NOTE

C H E M I S T R Y

‌‌HYDROCARBONS‌
LET US GET STARTED WITH
CHEMICAL PROPERTIES OF ALKANES

What you already know

• Introduction to hydrocarbons and their • Classification of hydrocarbons

importance in daily life • Preparation of alkanes

What you will learn

• Physical properties of alkanes • Mechanism of halogenation

• Chemical properties of alkanes • Purification of organic compounds: Sublimation
• Types of reactions

BOARDS MAIN
Physical Properties of Alkanes

The properties that do not change the chemical nature of matter are given as follows:

1 Physical state

2 Colour

3 Odour

4 Solubility

5 Boiling point

Physical states of alkanes

At room temperature (≈ 298 K),

C 1 – C4 Gases
At room
C5 – C17 Liquids
temperature, 298 K
Cn >– C18 Solids

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Colour of alkanes

Alkanes are colourless.

Odour of alkanes

• Alkanes are odourless.

• LPG is also an odourless gas. However, an odourant ethyl mercaptan is added to the LPG
prior to its supply for uses. The odourant makes it easier to detect any leakage during its
supply or use.

Solubility of alkanes

• Generally, polar substances are soluble in polar solvents, and non-polar substances are
soluble in non-polar solvents (like dissolves like).
• Thus, alkanes (being non-polar) are soluble in non-polar organic solvents whereas remain
insoluble in polar solvents such as water.
Examples:
1. Oil is insoluble in water.

Water Oil Oil pouring in to water Oil is insoluble in water

Fig. 1: Solubility of oil in water

2. Diesel is soluble in petrol.

Petrol Diesel Diesel pouring in to petrol Diesel is soluble in petrol

Fig. 2: Solubility of diesel in petrol

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1. Types of solvents
• Nonpolar solvent: A solvent with zero dipole moment is a nonpolar solvent.
Examples: Benzene, CCl4, hexane, etc.
• Polar solvent: A solvent with non-zero dipole moment is a polar solvent.
Examples: Methanol, ethanol, water, acetone, etc.
Polar solvents are of two types.
(a) Protic (b) Aprotic
Polar protic solvents (H-bonding is Polar aprotic solvents (H-bonding is not
present): These are the solvents that present): These are the solvents that do not
contain hydrogen atoms bonded to a highly readily donate H+ ions.
electronegative atom and can readily Examples: Diethyl ether, acetonitrile,
donate H+ ions. dimethylsulfoxide (DMSO), acetone,
Examples: Methanol, ethanol, water, etc. dimethylformamide (DMF), etc.

Boiling point

Molecular size van der Waals

Boiling point ∝ ∝ ∝ Molar mass
(or surface area) force

Melting point

Melting point depends on the following:

1. Intermolecular attraction
2. Packing in the crystal lattice. The tighter they fit, the more energy is required to break the
lattice and melt the compound.
Variation in melting points of odd and even alkanes

50

–50
Melting point (oC)

–100

–150

–200

0 2 4 6 8 10 12 14
Number of carbon atoms
Fig. 3: Variation in melting points of odd and even alkanes

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(1) In general, the alkanes with an odd number of carbons are packed less tightly than the alkanes
with an even number of carbons.

Odd number of carbons packed less tightly Even number of carbons packed more tightly

Hence, alkanes with an odd number of carbon atoms have weaker intermolecular attractions
and lower melting points.
(2) The alkane with an odd number of carbons has a low melting point compared to its preceding
homologue that has an even number of carbons.

Based on boiling point

Arrange the following compounds in the decreasing order of their boiling points.
CH4 H3C CH3 H3C CH2 CH3

Solution

There is a steady increase in boiling point with increase in molar mass.

