TAIBAH UNIVERSITY

COLLEGE OF SCIENCE
CHEMISTRY DEPARTMENT

CHAPTER 4
ALKANES
AND
CYCLOALKANES

Chapter 5:Alkanes & cycloalkanes 1

 Structure of hydrocarbon compounds
• Hydrocarbon: a compound composed only of carbon and
hydrogen only

• Saturated hydrocarbon: a hydrocarbon containing only single

bonds

• Unsaturated hydrocarbon: a hydrocarbon containing double

and triple bonds

.
Chapter 5:Alkanes & cycloalkanes 2
 Alkane
Classification of hydrocarbon Compounds

Chapter 5:Alkanes & cycloalkanes 3

 Alkane
v Alkane: a saturated hydrocarbon whose carbons are arranged
in a open chain or cyclic chain.

v The formula for an alkane with no rings in it must be CnH2n+2

where the number of C’s is n.They are also called aliphatic
compounds.

Chapter 5:Alkanes & cycloalkanes 4

 Alkanes
Structure 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.
• The 3-D representations and ball-and-stick models for these
alkanes indicate the tetrahedral geometry around each C atom.
In contrast, the Lewis structures are not meant to imply any 3-D
arrangement. Additionally, in propane and higher molecular
weight alkanes, the carbon skeleton can be drawn in a variety of
ways and still represent the same molecule.

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Chapter 5:Alkanes & cycloalkanes
 Alkanes
Classification of carbons:

• Carbon atoms in alkanes and other organic compounds are

classified by the number of other carbons directly bonded to them.

Chapter 5:Alkanes & cycloalkanes 6

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

Chapter 5:Alkanes & cycloalkanes 7

 Alkane Isomers
v Isomers are molecules that have the same molecular formula,
but have a different arrangement of the atoms in space
v Alkanes with 1-3 carbons, methane (CH4), ethane (C2H6), and
propane (C3H8,) do not exist in isomeric forms because there is
only one way to arrange the atoms in each formula so that
each carbon atom has four bonds.
v However, C4H10, has more than possible structure. The four
carbons can be drawn in a row to form butane or the can
branch to form isobutane.

8
Chapter 5:Alkanes & cycloalkanes
vAll of the alkanes containing 4 or more carbon atoms show
structural isomerism, meaning that there are two or more
different structural formulas that you can draw for each molecular
formula
v Constitutional isomers differ in the way the atoms are connected
to each other.

v C5H12 has three possible isomer. The compound at the far left is
pentane because it has all five carbon atoms in a continuous
chain.
v The compound in the middle is isopentane; like isobutane, it
has a one CH3 branch off the second carbon atom of the
continuous chain.

9
 Alkanes

vThe maximum number of possible constitutional

isomers increases dramatically as the number of
carbon atoms in the alkane increases.
vFor example, there are 75 possible isomers for an
alkane having 10 carbon atoms, but 366,319 possible
isomers for one having 20 carbons.
• The suffix “ane” identifies a molecule as an alkane.
• By increasing the number of carbons in an alkane by a
CH2 group, one obtains a “homologous series” of
alkanes, as shown in Table 4.1. The CH2 group is called
“methylene”.

Chapter 5:Alkanes & cycloalkanes 10

 Alkanes

Chapter 5:Alkanes & cycloalkanes 11

 Alkanes
Naming of alkanes
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.

Chapter 5:Alkanes & cycloalkanes 12

 Alkanes
Naming: 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.
-CH3 is “methyl” (from methane)
-CH2CH3 is “ethyl” (from ethane).
13
Chapter 5:Alkanes & cycloalkanes
 Alkanes
Naming: Alkyl groups
Naming three- or four-carbon alkyl groups is more
complicated because the parent hydrocarbons have more
than one type of hydrogen atom. For example, 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.

14

Chapter 5:Alkanes & cycloalkanes

 Alkanes
Naming
1. Find the parent carbon chain and add the suffix ane.

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

15
Chapter 5:Alkanes & cycloalkanes
 Alkanes
Naming
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.

16
Chapter 5:Alkanes & cycloalkanes
 Alkanes

Naming
2. Number the atoms in the carbon chain to give the first
substituent the lowest number.

17
Chapter 5:Alkanes & cycloalkanes
 Alkanes
Naming
If the first substituent is the same distance from both ends,
number the chain to give the second substituent the lower
number.

