University of Kerbala

College of Science
Department of Chemistry

ALKANES
Prof. Dr. Rahman Tama Haiwal 1
Alkanes

2
 Alkanes
Recall that alkanes are aliphatic hydrocarbons having C—C
and C—H  bonds. They can be categorized as acyclic or
cyclic.
• Acyclic alkanes have the molecular Acyclic Alkanes
formula CnH2n+2. They are also called
saturated hydrocarbons because they H3C CH3

have the maximum number of H3C

C
CH3
hydrogen atoms per carbon.
• Cycloalkanes contain carbons joined
in one or more rings. Because their Cyclic Alkanes
general formula is CnH2n,(n = 3 or
more) they have two fewer H atoms
than an acyclic alkane with the same
number of carbons.
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3-D Representation of Alkanes
• All C atoms in an alkane are surrounded by four groups, making
them sp3 hybridized and tetrahedral, and all bond angles are 109.50.
HH

C H
C2H6 CH3CH3 H C
Ethane
HH
3-D Representation
of Ethane

• The three-carbon alkane CH3CH2CH3, called propane, has a

molecular formula C3H8. Note in the 3-D drawing that each C atom
has two bonds in the plane (solid lines), one bond in front (on a
wedge) and one bond behind the plane (on a dashed line).
HH HH

C C
C3H8 CH3CH2CH3 H C H
Propane
HH
3-D Representation
of Propane 4
 Branched & Straight-Chain Alkanes
• There are two different ways to arrange four carbons, giving two
compounds with molecular formula C4H10, named butane and isobutane.
• Butane and isobutane are Constitutional isomers, two different
compounds with the same molecular formula.

HH HH H CH3
C C H H C H
H C C C C
HH HH HH HH
3-D Representation 3-D Representation
of Butane of Isobutane 5
 Types of Carbons in Alkanes
• Carbon atoms in alkanes and other organic compounds are
classified by the number of other carbons directly bonded to
them.

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Types of Hydrogens in Alkanes
• Hydrogen atoms are classified as primary (10), secondary (20),
or tertiary (30) depending on the type of carbon atom to which
they are bonded.

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Homologous Series of Straight-Chain Alkanes

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Types of fragments in Alkanes

• The suffix ―ane‖ identifies a molecule as an alkane.

• -CH3 is a Methyl
• -CH2- is a Methylene
• (R)3-CH is a Methyne
• By increasing the number of carbons in an alkane by a
CH2 group, one obtains a ―homologous series‖ of
straight-chain alkanes, as shown in Table 4.1. The CH2
group is called ―methylene‖.

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Homologous Series of Straight-Chain Alkanes

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 Hybridization

109°

CH4 C
H
H
H
2s 2px 2py 2pz
Molecule is tetrahedral

2nd row valence orbitals

H H

mixing
C C
H H
H H
H H
2s 2px 2py 2pz
All 4 sp3-orbitals on the carbon atom The-bonds between carbon and hydrogen

All 4 unhybridized orbitals Each orbital has "X", "Y" and "Z"-directionality and are 25% s-like and 75% p-like

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Cycloalkanes

Cycloalkanes have molecular formula CnH2n and contain

carbon atoms arranged in a ring. Simple cycloalkanes are
named by adding the prefix cyclo- to the name of the
acyclic alkane having the same number of carbons.

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Nomenclature
The name of every organic molecule has ―3‖ parts:
1. The parent name indicates the number of carbons in
the longest continuous chain.
2. The suffix indicates what functional group is present.
3. The prefix tells us the identity, location, and number of
substituents attached to the carbon chain.

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Alkyl Groups

• Carbon substituents bonded to a long carbon chain are

called alkyl groups.
• An alkyl group is formed by removing one H atom from
an alkane.
• To name an alkyl group, change the –ane ending of the
parent alkane to –yl. Thus, methane (CH4) becomes
methyl (CH3-) and ethane (CH3CH3) becomes ethyl
(CH3CH2-).

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Types of fragments in Alkanes

• The suffix ―ane‖ identifies a molecule as an alkane.

