ORGANIC CHEMISTRY

CHM 207

CHAPTER 2:
ALKANES
 Structure

Nomenclature Physical properties

Reactions:
SUBTOPICS  Free radical substitution
 Combustion

Industrial source and uses of aliphatic

hydrocarbons:
 petroleum and natural gas
 petroleum fractions: cracking and reforming and their uses
 ALKANE
 General formula:
CnH2n+2, where n = 1, 2, ….

 Only single covalent bonds are present

 Known as saturated hydrocarbons because
contain the maximum number of hydrogen
atoms that can bond with the number of carbon
atoms present.
 Can be assumed to be sp3-hydridized
 IUPAC Name
(International Union of Pure and Applied Chemistry)
• The name is used based on the unbranched
alkanes.

Nomenclature of straight HC
No of C atom, n Name No of C atom, n Name
1 Methane 6 Hexane
2 Ethane 7 Heptane
3 Propane 8 Octane
4 Butane 9 Nonane
5 Pentane 10 Decane
 Alkyl Group
• If a hydrogen is removed from an alkane, the structure
obtain is called an alkyl group. This group is named by
replacing the end –ane of the parent with –yl, eg:
– Removing a hydrogen atom in methane, CH4, gives a methyl
group, CH3-
– Removing a hydrogen atom in ethane, CH3CH3, gives an ethyl
group, CH3CH2-

 The general formula of an alkyl group is CnH2n+1.

 The letter “R” is often used in formulas to represent any

of the possible alkyl groups.
Examples of some alkyl groups
 NAMING OF ALKANE (CnH2n+2)

Step 1: Find the parent structure

a) Longest chain

1 2 3 4 5 6 1 2 3
CH3 CH2 CH CH2 CH2 CH3 CH3 CH2 CH CH2 CH2 CH3

CH3 NOT CH3

4
b) if 2 chains have same number of carbons, choose the
one with the more branch points

CH3
CH3

CH CH2 CH3
CH CH2 CH3
CH3 CH CH3
CH3 CH CH3

CH2
CH2
CH3
CH3

correct wrong
A hexane with 2 substituents A hexane with 1 substituent
 Step 2: Number the atoms in the main chain
a) Beginning at the end nearer the first branch point
(smallest number)
8 7 6 5 4 3 2 1 1 2 3 4 5 6 7 8

correct wrong

isopropyl group
1CH3
7 CH3
CH2 CH3
2
6 CH2 CH3

CH CH2 5CH
4 CH2
CH3 3 CH
CH3
4 CH
5 CH2 6
CH2
3 CH2 2
CH2
correct 7 CH3
wrong
1 CH3
b) If branching occurs at equal distance from both ends, begin
numbering at the end nearer the second branch point

8CH3 1CH3
CH2 CH3 2CH2 CH3
7
2 7
CH3 CH CH CH2 CH3 CH CH CH2 8
6 4 3 1 3 5 6
CH2 CH2 CH CH3 CH2 CH2 CH CH3
5 4

CH2 CH2
CH3 CH3

correct wrong
Step 3: Identify and number the substituents
a) Give each substituent a number that corresponds to
its position on the parent chain
8
9 CH2
CH3 CH2 CH3
7 parent: nonane
2
CH3 CH CH CH2 Substituents:
6 4 3 1
CH2 CH2 CH CH3 C3 CH2CH3 3-ethyl
5 C4 CH3 4-methyl
CH2 C6 CH2CH3 6-ethyl
CH3
b) Two substituents on the same carbon gets the same
number
CH3
CH2 CH3 parent: hexane

Substituents:
CH3 C CH C2 CH3 2-methyl
CH2 CH2 CH3 C4 CH3 4-methyl
CH3 C4 CH2CH3 4-ethyl

Step 4: Write the name as a single word (alphabetical order)

a) use hyphen (-) to separate prefixes and commas (,) to
separate numbers
b) for two or more identical substituents are present, use
multipliers (di, tri, tetra). Prefixes are not included in
alphabetical ordering (ethyl comes before dimethyl).
 Examples:
1 CH3
CH3
CH2
1 2
CH3 4 6
2CH 1 CH CH2 CH3 CH CH2
2 2 3 4
CH3 CH CH2 CH3 3 CH CH3
5 5
3
CH2 CH
6 CH2
CH3 CH2 CH3 5 CH2 6
4 CH3 CH2
3-methylhexane 3-ethyl-2-methylhexane
7 CH3

4-ethyl-3-methylheptane
H3C 8CH3
CH2 CH3 CH2 CH3
7
2
CH3 C CH CH3 CH CH CH2
4 3 2 1 6 4 3 1
6 CH2 CH2 CH CH3
CH2 CH2 CH3
5 5
CH3
4-ethyl-2,4-dimethyl hexane CH2
CH3
3,6-diethyl-4-methyloctane
• Alkanes can have many different types of
substituents.

