Intoductory

Organic
Unit 1 Topic 4
Chemistry and
Alkanes

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 INTRODUCTORY ORGANIC CHEMISTRY AND ALKANES
What is organic chemistry?
Hydrocarbons
The main feature of an organic compound is that it contains carbon. Almost all of
these compounds also contain hydrogen. Some of them most important compounds
contain elements such as nitrogen and oxygen as well.
Saturated or unsaturated?
Although there are many thousands of different hydrocarbons, most of them are
classed as saturated or unsaturated.
A hydrocarbon is saturated if it contains as much hydrogen as possible, which
depends on the number of carbon atoms in the molecule. If a hydrocarbon has fewer
hydrogen atoms than the maximum, then it is not saturated- we say it is unsaturated.
The formula of the simplest hydrocarbon, containing only one carbon atom, is:

When a hydrocarbon contains two carbon atoms, there is a maximum of six

hydrogen atoms.

A saturated cyclic hydrocarbon is one that contains single bonds only and forms a ring.

Different types of formulae

Displayed formulae
The formulae you saw in the previous section are all displayed formulae. They
show (display) every atom and every bond separately. In many situations, these are the
best type of formulae to use, but sometimes it is better to simplify them.

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An example is the hydrocarbon with this displayed formula (its name is butane):

Structural formulae
One way to simplify this displayed formula is to group all the atoms joined to a
particular carbon atom together. We can choose to show the bonds between the carbons,
or we can leave them out.
These are both structural formulae of butane:
CH3—CH2—CH2—CH3 and CH3CH2CH2CH3

Skeletal formulae

Another way to represent a compound is by a skeletal formula. The word skeletal

is connected with the word skeleton, which, shows only the bones in a human body.
A skeletal formula is a zig-zag line that shows only the bonds between the carbon
atoms. Every change in direction and every ending mean that there is a carbon atom (with
as many hydrogen atoms as needed). Atoms other than carbon and hydrogen need to be
shown.

This is the skeletal formula of butane:

The start and end both represent CH3, and the two junctions between lines each represent
CH2.
Molecular formulae
The displayed, structural and skeletal formulae above show the structures of the
molecules unambiguously. In other words, each formula represents only one compound.
Molecular formulae- they only show the numbers of each type of atom in the
molecule, and not its structure.
Examples are C3H7Cl and CH3OH.
Empirical formulae
Another type of formula is an empirical formula. This shows the compound like a
molecular formula, but the numbers of each atom are in their simplest possible whole-
number ratio. So, butane (molecular formula C4H10) has an empirical formula of C2H5.

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 Table (A): Different types of formula for chloroethane.

Functional groups and homologous series

Functional groups
A functional group in a molecule is an atom or group of atoms that gives the
compound some distinctive and predictable properties. For example, the functional group
of atoms shown as COOH gives molecules containing this group a sour, acidic taste.
There are many organic compounds containing this group. Here are some examples:
HCOOH, CH3COOH, CH3CH2COOH, CH3CH2CH2COOH

Homologous series
A homologous series is a set of compounds with the same functional group, similar
chemical properties and show trends in physical properties.
Alkanes
The organic compound that are mainly used as fuels are the alkanes. They are not
considered to contain a functional group, but otherwise they form a homologous series.
The displayed formulae of some of them are:

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General formulae
The table shows some of the homologous series together with their general formulae.
Table (A): Examples of homologous series.

Properties of a homologous series

Alkanes
We can use the alkanes to illustrate the similarity in chemical properties of a
homologous series. For example, when alkanes are burned completely in air, they all form
the same two products: carbon dioxide and water.
The commonest alkane is methane. The equation for its complete combustion is:

Alcohols
We can use the alcohols to illustrate the gradation in physical properties of a
homologous series. For example, the boiling temperatures of the first four alcohols are
shown in this table.

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Nomenclature
The simple rules of nomenclature

The table summarises the principles of naming organic compounds, including rules
for prefixes, suffixes and locants.
Table (A): The principles of naming organic compounds.

