OCR (B) Chemistry A-level

Storyline 5: What’s in a Medicine?

Detailed Notes

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Organic Functional Groups and Reactions

Carboxylic Acids
Carboxylic acids are organic compounds containing the functional group -COOH, made of a
carbonyl group (C=O) and an -OH acid group. When naming carboxylic acids, the suffix -anoic
acid is used. For example, a carboxylic acid containing a chain of four carbon atoms would be
called butanoic acid.

Example: The displayed structure of ethanoic acid.

Esters
Esters have the functional group -COO-. They are named after the alcohol and carboxylic acid
from which they are formed. For example, the ester formed from methanol and propanoic acid is
methyl propanoate and the ester formed from butanol and ethanoic acid is butyl ethanoate.

Example: The displayed structure of methyl ethanoate.

Aldehydes
Aldehydes are produced from the oxidation and distillation of primary alcohols. Aldehydes have a
carbonyl group at the end of the carbon chain (the carbonyl group is only attached to one other
carbon atom). This gives them the functional group -CHO.

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Ketones
Ketones also contain the functional group -C=O, a carbonyl group. They are produced from the
oxidation of secondary alcohols with acidified potassium dichromate(VI). Ketones have a
carbonyl group in the middle of a carbon chain (the carbonyl group is attached to two other
carbon atoms).

Acid Anhydrides
Acid anhydrides are identified by their functional group -COOCO-, which consists of two carbonyl
groups joined by an oxygen atom.

Ether
Ethers are identified by their functional group -O-, which consists of two alkyl chains connected to a
single oxygen atom.

Alcohols
Alcohols contain an -OH group and have the general formula CnH2n+1OH. They can be produced
via methods of fermentation or hydration. Alcohols are named according to IUPAC rules and have
the suffix -ol. Alcohols can be primary (1o), secondary (2o) or tertiary (3o), depending on the
position of the hydroxyl group.

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Phenols
Phenols are organic compounds containing a benzene ring with an OH alcohol group. This
makes them aromatic alcohols. Phenols are weak acids. They can be neutralised in a reaction
with NaOH but will not react with carbonates.

Phenols can be identified by using neutral iron(III) chloride solution (ferric chloride). When phenol
is present, an intense purple solution forms.

Production of Esters from Phenol and Acid Anhydride

Phenol reacts like an alcohol to produce an ester, this reaction often requires heating. The
reaction would occur faster with acyl chloride than an acid anhydride.

A similar reaction to the one shown above is used in the manufacture of aspirin.

Esterification
Carboxylic acids can react with alcohols in the presence of a strong acid catalyst (like
concentrated sulfuric acid) to form esters. Concentrated sulfuric acid is often used as the acid
catalyst. This reaction is called esterification and is carried out under reflux conditions.

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Example:

A method for remembering the reaction: Remove the -OH from the acid and the hydrogen
from the alcohol to make water. Then join the acid and alcohol together.

Esters are sweet-smelling compounds used in food flavourings and perfumes. They have low
boiling points and make good solvents for polar molecules.

Acid anhydrides can also be used to esterify alcohols. This occurs in an addition-elimination
mechanism. Acid anhydrides react less vigorously than acyl chlorides and do not produce toxic
HCl as a side product. As a result, they are often preferred as a reagent in esterification.

Oxidation of Alcohols
Primary and secondary alcohols can be oxidised to produce various products but tertiary
alcohols are not easily oxidised.

When primary alcohols are heated in the presence of acidified potassium dichromate(VI), they
are oxidised to aldehydes. Distillation is required to separate the aldehyde product.

Example: Oxidation of ethanol to ethanal

When an aldehyde is heated further with acidified potassium dichromate(VI) under reflux
conditions, the aldehyde is oxidised to a carboxylic acid. Primary alcohols are oxidised to
aldehydes and then to carboxylic acids.

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Example: Oxidation of ethanal to ethanoic acid

Secondary alcohols can be oxidised to ketones when heated in the presence of acidified
potassium dichromate(VI).

Example: Oxidation of propan-2-ol to propanone

Potassium Dichromate(VI) (K2Cr2O7)

Potassium dichromate(VI) is used as an oxidising agent in the oxidation of alcohols. As the
alcohol is oxidised, potassium dichromate(VI) is reduced. This reduction is observed as a colour
change from orange to green, which indicates the alcohol has undergone oxidation. The colour
change occurs due to the change in oxidation state of the chromium ion.

Example:

Elimination Reactions
Elimination - a small molecule is removed from a larger molecule, often forming a double bond.

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Alkenes can be formed from the dehydration of alcohols, where a molecule of water is removed
from the molecule. In order to do this, the alcohol is heated under reflux with concentrated
sulfuric acid, or heated using Al2O3.

Substitution Reactions
Alcohols can react with halogenating agents via nucleophilic substitution. The -OH group is
replaced by a halogen, producing a haloalkane.

A reaction mixture of concentrated sulfuric acid and potassium bromide can be used to produce
bromoalkanes. The potassium bromide reacts with the sulfuric acid to form HBr. This then reacts
with the alcohol to produce the bromoalkane.

CH3CH2OH + HBr → CH3CH2Br + H2O

Techniques and Procedures for making a Solid Organic Solvent

Filtration Under Reduced Pressure

This method of filtration is faster than gravity filtration due to the solvent and air being pulled
through the filter paper.

