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THE CHEMISTRY
OF ALKANES
Alkanes
Introduction
• Recall that alkanes are aliphatic hydrocarbons having
C—C and C—H bonds. They can be categorized as
acyclic or cyclic.
• Acyclic alkanes have the molecular formula CnH2n+2
(where n = an integer) and contain only linear and
branched chains of carbon atoms. They are also called
saturated hydrocarbons because they have the
maximum number of hydrogen atoms per carbon.
• Cycloalkanes contain carbons joined in one or more
rings. Because their general formula is CnH2n, they have
two fewer H atoms than an acyclic alkane with the same
number of carbons.
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• All C atoms in an alkane are surrounded by four groups, making
them sp3 hybridized and tetrahedral, and all bond angles are
109.5°.
• The 3-D representations and ball-and-stick models for these
alkanes indicate the tetrahedral geometry around each C atom.
In contrast, the Lewis structures are not meant to imply any 3-D
arrangement. Additionally, in propane and higher molecular
weight alkanes, the carbon skeleton can be drawn in a variety of
ways and still represent the same molecule.
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• The three-carbon alkane CH3CH2CH3, called propane,
has a molecular formula C3H8. Note in the 3-D drawing
that each C atom has two bonds in the plane (solid
lines), one bond in front (on a wedge) and one bond
behind the plane (on a dashed line).
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• Additionally, in propane and higher molecular weight
alkanes, the carbon skeleton can be drawn in a variety
of ways and still represent the same molecule. For
example, the three carbons of propane can be drawn in
a horizontal row or with a bend. These representations
are equivalent.
• In a Lewis structure, the bends in a carbon chain don’t
matter.
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• There are two different ways to arrange four carbons, giving
two compounds with molecular formula C4H10, named butane
and isobutane.
• Butane and isobutane are isomers—two different compounds
with the same molecular formula. Specifically, they are
constitutional or structural isomers.
• Constitutional isomers differ in the way the atoms are
connected to each other.
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• Carbon atoms in alkanes and other organic compounds are
classified by the number of other carbons directly bonded to
them.
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• Hydrogen atoms are classified as primary (1°), secondary (2°),
or tertiary (3°) depending on the type of carbon atom to which
they are bonded.
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• The maximum number of possible constitutional
isomers increases dramatically as the number of
carbon atoms in the alkane increases. For example,
there are 75 possible isomers for an alkane having 10
carbon atoms, but 366,319 possible isomers for one
having 20 carbons.
• The suffix “ane” identifies a molecule as an alkane.
• By increasing the number of carbons in an alkane by a
CH2 group, one obtains a “homologous series” of
alkanes, as shown in Table 4.1. The CH2 group is called
“methylene.”
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Cycloalkanes
Cycloalkanes have molecular formula CnH2n and contain
carbon atoms arranged in a ring. Simple cycloalkanes are
named by adding the prefix cyclo- to the name of the
acyclic alkane having the same number of carbons.
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Nomenclature
The name of every organic molecule has 3 parts:
1. The parent name indicates the number of carbons in
the longest continuous chain.
2. The suffix indicates what functional group is present.
3. The prefix tells us the identity, location, and number of
substituents attached to the carbon chain.
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• Carbon substituents bonded to a long carbon chain are
called alkyl groups.
• An alkyl group is formed by removing one H atom from
an alkane.
• To name an alkyl group, change the –ane ending of the
parent alkane to –yl. Thus, methane (CH4) becomes
methyl (CH3-) and ethane (CH3CH3) becomes ethyl
(CH3CH2-).
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Naming three- or four-carbon alkyl groups is more
complicated because the parent hydrocarbons have more
than one type of hydrogen atom. For example, propane has
both 1° and 2° H atoms, and removal of each of these H atoms
forms a different alkyl group with a different name, propyl or
isopropyl.
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1. Find the parent carbon chain and add the suffix.
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Also note that if there are two chains of equal length, pick the
chain with more substituents. In the following example, two
different chains in the same alkane have seven C atoms. We
circle the longest continuous chain as shown in the diagram
on the left, since this results in the greater number of
substituents.
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2. Number the atoms in the carbon chain to give the first
substituent the lowest number.
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If the first substituent is the same distance from both ends,
number the chain to give the second substituent the lower
number.
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When numbering a carbon chain results in the same numbers
from either end of the chain, assign the lower number
alphabetically to the first substituent.
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3. Name and number the substituents.
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4. Combine substituent names and numbers + parent and suffix.
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Cycloalkanes are named by using similar rules, but the prefix
cyclo- immediately precedes the name of the parent.
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2. Name and number the substituents. No number is needed to
indicate the location of a single substituent.
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With two different substituents, number the ring to assign the
lower number to the substituents alphabetically.
