FORMULAE, FUNCTIONAL GROUPS, AND HOMOLOGOUS SERIES

Different types of formulae

1. Displayed formulae show every atom and every bond in a
compound;
2. Structural formulae unambiguously show how the atoms are
joined together;
3. Skeletal formulae shows all the bonds between carbon atoms;
It is a zigzag line, where every change in direction and
every ending means a carbon atom, with as many hydrogen
bonded to each atom as needed. Atoms other than hydrogen and
carbon need to be shown.
4. Molecular formulae show the actual numbers of each atom in
the molecule;
5. Empirical formulae show the numbers of each atom in the
simplest integer ratio;
6. General formulae represents all compounds in a homologous
series.

Functional groups and homologous series

A functional group in a molecule is an atom or group of atoms
that gives the compound some distinctive and predictable
properties.

A homologous series is a set of compounds with the same

functional group, similar chemical and physical properties that
show a gradual change from one to the next.

Name General Formula Functional Group

Alkane CnH2n+2

Alkene CnH2n

Alcohol CnH2n+1OH R-OH

ISOMERISM

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structural isomers are compounds which have the same molecular
formula but different structural formulae.

Chain isomerism refers to molecules with different carbon

chains, whilst position isomerism refers to molecules with the
same functional group attached in different positions on the
same carbon chain.

stereoisomers have the same molecular formula and the same

structural formula, but they have a different arrangement.

Geometric isomers exist where there is a presence of a carbon

double bond since it leads to restricted rotation, hence the
groups can be differently attached to the carbon atoms.

ALKANES AND FUELS

There are 3 main processes to cover crude oil into fuels:

1. Fractional distillation;
2. Cracking;
3. Reforming.

Fractional distillation
Crude oil is a complex mixture of compounds, mostly
hydrocarbons. Fractional distillation separates the hydrocarbons
according to the chain length. This is done through the
following process:

1. Crude oil is heated in the bottom of a furnace which has a

temperature gradient (hottest in the bottom). It is now
mostly vapour.
2. As the vapour passes up the column through bubble caps,
different fractions condense at different stages depending
on the boiling temperature.

Some fractions still contain many different compounds, so this

does not lead to a pure substance.

Cracking

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Shorter chain hydrocarbons have many more uses than longer chain
hydrocarbons. Cracking converts the longer chains into shorter
ones.

This is done by passing the hydrocarbons through a heated

catalyst, usually zeolite (compound of aluminium, silicon and
oxygen), causing a larger molecule to split into two smaller
ones.

Reforming
When combusted, not all hydrocarbons burn in the same way.
Reforming coverts straight chain alkanes into branched chain
alkanes and cyclic compounds as they are combusted more
efficiently. This is done by heating them with a catalyst,
usually platinum. Hydrogen gas is usually a by-product of this
product.

Alkanes as fuels
The complete combustion of alkanes will always result in carbon
dioxide and water as products.

Incomplete combustion happens when there's a lack of oxygen or

when the process happens very quickly. All the hydrogen in
converted into water but not all carbon is converted into carbon
dioxide, causing harmful products to form. These include solid
carbon particles (soot or smoke) and the toxic gas carbon
monoxide.

Unburned hydrocarbons (HC) can also occur when a small

proportion of the hydrocarbons in the fuel are released into the
atmosphere unchanged.

Air pollution due to combustion

oxides of sulfur can be released into the atmosphere during
combustion as some of the molecules in crude oil contain atoms
of sulfur and not all are removed when processing it. The
equations are:

S + O2 → SO2

2SO2 + O2 → 2SO3

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These gasses then dissolve in water to form sulfurous and
sulfuric acid

SO2 + H2O → H2SO3

SO3 + H2O → H2SO4

oxides of nitrogen Can be formed at very high temperatures. The

main reactions are:

N2 + O2 → 2NO

2NO + O2 → 2NO2

Similar to oxides of sulfur, nitrogen dioxide is also acidic and

can dissolve in water to form nitrous and nitric acid:

2NO2 + H2O → HNO2 + HNO3

catalytic converters can help reduce pollution when they are fitted
to exhaust systems. Small quantities of precious metals such as
platinum, rhodium and palladium are spread thinly over a
honeycomb mesh to increase the surface area of the reaction.

