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Unit 5.1 and 5.2
Unit 5.1 and 5.2
Unit 5.1 and 5.2
1 Redox Equilibria
Redox Titrations
MnO4¯ (aq) + 8H+ (aq) + 5e¯ Mn2+ (aq) + 4H2O (l)
The iodine is obtained initially by the titration of the substance for analysis with KI (aq) – the
balanced symbol equation for this must be determined using the half equations for Iodide and
the substance.
The e.m.f. of a cell in which the left-hand component is a standard hydrogen electrode and the
right-hand component is the electrode system in question. All measurements at 298K, 100kPa
and 1 molar solutions.
You are not expected to be able to, or know how to, set up such apparatus but you should
appreciate the importance of the standard hydrogen electrode as a way of comparing the
relative reducing / oxidising powers of different ions.
Rule: The half equation with the most negative electrode potential will make negative progress
(that is, it will be reversed and so the ions/element will be oxidised)
Simply work out the direction in which both half equations go and you can then deduce if the
reaction in question is feasible.
1. If the reaction takes a more favoured course than the one thought.
2. The activation energy of the reaction is too high.
3. The e.m.f. is very small (i.e. the values for E are very close together)
4. Something escapes from the system.
Disproportionation
It is VERY IMPORTANT when choosing the half equations for working out the e.m.f. that BOTH
HALF EQUATIONS CONTAIN THE SPECIES WHICH IS DISPROPORTIONATING.
Rusting
Rusting is the attack of iron at sites where oxygen and a film of liquid water is present.
1. At sites where there are slight impurities in the iron, the electrode potential is slightly
different.
2. Fe (s) Fe 2+ (aq) + 2e-
3. This causes ‘pits’ in the iron.
4. The electrons flow through the iron to a point where water AND oxygen are present.
5. 2H2O (l) + O2 (g) + 4e- 4OH- (aq)
6. This reduction is assisted by acidic gases in the water (e.g. carbon dioxide) as it
removes the OH- ions, shifting the equilibrium to the right.
7. The Fe2+ ions (from 2) are oxidised to iron (III) ions when they come into contact with
oxygen.
8. An iron oxide hydrate is formed ( Fe2O3.H2O)
Corrosion of other metals occurs usually when two metals are in contact. Aluminium and
magnesium are good examples. Magnesium alloy rivets which are riveted into an aluminium
alloy (on ships) will corrode.
If the metal is coated in a more reactive metal, this metal will be corroded (oxidised) instead of
the metal we want to protect.
Metals are often dipped in molten zinc (galvanizing) which has a very negative E value. This is
called sacrificial protection – since the zinc is being sacrificed to save the metal.
Tinning
Zinc is not a safe metal for some uses (i.e. in food packaging) so tin is used. However, tin has a
less negative E value than many metals (e.g. steel) and so does not provide sacrificial
protection. If the tin coating is damaged, corrosion WILL occur.
5.2 Transition Elements
A transition element has at least one ion with a partially filled d sub-shell.
1. Dense metals
2. High melting / boiling points (compared to other metals)
3. Moderate to low reactivity
Formation of Ions
When transition elements form ions, the 4s electrons are always lost first, followed by the
loss of different numbers of 3d electrons.
Below is a list of the most common oxidation states of each transition element:
Ti +3 +4
V +3 +5
Cr +3 +6
Mn +2 +4 +7
Fe +2 +3
Co +2 +4
Ni +2
Cu +1 +2
These are the three elements that are likely to be used in the formation of complex ions and
during the ligand exchange process.
Complex Ions
A ligand is a molecule or ion (usually electron rich) which forms a dative covalent bond with a
central metal ion. It does this by donating a lone pair of electrons into a vacant d-orbital.
Apart from a complex ion with chlorine ligands, when the coordination number is 4 (because the
chloride ion is too large), the coordination number is almost always 6.
Ligand Name
Water Aqua- So a complex ion consisting of 6 water ligands
Ammonia Ammine- surrounding a central copper (II) ion would be called;
Chloride Chloro- hexaaquacopper (II) {Cu(H2O)6) 2+}
Cyanide Cyano-
NOTE: Chloride and Cyanide ligands are negatively charged. If you add 4 Cl- ligands to a
Cu (II) ion you will have an overall charge of -2. Instead of the name ending in ‘copper (II)’
the latin name is used. It would be tetrachloroferrate (II). Basically, take the latin name
and add –ate to the end of it;
When a ligand forms a dative covalent bond with a transition metal ion, it ‘splits the 3d sub-
shell’. This forms two different 3d energy levels (with an energy gap between them).
Energy from the absorption of light can be used to promote an electron from the lower 3d
energy level to the higher energy level. The light energy absorbed must be identical to the
energy gap between the two energy levels. Any light which is not absorbed (reflected) shows as
the colour of the ion.
Ligand Exchange
You don’t need to know this in great detail but need to be able to recognise it. Basically, if a
complex ion is placed into a solution containing ligand ions which are ‘stronger’ than the ligands
already attached, the ligands will swap.
The most common examples are when, say K+CN- is placed into a solution of aqua complexes.
The H2O ligands are replaced by the cyano ligands. In this case, the coordination will remain the
same, but if the H2O ligands were replaced with Cl- ligands, the coordination would decrease to
+4.
I have included all of the precipitates that are directly mentioned on the specification – so this
should be all that is required. It is probably worth printing out the following page and learning it
fully…
With NaOH or NH3 With NaOH in
Ion With NH3 in excess
(not in excess) excess
Cu(OH)2 + 2H2O +
Cu 2+ + 2OH- No further reaction, 4NH3
Cu (2+) Cu(OH)2 but ppte is [Cu(NH3)4(H2O)2] 2+ +
Pale blue appreciably soluble 2OH-
Deep blue solution
The number of hydroxide groups which are present in the initial ppte is the same as the ion
charge. Just remember the two 3+ ions and the rest are all the same. Unfortunately there are no
rules for remembering the colours and the effects of excess OH- ions and NH 3 ions – except
that they form SOLUTIONS and not precipitates.
The precipitates are formed by a process called deprotonation. The above ions are obtained
from the aqua complexes (but these have been excluded for simplicity – and you’re okay to do
this in the exam). So in actual fact, Cu(OH)2 is actually Cu(OH)2(H2O)4.
In a solution of hydroxide ions, H+ ions from the water ligands are deprotonated. The OH- ions
in solution form H2O (actually H3O+ ions are formed) and a OH- ligand is left. The number of
ligands that are deprotonated is the same as the charge of the ion (when OH- is not in excess).
So why does a solution of NH3 cause deprotonation? Because NH3 ions are reduced in solution
to form NH4+ ions and OH- ions.
Vanadium
Unfortunately that isn’t the end of learning colours! Vanadium exists in many oxidation states;
+5 VO2 + Yellow
+4 VO 2+ Green
+3 VO + / [V(H2O)6] 3+ Brown
+2 [V(H2O)6] 2+ Lavender
You also need to know how to do the interconversions between each oxidation state in solution;
To obtain +3 an even stronger reducing agent is required (that’s all it says in textbook!)
The lower the oxidation number, the stronger reducing agent it is (and so the stronger
the reducing agent required to reduce it is). V(+2) is rapidly oxidised in water.
Transition metals are important catalysts in many industrial processes. The reason that
transition metals are good catalysts is due to their variable oxidation states.
NOTE: This would be a good opportunity to have a brief look at each of these industrial
processes – this could quite easily be incorporated into a synoptic question.