3.2 Hydrocarbons

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CIE A Level Chemistry Your notes
3.2 Hydrocarbons
Contents
3.2.1 Alkanes
3.2.2 Combustion & Free Radical Substitution of Alkanes
3.2.3 Free Radical Substitution
3.2.4 Cracking of Alkanes
3.2.5 Chemical Reactivity of Alkanes
3.2.6 Combustion of Alkanes
3.2.7 Production of Alkenes
3.2.8 Reactions of Alkenes
3.2.9 Test for Unsaturation
3.2.10 Electrophilic Addition of Alkenes
3.2.11 Markovnikov's Rule
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3.2.1 Alkanes
Your notes
Production of Alkanes: Hydrogenation & Cracking
Alkanes are hydrocarbons that can be produced by the addition reaction of hydrogen to an alkene or
by cracking of longer alkane chains
Production of alkanes from addition reactions
Alkenes are unsaturated organic molecules and contain C-C double bonds
When hydrogen gas and an alkene are heated and passed over a finely divided Pt/Ni catalyst, the
addition reaction produces an alkane:
The Pt/Ni catalyst is finely divided to increase its surface area and therefore increase the rate of
reaction
Eg. butane from 1-butene
Hydrogen gas is added to 1-butene which are then heated and passed over a Pt/Ni catalyst to produce
butane
The addition reaction of alkenes with hydrogen is called hydrogenation

Hydrogenation is often used in the manufacture of margarine from vegetable oil
Vegetable oil is an unsaturated organic molecule with many C-C double bonds
When these are partially hydrogenated, their hydrocarbon chains become straighter
This raises the melting point of the oils which is why margarine is a soft solid and vegetable oil a
liquid at room temperature
Production of alkanes from cracking
In cracking large, less useful hydrocarbon molecules found in crude oil are broken down into smaller,
more useful molecules
The large hydrocarbon molecules are fed into a steel chamber and heated to a high temperature and
then passed over an aluminium oxide (Al2O3) catalyst
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The chamber does not contain any oxygen to prevent combustion of the hydrocarbon to water
and carbon dioxide
When a large hydrocarbon is cracked, a smaller alkane and alkene molecules are formed Your notes
Eg. octane and ethene from decane
Long hydrocarbons are cracked by heating them and using aluminium oxide catalyst into smaller
hydrocarbons and an alkene
Exam Tip
Remember that hydrogenation is an exothermic reaction and cracking is an endothermic reaction.
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3.2.2 Combustion & Free Radical Substitution of Alkanes

Your notes
Combustion & Free Radical Substitution of Alkanes
Alkanes are combusted (burnt) on a large scale for their use as fuels
They also react in free-radical substitution reactions to form more reactive halogenoalkanes
Complete combustion
When alkanes are burnt in excess (plenty of) oxygen, complete combustion will take place and all
carbon and hydrogen will be oxidised to carbon dioxide and water respectively
For example, the complete combustion of octane to carbon dioxide and water
The complete combustion of alkanes

Incomplete combustion
When alkanes are burnt in only a limited supply of oxygen, incomplete combustion will take place and
not all the carbon is fully oxidised
Some carbon is only partially oxidised to form carbon monoxide
For example, the incomplete combustion of octane to form carbon monoxide
The incomplete combustion of alkanes
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Carbon monoxide is a toxic gas as it will bind to haemoglobin in blood which can then no longer bind
oxygen
As no oxygen can be transported around the body, victims will feel dizzy, lose consciousness and if not Your notes
removed from the carbon monoxide, they can die
Carbon monoxide is extra dangerous as it is odourless (it doesn’t smell) and will not be noticed
Incomplete combustion often takes place inside a car engine due to a limited amount of oxygen
present
Free-radical substitution of alkanes
Alkanes can undergo free-radical substitution in which a hydrogen atom gets substituted by a
halogen (chlorine/bromine)
Since alkanes are very unreactive, ultraviolet light (sunlight) is needed for this substitution reaction to
occur
The free-radical substitution reaction consists of three steps:
In the initiation step, the halogen bond (Cl-Cl or Br-Br) is broken by UV energy to form two radicals
These radicals create further radicals in a chain type reaction called the propagation step
The reaction is terminated when two radicals collide with each other in a termination step
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3.2.3 Free Radical Substitution

