Chemistry, The Central Science, 10th edition

Theodore L. Brown; H. Eugene LeMay, Jr.; and Bruce E. Bursten

Chapter 20
Electrochemistry

Electrochemistry
Electrochemical Reactions

In electrochemical reactions, electrons

are transferred from one species to
another.

Electrochemistry
Oxidation Numbers

In order to keep
track of what loses
electrons and what
gains them, we
assign oxidation
numbers.

Electrochemistry
 Oxidation and Reduction

• A species is oxidized when it loses electrons.

Here, zinc loses two electrons to go from neutral
zinc metal to the Zn2+ ion.

Electrochemistry
 Oxidation and Reduction

• A species is reduced when it gains electrons.

Here, each of the H+ gains an electron and they
combine to form H2.

Electrochemistry
 Oxidation and Reduction

• What is reduced is the oxidizing agent.

H+ oxidizes Zn by taking electrons from it.
• What is oxidized is the reducing agent.

Zn reduces H+ by giving it electrons.
Electrochemistry
Assigning Oxidation Numbers

1. Elements in their elemental form have

an oxidation number of 0.
2. The oxidation number of a monatomic
ion is the same as its charge.

Electrochemistry
Assigning Oxidation Numbers
3. Nonmetals tend to have negative
oxidation numbers, although some are
positive in certain compounds or ions.

Oxygen has an oxidation number of −2,
except in the peroxide ion in which it has
an oxidation number of −1.

Hydrogen is −1 when bonded to a metal,
+1 when bonded to a nonmetal.

Electrochemistry
Assigning Oxidation Numbers
3. Nonmetals tend to have negative
oxidation numbers, although some are
positive in certain compounds or ions.

Fluorine always has an oxidation number
of −1.

The other halogens have an oxidation
number of −1 when they are negative;
they can have positive oxidation
numbers, however, most notably in
oxyanions.
Electrochemistry
Assigning Oxidation Numbers
4. The sum of the oxidation numbers in a
neutral compound is 0.
5. The sum of the oxidation numbers in a
polyatomic ion is the charge on the
ion.

Electrochemistry
Balancing Oxidation-Reduction
Equations
Perhaps the easiest way to balance the
equation of an oxidation-reduction
reaction is via the half-reaction method.

Electrochemistry
Balancing Oxidation-Reduction
Equations
This involves treating (on paper only) the
oxidation and reduction as two separate
processes, balancing these half reactions,
and then combining them to attain the
balanced equation for the overall reaction.

Electrochemistry
 Half-Reaction Method

1. Assign oxidation numbers to

determine what is oxidized and what is
reduced.
2. Write the oxidation and reduction half-
reactions.

Electrochemistry
 Half-Reaction Method

3. Balance each half-reaction.

a. Balance elements other than H and O.
b. Balance O by adding H2O.
c. Balance H by adding H+.
d. Balance charge by adding electrons.
4. Multiply the half-reactions by integers
so that the electrons gained and lost
are the same.
Electrochemistry
 Half-Reaction Method

5. Add the half-reactions, subtracting

things that appear on both sides.
6. Make sure the equation is balanced
according to mass.
7. Make sure the equation is balanced
according to charge.

Electrochemistry
 Half-Reaction Method

Consider the reaction between MnO4− and C2O42− :

MnO4−(aq) + C2O42−(aq) → Mn2+(aq) + CO2(aq)

Electrochemistry
 Half-Reaction Method

First, we assign oxidation numbers.

+7 +3 +2 +4

MnO4− + C2O42- → Mn2+ + CO2

Since the manganese goes from +7 to +2, it is reduced.
Since the carbon goes from +3 to +4, it is oxidized.
Electrochemistry
 Oxidation Half-Reaction

C2O42− → CO2

To balance the carbon, we add a

coefficient of 2:

C2O42− → 2 CO2

Electrochemistry
 Oxidation Half-Reaction

C2O42− → 2 CO2

The oxygen is now balanced as well.

To balance the charge, we must add 2
electrons to the right side.

C2O42− → 2 CO2 + 2 e−

Electrochemistry
 Reduction Half-Reaction

MnO4− → Mn2+

The manganese is balanced; to balance

the oxygen, we must add 4 waters to
the right side.

MnO4− → Mn2+ + 4 H2O

Electrochemistry
 Reduction Half-Reaction

MnO4− → Mn2+ + 4 H2O

To balance the hydrogen, we add 8 H+

to the left side.

8 H+ + MnO4− → Mn2+ + 4 H2O

Electrochemistry
 Reduction Half-Reaction

8 H+ + MnO4− → Mn2+ + 4 H2O

To balance the charge, we add 5 e− to

the left side.

