HYDROCARBONS
Introduction
The term ‘hydrocarbon’ is self-explanatory meaning compounds of carbon and hydrogen
only.
Classification
As we are quite aware that there are different types of hydrocarbons. Depending upon the
types of carbon-carbon bonds present, they can be classified into three main categories:
1. Saturated hydrocarbons.
2. Unsaturated hydrocarbons.
3. Aromatic hydrocarbons.
Saturated hydrocarbons contain carbon-carbon and carbon-hydrogen single bonds. If
different carbon atoms are joined together to form open chain of carbon atoms with single
bonds, they are termed as alkanes. On the other hand, if carbon atoms form a closed chain
or ring, they are termed as cycloalkanes.
Unsaturated hydrocarbons contain carbon-carbon multiple bonds i.e. double bonds, triple
bonds or both.
Aromatic hydrocarbons are a special type of cyclic compounds.
ALKANES
These are the saturated chains of hydrocarbons containing carbon-carbon single bonds.
Methane (CH4) is the first member of this family containing single carbon atom. Since it is
found in coal mines and marshy areas, is also known as ‘marsh gas’. These hydrocarbons
exhibited low reactivity or no reactivity under normal conditions with acids, bases and other
Structure of Methane
Page 1 of 16
reagents, they were earlier known as paraffins. The general formula for alkane is CnH2n+2,
where n stands for number of hydrogen atoms in the molecule.
Nomenclature
For nomenclature of alkanes in IUPAC system, the longest chain of carbon atoms containing
the single bond is selected. Numbering of the chain is done from the one end so that
maximum carbon will be included in chain. The suffix ‘–ane’ is used for alkanes.
Preparation of Alkanes
i. From unsaturated hydrocarbons: The addition of dihydrogen to unsaturated
hydrocarbons like alkenes and alkynes in the presence of a suitable catalyst under a given
set of conditions produces saturated hydrocarbons or alkanes. This process of addition of
dihydrogen is known as hydrogenation process.
𝑁𝑖/∆
CH2＝CH2 + H2 → CH3-CH3
𝑁𝑖/∆
CH☰CH + 2H2 → CH3-CH3
ii. From alkyl halides
a) Reduction: Alkyl halides undergo reduction with zinc and dilute hydrochloric acid to
𝑍𝑛/𝐻𝐶𝑙
give alkanes. In general, the reaction can be represented as CH3-Cl → CH4
b) Wurtz reaction: Alkyl halides on treatment with sodium metal in dry ether give
higher alkanes. This reaction is known as Wurtz reaction.
CH3Br + 2Na + BrCH3 ⟶ CH3-CH3 + 2NaBr
iii. From carboxylic acids
a) By decarboxylation of carboxylic acids: Sodium salts of carboxylic acids on heating
with soda lime give alkanes containing one carbon atom less than the carboxylic acid. A
molecule of carbon dioxide is eliminated which dissolves in NaOH to form sodium
carbonate.
CH3COONa + NaOH ⟶ CH4 + Na2CO3
b) Kolbe’s electrolytic method: An aqueous solution of sodium or potassium salt of a
carboxylic acid on electrolysis gives alkane containing even number of carbon atoms at
anode.
CH3COONa + 2H2O ⟶ CH3-CH3 + 2CO2 + H2 + NaOH
Page 2 of 16
Properties of Alkanes
Physical Properties
i. State: Due to the weak van der Waals forces, the first four members C1 to C4 i.e.,
methane, ethane, propane and butane are gases. From C5 to C17 are liquids and those
containing 18 carbon atoms or more are solids at 298 K. They all are colourless and
odourless.
ii. Solubility: Alkanes are generally insoluble in water or in polar solvents, but they are
soluble in non-polar solvents like, ether, benzene, carbon tetrachloride etc. The solubility of
alkanes follows the property ―Like dissolves like.
iii. Boiling point: The boiling points of straight chain alkanes increase regularly with the
increase of number of carbon atoms. This is due to the fact that the intermolecular van der
Waals forces increase with increase in the molecular size or the surface area of the
molecule.
