ORGANIC CHEMISTRY

Formulae of Functional Groups

 The general formula is a formula that represents a homologous series of compounds

using letters and numbers
 For example, the general formula of alkanes is CnH2n+2
 This means that in an alkane with 3 carbon atoms (n = 3) there are 8 hydrogen atoms (2
x 3 + 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 hydrocarbon side-chain is shown in brackets in the structural formula
 CH3CH(CH3)CH2CH3
 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

Functional groups & their nomenclature table

How many isomers are there of dibromopropane, C3H6Br2?

 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

o Functional group? No, as Br is the only functional group possible
o Chain? No, as the longest chain can only be 3
o Positional? Yes, as the two bromine atoms can be bonded to different carbon
atoms

How many isomers are there of the compound with molecular formula C 4H10?

 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
o Functional group? No, as there are no functional groups
o Positional? No, as there are no functional groups which can be positioned on
different carbon atoms
o Chain? yes!

How many isomers are there of the compound with molecular formula C 2H4Cl2?

 Step 1: Draw the possible structural formula of the compound

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

The compound has to be unsaturated for it to have molecular formula C 2H2Cl2 ; Due to the
double bond there is restricted rotation about the C-C bond; This compound will therefore
display geometrical isomerism

 Step 3: Determine whether it is optical or geometrical isomerism

o Optical? No, as there are no chiral centres
o Geometric? Yes!

  

Molecular & Empirical Formulae of Organic Compounds

  The molecular formula shows the number and type of each atom in a molecule
o Eg. the molecular formula of ethanoic acid is C 2H4O2
 The empirical formula shows the simplest whole number ratio of the elements present in
one molecule of the compound
o Eg. the empirical formula of ethanol is CH 2O

Homologous series

 A homologous series is a group of organic compounds that have the same functional
group, the same general formula and the same chemical properties

Ethanol and propanol belong to the same homologous series

Saturated & unsaturated hydrocarbons

 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 & heterolytic fission

 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
heterolytic fission in which the most electronegative atom takes both electrons in the covalent
bond and homolytic fission in which each atom takes one electron from the covalent bond

Radical chain reactions

 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

o ‘Nucleophile’ means ‘nucleus/positive charge loving’ as nucleophiles are
attracted to positively charged species
o Nucleophilic refers to reactions that involve a nucleophile
 An electrophile is an electron-deficient species that can accept a pair of electrons
o ‘Electrophile’ means ‘electron/negative charge loving’ as electrophiles are
attracted to negatively charged species
o Electrophilic refers to reactions that involve an electrophile

A nucleophile ‘loves’ a positive charge and an electrophile ‘loves’ a negative charge

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 H 2O 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
o In organic chemistry it often refers to the addition of oxygen or removal of
hydrogen atoms to a substance
o 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
o In organic chemistry it often refers to the removal of oxygen or addition of
hydrogen atoms to a substance
o In equations for organic redox reactions, the symbol [H] can be used to represent
one atom of hydrogen from a reducing agent

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
o Sigma bonds (σ)
o Pi bonds (π)

Ethane

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

The diagram shows a molecule of ethane in which each carbon atom forms four σ bonds to adopt a
tetrahedral configuration and minimise the repulsion between the bonding pairs of electrons

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 120º

The overlap of the two p orbitals results in the formation of a π bond in ethene (sp 2 hybridised molecule) in
which the bonding pair of electrons repel each other to force the molecule into a planar configuration with
bond angles of 120º

Shape of Benzene & Aromatic Molecules

Kekulé structure for benzene

 Kekulé suggested that benzene was a hexagon with three double bonds

 It was therefore equivalent to three ethene molecules

Problems with Kekulé’s structure for benzene

 Since benzene has three double bonds, it should have similar reactivity to ethene
 However, this turned out not to be the case
o Ethene undergoes addition reactions whereas benzene rarely does (only under very
harsh conditions) and instead undergoes substitution reactions
  The presence of three double bonds also suggested that benzene had shorter
double and longer single bonds
o In fact, the bond lengths in benzene were exactly the same
o They were found to be an intermediate between single and double bonds
 The benzene is also much more stable than Kekulé’s suggested structure for benzene
o Less energy was required to hydrogenate a benzene molecule compared to the
hydrogenation of three ethene molecules
o This means that the bonds broken in benzene are stronger than the double bonds in
ethene
 The increase in stability of benzene is known as the delocalisation energy and is caused by
the delocalised electrons in the benzene structure
 The C-C in benzene are an intermediate between single and double bonds which is a result
of these delocalised electrons