5 e− + 8 H+ + MnO4− → Mn2+ + 4 H2O

Electrochemistry
Combining the Half-Reactions
Now we evaluate the two half-reactions
together:

C2O42− → 2 CO2 + 2 e−

5 e− + 8 H+ + MnO4− → Mn2+ + 4 H2O

To attain the same number of electrons

on each side, we will multiply the first
reaction by 5 and the second by 2. Electrochemistry
 Combining the Half-Reactions

5 C2O42− → 10 CO2 + 10 e−

10 e− + 16 H+ + 2 MnO4− → 2 Mn2+ + 8 H2O

When we add these together, we get:

10 e− + 16 H+ + 2 MnO4− + 5 C2O42− →

2 Mn2+ + 8 H2O + 10 CO2 +10 e−
Electrochemistry
 Combining the Half-Reactions
10 e− + 16 H+ + 2 MnO4− + 5 C2O42− →
2 Mn2+ + 8 H2O + 10 CO2 +10 e−

The only thing that appears on both sides are the

electrons. Subtracting them, we are left with:

16 H+ + 2 MnO4− + 5 C2O42− →

2 Mn2+ + 8 H2O + 10 CO2
Electrochemistry
 Balancing in Basic Solution

• If a reaction occurs in basic solution, one

can balance it as if it occurred in acid.
• Once the equation is balanced, add OH−
to each side to “neutralize” the H+ in the
equation and create water in its place.
• If this produces water on both sides, you
might have to subtract water from each
side.
Electrochemistry
Electrochemistry
Voltaic Cells

In spontaneous
oxidation-reduction
(redox) reactions,
electrons are
transferred and
energy is released.

Electrochemistry
 Voltaic Cells

• We can use that

energy to do work if
we make the
electrons flow
through an external
device.
• We call such a
setup a voltaic cell.

Electrochemistry
Voltaic Cells

• A typical cell looks

like this.
• The oxidation
occurs at the anode.
• The reduction
occurs at the
cathode.

Electrochemistry
Voltaic Cells

Once even one

electron flows from
the anode to the
cathode, the
charges in each
beaker would not be
balanced and the
flow of electrons
would stop.
Electrochemistry
Voltaic Cells
• Therefore, we use a
salt bridge, usually a
U-shaped tube that
contains a salt
solution, to keep the
charges balanced.

Cations move toward
the cathode.

Anions move toward
the anode.
Electrochemistry
Voltaic Cells
• Remember-
Although anode and
cathode are labeled
with a – and + signs,
this is not the charge on
the electrode. The
charges on electrodes
are essentially zero.
The – and + label tells
us the electrode at
which electrons are
released to the external
circuit.

Electrochemistry
 Voltaic Cells
• In the cell, then,
electrons leave the
anode and flow
through the wire to
the cathode.
• As the electrons
leave the anode, the
cations formed
dissolve into the
solution in the
anode compartment.
Electrochemistry
 Voltaic Cells
• As the electrons
reach the cathode,
cations in the
cathode are
attracted to the now
negative cathode.
• The electrons are
taken by the cation,
and the neutral
metal is deposited
on the cathode.
Electrochemistry
Sample exercise

Electrochemistry
Practice exercise

Electrochemistry
 • Water only
spontaneously flows
one way in a
waterfall.
• Likewise, electrons
only spontaneously
flow one way in a
redox reaction—from
higher to lower
potential energy.
Electrochemistry
 Potential Difference

• The energy that would be required to

move a unit of electrical charge from
one point to the other against the
electrostatic field that is present. As
potential difference increases, the
current increases as well

Electrochemistry
 Cell Difference

It is measured in volts (V).

J
1V=1
C

Electrochemistry
 Electromotive Force (emf)

• The potential difference between the

anode and cathode in a cell is the
driving force for the electrons to move
across the external circuit hence it is
called the electromotive force (emf).
• It is also called the cell potential, and is
designated Ecell.
Electrochemistry
• Because Ecell is measured in volts it is
also called the cell voltage.
• For any reaction in a cell that is
spontaneous the cell potential will have
to be positive.

Electrochemistry
The cell potential or emf or Ecell
depends on:
• Specific reaction that occur at the
cathode and anode,
• Concentrations of the reactants and
products
• And the temperature, which we assume
as 25oC unless otherwise stated.
Electrochemistry
We are going to focus on cells that operate
under standard conditions of-

• 25oC
• 1M concentration of reactants and products
and 1 atm pressure for those that are gases.

