CHM 207

ORGANIC CHEMISTRY
CHAPTER 2

ALKANES
 TOPIC
• Nomenclature
1

• Physical properties
2

• Reactions of alkanes
4

• Industrial source and uses of aliphatic

5 hydrocarbons
 saturated unsaturated

H H
H C C H H C C H
alkenes alkynes

H H
H C C H
H H benzene
 ALKANES
 General formula:
CnH2n+2, where n = 1, 2, ….
n = number of carbon atoms
 Only single covalent bonds
 saturated hydrocarbons
propane
 sp3-hydridized
ethane
methane
 1. NOMENCLATURE OF ORGANIC
COMPOUNDS
 IUPAC (International Union of Pure and Applied Chemistry)
 Compounds are given systematic names by a process that
uses:

Prefix Parent Suffix

Where are the How many What is the

substituents that carbons are the highest priority
attached to the longest chain? functional group
parent chain? present?
Nomenclature Of Straight Chain (Unbranched) Alkanes
 The suffix ‘ane’ indicates that the compound is an alkanes.
 Nomenclature Of Branched Alkanes
 Branched-chain alkane:

RULE 1
Identify the longest carbon chain (not necessary straight) and write parent
name of the compound.

CH3-CH-CH2-CH3 CH3-CH-CH2-CH2-CH3
CH3 CH2-CH3

4 Carbon 6 Carbon
When a compound has two possible longest carbon chains,
select the chain/parent with more substituents.

1
CH3-CH-CH3
2 3 4 5 6 7
WRONG
CH3-CH2-CH-CH2-CH2-CH2-CH3
2 1
CH3-CH-CH3
3 4 5 6 7 CORRECT
CH3-CH2-CH-CH2-CH2-CH2-CH3
3-ethyl-2-methylheptane
 RULE 2: NUMBERING THE MAIN CHAIN

 To give the locations of the substituents, assign a number to

each carbon atom on the main chain.
 Number the longest chain, beginning with the end of the
chain nearest a substituent.
 Start the numbering from the end nearest a branch so the
numbers of the substituted carbons will be as low as possible.
7CH
3 1CH
3
5 6 3
CH3 CH CH2 CH3 CH
2
CH2
3
4CH CH CH2CH3 4 5
CH CH CH2CH3
CH3 2CH CH3 CH3 6CH CH3
1CH 7CH
3 3
CORRECT
INCORRECT
The first branch at C2
The first branch at C3 (carbon atom 3)
3-ethyl-2,4,5-trimethylheptane
 When the numbering could begin with either of two alkyl
groups or other substituents, begin with the one that is
alphabetically first.
 For example:
CH3 CH CH2 CH CH2 CH CH3
Cl CH3 CH3

 - This compound consists of Cl (chloro) and two methyl

(CH3) groups as substituents. According to alphabetically
order, Cl (start with C) is come first compared to methyl
(start with M). Thus, the numbering could begin from
the end nearest the Cl atom.
7 6 5 4 3 2 1 1 2 3 4 5 6 7
CH3 CH CH2 CH CH2 CH CH3 CH3 CH CH2 CH CH2 CH CH3

Cl CH3 CH3 Cl CH3 CH3

(INCORRECT) (CORRECT)
2-chloro-4,6-dimethylheptane

RULE 2: NAMING ALKYL GROUPS

 Name the substituent groups attached to the longest chain as alkyl
groups.
 Give the location of each alkyl group by the number of the main
chain carbon atom to which it is attached.
 Alkyl groups are named by replacing the –ane suffix of the
alkane name with –yl. Methane becomes methyl; ethane becomes
ethyl.
 The letter “R” is often used in formulas to represent any of
the possible alkyl groups.
R= CnH2n+1 (any alkyl group)
R = CH3 — methyl group
R = CH3CH2 — ethyl group
Examples Of Alkyl Groups
  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
RULE 4: ORGANIZING MULTIPLE GROUPS
 When two or more of the same substituent are present, use the
prefixes di-, tri-, tetra-, etc.
di- means 2 penta- means 5
tri- means 3 hexa- means 6
tetra- means 4
 When substituents are alphabetized, iso-, neo-, cyclo- are not
ignored. iso- is used as part of the alkyl group name, Isobutyl is
alphabetized with i,.
 hyphenated prefixes are ignored, n-butyl, t-butyl and sec-butyl
are alphabetized with b.
 The number prefixes di-, tri-, tetra-, etc are ignored in
alphabetizing.
Example 1
This chain has 6 carbon atoms.

