HYDROCARBONS

ALKANES
Methods of preparation
1. From unsaturated compounds- Alkenes and alkynes when hydrogenated with
hydrogen in the presence of metallic catalysts like nickel, palladium, platinum etc gives
alkanes. Platinum and palladium catalyse the reaction at room temperature while nickel
requires higher temperature and pressure. The reaction is called as Sebatier and
Senderen’s reaction.

2. From alkyl halides-

a) Alkyl halides when reduced with reducing agents such as H2 /Pd or nascent hydrogen
obtained from Zn and HCl gets converted to alkanes with the same number of carbon
atoms as the starting alkyl halide.

b) Wurtz reaction-Alkyl halides on heating with metallic sodium in ether medium gives
alkanes with double the number of carbon atoms as the starting alkyl halide.(Step-up
reaction).(Ether medium is used in order to prevent the explosive reaction of sodium
when it comes in contact with water and air and also to prevent the hydrolysis of alkyl
halide).The reaction follows free radical mechanism and new bonds are always formed
between α carbon atoms. Generally the alkyl halides used are the same otherwise it
leads to formation of mixture of products from which separation becomes difficult.
Hence final product will always have even number of carbon atoms. Methane cannot be
prepared by this method.

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3. From carboxylic acids-
a) Soda-lime decarboxylation
Sodium or potassium salts of carboxylic acids when heated with soda-lime (NaOH and
CaO in the ratio 3:1)gives an alkane with one carbon atom less than the starting
compound.(In this rection CaO does not participate in the reaction but helps in the
fusion of the reaction mixture).

b) Kolbe’s electrolytic decarboxylation- Sodium or potassium salts of carboxylic

acids when electrolysed in aqueous medium give hydrocarbon at the anode and
hydrogen at the cathode. Byproducts involve CO2 and NaOH which remain in solution.
Thus the pH of the solution will increase as the reaction proceeds. The reaction follows
free radical mechanism and new bonds are always formed between α carbon atoms.
Methane cannot be prepared by this method.

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The reaction is supposed to follow the following path :

Physical properties of alkanes.

Lower members (C1-C4) are gases,C5-C17 are liquids and higher members are solids.
They have low boiling points which increase with the increase in the number of carbon
atoms due to increase in the magnitude of van der Waals forces. Among isomeric
alkanes, straight chain isomers will have higher boiling points thsn branched chain
isomers. This is because branching decreases surface area and hence the magnitude
of dispersion forces leading to lower boiling points. Melting points do not show a very
smooth gradation. Increase in melting point is relatively more in moving from an alkane
having odd number of carbon atoms to the higher alkane while it is relatively less in
moving from an alkane with even number of carbon atoms to the higher alkane.This is
because alkanes with even number are more symmetrical and hence fits into the crystal
lattice more perfectly leading to higher melting points. Alkanes are insoluble in polar
solvents like water but are soluble in non-polar organic solvents like ether, carbon
tetrachloride etc. All alkanes are lighter than water.
Chemical Properties
1. Substitution reactions-One or more hydrogen atoms of alkanes can be replaced by
halogens, nitro group and sulphonic acid group. Halogenation takes place either at
higher temperature (573-773 K) or in the presence of diffused sunlight or ultraviolet
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light. Lower alkanes do not undergo nitration and sulphonation reactions. These
reactions in which hydrogen atoms of alkanes are substituted are known as substitution
reactions.

Halogenation-Alkanes when treated with halogens in presence of sunlight or diffused

light gets converted into halogen compounds. Fluorination is explosive and bromination
is slow whereas iodination is reversible as the HI produced as byproduct is a very
powerful reducing agent and reduces the iodoalkane back to alkane. Iodination must be
carried out in presence of strong oxidizing agents like HIO3 or HNO3 which converts HI
to iodine and thus pushes the reaction in the forward direction.

Reactivity of halogens towards alkanes follows the order-

fluorine>chlorine>bromine>iodine. Rate of replacement of hydrogens of alkanes is :3° >
2° > 1°.

E.g. chlorination of methane.

Mechanism
(i) Initiation : The reaction is initiated by homolysis of chlorine molecule in the presence
of light or heat. The Cl–Cl bond is weaker than the C–C and C–H bond and hence, is
easiest to break.

