10.

ALKANES

1. INTRODUCTION

1.1 Classification of Hydrocarbon

Hydrocarbon – Molecule with only C – C and C – H bonds

Hydrocarbon - Molecule with only C-C and H-C Bonds

Hydrocarbons

Open chain Closed chain or cyclic

or acyclic

Alicyclic Aromatic
(Cyclo alkanes (Arenes)
and cyclo alkenes)
Saturated Unsaturated
(Alkanes) (Alkanes and alkynes)
Flowchart 10.1: Flowchart on classification of hydrocarbon

Alkane – Hydrocarbons with only single bonds.

Alkene – Hydrocarbons with one or more double bonds.
Alkyne – Hydrocarbons with one or more triple bonds.

1.2 Saturated Hydrocarbons or Alkanes or Paraffin’s

 1. Alkanes have general formula CnH2n+2 where n ranges from 1 to n.
E.g., CH4 , C2H6 , C3H8
Methane Ethane Propane
 2. Alkanes are not very reactive by nature, and are hence also called paraffins. (latin: Parum = little, affins = affinity)
 3. Each carbon atom is sp3 hybridized and its four bonding orbitals are directed towards the four corners of a
regular tetrahedron at an angle of 109º28’ or 109.5º.
The tetrahedral of alkane is described below, e.g., C2H6.
1 0 . 2 | Alkanes

CH3 CH3
I II
ns² np²
I C II C
Ground state Ground state

I C II C
Excited state Excited state
(sp³)¹(sp³)¹(sp³)¹(sp³)¹ (sp³)¹(sp³)¹(sp³)¹(sp³)¹

Bond Energy -1 -1
82.76 k cal mol 98.67 k cal mol

Illustration 1: The compound that has one isopropyl group is:

(a) 2–Methyl pentane (b) 2, 2, 3, 3–Tetramethyl pentane
(c) 2, 2–Dimethyl pentane (d) 2, 2, 3–Tetramethyl pentane (IIT–JEE, 1989)

Sol: 2-methyl pentane contains one isopropyl group.

4
1 2 5
3
One isopropyl group
2-Methyl pentane
(a) 2,2,3,3-Tetramethyl pentane contains two butyl group

2 4
3 5
1
Two butyl groups
2,2,3,3-Tetramethyl penane

(b) 2, 2-dimethyl pentane contains one t-Butyl group.

2 4
5
1 3
One t-butyl group
2,2-Dimethyl pentane
(c) 2 2,3-Trimethyl pentane contains one isopropyl group and one t-butyl group

2 4
3 5
1
One t-butyl group
one isobutyl group
2,2,3- Trimethyl pentane
 Chem i str y | 10.3

1.3 Nomenclature and Structure of Alkanes

Sl. No. CnH2n+2 Structure
#Carbon CnH2n+2 Structure
1#Carbon CH4 CnH2n+2 Structure
H
H
1 CH
1#Carbon C
CHnH442n+2 Structure
H CC H H
#Carbon CnH2n+2 H H
Structure
1 CH4 H
H
H H C H
1 CH4
2 C2H6 HH3C — C CHH
3

22 CC22H H6 HH3CC H CH
CH3
6 3 H 3
33 C3H8 C3H8 H C CH3
3 C3H8 H33CC
2 C2H6 H 3 CH3 CH3 H3CC
2 C2H6 H3C CH3 H3
3 C3H8 H3C CH
CHCH CH3
43 C4H10C H 3 33 CH 3
H C CH
44 CC344H
H810
10
H33
H3C C 3 H
H33C
H C
3C
CH3 HCH
3C
CH 3 CHH3 3C CH3
CHH3C CH
3
4 C4H10 H3C CH3 CH 3
H3C CH33 3
455 CC45H
C H10
H 12 HH3CC H3CC
CH3 H HCH
3C 3
H3CC CH3
H
H CH
H 3C 3C CH
5 12 CH
5 C5H12 3 3 3 3
3
3 CH3 CH3 H3C CH3
5 C5H12 Straight chain
chain alkanes
alkanes Branched
CH3 H3C CH3
Straight
H3C CH3 H3C Branched
5 C5H12 “normal (n)’’
H3C “normal (n)’’CH3 H3C HC
akkanes CH3
akkanes 3
Straight chain alkanes Branched
Straight chain(n)’’
“normal alkanes Branched
akkanes
“normal (n)’’ akkanes

Nomenclature for Branched Alkyl Groups

Iso Neo Seo Tert

H CH3 CH3
C CH3 H2 H H2
C C CH3 C C CH3 C CH3
CH3
CH3 CH3 CH3
Pr s t
Bu Bu
Isopropyl Neopentyl Sec-butyl Tert-butyl
s-butyl t-butyl
CH3
H2H H2H2 CH3
C C CH3 C C C CH3 H2
C C CH3
CH3 CH3
CH3
Bu
Isobutyl Neohexyl Tert-pentyl
t-pentyl

Figure 10.1: Table showing nomenclature for branched alkyl group

 “normal (n)’’ Alkanes

1 0 . 4 | Alkanes

H by C C connectivity
H by C – C R R R
connectivity
H C H R C H R C R
H H H
Primary hydrogens Secondary hydrogens Tertiary hydrogens
O O O
3 1 2 3
sp C by C H connectivity
sp3 C by C – H
H H H H
connectivity
H C H R C H R C R R C R
H H H H
3
Methane Methyl Methylene Methine
sp C by C C connectivity
sp3 C by C – C R R R R
connectivity
H C H R C H R C R R C R
H H H R
Primary Secondary Tertiary Quaternary
carbon carbon carbon carbon
o o o o
1 2 3 1

Alcohols and halides by C C connectivity

Illustration 2: R R R
(a) Write the IUPAC name of the compound (A)Hwhose
C OHbond line structure
R C OH is R C OH
(b) Write the condensed formula of the compoundH(A) H R
(c) Define and identify all the primary (1º), secondary (2º), tertiary
Primary alcohol (3º), and
Secondary quaternary
alcohol (4º)alcohol
Tertiary carbon atoms.
o o o
1 2 3
(d) Identify all the 1º, 2º and 3º H atoms.
(e) Give the number of H atoms bonded to 1º, 2º, R
3º and 4º C atom in Ran alkane. R
(f) Give the number of C atoms bonded to 1º, 2º,
H 3ºC and
XH 4º C atomRin an
C alkane.
XH  H C XH (JEE
X= MAIN)
F, Cl, Br, I
H H H
Primary halide Secondary halide Tertiary halide
Sol: o o o
3 1
1 2 3
5
4 2
(a) 6 2, 4, 4–Trimethyl hexane

(b) CH3CH2C ( CH3 ) CH2CH ( CH3 ) Condensed formula

2 2
or
MeCH2C (Me ) CH2CHMe2
2
HHH

H
C (a)
H H (a) H C H
(c) 2
H C6 C5 C4 C3 C H
(a) (b) (d) (b) (c)
H H H H H
C (a) (c) 1
C H
HHH
H
a = 1º, b = 2º, c = 3º, d = 4º
(d) 1ºCarbon is bonded to only one other C, a 2ºCarbon is bonded to two other C atoms, a 3ºCarbon is bonded
to three other C atoms, and a 4ºCarbon is bounded to four other C atoms. (The C of CH4 is 1º)
 Chem i str y | 10.5

(e) 1º hydrogen atoms are those attached to primary carbon atoms, 2ºH atoms to secondary carbon atoms, and
3ºH atoms to tertiary carbon atoms; 4ºH atoms cannot exist because all four bonds to a quaternary carbon
are attached to other C atoms.
(f) H atoms bonded to 1º, 2º, 3º and 4ºC atoms are 3, 2, 1, and 0 respectively.
(g) C atoms bonded to 1º, 2º, 3º and 4ºC atoms are 1, 2, 3, and 4 respectively.

1.4 Isomerism in Alkanes

Isomers – Are structures with the same molecular formula but with a different atomic arrangement.

CH3 H3C CH3

C5H12 H3C CH3 CH3 H3C CH3
H3C

Constitutional isomers – Are isomers that differ in atom connectivity.

