W3

Equilibrium Electrochemistry
JSS/01172024
Reference:
Atkins (2023), Topic 6C Electrochemical cells
Why do you need to
know this material?
Reactions that take place in
electrochemical cells has enormous
fundamental, technological, and
economic significance.
Making very precise measurements
of potential differences means that
electrochemical methods can be
used to determine thermodynamic
properties of reactions that might
be inaccessible by other methods.
What is the key idea?
Electrical work of a reaction at
constant pressure and temperature
= Reaction Gibbs energy.
What do you need to know already?
• This Topic develops the relation
between the Gibbs energy and
non-expansion work.
• You need to be aware of how to
calculate the work of moving a
charge through an electrical
potential difference.
• The equations make use of the
definition of the reaction
quotient Q and the equilibrium
constant K.
Introduction
• An electrochemical cell consists
of two electrodes, or metallic
conductors, each in contact with
an electrolyte, an ionic
conductor (which may be a
solution, a liquid, or a solid).
Introduction
• An electrode and its electrolyte
comprise an electrode
compartment; the two
electrodes may share the same
electrolyte.
Introduction
• The various kinds of electrode
are summarized in Table 6C.1.
Introduction
• An option joins the
compartments by a salt bridge,
which is a tube containing a
concentrated electrolyte
solution (for instance, KCl in agar
jelly).
Introduction
• A galvanic cell is an
electrochemical cell that
produces electricity because of
the spontaneous reaction
occurring inside it.
• Galvanic cells can have different
electrodes or electrodes that
differ in either the electrolyte or
electrode concentration.
Introduction
• An electrolytic cell is an
electrochemical cell in which a
non-spontaneous reaction is
driven by an external source of
current.
Half-reactions and electrodes
• It should be familiar from
introductory chemistry that
oxidation is the removal of
electrons from a species,
reduction is the addition of
electrons to a species, and a
redox reaction is one in which
there is a transfer of electrons
from one species to another.
Half-reactions and electrodes
• The reducing agent (or
reductant) is the electron donor;
the oxidizing agent (or oxidant)
is the electron acceptor.
Half-reactions and electrodes
• Any redox reaction may be
expressed as the difference of
two reduction half-reactions,
which are conceptual reactions
showing the gain of electrons
Half-reactions and electrodes
• The reduced and oxidized
species in a half-reaction form a
redox couple.
Brief illustration 6C.1

The dissolution of silver chloride in water AgCl(s) → Ag+(aq) +

Cl−(aq), is not a redox reaction
This can be expressed as the difference of the
following two reduction half-reactions:

The redox couples are

Brief illustration 6C.2

The reaction for the reduction of O2 to H2O in acid

solution is
The reaction quotient is

The approximations used in the second step are:

• the activity of water is 1 (because the solution is
dilute) and 𝜃
• the oxygen behaves as a perfect gas → aO2 = pO2 / p𝜽
Half-reactions and electrodes
• The electrode at which oxidation
occurs is called the anode; the
electrode at which reduction
occurs is called the cathode.
Half-reactions and electrodes
• In a galvanic cell, the cathode
has a higher potential than the
anode: the species undergoing
reduction, Ox2, withdraws
electrons from its electrode (the
cathode, Fig. 6C.1), so leaving a
relative positive charge on it
(corresponding to a high
potential).
Varieties of cell
• In some cases, it is necessary to
immerse the electrodes in
different electrolytes, as in the
‘Daniell cell’ in which the redox
couple at one electrode is
Cu2+/Cu and at the other is
Zn2+/Zn (Fig. 6C.2).
Varieties of cell
• In an electrolyte concentration
cell, the electrode
compartments are identical
except for the concentrations of
the electrolytes.
Varieties of cell
• In an electrode concentration
cell, the electrodes themselves
have different concentrations,
either because they are gas
electrodes operating at different
pressures or because they are
amalgams (solutions in mercury)
or analogous materials with
different concentrations.
Varieties of cell
(a) Liquid junction potentials
• In a cell with two different
electrolyte solutions in contact,
as in the Daniell cell, there is an
additional source of potential
difference across the interface of
the two electrolytes.
• This contribution is called the
liquid junction potential, Elj.
• A liquid junction potential arises
at the junction of 2 electrolyte
solutions.
Varieties of cell
(a) Liquid junction potentials
• The contribution of the liquid
junction to the potential
difference can be reduced (to
about 1–2 mV) by joining the
electrolyte compartments
through a salt bridge (Fig. 6C.3).
Varieties of cell
(b) Notation
• The following notation is used
for electrochemical cells:
| An interface between
components or phases
⋮ A liquid junction
|| An interface for which it is
assumed that the junction
potential has been
eliminated
Brief illustration 6C.3
A cell in which two electrodes share the same Pt(s) |H2 (g) |HCl(aq) |AgCl(s) |Ag(s)
electrolyte is
The cell in Fig. 6C.2 is denoted (see below) Zn(s) |ZnSO4 (aq)⋮ CuSO4 (aq) |Cu(s)
The cell in Fig. 6C.3 is denoted (see below) Zn(s) |ZnSO4 (aq) ||CuSO4 (aq) |Cu(s)
An example of an electrolyte concentration cell in
which the liquid junction potential is assumed to be Pt(s) |H2 (g) |HCl(aq, b1 ) ||HCl(aq, b2 ) |H2 (g) | Pt(s)
eliminated is
The cell potential
• The cell reaction is the reaction
in the cell written on the
assumption that the right-hand
electrode is the cathode.
• A cell reaction is expressed as
the difference of two reduction
half-reactions; each half-
reaction Ox + n e− → Red
defines a redox couple denoted
Ox/Red.
Brief illustration 6C.4

For the cell Zn(s)|ZnSO4(aq)||CuSO4(aq)|Cu(s)

The two electrodes and their reduction half-reactions Right-hand electrode:
are Cu2+ (aq) + 2e- → Cu (s)
Left-hand electrode:
Zn2+ (aq) + 2e- → Zn (s)
The same number of electrons is involved in each half-
reaction.
The overall cell reaction is the difference Right − Left: Cu2+ (aq) + 2e- - Zn2+ (aq) – 2e- → Cu(s) – Zn(s)
which, after cancellation of the 2 e−, rearranges to Cu2+(aq) + Zn(s) → Cu(s) + Zn2+(aq)
The cell potential
(a) The Nernst equation
• A resulting potential difference is
called the cell potential, Ecell, of
the cell (formerly: electromotive
force, emf).
• The cell potential is the
potential difference measured
under reversible conditions.
• It is positive if a voltmeter shows
that the right-hand electrode (in
the specification of the cell is the
positive electrode.
The cell potential
(a) The Nernst equation

𝝂 Stoichiometric coefficient of the electrons in the

half-reactions into which the cell reaction can be
divided.
F Faraday constant, 96,486 C/mol
Ecell Potential difference
𝜟𝒓𝑮 Gibb’s energy of the cell reaction
The cell potential
(a) The Nernst equation
• Figure 6C.4
• A spontaneous reaction occurs in the
direction of decreasing Gibbs energy.
• The spontaneous direction of change
can also be expressed in terms of the
cell potential, Ecell.
• The cell reaction is spontaneous as
written when Ecell > 0.
• The reverse reaction is spontaneous
when Ecell < 0.
• When the cell reaction is at
equilibrium, the cell potential is zero.
Brief illustration 6C.5

Equation 6C.2 provides an electrical method for

measuring a reaction Gibbs energy at any composition simply measure the cell potential and convert it to
of the reaction mixture: ΔrG.
Conversely, if the value of ΔrG is known at a particular
composition, then it is possible to predict the cell potential.
For example, if ΔrG = −1.0 × 102 kJ mol−1 and
and n=1
using 1J=1CV
Then
The cell potential
(a) The Nernst equation

