Edexcel Chemistry Unit 5 – Notes on the Specification

By George Lewis

Yellow highlighting shows points from the specification

Redox and the chemistry of the transition metals

1 Application of redox equilibria

a) Demonstrate an understanding of the terms ‘oxidation number’, ‘redox’, ‘half-

reactions’ and use these to interpret reactions involving electron transfer
Rules for assigning oxidation number:
1 – Oxidation number for an un-combined element is 0.
2 – The sum of the Oxidation numbers in a compound is equal to the overall charge.
3 – Group 1 compounds are +1 & group 2 are +2.
4 – F is always -1 in a compound. And Cl is usually -1 except when it’s with O or F.
5 – H is +1 (except metal hydrides) and O is -2 (except Peroxides).

Redox is any reaction which involves one species being oxidised (loss of electrons)and another being
reduced (gain in electrons).

Half Equations are used to show which species is oxidised and which is reduced.

b) Relate changes in oxidation number to reaction stoichiometry

The number of electrons transferred in a reaction must always be the same on each side so by using
half equations you can split it up, eg the reaction between chloride ions and chromium (III) ions:
Cl-(aq) → Cl2(g) + 2e- x3 to make the electrons balance
3+ -
Cr (aq) + 3e → Cr(s) x2 to make the electrons balance
So this gives the overall equation:
2Cr3+(aq) + 6Cl-(aq) → 2Cr(s) + 3Cl2(g)

c) Recall the definition of standard electrode potential and standard hydrogen

electrode and understand the need for a reference electrode
Standard electrode potential ( E ) of a half cell is the emf measured when the half-cell is coupled to
a hydrogen electrode under standard conditions.
Standard electrode potentials always use a salt bridge soaked in Potassium Nitrate to connect the
two half cells.

An electrochemical cell can be represented like this:

LH Electrode |LH Electrolyte ¦¦ RH Electrolyte | RH electrode
- The double dotted line in the middle represents the salt bridge
- The standard Hydrogen electrode is always on the left.
- With multiple ions in one segment, the more oxidised ones are put
closer to the salt bridge, for example: Pt|2I -, I2¦¦……

The standard Hydrogen electrode must have:

- Hydrogen gas at 1 atm of pressure
- 298 K
- A Platinum electrode
- A 1 moldm-3 solution of H+(aq) ions from HCl.
d) Set up some simple cells and calculate values of Ecell from standard electrode
potential values and use them to predict the thermodynamic feasibility and extent of
reactions

To work out Ecell:

If given an overall reaction, look up the two half equations that are involved.
Since the values in the data book always show reduction, the species in the overall reaction which is
going in the same direction as its half equation is the one being reduced, so you leave its Ecell value
as it is.
The species in the reaction which is going the other way round in its half equation will be the one
getting oxidised, so you have to flip the sign round for Ecell.
All you need to do then is just add the two values together to get the correct answer.
For example:
An overall equation is: 2Fe3++ 2I- → 2Fe2+ + I2
The two reduction half cells as given in the data book are:
Fe3+,Fe2+|Pt +0.77 I2 ,2I-|Pt +0.54
These represent the half equations:
Fe3++ e- → Fe2+ I2 +2e- → 2I-
Comparing these to the overall equation, the Iron half equation is 'the right way round' since it is being reduced but the
Iodine half equation is 'the wrong way round' since it should be getting oxidised, this means we change its value to -0.54
Now that the necessary changing has been done, you just need to add the two values together:
0.77 + (-0.54) = +0.23 V

The more positive Ecell is, the more likely the reaction is to occur. So Ecell can be used to predict
thermodynamic feasibility and the extent of reactions.
>-0.6 -0.1 0 +0.1 +0.6<
No rxn Mainly Equal Mainly Full rxn
Reactants Products

e) Demonstrate an understanding that Ecell is directly proportional to the total

entropy change and to lnK for a reaction
Ecell  ΔSTot  lnK

No Reaction Mainly Equal Mainly Full Reaction

Reactants Proportions Products
Ecell <-0.6 -0.6 to -0.1 -0.1 to 0.1 0.1 to 0.6 0.6<
ΔEntropy Very negative -ve (not Around 0 +ve Very positive
spontaneous) (spontaneous)
K <1x10-10 - Around 1 - 1x1010<

f) Demonstrate an understanding of why the predictions in d) may not be borne out

in practice due to kinetic effects and nonstandard conditions
Limitations of Ecell:
- Ecell doesn’t account for kinetic stability. For example if a reaction has very high activation energy,
it may be feasible but occur at an unobservable, slow rate.
- Actual conditions may be different to the standard conditions.
- Electrode potentials apply only to aqueous equilibria so it can’t be used for lots of reactions.

g) Carry out and evaluate the results of an experiment involving the use of standard
electrode potentials to predict the feasibility of a reaction, eg interchange of the
oxidation states of vanadium or manganese
Oxidation states of Vanadium: Oxidation states of Manganese:
Species Oxidation no. Colour Species Oxidation no. Colour
V2+ +2 Purple Mn2+ +2 Pale Pink
V3+ +3 Green MnO2 +4 Black
VO2+ +4 Blue MnO4- +7 Purple
VO2+ +5 Yellow

h) Demonstrate an understanding of the procedures of the redox titrations below (1

and 2) and carry out a redox titration with one:

1 - Potassium manganate(VII), eg the estimation of iron in iron tablets

MnO4-(aq) is purple and Fe2+(aq) is colourless (But when concentrated, MnO4-(aq) is pale pink and Fe2+(aq)
is pale green). At the end point, the solution will turn pale pink by itself. So this is a self-indicating
reaction.

