Organic Chemistry

Introduction to the world of carbon

and hydrogen

Introduction to organic chemistry

Homologous Series

 Organic chemistry is the chemistry of carbon compounds

 Carbon forms a vast number of compounds because it can form strong covalent bonds
with itself
 This enables it to form long chains of carbon atoms, branched chains or cycles, and hence
an almost infinite variety of carbon compounds are known
 Carbon always forms four covalent bonds which can be single, double or triple bonds

There is an almost infinite variety of chains, branches and rings able to form
  A functional group is a specific atom or group of atoms which confer certain physical
and chemical properties onto the molecule
 Organic molecules are classified by the dominant functional group on the molecule
 Organic compounds with the same functional group, but with each successive member
different by CH2 are called a homologous series
o Every time a carbon atom is added to the chain, two hydrogen atoms are also
added, which is why the successive members differ by CH2

Hydrocarbons

 Hydrocarbons are compounds that are made up of carbon and hydrogen atoms ONLY

Alkanes

 A functional group is an atom or a group of atoms in an organic

molecule, which determines the physical and chemical properties of the
molecule
 Alkanes are the simplest hydrocarbons with no functional group
 They are made up of carbon and hydrogen atoms bonded to each other
with single covalent bonds
 Functional groups determine the physical and chemical properties of
molecules
 The general formula is a formula that represents a homologous
series of compounds using letters and numbers
o Eg. the general formula of alkanes is CnH2n+2
o A homologous series is a group of organic compounds that have
the same functional group, the same general formula and the
same chemical properties
 The structural formula is a formula that shows how the atoms are
bonded to each carbon atom in a molecule
 The displayed formula is a 2D representation of an organic molecule
showing all its atoms (by their symbols) and their bonds (by single,
double or triple bonds)
 The skeletal formula is a simplified displayed formula with all the
carbon and hydrogen (C-H) bonds removed
 Systematic nomenclature can be used to name organic compounds
and therefore make it easier to refer to them
 The alkanes provide the basis of the naming system and the stem of
each name indicates how many carbon atoms are in the longest
chain in one molecule of the compound
 If there are any side-chains or functional groups present, then the
position of these groups are indicated by numbering the carbon atoms
in the longest chain starting at the end that gives the lowest possible
numbers in the name
 The side-chain is named by adding ‘-yl’ to the normal alkane stem
 This type of group is called an alkyl group
 If there are more than one of the same alkyl side-chain or functional
groups, di- (for two), tri- (for three) or tetra- (for four) is added in front
of its name
 The adjacent numbers have a comma between them
 Numbers are separated from words by a hyphen
 If there is more than one type of alkyl side-chain, they are listed in
alphabetic order
 A homologous series is a group of organic compounds that have the
same functional group, the same general formula and the same
chemical properties
 Saturated hydrocarbons are hydrocarbons which contain single bonds
only resulting in the maximum number of hydrogen atoms in the
molecule
 Unsaturated hydrocarbons are hydrocarbons which contain carbon-
carbon double or triple bonds

 Homolytic fission is breaking a covalent bond in such a way that each

atom takes an electron from the bond to form two radicals
 Heterolytic fission is breaking a covalent bond in such a way that the
more electronegative atom takes both the electrons from the bond to
form a negative ion and leaving behind a positive ion
 A free radical is a species with one (or more than one) unpaired
electrons
 A free radical reaction is a reaction involving free radicals and is a
three-step reaction:
o Initiation is the first step and involves breaking a covalent bond
using energy from ultraviolet (UV) light from the sun to form two
free radicals
o The propagation step is the second step in which the formed
radical can attack reactant molecules to form even more radicals
 These in turn can again attack other molecules to form
more free radical and so on
o In the termination step, two free radicals react together to form a
product molecule
Nucleophiles & electrophiles

 A nucleophile is an electron-rich species that can donate a pair of

electrons

 ‘Nucleophile’ means ‘nucleus/positive charge loving’ as

nucleophiles are attracted to positively charged species
 Nucleophilic refers to reactions that involve a nucleophile

 An electrophile is an electron-deficient species that can accept a pair of

electrons

 ‘Electrophile’ means ‘electron/negative charge loving’ as

electrophiles are attracted to negatively charged species
 Electrophilic refers to reactions that involve an electrophile
Types of reactions

 An addition reaction is an organic reaction in which two (or more)

molecules combine to give a single product with no other products
 A substitution reaction is a reaction that involves replacing an atom or
group of atoms by another
 An elimination reaction is a reaction in which a small molecule (such as
H2O or HCl) is removed from an organic molecule
 A hydrolysis reaction is a reaction in which a compound
is broken down by water (it can also refer to the breakdown of a
substance by dilute acids or alkali)
 A condensation reaction is a reaction in which two organic molecules
join together and in the process eliminate small molecules (such as H2O
or HCl)
Oxidation & reduction

 An oxidation reaction is a reaction in which oxygen is added, electrons

are removed or the oxidation number of a substance is increased

 In organic chemistry it often refers to the addition of oxygen or

removal of hydrogen atoms to a substance
 In equations for organic redox reactions, the symbol [O] can be
used to represent one atom of oxygen from an oxidising agent
 A reduction reaction is a reaction in which oxygen is removed, electrons
are added or the oxidation number of a substance is decreased

 In organic chemistry it often refers to the removal of oxygen or

addition of hydrogen atoms to a substance
 In equations for organic redox reactions, the symbol [H] can be
used to represent one atom of hydrogen from a reducing agent
Terminology Used in Reaction Mechanisms

 In organic reaction mechanisms, curly arrows represent the movement

of electron pairs
 The arrow begins at a bond or a lone pair of electrons and points to the
species that accepts the lone pair of electrons

Curly arrows show electron pairs moving from the source (eg. a
nucleophile) to its destination (eg. an electrophile)
 A free-radical substitution reaction is a reaction in which halogen
atoms substitute for hydrogen atoms in alkanes
 It involves the initiation, propagation and termination steps
Electrophilic addition

 An electrophilic addition reaction is a reaction in which an electron rich

region in a molecule is attacked by an electrophile (a species that likes
electrons/negative charge) followed by the addition of a small molecule
to give one product only

Example of an electrophilic addition reaction to form ethanol from

ethane
Nucleophilic substitution
 A nucleophilic substitution reaction is a reaction in which an electron-
rich nucleophile displaces a halogen atom

The general nucleophilic substitution reaction mechanism

 The C-X carbon of the halogenoalkane is electron deficient and has a δ+

charge
o The halogen atom, X, is more electronegative than the carbon
atom which means that it pulls electrons towards itself and is δ–
 The nucleophile has a lone pair of electrons that it can donate to the δ+
carbon atom and form a covalent bond
 This causes the displacement of the halogen atom, X, which leaves as a
halide ion, X–
o The displaced halide ion is known as a leaving group
Nucleophilic addition

 A nucleophilic addition reaction is a reaction in which a nucleophile (a

species that likes a nucleus/positive charge) attacks an electron-deficient
region in a molecule followed by the addition of a small molecule to
give one product only
Straight, Branched & Cyclic Molecules

