Hydrocarbons

What are hydrocarbons?

The term hydrocarbon is self explanatory which refers to the compounds formed by
combination of carbon and hydrogen only. Hydrocarbons have very important role in our daily
life. The Vegetable oil which is part of our food and also the gasoline which we use to run our
vehicles is hydrocarbons. Hydrocarbons are the source of energy. The oil, ghee & butter are
the hydrocarbon which are part of our diet and provide our body with energy required to
perform various physical and biological functions.
LPG, CNG, LNG , Petrol, Diesel and Kerosene oil are the hydrocarbons which are used as fuels
for automobiles and domestic uses. LPG is the abbreviated form of liquified petroleum gas,
LNG is the abbreviated form of liquified natural gas whereas CNG stands for compressed
natural gas. Petrol, diesel and kerosene oil are obtained by the fractional distillation of
petroleum found under the earths crust while coal gas is obtained by the destructive
distillation of coal.
Hydrocarbons are also used for manufacture of polymers like polythene, polypropene,
polystyrene etc and also as solvents for paints. They are also used as the starting materials
for manufacture of many dyes and drugs.
List of Topics Covered:

Saturated Hydrocarbons

Unsaturated Hydrocarbons

Aromatic Hydrocarbons

Classification of Hydrocarbons

?Hydrocarbons are broadly divided into aliphatic hydrocarbons and aromatic hydrocarbons.
Aromatic hydrocarbons or arenes are the cyclic hydrocarbons with alternating double and
single bonds betweeen carbon atoms. Benzene is an example of aromatic hydrocarbon.
Aliphatic hydrocarbons can further be divided into saturated hydraocarbons or alkane and
unsaturated hydrocarbons. Saturated hydrocarbons contain only single bonds throughout the
length of carbon chain.
Unsaturated hydrocarbons contain one or more multiple bonds i.e double or triple bond,
between the carbon atoms anywhere throughout the carbon chain. Unsaturated hydrocarbons
with double bonds between the carbon atoms are called alkenes while those with triple bonds
are called alkynes.
There is another class of aliphatic hydrocarbons called alicyclic hydrocarbons. These
hydrocarbons are present in the form of rings.

Saturated Hydrocarbons

What are saturated Hydrocarbons?

Alkanes, also known as paraffins, are saturated hydrocarbons. These are chemical compounds
that consist only of the elements carbon (C) and hydrogen (H) (i.e.,hydrocarbons), wherein
these atoms are linked together exclusively by single bonds (i.e., they are saturated
compounds) without any cyclic structure (i.e. loops). Alkanes belong to a homologous series of
organic compounds in which the members differ by a constantrelative atomic mass of 14.Each
carbon atom must have 4 bonds (either C-H or C-C bonds), and each hydrogen atom must be
joined to a carbon atom (H-C bonds). A series of linked carbon atoms is known as the carbon
skeleto
n or carbon backbone. In general, the number of carbon atoms is often used to define the size
of the alkane (e.g., C2-alkane).
An alkyl group is a functional group or side-chain that, like an alkane, consists solely of singlybonded carbon and hydrogen atoms, for example a methyl or ethyl groups.
Saturated hydrocarbons can be linear (general formula CnH2n+2) wherein the carbon atoms are
joined in a snake-like structure, branched (general formulaC nH2n+2, n>3) wherein the carbon
backbone splits off in one or more directions, or cyclic (general formula CnH2n, n>2) wherein
the carbon backbone is linked so as to form a loop. According to the definition by IUPAC, the
former two are alkanes, whereas the third group is called cycloalkanes. Saturated
hydrocarbons can also combine any of the linear, cyclic (e.g., polycyclic) and branching
structures, and they are still alkanes (no general formula) as long as they are acyclic (i.e.,
having no loops)
We would study about saturated hydrocarbons in more detail under following topics:

General Methods of Preparation of Alkanes

Properties of Alkane

Cycloalkanes

Petroleum

The simplest possible alkane (the parent molecule) is methane, CH 4. There is no limit to the
number of carbon atoms that can be linked together, the only limitation being that the
molecule is acyclic, is saturated, and is a hydrocarbon. Saturated oils and waxes are examples
of larger alkanes where the number of carbons in the carbon backbone tends to be greater
than 10.
Alkanes are not very reactive and have little biological activity. Alkanes can be viewed as a
molecular scaffold upon which can be hung the interesting biologically-active/reactive
portions (functional groups) of the molecule.
Alkanes have general formula CnH2n+2 where n ranges from 1 to n,
e.g.,

CH4,

C2H6,

methane

ethane

C3H8 ...........
propane

Alkanes are also known as paraffins due to their less reactive nature. (latin : Parum = little;
affins = affinity)
Each carbon atom in alkane is sp 3 hybridized and its four bonding orbitals are directed towards
the four corners of regular tetrahedron at an angle of 109 o 28' or 109.5o.
The tetrahedral of alkane is described below, e.g., C 2H6

All the C-C & C-H bonds are strong sigma bonds.

Bond

C-C (sp3-sp3)

Bond length

1.54 A

Bond energy

82.76 k cal mol-1

C-H (sp3-s)
1.112 A
98.67 k cal mol-1

Carbon-carbon chain in alkanes consisting of more than two carbon atoms is not linear but
zig-zag as usually written for the sake of convenience of representation.
The simplest alkane CH4
is also known as marsh gas or fire damp.
constitutes 40% of coal gas.
is mean source for the preparation of synthesis gas.

The main source of alkanes is petroleum and natural gas.

Natural gas contains about 80% methane, 10% ethane and 10% rest mixture of higher
members. It also contains small amounts of H2, N2 and CO2 etc.
Rafer to the follwoing video for naming of alkanes:

Isomerism in alkanes :

Alkanes are open-chain (acyclic) hydrocarbons comprising the homologous series with the
general formula, CnH2n+2, where n is an integer. They have only single bonds and therefore are
said to be saturated.
1. Structural Isomerism in Alkanes:
The number of isomers of alkanes increases with increase in carbon atoms.
Alkanes
Possible Isomers

C4H10

C5H12

C6H14

C7H16

C8H18
9

C10H22
18

75

Monosubstituted alkanes with at least 3 carbon atoms show isomerism

CH3CH2CH2X and CH3CHXCH3 : Position isomerism
Disubstituted alkanes with at least two carbon atoms show isomerism e.g.
CH3CHX2 and CH2XCH2X : Position isomerism
2. Sterioisomerism In Alkanes:
Free Rotation about the Carbon-Carbon Single Bond: Conformations

Electron diffraction and spectroscopic studies have verified this structure in all respects,
giving the following measurements for the molecule : bond angles, 109.5 o; C-H length, 1.10;
C-C length, 1.53 . Similar studies have shown that with only slight variations, these values
are quite characteristic of C-H and C-C bonds and of carbon bond angles in alkanes.
This set of bond angles and bond lengths still does not limit the molecule of ethane to a single
arrangement of atoms, since the relationship between the hydrogens of one carbon and the
hydrogens of the other carbon is not specified. Different arrangement of atoms that can be
converted
into
one
another
by
rotation
about
single
bonds
are
called Conformations. Arrangement I is called the eclipsed conformation and arrangement II
is called its staggered conformation.

General Methods of Preparation of Alkanes

Decarboxylation:

Decarboxylation refers to the process of removal of CO 2 from the molecules having -COOH
group. Saturated monocarboxylic acid salt of sodium potassium on dry distillation with soda
lime gives alkane.

or

The alkane formed by decarboxylation process always contains one carbon atom less than the
original acid.The yield is good in case of lower members but poor for higher members.
Soda lime is prepared by soaking quick lime CaO in caustic soda solution and then drying the
products. It is generally written as NaOH + CaO. Its reaction is milder than caustic soda.
Otherwise the reaction will occur violently. Also CaO used alongwith NaOH keeps it dry (NaOH
is hygroscopic) to aid fusion.
The decarboxylation of sodium formate yields H2.
HCOONa + NaOH
CH3COONa + NaOH

H2 + Na2CO3
CH4 + Na2CO3

Wurtz reaction:

In wourtz reaction a solution of alkyl halide in ether on heating with sodium gives alkane.

An alkyl halide on Wurtz reaction leads to the formation of symmetrical alkane having an even number of
carbon atoms. Two different alkyl halides, on Wurtz reaction give all possible alkanes.

CH3X + Na + C2H5X CH3CH2CH3 + CH3CH3 + CH3CH2CH2CH3

The different involved are steps are:
CH3X + 2Na + C2H5X CH3CH2CH3 + 2NaX
CH3X + 2Na + C2H5X CH3CH3 + 2NaX
C2H5X + 2Na + C2H5X C2H5C2H5 + 2NaX
The separation of mixture into individual members is not easy because their boiling points are
near to each other and thus Wurtz reaction is not suitable for the synthesis of alkanes
containing odd number of carbon atoms.
When Zn is used in Wurtz reaction in place of Na, the reaction is named as Frankland method.

Limitations of Wurtz reaction :

a.Methane can not be obtained by this method
b.The reaction fails in case of tertiary halides
Mechanism of Wurtz reaction :

The mechanism of Wurtz reaction is although not clear however two mechanisms are
proposed for this reaction.
The first proposed mechanism of
Intermediate organometallic compound:

Wurtz

reaction

involved formation

of

an

RX + 2Na [RNa] + NaX

Intermediate

RX + [RNa] R-R + NaX

Another proposed mechanizm of Wurtz reaction involved formation of Intermediate free
radicals:
RX + Na R. + Nax
Free radicals

R. + R. R-R

By the reduction of alkyl halides:

Alkyl halides on reduction with nascent hydrogen form alkanes. R-X + 2[H]R-H + HX. The
nascent hydrogen may be obtained by any one of the following
1.

Zn + HCI

2.

Zn + CH3COOH

3.

Zn-Cu couple in ethanol

4.

Red P + HI

5.

Al-Hg + ethanol

Alkyl halides can also be reduced catalytically to alkane by H 2/Pd or LiAIH4 or by H2/Ni. The
yields are generally high and the hydrocarbons formed are pure.
Note : Zn-Cu couple is prepared by adding Zn granules in aqueous CuSO 4 solution where
copper is deposited on the Zn pieces.

By hydrogenation of alkenes((>C=C<) : Sabatier and

senderen's method

Alkenes and alkynes on catatlytic hydrogenation give alkanes

CH2 = CH2 + H2
CHCH + 2H2

CH3-CH3
CH3-CH3

Catalyst Ni is used in finely divided form. If Pt or Pd are used as catalyst, reaction occurs at
normal temperature. Also some times Raney nickel is used as catalyst. It is obtained by
boiling Ni-AI alloy with NaOH, when AI dissolves leaving Ni in finely divided state. The filtered,
washed and died Ni is known as Raney Nickel. Raney Ni is effective at room temperature and
atmospheric pressure.