2 - Sodium thiosulfate and iodine, eg estimation of percentage of copper in an alloy

Throughout the titration, I2 slowly turns from Brown to colourless I-. To clearly see the change, starch
is added near the end when the solution is pale yellow (otherwise Iodine is adsorbed onto it and
reduces accuracy) and will turn from blue-black to colourless.

A third example: Potassium manganate (VII) with ethanedioic acid

This reaction is an example of autocatalysis. The reaction is
catalysed by manganese (II) ions. So at the start there are none so
it goes slow and needs heating. But then once a few have been
produced, they will begin to catalyse it and the reaction goes
faster and faster. (This is shown in the graph).

i) Discuss the uncertainty of measurements and their implications for the validity of
the final results
Level of accuracy in a burette is ±0.05 cm3
When working out percentage of uncertainty in the reading, it has to be multiplied by two since you
read the burette once at the start and once at the end of the titration:
0.05
% uncertainty in a burette = 2 × × 100
𝑉𝑜𝑙𝑢𝑚𝑒 𝑀𝑒𝑎𝑠𝑢𝑟𝑒𝑑
Uncertainty in the readings can make the results less reliable.

j) Discuss the use of hydrogen and alcohol fuel cells as energy sources, including the
source of the hydrogen and alcohol, eg used in space exploration, in electric cars
Hydrogen Fuel cell:
Electrons are released at the hydrogen electrode and are used at the oxygen
electrode. The P.D. set up pushes the electrons into an external circuit.
LHS: 2H2(g) → 4H+(aq) + 4e-
RHS: O2(g) + 4H+(aq) + 4e- → 2H2O(l)
Overall: 2H2(g) + O2(g) → 2H2O(l)

Advantages:
- Hydrogen can come from the hydrolysis of water using a clean (non-fossil)
energy source.
- Hydrogen fuel cells don’t produce CO2 or nitrous oxides.

Disadvantages:
- Hydrogen is difficult to store.
Methanol Fuel Cell:
This uses a similar principle to the H fuel cell.
3
Overall: CH3OH(g) + 2O2(g) → CO2(g) + 2H2O(l)
Note: This occurs between 90 -120°C (BPT of CH3OH is 65°C).

Advantages:
- Ethanol/methanol can be obtained from biomass.
- It is easier to store than Hydrogen.

Disadvantages:
- Methanol is flammable and poisonous.
- It is less efficient than the hydrogen fuel cell since its proton membrane works less well.

Both of these processes are renewable unlike the extraction of fossil fuels.

k) Demonstrate an understanding of the principles of modern breathalysers based

on an ethanol fuel cell and compare this to methods based on the use of IR and to
the reduction of chromium compounds.
Dichromate (VI) breath analyser:
Any ethanol in the breath would be oxidised to ethanoic acid – reducing orange Potassium
dichromate(VI) to green Chromium(III). The colour change is detected by a meter which displays the
amount of alcohol present.

Fuel cell breathalyser:

Exhaled air goes in and any alcohol is oxidised by a piece of platinum to ethanoic acid, H+ & e-. The
Platinum electrodes are connected to an external ammeter; the more current generated, the more
alcohol is present.

IR spectroscopy and breath analysis:

IR radiation is passed through the sample and certain wavelengths are absorbed. The more
ethanol present in the sample, the greater the absorption peak will be. This gives the most
reliable results of the three.

Issues:
- Breath analysers must be calibrated regularly to be accurate.
- It is assumed the breath comes from deep within the lungs, but alcohol may have come
from mouth/throat etc. This means operators are trained to wait for at least 15-20 mins
before taking another reading.

2 Transition metals and their chemistry

a) Describe transition metals as those elements which form one or more stable ions
which have incompletely filled d orbitals
A transition metal is an element which can form at least one stable ion that has an incomplete d
orbital.

b) Derive the electronic configuration of the atoms of the d-block elements (Sc to
Zn) and their simple ions from their atomic number
Ar = 1s22s22p63s23p6
Sc = [Ar] 4s23d1 +3
Ti = [Ar] 4s23d2 +4, +3, +2
V = [Ar] 4s23d3 +5, +4, +3, +2, +1
Cr = [Ar] 4s13d5 +6, +5, +4 +3, +2, +1
Mn = [Ar] 4s23d5 +7, +6, +5, +4, +3, +2, +1
Fe = [Ar] 4s23d6 +6, +4, +3, +2, +1
Co = [Ar] 4s23d7 +5, +4, +3, +2, +1
Ni = [Ar] 4s23d8 +4, +3, +2, +1
Cu = [Ar] 4s13d10 +2, +1
Zn = [Ar] 4s23d10 +2

Blue = Stable ion

Red = Unstable ion

Don’t forget the aufbau (building up) principle when working out electron configurations.