(ii) Propagation : Chlorine free radical attacks the methane molecule and takes the
reaction in the forward direction by breaking the C-H bond to generate methyl free
radical with the formation of H-Cl,

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The methyl radical thus obtained attacks the second molecule of chlorine to form CH3 –
Cl with the liberation of another chlorine free radical by homolysis of chlorine molecule.

The chlorine and methyl free radicals generated above repeat steps (a) and (b)
respectively and thereby setup a chain of reactions.

(iii)Termination: The reaction stops after some time due to consumption of reactants
and / or due to the following side reactions .The possible chain terminating steps are:

The above mechanism helps us to understand the reason for the formation of ethane as
a byproduct during chlorination of methane.

2. Combustion.
Alkanes on burning in air or oxygen gets completely oxidized to carbon dioxide and
water with the evolution of large amount of heat.

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The general chemical equation for combustion may be written as:

Due to the evolution of large amount of heat during combustion, alkanes are used as
fuels. During incomplete combustion of alkanes with insufficient amount of air or
dioxygen, carbon black is formed which is used in the manufacture of ink, printer ink,
black pigments and as filters.

3.Controlled oxidation of alkanes gives useful products .e.g.

Ordinarily alkanes resist oxidation but alkanes containing tertiary hydrogen atoms can
be oxidized to alcohols on treatment with potassium permanganate.

4. Isomerisation-Straight chain alkanes on heating with anhydrous aluminium chloride

and hydrogen chloride gets converted into branched chain alkanes.

5. Reaction with steam-Methane reacts with steam at 1273K in the presence of nickel
as catalyst to form carbon monoxide and hydrogen (water gas).The reaction is used for
manufacture of dihydrogen.

6. Reforming or Aromatisation- is a process of conversion of aliphatic hydrocarbons

into aromatic hydrocarbons in the presence of suitable catalysts.

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7. Cracking or Pyrolysis- is a process of decomposing higher hydrocarbons into lower
hydrocarbons with low boiling points by strong heating.

ALKENES OR OLEFINS
Alkenes are unsaturated hydrocarbons containing at least one double bond. General
formula for alkenes is CnH2n.

Methods of preparation.
1. Dehydrohalogenation of alkyl halides-Alkyl halides when treated with alcoholic
KOH undergoes α-β elimination to form alkenes. In case more than one product is
formed, the major product will be according to saytzeff’s rule. Nature of halogen atom
and the alkyl group determine rate of the reaction. It is observed that for halogens, the
rate is: iodine > bromine > chlorine, while for alkyl groups it is : tertiary > secondary >
primary.

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2. Dehydration of alcohols in acidic medium-Alcohols when treated with acids
undergoes α-β elimination to form alkenes. In case more than one product is formed,
the major product will be according to saytzeff’s rule.

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3. Dehalogenation of vicinal dihalides-(Dihalides in which both the halogens are
attached to the same carbon are called as geminal or gem dihalides and those
attached to adjacent carbons are called as vicinal or vic-dihalides). Vicinal dihalides on
treatment with zinc metal lose a molecule of ZnX2 to form an alkene. This reaction is
known as dehalogenation.

4. By controlled hydrogenation of alkynes-Controlled hydrogenation with Lindlar’s

catalyst ( Palladised charcoal supported over barium sulphate and poisoned with
sulphur or quinoline)gives cis alkene and with sodium in liquid ammonia gives trans
alkene.

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Physical properties of alkenes.
Lower members (C1-C3) are gases,C4-C17 are liquids and higher members are solids.
They have low boiling points which increase with the increase in the number of carbon
atoms due to increase in the magnitude of vander Waals forces. Among isomeric
alkanes, cis isomers will have higher boiling points than trans- isomers. This is because
cis isomer has higher dipole moment leading to dipole-dipole attractions branching
decreases surface area and hence higher boiling points. Melting points are higher for
trans isomer because trans-alkenes with are more symmetrical and hence fits into the
crystal lattice more perfectly leading to higher melting points. Alkenes are insoluble in
polar solvents like water but are soluble in non-polar organic solvents like ether, carbon
tetrachloride etc. All alkenes are lighter than water.
Chemical properties:-
1. Hydrogenation – Alkenes when hydrogenated with hydrogen in the presence of
metallic catalysts like nickel, palladium, platinum etc gives alkanes.

2. Addition of halogens-Halogens especially chlorine and bromine add on alkenes to

form di-halogen derivatives. (The reaction is used to test unsaturation as the reddish
brown colour of bromine water is discharged when bromine adds up).

