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Chapter 8: Redox Equilibria and Electrode Potentials

8.1. Introduction
A redox reaction involves both oxidation and reduction
Oxidation is the loss of electrons
Reduction is the gain of electrons

(Remember OILRIG)

Redox reactions can be divided up into two half equations, one showing the reducing
agent and the other the oxidising agent.
A reducing agent is a species that loses electrons easily, becoming
oxidised in the process.
An oxidising agent is a species which gains electrons easily, becoming
reduced in the process
These half equations show how many electrons the reducing agent loses and how
many the oxidising agent loses. The change in oxidation number of the species is
directly related to the number of electrons transferred. Water and hydrogen ions also
often appear in half equations to balance any hydrogen or oxygen atoms.
e.g. the oxidation of hydrogen peroxide by dichromate(VI) ions,
Cr2O72- + 8H+ + 3H2O2 2Cr3+ + 7H2O + 3O2
(+6)(-2)
(+1) (+1)(-1)
(+3)
(+1)(-2) (0)
Each Cr in Cr2O72- gains 3 electrons to form Cr3+ - it is the oxidizing agent and
becomes reduced
2+
3+
Cr2O7 + 14H + 6e 2Cr + 7H2O
Each O in H2O2 loses 1 electron to form O2 - it is the reducing agent and
becomes oxidized
+
H2O2 O2 + 2H + 2e
In this chapter, the system of electrode potentials will be introduced. At a basic level,
electrode potentials are measurements which show the relative strengths of oxidizing
agents and reducing agents.
8.2. Electrode potentials and the electrochemical series
At GCSE level, test-tube displacement reactions are used to demonstrate that some
metals are more reactive than others. By comparing the results of such experiments, a
reactivity series can be drawn up.
So zinc must be
more reactive
than copper
zinc
metal

copper(II)
sulphate
solution

copper
metal
ppte.

- 68 -

zinc(II)
sulphate
solution

The displacement reaction between zinc and copper(II) sulphate is actually a redox
reaction, as shown by the changes in oxidation number:
CuSO4(aq) + Zn(s) Cu(s) + ZnSO4(aq)
(+2)
(0)
(0)
(+2)
In simple terms, the Cu2+ ions have gained two electrons and been reduced whilst the
zinc atoms have lost two electrons and been oxidised. The zinc is therefore a more
powerful reducing agent than copper.
At A-level, the reactivity series is called the electrochemical series as it is listed more
o

accurately using Standard Electrode Potentials (E ). The electrode potential of a


substance is measured in volts and shows its ability to lose or gain electrons. By
convention, electrode potentials are always written next to a half equation which has
electrons on the left hand-side, so that:
o

A positive E shows the forward reaction is thermodynamically favorable,


o

a negative E shows the reverse reaction is thermodynamically favoured

A small section of the electrochemical series


K+ + e-

Na+ + e-

E = -2.92 V
o

Na

E = -2.71 V

Zn2+ + 2e-

Zn

E = -0.76 V

Fe2+ + 2e-

Fe

E = -0.44 V

2H+ + 2e-

H2

E = 0.00 V

Cu2+ + 2e-

Cu

E = +0.34 V

I2 + 2e-

o
o
o
o

2I-

Br2 + 2e-

E = +0.54 V
o

2Br-

E = +1.09 V

Cr2O72- + 14H+ + 6e- 2Cr3+ + 7H2O


MnO4- + 8H+ + 5e-

Mn2+ + 4H2O

E = +1.51 V
o

Cl2 + 2e- 2ClF2 + 2e-

E = +1.33 V
E = +1.36 V
o

2F-

E = +2.87 V

The most powerful reducing agent in the list is potassium metal - the species which
loses electrons most effectively. As the very first equation has the most negative
electrode potential, it goes backwards most readily and potassium loses electrons.
The most powerful oxidizing agent is fluorine. The final equation has the most
positive electrode potential, goes forwards most readily and fluorine gains electrons.
The hydrogen equation has been given an electrode potential value of 0.00 volts by
chemists so that it acts as the standard.
- 69 -