 Straight, branched and cyclic organic molecules are also

called aliphatic compounds as long as they do not contain a benzene
ring

Straight-chain

 Straight-chain organic molecules are those in which the carbon atoms

are connected to each other in one continuous chain

Branched

 Branched organic molecules have side groups attached to the main

chain of carbon atoms
Cyclic

 Cyclic organic molecules are those in which the carbon atoms are
connected to each other in a ring shape
Hybridised Atoms: Shapes & Bond Angles in Molecules

 Each carbon atom has four electrons in its outer shell (electronic configuration: 1s22s22p2)
 Carbon atoms share these four electrons in four covalent bonds with other atoms to achieve
a full outer shell configuration
 These electrons are found in orbitals within the respective atoms
 When forming a covalent bond, the orbitals overlap in such a way to form two types of bonds

 Sigma bonds (σ)

 Pi bonds (π)

Hybridisation: sp3
 The electron pair in a σ bond is found in a region of space between the nuclei of the two atoms
that are sharing the electrons
 The electrostatic attraction between the electrons (negatively charged) and the
two nuclei (positively charged) holds the two atoms together
 Carbon atoms that form four σ bonds are said to be sp3 hybridised
 The four pairs of electrons around each carbon repel each other forcing the molecule to adopt a
configuration in which the bonding pairs of electrons are as far away from each other as
possible

 The molecule adopts a tetrahedral arrangement with bond angles of 109.5 o

Hybridisation: sp2

 When carbon atoms use only three of their electron pairs to form a σ bond, they are said to
be sp2 hybridised
o Each carbon atom will have a p orbital with contains one spare electron
 When the p orbitals of two carbon atoms overlap with each other, a π bond is formed (the π
bond contains two electrons)
 The two orbitals that form the π bond lie above and below the plane of the two carbon atoms to
maximise bond overlap
 The three bonding pair of electrons are in the plane of the molecule and repel each other
 The molecule adopts a planar arrangement with bond angles of 120 o
Hybridisation: sp
 Carbon atoms can also use only one of their electron pair to form a σ bond, in which case the
carbon atoms are said to be sp hybridised
o Each carbon atom will have two p orbitals with one spare electron each
 When the four p orbitals of the carbon atoms overlap with each other, two π bonds are formed
(each π bond contains two electrons)
 The two orbitals that form the π bond lie above and below the plane of the carbon atoms
 The two orbitals of the other π bond lie in front and behind the plane of the atoms
o This maximises the overlap of the four p orbitals
 The molecule adopts a linear arrangement with bond angles 180 o

 A double bond is a combination of a σ and π bond and a triple bond is a combination of

one σ and two π bonds.The strength of the bonds increases as follows: single < double <
triple bondThis is due to the increased electron density around the C-C atom, making the
bond stronger and more difficult to break.

 Hybridised Atoms: σ and π Bonds in Molecules

σ bonds

 Sigma bonds are formed from the end-on overlap of atomic orbitals

 S orbitals overlap this way as well as p orbitals

 The electron density in a σ bond is symmetrical about a line joining the nuclei of the atoms
forming the bond

 The pair of electrons is found between the nuclei of the two atoms
 The electrostatic attraction between the electrons and nuclei bonds the atoms to each
other

 The diagram below shows the arrangement of the σ bond in sp3, sp2 and sp hybridised carbon
atoms
The σ orbitals are formed from the end-on overlap of the atomic orbitals resulting in
symmetrical electron density on the atoms
π bonds
 Pi (π) bonds are formed from the sideways overlap of p orbitals
 The two lobes that make up the π bond lie above and below the plane of the atoms
o This maximises overlap of the p orbitals

π orbitals can be formed from the end-on overlap of p orbitals

 In triple bonds, there is an additional overlap of p orbital

 The two lobes of the π bond lie in front of and behind the plane of the atoms in the molecule

 This maximises overlap of the p orbitals

 The diagram below shows the arrangement of the π bond in sp3, sp2 and sp hybridised carbon
atoms
 Planar molecules have all their atoms in the same plane

 Eg. linear, bent, trigonal planar and square planar

 The presence of an sp2 hybridised carbon can force the molecule to

adopt a planar configuration (trigonal planar)
 The 3 σ bonds position themselves in a trigonal planar position so that
the bonding pair of electrons are as far away from each other and
therefore minimise the repulsion between them
Structural Isomerism: Chain, Position & Functional Group

 Structural isomers are compounds that have the

same molecular formula but different structural formulae

 There are three different types of structural isomerism:

 Chain isomerism
 Positional isomerism
 Functional group isomerism

Chain isomerism

 Chain isomerism is when compounds have the same molecular

formula, but their longest hydrocarbon chain is not the same
 This is caused by branching

Positional isomerism

 Positional isomers arise from differences in the position of a functional

group in each isomer

 The functional group can be located on different carbons

Functional group isomerism

 When different functional groups result in the same molecular

formula, functional group isomers arise
 The isomers have very different chemical properties as they have
different functional groups
Stereoisomerism: Geometrical & Optical

 Stereoisomers are compounds that have the same atoms connected to each other, however the
atoms are differently arranged in space
 There are two types of stereoisomerism:
o Geometrical (cis/trans) isomerism
o Optical isomerism

Geometrical (cis/trans) isomerism

 Geometrical isomerism is seen in unsaturated (double bond

containing) or ring compounds that have the same molecular formula
and order of atoms (the atoms are connected similarly to each other)
but different shapes
 Cis/trans nomenclature is used to distinguish between the isomers

 Cis isomers have functional groups on the same side of the

double bond/carbon ring
 Trans isomers have functional groups on opposite sides of the
double bond/carbon ring

 This causes the compounds to have

different chemical and physical properties
 For example, they may have different reaction rates for the same
reaction (chemical property) or different melting/boiling points (physical
property)
Optical isomerism

 Optical isomers arise when a carbon atom in a molecule is bonded to

four different atoms or groups of atoms
 The carbon atom is ‘asymmetric’ as there is no plane of symmetric in the
molecule and is also called the chiral centre of the molecule
 The two different optical isomers are also called enantiomers

 Just like the left hand cannot be superimposed on the right hand,
enantiomers too are non-superimposable
 Enantiomers are mirror images of each other

Both molecules are made up of the same atoms which are bonded to each
other identically, however the chiral centre (carbon with four different
groups) gives rise to optical isomerism

 Optical isomers differ in their ability to rotate

the plane of polarised light

 One enantiomer will rotate it clockwise and the

other anticlockwise
  In unsaturated compounds, the groups attached to the C=C carbons
remain fixed in their position
 This is because free rotation of the bonds about the C=C bond is not
possible due to the presence of a π bond

Chiral centres in non-cyclic molecules

 A chiral centre in a molecule is a carbon atom that has four different

atoms or group of atoms attached
 This gives rise to two optical isomers which are also called enantiomers
 The enantiomers are mirror images of each other and cannot be
superimposed
The presence of the chiral centre in the molecule allows two enantiomers
to exist which are stereoisomers as the molecules have the same atoms
bonded to each other, but they are differently arranged in space