The letter codes for the number of carbon atoms (up to ten) are shown in Table B.
Table (B):

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Applying the rules to write names
Alkanes The names of all the alkanes end in -ane.
Table (B): Naming alkanes from structural formulae using the rules of IUPAC
nomenclature.

Alcohols
The rules for these are a bit different because the presence of the alcohol functional
group is indicated by a suffix, not a prefix. The names for all the alcohols end in -ol.
Table (C): Naming alcohols from structural formulae using the rules of IUPAC
nomenclature.

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Applying the rules to write formulae
Here are some examples of applying the rules the other way round, i.e. writing a
structural formula for a compound from its IUPAC name.
Table (D): Writing a structural formulae from IUPAC names.

Structural Isomerism
Consider these two structures:

These two compounds are simple examples of structural isomers. They have the same
molecular formula C4H10, but different structural formulae.
Types of structural isomerism
There are two important types of Structural Isomerism.
Chain Isomerism
Chain isomerism refers to molecules with different carbon chain.
Butane and methylpropane (shown above) are examples of chain isomers because their
carbon chains are different.

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Position Isomerism
Position isomerism refers to molecules with the same functional group attached
in different positions on the same carbon chain. Propan-1-ol and propan-2-ol are simple
examples of position isomerism:

There are examples of position isomers because the carbon chains are the same, but
the two OH groups are attached to different carbon atoms in the chain.
You might see examples where both of these types of isomerism are present:

Worked Example
Draw the structural isomers for the molecular formula C4H8Cl2.
Step 1: The four carbon atoms can all be in a straight line, or in a straight line of three
with a branch from the middle carbon to the fourth carbon. Let’s start with the
straight line of four: C−C−C−C
Step 2: There are two Cl atoms. They could both be attached to C1 or to C2 in this chain.
You might think that they could be attached to C3 and C4 as well. They could
be, but counting from the light, C1 and C4 are the same, and C2 and C3 are the
same.
The two Cl atoms could also be attached to different carbon atoms, such as C1
and C2, or C2 and C3.
Step 3: Finally, add the necessary hydrogen atoms, making sure that every carbon atom
has four bonds.
Table (A): Shows the approach.

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Alkanes and cycloalkanes
With an alkane with 5 carbon atoms, there are only three different ways to arrange the
carbon atoms.

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Now for the cycloalkanes. There can be a ring of 5 carbon atoms; or a ring of 4 carbon
atoms with the 5th carbon atom attached to any one of the 4; or a ring of 3 carbon atoms
with the 4th and 5th attached to the same or different carbons in the ring. Remember that
each carbon atom must have 4 bonds, and the total number of hydrogen atoms must be
10. These are the possibilities.

Types of reaction
Addition Reactions
In an addition reaction, two reactant species combine together to form a single
product species. Usually all the species are molecules. A general equation for this type of
reaction is:
A+B→C
One example is the reaction between ethane and bromine:
C 2 H 4 + Br2 → C 2 H 4 Br2
Substitution reactions
In a substitution reaction, two reactant species combine together to form two
product species. Usually all the species are molecules or ions. A general equation for this
type of reaction is:
A+B→C+D
C2 H 5 Br + OH − → C2 H 5OH + Br −
In this reaction, the OH group has taken the place of, or substituted the Br atom.
Oxidation Reactions
In an oxidation reaction, one organic compound is oxidised.
The organic compound can either lose hydrogen or gain oxygen.
C2 H 5OH + O → CH 3CHO + H 2O
This reaction is classified as oxidation because the ethanol molecule loses two
hydrogen atoms.
Reduction reactions
In a reduction reaction, one organic compound is reduced, sometimes by hydrogen
gas and a catalyst and sometimes by an inorganic reagent. For example, reduction of an
alkene to an alkane by hydrogen gas and a nickel catalyst. The equation for the reaction
is:

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 C2 H 4 + H 2 → C2 H 6
Polymeristaion reactions
All Polymeristaion reactions you will meet are examples of addition
polymerization. In addition polymeristation, very large numbers of a reactant molecule
(sometimes of two different reactant molecules) react together to form one very large
product molecule.

