Physical Chemistry (CHM3101)

Equilibrium Electrochemistry
Reference: Atkins, 9th Edition, Chapter 6

Equilibrium Electrochemistry
Introduction
Half-reactions and electrodes
Varieties of Cells

Liquid Junction Potentials

The Cell Potential

The Nernst Equation

Cells at Equilibrium

Standard Electrode Potential

Applications of Standard Potential

The Electrochemical Series

The determination of activity coefficients

The determination of equilibrium Constants

The determination of thermodynamic functions

2

Introductio
n

An electrochemical cell is consisted of

two electrodes or metallic conductors in
contact with an electrolyte, an ionic
conductor.
An
electrode
and
its
electrolyte
compromise an electrode compartment.

 The

two electrode may share the same

compartment.
If the electrolytes are different, the two
compartments may be joined by a salt
bridge.
A salt bridge is a tube containing a
concentrated electrolyte solution such
as potassium chloride that completes
the electrical circuit and enables the cell
to function.

galvanic cell is an
electrochemical
cell
that
produces
electricity as a result
of the spontaneous
reaction
occurring
inside it.

An

electrolytic cell is
an electrochemical cell
in
which
a
nonspontaneous reaction
(redox
reaction)
is
driven by an external
source of current.
5

Half Reactions and Electrodes

Oxidation is the removal of electrons from the

species.
Reduction is the addition of electrons to a
species.
A redox reaction is a reaction in which there is a
transfer of electrons from one species to
another.
The reducing agent (or reductant) is the electron
donor.
The oxidizing agent (or oxidant) is the electron
acceptor.
Any redox reaction is expressed as the difference
of two reduction half-reactions.
The reduced and oxidized species in a halfreaction form a redox couple.
Ox + v e- Red
7

 For

example, consider this reaction:

AgCl (s) Ag+ (s) + Cl- (aq)

This

is not a redox reaction but it can be

expressed as:
AgCl (s) + e- Ag (s) + Cl- (aq)
Ag+ (aq) + e- Ag (s)

Thus,

the redox couple are AgCl/Ag and

Ag+/Ag.

Q.

Express the formation of H2O from H2

and O2 in acidic solution (a redox reaction)
as the difference of two reduction halfreactions.
8

For example, consider reaction below:

FeSO4 + KMnO4 +H2SO4 Fe2(SO4)3 + K2SO4 + MnSO4 + H2O

Concentrate first on the net ionic reaction:

Fe2+ + MnO4- + H+ Fe3+ + Mn2+ + H2O

At first glance you can see: Fe2+ Fe3+ (+2 to +3 = +1)

MnO4- Mn2+ (+7 to +2 = -5)

Balance these half reactions using electrons to balance

charge: Fe2+ Fe3+ + e-

Using simple balancing by inspection we will add two

coefficients to balance atoms:
MnO4- + 8H+ Mn2+ + 4H2O

Then: MnO4- + 8H+ + 5e- Mn2+ + 4H2O

Now: 5Fe2+ 5Fe3+ + 5e-

Add both reactions:

MnO4- + 8H+ + 5Fe2+ + 5e- Mn2+ + 4H2O + 5Fe3+ + 5e-

After cancelling electrons:

MnO4- + 8H+ + 5Fe2+ Mn2+ + 4H2O + 5Fe3+

2KMnO4 + 10FeSO4 + 8H2SO4 5Fe2(SO4)3 + K2SO4 + 2MnSO4 +

8H2O

Therefore, in a cell we
have;
Red1 Ox1 + v eOx2 + v e- Red2

The electrode at which

oxidation
occurs
is
called the anode.

The electrode at which

reduction
occurs
is
called the cathode.

In galvanic cell the

cathode has a higher
potential
than
the
anode.
10

Varieties of Cells
Galvanic

cell is the
simplest type of a
cell. There is a single
electrolyte common
to both electrodes.

Daniell

cell is a cell
with
different
electrolytes in which
the redox couple at
one
electrode
is
Cu2+/Cu and at the
other is Zn2+/Zn.
11

Concentrations Cells
Electrolyte
concentration
cell
has
identical
electrode
compartments
except
for
the
concentrations of the electrolytes

For example:
(Zn|Zn2+ (C1))/Anode || (Zn2+ (C2 )|Zn)/Cathode

In an electrode concentration cell, the electrodes

themselves have different concentrations.

They are gas electrodes operating at different pressures.