Kolbe's electrolysis method:

Alkanes are formed, on electrolysis of concentrated aqueous solution of sodium or potassium

salt of saturated mono carboxylic acids

Electrolysis of an acid salt gives symmetrical alkane. However, in case of mixture of carboxylic
acid salts, all probable alkanes are formed.
R1COOK + R2COOK

R1-R2 + 2CO2 + H2 + 2NaOH

(R1-R1 and R2-R2 are also formed).

By Grignard reagents:

Organic compounds in which a metal atom is directly linked to carbon atom are known as
organometallic compound. e.g. HCCNa, (C2H5)4 Pb, (C2H5)2 Zn
Alkyl or aryl magnesium halide (R-MgX) are also called Grignard reagents or organometallic
compounds.Grignard reagent on double decomposition with water or with other compounds
having active H(the hydrogen attached on O, N, F or triple bonded carbon atom are known as
active hydrogen) give alkane.

By reduction of alcohols, aldehydes, ketones or fatty

acids and their derivatives:

The reduction of either of the above in presence of red P & HI gives corresponding alkane.

By Reduction of Carbonyl compounds :

The reduction of carbonyl compounds by amalgamated zinc and conc. HCI also yields alkanes.
This is Clemmensen reduction.
CH3CHO + 2H2
CH3COOH + 2H2

CH3CH3 + H2O
CH3CH2CH3 + H2O

Carbonyl compounds may also be reduced to alkanes by Wolf Kishner reaction

By the hydrolysis of AI or Be carbides:

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

AI4C3 + 12H2O
Be2C + 4H2O

4AI(OH)3 + 3CH4
2Be(OH)2 + CH4

Note :
1. Calcium carbide reacts with water to give acetylene.
2. Magnesium carbide, Mg2C2 reacts with water to give propyne.
3. CH4 can be obtained by passing a mixture of H 2S and CS2 through red and Cu tube
CS2 + 2H2S

CH4 + 4Cu2S

By hydroboration of alkenes :

Alkenes on hydroboration give trialkyl borane as a result of addition of diborane on olefinic

bond. This trialkyl borane on treatment with acetic acid or propanoic acid yields alkane.
2R - CH=CH2

2(RCH2CH2)3B

2RCH2CH3

ByCorey-House synthesis :

Alkyl chloride say chloroethane reacts with lithium in presence of ether to give lithium alkyl
then reacts with CuI to give lithium dialkyl cuprate. This lithium dialkyl cuprate now again
reacts with alkyl chloride to given alkane.
CH3CH2CI + 2Li

CH3CH2Li + LiCl

2CH3CH2Li + CuI Li(CH3CH2)2 Cu + LiL

Li(CH3CH2)2Cu + CH3CH2CI CH3CH2CH2CH3 + CH3CH2Cu + LiCl

Properties of Alkanes

Physical Properties of alkanes

(a) Physical State:

All are colourless & possess no characteristic odour.Lower alkanes (C1 to C4) are gases, middle
one (C3 to C17) are liquids and higher are solids.The boiling point of alkanes increases with
increase in molecular weight due to increase in van der waals forces with increase in
molecular weight i.e.,B.pt. order : pentane < hexane < heptanes.
Also the branching in alkanes gives a decrease in surface area (as the shape approaches to
spherical) which results in decrease in van der Waals forces. That is why b.pt. of isomeric
alkanes who the order : pentane > isopentane > neopentane
The melting points of alkanes do not show a regular trend. Alkanes with even number of
carbon atoms have higher m.pt. than their adjacent of odd number of carbon atoms.
M.pt. order :

propane
(-187.7oC)

<

ethane

(-172.0oC)

<

methane

(-182.5oC)

The abnormal trend in m.pt. is probably due to the fact that alkanes with odd carbon atoms
have their end carbon atom on the same side of the molecule and in even carbon atom
alkane, the end carbon atom on opposite side. Thus alkanes with even carbon atoms are
packed closely in crystal lattice to permit greater intermolecular attractions.

(b) Density : The density of alkanes increases with increase in molecular weight and
becomes constant at 0.76 g/ml. Thus all alkanes are lighter than water.
(c) Solubility :
Alkanes being non polar and thus insoluble in water but soluble in non polar solvents e.g.,
C6H6, CCI4, ether etc. The solubility of alkanes decreases with increase in molecular
weight.Liquid alkanes are themselves good, non polar solvents.
Refer following Video for Properties of Alkane

Chemical properties of Alkanes:

Alkanes are quite inert substances with highly stable nature. Their inactiveness has been
explained as:
1.

In alkanes all the C-C & C-H bonds being stonger sigma bonds and are not influenced
by acids, alkalies, oxidants under ordinary conditions.

2.

The C-C (completely non polar) & C-H (weak polar) bonds in alkanes- are practically non
polar because of small electronegativity difference in C (2.6) and H (2.1). Thus polar species
i.e., electrophiles or nucleophiles are unable to attack these bonds under ordinary conditions.

?
Inspite of less reactive nature, alkanes show some characteristic reactions.
Oxidation Reactions of Alkane:
Oxidation of alkanes gives different products under different conditions.
1. Complete oxidation or combustion : Alkanes burn readily with non luminous flame in
presence of air or oxygen to give CO 2 & water along with evolution of heat. Therefore alkanes
are used as fuels.

CnH2n+2 + [(3n+1)/2]O2 nCO2 + (n+1)H2O;

CH3 + 2O2 CO2 + 2H2O;

H = -ve

H = -ve

2. Incomplete oxidation : Incomplete oxidation of alkanes in limited supply of air gives

carbon black and carbon monoxide.
2CH4 + 3O2 2CO + 4H2O
CH4 + O2

+ 2H2O

carbon black
3. Catalytic oxidation :
Lower alkanes are easily converted to alcohols and aldehydes under controlled catalytic
oxidation.

Higher alkanes on oxidation in presence of manganese acetate give fatty acids.

CH3(CH2)nCH3 + 3O2

CH3(CH2)nCOOH

4. Chemical oxidation : Tertiary alkanes are oxidized to tertiary alcohols by KMnO 4

Substitution reactions of alkanes :

Substitution in alkanes shows free radical mechanism. For mechanism see free radical
substitution.Following substitution reactions in alkanes are noticed.
1. Halogenation of Alkanes :

Chlorination may be brought about by photo irradiation, heat or catalysts, and the extent of
chlorination depends largely on the amount of chlorine used. A mixture of all possible isomeric
monochlorides is obtained, but the isomers are formed in unequal amounts, due to difference
in reactivity of primary, secondary and tertiary hydrogen atoms.
The order of ease of substitution is
Tertiary Hydrogen > Secondary Hydrogen > Primary Hydrogen
Chlorination of isobutane at 300 oC gives a mixture of two isomeric monochlorides

The tertiary hydrogen is replaced about 4.5 times as fast as primary hydrogen. Bromination is
similar to chlorination, but not so vigorous. Iodination is reversible, but it may be carried out
in the presence of an oxidising agent such as HIO 3, HNO3 etc., which destroys the hydrogen
iodide as it is formed and so drives the reaction to the right, e.g.
CH4 + I2
5HI + HIO3

CH3I + HI
3I2 + H2O

Iodides are more conveniently prepared by treating the chloro or bromo derivative with
sodium iodide in methanol or acetone solution. e.g
RCl + NaI

RI + NaCl

This reaction is possible because sodium iodide is soluble in methanol or acetone, whereas
sodium chloride and sodium bromide are not. This reaction is known as Conant Finkelstein
reaction.
Direct fluorination is usually explosive; special conditions are necessary for the preparation of
the fluorine derivatives of the alkanes.
RH + X2

RX + HX

(Reactivity of X2: F2 > Cl2 > Br2; I2 does not react)

The mechanism of methane chlorination is:
Initiation Step
Cl : Cl

2Cl

DH = + 243 KJ mol-1

The required enthalpy comes from ultraviolet (uv) light or heat.

Propagation Step
i). H3C : H + Cl H3C + H : Cl

H = - 4KJ mol-1 (rate determining)

ii). H3C + Cl : Cl H3C : Cl + Cl

H = - 96 KJ mol-1

The sum of the two propagation steps in the overall reaction,

CH4 + Cl2 CH3Cl + HCl

H= - 100 KJ mol-1

In propagation steps, the same free radical intermediates, here Cl and H3C, being formed and
consumed. Chains terminate on those rare occasions when two free-radical intermediates
form a covalent bond.
Cl + Cl

Cl2 ; H3C + Cl CH3 : Cl

H3C + CH3 H3C : CH3

Inhibitors stop chain propagation by reacting with free radical intermediates, e.g.

In more complex alkanes, the abstraction of each different kind of H atom gives a different
isomeric product. Three factors determine the relatives yields of isomeric product.
Probability Factor: This factor is based on the number of each kind of H atom in the
molecule. For example, in CH 3CH2CH2CH3 there are six equivalent 1o Hs and four
equivalent 2o Hs. The ratio of abstracting a 1oH are thus 6 to 4, or 3 to 2.
Reactivity of H : The order of reactivity of H is 3o > 2o > 1o.
Reactivity of X : The more reactive Cl is less selective and more influenced by the
probability factor. The less reactive Br is more selective and less influenced by the
probability factor, as summarized by the Reactivity-Selectivity Principle. If the
attacking species is more reactive, it will be less selective, and the yields will be closer
to those expected from the probability factor.

In the chlorination of isobutane abstraction of one of the nine primary hydrogens leads to the
formation of isobutyl chlorides, whereas abstraction of a single tertiary hydrogen leads to the
formation of tert-butyl chloride. The probability favour formation of isobutyl chloride by the
ratio of 9:1. But the experimental results show the ratio roughly to be 2:1 or 9:4.5. Evidently,
about 4.5 times as many collisions with the tertiary hydrogen are successful as collisions with
the primary hydrogens. The E act is less for abstraction of a tertiary hydrogen than for
abstraction of a primary hydrogen.
The rate of abstraction of hydrogen atoms is always found to follow the sequence 3 o > 2o > 1o.
At room temperature, for example, the relative rate per hydrogen atom are 5.0:3.8:1.0. Using
these values we can predict quite well the ratio of isomeric chlorination products from a given
alkane. For example:

Inspite of these differences in reactivity, chlorination rarely yields a great excess of any single
isomer.
The same sequence of reactivity, 3 o > 2o > 1o, is found in bromination, but with enormously
larger reactivity ratios. At 127oC, for example, the relative rates per hydrogen atom are
1600:82:1. Here, differences in reactivity are so marked as vastly to outweigh probability
factors. Hence bromination gives selective product.
In bromination of isobutane at 127oC,

Hence, tert-butyl bromide happens to be the exclusive product (over 99%).