Chemical Properties
Generally, alkanes show inertness or low reactivity towards acids, bases, oxidizing and
reducing agents at ordinary conditions because of their non-polar nature and absence of π
bond. The C–C and C–H bonds are strong sigma bonds which do not break under ordinary
conditions but they undergo certain reactions under given suitable conditions.
i. Halogenation reaction: When hydrogen atom of an alkane is replaced by a halogen,
it is known as halogenation reaction. Halogenation takes place either at high temperature
(300–500°C) or in the presence of diffused sunlight or ultraviolet light.
CH4 + Cl2 ⟶ CH3Cl + HCl
ii. Combustion: Alkanes on heating in presence of air gets completely oxidized to
carbon dioxide and water. It burns with a non-luminous flame. The combustion of alkanes is
an exothermic process i.e.; it produces a large amount of heat. CH4 + 2O2 ⟶ CO2 + 2H2O
iii. Controlled oxidation: When methane and dioxygen compressed at 100 atm are
passed through heated copper tube at 523K yield methanol.
2CH4 + O2 ⟶ 2CH3OH
iv. Aromatization: The conversion of aliphatic compounds into aromatic compounds is
known as aromatisation. n-Alkanes having six or more carbon atoms on heating to 773K at
10–20 atmospheric pressure in the presence of oxides of vanadium, molybdenum or
Page 3 of 16
chromium supported over alumina get dehydrogenated and cyclised to benzene and its
homologues. This reaction is also known as reforming.
v. Reaction with steam: Methane reacts with steam at 1273K in the presence of nickel
catalyst to form carbon monoxide and dihydrogen. This method is used for industrial
preparation of dihydrogen gas.
CH4 + H2O ⟶ CO + 3H2
Conformations
Spatial arrangements of atoms which can be converted into one another by rotation around
a C-C single bond are called conformations or conformers or rotamers.
Conformations of ethane:
There are infinite number of conformations of ethane.
However, there are two extreme cases.
Eclipsed conformation: - conformation in which hydrogen atoms attached to two carbons
are as closed together as possible is called eclipsed conformation and
Staggered conformation: - conformation in which hydrogens are as far apart as possible is
known as the staggered conformation.
Skew conformation: -Any other intermediate conformation is called a skew
Projection of Eclipsed and Staggered Conformations of Ethane
Sawhorse Projection Newman projections
Relative stability of conformations
The repulsive interaction between the electron clouds, which affects stability of a
conformation, is called torsional strain.
Magnitude of torsional strain depends upon the angle of rotation about C–C bond. This
angle is also called dihedral angle or torsional angle.
Page 4 of 16
Out of all the conformations of ethane, the staggered form has the least torsional strain and
the eclipsed form, the maximum torsional strain.
Therefore, staggered conformation is more stable than the eclipsed conformation.
Order of stability: -
Staggered conformation > skew conformation > eclipsed conformation
ALKENES
Alkenes are unsaturated hydrocarbons containing at least one carbon-carbon double bond
with general formula CnH2n.
Nomenclature
For nomenclature of alkenes in IUPAC system, the longest chain of carbon atoms containing
the double bond is selected. Numbering of the chain is done from the end which is nearer to
the double bond. The suffix ‘-ene’ replaces ‘-ane’ of alkanes. The first member of the alkene
series is C2H4 known as ethylene (common name) or ethane (IUPAC name).
Geometrical isomerism in Alkenes
The stereoisomers having same molecular formula and same structures but different spatial
(space) arrangement of atoms or groups attached to doubly bonded carbon atoms are
called geometrical isomers and this phenomenon is called geometrical isomerism.
Condition: - each double bonded carbon atom should be attached with two different atoms.
The geometrical isomer in which two identical atoms or groups lie on the same side of the
double bond is called cis isomer and the geometrical isomer in which identical atoms or
groups lie on the opposite sides of the double bond is called trans isomer. The geometrical
isomers are also known as cis-trans isomers.
Preparation
i. From alkynes: Alkynes undergo partial reduction with calculated amount of
dihydrogen producing alkenes.
Page 5 of 16
𝑃𝑑/𝐶
CH☰CH + H2 → CH2＝CH2
ii. From alkyl halides: Alkyl halides (R–X) on heating with alcoholic potash eliminates
one molecule of halogen acid to form alkenes. This reaction is known as
dehydrohalogenation i.e., removal of halogen acid.