C55H
C H12 shows three chain isomers:
12 shows three chain isomers :
C5H12 shows three chain isomers :
2 4
2 4
I) 1
I) 1 5 II)
II) III)
III)
53
3
Pentane Pentane lso-pentane lso-pentane Neo pentane Neo pentane
C6H14 shows five chain isomers:
C6H
C6H14 shows 14 shows
five five chain
chain isomers : isomers :
4 2
6 4
2 2 4 26 4 2 4 2 4
6 36 3
I) 1 I)3 1 II) lll) 1 lll) 15
3II) 1 5
5 3 1 5
5 3 5
Hexane Hexane 2-Methyl pentane 3-Methyl pentane
2-Methyl pentane 3-Methyl pentane
2 4 2 4
3 2 4 3 2 4
IV) 1 V) 1
IV) 1 3 V) 3
1
2,3-Dimethyl 2,3-Dimethyl
butane 2,3-Dimethyl butane 2,3-Dimethyl
butane butane

Conformational Isomers:
Infinite number of spatial arrangments that a molecule can adopt in space due to rotation about σ bonds are called
rotational or conformational isomers. Analysis of energy changes during these rotations is called conformational
analysis.
(a) Conformations of ethane:

H H
H H
H H

H H
H H
H H
Eclipsed Staggered

Sawhorse projection formula

HH H

H H
 H H
Eclipsed Staggered

1 0 . 6 | Alkanes Sawhorse projection formula

HH H

H H

H H H H
H H
H
Eclipsed Staggered

Newman projection formula

Figure 10.2: Conformation of ethane in newman and sawhorse projection formula

(b) Conformation of butane (Newman projection formula):

Me Me Me H Me H

H H Me
H H H
H H H Me H H

l ll lll
Fully eclipsed
Partially eclipsed

Me Me Me

H Me Me H H H

H H H H H H

H H Me
lV V Vl
Skew or gauche Staggered (or anti)

Figure 10.3: Conformation of butane in newman projection formula

Illustration 3: Write the IUPAC name, bond line structure, and condensed formula for the following alkanes with
the greatest number of (Me) groups.
(a) C7H16 (b) C8H18 (c) C10H22 (d) C11H24

Sol:
(a) Bond line structure 2 4
(a) Bond line structure: 3
1

IUPAC name: 2, 2, 3–Trimethyl butane

Condensed formula: (CH3)3CCH(CH3)2 or Me3CCHMe2

(b) Bond line structure: 1 4

1 2 3 2 3
(b) Bond line structure 4

IUPAC name: 2, 2, 3, 3–Tetramethyl butane

 Chem i str y | 10.7

Condensed formula: (CH3)3C.C(CH3)3 or Me3C.CMe3

1 5
(c) Bond lineline
( c) Bond structure:
structure 2 3 4 5 2 34
1

IUPAC name: 2, 2, 3, 4, 4–Pentamethyl pentane

Condensed formula: (CH3)3CCH(CH3)C(CH3)3 or Me3C.CH(Me) CMe3
1 5
(d) Bond(d)
line structure:
Bond
line structure 1 2 3 4 5 2 3 4

IUPAC name: 2, 2, 3, 3, 4, 4–Hexamethyl pentane

Condensed formula: (CH3)3C.C(CH3)2C(CH3)3 or Me3C.C(Me)2.CMe3

Illustration 4: Which conformers of ethylene chlorohydrin and ethylene glycol is more stable:
The most stable conformer of ethylene chlorohydrin and ethylene glycol is the gauche conformer. The gauche form
is more stable due to intra molecular Hydrogen –bonding. In case of ethylene chlorohydrin H-Bonding is formed
between the Hydrogen of OH group and Cl and in case of ethylene glycol hydrogen bonding is formed between
two OH groups.
Sol: OH Cl
2
OH
Cl
1
Ethylene H
chlorohydrin H H
H
or
Eclipsed
2-Cholorethanol

O-H OH

H Cl H H

H H H H
H Cl
Skew or gauche Staggered
(Most stable) (or Anti)

OH
1 OH
OH
HO
2
Ethylene glycol
or H H
Ethane-1,2-diol H H
or Glycol Eclipsed
O-H OH

H OH H H

H H H H

H OH
Skew or gauche Staggered
(Most stable) (or Anti)
1 0 . 8 | Alkanes

2. PREPARATION OF ALKANES

2.1 From Unsaturated Hydrocarbons

1. Hydroboration/ 2. Reduction
Hydrogenation or reduction is the process by which hydrogen is added to an unsaturated compound in the
presence of a catalyst.

H2+Pt 2 mol
I) O
at 80 C Me Me H2+Pt
Propane O
at 80 C Cyclopropane

H2+Pt Me 2 mol
II) O
at 200 C Me H2+Pt
O
Butane at 200 C

Alkenes and alkynes add one and two molecules of hydrogen, respectively, in the presence of a catalyst, such as
finely divided nickel or palladium or platinum at 523–573 K to form alkanes. This reaction is commonly referred to
as Sabatier and Senderson’s reduction.

Ni or Pt or Pd
H2C = CH2 + H2 → H3C — CH3
523 − 723K
Ethene or (Ethylene)    Ethane
Ni or Pt or Pd
HC ≡ CH + 2H2 → H3C — CH3
523 − 723K
Ethene or (Acetylene)    Ethane

Cycloalkane on hydrogenation gives alkane. The reactivity order of cycloalkanes is:

> > >

This is due to the angle strain. Greater the angle strain in the ring, less stable and more reactive is the compound.
So, cyclopropane is the most reactive and gives propane on hydrogenation at lower temperature, whereas higher
cycloalkanes require high temperature.

2.2 From Alkyl Halides

2.2.1 Using Grignard Reagent

RX + Mg → RMgX.
For a given alkyl halide, the degree ease of formation of G.R. is: iodide > bromide > chloride. Similarly, for a halogen
atom, the ease of formation of G.R. is greater with a smaller alkyl group than that with bigger alkyl groups. For
example, CH3I > C2H5I > C3H7I
OH
(i) IMg — CH 3 + H — OH CH 4 + Me
I

OC2 H5
(ii) IMg — CH 3 + H — OC2H5 CH 4 + Me
I
 Chem i str y | 10.9

NHC2 H5
(iii) IM g — CH3 + H — HNC2 H5 CH 4 + M e
I
(iv) IMg — CH3 + H — OOCCH3 → CH4 + IMg – OCOCH3

(v) RMgI + R’I → R — R’ + MgI2

Ni
(vi) 2R MgX + 2H2  → 2RH + MgH2 + MgX2

X
(vii) RMgX + NH3 → Me + RH
NH2

(viii) CH3MgI + RNH2 → CH4 + RNHMgI

MgI
(ix) CH3MgI + R2NH → CH4 + RN
MgI

(x) R—C C — H + CH 3 — MgI R—C C — MgI + CH 4

(xi) IMg — CH 3 + H — C C — H + CH 3 — MgI 2CH 4+ IMgC C — MgI

Illustration 5:  (JEE ADVANCED)

(a) 0.21 gm of but–3–yn–2–ol is treated with excess of C2H5MgBr at standard conditions. The volume of gas
evolved is:
(A) 134.4 mL (B) 146.4 mL (C) 67.2 mL (D) 73.2 mL
(b) 0.46 gm of a compound with molecular mass of 92 gm gave 336 mL of a gas at STP when treated with excess
of CH3MgI. The number of moles of gas evolved or the number of active H atoms in the compound is
(A) 0.1 (B) 2 (C) 3 (D) 4
(c) The treatment of CH3OH with CH3MgI releases 1.04 mL of a gas at STP. The mass of CH3OH added is:
(A) 1.49 mg (B) 2.98 mg (C) 3.71 mg (D) 4047 mg
(d) The addition of 4.12 mg of an unknown alcohol ROH, to CH3MgI releases 1.56 mL of a gas at STP. The molar
mass of alcohol is
(A) 32 gm mol/L (B) 46 gm mol/L (C) 59 gm mol/L (D) 74 gm mol/L
(e) The sample of 1.79 mg of a compound of molar mass 90 gm mol/L when treated with CH3MgI releases 1.34
mol of a gas at STP. The number of moles of active hydrogen in the molecule is:
(A) 1 (B) 2 (C) 3 (D) 4

Sol: At STP condition,

Volume of 1 mol of a gas = 22.4 litres (when P = 1 atm, T = 273K).
If P = 1 bar and T = 273 K, then volume = 22.7 litres.
Similarly, at standard condition, when P = 1atm and T = 298 K, then volume = 24.4 litres
When P = 1 bar and T = 298 K, then volume = 24.7 litres.
(a) Correct answer is B
1 0 . 1 0 | Alkanes

CH3 − C H − C ≡ CH
|
OH

(It contains two active H atoms).

