AN INTRODUCTION TO
THE CHEMISTRY
OF ALKANES
KNOCKHARDY PUBLISHING
THE CHEMISTRY OF ALKANES
CONTENTS
• Structure of alkanes
• Physical properties of alkanes
• Chemical properties of alkanes
• Breaking covalent bonds
• Chlorination via free radical substitution
• Cracking
• Revision check list
ALKANES
General
members of a homologous series
general formula is CnH2n+2 - for non-cyclic alkanes
saturated hydrocarbons - all carbon-carbon bonding is single
bonds are spaced tetrahedrally about carbon atoms.
Isomerism
the first example of structural isomerism occurs with C4H10
BUTANE
2-METHYLPROPANE
Structural isomers have the SAME MOLECULAR FORMULA BUT
DIFFERENT STRUCTURAL FORMULA
They possess different physical properties such as boiling point,
melting point and density
HYBRIDISATION OF ORBITALS
The electronic configuration of a
carbon atom is 1s22s22p2
2p
2
2s
1
1s
HYBRIDISATION OF ORBITALS
The electronic configuration of a
carbon atom is 1s22s22p2
2p
2
2s
1
If you provide a bit of energy you
can promote (lift) one of the s
electrons into a p orbital. The
configuration is now 1s22s12p3
1s
2p
2
2s
1
1s
The process is favourable because the of arrangement of
electrons; four unpaired and with less repulsion is more stable
HYBRIDISATION OF ORBITALS IN ALKANES
The four orbitals (an s and three p’s) combine or HYBRIDISE to give four
new orbitals. All four orbitals are equivalent.
Because one s and three p orbitals are used, it is called sp3 hybridisation
2s22p2
2s12p3
4 x sp3
THE STRUCTURE OF ALKANES
In ALKANES, the four sp3
orbitals of carbon repel each
other into a TETRAHEDRAL
arrangement with bond angles
of 109.5º.
Each sp3 orbital in
carbon overlaps with
the 1s orbital of a
hydrogen atom to form
a C-H bond.
109.5º
Alkanes - Nomenclature
The names of alkanes are composed of two parts –
(i) a prefix which comes from the number of carbon atoms in the longest straight
chain in the molecule.
Apart from the first four, which have trivial names, the number of carbons atoms
is indicated by a prefix derived from the Greek numbering system.
Prefix
methethpropbutpenthexheptoctnondec-
C atoms
1
2
3
4
5
6
7
8
9
10
Alkane
methane
ethane
propane
butane
pentane
hexane
heptane
octane
nonane
decane
(ii) a suffix or ending which shows which type of organic compound it is. With alkanes this
suffix is ___ane. Examples -ethane - octane -
I.U.P.A.C. NOMENCLATURE
How long is a chain?
Because organic molecules are three dimensional and paper is two dimensional it
can confusing when comparing molecules. This is because...
1. It is too complicated to draw molecules with the correct bond angles
2. Single covalent bonds are free to rotate
All the following written structures are of the same molecule - PENTANE C5H12
CH3 CH2 CH2 CH2 CH3
CH3
CH2 CH2 CH2 CH3
CH3
CH2 CH2 CH2
CH3 CH2 CH3
CH3
CH2 CH2
A simple way to check is to run a finger along the chain and see how many carbon
atoms can be covered without reversing direction or taking the finger off the page.
In all the above there are... FIVE CARBON ATOMS IN A LINE.
I.U.P.A.C. NOMENCLATURE
How long is the longest chain?
Look at the structures and work out how many carbon atoms are in the longest chain.
CH3
THE ANSWERS ARE
ON THE NEXT SLIDE
CH2
CH3 CH CH2 CH3
CH3
CH3 CH2 CH2 CH2 CH CH3
CH3
CH3 CH2
CH3 CH2 CH CH CH3
I.U.P.A.C. NOMENCLATURE
How long is the longest chain?
Look at the structures and work out how many carbon atoms are in the longest chain.
CH3
LONGEST CHAIN = 5
CH2
CH3 CH CH2 CH3
CH3
LONGEST CHAIN = 6
CH3 CH2 CH2 CH2 CH CH3
CH3
CH3 CH2
CH3 CH2 CH CH CH3
LONGEST CHAIN = 6
I.U.P.A.C. NOMENCLATURE
How long is the longest chain?
