NSSCAS Chemistry

Theme 4
Topic 4.5
Topic 4.6
Topic 4.7
 Topic 4.5
Isomerism: structural and
stereoisomerism

Topic 4.6
Carbonyl compounds

Topic 4.7 Carboxylic acids and derivatives

 Topic 4.5 Isomerism -
structural and stereoisomerism
• deduce (draw and name) the possible isomers for an
organic molecule of known molecular formula
• describe structural isomerism and its division into
chain, positional and functional group isomerism
• describe stereoisomerism and its division into
geometrical (cis-trans) and optical isomerism (use of
E, Z nomenclature is acceptable but is not required)
• describe geometrical (cis-trans) isomerism in
alkenes, and explain its origin in terms of restricted
rotation due to the presence of double bonds
 Topic 4.5 Isomerism -
structural and stereoisomerism
• explain what is meant by a chiral centre and that such
a centre normally gives rise to optical isomerism
• (NB: Learners should appreciate that compounds can
contain more than one chiral centre, but knowledge
of meso compounds, or nomenclature such as
diastereoisomers is not required)
• identify chiral centres and geometrical (cis-trans)
isomerism in a molecule of given structural formula
 What are isomers?
• Isomers are two or more compounds with the
same molecular formula but a different
arrangement of atoms in space.
• Organic molecules which exhibit this property
show isomerism.
• This excludes any different arrangements which
are simply due to the molecule rotating as a
whole, or rotating about particular bonds.
 What are isomers?
• For example, both of the following are the same molecule.
They are not isomers, both are butane.
• Isomers must have different names.
• A good way to identify isomers is by naming the molecules,
molecules with the same name are not isomers.
 Two types of isomerism
Structural isomerism Stereoisomerism
• chain isomerism • geometrical (cis-
• positional trans) isomerism
isomerism • optical isomerism
• functional group
isomerism
 Structural isomerism
Structural isomers are molecules
with the same molecular formula /
same number of atoms of each
element but different structural /
displayed formulae/ different
arrangement of bonds.
 Structural isomerism –
chain isomerism
• Chain isomerism arises due to the different
arrangement of carbon atoms in a chain. The carbon
atoms may be arranged in a straight chain or branched
chain.
 Structural isomerism –
positional isomerism
Positional isomerism arises due to different
positions of a functional group in the carbon chain.
The functional group is the same on each carbon
chain, they are just at different positions.
 Structural isomerism –
functional isomerism
• Functional isomerism arises due to different
functional groups, e.g. propanal (aldehyde) and
propanone (ketone) belong to different
homologous series.
Structural isomerism –
functional isomerism

Some isomers of
 Stereoisomerism
• Molecules having the same structural formula
and same molecular formula but different
orientation and arrangements or bonds in
space.
• Stereos, from Greek meaning solid.
 Stereoisomerism –
Geometrical (cis-trans or E-Z) isomerism
• Geometrical isomerism arises due to the
rotation about a bond is restricted.
• Geometrical isomerism is common in
compounds containing carbon-carbon double
bond (C=C bond) and certain ring systems.
 Stereoisomerism –
Geometrical (cis-trans or E-Z) isomerism
• E stands for entangen (opposite in German).
Trans means ‘on the other side’ meaning
opposite.
• Z stands for zusammen (together in German)
• Cis from greek means ‘on this side’ meaning
together or same side.
 Stereoisomerism –
Geometrical (cis-trans or E-Z) isomerism
• A C=C bond cannot be rotated due to the presence of π
bond.
• A π bond will break if a rotation occurs. Conversely, a
carbon-carbon single bond is rotatable.
• In ring systems, rotation about a bond is restricted due to
the linkage of the ring because the C-C bond is now part of
the ring system.
 Stereoisomerism –
Geometrical (cis-trans or E-Z) isomerism
• Geometrical isomers occur in pairs, differing from each other in the
positioning of the two groups across the double bond.
• A cis-isomer has the two groups on the same side of the double
bond.
• A trans-isomer has the two groups on the opposite sides of the
double bond.
 Stereoisomerism –
Geometrical (cis-trans or E-Z) isomerism
• To identify geometrical (cis-trans) isomers, it is essential to draw
the groups around the double bond showing the correct bond
angles (120°).
• Geometrical (cis-trans) isomerism cannot exist if either carbon
carries identical groups.
• In short, to have geometrical isomers, it is essential to have two
different groups on the left and two different groups on the right.
 Stereoisomerism - optical isomerism
• Optical isomerism arises due to the ability of
compounds to rotate the plane of polarisation
of a plane-polarised light.
• A compound is said to be optically-active
(optical isomerism exists) if it rotates the plane
of polarised light.
• If it does not, it is said to be optically-inactive.
• Optical isomerism is measured using a
polarimeter.
 Stereoisomerism - optical isomerism
For a compound to be optically active:
• It needs to have an asymmetrical carbon with
four different groups attached to it so that
there is no plane of symmetry.
• The carbon atoms with four different groups
attached to it is called the chiral carbon or chiral
centre.
• The isomers must be mirror-images of each
other and are non-superimposable. That is, no
matter how the molecules are rotated, they
never fully resemble each other.
Stereoisomerism - optical isomerism
Stereoisomerism - Optical isomerism
 Identifying chiral centres
• In chain systems, check which carbon has four
different groups attached to it.
• In ring systems, check also which carbon has
four different groups attached to it.
• A different group here can be identified by
tracking around that ring from a particular
carbon atom in either clockwise or anti-
clockwise direction.
 isomerism