One mole of compound (70 gm) gives 2 mol of C2H6 gas Seventy grams of compound ⇒ 2 × 24.4 litres
of C2H6 gas at standard condition.
2 × 2.24 × 0.21
∴ 0.21 gm of the compound = = 0.1464 litre = 146.4 m
70
(b) Correct option is C
Since 0.46 gm of a compound gives off 336 mL of a gas at STP.
336 × 92 67200
∴ 92 gm of a compound would give ⇒ = 67200 mL = = 3 mol
0.46 22400
Therefore, number of active H atoms = 3.

(c) Correct answer is A

CH3OH contains only one active H atom. (Active hydrogen –OH)
So, 1 mol of CH3OH gives 1 mol of CH4 gas.
22400 mL of CH4 gas is obtained from 32 gm of Methanol. (Molecular mass of MeOH–32)
32 × 1.04
∴ 1.04 mL of CH4 gas is obtained ⇒ ⇒ 0.00148 g ⇒ 1.49 mg
22400
(d) Correct option is C
Here it is given that 1.56 mL of a gas is obtained from 4.12 × 10–3 gm of ROH.
4.12 × 10−3 × 22400
Therefore, 22400 mL of a gas is obtained from = 59.15 gm mol/L
1.56

(e) Correct option is C

Let 1 mol of a compound gives x mol of a gas.
∴ 90 gm of a compound would give = x × 22400 mL of gas
x × 22400 × 10−3
1.79 × 10–3 gm of a compound gives ⇒
90
x × 22400 × 1.79 × 10−3
∴ = 1.34 ∴ x=3
90

2.2.2 Wurtz reaction

Wurtz reaction: The reaction of an Alkyl halide with sodium in dry ether to give a hydrocarbon containing double
the number of carbon atoms present in the halide.

2RX + 2Na ––––––––––> R — R + 2NaX

R — X + 2 Na ––––––––––> R– Na+ + NaX

R–Na+ + R — X ––––––––––> R–R + NaX

 Chem i str y | 10.11

Pure & dry

Examples: RX + 2Na + RX → R — R + 2NaX
Ether

Pure & dry

CH3Cl + 2Na + Cl CH3 → CH3CH3 + 2NaCl
Ether

Pure & dry

2CH3 – CH – Cl + 2Na → CH3 CH – CHCH3 + 2NaCl
Ether
CH3 CH3 CH3
Pure & dry
RX + 2Na + XR’ → Mixture of R’ – R’ + R’ – R + R – R (mixture of three)
Ether

Pure & dry

CH3Cl + 2Na + Cl C2H5 → CH3CH3 + C3H8 + C4H10
Ether

Fittig reaction
Haloarene reacts with a metallic sodium in the presence of an anhydrous ether to form a Diphenyl which is an
aromatic hydrocarbon

Cl Cl
2Na
+ + NaCl
Dry ether

Wurtz–fittig reaction
The mixture of an alkyl halide gives an alkyl arene when treated with sodium in presence of dry ether
Cl
2Na
+ CH3Cl CH3 + NaCl
Dry ether

Chloro Benzene Methyl Benzene

MASTERJEE CONCEPTS

Exceptions: a. Limitations of the reaction: If the same RX is used the alkane containing odd number
of C atoms or unsymmetrical alkanes cannot be prepared. If different alkyl halides are used, a mixture of
alkanes and alkenes is obtained.

Dry
R — X – 2Na +X — R' → R — R’ + R — R + R’ — R’ + Alkene + 2NaX
Ether

Dry
CH3 − Br + 2Na + Br − C2H5 → CH3 — CH3 + CH3 — C2H5 + C2H5 — C2H5 + CH2 = CH2 + 2NaBr
Ether

Ethane Propane Butane Ethene

Saurabh Gupta (JEE 2010, AIR 443)

1 0 . 1 2 | Alkanes

Illustration 6:  (JEE ADVANCED)

Dry ether
(a) A + 2Na  → Me2CH – CHMe2
Dry ether
(b) A + 2Na  → Me3C – CMe3
(c) One mole of CH3Br and 1 mole of C2H5Br are reacted with 2 mol of sodium metal in dry ether.
The products thus obtained are:
(i) Ethane + 2NaBr
(ii) Ethane + Propane + 2NaBr
(iii) Ethane + Propane + Butane + 2NaBr
(iv) Ethane + Propane + Butane + Ethane + 2NaBr

Sol: Me Me Me

(a) 2Me C Br + 2Na Me C C Me

H H H
2-Bromo propane
or
Isopropyl bromide

Me Me Me

(b) 2Me C Br + 2Na Me C C Me

Me Me Me

(c) Answer (iv)

Reaction of 2 moles of methyl bromide with sodium produces ethane.
2CH3Br + 2Na → CH3 — CH3 (Ethane) + 2NaBr
Reaction of 2 moles of ethyl bromide with sodium produces butane
2C2H5Br + 2Na → C2H5 — C2H5 (Butane) + 2NaBr
Reaction of two different alkyl halide with sodium produces propane
CH3Br + Na + BrC2H5 → CH3 — C2H5 (Propane)

Disproportionation
2C2H5  → C2H6 + CH2 = CH2

2.2.3 Ullmann Reaction

When an iodoarene is heated with Cu powder in a sealed tube, di-aryl is formed (proceeds via free–radical
mechanism).
∆
→ Ph – Ph + CuI
Ph – I + 2Cu + I – Ph 
Sealed tube
Diphenyl

2.2.4 Reduction of Alkyl Halide

RX + 2H → RH + HX
RX can be reduced by any one of the following reagents (which provide nascent H):
(i) Zn + CH3COOH or Zn + dil. HCI or Zn + NaOH
 Chem i str y | 10.13

(ii) (Zn + Cu) Couple + Ethanol (C2H5OH)

(iii) LiAIH4 (or LAH) + Ether (it reduces 1º and 2º RX to RH but 3º RX to alkene)
(iv) Heating with Red P + HI at 420 K (or 150ºC)
(v) TPH [Triphenyl tin hydride (Ph3SnH)]
(vi) NaBH4 + C2H5OH (it reduces only 2º and 3º RX to RH not 1º RX)
(vii) Mg + ether followed by H2O
Zn → Zn2+ + 2e–

RX + e− → R • + X !
R • + e− → R !
R Θ + CH3COOH → R — H + CH3CO O!
It
 is an e transfer from metal to substrate followed by the addition of a proton from the solvent. Earlier it was
–

considered that reduction is carried out by nascent hydrogen (H).

Examples:
(i) Me Me

(a) Zn + Acid Me
Me Cl (b) TPH Me
o
1 RX (c) NaBH4
(d) Red P + Hl

NaBH4
No reaction

(ii) Me Me Me
Me Me (a) Zn + Acid Me
or
Me Me Cl (b) TPH Me
Cl (c) NaBH4
o o
2 RX 3 RX (d) Red P + Hl

Me

Me
Me

2.2.5 Frankland Reaction

When an alkyl halide is heated with zinc powder, a higher alkane is formed.
R — I + Zn + I — R → R-R + ZnI2

2.2.6 Corey House Synthesis

This reaction is used for the preparation of even, odd, symmetric and unsymmetrical alkanes.
Ether
RX + 2Li  → RLi + Lix
2RLi + CuI → R2LiCu + LiI
  Dialkyl lithium cuprate
R'X
R2LiCu 
→ R – R’ + RCu + LiX
1 0 . 1 4 | Alkanes

1. Li
For example: CH3CH2Cl → (CH3CH2)2LiCu
2. CuI

-
R
+
Cu Li + R’ X R R’ + RCu + Lix
R Alkane Alkylcopper

(Where R and R’ may be same or different alkyl groups)

Dry ether
E.g., CH3 — CH2 — Br + 2Li → CH3 — CH2 — Li + LiBr

Ethyl bromide Ethyllithium
2CH3 — CH2 — Li + CuI → (CH3 — CH2) 2 CuLi + LiI
Ethyllithium Lithium diethylcopper
Dry ether
(CH3 — CH2)2CuLi + CH3CH2CH2 — Br 
→ CH3CH2CH2CH2CH3 + CH3CH2Cu + LiBr
n–Propyl bromide n–Pentane Ethylcopper

Illustration 7:  (JEE MAIN)

(a) Me
1.Li
Br (A) (B)
2. Cul
Me Me
Me 1
Isopropyl
bromine
2 Br
3
Me
Isobutyl bromide or
1-Bromo-2-methyl propane
(b) 3 Me
Br
1.Li
(C) (D)
4 2. Cul
Me 2 CH3CH2Br
1
Me
2-Bromo-2-methlybutane