Look at the structures and work out how many carbon atoms are in the longest chain.
CH3
LONGEST CHAIN = 5
CH2
CH3 CH CH2 CH3
CH3
LONGEST CHAIN = 6
CH3 CH2 CH2 CH2 CH CH3
CH3
CH3 CH2
CH3 CH2 CH CH CH3
LONGEST CHAIN = 6
NOMENCLATURE
Ideally a naming system should tell you everything about a structure without ambiguity.
There are two types of naming system commonly found in organic chemistry;
Trivial :
Systematic :
based on some property or historical aspect;
the name tells you little about the structure
based on an agreed set of rules (I.U.P.A.C);
exact structure can be found from the name (and vice-versa).
trivial name
paraffin
olefin
fatty acid
trivial name
methane
butane
acetic acid
HOMOLOGOUS SERIES
systematic name
example(s)
alkane
methane, butane
alkene
ethene, butene
alkanoic (carboxylic) acid
ethanoic acid
INDIVIDUAL COMPOUNDS
derivation
systematic name
methu = wine (Gk.)
methane (CH4)
butyrum = butter (Lat.)
butane (C4H10)
acetum = vinegar (Lat.)
ethanoic acid (CH3COOH)
I.U.P.A.C. NOMENCLATURE
SIDE-CHAIN
carbon based substituents are named before the chain name.
they have the prefix -yl added to the basic stem (e.g. CH3 is methyl).
Alkyl radicals
methyl
CH3 -
CH3
ethyl
propyl
CH3- CH2CH3- CH2- CH2-
C2H5
C3H7
Number the principal chain from one end to give the lowest numbers.
Side-chain names appear in alphabetical order
butyl, ethyl, methyl, propyl
Each side-chain is given its own number.
If identical side-chains appear more than once, prefix with di, tri, tetra, penta, hexa
Numbers are separated from names by a HYPHEN
e.g.
2-methylheptane
Numbers are separated from numbers by a COMMA
e.g. 2,3-dimethylbutane
I.U.P.A.C. NOMENCLATURE
SIDE-CHAIN
carbon based substituents are named before the chain name.
they have the prefix -yl added to the basic stem (e.g. CH3 is methyl).
Alkyl radicals
methyl
CH3 -
CH3
ethyl
propyl
CH3- CH2CH3- CH2- CH2-
C2H5
C3H7
Number the principal chain from one end to give the lowest numbers.
Side-chain names appear in alphabetical order
butyl, ethyl, methyl, propyl
Each side-chain is given its own number.
If identical side-chains appear more than once, prefix with di, tri, tetra, penta, hexa
Numbers are separated from names by a HYPHEN
e.g.
2-methylheptane
Numbers are separated from numbers by a COMMA
e.g. 2,3-dimethylbutane
I.U.P.A.C. NOMENCLATURE
SIDE-CHAIN
carbon based substituents are named before the chain name.
they have the prefix -yl added to the basic stem (e.g. CH3 is methyl).
Alkyl radicals
methyl
CH3 -
CH3
ethyl
propyl
CH3- CH2CH3- CH2- CH2-
C2H5
C3H7
Number the principal chain from one end to give the lowest numbers.
Side-chain names appear in alphabetical order
butyl, ethyl, methyl, propyl
Each side-chain is given its own number.
If identical side-chains appear more than once, prefix with di, tri, tetra, penta, hexa
Numbers are separated from names by a HYPHEN
e.g.