structural isomerism stereoisomerism

• chain isomerism • geometrical (cis-trans) isomerism

• positional isomerism • optical isomerism
• functional group isomerism

Structural isomers have the same Stereoisomers have same molecular

molecular formula but different and structural formula but different
structural formula arrangement of their atoms in space

Arises from the different ways in which Arises from the different ways in which
atoms join together to form molecules the various groups in the molecules can
arrange in space

The atoms are linked in different The atoms are linked in the same
sequences and different ways sequence and in the same way but
differ in their arrangements in space
 Topic 4.6.1 Aldehydes and ketones

• interpret and use the general, structural (condensed /

semi-structural and displayed) and skeletal formulae
of the aldehydes and ketones
• recall and use systematic nomenclature of aldehydes
and ketones with chain length up to six carbon atoms,
e.g. pentan-2-one
• deduce the molecular formula of aldehydes and
ketones, given their structural or skeletal formula
• describe the formation of aldehydes and ketones from
primary and secondary alcohols respectively using
Cr2O7 2–/H+
 What are carbonyl compounds?
• Carbonyl compounds are compounds that contain the
C=O (carbonyl) group.
• Examples are aldehydes and ketones.
Aldehydes Ketones

• The C=O group is at the end • The C=O group is in the

of the carbon chain. carbon chain.
• There is at least one H atom • There are two alkyl or aryl
attached to the C atom on groups attached to the C
the carbonyl (C=O) atom on the carbonyl (C=O)
recall: aldehydes and ketones –
functional groups
Aldehydes in everyday life
• Formaldehyde is a gas…
• Formaldehyde is used
in embalming, tanning,
preparing glues and
polymeric products, as
germicides, insecticides, and
fungicides for plants. When
reacted with phenol,
formaldehyde forms Bakelite,
which is used in plastics,
coatings, and adhesives.
Examples of aldehydes
Examples of ketones
 Naming aldehydes and ketones
Recall the order of priority of naming of naming the
functional groups according to IUPAC.
1. alkene
2. alkyne
3. halogenoalkane
4. carboxylic acid
5. ester
6. aldehyde
7. ketone
8. alcohol
9. amine
 Naming aldehydes and ketones
• Aldehydes are named by using the
prefix depending on the number of
carbon atoms (e.g. meth, eth, prop,
but, pent, hex) and adding the suffix -
anal.
• Ketones are named by using the prefix
depending on the number of carbon
atoms (e.g. meth, eth, prop, but, pend,
hex) and adding the suffix -anone.
Reactions of aldehydes and ketones
• The C=O bond of the carbonyl group
is highly polarised due to oxygen
atom being more electronegative.
• This causes the slightly positive
carbon atom to be susceptible to
nucleophilic attacks.
• Thus, carbonyl compounds will
undergo:
1. Reduction
2. Oxidation
3. Reaction with hydrogen cyanide,
HCN
You are required to describe the
formation of aldehydes and ketones
from primary and secondary alcohols
respectively.
 Formation of aldehydes and ketones
• Aldehydes and ketones can be made by
oxidising primary and secondary alcohol
respectively.
• Recall that tertiary alcohols are difficult to
oxidise using mild oxidising agents.
• The oxidising agent used is either acidified
potassium dichromate (VI), or acidified
potassium manganate(VII), KMn.
 Formation of aldehydes
• The primary alcohol used must be in excess and
heated under reflux with acidified acidified
potassium dichromate (VI), or acidified
potassium manganate(VII), KMn.
• The aldehyde formed must be distilled off as
soon as possible.
• Under these conditions, a primary alcohol is
oxidised to an aldehyde.
• Take ethanol as an example, ethanal is
produced. OH + [O] → CHO + O
 Formation of aldehydes
Oxidising of a primary alcohol by the
removal of hydrogen from the –OH
group and removal of hydrogen from the
carbon which is bearing the –OH group.
Formation of aldehydes
 Formation of ketones
Oxidising of a secondary alcohol by the removal
of hydrogen from the –OH group and removal of
hydrogen from the carbon which is bearing the
–OH group.
 Formation of ketones
• To make a ketone:
• The secondary alcohol is heated under reflux
with acidified /KMn.
• Under these conditions, a secondary alcohol is
oxidised to a ketone.
• Take propan-2-ol an example:
• + [O] → CO + O
 Tertiary alcohol – no oxidation
Tertiary alcohol cannot be
oxidised because the
carbon bearing the –OH
group is only attached to
alkyl groups so there is
no hydrogen directly
bonded to the carbon
bearing the –OH group.
4.7 Carboxylic acids and derivatives

