Redox reactions Page 79

17 Redox reactions
Redox reactions involve reduction and oxidation. In fact, as we will see,
reduction and oxidation always go together since if a species is reduced,
another species must be oxidised.

Oxidation is the loss of electrons (OIL).

Fe2+(aq) Fe3+(aq) + e-

Oxidation can also be defined as an increase in oxidation number. In this

case the Fe2+ ion, being a simple ion, has an oxidation number with the
value of its charge at +2 and the Fe3+ ion has an oxidation number of
+3. In this reaction the iron’s oxidation number has increased and so
the iron has been oxidised.

Reduction is the gain of electrons (RIG).

Br2(aq) + 2e- 2Br-(aq)

Reduction can also be said to be a decrease in oxidation number. In this

case the bromine in the bromine molecule starts with an oxidation
number of zero since it is an element that is not combined with
another element. It ends up as a bromide ion and being a simple ion has
an oxidation number equivalent to its charge at -1 and consequently here
the bromine has been reduced.

Adding half equations

These two equations are known as half equations and we may add
together a reduction half equation and an oxidation half equation to
give an overall ionic equation for the redox reaction. Before we add half
equations however, we must ensure the number of electrons in each half
equation is the same. In this case we must multiply the equation
involving the oxidation of Fe2+ by 2. now the two half equation
have the same number of
2Fe (aq)
2+
2Fe (aq) + 2e-
3+ electrons involved, we can
Br2(aq) + 2e- 2Br-(aq) add them together to get
the overall ionic equation
2Fe2+(aq) + Br2(aq) + 2e- 2Fe3+(aq) + 2e- + 2Br-(aq)
Because we have the same number of electrons on each side of the
equation, these cancel.
2Fe2+(aq) + Br2(aq) 2Fe3+(aq) + 2Br-(aq)
Page 80 Redox

17 Oxidising and reducing agents

OXIDATION

2Fe2+(aq) + Br2(aq) 2Fe3+(aq) + 2Br-(aq)

The Br2 is oxidising the Fe2+ and is therefore the oxidising agent

2Fe2+(aq) + Br2(aq) 2Fe3+(aq) + 2Br-(aq)

REDUCTION

The Fe2+ is reducing the Br2 and is therefore the reducing agent

Oxidising agents oxidise other species but are themselves reduced.

Reducing agents reduce other species but are themselves oxidised.

Constructing overall ionic equations from half equations

2I-(aq) I2(aq) + 2e- oxidation half equation

MnO4-(aq) + 8H+(aq) +5e- Mn2+(aq) + 4H2O(l) reduction half equation

Before we add the half equations, we must first make sure they both
involve the same number of electrons. To do this we find a common
multiple of 2 (since 2 electrons in the top equation) and 5 (since 5
electrons in the bottom equation). 10 is the lowest common multiple so
we multiply the top equation by 5 and the bottom equation by 2 to
give us an equal number of electrons in both half equations.
now these half
10I-(aq) 5I2(aq) + 10e- equations have the
same number of
2MnO4-(aq) + 16H+(aq) +10e- 2Mn2+(aq) + 8H2O(l) electrons, they can
be added

10I-(aq) + 2MnO4-(aq) + 16H+(aq) +10e- 5I2(aq) + 10e- + 2Mn2+(aq) + 8H2O(l)

we can now cancel the
electrons that appear
on both sides

10I-(aq) + 2MnO4-(aq) + 16H+(aq) 5I2(aq) + 2Mn2+(aq) + 8H2O(l)

 Redox - oxidation numbers Page 81

18 Use of oxidation numbers

We have seen how we can use two half equations to produce the full
ionic equation for a redox reaction. We will now look at working out the
full ionic equation for a redox reaction from oxidation numbers.

Suppose we are told that hydrogen sulphide, H2S, reacts with nitric acid,
HNO3, and sulphur and nitrogen monoxide are two of the products.