Numbers are separated from numbers by a COMMA
e.g. 2,3-dimethylbutane
Example
longest chain 8 (it is an octane)
3,4,5 are the numbers NOT 4,5,6
order is ethyl, methyl, propyl
3-ethyl-5-methyl-4-propyloctane
2-methylheptane
CH3 CH3
CH3 CH2 CH2 CH
CH2
CH3 CH2 CH2 CH
CH
CH2
CH3
I.U.P.A.C. NOMENCLATURE
Apply the rules and name these alkanes
THE ANSWERS ARE ON THE NEXT SLIDE
CH3
CH2
CH3 CH CH2 CH3
CH3
CH3 CH2 CH2 CH2 CH CH3
CH3
CH3 CH2
CH3 CH2 CH CH CH3
I.U.P.A.C. NOMENCLATURE
Apply the rules and name these alkanes
CH3
CH2
CH3 CH CH2 CH3
CH3
CH3 CH2 CH2 CH2 CH CH3
CH3
CH3 CH2
CH3 CH2 CH CH CH3
I.U.P.A.C. NOMENCLATURE
Apply the rules and name these alkanes
Longest chain = 5 so it is a pentane
CH3
A CH3, methyl, group is attached to the
third carbon from one end...
CH2
CH3 CH CH2 CH3
3-methylpentane
CH3
CH3 CH2 CH2 CH2 CH CH3
CH3
CH3 CH2
CH3 CH2 CH CH CH3
I.U.P.A.C. NOMENCLATURE
Apply the rules and name these alkanes
Longest chain = 5 so it is a pentane
CH3
A CH3, methyl, group is attached to the
third carbon from one end...
CH2
CH3 CH CH2 CH3
3-methylpentane
CH3
CH3 CH2 CH2 CH2 CH CH3
Longest chain = 6 so it is a hexane
A CH3, methyl, group is attached to the
second carbon from one end...
2-methylhexane
CH3
CH3 CH2
CH3 CH2 CH CH CH3
I.U.P.A.C. NOMENCLATURE
Apply the rules and name these alkanes
Longest chain = 5 so it is a pentane
CH3
A CH3, methyl, group is attached to the
third carbon from one end...
CH2
CH3 CH CH2 CH3
3-methylpentane
CH3
CH3 CH2 CH2 CH2 CH CH3
Longest chain = 6 so it is a hexane
A CH3, methyl, group is attached to the
second carbon from one end...
2-methylhexane
CH3
CH3 CH2
CH3 CH2 CH CH CH3
Longest chain = 6 so it is a hexane
CH3, methyl, groups are attached to the
third and fourth carbon atoms
(whichever end you count from).
3,4-dimethylhexane
PHYSICAL PROPERTIES OF ALKANES
Boiling point
increases as they get more carbon atoms in their formula
more atoms = greater intermolecular Van der Waals’ forces
greater intermolecular force = more energy to separate the molecules
greater energy required = higher boiling point
CH4 (-161°C)
C2H6 (-88°C)
C3H8 (-42°C)
C4H10 (-0.5°C)
difference gets less - mass increases by a smaller percentage
straight chains molecules have greater interaction than branched
“The greater the branching, the lower the boiling point”
Melting point
general increase with molecular mass
the trend is not as regular as that for boiling point.
Solubility
alkanes are non-polar so are immiscible with water
they are soluble in most organic solvents.
CHEMICAL PROPERTIES OF ALKANES
Introduction
- fairly unreactive; (old family name, paraffin, meant little reactivity)
- have relatively strong, almost NON-POLAR, SINGLE covalent bonds
- they have no real sites that will encourage substances to attack them
Combustion
- make useful fuels - especially the lower members of the series
- react with oxygen in an exothermic reaction
BUT
Handy tip
complete
combustion
CH4(g)
+
2O2(g)
incomplete
combustion
CH4(g)
+ 1½O2(g)
——>
CO2(g) +
2H2O(l)
——>
CO(g)
2H2O(l)
+
the greater the number of carbon atoms, the more energy produced
the greater the amount of oxygen needed for complete combustion.
When balancing equations involving complete combustion, remember...
every carbon in the original hydrocarbon gives one carbon dioxide and
every two hydrogen atoms gives a water molecule.
Put the numbers into the equation, count up the O’s and H’s on the RHS
of the equation then balance the oxygen molecules on the LHS.
POLLUTION
Processes involving combustion give rise to a variety of pollutants...
power stations
internal combustion engines
Removal
SO2
CO and NOx
SO2 emissions produce acid rain
CO, NOx and unburnt hydrocarbons
react effluent gases with a suitable compound (e.g. CaO)
pass exhaust gases through a catalytic converter
Catalytic converters
In the catalytic converter ... CO is converted to CO2
NOx are converted to N2
Unburnt hydrocarbons are converted to CO2 and H2O
e.g.