A familiar example of this type of reaction is the polymerisation of ethane to poly(ethane).

Bond Breaking in organic reactions

Organic compounds contain covalent bonds, for example between:

• Two carbon atoms.
• A carbon atom and a hydrogen atom.
• A carbon atom and a halogen atom.
There are two different ways for the covalent bond to break. These are homolytic
fission and heterolytic fission.
Homolytic fission
'Homolytic' comes from Greek: 'homo' indicates 'same' and 'lytic' indicates 'splitting'.
In hemolytic fission, the shared pair of electrons in the covalent bond divide equally
between the two atoms. This can be shown like this:

C •C → C + •C
Each product species keeps one of the electrons from the covalent bond. These
species are called free radicals. Each free radical has an unpaired electron and is
uncharged.
Homolytic fission usually occurs when the two atoms bonded together are identical
or when they have similar electronegativities.

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 Heterolytic Fission
'Heterolytic' is another term from Greek: 'hetero' indicates 'different' and 'lytic'
indicates 'splitting'.
In heterolytic fission, both electrons of the shared pair in the covalent bond are kept
by one of the atoms. This can be shown like this:
 
C •C → C • + C
The left-band product species keeps both of the electrons from the covalent bond.
This species is a negative ion. The right-hand product species does not keep either of the
electrons from the covalent bond. This species is a positive ion.
Heterolytic fission could also occur like this:
 
C •C → C + •C
Here there are still two ions formed, but this time the right-hand product is the
negative ion.
Heterolytic fission usually occurs when the two atoms bonded together have
different electronegativities. The atom with the higher electronegativity is the one that
keeps both electrons from the bond.
Electrophiles
The origin of the term electrophile is 'electron', which indicates negative charge,
and 'phile', which means liking.

Hazards, risks and risk assessments

The hazard of a chemical substance relates to the inherent properties of the
substance. The risk is more to do with how you plan to use it and the chance of it causing
harm.

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Hazard warning symbols
Table (A): Some pictograms used for chemical hazards.

Risk assessments and control measures

The person in charge of a laboratory (or any other place of work) is responsible for
making risk assessments. First, they look at hazards of all the chemical substances, being
guided by the hazard symbols. Then they consider the ways in which these substances
will be used (this is assessing the risk). Finally, they write some guidelines for those who
use the laboratory (these are the control measures).
Exam Hint
If an exam question asks you to suggest a precaution when tackling a practical
assignment, it is NOT enough to say 'wear a lab coat and goggles'. This should be standard
practice for any practical assignment. You should comment on a particular procedure in
the practical, such as, 'HCl gas is produced and so this step should be carried out in a fume
cupboard'.
The control measures may refer to:
• The type of eye protection that should be worn.
• The need to wear gloves.
• Keeping the cap on the bottle after removing some of the substance.
• Keeping the substance away from a source of heat.
• What to do if some of the substance is spilled on the floor or gets on the skin.

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Apparatus
Don't forget about the apparatus you might use in chemistry laboratories. Some of
this apparatus may also have hazards.
For example, mercury thermometers obviously contain mercury, which is a
hazardous substance. This is why you are more likely to use spirit thermometers and
digital thermometers, their hazards are much lower.
Another example is methods of heating. Traditionally, heating involved the use of
a Bunsen burner, tripod and gauze. Perhaps an electrical heating mantle would be safer,
as well as easier to use.
In organic chemistry, some experiments involve glass apparatus for techniques such
as distillation. A long time ago, the traditional way to connect the different pieces of glass
apparatus was by using connecting glass tubing with corks or rubber bungs. More
recently, apparatus made only of glass, connected mainly by ground glass joints, has been
used. This is less hazardous because it does not involve the risks involved in assembling
the apparatus.