 When the molecule contains more than one chiral centre (asymmetric
carbon) more than two optical isomers will be formed

 If there are two chiral centres, each chiral centre will rotate the
plane of polarised light clockwise and anticlockwise
 There are four possible optical isomers
Chiral centres in cyclic molecules

 To determine the chiral centre in a cyclic molecule, the carbon bonded

to four different atoms or groups of atoms should be found
o Eg. 1,2-aminocyclohexanol has two chiral centres so it can form
four optical isomers
Identifying Chirality & Geometrical Isomerism

Identify chirality

 Identifying chiral centres in cyclic and non-cyclic compounds is very

straightforward as it is the carbon with four different atoms or atom
groups in a molecule
 This gives rise to two optical isomers
 When more than two chiral centres are present, more than two optical
isomers exist
 A molecule with three chiral centres will have six optical isomers
 A molecule containing chiral centres is called a chiral molecule

Identifying geometrical isomers

 Molecules with restricted rotation about the C-C bond can have
geometrical isomers
 This includes unsaturated and cyclic compounds
o Eg. alkenes and cyclopentane
 When the groups are positioned on the same side of the C-C double
bond, the compound is a cis isomer
 When the groups are positioned on opposite sides of the C-C double
bond the compound is a trans isomer
Deducing Isomers of a Compound

 You should be able to deduce all possible isomers for organic

compounds knowing their molecular formula

 Step 1: Draw the structural formula of the compound

 Step 2: Determine whether it is a stereo or structural isomer

There is no restricted bond rotation around the C-C bond and there is
no chiral centre so it is structural isomerism

 Step 3: Determine whether it is a functional group, chain or positional

isomerism

 Functional group? No, as Br is the only functional group possible

 Chain? No, as the longest chain can only be 3
 Positional? Yes, as the two bromine atoms can be bonded to
different carbon atoms
Alkanes
 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:
o The Pt/Ni catalyst is finely divided to increase its surface area and
therefore increase the rate of reaction

 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
o 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
o Eg. octane and ethene from decane
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

 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 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:
o In the initiation step, the halogen bond (Cl-Cl or Br-Br) is broken
by UV energy to form two radicals
o These radicals create further radicals in a chain type reaction
called the propagation step
o The reaction is terminated when two radicals collide with each
other in a termination step
  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

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

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

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)
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

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

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
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
o Eg. octane and ethene from decane

 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
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
 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
 Due to the unreactivity of alkanes, they only react in combustion
reactions and undergo substitution by halogens

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)
  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

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

Catalytic removal
 To reduce the amount of pollutants released in cars’ exhaust fumes, many cars are now fitted
with 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

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
o 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

 The eliminated H+ in HBr reacts with the ethanolic OH- to form water
 The eliminated Br- in HBr reacts with Na+ to form 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
 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
  The smaller alkenes (such as ethene, propene and butene) are
all gases at room temperature and can be 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

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 bond
 They can therefore be used as feedstock for making new products
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
The diagram shows an overview of the different electrophilic addition
reactions alkenes can undergo
Oxidation

 Alkenes can also be oxidised by acidified potassium

manganate(VII) (KMnO4) which is a very powerful 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
Alkenes can be oxidised by cold dilute and hot concentrated KMnO4 to
give different products
The above reactions can be used to predict where the double bond in a
larger molecule is
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
o Monomers are small, reactive molecules that react together to
make the polymer
o 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
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
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)

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
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)
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)
Markovnikov’s rule

 In addition reactions, an electrophile reacts with the double bond of

alkenes

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

 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.
 HalogenoAlkanes
 Halogenoalkanes are alkanes that have one or more halogens
 They can be produced from:

 Free-radical substitution of alkanes

 Electrophilic addition of alkenes
 Substitution of an alcohol

Substitution of alcohols

 In the substitution of alcohols an alcohol group is replaced by a

halogen to form a halogenoalkane
 The subustition of the alcohol group for a halogen can be achieved by
reacting the alcohol with:
 HX (or KBr with H2SO4 or H3PO4 to make HX)
 PCl3 and heat
 PCl5 at room temperature
 SOCl2
Classifying Halogenoalkanes

 Depending on the carbon atom the halogen is attached to,

halogenoalkanes can be classified as primary, secondary and tertiary

 A primary halogenoalkane is when a halogen is attached to a

carbon that itself is attached to one other alkyl group
 A secondary halogenoalkane is when a halogen is attached to a
carbon that itself is attached to two other alkyl groups
 A tertiary halogenoalkane is when a halogen is attached to a
carbon that itself is attached to three other alkyl groups
Nucleophilic Substitution Reactions of Halogenoalkanes

 Halogenoalkanes are much more reactive than alkanes due to the

presence of the electronegative halogens

 The halogen-carbon bond is polar causing the carbon to carry a

partial positive and the halogen a partial negative charge

 A nucleophilic substitution reaction is one in which

a nucleophile attacks a carbon atom which carries
a partial positive charge
 An atom that has a partial negative charge is replaced by the
nucleophile

Due to large differences in electronegativity between the carbon and

halogen atom, the C-X bond is polar

Reaction with NaOH

 The reaction of a halogenoalkane with aqueous alkali results in the

formation of an alcohol
 The halogen is replaced by the OH-
 The aqueous hydroxide (OH- ion) behaves as a nucleophile by
donating a pair of electrons to the carbon atom bonded to the halogen
 Hence, this reaction is a nucleophilic substitution
 The halogen is replaced by a nucleophile, OH-

Reaction with KCN

 The nucleophile in this reaction is the cyanide, CN- ion

 Ethanolic solution of potassium cyanide (KCN in ethanol)
is heated under reflux with the halogenoalkane
 The product is a nitrile

The halogen is replaced by a cyanide group, CN-

 The nucleophilic substitution of halogenoalkanes with KCN adds

an extra carbon atom to the carbon chain
 This reaction can therefore be used by chemists to make a compound
with one more carbon atom than the best available organic starting
material

Reaction with NH3

 The nucleophile in this reaction is the ammonia, NH3 molecule

 An ethanolic solution of excess ammonia (NH3 in ethanol)
is heated under pressure with the halogenoalkane
 The product is a primary amine

The halogen is replaced by an amine group, NH3

  It is very important that the ammonia is in excess as the product of the
nucleophilic substitution reaction, the ethylamine, can act as a
nucleophile and attack another bromoethane to form the secondary
amine, diethylamine

Reaction with aqueous silver nitrate

 Halogenoalkanes can be broken down under reflux by water to

form alcohols
o The breakdown of a substance by water is also called hydrolysis
 This reaction is classified as a nucleophilic substitution reaction
with water molecules in aqueous silver nitrate solution acting as
nucleophiles, replacing the halogen in the halogenoalkane

The halogen is replaced by a hydroxyl group, OH-

 This reaction is similar to the nucleophilic substitution reaction of

halogenoalkanes with aqueous alkali, however, hydrolysis with water is
much slower than with the OH- ion in alkalis