2. Nitration :
Replacement of H atom of alkane by -NO2 group is known as nitration.Nitration of alkane is
made by heating vapours of alkanes and HNO 3 at about 400oC to give nitroalkanes. This is also
known as vapour phase nitration.
CH4(g) + HNO3(g)

CH3NO2 + H2O

During nitration, C-C bonds of alkanes are also decomposed due to strong oxidant nature of
HNO3 to produce all possible nitroalkanes.

The nitration of alkane also shows the order:T.H. > S.H. > P.H. > methane
The nitration of alkanes follows free-radical mechanism
HONO2

HO + NO2

C3H7-H + HO C3H7 + H2O

C3H7 + NO2 C3H7NO2
3. Sulphonation :
Replacement of H atom of alkane by -SO 3H is known as sulphonation. Lower normal alkanes
are not suphonated, but higher normal alkanes show sulphonation (hexane onwards) when
heated with oleum (i.e., conc. H2SO4) at 400oC.
C6H14 + H2SO4 C6H13SO3H + H2O
Lower members are sulphonated in vapour phase sulphonation.The reactivity order for
sulphonation is T.H. > S.H. > P.H. Thus isobutene is easily sulphonated as it contains tertiary
hydrogen atom.

Sulphonation of alkanes also follows free radical mechanism.

HOSO3H

HO + SO3H

C3H13-H + OH C6H13 + H2O

C3H13 + SO2H C6H13SO3H
4. Isomerization :
The process of conversion of one isomer into other is known isomerization.Straight chain
alkanes on heating with AICI3 + HCI at about 200oC and 35 atm pressure are converted into
branched chain alkanes.

5. Aromatization :
The process of conversion of aliphatic compound into aromatic compound is known as
aromatization. Alkanes having six to 10 carbon atoms are converted into benzene and its
homologues at high pressure and temperature in presence of catalyst.

C6H14

+ 4H2

6. Dehydrogenation : Alkanes are dehydrogenated on heating in presence of catalyst to

produce corresponding alkenes.

C3H8

C3H6 + H2

7. Pyrolysis :
The decomposition of a compound on heating in absence of air is known as pyrolysis. The
phenomenon of pyrolysis of alkane is also known as cracking. Alkane vapours on passing
through red hot metal tube in absence of air decomposes to simpler hydrocarbons. The
product formed during cracking depends upon

(a) nature of alkane

(b) temperature and pressure
(c) presence or absence of catalyst
The ease of cracking in alkanes increases with increase in molecular weight and branching in
alkane.Fission of C-C bonds produces alkane and alkenes whereas fission of C-H bonds
produces alkene and hydrogen.
Presence of Cr2O3, V2O2, MoO3 catalyses C-H bond fission and presence of SiO 2, AI2O3, ZnO
catalyses C-C bond fission.The no. of products obtained during cracking increases with
increase in molecular weight of alkane undergoing cracking.

Cracking has an important role in petroleum industry. Higher alkanes are converted into lower
one (petrol C6 to C11) by cracking.

Cycloalkanes
This class of hydrocarbons are carbocyclic hydrocarbons in which carbon atoms are joined by
single covalent bonds to form a closed ring of carbon atoms. They are alicyclic in nature and
have the general formula CnH2n. Following are some homologous members of this category.

The nomenclature of cycloalkanes has already reported in chapter-1.Lower members of cyclo

alkanes are usually reported by simple geometrical drawing as
etc. i.e. a triangle
for cyclopropane, a square for cyclobutane, a pentagon for cyclopentane and a hexagon for
cyclohexane.The removal of one H atom from cycloalkanes give rise to cycloalkyl radicals e.g.

Preparation of cycloalkanes

Following methods are commonly used for the preparation of cycloalkanes.

(a) From dihalogen compounds : - elimination from dihalides having halogen atoms on
two ends of carbon chain (- dihalides) with Na or Zn dust gives rise to the formation of
cycloalkanes. The method can be regarded as intramolecular Wurtz reaction and is called
Freund reaction. This can be used to prepare cycloalkanes from three to six carbon atoms.

(b) By Clemmensen reduction : The reduction of cyclic ketones by Zn-Hg/HCI gives

cycloalkanes.

(c) From alkenes : Alkenes on treating with CH2I2 in presence of Zn-Cu couple or by
diazomethane (CH2N2) in presence of U.V. light gives derivatives of cycloalkanes.

(d) By Dieckmann cylisation : Esters of dicarboxylic acids on heating in presence of sodium

ethoxide undergo intramolecular Claisen condensation to gives cyclic -keto esters. These keto esters on hydrolysis and subsequent heating gives cyclic ketones which are reduced by
Zn-Hg/HCI to give cycloalkanes.

(e) From aromatic compounds: Six membered cyclo compounds can be easily obtained by
the catalytic reduction of benzene and its derivatives.

Physical Properties of Cycloalkanes

1.

Cyclopropane and cyclo butane are gases, next three members are liquid and higher
members are solid.
2.
These are insoluble in water but soluble in alcohol or acetone.
3.
Their density increases with increase in molecular weight. Lower members are lighter
than water and floats over it. It is therefore cyclohexane floats over water.
4.
The boiling points increase with increase in molecular weight. The boiling point are also
higher than their corresponding alkenes and alkanes.

Chemical Properties of Cycloalkanes

Cyclopropane and cyclobutane are comparatively less stable due to more strain in ring (Follow
Baeyer's strain theory) and thus tend to breakup and open the ring to act like a double bond
species to give addition reactions. The cycloalkanes from cyclopentane and onwards show
remarkable similaries with alkanes due to their stability. The stability of higher cycloalkanes is
due to less strained ring as well as each carbon atom being sp 3 hybridized like alkanes. It is

therefore higher cycloalkanes are not attacked by acids, alkalies and common oxidizing under
normal conditions. Following are some important reaction of cycloalkanes.
(a) Free radical substitution : Cycloalkanes are halogenated in presence of sun light or UV
light like alkane.

(b) Addition reactions : Cyclopropane being the most strained ring and more reactive
undergoes addition reactions like alkenes.

Cyclobutane is relatively less reactive as it does not undergo addition reactions under normal
conditions. However it undergoes these reactions under special conditions.

(c) Oxidation : Cycloalkanes are oxidized by alkaline potassium permanganate to

dicarboxylic acids involving ring fusion.

Petroleum
Petroleum is an essential source of hydrocarbons and fuels. It has petrol, kerosene, diesel and
other important fuels in addition to many useful solvents, lubrication oil, paraffin wax and
many other useful compounds.

Source of Petroleum :

Crude petroleum is dark yellow, brown or green coloured oily liquid lighter than water. It is
found inside the impervious rocks and thus named as petroleum(petra-rocks; oleum-oil). It is
also known as crude oil or mineral oil.

Composition of Petroleum:

petroleum is a complex oily liquid mixture of hydrocarbons. In addition to alkanes it has cyclo
alkanes, aromatic hydrocarbons and compounds of O, S and N. The composition of petroleum
depends upon its source from where it is obtained.

Refining & mining of Petroleum

Imprevious rocks are drilled by machines and the petroleum comes out of these holes due to
the pressure developed by gases inside the rocks. The final extraction is made by passing air
at high pressure inside the rocks.
The crude petroleum is refined in refinery. Petroleum is mainly found in Assam, Gujrat,
Maharashtra (Bombay high).
Petroleum is refined by fractional distillation. Further fractional distillation of its products gives
a no. of refined products given below.
S.No.

Fraction

Boiling range

Comp.

Uses

1.

Gaseous hydrocarbon

Below 20oC

C1-C4

Fuel for domestic

use

2.

Petroleum ether

20-60oC

C5-C6

Solvent

3.

Benzene

70-90oC

C6-C7

Solvent

4.

Ligroin

80-120oC

C6-C8

Solvent

5.

Gasoline

70-120oC

C6-C11

Fuel for motors

6.

Kerosene

200-275oC

C12-C16

For lightening
stoves, fuel, oil gas

7.

Gas oil or Diesel oil or

Heavy oil

275oC to above

C15-C18

Diesel Engine oil,

furnace oil

8.

Lubricant oil

Non volatile liquids

C16-C20

Lubricant

9.

Petroleum jellies

Non volatile liquids

C18-C22

Medicine
preparation

10.

Parrafin wax

Non-volatile liquids

C18-C22

Wax industry

11.

Petroleum cake & asphalt

Non-volatile liquids

C30-C40

Carbon electrode,
road manufacture

Knocking :

In an internal combustion engine, the fuel mixture of gasoline vapours and air burns in
cylinder. The mixture is fired by means of a spark in the compressed state. For better and
maximum efficiency, the fuel mixture is highly compressed before firing in cylinder. A good
fuel on sparking burns steadily, completely in time at a definite compression ratio. However, if
compression ratio exceeds a limit, the sparking to a fuel gives rise to knocking i.e., all the fuel
does not burn smoothly and a part of fuel burns suddenly with explosive nature giving rise
to metallic rattle or knocking. This results in loss of power. The knocking however falls with
nature of product fuel.
Knocking order falls with branching, unsaturation, aromatization etc. The knocking order is:
Straight chain paraffins > branched chain paraffins > olefins > naphthenes > Arenes.
The knocking may be prevented by adding compounds like TEL or tetra ethyl lead. The
gasoline from petrol pump which we get contain anti knock compounds (TEL).
Octane no. of gasoline is the no. for rating anti knock qualities of gasoline. The higher the
octane no., lesser the tendency for knocking and better being the fuel. Octane no. is derived
by assuming 100 arbitrary value for isooctane and zero for n-heptane. Thus no. is the % of
isooctane in a mixture of isooctane and n-heptane whose knocking resembles with the
knocking of fuel used.
The octane no. of fuel is increased by two to three units by adding 2 to 4 ml of TEL in one
Gallon petrol. Tetra ethyl lead is supposed to dissociate as
(C2H5)4Pb 4C2H5. +Pb
Ethyl free radical
The ethyl free radical converts some of the straight chain hydrocarbons into branched chain
hydrocarbons and thus increases the octane number. In addition to TEL, a little ethylene
dibromide is also added which converts Pb to PbBr 2, which comes out through exhaust and
prevents its deposition in engine due to decomposition of TEL.
Pb + CH2BrCH2Br PbBr2 + CH2=CH2

Volatile
A gasoline fuel with octane no. 30 or above is good fuel. The efficiency of fuel increases as the
octane no increases.
Addition of TEL in petro, no doubt improves the octane number of fuel but it also causes lead
pollution in atmosphere. The attempts are therefore been made to improve octane number of
fuel by some other means. Unleaded or lead free gasoline marketed today is the gasoline
obtained by isomerisation and alkylation blended with BTX (Benzene, toluene, xylene) or
methyl-t. butyl ether. Its octane number is 90. Thus following processes are used for getting
lead free gasoline with better octane number.
(i) Isomerisation (Reforming) : By passing gasoline vapours over aluminium chloride
(AICI3) at 200oC.