Shape of benzene

 Benzene is a planar regular hexagon with bond angles of 120º

o All the bonds are identical due to the delocalization of electrons
 Each sp2 hybridised carbon atom in benzene forms:
o A σ bond with two other carbons
o A σ bond with one hydrogen atom
 The remaining p orbital is overlapping with the p orbitals on both sides of it
o To achieve maximum overlap, the benzene ring must be planar
 This results in the formation of a system of π bonds spread out over the whole ring
 Due to this, the electrons are not bound to specific atoms but can instead freely move
around the structure and are said to be delocalised

Benzene has a π system of delocalised electrons with carbon atoms that have bond angles of 120º

Predicting shapes of similar molecules

 Carbon atoms with four single bonds, that carbon atom will have a tetrahedral structure
with bond angles of 109.5º
 A carbon atom with two single and one double bond will have a planar structure with bond
angles of 120º
 A benzene ring is always planar

Structural Isomerism: Chain, Position & Functional Group

 Structural isomers are compounds that have the same molecular formula but

different structural formulae
o Eg. propene and cyclopropane
Both propene and cyclopropane are made up of 3 carbon and 6 hydrogen atoms but the
structure of the two molecules differs

 There are three different types of structural isomerism:

o Chain isomerism
o Positional isomerism
o 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
o Eg. pentane and 2,2-dimethylpropane

Both compounds are made up of the same atoms however the longest carbon chain in
pentane is 5 and in 2,2-dimethylpropane 3 (with two methyl branches)

Positional isomerism

 Positional isomers arise from differences in the position of a functional group in each isomer
o The functional group can be located on different carbons
o For example, butanol and 2-butanol

Both compounds have an alcohol group and are made up of 4 carbon, 10 hydrogen and
one oxygen atom however in butanol the functional group is located on the first carbon
and in 2-butanol on the second carbon
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
o For example, butanol and ethoxyethane

Both compounds have the same molecular formula however butanol contains an alcohol
functional group and ethoxyethane an ether functional group

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/rans) 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
o Cis isomers have functional groups on the same side of the double bond/carbon ring
o Trans isomers have functional groups on opposite sides of the double bond/carbon
ring

Geometrical isomerism in unsaturated compounds

Geometrical isomerism in cyclic compounds

 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
o Just like the left hand cannot be superimposed on the right hand, enantiomers too
are non–superimposable
o 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

o One enantiomer will rotate it clockwise and the other anticlockwise

Geometrical Isomerism in Alkenes

Unsaturated compounds

 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

The presence of a π bond in unsaturated compounds restricts rotation about the C=C bond
forcing the groups to remain fixed in their position and giving rise to the formation of
geometrical isomers

Chirality & Enantiomers

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

Each chiral centre gives rise to two optical isomers; therefore, the molecule has a total of
four 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
To decide where the chiral centres are in a cyclic molecule, the carbon atoms bonded to
four different atoms or atom groups should be found

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

Chemical Reactivity of Alkanes

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

 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
o They have no electron-deficient areas to attract nucleophiles
o And also lack electron-rich areas to attract electrophiles

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

o Both processes require the input of a lot of heat (energy) and are therefore
exothermic reactions

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
o For example, the complete combustion of octane to carbon dioxide and water
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
o For example, the incomplete combustion of octane to form carbon monoxide

 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

Free Radical Substitution Mechanism

 Alkanes can undergo free-radical substitution in which a hydrogen atom

gets substituted by a halogen (chlorine/bromine)
o Ultraviolet light (sunlight) is needed for this substitution reaction to occur
 The free-radical substitution reaction consists of three steps
The fact that the bromine color 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

