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Benzene
Benzene, C6H6, consists of a sigma-bonded
framework of carbon and hydrogen atoms.
Above and below the plane of atoms is a bond,
which consists of a delocalised electron cloud.
The Kekul structure of benzene assumes that all
the bonds are localised i.e. cannot move. However,
evidence to support the delocalised form of benzene
comes from bond lengths, enthalpy change of
hydrogenation and resistance to reaction.
Electrophiles (accept lone pair of electrons) can
attack a benzene ring usually resulting in an
electrophilic substitution process as a mechanism
for a reaction.
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Phenols
Phenol has the molecular formula C6H5OH. It is
used in the production of plastics, antiseptics,
disinfectants and resins for paints.
Phenol reacts with:
a) alkalis to form sodium phenoxide (a salt) and
water
b) sodium to form sodium phenoxide and
hydrogen.
Phenol reacts rapidly with bromine to form 2,4,6tribromophenol and hydrogen bromide. This
reaction is faster than with benzene because the
oxygen lone pair of electrons in phenol overlaps
with the system on the ring, increasing its
electron density and facilitating electrophilic attack.

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Reactions of benzene
Benzenes chemical reactions tend to have a high
activation energy due to the delocalised -electron
system.
Benzene can react with the following:
a) concentrated nitric acid in the presence of
concentrated sulfuric acid to form nitrobenzene
b) a halogen in the presence of a halogen carrier to
form a mono-halogenated benzene compound
e.g. chlorobenzene or bromobenzene. This
reaction is slower than with cyclohexene due to
the enhanced thermodynamic stability provided
by the delocalised electron system in benzene.

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Tests for carbonyl compounds
2,4-dinitrophenylhydrazine (2,4-DNP/2,4-DNPH/
Bradys reagent) is used to detect the presence of
the >C=O group in aldehydes and ketones if
present, an orange precipitate is formed.
The precipitate may be recrystallised in ethanol and
its melting point measured this information may
then be used to determine the identity of the original
molecule.
Tollens reagent (ammoniacal silver(I) nitrate) is
used to detect the presence of an aldehyde group. A
silver mirror is formed on warming the aldehyde with
Tollens reagent and a carboxylic acid is also
formed. There is no reaction with ketones.

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Carboxylic acid and esters
Carboxylic acids contain the COOH group. This
group is highly polar, and that is why carboxylic acids:
a) have higher melting and boiling points than
expected hydrogen bonding between
molecules
b) are water-soluble hydrogen bonding between
carboxylic acid and water molecules.
Carboxylic acids are weak acids and will react with
reactive metals, metal oxides (and hydroxides) and
metal carbonates to form carboxylate salts containing
the COO ion.

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Carbonyl compounds
Carbonyl compounds include aldehydes and ketones.
Aldehydes can be oxidised in the presence of acidified
potassium dichromate(VI) to form carboxylic acids.
The orange dichromate(VI) ion is reduced to the green
chromium(III) ion.
Ketones cannot be oxidised under these conditions.
Aldehydes can be reduced using sodium borohydride
to form primary alcohols.
Ketones can be reduced using sodium borohydride to
form secondary alcohols.

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Reactions of carboxylic acids
Carboxylic acids react reversibly with alcohols, in
the presence of an acid catalyst, to form esters
used in perfumes and flavourings.
Esters may be hydrolysed in the presence of:
a) hot alkalis to form the corresponding alcohol
and the carboxylate salt
b) hot acids to form the corresponding alcohol
and the carboxylic acid.
Fats and oils are naturally occurring esters. The
fatty acid part of the molecule may be either:
a) saturated or
b) unsaturated can be either cis or trans.

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Amines
Amines are molecules containing a nitrogen atom
e.g. the primary amine functional group NH2.
Amines are bases since they can accept a proton by
using the lone pair of electrons on the nitrogen atom.
Amines react with acids to form salts.