Note that Chromium and Copper break the trend by only having 1 electron in the 4s orbital. This is
because it is more stable to take the electron and make a half full/completely full 3d orbital.

Also remember that when forming an ion the d block elements lose their 4s electrons first.

c) Discuss the evidence for the electronic configurations of the elements Sc to Zn

based on successive ionization energies
Recap ionisation energy; First ionization energy is the energy required to remove the outermost
electron from one mole of gaseous atoms to produce 1 mole of gaseous ions with charge 1+. It is
affected by:
- Charge of the nucleus: The more protons in the nucleus, the more dense its positive charge is and
so the greater the attraction it will have on the electrons.
- Distance of electron from nucleus: The further away the electron is from the nucleus, the less
energy is required to move it away.
- Shielding: The more electrons there are between the outermost electron and the nucleus, the
easier it will be to remove.

On the whole though, the transition metals have fairly similar first ionisation energies all around
600/700 (increasing slightly from element to element).
But when looking at the successive ionisations for different metals you can see that there are larger
jumps between the 4s and 3d blocks than anywhere else, as would be expected. This is because the
outer 4s electron is far away from the nucleus and shielded lots but the 3d subshell is comparatively
stable and requires more energy to take away the electron.
Therefore after the first 2 electrons have been taken (or after the first one in Cr or Cu) there will be a
larger gap between the 2nd and third ionisation energies.

d) Recall that transition elements in general:

1 - Show variable oxidation number in their compounds, eg redox reactions of

vanadium
2 - Form coloured ions in solution

3 - Form complex ions involving Monodentate and bidentate ligands

Only larger molecules can act as polydentate ligands since:
- Even if a molecule has two lone pairs, only a longer will have them far enough apart to bond.
- The dative covalent bonds/lone pairs will be too close on a short molecule and repel.
- Bond angles will be too acute and put too much ring strain on the short molecule.

4 - Can act as catalysts both as the elements and as their compounds

e) Recall the shapes of complex ions limited to linear [CuCl2]-, planar [Pt(NH3)2Cl2],
tetrahedral [CrCl4]- and octahedral [Cr(NH3)6]3+, [Cu(H2O)6]2+ and other aqua
complexes

Ions like CuCl2 are linear:

Any complex ion with Platinum in is usually planar like Pt(NH3)2Cl2, note it can form stereoisomers:

Z E

Most other complex ions with 4 ligands like CrCl4- will be a tetrahedral shape:

Any hexa- complex ions will have an octahedral shape:

f) Use the chemistries of chromium and copper to illustrate and explain some
properties of transition metals as follows:
1 - The formation of a range of compounds in which they are present in different
oxidation states
Copper:
Chromium:

2 - The presence of dative covalent bonding in complex ions, including the aqua-ions
The bond between metal ions and ligands is a dative covalent bond. The ligand must have a lone pair
of electrons which it can donate.

3 - The colour or lack of colour of aqueous ions and other complex ions, resulting
from the splitting of the energy levels of the d orbitals by ligands
An isolated metal ion will have 5 d orbitals with equal energy in each. However, when it joins with
ligands, the orbitals closer to the ligands get more energy and so the d orbitals are split into different
levels. Some frequencies of light can then be absorbed to promote electrons in the d level. The
remaining light is then reflected with the complementary colour to what was absorbed. This is
Crystal Field Theory.

4 - Simple ligand exchange reactions

See f)1

5 - Relate relative stability of complex ions to the entropy changes of ligand

exchange reactions involving polydentate ligands (qualitatively only), eg EDTA
Polydentate ligands are more stable than Monodentate ligands since there is a large increase in
entropy of system when they replace other ligands since more molecules are given out (Chelate
Effect).

Note: For hexaaqua complexes, a higher overall charge indicates a lower pH. This is because the
higher charge draws more electrons density from the O-H bond towards it so they are more likely to
break and give H+ ions. For example [Cu(H2O)6]2+ has a higher pH than [Cr(H2O)6]3+.

6 - Relate disproportionation reactions to standard electrode potentials and hence to

Ecell
Disproportionation is when the same element is both oxidised and reduced in one reaction. Whether
or not this will occur can be predicted using Ecell values. For example:
Cu2SO4(aq)→Cu(s) + CuSO4(aq) Ecell=+0.37V
Ecell is positive so Cu(I) will disproportionate, this is expected since Cu(I) is comparatively unstable.

g) Carry out experiments to:

1 - Investigate ligand exchange in copper complexes
2 - Study the redox chemistry of chromium in oxidation states Cr(VI), Cr(III) and
Cr(II)
See f)1

3 - Prepare a sample of a complex, eg chromium(II) ethanoate

Cr2+ is usually unstable but can be stabilised in this complex. HCL reacts with Zn to make H which
reduces sodium dichromate (orange) to Cr2+ (blue). Then you allow a build-up of H to create enough
pressure to force the contents into a tube of sodium ethanoate. This gives a brick red precipitate of
Chromium (II) Ethanoate which can be filtered and dried in Nitrogen.

h) Recall that transition metals and their compounds are important as catalysts and
that their activity may be associated with variable oxidation states of the elements
or surface activity, eg catalytic converters in car exhausts
Transition metals make good catalysts since they have variable oxidation states: They lower the
activation energy for the reaction by providing an alternate mechanism. This means a greater
proportion of collisions are successful.
For a heterogeneous catalyst:
- Reactants are adsorbed onto the surface of the metal.
- They then react and desorb.
- The bonds in the reactants are weakened.
- The reactants may be oriented in a more favourable position.
- Reactants can migrate towards each other over the surface of the catalyst.
- This increases the likelihood of the reactants coming into contact.
- By adsorbing to the surface, more reactant molecules are in the same space.

