OH .CH 2 NO 2
Ethene 2 - Nitroethan ol

(xxiii) Addition of Acetyl chloride: CH 2  CH 2  CH 3 COCl  CH 2 ClCH 2 COCH 3

Ethene 4 - Chlorobutanone- 2

(6) Uses

(i) For the manufacture of polythene – a plastic material; (ii) For artificial ripening of fruits; (iii) As a general
anesthetic; (iv) As a starting material for a large number of compounds such as glycol, ethyl halides, ethyl
alcohol, ethylene oxide, etc.; (v) For making poisonous mustard gas (War gas); (vi) For making ethylene-
oxygen flame.

28
6. Alkynes.

These are the acyclic hydrocarbons which contain carbon-carbon triple bond are called alkynes. General
formula is C n H 2n  2 . Ex. Ethyne CH  CH ; Propyne CH 3  C  CH

(1) Structure

(i) Hybridization in alkynes is sp . UNHYBRIDISED

(ii) Bond angle in alkynes is 180 o . ORBITALS

(iii) Geometry of carbon is linear.

H sp sp sp
(iv) C  C Triple bond length is 120 Å sp H
(v) C  H Bond length is 108 Å
(vi) C  C Triple bond energy is 190 Kcal / mol . Acetylene

(vii) C  H Bond energy is 102.38 Kcal / mol .

(2) Isomerism
CH 3
(i) Chain Isomerism: CH 3 CH 2 CH 2 C  CH ; CH  C  CH
1-Pentyne 3 - Methyl-1 - butyne
CH 3

(ii) Position isomerism: CH 3 CH 2 CH 2 C  CH ; CH 3 CH 2 C  CCH 3

1- pentyne 2- pentyne

(iii) Functional isomerism: CH 3  C  CH ; CH 2  C  CH 2

Propyne 1, 2- propadiene (Allene)

29
(3) General methods of preparation

CH2Br – CH2Br alc KOH or NaNH2

CH3 – CHBr2 alc KOH, NaNH2
Ag dust(Powder)
CHCl3

CHBr2 – CHBr2 Zn dust

CHBr
Zn
||
CHBr alc KOH, NaNH2
CH = CH – Cl
2 C2H2 [Acetylene]
HC – COONa
Kolbe’s electrolytic synthesis
||
HC –2 COONa H2O (Laboratory method)
CaC
Electric arc, 1200oC
2C+ H2
Berthelot’s process
(i) Na (ii) R-X
CH3 – C CH
(i) CH3MgI (ii) R-X
CH3 – C CH

Note: In reaction with gem dihalide, Alc. KOH is not used for elimination in 2 nd step.
In reaction with vicinal dihalide, if the reactant is 2-butylene chloride then product is 2-butyne as major product.

Preparation of higher alkynes (by metal acetylide)

Acetylene gives salt with NaNH 2 or AgNO 3 (ammonical) which react with alkyl halide give higher
alkyne.
CH 3 I  Na  C  C  Na  I  CH 3  CH 3  C  C  CH 3
Butyne

2CH  CH   Na  C  C  Na 
NaNH
 CH 3  C  C  CH 3
2 CH I
2 3
Butyne

RX
CH 3  C  CH  CH 3  Mg  X  CH 3  C  C  Mg  X  CH 4  CH 3  C  C  R  MgX 2
Alkyne

30
(4) Physical properties

(i) Acetylene is a colorless gas. It has a garlic odour. The odour is due to presence of impurities. However,
pure acetylene has pleasant odour.

(ii) It is insoluble in water but highly soluble in acetone and alcohol. Acetylene is transported under high
pressure in acetone soaked on porous material packed in steel cylinders.

(iii) Its boiling point is  80 o C .

(iv) It is lighter than air. It is somewhat poisonous in nature.

(v) It burns with luminous flame and forms explosive mixture with air.