Alkanes from crude oil

The three main processes used to convert crude oil into fuels are:
• Fractional distillation.
• Cracking.
• Reforming.
Fractional distillation
Crude oil is a complex mixture of compounds, mostly hydrocarbons.
It involves converting the crude oil into a small number of fractions.
Fractionation is done in a distillation column.
The process
The crude oil is first heated in a furnace, which turns most of it into vapour, which
is then passed into the column near the bottom. There is a temperature gradient in the
column: it is hotter near the bottom and cooler near the top.
As the vapour passes up the column through a series of bubble caps, different
fractions condense at different heights in the column, depending on the boiling
temperature range of the molecules in the fraction.
• Near the bottom of the column, the fractions contain larger molecules with longer
chains and higher boiling temperatures.
• Near the top of the column, the fractions contain smaller molecules with shorter chains
and lower boiling temperatures.
• Some of the hydrocarbons in crude oil are dissolved gases, and they rise to the top of
the column without condensing.

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 Some fractions still contain many different compounds, so they may undergo
further fractional distillation separately.
Cracking
The world has fewer uses for longer-chain hydrocarbons so there is a surplus of
these. The demand for shorter-chain hydrocarbons is much higher because they are
i) better fuels and ii) can be used to make other substances such as polymers.
Unfortunately, there are not enough of these to satisfy the demand. The solution is convert
these longer chains into shorter chains, which is what happens in cracking.
The process
Cracking is done by passing the hydrocarbons in the heavier (longer chain) fractions
through a heated catalyst, usually of zeolite, which is a compound of aluminium, silicon
and oxygen. This causes larger molecules to break up into smaller ones. From one large
molecule, at least two smaller molecules are formed.
A good example is the cracking of decane into octane and ethane:

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Reforming
During the very rapid combustion of fuels in vehicle engines, not all hydrocarbons
when used as fuels burn in the same way.
Those with straight chains burn less efficiently than those with branched chains and
those with rings (cyclic compounds).
The process is to convert straight-chain alkanes into branched-chain alkanes and
cyclic hydrocarbons by heating them with a catalyst, usually platinum. This helps them
to burn more smoothly in the engine.
Examples
In the first one, pentane (C5H12) is converted into a cyclic alkane:

In the second one, heptane (C7H16) is converted into methylbenzene, which is a

cyclic hydrocarbon but not an alkane. You will learn the meaning of the circle inside the
hexagon later.

In each example, hydrogen is formed. It is a useful by-product.

Alkanes as fuels
The complete combustion of alkanes
Alkanes are burnt in large quantities to provide us with energy. An example is the
burning of propane.
C3 H 8 + 5O2 → 3CO2 + 4 H 2O

The products of combustion

One of the products of combustion is water, which is not a problem as it simply
adds to the total quantity of global H2O.
The other product is carbon dioxide. As you know, this is a greenhouse gas and
most scientists consider its increasing production to be responsible for global warming,
climate change and other problems.
Exam hint
Remember, carbon dioxide works by trapping infrared radiation that is emitted from
the Earth's surface and so prevents it from escaping back into space.

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Incomplete combustion
Sometimes the combustion of an alkane is incomplete because there is not enough
oxygen present, or because the combustion is very rapid.
Its products can cause harm.
Carbon
You can often see when incomplete combustion forms solid carbon. This can be
seen as smoke in the air or soot on the burner.
C3 H 8 + 4O2 → C + 2CO2 + 4 H 2O

Carbon monoxide
Carbon monoxide is a toxic gas that causes the death.
C3 H 8 + 4O2 → 2CO + CO2 + 4 H 2O