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3. Addition of halogen acids takes place according to Markownikov or anti-
Markownikov addition. The order of reactivity towards halogen acids is HI>HBr>HCl.

4. Addition of sulphuric acid- Cold concentrated sulphuric acid adds to alkenes

according to Markownikov’s rule to form alkyl hydrogen sulphate.

5. Additon of water-water adds to alkenes in presence of dilute mineral acids

according to Markownikov’s rule to form alcohols.

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 6.

Reaction with KMnO4-Cold dilute alkaline KMnO4 is called as Baeyer’s reagent and is
a hydroxylating agent. It converts alkenes to glycols (diols). Decolorisation of KMnO 4
solution is used as a test for unsaturation.

Reaction with KMnO4 under drastic conditions-Under drastic conditions acidic

KMnO4 cleaves the double bond and gives different products depending on the groups
attached to the carbon-carbon double bond.

E.g.

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7. Ozonolysis- refers to addition of ozone followed by hydrolysis with Zn/H2O to
produce carbonyl compounds (aldehydes and ketones).It is a step down reaction and
proceeds via the formation of an ozonide intermediate. Symmetrical alkenes give one
type of product whereas unsymmetrical ones give more than one product. From the
products of ozonolysis it is possible to locate the position of the double bond. (Remove
the two oxygens of carbonyl compounds and join them by a double bond). Thus this
reaction is highly useful in detecting the position of the double bond in alkenes or other
unsaturated compounds.

E.g.

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8. Polymerisation- is the process in which a large number of simple molecules
( monomers) combine under suitable conditions to form a large molecule called as a
macromolecule or polymer. e.g. Ethene or ethylene polymerises at high pressure and
temperature to form polythene or polyethylene.

ALKYNES
Alkynes like alkenes are also unsaturated hydrocarbons. They contain at least one triple
bond between two carbon atoms. The number of hydrogen atoms is still less in alkynes
as compared to alkenes or alkanes. Their general formula is CnH2n–2
Methods of preparation:-
1. From vicinal dihalides- Vicinal dihalides when treated with alcoholic KOH
undergoes dehydrohalogenation to form alkynes.

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2. From tetrahalides- Tetrahalides when treated with zinc dust undergoes
dehalogenation to form alkynes.

3. Acetylene is conveniently prepared from calcium carbide by reaction with water.

CaC2 + H2O C2H2 + Ca(OH)2 .

4. Higher alkynes are prepared from lower alkynes like acetylene.(stepping up of alkyne
series).

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Physical properties

Lower members (C1-C3) are gases, C4-C11 are liquids and higher members are solids.
They have low boiling points which increases with the increase in the number of carbon
atoms due to increase in the magnitude of van der Waals forces.They are less volatile
than alkanes or alkenes. Alkenes are insoluble in polar solvents like water but are
soluble in non-polar organic solvents like ether, carbon tetrachloride etc. All alkynes are
lighter than water. Their melting point, boiling point and density increase with increase in
molar mass.
Chemical properties.
1.Acidic nature of terminal alkynes-Terminal alkynes behave as very weak acids and
liberate hydrogen when reacted with highly electropositive metals like sodium. Terminal
alkynes are acidic because they are attached to sp hybridized carbon atom which is
more electronegative than sp2 or sp3 hybridised carbon. Due to the maximum
percentage of s character (50%), the sp hybridised orbitals of carbon atoms in ethyne
molecules have highest electronegativity; hence, these attract the shared electron pair
of the C-H bond of ethyne to a greater extent than that of the sp 2 hybridised orbitals of
carbon in ethene and the sp3 hybridised orbital of carbon in ethane. This sp hybridized
carbon pulls the C-H bond towards itself more strongly leading to positive charge over
hydrogen atom and its eventual release as H+. Thus in ethyne, hydrogen atoms can be
liberated as protons more easily as compared to ethene and ethane. Hence, hydrogen
atoms of ethyne attached to triply bonded carbon atom are acidic in nature.

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These reactions are not shown by alkenes and alkanes, hence are used for distinction
between alkynes, alkenes and alkanes.

Alkanes, alkenes and alkynes follow the following trend in their acidic behaviour :

2. Catalytic hydrogenation.

Addition in unsymmetrical alkynes takes place according to Markovnikov rule. Majority

of the reactions of alkynes are the examples of electrophilic addition reactions.