CH3CH2Cl + KOH (alc)⟶ CH2＝CH2 + KCl + H2O
iii. From alcohols by acidic dehydration: Alcohols on heating with concentrated
sulphuric acid form alkenes with the elimination of one water molecule since a water
molecule is eliminated from the alcohol molecule in the presence of an acid, this reaction is
known as acidic dehydration of alcohols.
𝐶𝑂𝑁𝐶 𝐻2𝑆𝑂4/∆
CH3CH2OH → ⟶ CH2＝CH2 + H2O
Properties of Alkenes
Physical properties
i. The first three members of alkenes are gases, the next fourteen are liquids and the
higher ones are solids.
ii. Ethene is a colourless gas with a faint sweet smell. All other alkenes are colourless
and odourless, insoluble in water but fairly soluble in non-polar solvents like benzene,
petroleum ether.
iii. They show a regular increase in boiling point with increase in size i.e., every — CH2
group added increase the boiling point by 20–30K.
Chemical properties
i. Addition of dihydrogen: Alkenes adds one mole of dihydrogen gas in presence of
catalysts such as Ni at 200–250°C, or finely divided Pt or Pd at room temperature to give an
alkane.
CH2＝CH2 + H-H ⟶ CH3-CH3
ii. Addition of halogens: Halogens like bromine or chlorine add up to alkene to form
vicinal dihalides in presence of CCl4 as solvent. The order of reactivity of halogens is F2 > Cl2
> Br2 > I2.
CH2＝CH2 + Br-Br ⟶ Br-CH2-CH2-Br
iii. Addition of hydrogen halides: Hydrogen halides (HCl, HBr, HI) add upto alkenes to
form alkyl halides. The order of reactivity of hydrogen halides is HI > HBr > HCl. Like addition
Page 6 of 16
of halogens to alkenes, addition of hydrogen halides is an example of electrophilic addition
reaction.
CH2＝CH2 + H-Br ⟶ CH3-CH2-Br
Markovnikov rule: According to the rule, the negative part of the addendum (adding
molecule) adds to that carbon atom of the unsymmetrical alkene which is maximum
substituted or which possesses lesser number of hydrogen atoms. CH3CH＝CH2 + HBr ⟶
CH3-CH(Br)-CH3
Mechanism of Addition according to Markovnikov Rule
Anti Markovnikov addition or Peroxide effect or Kharash effect: In the presence of
peroxide, addition of HBr to unsymmetrical alkenes like propene takes place contrary to the
Markovnikov rule. This happens only with HBr but not with HCl or HI. This reaction is known
as peroxide or Kharash effect or addition reaction anti to Markovnikov rule.
CH3CH＝CH2 + HBr (in the presence of peroxide) ⟶ CH3-CH2-CH2-Br
Mechanism of Addition according to AntiMarkovnikov Rule
Page 7 of 16
Ozonolysis: (Reductive ozonolysis)
Ozonolysis of alkenes involves the addition of ozone molecule to alkene to form ozonide,
and then cleavage of the ozonide by 𝑍𝑛−H2O to smaller molecules.
Products are carbonyl compounds (aldehyde and /or ketone)
This reaction is highly useful in detecting the position of the double bond in alkenes or other
unsaturated compounds.
iv. Polymerisation: Polymerisation is the process where monomers combine together
to form polymers. The large molecules thus obtained are called polymers. Other alkenes
also undergo polymerisation.
Alkynes
Like alkenes, alkynes are also unsaturated hydrocarbons with general formula CnH2n–2. They
contain at least one triple bond between two carbon atoms. These have four H- atoms less
compared to alkanes. The first stable member of alkyne series is ethyne commonly known
as acetylenes.
Nomenclature
In common system, alkynes are named as derivatives of acetylene. In IUPAC system, they
are named as derivatives of the corresponding alkanes replacing ‘-ane’ by the suffix ‘-yne’.
