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Week 8, Lesson 1

Chapter 16 Redox
Chemistry & Corrosion

Oxidation & Reduction


Redox reactions are reactions that are
called oxidation-reduction reactions.
Many of the chemical reactions that
play a significant role in maintaining
our environment are redox reactions.
For example, the reactions of water
and the gases of the atmosphere that
cause corrosion and so the
deterioration of metals are redox
reactions.

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.

Redox Reactions cont


Once the reactive component of air was first
produced by Joseph Priestley identified by
Antoine Lavoisier as the element oxygen,
reactions such as these were described as
oxidation reactions.
In air, the combustion of carbon, sulfur, iron or
even octane always produced at least one
oxide.
This type of reaction was classified as
oxidation, which here means the addition of
oxygen.

Redox Reactions cont


When oxygen reacts with an element,
the element is said to be oxidised.
The iron that society uses has been
extracted from iron ores.
This process involves reduction of the
iron oxide to iron.
When oxygen has been removed from a
substance the material has been
reduced.

Redox Reactions Example


The iron (III) oxide has lost oxygen
it has been reduced.
Reduction can not occur without
oxidation occurring at the same time.
In this reaction it is the carbon
monoxide that has gained oxygen
and it is said to have been oxidised.
Oxidation and reduction always occur
simultaneously.

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)

Electron Transfer cont


Magnesium oxide is an ionic compound and consists of
Mg2+ and O2- ions.
Each magnesium atom has lost 2 electrons to form this
ion.
Each oxygen molecule has gained 2 electrons to form
this ion.
The reaction can be represented by two half equations.
The first shows the loss of electrons:
Mg(s) Mg2+(s) + 2e The second shows the gain of electrons:
O2(g) + 4e- 2O2-(s)

Electron Transfer cont


Therefore oxidation is defined as the
loss of electrons.
Reduction is defined as the gain of
electrons.
Reactions that involve oxidation and
reduction are called redox reactions.

Writing Half Equations


example
When a strip of copper wire is suspended in a solution of
silver nitrate, long crystals of silver metal can be observed.
The solution changes to a pale blue colour, indicating the
presence of Cu2+ ions. Write half equations for this reaction
and identify the substance oxidised and reduced.
STEP 1: The first equation is the copper metal forming copper
ions.
Cu(s) Cu2+(aq) + 2eSTEP 2: The second equation involves the silver ions form
silver metal.
Ag+(aq) + e- Ag(s)
Since the copper has lost electrons is has undergone
oxidation and the silver has undergone reduction.

Writing an Overall Redox


Reaction
When writing equations for redox
reactions, normally the two half equation
are written first and then they are added
together to produce an overall equation.
In an overall equation, no electron
transfer is shown.
That is, the electrons that are lost in
oxidation, are gained in the reduction
reaction.

Writing an Overall Redox


Reaction Example
In the example of copper and the solution of silver ions:
- Each copper atom that is oxidised loses two electrons.
- Each silver ion that is reduced gains on electron.
Two silver ions must be reduced to take up the electrons lost by
each copper atom oxidised.
To write an overall equation, the half equation involving the
reduction of silver is multiplied by 2, before it is combined
with the half equation for the oxidation of copper.
Cu(s)Cu2+(aq) + 2e(Ag+(aq) + e- Ag(s)) x 2
The overall equation is
Cu(s) + 2Ag+(aq) Cu2+(aq) + 2Ag(s)

Overall Redox Reactions


cont
Remember in both half and full redox
equations:
The number of atoms of each element
present in the products is equal to the
number present in the reactants. Atoms
are conserved in all reactions.
The total charge on the product side of
the equation is equal to the total charge
on the reactants side of the equation.
Charge is conserved in all reactions.

Oxidants and Reductants


An oxidant (or oxidising agent) is a species
that causes another to be oxidised.
A reductant is a species that causes
another to be reduced.
An oxidant causes oxidation and is
reduced.
A reductant causes reduction and is
oxidised.

Oxidants and Reductants


cont

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.