For example:

(Pt,H2 (Pressure p1))/Anode |H+ | (H2 (Pressure p2)Pt)/Cathode

They are amalgams (solutions in mercury) with different

concentrations.
Cd(s), Hg(s) | CdCl2(aq) || AgCl(s) | Ag(s)

12

Liquid Junction Potential

Two solutions of different concentrations are in

contact with each other.
The more concentrated solution will have a
tendency to diffuse into the comparatively less
concentrated one.
The rate of diffusion of each ion will be roughly
proportional to its speed in an electric field.
If anion diffuses more rapidly than the cation, it
will diffuse ahead into the dilute solution leaving
the
later
negatively
charged
and
the
concentrated solution positively charged.
So an electrical double layer of positive and
negative charges will be produced at the junction
of the two solutions & as a result, a difference of
potential will develop because of the ionic
transfer.
This potential is called liquid junction potential
13
or diffusion potential.

Consider a Daniall cell. Here,

there is an additional source
of potential difference across
the
interface
of
two
electrolytes. This potential is
called
liquid
junction
potential, Elj.

The contribution of Elj can be

reduced (to about 1 to 2 mV)
by joining the electrolyte
compartments through a salt
bridge.

Or another example can be different concentrations

of hydrochloric acid. At the junction the mobile H+
ions diffuse into the more dilute solution. The
bulkier Cl- ions follow, but initially do so more
slowly which results in a potential difference at the
junction.
14

Notation
Phase

boundaries are denoted by a

vertical bar, For example:
Pt (s) | H2(g) | HCl(aq) | AgCl (s) | Ag (s)

double vertical line means there is no

liquid junction potential, such as:
Zn (s) | ZnSO4 (aq) || CuSO4 (aq) | Cu (s)

Some

gas electrodes
Pt | Cl2, HCl (aq, 0.1 mol L-1)
Pt | H2, H3O+ (aq, 1 mol L-1)
15

The Cell Potential

Consider a galvanic cell. The current produced by

this cell comes from the spontaneous reaction
taking place inside it.

The cell reaction is the reaction in the cell written

on the assumption that;

For example, In a cell such as;

Zn (s) | ZnSO4 (aq) || CuSO4 (aq) | Cu (s)

The right-hand electrode is the cathode

Thus, the spontaneous reaction is the reduction at the righthand compartment.

Right-hand electrode:
Left-hand electrode:

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

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

Therefore;
Cu2+ (aq) + Zn (s) Cu (s) + Zn2+ (aq)

16

Question

Write the cell reaction and electrode halfreactions for following cells:

Pt|Cl2

(g)| HCl (aq) || Ag2CrO4 (aq)|Ag (s)

Pt|Fe3+ (aq),

Fe2+ (aq) || Sn4+ (aq), Sn2+ (aq) |

Pt
Cu|Cu2+ (aq) || Mn2+ (aq), H+ (aq) | MnO2(s) |
Pt

17

Standard Electrode Potential (E0)

The potential difference across an electrochemical cell is the potential

difference measured between two electronic conductors connected to
the electrodes.

In the external circuit, the electrons will flow from the most negative
point to the most positive one and, by convention, the current will flow
in the opposite direction.

Since the electrode potential can be either positive or negative, the

electrons in the external circuit can also be said to flow from the least
positive electrode to the most positive electrode.

A voltmeter may be used to measure the potential differences across

electrochemical cells but cannot measure directly the actual potential
of any single electrode.

Nevertheless, it is convenient to assign part of the cell potential to one

electrode and part of that to the other.

The standard electrode potential, E is the measure of individual

potential of a reversible electrode at standard state, which is with
solutes at an effective concentration of 1 mol dm3, and gases at 18
a

The potential bench mark is the half-cell in

which hydrogen gas is bubbled over a platinum
electrode immersed in a solution having a
known concentration of hydrogen ions.

The specially selected electrode is the standard

hydrogen electrode (SHE) at all temperatures:
Pt (s) | H2 (g) | H+ (aq) E0=0

The SHE is also called "normal hydrogen

electrode" (NHE) in reference to a solution
containing one equivalent of protons.

It is better to use activity rather than

concentration of hydrogen ions and fugacity
(=f/p) rather than pressure. To achieve the
standard condition, we should have pH=0.
19

SHE
1.

Platinized platinum electrode

2.

Hydrogen blow

3.

Solution of the acid with activity of H+ =

1 mol.dm-3

4.

Hydroseal for prevention of the oxygen

interference

5.

Reservoir through which the second

half-element of the galvanic cell should
be attached.