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
o Free radicals are very reactive and will attack the unreactive alkanes
o A C-H bond breaks homolytically (each atom gets an electron from the covalent
bond)
o An alkyl free radical is produced
o This can attack another chlorine/bromine molecule to form
the halogenoalkane and regenerate the chlorine/bromine free radical
o 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

o This reaction is not very suitable for preparing specific halogenoalkanes as

a mixture of substitution products are formed
o If there is enough chlorine/bromine present, all the hydrogens in the alkane will
eventually get substituted (eg. ethane will become C 2Cl6/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
o Multiple products are possible

The final step in the substitution reaction to form a single unreactive molecule

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:
o The Pt/Ni catalyst is finely divided to increase its surface area and therefore
increase the rate of reaction
o 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
o Vegetable oil is an unsaturated organic molecule with many C-C double bonds
o When these are partially hydrogenated, their hydrocarbon chains become
straighter
o 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 aluminum 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

Long hydrocarbons are cracked by heating them and using aluminum oxide catalyst into
smaller hydrocarbons and an alkene
*Remember that hydrogenation is an exothermic reaction and cracking is an endothermic
reaction.
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

 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

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
 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

Long hydrocarbon fraction is cracked into two smaller ones

 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
o This makes them useful for the chemical industry as the starting compounds
(feedstock) for making new products
o 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

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:
o Hydrogen (also known as hydrogenation reaction)
o Steam (H2O (g))
 o Hydrogen halide (HX)
o Halogen

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
o When shaken with cold dilute KMnO4 the pale purple solution
turns colourless and the product is a diol
o When alkenes are reacted with hot concentrated KMnO4 the conditions are
harsher causing the C-C double bond to completely break
o The O-H groups in the diol formed are further oxidised
to ketones, aldehydes, carboxylic acids or carbon dioxide gas
o 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 KMnO 4 to give different products

 The reactions of alkenes with hot concentrated KMnO 4 can be used to determine the
position of the double bond in larger alkenes

The above reactions can be used to predict where the double bond in a larger molecule is

What are the products of the oxidation of 2-methylprop-1-ene with hot, concentrated
acidified KMnO4 (aq)?
The products are propanone (a ketone), carbon dioxide and water.
The oxidation of an alkene produces carbon dioxide gas, water and propanoic acid. Identity the
alkene.
The alkene is 1-butene.

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

 
 

 Other alkenes and substituted alkenes can also polymerise to make polymers with

different properties
o Eg. poly(chloroethene), also known as PVC is the most versatile plastic used

Poly(chloroethene) is used as plastic

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
o 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)

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
o 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) 

*The stability of the carbocation intermediate is as follows:

tertiary > secondary > primary
When 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.

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

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

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.

Addition Polymerization: Polythene & PVC

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
o 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
o Eg. poly(ethene) and poly(chloroethene) (also known as PVC) are polymers made
up of the ethene and chloroethene monomers respectively and are commonly used
in making plastics

The general formulae of the addition polymerisation of ethene (1) and chloroethene (2)

The general formulae of the addition polymerisation of ethene (1) and chloroethene (2)

 Just like any other addition reaction of alkenes, addition polymerisation gives

only one product

Deducing repeat units

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

 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
o Throwing away poly(alkenes) therefore cause the long-term pollution of the
environment
 Burning the polymers results in harmful combustion products which again cause them.
*The disposal of polymers is a challenge due to their unreactivity, their non-
biodegradability, and the formation of harmful combustion products when burnt.

Combustion of Alkanes & the Environment

Alkanes as fuels

 Alkanes can be burnt in oxygen in a process called combustion

o Complete combustion is when alkanes burn in excess oxygen to form carbon dioxide
and water
Alkanes + oxygen (excess) → carbon dioxide + water

o Incomplete combustion is when alkanes burn in a limited supply of oxygen to form

the toxic carbon monoxide and carbon (soot)
Alkanes + oxygen (limited) → carbon monoxide + water (+ carbon)

 The longer the alkane chains, the more energy is required to burn them when used as fuels
o The bigger the alkane molecules, the stronger the van der Waals forces between the
molecules
 Alkanes are suitable to be used as fuels in industry, in the home and in transport as:
o They are readily available
 o Burn cleanly in the presence of excess oxygen
o Have high enthalpy changes of combustion and thus release a lot of energy when
burnt