Your notes
Free Radical Substitution Mechanism
Alkanes can undergo free-radical substitution in which a hydrogen atom gets substituted by a
halogen (chlorine/bromine)
Ultraviolet light (sunlight) is needed for this substitution reaction to occur
The free-radical substitution reaction consists of three steps
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Your notes
The fact that the bromine colour has disappeared only when mixed with an alkane and placed in sunlight
suggests that the ultraviolet light is essential for the free radical substitution reaction to take place
Initiation step
In the initiation step the Cl-Cl or Br-Br is broken by energy from the UV light
This produces two radicals in a homolytic fission reaction
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Your notes
The first step of the free-radical substitution reaction is the initiation step in which two free radicals are
formed by sunlight
Propagation step
The propagation step refers to the progression (growing) of the substitution reaction in a chain type
reaction
Free radicals are very reactive and will attack the unreactive alkanes
A C-H bond breaks homolytically (each atom gets an electron from the covalent bond)
An alkyl free radical is produced
This can attack another chlorine/bromine molecule to form the halogenoalkane and regenerate
the chlorine/bromine free radical
This free radical can then repeat the cycle
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Your notes
The second step of the free-radical substitution reaction is the propagation step in which the reaction
grows in a chain type reaction
This reaction is not very suitable for preparing specific halogenoalkanes as a mixture of
substitution products are formed
If there is enough chlorine/bromine present, all the hydrogens in the alkane will eventually get
substituted (eg. ethane will become C2Cl6/C2Br6)
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Your notes
The free-radical substitution reaction gives a variety of products and not a pure halogenoalkane
Termination step
The termination step is when the chain reaction terminates (stops) due to two free radicals reacting
together and forming a single unreactive molecule
Multiple products are possible
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Your notes
The final step in the substitution reaction to form a single unreactive molecule
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Exam Tip
Your notes
You could be asked to draw the mechanism for initiation and termination steps for free radical
substitution. This mechanism will uses half headed arrows to show the movement of one electron
(double headed arrows show the movement of a pair of electrons). A half headed arrow is known as a
‘fish hook’ arrow.
Initiation:
Termination:
The key is the use of the ‘fish hook’ arrow to show the homolytic fission of the bond in initiation and the
formation of the bond in termination.
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3.2.4 Cracking of Alkanes

Your notes
Obtaining Useful Compounds by Cracking
Crude oil
Crude oil is a mixture of hydrocarbons containing alkanes, cycloalkanes and arenes (compounds with
a benzene ring)
The crude oil is extracted from the earth in a drilling process and transported to an oil refinery
At the oil refinery the crude oil is separated into useful fuels by fractional distillation
This is a separating technique in which the wide range of different hydrocarbons are separated into
fractions based on their boiling points
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Your notes
Crude oil is initially separated into fractions with similar boiling points in a process called fractional
distillation
However, the smaller hydrocarbon fractions (such as gasoline fractions) are in high demand compared
to the larger ones
Therefore, some of the excess heavier fractions are broken down into smaller, more useful
compounds
These more useful compounds include alkanes and alkenes of lower relative formula mass (Mr)
This process is called cracking
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Your notes
The heavier fractions that are obtained in fractional distillation are further cracked into useful alkane and
alkenes with lower Mr values
Cracking
The large hydrocarbon molecules are fed into a steel chamber and heated to a high temperature and
then passed over an aluminium oxide (Al2O3) catalyst
The chamber does not contain any oxygen to prevent combustion of the hydrocarbon to water
and carbon dioxide
When a large hydrocarbon is cracked, a smaller alkane and alkene molecules are formed
Eg. octane and ethene from decane
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Long hydrocarbon fraction is cracked into two smaller ones