For example:
NO2 Br
1 2 3 4 5
CH3 CH CH CH3 CH3
3-bromo-2-nitropentane
 Exercises:

Exercise 1: Write the IUPAC name for the following alkane

CH3
CH2 CH3

CH CH2 CH
CH3 CH2 CH2 CH3

Exercise 2: Draw the structure for 3-isopropyl-2-methylhexane

 CYCLOALKANE (CnH2n)

 alicyclic compounds
 A hydrocarbon that contains C atoms joined to form a ring.
 Cycloalkanes – all carbons of the ring are saturated

cyclopropane cyclobutane cyclopentane cyclohexane

 NAMING OF CYCLOALKANE (CnH2n)

Similar to that alkanes.

Step 1: Find the parent structure

• For a ring to become a parent, the number of atoms in
the ring must be more than the substituent.

ethylcyclopentane 1-cyclopropylbutane
Step 2: Number the substituent and write the name
a) Start at a point of attachment and number the
substituents so that the second substituent has the
lowest possible number
b) If necessary, proceed to the next substituent until a
point of difference is found

1 1

2 2 6
6

3 5
5 3

4 4

1,5-dimethylcyclohexane
1,3-dimethylcyclohexane

correct wrong
lower higher
• When the acyclic portion of the molecule contains more
carbon atoms than the cyclic portion (or when it contains
an important fuctional group), the cyclic portion is named
as a cycloalkyl substituent.

Example:

H C C CH2 CH2 CH2

4-cyclopropyl-3-methyloctane 5-cyclobutyl-1-pentyne
 ISOMERISATION

Structural isomers:
- Molecules that have the same molecular formula, but
different structure

Three isomers of pentane (C5H12)

STRUCTURE ISOMERS FOR ALKANES

NAME MOLECULAR FORMULA TOTAL OF ISOMERS

Methane CH4 1
Ethane C2H6 1
Propane C3H8 1
Butane C4H10 2
Pentane C5H12 3
Hexane C6H14 5
Heptane C7H16 9
Octane C8H18 18
Nonane C9H20 35
Decane C10H22 75
PHYSICAL PROPERTIES OF ALKANES

Solubilities and densities

Boiling points
Melting points
 SOLUBILITIES AND DENSITIES OF ALKANES
1) Solubilities:

 The C-H bond having only a very weak dipole moment.

 Alkanes are weak polar molecules and considered as

non-polar molecules.

 Soluble in non-polar solvents such as benzene and

weak non-polar organic solvents such as dimethyl
ether (CH3-O-CH3).

 Insoluble in water:
- alkanes are non-polar and do not form hydrogen
bonds with water molecules.
- described as ‘hydrophobic’ (water hating).
2) Densities:

- alkanes have densities around 0.7 g/mL,

compared to density of water (1.0 g/mL).

- alkanes is less dense than water and insoluble in

water.

- water combined with alkanes will form two phase

with the alkanes on the top.
 oil

water
BOILING POINTS AND MELTING POINTS OF
ALKANES
 BOILING POINTS OF ALKANES
Effect of relative molecular mass on boiling point.
- the first four chain alkanes are gases.
- alkanes from C5H12 to C18H38 are liquids at room
temperature because their melting point are lower
than 28oC (301K).
- alkanes above C18H38 are solids at room
temperature.
- the boiling points of straight chain alkanes increase
steadily with relative molecular mass (due to
increasing forces of attraction between molecules).
* A larger molecule, with greater surface area and
greater van der Waals attractions, boils at higher
temperature *
Boiling points of the straight chain of
alkanes
Effect of branching on boiling point.

- Branched chain alkanes boils at a lower

temperature (more volatile) than the straight chain
alkane with the same number of carbon atoms.

- Examples: hexane boils at 68.7oC, 3-

methylpentane (one branch) boils at 63.3oC and
2,3-dimethylbutane (two branches) boils at 58 oC.

- Reason: the branched chain alkanes are more

compact (nearly spherical), have smaller surface
area, smaller van der Waals forces of attraction
and boils at lower temperature.
 MELTING POINTS OF ALKANES
 The melting points increase with increasing of molecular
weight.