We first write down what we know in the form of an equation. We will

not worry about the fact the equation isn’t balanced at this stage.
we need to now work out
Rule: H2S + HNO3 S + NO the oxidation numbers
hydrogen when to establish which species
not part of a have been oxidised and
metal hydride which reduced
has an Ox No.
S being an element
= +1
H +1 has an Ox No. of 0
Rule:
H +1
Oxygen, when not
S ? N ?
part of a peroxide
total =0 O -2
has an Ox No. = -2.
S in H2S must total =0
have an Ox No. H +1 N in NO
N in HNO3 must
= -2 N ? must = +2
be +5 to make
O -2
total = 0
O -2
Remember, the total of
O -2
the oxidation numbers has
total =0
the same value as the
overall charge

The oxidation numbers for the species that changed:

H2S + HNO3 S + NO
-2 +5 0 +2

the total Ox No. of S the total Ox No. of N

has increased from -2 has decreased from +5
to 0, a change of +2 to +2, a change of -3
(oxidation) (reduction)
To balance the equation, we must adjust the molar quantities in the
equation so that the change in the total of the oxidation numbers for
the oxidation and reduction is the same but opposite.
Page 82 Redox - oxidation numbers

18 To do this, we must find a common multiple of 2

(relating to the change in S) and 3 (relating to the
change in N). 6 is the lowest common multiple so
we multiply the H2S and S by 3 and the HNO3 and
NO by 2 so the the change in the totals of oxidation
number are +6 and -6 respectively. That is, the are
equal and opposite.

3H2S + 2HNO3 3S + 2NO

3 x(-2)=-6 2 x (+5)=+10 0 2 x (+2)= +4

the total Ox No. of S the total Ox No. of N

has increased from -6 has decreased from +10
to 0, a change of +6 to +4, a change of -6

We should notice however, the equation still does not balance. We have
8 hydrogens on the left hand side and none on the right. And 6
oxygens on the left hand side and only 2 on the right. So we are 4
oxygens and 8 hydrogens short on the right hand side. From these we
can make 4 molecules of water and so we can now balance the equation
by adding these water molecules.

3H2S + 2HNO3 3S + 2NO + 4H2O

When doing these problems, it is often necessary to add other species
to the equation in order to get the equation to balance. If the
reaction is carried out under acidic conditions, and you are short of
hydrogens, you may need to add H+ ions, if the reaction is carried under
alkaline conditions, you may need to add OH-. With practice, they do
become quite easy to do.
 Redox titrations Page 83

19 Redox titrations
In this experiment we will go through the stages of determining the
amount of anhydrous iron (II) sulfate in some iron (II) sulfate tablets.
Iron (II) sulfate can be used as a nutritional supplement for those that
suffer from iron deficiency anaemia. When making any kind of medicine it
is essential that the medicine contains the correct dose and so medicines
are always tested to ensure this is the case.

80 80

100mL 60 100mL 60

40 40

20 20

We take 10 tablets We then add around 40 cm3 of

containing iron (II) 1 mol dm-3 sulfuric acid and allow the
sulfate and add them to tablets to disintegrate. We stir with
a beaker. a glass rod and ensure all the iron (II)
sulfate has been dissolved up.
80

We then pass this though some filter

60

40

20
100mL

paper to filter out the insoluble

ingredients that make up the tablet.
We rinse the glass rod and beaker
thoroughly with distilled water and
rinse the residue on the filter paper to
ensure all traces of iron (II) sulfate end
up in the 100 cm3 volumetric flask. We
then make the solution up to the mark
100 cm3 with distilled water and mix by
inverting the flask several times.
Page 84 Redox titrations

19

We pipette 25 cm3 of our iron (II)

sulfate solution into a conical flask and
0.0200 mol dm-3
titrate with 0.0200 mol dm-3
KMnO4 solution
potassium manganate (VII), KMnO4,
solution.
The manganate (VII) ion is a deep
purple colour and when it reacts with
Fe2+ it forms Mn2+ which is not
coloured. As a result, this titration is
self indicating since as long as there are
Fe2+ ions present in the conical flask,
the solution will remain colourless.

The first sign of a permanent

purple/pink colouration means all the
Fe2+ has reacted.
250 cm 3 200 cm3
PYRE X®
Made in Germany

150

100 25 cm3
50 iron (II) sulfate
solution

We can then calculate how many moles of manganate (VII) it took to

react with all the Fe2+ and then, if we know the stoichiometry* of the
reaction between manganate (VII) and Fe2+ we can work out how many
moles of Fe2+ there are in the 25 cm3 of solution we titrated and
consequently the concentration of the iron (II) sulfate solution. From
this we can then the amount of iron (II) sulfate contained in the ten
tablets.