(5) Chemical reactivity of alkynes: C  C is less reactive than the carbon-carbon double bond towards
electrophilic addition reaction. This is because in alkyne carbon has more has S-character than more
strongly will be the attraction for  electrons. Alkyne also undergo nucleophilic addition with electron
rich reagents. Ex. Addition of water, cyanide, carboxylic acid, alcohols. Nucleophilic addition can be
explained on the basis that alkynes form vinylic carbanion which is more stable than alkyl carbanion
formed by alkene
Nu Nu
|  | 
 C  C   Nu    C  C   C  C   Nu    C  C 

Vinylic carbanion (alkyl carbanion)

(More stable) (less stable)

(i) Acidity of alkynes: Acetylene and other terminal alkynes (1- alkynes) are weakly acidic in character
1
Ex. CH  CH  NaNH 2  H  C  C Na   H 2 (Monosodium acetylide)
2
The acetylenic hydrogen of alkynes can be replaced by copper (I) and silver (I) ions. They react with
ammonical solutions of cuprous chloride and silver nitrate to form the corresponding copper and silver
alkynides.
CH  CH  2[Cu (NH 3 )2 ]Cl  Cu  C  C  Cu  2 NH 4 Cl  2 NH 3 Dicopper acetylide (Red ppt)
CH  CH  2[ Ag(NH 3 )2 ]NO 3  AgC  C  Ag  2 NH 4 NO 3  2 NH 3 Disilver acetylide (white ppt)

31
This reaction can be used to distinguish between 2-alkynes and 1-alkynes. 1-alkynes will give this test
while 2-alkynes, will not give this test.
CH 3  C  CH  2[ Ag(NH 3 )2 ] NO 3  CH 3  C  C  Ag
1- propyne

CH 3  C  C  CH 3  2[ Ag(NH 3 )2 ]NO 3  No reaction

Explanation for the acidic character: It explained by sp hybridization. We know that an electron in s 
orbital is more tightly held than in a p -orbital. In sp hybridization s -character is more (50%) as
compared to sp 2 (33%) or sp 3 (25%), due to large s -character the carbon atom is quite electronegative.

(ii) Reaction with formaldehyde

HC  CH  2CH 2 O  CH 2  C  C  CH 2   CH 2  CH  CH  CH 2 OH
Li / NH 3
[Trans-product]
| |
OH OH

(6) Chemical properties of acetylene

 Benzene : By passing acetylene through red hot tube, 3C 2 H 2  C 6 H 6
 Pyrrole : By heating with NH 3 , 2C2 H 2  NH 3  C4 H 5 N  H 2
CHCH Thiophene : By heating with S or H 2 S , 2C 2 H 2  S  C4 H 4 S

Acetylene
 Acetaldehyde : By passing acetylene through 40% H 2 SO 4 and 1% HgSO 4 at 80 o C ,
CH  CH  H 2 O  CH 3 CHO or by heating ethylidene acetate,
CH 3 CO
2
CH  CH  2CH 3 COOH 
Hg
 CH 3 CH (OOCCH 3 )2  CH 3 CHO  O
80 o C Ethylidene acetate
[Kucherov' s reaction] CH 3 CO
Acetaldehyde so prepared may be used for the preparation of :
 Ethyl alcohol : By reduction with H 2 in presence of Ni at 140 o C ,
CH 3 CHO  H 2  CH 3 CH 2 OH
 Acetic acid : By oxidation in presence of manganese acetate or platinum wire at
70 o C ,
CH 3 CHO  O  CH 3 COOH
 Ethyl acetate : By esterification of acetic acid and alcohol or by condensation of
acetaldehyde in presence of aluminum ethoxide, 2CH 3 CHO   CH 3 COOC 2 H 5
Al(OC 2 H 5 )3

 Westron and Westrosol : Used as solvents,

CH CHCl 2 CHCl
| | |  Cl 2  |   | |
Alc.
KOH
CH CHCl 2 CCl 2
(Westron) (Westrosol)

 Lewsite : A poisonous gas used during wars,

CH CHCl
| | |  ClAsCl2   | |
AlCl3
 Cadet and Busen reaction
CH CHAsCl 2
Lewisite

32
  Vinyl acetate : By reacting with acetic acid in presence of Hg 2 ,
2
CH  CH  CH 3 COOH 
Hg
 CH 2  CHOOCCH 3
Vinyl acetate is used in paints
 Vinyl chloride : By reacting with HCl in presence of Hg 2 at 60 o C ,
2
CH  CH  HCl o CH 2  CHCl
Hg
60 C

Vinyl chloride is used for the manufacture of PVC plastic.