Preparation
i. From calcium carbide: On industrial scale, ethyne is prepared by reacting calcium
carbide with water. Calcium carbide is prepared by heating quick lime with coke. Quick lime
can be obtained by heating limestone as shown in the following reactions:
CaCO3 ⟶ CaO + CO2
CaO + 3C ⟶ CaC2 + CO
Page 8 of 16
CaC2 + 2H2O ⟶ Ca(OH)2 + C2H2
ii. From vicinal dihalides: Vicinal dihalides on treatment with alcoholic potassium
hydroxide undergo dehydrohalogenation. One molecule of hydrogen halide is eliminated to
form alkenyl halide which on treatment with sodamide gives alkyne.
CH2(Br)-CH2(Br) + KOH ⟶ CH2＝CHBr-----KOH ⟶ CH☰CH
Properties of Alkynes
Physical properties
i. The first three members (acetylene, propyne and butynes) are gases, the next eight
are liquids and higher ones are solids.
ii. All alkynes are colourless. All alkynes except ethyne which have an offensive
characteristic odour, are odourless.
iii. Alkynes are weakly polar in nature and nearly insoluble in water. They are quite
soluble in organic solvents like ethers, carbon tetrachloride and benzene.
iv. Their melting point, boiling point and density increase with increase in molar mass.
Chemical properties
Acidic character of alkynes
These reactions have not been observed in case of ethene and ethane thus indicating that
ethyne is acidic in nature in comparison to ethene and ethane.
i. Addition of dihydrogen: Alkynes contain a triple bond, so they add up, two
molecules of dihydrogen.
CH☰CH + H2 ⟶ CH2＝CH2 ⟶ CH3-CH3
ii. Addition of halogens: Alkynes contain a triple bond, so they add up, two molecules
of halogen.
CH☰CH + Cl2 ⟶ CH(Cl)＝CH(Cl) ⟶ CH(Cl)2-CH(Cl)2
Page 9 of 16
iii. Addition of hydrogen halides: Two molecules of hydrogen halides (HCl, HBr, HI) add
to alkynes to form gemdihalides (in which two halogens are attached to the same carbon
atom).
CH☰CH +2HCl ⟶ CH3-CHCl2
iv. Addition of water: Like alkanes and alkenes, alkynes are also immiscible and do not
react with water. However, one molecule of water adds to alkynes on warming with
mercuric sulphate and dilute sulphuric acid at 333K to form carbonyl compounds.
v. Polymerisation: Ethyne on passing through red hot iron tube at 873K undergoes
cyclic polymerization. Three molecules polymerise to form benzene, which is the starting
molecule for the preparation of derivatives of benzene, dyes, drugs and large number of
organic compounds.
vi. Combustion:
2C2H2 + 5O2 ⟶ 4CO2 + 2H2O
Aromatic Hydrocarbon
Aromatic hydrocarbons are also known as ‘arenes‘. Since most of them possess pleasant
odour (Greek; aroma meaning pleasant smelling), the class of compounds are known as
‘aromatic compounds’. Most of the compounds are found to have benzene ring. Benzene
ring is highly unsaturated and in a majority of reactions of aromatic compounds, the
unsaturation of benzene ring is retained. Aromatic compounds containing benzene ring are
known as benzenoids and those, not containing a benzene ring are known as non-
benzenoids.
Nomenclature
Since all the six hydrogen atoms in benzene are equivalent; so it forms one and only one
type of monosubstituted product. When two hydrogen atoms in benzene are replaced by
two similar or different monovalent atoms or groups, three different position isomers are
Page 10 of 16
possible which differ in the position of substituents. So we can say that disubstituted
products of benzene show position isomerism. The three isomers obtained are 1, 2 or 1, 6
which is known as the ortho (o-), the 1, 3 or 1, 5 as meta (m-) and 1, 4 as para (p-)
disubstitued compounds.
Structure
The molecular formula of benzene, C6H6, indicates a high degree of unsaturation. All the six
carbon and six hydrogen atoms of benzene are identical. On the basis of this observation
August Kekule in 1865 proposed the following structure for benzene having cyclic
arrangement of six carbon atoms:
Resonance
Even though the double bonds keep on changing their positions. The structures produced is
such that the position of nucleus remains the same in each of the structure. The structural
formula of such a compound is somewhat intermediate (hybrid) between the various
propose formulae. This state is known as Resonance.