 Environmental consequences

 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
o The CO binds to haemoglobin which therefore cannot bind oxygen and carbon
dioxide
o Oxygen is transported to organs
o Carbon dioxide is removed as waste material from organs

Oxides of nitrogen & unburnt hydrocarbons

 Normally, nitrogen is too unreactive to react with oxygen in air

 However, in a car’s engine, high temperatures and pressures are reaches 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
can cause acid rain
o This can cause corrosion of buildings, endangering plant-life, aquatic life as lakes and
rivers get too acidic and damaging human health

Enhanced greenhouse effect

 When sunlight hits the Earth’s surface, some of the light gets reflected back into the
atmosphere as infrared (IR) radiation
 Molecules such as water vapour, CO2 and hydrocarbons absorb this IR radiation and pass it
onto other molecules during collisions
 As a result of this the atmosphere warms up
 This process is known as the greenhouse effect and keeps the Earth’s temperature suitable
for life
  However, burning excessive fossil fuels increases the amount of CO2 in the atmosphere
which increase the greenhouse effect causing the Earth to warm up
 This is known as the enhanced greenhouse effect

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:
o Oxidation of CO to CO2:
2CO + O2 → 2CO2
or|
2CO + 2NO → 2CO2 + N2

o Reduction of NO/NO2 to N2:

2CO + 2NO → 2CO2 + N2

o Oxidation of unburnt hydrocarbons:

CnH2n+2 + (3n+1) [O] → nCO2 + (n+1) H2O

Pollutants: formation, effect & catalytic removal table

Use of Infrared Spectroscopy in Monitoring Air Pollution

 Air pollutants can be detected by infrared (IR) spectroscopy

 IR spectroscopy identifies particular bonds in a molecule
 Therefore, each pollutant will show a different pattern of absorptions
 The concentrations of the pollutants can also be determined by IR spectroscopy by looking
at the intensities of the peaks

Halogenoalkanes
Substitution & Elimination Reactions of Halogenoalkanes

 Halogenoalkanes are much more reactive than alkanes due to the presence of

the electronegative halogens
o 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
o An atom that has a partial negative charge is replaced by the nucleophile
 In an elimination reaction of halogenoalkanes, a halogen halide is eliminated to form
an alkene

Hydrolysis

 Halogenoalkanes can be broken down under reflux by water to form an alcohol

o The breakdown of a substance by water is also called hydrolysis
 The reaction is classified as a nucleophilic substitution reaction as a water molecule in
the silver nitrate solution acts as a nucleophile and replaces the halogen
o Eg. bromoethane reacts with aqueous silver nitrate solution to form ethanol
The halogen is replaced by an hydroxyl group, OH–

 This reaction is similar to the nucleophilic substitution reaction of halogenoalkanes with

aqueous alkali, however the hydrolysis with water is much slower than with the OH– ion
o The hydroxide ion is a better nucleophile than water as it carries a full formal
negative charge
o 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

Formation of nitriles

 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
o Eg. bromoethane reacts with ethanolic potassium cyanide when heated under reflux
to form propanenitrile

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

Formation of primary amines by reaction with ammonia

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

  Ethanolic solution of excess ammonia (NH3 in ethanol) is heated under pressure with the
halogenoalkane
 The product is a primary amine
o Eg. bromoethane reacts with excess ethanolic ammonia when heated under
pressure to form ethylamine

The halogen is replaced by an amine group,  NH3

Elimination reaction

 The halogenoalkanes are heated with ethanolic sodium hydroxide causing the C-X bond to

break heterolytically, forming a X– ion and leaving an alkene as organic product
o Eg. bromoethane reacts with ethanolic sodium hydroxide when heated to form
ethene

Hydrogen bromide is eliminated to form ethene

*The reaction conditions in a reaction are extremely important.

If NaOH(ethanol) is used, an elimination reaction takes place to form an alkene from a
halogenoalkane.
If NaOH(aq) is used, a nucleophilic substitution reaction takes place to form an alcohol from a
halogenoalkane.