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Figure 4.3
Examples of cycloalkane
nomenclature
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Nomenclature—Common Names
Some organic compounds are identified using common
names that do not follow the IUPAC system of
nomenclature. Many of these names were given long ago
before the IUPAC system was adopted, and are still widely
used. Additionally, some names are descriptive of shape
and structure, like those below:
Figure 4.4
Common names for some
polycyclic alkanes
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Physical Properties of Alkanes
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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
THE CHEMISTRY OF ALKANES
BUTANE 2-METHYLPROPANE
2p
The electronic configuration of a 2
carbon atom is 1s22s22p2 2s
1 1s
HYBRIDISATION OF ORBITALS
2p
The electronic configuration of a 2
carbon atom is 1s22s22p2 2s
1 1s
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
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
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
the greater the number of carbon atoms, the more energy produced
BUT the greater the amount of oxygen needed for complete combustion.
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...
Removal
SO2 react effluent gases with a suitable compound (e.g. CaO)
CO and NOx 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
There are 2 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
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
Mixtures free radicals are very reactive - they are trying to pair their electron
with sufficient chlorine, every hydrogen will eventually be replaced.
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
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
Removing the
reactive free
radicals brings an
end to the reaction.
OVERVIEW
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
RADICALS
Initiation
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...
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
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
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
THE CHEMISTRY
OF ALKANES
THE END
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– Substitution – parts from two molecules exchange
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– Rearrangement reactions – a molecule undergoes
changes in the way its atoms are connected
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5.2 How Organic Reactions
Occur: Mechanisms
• In a clock the hands move but the mechanism behind the
face is what causes the movement
• In an organic reaction, we see the transformation that has
occurred. The mechanism describes the steps behind the
changes that we can observe
• Reactions occur in defined steps that lead from reactant to
product
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Steps in Mechanisms
• We classify the types of steps in a sequence
• A step involves either the formation or breaking of a
covalent bond
• Steps can occur in individually or in combination with
other steps
• When several steps occur at the same time they are said to
be concerted
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Types of Steps in Reaction
Mechanisms
• Bond formation or breakage can be symmetrical or
unsymetrical
• Symmetrical- homolytic
• Unsymmetrical- heterolytic
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Indicating Steps in
Mechanisms
• Curved arrows indicate breaking and
forming of bonds
• Arrowheads with a “half” head (“fish-
hook”) indicate homolytic and
homogenic steps (called ‘radical
processes’)
• Arrowheads with a complete head
indicate heterolytic and heterogenic
steps (called ‘polar processes’)
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5.3 Radical Reactions
• Not as common as polar reactions
• Radicals react to complete electron octet of valence shell
– A radical can break a bond in another molecule and
abstract a partner with an electron, giving substitution
in the original molecule
– A radical can add to an alkene to give a new radical,
causing an addition reaction
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Steps in Radical Substitution
• Three types of steps
– Initiation – homolytic formation of two reactive species with
unpaired electrons
• Example – formation of Cl atoms form Cl2 and light
– Propagation – reaction with molecule to generate radical
• Example - reaction of chlorine atom with methane to
give HCl and CH3.
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Polarizability
• Polarization is a change in electron distribution as a
response to change in electronic nature of the surroundings
• Polarizability is the tendency to undergo polarization
• Polar reactions occur between regions of high electron
density and regions of low electron density
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Generalized Polar Reactions
• An electrophile, an electron-poor species, combines with a
nucleophile, an electron-rich species
• An electrophile is a Lewis acid
• A nucleophile is a Lewis base
• The combination is indicate with a curved arrow from
nucleophile to electrophile
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5.5 An Example of a Polar Reaction:
Addition of HBr to Ethylene
• HBr adds to the part of C-C double bond
• The bond is electron-rich, allowing it to function as a
nucleophile
• H-Br is electron deficient at the H since Br is much more
electronegative, making HBr an electrophile
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Mechanism of Addition of HBr
to Ethylene
• HBr electrophile is attacked by
electrons of ethylene
(nucleophile) to form a
carbocation intermediate and
bromide ion
• Bromide adds to the positive
center of the carbocation,
which is an electrophile, forming
a C-Br bond
• The result is that ethylene and
HBr combine to form
bromoethane
• All polar reactions occur by
combination of an electron-rich
site of a nucleophile and an
electron-deficient site of an
71 electrophile
5.6 Using Curved Arrows in
Polar Reaction Mechanisms
• Curved arrows are a way to keep track of changes in
bonding in polar reaction
• The arrows track “electron movement”
• Electrons always move in pairs
• Charges change during the reaction
• One curved arrow corresponds to one step in a reaction
mechanism
• The arrow goes from the nucleophilic reaction site to the
electrophilic reaction site
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Rules for Using Curved
Arrows
• The nucleophilic site can be neutral or negatively charged
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• The electrophilic site can be neutral or
positively charged
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