Boiling point ∝ Molecular size (or surface area) ∝ van der Waals force ∝ Molar mass
Hence, the correct order of boiling point is as follows:
CH4 < H3C CH3 < H3C CH2 CH3

Based on boiling
finding point
the order of boiling points of the given compounds

Arrange the following compounds in the decreasing order of their boiling points.
CH3

H3 C CH2 CH2 CH2 CH3 H3 C CH2 CH CH3 CH3 C CH3

CH3 CH3
A B C

Solution

The molar masses of all the given compounds is 72 g mol–1. For organic compounds with the same
molar mass, as the branching increases, the overall surface area decreases. This results in the
decrease in the intermolecular forces of attraction, thereby decreasing the boiling point of the
compounds.
Boiling point ∝ Molecular size (or surface area) ∝ van der Waals force ∝ Molar mass

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Molar mass Boiling point

Compounds
(g mol–1) (K)

H3 C CH2 CH2 CH2 CH3 72 309.1

H3C CH2 CH CH3

72 300.9
CH3
CH3

CH3 C CH3 72 282.5

CH3

Therefore, the correct order of boiling point is A > B > C, i.e.,

CH3

H3 C CH2 CH2 CH2 CH3 > H3 C CH2 CH CH3 > CH3 C CH3

CH3 CH3

Based on boiling
finding point
the order of boiling points of the given compounds

Which of the following compounds has the highest boiling point?

(a) (b) (c) (d)

Solution

In options (a), (b), and (d), the alkanes have the same molecular formula (C5H12) and molar mass. As
the branching increases, a < b < d, the overall surface area decreases. This results in the decrease
in the intermolecular forces of attraction, thereby decreasing the boiling point of the compounds.
Boiling point ∝ Molecular size (or surface area) ∝ van der Waals force ∝ Molar mass
The given alkane in option (c) has a six-carbon long chain and has the highest molar mass among
the given options. So, in option (c), the alkane (C6H14) has the maximum boiling point.
Therefore, the order of boiling point of the given alkanes is: c > a > b > d, i.e.,

> > >

Hence, option (c) is the correct answer.

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Based on finding the order of boiling point of the given compounds

boiling point

Based on branching, the isomers of hexane can be divided into three distinct classes as shown in
the figure. What is the correct order of their boiling points?

& &

(I) (II) (III)

(I) 2,3-Dimethylbutane and 2,2-Dimethylbutane
(II) 2-Methylpentane and 3-Methylpentane
(III) n-Hexane
(a) (I) > (II) > (III) (b) (III) > (II) > (I) (c) (II) > (III) > (I) (d) (III) > (I) > (II)

Solution

For the hydrocarbons with the same molar mass, as the branching increases, the overall surface
area decreases. This results in the decrease in the intermolecular forces (London dispersion forces),
decreasing the boiling point of hydrocarbons.
Boiling point ∝ Molecular size (or surface area) ∝ van der Waals force ∝ Molar mass
The increasing order of branching of the given set of molecules is as follows:
(I) > (II) > (III)
Therefore, the order of boiling point is as follows:
(III) > (II) > (I)
Hence, option (b) is the correct answer.

BOARDS
Chemical Properties of Alkanes

The properties that change the chemical nature of matter are as follows:
• High molecular weight alkanes are known as paraffins. They have little affinity towards general
reagents under normal conditions.
• Alkanes are non-reactive as they are non-polar and have no π bonds (sigma bonds only).
Under normal conditions, alkanes are inert to most reagents.
• At certain conditions, alkanes undergo the following reactions:
• Pyrolysis • Isomerisation • Aromatisation
• Combustion • Reaction with steam • Substitution reaction
• Controlled oxidation

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BOARDS
Types of Reactions

Types of reactions

Substitution Addition Elimination Rearrangment

Substitution reaction

It is defined as a reaction in which the functional group of one chemical compound is substituted
by another group, or it is a reaction that involves the replacement of one atom or molecule of a
compound with another atom or molecule.

A + B C A B + C

Fig. 4: Substitution reaction

Here, C is substituted by A.

Addition reaction

It is a chemical reaction in which two or more reactants come together to form a larger single
product.

A + C A C

Fig. 5: Addition reaction

Here, A combines with C to form the larger addition product.

Elimination reaction

It is a type of reaction that is mainly used to transform saturated compounds (organic compounds
that contain single carbon-carbon bonds) to unsaturated compounds (compounds that feature
double or triple carbon-carbon bonds).

A B B C B B + A + C

Fig. 6: Elimination reaction

Here, A and C atoms are eliminated from the reactant to give an unsaturated product.