Oxidation Number Rules


Oxidation numbers are determine according to the following rules in
ascending order:
1. The oxidation number of a free element is 0.
2. The oxidation number of a simple ions is equal to the charge on that ion.
3. In compounds, some elements have oxidation numbers that are regarded
as fixed, except in a few exceptional circumstances.
a) Main group elements have an oxidation number equal to their valency.
b) Fluorine has an oxidation number of -1.
c) Hydrogen has an oxidation number of +1 when is forms compounds with
non metals and -1 in metal hydrides.
d) Oxygen almost always has an oxidation number of -2. In F 2O it has an
oxidation number of +2 and in peroxides such as H 2O2 and BaO2 its
oxidation number is -1.
4. The sum of oxidation numbers in a neutral compound is zero.
5. The sum of oxidation number in a polyatomic ion is equal to the charge on
the ion.

Using Oxidation Numbers


A change in oxidation numbers is an
indication that a redox reaction have
taken place.
Oxidation involves an increase in
oxidation number.
Reduction involves a decrease in
oxidation number.

Week 8, Lesson 3

Half Equations for Complex


Redox Reactions

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

Evidence for Electron


Transfer

When zinc metal is placed in a solution of


copper (II) sulfate, the zinc is oxidised and a
brown deposit of copper metal forms.
Electrons flow from the zinc atoms to the
copper(II) ions as these collide.
Evidence for this flow can be obtained by
setting up an electrochemical or galvanic
cell.
A galvanic cell is an energy converter that
separates the oxidant from the reductant.

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.

Galvanic Cells cont


When this particular galvanic cell operates,
the galvanometer indicates that electrons
are flowing from the zinc strip in beaker B to
the copper strip in beaker A.
This observation provides evidence that the
oxidation and reduction reactions between
zinc atoms and copper ions also occur what
reactants are separated in a galvanic cell.
It also supports the idea that there is a
transfer of electrons.

Zinc and Copper Galvanic


Cell
At the copper strip, in beaker A, Cu2+ ions accept
electrons to form copper atoms:
Cu2+(aq) + 2e- Cu(s)
At the zinc strip in beaker B, zinc atoms lose electrons to
form zinc ions:
Zn(s) Zn2+(aq) + 2e Because of these reactions, the electrons flow through the
zinc strip and connecting wire towards the copper strip.
The zinc is the source of negatively charged electrons so
it is assigned a negative charge.
The electrons are attracted to the copper strip so this is
assigned a positive charge.

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 Cells cont


In galvanic cells the anode is the negatively charged electrode.
The cathode is the positively charged electrode.
In the previous example, the copper ions are reduced to copper
atoms at the cathode.
Cations will migrate from the salt bridge in the beaker
containing the cathode to compensate for the loss of copper
ions.
At the anode, zinc metal is oxidised and so more zinc ions are
added to the solution in the beaker.
To avoid a build up of positive charge, anions will migrate from
the salt bridge into the beaker and so maintain electrical
neutrality.
An electrolyte contains ions that are free to move through the
solution.

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.

Predicting Redox Reactions


The electrochemical series is useful for predicting redox
reactions.
More reactive metals tend to be found on the lower right of the
series.
A more reactive metal will be oxidised by and donate its
electrons to the cation of a less reactive metal.
The cation receives the electrons and is reduced.
A spontaneous reaction can be expected to occur when a
relatively strong oxidant is mixed with a relatively strong
reductant.
The oxidant is reduced and the half reaction occurs in the
forwards direction.
The reductant is oxidised and its half equation is the reverse of
that on the electrochemical series.

Predicting Redox Reactions


cont
Oxidant

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-

AN OIL RIG CAT


Use the following phrase to help you
remember the process:
ANode: Oxidation Is Loss of electrons
Reduction Is Gain of electrons
CAThode.

Week 9, Lesson 2

The Corrosion Process


Direct reaction with oxygen in the air to form a
metal ocise is known as dry corrosion.
In cases such as aluminium, dry corrosion forms a
tough, impervious oxide coating that protects the
metal underneath from further contact from
oxygen.
When moisture is present, the corrosion of iron
quickens.
This process is known as wet corrosion.
The most well known form of wet corrosion is the
formation of rust.