• -CH3 is a Methyl
• -CH2- is a Methylene
• (R)3-CH is a Methyne
• By increasing the number of carbons in an alkane by a
CH2 group, one obtains a ―homologous series‖ of
straight-chain alkanes, as shown in Table 4.1. The CH2
group is called ―methylene‖.

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Naming Alkyl Groups

Naming three- or four-carbon alkyl groups is more

complicated, e.g. propane has both 10 and 20 H atoms, and
removal of each of these H atoms forms a different alkyl group
with a different name, propyl or isopropyl.

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Butane - C4 Derived Groups

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How to Name Simple Alkanes

1. Find the parent carbon chain and add the suffix.

Note that it does not matter if the chain is straight or it bends.

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Carbon Chains of Equal Length

Also note that if there are two chains of equal length, pick the
chain with more substituents. In the following example, two
different chains in the same alkane have seven C atoms. We
circle the longest continuous chain as shown in the diagram
on the left, since this results in the greater number of
substituents.

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Step #2 - Numbering Substituents

2. Number the atoms in the carbon chain to give the first

substituent the lowest number.

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Numbering Substituents

If the first substituent is the same distance from both ends,

number the chain to give the second substituent the lower
number.

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Numbering Substituents

When numbering a carbon chain results in the same numbers

from either end of the chain, assign the lower number
alphabetically to the first substituent.

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Step #3 - Name and number the substituents.

• Name the substituents as alkyl groups.

• Every carbon belongs to either the longest chain or a
substituent, not both.
• Each substituent needs its own number
• If two or more identical substituents are bonded to the
longest chain, use prefixes to indicate how many: di- for two
groups, tri- for three groups, tetra- for four groups, and so
forth.

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Step # 4 -
Combine substituent names and numbers + parent and suffix.

• Precede the name of the parent by the names of the substituents.

• Alphabetize the names of the substituents, ignoring all prefixes
except iso, as in isopropyl and isobutyl.
• Precede the name of each substituent by the number that indicates
its location.
• Separate numbers by commas and separate numbers from letters
by hyphens. The name of an alkane is a single word, with no
spaces after hyphens and commas.

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 Structural Isomers
How many structural isomers – compounds with the same chemical formula but different
connectivity – are there with the formula C7H16?
IUPAC Name CH3 IUPAC Name
2 4 6 4
2
heptane 2,2-dimethylpentane
1 3 5 7 1 CH3 3 5

CH3 CH3
4 6 3
2 2-methylhexane 2 4 2,3-dimethylpentane
1 3 5 1 5
CH3

2 4 6 CH3 CH3
3
3-methylhexane
1 5 2 4 2,4-dimethylpentane
CH3 1 3 5

CH3 2 CH3 4
2 6 3,3-dimethylpentane
4 4-methylhexane 1 3 5
1 3 5 CH3

2 4
CH3 3
–2 3 –6 3-ethylpentane
1 5
6 5 4 –4 2 3-methylhexane
1
–1 –3 5– 1 CH3
2
3-methylhexane
3 –4
2 4 4 6 2-ethylpentane
H3C –2 5
2,2,3-Trimethyl-butane –3 5–
1 3 1– 31
Isomers

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There are several common branched alkyl groups that
you need to know

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Nomenclature for Cycloalkanes

Cycloalkanes are named by using similar rules, but the prefix

cyclo- immediately precedes the name of the parent.

1. Find the parent cycloalkane.

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Substituents on Cyclic Compounds

2. Name and number the substituents. No number is needed to

indicate the location of a single substituent.

For rings with more than one substituent, begin numbering at

one substituent and proceed around the ring to give the
second substituent the lowest number.

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Cycloalkane with Different Substituents

With two different substituents, number the ring to assign the

lower number to the substituents alphabetically.

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Note the special case of an alkane composed of both a ring
and a long chain. If the number of carbons in the ring is
greater than or equal to the number of carbons in the longest
chain, the compound is named as a cycloalkane.

