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ORGANIC CHEMISTRY 1

CHM 207

CHAPTER 2
ALKANES

NOR AKMALAZURA JANI


TOPICS
Nomenclature
Physical properties
Preparations of alkanes
Reactions of alkanes
Industrial source and uses of
aliphatic hydrocarbons
HYDROCARBONS
Organic compounds that contain only carbon and
hydrogen.

Hydrocarbons

Aliphatic Aromatic
hydrocarbons hydrocarbons

Alkanes benzene rings


Alkenes or arenes
Alkynes
SATURATED AND UNSATURATED
HYDROCARBONS

Hydrocarbons

Saturated Unsaturated
-Only contain carbon-carbon -Molecule that contain multiple
single bonds (C-C). bonds such as double bond or
-Has no multiple bonds (double triple bonds.
or triple bonds). - Examples: Alkenes, alkynes,
- Has the maximum number of arenes
bonded hydrogen atoms.
- Examples: Alkanes,
cycloalkanes
SATURATED AND UNSATURATED
HYDROCARBONS

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 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


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 What family?


How many
substituents? carbons?
NOMENCLATURE OF STRAIGHT CHAIN
(UNBRANCHED) ALKANES
The first part (prefix) indicates the number of carbon atoms.
The suffix ane indicates that the compound is an alkanes.
Number of carbon atoms, n Name
1 Meth
2 Eth
3 Prop
4 But
5 Pent
6 Hex
7 Hept
8 Oct
9 Non
10 Dec
Examples

H H H
H C H H C C H

H H H
no. of carbon = 1 no. of carbon = 2
name: Methane name: ethane

H H H H H H H H H H H H H
H C C C C C H H C C C C C C C C H
H H H H H H H H H H H H H
no. of carbon = 5 no. of carbon = 8
name: Pentane name: Octane
NOMENCLATURE OF BRANCHED CHAIN ALKANES
USING IUPAC RULES

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.
1CH
7CH 3
3 3 2
5 6 CH3 CH CH2
CH3 CH CH2
4 5
3 CH CH CH2CH3
4CH CH CH2CH3
CH3 6CH CH3
CH3 2CH CH3 7CH
3
1CH
3 INCORRECT
CORRECT
The first branch at C2 The first branch at C3 (carbon
3-ethyl-2,4,5-trimethylheptane atom 3)
- 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 is 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 3: 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 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.

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 substituents are present, list them in


alphabetical order.
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- is used as part of
the alkyl group name, but the hyphenated prefixes are not.
Isobutyl is alphabetized with i, but 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
This is the longest continuous chain.

Select this chain as the parent compound.

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

The name of the compound is 33-methylhexane.


Example 2

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
Exercises
Give the IUPAC name of the following compounds:
i)

ii) CH3CH(Cl)CH(CH2CH3)CH2CH(CH3)CH3
Draw the structural formula for each of the
following compounds.

i) 5-isobutylnonane

ii) 4-chloro-3,3-diethyl-5-isopropyloctane

iii) 3-iodo-3-methylpentane
NOMENCLATURE OFALKANES
(COMMON NAMES / TRIVIAL NAMES)
Alkanes with molecular formula C4H10

CH3
H3C C CH3
CH3CH2CH2CH3
H
butane or n-butane ("normal" butane) isobutane meaning "isomer of butane"

Alkanes with molecular formula C5H12


CH3
CH3
H3 C C CH3
CH3CH2CH2CH2CH3 CH3CHCH2CH3
CH3
pentane (n-pentane) isopentane neopentane
PHYSICAL PROPERTIES OF
ALKANES

Solubilities and densities


Boiling 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 58oC.

- 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.
Formula: C6H14

H3C H3C CH3 CH3


CH CH2 CH2 CH3 CH CH H3C C CH2 CH3
H3C H3C CH3 CH3
bp 60oC
bp 58oC o
bp 50 C
o
mp -154 C mp -135oC mp -98oC

Melting points increase, boiling points decrease


Shape of the molecule become more highly branched and compact
REACTIONS OF ALKANES

Combustion
Halogenation
Cracking and reforming of petroleum
REACTIONS OF ALKANES

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 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
REACTIONS OF ALKANES

HALOGENATION OF ALKANES

- At room temperature, 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. Tha 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 *
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.
Fluorine is very reactive and difficult to control.
Iodine is generally unreactive.
Chlorination and bromination are exothermic
(release heat to the system).
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).
Reaction of Organic Compounds
Covalent bond cleavage
- during the organic reaction, chemical bonds have to be
broken in order that new compounds may be formed.
- the breaking of chemical bonds is called fission.
- When organic compounds react, their bonds can split up in
the following ways:
- Each atom retains one of the electrons
XY X Y present in the covalent bond.
- known as homolytic fission / homolytic
X
XYY X
X Y
Y cleavage
XY X Y
X
XYY X
X Y
Y - either X or Y retains both electrons
XY X Y - known as heterolytic fission / heterolytic
X
XYY X Y cleavage
X Y
HOMOLYTIC FISSION (RADICAL
CLEAVAGE)
Homolytic fission: two shared electrons of the
covalent bond are split equally between the two atoms
joined by the bond.
Also known as homolysis.
One electrons goes to X and the others goes to Y.
The resulting species is called free radicals.

