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REDOX REACTIONS

DEFINITIONS OF OXIDATION AND REDUCTION (REDOX)

This page looks at the various definitions of oxidation and reduction (redox) in terms of
the transfer of oxygen and electrons. It also explains the terms oxidising agent and
reducing agent. Many of these topics have been already learnt in 9th EGB

Oxidation and reduction in terms of oxygen transfer

Definitions

• Oxidation is gain of oxygen.

• Reduction is loss of oxygen.

For example, in the extraction of iron from its ore:

Because both reduction and oxidation are going on side-by-side, this is known as a
redox reaction.

Oxidising and reducing agents

An oxidising agent is substance which oxidises something else. In the above example,
the iron (III) oxide is the oxidising agent.
A reducing agent reduces something else. In the equation, the carbon monoxide is the
reducing agent.

• Oxidising agents give oxygen to another substance.

• Reducing agents remove oxygen from another substance.

Oxidation and reduction in terms of electron transfer

This is easily the most important use of the terms oxidation and reduction.
Definitions

• Oxidation is loss of electrons.

• Reduction is gain of electrons.

It is essential that you remember these definitions. There is a very easy way to do this.
As long as you remember that you are talking about electron transfer:

A simple example
The equation shows a simple redox reaction which can obviously be described in terms
of oxygen transfer.
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Copper (II) oxide and magnesium oxide are both ionic. The metals obviously aren't. If
you rewrite this as an ionic equation, it turns out that the oxide ions are spectator ions
and you are left with:

If you look at the equation above, magnesium is reducing the copper (II) ions by giving
them electrons to neutralise the charge. Magnesium is a reducing agent.
Looking at it the other way round, copper (II) ions are removing electrons from
magnesium to create the magnesium ions. The copper (II) ions are acting as an
oxidising agent.

OXIDATION STATES (OXIDATION NUMBERS)

The oxidation number of an atom in a chemical species (ion, molecule etc.) is calculated
as the number of electrons lost (positive oxidation number) or gained (negative
oxidation number) when the bonds are considered to be all ionic and the electrons of
the bonds are assigned to the most electronegative of both atoms .

The oxidation number of chlorine in some of its compounds

Sodium chloride
Sodium chloride is ionic so Cl is as a mononegative anion Cl- Its oxidation number is
thus -1
Hydrogen chloride
The bond in this case is covalent. Now if we consider it to be ionic, being the
electronegativity of chlorine higher than hydrogen’s the electrons of the bond are
assigned to Cl. Chlorine has gained an electron and hydrogen has lost it. The oxidation
number of Cl is thus -1 (and hydrogen’s is +1)

Dichlorine oxide
In Cl2O the electrons of the covalent bonds are assigned to the central oxygen atom
(except for O-F bonds, oxygen is always a “winner”). Both chlorine atoms became in
this case monopositive cations. The electrons “given” are coloured red. The oxidation
number of Cl in this case is +1.
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Chloric acid (hydrogen chlorate)

Working as show the oxidation number for chlorine in this case is +5. The electrons
supplied by chlorine to the bonds are 5 because two of the bonds are dative covalent
Hydrogen’s will be +1 and all the three oxygen atoms will as usual show an oxidation
number -2

REDOX REACTIONS IN TERMS OF OXIDATION STATES

Oxidation state shows the total number of electrons which have been removed from an
element (a positive oxidation state) or added to an element (a negative oxidation state)
to get to its present state.

Oxidation involves an increase in oxidation state

Reduction involves a decrease in oxidation state

Recognising this simple pattern is the single most important thing about the concept of
oxidation states. If you know how the oxidation state of an element changes during a
reaction, you can instantly tell whether it is being oxidised or reduced without having to
work in terms of electron-half-equations and electron transfers.

WORKING OUT OXIDATION STATES

You don’t work out oxidation states by counting the numbers of electrons transferred. It
would take far too long. Instead you learn some simple rules, and do some very simple
sums!

• The oxidation state of an uncombined element is zero. That's obviously so,

because it hasn't been either oxidised or reduced yet! This applies whatever the
structure of the element - whether it is, for example, Xe or Cl 2 or S8, or whether
it has a giant structure like carbon or silicon.
• The sum of the oxidation states of all the atoms or ions in a neutral compound is
zero.
• The sum of the oxidation states of all the atoms in an ion is equal to the charge
on the ion.
• The more electronegative element in a substance is given a negative oxidation
state. The less electronegative one is given a positive oxidation state. Remember
that fluorine is the most electronegative element with oxygen second.
• Some elements almost always have the same oxidation states in their
compounds:
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usual oxidation
element exceptions
state