Aromaticity
Benzene was considered as parent ‘aromatic’ compound. Now, the name is applied to all
the ring systems whether or not having benzene ring, possessing following characteristics.
(i) Planarity
(ii) Complete delocalisation of the π electrons in the ring
(iii) Presence of (4n + 2) π electrons in the ring where n is an integer (n = 0, 1, 2, . . .). This
is often referred to as Hückel Rule.
Page 11 of 16
Some examples of aromatic compounds are given below:
Preparation of Benzene
i. Cyclic polymerisation of ethyne: Ethyne on passing through red hot iron tube at
873K undergoes cyclic polymerization.
ii. Decarboxylation of aromatic acids: Sodium salt of benzoic acid i.e., sodium benzoate
on heating with sodalime gives benzene.
iii. Reduction of phenol: Phenol is reduced to benzene by passing its vapour over
heated zinc dust.
Properties of Benzene
Physical Properties
i. Aromatic hydrocarbons are non-polar molecules and are usually colourless liquids or
solids with a characteristic aroma.
Page 12 of 16
ii. The napthalene balls used in toilets and for preservation of clothes because of
unique smell of the compound.
iii. Aromatic compounds are insoluble in water but soluble in organic solvents such as
alcohol and ether.
iv. They burn with sooty flame.
Chemical properties
i. Halogenation: Arenes undergo halogenation when it is treated with halogens in
presence of Lewis catalyst such as anhy. FeCl3, FeBr3 or AlCl3 to yield haloarenes.
ii. Nitration: A nitro group is introduced into the benzene ring when benzene is heated
with a mixture of concentrated nitric acid and concentrated sulphuric acid.
iii. 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 or
oleum (conc. H2SO4 + SO3).
iv. Friedel-Crafts alkylation reaction: When benzene is treated with an alkyl halide in
the presence of anhydrous aluminium chloride, alkylbenzene is formed.
Page 13 of 16
(v) Friedel-Crafts acylation reaction:
Mechanism of electrophilic substitution reactions:
According to experimental evidences, SE (S = substitution; E = electrophilic) reactions are
supposed to proceed via the following three steps:
(a) Generation of the eletrophile
(b) Formation of carbocation intermediate
(c) Removal of proton from the carbocation intermediate
(a) Generation of electrophile E⊕: During chlorination, alkylation and acylation of
benzene, anhydrous AlCl3, being a Lewis acid helps in generation of the elctrophile Cl⊕, R⊕,
RC⊕O (acylium ion) respectively by combining with the attacking reagent.
(b) Formation of carbocation intermediate (arenium ion)
The arenium ion gets stabilised by resonance:
Page 14 of 16
(c) Removal of proton from the carbocation intermediate
Directive influence of a functional group in monosubstituted benzene
Ortho and para directing groups: (activating Groups)
• The groups which direct the incoming group to ortho and para positions are called
ortho and para directing groups.
• Examples are −OH, − NH2 , − NHR, − NHCOCH3 , − OCH3 , − CH3 , −C2 H5 etc.
Ortho and para directing groups: (Deactivating Groups)
In the case of aryl halides, halogens are moderately deactivating. Because of their strong – I
effect, overall electron density on benzene ring decreases. It makes further substitution
difficult. However, due to resonance the electron density on o– and p– positions is greater
than that at the m-position. Hence, they are also o– and p– directing groups.
Meta directing group:-(Deactivating groups)
The groups which direct the incoming group to meta position are called meta directing
groups.
Some examples of meta directing groups are −𝑁𝑂2 , − 𝐶𝑁, − 𝐶𝐻𝑂, − 𝐶𝑂𝑅, −
𝐶𝑂𝑂𝐻, − 𝐶𝑂𝑂𝑅, − 𝑆𝑂3 𝐻 etc.
Page 15 of 16
CARCINOGENICITY AND TOXICITY
Benzene and polynuclear hydrocarbons containing more than two benzene rings fused
together are toxic and said to possess cancer producing (carcinogenic) property. Such
polynuclear hydrocarbons are formed on incomplete combustion of organic materials like
tobacco, coal and petroleum. They enter into human body and undergo various biochemical
reactions and finally damage DNA and cause cancer.
Page 16 of 16