1 2 3 4 5 6

CH3 CH2 CH CH2 CH2 CH3

CH3
This chain has 4 carbon atoms.

1 2 3

CH3 CH2 CH CH2 CH2 CH3

CH3
4
Select this chain as the parent compound.

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

CH3 is a methyl group

It is a branch chain and can be

considered to have replaced a
hydrogen on the parent compound.
 1 2 3 4 5 6
CH3 CH2 CH CH2 CH2 CH3
CH3 methyl

The name of the compound is 3-methylhexane.

Example 2
3-ethyl-4-methyloctane
1 2 3 4 5 6 7 8

methyl
ethyl

3-ethyl-4-methyloctane
Example 3

CH3 CH3
2 1
CH3CHCH2CHCHCH3
6 5 4 3
CH3

2,3,5-trimethylhexane
 NOMENCLATURE CYCLOALKANES
 Add cyclo- to the name of the corresponding open-chain
alkane and name each substituent on the ring.

 If only one substituent, it does not need to be numbered.

Isopropylcyclopentane √

1-isopropylcyclopentane X
 If there are two substituent , number in a way that yields the
smallest numbers possible in the finished name. If there are
identical sets of numbers, use alphabetical priority.

1, 2, 4 1, 3, 6 1, 3, 4
3 1
4 4 2 6 2
5 3 1
5 5
6
1 2 6 4 3

 Name the compound as a cycloalkyl-substituted alkane if the

substituent has more carbons than the ring.
 Example
 Give the IUPAC name of the following
Q1 compounds:
 1. 2.

3. 4.
Q3 Give the systematic IUPAC names for the
cycloalkanes with the following formula:

6. 7.

8.
Q3 Give the systematic IUPAC names for the
cycloalkanes with the following formula:

5. 6.

1,1,2-trimethylcyclohexane 1-bromo-2-methylcyclohexane

7.

1-chloro-2-ethyl-4-methylcyclohexane
2. PHYSICAL PROPERTIES OF
ALKANES

 Solubilities and densities

 Boiling points
 Reactivity
 Solubilities

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

(Given this small difference in the Pauling scale, we
classify a C-H bond as nonpolar covalent).
 Interaction between their molecules are the very weak
Van der Waals’ London dispersion forces.
 Insoluble in water (hydrophobic) or highly polar solvents
because unable to form hydrogen bonds with water
molecules.
 “like dissolves like” only soluble in non-polar solvents
such as benzene and weak non-polar organic solvents
such as dimethyl ether (CH3-O-CH3).
 Densities

 All alkanes and cycloalkanes

have densities around 0.7 g/mL
less than water (1 g cm–3).
 water combined with alkanes
will form two phase with the alkane
alkanes on the top.

water
 BOILING POINTS AND MELTING POINTS

• At R.T., C1 – C4: gases ; C5 – C17: liquids ; > C18: waxy solid

 Melting Point of alkanes

 The boiling points and melting point of straight chain alkanes

increase steadily with relative molecular mass (REASON:
increasing forces of attraction between molecules).
MP are affected by the shape and the way they pack so they do not change uniformly.
 Branching tends to lower the boiling point and raise the melting point.

Shape of the molecule become more highly branched and compact

Surface area , Van der Waals’ force , boiling points , melting point

• linear VS. branched  higher melting/boiling points  better stacking (Van der
Waals’ force) and surface area contact.
• HIGHLY branched VS. branched  more sphere-like  lower surface area  lower
boiling point.
 REACTIVITY
 Very unreactive. WHY?

 The C-C and C-H bonds in alkanes are very strong.

 lack of electron-deficient or electron-rich sites on
the alkanes molecules.

 Don’t react with concentrated sulfuric acid or

concentrated bases.
 Don’t react with strong oxidants (potassium manganate
(VII) or potassium dichromate (VI)).
 Can undergo combustion reaction and substitution
reaction.
 will burn and react with halogens (Will react with
bromine but only if heated or in strong sunlight).
 4. REACTION OF ALKANES

 Combustion
 Halogenation
 COMBUSTION REACTION

 At high temperature, alkanes burn rapidly in the presence of

oxygen.
 The production of combustion reaction are carbon dioxida
and water.
 General formula:
 Example:
- Chemical equation for a combustion of propane:

C3H8 + ( 3 + 8/4 )O2 → 3CO2 + 8/2 H2O

C3H8 + 5O2 → 3CO2 + 4H2O

- In a limited supply of air, combustion of alkanes produces carbon
monoxide and water

C2H6 + 5 O2 → 2CO + 3H2O

2

- In a VERY limited supply of air, alkanes burn to form carbon as one of

the product.