Group 1
always +1
metals

Group 2
always +2
metals

Oxygen usually -2 except in peroxides and F2O (see below)

except in metal hydrides where it is -1

Hydrogen usually +1
(see below)

DECIDING WHETHER A REACTION IS A REDOX REACTION

In each of the following examples, we have to decide whether the reaction involves
redox, and if so what has been oxidised and what reduced.
Example:
This is the reaction between magnesium and hydrochloric acid or hydrogen chloride
gas:

Have the oxidation states of anything changed? Yes they have. There are two elements
which are in compounds on one side of the equation and as uncombined elements on the
other. Check all the oxidation states to be sure:

Magnesium's oxidation state has increased - it has been oxidised. The hydrogen's
oxidation state has fallen - it has been reduced. Chlorine is in the same oxidation state
on both sides of the equation - it hasn't been oxidised or reduced.

SOME IMPORTANT REDOX REACTIONS

• Combustion: combustion is a redox reaction in which a fuel combines with

oxygen. In a highly exothermic reaction that releases energy as heat and light.
We use combustions to move cars, lorries, ships and planes, to cook and heat our
homes or to generate electric energy. The most important fuels used are
petroleum derivatives (hydrocarbons) and coal. Complete combustion leads to
the formation of CO2 and, in the case of hydrocarbons, also H2O. Incomplete
combustion (oxygen below the stoichiometric requirements) forms CO (carbon
monoxide) a highly poisonous gas.
• Batteries: batteries are “electrochemical cells” (to be studied further in this unit)
and are made by dissociation of redox reactions in two compartments and
forcing the electrons to flow along metal wires, generating an electric current.
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• Metallurgy: Just a few metals (gold, silver, platinum and copper) are found
native (uncombined). Metals are usually forming the cation in oxides, silicates,
sulphides and carbonates. These are most times changed into the corresponding
oxide to be further reduced by heating, generally with coke or other carbon
enriched products. Iron is extracted from haematite (an iron oxide, its most
important ore) in blast furnaces mixing with coke and other chemicals. The
reducing agent is not carbon itself but carbon monoxide formed in it.
Electrolysis is used for more reactive metals.
• Electrolysis: We have already seen that electrolysis is the decomposition of
compounds by means of an electric current. Oxidations occur at the anode of the
tank and reductions at its cathode Aluminium is obtained by electrolysis of
molten bauxite (aluminium oxide). High purity copper that is needed for electric
wiring is prepared by means of electrolysis. Caustic soda (sodium hydroxide)
the most important alkali, and chlorine used in the plastics’ industry (PVC), as a
bleaching agent in the textile industry, or as a disinfectant, are prepared by
electrolysis of Brine (concentrated sodium chloride solution).
• Corrosion and rusting of metals: in this case, redox reactions (oxidation of the
metals) have to be avoided. Rust prevention of iron or other metals by coating,
oiling, galvanising or other procedures is continuously investigated.
• Photosynthesis and respiration: these processes constitute the very basis of life
so we can hardly overestimate their importance. Photosynthesis is the
chlorophyll-catalysed endothermic reduction of carbon dioxide to glucose using
light energy. Glucose is further used as a fuel in the cells, firstly by oxidative
degradation to pyruvic acid and then entering the so called Krebs cycle to be
oxidised back to carbon dioxide and water.

REVERSIBLE REACTIONS

Before we go on discussing redox reactions let us speak a word about chemical

equilibria. A reversible reaction is one which can be made to go in either direction
depending on the conditions. If you pass steam over hot iron the steam reacts with the
iron to produce a black, magnetic oxide of iron called tri-iron tetroxide, Fe3O4.

The hydrogen produced in the reaction is swept away by the stream of steam.

Under different conditions, the products of this reaction will also react together.
Hydrogen passed over hot tri-iron tetroxide reduces it to iron. Steam is also produced.

This time the steam produced in the reaction is swept away by the stream of hydrogen.
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These reactions are reversible, but under the conditions normally used, they become
one-way reactions. The products aren't left in contact with each other, so the reverse
reaction can't happen.

Reversible reactions happening in a closed system

What if iron is being heated in steam in a closed container? Heat is being added to the
system, but none of the substances in the reaction can escape. The system is closed.

As the tri-iron tetroxide and hydrogen start to be formed, they will also react again to
give the original iron and steam. So, if you analysed the mixture after a while, what
would you find? You would find that you had established what is known as a dynamic
equilibrium

The reaction has reached equilibrium in the sense that there is no further change in the
numbers of molecules or ions. However, the reaction is still continuing. For every
reactant species turning into product, somewhere in the mixture it is replaced by a
products species turning back into reactants

This is known as a dynamic equilibrium. The word dynamic shows that the reaction is
still continuing. You can show dynamic equilibrium in an equation for a reaction by the
use of special arrows.