2NO
+
2CO
———>
N2
+
2CO2
• catalysts are made of finely divided rare metals Rh, Pd, Pt
• leaded petrol must not pass through the catalyst as the lead
deposits on the catalyst’s surface and “poisons” it, thus blocking
sites for reactions to take place.
BREAKING COVALENT BONDS
There are 3 ways to split the shared electron pair in an unsymmetrical covalent bond.
UNEQUAL SPLITTING
produces IONS
known as HETEROLYSIS or
HETEROLYTIC FISSION
EQUAL SPLITTING
produces RADICALS
known as HOMOLYSIS or
HOMOLYTIC FISSION
•
•
•
•
If several bonds are present the weakest bond is usually broken first
Energy to break bonds can come from a variety of energy sources - heat / light
In the reaction between methane and chlorine either can be used, however...
In the laboratory a source of UV light (or sunlight) is favoured.
FREE RADICALS
TYPICAL PROPERTIES
• reactive species (atoms or groups) which possess an unpaired electron
• their reactivity is due to them wanting to pair up the single electron
• formed by homolytic fission (homolysis) of covalent bonds
• formed during the reaction between chlorine and methane
• formed during thermal cracking
• involved in the reactions taking place in the ozone layer
CHLORINATION OF METHANE
Reagents
chlorine and methane
Conditions
UV light or sunlight - heat is an alternative energy source
Equation(s)
CH4(g) + Cl2(g)
——> HCl(g)
+ CH3Cl(g)
chloromethane
CH3Cl(g) + Cl2(g) ——> HCl(g)
+ CH2Cl2(l)
dichloromethane
+ CHCl3(l)
trichloromethane
+ CCl4(l)
tetrachloromethane
CH2Cl2(l) + Cl2(g)
——> HCl(g)
CHCl3(l) + Cl2(g) ——> HCl(g)
Mixtures
free radicals are very reactive - they are trying to pair their electron
with sufficient chlorine, every hydrogen will eventually be replaced.
CHLORINATION OF METHANE
Reagents
chlorine and methane
Conditions
UV light or sunlight - heat is an alternative energy source
Equation(s)
CH4(g) + Cl2(g)
——> HCl(g)
+ CH3Cl(g)
chloromethane
CH3Cl(g) + Cl2(g) ——> HCl(g)
+ CH2Cl2(l)
dichloromethane
+ CHCl3(l)
trichloromethane
+ CCl4(l)
tetrachloromethane
CH2Cl2(l) + Cl2(g)
——> HCl(g)
CHCl3(l) + Cl2(g) ——> HCl(g)
Mixtures
free radicals are very reactive - they are trying to pair their electron
with sufficient chlorine, every hydrogen will eventually be replaced.
Mechanism
Mechanisms portray what chemists think is going on in the reaction,
whereas an equation tells you the ratio of products and reactants.
Chlorination of methane proceeds via FREE RADICAL SUBSTITUTION
because the methane is attacked by free radicals resulting in
hydrogen atoms being substituted by chlorine atoms.
The process is a chain reaction.
In the propagation step, one radical is produced for each one used
CHLORINATION OF METHANE
Cl2 ——> 2Cl•
Initiation
RADICALS CREATED
The single dots represent UNPAIRED ELECTRONS
During initiation, the WEAKEST BOND IS BROKEN as it requires less energy.
There are three possible bonds in a mixture of alkanes and chlorine.
412
348
242
Average bond enthalpy kJ mol-1
The Cl-Cl bond is broken in preference to the others as it is the weakest and
requires requires less energy to separate the atoms.
CHLORINATION OF METHANE
Propagation
Cl• + CH4 ——> CH3• + HCl
Cl2 + CH3• ——> CH3Cl + Cl•
RADICALS USED and
then RE-GENERATED
Free radicals are very reactive because they want to pair up their single electron.