For a homogeneous catalyst:

- Transition metals form variable oxidation states.
- They can donate and receive electrons.
- The energy differences between oxidation states are small.
If molecules that weren’t intended to react, bind with the catalyst, then it becomes poisoned and
doesn’t work as well.

i) - explain why the development of new catalysts is a priority area for chemical
research today and, in this context, explain how the scientific community reports
and validates new discoveries and explanations, eg the development of new
catalysts for making ethanoic acid from methanol and carbon monoxide with a high
atom economy (green chemistry)
Catalysts are good because they:
- Speed up chemical reactions (time & cost saving).
- Reduce the heat required to carry out a chemical reaction (energy & cost saving).
- Alter the balance of reaction products (less waste, less energy separating reaction products).
- Enable the use of more benign reaction conditions such as lower pressures (safer).
- Reduce the quantity of waste products such as organic solvents (cleaner, more environmentally
friendly).

j) Carry out and interpret the reactions of transition metal ions with aqueous sodium
hydroxide and aqueous ammonia, both in excess, limited to reactions with aqueous
solutions of Cr(III), Mn(II), Fe(II), Fe(III), Ni(II), Cu(II), and Zn(II)
Cr3+ Mn2+ Fe2+ Fe3+ Ni2+ Cu2+
Aqueous Violet/Green Pale pink Pale Blue- Yellow Green Blue
Green
Small amount of Blue Violet White Green Red Brown Green Blue
OH/NH3 Cr(H2O)3(OH)3 Mn(OH)2 Fe(OH)2 Fe(H2O)3(OH)3 Ni(OH)2 Cu(OH)2
(makes precipitates)
Excess OH (solutions) Green - - - - -
[Cr(H2O)2(OH)4]-
Excess NH3 Yellow - - - Lavender Deep Blue
(solutions) [Cr(NH3)6]3+ Blue [Cu(NH3)4(H2O)2]2+
[Ni(NH3)6]2+
( - means insoluble in excess)
Zinc is not a transition metal so even though it will form these complex ions; the precipitates are
white in colour and the solutions are colourless.

k) Write ionic equations to show the difference between amphoteric behaviour and
ligand exchange in the reactions in 5.3.2g
An amphoteric compound is one that can act as an acid or a base.
For example triaqua trihydroxo chromium (III) reacts with acids to give hexaaqua chromium (III) and
bases to give hexahydroxo chromium (III):
[Cr(H2O)3(OH)3] + [Acid] → [Cr(H2O)6]3+
[Cr(H2O)3(OH)3] + [Base] → [Cr(OH)6]3-

l) Discuss the uses of transition metals and/or their compounds, eg in polychromic

sun glasses, chemotherapy drugs.
Transition metals are useful as drugs for chemotherapy treatments:
- Platinum which when combined with other drugs can enhance their effects and reduce the serious
side effects which are produced otherwise.
- Gold nanoparticles can be used to deliver drugs specifically to the cancer. They can also be heated
up with lasers which help them to remove the cancer.

Transition metals are also used in photochromic sunglasses which rely on energy from sunlight to
move the equilibrium: Cu+(s) + Ag+(s) ⇌ Cu2+(s) + Ag(s)
Organic chemistry – arenes, nitrogen compounds and
synthesis

1 Arenes: benzene

a) Use thermochemical, x-ray diffraction and infrared data as evidence for the
structure and stability of the benzene ring Students may represent the structure of
benzene as or as appropriate in equations and mechanisms

Benzene is a colourless liquid with the formula C6H6.It has a ring of delocalised electrons in the
centre.

Thermochemical Evidence for Benzene

Theoretical Enthalpy change for the hydrogenation of benzene in the Kekulé structure would be 3x
the hydrogenation of cyclohexene; -360 kJmol-1. However, Benzene is actually more energetically
stable and the experimental value is -208 kJmol-1.
It’s less than expected since there are delocalised electrons around the ring in the π system.
This gives the molecule greater stability so more energy is needed to break the bonds and hence it’s
less exothermic.

Infrared Evidence for Benzene

An IR spectrum for benzene and cyclohexene shows that benzene is simpler, which can be explained
since benzene has more symmetry than cyclohexene.

X-Ray Diffraction Evidence for Benzene

X-ray diffraction is a method of measuring bond lengths. It shows C-C bonds to be 0.154 nm long and
C=C bonds to be 0.133 nm long. If the Kekulé structure was correct then you would expect 2
different bond lengths in benzene, however, there’s just one at 0.139nm.

