Alkenes

● Unsaturated Hydrocarbons
● General formula C_n H_2n for all non-cyclic alkenes
● C=C
● Can polymerise
● Decolourises bromine water
● More reactive than alkanes due to double bond – means they are more useful
● Spatial arrangement around C=C is trigonal planar, bond angle 120°
● Suffix –ene, name from end nearest the double bond

Sp2 hybridisation in alkenes

● The atoms affected are the carbons in the
carbon-carbon double bond
● Sp2 hybridisation is the blending of the s
orbital and 2 p orbitals, leading to three sp2
hybrid orbitals, with one electron in each
● The fourth electron stays in an unhybridised p orbital
● So the carbon atoms are surrounded by the three sp2 orbitals and
one p orbital

★ In alkenes, the first sp2 orbital overlaps with the sp2 orbital of another
carbon to form a covalent bond, and the other two for each carbon each
overlap with a hydrogen orbital
★ The singular p orbitals for the two carbons both expand above and below
the sigma bond until they too overlap, forming a new region of space wherein the pair of
electrons can be either above or below the sigma bond at any one time
★ The new region is called a pi bond as they are formed from the sideways (rather than
end to end) overlap of orbitals

Pi (π) bond- a shared pair of electrons in a region of space formed by the sideways overlap of
two p orbitals
● The sigma bond is much stronger than a pi bond

Lack of rotation in C=C double bonds

● Because in sigma bonds only the end of the orbitals overlap, this creates an axis by
which the atoms can rotate, allowing free rotation
● In the alkene double bond, the Pi bond locks the two carbon atoms in space, so no
rotation can occur

Structural isomerism- structural isomers have the same molecular formula, but different
structural formula

Types of structural isomerism:

 - Chain Isomerism – The carbon chain is arranged differently
- Positional Isomerism – The functional group is attached to a different
carbon atom, this also occurs in alkenes with 4 or more carbon atoms
- Functional Group Isomerism – Contains different functional group, different
homologous series, e.g. Both alcohols and ethers have the same general formula

of

Stereoisomerism
Stereoisomers- species with the same structural formulae, but different spatial arrangements of
atoms or groups

The two forms of stereoisomerism:

- Cis-Trans Isomerism
- Optical Isomerism

● The stereoisomer naming system is the E/Z system

● E= Entgegen (opposite, one below the bond, one above)
● Z= Zusammen (together, so same side of double bond)
● To work out which is which, we use the Cahn-Ingold-prelog rules
● First we establish the priority group (the priority group is the heavier one with the higher
atomic number, and (if all else fails) is bonded to higher priority atoms, so basically
anything that isn’t hydrogen)
● Then we work out where the priority groups are in relation to each other

★ To work out if E/Z isomerism is possible in an alkene, check if the groups on the carbons
are the same
★ If they are different (both carbons have two different species bonded to them) , then it is
possible, and if not, it is not

● E/Z isomers can be called cis/trans (cis=Z, trans= E) if on each carbon of the double
bond you have a hydrogen and non-hydrogen group

Reaction of alkenes
★ When alkenes react, the pi bond in the double bond breaks so into two sigma bonds so
that new atoms can become part of the compound
★ This scenario is an electrophilic addition reaction

Hydrogenation of alkenes
● When alkenes react with hydrogen, the pi bond in the double bond is broken, making
two single bonds which allow the hydrogen atoms to become part of the compound
● For this reaction to occur, a nickel catalyst and temperature of 150 degrees is needed
● The number of double bonds and moles of hydrogen must be the same in order for all
double bonds to be broken
 ★ In naturally occurring molecules, the hydrogen atoms are on the same side of the double
bond
★ Species with more than one double bond= polyunsaturated

● The more saturated, the higher the melting point, so hydrogen may be added to
polyunsaturated fats to ‘harden’ them
● In this process, a cis fat can stay cis or become trans
● However, trans fatty acids are linked to heart disease as they raise low-density-
lipoprotein levels

Reaction of alkenes with halogens

● These reactions happen at room temperature
● When bromine water reacts with alkenes, it goes from orange to decolourized

Reactions of alkenes with hydrogen halides

● There are no specific conditions for this reaction

Alkene hydration reaction

● This react occurs at over 100 degrees, and Phosphoric acid (H3PO4) or sulphuric acid
(H2SO4) can be used to catalyse it
● In the reaction water vapour is split into a hydrogen and a hydroxide before bonding into
the compound
● For hydroxide, the line should always be shown joining to the O, not the H
● Symmetrical alkenes produce only one product, but non-symmetrical can produce two

Electrophilic addition mechanism

Electrophile- electron pair acceptor
The reaction is called an addition reaction because the halide is added across the double bond,
and because the two reactants make one product

● This is the reaction of any alkene with molecules such as halogens and hydrogen
halides
● Halogen atoms are non-polar, as both atoms in the diatomic molecule have the same
electronegativities, meaning that the electron pair is exactly in the middle
● The double bond in alkenes contain twice the number of electrons as single bonds
● Due to this increased electron density, the electrons in the double bond will repel the
electrons in the single bond of the halogen, pushing the majority of the density to one
side and inducing creating a dipole (the closest atom becomes electron deficient, the
other becoming electron-rich)