(c) Me 1
1.Li
(E) (F)
Me 3 2 Br 2. Cul CH3CH2Br

Me
1-Bromo-2,2-
dimethyl propane

Sol:

(a) (A) 
  Me

Me

Di-isopropyl lithium
2
CuLi (B) 
Me 1

Me
2
3
4

2,4-Dimethyl pentane
5 Me

Me

cuprate
 Chem i str y | 10.15

  3 Me 2 Me 4
1
1 5
4
(b) (C) 
Me 2 CuLi (D) 
Me 3
Me

Me 2 Me
3,3-Dimethyl pentane
Di-(2-methyl butyl)
lithium cuprate

 
Me Me 4
3 2
1
1 5
(c) (E) 
4
2 CuLi (F)  Me
Me Me 3
Me 2 Me
3,3-Dimethyl pentane
Di-(2-methyl butyl)
lithium cuprate

2.3 From Carboxylic Acids

2.3.1 Decarboxylation
The process by which a molecule of CO2 is removed from an organic compound, is called decarboxylation.
When a carboxylic acid is heated with soda-lime (NaOH + CaO in the ratio 3: 1) at about 630 K a molecule of CO2
is lost and an alkane with one carbon atom less than the carboxylic acid is formed.
R – COOH + NaOH → R – COONa + H2O
Carboxylic acid
CaO, 630K
R — COONa + NaOH R — H + Na 2CO 3
Alkane

E.g., CH3COOH + NaOH → CH3COONa + H2O

Ethanoic acid Sod. ethanoate
(Acetic acid)
CaO, 630K
CH3 COONa + NaO H CH4 + Na 2CO 3
Sod. acetate Methane
CaO
Similarly , CH3CH2COOH + 2NaOH CH3 – CH3 + Na2CO3 + H2O
630 K
Propanoic acid Ethane
(Propionic acid)
NaOH alone could have been used in the above reaction but soda–lime is preferred because of the following two
reasons:
(i) CaO permits the reaction to be carried out at a relatively higher temperature to ensure complete decarboxylation.
(ii) CaO keeps NaOH dry because it is quite hygroscopic (absorbs moisture from air) in nature.

2.3.2 Kolbe’s Electrolysis

The electrolysis of an aqueous solution of sodium or potassium salt of a fatty acid gives a higher alkane, and
the electrolysis of an aqueous solution of the sodium or potassium salt of dibasic acid gives alkene, whereas the
electrolysis of aqueous solution of sodium or potassium salt of dibasic unsaturated fatty acid gives alkyne.
!
Electrolysis
2RCOONa  → R – R + 2CO2 + 2OH + H2
Mechanism (free radical)
1 0 . 1 6 | Alkanes

..
Electrolysis 2RCOO + 2Na
2RCOONa

At anode (oxidation)
Electrolysis
2RCOO!  → 2e! + 2RCOO•
• R—R
2R + 2CO2
Alkane

At cathode (reduction): Reduction of H2O takes place since its reduction potential is greater than Na⊕ .
2H2O + 2e 2OH + H 2

Methane cannot be prepared by this method.

Some examples:
Electrolysis
Electrolysis
(a) CH
CH33COONa
COONa CH
CH33 CH
CH33 +
+ 2CO
2CO22
 +H
+ +
H22+ 2CH
2CH22
(a)
Sodium
Sodium acetate
acetate Ethane
Ethane (At
(At anode)
anode) (At
(At cathode)
cathode)

Electrolysis
Electrolysis CH COO
(b)
(b)
CH
CH22COONa
CH
COONa

CH22COONa
COONa
CH22COO
CH
CH22 COO
COO
+
+ 2Na
2Na
 2H O+
2H22O + 2e
Reduction
Reduction
2e at cathode 2OH
at cathode
2OH +
+HH22


Di-sodium
Di-sodium succinacte
succinacte Oxidation
Oxidation
at
at anode
anode

H
H22C CH

 
CH
CH22 CH
CH22 CH
CH22COO
COO C CH22 Dimerisation
Dimerisation
- +
+
+ 2CO
2CO22
 + 2e-
+ 2e +
CH CH
CH22 CH
CH22COO
COO H
H22C
C CH
CH22
CH22 Cyclobutane
Cyclobutane
Ethane (Very minor)
(Very minor)
Ethane

Electrolysis
Electrolysis +
+ 2Na
(( cc )) CHCOONa
CHCOONa
CH
CH22COONa
COONa
CHCOO
CHCOO
CHCOO
CHCOO
2Na
2H O+
2H22O + 2e
Reduction
Reduction
2e at cathode 2OH
at cathode
2OH +
+HH22


Disodium
Disodium maleate
maleate
or Disodium
or Disodium fumerate
fumerate Oxidation
Oxidation
at
at anode
anode

CHCOO HC
HC CH
CH Dimerisation
CH
CH22 CH
CH22 CHCOO - Dimerisation
+ + 2e-
+ 2e +
+
+ 2CO
2CO22

CH CH CHCOO
CHCOO HC
HC CH
CH
CH22 CH22 Cyclobutane
Cyclobutane
(Very
(Very minor)
minor)
Ethylene
Ethylene or
or
acetylene
acetylene CH
CH33CH
CH22Cl
Cl
CH
CH33CH
CH22CH
CH22CH
CH33

2.3.3 Reduction of Carbonyl compound to Alkane by Clemmenson’s and Wolf Kishner’s

Reduction
1
3 Me 3
4 2 (a) Zn - Hg + Conc. HCl 4
O
Me or 2 Me
1
Me (b) NH2 - NH2 + OH Butane
Butan-2-one
 Chem i str y | 10.17

2.3.4 With HI and Red Phosphorus

Reduction of Acids and Carbonyl Compounds with red P + HI to Alkane

4 2
Me Me
1 Red P + HI
3 COOH
Me
O Butane
Me
3 - Oxobutanoic acid

2.3.5 The Mozingo reduction

A chemical reaction capable of fully reducing a ketone or aldehyde to the corresponding alkane is called the
Mozingo reaction or thioketal reaction. The reaction scheme is as follows:

2.4 From Carbides

4. By the action of water on beryllium and aluminium carbide. Both these carbides on treatment with water yield
methane.
Be2C + 4H2O → CH4 + 2Be(OH)2
Beryllium carbide Methane
Al4C3 + 12H2O → 3CH4 + 4Al(OH)3
Aluminium carbide Methane

3. PROPERTIES OF ALKANES
 1. Boiling points: In straight chain alkane C1 to C4 are gases, C5 to C17 are liquids and C18 on words are
colorless waxy solids. With increase in the molecular size the surface area increases and hence Vander-Waals
forces increases which increases B.P. accordingly. B.P. of branched chain isomers are lower than corresponding
n-alkanes due to decreased surface area.

CH3CH2CH2CH2CH3 n-pentane B.P.=309.1K,m.p. 143.3K

CH3CH(CH3 )CH2 CH3 Iso-pentane B.P.= 301K, m.p. 113.1K

CH3C(CH3 )2 CH2 CH3 Neo-pentane B.P. 282.5, m.p. 256.14K

 2. Melting points: Melting points of alkanes also increase with the increase in carbon content but the variation
is not regular. Alkanes with even number of carbon atoms have higher m.p. than those with odd number of
carbons atoms. This property is commonly known as the alternation effect.
 3. Solubility: ‘Like dissolves like’ is the general rule of solubility. Non polar alkanes which are insoluble in polar
solvents such as water, alcohol, etc. are highly soluble in non–polar solvents such as petroleum ether, benzene,
carbon tetrachloride, etc. greases are mixtures of higher alkanes and hence are non–polar and hydrophobic
(water repelling) in nature.
 4. Density: The densities of alkanes increase with increase in the molecular masses till the limiting value of about
0.8g cm–3. This means that all alkanes are lighter than water.
1 0 . 1 8 | Alkanes

Illustration 8: Arrange the compounds of (i) in the order of decreasing boiling points and (ii) in the order of
decreasing solubility in water.
(a) (1) Ethanol, (2) Propane, (3) Pentanol
(b) (1) Butane, (2) 1, 2, 3–Pentane triol, (3) Butyl alcohol
(c) (1) Pentane, (2) Pentanol, (3) Hexanol

Sol: 8 (a) (i) Alcohol has higher boiling point compared to alkane (of same molecular mass). Water is a polar solvent
it will dissolves polar molecule.
The correct Decreasing order of boiling point is:
Pentanol > Ethanol > Propane (3>1 >2).
Both Pentanol and ethanol have H–bonding, but Pentanol has higher molecular mass than ethanol, so it has high
boiling point.
Propane has the least boiling point due to its non–polar character and weak Vander Waals forces of attraction.
(ii) The decreasing order of solubility in H2O is:
Ethanol > Pentanol > Propane (1 > 3 > 2).
Like dissolves like.
Since water is a polar solvent it will dissolves polar molecule.
Due to non-polar character of propane it is least soluble in water.
Solubility of ethanol and Methanol is explained as follows:
Both ethanol and Pentanol involves hydrogen bonding, but non-polar (Carbon chain) part  OH in

Pentanol is larger than non–polar

 OH  part in ethanol. So ethanol is more soluble in H2O than Pentanol.