4.7.1 Carboxylic acids

4.7.2 Esters and amines

 4.7.1 Carboxylic acids
• interpret and use the general, structural (condensed / semi-
structural and displayed) and skeletal formulae of the
carboxylic acids
• recall and use systematic nomenclature of carboxylic acids
chain length up to six carbon atoms, e.g. butanoic acid
• deduce the molecular formula of carboxylic acids, given its
structural or skeletal formula
• describe the formation of carboxylic acids from alcohols and
aldehydes
• describe the reactions of carboxylic acids in the formation
of:
– salts, by the use of reactive metals, alkalis or carbonates
– alkyl esters
 What are carboxylic acids?

Carboxylic
acids are
compounds
that contain
the -COOH
group.
 Formation of carboxylic acids
• There are three ways to produce carboxylic
acids:
– Oxidation of primary alcohol.
– Oxidation of aldehyde.
 Oxidation of primary alcohols to
aldehydes
• If the alcohol used is in excess and the product formed is distilled off
as soon as possible, aldehydes are formed. This is because the
aldehyde has a lower boiling point than alcohol.
• Take ethanol as an example, ethanal is formed. OH + [O] → CHO + O
Oxidation of primary alcohols to aldehydes
then carboxylic acids
• If the alcohol used is limited and heated
under reflux, the primary alcohol will be
oxidised to aldehyde then to carboxylic acid.
• This means to form a carboxyllic acid, the
oxidising agent should be in excess
• Take ethanol as an example, from the
aldehyde formed, ethanoic acid is formed.
• OH + 2[O] → COOH + O
Oxidation of primary alcohols to
aldehydes then carboxylic acids
 Formation of carboxylic acids –
Acidic hydrolysis of nitrile

• When nitrile is heated under reflux

with a dilute acid such as dilute
hydrochloric acid, carboxylic acid will
be formed.
• Using ethanenitrile as an example,
ethanoic acid is formed.
• CN + O + H⁺ → COOH +
 Formation of carboxylic acids –
alkaline hydrolysis of nitrile
• When nitrile is heated under reflux with an alkali
such as sodium hydroxide, salt of carboxylic acid
(carboxylate salt) is produced.
• Using ethanenitrile as an example, ethanoate ion
is formed.
• CN + 2O + OH⁻ → COO⁻ +
• Ethanoate ion can be converted to ethanoic acid
by the addition of acid.
• COO⁻ + H⁺ → COOH
 Reactions of carboxylic acids
You are required to describe the reactions of
carboxylic acids:

1. carboxylic acid + metal salt + hydrogen

2. carboxylic acid + alkali salt + water
3. carboxylic acid + carbonate salt + water +
carbon dioxide
 acidity of carboxylic acids

• Carboxylic acids are acidic because they can

donate a proton to form carboxylate ion and
hydroxonium ion.
• The presence of hydroxonium ions makes the
solution acidic.
• RCOOH + O ⇌ RCOO⁻ + O⁺
• However, carboxylic acids are only weak acids.
 Reactions of carboxylic acids with bases