It is important to realise that this doesn't just mean that the reaction is reversible. It
means that you have a reversible reaction in a state of dynamic equilibrium.

The change from left to right in the equation (in this case from blue to
orange as it is written) is known as the forward reaction. The change
from right to left is the back reaction. If the conditions of the
experiment change (by altering the relative chances of the forward and
back reactions happening), the composition of the equilibrium mixture
will also change. How did the system get to that state?

Let's assume that we started with A and B. At the beginning of the

reaction, the concentrations of A and B were at their maximum. That
means that the rate of the reaction was at its fastest. As A and B react,
their concentrations fall. That means that they are less likely to collide
and react, and so the rate of the forward reaction falls as time goes on.

In the beginning, there isn't any C and D, so there can't be any reaction between them.
As time goes on, though, their concentrations in the mixture increase and they are more
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likely to collide and react. With time, the rate of the reaction between C and D
increases:

Eventually, the rates of the two reactions will become equal. A and B will be converting
into C and D at exactly the same rate as C and D convert back into A and B again.

At this point there won't be any further change in the amounts of A, B, C and D in the
mixture. As fast as something is being removed, it is being replaced again by the reverse
reaction. We have reached a position of dynamic equilibrium.

If you change the conditions in a way which changes the relative rates of the forward
and back reactions you will change the position of equilibrium - in other words, change
the proportions of the various substances present in the equilibrium mixture.

LE CHATELIER'S PRINCIPLE

The following is a practical principle very frequently used to analyse what happens to
equilibria when external conditions are changed:

The following example will make things more clear. Suppose you have an equilibrium
established between four gaseous substances A, B, C and D the forward reaction being
exothermic.

According to Le Chatelier’s principle:

• If you increase the concentration off any reactant, the equilibrium will move to
the right and vice versa
• If you increase the pressure, the equilibrium will be shifted again to the right
because there are two molecules instead of three (less pressure)
• If you increase the temperature the equilibrium will shift to the left because the
back reaction is endothermic and the extra heat given will be absorbed

THE DIFFERING REACTIVITIES OF METALS

When metals react, they give away electrons and form positive ions. We might want to
compare the ease with which a metal does this to form hydrated ions in solution - for
example Mg2+(aq) or Cu2+(aq) that is, the ease with which these two changes take place:

Magnesium is more reactive than copper. The first reaction happens much more readily
than the second one. Let’s have a more detailed look at these two systems.
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Looking at this from an equilibrium point of view

Suppose you have a piece of magnesium in a beaker of water. There

will be some tendency for the magnesium atoms to shed electrons and
go into solution as magnesium ions. The electrons will be left behind
on the magnesium. In a very short time, there will be a build-up of
electrons on the magnesium, and it will be surrounded in the solution
by a layer of positive ions. These will tend to stay close because they
are attracted to the negative charge on the piece of metal.

Some of them will be attracted enough that they will reclaim their electrons and stick
back on to the piece of metal.

A dynamic equilibrium will be established when the rate

at which ions are leaving the surface is exactly equal to
the rate at which they are joining it again. At that point
there will be a constant negative charge on the
magnesium, and a constant number of magnesium ions
present in the solution around it. (The “bites” in the metal
have been omitted in the diagrams to follow.)

How would this be different if you used a piece of copper instead of a piece of
magnesium? Copper is less reactive and so forms its ions less readily. Any ions which
do break away are more likely to reclaim their electrons and stick back on to the metal
again. You will still reach an equilibrium position, but there will be less charge on the
metal, and fewer ions in solution. Compare in the diagram both situations:

If we write the two reactions as equilibria, then what we are doing is comparing the two
positions of equilibrium.
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The position of the magnesium equilibrium lies further to the left than that of the copper
equilibrium. By convention, all these equilibria are written with the electrons on the
left-hand side of the equation.

OXIDATION POTENTIALS AND THE REFERENCE ELECTRODE

In the case of magnesium, there is a lot of difference between the negativeness of the
metal and the positiveness of the solution around it. In the copper case, the difference is
much less. There is a different potential difference (voltage) between each metal and
the solution around it. It can be recorded as a voltage: the bigger the difference between
the positiveness and the negativeness, the bigger the voltage.

To compare the “easiness” with which a metal gets oxidised (move an ion into the
solution and leave its electrons in the electrode) the
potential difference established between the metal and the
solution is compared with a standard system called the
reference electrode.