(ii) Alkylation : Isobutylene formed during cracking on alkylation with isobutene forms isooctane in presence of concentrated H 2SO4.

(iii) Aromatisation : A mixture of benzene, toluene and xylenes known as BTX is obtained
when
crude
naptha
vapours
are
passed
over
a
catalyst
o
(Pt + AI2O3) at 500 C.

Note :
1.Octane number may be less than zero (e.g. n-nonane has octane number = -45) as well as it
may be greater than 100 (e.g. Triptane or 2, 3, 3-trimethyl butane has octane no. = 124)
2.To avoid lead pollution, a new anti knock agent AK-33-X i.e. cyclopentadienyl manganese
carbonyl
is used in developed countries in unleaded petrol.
3.Commercial TEL used as antiknock has following mixture. TEL = 63%; Ethylene bromide =
25%; Ethylene chloride = 9%, methylene blue dye (2%)

4.Octane number of gasoline can be increased by addition of BTX (benzene, toluene and
xylene).
5.The fraction obtained during fractional distillation with offensive odour due to the presence
of sulphur compounds as well as dark coloured due to the presence of aromatic compound is
called sour gasoline.
6.The process of purification of sour gasoline is called Doctors sweetening process.
Synthetic Petrol : With the advantage of civilization, the consumption of gasoline has
increased much and demand still on increase led chemists to prepare gasoline. Following
method were given during the short supply of petrol in II world war by German chemists.
1. Bergius method : Coal is a mixture of solid hydrocarbons and may be hydrogenated to
produce low boiling hydrocarbons.
Coal tar or Coal dust + heavy oil make a paste

Paste + H2
Crude oil

Crude oil
1. Gasoline (Petrol) , 2. Middle oil , 3. Heavy oil

2.Fischer Tropsch Process :

Pass steam to red hot coke Water gas (CO + H 2)

Cetane Number

Cetane number is used for grading the diesel oils. Hexadecane (cetane) has been assigned
cetane number 100 while -methyl naphthalene is assigned zero cetane number arbitrarily.
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 in question under similar experimental conditions. The diesel oil having cetane number 75
has same ignition property as a mixture of 75% cetane and 25% -methyl naphthalene.

Flash Point

Volatile nature of a liquid hydrocarbon determines its explosive nature. The lowest
temperature at which an oil gives sufficient vapours to form an explosive mixture with air is
referred to as flash point of the oil.
The flash point fixed for a particular oil varies from country to country, depends on its climate
and controls the percentage of highly volatile hydrocarbons in the oil. The flash point is high

for a hot country and low for a cold country. The flash point in India is fixed at 44 oC, in France
it is fixed at 35oC and in England at 22.8oC.

Unsaturated Hydrocarbons

What are unsaturated Hydrocarbons?

Unsaturated hydrocarbons are hydrocarbons have multiple bonding i.e. double or triple
covalent bonds, between adjacent carbon atoms. Unsaturated hydrocarbons having double
bonds are called alkenes while those having triple bonds are known as alkynes.
We would study about unsaturated hydrocarbons in more details under following subtopics:

Methods of Preparation of Alkenes

Properties of Alkenes

Methods of Preparation of Alkynes

Properties of Alkynes

What are Alkenes?

In organic chemistry, an alkene, olefin, or olefine is an unsaturated chemical compound

containing at least one carbon-to-carbon double bond. The simplest acyclic alkenes, with only
one double bond and no other functional groups, form a homologous series of hydrocarbons
with the general formula CnH2n.
The simplest alkene is ethylene (C2H4), which has the International Union of Pure and Applied
Chemistry (IUPAC) name ethene. Alkenes are also called olefins (an archaic synonym, widely
used in the petrochemical industry). Aromatic compounds are often drawn as cyclic alkenes,
but their structure and properties are different and they are not considered to be alkenes.
Alkenes (olefins) contains the structural unit >C=C< and have the general formula CnH2n.
These unsaturated hydrocarbons are isomeric with the saturated cycloalkanes.

Carbon atoms of alkenes involved in double bond are sp2 hybridized having trigonal planar
structure with an angle of 120oC.

The coplanar structure of C=C has been described below, e.g. C2H4

Alkenes have the following characteristic bond lengths and bond energy.

Bond length

C=C
sp2-sp2()
1.34 A

=C-H
sp2-1s ()
1.108 A

Bond energy

143.1 kcal mol-1

98.69 kcal mol-1

IUPAC nomenclature of Alkenes :

The IUPAC name is derived from the IUPAC name of alkanes by replacing ending 'ane' by 'ene'
alongwith the position of double bonds.

(e.g. alkane - ane + ene = alkene). CH3CH=CH-CH3 is known as but-2-ene or butene-2 or 2butene.
In case of two double or two triple bonds, the ending 'ne' of alkanes is suitably replaced by
diene or triene accordingly.
CH3CH=C=CH2 : buta-1, 2-diene; CH2=CH-CH=CH2: buta-1. 3-diene
Alkenyl groups : Residual part left after the removal of one H atom from alkene is known as
alkenyl group. According to IUPAC nomenclature, these groups are named by replacing
terminal 'e' of alkene by 'yl' e.g.
Group
2

Trivial name

IUPAC name

vinyl

ethenyl

allyl

prop-2-enyl

prop-1-enyl

crotyl

but-2-enyl

CH2=CH3

CH2=CH-CH21

-CH=CH-CH3
1

-CH2-CH=CH-CH3
The numbering in alkenyl group is started from the carbon with free valencies.

Isomerism in Alkenes

The cis -trans system for alkenes:

The C=C consists of a s bond and a p bond, in a plane at right angles to the plane of the
single s bonds to each C. The p bond is weaker and more reactive than the s bond. The
reactivity of the p bond imparts the property of unsaturation to alkenes; alkenes therefore
readily undergo addition reactions. The p bond prevents free rotation about the C=C and
therefore an alkene having two different substituents on each doubly bonded C has geometric
isomers. For example, there are two 2-butenes.

Geometric (cis - trans) isomers are stereoisomers because they differ only in the spatial
arrangement of the groups. They are diastereomers and have different physical properties
(m.p., b.p., etc.). In place of cis-trans, the letter Z is used if the higher - priority substituents
on each C are on the same side of the double bond. The letter E is used if they are on
opposite sides.
The (E) - (Z) System for Designating Alkene Diastereomers:

The term cis- and trans-, where, when used to designate the stereochemistry of alkene
diastereomers, are unambiguous, only when applied to disubstituted alkenes. If the alkene is
trisubstituted or tetrasubstituted, the terms cis and trans are either ambiguous or do not
apply at all. In the following alkene

it is impossible to decide whether A is cis or trans since no two groups are the same.
A newer system is based on the priorities of groups in the Cahn - Ingold - Prelog convention.
This system called the (E) - (Z) system, applies to alkene diastereomers of all types. In the (E)
- (Z) system, we examine the two groups attached to one carbon atom of the double bond
and decide which has the higher priority. Then we repeat the operation at the other carbon
atom.

We take the group of higher priority on one carbon atom and compare it with the group of
higher priority on the other carbon atom. If two groups of higher priority are on the same side
of the double bond, the alkene is designated (Z). If the two groups of higher priority are on
opposite sides of the double bond, the alkene is designated (E). The following examples
illustrate this :

What are Alkynes or Acetylenes?

?In organic chemistry, an Alkynes or Acetylenes are unsaturated chemical compounds

containing at least one carbon-to-carbon triple bond. The simplest acyclic alkenes, with only
one double bond and no other functional groups, form a homologous series of hydrocarbons
with the general formula CnH2n-2.
e.g.

C2H2
acetylene or ethyne

C3H4
allylene or propyne

C4H6
butyne

Acetylene is known experimentally to have a linear structure. The C C distance of 1.20 is

the shortest carbon-carbon bond length known. The carbon-hydrogen bond length of 1.06 is
shorter than that in ethylene (1.08 ) or in ethane (1.10 ) . These structural details are
readily interpreted by an extension of the s-p electronic structure of double bonds. In
acetylene the s-framework consists of Csp-hybrid orbitals as indicated in .
The sp2-s s-bonds are shorter than are sp 3-s s-bonds. The trend also holds for the sp-s bonds in
acetylene.

Acetlyenes are highly reactive and thus do not exist freely in nature. Carbon atoms involved in
triple bond are sp hybridized having linear nature with an angle of 180 o.

CHCH

CH3CCH

2 2

sp sp

sp3

2 2
sp sp

The linear structure of CC has been described below, e.g. C 2H2

Alkynes have the following characteristic bond lengths and bond energy.
CC
spsp
1.20 A

Bond length
Bond energy

CH
sp1s
1.08 A

192 kcal mol-1

102.38kcal mol-1

In acetylene the CC involves one bond formed by head on overlapping of sp-sp orbital as
well as two bonds formed by lateral overlapping of pp orbitals. The comparative chart of
bond energy and bond length of alkane, alkene and alkyne is given below :
Bond

Hybridized bond orbitals

Bond length

Bond energy

Alkane

CC C sp3sp3 sp31s
H

1.54 A 1.112 A

82.76 kcal mol1 98.67

kcal mol1

Alkene

C==C C
H

1.34 A 1.108 A

143.1 kcal mol1 98.69

kcal mol1

Alkyne

CC C spsp sp1s
H

1.20 A 1.08 A

192.00 kcal mol

1
102.38 kcal mol1

sp2sp2 sp21s

Some important orders for alkanes, alkenes and alkynes are given below:
Bond length

CC > C=C > CC

Bond energy

CC < C=C < CC

Stability of bond

CC < C=C < CC

Reactivity of bond

CC < C=C < CC

Rigidity in bond

CC < C=C < CC

The more reactivity of CC inspite of higher bond energy is due to the presence of pbonds.
Acetylene and all terminal alkynes are acidic in nature i.e. H atom attached on triple bonded C
atom behaves as acidic. The acidic character is due to the fact that in acetylene or triply

bonded C atom, an increase in s character (sp hybridization) give rise to higher

electronegativity to C atom and thus H atom in CH (i.e. sp1s) bond acquires more polarity
to show acidic nature.
The acidic nature order however shows H2O > C2H2 > C2H4 > C2H6
Furthermore, a decreasing trend of bond lengths (in CC & CH bonds) from alkane to alkyne
can also be explained due to increasing s character from alkane to alkyne which leads to
smaller size of hybrid orbitals and therefore showing more tendency for overlapping leading to
smaller bond lengths.
UPAC Nomenclature : The IUPAC name is derived from the IUPAC name of alkanes by replacing
ending ane by yne alongwith the position of triple bond e.g. Alkaneane + yne = Alkyne
CH3CH2CCH but-1-yne
Alkynyl groups : Residual part left after the removal of one H atom from alkyne is known as
alkynyl group. According to IUPAC nomenclature, these groups are named by replacing
terminal (e) of alkyne by yl e.g.
HCC

ethynyl

HCCCH2

2-propynyl

CCCH3

1-propynyl

Test for unsaturation

By Br2 in CCI4 : The decolorization of 5% Br2 in CCI4 by a compound confirms the presence of
unsaturation in molecule.
By Baeyers reagent : The decolorization of pink colour of 1% cold alkaline KMnO 4 by a
compound confirms the presence of unsaturation in molecule.
Note :
1.
2.