Note: Benzene doesn’t decolourise bromine water which surprised Kekulé since he thought it had
double bonds in it. However, phenol does react with bromine water:

b) Describe the following reactions of benzene, limited to:

1 - Combustion to form a smoky flame

Due to the high carbon to hydrogen ratio in benzene, it burns with a smoky yellow flame.
2C6H6(l) + 15O2 → 12CO2(g) + 6H2O(l)

Treatment with:
2 - Bromine
Electrophilic substitution; Halogenation:
C6H6 + Br2 → C6H5Br + HBr (FeBr3 Catalyst)
FeBr3 polarises the Br2 molecule to make part of it δ+ so it acts as an electrophile. Electrons from
benzene attack the positive Br2 forming a weak intermediate where the benzene ring is partly
broken. Then electrons from the C-H bond regenerate the ring. So Br substitutes for H.
(Note: Type-Substitution, Mechanism: electrophilic).

3 - Concentrated nitric and sulphuric acids

Electrophilic substitution; Nitration:
Benzene and concentrated nitric acid react to make nitro benzene.
It requires conc. H2SO4 to catalyse the reaction and temperatures
below 55˚C (to stop multiple substitutions).
HNO3 +2H2SO4 ⇌ NO2+ + 2HSO4- + H3O+
The NO2+ then reacts with the benzene ring.

When phenol does this reaction, it only requires dilute nitric acid since it is more reactive.

4 - Fuming sulphuric acid

Electrophilic substitution; Sulphonation:
Fuming Sulphuric acid is concentrated H2SO4 that contains additional sulphur trioxide (an effective
electrophile) so it reacts with benzene better. It produces benzenesulphonic acid.
C6H6 + SO3 → C6H5(SO3H)

5 - Halogenoalkanes and acyl chlorides with aluminium chloride as catalyst (Friedel-

Crafts reaction)
Electrophilic substitution; Friedel-Crafts reaction:
Benzene reacts with a halogenoalkane for alkylation or acyl chloride for acylation. Both use an AlCl3
catalyst to form a carbocation, for example:
CH3CH2Br + AlCl3 → CH3CH2+ + AlCl3Br -
A new C-C bond can then be formed onto the benzene ring.

6 - Addition reactions with hydrogen

Hydrogenation:
When benzene is mixed with a Raney Nickel catalyst and Hydrogen at 150˚C it undergoes an addition
reaction to form cyclohexane.
C6H6 + 3H2 →C6H12

Halogen Addition:
Benzene undergoes rapid addition with bromine in the presence of UV light to form 1,2,3,4,5,6-
hexabromocyclohexane. It is a free radical reaction.
C6H6 + 3Br2 →C6H6Br6

7 - (Extra) explain why many of benzene’s reactions are substitution reactions

Benzene has delocalized electrons which stabilise its structure.
By partaking in substitution reactions rather than addition, it can maintain this stable structure.
Note that when reagents are added, they usually substitute into positions 2,4 & 6 of the benzene
ring.

c) Describe the mechanism of the electrophilic substitution reactions of benzene in

halogenation, nitration and Friedel-Crafts reactions including the formation of the
electrophile
See above mechanisms.

d) Carry out the reactions in 5.4.1b where appropriate (using methylbenzene or

methoxybenzene)
Methylbenzene and methoxybenzene are used as substitutes since Benzene itself is a carcinogen.

e) Carry out the reaction of phenol with bromine water and dilute nitric acid and use
these results to illustrate the activation of the benzene ring.
Phenol is a benzene ring with a hydroxyl group, it is a white solid. It will perform similar electrophilic
reactions to benzene but is more reactive since the benzene ring is activated: One lone pair from the
oxygen is drawn into the delocalised π electron system in the benzene ring which makes it more
electron dense. Therefore is a better target for electrophiles. The oxygen must be directly attached
to the benzene ring to have the greatest effect:

It is an acid but weaker than carbonic so it doesn’t react with carbonate.

Methyl groups can also activate benzene since methyl groups are electron donating.

2 Organic nitrogen compounds: amines, amides, amino acids and

proteins

a) Give examples of:

1 - Molecules that contain amine and amide functional groups

Amines:
Amides: Hydrazine:

2 - Amino acids
This is the general structure for Amino acids:
There are 20 which depend on what R is.
If R is… Name
H Glycine
CH3 Alanine
CH2OH Serine
CH2CH(CH3)2 Leucine

b) Describe and carry out, where appropriate (using butylamine and phenylamine),
reactions to investigate the typical behaviour of primary amines. This will be limited
to:

1 - Characteristic smell
Amines have a characteristic fishy smell.

2 - Miscibility with water as a result of hydrogen bonding and the alkaline nature of
the resulting solution
Small amines are miscible in water since they can form and accept
Hydrogen bonds. Longer amines have more electrons ∴ larger London
forces & ∴ are less soluble.