C2H6 + 3 O2 → 2C + 3H2O
2
HALOGENATION OF ALKANES (free radical substitution)
 Alkanes react with molecular halogens (typically Cl2 and Br2) to
form halogenated alkanes (hydrocarbon that contains at least one
halogen atom). Alkanes do not react with chlorine or bromine in
the dark.
 If the mixture of alkanes and chlorine or bromine is heated at high
temperature (300-400 oC), or irradiated by ultraviolet light
(provides energy that is absorbed by reactant molecules to
produce free radicals), the hydrogen atoms in the alkanes can be
replaced by chlorine or bromine atoms to produce a mixture of
products.
 The reactivity of the halogens decreases in the following order :

F2 > Cl2 > Br2 > I2

 Bromine reacts with alkanes in the same way as chlorine but at a

lower rate. (If the halogen is chlorine – called chlorination. If the
halogen is bromine – called bromination)

 Fluorine is very reactive and difficult to control.

 Iodine is generally unreactive.

Equations for the reactions of methane with chlorine:
CH 4 ( g )  Cl 2 ( g ) UV
light

 CH 3Cl( g )  HCl( g )
CH 3Cl( g )  Cl 2 ( g ) UV
light

 CH 2Cl 2 ( g )  HCl( g )
CH 2Cl 2 ( g )  Cl 2 ( g ) UV
light

 CHCl 3 ( g )  HCl( g )
CHCl 3 ( g )  Cl 2 ( g ) UV
light

 CCl 4 ( g )  HCl( g )

 A mixture of products (CH3Cl, CH2Cl2, CHCl3, CCl4) is

formed with the replacement of hydrogen by one or more
chlorine atom.
 If methane is in excess, CH3Cl is major product
 If chlorine is in excess, CCl4 is major product
* Bromine reacts with alkanes in the same way of chlorine,
but iodine do not react well with alkanes *
MECHANISM OF FREE RADICAL SUBSTITUTION
REACTIONS

3 STEPS

INITIATION PROPAGATION TERMINATION

STEP STEP STEP
 Reaction Mechanism:

1. Chain initiation
.
 homolytic cleavage of chlorine
molecules by heat or light into
two chlorine radicals hv
Cl Cl Cl Cl
chlorine atoms
(free radicals)
2. Chain propagation

 Free radicals is highly reactive.

 Free radical species produce another free radical species.
 Step 1:
 Step 2
 Methyl radical propagates a chain reaction as the methyl free
radical then reacts with another chlorine molecule to form
chloromethane and a chlorine free radical.

 steps 2 and 3 repeat hundreds or thousands of time due to

formation of the reactive intermediate in each step
 chain reaction
Further substitution occurs
2. Chain termination

 The reaction STOPS when two free radicals collide and

combine to form a neutral molecule.
 SUMMARY
uv light
CH4 + Cl2 CH3Cl + HCl
1) Initiation step:
hv
Cl Cl Cl Cl
2) Propagation steps:
H
Cl H C H HCl + CH3
H
CH3 Cl2 CH3Cl + Cl
3) Termination steps:
Cl Cl Cl2
CH3 Cl CH3Cl
CH3 CH3 H3C CH3
(by product)
 FREE RADICAL SUBSTITUTION REACTIONS OF
ETHANE AND BROMINE

CH3CH3 + Br2 hv CH3CH2Br + HBr

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

Further propagation steps can take place until CBr3CBr3 is finally

produced
 FREE RADICAL SUBSTITUTION REACTIONS OF
PROPANE AND BROMINE
Br Br2 Br
CH3CHCH3 CH3CHCH3 Br
o
2 alkyl radical 2-bromopropane
CH3CH2CH3
MAIN PRODUCT
Br CH3CH2CH2 Br2
CH3CH2CH2Br Br
1o alkyl radical 1-bromopropane
 2-bromopropane is the main product because:
- Cl . would remove a hydrogen most rapidly from the carbon forming the
weakest C-H bond.
- it is easier for halogen free radical to extract a hydrogen atom from a 2o
carbon atom than 1o carbon atom.
H H R R
H C H R C H R C H R C R
primary secondary tertiary
methyl radical
radical radical radical

stability increases
The major product of halogenation of alkanes is the most
stable product which are:

Alkyl halide 3° > 2° > 1°

Q2 Bromonation of alkanes is a much slower reaction
than chloronation. Determine the major organic
product when 2-methylbutane is allowed to react
with Br2 in the presence of UV light or heat and
also show the mechanism of reaction?
4. Industrial source and uses of aliphatic
hydrocarbons

 Petroleum and natural gas

 Petroleum refining: reforming and
the importance of cracking.
 Petroleum and natural gas

 Three major sources of alkanes from fossil fuels which are natural
gas, petroleum and coal.