 The hydroxide ion is a better nucleophile than water as it carries a

full formal negative charge
 In water, the oxygen atom only carries a partial negative charge
 A hydroxide ion is a better nucleophile as it has a full formal negative
charge whereas the oxygen atom in water only carries a partial negative
charge; this causes the nucleophilic substitution reaction with water to be
much slower than with aqueous alkali

 The halogenoalkanes have different rates of hydrolysis, so this reaction

can be used as a test to identify halogens in a halogenoalkane by
measuring how long it takes for the test tubes containing the
halogenoalkane and aqueous silver nitrate solutions to become opaque
Halogenoalkanes: Elimination Reactions

 In an elimination reaction, an organic molecule loses a small molecule

 In the case of halogenoalkanes this small molecule is a hydrogen

halide (eg. HCl)

 The halogenoalkanes are heated with ethanolic sodium

hydroxide causing the C-X bond to break heterolytically, forming an
X- ion and leaving an alkene as an organic product

Halogenoalkanes: SN1 & SN2 Mechanisms

 In nucleophilic substitution reactions involving halogenoalkanes, the

halogen atom is replaced by a nucleophile
 These reactions can occur in two different ways (known
as SN2 and SN1 reactions) depending on the structure of the
halogenoalkane involved
SN2 reactions

 In primary halogenoalkanes, the carbon that is attached to the

halogen is bonded to one alkyl group
 These halogenoalkanes undergo nucleophilic substitution by
an SN2 mechanism

 ‘S’ stands for ‘substitution’

 ‘N’ stands for ‘nucleophilic’
 ‘2’ means that the rate of the reaction (which is determined by the
slowest step of the reaction) depends on the concentration of
both the halogenoalkane and the nucleophile ions

 The SN2 mechanism is a one-step reaction

 The nucleophile donates a pair of electrons to the δ+ carbon

atom to form a new bond
 At the same time, the C-X bond is breaking and the halogen (X)
takes both electrons in the bond (heterolytic fission)
 The halogen leaves the halogenoalkane as an X- ion
 The mechanism of nucleophilic substitution in bromoethane which is a
primary halogenoalkane

SN1 reactions
 In tertiary halogenoalkanes the carbon that is attached to the halogen
is bonded to three alkyl groups
 These halogenoalkanes undergo nucleophilic substitution by
an SN1 mechanism

 ‘S’ stands for ‘substitution’

 ‘N’ stands for ‘nucleophilic’
 ‘1’ means that the rate of the reaction (which is determined by the
slowest step of the reaction) depends on the concentration of only
one reagent, the halogenoalkane
  The SN1 mechanism is a two-step reaction

 In the first step, the C-X bond breaks heterolytically and the
halogen leaves the halogenoalkane as an X- ion (this is
the slow and rate-determining step)
 This forms a tertiary carbocation (which is a tertiary carbon atom
with a positive charge)
 In the second step, the tertiary carbocation is attacked by
the nucleophile

 For example, the nucleophilic substitution of 2-bromo-2-methylpropane

by hydroxide ions to form 2-methyl-2-propanol

The mechanism of nucleophilic substitution in 2-bromo-2-methylpropane

which is a tertiary halogenoalkane

Carbocations

 In the SN1 mechanism, a tertiary carbocation is formed

 This is not the case for SN2 mechanisms as a primary
carbocation would have been formed which is much less stable than
tertiary carbocations
 This has to do with the positive inductive effect of the alkyl groups
attached to the carbon which is bonded to the halogen atom
  The alkyl groups push electron density towards the positively
charged carbon, reducing the charge density
 In tertiary carbocations, there are three alkyl groups stabilising the
carbocation whereas in primary carbocations there is only one
alkyl group
 This is why tertiary carbocations are much more stable than
primary ones

The diagram shows the trend in stability of primary, secondary and

tertiary carbocations

 Secondary halogenoalkanes undergo a mixture of both SN1 and SN2

reactions depending on their structure

Aqueous silver nitrate

 Reacting halogenoalkanes with aqueous silver nitrate solution will

result in the formation of a precipitate
 The rate of formation of these precipitates can also be used to
determine the reactivity of the halogenoalkanes
 Halogenoalkane Precipitates Table

 The formation of the pale yellow silver iodide is the fastest

(fastest nucleophilic substitution reaction) whereas the formation of
the silver fluoride is the slowest (slowest nucleophilic
substitution reaction)
 This confirms that fluoroalkanes are the least reactive and iodoalkanes
are the most reactive halogenoalkanes
Alcohols
Production of Alcohols

 Alcohols are compounds that contain at least one hydroxy (-OH) group
 The general formula of alcohols is CnH2n+1OH
 Alcohols can be prepared by a wide range of chemical reactions

Electrophilic addition of alkenes

 When hot steam is reacted with an alkene, using concentrated phosphoric(VI) acid (H3PO4)as a
catalyst, electrophilic addition takes place to form an alcohol

Electrophilic addition of steam to alkenes to form an alcohol

Oxidation of alkenes
 Cold, dilute KMnO4 is a mild oxidising agent and oxidises alkenes
 The C-C double bond is not fully broken and a diol is formed

 A diol is a compound with two hydroxy, -OH, groups

Nucleophilic substitution of halogenoalkanes

 The halide atom in halogenoalkanes can be substituted when heated with aqueous NaOH in
a nucleophilic substitution reaction
Reduction of aldehyde & ketones
 Aldehydes and ketones can be reduced by reducing agents such as NaBH4 or LiAlH4

 Aldehydes are reduced to primary alcohols

 The carbon attached to the hydroxy group is bonded to one other alkyl group

 Ketones are reduced to secondary alcohols

 The carbon attached to the hydroxy group is bonded to two other alkyl groups

Reduction of aldehydes and ketones to form primary and secondary alcohols

Reduction of carboxylic acids

 Similarly, carboxylic acids are reduced by NaBH4 or LiAlH4 to primary alcohols
 Carboxylic acids can also be reduced by H2 using a nickel catalyst and heat
 Reduction of carboxylic acids to primary alcohols

Hydrolysis of ester

 Esters are made by a condensation reaction between an alcohol and a carboxylic acid
 When an ester is heated with dilute acid or alkali, hydrolysis will take place and the carboxylic
acid and alcohol will be reformed

Hydrolysis of esters to form alcohols

Alcohol production reactions table
Reactions of Alcohols

 Alcohols are reactive molecules which undergo a wide range of

reactions

Combustion of alcohols

 Alcohols react with oxygen in the air when ignited and

undergo complete combustion to form carbon dioxide and water

Alcohol + oxygen → carbon dioxide + water

Complete combustion of alcohols to produce carbon dioxide and water

Substitution of alcohols

 In the substitution of alcohols, a hydroxy group (-OH) is replaced by a

halogen to form an halogenoalkane
 The substitution of the alcohol group for a halogen can be achieved by
reacting the alcohol with:
o HX (rather than using HBr, KBr is reacted with H2SO4 or H3PO4 to
make HBr that will then react with the alcohol)
o PCl3 and heat
o PCl5 at room temperature
o SOCl2
Substitution of alcohols to produce halogenoalkanes
Reaction with Na