3 - Formation of salts
- Amines are Brønsted-Lowry bases, they act as proton acceptors. They form salts, for example:
CH3CH2NH2 + HCl → CH3CH2NH3+Cl-
They’re more basic than NH3 since alkyl groups donate electrons to increase the electron density of
the N lone pair. However, phenylamine is an even weaker base (higher pH) because the lone pairs
which would usually be donated to make it act as a base are taken up by the benzene ring.
So from most to least basic: CH3CH2NH2 > NH3 > C6H5NH2

4 - Complex ion formation with copper(II) ions

They can form complex ions with TM’s due to the lone pair of electrons on the Nitrogen, e.g. Copper
(II) with phenylamine: [Cu(C6H5NH2)2(H2O)4 ]2+(aq)

5 - Treatment with ethanoyl chloride and halogenoalkanes, eg making paracetamol

Amines are nucleophiles and so they react with Ethanoyl Chloride:
Ethanoyl chloride + ethylmethylamine

They can also attack halogenoalkanes:

Paracetamol
Paracetamol is made in 4 steps starting with phenol:
Step 1: Nitration. (Since it’s activated conc. H2SO4 & conc. HNO3 aren’t
needed. Just dilute H2SO4 & NaNO3).
Step 2: Fractional distillation separates 4-nitrophenol out.
Step 3: Reduction using NaBH4 to 4-aminophenol.
Step 4: Ethanoic anhydride (CH3CO.O.OCCH3) is added to make Paracetamol. No chiral centre
simplifies process. It’s an analgesic (painkiller).

c) Describe the reduction of aromatic nitro-compounds using tin and concentrated

hydrochloric acid to form amines
Nitrobenzene can be reduced to phenylamine using Tin & conc. HCl. The reaction is carried out using
reflux apparatus.
Sn(s) + 2HCl(aq) → Sn2+(aq) + 2Cl-(aq) + H2(g)
Sn2+ → Sn4+(aq) + 2e-
These tin(IV) ions then reduce the nitrobenzene:
C6H5NO2(l) + 6H+(aq) + 6e- → C6H5NH2(l) + 2H2O(l)
Steam distillation separates the phenylamine-water mixture. NaCl is added and the mixture goes
through a separating funnel. KOH is added and finally the product is distilled.

d) Describe and carry out, where appropriate, the reaction of aromatic amines with
nitrous acid to form benzenediazonium ions followed by a coupling reaction with
phenol to form a dye
Nitrous acid is made in situ since it’s so unstable:
NaNO2(aq) + HCl(aq) → NaCl(aq) + HNO2(aq) (Rxn under 5˚C)
At 5˚C, nitrous acid + phenylamine make:
C6H5NH2(aq) + HNO2(aq) + HCl(aq) → C6H5N+≡NCl-(aq) + 2H2O(l)
Above 5 ˚C will produce phenol but below there will not be enough energy to complete the reaction.
Benzodiazonium Chloride + phenol dissolved in alkali then makes:
C6H5N+≡NCl- + C6H5OH → C6H5N=NC6H5OH + HCl
This is a coupling reaction which produces the N=N bond which absorbs different light depending
what it’s joined to. This makes it a good dying agent.

e) Recall the synthesis of amides using acyl chlorides

Acyl Chloride and ammonia or carboxylic acid and ammonium carbonate will make an amide group.

f) Describe:
1 - Condensation polymerization for the formation of polyesters such as Terylene
and polyamides such as nylon and Kevlar
Condensation polymerisation involves eliminating a small molecule from 2 monomers. They include
polyesters and polyamides. Common ones are:
- Nylon: A polyamide used to make fibres, ropes & clothes.
- Kevlar: A polyamide used to make bullet-proof vests, H-bonding makes it strong.
- Terylene: A polyester used to make thermoplastic PET containers (like plastic bottles).

2 - Addition polymerization including poly(propenamide) and poly(ethenol)

Addition polymers are made by connecting monomers with double bonds. These include
polypropenamide (left) and polyethanol (right).

g) Draw the structural formulae of the repeat units of the polymers in 5.4.2f
See above.

h) Comment on the physical properties of polyamides and the solubility in water of

the addition polymer poly(ethenol) in terms of hydrogen bonding, eg soluble laundry
bags or liquid detergent capsules (liquitabs)
Polyamides break down easily since they react with acids and alkalis, they can be hydrolysed.
Addition polymers are often difficult to break down and cause long-term pollution problems.
However, polyethanol is soluble in water due to H-bonding from its OH groups. This means it can be
used to make disposable laundry bags that dissolve and liquitabs for washing up machines.

i) Describe and carry out, where appropriate, experiments to investigate the

characteristic behaviour of amino acids. This is limited to:
1 - Acidity and basicity and the formation of zwitterions
The COOH group in amino acids is acidic and the NH2 group is basic. This means that they are
amphoteric and can act as both acids and bases. When in alkaline conditions, the COOH donates a
Hydrogen atom and in acidic conditions the NH2 receives an extra proton.
In neutral solutions, amino acids can exist with both positive and negative ions on the same
molecule. This is called a Zwitterion (meaning hybrid).
They have high melting points since there are strong ionic forces between different zwitterions so
they take more energy to break bonds. Due to this, zwitterions are often solid.