Ecell𝜽 Standard cell potential

𝜟𝒓𝑮𝜽 Standard reaction Gibbs energy
𝝂 Stoichiometric coefficient of the electrons in the
half-reactions into which the cell reaction can be
divided.
F Faraday constant, 96,486 C/mol

The standard cell potential may be used to calculate the standard Gibbs energy of the cell reaction
and hence its equilibrium constant.
The cell potential
(a) The Nernst equation

Ecell Cell potential

Ecell𝜽 Standard cell potential
R Gas constant, 8.314 J/mol∙ 𝐾
T Temperature in K
𝝂 Stoichiometric coefficient of the electrons in the half-reactions into which the cell
reaction can be divided.
F Faraday constant, 96,486 C/mol
Q Composition of the reaction mixture
The Nernst equation relates the cell potential to the composition of the reaction mixture.
The cell potential
(a) The Nernst equation
• Figure 6C.5
• The variation of cell potential with
the value of the reaction quotient
for the cell reaction for different
values of 𝝂 (the number of
electrons transferred).
• At 298 K, RT/F = 25.69 mV, so at
this temperature the vertical scale
refers to multiples of this value.
• Note that the horizontal axis is the
common (base 10) logarithm of Q.
Brief illustration 6C.6

Because RT/F = 25.7 mV at 25 °C,

A practical form of the Nernst equation at this
temperature is

It then follows that, for a reaction in which 𝜈=1

If Q is increased by a factor of 10
With ln 10 = 2.303
Then the cell potential decreases by 59.2 mV
The cell potential
(b) Cells at equilibrium

At equilibrium, Q = K K – equilibrium constant

Ecell Cell potential = 0 as no work is done
Brief illustration 6C.7

The standard potential of the Daniell cell is 1.10 V

Therefore, the equilibrium constant for the cell Cu2+(aq) + Zn(s) → Cu(s) + Zn2+(aq)
reaction 𝜈=2
K = 1.5 × 1037 at 298 K
That is, the displacement of copper by zinc goes
virtually to completion.
Note that a cell potential of about 1 V is easily
measurable but corresponds to an equilibrium
constant that would be impossible to measure by
direct chemical analysis.
Brief illustration 6C.8

In the cell
The reaction taking place is
Except for Ag+(aq), the standard Gibbs energy of
formation of all the species in this cell are zero by
convention, and so it follows that
Therefore, with 𝜈 = 1,

which is in close agreement with the value in Table

2C.7 of the Resource section.
The determination of thermodynamic
functions

dEcell𝜽 / dT The temperature coefficient of the standard cell

potential, gives the standard entropy of the cell
reaction.
𝚫 r S𝜽 Standard entropy of the cell reaction
𝝂 Stoichiometric coefficient of the electrons in the
half-reactions into which the cell reaction can be
divided.
F Faraday constant, 96,486 C/mol
The temperature coefficient of the standard cell potential is used to measure the standard entropy
and standard enthalpy of the cell reaction.
 W3
Equilibrium Electrochemistry
JSS/01172024
Atkins (2023): Topic 6D Electrode Potentials
Why do you need to know this material?
• A very powerful, compact, and widely
used way to report standard cell
potentials is to ascribe a potential to
each electrode.
• The standard potential for any cell
can be calculated by subtracting the
standard reduction potential of the
half-reaction occurring at the anode
from the standard reduction potential
of the half-reaction occurring at the
cathode.
• Electrode potentials are used in
chemistry to assess the oxidizing and
reducing power of redox couples and
to infer thermodynamic properties,
including equilibrium constants.
• In electrochemistry, electrode
potential is the voltage of a galvanic
cell built from a standard reference
electrode and another electrode to be
characterized.
• By convention, the reference
electrode is the standard hydrogen
electrode (SHE).
• It is defined to have a potential of zero
volts.
What is the key idea?
• Each electrode of a cell can be
supposed to make a characteristic
contribution to the cell potential.
• The cell potential, Ecell, is the measure
of the potential difference between
two half cells in an electrochemical
cell.
• The potential difference is caused by
the ability of electrons to flow from
one half cell to the other.
• Redox couples with low electrode
potentials tend to reduce those with
higher potentials.
• Redox couples are analogous to
conjugate acid-base pairs and behave
in much the same way.
• The stronger an oxidizing agent, the
weaker the corresponding reducing
agent, and the stronger a reducing
agent, the weaker the corresponding
oxidizing agent.
• Thus, the strong oxidizing agent F2
produces the weak reducing agent F–.
What do you need to know already?
• This Topic develops the concepts
in the previous Topic, so you
need to understand the concept
of cell potential and standard
cell potential; it also makes use
of the Nernst equation.
• The measurement of standard
potentials makes use of the
Debye–Hückel limiting law.
Standard potentials
• The specially selected electrode
is the standard hydrogen
electrode (SHE):