8.3. Using electrode potentials to predict chemical reactions


Just as half equations can be combined to give full redox equations, electrode
potentials can be added to show whether redox reactions are thermodynamically
favoured or not. Even though half equations are sometimes multiplied through by
whole numbers to ensure electrons cancel, electrode potentials are not they are
simply added together to give E
A positive E

a negative E

reaction

reaction

values. Again,

shows the forward reaction is thermodynamically feasible,

reaction

shows the reverse reaction is thermodynamically feasible.

e.g.1 for the reaction between manganate(VII) ions and iodide ions,
(1) MnO4- + 8H+ + 5e(2) 2I-

Mn2+ + 4H2O

E = +1.51 V
o

I2 + 2e-

E = -0.54 V

Equation (1) is multiplied by 2 and equation (2) by 5 before combination gives:


2MnO4- + 16H+ + 10I- 2Mn2+ + 8H2O + 5I2
But E

reaction

is simply (+1.51) + (-0.54) = +0.98 V


As E

reaction

is positive, the forward reaction is feasible.

e.g.2 for the reaction between manganate(VII) ions and fluoride ions,
(3) MnO4- + 8H+ + 5e(4) 2F-

Mn2+ + 4H2O

E = +1.51 V
o

F2 + 2e-

E = -2.87 V

Equation (3) is multiplied by 2 and equation (4) by 5 before combination gives:


2MnO4- + 16H+ + 10F- 2Mn2+ + 8H2O + 5F2
and E

reaction

= (+1.51) + (-2.87) = -1.36 V


As E

is negative, the forward reaction is


not feasible (but the reverse reaction is!)

reaction

Problems with E predictions


o

A positive value for E reaction shows that a reaction is feasible, not that it definitely will
happen. There are 2 main reasons why reactions that are feasible do not actually
occur in reality:
o

a) E predictions take no account of the size of the activation energy.


Kinetically stable reactions may be so slow that they appear not to occur at all.

- 70 -

b) E predictions are only valid for reactions mixed under standard conditions.
Real reactions are rarely mixed at 25C, 1 atm and 1 moldm-3.
Methods for answering exam questions
o

There are two general methods for answering exam questions on E predictions. The
second method is much faster than the first, but it is best to be able to master both.
Method 1 calculating E

reaction

To see if a reaction is feasible or not, the half equations are combined and E reaction
calculated as before. However, before this can be done, one of the half-equations
must be reversed and the sign of its electrode potential changed. To decide which
half-equation to reverse, look closely at the reactants in the question these must
both appear on the left of the final overall equation.
e.g.1. Will zinc reduce copper(II) ions to copper metal?
o

(1) Zn2+ + 2e-

Zn

E = -0.76 V

(2) Cu2+ + 2e-

Cu

E = +0.34 V

As zinc and copper(II) ions are the reactants, equation (1) must be flipped
[zinc is on the right in equation (1)].
Zn + Cu2+ Zn2+ + Cu

So,

and E

= (+0.76) + (+0.34) = +1.10 V,


positive, therefore reaction is feasible.

reaction

e.g.2. Is the following reaction feasible?


Br2 + 2Cl- 2Br- + Cl2
o

(1) Br2 + 2e-

2Br-

E = +1.09 V

(2) Cl2 + 2e-

2Cl-

E = +1.36 V

As chloride ions are reactants, equation (2) has been flipped.


So E

reaction

= (+1.09) + (-1.36) = -0.27 V, negative, therefore no reaction.


o

Method 2 direct comparison of E values


o

A simple comparison of the E values of two half equations will show which will
proceed forwards (the most positive) and which will go backwards (the most
negative). Again, a close inspection of the reagents in the question will then show
whether or not reaction will occur.
e.g.1. Will manganate(VII) ions oxidize chloride ions to chlorine?
(1) MnO4- + 8H+ + 5e(2) Cl2 + 2e-

Mn2+ + 4H2O

E = +1.51 V
o

2Cl-

E = +1.36 V

- 71 -

Equation (1) will go forwards as its E is more positive, and (2) will go backwards.
So MnO4- will oxidise Cl- as E

MnO4-/Mn2+

is more positive than E

Cl2/Cl-

e.g.2. Will zinc reduce magnesium ions to magnesium metal?