• Since carboxylic acids are acids, they will react

with a base such as sodium hydroxide to
produce a carboxylate salt and water.
• This is a simple neutralisation reaction.
• Take ethanoic acid and sodium hydroxide as an
example:
• COOH + NaOH → COONa + O ...and the ionic
equation is: H⁺ + OH⁻ → O
Reactions of carboxylic acids with metals

• Carboxylic acids will react with reactive metals

such as sodium to produce a carboxylate salt
and hydrogen gas.
• Take ethanoic acid and sodium metal as an
example: 2COOH + 2Na → 2 COONa +
 Reaction with carbonates and
hydrogencarbonates
• Carboxylic acids will react with carbonates and
hydrogencarbonates to produce a carboxylate salt, carbon
dioxide gas and water.
• Take ethanoic acid and sodium carbonate as an example:
2COOH + → 2 COONa + + O ...and the ionic equation is:
2H⁺ + CO3²⁻ → + O
• Take ethanoic acid and sodium hydrogencarbonate as an
example: COOH + NaH → COONa + + O ...and the ionic
equation is: H⁺ + → + O
• This is a useful test to distinguish carboxylic acids from
alcohols and phenols. This is because alcohols and phenols
are not acidic enough to react with these.
 Reactions of carboxylic acids
Step 1
• In the first step, the ethanoic acid takes a proton
(a hydrogen ion) from the concentrated sulfuric
acid .
Step 2
The positive charge on the carbon atom is
attacked by one of the lone pairs on the oxygen of
the ethanol molecule.
 Reactions with metals
• Carboxylic acids react with the more reactive
metals to produce a salt and hydrogen.
 Reaction with carbonates and hydrogen
carbonates
• Carboxylic acids react with both carbonates
and hydrogen carbonates to give salts, carbon
dioxide and water.
 4.7.2 Esters and amines
• interpret and use the general, structural (condensed / semi-
structural and displayed) and skeletal formulae of the amines
(primary only) and esters
• recall and use systematic nomenclature of esters and amines,
with chain length up to six carbon atoms, including:
– using the parent alcohol and carboxylic acid to name esters e.g. methyl
ethanoate.
– naming amines, e.g. 2-aminobutane
• deduce the molecular formulae of esters and amines (primary
only) given their structural or skeletal formula
• describe the acid and base hydrolysis of esters and draw the
structure of the hydrolysis of the products of any ester given
• explain why esters are used as solvents, perfumes, flavourings
 What are esters?
• Esters are derivatives of carboxylic acids. In an
ester, the hydrogen from the -COOH group of
carboxylic acid is replaced by an alkyl group.
• The alkyl group came from the alcohol.
• Esters have the functional group R-COO-R.
 Some common esters and their naming
Note that the name of an ester is 'alcohol + carboxylic acid'.
 What are amines?
• Amines are compounds with the functional group
– represented as R-
• To name an amine, name the alkyl group and add
amine, giving alkyl amine.

Examples:
• = methyl amine
• = dimethyl amine
• = ethyl methyl amine
Formulae of the amines (primary
only) and esters
 Hydrolysis of esters
• Hydrolysis is a reaction in which water is
added.
 Uses of esters
• Perfumes – they are volatile, when applied to the
skin, the heat from the skin helps them evaporate
and spread the nice fragrance around the room
• After shaves
• Food additives e.g. fizzy drinks, cakes, biscuits etc
due to solubility
• Glues – they are used as a solvent in glues, when
applied, the ester evaporates, leaving the sticky
glue behind, the smell we get when applying glue
is the smell of an ester
• Plasticisers, used to soften plastics such as PVCs
Organic synthesis
 reactant reaction conditions product
alcohol aldehyde
(primary alcohol,
1) distillation, heat

aldehyde carboxylic acid

reflux, heat

alcohol ketone
(secondary alcohol,
2) reflux, heat

alcohol concentrated or alkene

concentrated
heat
alkene steam (hydration reaction) alcohol
catalyst
pressure 60 atm
temperature 300
alcohol NaX (X = halide) halogenoalkane
concentrated
at room temperature

halogenoalkane warm NaOH, O, reflux alcohol

alkene HX (X = halide) halogenoalkane
at room temperature

alkene (X = halogen) dihalogenoalkane

alkene alkane
nickel catalyst
150

alkane (X = halogen) halogenoalkane

UV light
End of topic activity