A three-way catalyst can remove three pollutants: CO, NOx and

HC. They are not ideal to remove sulfur compounds, hence they
are usually removed when the crude oil is being processed.

Exhaust gases from the engine pass through the converter so

different reactions can occur. These include:

2CO + O2 → 2CO2

C8H18 + 12.5O2 → 8CO2 + 9H2O

2NO + 2CO → N2 + 2CO2

Biofuels
Biodiesel is a fuel made from vegetable oils obtained from
plants. It can also be mixed with ordinary diesel. Bioalcohols
are fuels made from plant matter, often using enzymes or
bacteria.

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A comparison of fossil fuels and biofuels:

Biofuel Natural gas

Land use A lot is needed No landed required

Yield Low, but gradually Very high

increasing

Manufacture Substantial costs in Very high exploration

growing, processing and and drilling costs
transport

Carbon neutrality Much closer to being Definitely not carbon

carbon neutral neutral

SUBSTITUTION REACTIONS OF ALKANES

A substitution reaction is one in which an atom or group is

replaced by another atom to group.

A mechanism is the sequence of steps in an overall reaction.

Each step shows what happen to the electrons involved in bond
breaking or formation.

Chlorination of methane
For chlorine and methane to occur, the mixture must be exposed
to UV light. The mechanism for the reaction is as following:

1. The first step is known as initiation. The UV light breaks

the chlorine molecule into chlorine atoms, leading each atom
to take one electron from the shared pair. This is known as
homiletic fission.

Cl2 → Cl• + Cl•

Cl• indicates a radical, a species with an unpaired

electron.

2. The second step is known as propagation. Chlorine radicals

will then collide with methane molecule and react by
removing a hydrogen atom.

Cl• + CH4 → HCl + CH3•

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 The methyl radical will then react with chlorine molecules
to form chloromethane.

CH3• + Cl2 → CH3Cl + Cl•

3. The final step is known as termination. Radicals will

eventually collide, forming a covalent bond between them.
There are three possibilities for this:

1. Cl• + Cl• → Cl
2. Cl• + CH3• → CH3Cl
3. CH3• + CH3• → C2H6

Further substitutions can occur in a similar way since the

alkane still contains hydrogen atoms to form, di-, tri- and
tetra-chloromethane.

ADDITION REACTIONS OF ALKENES

An addition reaction in one in which two molecules combine to

form one molecule. Alkenes react by breaking the double bond.
The sigma bond remains unchanged, but the pi bond electrons are
used to form new (sigma) bonds with the attacking molecule. This
forms a saturated product.

hydrogenation occurs when hydrogen is added to an alkene, forming

an alkane.

hydration occurs when water is added to an alkene. This is

usually done by heating the alkene with steam over a catalyst of
phosphoric acid. This forms an alcohol.

Oxidation to diols
An alkane can undergo oxidation followed by addition in order to
form a diol, a compound containing to OH groups. The oxidising
agent is acidified (H2SO4(aq)) potassium manganate VII. One
oxygen atom is provided by the oxidising agent and with the
water in the solution, two OH groups are obtained.

CH2=CH2 + [O] + H2O → CH2OH-CH2OH

[O] represents the oxygen provided by the oxidising agent.

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 Halogenation and electrophilic addition
Halogenation occurs when a halogen is added to an alkene,
forming a dihalogenoalkane. Similarly, if you add a hydrogen
halide to an alkene, the product will be a halogenoalkane.

Since a C=C has a high electron density, polar molecules such as

hydrogen halides (e.g. HBr) are attracted to it due to H+ being
less electronegative than Br-. Therefore, the HBr is considered
to be an electrophile, a species that is attracted to negative
charge.

The mechanism for the reaction between ethene and HBr goes as
following:

Both electrons from the pi bond move to the H∂+ as one of the
carbon atoms in the double bond bonds with the hydrogen.
This causes both electrons in the H-Br to move to the
bromine as it is more electronegative. This is known as
heterolytic fission, the breaking of a covalent bond so that
both bonding electrons are taken by one atom.

Furthermore, the second carbon atom in the double bond now

only has 3 bonds, hence it has become a positive ion, a
carbocation.

The two oppositely charged ions attract each other and react
to form a new covalent bond.