• Standard conditions:
• a, activity H+ = 1
• pH = 0
• pH2 = 1 bar
Standard potentials
• The standard potential, E⦵(X), of another redox couple X is then
equal to the cell potential in which it forms the right-hand electrode,
and the standard hydrogen electrode is the left-hand electrode:

• The standard potential of a couple is the potential of a cell in which

the couple forms the right-hand electrode, and the left-hand
electrode is a standard hydrogen electrode, all species being present
at unit activity.
Standard potentials
• The standard potential of a cell of the form L||R, where L is the left-
hand electrode of the cell as written (not necessarily as arranged on
the bench) and R is the right-hand electrode, is then given by the
difference of the two standard (electrode) potentials:
Standard potentials
• A list of standard potentials at
298 K is given in Table 6D.1, and
longer lists in numerical and
alphabetical order are in the
Resource section.
Brief illustration 6D.1
The cell Ag(s)|AgCl(s)|HCl(aq)|O2(g)|Pt(s)
The cell can be regarded as formed from the following
two electrodes, with their standard potentials taken
from the Resource section:
Example 6D.2 Evaluating a standard potential
from two others
Given that the standard potentials of the Cu2+/Cu and E⦵(a) = +0.340 V
Cu+/Cu couples are +0.340 V and +0.522 V, E⦵(b) = +0.522 V,
respectively, evaluate E⦵(Cu2+,Cu+).
Collect your thoughts
First, note that reaction Gibbs energies may be added
(as in a Hess’s law analysis of reaction enthalpies).
−𝜈FE⦵ = ΔrG⦵
Therefore, you should convert the E⦵ values to ΔrG⦵
by using eqn. 6C.3 (−𝜈FE⦵ = ΔrG⦵), add them
appropriately, and then convert the overall ΔrG⦵ to
the required E⦵ by using eqn. 6C.3 again.

This roundabout procedure is necessary because, as

seen below, although the factor F cancels (and should
be kept in place until it cancels), the factor 𝜈 in
general does not cancel.
Example 6D.2 Evaluating a standard potential
from two others
The solution
The electrode half-reactions are as follows: (a) Cu2+(aq) + 2 e− → Cu(s) E⦵(a) = +0.340 V
−𝜈FE⦵ = ΔrG⦵
so ΔrG⦵(a) = −2 × (+0.340 V)F = (−0.680 V)F

(b) Cu+(aq) + e− → Cu(s) E⦵(b) = +0.522 V

so ΔrG⦵(b) = −(+0.522 V)F = (−0.522 V)F
The required reaction is (c) Cu2+(aq) + e− → Cu+(aq)
E⦵(c) = −ΔrG⦵(c)/F
Because (c) = (a) − (b), the standard Gibbs energy of
reaction (c) is

Therefore, E⦵(c) = −ΔrG⦵(c)/F = +0.158 V

Self-test 6D.2 Evaluate E⦵(Fe3+,Fe2+) from E⦵(Fe3+,Fe) and
E⦵(Fe2+,Fe).
Standard potentials
(b) Combining measured values
• The generalization of the calculation in Example 6D.2 is