(b) Methodology: It is obvious that alcohol has higher boiling point compared to alkane (of s same molecular mass).
Water is a polar solvent it will dissolves polar molecule
(i) The correct order of decreasing boiling point is:
1, 2, 3–Pentane triol > Butyl Alcohol > Butane (2 > 3 > 1).
Due to three (OH) groups in compound (2), it has more H–bonding than in alcohol (3).
(ii) Decreasing solubility in H2O: (2) > (3) > (1).
Butane is least soluble.There is more H–bonding in compound (2) than in (3), hence it has more solubility in H2O.

(c) It is obvious that alcohol has higher boiling point compared to alkane (of s same molecular mass). Water is a polar
solvent it will dissolves polar molecule
(i) The decreasing order of boiling point is:
Hexanol > Pentanol > Pentane
(3 > 2 > 1)
In this case both the alcohols have same Hydrogen bonding, but molecular mass of Hexanol is higher than that of
Pentanol. Hence, it has higher boiling point.
Pentane has low boiling point.
(ii) The decreasing order of solubility in H2O:
Pentanol > Hexanol > Pentane
 Chem i str y | 10.19

Illustration 9: Arrange the following in the decreasing order of their boiling points.
(a) (1) C3H8, (2) C2H5OH, (3) (CH3)2O, (4) HOH2C–CH2OH
(b) (1) 3–Pentanol, (2) n–Pentane, (3) 2, 2–Dimethyl propanol, (4) n–Pentanol

Sol: It is obvious that alcohol has higher boiling point compared to alkane (of s same molecular mass).
(a) The decreasing order of boiling point is:
HOCH2 – CH2OH > C2H5OH > (CH3)2O > C3H8
(4 > 2 > 3 > 1)
(Same explanation as I (B) (a) above)
(b) The decreasing order of boiling points is:
n–Pentanol > 2,2–Dimethyl propanol

Me 2 4

 Me
2

Me 1
OH
  >
1
Me
3
1
OH
5
Me

3-Pentanol

> n–Pentane (4 > 3 > 1 > 2)

All the Alcohols (4), (3), and (1) have H–bonding, but n–pentanol is a straight chain compound and thus it has a
large surface area, (so the highest boiling point).
Alcohol (3) is sterically hindered than alcohol (1), hence it requires more energy to boil off. Therefore, boiling point
of alcohol (3) > alcohol (1).

4. REACTION OF ALKANES

4.1 Combustion
In sufficient oxygen, alkane gives water and carbon dioxide as products. The complete combustion reaction of
butane is:
2C4H10(g) + 13O2(g) → 8CO2(g) + 10H2O(g) ∆H = –5754 kJ mol/L
In general, the formula for complete combustion of alkanes is:
 y y
CxHy(g) +  x +  O2(g) → xCO2(g) + H O(g)
 4 2 2
In insufficient supply of O2 by incomplete combustion, carbon monoxide and elemental carbon are formed.
Incomplete combustion of octane: 2C8H18(l) + 17O2(g) → 16CO(g) + 18H2O(g)

4.2 Substitution Reactions

4.2.1 Halogenation
In this reaction, hydrogen of alkane is replaced by halogen. Reaction proceed by “Homolytic fission” in which free
radicals are formed.
(i) Chlorination: During chlorination of methane, all the four hydrogen atoms are replaced one by one to form a
mixture of products. For example,
hv or
CH4 + Cl2 → CH3Cl + HCl
520 −670K
1 0 . 2 0 | Alkanes

Methane Chloromethane
(Methyl chloride)
hv or
CH3Cl + Cl2 → CH2Cl2 + HCl
520 −670K
Chloromethane Dichloromethane
(Methylene chloride)
hv or
CH2Cl2 + Cl2 → CHCl3 + HCl
520 −670K
Dichloromethane Trichloromethane
(Chloroform)
hv or
CHCl3 + Cl2 → CCl4 + HCl
520 −670K
Trichloromethane Tetrachloromethane
(Carbon tetrachloride)
Let’s look at the mechanism behind the substitution reaction of bromine reacting with methane.
Initiation: UV breaks the bond between Br2 leaving free radicals
UV light
Br – Br  → Br• + Br•
UV light
Br Br Br + Br

520-670K or UV light
Cl Cl 2Cl
Homoly tic fission Chlorine fr ee radical

Propagation: Br reacts with methane, leaving another radical CH4 − Br • → CH3 • + HBr

(a) Propagation: The methyl radical reacts with another bromine molecule CH3 • +Br − Br → CH3Br + Br •

(b) Chain propagation: Each propagation step consists of two reactions. In the first reaction, the Cl radical attacks
the CH4 molecule and abstracts a hydrogen atom forming •CH3 and a molecule of HCI as shown reaction (i) in
the second reaction, •CH3 thus produced reacts further with a molecule of Cl2 forming a molecule of methyl
chloride and another •Cl as shown in reaction (ii). The newly formed •Cl reacts with another molecule of CH4
(reaction (i)) to produce another molecule of HCl and another •CH3 . This •CH3 can again repeat reaction (ii)
and so on. Thus, the sequence of reactions depicted in equations (i) and (ii) is repeated over and over again
and the chain gets propagated. In other words, a single photon of light absorbed by Cl2 can bring about the
conversion of a large number of CH4 molecules into CH3Cl. Such reactions are called chain reactions.
H H

H C H + Cl H C + HCl
Chlorine
H free radical H
Methyl fr ee radical

H H

H C + Cl Cl H C C+ Cl

H H
Methyl chloride
When sufficient amount of methyl chloride has been formed, the ·Cl produced in reaction (ii) has a greater chance
of colliding with a molecule of CH3Cl rather than a molecule of CH4. If such a collision occurs, a new free radical
(·CH2Cl) is produced (reaction (iii)) which may subsequently react with Cl2 producing a molecule of CH2Cl2 (reaction
(iv)) and another ·Cl. This process continues till all the hydrogen atoms of methane are replaced by halogen atoms
(reactions (v), (vi), (vii) and (viii)).
 Chem i str y | 10.21

(iii) CH3Cl + ·Cl → ·CH2Cl + HCl (iv) ·CH2Cl + Cl2 → CH2Cl2 + ·Cl
(v) CH2Cl2 + ·Cl → ·CHCl2 + HCl (vi) CHCl2 + Cl2 → CHCl3 + ·Cl
(vii) CHCl3 + ·Cl → ·CCl3 + HCl (viii) CCl3 + Cl2 → CCl4 + ·Cl

Termination: Two radicals react and complete the reaction * Lots of Bromine will mean more substitution (dibromo,
tribromo, etc.)
Br· + Br· → Br2
CH3· + Br· → CH3Br
CH3· + CH3· ¾→ C2H6

Iodination: Iodination of alkanes is generally not carried out to prepare RI as the reaction is highly endothermic
and reversible. But is carried out in the presence of an oxidizing agent, such as HIO3, HgO and HNO3, as it removes
the HI formed in the reaction.
CH3CH3 + I2→ CH3CH2I + HI ; 5HI + HIO3 → 3I2 + 3H2O
2HI + HNO3 → 2NO2 + H2O + I2 ; HgO + HI → HgI2 + H2O

MASTERJEE CONCEPTS

The order of reactivity of different halogens in these reactions is: F2 > Cl2 > Br2 > I2
However reaction with fluorine is very explosive and so never carried out.
B Rajiv Reddy (JEE 2012, AIR 11)