Alkenes without any hydrogen atom on olefinic bond do not show these tests e.g.
Aldehydes, primary and secondary alcohols which are readily oxidized by alk.
KMnO4 and thus decolorize alk. KMnO4

To locate the position of unsaturation : By ozonolysis

To distinguish
1.

Alkane and alkene : By Br2 in CCI4 or By Baeyers reagent

2.

Alkane and alkyne : As above

3.

Alkene-1 and alkene-2 : By ozonolysis

4.

Alkyne-1 and alkyne-2 : By Amm. AgNO4 or Amm. Cu2CI2

To separation a mixture of alkane, alkene and alkyne-1

The mixture is passed through amm. Cu 2CI2 or amm. AgNO3 where alkyne-1 are retained in it
and alkane, alkene mixture comes out. The mixture is then passed through conc. H 2SO4 which
absorbs alkene and alkane comes out.

General Methods of Preparation of Alkenes

Dehydration of alcohols :

Heating most alcohols is a general method of preoarationof alkenes. Heating alcohols with a
strong acid causes them to lose a molecule of water (to dehydrate) and form an alkene.

The reaction is an elimination and is favoured at higher temperatures. The most commonly
used acids in the laboratory are Bronsted acids - proton donors such as sulphuric acid and
phosphoric acid. Lewis acids such as alumina (Al2O3) are often used in industrial, gas phase
dehydrations.
Dehydration reactions of alcohols show several important characteristics which shall be
explained.
?The experimental conditions-temperature and acid concentration-that are required to bring
about dehydration are closely related to the structure of the individual alcohol. Alcohols in
which the hydroxyl group is attached to a primary carbon (primary alcohols) are the most
difficult to dehydrate. Dehydration of ethanol, for example, requires concentrated sulphuric
acid and a temperature of 180C.

Secondary alcohols usually dehydrate under milder conditions. Cyclohexanol, for example,
dehydrates in 85% phosphoric acid at 165-170C.

Tertiary alcohols are usually so easily dehydrated that extremely mild conditions can be used,
ter-butyl alcohol, for example, dehydrates in 25% H2SO4 at a temperature of 85C.

Thus, overall, the relative ease with which alcohols undergo dehydration is in the following
order
Ease of Dehydration: 3 Alcohol > 2 Alcohol > 1 Alcohol
This behaviour, is related to the stability of the carbocation formed in each reaction.
Some primary and secondary alcohols also undergo rearrangements of their carbon skeleton
during dehydration.
Mechanism of Alcohol Dehydration : An E1 Reaction
The mechanism is an E1 reaction in which the substrate is a protonated alcohol (or an
alkyloxonium ion). We consider the dehydration of CH3CHOHCH3 that proceeds through a
carbonium ion intermediate. A catalytic role is assigned to the acid and O in ROH is a basic
site.

Instead of HSO4-, a molecule of alcohol could act as a base in step 3 to give ROH2+.
Because step 2 is then, the rate determining step, it is the step that determines the reactivity
of alcohols toward dehydration. The formation of a tertiary carbocation is easiest because the
free energy of activation for step 2 of a reaction leading to a tertiary carbocation is lowest.
The order of reactivity of the alcohols reflects the order of stability of the incipient carbonium
ion (3>2>1).

Carbocation Stability and the Occurrence of Molecular Rearrangements

Let us consider the rearrangement that occurs when 3,3-dimethyl-2-butanol is dehydrated

The first step of this dehydration is the formation of the protonated alcohol in the usual way.
In the second step the protonated alcohol loses water and a secondary carbocation is formed.
Next the less stable, secondary carbocation rearranges to a more stable tertiary carbocation.

The rearrangement occurs through the migration of an alkyl group (methyl) from the carbon
adjacent to the one with positive charge. The methyl group migrates with its electron pair,
i.e., as a methyl anion, -:CH3. After the migration is complete, the carbon atom that the
methyl anion left has become a carbocation and the positive charge on the carbon atom to
which it migrated becomes neutralized. Because a group migrates from one carbon to the
next, this kind of rearrangement is often called a 1,2-shift.
The final step of the reaction, is the loss of proton from the new carbocation, and the
formation of an alkene.

Path (b) leads to the highly stable tetrasubstituted alkene, and this path is followed by most of
the carbocations. Path (a) leads to the less stable, disubstituted alkene and produces the
minor product of the reaction.
The formation of the more stable alkene is the general rule (Saytzeffs rule) in the acidcatalyzed dehydration of alcohols.
Reactions involving carbocations show that rearrangements are general phenomena. They
occur almost invariably when the migration of an alkanide ion or hydride ion can lead to a
more stable carbocation. The following are examples.

Rearrangements of carbocations can also lead to the change in ring size, as the following
example shows:

Dehydrohalogenation of monohalides: ?

(a)Removal of HX from a substrate by alcoholic KOH or NaNH2

(b)This too is elimination

(c)RCH2CH2X

RCH=CH2

CH3CH2CHCH3
|

CH3CH = CHCH3 + CH3CH2CH=CH2

Major

Minor

(Cf. Saytzeff rule)

(d)The case of dehydrohalogenation shows the order:

For alkyl halides: tertiary > secondary > primary alkyl halides
For halogens in halides : iodide > bromide > chloride

Dehalogenations of dihalides:

Vicinal (or vic) dihalides are dihalo compounds in which the halogens are situated on adjacent
carbon atoms. The name geminal (or gem) dihalide is used for those dihalides where both
halogen atoms are attached to the same carbon atom.Vic-dibromides undergo debromination
when they are treated with a solution of sodium iodide in acetone or a mixture of Zn dust in
acetic acid (or ethanol).

Debromination by sodium iodide takes place by an E2 mechanism similar to that for

dehydrohalogenation.

Kolbes electrolysis :

Electrolysis of aqueous solutions of sodium or potassium salts of saturated dicarboxylic acids

gives alkene.

Partial hydrogenation of alkynes:

Hydrogenation of alkynes in presence of Lindlar catalyst gives alkenes.

CHCH

CH2=CH2

RCCH

RCH=CH2

Lindlar catalyst is Pd on CaCO3 deactivated by lead acetate which prevents further

hydrogenation.
Use of Pd or Pd-charcoal poisoned by BaSO4 and quinoline give better results. (Cram et. Al)

By heating quaternary ammonium compounds :

By Grignard reagents :

(ix)Action of Copper alkyl on Vinyl Chlorides : Vinyl chloride on alkylation with copper alkyl
form higher alkenes.
2H2C = CHCI

2H2C=CHR + CuCI2

2H2C = CHCI

2H2C=CHR + CuCI2

Properties of Alkene

Physical Properties of Alkenes :

All are colourless & have no characteristic odour. Ethene has pleasant smell.
Lower members (C2 to C4) are gases, middle one (C3 to C17) are liquids, higher are solids.
The boiling points, melting points, and specific gravities show a regular increase with increase
in molecular weight, however less volatile than corresponding alkanes.
A cis isomer has high boiling and melting point than trans isomer because of more polar
nature.
Like alkanes, these too are soluble in non polar solvents.
Alkenes are weak polar. The polarity of cis isomer is more than trans which are either non
polar or less polar. (e.g. trans butene-2 is non polar; trans pentene-2 is weak polar).

Chemical Properties of Alkenes:

Alkenes are highly reactive due to unsaturation. The double bond consist of a strong and a
weaker bond. The electrons are loosely held and are easily polarized on the need of an
attacking reagent as a result of electromeric effect. This gives rise to the formation of

C+ & C- centres at the unsaturation point provide sites for electrophilic additions
The reactivity order for alkenes has been given as:
CH2==CH2 > R-CH==CH2 > RCH==CHR > Cis R2C == CHR > trans-R2C == CR2
The reactivity order of alkenes has been dealt in terms of heat of hydrogenation of alkene.
More is heat of hydrogenation (H = -ve), more is reactivity of alkene. The reactivity of alkene
is however also related to
1.

Steric effect

2.

Hyper conjugation

3.

Heat of combustion

Conversion to Alkanes

?
The relative rates of hydrogenation
H2C=CH2 > RCH=CH2 > R2C=CH2, RCH=CHR > R2C=CHR > R2C=CR2
Indicate that the rate is decreased by steric hindrance.

Electrophilic Addition Reactions

Table shows the results of electrophilic addition of polar reagents to ethylene.

Reagent

Product

Name

Structure

Name

Structure

Halogens (Cl2, Br2 only)

X:X

Ethylene dihalide

CH2XCH2X

Hydrohalic acids

H:X

Ethyl halide

CH3CH2X

Hypohalous acids

X:OH

Ethylene halohydrin

CH2XCH2OH

Sulfuric acid (cold)

H:OSO2OH

Ethyl bisulfate

CH3CH2OSO3H

Water (dil. H3O+)

H:OH

Ethyl alcohol

CH3CH2OH

Borane

H2B:H

Ethyl borane

(CH3CH2BH2)
(CH3CH2)3B

Peroxyformic acid

H:O - OCH = O

Ethylene glycol

CH2OHCH2OH

(HCO3H)
1.

Addition of Hydrogen Halides to Alkenes ?

Hydrogen halides (HCl, HBr and HI) add to the double bond of alkenes : >C=C< + HX >CHCX<
Mechanisms for addition of hydrogen halide to an alkene involves the following two steps :

The addition of HBr to some alkenes give a mixture of the expected alkyl bromide and an
isomer formed by rearrangement.

With this understanding of the mechanism for the ionic addition of hydrogen halides to
alkenes, a statement can be made :
In the ionic addition of an unsymmetrical reagent to a double bond, the positive portion of
the reagent attaches itself to a carbon atom of the double bond so as to yield the more stable
carbocation as intermediate. Because this is the step that occurs first, it is the step that
determines the overall orientation of the reaction.
When HI is added to 1-butene the reaction leads to the formation 2-iodobutane, that contains
a stereocenter.