 Vinyl cyanide : By reacting with HCN in presence of Ba(CN )2 ,
CH  CH  HCN   CH 2  CHCN
Ba(CN )2

It is employed for making orlon and buna-N rubber.

 Chloroprene: See polymerization reactions.
 Cuprene: See polymerization reactions.
 Hexachloro ethane: C 2 Cl 6 -used as artificial camphor.
 Ethylene : C 2 H 2  H 2   C 2 H 4 (Cis)
Lindlar ' s
Catalyst

 Ethane : C 2 H 2  2 H 2  C 2 H 6

Ni
300

 Higher alkynes : HC  CNa  XR  HC  C  R

Sod. acetylide

 Glyoxal: By oxidation with O 3 or SeO 2 .

 Oxalic acid: By oxidation with alk. KMnO4
CH COOH
| | |  4 O  |
CH COOH

Consequently the electron pair of H  C  bond get displaced more towards the carbon atom and helps
in the release of H  ion.
R  C  C....... H (Cleavage of bond is easy)

Oxidative–Hydroboration: Alkynes react with BH 3 (in THF) and finally converted into carbonyl
compounds.
3 CH 3  C  CH   (CH 3  CH  CH )3 B 
BH 3 / THF

H 2 O2

 CH 3  CH  CHOH   CH 3 CH 2 CHO
Tautomerises

Propyne OH (Propanal)

O
||
or   CH 3  C  CH 3 (Acetone)
H 2 SO 4
HgSO 4

Thus it is useful for preparing aldehyde from terminal alkyne.

Reduction of Alkyne: Alkynes add on hydrogen in presence of suitable catalysts like finely divided Ni,
Pd.
CH  CH  H 2 
Ni
CH 2  CH 2 
Ni
CH 3  CH 3
H2

If the triple bond is not present at the end of the carbon chain of the molecule, the alkene formed may
be cis and trans depending upon the choice of reducing agents.

33
With Na / NH 3 or Li / NH 3 in (liquid ammonia) trans alkene is almost an exclusive product while catalytic
reduction at alkyne affords mainly cis alkenes.
R R R H
CC     R  C  C  R  
H2 Li / NH 3
CC
Pd . / BaSO 4 / quinoline
H H (Lindlarcat alyst) H R
cis Trans

CC–CC

Trans product

Cis product

Degree of unsaturation: The number of degree of unsaturation in a hydrocarbon is given by

2n1  2  n2
, Where n1 is the number of carbon atoms; n 2 is the number of hydrogen atoms.
2
2  6  2  12
For example in C6 H12 , the degree of unsaturation is  1
2
So, C6 H12 with 1o of unsaturation can have different arrangements.
(i) or or
(ii) or or
(iii) or or

(iv) or or or

Other examples have the following degree of unsaturation.

(i) C6 H 6  4 o (ii) C5 H 8  2 o (iii) C7 H10  3 o (iv) C8 H12  3 o (v) C10 H16  3 o (vi) C12 H10  8 o

(vii) C3 H 3 Cl (like C3 H 6 )  1o (viii) C3 H 4 O (like C3 H 4 )  2 o (ix) C4 H 5 N (like C4 H 4 )  3 o

(x) C5 H 9 Cl (like C5 H10 )  1o

34
Test of unsaturation
(a) Baeyer’s reagent: It is 1% KMnO 4 solution containing sodium carbonate. It has pink color. An
aqueous solution of the compound, a few drops of Baeyer’s reagent are added, the pink color of the
solution disappears. The decolourisation of pink color indicates the presence of unsaturation in the
compound.
R R
Note: Alkene without any hydrogen atom on the carbon forming the double bond CC don't show
R R
this test.

(b) Bromine- carbon tetrachloride test: The compound is dissolved in carbon tetrachloride or chloroform
and then a few drops of 5% bromine solution in carbon tetrachloride are added to it, the color of bromine
disappears. It indicates the presence of unsaturation.
R R
Note: This test also fails in the case of alkene of the CC .
R R

(7) Uses

(i) Acetylene is used as an illuminant.

(ii) It is used for the production of oxy-acetylene flame. The temperature of the flame is above 3000 o C .
is employed for cutting and welding of metals.

(iii) Acetylene is used for artificial ripening of fruits.

(iv) It is used as a general anesthetic under the name naracylene.

(v) Acetylene has synthetic applications. It serves as a starting material for the manufacture of a large
variety of substances.

