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Chapter 16 Redox
Chemistry & Corrosion
Redox Reactions
Redox reactions include:
The respiration reaction that is the source of
energy in almost all living things
Photosynthesis in green plants
Burning of fuels to propel cars
Combustion of coal in electricity power
stations
Use of chemicals such as chlorine to disinfect
swimming pools
Manufacture and use of explosives
Use of electrolytes to produce many chemicals
Production and us of fertilisers.
An Improved Definition
Electron Transfer
While the definition of oxidation as the addition of
oxygen was adequate for combustion reactions
occuring in air, many similar reactions not involving
oxygen as a reactant have since been investigated.
Magnesium ribbon is often dull and covered with a
coating that needs to be scraped of. This is magnesium
oxide which results from the corrosion of Mg in air.
The magnesium reacted with atmospheric oxygen to
form magnesium oxide the magnesium has been
oxidised.
This reaction is represented by the equation:
2Mg(s) + O2 2MgO(s)
Week 8, Lesson 2
Oxidation Numbers
To determine whether or not an
equation is a redox reaction and to
help us identify oxidants and reactants,
oxidation numbers are assigned to
elements involved in a reaction.
These numbers are determined by
applying a set of rules that consider
unequal sharing of electrons between
two atoms.
Week 8, Lesson 3
Look at the half equation for the oxidation of iron (II) ions to iron (III)
ions:
Fe2+(aq) Fe3+(aq) + e The conversion of MnO4- to Mn2+ involves reduction.
The following steps are used to balance this half equation:
1. Balance all atoms in the half equation except hydrogen and oxygen.
2. Balance the oxygen by adding water.
3. Balance the hydrogen atoms by adding H+
4. Balance the charges on both sides by adding electrons to the more
positive side.
Then add the oxidation half equation to the reduction half equation to
get the overall equation.
Make sure the number of electrons used in reduction equals the
number of electrons released during oxidation.
Week 9, Lesson 1
Galvanic Cells
The zinc metal and solution containing copper(II) ions are in
separate beakers.
A copper strip, dipping in the solution of copper (II) ions is
connected by a piece of wire to a galvanometer.
A galvanometer is a meter for detecting a flow of electrons.
A zinc strip, dipping into a solution of zinc chloride is also
connected to this by a piece of wire.
The solutions in the two beakers are connected by a salt bridge.
The salt bridge contains an ionic compound.
The ions flow through the salt bridge between the solutions to
complete the circuit.
The salt bridge can be a piece of filter paper soaked in
potassium nitrate.
Salt Bridge
To maintain the balance of positive and negative
charge in each beaker, ions flow from the salt bridge
into the two solutions.
In the beaker containing the copper sulfate solution,
Cu2+ ions are reduced to Cu atoms, leaving SO42- ions
in the solution.
The K+ ions flow from the salt bridge into this beaker
to replace the Cu2+ ions.
At the same time, NO3- ions flow into the beaker
containing ZnCl2 solution to balance the positive
charge of the Zn2+ ions being produced at the zinc
electrode.
Galvanic Cells
All galvanic cells are composed of two half cells.
Oxidation occurs in one and reduction in the
other.
A half cell must contain al electrode and
electrolyte.
An electrode is an electronic conductor a
material that can move through the circuit.
The electrode at which oxidation takes place is
called the anode.
The electrode at which reduction takes place is
call the cathode.
Galvanic Cell
Electrochemical Series
Sodium, magnesium and iron are metals that
easily corrode because they are easily oxidised.
Chemists have combined such information with
experimental data from constructing galvanic
cells from various combinations of half cells to
produce the electrochemical series.
The electrochemical series lists half equations
in order of their tendency to occur as reduction
reactions.
Electrochemical Series
cont
Electrochemical Series
cont
The half cell represented by the equation at the
top of the list attracts electrons most strongly.
It will form the positive half cell when it is
connected to any other half cell represented in
the series.
An electrochemical series shows the relative
reactivities of a number of metals and their
corresponding.
The most reactive metals are those that are
oxidised most easily; the most reactive metal
cations are those that are reduced most readily.
Electrochemical Series
cont
As you go down the series, the:
- Metals, which are on the right hand side, become
increasingly easy to oxidise and therefore are
more reactive. Metals lower in the series lose
electrons more readily and so are stronger
reductants.
- Metal cations which are on the left hand side,
become increasingly hard to reduce and therefore
are less reactive. Cations higher in the series have
a greater attraction for electrons and so are more
readily reduced, and therefore are strong oxidants.
Is reduced
Reacts with
Reductant
Is oxidised
Predicting Reactions in
Galvanic Cells
An electrochemical series can be used to
predict the processes that occur when two
half cells are joined in an electrochemical
cell.
The galvanic cell on the next slide is made
by joining Ag+/Ag half cell with the Cu2+/Cu
half cell and linking them with a salt bridge.
In this galvanic cell the two possible
oxidants are Ag+ and Cu2+ and the two
possible reductants are Cu and Ag.
Predicting Reactions in
Galvanic Cells cont
Ag+(aq) is higher on the left-hand
side of the electrochemical series
than Cu2+ and so is the stronger
of the two oxidants.
This means that Ag+ attracts
electrons more strongly than Cu2+,
so electrons in the wire will flow
away from the copper electrode
towards the silver electrode.
Since oxidation occurs at the
anode and the reduction at the
cathode, the half cell reactions
are:
At the cathode: Ag+(aq) + e- Ag(s)
At the anode: Cu(s) Cu2+(aq) + 2e-
Week 9, Lesson 2
Wet Corrosion
Surface Protection
Electrochemical Protection
Impressed Current Cathodic
Protection
Impressed current
protection involved reversing
Electrochemical Protection
Sacrificial Protection
This also involves the iron acting as the cathode.
A more easily oxidised metal, such as zinc, forms the
anode and is sacrificed.
The more reactive metal loses electrons and forms
metal cations in preference to the iron.
The iron is not oxidised in the presence of zinc
because the zinc has protected the iron from
corrosion.
This type of protection is known as electrochemical or
sacrificial protection.
This form of protection is used in roofing, galvanised
iron is iron with a zinc coating.