They do this by abstracting a hydrogen atom from methane; a methyl radical is formed
The methyl radical is also very reactive and attacks a chlorine molecule
A chlorine radical is produced and the whole process can start over again
CHLORINATION OF METHANE
Termination
Cl• + Cl• ——>
Cl• + CH3• ——>
CH3• + CH3• ——>
Cl2
CH3Cl
C2H6
RADICALS REMOVED
Removing the
reactive free
radicals brings an
end to the reaction.
This is not very
likely at the start of
the reaction
because of their low
concentration.
CHLORINATION OF METHANE
OVERVIEW
Initiation
Cl2
Propagation
Cl• + CH4
Cl2 + CH3•
Termination
Cl• + Cl•
Cl• + CH3•
CH3• + CH3•
——> 2Cl•
radicals created
——> CH3• + HCl
——> CH3Cl + Cl•
radicals used and
then re-generated
——>
——>
——>
radicals removed
Cl2
CH3Cl
C2H6
Summary
Due to lack of reactivity, alkanes need a very reactive species to persuade them to react
Free radicals need to be formed by homolytic fission of covalent bonds
This is done by shining UV light on the mixture (heat could be used)
Chlorine radicals are produced because the Cl-Cl bond is the weakest
You only need one chlorine radical to start things off
With excess chlorine you get further substitution and a mixture of chlorinated products
CHLORINATION OF METHANE
Initiation
RADICALS
PRODUCED
Propagation
RADICALS USED
AND REGENERATED
Termination
RADICALS
REMOVED
CHLORINATION OF METHANE
Further
propagation
If excess chlorine is present, further substitution takes place
The equations show the propagation steps for the formation of...
dichloromethane
Cl• + CH3Cl
Cl2 + CH2Cl•
——>
——>
CH2Cl• + HCl
CH2Cl2 + Cl•
trichloromethane
Cl• + CH2Cl2
Cl2 + CHCl2•
——>
——>
CHCl2• + HCl
CHCl3 + Cl•
tetrachloromethane
Cl• + CHCl3
Cl2 + CCl3•
——>
——>
CCl3• + HCl
CCl4 + Cl•
Mixtures
Because of the many possible reactions there will be a mixture of products.
Individual haloalkanes can be separated by fractional distillation.
CRACKING
Involves the breaking of C-C bonds in alkanes
Converts heavy fractions into higher value products
THERMAL
CATALYTIC
proceeds via a free radical mechanism
proceeds via a carbocation (carbonium ion) mechanism
THERMAL
HIGH PRESSURE ... 7000 kPa
HIGH TEMPERATURE ... 400°C to 900°C
FREE RADICAL MECHANISM
HOMOLYTIC FISSION
PRODUCES MOSTLY ALKENES ... e.g. ETHENE for making polymers and ethanol
PRODUCES HYDROGEN ... used in the Haber Process and in margarine manufacture
Bonds can be broken anywhere in the molecule by C-C bond fission or C-H bond fission
CRACKING
Involves the breaking of C-C bonds in alkanes
Converts heavy fractions into higher value products
THERMAL
CATALYTIC
proceeds via a free radical mechanism
proceeds via a carbocation (carbonium ion) mechanism
CATALYTIC
SLIGHT PRESSURE
HIGH TEMPERATURE ... 450°C
ZEOLITE CATALYST
CARBOCATION (IONIC) MECHANISM
HETEROLYTIC FISSION
PRODUCES BRANCHED AND CYCLIC ALKANES, AROMATIC HYDROCARBONS
USED FOR MOTOR FUELS
ZEOLITES are crystalline aluminosilicates; clay like substances
REVISION CHECK
What should you be able to do?
Recall and explain the physical properties of alkanes
Recall the use of alkanes as fuels
Recall and explain the different ways to break a covalent bond
Write balanced equations representing combustion and chlorination
Understand the conditions and mechanism of free radical substitution
Recall the conditions and products from thermal and catalytic cracking
CAN YOU DO ALL OF THESE?
YES
NO
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relevant topic(s) again
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WELL DONE!
Try some past paper questions
AN INTRODUCTION TO
THE CHEMISTRY
OF ALKANES
THE END
© 2003 JONATHAN HOPTON & KNOCKHARDY PUBLISHING