Under these conditions the emf is called the

standard emf or the standard cell potential
Electrochemistry
So for the Zn/Cu voltaic cell

Zn(s) + Cu 2+ (aq,1M)  Zn 2+(aq) + Cu(s) Eocell =+1.10V

The superscript o indicates standard state conditions

Electrochemistry
 Standard Reduction (Half Cell)
Potential

• We can tabulate the standard cell

potential for al the possible cathode /
anode combinations.
• But it is not really needed to do so.

Electrochemistry
• The cell potential is the difference
between two electrode potentials
• By convention the potential associated
with each electrode is the potential for
reduction to occur at that electrode.
• Thus standard electrode potentials are
the standard reduction potentials
denoted Eored

Electrochemistry
• The cell potential is given by the
standard reduction potential of the
cathode reaction minus the standard
reduction potential of the anode reaction

EoCell = Eored (cathode)- Eored (anode)

Electrochemistry
Standard Reduction Potentials

Reduction potentials
for many electrodes
have been measured
and tabulated.

The standard
Hydrogen electrode
(SHE) has a
potential of 0

Electrochemistry
 Standard Hydrogen Electrode
• Their values are referenced to a standard
hydrogen electrode (SHE).
• By definition, the reduction potential for
hydrogen is 0 V:
2 H+ (aq, 1M) + 2 e− → H2 (g, 1 atm)

Electrochemistry
Electrochemistry
PRACTICE EXERCISE
A voltaic cell is based on the half-reactions

The standard emf for this cell is 1.46 V. Using the data in Table 20.1, calculate for the reduction of In3+ to
In+.

Electrochemistry
PRACTICE EXERCISE
A voltaic cell is based on the half-reactions

The standard emf for this cell is 1.46 V. Using the data in Table 20.1, calculate for the reduction of In3+ to
In+.

Electrochemistry
For the Zn-Cu2+ voltaic cell shown in Figure 20.5, we have

Given that the standard reduction potential of Zn2+ to Zn(s) is –0.76 V, calculate the for the reduction of
Cu2+ to Cu:

Electrochemistry
For the Zn-Cu2+ voltaic cell shown in Figure 20.5, we have

Given that the standard reduction potential of Zn2+ to Zn(s) is –0.76 V, calculate the for the reduction of
Cu2+ to Cu:

Answer: –0.40 V

Electrochemistry
Using the standard reduction potentials listed in Table 20.1, calculate the standard emf for the voltaic cell
described in Sample Exercise 20.4, which is based on the reaction

Electrochemistry
PRACTICE EXERCISE
Using data in Table 20.1, calculate the standard emf for a cell that employs the following overall cell reaction:

Electrochemistry
PRACTICE EXERCISE
Using data in Table 20.1, calculate the standard emf for a cell that employs the following overall cell reaction:

Answer: +2.20 V

Electrochemistry
 Standard Cell Potentials

The cell potential at standard conditions

can be found through this equation:

° (cathode) − Ered
° = Ered
Ecell ° (anode)

Because cell potential is based on

the potential energy per unit of
charge, it is an intensive property. Electrochemistry
Cell Potentials
• For the oxidation in this cell,
° = −0.76 V
Ered

• For the reduction,

° = +0.34 V
Ered

Electrochemistry
 Cell Potentials

Ecell ° (cathode) − Ered

° = Ered ° (anode)
= +0.34 V − (−0.76 V)
= +1.10 V

Electrochemistry
• If we use Hess’s Law

Electrochemistry
• In any voltaic cell the reaction at the
cathode has more positive value of Eored
than does the reaction at the anode.

Electrochemistry
Electrochemistry
Oxidizing and Reducing Agents

The greater the

difference between
the two, the greater
the voltage of the
cell.

Electrochemistry
A voltaic cell is based on the following two standard half-reactions:

By using the data in Appendix E, determine (a) the half-reactions that occur at the cathode and
the anode, and (b) the standard cell potential

Electrochemistry
Strengths of Oxidizing and Reducing Agents
• The more positive the Eored value of the
half reaction, the greater is the tendency
of the reactant of the half reaction to be
reduced and therefore to oxidize other
species.
Zn(s) + Cu 2+(aq)  Zn 2+(aq) + Cu(s)
The Eored value for Cu 2+ is 0.34 V and for
Zn is -0.76V

Electrochemistry
Frequently used Oxidizing Agents
• Halogens
• O2
• Oxianions whose central atoms have
high oxidation states
MnO4 –
Cr2O72-
NO3-
All these undergo reduction with
Large positive values of Eored
Electrochemistry
Frequently used Reducing Agents
• H2
• Active metals
Alkali and Alkaline earth metals
• Zn and Iron – the metals with negative
Eored values.

