5.

1 Redox Equilibria

Redox Titrations

MnO4 (aq) + 8H+ (aq) + 5e Mn2+ (aq) + 4H2O (l)

2S2O3 (aq) + I2 (aq) S4O6 (aq) + 2I (aq)


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.

Standard Electrode Potentials

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.

Predicting the Feasibility of a Reaction

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.

When does a feasible reaction not happen?

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

Disproportionation is the simultaneous oxidation and reduction of a species.

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.

Corrosion can be prevented by using water repellent or frequent painting.

Sacrificial Protection Galvanizing

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.

Scandium and Zinc are NOT Transition Elements
Although Scandium and Zinc are d-block elements, Scandium only forms Sc+ ions (with no
electrons in the d sub-shell) and Zinc loses its two 4s electrons to form Zn2+ (with a full 3d sub-
shell)

The Electron Configurations
Remember that the 4s sub-shell is of a lower energy than the 3d sub-shell and so fills first.

However, Chromium and Copper are exceptions.
In copper there is a half filled 3d sub-shell and a half filled 4s sub-shell.
In chromium there is a full 3d sub-shell and a half filled 4s sub-shell.

Remember, half filled sub-shells are relatively stable.

Typical Properties of Transition Elements

1. Most have multiple oxidation states
2. Form coloured compounds and ions
3. Form complex ions (discussed later) with ligands
4. Show many useful catalytic properties

A few (less important) physical properties:

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

The Chemistry of Chromium, Iron and Copper
It is most important to remember the common oxidation states of these three elements
(because the specification directly mentions them).

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.

A complex ion is the central metal ion surrounded by ligands.

The coordination number of a complex ion is the total number of coordinate (dative) bonds.

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.

Naming Complex Ions

Ligand Name
Water Aqua-
Ammonia Ammine-
Chloride Chloro-
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;

Chromate, Ferrate, Cupprate

Shapes of Complex Ions
The only two possibilities really are octahedral (coordination number 6) and tetrahedral
(coordination number 4) remember that the bond angles are 90 and 109.5 respectively and
that dative bonds are drawn with arrows (instead of lines) to show the donation of the two
electrons.

Colours of Complex Ions
You are not expected to remember the colours of these complex ions, but understand why they
are coloured.

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 dont 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.

The Formation of Hydroxide Precipitates
This is a bit of a mammoth Im afraid! You need to know what happens during the formation of
these precipitates, the formulae and colour of all of the hydroxide precipitates that form when
NaOH or NH3 solutions are added and what happens when these are added in excess.

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

So a complex ion consisting of 6 water ligands
surrounding a central copper (II) ion would be called;
hexaaquacopper (II) {Cu(H2O)6) 2+}
Ion
With NaOH or NH3
(not in excess)
With NaOH in
excess
With NH3 in excess
Cr (3+)
Cr 3+ + 3OH-
Cr(OH)3
Green or violet
Cr(OH)3 + 3OH-
[Cr(OH)6] 3-
Deep green solution
No further reaction
Mn (2+)
Mn 2+ + 2OH-
Mn(OH)2
Brown which darkens
in air (MnO2 forms)
No further reaction No further reaction
Fe (2+)
Fe 2+ + 2OH-
Fe(OH)2
Pale green surfaces
darkens (brown) as
Fe(OH)3 forms
No further reaction No further reaction
Fe (3+)
Fe 3+ + 3OH-
Fe(OH)3
Red-brown
No further reaction No further reaction
Co (2+)
Co 2+ + 2OH-
Co(OH)2
Blue turns brown in
air as Co(OH)3 forms
No further reaction
Co(OH)2 + 6NH3
[Co(NH3)6]2+
Blue solution
Ni (2+)
Ni 2+ + 2OH-
Ni(OH)2
Pale green
No further reaction
Ni(OH)2 + 6NH3
[Ni(NH3)6]2+
Lavender solution
Cu (2+)

Cu 2+ + 2OH-
Cu(OH)2
Pale blue

No further reaction,
but ppte is
appreciably soluble

Cu(OH)2 + 2H2O +
4NH3
[Cu(NH3)4(H2O)2] 2+
+ 2OH-
Deep blue solution

Zn (2+)
Zn 2+ + 2OH-
Zn(OH)2
White
Zn(OH)2 + 2OH-
Zn(OH)4 2-
Colourless solution
Zn(OH)2 + 4NH3
[Zn(NH3)4] 2+ + 2OH-
Colourless 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 NH3 ions except
that they form SOLUTIONS and not precipitates.

How the precipitates form not a ligand exchange!!!
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 youre 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 isnt the end of learning colours! Vanadium exists in many oxidation states;
Oxidation State Common Ion in Water
+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 convert +5 to +4, use an acidified sulphite solution
To obtain +3 an even stronger reducing agent is required (thats 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 as Catalysts
Transition metals are important catalysts in many industrial processes. The reason that
transition metals are good catalysts is due to their variable oxidation states.
Haber Process Iron (II) catalyst
Contact Process Vanadium (V) Oxide catalyst
Hydrogenation of Alkenes Nickel catalyst
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.
MEMORY AID YOU GREAT BIG LEMON!
Just remember to put the +5 first!