3. Controlled hydrogenation.

3. Addition of halogens-Halogens adds across the multiple bonds of alkynes to form

tetrahalides.

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(Reddish orange colour of the solution of bromine in carbon tetrachloride is
decolourised. This is used as a test for unsaturation).

4. Addition of hydrogen halide-

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5. Addition of water-Alkynes undergoes hydrolysis in presence of mercuric ion at 333K
to form aldehydes or ketones. Addition takes place according to Markownikov’s rule to
first form an enol which undergoes tautomerism to form the carbonyl compound.

6. Cyclic trimerisation-Alkynes undergo trimerisation when passed through red hot

iron tube at 873K to form aromatic compounds.e.g. Acetylene gives benzene and
propyne gives mesitylene.

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7. Linear polymerization-Under suitable conditions ethyne undergoes linear
polymerization to form polyethyne.

AROMATIC HYDROCARBONS

These hydrocarbons are also known as ‘arenes’. Aromatic compounds containing

benzene ring are known as benzenoids and those not containing a benzene ring are
known as non-benzenoids. Some examples of arenes are:-

Physical properties-Aromatic hydrocarbons are non- polar molecules and are usually
colourless liquids or solids with a characteristic aroma. Aromatic hydrocarbons are
immiscible with water but are readily miscible with organic solvents. They burn with
sooty flame.

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 BENZENE
Structure of Benzene

The molecular formula of benzene, C6H6, indicates a high degree of unsaturation.

Benzene was found to be a stable molecule and found to form a triozonide which
indicates the presence of three double bonds. Benzene was further found to produce
one and only one monosubstituted derivative which indicated that all the six carbon and
six hydrogen atoms of benzene are identical. On the basis of this observation Kekulé
proposed the following structure for benzene having cyclic arrangement of six carbon
atoms with alternate single and double bonds and one hydrogen atom attached to each
carbon atom.

The Kekulé structure indicates the possibility of two isomeric 1, 2-dibromobenzenes. In

one of the isomers, the bromine atoms are attached to the doubly bonded carbon atoms
whereas in the other, they are attached to the singly bonded carbons.

However, benzene was found to form only one ortho disubstituted product. This
problem was overcome by Kekulé by suggesting the concept of oscillating nature of
double bonds in benzene as given below.

Even with this modification, Kekulé structure of benzene fails to explain unusual stability
and preference to substitution reactions than addition reactions, which was later
explained by resonance.

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Resonance and stability of benzene

Benzene is a hybrid of various resonating structures. The two structures, A and B given
by Kekulé are the main contributing structures. The hybrid structure is represented by
inserting a circle or a dotted circle in the hexagon The circle represents the six electrons
which are delocalised between the six carbon atoms of the benzene ring.

All the six carbon atoms in benzene are sp2 hybridized.Two sp2 hybrid orbitals of each
carbon atom overlap with sp2 hybrid orbitals of adjacent carbon atoms to form six C—C
sigma bonds which are in the hexagonal plane. The remaining sp2 hybrid orbital of
each carbon atom overlaps with s orbital of a hydrogen atom to form six C—H sigma
bonds. Each carbon atom is now left with one unhybridised p orbital perpendicular to
the plane of the ring.

The unhybridised p orbital of carbon atoms are close enough to form a π bond by lateral
overlap. There are two equal possibilities of forming three π bonds by overlap of p
orbitals of C1 –C2, C3 – C4, C5 – C6 or C2 – C3 , C4 – C5,C6 – C1 respectively as shown in
the following figures.

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These structures correspond to the two Kekulé’s structure with localised π bonds. The
internuclear distance between all the carbon atoms in the ring has been determined to
be the same; thus there is equal probability for the p orbital of each carbon atom to
overlap with the p orbitals of adjacent carbon atoms. This can be represented in the
form of two doughnuts (rings) of electron clouds one above and one below the plane of
the hexagonal ring as shown below:

The six π electrons are thus delocalised and can move freely about the six carbon
nuclei, instead of any two. The delocalised π electron cloud is attracted more strongly
by the nuclei of the carbon atoms than the electron cloud localized between two carbon
atoms. Therefore, presence of delocalised π electrons in benzene makes it more stable
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than the hypothetical cyclohexatriene. All the six C—C bond lengths are of the same
order (139 pm) which is intermediate between C— C single bond (154 pm) and C—C
double bond (133 pm). Thus the absence of pure double bond in benzene accounts for
the reluctance of benzene to show addition reactions under normal conditions, thus
explaining the unusual behaviour of benzene.