Wet Corrosion

Wet corrosion can occur in moist air or by direct


immersion in water.
Several factors affect the rate at which wet corrosion
occurs.
In general, corrosion is accelerated in the presence of:
Water corrosion in dry air is very slow
Impurities such as salt and acidic pollutants that dissolve in
the water
Impurities such as carbon in the iron

Corrosion is reduced however when the iron:


Is alloyed with certain other materials
Has a protective coating

The Wet Corrosion Process


Analysis of rust shows that it is a
hydrated oxide of iron with the
formula Fe2O3.xH2O.
x represents a number between 1
and 3 and xH2O indicates that this is
the number of water molecules
associated with the iron oxide.

The Wet Corrosion Process


cont
Experimental results indicate that the first step
in the formation of rust is the oxidation of iron
to form Fe2+ ions.
These ions can be detected in solution on the
surface of the iron.
An Fe2+ ion has two less electrons than and iron
atom.
This step therefore involves the loss of electrons
and can be represented by the half equation:
Fe(s) Fe2+(aq) + 2e-

The Wet Corrosion Process


cont
This only represents have the equation.
The electrons lost by the iron must be
accepted by another reactant.
Oxygen is also involved in corrosion it
gains the electrons lost by the iron.
The oxygen is reduced in the presence
of water to hydroxide ions, represented
by:
O2(aq) + 2H2O(l) + 4e- 4OH-(aq)

The Wet Corrosion Process


cont
The overall equation can be written
as:
2Fe(s) + O2(aq) + 2H2O(l) 2Fe2+(aq)
+ 4OH-(aq)

The Wet Corrosion Process


cont
The iron (II) ions then react with the
hydroxide ions to form a green
precipitate of iron(II) hydroxide.
On exposure to more moisture and
oxygen, the iron(II) hydroxide is
further oxidised to iron(III) hydroxide,
a red brown precipitate.

The Wet Corrosion Process


cont
The wet corrosion of iron is a galvanic process.
Galvanic cells are set up on the metal surface
where different regions act as anodes and
cathodes:
The cathode region, where oxygen gains electrons
and is reduced, occurs at sites of high oxygen
concentration.
The anode region, where iron loses electrons and is
oxidised, oftern occurs in an area of stress in the
metal where the metal lattice has been deformed,
for example at the tip of a nail.

The Wet Corrosion Process


cont
The anode region is one where there is a lower
concentration of oxygen.
Corrosion is therefore greatest at the centre of
a water drop or under a layer of chipped paint.
The cathode region is at the edge of the water
drop or where paint is missing as the oxygen
concentration is the greatest.
Wet corrosion is accelerated by the presence of
dissolved salts, if the iron contains impurities or
if it is in less contact with a less reactive metal.

Protecting Against Corrosion


There are several ways to protect iron and steel
structures against corrosion.
These depend on the environment in which the
structure is located, the design and intended use
of the structure, as well as the relative costs of
various protection measures.
The simplest of these methods involves creating
a barrier between the iron and oxygen and water
to provide surface protection.
Other methods are based on an understanding
of the electrochemical nature of corrosion.

Surface Protection

Involves covering the surface of the iron to prevent contact


with oxygen and moisture.
Materials such as paint and plastic can be used for this
purpose.
Iron can also be protected by alloying with small quantities of
metals such as chromium, nickel, manganese and
molybdenum to produce stainless steel.
The atoms of these metals used to make the allot are all
bonded into the metallic lattice.
These metals oxidise slightly in air, but the oxide coating
produced is continuous and unreactive.
This oxide layer forms a dense, impervious barrier between
the metal and oxygen and water, protecting the iron from
further oxidation.

Surface Protection cont


Metals such as iron and steel can
also be coated with thin layers of
other metals in a process known as
electroplating.
These other metals, which include
chromium and nickel, again form
protective oxide coatings.

Electrochemical Protection
Impressed Current Cathodic
Protection
Impressed current
protection involved reversing

the direction of electron flow by using a low


voltage direct current power supply to give the
iron being protected a negative charge.
Because the iron is receiving electrons, oxidation
is inhibited (oxidation would produce more
electrons).
The iron becomes the site of the reduction
reaction, that is the cathode.
This method is used to protect large scale steel
structures such as wharves and pipelines.

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.