o

(1) Zn2+ + 2e-

Zn

E = -0.76 V

(2) Mg2+ + 2e-

Mg

E = -2.37 V

Equation (1) will go forwards as its E is more positive, and (2) will go backwards.
So Zn will NOT reduce Mg2+ as E

Zn2+/Zn

is less negative than E

Mg2+/Mg

There are always four possible ways to express the answer using this method (E
o

A/B

more positive than E C/D or E C/D less positive than E A/B etc.). Care must be taken to
avoid silly errors. The advantage of this method lies in the fact that it allows a large
range of reactants to be compared quickly. Many A-level questions rely on this skill.
e.g.3 Which metal ions can be reduced by zinc metal?
o

K+ + e -

E = -2.92 V

Na+ + e-

Na

E = -2.71 V

Zn2+ + 2e-

Zn

E = -0.76 V

Fe2+ + 2e-

Fe

E = -0.44 V

Ni2+ + 2e-

Ni

E = -0.25 V

Cu2+ + 2e-

Cu

E = +0.34 V

o
o
o

Ag+ + e- Ag
E = +0.80 V
The zinc equation must go backwards and be more negative than the other half
equation if reaction is to occur.
So Zn will reduce Fe2+, Ni2+, Cu2+ and Ag+ because E
more negative than E

Fe2+/Fe

,E

,E

Ni2+/Ni

Cu2+/Cu

and E

Zn2+/Zn

Ag+/Ag

is
.

8.4. Disproportionation
Just as electrode potentials can be used to predict the feasibility of normal redox
reactions, they can also reveal the possibility of a species undergoing
disproportionation.
Disproportionation is the simultaneous oxidation and
reduction of a single species
A species must be able to undergo oxidation and reduction and will therefore appear
on the left in one half equation and on the right in another. Reversing one of these
and adding it to another then gives a disproportionation equation the overall sign of
o

E then shows feasibility.


e.g. Will copper(I) ions disproportionate?
(1) Cu2+ + e(2) Cu+ + e-

Cu+

E = +0.15 V
o

Cu

E = +0.52 V

- 72 -

Reversing (1) and adding gives

Cu+ + Cu+ Cu + Cu2+

and E reaction = +0.37 V disproportionation is feasible.


8.5. Electrochemical cells
An electrochemical cell is the scientific term for the basic component in a battery.
Cells are basically powered by redox reactions.
Consider again the displacement reaction between zinc metal and copper(II) sulphate.
As reaction occurs, the blue
colour of the Cu2+ ions fades,
the zinc metal dissolves, a pink
precipitate of copper is seen
and heat energy is released
Zn(s) + CuSO4(aq) ZnSO4(aq) + Cu(s)
This is a simple redox reaction: The zinc loses electrons and is oxidised,
the copper(II) ions gain electrons and are reduced.
In an electrochemical cell exactly the same reaction occurs, but the redox reagents are
placed in separate pots (or half-cells). The half-cells are connected with a metal
wire so that electrons can flow from one reagent to the other when the circuit is
completed.
e.g. the zinc metal copper ion cell

ezinc metal

zinc(II) sulphate
solution
i.e. Zn2+(aq)

copper metal

salt
bridge

copper(II) sulphate
solution
i.e. Cu2+(aq)

The salt-bridge is used to complete the circuit without using a metal wire metals
are good reducing agents and would set up more competing redox reactions. A salt
bridge can be made by dipping a filter paper in an aqueous solution of potassium
nitrate and allows ions to flow between half cells.
The reaction driving the cell is the same as that above in the test-tube reaction but
electrical energy is produced instead of heat.
Zn(s) + CuSO4(aq) ZnSO4(aq) + Cu(s)
(0)
(+2)
(+2)
(0)
In this circuit, electrons travel from left to right because the zinc has lost electrons
and the copper(II) ions have gained them.