(vi) On electrical decomposition acetylene produces finely divided carbon and hydrogen. Hydrogen is
used in airships. C 2 H 2  2C  H 2

35
(8) Interconversion

(i) Conversion of ethane into ethene: (Alkane into alkene)

CH 3  CH 3 
 C 2 H 5 Br 
Br2
 CH 2  CH 2
Alc .

Ethane hv Ethyl bromide KOH Ethene

(ii) Ethene into ethane: (Alkene into alkane)

CH 2  CH 2 
o CH 3  CH 3
H2

Ethene Ni, 300 C Ethane

(iii) Ethane into ethyne (acetylene): i.e., alkane into alkyne

CH 3  CH 3  CH 3 CH 2 Br 
Br2
 CH 2  CH 2 
Alc .
 CH 2 Br  CH 2 Br 
Br2
 CH  CH
Alc . KOH

Ethane hv KOH Ethene CCl4 1, 2-Dibromoeth ane or NaNH 2 Ethyne

(iv) Ethyne into ethane: (Alkyne into alkane)

CH  CH 
o CH 2  CH 2 
H2
o CH 3  CH 3
H2
Ethyne Ni, 300 C Ethene Ni, 300 C Ethane

(v) Ethene into propene: Ascending in alkene series

CH 2  CH 2 
HI
 CH 3 CH 2 I  CH 3 CH 2 CN 
KCN
 CH 3 CH 2 CH 2 NH 2 
[H ]
 CH 3 CH 2 CH 2 OH
HNO 2

Ethene Iodoethane Propane nitrile Reduction 1- Aminopropa ne 1Propanol

(Ethyl cyanide)

CH 3 CH  CH 2 
 CH 3 CH 2 CH 2 Br 
Alc .

PBr3

Propene KOH 1Bromopropa ne

or CH 2  CH 2  CH 3 CH 2 I 
HI
 CH 3 CH 2 CH 3 
Li(CH 3 )2 Cu
 CH 3 CH 2 CH 2 Cl 
Cl2
 CH 3 CH  CH 2
Alc .

Ethene Iodoethane Propane hv 1-Chloro propane KOH Propene

or CH 2  CH 2  CH 3 CH 2 I  CH 3 CH 2 CH 3 
HI
 CH 3 CH 2 CH 2 Cl 
CH 3 I / Na
 CH 3 CH  CH 2 Cl2 Alc .

Propane hv 1-Chloro propane KOH Propene

(vi) Propene into ethene: Descending an alkene series

CH 3  CH  CH 2   CH 3 CHO 
O3 / H 2 O
 CH 3 CH 2 OH 
[H ]
  CH 2  CH 2
H 2 SO 4
o
Propene Ethanal LiAlH 4 Ethanal 170 C Ethene

(vii) Acetylene into propyne (methyl acetylene): (Ascent)

CH  CH 
 CH  CNa 
Na
 CH  C  CH 3
CH 3 I
Acetylene Monosodium Propyne
acetylide

(viii) Propyne into acetylene: (Descent)

CH 3 C  CH   CH 3 CH  CH 2 
Lindlar' s catalyst
 CH 3 CHO 
O3 / H 2 O
 CH 3 CHCl 2 
PCl 5
 CH  CH
Alc .

Propyne Propylene Acetaldehy de Ethylidene KOH Acetylene

chloride

36
(ix) 1-Butyne into 2-pentyne: (Ascent)
CH 3 CH 2 C  CH   CH 3 CH 2 C  C  Na 
NaNH2
 CH 3 CH 2  C  CCH 3
CH 3 I

1Butyne 2 Pentyne

(x) 1-Butyne into 2-pentanone: (Not more than three steps)

O
||
CH 3 CH 2 C  CH   CH 3 CH 2 C  CNa 
NaNH 2
 CH 3 CH 2 C  CCH 3 
CH 3 I
 CH 3 CH 2 CH 2 C CH 3
H 2 O , H 2 SO 4

1-Butyne ( Liq . NH 3 ) 2 Pentyne HgSO 4 2 Pentanone

6. Separation of alkane, alkene and alkyne.

The gaseous mixture is passed through ammonical cuprous chloride solution. The alkyne (acetylene)
reacts with Cu 2 Cl 2 and forms a red precipitate. It is filtered. The alkyne or acetylene is recovered by
decomposition of the precipitate with an acid.
C 2 H 2  Cu 2 Cl 2  2 NH 4 OH  C 2 Cu 2  2 NH 4 Cl  2 H 2 O ; C 2 Cu 2  2 HNO 3  C 2 H 2  Cu 2 (NO 3 )2
(Red ppt.)