The product, therefore, can exist as a pair of enantiomers. The carbocation that is formed in
this first step of the addition is trigonal planar and is achiral. When the iodide ion reacts with
this flat carbocation, reaction is equally likely at either face. The reaction leading to the two
enantiomers occur at the same rate, and the enantiomers, therefore, are produced in equal
amounts as a racemic form.
Markovnikovs Rule: Arrording to thies rule negative part of the addendum (adding
molecule) gets attached to that carbon atom which possesses lesser number of hydrogen
atoms.

So according to Markonikovs rule, during addition of hydrogen halide to alkene, the hydrogen
does to that double bonded carbon atom which contains greater number of H atoms already
attached to it while the halide ion goes to the one which contians leseer number of H atoms
alredy attached to it.
i.e. CH3-CH=CH2+ HX CH3-CH(Br)-CH3

Mechanism of Markonikovs Addition:

Refer following Video for Markonikovs Addition

Effect of Peroxide( Markonikovs Addition):
In presence of peroxides addition of HX to alkenes takes place contarary to Markonikovs
Rule.This happens only with HBr and not HCl and HI

Mechanism of Aniti-Markonikovs Addition: Follows free radical

mechanisms.
Peroxide effect proceeds via free radical chain mechanism.

2.

Addition of Bromine And Chlorine To Alkenes

Alkenes react rapidly with bromine at room temperature and in absence of light. If bromine is
added to an alkene, the red-brown colour of the bromine disappears almost instantly as long
as the alkene is present in excess. The reaction is one of addition .

Oxidation of Alkenes:

1. Combustion : The combustion of alkenes is also exothermic with high calorific values and
thus used for welding purposes in oxy-ethylene welding.
CH2=CH2 + 3O2 2CO2 + 2H2O; H = -ve

CnH2n + (3n/2)O2 nCO2 + nH2O; H = -ve

2. Oxidation by Baeyers' reagent or hydroxylation : A test for unsaturation
Alkenes on passing through dilute alkaline, 1% cold KMnO 4 (i.e. Baeyers reagent) decolorize
the pink colour of KMnO4 and forms dihydroxy compounds (e.g. glycols)

3. Oxidation by alkaline KMnO : Oxidation of alkenes by hot alkaline KMnO gives

4

two acid salts showing fission of C=C bond

RCH=CHR'

RCOOK + R'COOK
alk. KMnO

4. Oxidation by acidic KMnO4 or K2Cr2O7 :

Oxidation of alkenes by acidic KMnO 4 or K2Cr2O7 gives carboxylic acids. If HCOOH is acid, it is
further oxidized to CO2 & H2O.

CH3-CH = CH2
RCH = CHR'

CH3COOH + HCOOH
RCOOH + R'COOH

Same products are obtained if oxidation is made by per iodic acid or lead tetra acetate.
The nature of acid formed decides the position of unsaturation in molecule.
Note : Alkenes on oxidation by osmium tetraxide gives an intermediate product which on
refluxing with NaHSO3 (alc.) gives glycols.

Ozonolysis of Alkenes

Ozonolysis of alkenes : A test for unsaturation in molecule.

A more widely used method for locating the double bond of an alkene involves the use of
ozone (O3). Ozone reacts vigorously with alkenes to form unstable compounds called initial
ozonides, which rearranges spontaneously to form compounds known as ozonides. Ozonides,
themselves are unstable and reduced directly with Zn and water. The reduction produces
carbonyl compounds that can be isolated and identified.

(a)On passing ozone through a solution of alkenes in inert solvent i.e. CHCI 3 or CCI4 or ether,
addition of ozone takes place round double bond of alkene to form ozonides.
(b)The mono ozonides are highly explosive in nature and are generally decomposed during
hydrolysis or by reduction with hydrogen in presence of catalyst to give two molecules of
carbonyl compounds.
(c)The complete process of ozonide formation (step a) and then their decomposition to give
carbonyl compounds (step b) is known as ozonolysis.
(d)The ozonolysis thus involves the replacement of an olefinic bond C=C by two carbonyl
groups C =O. The total number of carbon atoms in two carbonyl compound is equal to total
number of carbon atoms in alkene.
(e)The ozonolysis is used to detect the position and nature of unsaturation in a molecule. For
this purpose first ozonides are formed. The solution is evaporated to get the ozonides as
viscous oil which are then either hydrolysed directly with water using Zn dust as reducing
agent or reduced by H 2 is presence of Pd or Pt. The Zn dust used during hydrolysis checks the
formation of H2O2which can otherwise oxidize the products (carbonyl compounds) to
respective acids. Identification of aldehydes & ketones formed during ozonolysis suggests the
nature & position of unsaturation in molecule.
(f)A symmetrical alkene give rise to two molecules of same carbonyl compound.
Examples:

An alkene of the type RCH=CHR gives two aldehydes RCHO & RCHO

An alkene of the type R2C = CHR gives R2C = O + RCHO

An alkene of the type R2C=CR2 gives ketones only R2C=O&R2C=O
Reduction of ozonide can also be made by Zn/Acid, H2-Raney Ni or triphenyl phosphine to
carbonyl compounds.
Reduction of ozonide by LiAIH4 or sodium borohydride gives corresponding alcohols.

Isomerization of alkenes

Alkenes on heating to 500 to 700 oC or on heating in presence of catalyst {AICI 3 or AI2(SO4)3}

undergo isomerization. The isomerisation involves migration of olefinic bond or alkyl group.
CH3CH2CH = CH2
butene-1

CH3CH=CHCH3 or (CH3)2C=CH2
butene-2

isobutene

Allylic substitution of alkenes

The alkyl group of the alkene (except C 2H4) undergoes substitution at high temperature in
presence of CI2 or Br2.
It is free radical substitution
The substitution occurs at acarbon to the double bond.
CH3CH=CH2 + CI2
CH3CH2CH=CH2 + CI2

CH3CICH=CH2 + HCI
CH3CHCICH = CH2 + HCI

Note :At normal temperature halogens show addition reactions with alkenes.

Wohl-Ziegler bromination. (Allylic bromination with

NBS)

Oxy-mercuration-demercuration

?Alkenes react with mercuric acetate in the presence of water to give hydroxymercurial
compounds which on reduction yield alcohols.
The first stage, oxymercuration, involves addition of -OH and HgOAc to the C-C double bond.
Then, in demercuration, HgOAc is replaced by H. The reaction sequence amounts to
hydration of the alkene, but is much more widely applicable than direct
hydration. Oxymercuration-demercuration gives alcohols corresponding to Markovnikov
addition of water to the carbon-carbon double bond. For example :

Heats of Hydrogenation of Alkenes:

Hydrogenation provides a way to measure the relative stabilities of certain alkenes. The
reaction of an alkene with hydrogen is an exothermic reaction; the enthalpy change involved
is called the heat of hydrogenation. Most alkenes have heats of hydrogenation near - 30 kcal
mol-1.
For example,

In each reaction the product is the same. A different amount of heat is evolved in each and
this difference is related to different relative stabilities of the individual butenes. 1-Butene
evolves the greatest amount of heat when hydrogenated, and trans-2 butene evolves the
least. Hence, 1-butene must have the greatest potential energy and be the least stable
isomers. Trans - 2 butene must have the lowest P.E and be the most stable isomer.

Hydroboration-Oxidation

With the reagent diborane, (BH 3)2, alkenes undergo hydroboration to yield alkylboranes, R 3B,
which on oxidation gives alcohols. For example:

The hydroboration oxidation process gives products corresponding to anti-Markovnikov

addition of water to the C-C double bond. This reaction is free from rearrangement.
Examples :

Dienes or Diolefins or Alkadienes

Hydrocarbons having two double bonds ae known as alkadienes. Alkadienes are classified into
three categories on the basis of location of two double bonds.
Cumulative dienes: Two double bonds are on adjacent carbon atoms e.g.
CH2 = C = CH2 allene or 1, 2-propadiene
Conjugated dienes: Molecules having alternate single & double bonds e.g.
CH2 = CH-CH = CH2 buta-1, 3-diene
Isolated diene : Molecules having two double bonds separated by more than one single
bond.
CH2=CH-CH2-CH=CH2

1, 4-pentadiene

CH=CH-CH2-CH2-CH=CH2

1, 5-hexadiene

Among the three types of dienes, conjugated alkadienes have some characteristic nature and
undergo addition reactions in a peculiar manner. The simplest conjugated alkadiene is buta-1,
3-diene. It has following note worthy features.
All carbon atoms in CH2=CH-CH=CH2 (buta-1, 3-diene) are sp2 hybridized

The delocalization of electrons results in resonance in molecule to show extra stable nature
than corresponding non conjugated alkadienes (Resonance energy of buta-1, 3-diene is 3 kcal
mol-1)
CH2=CH-CH=CH2 CH2+ -CH=CH-CH2 CH2-CH=CH-CH2
The addition of H2, Br2 or HBr ........ etc on conjugated alkadienes takes place in two ways
either 1, 2 or 1, 4-addition.

Non ionizing solvent favours 1, 2-addition whereas ionizing solvent favours 1, 4-addition.
However in each case mixture of both type of addition products are formed, the one
predominating on the other as the case may be.
It undergoes polymerization in presence of peroxides to give polybutadiene (Buna Rubber).
nCH2=CH-CH=CH2

(CH2-CH=CH-CH2)n
Buna rubber

Uses of Alkenes:

1.

In plastic formation i.e., polyethene, polypropene etc. and synthetic rubber formation.

2.

In oxy-ethylene welding.

3.

As food preservatives (C2H4) and ripening of fruits.

4.

As general anesthetic (C2H4 with 10% O2)

5.

In preparation of mustard gas An oily liquid having high vaporizing tendency. Its
vapours have high penetrating power and penetrate even thick boots and causes painful
blisters on skin as well as inside the body, causing death ultimately. It was used I world war.

Methods of Preparation of Alkynes

Acetylene itself is formed from the reaction of the inorganic compound calcium carbide with
water.
CaC2 + 2 H2O Ca(OH)2 + HCCH
This method was once an important industrial process for the manufacture of acetylene.
However, the method has now been replaced by a process in which methane is pyrolyzed in a
flow system with short contact time.

This reaction is endothermic at ordinary temperatures, but is thermodynamically favored at

high temperatures.

Laboratory Methods of Preparation of Alkynes:

1.

Dehydrohalogenation of vic-Dihalides or gem-Dihalides

2.

Dehalogenation of vic-Tetrahalogen Compounds

This reaction has the drawback that the halogen compound is itself prepared by halogen
addition to alkynes.
3.

Alkyl Substitution in Acetylene; Acidity of

There is a fair amount of variety possible using this method. Acetylene itself may be alkylated
either once to make a terminal alkyne or twice to make an internal alkyne.