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Examples of Cycloalkanes

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 Cycloalkanes
Cycloalkanes

Compound Name Structure Group Name Structure

cyclopropane cyclopropyl

cyclobutane cyclobutyl

cyclopentane cyclopentyl

cyclohexane cyclohexyl

cycloheptane cycloheptyl

cyclooctane cyclooctyl

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 Structural Isomers of C7H16

2 4 6
1 7 heptane
What if we attatch the two ends together?
3 5

1 H2
7 2 C
H2C CH2
6 3
H2C CH2

5 4 H2C CH2

cycloheptane C7H14

Cycloheptane contains two fewer hydrogens than heptane. They are not structural isomers.

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Fossil Fuels: Alkanes in Natural Gas & Petroleum

Petroleum is a complex mixture of compounds, most of which are

hydrocarbons containing one to forty carbon atoms. Distilling
crude petroleum (called refining), separates it into usable
fractions that differ in boiling point.
gasoline: C5H12—C12H26
kerosene: C12H26—C16H34
diesel fuel: C15H32—C18H38

Natural gas is com-

posed largely of
methane, with lesser
amounts of ethane,
propane and butane.

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 Alkanes—An Introduction
Fossil Fuels:
Figure 4.5 Refining crude petroleum into usable fuel and other petroleum
products. (a) An oil refinery. At an oil refinery, crude petroleum is
separated into fractions of similar boiling point by the process of
distillation. (b) Schematic of a refinery tower. As crude petroleum is
heated, the lower-boiling, more volatile components distill first, followed
by fractions of progressively higher boiling point.

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 Physical Properties of Alkanes

• Nonpolar
• Insoluble in water.
• Lower density than water.
• Low boiling and melting points.
• Gases with 1-4 carbon atoms.
(methane, propane, butane)
• Liquids with 5-17 carbon atoms.
(kerosene, diesel, and jet fuels)
• Solids with 18 or more carbon
atoms.
(wax, paraffin, Vaseline)
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physical properties
non-polar or only weakly polar, cannot hydrogen
bond  relatively weak intermolecular forces
lower mp/bp; increase with size; decrease with
branching
@ room temperature:
C1 – C4 are gases
C5 – C17 are liquids
> C17 are solids
alkanes are water insoluble

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alkane mp oC bp oC
methane -183 -162
ethane -172 -89
propane -187 -42
n-butane -138 0
n-pentane -130 36
n-hexane -95 69
…
n-heptadecane 22 292
n-octadecane 28 308

branching lowers mp/bp

n-pentane -130 36
isopentane -160 28 47
Two isomers of butane C4H10:

CH3CH2CH2CH3 n-butane

bp 0 oC
mp –138 oC
d 0.622 g/cc

CH3
CH3CHCH3 isobutane

bp -12 oC
mp -159 oC
d 0.604 g/cc
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1- By hydrogenation of alkenes and alkynes:
 Alkenes and alkynes catalytic hydrogenation give
on alkanes

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Alkyl halides on reduction with new hydrogen form
alkanes.

The new hydrogen may be obtained by any one of the

fallowing methods:

(i) Zn + HCl
(ii) Zn + CH3COOH

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(i) The reduction of carbonyl compounds by
amalgamated zinc and conc. HCl also yields
alkanes. This is clemmensen reduction.
Zn +Hg / HCl
RCHO RCH3 + H2O

Zn + Hg / HCl CH3CH2CH3 + 2H2O

CH3COCH3

(ii) Carbonyl compounds may also be reduced

to alkanes by Wolf Kishner reaction.

KOH
+ NH2NH2 C NNH2 CH2 + NH2NH2
C O o
200 C 53
A solution of alkyl halide in ether on heating
with sodium gives alkane.
Dry ether R R + 2NaX
R X + 2Na
2

An alkyl halide on Wurtz reaction leads to the

formation of symmetrical alkane having an
even number of carbon atoms.
Two different alkyl halides, on Wurtz reaction
give all possible alkanes.
CH3X + CH3CH2X + 2 Na CH3CH3 + CH3CH2CH2CH3 + CH3CH2CH3

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