The connection can be direct, through a

narrow tube to reduce mixing, or
through a salt bridge, depending on the
other electrode and solution. This
creates an ionic conductive path to the
working electrode of interest.
20

The Electrochemical Series

Remember
the
cell
convention: For two redox
couples;
Red1,Ox1 || Red2, Ox2

Cell reaction is;

Red1 + Ox2 Ox1 + Red2

This reaction has a K > 1

if
E0cell > 0, so E02 > E01

Since Red1 reduces to Ox1,

Red1
has
a
thermodynamic tendency
to reduce Ox2 if E01 > E02

Thus, low reduces high.

21

 Table

below lists the standard potential at

298 K:

They are unchanged even after multiplying by a

numerical factor.
By this, a cell potential is independent of the
physical size of the cell.
22

 The

values are based on their ability to

be reduced, thus, the bigger the
standard reduction potentials, the easier
they are to be reduced or they are better
oxidizing agents.

For

example, Zn2+ whose

reduction potential is 0.76V :

standard

can

be oxidized by any other electrode

whose standard reduction potential is
greater than 0.76V (e.g. H+, Cu2+, F2).

can

be reduced by any electrode with

standard reduction potential less than
0.76V (e.g. H2, Na+, Li+).

23

For example consider a galvanic cell:

Here, a spontaneous redox reaction drives the cell to

produce an electric potential. So, the Gibbs free energy,
G must be negative according to this equation:
Gcell = nFEcell

where n is number of moles of electrons per mole of products and F is

the Faraday constant (F=eNA), ~96485 C/mol.

As such, the following rules apply:

If Ecell > 0, then the process is spontaneous (galvanic cell)

If Ecell < 0, then

(electrolytic cell)

By this, in order to have a spontaneous reaction (G <

0), Ecell must be positive.

the

process

is

nonspontaneous

Ecell = Ecathode Eanode

where Eanode is the standard potential at the anode and Ecathode is the
standard potential at the cathode as given in the table of standard
electrode potential.
24

Consider this redox reaction:

Electrochemical cell for this reaction is:

The cell potential (emf) of this electrochemical cell under standard

conditions is 1.10 V (volt) which is come from of
Ecell = Ecathode Eanode = (+0.34 V)-(-0.76 V)=1.10 V

It means that the electrons flow in the external circuit from the
anode (Zn), where oxidation takes place, to the cathode (Cu), where
reduction happens.

Now, consider the two half-reactions:

Since the cell causes electrons to flow in the external circuit from Zn
to Cu, it means that reaction (2) takes place rather than reaction (1).
Reaction (2) takes place because the REVERSE of reaction (1)
supplies the 2 electrons required.
25

 What

is the potential for the cell;

Ag | Ag+(1.0 M) || Li+(1.0 M) | Li

If E0Li+/Li= -3.05 V and E0

Ag+/Ag

= +0.80 V

Exercises

6.20(a), 6.20(b), 6.21(a), 6.21(b)

26

The Nernst Equation

The Nernst equation is an equation to determine the equilibrium

reduction potential of a half-cell in an electrochemical cell.

It can also be used to determine the cell potential

(electromotive force or emf) for a full electrochemical cell.

A cell is at equilibrium when the potential difference for the

overall reaction is zero (no work).

A cell is not at equilibrium when it can do electrical work. The

amount of work can be small or large depends on the potential
difference of the overall reaction.

You know that the maximum non-expansion

electrochemistry=electrical work) for a cell) is;
Wadd,exp= G = rG .

Assignment.
rules.

work

(in

Derive the equation above using thermodynamic

Maximum work is produced when a change occurs reversibly.

27

Thus, we suppose that the cell is operating

reversibly at a specific, constant composition.

This is achieved by measuring cell potential

when it is balanced by an exactly opposing
source of potential.

The resulting potential difference is called the

cell potential, Ecell, of the cell.
-vFEcell= rG
F is Faraday `s constant; F= eNA.
v is stoichiometric coefficient of the electrons in the
half-reactions

This equation shows the key connection

between
electrical
measurements
and
thermodynamic properties.
28

From
equation,
a
negative Gibbs energy,
corresponding
to
a
spontaneous
cell
reaction, corresponds to
a positive cell potential.

Or, the cell potential is

proportional to the slope
of the Gibbs energy with
respect to the extent of
the reaction.

For example, when the

slope is close to zero
(close
to
equilibrium
condition),
the
cell
potential is small.

The change in G can be

considered
by
an
infinitesimal
amount
called
extent
of
the
reaction when the cell
reaction proceeds.

29

 Now,

we can relate the cell potential to

the activities of the participants in the
cell reaction.