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Amino acids
The general formula for an -amino acid is
RCH(NH2)COOH.
As an amino acid has both an acidic group (COOH)
and a basic group (NH2), it can act as both an acid
(proton donor) and a base (proton acceptor).
At a certain pH known as the isoelectric point, a
zwitterion forms. This contains the NH3+ group and
the COO group in the same molecule.
Amino acids polymerise to form proteins while
proteins can undergo hydrolysis to form -amino
acids.

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Optical isomerism
Optical isomers are non-superimposible mirror images
about an organic chiral centre four different groups
attached to a carbon atom.
When a chiral molecule is synthesised in the
laboratory, usually many optical isomers can form.
However, if an enzyme is involved in the synthesis,
normally only one optical isomer forms.
If pharmaceutical products contain only one optical
isomer the possibility of side effects is reduced and the
pharmacological activity is improved.
Separating optical isomers is expensive, so chiral
synthesis producing just one isomer is better.

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Condensation polymers
Examples of condensation polymers are polyesters
(e.g. Terylene) and polyamides (e.g. nylon-6,6).
When a condensation polymer is formed, a small
molecule such as water or hydrogen chloride is also
formed.
Terylene is made from benzene-1,4-dicarboxylic acid
and ethane-1,2-diol.
Nylon-6,6 is made from 1,6-diaminohexane and
hexane-1,6-dicarboxylic acid.
Kevlar is a special type of nylon that is made from
benzene-1,4-diamine and benzene-1,4-dicarboxylic
acid.

Aliphatic amines may be prepared by the substitution


of halogenoalkanes with excess ammonia.
Aromatic amines can be prepared by reducing
nitroarenes with tin and concentrated hydrochloric
acid.
Azo dyes are made by reacting an aromatic amine
with nitrous acid and then phenol in alkali.

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Hydrolysis and degradable polymers
Condensation polymers have chemical groups that are
vulnerable to chemical attack from either acids or
alkalis polyesters (ester group) and polyamides
(amide group). This process is known as hydrolysis
and results in the breakdown of the polymer.
Disposing of polymers is an environmental problem.
Scientists are working to develop degradable polymers
similar in structure to poly(lactic acid).
Condensation polymers may photodegrade as the C=O
bond absorbs radiation.

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Synthetic routes
Novel, useful molecules can be synthesised using
organic chemistry.
A chiral molecule is more difficult to synthesise since
many other optical isomers may also form costly in
money and time to separate or resolve the isomers.
Enzymes, bacteria, chiral catalysts and chiral-starting
points (e.g. L-amino acids) are used to promote the
formation of one chiral product.
The chemical reactions you study during your A level
chemistry course may be used to suggest how a
target molecule can be synthesised, starting with a
particular organic molecule.

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Types of chromatography
Chromatography is an analytical technique that
separates components in a mixture between a mobile
phase and a stationary phase.
The mobile phase may be a liquid or a gas.
The solid phase may be:
a) a solid (as in thin-layer chromatography(TLC)) or
b) a liquid or a solid on a solid support (as in gas
chromatography (GC)).
The Rf value measures the ratio of the distance moved
by the solute to the distance moved by the solvent.
GC does have limitations e.g. similar compounds
have similar retention times.

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Proton NMR spectroscopy
In NMR, protons (hydrogen atoms) in a sample absorb
and emit low-energy radiowave radiation in the
presence of a powerful magnetic field.
The number of peaks gives information about the
number of proton environments.
The area under each peak gives information about the
number of hydrogen atoms in each environment.
Their horizontal position in a spectrum gives the
chemical nature of each proton region.
Protons that are adjacent to unequivalent protons may
be split into more peaks, where n+1 gives the number
of splits (if adjacent to n hydrogen atoms).