Your notes
The low-molecular mass alkanes formed make good fuels and are in high demand
The low-molecular mass alkenes are more reactive than alkanes due to their double bond
This makes them useful for the chemical industry as the starting compounds (feedstock) for
making new products
Eg. they are used as monomers in polymerisation reactions
Alkenes are reactive molecules and can undergo many different types of reactions making them useful
as starting compounds
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3.2.5 Chemical Reactivity of Alkanes

Your notes
Unreactivity of Alkanes
Strength of C-H bonds
Alkanes consist of carbon and hydrogen atoms which are bonded together by single bonds
Unless a lot of heat is supplied, it is difficult to break these strong C-C and C-H covalent bonds
This decreases the alkanes’ reactivities in chemical reactions
Lack of polarity
The electronegativities of the carbon and hydrogen atoms in alkanes are almost the same
This means that both atoms share the electrons in the covalent bond almost equally
The Pauling Scale shows that the difference in electronegativity between carbon and hydrogen is only
0.4
As a result of this, alkanes are nonpolar molecules and have no partial positive or negative charges (δ+
and δ- respectively)
Alkanes therefore do not react with polar reagents
They have no electron-deficient areas to attract nucleophiles
And also lack electron-rich areas to attract electrophiles
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Your notes
Ethane is an example of an alkane that lacks polarity due to almost similar electronegativities of the
carbon and hydrogen atoms
Due to the unreactivity of alkanes, they only react in combustion reactions and undergo substitution by
halogens
Exam Tip
Remember: nucleophiles are negatively charged and are attracted to electron-deficient
regions.Electrophiles are positively charged and attracted to electron-rich regions.
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3.2.6 Combustion of Alkanes

Your notes
Combustion of Alkanes & the Environment
Cars’ exhaust fumes include toxic gases such as carbon monoxide (CO), oxides of nitrogen (NO/NO2)
and volatile organic compounds (VOCs)
When released into the atmosphere, these pollutants have drastic environmental consequences
damaging nature and health
Carbon monoxide
Carbon monoxide is formed in the incomplete combustion of alkanes inside a car engine
Due to lack of enough oxygen in the engine, some of the carbon is only partially oxidised to CO instead
of carbon dioxide (CO2)
Incomplete combustion of alkanes is caused by a limited supply of oxygen

CO is a toxic and odourless gas which can cause dizziness, loss of consciousness and eventually death
The CO binds to haemoglobin which therefore cannot bind oxygen and carbon dioxide
Oxygen is transported to organs
Carbon dioxide is removed as waste material from organs
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Your notes
The high affinity of CO to haemoglobin prevents it from binding to O2 and CO2

Oxides of nitrogen
Normally, nitrogen is too unreactive to react with oxygen in air
However, in a car’s engine, high temperatures and pressures are reached causing the oxidation of
nitrogen to take place:
N2(g) + O2(g) → 2NO(g)
N2(g) + 2O2(g) → 2NO2(g)
The oxides of nitrogen are then released in the car’s exhaust fumes into the atmosphere
Car exhaust fumes also contain unburnt hydrocarbons from fuels and their oxides (VOCs)
In air, the nitrogen oxides can react with these VOCs to form peroxyacetyl nitrate (PAN) which is the
main pollutant found in photochemical smog
PAN is also harmful to the lungs, eyes and plant-life
Nitrogen oxides can also dissolve and react in water with oxygen to form nitric acid which is a cause of
acid rain
Acid rain can cause corrosion of buildings, endangers plant and aquatic life (as lakes and rivers become
too acidic) as well as directly damaging human health
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Catalytic removal
To reduce the amount of pollutants released in cars’ exhaust fumes, many cars are now fitted with Your notes
catalytic converters
Precious metals (such as platinum) are coated on a honeycomb to provide a large surface area
The reactions that take place in the catalytic converter include:
Oxidation of CO to CO2:
2CO + O2 → 2CO2
or
2CO + 2NO → 2CO2 + N2
Reduction of NO/NO2 to N2:
2CO + 2NO → 2CO2 + N2
Oxidation of unburnt hydrocarbons:
CnH2n+2 + (3n+1)[O] → nCO2 + (n+1)H2O
Pollutants, their effect & removal table
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Your notes
Exam Tip
Though CO2 is not a toxic gas, it is still a pollutant causing global warming and climate change.
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3.2.7 Production of Alkenes