2 - Separation and identification by chromatography

- Spot the mixture of amino acids onto the chromatography paper.
- Run in a suitable solvent such as butan-1-ol, ethanoic acid & water in one direction.
- Develop in a different solvent at right angles.
- Spray with ninhydrin and heat.
- Measure and compare Rf values to known amino acids.

3 - Effect of aqueous solutions on plane-polarised monochromatic light

All amino acids have chiral centres except for glycine. (All natural ones are L enantiomers.)
This means they will rotate the plane of plane-polarised monochromatic light.
This can be demonstrated using a polarimeter. Opposite isomers rotate in different directions and so
a racemic (50/50) mixture will not affect light since the two isomers cancel out each other’s effects.

4 - Formation of peptide groups in proteins by condensation polymerization

A peptide bond forms after a condensation reaction (eliminating H2O) with 2 amino acids.
It is the C(=O)NH group. Condensation polymerisation results in the productions of proteins.

5 - Reaction with ninhydrin.

Adding Ninhydrin is a test for the presence of amino acids. With a positive result, a purple product
will be formed. (It reacts with the amine group).
It can be used to detect fingerprints also since they leave behind lysine.

3 Organic synthesis

a) Give examples to illustrate the importance of organic synthesis in research for the
production of useful products
Organic synthesis is important in preparing useful products. It often involves a complicated sequence
of reactions each with a limited yield and sensitive conditions to give the product.
Sweeteners Saccharin, Cyclamate and Aspartame all have complex steps such as those for
aspartame:
Bacteria are fermented to produce 2 amino acids. Enantiomers are separated and modified then L
isomers react together. Complex filtration leaves a pure product behind.

b) Explain why sensitive methods of chemical analysis are important when planning
and monitoring organic syntheses
A common method of organic synthesis is retro-synthetic analysis.
This involves working backwards from the end product so that it can be made from a series of
defined steps. At each stage sensitive analysis:
- Ensures that the products are made in the best proportions possible.
- Makes sure any toxic or hazardous products are identified.
- Checks for stereo-selectivity.

c) Deduce the empirical formulae, molecular formulae and structural formulae from
data drawn from combustion analysis, elemental percentage composition,
characteristic reactions of functional groups, infrared spectra, mass spectra and
nuclear magnetic resonance
Combustion Analysis
You will be given the mass of the sample initially, mass of CO2 produced and mass of H2O produced:
1 – Calculate the mass of C and H produced.
2 – Subtract the mass of C & H from initial mass to find the mass of Oxygen produced.
3 – Calculate moles of C, H & O produced.
4 – Find the empirical formula by putting moles in a ratio.

Percentage Composition
Given the % of each element in the compound:
1 – Divide each percentage by the RAM of the element.
2 – Put the results into a ratio.
3 – Divide through by the smallest answer to give a simple whole number ratio.

% → % ÷ RAM → X:Y:Z

IR spectroscopy
- The wavenumber of different peaks correspond to different bonds absorbing energy in the
molecule which can be looked up in a data book.

Mass spectroscopy
- Parent peak ion gives RMM of compound.
- Particularly abundant peaks show where a group of the compound has broken off.

NMR
- No. of peaks = No. of H environments.
- Splitting number shows 1 more than the number of adjacent H environments.
- Area beneath graph represents number of H’s in that environment.

Characteristic functional groups

Functional Group Test Positive Result
C=C -Bromine -Orange → Colourless
-KMnO4 acidified -Purple → Colourless
-OH -PCl5 -Steamy Fumes
-Na -Fizzing
C=O (Aldehyde/Ketone) Brady’s Reagent Yellow/Orange Precipitate
C=O (Aldehyde) -Benedict’s or Fehling’s & heat -Blue → Brick Red Precipitate
-Tollens Reagent -Silver precipitate
-COOH -Sodium Carbonate -Fizzing
-Indicator -Colour change
Carbonyl (or alcohol) Iodoform reaction: Add Iodine and Pale yellow precipitate and
adjacent to methyl NaOH then warm faint medical smell
Amino Acid Ninhydrin Goes Purple
High C:H ratio Combustion Smokey flame
-Cl Nitric acid & silver nitrate solution - White precipitate
-Br - Cream precipitate
-I - Yellow precipitate
Ester Smell Fruity
Hydrogen Lit Splint Squeaky pop
Ammonia HCl White smoke
NO2 Appearance Brown gas
CO2 Limewater Goes Cloudy
Cl2 Litmus paper Bleached white
Oxygen Glowing splint Relights

d) Use knowledge of organic chemistry contained in this specifications to solve

problems such as:
1 - Predicting the properties of unfamiliar compounds containing one or more of the
functional groups included in the specification, and explain these predictions
2 - Planning reaction schemes of up to four steps, recalling familiar reactions and
using unfamiliar reactions given sufficient information
3 - Selecting suitable practical procedures for carrying out reactions involving
compounds with functional groups included in the specification
See g)

4 - Identifying appropriate control measures to reduce risk during a synthesis based

upon data of hazards
Hazard is the potential of a substance to cause harm.
Risk is the likelihood of it actually harming you.

For example K2Cr2O7 is highly toxic and carcinogenic so it is very hazardous. But it was used in
breathalysers in a sealed tube so the risk to the subject was very low.