★ The side of the diatomic molecule with the delta

positive charge will be the one closest to the
double bond, and as opposites attract, the
 electrons will leave the weaker pi bond (destroying it) to join with the delta positive side
of the molecule
★ The new electrons at the previously delta positive side repel the shared pair of electrons
and the delta negative side, breaking the bond and leading to two halide ions
★ This is heterolytic fission, as one side gets both the
electrons from the originally shared pair
★ The previously delta positive halide then joins onto
the compound, and because one of the carbons is
now positively charged (as it has in effect lost one
of its electrons that was originally in the pi bond to
form the bond holding the first halide in place), and
because the compound contains carbon, the
overall compound is called a Carbocation(carbon
containing cation)
★ The halide ion that was originally the delta negative
part of the molecule has become a negative ion as
due to the heterolytic fission it has gained one
electron that originally belonged to the delta
positive side
★ This negative halide ion is now attracted to the positive carbocation, and bonds to
become part of the new halogenoalkane molecule

● Electrophilic addition does not happen with alkanes as they do not have a double bond,
so there is not a great enough electron density to convert the halogen molecule into a
dipole
● If the reaction occurs with a polar molecule, the dipole is pre-existing, not created, and
the more electronegative element will be delta negative

Markovnikov's Rule
● When electrophilic addition occurs, if the alkene involved is
symmetrical, then only one product can be produced
● If it is asymmetrical, then two products are possible
● However, the production of both products is not equal
● One product is more likely to be produced (this is called the major product), and so
consequently the other (the minor product) is less often produced
● Markovnikov’s rule helps to establish the major and minor products of electrophilic
addition of unsymmetrical alkene (one where the molecule involved is polar)

★ A primary carbocation is where the carbocation

involved only has one carbon directly attached to it
★ Secondary is when it’s directly attached to two,
tertiary is when it’s directly attached to three
 ● The more carbons directly bonded to the
carbocation, the more alkyl groups (bits that aren’t
the carbocation so look like branches) will be
present
● Alkyl groups (regardless of whether they are ethyl,
methyl ..etc) are electron-releasing, so release
electron density towards the positive charge of the
carbocation, spreading the positive charge around
the carbocation, and make it slightly more stable
because the charge is spread out

★ The more alkyl groups there are, the greater this effect is, so tertiary carbocations are
more stable than secondary, which are more stable than primary

● Markovnikov’s rule states that the more stable carbocation will always be the major
product as a result of its stability

★ When trying to work out which product will be major, the hydrogen (if there is one)
prefers to go to the carbon with the most hydrogens
attached

Addition polymers from alkenes

Addition polymerisation- formation of a very long molecular chain
(addition polymer) by repeated addition reactions of many
unsaturated alkene molecules (monomers)

● When alkenes are exposed to a high temperature and

pressure with a catalyst present, it breaks their double bond
● If there are lots of alkene monomers, when the double
bonds are broken, they join together in a long chain to form a polymer(typically 2000-
20,000 monomers long)

★ The repeat unit is the section of polymer we draw when

asked what the polymer version of a certain monomer would
be like
★ It is the shortest repeating unit of the polymer

● The name of the polymer formed from monomers is the

name of the monomer with ‘poly’ in front
● Always make your monomer look like an ethene molecule
(so put the double bond in the middle, rest condensed to fit on the four branches
available)
 ★ When asked to draw more than one repeat unit, show that many monomers joined

together without the brackets or n, like this:

● To identify the monomer used to make a polymer, simply find the shortest repeating unit
and revert it back to normal alkene state (putting the double bond back, having no bonds
extending outwards that aren’t filled ..etc)

Examples:
Ethene – polyethene/polythene (plastic bags)
Propene – polypropene (rope)
Phenylethne – polyphenylethene/polystyrene (packaging)
Chloroethene – polychloroethene/PVC (insulation)

Problems with plastics:

They are very unreactive, so they don’t degrade

Disposal Methods:
● Combustion
● Recycling
● Reusing
● Landfill
● Organic feedback

Landfill
● Positives – Cheap and easy
● Negatives – visual pollution, smell, hurts animals, things could contaminate water

Recycling
● Positives – minimises waste, uses less fossil fuels – save energy from cracking
● Negatives – sorting takes time and money

Reusing
● Positives – minimises waste, uses less fossil fuels – save energy from cracking
● Negatives – if photodegradable, may degrade

Combustion
● Positives – provides energy – polymers are highly calorific
● Negatives – produces CO2, produces toxic or polluting gases

Organic Feedback – (broken down into smaller organic molecules – used in other processes)
● Positives – (same as recycling), other uses
● Negatives – doesn’t solve long term disposal issues
Biodegradable plastics
● Plastics can be made biodegradable by adding small amounts of biodegradable matter –
degrades faster into small bits
● Bioplastic – only biodegradable polymers used – used for food packaging – can’t be
used for hot stuff
● Requires lots of plant matter and land – farming methods must be sustainable for carbon
neutrality
● Photodegradable- absorbs visible light – weakens bonds, will break down quicker, but
won’t photodegrade in landfill