Your notes
Production of Alkenes: Elimination, & Dehydration Reactions &
Cracking
Alkenes can be made by a series of reactions including elimination, dehydration reactions and
cracking
Elimination reaction
Alkenes can be produced from the elimination reaction of a halogenoalkane
An elimination reaction is one in which a small molecule is lost
In the case of halogenoalkanes, the small molecule that is eliminated is a hydrogen halide, HX,
where X is the halogen
The halogenoalkane is heated with ethanolic sodium hydroxide
Production of an alkene from a halogenoalkane by reacting it with ethanolic sodium hydroxide and
heating it
The eliminated H+ in HBr reacts with the ethanolic OH- to form water
The eliminated Br- in HBr reacts with Na+ to form NaBr
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Your notes
The eliminated HBr reacts with ethanolic OH- and Na+ to form H2O and NaBr
Note that the reaction conditions should be stated correctly as different reaction conditions will result
in different types of organic reactions
NaOH (ethanol): an elimination reaction occurs to form an alkene
NaOH (aq): a nucleophilic substitution reaction occurs, and an alcohol is one of the products
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Your notes
Different reaction conditions will give different products

Dehydration reaction
Alkenes can also be produced from the elimination reaction of alcohols in which a water molecule is
lost
This is also called a dehydration reaction
Alcohol vapour is passed over a hot catalyst of aluminium oxide powder (Al2O3)
Concentrated acid, pieces of porous pot or pumice can also be used as catalysts
Production of an alkene from an alcohol by using a hot aluminium oxide powder catalyst
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Your notes
The formation of ethene from ethanol is an example of a dehydration reaction of alcohols
The smaller alkenes (such as ethene, propene and butene) are all gases at room temperature and can
be collected over water
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Your notes
The smaller alkenes are gases at room temperature and collected over water
Cracking
Alkenes can also be produced from the cracking of long hydrocarbon molecules in crude oil
An aluminium oxide (Al2O3) catalyst and high temperatures are used to speed up this reaction.
It is important to ensure that the crude oil doesn’t come into contact with oxygen as this can cause
combustion of the hydrocarbons to produce water and carbon dioxide
The cracking of crude oil produces a smaller alkane and alkene molecules
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Long hydrocarbon fraction is cracked into two smaller ones

The low-molecular mass alkenes are more reactive than alkanes as they have an electron-rich double Your notes
bond
They can therefore be used as feedstock for making new products
Alkenes are reactive molecules and can undergo many different types of reactions making them useful
as starting compounds
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3.2.8 Reactions of Alkenes