Rearrangement reaction

It is an organic reaction where the carbon skeleton of a molecule is rearranged to give products.

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BOARDS MAIN
Substitution Reactions of Alkanes

In this reaction, one or more hydrogen atoms/substituents of an alkane are replaced by −X, −NO2,
−SO3H, etc.
Where, X is halogen atoms.
Substitution
reactions of alkanes

Halogenation Nitration Sulphonation

Halogenation

When one or more hydrogen atoms of an alkane are replaced by halogen(s) (F, Cl, Br, I), such reactions
are known as halogenation reactions. Halogenation takes place in the following conditions:
At high temperature In the presence of
Take place
(573-773 K) ultraviolet light (UV)

Examples:
hv
CH4 + Cl2 CH3Cl + HCl
Methane Chloromethane
hv
C2H 6 + Cl2 C2H5Cl + HCl
Ethane Chloroethane
Complete halogenation of CH4
hv
CH4 + Cl2 CH3Cl + HCl
hv
CH3Cl + Cl2 CH2Cl2 + HCl
hv
CH2Cl2 + Cl2 CHCl3 + HCl
hv
CHCl3 + Cl2 CCl4 + HCl
In this reaction, one or more hydrogen atoms/substituents of an alkane are replaced by −X, −NO2,
−SO3H, etc. Where, X is halogen atoms.
Halogenation proceeds through a free radical chain mechanism involving three steps i.e., initiation,
propagation and termination.
Analogy for free radical mechanism
This picture is to explain the idea of chain initiation, propagation, and termination.

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• Initiation step: The man in the blue shirt is

assumed to be the first infected person or
the reaction initiates with him.

Fig. 7: Analogy for initiation step

• Propagation step: He meets different people and starts spreading the virus. The virus spreads
at the global level.

Fig. 8: Analogy for propagation step Fig. 9: Disease spreading at global level

• Termination step: Scientists discover an

antiviral drug as a cure.

Fig. 10: Analogy for termination

Free radical: It is an uncharged species that contains an unpaired electron in its atomic orbitals
and can exist independently.
Halogenation proceeds through a free radical chain mechanism involving the following three steps:
(1) Initiation
The homolytic cleavage of Cl2 molecules takes place in the presence of heat or light. In the
homolytic cleavage, the two electrons of covalent bond are divided equally between the
products.
hv
Cl Cl homolysis Cl + Cl

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Note

Cl (not R or H) is formed in the initiation step because the Cl−Cl bond is weaker than the C−C and
C−H bonds. Hence, it is easier to break and form chlorine free radicals in the initiation step.

(2) Propagation
Step 1: Cl attacks CH4, and the reaction proceeds by breaking the C−H bond to generate CH3
along with HCl.
hv
CH4 + Cl homolysis CH3 + HCl

Step 2:
CH3 attacks the second molecule of Cl2 to form CH3−Cl and releases another Cl.
The CH3 formed in step 1 and the Cl in step 2 are repeated, thereby setting up a chain of
reactions.
CH3 + Cl Cl CH3Cl + Cl

Steps 1 and 2 have more focus since they produce the principal product (CH3Cl).

However, other steps are also possible to generate more halogen substituted products.
CH3 Cl + Cl CH2 Cl + HCl
CH2 Cl + Cl Cl CH2Cl2 + Cl

(3) Termination
The reaction stops after sometime due to the following:
(a) Consumption of reactant (b) Side reactions
The possible termination steps are as follows:
(i) Cl + Cl Cl−Cl
(ii) CH3 + CH3 CH3−CH3
(iii) CH3 + Cl CH3−Cl
Here, the product is formed, but the free radicals are consumed. Hence, the chain is
terminated.
Rate of reaction of an alkanes with halogens
The rate of reaction of halogens with alkanes is in order:
Very slow and
Explosive, reversible.
violent, Carried out in
F2 > Cl2 > Br2 > I2
and the presence of
uncontrollable oxidising agents
like HIO3/HNO3.