 Alkanes with even numbers of carbon atoms pack better into

a solid structure, so higher temperatures are needed to melt
them (high melting point).

 Alkanes with odd numbers of carbon atoms do not pack as

well, and melt at lower temperatures (low melting points).

 Branched chain alkanes melts at a higher temperature than

n-alkanes (straight alkanes) with same numbers of carbon
atoms.
- Reason: 3D-structure of branched alkanes are more
compact, pack more easily into solid structure and melt at
higher temperatures.
 Formula: C6H14
H3 C H3C CH3 CH3
CH CH2 CH2 CH3 CH CH H3C C CH2 CH3
H3C H 3C CH3 CH3
bp 60oC bp 58oC
o bp 50oC
mp -154 C o
mp -135 C mp -98oC

Melting points increase, boiling points decrease

Shape of the molecule become more highly branched and compact
 UNREACTIVITY OF ALKANES
• Alkanes is chemically inert to most reagents.
• For example, acids, alkalis, and oxidising agents such as
potassium manganate (VII) or potassium dichromate (VI)
do not react with alkanes.
• Alkanes reacts with oxygen and halogens in suitable
conditions.
• Why alkanes has low reactivity?
- lack of electron-deficient or electron-rich sites on the
alkanes molecules.
- polar molecules, positive and negative ions (such as H+
and OH-), do not react with alkanes because the C-H bond
is weak polar and C-C bond is non-polar.
 REACTIONS OF
ALKANES

COMBUSTION HALOGENATION
(WITH OXYGEN) (FREE RADICAL
REACTIONS)
 REACTIONS OF ALKANES
i. COMBUSTION
- Alkanes burn in a plentiful supply of air or oxygen to
produce water and CO2 only.
- for example:
C3H8 + 5 O2 → 3CO2 + 4H2O
- In a limited supply of air, combustion of alkanes
produces carbon monoxide and water

C2H6 + 5/2 O2 → 2CO + 3H2O

- In a very limited supply of air, alkanes burn to form

carbon as one of the product.

C2H6 + 3/2 O2 → 2C + 3H2O

 REACTIONS OF ALKANES

ii. HALOGENATION OF ALKANES

- At RT, alkanes do not react with chlorine or bromine in

the dark.

- if the mixture of alkanes and chlorine or bromine is

heated at high temparature (300-400oC), or irradiated by
ultraviolet light, the hydrogen atoms in the alkanes are
successively replaced by chlorine or bromine atoms to
produce a mixture of products (halogenated alkanes).
 Equations for the reactions of methane with chlorine:
CH4 + Cl2 CH3Cl + HCl (1)

CH3Cl + Cl2 CH2Cl2 + HCl

CH2Cl2 + Cl2 CHCl3 + HCl

CHCl3 + Cl2 CCl4 + HCl (2)

• Equation 1: reaction with limited supply of chlorine and

excess of methane. The major product is chloromethane.
• Equation 2: reaction with the excess of chlorine. The
major product is tetrachloromethane.

* Bromine reacts with alkanes in the same way of chlorine,

but iodine do not react well with alkanes *
• This reaction is called a substitution reaction (an atom or
a group atom in an organic compound is replaced by
another atom or a group of atoms).
• Involves a halogen - called halogenation
• If the halogen is chlorine – called chlorination.
• If the halogen is bromine – called bromination.

* Condition of reaction:
light or heat (high temperature) or ultraviolet radiation
(provides energy that is absorbed by reactant molecules
to produce free radicals).
 MECHANISM OF FREE RADICAL
SUBSTITUTION REACTIONS

3 STEPS

INITIATION PROPAGATION TERMINATION

STEP STEP STEP
 MECHANISM OF FREE RADICAL
SUBSTITUTION REACTIONS
1) INITIATION STEP
- homolytic fission

hv
Cl Cl Cl Cl
chlorine atoms
ΔH = +242 kJMol-1 (free radicals)

hv = radiation energy
= movement of single electron (radical)
 2) PROPAGATION STEPS
- Free radical species produce another free
radical species.
H
Cl H C H HCl + CH3
H methyl radical
methane

- Methyl free radical then reacts with another

chlorine molecule to form chloromethane and a
chlorine free radical.
CH3 Cl2 CH3Cl + Cl
methyl
radical chloromethane
3) TERMINATION STEPS
- The reaction stops when two free radicals
collide and combine.
- highly exothermic.