Your notes
Reactions of Alkenes
Alkenes are very useful compounds as they can undergo many types of reactions
They can therefore be used as starting molecules when making new compounds
Electrophilic addition
Electrophilic addition is the addition of an electrophile to a double bond
The C-C double bond is broken, and a new single bond is formed from each of the two carbon atoms
Electrophilic addition reactions include the addition of:
Hydrogen (also known as hydrogenation reaction)
Steam (H2O (g))
Hydrogen halide (HX)
Halogen
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Your notes
The diagram shows an overview of the different electrophilic addition reactions alkenes can undergo
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Oxidation
Alkenes can also be oxidised by acidified potassium manganate(VII) (KMnO4) which is a very powerful Your notes
oxidising agent
Alkenes can be oxidised by both hot and cold KMnO4 which will result in different products being
formed
When shaken with cold dilute KMnO4 the pale purple solution turns colourless and the product is
a diol
When alkenes are reacted with hot concentrated KMnO4 the conditions are harsher causing the
C-C double bond to completely break
The O-H groups in the diol formed are further oxidised to ketones, aldehydes, carboxylic acids or
carbon dioxide gas
The actual products formed depend on what is bonded to the carbon atoms in the alkene
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Your notes
Alkenes can be oxidised by cold dilute and hot concentrated KMnO4 to give different products
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The reactions of alkenes with hot concentrated KMnO4 can be used to determine the position of the
double bond in larger alkenes Your notes
The above reactions can be used to predict where the double bond in a larger molecule is
Worked example: Oxidation of alkenes
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Your notes
Answer
The products are propanone (a ketone), carbon dioxide and water.
Worked example: Identifying alkenes from oxidation reactions
Answer
The alkene is 1-butene.
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Your notes
Addition polymerisation
Addition polymerisation is the reaction of many monomers containing at least one double C-C bond
to form the long-chain polymers as the only product
Monomers are small, reactive molecules that react together to make the polymer
A polymer is a long-chain molecule made up of many repeating units (monomers)
In addition polymerisation reaction, the C-C double bond is broken to link together the monomers and
form a polymer
This is a common method to make plastics
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Your notes
The diagram shows a polymerisation reaction of ethene to poly(ethene)
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Your notes
The diagram shows a polymerisation reaction of propene to poly(propene)

Other alkenes and substituted alkenes can also polymerise to make polymers with different
properties
Eg. poly(chloroethene), also known as PVC is the most versatile plastic used
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Your notes
Poly(chloroethene) is used as plastic
Page 38 of 46
3.2.9 Test for Unsaturation

Your notes
Test for Unsaturation
Halogens can be used to test if a molecule is unsaturated (i.e. contains a double bond)
Br2(aq) is an orange or yellow solution, called bromine water and this is the halogen most commonly
used
The unknown compound is shaken with the bromine water
If the compound is unsaturated, an addition reaction will take place and the coloured solution will
decolourise
The decolourisation of bromine water by an unsaturated compound as a result of an addition reaction
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3.2.10 Electrophilic Addition of Alkenes

Your notes
Alkenes: Electrophilic Addition
The double bond in alkenes is an area of high electron density (there are four electrons found in this
double bond)
This makes the double bond susceptible to attack by electrophiles (electron-loving species)
An electrophilic addition is the addition of an electrophile to a double bond
Electrophilic addition of hydrogen bromide
A molecule of hydrogen bromide (HBr) is polar as the hydrogen and bromine atoms have different
electronegativities
The bromine atom has a stronger pull on the electrons in the H-Br bond
As a result of this, the Br atom has a partial negative and the H atom a partial positive charge
Due to differences in electronegativities of the hydrogen and bromine atom, HBr is a polar molecule
In an addition reaction, the H atom acts as an electrophile and accepts a pair of electrons from the C-C
bond in the alkene
The H-Br bond breaks heterolytically, forming a Br- ion
This result in the formation of a highly reactive carbocation intermediate which reacts with the Br-
(nucleophile)
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Your notes
Example of an electrophilic addition reaction of HBr and propene to form 1-bromopropane and 2-
bromopropane
Electrophilic addition of bromine
Bromine (Br2) is a non-polar molecule as both atoms have similar electronegativities and therefore
equally share the electrons in the covalent bond
However, when a bromine molecule gets closer to the double bond of an alkene, the high electron
density in the double bond repels the electron pair in Br-Br away from the closest Br atom
As a result of this, the closest Br atom to the double bond is slightly positive and the further Br atom is
slightly negatively charged
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Your notes
Br2 is a non-polar molecule however when placed close to an area of high electron density it can get
polarised
In an addition reaction, the closest Br atom acts as an electrophile and accepts a pair of electrons from
the C-C bond in the alkene
The Br-Br bond breaks heterolytically, forming a Br- ion
This results in the formation of a highly reactive carbocation intermediate which reacts with the Br-
(nucleophile)
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Example of an electrophilic addition reaction of Br2 and ethene to form dibromoethane