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
o ‘S’ stands for ‘substitution’
o ‘N’ stands for ‘nucleophilic’
o ‘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
o The nucleophile donates a pair of electrons to the δ+ carbon atom to form a new
bond
o At the same time, the C-X bond is breaking and the halogen (X) takes both
electrons in the bond (heterolytic fission)
o The halogen leaves the halogenoalkane as an X – ion
 For example, the nucleophilic substitution of bromoethane by hydroxide ions to form
ethanol

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
o ‘S’ stands for ‘substitution’
o ‘N’ stands for ‘nucleophilic’
o ‘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

o 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)
o This forms a tertiary carbocation (which is a tertiary carbon atom with a
positive charge)
o 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
o The alkyl groups push electron density towards the positively charged carbon,
reducing the charge density
o In tertiary carbocations, there are three alkyl groups stabilising the carbocation
whereas in primary carbocations there is only one alkyl group
o 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

Reactivity of Halogenoalkanes

 The halogenoalkanes have different rates of substitution reactions

 Since substitution reactions involve breaking the carbon-halogen bond
the bond energies can be used to explain their different reactivities
  C-I bond requires the least energy to break and is therefore the weakest carbon-halogen
bond
 During substitution reactions the C-I bond will therefore heterolytically break as follows:
R3C-I + OH– → R3C-OH + I–

 The C-F bond, on the other hand, requires the most energy to break and is, therefore,
the strongest carbon-halogen bond
 Fluoroalkanes will therefore be less likely to undergo substitution reactions

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

 The formation of the pale yellow silver iodide was the fastest (fastest nucleophilic
substitution reaction) whereas the formation of the silver fluoride was the slowest
(slowest nucleophilic substitution reaction)
 This confirms that fluoroalkanes are the least reactive and iodoalkanes are the most
reactive halogenoalkanes

Uses of Fluoroalkanes & Fluorohalogenoalkanes

 Fluoroalkanes and fluorohalogenoalkanes are chemically inert

 The amount of energy required to break the halogen-carbon bond is so high that
fluoroalkanes and fluorohalogenoalkanes are very unreactive

Fluorohalogenoalkanes

 The most common fluorohalogenoalkanes are chlorofluorocarbons (CFCs)

 These compounds contain carbon atoms with chlorine and fluorine atoms attached to them
 o Eg. CCl3F and CCl2F
 CFCs have many uses due to their chemical inertness as they are non-flammable and non-
toxic
o They are used as refrigerators
o Propellants for aerosols
o As solvents for dry cleaning

Fluoroalkanes

 Hydrofluorocarbons (HFCs) are compounds that contain a carbon attached to hydrogen and

fluorine atoms only
o Eg. CH2F-CF3
 As with CFCs, HFCs are chemically inert and are therefore used for a wide range of purposes

Fluorohalogenoalkanes & the Ozone Layer

 The most common example of Fluorohalogenoalkanes is chlorofluorocarbons (CFCs)

 Though chlorofluorocarbons (CFCs) have many beneficial uses, they also have devastating
effects on the ozone layer:
o CFCs absorb a lot of UV radiation in the upper atmosphere
o The CFCs are then broken down by the UV light causing the formation of chlorine
radicals
o These radicals react with ozone and break down the ozone layer
 This is why hydrofluorocarbons (HFCs) are often used as an alternative to CFCs
 As these compounds don’t contain any chlorine atoms, they will not have adverse effects on
the ozone layer

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

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 H 2SO4 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
o 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 
 o Acidified means that that the potassium dichromate(VI) is in a solution
of dilute acid (such as dilute sulfuric acid) 
o For potassium dichromate(VI) to act as an oxidising agent, it itself needs to be
reduced
o This reduction requires hydrogen (H+) ions which are provided by the acidic
medium
 When alcohols are oxidised the orange dichromate ions (Cr2O72-) are
reduced to green Cr3+ ions
 Acidified potassium manganate(VII), KMnO4, is a purple oxidising agent 
o 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 ethanol by acidified K2Cr2O7 to form an aldehyde by distillation and carboxylic

acid by refluxing

Oxidation of propan-2-ol by acidified K 2Cr2O7 to form a ketone by distillation

Dehydration of alcohols

 Alcohols can also undergo dehydration to form alkenes

o Dehydration is a reaction in which a water molecule is removed from a larger
molecule
 o 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
*The first part of an ester’s name comes from the alcohol, whereas the second part comes
from the carboxylic acid.