Diagram: Vacuum filtration apparatus

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Recrystallisation
Recrystallization is a method of purifying an impure compound using a solvent. This method
relies on the fact that the solubility of most organic solids increases with temperature. To
complete recrystallization an impure solid is dissolved in a minimum amount of a hot solvent, as
the solution is cooled the solubility of the solid decreases and the crystals will form.

The solvent used will need to dissolve the solid being purified when hot but not when cold.

Melting Point Determination

The melting point of an organic solid can be found by heating up a sample in a capillary tube,
where the change of state can be observed.

Diagram: Melting point apparatus

Thin-Layer Chromatography (TLC)

In TLC chromatography, a metal plate is coated with a thin layer of silica and the sample being
analysed is dotted on the plate. These initial samples must be placed above the level of the solvent
in the container.

The solvent is then allowed to move up the plate, separating the substances within the sample.
The plate is taken out of the container and the solvent front is marked in pencil when it is roughly
1 cm from the top of the plate. This is the distance that the solvent has traveled - this value is
needed for Rf value calculations.

The plate is then dried in a fume cupboard to reduce toxic fumes. The chemical traces can then
be viewed using a UV lamp and the distances travelled by the separated substances can be
measured. Alternatively, a developing agent can be added, such as iodine, to allow the
colourless traces to be seen by the naked eye.

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Diagram: TLC plate and TLC plate apparatus

Techniques and Procedures for Preparing and Purifying a Liquid

Organic Product

Heating under Reflux

Reflux apparatus is used to continually heat the contents of the flask to allow reactions like the
oxidation of primary alcohols to proceed all the way to the formation of carboxylic acids. The
condenser helps ensure the vapours condense and return to the flask for further heating. This
ensures the product vapours do not escape.

Distillation
Distillation apparatus is used to separate liquids with different boiling points. The
round-bottomed flask is heated and the liquid with the lower boiling point will evaporate first. It
rises out of the flask and into the attached tubing which is surrounded by a condenser. The
condenser causes the vapour to cool and condense back into a liquid, which is then collected in a
separate flask.

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Diagrams: Reflux apparatus (left) and distillation apparatus (right)

Separating Funnel
A separating funnel is used to separate two liquids with different densities. The mixture is added
to the flask, and then the flask is stoppered and inverted to mix the contents. The liquids are
allowed to separate into two layers. The tap can then be opened to collect the bottom, denser
liquid in one flask and the second, less dense liquid in a second flask. Usually, these layers will be
distinguished to be an aqueous and an organic layer.

Diagram: Separating funnel

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Green Chemistry
Green chemistry has the aim of reducing the impact of chemistry on human health and the
environment by using alternative environmentally-friendly reactions, such as ones that require
lower temperatures. They often try to follow the ‘12 Principles of Green Chemistry’, for example
choosing a reaction with an efficient atom economy, using a catalyst to reduce reaction
temperatures and reducing the production of pollutants.

Modern Analytical Techniques - Mass Spectrometry

This is an analytical technique used to identify different molecules and find their relative
molecular mass. During mass spectrometry, a vaporised sample (atoms or molecules) is ionised
to form positive ions. The ions are then accelerated, deflected by a magnetic field and detected. A
graph is produced with the mass to charge ratio (m/z) on the x-axis and relative abundance on
the y-axis.

Example:

The M+ Peak
The molecular ion peak (M+) is the peak with the greatest mass to charge ratio. The molecular
mass (Mr) of a compound is equal to the m/z value of this peak. This is the peak that is furthest to
the right on the spectrum. Other techniques can be used to determine the empirical formula, then
scaled up to the Mr value from mass spectrometry to give the molecular formula.

The M+1 Peak

The M+1 peak is a small peak which is 1 unit to the right of the molecular ion peak. This is caused
by the presence of the 13C isotope (the relative abundance of 13C is 1.11%). 13C has one more
neutron than 12C meaning that the relative formula mass is increased by 1.

Fragmentation
Fragment ions are formed when an unstable molecular ion breaks up into a positive ion and an
uncharged free radical (a species which contains an unpaired electron):
M+ → X+ + Y●

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Only charged particles are detected so the free radical (Y●) will not produce a line on the
spectrum. Each line on the mass spectrum represents a different fragment ion. Fragments can
also help to deduce the structure of the compound.

Modern Analytical Techniques - Infra-red Spectroscopy

When infra-red radiation is directed at a compound, specific frequencies are absorbed by bonds
in the molecule. The percentage transmittance of infra-red at each frequency is recorded by a
detector and then plotted on a graph.

Energy that is absorbed by the compound causes bonds to vibrate, meaning the bond stretches
or bends. The amount of vibration depends on the length of the bond and the mass of the atoms.

The peaks on an infra-red spectrum can be used to identify the functional groups present in a
molecule, as each bond absorbs a specific frequency of IR radiation. A peak can be compared
with known values from a databook to identify the bond.

The fingerprint region on an infra-red spectrum is the region (typically between 1500cm-1 and
500cm-1) that contains a complicated series of absorptions. Every compound has a unique
fingerprint region.

A spectrum is produced from the measurements which has characteristic curves for the different
functional groups:

-OH Alcohol Group

The characteristic peak is in the range 3230-3550 cm-1

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-OH Acid Group

The characteristic peak is in the range 2500-3300 cm-1

C=C Unsaturated Group

The characteristic peak is in the range 1620-1680 cm-1

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C=O Carbonyl Group

The characteristic peak is in the range 1680-1750 cm-1

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