*this is the molar ratios in the balanced chemical equation

Let’s work out the balanced equation for the reaction between
manganate (VII) and Fe2+. When manganate (VII) reacts with Fe2+,
Mn2+ and Fe3+ are amongst the products so let’s write down what we
know in the form of an equation:

MnO4-(aq) + Fe2+(aq) Mn2+(aq) + Fe3+(aq)

 Redox titrations Page 85

19
MnO4-(aq) + Fe2+(aq) Mn2+(aq) + Fe3+(aq)

Mn ? The Ox No. Mn2+ and Fe3+ being simple

O -2 for iron will ions (i.e. not molecular ions like
O -2 be equivalent MnO4-) means they will have an
O -2 to its charge Ox No. equivalent to their charge
total -1 i.e. +2 of +2 and +3 respectively
Mn must
have Ox No.
+7

MnO4-(aq) + Fe2+(aq) Mn2+(aq) + Fe3+(aq)

+7 +2 +2 +3

the total change in

the total change in
Ox Nos for Mn is
Ox Nos for Fe is
-5 (reduction)
+1 (oxidation)

To get the change in the totals for the oxidation numbers to be equal
and opposite, we need to multiply the molar amounts of Fe2+ and Fe3+
by 5.

MnO4-(aq) + 5Fe2+(aq) Mn2+(aq) + 5Fe3+(aq)

+7 5 x (+2) = +10 +2 5 x (+3) = +15

the total change in

Ox Nos for Mn is the total change in
-5 Ox Nos for Fe is
+5

The equation still does not balance however since we have 4 oxygens on
the left hand side and none on the right. The reaction took place
under acidic conditions, as we added 1 mol dm-3 sulfuric acid to digest
the iron (II) sulfate tablets, so we could add 8H+ ions on the left to
make 4 molecules of water.

MnO4-(aq) + 5Fe2+(aq) + 8H+(aq) Mn2+(aq) + 5Fe3+(aq) + 4H2O(l)

The equation now balances. You may notice the the total of the
charges from both sides do not equal zero. This is not a problem
providing the charges on both sides total the same. In this case they
both total 17+.
Page 86 Redox titrations

19

For our titrations, the average titre of 0.0200 mol dm-3 potassium
manganate (VII) solution from 2 concordant results was 32.9 cm3.
To find the number of moles we use n = v x c, remembering to divide
the 32.9 cm3 by 1000 to convert to dm3. The number of moles of
manganate was 0.0329 x 0.0200 = 6.58 x 10-4

1 mol 5 mol
MnO4-(aq) + 5Fe2+(aq) + 8H+(aq) Mn2+(aq) + 5Fe3+(aq) + 4H2O(l)
c/mol dm-3 0.0200
v / dm3 0.0329
n / mol 6.58 x 10-4 3.29 x 10-3

x 5
our balanced chemical
equation tells us that
1 mol MnO4- reacts with
5 mol Fe2+

Therefore there were 3.29 x 10-3 moles of Fe2+ in the 25 cm3 we

pipetted into the conical flask. We can work out the concentration of
the iron (II) sulfate solution using:

c = n c = 3.29 x 10-3
n v 0.025

v c c = 0.1316 mol dm-3

 Redox titration Page 87

19
We can work out the number of mol of Fe2+ ions and consequently the
number of mol of FeSO4 in the 100 cm3 (0.100 dm3) solution using:
n = v x c

n
n = 0.100 x 0.1316

v c n = 0.01316 mol

To calculate the mass of the FeSO4 we can use this relationship:

m = M x n Fe 1 x 55.8 = 55.8
m S 1 x 32.1 = 32.1
O 4 x 16.0 = 64.0
m = 151.9 x 0.01316
M n 151.9
m = 1.999004 g

This is the mass of FeSO4 in 10 tablets. To get the amount of FeSO4

in each tablet we divide this by 10 and so each tablet contains
0.1999004 grams of FeSO4.
x 1000