- 73 -

As electrons flow through the wire away from the zinc, the metal dissolves, the
copper electrode grows fatter and the blue colour of the copper(II) ion fades. When
either reagent runs out, the cell becomes flat.
8.6. Electromotive force (emf) and electode potentials
Consider the cell produced if the zinc above is replaced with magnesium. As
magnesium is more reactive (i.e. a better reducing agent) than zinc, it pushes electrons
around the circuit much more strongly. If a voltmeter is added in place of the bulb, it
will measure the electromotive force (emf) of the cell.
high resistance voltmeter
V

magnesium
metal

copper metal

copper(II) sulphate
solution
i.e. Cu2+(aq)

magnesium
sulphate solution
i.e. Mg2+(aq)

As electrode potentials are used to show the strength of oxidizing agents and reducing
agents, they can be used to predict the emf of any cell. Electrode potentials are
actually measured using cells; this is why they have units of volts.
The half equations for the cell above are:
o

(1) Cu2+ + 2e-

Cu

E = +0.34 V

(2) Mg2+ + 2e-

Mg

E = -2.37 V

Equation 2 will go backwards as its E is more negative, so the cell reaction is


Cu2+ + Mg
Cu + Mg2+
and emf = (+0.34) + (+2.37) = 2.71v
So if the cell is connected up as shown, the voltmeter will read 2.71v. There are
several ways of representing emf, such as E

reaction

and E

cell

Again, electrons flow away from the mort reactive metal (magnesium) until all of it
dissolves or all of the copper(II) ions have reacted. If the voltmeter is replaced with
an electrical supply with a voltage higher than 2.71v, electrons can be pushed back to
the magnesium and the cell is re-charged. During this process, the reverse reaction
occurs.
8.7. Measuring electrode potentials
As a circuit is required to measure a potential difference, single electrode potentials
cannot be measured. Instead, chemists have chosen a standard electrode against
which all other electrodes are then compared. The standard hydrogen electrode has

- 74 -

been given an electrode potential of 0.0v and is included in circuits to measure other
electrode potentials.
o

a) The circuit used to measure E for metal systems at 25C


o

e.g. to measure E for Cu2+ + 2e-

Cu
voltmeter
V
copper metal

H2(g)
1atm
platinum
metal

copper(II) sulphate
solution 1 moldm-3
i.e. Cu2+(aq)

H+(aq)
1 moldm-3
The Cu2+/Cu
electrode
(half cell)

The Standard
Hydrogen
Electrode
2H+ + 2e-

H2

E = 0.00v

E =?

As the electrode potential of hydrogen has been given a value of 0.0v, the voltmeter
o

reading gives E for the copper(II)/copper half equation, in this case, +0.34v.
The whole apparatus can be placed in a temperature controlled waterbath at 25C
for more accurate results.
o

b) The circuit used to measure E for gaseous systems at 25C


o

e.g. to measure E for Cl2 + 2e-

2ClV

H2(g)
1atm

Cl2(g) 1 atm

platinum
metal

platinum
metal

H+(aq)
1 moldm-3
(e.g. HCl)

Cl-(aq) 1 moldm-3
(e.g. NaCl)

- 75 -

The voltmeter reading again gives the E value for Cl2/Cl-. The platinum electrode
must be in contact with both chlorine and chloride ions dissolved in water. A
temperature controlled waterbath increases the accuracy of results.
o

c) The circuit used to measure E for aqueous ions at 25C


o

e.g. to measure E for MnO4- + 5e- + 8H+

Mn2+ + 4H2O

H2(g)
1atm
platinum
metal
H+(aq)
1 moldm-3
(e.g. HCl)

platinum
metal
MnO4-(aq)
+
Mn2+(aq)
+
H+(aq)

all at
1 moldm-3

Notice than in the half-cell under test, the platinum electrode must be in contact with
both reactants (MnO4-, H+) and products (Mn2+). The voltmeter reading again gives
the electrode potential for the MnO4-/Mn2+ system.

8.8. The definition of electrode potential


The actual definition of electrode potential follows directly from the circuits needed to
measure them. In general terms,
an electrode potential is the emf of a cell composed of the standard hydrogen
electrode connected to the half-cell, when all concentrations are 1moldm-3,
pressures are 1atm and temperature is 298K.
This definition should then be applied to the actual half cell concerned.
e.g.1 for a metal, such as copper
the electrode potential is the emf of a cell composed of the standard hydrogen
electrode connected to copper metal in a solution of Cu2+ ions when all
concentrations are 1moldm-3, pressures are 1atm and temperature is
298K.
e.g.2 for a gas, such as chlorine
the electrode potential is the emf of a cell composed of the standard hydrogen
electrode connected to platinum metal in contact with Cl2 gas and a
solution of Cl- ions with concentrations of 1moldm-3, pressures of 1atm
- 76 and a temperature
of 298K.

e.g.3 for an aqueous ion, such as manganate(VII)


the electrode potential is the emf of a cell composed of the standard hydrogen
electrode connected to platinum metal in an aqueous solution of MnO4-,
H+ and Mn2+ with concentrations of 1moldm-3, pressures of 1atm and a
temperature of 298K.