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The mechanism for halogenation reacts is very similar. Halogens
are non-polar, but as a molecule approaches the carbon bond, a
temporary dipole is induced, so they become polar and the
reaction starts.

unsymmetrical molecules leads to two possible products when they

are attacked by electrophiles since they can be placed in two
different places. For example:

There is a major product and a minor product which is due to the

different carbocations that are formed.

CH3-⨁CH-CH3: the carbocation is attached to two alkyl groups,

hence it is secondary and it is the major product.

-⨁CH2-CH2-CH3: the carbocation is attached to one alkyl group,

hence it is primary and it is the minor product.

The more alkyl groups there are attached to the carbocation, the
more stable the molecule is since the positive charge can be
spread over more atoms since alkyl groups are electron
releasing, meaning they push electrons towards the atom it is
joined to. Tertiary carbocations are even more stable.

Polymerisation reactions

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Polymerisation reactions are addition reactions of molecules
with C=C (monomers) to form a saturated molecule with a long
chain (polymer). Polymers don't have a fixed molecular formula,
so they are represented as following:

Polymer waste is mostly non biodegradable, and can be dealt with

the following ways:

1. Recycling: the polymer is converted into other materials.

The materials must be sorted due to the various different
types of polymers and then they are processed, where the
waste is shred to pieces and washed. This material is then
used to make new materials via melting, moulding or fibre
production.

2. Incineration: the waste is burned in order to provide heat

and electricity for homes and factories, but the pollutants
are a downside to this.

3. Chemical feedstock: the waste is broken down into gases,

mainly hydrogen and carbon monoxide, in order to produce a
feedstock that can be used in other chemical reactions.

4. Biodegradable polymers: these are made from plant materials

and break down by microbes in the environment.

HALOGENOALKANES

Halogenoalkanes are reactive due to the polarity of the C-X

bond, causing the carbon atom to be have a slightly positive
charge. These carbon atoms attract nucleophiles, a species that
donates a lone pair of electrons to form a covalent bond with an
electron-deficient atom.

Hydrolysis

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Hydrolysis mean splitting with water, and when a halogenoalkane
is added to water the R-X bond is broken to form an alcohol
instead. This is an example of a substitution reaction.

R-X + H2O → R-OH + H+ + X-

The H+ and X- ions will combine to form a hydrogen halide. This

reaction occurs since water has a lone pair of electrons and
thus oxygen is slightly negative.

the rate of hydrolysis can be compared by:

1. Add aqueous silver nitrate to the halogenoalkane;

2. Add ethanol as a solvent for the mixture;
3. Time the appearance of the precipitate by seeing how long it
takes for a cross to disappear.

Different halogenoalkanes will react according to the halogen

atom involved and to the structure of the compound.

For compounds with the same structure but different halogen

atoms, the reaction is faster as you go down the group. This is
due to a decrease in bond enthalpy, meaning less energy is
required to overcome the C-I than C-Br than C-Cl bond.

For compounds with the same halogen atom but different

structures, a tertiary molecule will react faster than a
secondary one, which is faster than a primary molecule.

Nucleophilic substitution reactions

rx and koh(aq) react under reflux to make an alcohol. The attacking
nucleophile is the OH-. For example:

CH3CH2Br + KOH → CH3CH2OH + KBr

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rx and kcn react when dissolved in ethanol under reflux to make a
nitrile, an organic compound containing the C-CN group. The
attacking nucleophile is the CN- ion. For example:

CH3CH2Br + KCN → CH3CH2CN + KBr

This reaction extends the carbon chain.

rx and nh3(aq) react to make primary amines when heated in a sealed

tube. Primary amines are compounds containing the C-NH2 group.
The attacking nucleophile is the NH3 molecule. For example:

CH3CH2Cl + NH3 → CH3CH2NH2 + HCl

However, since the organic product is a base, it will react with

the HI, so a better reaction is:

This a salt, so it will react with the excess NH3 which acts as
a base and removes a hydrogen ion from the ion formed.

The NH4+ will combine with the Cl- to give NH4Cl

Elimination
An elimination reaction reaction is one which a molecules loses
atoms attached to adjacent carbon atoms, forming a C=C double
bond.