• with the 𝝂r the stoichiometric coefficients of the electrons in each

half-reaction.
Applications of standard electrode potentials
(a) The electrochemical series
• The electrochemical series lists the metallic elements in the order of
their reducing power as measured by their standard potentials in
aqueous solution: low reduces high.
• Table 6D.2 shows a part of the electrochemical series, the metallic
elements (and hydrogen) arranged in the order of their reducing
power as measured by their standard potentials in aqueous solution.
• A metal low in the series (with a lower standard potential) can reduce
the ions of metals with higher standard potentials.
(next slide)
Applications of standard electrode potentials
(a) The electrochemical series
Brief illustration 6D.2
Zinc lies above magnesium in the electrochemical series, so zinc cannot reduce magnesium ions in aqueous
solution.
Zinc can reduce hydrogen ions, because hydrogen lies higher in the series.
However, even for reactions that are thermodynamically favorable, there may be kinetic factors that result in
very slow rates of reaction.
Applications of standard electrode potentials
(b) The determination of activity coefficients
• Once the standard potential of an electrode in a cell is known, it can
be used to determine mean activity coefficients by measuring the cell
potential with the ions at the concentration of interest.
• The difference of the cell potential from its standard value is used to
measure the activity coefficient of ions in solution.
• For example, in the Harned cell, the mean activity coefficient of the
ions in hydrochloric acid of molality b is obtained from the relation.
Brief illustration 6D.3

Data include the fact that → when b = 9.138 × 10−3b⦵

Ecell = 0.468 60 V
Because → 2RT/F = 0.051 39 V at 298 K
It is established that → Ecell 𝜽 = 0.2232 V
mean activity coefficient at this molality is

Therefore γ± = 0.9232
Applications of standard electrode potentials
(c) The determination of equilibrium constants
• The principal use for standard potentials is to calculate the standard
potential of a cell formed from any two electrodes and then to use
that value to evaluate the equilibrium constant of the cell reaction.
• To do so, construct E𝜽cell = E𝜽(R) - E𝜽(L)
• And then use

• Re-arrange into ln K = 𝝂FE𝜽cell / RT

Brief illustration 6D.4
A disproportionation reaction is a reaction in which a species is both oxidized and reduced.
To study the disproportionation 2 Cu+(aq) → Cu(s) + Cu2+(aq) at 298 K
Combining the following electrodes:

The cell reaction is therefore 2 Cu+(aq) → Cu(s) + Cu2+(aq)

and the standard cell potential is E𝜽cell = (+0.52 V) - (+0.16 V) = +0.36 V
Now calculate the equilibrium constant of the cell 𝝂=1
reaction. Because →

RT/F = 0.025 693 V

Hence K = 1.2 x 106

Exercises (6C)
1. Write down the half equations for the following electrodes:
i. Zn(s) in contact with an aqueous solution of Zn2+ ions.
ii. H+(aq) in contact with H2(g), with an inert Pt electrode.
iii. H+(aq) in contact with O2(g), with an inert Pt electrode (solvent H2O can be
used to balance the equation).
2. Write down the two half reactions for each of the following cells
Pt(s)|Fe3+(aq), Fe2+(aq)||H+(aq)|H2(g)|Pt(s)
i. Ag(s)|AgCl(s)|HCl(aq)|Cl2(g)|Pt(s)
ii. Pt(s)|O2(g)|H+(aq)|H2(g)|Pt(s)
Exercises (6D)
1. Given the data below, will mercury produce zinc metal from
aqueous zinc sulfate under standard conditions?

2. Calculate the equilibrium constant of the following reaction at 25 °C

from the standard potential data given below:
Exercises (6D)
3. Use the data given below to calculate the standard potential of the
cell Ag(s)|AgNO3(aq)||Cu(NO3)2(aq)|Cu(s) and the standard Gibbs
energy of the cell reaction at 25 °C.
 W3
Equilibrium Electrochemistry
JSS/01172024
Atkins (2023):
Topic 6C Electrochemical Cells
Topic 6D Electrode Potentials