Since acetylide ions are highly basic, competing elimination is a common side reaction.
The products of such an elimination reaction are an alkene (from the alkyl halide) and an
alkyne.

In practice, the alkylation of acetylene or another terminal alkyne is only a good method for
the synthesis of alkynes when applied to primary halides that do not have branches close to
the reaction centre. With secondary halides, and even with primary halides that have
branches close to the reaction center, elimination is usually the major reaction.

Industrial Method for preparation of alkynes:

old method :

2C + H2

Modern method :
or

C2H2 (Bertholots reaction)

6CH4 + O2
2CH4

2CHCH + 2CO + 10H2

CHCH + 3H2

Preparation of higher alkynes : Higher alkynes may be obtained b acetylene.

a) CHCH + Na

CHCNa + 1/2H2

CHCNa + RX CHCR + NaX

RX
b) CHCH + RMgX XMg-CCH R-CCH + MgX2

Some Other General

Alkynes:

Methods of Preparation of

1. By Haloform : Only for acetylene

CHX3 + 6Ag + X3HC

CHCH + 6AgX

Powder

2. By Kolbe's electrolytic method :

Properties of Alkynes:

Physical Properties of Alkynes :

The physical properties of alkynes are similar to those of the corresponding alkenes. The lower
members are gases with boiling points somewhat higher than those of the corresponding
alkenes. Terminal alkynes have lower boiling points than isomeric internal alkynes and can be
separated by careful fractional distillation.
The CH3-C bond in propyne is formed by overlap of a C sp -hybrid orbital from the methyl carbon
with a Csp-hydrid from the acetylenic carbon. The bond is C sp -Csp. Since one orbital has more scharacter than the other and is therby more electronegative, the electron density in the
resulting bond is not symmetrical. The unsymmetrical electron distribution results in a dipole
moment larger than that observed for an alkene, but still relatively small.
3

CH3CH2CCH

CH3CH2CH=CH2

CH3CCCH3

m = 0.80 D

m = 0.30 D

m=0D

Chemical Properties of Alkynes

An alkyne molecule (except ethyne) has three parts

R- CC-H
R-

-CC-

-H

Alkyl part

Alkyne part

Acidic Hydrogen

Alkyl part : The alkyl part being inert in alkyne & thus does not show substitution reaction.
Alkyne part : It consists of one & 2 bonds. Due to more strain than alkene, bonds are
highly reactive and less stable. The polarization of bonds in alkynes leads to addition
reaction. Unlike alkene, alkyne reacts with two molecules of additive to form saturated
molecule.
Acidic hydrogen part : H atom attached to sp hybridized carbon or triply bonded carbon
atom is acidic in nature. The acidic character is due to the fact than an increase in s character
of carbon atom give rise to higher electonegativity to it and thus H atom attached on sp
hybridized carbon acquires polarity to show acidic nature.
Type of Bonds

C-H

s character
Thus

=C-H

50% or 1/2
R-CC-H+ + Base

33.3% or 1/3

-C-H
25% or 1/4

R-CC- + H-Base

The hybridized carbon atom being more electronegative, is best able to accommodate the
electron pair in the anion left after the removal of proton.
Relative acidic nature :

HOHHOR > HCCR > HNH2 > H2C=CH2 > CH3-CH3

Relative basic nature :

OH-OR- < CCR < NH2 < CH=CH2 < CH2-CH3

Acidity of Alkynes

The hydrogens in terminal alkynes are relatively acidic. Acetylene itself has a pKa of about 25.
It is a far weaker acid that water (pKa 15.7) or the alcohols (pKa 16-19), but it is much more
acidic than ammonia (pKa 34). A solution of sodium amide in liquid ammonia readily converts

acetylene and other terminal alkynes into the corresponding carbanions. RCCH + NH2
RC C + NH3
This reaction does not occur with alkenes or alkanes. Ethylene has a pK a of about 44 and
methane has a pKaof about 50.
From the foregoing pK'as we see that there is a vast difference in the stability of the
carbanions RC C, CH2 = CH, and CH3. This difference may readily be explained in terms of
the character of the orbital occupied by the lone-pair electrons in the three anions. Methyl
anion has a pyramidal structure with the lone-pair electrons in an orbital that is
approximately sp3(1/4 s & p). In vinyl anion the lone-pair electrons are in ansp2- (1/3 s &
2/3 p).orbital . In acetylide ion the lone pair is in an sp-orbital (1/2 s & 1/2 p).

Electrons in s-orbitals are held, on the average, closer to the nucleus than they are in porbitals. This increased electrostatic attraction means that s-electrons have lower energy and
greater stability than p-electrons. In general, the greater the amount of s-character in a hybrid
orbital containing a pair of electrons, the less basic is that pair of electrons, and the more
acidic is the corresponding conjugate acid.

Of course, the foregoing argument applies to hydrogen cyanide as well. In this case, the
conjugate base, NC, is further stabilized by the presence of the electronegative nitrogen.
Consequently, HCN is sufficiently acidic (pK a 9.2) that it is converted to its salt with hydroxide
ion in water. HCN + OH CN + H2O
Alkynes are also quantitatively deprotonated by alkyllithium compounds, which may be
viewed as the conjugate bases of alkane: CH3(CH2)3CCH + n-C4H9Li CH3(CH2)3CCLi + n-C4H10
The foregoing transformation is simply an acid-base reaction, with l-hexyne being the acid
and n-butyllithium being the base. Since the alkyne is a much stronger acid than the alkane
(by over 20 pK units), equilibrium lies essentially completely to the right.
Terminal alkynes give insoluble salts with a number of heavy metal cations such as Ag + and
Cu+. The alkyne can be regenerated from the salt, and the overall process serves as a method
for purifying terminal alkynes. However, many of these salts are explosively sensitive when
dry and should always be kept moist. CH3(CH2)3CCH + AgNO3 CH3(CH2)3CCAg + HNO3

Addition reactions of Alkynes :

?Nucleophilic pi electrons of alkynes add electrophiles in reactions similar to additions to

alkenes. Alkynes can add two moles of reagent but are less reactive (except to H 2) than
alkenes.
1. Hydrogenation of Alkynes :
Addition of two molecules of H2 takes place on alkyne.

However the addition of 2nd H2 molecule can be checked if Lindlar catalyst is used.
Dialkyl acetylenes may be catalytically reduced to a mixture of cis and trans alkenes, the
former is formed predominantly if Lindlar catalyst is used.

However reduction with sodium in liq. NH 3 or by LiAIH4 produces trans alkene.

2. Electrophilic addition :
Acetylenic bond in alkyne is a combination of one sigma bond and two bonds. Like alkenes,
alkynes also show characteristic electrophilic addition reactions which take place in two
stages involving the formation of olefinic intermediate. Thus alkynes shows addition of two
molecules of addendum.

However the rate of electrophilic addition in acetylene is rather show than that of ethene
inspite of the fact that alkynes has excess of pi electron. This fact is also supported than in
many of electrophilic addition reaction, presence of catalyst such as Hg 2+ ions is needed. The
low reactivity of acetylene is not yet clear.
3. Addition of Halogens :

a.

Western and westrosol are good industrial solvents for rubber, fats and varnishes.
Western also have some insecticidal action.

b.

The rate of reaction increases in presence of light.

c.

The reactivity order for halogens is : CI 2 > Br2 > I2

CH CH + Br2 CHBr = CHBr (only)
CH CH + Br2 CHBr2-CHBr2
n CCI4
CHCH + I2

CHI=CHI

in alcohol
d.

Direct combination of acetylene with chlorine may be accompanied with explosions, but
it is prevented by the presence of metallic chloride as catalyst.
e. The predominant product during addition of one molecule of halogen on alkyne in trans
isomer.
4. Addition of halogen acids :
CHCH + HX

CH2=CHX
vinyl halide

CH3-CHX2
ethylidene dihalide

The reactivity order is : HI > HBr > HCI

Acetylene reacts with dil HCI in presence of Hg 2+ at 65oC to give vinyl chloride, used in
preparation of poly vinyl chloride, a synthetic polymer.
CHCH + dil. HCI CHg2 + CH2=CHCI
Note :
1.

Peroxides have the same effect on the addition of HBr to unsymmetrical alkynes as
they have on alkenes.
2. Because of -I effect of the bromine atom, the availability of the electrons during the
second molecule addition becomes much slower than ethylene.
5. Addition of hypohalous acids :

Note :
1.

Presence of two or more OH gp on one carbon atom makes it unstable and the
molecules loses H2O molecule.

2.

However two exceptions to this rule; one is chloral hydrate CCI 3CH(OH)2and the other is
carbonic acid
Chloral hydrate is extra stable inspite of two OH gp on one
carbon atom due to H-bonding.

6. Addition of AsCI3 :
CHCH + AsCI3

CHCI=CHAsCI2

bchlorovinyl dichloroarsenic (Lewsite),

A poisonous gas, more poisonous than mustard gas

7. Addition of HCN :

8. Addition of acetic acid :

9. Addition of CO and H2O :

10. Polymerisation or self addition : Alkynes undergo polymerization yielding different

types of polymeric compounds under different conditions.
(a) Cyclic polymerization :

(b) Linear Polymerisation :

Vinyl acetylene on reaction with HCI forms 2-chloro, 1, 3-butadiene (or chloroprene) which on
exposure to air polymerizes to give synthetic rubber neoprene

Note : Acetylene on heating with spongy copper or its oxide gives a cork like substance, used
in manufacture of linoleum.
11. Addition of H2SO4 :
CHCH + H2SO4
(cold & conc.)

CH2=CHHSO4
vinyl hydrogen
sulphate

CH3CH(HSO4)2
Ethylidine dihydrogen
sulphate

The above reaction can also be made as:

Vinyl alcohol CH2=CHOH, which is rapidly converted into an equilibrium mixture that is almost
CH3CHO is an example of keto-enol tautomerism.

Note : Only C2H2 on addition of H2O gives aldehyde and rest all alkynes give ketone.
12. H2O (Hydration to Carbonyl Compounds): When passed into dilute sulphuric acid at
60oC in the presence of mercuric sulphate as catalyst, acetylene adds on one molecule of
water to form acetaldehyde. The mechanism of this hydration takes place via the formation of
vinyl alcohol as an intermediate.

The homologues of acetylene form ketone when hydrated, example, propyne gives acetone

13. Addition of Boron Hydride

with dialkylacetylenes, the products of hydrolysis and oxidation are cis-alkenes and ketones,
respectively

Ozonolysis :

Addition of O3 on alkynes gives their monoozonides which on hydrolysis forms dicarbonyl

compounds which are further oxidized to carboxylic acids.
In alkenes two molecules of carbonyl compounds are formed during ozonolysis and in alkyne
one molecule of dicarbonyl compound is formed which is further oxidized to two acids.