Methods of preparation of benzene:-

1. From acetylene-

2. Decarboxylation of aromatic acids-

3. From phenol- Phenol is reduced to benzene when its vapours are passed over
heated zinc dust.

4 .By Friedel-Crafts alkylation -Alkyl benzenes can be prepared from benzene by

Friedel-craft’s alkylation (step-up reaction).

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Chemical properties:-
1. Electrophilic substitution reactions-

a) Halogenation: Arenes react with halogens in the presence of a Lewis acid like
anhydrous FeCl3, FeBr3 or AlCl3 to yield haloarenes.

If excess of electrophilic reagent is used, further substitution reaction may take place in
which other hydrogen atoms of benzene ring may also be successively replaced by the
electrophile. For example, benzene on treatment with excess of chlorine in the presence
of anhydrous AlCl3 can be chlorinated to hexachlorobenzene.

b) Nitration:A nitro group is introduced into benzene ring when benzene is heated with
a mixture of concentrated nitric acid and concentrated sulphuric acid (nitrating mixture).

c) Friedel-Crafts alkylation reaction:When benzene is treated with an alkyl halide in

the presence of anhydrous aluminium chloride, alkylbenene is formed.

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d) Friedel-Crafts acylation reaction: The reaction of benzene with an acyl halide or
acid anhydride in the presence of Lewis acids (AlCl3) yields acyl benzene.

e) Sulphonation: The replacement of a hydrogen atom by a sulphonic acid group in a

ring is called sulphonation. It is carried out by heating benzene with fuming sulphuric
acid (oleum).

2. Addition reactions-

a) Addition with hydrogen-Under drastic conditions, benzene undergoes addition to

form cyclic products. e.g. It reacts with hydrogen at 475-500K in presence of nickel or
platinum catalyst to form cyclohexane.

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b) Reaction with chlorine-Benzene reacts with chlorine in presence of sunlight and in
the absence of halogen carriers like AlCl3, FeCl3 to form benzene hexachloride (B.H.C)
an insecticide. B.H.C is also known as 666 and is commercially known as lindane or
gammexene.

3. Side chain oxidation-The side chain alkyl group attached to benzene always gets
oxidized to –COOH group irrespective of the number of carbon atoms.

CARCINOGENICITY AND TOXICITY

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

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 EXERCISES

1. Sodium salt of which acid will be needed for the preparation of propane? Write
chemical equation for the reaction.

2. Why is Wurtz reaction not preferred for the preparation of alkanes containing odd
number of carbon atoms? Illustrate your answer by taking one example.

3. How do you account for the formation of ethane during chlorination of methane?

4. What effect does branching of an alkane chain has on its boiling point?

5. Propanal and pentan-3-one are the ozonolysis products of an alkene? What is the
structural formula of the alkene?

6. An alkene ‘A’ on ozonolysis gives a mixture of ethanal and pentan-3- one. Write
structure and IUPAC name of ‘A’.

7. Write IUPAC names of the products obtained by the ozonolysis of the following
compounds: (i) Pent-2-ene (ii) 3,4-Dimethylhept-3-ene (iii) 2-Ethylbut-1-ene (iv) 1-
Phenylbut-1-ene.

8. An alkene ‘A’ contains three C – C, eight C – H σ bonds and one C – C π bond. ‘A’
on ozonolysis gives two moles of an aldehyde of molar mass 44 u. Write IUPAC name
of ‘A’.

9. Write structures of all the alkenes which on hydrogenation give 2-methylbutane.

10. Write down the products of ozonolysis of 1, 2-dimethylbenzene (o-xylene). How

does the result support Kekulé structure for benzene?

11. How will you convert ethanoic acid into benzene?

12. How would you convert the following compounds into benzene? (i) Ethyne (ii)
Ethene (iii) Hexane.

13. How will you convert benzene into (i) p-nitrobromobenzene (ii) m-
nitrochlorobenzene (iii) p - nitrotoluene (iv) acetophenone?

14. Write chemical equations for combustion reaction of the following hydrocarbons: (i)
Butane (ii) Pentene. (iii) Hexyne (iv) Toluene.

15. Arrange benzene, n-hexane and ethyne in decreasing order of acidic behaviour.
Also give reason for this behavior.

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