Cl Cl Cl2
CH3 Cl CH3Cl
CH3 CH3 H3C CH3
(by product)
 FREE RADICAL SUBSTITUTION REACTIONS OF ETHANE

hv
Br Br Br Br initiation step

CH3CH3 Br CH2CH3 HBr propagation step

CH2CH3 Br2 CH3CH2Br Br

Br Br Br2
CH3CH2 Br CH3CH2Br termination step

CH3CH2 CH3CH2 CH3CH2CH2CH3

INDUSTRIAL SOURCE AND USES OF
ALIPHATIC HYDROCARBON
Major sources of alkanes
i) Natural gas
- consists of 90-95% methane, 5-
10% ethane, and a mixture of other
relatively low boiling alkanes, which
are propane, butane and 2-
methylpropane.
Uses:
- as a fuel to heat buildings and
generate electricity as well as
starting material for the production
of fertilizers.
ii) Petroleum
-a thick, viscous liquid mixture of
literally thousands of compounds,
mostly are hydrocarbons, formed from
the decomposition of ancient marine
plants and animals.
Uses:
a) fuel for automobiles, aircraft and
train.
b) provide most of the greases and
lubricants required for the
machinery of highly industrialized
society.
c) petroleum with natural gas provides
90% of organic raw materials for
the synthesis and manufacture of
synthetic fibers, plastics,
detergents, drugs and dyes.
 Petroleum Refining

- Process whereby the petroleum is separated into its

components along with the separation of impurities.

- Refining is done by fractional distillation. Each hydrocarbon

component with its own boiling point separates out neatly
when the petroleum is heated.

- The fractions are further treated to convert them into

mixtures of more useful saleable products by various
methods such as cracking and reforming.
 i. Fractional distillation
• Crude oil enters a refinery and then goes to distillation units where it is
heated to temperatures as high as 370 to 425oC and separates into
fractions.
• Volatile components (low boiling point) will come out first.
• Common names of fractions and their uses:
a) Gases boiling below 20oC
- taken off at the top of distillation column.
- mixture of low-molecular-weight hydrocarbons, mainly propane,
butane and 2-methylpropane.
- substances can be liquefied under pressure at RT.
- uses: liquefied petroleum gas (LPG) is a convenient source of gaseous
fuel for home heating and cooking.
b) Naphthas, bp 20-200 oC
- mixture of C5 to C12 alkanes and cycloalkanes, small
amount of benzene, toluene, xylene and aromatic
hydrocarbons.
- light naphtha fraction (bp 20-150oC) is a source of
straight-run gasoline.
- uses: motor fuel, source of raw materials for the
organic chemical industry.

c) Kerosene, bp175 to 275 oC

- mixture of C9 to C15 hydrocarbons
- uses: heat, jet fuel
d) Fuel oil (diesel), bp 250 to 400 oC
- mixture of C15 to C18 hydrocarbons
- motor fuel

e) Lubricating oil and heavy fuel oil distill (above 350oC)

- mixture of C16-C30 hydrocarbons
- uses: heating, lubrication

f) Asphalt
- black, tarry residue remaining after removal of the other
volatile fractions
- C35 and above
Fractional distillation
 ii. Cracking and Reforming Process

a) Cracking:
 A process whereby a saturated hydrocarbon is
converted into an unsaturated hydrocarbon and
hydrogen.
 Ethane is cracked by heating in furnace at 800 to 900 oC.

800-900oC
CH3CH3 thermal cracking H2C CH2 H2
ethane ethene
b) Catalytic reforming:
- A process for increasing the octane number of
naphthas.

- It involves isomerization of alkanes, dehydrogenation of

cyclohexanes to aromatic hydrocarbons, isomerization
and dehydrogenation of alkylcyclopentanes, and
dehydrocyclization of alkanes.
- Example:

catalyst catalyst
CH3CH2CH2CH2CH2CH3 -H2 -H2

hexane cyclohexane benzene

 Octane number / octane rating
* The quality of gasoline as a fuel for internal combustion engines.

* Fuel that have high octane number, has very good antiknock
properties (the fuel /air mixture burns smoothly in the combustion
chamber).

* 2,2,4-trimethylpentane (isooctane) has very good antiknock

properties with octane number 100 compared to heptane which has
poor antiknock properties (octane number 0).

* If other fuel has octane number 90, means that the knock
properties of the fuel is same as those mixture of 10% heptane and
90% isooctane.