Physical Properties

Solubility: hydrophobic
Density: less than 1 g/mL
Boiling points increase with increasing

carbons (little less for branched chains).

Melting points increase with
increasing carbons (less for oddnumber of carbons).
1

Chemical properties Properties of

Alkanes
Called paraffins (low affinity compounds) because

they do not react as most chemicals

They will burn in a flame, producing carbon dioxide,

water, and heat

They react with Cl2 in the presence of light to replace

Hs with Cls (not controlled)

They can cracked under high temperature and

pressurre

Reactions of Alkanes

Reactions of Alkanes
Combustion
Halogenation
Cracking

Combustion
Burning of hydrocarbons in the presence of

oxygen (high temperature oxidation of

hydrocarbon fuels) yields a large amount of
energy as heat and products which are stable
oxides
CH4 + 2O2 CO2 + 2H2O
(bond energies energy release ~810 kJ)

Heats of Combustion Alkane + O2 CO2 + H2O

166.6
157.4

Long-chain

164.0

158.7

157.4

158.3

158.6

=>

Bond Making and Bond Breaking

During chemical reactions, energy is

either released to the environment
(exothermic reaction) or absorbed from
the environment (endothermic reaction).
During chemical reactions, bonds are
broken in the reactants and new ones are
made in the products. Bond-breaking is an
endothermic process and bond-making is
an exothermic process. The average bond
dissociation energies of some chemical
bonds are shown in the following table.
7

Selected Bond Energies

H-H

Bond
Energy(kJ/
mole)
432

O=O
O-H

Bond

C=O

Bond
Energy(kJ/
mole)
799

494

C-C

347

460

C=C

611

C-H

410

C-O

360

Bond

C=C
(aroma 519
tic)
N=O
623

The negative value of the Enthalpy of Reaction

indicates that the reaction is a heat producing or
exothermic.

Oxidation is easy to recognize when an

element changes changes oxidation state
become an ion. However when dealing with
organic molecules, atoms are joined by
covalent bonds rather than ionic ones so
oxidation is not as easily recognized.

In organic molecules, an atom is oxidized if during a reaction it becomes

bonded to a more electronegative element which pulls electron density
away from it.
10

In general, oxidation occurs if the oxygen content of a covalently bonded molecule

increases or if the hydrogen content decreases.The carbon atom in methane (CH 4)
is more reduced than the carbon atom in carbon dioxide (CO 2)
11

Cycloalkane Stability
5- and 6-membered rings most stable
Bond angle closest to 109.5
Angle (Baeyer) strain
Measured by heats of combustion

per -CH2 =>

FREE RADICAL HALOGENATION

Example: methane + chlorine

H
H

H
H

Cl2

Cl
H

H
H

H Cl

multistep process involving radicals

Halogenation = Substitution
CH4 + Cl2 CH3Cl + HCl

Free Radicals

very reactive species

with an odd (unpaired)
electron (a total of only
7 electrons)
sp2 hybridised
trigonal planar

H
H

C
H

ALKANES - HALOGENATION
Mechanism involves three stages
Step 1.

Initiation

the initial production of free radicals

Cl

Cl

Cl

Cl

reactive
species

Step 2.

Propagation

radicals undergo substitution reactions

chain reaction
H3C
H3C

Cl

Cl

H3C

Cl

H3C

+ H
Cl

Cl

+ Cl

Step 3.

Termination

radicals collide and form stable products

destruction / removal of free radicals
chain reaction is broken
Cl

Cl

H3C

CH3

H3C

Cl

Cl
H3C
H3C

Cl
CH3
Cl

Cracking= Pyrolysis

19

C2H6(g) => C2H4(g) + H2(g)

C3H8(g) => C2H4(g) + CH4(g)
20

Cracking is the process by which hydrocarbons with

relatively high molecular mass are chemically
converted to hydrocarbons with lower molecular
mass. This process makes greater use of the
saturated hydrocarbons found in crude oil.
Unsaturated hydrocarbons, with small molecular
mass, such as ethene, propene and butadiene are of
greater use to modern society as fuels and as raw
materials for the production of plastics.

21

Cracking

large molecule

Catalyst + heat

smaller molecules

Cracking is the name given to the process by which large hydrocarbon

molecules are broken into shorter chains or monomers. This is done
under high pressures and temperatures, but a catalyst allows slightly
lower pressures and temperatures to be used.

Cracking
An example of possible fractions naphtha might split into
is shown below.

Once separated the hydrocarbons are filtered to purify them.

http://www.doitpoms.ac.uk/tlplib/recycling-polymers/origin.php

THERMAL CRACKING, WITHOUT CATALYSTS.

PYROLYSIS
The first step in the process is the homolytic cleavage of a
hydrocarbon.

24

THE RADICALS RECOMBINATION

potential
products:

25

DISPROPORTIONATION REACTION

During this process, a hydrogen atom is transferred from one

hydrocarbon radical to another

26

Catalytic Cracking
In Petroleum industry

C(m+n)H2(m+n)+2
alkane
(kerosene
gas/oil size)

CmH2m + CnH2n+2
alkene
alkane
(gasoline size)

The industrially used catalysts are zeolites (finely-porous

aluminosilicates), which are mixed with the naphtha (gasoline range)
as a fine powder. This is blown through a chamber at 500C.

27

Cracking In Petroleum industry

The introduction of catalytic cracking and polymerization
processes in the mid- to late 1930's met the demand by providing
improved gasoline yields and higher octane numbers.

. Higher-compression gasoline engines required higheroctane gasoline with better antiknock characteristics.

28

Cracking In Petroleum industry

Catalytic - uses a catalyst to speed up the cracking

reaction. Catalysts include zeolite, aluminum hydrosilicate,
bauxite and silica-alumina.
fluid catalytic cracking - a hot, fluid catalyst (1000
degrees Fahrenheit / 538 degrees Celsius) cracks heavy
gas oil into diesel oils and gasoline.
hydrocracking - similar to fluid catalytic cracking, but
uses a different catalyst, lower temperatures, higher
pressure, and hydrogen gas. It takes heavy oil and
cracks it into gasoline and kerosene (jet fuel).
http://science.howstuffworks.com/oil-refining5.htm

31