The remaining gaseous mixture is passed through concentrated H 2 SO 4 . Alkene is absorbed. The
Hydrogen sulphate derivatives is heated at 170oC.

C 2 H 4  H 2 SO 4  C 2 H 5 HSO 4 
o
C 2 H 4  H 2 SO 4
170 C

The methane or ethane is left behind.

7. 3.8 Distinction between alkanes, alkenes and alkynes.

Property Alkane (Ethane) Alkene (Ethene) Alkyne (Ethyne)

Molecular CnH2n+2(C2H6) CnH2n(C2H4) CnH2n–2(C2H2)

formula

Nature Saturated Unsaturated Unsaturated

Single bond between Double bond between two Triple bond between two
carbon atoms. Each carbon carbon atoms. Both carbon carbon atoms both carbon
atom is sp -hybridized
3
atoms are sp -hybridized
2
atoms are sp-hybridized
C–C C=C –CC–

37
 Bond length 1.54 Å 1.34 Å 1.20 Å
Bond energy : 83 Kcal mol– 146 Kcal mol–1 200 Kcal mol–1
1

Burning Burns with nonluminous Burns with luminous flame Burns with smoky flame
flame C2H4+3O2  2CO2+2H2O C2H2+5/2O2  2CO2+H2O
C2H6+7/2O2 
2CO2+3H2O
Reaction with – Forms alkane Forms alkene and alkane
H2
CnH2n + H2 
Ni CnH2n+2
Alkane
CnH2n + H2 
Ni CnH2n+2
Alkane
o o
300 C 300 C

C2H4 + H2  C2H6 CnH2n–2 + H2 

Ni CnH2nAlkene
o
300 C

Reaction with – Addition Addition

conc. H2SO4 and C2H4+H2SO4  C2H5HSO4 C2H2 CH3CH(HSO4)2
hydrolysis
C2H5OH   Aldehyde
H 2O
Alcohol
 
H 2O

CH3CHO

Br2/CCl4 – Decolorizes Decolorizes

Dibromo derivative, Tetrabromo derivative,
C2H4 + Br2  C2H4Br2 C2H2Br4
Baeyer’s – Decolorizes Decolorizes
reagent (Alk. Glycol is formed Oxalic acid is formed
KMnO4) CH 2 CH 2 OH CH COOH
||  H 2O  O | |||  4 O |
CH 2 CH 2 OH CH COOH

Ammonical – – Red precipitate

Cu2Cl2 CH CCu
|||  Cu 2 Cl 2  2 NH 4 OH  | | |
CH CCu
(Red)

+ 2NH4Cl + 2H2O
Ammonical – – White precipitate
silver nitrate CH C  Ag
|||  2 AgNO 3  2 NH 4 OH  | | |
CH C  Ag

+ 2NH4Cl + 2H2O

38
8. Cycloalkane.

They are carbocyclic hydrocarbons in which carbon atoms are joined by single covalent bonds to form a
ring. They have general formula Cn H 2 n .
CH2 CH2
H2C CH2
For Ex. ; ; CH2 CH2
H2C CH2 H2C CH2
CH2 CH2
Cyclo propane Cyclo Butane
CH2
Cyclo Hexane
(1) Methods of preparation
(i) From dihalogen compounds [Freund reaction]
CH2
CH2 Cl
CH2 + 2Na H2C CH2 + 2NaCl
CH2 Cl Cyclo propane
1, 3-Dichloropropane

Note: It is useful in preparation of three to six membered ring.

It is also known as intramolecular wurtz reaction.