Oxidation of Alkynes:

1. Combustion : CnH2n-2 + (3n-1)/2O2 nCO2 + (n-1)H2O; H = -ve

2. Oxidation by alkaline KMnO4 :

R-CCH + 4[O] RCOOH + HCOOH

3. Oxidation by H2CrO4 or acidified K2Cr2O7 :
CHCH + O + H2O CH3COOH
R-CCH + O + H2O RCH2COOH
4. Oxidation by acidified KMnO4 :
CHCH + 3[O] + H2O 2HCOOH
R-CCH

H2O + CO2

RCOOH + HCOOH

5. Oxidation by selenium dioxide :

CH3-CCH

CH3COCHO
2-ketopropanal

Isomerization of Alkynes:

Action of N2 to Alkynes:

CHCH + N2

2HCN

Formation of heterolytic compounds :

Nucleophilic addition :

Acetylene undergoes nucleophilic addition with CH3OH in presence of CH3ONa.

Substitution reaction :

Acetylene on passing through sodium hypochlorite solution at 0 oC in absence of light shows

substitution of H by chlorine atom.
1. Formation of sodium acetylide or alkynides :

2. Formation of Acetylenic Grignard reagent :

CHCH + R MgX CHCMgX
3. Formation of copper alkynides : on passing alkynes through ammoniacal cuprous
chlorides solution, a red precipitate of cuprous alkynide is obtained.

4. Formation of silver alkynides : On passing alkynes through ammoniacal silver nitrate

solution (Tollens reagent) a white precipitate of silver alkynides is obtained
CHCH + 2AgNO3 + 2NH4OH AgCCAg + 2NH4NO3 + 2H2O
silver acetylide
while ppt.)
RCCH + AgNO3 + NH3OH RCCAg + NH4NO3 + H2O
Note :
1.

These alkynides are ionic in nature

2.

Alkynides are generally explosive and unstable when dry.

3.

Copper and silver alkynides are very sensitive to shock when dry & may explode

4.

These alkynides are easily converted to original alkynes when treated with dilute
acids.NaCCNa + 2HNO3 HCCH + 2NaNO3

5.

Acidic nature of alkyne can be utilized to separate, purify and identify alkyne-1 from
other hydrocarbons.

Uses of Alkynes :
1.

Among alkynes, acetylene has got wide applications in industries.

2.

As oxy-acetylene flame for welding.

3.

As illuminating agent in hawker's lamps and light houses.

4.

In artificial ripening of fruits.

5.

6.
7.
8.

In preparation of monomeric unit (vinyl chloride, vinyl cyanide, vinyl cyanide, vinyl
acetate, vinyl acetylene, etc.) to get polymers (PVC, PVA, chloroprene, Buna-S etc.)
widely used in textile, plastic, shoe and rubber industries.
In preparation of poisonous gas, Lewiste.
In preparation of solvents such as westron, westrosol and other useful chemicals e.g.,
C6H6, acetaldehyde, acetone etc.
It is used as general anesthetic under the name Naracylene

Aromatic Hydrocarbons
The term aromatic (Greek; aroma means fragrance) was first used for compounds having
pleasant odour although the structure was not known. Now the term aromatic is used for a
class of com

pounds having a characteristic stability despite having unsaturation. These may have one or
more benzene rings (benzenoid) or may not have benzene ring
(non-benzenoid). Benzenoid compounds include benzene and its derivatives having aliphatic
side chains (arenes) or polynuclear hydrocarbons, eg. naphthalene, anthracene, biphenyl etc.

Structure of Benzene

Benzene has been known since 1825 when it was first isolated by Michel Faraday. Form
elemental analysis and molecular mass determination, it was found that the molecular
formula of benzene is C6H6 indicating high unsaturation. However, benzene does undergo
addition reactions in contrast to unsaturated hydrocarbons, although it mainly undergoes
substitution reactions.
In 1865 Friedrich August Kekule proposed a ring structure for benzene (I). However, many
alternative structures have been proposed from time to time by different workers. (II-IV).

Then main objection against Kekule structure was that it should yield two ortho disubstituted
products when it reacts with bromine. However, experimentally benzene was found to yield
only one product.
Kekule removed this objection by proposing that the double bonds in benzene are
continuously oscillating back and forth between two adjacent positions. Since positions of
double bonds are not fixed, only one product is formed. This structure came to be known as
Kekules dynamic formula, which formed the basis for the present electronic structure of
benzene.

Stability of Benzene (Resonance)

Benzene resists addition whereas it readily undergoes substitution reactions, like nitration,
halogenation etc. This indicates that benzene is more stable than the hypothetical
cyclohexatriene molecule. This has been proved by the fact that the enthalpies of
hydrogenation and combustion of benzene are lower than expected. Enthalpy of
hydrogenation is the change in enthalpy when one mole of an unsaturated compound is
hydrogenated. It has been found experimentally that enthalpy of hydrogenation for
disubstituted alkenes, R-CH=CH-R varies between 117-125 kJ mol -1. Accordingly, the values for

cyclohexene and cyclohexa-1, 3-diene and hypothetical cyclohexa-1, 3, 5-triene were

calculated compared with their experimental values.
While the experimental values of enthalpy of hydrogenation for cyclohexene is similar to the
value expected, the variation in the case of cyclohexa-1, 3-diene is small and is due to
delocalization. The expected value of enthalpy of hydrogenation of benzene is much higher
than the corresponding calculated value for hypothetical cyclohexa-1, 3, 5-triene indicating
that benzene does not have this type of structure.
X-ray studies show that it is planar molecule and that all six C-C bonds in benzene are of
equal length (139 pm), intermediate between C-C single bond (154 pm) and C=C (134 pm).
All six carbons are sp2 hybridized and all bond angles are 120 o. Benzene is a hybrid of various
resonating structures, the two Kekule structures A and B, being the main contributing forms.

Aromaticity in Benzene and Related Systems

After the structure of benzene was established, the term aromatic was adapted for such
compounds which despite having p bonds (unsaturation) resist addition and instead undergo
substitution. The aromaticity in benzene is attributed to the six delocalized pi electrons in the
coplanar carbon hexagon. When a bonding orbital is not restricted to two atoms but is spread
over more than two atoms, e.g. six in benzene, such bonding orbitals are said to be
delocalized. Delocalisation results in greater stability.
The modern theory of aromaticity was advanced by Eric Huckel 1931. Aromaticity is a function
of electronic structure. Any polynuclear compound, heterocyclic rings or cyclic ions may be
aromatic if these have a specific electronic structure. The important features of the theory are
1. Delocalization: Complete delocalization of p electron cloud of the ring
necessary requirement for aromatic character.

system is a

2. Planarity: Complete delocalization of p-electron cloud is possible only if the ring is planar.
This is the reason that benzene is aromatic but cyclooctatetraene is not, since the latter is not
a planar molecule.
Huckels rule or (4n + 2)p electron rule:
The rule states that in a conjugated, planar, cyclic system if the number of delocalized pelectrons is (4n + 2) where n is an integer, i.e., 1, 2, 3 etc. Benzene, naphthalene, anthracene
and phenanthrene are aromatic as they contain (4n + 2)p electrons i.e. 6, 10, 14, p electrons
in a conjugated cyclic system. The cyclopentadiene and cyclooctatetraene are non-aromatic
as instead of (4n + 2)p e-these have 4n p e-. Moreover, they are non-planar.

Benzene was first isolated by Faraday from cylinders of compressed illuminating gas obtained
from the pyrolysis of whale oil.
Benzene was first synthesised by Berthelot by passing acetylene through a red hot tube.

In the laboratory it was first prepared by heating benzoic acid or phthalic acid with calcium
oxide.

Properties of Benzene:
1.

It is a colourless liquid with boiling point of

2.

It is inflammable, burning with a smoky flame due to high carbon content.

3.

It

is

slowly

attacked

by

acid

permanganate

4.

5.

Reaction of Benzene:

Major reactions of benzene ring are electrophilic substitution reactions.

to

form

1. Nitration of Benzene:
(i) Formation of electrophile

(base) (acid)

(nitronium ion)

(ii) Electrophilic attack by

In the intermediate, attacked carbon atom changes its state of hybridization from trigonal to
tetrahedral.

(iii) Loss of proton :

2. Friedel Craft Alkylation:

This reaction involves the introduction of alkyl group into benzene ring in presence of catalyst.
The alkylating agent may be R X, ROH or alkene. The catalyst is a Lewis acid,

Mechanism:

Step I:
Formation of electrophile (carbonium ion) stability order of carbonium ion is

with RX

With ROH:

With alkene:

Step II:

Step III:

Examples:

or

carbonium ion.

This is an example of intermolecular Friedel Craft alkylation. But if the side chain contains four
or five carbons with halogen at the end then it may undergo intramolecular Friedel Craft
reaction.

3.

Friedel Craft Acylation:

Replacement of
of benzene by
group using carboxylic acid, esters, acid chloride or
acid anhydride as acylating agent in the presence of Lewis acid.

Mechanism:
(i)

(II) is more stable than (I) because each atom has a complete octet.
(ii)

(iii)

Examples:

Reactions of side chains

1. Halogenation:

With

in presence of

undergoes electrophilic substitution at o- and p- position and in the

absence of
and in the presence of light or high temperature undergoes substitution in
the side chain (free radical substitution).

Toluene

1. Halogenation of Toluene:
For side chain halogenation, case of abstraction of hydrogen atom is as follows:

the stability order of free radicals is

Bromine is more selective than chlorine.

2. Oxidation of Toluene:
Benzene ring is usually very resistant to oxidation, hence the side chain is always attacked.
Whatever the length of side chain the ultimate oxidation product is benzoic acid.

When two side chains are present, it is possible to oxidize them at same time.

But, if the C attached to benzene ring does not have any hydrogen then it will not give
benzoic acid.

When an electron withdrawing group (-I and / or R) is present, the ring is stable and the
result of oxidation is a substituted benzoic acid.

If OH or
is present, the ring is very sensitive to oxidation and is largely broken down,
whatever be the nature of oxidizing agent. Ring rupture can be prevented by protection of the
group.

Alkenyl Bemzene

Alkenyl benzenes contain a double bond in the side chain of benzene ring e.g.

These compounds are prepared as follows:

The reactivity of the double bond is greater than the benzene towards electrophilic reagents.
Thus mild conditions are required for the addition reaction across the double bond as
compared to those required for the benzene ring.

First step is the formation of carbocation or free radical.

The higher stability of benzyl cation or radical relative to the conjugated alkenyl benzene
makes the latter more reactive than simple alkenes.

In the presence of peroxides, the reaction taking place is (peroxide effect) as follows.