XY X Y

Free radicals
XY X Y
Examples of free radicals:
i) hydrogen radical, H
ii)chlorine radical, Cl
iii)methyl radical, CH3 or CH3
iv)ethyl radical, CH3CH2 or CH3CH2
Free radicals are reaction intermediates.
They are very reactive and many may only exist for a
split second.
The movement of a single electron in homolytic fission
is shown by a curved half-arrow.

C CI C CI

Occurs in reactions which take place in the gas phase or


in non-polar solvents.
The reactions are often catalysed by sunlight, ultraviolet
light or high temperatures.
HETEROLYTIC FISSION (IONIC CLEAVAGE)
Heterolytic fission: the breaking of a covalent bond in
which both electrons remain on one of the atoms.
Known as heterolysis.
Produces positive and negative ions.
The breaking of the bond (C-Y) can happen in 2 ways,
depending on the electronegativities of the carbon
atom and the atom Y.

C Y (Y is more electronegative than C)


cation anion
heterolysis
C Y

C Y (C is more electronegative than Y)


anion cation
MECHANISM OF FREE RADICAL
SUBSTITUTION REACTIONS

3 STEPS

INITIATION PROPAGATION TERMINATION


STEP STEP STEP
MECHANISM OF FREE RADICAL SUBSTITUTION REACTIONS
Example:
CH4 + Cl2 uv light CH3Cl + HCl

1) INITIATION STEP
- The chain is initiated (started) by UV light breaking a
chlorine molecule into free radicals. This process is called
photochemical homolytic fission/cleaveage.

hv
Cl Cl Cl Cl

H = +242 kJMol-1 chlorine atoms


(free radicals)
hv = radiation energy
= movement of single electron (radical)
2) PROPAGATION STEPS
- Free radical species produce another free radical
species.
- Free radicals is highly reactive.

H
Cl H C H HCl + CH3
H methyl radical
methane
- 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.

CH3 Cl2 CH3Cl + Cl


methyl
radical chloromethane

- Chlorine free radical produced then react with


another methane molecule and the cycle is
repeated.
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)
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)
- If a large excess of methane is used, CH3Cl is
obtained as the main organic product.

- In excess of chlorine, the propagation steps may


proceed with the reaction between a chlorine free
radical with chloromethane to produce
dichloromethane.

- The reaction may continue to produce


trichloromethane and finally tetrachloromethane.
Propagation steps for reaction between an excess Cl2
and CH4. CCl4 will formed at the end of the reaction.
CH3Cl Cl CH2Cl HCl
CH2Cl Cl2 CH2Cl2 Cl
dichloromethane

CH2Cl2 Cl CHCl2 HCl


CHCl2 Cl2 CHCl3 Cl
trichloromethane

CHCl3 Cl CCl3 HCl


CCl3 Cl2 CCl4 Cl
tetrachloromethane
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

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:


- it is easier for halogen free radical to abstract 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


Reforming process

i) 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
900oC.
800-900oC
CH3CH3 thermal cracking H2C CH2 H2
ethane ethene
Cracking is a process where large hydrocarbon
molecules (from crude oil) are broken down into
smaller and more volatile molecules.

There are two types of cracking:


i) thermal cracking
ii) catalytic cracking

Thermal cracking makes use of high temperature and


high pressure to bring about the cracking process.
Catalytic cracking, as the name implies, makes use
of suitable catalysts for the process, which can be
carried out at lower temperature and pressure. The
catalysts used are alumina (aluminium oxide), silica
(silicon dioxide) or zeolites.

Catalytic cracking produces more branched chain


alkanes than thermal cracking.
ii) Catalytic reforming:
- increases branching of hydrocarbon chains
- branched hydrocarbons have better burning
characteristics for automobile engines
- 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
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).
The products are used in petrol and as feedstock for
producing a wide range of organic compounds.

Example:
INDUSTRIAL SOURCE AND USES
OF ALIPHATIC HYDROCARBON

Three major sources of alkanes are the fossil fuels


which are natural gas, petroleum and coal.

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.

- used primarily as a fuel to heat buildings and


generate electricity as well as starting material for
the production of fertilizers.
ii) Petroleum

- 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 along with the separation of
impurities.

- 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 saleable products by
various methods such as cracking and reforming.
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:
i) 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.
ii) 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.

iii) Kerosene, bp175 to 275 oC


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

v) Lubricating oil and heavy fuel oil distill (above


350oC)
- mixture of C16-C30 hydrocarbons
- uses: heating, lubrication

vi) Asphalt
- black, tarry residue remaining after removal of the
other volatile fractions
- C35 and above
Fractional distillation