(ii) From calcium salts of dicarboxylic acids

(a) Clemmensen reduction

O

CH2CH2 C CH2CH2 CH2CH2

O– Ca2+ C=O CH2
CH2CH2 C CH2CH2 CH2CH2
O– Cyclopentane
Cyclopentanone
O
Calcium adipate
COOC2H5

CH2 CH
H2C
(b) Diekmann Cyclization H2C COOC2H5
C= O
H2C COOC2H5 H2C
CH2 CH2
Diethyl adipate

39
 COOH

CH CH2
H2C H2C H2C – CH2
C= O C= O CH2
H2C H2C H2C – CH2
CH2 CH2 Cyclopentane
Cyclopentanone

(iii) From alkenes: CH 3  CH  CH 2  CH 2 I 2 

Zn  Cu alloy
 CH 3  CH  CH 2
Propene
CH 2
Methyl cyclopropane

(iv) From Aromatic compounds

+ 3H2

Benzene Cyclohexane

(2) Physical properties

(i) First two members are gases, next three members are liquids and higher ones are solids.

(ii) They are insoluble in water but soluble in alcohol and ether.

(iii) Their boiling points show a gradual increase with increase of molecular mass. Their boiling points are
higher than those of isomeric alkenes or corresponding alkanes.

(iv) Their density increase gradually with increase of molecular mass.

(3) Chemical properties: Cycloalkanes behave both like alkenes and alkanes. All cycloalkanes undergo
substitution reaction with halogen in the presence of light (like alkane). All cycloalkane (lower members)
undergo addition reaction (ex. Addition of H 2 , HX , X 2 ). Further the tendency of forming addition
compounds. Decreases with increase in size of ring cyclopropane > Cyclobutane > Cyclopentane.
Relative ring opening of ring is explained by Baeyer strain theory.

40
(i) Addition in spiro cycloalkane: If two cycloalkane fused with one another then addition take place in
small ring
+ H2

Spiro compound

Because small ring is more unstable than large ring

Higher cycloalkanes do not give addition due to more stability.

(ii) Free radical substitution with Cl2

CH 2  CH 2  Cl 2 
hv
CH 2  CH Cl  HCl
CH 2 CH 2
Cyclopropane Chlorocyclopropane

(iii) Addition reaction

Br2 BrH2C – CH2 – CH2Br
(CCl4) dark 1, 3-Dibromopropane
HBr
H2C – CH2 CH3 – CH2 – CH2Br
1-Bromopropane
CH2
(i) Conc. H2SO4 CH – CH – CH OH
Cyclopropane 3 2 2
(ii) H2O 1-Propanol
H2, Ni CH3 – CH2 – CH3
80oC Propane

(iv) Oxidation CH2

H2C CH2 CH2CH2COOH
+ 5[O]
H2C CH2 CH2CH2COOH
CH2 Adipic acid
Cyclohexane

41
9. Cycloalkene.

Carbocyclic compounds with double bonds in the ring are called cycloalkenes. Some of the common
cycloalkenes are 6
5 1
4 2
3
Cyclobutene Cyclopenten Cyclohexene 1, 4-Cyclohexadiene
e
Cycloalkenes can be easily obtained by Diels-Alder reaction. These compounds undergo the electrophilic
addition reactions which are characteristic of alkenes, while the ring remains intact. Cycloalkenes
decolorize the purple color of dilute cold KMnO 4 or red color of bromine in carbon tetrachloride.

+ Br2 +O + H2O
KMnO4(aq.)
Br
Cyclopentene OH
Br Cyclopent-1-ene
OH
1, 2-Dibromo Cyclopentane
cyclopentane 1,2-diol
CH2
O H2O
+ O3 O CH2 CHO
O
(Cyclohexene) CH2 CHO
CH2

10. Dienes.

These are hydrocarbon with two carbon-carbon double bonds. Dienes are of three types
(1) Conjugated dienes: Double bonds are separated by one single bond.
Ex: CH 2  CH  CH  CH 2 (1, 3-butadiene)

(2) Cumulative dienes: Double bonds are adjacent to each other.

Ex: CH 2  C  CH 2 Propadiene [allene]

(3) Isolated or Non-conjugated: Double bonds are separated by more than one single bond.
Ex: CH 2  CH  CH 2  CH  CH 2 (1, 4 pentadiene)
The general formula is Cn H 2n2 . The predominant member of this class is 1, 3-butadiene.