 When an alcohol reacts with a reactive metal such as sodium (Na), the
oxygen-hydrogen bond in the hydroxy group breaks
 Though the reaction is less vigorous than sodium reacting with
water, hydrogen gas is given off and a basic compound (alkoxide) is
formed

 If the excess ethanol is evaporated off after the reaction a white

crystalline solid of sodium alkoxide is left

Alcohol + sodium → sodium alkoxide + hydrogen

 The longer the hydrocarbon chain in the alcohol, the less vigorous the
reaction becomes

Alcohols react with Na to form a basic sodium alkoxide salt and

hydrogen gas
Oxidation of alcohols

 Primary alcohols can be oxidised to form aldehydes which can undergo

further oxidation to form carboxylic acids
 Secondary alcohols can be oxidised to form ketones only
 Tertiary alcohols do not undergo oxidation
 The oxidising agents of alcohols include acidified K2Cr2O7 or acidified
KMnO4
 Acidified potassium dichromate(VI), K2Cr2O7, is an orange oxidising
agent

 Acidified means that that the potassium dichromate(VI) is in a

solution of dilute acid (such as dilute sulfuric acid)
 For potassium dichromate(VI) to act as an oxidising agent, it itself
needs to be reduced
 This reduction requires hydrogen (H+) ions which are provided by
the acidic medium

 When alcohols are oxidised the orange dichromate ions (Cr2O7 ) 2-

are reduced to green Cr3+ ions

 Acidified potassium manganate(VII), KMnO4, is a purple oxidising

agent

 As with acidified K2Cr2O7 the potassium manganate(VII) is in an

acidic medium to allow reduction of potassium manganate(VII) to
take place

 When alcohols are oxidised, the purple manganate ions (MnO4-)

are reduced to colourless Mn2+ ions
 Warm primary alcohol is added to the oxidising agent
 The formed aldehyde has a lower boiling point than the alcohol reactant
so it can be distilled off as soon as it forms
  If the aldehyde is not distilled off, further refluxing with excess oxidising
agent will oxidise it to a carboxylic acid
 Since ketones cannot be further oxidised, the ketone product does not
need to be distilled off straight away after it has been formed

Oxidation of propan-2-ol by acidified K2Cr2O7 to form a ketone by

distillation

Dehydration of alcohols

 Alcohols can also undergo dehydration to form alkenes

 Dehydration is a reaction in which a water molecule is removed

from a larger molecule
 A dehydration reaction is a type of elimination reaction

 Alcohol vapour is passed over a hot catalyst of aluminium oxide (Al2O3)

powder OR pieces of porous pot or pumice as well as concentrated acid
can be used as catalysts
Esterification of Alcohols

 Esterification is a condensation reaction between a carboxylic acid and

an alcohol to form an ester and a water molecule
 For esterification to take place, the carboxylic acid and alcohol
are heated under reflux with a strong acid catalyst (such as H2SO4 or
H3PO4)

Carboxylic acid + alcohol → ester + water

 The reaction is reversible so an equilibrium mixture can be established

with all the reactants and products
 Esters have sweet, fruity smells

Esterification of ethanol and ethanoic acid using a strong acid catalyst to

form ethyl ethanoate and water
  Primary alcohols are alcohols in which the carbon atom bonded to the -OH group is attached
to one other carbon atom (or alkyl group)
 Secondary alcohols are alcohols in which the carbon atom bonded to the -OH group is attached
to two other carbon atoms (or alkyl groups)
 Tertiary alcohols are alcohols in which the carbon atom bonded to the -OH group is attached
to three other carbon atoms (or alkyl groups)

Classifying primary, secondary and tertiary alcohols and alcohols with more than one alcohol
group

 Only primary and secondary alcohols can get oxidised when mildly oxidised with acidified
K2Cr2O7
o Primary alcohols get mildly oxidised to aldehydes
o Secondary alcohols get mildly oxidized to ketones
 Tertiary alcohols do not undergo oxidation with acidified K2Cr2O7
  Therefore, only the oxidation of primary and secondary alcohols will change the colour of
K2Cr2O7 solution as the orange Cr2O72- ions are reduced to green Cr3+ ions

Only propan-1-ol and propan-2-ol, which are primary and secondary alcohols respectively,
can get oxidised, turning the orange solution green; no colour change is observed with 2-
methyl-propan-2-ol, which is a tertiary alcohol

Test for Alcohols

 Tri-iodomethane (also called iodoform) forms a yellow precipitate with methyl ketones
o Methyl ketones are compounds that have a CH3CO-group
o Ethanal also contains a CH3CO- group and therefore also forms a yellow precipitate with
iodoform
 The reagent is heated with an alkaline solution of iodine
 This reaction involves a halogenation and hydrolysis step
o In the halogenation step, all three H-atoms in the -CH3 (methyl) group are replaced for
iodine atoms, forming -CI3
o The intermediate compound is hydrolysed by alkaline solution to form a sodium salt
(RCO2- Na+) and a yellow precipitate of CHI3

The reaction of methyl ketones with iodoform results in the formation of a yellow
CHI3 precipitate
Iodoform & alcohols

 The position of a secondary alcohol can be deduced by reacting the compound with alkaline I2
 If the -OH group is on the carbon atom next to a methyl group, it will firstly get oxidised to
CH3CH(OH)- by the alkaline solution
 This will result in the formation of a methyl ketone RCOCH3
 The methyl ketone will then first get halogenated and then hydrolysed to form the sodium salt
and the yellow precipitate
 If no yellow precipitate is formed, then this means that the secondary alcohol is not on a carbon
next to a methyl group

The secondary alcohol butan-2-ol will firstly get oxidised to the methyl ketone butanone which
will form a yellow precipitate when reacted with alkaline I2
  Alcohols have a low degree of dissociation

 This means, that when dissolved in water, alcohol molecules do

not dissociate (split up) to a great extent

ROH (aq) ⇄ RO- (aq) + H+ (aq)

Alcohol alkoxide ion

 The position of the equilibrium lies to the left, meaning that there are
far more alcohol molecules than RO- and H+ ions
 When water dissociates, the position of the equilibrium still lies to
the left, but there are more H+ ions compared to the dissociation of
alcohols

H2O (l) ⇄ OH- (aq) + H+ (aq)

 As alcohols have a lower [H+ (aq)] in solution compared to

water, alcohols are weaker acids than water

The inductive effect in alcohols

 Electron-donating species such as alkyl groups push electrons into a

covalent bond and are said to have a positive inductive effect
 In alcohols, the oxygen atom in the alkoxide ion is bonded to
an electron-donating alkyl group
 This means that there is more electron density on the O- atom
 The alkoxide ion is, therefore, more likely to accept an H+ ion and form
the alcohol again
Carbonyl Compounds
 ldehydes and ketones are carbonyl compounds containing a C=O
group
 They can be prepared from the oxidation
of primary and secondary alcohols respectively