8.9. Analysing redox reagents via titration


8.9.1. Analsing reducing agents using potassium manganate(VII)
Potassium manganate(VII) is a powerful oxidizing agent and reacts rapidly with many
reducing agents. Other salts are known [e.g. NaMnO4, Ba(MnO4)2] and all are purple
in colour due to the manganate(VII) ion:
MnO4- + 8H+ + 5e-
(purple)

Mn2+ + 4H2O
(colourless)

As can be seen from the half equation, mandanate(VII) ions only work in the presence
of acid for this reason, dilute sulphuric acid must be added to any reducing agent
before titration commences.
As the titration proceeds, the
purple colour of the manganate
disappears until the end-point
is reached.

KMnO4 solution
in burette

2+

reducing agent (e.g. Fe )


AND
dilute H2SO4

Despite the difficulties in


reading the burette, the
manganate(VII) is placed in the
burette because a colourless to
pink end-point is easier to
spot than pink to colourless

A typical manganate(VII) analysis


1. A sample of steel (4.0g) was dissolved in acid to form 250cm3 of Fe2+ solution.
2. A 25cm3 sample was taken via pipette and placed in a conical flask and treated
with excess dilute sulphuric acid.
3. A burette was rinsed and then filled with potassium manganate(VII) solution of
concentration 0.05 moldm-3.
4. The Fe2+/H2SO4 solution was then titrated with swirling until a permanent pink
colour remained in the flask.
5. The titre was noted and the analysis repeated until concordant results were
achieved.
- 77 -

6. On average, 28.2cm3 of the manganate(VII) solution was needed for reaction.

MnO4- + 8H+ + 5Fe2+

Mn2+ + 4H2O + 5Fe3+

Calculation:
moles of MnO4- used = 28.2 x 0.05 = 1.41 x 10-3
1000
2+
moles Fe = 5 x 1.41 x 10-3 = 7.05 x 10-3 in 25 cm3
= 0.0705 in 250 cm3
2+
mass Fe = mass Fe = moles x rmm
= 0.0705 x 56 = 3.948g
so % Fe in the steel = 3.948 x 100 = 98.8%
4.0
Standardisation of manganate(VII) solutions
Manganate(VII) ions are such strong oxidizing agents that they will react with dust in
the air. This means that manganate(VII) solutions go off and their concentration
must be checked before super-accurate analyses. This is done via titration of a known
mass of sodium ethandioate (Na2C2O4). The ethandioate ions are oxidized to carbon
dioxide:
2MnO4- + 5C2O42- + 16H+ 2Mn2+ + 8H2O + 10CO2
A typical standardization calculation:
A 5.0g mass of sodium ethandioate was dissolved in water and made up to 250cm3.
When a 25cm3 sample was titrated with manganate(VII) solution, a volume of
16.8cm3 was needed for reaction.
Moles Na2C2O4 used = mass = 5.0 = 0.03731 in 250cm3
rmm 134
= 3.731 x 10-3 in 25cm3
-3
moles MnO4 = 3.731 x 10 x 2 = 0.01492
5
conc. MnO4 = moles x 1000 = 0.01492 x 1000 = 0.0888 moldm-3
volume
16.8
8.9.2. Analysing oxidizing agents with potassium iodide and sodium thiosulphate
In these analyses, the oxidizing agent is first treated with a large excess of potassium
iodide (KI) solution. The iodide ions are oxidized to iodine and the reaction mixture
turns brown. The amount of iodine is then found by titration with sodium
thiosulphate solution (Na2S2O3):
2S2O32- + I2
brown

S4O62- + 2Icolourless

During the titration, the brown colour of


the iodine slowly fades to a yellow colour.
Starch solution is then added before the
end-point is reached as a blue-black to
colourless change is easier to spot.
- 78 -