1 g = 1000 mg

÷ 1000

Each tablet therefore contains 199.9004 mg. Now so far we have not
rounded any of the numbers from our calculations at all and we will
only round up now that we have our final result. We should not quote
our final result to a greater number of significant figures than any of
the values we have used to calculate the result. The concentration of
potassium manganate (VII) was given as 0.0200 mol dm-3 and the
mean titre value 32.9 cm3. Both of these were to 3 significant figures
and we should not give our answer to greater than 3 significant figures
and so we will quote our final result as 200 mg of FeSO4 per tablet.
Page 88 Electrochemical cells

20 Electrochemical cells
Devices that are powered by batteries utilise
electrical energy that is generated by a redox
reactions. Such batteries provide a flow of
electrons and we will now discover how redox
reactions are able to provide this flow of
electrons.
We will work with a very simple type of
battery, or to be more correct, we should say
electrochemical cell.

If we place a strip of zinc metal into a solution of copper (II) sulfate,

the zinc quickly discolours and a pink deposit of fresh copper metal forms
on the surface of the zinc strip.

zinc
copper
metal

80 80 80
copper (II) 100mL 60 100mL 60 100mL 60
sulfate
40 40 40

20 20 20

What is happening here is a displacement reaction. The zinc will more

readily oxidise than copper:
Zn(s) Zn2+(aq) + 2e-

The copper is reduced with the Cu2+ ion accepting two electrons to
form solid copper metal:
Cu2+(aq) + 2e- Cu(s)

The overall ionic equation can be arrived at as usual by adding together

the two half equations, ensuring the number of electrons involved in
each half equation is the same so that they cancel once they have been
added:

Zn(s) + Cu2+(aq) + 2e- Zn2+(aq) + 2e- + Cu(s)

 Electrochemical cells Page 89

20
What is happening here is two electrons from the Zn metal are released
and these electrons are accepted by the Cu2+ ion. What we have
therefore, is a flow of electrons from the zinc to the copper.

Zn Cu
2+ Zn2+ Cu

In an electrochemical cell we are able to get the electrons that are

transferred during a redox reaction to travel along a piece of wire and
we use resulting electrical energy to power our electrical devices.
A simple electrochemical cell

lamp
connecting wire

zinc electrode copper electrode

salt bridge
80 80

100mL 60 100mL 60
zinc copper (II)
40
sulfate solution
40 sulfate solution
20 20

For our cell here we have a piece of zinc metal acting as a electrode
and this is dipped into a solution of 1 mol dm-3 zinc sulfate solution.
The other electrode consists of a copper metal electrode in contact
with 1 mol dm-3 copper sulphate solution. The two electrodes are
connected together with a piece of wire and we have a small pea bulb
that illuminates when electrical current flows through the wire.
To complete the circuit, we have what is known as a salt bridge which
is just a piece of filter paper that is soaked in a concentrated solution
of potassium nitrate.
Page 90 Electrochemical cells

20
Now let’s look at what is happening at the surface of the two electrodes
that enables a flow of electrons to take place along the wire to power
the bulb.
At the copper electrode, Cu2+ ions accept 2 electrons from the copper to
form copper metal.

Cu2+ Cu

Cu2+(aq) + 2e- Cu(s)

At the zinc electrode, the zinc metal releases 2 electrons to form Zn2+
ions which then enter the solution.

Zn Zn Zn2+

Zn(s) Zn2+(aq) + 2e-

As we know, metals contain delocalised electrons and so the delocalised
electrons in the metal wires are free to flow from the zinc side to
the copper side along the wires and it is this flow of electrons that is
able to power the bulb.

In this cell, the zinc electrode is slowly being eroded away and the
copper electrode is becoming heavier.

Function of the salt bridge

On the zinc side, electrons are being removed and for every two
electrons that leave, two NO3-(aq) from the salt bridge enter the
solution to replace them. The solution therefore remains electrically
neutral.
On the copper side, Cu2+(aq) are being removed from the solution and
so to replace these, K+(aq) ions from the salt bridge enter the solution
and keep this side electrically neutral.
 Electrochemical cells Page 91

20
Utilising the electron transfer of redox reactions in this way is the
principle of all electrical batteries. With disposable batteries, the
batteries continue to function until the chemicals inside the battery
become depleted and then we say the batteries are dead and they
need to be disposed of. Rechargeable batteries involve a redox
reaction that is readily reversed by applying an electric current to
drive the reaction in the opposite direction and this allows the
batteries to be reused.