Electrochemistry
Oxidizing and Reducing Agents

• The strongest
oxidizers have the
most positive
reduction potentials.
• The strongest
reducers have the
most negative
reduction potentials.

Electrochemistry
Standard Reduction Potentials

Reduction potentials
for many electrodes
have been measured
and tabulated.

The standard
Hydrogen electrode
(SHE) has a
potential of 0

Electrochemistry
Free Energy and Redox Reactions

• We know by now that Voltaic Cells use

redox reactions that occur
spontaneously
• How do we find out if a redox reaction
will be spontaneous

Electrochemistry
 • Do you remember the reaction:

° (cathode) − Ered
° = Ered
Ecell ° (anode)
• We can rewrite this equation more generally
as:
E° ° (reduction process) − °Ered (oxidation process)
= Ered

A positive value of E indicates a spontaneous

process and a negative value indicates a
nonspontaneous process
Electrochemistry
 Using standard reduction potentials (Table 20.1), determine whether the following reactions are spontaneous
under standard conditions.

a. Now find out which one is the oxidation and

which one is the reduction reaction
b. Then find the Eored valus from a table
c. Now fill these values in the formula
E° ° (reduction process) − °Ered (oxidation process)
= Ered

Now remember that a positive value means a

spontaneous process.
If the value is negative the reverse reaction will
Electrochemistry

be spotaneous.
Using standard reduction potentials (Table 20.1), determine whether the following reactions are spontaneous
under standard conditions.

Electrochemistry
PRACTICE EXERCISE
Using the standard reduction potentials listed in Appendix E, determine which of the following reactions are
spontaneous under standard conditions:

Electrochemistry
• Do you remember the activity series
from chapter 4?

Electrochemistry
• Do you remember the activity series
from chapter 4?
• You do not !!!!?????
• How could you

Electrochemistry
Activity Series

• Decreasing ease of
oxidation
• Active metals to noble
metals
• Any metal on the list
can be oxidized by the
ions of elements below
it
• 2Li + Cu 2+ 2Li + + Cu
LEO GER
Electrochemistry
 2Li + Cu 2+  2Li + + Cu
LEO GER

E° ° (reduction process) − °Ered (oxidation process)

= Ered

Eo = (+0.34V) – (-3.05V) = 0.34 V + 3.05 V= +3.39 V

Because cell potential is based on the potential energy per unit of charge,
it is an intensive property.
So even if the ions are doubled in the reaction the reduction potential is
not.
Electrochemistry
 Gibbs Free Energy

• ΔG = ΔH + TΔS Δ H= Change in enthalpy

Δ S= Change in entropy
The change in Gibbs Energy (free energy change) is a
measure of the spontaneity of a process at constant
temperature and pressure.
Because emf, E of a redox reaction is an indication of
the spontaneity of the reaction there is a relationship
between ΔG and E

Electrochemistry
 Free Energy
∆G for a redox reaction can be found by
using the equation

∆G = −nFE

where n is the number of moles of

electrons transferred, and F is a
constant, the Faraday.
1 F = 96,485 C/mol = 96,485 J/V-mol
Electrochemistry
 Free Energy
As n and F are both positive values a
positive value of E leads to a negative
value of ΔG.
Therefore
A positive value of E and a negative value
of ΔG both represent a spontaneous
reaction

Electrochemistry
Under standard conditions,
∆G° = −nFE°
This is an important equation which relates
the standard emf Eo to the standard free
energy change ∆G°
∆G° is related to the equilibrium constant K
∆G° = - RT In K
the Eo can be related to the K too.
Electrochemistry
• Problem

Electrochemistry
 Nernst Equation

• Remember that
∆G = ∆G° + RT ln Q

• This means
−n FE = −nFE° + RT ln Q

Electrochemistry
 Nernst Equation

Dividing both sides by −nF, we get the

Nernst equation:
RT
E = E° − ln Q
nF
or, using base-10 logarithms,
2.303 RT
E = E° − ln Q
nF
Electrochemistry
 Nernst Equation

At room temperature (298 K),

2.303 RT
= 0.0592 V
F

Thus the equation becomes

0.0592
E = E° − ln Q
n
Electrochemistry
 Concentration Cells

• Notice that the Nernst equation implies that a cell

could be created that has the same substance at
both electrodes.
° would be 0, but Q would not.
• For such a cell, Ecell
• Therefore, as long as the concentrations
Electrochemistry
are different, E will not be 0.
 Applications of
Oxidation-Reduction
Reactions

Electrochemistry
Batteries

Electrochemistry
Alkaline Batteries

Electrochemistry
Hydrogen Fuel Cells

Electrochemistry
Corrosion and…

Electrochemistry
…Corrosion Prevention

Electrochemistry