Oxidising agents

 The oxidising agents used to prepare aldehydes and ketones from

alcohols include acidified potassium dichromate (K2Cr2O7)
and acidified potassium manganate (KMnO4)
 Acidified with dilute sulfuric acid, potassium dichromate(VI), K2Cr2O7, is
an orange oxidising agent

 When the alcohols are oxidised the orange dichromate ions

(Cr2O72-) are reduced to green Cr3+ ions

 Acidified with dilute sulfuric acid, potassium manganate(VII), KMnO4 is

a purple oxidising agent

 When the alcohols are oxidised the purple manganate ions

(MnO4-) are reduced to colourless Mn2+ ions
The oxidising agents change colour when they oxidise an alcohol and get
reduced themselves

Synthesis of aldehydes

 To make an aldehyde, warm primary alcohol is slowly added to the

oxidising agent
 The formed aldehyde has a lower boiling point than the alcohol and can
therefore be distilled off as soon as it forms
 The aldehyde is then condensed into a liquid and collected
Synthesis of ketones

 To make a ketone, warm secondary alcohol is slowly added to the

oxidising agent
 Since the formed ketone cannot be further oxidised it does not need to
be distilled off straightaway after it has been formed

Reduction of aldehyde & ketones

 Aldehydes and ketones can be reduced by reducing agents such as NaBH4 or LiAlH4
 Aldehydes are reduced to primary alcohols
 Ketones are reduced to secondary alcohols
Nucleophilic addition with HCN
 Aldehydes and ketones can undergo nucleophilic addition with hydrogen cyanide,
HCN
 The cyanide ion, CN-, acts as a nucleophile and adds across the C-O bond
 Aldehydes and ketones react with HCN, KCN as catalyst and heat to
produce hydroxynitriles
o Hydroxynitriles are nitriles containing a hydroxy, -OH, group
  The carbonyl group -C=O, in aldehydes and ketones is polarised
 The oxygen atom is more electronegative than carbon drawing electron density
towards itself
 This leaves the carbon atom slightly positively charged and the oxygen
atom slightly negatively charged
 The carbonyl carbon is therefore susceptible to attack by a nucleophile, such as the
cyanide ion

Nucleophilic addition
 The nucleophilic addition of hydrogen cyanide to carbonyl compounds is a two-step
process
 In step 1 the cyanide ion attacks the carbonyl carbon to form a negatively charged
intermediate
 In step 2 the negatively charged oxygen atom in the reactive intermediate quickly reacts
with aqueous H+ (either from HCN, water or dilute acid) to form 2-hydroxynitrile
Testing for Carbonyls: 2,4-DNPH

 2,4-dinitrophenylhydrazine (also known as 2,4-DNPH) is a reagent which detects the

presence of carbonyl compounds (compounds with -C=O group)
 The carbonyl group of aldehydes and ketones undergoes a condensation reaction with
2,4-dinitrophenylhydrazine
o A condensation reaction is a reaction in which two molecules join together and a
small molecule (such as H2O or HCl) is eliminated
 The product formed when 2,4-DNPH is added to a solution that contains an aldehyde or
ketone is a deep-orange precipitate which can be purified by recrystallisation
 The melting point of the formed precipitate can then be measured and compared to
literature values to find out which specific aldehyde or ketone had reacted with 2,4-
DNPH

 The presence of an aldehyde group (-CHO) in an unknown compound can be

determined by the oxidising agents Fehling’s and Tollens’ reagents

Fehling’s solution

 Fehling’s solution is an alkaline solution containing copper(II) ions which act as the
oxidising agent
 When warmed with an aldehyde, the aldehyde is oxidised to a carboxylic acid and
the Cu2+ ions are reduced to Cu+ ions

 In the alkaline conditions, the carboxylic acid formed will be neutralised to a

carboxylate ion (the -COOH will lose a proton to become -COO- )
 The carboxylate ion (-COO-) will form a salt with a positively charged metal
ion such as sodium (-COO-Na+)
  The clear blue solution turns opaque due to the formation of a red
precipitate, copper(I) oxide
 Ketones cannot be oxidised and therefore give a negative test when warmed with
Fehling’s solution

Tollens’ reagent

 Tollens' reagent is an aqueous alkaline solution of silver nitrate in excess ammonia

solution
o Tollens' reagent is also called ammoniacal silver nitrate solution
 When warmed with an aldehyde, the aldehyde is oxidised to a carboxylic acid and the
Ag+ ions are reduced to Ag atoms
o In the alkaline conditions, the carboxylic acid will become a carboxylate ion and
form a salt
 The Ag atoms form a silver ‘mirror’ on the inside of the tube
 Ketones cannot be oxidised and therefore give a negative test when warmed with
Tollens’ reagent
 Tri-iodomethane (also called iodoform) forms a yellow
precipitate with methyl ketones
o Methyl ketones are compounds that have a CH3CO-group
o Ethanal also contains a CH3CO- group and therefore also forms a yellow
precipitate with iodoform
 The reagent is heated with an alkaline solution of iodine
 This reaction involves a halogenation and hydrolysis step
o In the halogenation step, all three H-atoms in the -CH3 (methyl) group are
replaced with iodine atoms, forming a -CI3 group
o The intermediate compound is hydrolysed by an alkaline solution to form
a sodium salt (RCO2- Na+) and a yellow precipitate of CHI3
Carboxylic Acids
 Carboxylic acids are compounds with a -COOH functional group
 They can be prepared by a series of different reactions

Oxidation of primary alcohols & aldehydes

 Carboxylic acids can be formed from the oxidation of primary

alcohols and aldehydes by either acidified K2Cr2O7 or acidified KMnO4 and reflux
 The oxidising agents themselves get reduced causing the solutions to change colour

 In K2Cr2O7 the orange dichromate ions (Cr2O72-) are reduced to green Cr3+ ions
 In KMnO4 the purple manganate ions (MnO4-) are reduced to colourless
Mn2+ ions

Oxidation of primary alcohols (1) and aldehydes (2) gives carboxylic acids

Hydrolysis of nitriles

 Carboxylic acids can also be prepared from the hydrolysis of nitriles using either dilute
acid or dilute alkali followed by acidification
o Hydrolysis by dilute acid results in the formation of a carboxylic acid and
ammonium salt
o Hydrolysis by dilute alkali results in the formation of a sodium carboxylate salt
and ammonia; Acidification is required to change the carboxylate ion into a
carboxylic acid
 The -CN group at the end of the hydrocarbon chain is converted to a -COOH group
Hydrolysis of esters
 Esters are formed from the condensation reaction between an alcohol and carboxylic
acid
 Hydrolysis of esters by dilute acid or dilute alkali and heat followed by
acidification will reform the alcohol and carboxylic acid
o Hydrolysis by dilute acid, is a reversible reaction and an equilibrium is
established
o Hydrolysis by dilute alkali is an irreversible reaction as all the ester is broken
down to form a sodium carboxylate salt and an alcohol; acidification is required
to change the carboxylate ion into a carboxylic acid
Reactions of Carboxylic Acids