You

know that;

After

The

dividing both sides by vF, we have;

standard potential (in volts) is;

By

this, the Nernst equation (which is

the equation for cell potential in terms of
the composition) will be;
30

31

32

 For

example, consider the Harned cell;

Pt (s) | H2 (g) | HCl (aq) | AgCl (s) | Ag (s)

The overall reaction is:

H2 (g) + AgCl (s) HCl (aq) + Ag (s)

We

The

The

have;

Nernst equation is;

activity
Therefore;

of

H2

equals

to

1.

33

 Now,

we express the activity in terms of

molality, b, of HCl (aq);

After

rearranging this equation with b/b0=b

for simplicity:

Or;
From

Debye-Huckel law for 1,1-electrolyte

(meaning you have a solution of singly
charged M+ & X- ions) we know that;

If

F/2RT=C, the expression will be ;

34

Example. Given that the standard potential of

the Cu2+/Cu and Cu+/Cu couples are +0.340 V and
+0.522 V, respectively, calculate E0(Cu2+, Cu+ ).

35

Cells at Equilibrium
The

most important application of the

Nernst equation is pH determination of a
solution. This can done using a suitable
choice
of
electrodes,
of
the
concentration of the other ions.

special case is when the reaction has

reached equilibrium (Q=K).
K is
equilibrium constant.

There

is no work when a chemical

reaction is at equilibrium,
so the
potential difference is zero (for a
galvanic cell)(Ecell=0). Therefore;
36

The Determination of Activity Coefficients

If

you know the standard potential of an

electrode in a cell:
Mean activity coefficient can be determined.
This can be done by measuring the cell
potential with the ions at any concentration.

For

example, in HCl of molality b, the

mean activity coefficient of ions is equals
to;

37

The Determination of Equilibrium Constants

Standard potential are used to calculate the

standard potential of a cell formed from any
two electrodes.

Thus, we subtract the standard potential of

the left-hand electrode from the right-hand
one;

You already know that;

Therefore, if we have E0cell> 0, then the cell

reaction has K > 1.
38

For example; 2Cu+(aq) Cu (s) + Cu2+(aq)

For right-hand electrode (cathode):

Cu (s) | Cu+(aq)

Cu+(aq) + e- Cu(aq)

E0=+0.52 V

For left-hand electrode (anode):

Pt (s) | Cu2+(aq), Cu+(aq) Cu2+(aq) + e- Cu+(s)

E0=+0.16 V

At 298 K, we have:
E0cell= + 0.52 V - 0.16 V = + 0.36 V

Now, we can calculate K for the cell reaction.

ln K = vFE0cell /RT
K=1.2 106
39

The Determination of Thermodynamic

Functions
We

know that; -vFE0cell= rG0

For

example;

Pt (s) | H2 | H+(aq) || Ag+(aq) | Ag (s)

The

E0cell= +0.7996 V

cell reaction is:

Ag+(aq) + H2(g) H+(aq) + Ag (s)

rG0= -fG0 (Ag+,aq)

fG0(Ag+,aq) = - (- vFE0cell) = ( FE0cell) = +77.15 kJ/mol

Using

the temperature coefficient of the

standard cell potential, dE0cell/dT, we can get
the standard entropy of the cell reaction.
40

Because;

We know that;

If we combine these equations;

If we combined all the results we obtained until now,

the standard enthalpy of a reaction will be;

By this, we have a non-calorimetric method for

measuring the enthalpy.

From the convention, rH0(H+,aq)=0, therefore, all

standard enthalpies of formation of ions in solutions
can be calculated.

41

 Example;

consider this cell;

Pt (s) | H2 (g) | HBr (aq) | AgBr (s) | Ag (s)

The

standard potential measured over a

range of temperatures is:
E0cell / V= 0.07131- 4.9910-4 (T/K-298) - 3.4510-6
(T/K-298)2

The

cell reaction is:

AgBr (s) + H2 (g) Ag (s) + HBr (aq)

Evaluate the standard reaction Gibbs

energy, enthalpy, and entropy at 298 K.
42

At, T= 298 K, E0cell= +0.07131 V, so;

rG0 = - vFE0cell= - (1) (9.6485 104C mol-1) (+ 0.07131 V)
= - 6.880 103 V C mol-1 = - 6.880 kJ mol-1

Now, for the temperature coefficient of the cell

potential we have,
dE0cell/dT = - 4.99 10-4 V K-1 2 (3.45 10-6) (T/K-298)V K-1

At, T= 298 K;
dE0cell/dT = - 4.99 10-4 V K-1

Therefore;
rS0 = 1 (9.6485 104 C mol-1) (- 4.99 10-4 V K-1)
= - 48.1 J K-1mol-1
rH0 = rG0 + TrS0 = - 6.880 kJ mol-1 + (298 K) (- 0.0481 J K -1mol1)
= - 21.2 kJ mol-1
43