Classifying Alcohols

 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

Production of Aldehydes & Ketones

Formation of aldehydes & ketones

 Aldehydes and compounds are carbonyl compound which contain a C=O group

 They can be prepared from the oxidation of primary and secondary alcohols
 Acidified potassium dichromate (K2Cr2O7) is an orange oxidising agent
 When the alcohols are oxidised the orange dichromate ions (Cr2O72-) are reduced to green
Cr3+ ions
 Secondary alcohols are oxidised to ketones
o To make a ketone, warm secondary alcohol is slowly added to the oxidising
agent
o Since the formed ketone cannot be further oxidised it does not need to
be distilled off straightway after it has been formed
o Eg. propan-2-ol will get oxidised to propanone
 Primary alcohols are oxidised to aldehydes
o To make an aldehyde, warm primary alcohol is slowly added to the oxidising
agent
 o The formed aldehyde has a lower boiling point than the alcohol and can therefore
be distilled off as soon as it forms
o The aldehyde is then condensed into a liquid and collected
o If the aldehyde formed is not distilled off, further refluxing with excess oxidising
agent will oxidise the aldehyde to a carboxylic acid
o Eg. propan-1-ol will get oxidised to propanal

Reduction of aldehyde & ketones

 Aldehydes and ketones can be reduced by reducing agents such as NaBH 4 or LiAlH4

 Aldehydes are reduced to primary alcohols
o Eg. butanal is reduced to butan-1-ol
 Ketones are reduced to secondary alcohols
o Eg. butanone is reduced to butan-2-ol

Reaction of aldehyde & ketones with hydroxynitrile

 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 and NaCN (or KCN) as the catalyst and heat to
produce hydroxynitriles
o Hydroxynitriles are nitriles containing a hydroxy, -OH, group
o Eg. propanal reacts with HCN to form 2-hydroxybutanenitrile

*The nucleophilic addition of HCN to an aldehyde or ketone increases the length of the carbon chain
by one carbon atom!

Reaction of Hydrogen Cyanide with Aldehydes & Ketones

 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
The cyanide ion attacks the carbonyl carbon to form a negatively charged intermediate which
quickly reacts with a proton to form a 2-hydroxynitrile compound
*The actual negative charge on the cyanide ion is on the carbon atom and not on the nitrogen
atom

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

Ketones and aldehydes react with 2,4-DNPH in a condensation reaction

*The 2,4-DNPH is especially useful as other carbonyl compounds such as carboxylic acids
and esters do not give a positive test.
Identifying Carbonyls: Fehling's Solution & Tollens' Reagent

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

The copper(II) ions in Fehling’s solution are oxidising agents, oxidising the aldehyde to a
carboxylic acid and getting reduced themselves to copper(I) ions in the Cu2O precipitate

Tollens’ reagent

 Tollen’s reagent is an aqueous alkaline solution of silver nitrate in excess ammonia solution
o Tollen’s 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
 The  Ag+  ions in Tollens’ reagent are  oxidising agents,  oxidising the aldehyde to a
carboxylic acid and getting reduced themselves to silver atoms

Iodoform Reaction

 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

The reaction of ethanal with iodoform results in the formation of a yellow CHI 3 precipitate

Production of 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
o In K2Cr2O7 the orange dichromate ions (Cr2O72-) are reduced to green Cr3+ ions
o 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 nitriles by either dilute acid (1) or dilute alkali and acidification (2) will form
a carboxylic acid

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
Hydrolysis of esters by either dilute acid (1) or dilute alkali and heat followed acidification (2) will
form 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:
o Redox reactions with reactive metals
o Neutralisation reactions with alkali
o Acid-base reactions with carbonates
o Esterification with alcohols
o Reduction by LiAlH4

 
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)

 
Ester hydrolysis by dilute alkali is an irreversible reaction forming a sodium carboxylate
salt and alcohol

Commercial Uses of Esters

 Esters have sweet and fruity smells

 They are therefore commercially used in perfumes and flavorings
 The smaller esters such as ethyl acetate are furthermore used as solvents in organic
chemistry as it can dissolve in a wide range of organic compounds

Infra-Red Spectroscopy
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

Absorption range of bonds table

  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