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When a halogenoalkane reacts with ethanol potassium hydroxide,
the OH- acts as a base, not a nucleophile. Therefore, it will
react with the hydrogen ions next to the C-X bond to form an
alkene, water and KX. For example:

CH3-CHBr-CH3 + KOH → CH2=CH-CH3 + H2O + KBr

ALCOHOLS

Reactions of alcohols
The main reactions are alcohols are:

1. Combustion:
When alcohols completely burn, the products are carbon
dioxide and water.

2. Conversions to halogenoalkanes:
The hydroxyl group is replaced with a halogen atom, this is
known as halogenation.

1. Chlorination is carried out using phosphorous(V)

chloride. There are two inorganic products, phosphorus
oxychloride and hydrogen chloride. For example:

CH3CH2OH + PCl5 → CH3CH2Cl + POCl3 + HCl

If the alcohol is tertiary, mixing it with concentrated

HCl will also replace the OH group.

(CH3)3COH + HCl → (CH3)3CCl + H2O

2. Bromination is carried out with a mixture of KBr and 50%

concentrated H2SO4 which is warmed. The inorganic
reactants will react to form HBr:

KBr + H2SO4 → KHSO4+ HBr or 2KBr + H2SO4 → K2SO4 + 2HBr

The alcohol will their react with the HBr to form a

bromoalkane and water, for example:

CH3CH2CH2OH + HBr → CH3CH2CH2Br + H2O

3. Iodination is carried out using a mixture of red

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 phosphorus and iodine which is heated under reflux.

2P + 3I2 → 2PI3

3C2H5OH + PI3 → 3C2H5I + H3PO3

3. Dehydration to alkenes:
The alcohol is heated with concentrated phosphoric acid to
form an alkene and water. There are three possible products:

CH3CH(OH)CH2CH3 → CH2=CHCH2CH3 + H2O (but-1-ne)

CH3CH(OH)CH2CH3 → CH3CH=CH2CH3 + H2O (cis or trans but-2-ne)

Oxidation reactions
Oxidation only affects one carbon atom. The hydrogen in the OH
group and a hydrogen atom attached to the same carbon atom are
removed so a double bond C=O, a carbonyl, is formed. Due to
this, only primary and secondary alcohols can be oxidised, not
tertiary ones.

The reagent for these oxidations is a mixture of potassium

dichromate(VI) and dilute sulphuric acid, where the oxidising
agent is represented by [O] in equations. There is a colour
change from orange to green when the alcohol is oxidised.

the oxidation of primary alcohols results in an aldehyde (RCHO),

however aldehydes are easily further oxidised where it gains an
oxygen atom, forming a carboxylic acid (RCOOH).

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For example:

Propan-1-ol to propanal: CH3CH2CH2OH + [O] → CH3CH2CHO + H2O

Propanal to propanoic acid: CH3CH2CHO + [O] → CH3CH2COOH

A distillation apparatus ensures that the oxidation isn't

complete, whilst using reflux would result in a full oxidation.

the oxidation of secondary alcohols results in a ketone, which has a

simplified formula of RCOR. The only possible outcome is a
ketone since only one hydrogen atom can be removed. Example:

CH3CH(OH)CH3 + [O] → CH3COCH3 + H2O

Purifying organic liquids

The techniques of purifying include:

1. Simple distillation:

1. The impure liquid is heated in a pear shaped flask,

which is connected to a condenser.
2. The liquid with the lowest boiling temperature
evaporates first and is collected in the receiver once
it has been condensed.
3. Now the liquids are separated according to their boiling
points.

2. Fractional distillation:

The same apparatus as simple distillation is used, but with

a fractionating column between the heating flask and the
still head. The column is filled with glass beads where the
vapour condenses on. As the temperature increases, they will
evaporate again.

3. Solvent extraction:

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 This involved using a solvent to removed the organic product
from the other substances.
1. The reaction mixture is placed in a separating funnel
and then the solvent is added;
2. Shake the container and allow the contents to settle
into two layers;
3. Open the tap and drain the lower layer as the organic
layer is always the one on top;
4. Use distillation to separate the organic product from
the solvent used.

4. Drying:

Water can be removed from an organic substance with the use

of a drying agent, often calcium, magnesium or sodium
sulfate. Calcium chloride can also be used as long as it
doesn't react with the organic product.
1. Add the drying agent to the mixture and shake it;
2. Lumps are formed as the water is removed. Keep adding
the powder until no lumps are formed;
3. Filter the mixture to remove the drying agent or use
decantation.

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