Combining mass spectrometry with


chromatography
Mass spectrometry (MS) can be combined with
chromatography:
a) to provide a far more powerful analytical tool
than using chromatography alone
b) to generate mass spectra that can be analysed
or compared with a spectral database by a
computer for positive identification of a
component.
GCMS can be used in analysis (e.g. in forensics),
environmental analysis, airport security and space
probes.
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Carbon-13 NMR spectroscopy
The number of peaks in a carbon-13 spectrum is the
same as the number of different carbon
environments.
The relative position of each peak on the horizontal
axis (the chemical shift) suggests the chemical
environment of a particular carbon atom.
This means it is possible from the carbon-13
spectrum alone to suggest the likely structure of a
molecule by counting the number of peaks and
deducing the chemical nature of the bonded atoms to
each carbon.

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Rate graphs and orders
Rate of reaction is defined as the rate of change of
concentration with time and has units of moldm3s1.
When a graph is plotted of concentration against time,
a characteristic shape is formed depending on the
order of the reactant:
a) Zero order a straight line of decreasing value.
b) First order the rate is directly proportional to the
concentration (exponential decay curve).
c) Second order the rate is proportional to square
of the concentration (half-life increases with time).
When rate is plotted against concentration:
a) Zero order a horizontal line is formed
b) First order a sloping straight line through the
origin.
c) Second order the rate vs. concentration graph
is not a straight line.

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Rate equations
The rate equation summarises the link
between the rate of reaction and the concentrations
of the reactants raised to their appropriate powers
(orders).
The constant of proportionality in the
equation is called the rate constant its units
depend on the overall order of the process.
The rate determining step in a
mechanism is the slowest step it will always
consist of chemicals that are also involved in the
rate equation (as non-zero powers).
Zero-order species is not involved in
the slowest step of the mechanism.

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BrnstedLowry acids and bases
BrnstedLowry acids are proton donors.
BrnstedLowry bases are proton acceptors.

A weak acid e.g. ethanoic acid dissociates in water


to form a strong conjugate base:
CH3COOH(aq) + H2O(l) CH3COO(aq) + H3O+(aq)
A strong acid forms a weak conjugate base e.g. HCl
forms the weak conjugate base, Cl.

The acid dissociation constant, Ka, is an


equilibrium constant that can be written for any
weak acid.
The term pKa = log10Ka.

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Chemical equilibrium
Chemical equilibrium is a special state that is
achieved when the forward and reverse processes in
a closed system are occurring at an equal rate.
An equilibrium constant, Kc, may be written:
for aA + bB cC + dD
Kc =
[C]c [D]d
[A]a [B]b
Kc therefore has units that depend on the reaction
being considered.
Changing the temperature will affect Kc but how it
changes depends on the enthalpy change of the
forward reaction.
For example, if the forward reaction is exothermic the
value of Kc decreases with increasing temperature.
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pH
pH is defined as log10[H+(aq)] (or log10[H3O+]).
Rearranging this equation gives [H+] = 10pH.
The ionic product of water, Kw, is equal to
[H+(aq)] [OH(aq)] and its value at 298K is
1014mol2dm6.
The pH of a strong acid may be calculated by using pH
= log10[H+] where complete dissociation is assumed.
The pH of a strong base is calculated by first finding
[H+] from Kw = [H+] [OH] knowing [OH], from the
concentration of the solution, and Kw (if at 298K).

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Buffers
A buffer is defined as a system that minimises pH
changes when small amounts of an acid or a base
are added.
An acid buffer (pH less than 7) is usually a mixture of
a weak acid and the sodium salt of that weak acid
e.g. ethanoic acid and sodium ethanoate.
When acid is added to a buffer, the strong conjugate
base reacts with the excess acid thereby reducing
its impact.
Both carbonic acid and hydrogencarbonate are found
in blood and help control its pH.