4.2.2 Nitration
Nitration: Replacement of a hydrogen atom by a nitro (–NO2) group is called nitration. At ordinary temperature,
alkanes do not react with HNO3. However, when a mixture of an alkane and fuming HNO3 vapours are heated at
423–673 K under pressure (vapour phase nitration), alkanes undergo nitration giving a mixture of nitroalkanes
resulting through cleavage of carbon–carbon bonds. For example,

CH3 – H + HNO3 → CH3 — NO2 + H2O

Methane (Fuming) Nitromethane (low yield)
Fuming HNO3
CH3 – CH3  → CH3CH2 – NO2 + CH3 — NO2
673K
Ethane Nitroethane (80%) Nitromethane (20%)

NO2
CH3CH2CH2NO2 + CH3 CH CH3 + CH3CH2 NO2
Fuming HNO3 1-Nitropropane (25%) 2-Nitropropane (40%) Nitroethane (10%)
CH3CH2CH3
Propane 673K + CH3 NO3 + Other oxidation products +CO2, NO2, H2O, etc)
Nitromethane (25%)

The order of reactivity of different hydrogens in this reaction is: 3º > 2º > 1º.
When nitration is carried out in vapour phase between 420K and 720K, a mixture of all possible mononitro
derivatives is obtained (directly or after fission). For example,
1 0 . 2 2 | Alkanes

NO2
2 2
NO2
3 1 HNO 3 + 3 1
Me Me Me Me Me
670K
1- Nitropropane 2- Nitropropane

+ + MeNO 2
Me NO2
Nitroethane Nitromethane
4.2.3 Sulphonation
When alkane is treated with oleum (H2S2O7) of fuming H2SO4 (H2SO4 + SO3). H atom is replaced by (–SO3H) group.
The order of reaction is 3º > 2º > 1º.
Me Me3
Me + (H2SO4 + SO3) 2 1 Me + H O
2

Me Me
H SO3H
Isobutane 2-Methylpropane-2-sulphonic acid

4.3 Catalytic oxidation

(i) When CH4 and O2 (9: 1) are heated at 100 atm pressure and passed through copper wires at 470K, CH4 is
oxidized to CH3OH.
2CH4 + O2 → 2CH3OH

(ii) CH4 and O2, when heated with molybdenum oxide, give methanal.
∆
CH4 + O2 → HCHO + O2
MoO2
(iii) Higher alkane (C16) on oxidation with manganese acetate at 370–430 K produces higher fatty acids.
∆
2C16H34 + 3O2  → 2C15H31COOH + 2H2O
(CH3COO)2 Mn
(iv) With alkaline KMnO4, 3ºH atom is oxidized to (–OH) group.
Me Me 3
Alkaline 2 1Me
Me
KMnO4
Me H Me OH
Isobutane t-Butyl alcohol
or
2-Methyl propan-2-ol
Because of the +I effect of the three CH3 groups, e– density at 3ºC atom is relatively high, which accounts for its
easier oxidation.

(v) Partial oxidation: When CH4 and C2H6 are treated with O2 at high pressure and low temperature, H atom
changes to (–OH) group, successively.
OH
[O] → CH OH 
[O] → CH −H2O [O] → HCOOH 
[O] → CO + H O
CH4  3 2  → HCHO  2 2
OH
 Chem i str y | 10.23

4.4 Isomerization
Alkanes on heating with AlCl3 at 570K isomerize to give branched–chain alkane [takes place via 1, 2 HΘ (hydride)
or Me shift]
Me
Me AlCl3 +
570 K Me Me Me Me
Me
Me
2-Methylpentane 3-Methylpentane

Me
Me 4 Me Me
2
2 AlCl3 3 AlCl3 + HCl 2
1
1 3 Me 1 3
Me Me 570K 298K Me Me
1-Isobutane
or
2-Methy propane
Me 1
Me
2 4
AlCl3 + HCl 2 4 Me
1 3 5
Me Me 3
298K Me
Me
2-Methy pentane 2-Dimethy butane

4.5 Aromatization
Alkanes containing six to eight carbon atoms when heated to about 773K under 10–20 atm pressure in the presence
of a catalyst consisting of oxides of chromium, vanadium and molybdenum supported over alumina, get converted
into aromatic hydrocarbons. This process which involves cyclization, isomerization and dehydrogenation is called
aromatization. For example
CH3
CH2 CH3 Cr2O3, V2O5, Mo2O3/Al2O3 Dehydrogenation
CH2 CH2 773K, 10-20 atm (-3H2)
CH2 Cyclization (-H2) Cyclohexane Benzene
n-Hexane
Under similar conditions, n–heptane gives toluene while n–octane gives a mixture of o–, m– and p–xylenes.
CH3

CH2 CH3
CH2 CH3 Cr2O3, V2O5, Mo2O3/Al2O3 Dehydrogenation
CH2 CH2 773K, 10-20 atm (-3H2)
Cyclization (-H2)
CH2 Methylclohexane Toluene
n-Hexane

Cr2O3, V2O5, Mo2O3/Al2O3 C6H4(CH3)2

CH3 (CH3)6 CH3
773K, 10-20 atm, Cyclization Mixture of o-m-and p-Xylene
n-Octane and dehydrogenation (-4H2)

4.6 Pyrolysis
Pyrolysis of higher alkanes to give a mixture of lower alkanes, alkenes, etc. is called cracking. It is usually carried out
by heating higher alkanes to high temperatures (773–973K) under a pressure of 6–7 atmospheres in presence or
absence of a catalyst. For example
773K
C6H14  → C6H12 + H2 + C 4H8 + C2H6 + C3H6 + C2H4 + CH4
Hexane 6 −7atm     
Hexane Hydrogen Butene Ethane Pr opene Ethene Hydrogen
1 0 . 2 4 | Alkanes

Pyrolysis of alkanes involves breaking of C – C and C – H bonds and occurs by a free radical mechanism. Preparation
of oil gas from kerosene oil and petrol gas from petrol is based upon the process of pyrolysis. For example,
dodecane, a constituent of kerosene oil, on heating to 973K in presence of Pt, Pd or Ni, gives a mixture of heptane
and pentene along with other products.
Pt or Pd or Ni
C12H26 → C7H16 + C5H10 + other product
Dodecane 973K Heptane Pentene

5. USES OF ALKANES
(i) Methane in form of natural gas is used for running scooters, cars, buses, etc. LPG (a mixture of butane and
isobutane) is used as a fuel in homes as well as in industry.
(ii) Methane is used to make carbon black which is used in manufacture of printing inks, paints and automobile
tyres.
(iii) Catalytic oxidation of alkane gives alcohols, aldehydes and carboxylic acids.
(iv) Higher alkanes in form of gasoline, kerosene oil, diesel, lubricating oils and paraffin wax are widely used.
(v) Methane is used for the manufacture halogen containing compounds such as CHCl3, CH2Cl2, CCl4, etc. which
are used as solvents both in laboratory and industry.

6. PETROLEUM
Petroleum is a dark viscous oily liquid. It is believed that it is formed by the decomposition of marine animals under
pressure and temperature. Petroleum is found deep below the earth’s crust, trapped within rock structures much
below the seabed. Petroleum or crude oil is obtained in a complex mixture of hydrocarbons (chiefly aliphatic with
small amount of aromatic hydrocarbons) along with small amount or organic compounds of sulphur and nitrogen.

S. No. Fraction Approximate Boiling range (in K) Uses

composition
1. Gaseous hydrocarbons C1–C4 Upto 303 As fuel gas after liquification and
as carbon black.
2. Crude naphtha C3–C10 303–423 As solvent in varnish and rubber
1. Petroleum C5–C7 303–363 industries, and for
2. Petrol or gasoline C7–C9 363–393 As motor fuel; for dry cleaning
3. Benzene C9–C10 393–423 For dry cleaning
3. Kerosene oil C10–C13 423–513 Fuel for stoves; in manufacture of
oil gas as illuminant
4. Fuel oil C13–C18 513–623 Fuel for diesel engine and tractors;
1. Gas oil in sizing paper.
2. Diesel oil
3. Furnace oil
5. Lubricant oil C15–C18 Above 543 Paint oil; transformer oil, in
1. Medicinal oil lubrication; in sizing paper.
2. Motor oil
3. Grease
6. Paraffin wax C18–C30 673 upwards Ointments, candles, paraffin wax,
1. Petroleum jelly for matches, paints, water proofing
solid fuel, protecting paints
2. Petroleum wax
3. Petroleum coke
 Chem i str y | 10.25

7. Heavy fuel oil and C30 onwards From residue Paints; road surfacing
Bitumen

6.1 Knocking
Knocking may be defined as the pre–ignition of fuel–air mixture in the cylinder ahead of the flame. It reduces the
efficiency of the engine and also causes damage to the cylinder and piston of the engine.
 1. The extent of knocking depends on the quality of the fuel used. In other words, a fuel that produces minimum
knocking is considered as a good–quality fuel.
 2. The anti–knocking property or the quality of a fuel is usually expressed in terms of the octane number.