18
Chapter 5:Alkanes & cycloalkanes
 Alkanes
Naming
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.

19
Chapter 5:Alkanes & cycloalkanes
 Alkanes
Naming
3. Name and number the substituents.
• Name the substituents as alkyl groups.
• 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.

20
Chapter 5:Alkanes & cycloalkanes
 Alkanes
Naming
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 (Di-, Tri-
..) 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.

Chapter 5:Alkanes & cycloalkanes 21

Complex substituents

Chapter 5:Alkanes & cycloalkanes 22

 23

Chapter 5:Alkanes & cycloalkanes

 Alkanes
Naming: Cycloalkanes
Cycloalkanes are named by using similar rules, but the
prefix cyclo- immediately precedes the name of the parent.

1. Find the parent cycloalkane.

Chapter 5:Alkanes & cycloalkanes 24

 Alkanes
Naming: Cycloalkanes
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.

25

Chapter 5:Alkanes & cycloalkanes

 Alkanes
Naming: Cycloalkanes
With two different substituents, number the ring to assign the
lower number to the substituents alphabetically.

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.

Chapter 5:Alkanes & cycloalkanes 26

 Alkanes
Naming: Cycloalkanes
Naming compounds containing both a ring and a long chain
of carbon atoms

27
Chapter 5:Alkanes & cycloalkanes
 Alkanes
Naming: Cycloalkanes
Examples of cycloalkanes

28

Chapter 5:Alkanes & cycloalkanes

 Alkane
Physical Properties of Alkanes
Ø Solubility: hydrophobic
ØDensity: less than 1 g/mL
ØBoiling Point: As the intermolecular Van Der Waals forces
increase with the increase of the molecular size or the
surface area of the molecule we observe:
1- The boiling point of alkanes increases with increasing molecular
weight.
2- The straight-chain alkanes are observed to have a higher boiling point
in comparison to their structural isomers.

Chapter 5:Alkanes & cycloalkanes 29

Ø Melting Point:
Ø The melting point of alkanes follows the same trend as
their boiling point, that is, it increases with an increase in
molecular weight.
Ø This is attributed to the fact that higher alkanes are solids
and it’s difficult to overcome intermolecular forces of
attraction between them.
Ø even-numbered alkanes have a higher trend in melting
point in comparison to odd-numbered alkanes as the even-
numbered alkanes pack well in the solid phase, forming a
well-organised structure which is difficult to break.

Chapter 5:Alkanes & cycloalkanes 30

 Alkane
Physical Properties of Alkanes: Branched Alkanes

Ø Lower b.p. with increased branching

Ø Higher m.p. with increased branching
Examples:

CH3
CH3 C CH2 CH3
CH3 CH3 CH3
CH CH2 CH2 CH3 CH CH CH3
CH3 CH3 CH3
bp 60°C bp 58°C bp 50°C
mp -154°C mp -135°C mp -98°C

Chapter 5:Alkanes & cycloalkanes 31

 Alkanes
Physical Properties of Alkanes

Chapter 5:Alkanes & cycloalkanes 32

33
 Alkanes

Preparation of Alkanes
ØReduction reactions
1. Alkene/ Alkynehydrogenation
2. Alkyl halide zinc/acid reduction
3. Grignard formation/destruction

Chapter 5:Alkanes & cycloalkanes 34

 Alkanes
1- Hydrogenation of Alkenes and Alkynes

• Example:

Chapter 5:Alkanes & cycloalkanes 35

 Alkanes

2. Reduction of an alkyl halide

a) hydrolysis of a Grignard reagent : (two steps)
Ø Grignard reagents react rapidly with acidic hydrogen
atoms in molecules such as alcohols and water.
Ø When a Grignard reagent reacts with water, a proton
replaces the halogen, and the product is an alkane.
The Grignard reagent therefore provides a pathway for
converting a haloalkane to an alkane in two steps.