 Carboxylic acids are weak acids as they do not completely dissociate in water
 This means that the position of the equilibrium lies to the left and that the concentration
of H+ is much smaller than the concentration of the carboxylic acid
 The solution has a pH value of less than 7
Carboxylic acids are weak acids that do not fully dissociate in water, the position
of the equilibrium lies to the left

 Carboxylic acids are reactive compounds which can undergo many types of reactions
including:

 Redox reactions with reactive metals

 Neutralisation reactions with alkali
 Acid-base reactions with carbonates
 Esterification with alcohols
 Reduction by LiAlH4
Esters
Production of Esters

 Esters are compounds with an -COOR functional group and are characterised by
their sweet and fruity smells
 They are prepared from the condensation reaction between a carboxylic
acid and alcohol with concentrated H2SO4 as catalyst

 This is also called esterification

 The first part of the ester’s name comes from the alcohol and the second part of the
name comes from the carboxylic acid

 E.g. Propanol and ethanoic acid will give the ester propyl ethanoate

Hydrolysis of Esters

 Esters can be hydrolysed to reform the carboxylic acid and alcohol by either dilute
acid or dilute alkali and heat
 When an ester is heated under reflux with dilute acid (eg. sulfuric acid) an equilibrium
mixture is established as the reaction is reversible
Ester hydrolysis by dilute acid is a reversible reaction forming carboxylic acid and
alcohol

 However, heating the ester under reflux with dilute alkali (eg. sodium hydroxide) is
an irreversible reaction as the ester is fully hydrolysed
 This results in the formation of a sodium carboxylate salt which needs
further acidification to turn into a carboxylic acid
o The sodium carboxylate (-COO-) ion needs to get protonated by an acid (such as
HCl) to form the carboxylic acid (-COOH)
Nitrogen Compounds
Production of Amines

 Amines are compounds with the amine (-NH2) functional group

 They can be produced as a result of nucleophilic substitution reactions of
halogenoalkanes when they are heated under pressure with ethanolic ammonia (NH3 in
ethanol)
 The halogen atom in halogenoalkanes is more electronegative than the carbon atom it
is bonded to
 The halogen, therefore, draws electron density from the C-X bond (where X is the
halogen) towards itself
 The carbon, therefore, has a partial positive charge and the halogen itself has a partial
negative charge
 The lone pair of electrons on the nitrogen atom (in NH3) acts as a nucleophile and
attacks the partial positively charged carbon
 As a result of this nucleophilic attack, the C-X bond is broken and the halogen is
substituted by an amine group

Production of Nitriles

 Nitriles are compounds with a -CN functional group

 They can be prepared from the nucleophilic substitution of halogenoalkanes
Reaction with KCN

 The nucleophile in this reaction is the cyanide, CN- ion

 Ethanolic solution of potassium cyanide (KCN in ethanol) is heated under reflux with
the halogenoalkane
 The product is a nitrile

 If an aqueous solution of potassium cyanide (KCN (aq)) is heated under reflux

with the halogenoalkane, an alcohol can be formed instead of the nitrile

Production of Hydroxynitriles

 Hydroxynitriles are compounds with both a hydroxy (-OH) and cyanide (-CN) functional
group
 They can be prepared from the nucleophilic addition of aldehydes and ketones

2-hydroxy-2-methylpropanenitrile

Reaction with HCN

 The nucleophilic addition of hydrogen cyanide to carbonyl compounds is a two-step

process
 In step 1, the cyanide ion attacks the carbonyl carbon to form a negatively charged
intermediate
 In step 2, the negatively charged oxygen atom in the reactive intermediate quickly reacts
with aqueous H+ (either from HCN, water or dilute acid) to form a 2-hydroxynitrile
Hydrolysis of Nitriles

 Nitriles are hydrolysed by either dilute acid or dilute alkali followed by acidification to
give a carboxylic acid
o Hydrolysis is the breakdown of a compound using water

Hydrolysis of nitriles

 Nitriles are hydrolysed by either dilute acid or dilute alkali followed by acidification

 Hydrolysis by dilute acid results in the formation of a carboxylic acid and

ammonium salt
 Hydrolysis by dilute alkali results in the formation of a sodium carboxylate salt
and ammonia; Acidification is required to change the carboxylate ion into a
carboxylic acid

 The -CN group at the end of the hydrocarbon chain is converted to a -COOH group
Polymerisation
Addition polymerisation

 Addition polymerisation is one of the most important addition reactions of alkenes

which form the basis of the plastic industry
 Addition polymerisation is the reaction in which many monomers containing at least
one C-C double bond form long chains of polymers as the only product

 Just like in other addition reactions of alkenes, the π-bond in each C-C bond
breaks and then the monomers link together to form new C-C single bonds

 A polymer is a long-chain molecule that is made up of many repeating units

 The small, reactive molecules that react together to form the polymer are
called monomers
 A polymerisation reaction can be represented by a general formula or by
using displayed formulae

Deducing repeat units

 A repeat unit is the smallest group of atoms that when connected one after the other
make up the polymer chain

 It is represented by square brackets in the displayed and general formula

 In poly(alkenes) (such as poly(ethene)) and substituted poly(alkenes) (such as PVC)

made of one type of monomer the repeating unit is the same as the monomer except
that the C-C double bond is changed to a C-C single bond
 Though poly(alkenes)s are extremely important in everyday such as their use
as plastics, the disposal of these polymers is problematic
 Poly(alkenes) are very large alkane molecules which are unreactive and therefore
do not undergo any chemical reactions; they are resistant to chemical attack
 Due to their unreactivity, polymers are non-biodegradable and take up to
hundreds of years to decompose when dumped in landfill sites

 Throwing away poly(alkenes) therefore cause the long-term pollution of

the environment

 Burning the polymers results in harmful combustion products which again

cause the pollution of the environment
Organic Synthesis
Elucidating Organic Molecules

 You are expected to be able to identify organic functional groups, their properties, how
to test for their presence and how they are made

Functional groups

 The table below summarises the tests to identify the presence of certain functional
groups and the reactions to make them

Functional groups, their reactions & identifying tests table

Types of reactions

 You should also be aware of the different type of reactions that functional groups can
undergo
Oxidising & reducing agents

 Certain functional groups only react with specific oxidising and reducing agents which
you should be aware of
Tests

 The test also requires you to distinguish between the different tests that identify
functional groups in a compound
Analytical Chemistry
Interpreting IR Spectra

 Infrared (IR) spectroscopy is a technique used to identify compounds based on

changes in vibrations of atoms when they absorb IR of certain frequencies
 A spectrophotometer irradiates the sample with electromagnetic waves in the infrared
region and then detects the intensity of the wavelength of IR radiation which goes
through the sample
 All organic molecules absorb IR radiation and depending on which energies of radiation
are absorbed, bonds between atoms will vibrate by stretching, bending and twisting
 The molecules will only vibrate at a specific frequency
 The resonance frequency is the specific frequency at which the molecules will vibrate to
stimular larger vibrations
 Depending on the rest of the molecule, each vibration will absorb specific wavelengths
of IR radiation which are also shown as the reciprocal of the wavelength
o This unit is called the wavenumber (cm-1)
 Particular absorbance have characteristic widths (broad or sharp) and intensities (strong
or weak)
o For example, hydrogen bonds cause the O-H bonds in alcohols and carboxylic
acids to be broad whereas the C-O bond in carbonyl (C=O) groups have a
strong, sharp absorbance peak
 The energies absorbed by different functional groups are given as a range and an
unknown compound can be identified by comparing its IR spectrum to the IR spectrum
of a known compound
 Due to some absorption bands overlapping each other, other analytical techniques such
as mass spectroscopy should be used alongside IR spectroscopy to identify an unknown
compound
Interpreting Mass Spectra