6.2 Octane Number

Octane number is a scale that is used to determine the quality of a fuel.
It may be defined as the percentage of iso–octane by volume in the mixture of isooctane and n–heptane that has
the same anti–knocking properties as the fuel under examination.
 1. Straight–chain aliphatic hydrocarbons have a higher tendency to knock than branched–chain hydro–carbons.
 2. Two pure hydrocarbons have been selected as standards;
a. n–Heptane has poor anti–knocking property, therefore, arbitrarily it has been assigned an octane number
of zero.
b. 2, 2, 4–Trimethylpentane (isooctane), a branched–chain hydrocarbon, has the highest anti–knocking
property. Therefore, it has been given the octane number of 100. The octane number of nonane is –45 and
that of 2, 2, 3–trimethylpentane,

 
Me
2 4
1 3 5
Me Me Me called as triptane, is 116.
Me

2 4 6
1 3 5 7
Me Me n–Heptane, octane number = 0
Me Me
2
1 4 5
Me Me 3 Me 2, 2, 4–Trimethyl pentane or isooctane, Octane number= 100

Alkanes Octane number

CH4 122
C2H6 101
C3H8 96
C4H10 89

 3. Straight–chain alkanes have very low octane numbers. As the length of the chain increases, the octane number
decreases.
 4. Branched–chain alkanes have higher octane numbers. As the branching increases, the octane number
increases.
 5. Cycloalkanes have higher octane numbers. As the extent of branching increases, octane number further
increases.
The tendency of knocking decreases in the order.
Straight–chain alkane > branched–chain alkane > alkenes > cycloalkanes > aromatic hydrocarbon
1 0 . 2 6 | Alkanes

6.3 Anti Knocking Agents

Compounds that are added to gasoline and reduce knocking are called anti–knocking agents. The best anti–knocking
agent is tetraethyl lead (TEL) or Pb (C2H5)4. This is added to the extent of 0.001% in gasoline. Such a gasoline is called
ethyl gasoline we leaded gasoline.
In the cylinder of an engine, TEL decomposes to produce ethyl radicals that combine with the radicals produced
due to irregular combustion. As a result, reaction chain is broken and smooth burning of the fuel occurs. This
Heat
prevents knocking. Pb(C2H5)4  → Pb + 4C2H5 (Ethyl radical)
The lead deposited in the cylinder is removed by adding 1, 2–dibromoethane (ethylene bromide) that decomposes
into ethane (ethylene) and bromine. The bromine thus obtained combines with lead to form lead bromide which,
being volatile, is carried off from the engine by exhaust gases.
BrCH2CH2Br → CH2 = CH2 + Br2 ; Pb + Br2 → PbBr2 (volatile)

6.4 Cetane Number

 1. Cetane number is a scale that is used to determine the quality of diesel fuel. Cetane number is the percentage
of cetane by volume in a mixture of cetane and α–methylnaphthalene that has the same ignition properties
as the diesel under examination in a test engine.
C6H34(n–Hexadecane), cetane number = 10 (ignites spontaneously)
CH3

α–Methylnaphthalene, cetane number = 0 (ignites slowly) or 1–Methylnaphthalene

 2. LPG and CNG: The term LPG (liquefied petroleum gas) refers to the mixture of hydrocarbons containing three
or four C atoms. This includes propane (C3H8), propene (C3H6), n–butane (C4H10), isobutene (methylpropane),
and various butanes with a little amount of ethane (C2H6). The major sources of LPG are natural gas, refining and
cracking of petroleum. Alkenes are mainly produced during cracking. LPG is mainly used in the manufacturing
of chemicals, as a fuel for households, and in the petro–chemical industry.
CNG (compressed natural gas) is a highly compressed form of natural gas. Many vehicles are designed to
operate on CNG. Natural gas has an octane rating of 130.

Illustration 10: A sample of diesel has the same characteristics as a 60 mL mixture of cetane and α–methyl
naphthalene mixed in 2: 1 ratio (v/v). What is the cetane number of the diesel sample?

Sol: 60 mL of a mixture contains 40 mL cetane and 20 mL of α–methylnaphthalene.

40 × 100
Therefore, cetane number = = 66.6%
60

Illustration 11: Give the decreasing order of octane rating of the following:
Me
Me
i. Me ii.

Me
Me Me Me
iii. iv.
Me Me Me

v. vi.
 Chem i str y | 10.27

Sol: The tendency of knocking in the decreasing order is: Straight–chain alkane > branched–chain alkane > alkenes >
cyclo alkane > aromatic hydrocarbons. The octane rating is in the reverse order as that of knocking tendency:
(vi) > (v) > (iv) > (iii) > (ii) > (i)

7. CYCLOALKANES
7.1 Nomenclature

Cyclopropane Cyclobutane Cyclopentane

(27.6 kcal/mol) (26.4 kcal/mol) (6.4 kcal/mol)

Cyclohexane Cycloheptane Cyclooctane

no ring strain (6.3 kcal/mol) (9.6 kcal/mol)

2 Br 2 5
1 9 1 6 7
3 4
3 7 CH3
8 CH3
4 4 3
6 1 8
6 7 2
5 5
Br Cl
trans-1,6-Dibromo- 7,7-Dimethyl- 2-Chloro-
bicyclo[4.3.0]nonane bicyclo[4.1.0]heptane bicyclo[4.2.0]octane

7
Cl
1
2 6

4
3 5
Bicyclo [2.2.1] 3-Chlorospiro[5.3]nonane
hept-2-ene

Figure: 10.4 Nomenclature of fused cycloalkane

The energy change in the ring–flip of cyclohexane (chair chair)

Half-chair Half-chair

Boat
Energy

Twist-boat Twist-boat

Chair Chair

Figure: 10.5 Stability of different conformers of cyclohexane

1 0 . 2 8 | Alkanes

Illustration 12: Give IUPAC name of the following compounds:

Me Me
Me Me
Me
1. 2. Me 3. Br 4.
Me HO Me
Me

Me O
Cl
5. 6. 7. HO Br 8.

Note: The superscripts 1, 6 indicate the fused C atoms.

 1. 1,2-trimethyl-3-isopropylcyclobutane.

 2. (3-methylcyclobutyl) cyclopentanol.

Me
Me
 3. Me
Me 4. 8
9
1
10 2 7 2
1
9 3
6 10 3 Me
8 5 4
6 4 Me
7 5

a. 1, 2, 4–Trimethyl bicycle [4.4.01.6] decane. a. 1, 3, 9–Trimethyldecalin

b. Bicyclo compound

5. Me O 1 2
1 2
6 3
Cl 7 5
6. 11 4
10 5
9 6
8 11 4 3 8 7
9 10

a. Spiro 7–chloro–6–methyl [6.4] undecan–2–one a. Cyclododecane

or b.Monocyclic compound
7–chloro–6–methyl [4.6] undecan–2–one
7
8
1 5
7. 8. 1
2 6
2 6
HO Br
4
3 4 5
3 7

a. 6–Bromospiro [3.3] hexan–2–ol a. Tricyclo [2.2.2.01.4] octane

b. Spiro compound b. Tricyclo compound

7.2 Physical Properties of Cycloalkanes

 1. Lighter than water, non-polar, soluble in organic solvents such as alcohol and ether.
 2. M.P and B.P. are higher than corresponding alkanes because of their compact shape.
 3. Carbon hydrogen bond is shorter than corresponding alkanes. Cycloalkanes are more acidic than corresponding
alkanes, e.g., cyclopropane is more acidic than propane, because (C – H) bonds of cyclopropane have more s
character in hybrid orbital used by C to form a bond.
 Chem i str y | 10.29

Stability of cyclohexane: Cyclohexane exists in three non–planar or puckered conformations, called chair, twist
boat, and boat forms.
In the chair form, all the (C – H) bonds on the adjacent carbons are in the skew position. In the boat form, there
are four skew interactions (1, 2; 3, 4; 4, 5 and 6, 1) and two eclipsed interactions (2, 3 and 5, 6). At the same time,
there is some bond opposition strain for these two pairs of eclipsed bonds (2, 3 and 5, 6) and also steric repulsion
between the flagpole (fp) hydrogens (at 1 and 4), which are 1.83Å or 183 pm apart. Hence, the total strain in the
boat conformations is larger than that in the chair conformation and therefore, the chair form is more stable than
boat form.