Chemists have chosen as a reference electrode the

“standard hydrogen electrode”.

The standard hydrogen electrode looks like this:

What is happening?

As the hydrogen gas flows over the porous platinum, an equilibrium is set up between
hydrogen molecules and hydrogen ions in solution. The reaction is catalysed by the
platinum sponge.

This is the equilibrium that is used to compare all the others with. The position of any
equilibrium can be changed by changing conditions. That means that the conditions
must be standardised so that you can make fair comparisons. The standard conditions
have been chosen as 1 atmosphere (H2 pressure) and 25°C (temperature). The
concentration of the hydrogen ions in solution is 1 mol dm -3 Changing concentrations is
one of the ways of changing the position of an equilibrium. Throughout this topic, all
ions concentrations are taken as being 1,000 mol dm-3.

Using the standard hydrogen electrode

The standard hydrogen electrode is attached to the electrode system you are
investigating - for example, a piece of magnesium in a solution containing magnesium
ions. The whole of this set-up is described as an electrochemical cell or just a cell. It is
a simple system which generates a voltage. Each of the two beakers and their contents
are described as half cells.
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The salt bridge is included to complete the electrical circuit but without introducing any
more bits of metal into the system. It is just a glass tube filled with an electrolyte like
potassium nitrate solution. The ends are "stoppered" by bits of cotton wool to stop too
much mixing of the contents of the salt bridge with the contents of the two beakers.

These two equilibria are set up on the two electrodes (the magnesium and the porous
platinum):

Magnesium has a much greater tendency to form its ions than hydrogen does. The
position of the magnesium equilibrium will be well to the left of that of the hydrogen
equilibrium.

That means that there will be a much greater build-up of

electrons on the piece of magnesium than on the platinum.
There is a major difference between the charge on the two
electrodes, a potential difference which can be measured with
a voltmeter. The voltage measured would be 2.37 volts and
the voltmeter would show the magnesium as the negative
electrode and the hydrogen electrode as being positive. This voltage in standard
conditions is known as the Redox Potential (Eº) of magnesium. The easiness of any
metal to get oxidised (or of any other redox reaction) can be compared this way.

E° values give you a way of comparing the positions of equilibrium when these
elements lose electrons to form ions in solution.

• The more negative the E° value, the further the equilibrium lies to the left - the
more readily the element loses electrons and forms ions.
• The more positive (or less negative) the E° value, the further the equilibrium lies
to the right - the less readily the element loses electrons and forms ions.
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ARRANGING REDOX EQUILIBRIA IN ORDER OF THEIR E° VALUES

The electrochemical series is built up by arranging various redox equilibria in order of

their standard electrode potentials (redox potentials). The most negative E° values are
placed at the top of the electrochemical series, and the most positive at the bottom.
Metals at the top of the series are good at giving away electrons. They are good
reducing agents. The reducing ability of the metal increases as you go up the series.
Metal ions at the bottom of the series are good at picking up electrons. They are good
oxidising agents. The oxidising ability of the metal ions increases as you go down the
series. This chart shows just some metal’s redox potentials. Chemists use tables that
include hundreds of possible semi reactions.

The electrochemical series

equilibrium E° (volts)

-3.03

-2.92

-2.71

-2.37

-1.66

-0.76

-0.44

-0.13

+0.34

+0.80

+1.50
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COMBINING TWO METALS’ HALF CELLS: ZINC AND COPPER

So far we have looked at combinations of a hydrogen electrode with the half cell we
have been interested in. However, there isn't any reason why you can't couple any two
half cells together.

What happens if you combine a zinc half cell with a copper half cell?

In the presence of a high resistance voltmeter

The two equilibria which are set up in the half cells are:

The negative sign of the zinc E° value shows that it releases

electrons more readily than hydrogen does. The positive sign
of the copper E° shows that it releases electrons less readily than hydrogen.

That means that you can compare any two equilibria directly.
For example, in this case you can see that the zinc releases
electrons more readily than the copper does. Stripping
everything else out of the diagram, and looking only at the build
up of electrons on the two pieces of metal:

Obviously, the voltmeter will show that the zinc is the negative electrode, and copper is
the (relatively) positive one. It will register a voltage showing the difference between
them.

Removing the voltmeter

The high resistance of the voltmeter is deliberately designed to stop

any current flow in the circuit. What happens if you remove the
voltmeter and replace it with a bit of wire? Electrons will flow from
where there are a lot of them (on the zinc) to where there are
fewer (on the copper). The movement of the electrons is an
electrical current.