Na2S2O3 solution
in burette
oxidising agent (e.g. Cu2+)
and
excess KI produces I2

A typical iodide/thiosulphate analysis


1. A brass coin (3.0g) was dissolved in acid to form 250cm3 of Cu2+ solution.
2. A 25cm3 sample was taken via pipette and placed in a conical flask and treated
with excess potassium iodide to form a brown solution of iodine.
2Cu2+ + 4I- 2CuI + I2
3. A burette was rinsed and then filled with sodium thiosulphate solution of
concentration 0.2 moldm-3.
4. The iodine solution was then titrated with swirling until a yellow colour remained.
After adding starch, the titration continued until the blue black colour disappeared.
5. The titre was noted and the analysis repeated until concordant results were
achieved.
6. On average, 18.4cm3 of the thiosulphate solution was needed for reaction.
Calculation:

moles of S2O32- used = 18.4 x 0.2 = 3.68 x 10-3


1000
2S2O32- + I2 S4O62- + 2Imoles I2 formed = 3.68 x 10-3 2 = 1.84 x 10-3 in 25 cm3
moles Cu2+ formed = 1.84 x 10-3 x 2 = 3.68 x 10-3 in 25 cm3
= 0.0368 in 250 cm3
mass Cu2+ = mass Cu = moles x rmm
= 0.0368 x 63.5 = 2.337g
so % Cu in the coin = 2.337 x 100 = 77.9%
3.0

Note: The thiosulphate ion can actually be oxidized in two different ways depending
on the strength of the oxidizing agent. This is shown by the following half equations:
2SO42- + 10H+ + 8eS4O62- + 2eo

As E

I2/I-

S2O32- + 5H2O

2S2O32-

E = +0.57 V
o

E = +0.09 V

is only +0.54 V, iodine will only react to form S4O62-. Stronger oxidizing
o

agents like chlorine (E Cl2/Cl- = 1.36 V) makes both S4O62- and SO42- simultaneously in
different reactions and can therefore not be analysed by titration with thiosulphate.

- 79 -

8.10. The rusting of iron


Rust is hydrated iron(III) oxide, Fe2O3.nH2O. The rusting of iron metal is an
electrochemical process and occurs when the surface is in contact with water which
contains dissolved oxygen.
When iron metal is impure, heated or mechanically worked, areas of the metallic
lattice are weakened and some iron(II) ion start to dissolve in the water this kicks
off the rusting process:
Diagram of the rusting process:
3. Further oxidation to Fe3+
1. Fe2+ ions dissolve

OH-

water with
dissolved O2

O2
2. oxygen
reduced

iron
metal

1. At areas of weakness, iron(II) ions dissolve, leaving behind electrons in the metal:
Fe Fe2+ + 2e-

(oxidation)

2. Electrons travel through the metal to another point on the surface where oxygen is
reduced to hydroxide ions:
O2 + 2H2O + 4e- 4OH(reduction)
3. The iron(II) hydroxide now present in the water is further oxidized to rust
2Fe(OH)2 + O2 Fe2O3 + 2H2O
As more and more rust forms it flakes away from the surface, exposing fresh metal
and so deep pitting eventually results where the iron(II) ions dissolve.
Rust prevention
There are two general methods used to prevent iron from rusting:
a) Coverage of the iron surface
If water and oxygen are not in contact with the metal then no rusting can occur.
Painting, oiling and tinning all work in this way. As tin is unreactive, it does not
readily corrode.
o

Fe2+ + 2e-

Fe

E = -0.44 V

Sn2+ + 2e-

Sn

E = -0.14 V

b) Sacrificial protection

- 80 -

If a block of a reactive metal (magnesium or zinc) is placed in contact with the


iron, the reactive metal loses electrons to the iron, preventing the formation of Fe2+
ions. The reactive metal dissolves as ions instead, sacrificed for the iron. The
reactive metal must therefore be replaced readily.
o

Mg2+ + 2e-

Mg

E = -2.37 V

Zn2+ + 2e-

Zn

E = -0.76 V

Fe2+ + 2e-

Fe

E = -0.44 V

o
o

- 81 -

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