Lithium batteries
The use of lithium batteries has become increasingly widespread since
they have the advantage of having a high energy density. This means
they are able to store a large amount of energy for their mass/size.
However, there are increased risks from these batteries and there
have been some well publicised incidents in the media regarding these
batteries causing fires and explosions. There are also concerns about
the toxicity of these batteries.
Page 92 Standard electrode potentials, E

21 Standard electrode potentials, E

electron lamp
flow connecting wire

zinc electrode copper electrode

salt bridge
80 80

100mL 60 100mL 60
zinc copper (II)
40
sulfate solution
40 sulfate solution
20 20

Zn(s) Zn2+(aq) + 2e- Cu2+(aq) + 2e- Cu(s)

Cells like the one above are made up of two so-called half cells. Here
we have a Zn2+/Zn and Cu2+/Cu half cells.

If we replace the Cu2+/Cu half cell with another type of half cell, one
that involves magnesium metal in contact with a 1 mol dm-3
MgSO4(aq), the electrons travel in the opposite direction.

electron
flow

magnesium
zinc electrode electrode
salt bridge
80 80

100mL 60 100mL 60

40 zinc 40
magnesium
sulfate solution sulfate solution
20 20

Zn2+(aq) + 2e- Zn(s) Mg(s) Mg2+(aq) + 2e-

 Standard electrode potentials, E Page 93

21
That is they travel from the magnesium side to the zinc side. In this
cell the Zn2+ ions are accepting two electrons from the zinc metal and
being converted to zinc metal. The magnesium metal is releasing two
electrons and forming the Mg2+ ion which then enters the solution. This
is happening because magnesium is more readily oxidised than zinc or we
could say magnesium is a stronger reducing agent because it is able to
reduce the Zn2+ to zinc metal.

The overall ionic equation is:

Mg(s) + Zn2+(aq) Mg2+(aq) + Zn(s)

To Summarise
So far then we have learned that:
.You can make a half cell by having a metal in contact with a
solution of its ions.
.Two dissimilar half cells can be joined together to make a
cell.
.Whether oxidation or reduction occurs in a half cell depends
on the species it is being paired with. Oxidation, that is the
release of electrons, will occur in the cell in which the species
is more readily oxidised and this will form the negative
terminal of the cell.

So, are we able to predict which way the electrons will flow when we
pair together any two half cells and are we able to predict the force by
which electrons are pushed around, the so called overall cell potential
which is measured in volts using a voltmeter connected to the circuit?

The answer to both these questions is yes...sort of. We will now learn
how it is possible to make these predictions and learn about the
limitations of such predictions.

Standard hydrogen half cell

The way we can rank the relative ease by which metal ions are reduced,
that is gain electrons, is by measuring the overall cell potential when a
particular half cell is measured against a standard half cell. The standard
electrode we use is the standard hydrogen half cell.
Page 94 Standard electrode potentials, E

21

H2(g)
1 atm
Temperature = 25°C
80

100mL 60
hydrochloric acid solution platinum electrode
40
[H (aq)] = 1 mol dm
+ -3

20

The standard hydrogen half cell

The redox half equation involved:

2H+(aq) + 2e- H2(g)

Because hydrogen is a gas, we cannot use it to make an electrode

from in the same way we can for half cells that involve pure metals.
We therefore use a platinum electrode and we bubble hydrogen gas
alongside this electrode and the electron exchange takes place on the
surface of the platinum. Platinum is suitable since it is an unreactive
metal.

For the standard hydrogen half cell, we standardise on one atmosphere

of pressure for the hydrogen gas and a solution of 1 mol dm-3
hydrochloric acid to provide the H+ ions. We can then connect other
half cells to this and measure the overall cell potential using a
voltmeter. The cell potential observed is known as the standard
electrode potential, E , for the species being studied.