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BornHaber cycles
Lattice enthalpy is defined as the enthalpy change
when one mole of an ionic compound is formed from
its constituent gaseous ions under standard conditions.
The lattice enthalpy for a compound is determined by
constructing a BornHaber cycle.
The enthalpy of solution of a compound depends on:
a) lattice enthalpy (must be overcome so requires
energy input) and
b) hydration enthalpy of the ions formed
(exothermic).
Lattice and hydration enthalpies both depend on the
ionic charges and radii.

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Entropy
Entropy, S, is a measure of the disorder of a system.
A system becomes more energetically stable when it
becomes more disordered.
Solids have a relatively low entropy compared with
liquids and especially gases. This is because solids
have more order to their structure.
When a solid dissolves, entropy increases the
system is becoming more disordered.
In a reaction in which more gas molecules are
formed than are consumed, the entropy will increase
the system is becoming more disordered.

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Free energy change
Free energy change, G, is a measure of the energy
available during a process that can be useful.
The more free energy, the more spontaneous the
process.
G must be negative for a reaction to be spontaneous.

If G is positive, the reaction will not be spontaneous


i.e. it will not happen on its own.
The equation G = H TS relates free energy
change to the reaction enthalpy and the entropy
change of the system.
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Redox reactions
A redox reaction is one involving oxidation (loss of
electrons) and reduction (gaining electrons).
Half-equations may be written that summarise the
two processes taking place. For example, in the
reaction between iron and chlorine gas:
a) Fe Fe3+ + 3e an oxidation
b) Cl2 + 2e 2Cl a reduction.

Oxidation numbers are the formal charges on a


bonded atom and can be assigned whether the
bonding is covalent or ionic. In the reaction above:
a) The oxidation number of iron changes from 0 to
+3.
b) Chlorines oxidation number, however, changes
from 0 to 1.

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Electrode potentials
An electrode potential indicates the observed potential
when the appropriate half cell is connected to the
standard hydrogen electrode, and is measured in volts.
The standard hydrogen electrode is arbitrarily assigned
the value zero volts.
Electrode potentials for two half-equations combine to
give the cell potential for the overall process.
The half cell with the more positive electrode potential
will be reduced in the overall cell reaction.
However, cell potentials do not indicate whether a
reaction takes place at an appreciable rate, and
standard electrode potentials apply only to standard
concentrations.

29 Storage and fuel cells


A fuel cell uses the energy from the reaction
between a fuel and oxygen to create a voltage.
The hydrogenoxygen fuel cell is important:
a) Hydrogen is oxidised in the electrochemical
process it loses electrons.
b) Oxygen is reduced it gains electrons.
The two half cells are then connected so that an
electrical current may flow.
Fuel cell vehicles (FCVs) are being developed to be
fuelled by hydrogen or hydrogen-rich fuels.
FCVs have advantages over petrol- or dieselpowered vehicles less pollution and greater
efficiency.

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Transition metals
Transition metals are found in the d-block of the
periodic table.
They form one or more ions that have a partially filled
d-orbital.
They also:
a) form coloured ions
b) have variable oxidation states on their ions
c) form complexes
d) often have catalytic properties.
Ions can react with sodium hydroxide solution to form
metal hydroxide precipitates of certain colours: Fe 2+
green; Fe3+ brown; Cu2+ light blue; and Co2+ blue.

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Complexes
Transition metal ions may bond with ligands to form
complexes.
Ligands are species that may donate a lone pair to
form a dative bond with a transition metal.
Ligands may be able to donate:
a) one lone pair per ligand monodentate ligands
b) two lone pairs per ligand bidentate ligands.
Complexes are able to exhibit: structural;
geometrical; and optical isomerism.
Cis-platin is a complex used in the treatment of
cancer

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Transition metal complexes
A ligand substitution is a process in which one ligand
bonded to the complex is swapped or substituted for
another.
A stability constant, Kstab, may be written for a complex.
The greater its value, the more energetically stable the
complex relative to its constituent ions, and vice versa.
Manganate(VII) ions in acidic conditions may be used
to determine the concentration of solutions containing
iron(II) ions.

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