Natural Gas
 Composition: hydrocarbon gas mixture of relatively low boiling
alkanes (methane, butane, propane, butane and 2-methylpropane)
(C4 and below).
 Used:
 as a fuel to heat buildings and generate electricity
 starting material for the production of fertilizers.
 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:

- The process whereby the petroleum is separated

into its components by their boiling point.
- The 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 products by various
methods such as cracking and reforming.
 Cracking and Reforming Process

Cracking of Petroleum
 A process whereby a saturated hydrocarbon is converted into an
unsaturated hydrocarbon and hydrogen.
 process of breaking down of large alkane molecules (from crude
oil) into lighter fractions of smaller molecules in the absence of air.
 e.g. C11H24  C9H20 + CH2 = CH2
C14H30  C8H18 + 2CH2 = CH2 + 2C + 2H2

 There are two types

of cracking:
i) thermal cracking
ii) catalytic cracking
Thermal cracking :
in the ABSENCE of catalyst, unbranched chains formed
Catalytic cracking :
in the PRESENCE of catalyst, smaller and highly branched
hydrocarbons formed

 Thermal cracking makes use of high temperature and high pressure

to bring about the cracking process.
 Catalytic cracking can be carried out at lower temperature and
pressure with the help of catalyst. The catalysts used are alumina
(aluminium oxide), silica (silicon dioxide) or zeolites.
 Reforming
 Reforming is a process in which straight-chain alkanes are heated
under pressure in the presence of a platinum catalyst. The chains
break up and reform to give branched-chain molecules.
 branched hydrocarbons have better burning
characteristics for automobile engines

 The products are used in petrol and as feedstock for producing a wide
range of organic compounds
 Example:
-Alkanes are converted to cycloalkanes and cycloalkanes are
converted to arenes in the presence of heat, pressure and
bimetallic catalyst (platinum and rhenium or platinum and
iridium).

catalyst catalyst
CH3CH2CH2CH2CH2CH3 -H2
-H2
hexane cyclohexane benzene

 Other example: isomerization of alkanes, dehydrogenation

of cyclohexanes to aromatic hydrocarbons, isomerization
and dehydrogenation of alkylcyclopentanes, and
dehydrocyclization of alkanes.
 Fractional distillation

 Petroleum is separated into different fractions in the fractionating

tower.
 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.
 Each fraction is a simple mixture and has specific uses
 Volatile components (low boiling point) will come out first.
Gases boiling below 20 oC
- taken off at the top of
distillation column.
- mixture of low-molecular-
weight hydrocarbons (C1-C4),
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.
Gasoline (40-75 oC)
- petroleum-derived liquid
mixtures used as fuels.
- mixture of C5 to C10
Naphthas, bp 75-200 oC

- mixture of C7 to C14 alkanes

and cycloalkanes, small amount
of benzene, toluene, xylene and
aromatic hydrocarbons.
- uses: motor fuel, source of raw
materials for the organic
chemical industry.
Kerosene, bp 175 to 275 oC
-mixture of C11 to C16
hydrocarbons
-uses: heating and cooking, jet
fuel
Fuel oil (diesel), bp 250 to 400 oC
-mixture of C15 to C18
hydrocarbons
- Fuel for diesel engine.
Lubricating oil and heavy fuel oil
distilled (above 350oC)
-mixture of C16-C30
hydrocarbons
-uses: heating, lubrication, making
waxes

Asphalt/bitumen
-black residue remaining after
removal of the other volatile
fractions
- C35 and above
 Boiling Number of carbon
Fraction point range atoms that the Major uses
(°C) molecules contain
As gaseous fuel, raw materials for
Fuel gas < 40 1–4
manufacture of chemicals
Petrol Fuel for motor vehicles
40 – 150 5 – 10
Naphtha Fuel for manufacture of town gas
Fuel for aeroplanes, domestic
Kerosene 150 – 220 10 – 14
liquid fuel
Fuel for trucks, lorries and
Gas oil 220 – 350 14 – 25
locomotives
Fuel for cargo ships and to
Fuel oil > 350 > 25 generate electricity in power
stations
Lubricating Lubricating oil for moving parts
> 350 > 25
oil of machinery
Bitumen > 350 > 25 For surfacing roads and roofs
THANK YOU