Unburned hydrocarbons
The ultimate example of incomplete combustion is when the hydrocarbon does not
burn at all. A small proportion of the hydrocarbons in a fuel are released into the
atmosphere unchanged. They are known as unburned hydrocarbons.
Oxides of sulfur
Some of the molecules in crude oil contain atoms of sulfur, and these may not be
removed by the fractional distillation, cracking or reforming processes. During the
combustion of alkanes, these atoms of sulfur form sulfur dioxide gas, and then can react
in the atmosphere to form sulfur trioxide gas. The equation for these reactions are:
S + O2 → SO2 and 2SO2 + O2 → 2SO3
Both sulfur gases are acidic oxides. When they dissolve in water in the atmosphere,
they form sulfurous acid and sulfuric acid:
SO2 + H 2O → H 2 SO3 and SO3 + H 2O → H 2 SO4
Both acids contribute to the formation of acid rain. Acid rain is responsible for a lot
of environmental damage, including damage to aquatic life in lakes and rivers, and
damage to crops and forests.
Oxides of Nitrogen
Although very few molecules used as alkane fuels contain atoms of nitrogen, their
combustion occurs at very high temperatures. Under these conditions, especially around
the spark plugs in cars, these very high temperatures cause nitrogen molecules in the air
to react with oxygen molecules. These reactions lead to the formation of oxides of
nitrogen. They are represented by the formula NOx. There are several of these oxides, but
the main ones are nitrogen monoxide (NO) and nitrogen dioxide (NO2).
At very high temperatures, the main reaction is:
N 2 + O2 → 2 NO

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 However, nitrogen monoxide can then react with more oxygen in the atmosphere
as follows:
2 NO + O2 → 2 NO2
Nitrogen dioxide is acidic and can dissolve in water in the atmosphere, forming
nitrous acid and nitric acid:
2 NO2 + H 2O → HNO2 + HNO3
Both acids contribute to environmental damage in the same way as sulfurous acid
and sulfuric acid.
Catalytic convertes to the rescue
Cars and other road vehicles are responsible for a lot of air pollution. The
widespread use of catalytic converters fitted to exhaust systems has made pollution less
of a problem.
There are different types of catalytic converter, but they all use small quantities of
precious metals such as platinum, rhodium and palladium.

Fig (B): A three-way catalytic converter.

Examples are the oxidation of the carbon monoxide and the oxidation of unburned
hydrocarbons:
1
2CO + O2 → 2CO 2 and C8 H 18 +12 O2 → 8CO2 + 9 H 2 O
2
Here is another useful reaction that removes two pollutants at the same time:
2 NO 2 + 2CO → N 2 + 2CO 2

Alternative fuels
THE NEED FOR ALTERNATIVE FUELS
We have already discussed the pollution caused by the combustion of alkanes.
The other concerns are:
• The depletion of natural resources
• Global warming and climate change
Recently, more attempts were made to produce alternative fuels mainly “biofuels”

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 The terms ‘renewable’ and ‘non-renewable’ are often used when discussing
energy sources. Non-renewable usually refers to coal, oil and natural gas. Renewable
sources include biofuels, but also sunlight, wind, waves and tides, and geothermal
energy.
CARBON NEUTRALITY
WHAT DOES CARBON NEUTRAL MEAN?
‘Carbon neutral’ is a term used to represent the idea of carbon dioxide neutrality.
For example, when a tree grows, it absorbs carbon dioxide from the atmosphere, and the
carbon atoms become part of the structure of the tree. If the tree is cut down and the wood
is burned, then carbon dioxide is formed during its combustion. If the amount of carbon
dioxide formed in the combustion is the same as the amount absorbed during the tree’s
growth, then the wood used is described as carbon neutral.
BIOALCOHOLS
You might think that bioalcohols (as bioethanol that comes from the fermentation
of sugars) are carbon neutral fuels because they are made from recently-grown plants that
have absorbed carbon dioxide from the atmosphere.
However, this does not recognise the fact that the plants have to be harvested,
transported to a factory and processed in the factory, and the products transported to a
point of sale. All these stages involve the use of energy, much of which involves the
formation of carbon dioxide. But they are closer to carbon neutrality than fossil fuels.
BIOETHANOL
Currently, the commonest bioalcohol is bioethanol.
It is now possible to use a wide range of plants waste to produce ethanol.
COMPARING FUELS BIOFUELS
The choice of alternative fuels is continually changing, as new sources of starting
material and new processing methods are investigated. There are many factors to consider
in any comparison, but for biofuels such as bioethanol these include the following.
• Land use – how much land is used to grow the crop? Should the land be used for other
purposes, especially to grow food to feed people?
• Yield – how much of a crop can be grown on a given piece of land, and how quickly
does it grow? What percentage of the carbon and hydrogen atoms in the crop ends up
in the fuel?
• Manufacture and transport – how much energy is used in growing (including any
fertilisers), processing and transporting the crop?
• Carbon neutrality – how close is the fuel to being carbon neutral?
HYDROGEN
Hydrogen is not a biofuel but
• It can be burned instead of a fossil fuel such as petrol or natural gas.
• It can be used in a fuel cell to generate electricity that powers an electric motor.
No carbon dioxide is produced, which suggests no increase in the greenhouse effect.