The standard electrode potential, E , is the electromotive force

(e.m.f.) of a half cell compared with a standard hydrogen half
cell.
 Standard electrode potentials, E Page 95

The reading on the voltmeter is

21 the standard electrode potential,
E , for the Cu2+/Cu half cell
+0.34 V
Temperature = 25°C

electron
flow

copper electrode H2(g)

1 atm
80 80

100mL 60 100mL 60

1 mol dm-3 40 40 platinum electrode

CuSO4 20 20 [H+(aq)] = 1 mol dm-3

Cu2+(aq) + 2e- Cu(s) H2(g) 2H+(aq) + 2e-

Reduction Oxidation
H2(g) is more readily oxidised that Cu(s), since H2 is the stronger
reducing agent as it is able to reduce Cu2+(aq) to Cu(s).

note, the sign

on the volt meter The reading on the voltmeter is
display is negative. -0.76 V the standard electrode potential,
This is because the
E for the Zn2+/Zn half cell
electrons are flowing
in the opposite
direction electron
flow

zinc electrode

80 80

100mL 60 100mL 60
standard hydrogen
1 mol dm-3 half cell
40 40
ZnSO4
20 20

Zn(s) Zn2+(aq) + 2e- 2H+(aq) + 2e- H2(g)

Oxidation Reduction
Page 96 Standard electrode potentials, E

21
A series of various half cells placed in order of increasing standard
electrode potentials is called the electrochemical series. Species that
are most readily reduced, that is the better oxidising agents have more
positive standard electrode potentials whereas those species that are
more readily oxidised, that is are the better reducing agents have more
negative standard electrode potentials.
reduction direction
E / volt
Na+(aq) + e- Na(s) -2.71

ease of reduction increases

Mg2+(aq) + 2e- Mg(s) -2.37
Al3+(aq) + 3e- Al(s) -1.66
Zn2+(aq) + 2e- Zn(s) -0.76
Pb2+(aq) + 2e- Pb(s) -0.13
2H+(aq) + 2e- H2(g) 0.00
Cu2+(aq) +2e- Cu(s) +0.34
Fe3+(aq) + e- Fe (aq)
2+
+0.77
Ag+(aq) + e- Ag(s) +0.80
MnO4-(aq) + 8H+(aq) + 5e- Mn (aq) + 4H2O(l) +1.54
2+

F2(g) + 2e- 2F-(aq) +2.87

oxidation direction

By convention the half equations describing the redox reaction in the

electrochemical series are written in the reduction direction.

You will notice some non-metals in the series and some species that do
not involve the oxidation of the pure metal like for example, the
reduction of Fe3+ to Fe2+. In these cases, like with the hydrogen half
cell, a platinum electrode is used as a surface for the electron exchange
to take place.

80

100mL 60 the concentration of

1 mol dm-3 Fe3+(aq)
each species of the
Platinum 40 +
same element needs
electrode 1 mol dm Fe2+(aq)
-3
to be 1 mol dm-3
20
 Standard electrode potentials, E Page 97

21
We now know how standard electrode potentials are measured and we will
now learn how we can predict which way the electrons will flow when
connecting two half cells. We will stick with our cell that involves Cu2+/Cu
and Zn2+/Zn half cells. Let’s look up the standard electrode potentials
for both these:
the half cell with the
more negative standard
electrode potential will
Zn2+(aq) + 2e- Zn(s) E = -0.76 V form the negative terminal
where oxidation takes place

Cu2+(aq) + 2e- Cu(s) E = +0.34 V

The half equations therefore become:

Zn(s) Zn2+(aq) + 2e- Oxidation - electrons are released

electron flow

Cu2+(aq) + 2e- Cu(s) Reduction - electrons are gained

To predict the cell potential from the standard electrode potentials,

we just take the difference between the two standard electrode
potential values.

-3.00 -2.00 -1.00 0.00 1.00 2.00 3.00

Ecell = 1.10 V volt

EZn/Zn2+ =-0.76 V

ECu/Cu2+ = +0.34
As a formulae, the standard cell potential, Ecell , is given by:

Ecell = Epositive terminal - Enegative terminal

Ecell = 0.34 - (-0.76) V
Ecell = 1.10 V
Page 98 Standard electrode potentials, E

21 Predicting feasibility of redox reactions using

E values
We can use standard electrode potentials to predict the feasibility of
redox reactions. Just a look at where the different species are in the
electrochemical series will show that the species with a more positive
standard electrode potential will oxidise a species with a less positive
standard electrode potential.
reduction direction
E / volt
Na+(aq) + e- Na(s) -2.71
Mg2+(aq) + 2e- Mg(s) -2.37
Al3+(aq) + 3e- Al(s) -1.66
Zn2+(aq) + 2e- Zn(s) -0.76
Cu2+ will Pb2+(aq) + 2e- Pb(s) -0.13
oxidise Zn 2H+(aq) + 2e- H2(g) 0.00
Cu2+(aq) +2e- Cu(s) +0.34
Cu2+ will
Fe3+(aq) + e- Fe (aq)
2+
+0.77
NOT oxidise
Ag Ag+(aq) + e- Ag(s) +0.80
MnO4-(aq) + 8H+(aq) + 5e- Mn2+(aq) + 4H2O(l) +1.54
F2(g) + 2e- 2F-(aq) +2.87
oxidation direction

Such predictions do have limitations however because a given reaction

may appear feasible but the activation energy for the reaction is so
high, the reaction may not occur or, the rate of reaction may be
extremely slow.

As a rule of thumb, if the calculated standard cell potential is less than

+0.40 V, it is unlikely the reaction will occur. Also, we must remember
that standard electrode potentials are measured under a standardised
set of conditions. The solutions of each species of the same element are
1 mol dm-3 or equimolar and the temperature is 25°C and any
deviations from these conditions could affect the validity of any
predictions.
 Standard electrode potentials, E Page 99

21 Redox equilibria
We can think of each half cell as a pair of species in equilibrium:

Zn2+(aq) + 2e- Zn(s)

In the case of the zinc half cell, Cu2+ being a stronger oxidising agent is
able to remove electrons from the left hand side and therefore push the
equilibrium to the left.

Zn2+(aq) + 2e- Zn(s)

Copper removes the electrons causing the
equilibrium to shift to the left
On the copper side, because zinc is a stronger reducing agent, it is able
to add electrons to the left of this half equation and therefore push the
equilibrium to the right.

Cu2+(aq) + 2e- Cu(s)

Zinc adds electrons causing the
equilibrium to shift to the right
Page 100 Fuel cells

22 Fuel cells
The idea of producing electrical cells with sufficient energy storage to
power road vehicles is becoming increasingly attractive since this will
reduce air pollution and reduce carbon emissions as an increasing amount
of our electricity comes from renewable sources.

Great strides have been made in this area and lithium ion batteries
used in the Tesla range of cars can now give ranges up to 300 miles on
a single charge. However, long recharging times still present a major
disadvantage to electric road vehicles.

A possible solution is the use of fuel cells. Fuel cells produce electricity
but rather than require recharging they just need to be refuelled.
There are various types of fuel cell but we will look at a alkaline
hydrogen fuel cell.

H2O(g) (waste)

pourous electrode pourous electrode

H2(g) hot O2(g)/air

OH-(aq)

This type of cell consists of a solution of hydroxide which acts as the

electrolyte that is heated and the hydrogen fuel is fed into the cell
and comes into contact with the hydroxide via a porous electrode. The
other half cell involves oxygen coming into contact with the hydroxide
via another porous electrode. The only waste product, as we will see is
pure water.
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The redox half equations with their standard electrode potentials are as
follows.
2H2O(l) + 2e- H2(g) + 2OH-(aq) E = -0.83 V

½O2(g) + H2O(l) + 2e- 2OH-(aq) E = +0.40 V

If we remember, the half cell with the most negative standard electrode
potential will form the negative terminal where electrons are released.
As a result, this is where oxidation takes place and so the half equation
is:
H2(g) + 2OH-(aq) 2H2O(l) + 2e-

Reduction occurs at the other electrode:

electron flow

½O2(g) + H2O(l) + 2e- 2OH-(aq)

To get the overall equation, we add the half equations. And cancel
whatever is on both sides.

H2(g) + 2OH-(aq) + ½O2(g) + H2O(l) + 2e- 2H2O(l) + 2e- + 2OH-(aq)

H2(g) + ½O2(g) H2O(l)

To calculate the overall cell potential we use:

Ecell = Epositive terminal - Enegative terminal

Ecell = 0.40 - (-0.83) V
Ecell = 1.23 V