Chapter 5:Alkanes & cycloalkanes 36

CH3CH2CH2-Br + Mg à CH3CH2CH2-MgBr
n-propyl bromide n-propyl magnesium bromide

CH3CH2CH2-MgBr + H2O à CH3CH2CH3 + Mg(OH)Br

propane

Chapter 5:Alkanes & cycloalkanes 37

 Alkanes

b) with an active metal and an acid

R—X + metal/acid à RH
active metals = Sn, Zn, Fe, etc.
acid = HCl, etc. (H+)

CH3CH2CHCH3 + Sn/HCl à CH3CH2CH2CH3 + SnCl2

Cl
sec-butyl chloride n-butane

CH3 CH3
CH3CCH3 + Zn/H+ à CH3CHCH3 + ZnBr2
Br
tert-butyl bromide isobutane 38
Chapter 5:Alkanes & cycloalkanes
 Alkanes

Reactions of Alkanes
1. Combustion (oxidation)
2. Pyrolysis (cracking)
3. Halogenation

Chapter 5:Alkanes & cycloalkanes 39

 Alkanes
Reaction of alkanes: Oxidation of Alkanes
ØSince alkanes are the only family of organic molecules that
have no functional group, they undergo very few reactions.
ØOne of the most reaction that alkanes undergo is combustion.

Chapter 5:Alkanes & cycloalkanes 40

 Alkanes
Oxidation of Alkanes:
Recall
• Oxidation results in an increase in the number of C—O bonds; or
Oxidation results in a decrease in the number of C—H bonds.
• Reduction results in a decrease in the number of C—O bonds; or
Reduction results in an increase in the number of C—H bonds.

The oxidation and reduction of

carbon compound 41
Chapter 5:Alkanes & cycloalkanes
 Alkanes

Reactions of Alkanes

1. Combustion (oxidation)

CnH2n+2 + (xs) O2, flame à n CO2 + (n+1) H2O + heat

gasoline, diesel, heating oil…

Chapter 5:Alkanes & cycloalkanes 42

 Alkanes
Reaction of alkanes: combustion of Alkanes
• Alkanes undergo combustion—that is, they burn in the presence
of oxygen to form carbon dioxide and water.
• This is an example of oxidation. Every C—H and C—C bond in
the starting material is converted to a C—O bond in the product.

Chapter 5:Alkanes & cycloalkanes 43

 Alkanes
2. Pyrolyis (cracking)
When higher alkanes are heated to high tempreture in the presence of alumina
or silica catalysts, the alkanes break down to lower alkanes and alkenes.

alkane, 400-600oC à smaller alkanes + alkenes + H2

Ø Used to increase the yield of gasoline from

petroleum. Higher boiling fractions are
“cracked” into lower boiling fractions.
Ø The alkenes can be separated and used in to
make plastics. 44
Chapter 5:Alkanes & cycloalkanes
3. Halogenation

Ø Halogenation of an alkane produces a hydrocarbon

derivative in which one or more halogen atoms have
been substituted for hydrogen atoms.

Ø Alkanes are notoriously unreactive compounds because

they are non-polar and lack functional groups at which
reactions can take place.

Chapter 5:Alkanes & cycloalkanes 45

The following facts must be accomodated by any reasonable
mechanism for the halogenation reaction.
1.The reactivity of the halogens decreases in the following
order: F2 > Cl2 > Br2 > I2.
2. We shall confine our attention to chlorine and bromine,
since fluorine is so explosively reactive it is difficult to
control, and iodine is generally unreactive.
3. Chlorinations and brominations are normally
exothermic.
4. Energy input in the form of heat or light is necessary to
initiate these halogenations.
5. The reactivity of H-atoms depend upon the stability of free
radicals follows the order : Tertiary > Secondary > Primary,
therefore,

46
 Alkanes

Example of chlorination
CH3CH3 + Cl2, hv à CH3CH2-Cl + HCl
ethane ethyl chloride

CH3CH2CH3 + Cl2, hv à CH3CH2CH2-Cl + CH3CHCH3

propane Cl
n-propyl chloride 45 % isopropyl chloride 55%

Ø Long carbon chains gives a mixture of both the

possible alkyl halides.

Ø 2º-hydrogens are more reactive than 1º-hydrogens,

Further experiments showed that 3º-hydrogens are even
more reactive toward halogen atoms. 47

Chapter 5:Alkanes & cycloalkanes

 Alkanes
CH3CH2CH2CH3 + Cl2, hv à CH3CH2CH2CH2-Cl
n-butane n-butyl chloride 28%
+
CH3CH2CHCH3
Cl
sec-butyl chloride 72%

CH3 CH3
CH3CHCH3 + Cl2, hv à CH3CHCH2-Cl
isobutane isobutyl chloride
+
CH3
CH3CCH3
Cl
tert-butyl chloride

Chapter 5:Alkanes & cycloalkanes 48