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 Obtaining hydrogen from water requires energy which could come from electricity.
Another major problem is hydrogen storage. The gas has a very low density, so storing
enough inside a car needs a container under very high pressure. This means a very strong
container and therefore one that is very heavy. It could be stored as a liquid, but as its
boiling temperature is –253 ºC, the container would need to be very cold and very well
insulated.

Fig. C Comparing bioethanol with natural gas as fuels for cars.

• Biofuel fuel obtained from living matter that has died recently.
• Bioalcohol fuel made from plant matter, often using enzymes or bacteria.
• Carbon neutral a considered net zero effect on the amount of carbon dioxide in the
atmosphere.

SUBSTITUTION REACTIONS OF ALKANES

Alkanes, apart from readily undergoing combustion, are fairly unreactive because
they contain only carbon and hydrogen atoms and only single bonds where these bonds
are not very polar and so unreactive.
There is a type of reaction that alkanes undergo, called a substitution reaction.
CH4 + Cl2 → CH3Cl + HCl is an example that occurs in Ultraviolet light.
The reaction can be described as chlorination or, in general (if another halogen
were used), halogenation.

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MECHANISMS
THE CHLORINATION OF METHANE
STEP 1 Initiation step.
Ultraviolet radiation breaks the chlorine molecule into chlorine atoms. This kind of
bond breaking is called homolytic fission.

Step 1 can be represented in an equation:

Cl2 → Cl• + Cl•
However, it is better to use a different type of equation that shows clearly what happens
to the electrons in the Cl–Cl bond.

The formula Cl• does not represent an ion or a molecule; it is a free radical.

STEP 2 Propagation step

Chlorine free radicals are very reactive species and when they collide with methane
molecules they react by removing a hydrogen atom. An equation for this process is:
Cl• + CH4 → HCl + CH3•
Notice that CH3• is formed. This is a methyl free radical and, like Cl•, it is also very
reactive. It can then react with chlorine molecules as follows:
CH3• + Cl2 → CH3Cl + Cl•
STEP 3 Termination step
With all these free radicals being formed, it is likely that two of them will collide
with each other. When this happens, they react to form a molecule, as the two unpaired
electrons are shared to form a covalent bond. As there are two different free radicals
available, this means that there are three possibilities:
Cl• + Cl• → Cl2
Cl• + CH3• → CH3Cl
CH3• + CH3• → C2H6
You now know that a hydrogen atom in methane can be replaced by a chlorine atom
in a substitution reaction. You can also see that the product chloromethane (CH3Cl) still
contains hydrogen atoms. These three hydrogen atoms can also be replaced, one by one,
by chlorine atoms in similar substitution reactions.

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The formation of dichloromethane
CH3Cl + Cl2 → CH2Cl2 + HCl
The formation of trichloromethane
CH2Cl2 + Cl2 → CHCl3 + HCl
The formation of tetrachloromethane
CHCl3 + Cl2 → CCl4 + HCl

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