42
(1) Method of preparation
(i) From acetylene: 2 HC  CH   HC  C  CH  CH 2 
Cu 2 Cl2
 CH 2  CH  CH  CH 2
H2
NH 4 Cl Vinylacetylene Pd / BaSO 4 1, 3 -Butadiene

Cl Cl
| |
(ii) From 1, 4-dichlorobutane: CH 2 CH 2 CH 2 CH 2   CH 2  CH  CH  CH 2
Alc . KOH

1,4 -Dichlorobutane 1, 3 -Butadiene

OH OH
| |
(iii) From 1,4-butanediol: CH 2 CH 2 CH 2 CH 2   CH 2  CH  CH  CH 2
H 2 SO 4

1, 4 -Butanediol heat 1, 3 -Butadiene

(iv) From butane: CH 3 CH 2 CH 2 CH 3    CH 2  CH  CH  CH 2 (Cr2O3 used as catalyst.)

Catalyst
o
n -Butane 600 C 1, 3 -Butadiene

(v) From cyclohexene:  CH 2  CH  CH  CH 2  CH 2  CH 2

1, 3 - Butadiene Ethene

(2) Physical property: 1, 3-butadiene is a gas.

CH2BrCHBrCH=CH2
3,4-Dibromo-1-butene (1, 2-Addition)
predominates (62%) in non-ionising
(3) Chemical properties solvent (hexane)
CH2 = CHCH = CH2 + Br2
(i) Addition of halogens:
CCl4
1, 3-Butadiene

CH2BrCH=CH.CH2Br
1,4-Dibromo-2-butene (1, 4-Addition)
predominates (70%) in an ionising
solvent (acetic acid)

Mechanism
Step I: The halogen molecule (Br2 ) undergoes heterolytic fission.

Br2  Br   : Br 
Bromonium Bromide
ion ion

Step II: The bromonium ion attacks the double bond to give a resonance stabilized carbonium ion.

BrCH 2  C H  CH  CH 2 ( A)

Br  CH 2  CH  CH  CH 2  

BrCH 2  CH  CH  C H 2 (B)

43
Step III: The bromide ion combines with (A) to form 3, 4-dibromo-1-butene (1, 2-addition). It combines
with (B) to form 1, 4-dibromo-2-butene (1, 4-addition).
Br  CH 2  CH  CH  CH 2 1, 2-product; Br  CH 2  CH  CH  CH 2  Br 1, 4-product
|
Br CH3CHBrCH=CH2
(1, 2-Addition)
(ii) Addition of halogen acids: CH2 =CH–CH=CH2 +HBr 3-Bromo-1-butene

CH3–CH=CH–CH2Br
(1, 4-Addition)
1-Bromo-2-butene
(Major yield at high temp.)

CH3CHOHCH=CH2
3-Butenol-2
(iii) Addition of water: CH2 =CH–CH=CH2 +H2O

CH3CH=CHCH2OH
2-Butenol-1

(iv) Polymerization: nCH 2  CHCH  CH 2  [ CH 2 CH  CHCH 2 ]n

Peroxide

1, 3 - Butadiene Buna rubber

Diels-alder reaction:
CH2 CH2
H–C CH2 HC CH2
+
H–C CH2 HC CH2
Ethene CH2
CH2 (Dienophile)
1, 3-Butadiene Cyclohexene
(Adduct)

Note: Diene is known as Diene and alkene or alkyne is known as Dienophile.

If product is cyclohexene then dienophile is alkene or alkene derivative.
If product is 1, 4-cyclohexadiene then dienophile is alkyne or alkyne derivative.
Dienophiles of the reaction may be one of the following,

O O
C
Alkenes; Alkynes; CH 2  C  CH 2 ; ; O ;
C
O
O

44
Mechanism (FMO)
CH2 CH2 CH2
CH CH2 CH CH2 CH CH2
+
CH CH2 CH CH2 CH CH2
CH2 CH2 CH2
Cyclic transition state Cyclohexene

Stability of conjugated dienes: It explained on the basis of delocalization of electron cloud between
carbon atoms.

The four  electrons of 1, 3-butadiene are delocalized over all the four atoms. This delocalization of the
 electrons makes the molecule more stable.

C C C C C C C C–

 - Delocalised
electron’s

(v) Ozonolysis: CH 2  CHCH  CH 2  2O3   2 HCHO  OHCCHO

Zn / H 2 O

O3
H2O
CH2–O–CH – CH–O–CH2

O O O O
(Diozonide)

45