These are just simple equilibria, and you can apply Le Chatelier's Principle to them.
Electrons are flowing away from the zinc equilibrium. According to Le Chatelier's
Principle, the position of equilibrium will move to replace the lost electrons. Electrons
are being dumped onto the piece of copper in the copper equilibrium. According to Le
Chatelier's Principle, the position of equilibrium will move to remove these extra
electrons. If electrons continue to flow, the positions of equilibrium keep on shifting.
The two equilibria essentially turn into two one-way reactions. The zinc continues to
ionise, and the copper(II) ions keep on picking up electrons.
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Taking the apparatus as a whole, there is a chemical reaction going on in which zinc
is going into solution as zinc ions, and is giving electrons to copper(II) ions to turn
them into metallic copper.

Relating this to a test tube reaction

This is exactly the same reaction that occurs when you drop a piece of zinc into some
copper(II) sulphate solution. The blue colour of the solution fades as the copper(II) ions
are converted into brown copper metal. The final solution contains zinc sulphate. (The
sulphate ions are spectator ions.)

You can add the two electron-half-equations above to give the overall ionic equation for
the reaction.

The only difference in this case is that the zinc gives the electrons directly to the
copper(II) ions rather than the electrons having to travel along a bit of wire first.

The test tube reaction happens because of the relative tendency of the zinc and copper to
lose electrons to form ions. You can find out this relative tendency by looking at the E°
values. That means that any redox reaction could be discussed in a similar way.

A useful "rule of thumb"

Whenever you link two of these equilibria together (either via a bit of wire, or by
allowing one of the substances to give electrons directly to another one in a test tube):

• The equilibrium with the more negative (or less positive) E° value will move to
the left.
• The equilibrium with the more positive (or less negative) E° value will move to
the right.

PROBLEMS

1- State the meaning of oxidation and reaction from the most restricted to
the most comprehensive point of view

2- Calculate the oxidation state for the elements in the following ions or
molecules:
PbO2 AlH3 KMnO4 MnCl2 SO3= Al2 (SO3)3 C4H10 NH3 NH4+
Na3PO4 CaSO4 H2SO4 VO+ VO2+

3- Your results for the oxidation number of C4H10 should have been
disturbing. Why? The structure of two molecules corresponding to the same formula
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is shown below. Calculate the oxidation state for all four carbons in both structures
and let your heart be appeased.

4- Decide if the following are redox reactions. In case they were, find both
the oxidizing and reducing agent

a- 2 Ti Cl4 + Zn → 2 Ti Cl3 + ZnCl2

b- Be(OH)2 + 2 Na(OH) → Na2BeO2 + 2 H2O
c- Cl2 + 2 KBr → 2 KCl + Br2
d- S + O2 → SO2 and 2 SO2 + O2 → SO3
e- SO3 + H2O → H2SO4
f- 2 HClO3 → 2 HCl + 3 O2
g- CH4 + Cl2 → CCl4 + 4 HCl
h- C2H4 + H2 → C2H6
i- ZnO + 2 HCl → ZnCl2 + H2O
j- Cl2 + 2 NaOH → NaCl + NaClO

5- a- Write a complete balanced equation for the complete combustion of butane

b- Although aluminium is far more reactive than iron it doesn’t seem to corrode as
iron does. Find an explanation
c- What is galvanisation? What is it used for?
d- What is meant by “sacrificial protection”?

6- More than 130 million tonnes per year of ammonia (used both in chemistry and
agriculture) are made by the Haber process: a mixture of hydrogen and nitrogen are
heated at 500 ºC at 150 - 200 atmospheres with an iron catalyst. The exothermic
reaction is not completed and unreacted gases are recycled for economic reasons.
The first commercial plant with a capacity of 30 tons/day was set up by the
German chemical giant BASF in Germany. Using part of the previous information
answer the following:
a- Write a complete balanced equation for the Haber process
b- Is it a redox reaction?
c- Write the equilibrium constant for it. Remember that the concentration of a
gas can be replaced by its pressure.
d- How does temperature shift the equilibrium?
e- How does pressure shift the equilibrium?
f- Think a reason for carrying out the process in the conditions previously
described.

7- Which of the following reactions may take place under adequate conditions:
a- Fe2O3 + 2 Al → 2 Fe + Al2O3
b- Zn + 2HCl → ZnCl2 + H2
c- H2SO4 + Cu → CuSO4 + H2
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8- The chart below shows some redox potentials. Use the information in it to answer
the following questions:
a- Does copper metal displace silver from AgNO3?
b- Can chlorine oxidise FeCl2 to FeCl3?
c- Is silver attacked by hydrochloric acid or chlorine?
d- Is gold attacked by any of the two?

+0.34

+0.77

+0.80

+1.33

+1.36

+1.50