 Mass spectroscopy is an analytical technique used to identify unknown compounds

 The molecules in the small sample are bombarded with high energy electrons which can
cause the molecule to lose an electron
 This results in the formation of a positively charged molecular ion with one unpaired
electron
o One of the electrons in the pair has been removed by the beam of electrons

 The molecular ion can further fragment to form new ions, molecules, and radicals

Fragmentation of a molecule in mass spectroscopy

 These fragmentation ions are accelerated by an electric field

 Based on their mass (m) to charge (e) ratio, the fragments of ions are then separated by
deflecting them into the detector
  For example, an ion with mass 16 and charge 2+ will have a m/e value of 8

 The smaller and more positively charged fragment ions will be detected first as they will
get deflected the most and are more attracted to the negative pole of the magnet
 Each fragment corresponds to a specific peak with a particular m/e value in the mass
spectrum
 The base peak is the peak corresponding to the most abundant ion

Isotopes

 Isotopes are different atoms of the same element that contain the same number
of protons and electrons but a different number of neutrons.
o These are atoms of the same elements but with different mass number
o For example, Cl-35 and Cl-37 are isotopes as they are both atoms of the same
element (chlorine, Cl) but have a different mass number (35 and 37 respectively)
 Mass spectroscopy can be used to find the relative abundance of the isotopes
experimentally
 The relative abundance of an isotope is the proportion of one particular isotope in a
mixture of isotopes found in nature
o For example, the relative abundance of Cl-35 and Cl-37 is 75% and 25%
respectively
o This means that in nature, 75% of the chlorine atoms is the Cl-35 isotope and
25% is the Cl-37 isotope
 The heights of the peaks in mass spectroscopy show the proportion of each isotope
present
Calculating Relative Atomic Mass

 Isotopes are different atoms of the same element that contain the same number
of protons and electrons but a different number of neutrons.
o These are atoms of the same elements but with different mass numbers
 Because of this, the mass of an element is given as relative atomic mass (Ar) by using
the average mass of the isotopes
 The relative atomic mass of an element can be calculated by using the relative
abundance values
o The relative abundance of an isotope is either given or can be read off the mass
spectrum
Mass Spectrometry: Deducing Molecular Formula

 Each peak in the mass spectrum corresponds to a certain fragment with a

particular m/e value
 The peak with the highest m/e value is the molecular ion (M+) peak which gives
information about the molecular mass of the compound
 The molecular ion is the entire molecule that has lost one electron when bombarded
with a beam of electrons

 The [M+1] peak is a smaller peak which is due to the natural abundance of the isotope
carbon-13
 The height of the [M+1] peak for a particular ion depends on how many carbon atoms
are present in that molecule; the more carbon atoms, the larger the [M+1] peak is
o For example, the height of the [M+1] peak for an hexane (containing six carbon
atoms) ion will be greater than the height of the [M+1] peak of an ethane
(containing two carbon atoms) ion

Identifying Molecules using Fragmentation

 The molecular ion peak can be used to identify the molecular mass of a compound
 However, different compounds may have the same molecular mass
 To further determine the structure of the unknown compound, fragmentation is used
 Fragments may appear due to the formation of characteristic fragments or
the loss of small molecules
o For example, a peak at 29 is due to the characteristic fragment C2H5+
o Loss of small molecules give rise to peaks at 18 (H2O), 28 (CO), and 44 (CO2)

Alkanes

 Simple alkanes are fragmented in mass spectroscopy by breaking the C-C bonds
 M/e values of some of the common alkane fragments are given in the table below
 Mass spectrum showing fragmentation of alkanes

Halogenoalkanes

 Halogenoalkanes often have multiple peaks around the molecular ion peak
 This is caused by the fact that there are different isotopes of the halogens
 Mass spectrum showing different isotopes of the halogens in the molecular ion

Alcohols

 Alcohols often tend to lose a water molecule giving rise to a peak at 18 below the
molecular ion
 Another common peak is found at m/e value 31 which corresponds to the CH2OH+
fragment
 For example, the mass spectrum of propan-1-ol shows that the compound has
fragmented in four different ways:

 Loss of H• to form a C3H7O+ fragment with m/e = 59

 Loss of a water molecule to form a C3H6+ fragment with m/e = 42
 Loss of a •C2H5 to form a CH2OH+ fragment with m/e = 31
 And the loss of •CH2OH to form a C2H5+ fragment with m/e = 29
Determine Number of Carbon Atoms Using M+1 Peak

 The [M+1] peak is caused by the presence of the carbon-13 (13C) isotope in the molecule
 Carbon-13 makes up approximately 1.1% of all carbon atoms
 Therefore, the [M+1] peak is much smaller than the M peak as the isotope is less
common
o The ratio of 13C to 12C is approximately 1:99
 Thus, the greater the number of carbon atoms present in a molecule the greater the
height of the [M+1] peak
 The number of carbon atoms, n, in a compound can be deduced using the [M+1] peak
and the following formula:

Detecting Bromine & Chlorine Atoms Using M+2 Peak

 The presence of bromine or chlorine atoms in a compound gives rise to a [M+2] and
possibly [M+4] peak

Chlorine

 Chlorine exists as two isotopes, 35Cl and 37Cl

 A compound containing one chlorine atom will therefore have two molecular ion peaks
due to the two different isotopes it can contain
o 35Cl = M+ peak
o 37Cl = [M+2] peak
o The ratio of the peak heights is 3:1 (as the relative abundance of 35Cl is 3x greater
than that of 37Cl)
 A compound containing two chlorine atoms will have three molecular ion peaks due to
the different combinations of chlorine isotopes they can contain
o 35Cl + 35Cl = M+ peak
o 35Cl + 37Cl = [M+2] peak
o 37Cl + 37Cl = [M+4] peak
o The ratio of the peak heights is 9:6:1
 Mass spectrum of compounds containing one chlorine atom (1) and two chlorine
atoms (2)

Bromine

 Bromine too exists as two isotopes, 79Br and 81Br

 A compound containing one bromine atom will have two molecular ion peaks
o 79Br = M+ peak
o 81Br = [M+2] peak
o The ratio of the peak heights is 1:1 (they are of similar heights as their relative
abundance is the same!)
 A compound containing two bromine atoms will have three molecular ion peaks

 79Br + 79Br= M+ peak

 79Br+ 81Br = [M+2] peak
81Br + 81Br= [M+4] peak

 The ratio of the peak heights is 1:2:1

Mass spectrum of compounds containing one bromine atom