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Iodination of alkanes
CH4 + I2  CH3I + HI
HIO3 + 5HI → 3I2 + 3H2O
HIO3 reacts with the product (HI) of the above reversible reaction causing the removal of HI which
enhances the forward reaction as per the Le Chatelier’s principle.
Rate of replacement of H from alkanes
The order of rate of replacement of H from alkanes is 3° > 2° > 1° > CH4

∝ Stability of the intermediate

Rate of halogenation
(alkyl radical) formed

The number of hyperconjugative structures is proportional to number of α-hydrogen. The more the
number of hyperconjugative structures, the more is the stability of free radicals. Thus, the order of
stability of free radicals is 3° > 2° > 1° > CH3. Due to hyperconjugation, the rate of replacement of
hydrogen from 3° carbon is more than that of 2° and 1° carbon.

Based on finding the order of reactivity of alkanes

CH2 −H1

Which of the following orders is correct for the

reactivities of the indicated hydrogen atoms on
monochlorination?
CH−CH2 −H3

H2
(a) H1 > H2 > H3 (b) H3 > H2 > H1 (c) H3 > H1 > H2 (d) H2 > H1 > H3

Solution

The monochlorination of alkanes proceeds through a free radical mechanism. The radical formed
by the removal of the H1 atom is stabilised by resonance with the phenyl ring.
1
CH2 −H CH2

–H
3 3
CH−CH2 −H CH−CH2 −H
2 2
H H
The radical formed by the removal of the H atom is stabilised by both hyperconjugation and
2

resonance.

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1 1
CH2 −H CH2 −H

–H
3 3
CH−CH2 −H CH−CH2 −H
2
H
The radical formed by the removal of the H3 atom is stabilised by hyperconjugation only.
1 1
CH2 −H CH2 −H

–H
3
CH−CH2 −H CH−CH2
2 2
H H
So, according to AERHI, the radical formed by the removal of H2 is the most stable followed by
H1 and then H3. The rate of monochlorination is directly proportional to the stabilities of the free
radicals.
Therefore, the correct order of reactivity of hydrogen atom is given as follows:
H2 > H1 > H3
Hence, option (d) is the correct answer.

Based on finding the order of reactivity of alkanes

Consider the following reaction and identify the major product.

H3C−CH−CH−CH3 + Br X + HBr

D CH3
(a) H3C−CH−CH−CH2 (b) H3C−CH−C−CH3

D CH3 D CH3
(c) H3C−C−CH−CH3 (d) H3C−CH−CH−CH3

D CH3 CH3

Solution

All options provided here are free radical intermediates. We have to choose the most stable free
radical among these options.
As we know more alpha hydrogens give more hyperconjugative structures and hence, more is the
stability of the free radical.

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α α α α α α α
H3C−CH−CH−CH2 H3C−CH−C−CH3 H3C−C−CH−CH3 H3C−CH−CH−CH3
α
D CH3 D CH3 D CH3 CH3
Option (a), (b), (c) and (d) have one, seven, four and four alpha hydrogen respectively. In option (b)
-D can also show hyperconjugation.
Hence, option (b) is the correct answer.

BOARDS
Previous Session’s Homework Question

Purification of organic compounds

The methods used for the purification of organic compounds are based on the nature of the
compounds and impurities present in it. Some of the purification techniques are as follows:
(1) Sublimation (2) Crystallisation (3) Distillation (4) Differential extraction (5) Chromatography

Sublimation

This technique is used to separate sublimable compounds from non-sublimable impurities.

We need pure benzoic acid, but it is present with some mixed impurities. How can we purify the
impure benzoic acid?
Sublimation technique is used for the purification of benzoic acid from its impurities. The impure
benzoic acid is taken in a china dish. An inverted funnel is placed over the china dish with a cotton
plug at the end of the stem of the funnel. On heating, the benzoic acid evaporates from the impure
mixture, leaving behind the impurities, and on condensation, pure benzoic acid is obtained.
Cotton plug
Pure benzoic acid
Inverted funnel
Impurities

Impure benzoic acid

in china dish

Burner

Pure benzoic acid starts

evaporating from the mixture
Fig. 11: Sublimation method for separation of pure benzoic acid

PreviousHomework
Session’s Homework
Question Question

How can we separate a mixture of chloroform and aniline?

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