Your notes
Exam Tip
The stability of the carbocation intermediate is as follows:tertiary > secondary > primaryWhen more
than one carbocations can be formed, the major product of the reaction will be the one that results
from the nucleophilic attack of the most stable carbocation.
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3.2.11 Markovnikov's Rule

Your notes
Alkenes: Stability of Cations & Markovnikov's Rule
Carbocations are positively charged carbon atoms with only three covalent bonds instead of four
There are three types of carbocations: primary, secondary and tertiary
Inductive effect
The alkyl groups attached to the positively charged carbon atoms are ‘electron donating groups’
This is also known as the inductive effect of alkyl groups
The inductive effect is illustrated by the use of arrowheads on the bonds
The alkyl groups push electrons away from themselves towards the positively charged carbon
This causes the carbocation to become less positively charged
As a result of this, the charge is spread around the carbocation which makes it energetically more
stable
This means that tertiary carbocations are the most stable as they have three electron-donating alkyl
groups which energetically stabilise the carbocation
Due to the positive charge on the carbon atom, carbocations are electron-loving species
(electrophiles)
Alkyl groups push electron density towards the carbocation making it energetically more stable; the
more alkyl groups the carbocation is bonded to, the more stabilised it is
Markovnikov’s rule
In addition reactions, an electrophile reacts with the double bond of alkenes
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Your notes
The electrophile reacts with the electron-rich C-C double bond

The electrophile will add to the carbon to give the most stable carbocation
The most stable carbocation is the major product of the nucleophilic attack on the C-C double bond
Therefore, the nucleophile will bond to the C-C carbon atom with the highest number of alkyl groups
bonded to it
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Your notes
The nucleophile ends up to the most substituted C-C carbon atom
This is also known as the Markovnikov’s rule which predicts the outcome of addition reactions and
states that:
In an addition reaction of a halogen halide (HX) to an alkene, the halogen ends up bonded to the most
substituted carbon atom.
Page 46 of 46

3.2 Hydrocarbons

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CIE A Level Chemistry Your notes

The addition reaction of alkenes with hydrogen is called hydrogenation

3.2.2 Combustion & Free Radical Substitution of Alkanes

The complete combustion of alkanes

The incomplete combustion of alkanes

3.2.3 Free Radical Substitution

3.2.4 Cracking of Alkanes

Long hydrocarbon fraction is cracked into two smaller ones

3.2.5 Chemical Reactivity of Alkanes

3.2.6 Combustion of Alkanes

Incomplete combustion of alkanes is caused by a limited supply of oxygen

The high affinity of CO to haemoglobin prevents it from binding to O2 and CO2

3.2.7 Production of Alkenes

Different reaction conditions will give different products

The formation of ethene from ethanol is an example of a dehydration reaction of alcohols

Long hydrocarbon fraction is cracked into two smaller ones

3.2.8 Reactions of Alkenes

Worked example: Identifying alkenes from oxidation reactions

The diagram shows a polymerisation reaction of ethene to poly(ethene)

The diagram shows a polymerisation reaction of propene to poly(propene)

Poly(chloroethene) is used as plastic

3.2.9 Test for Unsaturation

The decolourisation of bromine water by an unsaturated compound as a result of an addition reaction

3.2.10 Electrophilic Addition of Alkenes

Example of an electrophilic addition reaction of Br2 and ethene to form dibromoethane

3.2.11 Markovnikov's Rule

The electrophile reacts with the electron-rich C-C double bond

The nucleophile ends up to the most substituted C-C carbon atom

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