Some precautions that can be taken are to:

- Use a fume cupboard to vent harmful gases.
- Reduce the scale of working so if something goes wrong, adverse effects are minimised.
- Look for an alternative route of synthesis.
- Replace a reactant for a safer one with similar chemical properties.

Common hazards:
- Corrosive
- Flammable
- Toxic
- Caustic
- Carcinogenic
- Explosive

5 - Understanding why, in the synthesis of stereo-specific drugs, it is important to

understand the mechanism of the reaction and how this can help to plan the
synthesis
It is important to know the effects that different enantiomers can have since they affect the body in
different ways. Different mechanisms result in different isomers being made.
For example, the SN1 & SN2 mechanisms with halogenoalkanes, the first way makes a trigonal planar
intermediate which can be attacked from either side giving a racemic mixture. The 2nd way though
only has one way of reacting so it gives a scalemic mixture.

e) Explain why the pharmaceutical industry has adopted combinatorial chemistry in

drug research, including passing reactants over reagents on polymer supports
In combinatorial chemistry a lead (l-ee-d) compound with known useful properties is chosen and
then huge numbers of similar but slightly different compounds are tested. Products that are
successful in these preliminary tests are saved in a ‘chemical library’ for further testing.
Combinatorial chemistry can be further refined binding compounds covalently to polymer beads.
Reactions can occur and then the excess reactants can be washed away leaving only the desired
product stuck to the beads which can then be released by cleaving the bond.

f) Describe and carry out, where appropriate, the preparation of a compound, eg

cholesteryl benzoate (a liquid crystal) and of methyl 3-nitrobenzoate, requiring some
of the following techniques:

1 – Refluxing
Use a condenser while heating to minimise the loss of product while allowing the reaction to go to
completion.

2 - Purification by washing, eg with water and sodium carbonate solution

This is a method of purification that can for example clean a non-polar product with a polar solvent.
Na2CO3 can absorb any excess acid and water can dissolve any water soluble impurities (like sodium
salts).

3 - Solvent extraction
Separating funnels can be used to separate immiscible liquids. Different solvents are added to
dissolve the product in them and then separated out at the bottom of the funnel.

4 - Recrystallization
- Dissolve impure crystals in the minimum amount of hot solvent possible (this creates a saturated
solution so the crystals are more likely to re-precipitate out).
- Cool and put through Buchner funnel.
- Rinse with ice cold water (this rinses off any insoluble purities stuck to the surface).
- Dry the product.

5 - Drying
Can be done in an oven or padded using filter paper to remove liquid from crystals etc. Alternatively
use anhydrous CaCl2 to absorb any water.

6 - Distillation
Used to separate mixtures with different boiling points; requires thermometer and Liebig condenser.

7 - Steam distillation
It is used to separate organic products which might otherwise decompose from sustained heating.

8 - Melting temperature determination

Put crystal sample into capillary tube and place into melting point apparatus to find it out.
9 - Boiling temperature determination.

Use distillation apparatus to determine the BP.

10 (Extra) - Shaking
Shaking mixtures can expose them to the air and so in some cases this is enough to cause oxidation
from Oxygen in the air.

g) (Extra) Reactions from the specification applicable to organic synthesis

Creating C-C bonds:

- Nucleophilic Addition to an aldehyde with HCN and a KCN catalyst: Changes =O to –OH and adds on
a C≡N.
- Friedel-Crafts reaction: Benzene reacts with a halogenoalkane for alkylation or acyl chloride for
acylation. Both use an AlCl3 catalyst.

Reduction:
- LiAlH4 dissolved in dry ether reduces carbonyls and carboxylic acids to alcohols.
- Sn & conc. HCl reduces –NO2 to –NH2

Oxidation:
-Na2Cr2O7 and sulphuric acid oxidise to carbonyls or carboxylic acids. Colour change from orange to
green.

Making –OH Groups:

- Adding KMnO4 to alkenes will create 2 –OH groups around where the double bond was.
You also observe a colour change from purple to colourless.

Adding on Halogens:
- A diatomic halogen molecule or a hydrogen halide will react with alkenes to add on 2 or 1 halogen
respectively. (Remember Markovnikov’s rule with HX)
- Alcohol/Carboxylic acids and PCl5 adds –Cl in place of –OH & gives off steamy fumes of HCl.
- Halogens with an FeBr3 catalyst will substitute halogens onto a benzene ring.

Adding on a Nitrogen Group:

- Conc. HNO3 & conc. H2SO4 refluxed with benzene will substitute an NO2 group on.
- Acyl Chloride and ammonia or carboxylic acid and ammonium carbonate will make an amide group.
- Reducing a nitrile with LiAlH4 and then adding a weak acid produces amines.
- NH3 and halogenoalkanes → NH2 replaces the halogens.

Esterification:
- Add an alcohol to a carboxylic acid or acyl chloride (with an acid catalyst like H2SO4) to get a
condensation reaction resulting in an ester.

Hydrogenation:
- Benzene and alkenes both have an addition reaction when Hydrogen is added in the presence of a
Nickel catalyst.