MASTERJEE CONCEPTS

Stability order: Chair > Twist boat > Boat > Half chair
In substituted cyclohexane, the more stable form is the one in which the bulkier group is present at
e(equatorial) position, since (e) bonds are away from the ring and hence have less or no steric hindrance
than a (axial bonds). The examples are as follows.
a. The stable form of methyl cyclohexane is that in which methyl group is one(equatorial) position. There
are two conformationalH isomers e.g., Me
H Me
Me H
and Me H
and
(1e-Me) (1a-Me)
(I) More stable (1e-Me) (II) Less stable (1a-Me)
(I) More stable (II) Less stable
b. The stable form of cis–1, 2–dimethylcyclohexane is (1a, 2e) or (1e, 2a). There is one conformational
isomer.
Me H Me
H
Me 1 1
1 Me H
2 H or
2 Me 2H

(1a:2a) (1e:2e)
(Trans) H Me
(Two Me gps, one downward (Two Me gps, one downward
and other upward, i.e., and other upward, i.e.,
oppsoite side hence trans) opposite side hence trans)

(I) More stable (II) Less stable

c. The stable form of trans–1, 2–dimethylcyclohexane is (1e: 2e). Two conformational isomers are as
below:

Me Me H
H
Me 1
1 H Me
2 H or
2 Me 2 H
(1a:2e) (1e:2a)
(Cis) H Me
(Two Me gps, upwar d position (Two Me gps, downwar d position
i.e. same side hence cis) i.e. same side hence cis)

Rohit Kumar (JEE 2012, AIR 79)

1 0 . 3 0 | Alkanes
+HBr Br +HBr
i. i. Br
Me
7.3 Reaction of Cycloalkanes
(Ring-opening addition r eaction)
Me
(Ring-opening addition r eaction)

+HBr Br Br Br Br
i.ii. +Br 2 Br ii. +Br 2
Me
(Ring-opening addition r eaction)
(Ring-opening addition r eaction) (Ring-opening addition r eaction)
Br Br
hv Br Br
ii.
iii. +Br 2
+Br +HBr hv
2
iii. +Br 2 +HBr
(Ring-opening addition r eaction)
(Substitution reaction)
Br (Substitution reaction)

+Br 2 hv
iii. +HBr

POINTS TO REMEMBER
(Substitution reaction)

Preparation of Alkanes:
From alkyl halide : (I) Y-Compound
containing active
+ hydrogen
Grignard
RX+Mg RMgX RH
reaction
(II) (H₂O)

[ Y can be -ROH, RNH2, RCOOH, C  C, NH3, RX]

Dry
2RX + 2Na R R +2NaX
ether

Wurtz Dry
2ArX + 2Na
reaction ether
(Fitting reaction)

2Na
ArX + RX Ar R + NaX
Dry
ether
RX
Alkyl Ullmann 
2Ar X + 2Cu Ar Ar + 2Cul2
halide reaction

Reduction
RX + 2H RH + HR
reaction

(Reduction agents used are - Zn, Cu / C2H5OH

Zn / HCl, LiAlH4, NaBH4 + C2H5OH, H2, Pt.
Red PHl)

Frank land
2R l + Zn R R + Znl2
reaction

Corey
CuX R’X
House RX + Li RLi R2CuLi R R’
Synthesis
 Chem i str y | 10.31

From Alkene or Alkyne by catalytic hydrogenation.

Ni, 673K
RCH = CH2 + H2  → RCH2CH3
From sodium salt of carboxylic acid.

Decarboxylation
Decarboxylation
R RH +
H Na
+ Na2CO3
2CO3

Sodalime,
Sodalime,
(NaOH++CaO)
(NaOH CaO)
O
O

R C
C
ONa
ONa

Kolbe’s
Kolbe’sElectrolysis
Electrolysis
R RR (At anode)
R (At anode)

By reduction of carbonyl compounds :

a) Zn Hg + conc. HCL
a) Zn Hg + conc. HCL
Clemmensons Me
O Clemmensons Me
O Reaction
Me Reaction Me
Me b) NH2- NH2 + OH Me
Me b) NH2- NH2 + OH
Me Wolf Kishner’s
Wolf Kishner’s
reduction
reduction

By reduction of acid and carbonyl compounds with Red P + HI

4 2
Me Me
1 Red P +Hl
3 COOH
Me
O Butane
3-Oxobutanoic acid

Properties
•• For straight line hydrocarbons, the boiling point increases as the number of carbon atom increases,(Surface
area increases thus Vander Waal force of attraction increases)
•• For isomers as the branching increases, boiling point decreases.(Surface area decreases)
•• ‘Like dissolves like’ is the general rule of solubility. As alkanes have non polar character they are soluble in non-
polar solvents.
•• The densities of alkanes increase with the increase in the molecular masses, they are lighter than water.
1 0 . 3 2 | Alkanes

Reactions of Alkane: In presence of sufficient oxygen

alkane will burn to form water
& carbon Dioxide .
Combustion
In presence of limited supply of
oxygen-carbon monoxide and
elemental carbon are formed
(Both are toxic)

Halogenation
F2 > Cl2 > Br2 > l2
Iodination is reversible
thus it is carried out
in presence of an
oxidizing agent
tert alkane > sec > Primary

Presence of O2 slow
down the reaction

Substitution Nitration Mixture of nitro alkanes

reaction Fuming are obtained
HNO3

Sulphonation H - atom is replaced

by -SO3 H group
Oleum of
Order - 3o > 2o >1o
Fuming H2SO4

Insertion occurs
Methylene insertion at C - H bond.
with CH2N, CH2 = C = O Straight as well as
RCH2CH3
branched product
(alkane)

Only O2
Alcohol is formed
at 100 atm

O2, MoO2
Aldehyde is formed
Catalytic

oxidation
Higher alkane + 3O2
Acid is formed
 , (CH3COO)2Mn

With KMnO4 o
3 H is oxidized to - OH Group

AlCl3 Isomerization in takes place

Isomerization Vai 1,2 hydride shift or
57O K
1,2-methyl shift

Alkanes containing
Cr2O3, V2O3, Mo2O3/Al2O3 6 to 8 carbon atom
Aromatization gets converted to
773K, 10 -20 atom
aromatic hydrocarbons
cyclization (-H2)

773K Breaking of C - C & C - H

Pyrolysis
6-7 atoms bonds to give a mixture
of lower alkenes
 Chem i str y | 10.33

Hydrocarbons :
•• The main sources of hydrocarbons are coal, petroleum and natural gas.
•• Coal is the major source of aromatic hydrocarbons whereas petroleum is for aliphatic ones.

Fraction of destructive distillation of coal :

1 Light oil Benzene, Toluene, Xylene

2 Middle oil Naphthalene, Phenols and Cresols
3 Heavy oil Naphthol, Cresols
4 Green oil Anthracene, Phenanthrene
4 Pitch Anthracene, Phenanthrene carbon

Fractional distillation of petroleum gives following fractions:

1 Petroleum gas C1 to C4
2 Petroleum ether C5 to C7
3 Gasoline C12 to C15
4 Kerosene C12 to C15
5 Gas oil, fuel oil, Diesel oil C15 to C1
6 Lubricating oil C16 onwards
7 Paraffin wax C20 onwards

Cracking: Thermal decomposition of higher hydrocarbons into lower ones. This can be in the vapour phase,
thermal, steam, liquid phase etc.

Reforming or Platforming: The process of converting, aliphatic or alicyclic hydrocarbons into aromatic
hydrocarbons in the presence of suitable catalyst like Pt, Pd or Ni.

Pt, 670K Pt, 670K

C6H14  → C6H12 → C6H6

Octane number: The percentage by volume of isooctane in a mixture of isooctane and n–heptane that has the
same knocking value as the fuel under test.
Branched chain, cyclic, unsaturated and aromatic Hydrocarbons have higher octane number.
Fuel Octane number
N–heptane Zero
2,2,4 trimethylpentane 100
2,2,3 trimethylpentane 116
(triptane)

Cetane number: The percentage volume of cetane in a mixture of cetane and α–methyl naphthalene that has the
same initiation quality as the fuel under investigation is known as cetane number.