CHAPTER 3

ELECTROCHEMICAL CELLS
BY
MDM HAIRUL AMANI BINTI ABDUL HAMID

OUTLINE
Components of a cell
Conventional representation of a cell
Potential of cells and electrodes
Thermodynamic of cells
Work and free energy
Standard electrode potentials
Equilibrium constant
Nernst equation

OUTLINE
Types of electrodes and general form of
Nernst equation for an electrode
QUIZ 4
Types of galvanic cells and general form of
Nernst equation for a galvanic cell
Applications of galvanic cell potentials
Activity coefficients
Equilibrium constants
Solubility constants
pH
3
TEST 2

ELECTROCHEMICAL CELLS

Consists of electrode in contact with an electrolyte in the

electrode compartment(s)
Salt bridge concentrate electrolyte solution in agar jelly;
completes the electrical circuit, and exchange of ions between 2
different electrode compartments and enable the cell to function.
4

Electrolytic cell vs Voltaic Cell

Redox Reaction
- Is a reaction in which there is a transfer of electron

from one species to another.

OilRig Oxidation is loss, reduction is gain
Oxidation a process in which there is a loss of electron
Reducing agent/reductant is the electron donor

Reduction a process in which there is a gain of electron.

Oxidazing agent/oxidant is the electron acceptor
6

Redox Reaction

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

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

Half reactions
Cu2+(aq) + 2e- Cu(s) (Reduction of Cu2+)
Zn(s) Zn2+(aq) + 2e- (Oxidation of Zn)
Cu2+(aq) + Zn(s) Cu(s) + Zn2+(aq) (Overall)
The reduced and oxidised substances in half
reactions form redox couple:
Cu2+/Cu and Zn/Zn2+

Half reactions
In general the redox couple is written as Ox/Red with
the half reaction as:
Ox + ne- Red
Example:
Cu2+(aq) + 2e- Cu(s)
Zn2+(aq) + 2e- Zn(s)

Redox couple
Cu2+/Cu
Zn2+/Zn

Reaction Quotient, Q
For half reaction:
Cu2+(aq) + 2e- Cu(s)

Q=

1
(Cu2+)
Zn2+(aq) + 2e- Zn(s)
Q= 1
(Zn2+)
For the standard state of pure material
(element) it has unity activity eq Cu = 1

10

Reaction Quotient, Q
Reaction quotient for the reudction of O2 to H2O in
acid solution,
O2(g) + 4H+(aq) + 4e- 2H2O(l)
Q = 2H2O since O2 behaves as perfect gas
4H+ O2
O2 = PO2
= P
P
4H+ PO2
and 2H2O = 1

11

Reactions at electrode
When spontaneous
reaction takes
place in a galvanic
cell, electron are
deposited in
anode(oxidation)
and collected from
cathode (reduction)

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

12

Galvanic cell

Electrolytic cell

Cathode has higher potential Oxidation occur at the

than the anode.
anode, but electrons are
withdrawn from the species
Species in the electrolyte
since process is not
undergoing reduction,
spontaneous.
withdraws electrons from
cathode, leaving a relative
Anode is relatively positive to
positive charge on the
cathode.
cathode.
At the cathode, must have
At anode, oxidation caused
supply of electrons to drive
the transfer of electrons to
the reduction.
the electrode, give it a
relative negative charge
13

Galvanic vs Electrolytic cell

Galvanic cell
The difference in electrical potential between the
anode and cathode is called
cell voltage/electromotive force (emf)/cell
potential
Electrolytic cell
External source of current, so emf does not apply.

14

Varieties of electrode
1. Metal/metal ion electrode

Cu2+ + 2e- Cu

15

Varieties of electrode
2. Redox electrode
Species exist in solution in 2
oxidation state.

Electrode used is an inert

metal Pt
Eg:

Fe3+ to Fe2+

16

Varieties of electrode
3. Gas electrode

Standard hydrogen electrode

17

Varieties of electrode
3. Gas electrode (Cont)
eg. Hydrogen electrode
inert metal as electrode.
gas in equilibrium with its ion
2H+(aq) + 2e- H2 (g) (Reduction)
Redox couple: H+/H2
It may either be a cathode or an anode
The standard hydrogen electrode is attached to the electrode
system under investigation.

18

Metal/Insoluble salt electrode

A metal M covered by porous layer of insoluble MX
salt, immersed in a solution of X ions.

AgCl(s) + e
Ag(s) + Cl-(sat)

19

Cell Notation
ZnZn2+(1 M) Cu2+(1 M)Cu
Phase
boundary
Single cell
compartment

interphase
Anode
(oxidation)

Salt bridge

Cathode
(reduction)

Half Equations:
Zn(s) Zn2+(aq) + 2e
20

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

Cell reaction
The reaction in the cell written on the assumption that righthand electrode is cathode and with spontaneous reaction,
reduction is taking place in the right-hand compartment
Cu2+(aq) + 2e Cu(s)
(Reduction)
Zn(s) Zn2+(aq) + 2e

(Oxidation)

Cu2+(aq) + Zn(s) Cu(s) + Zn2+(aq) (overall)

Left: Zn(s) Zn2+ + 2e
Right: Cu2+(aq) + 2e Cu(s)
Cell Notation: ZnZn2+ Cu2+Cu

21

Example 1
Write the half-equations and cell reactions for each
of the following cells:
a) AgAg+H+H2, Pt
b) PtCr2O72, Cr3+, H+BrBr2(l), Pt

22

Answer:
a) AgAg+H+H2, Pt
Ag Ag+ + e (Oxidation) (2x)
2H+ + 2e H2 (Reduction)
2Ag + 2H+ 2Ag+ + H2(g) (overall = cell reaction)
b) PtCr2O72, Cr3+, H+BrBr2(l), Pt
2Cr3+ + 7H2O Cr2O72 + 14H+ + 6e (Oxidation)
(Br2(l) + 2e 2Br) 3
(Reduction)
2Cr3+ + 7H2O + 3Br2(l) Cr2O72 + 14H+ + 6Br
23

Example2
Describe in shorthand notation a galvanic cell for
which the cell reaction is
Cu(s) + 2Fe3+(aq) Cu2+(aq) + 2Fe2+(aq)
Answer:
Oxidation:
Cu(s) Cu2+(aq) + 2e
Reduction:
Fe3+ + e Fe2+
Cell Notation: CuCu2+ Fe2+, Fe3+Pt
(Since both Fe2+ and Fe3+ are in solution, a Pt electrode
is used.)
24

Varieties of cells
1. Daniell cell

25

Varieties of cells
2.

Electrolyte concentration cell.

electrodes are identical but these are immersed in

solutions of the same electrolyte of different
concentrations
Zn|Zn2+ (C1))/Anode || (Zn2+ (C2 )|Zn)/Cathode
- The source of electrical energy in the cell is the tendency
of the electrolyte to diffuse from a solution of higher
concentration to that of lower concentration.
- With the expiry of time, the two concentrations tend to
become equal.
- At the start the emf of the cell is maximum and it
gradually falls to zero.
26

Varieties of cells
3. Electrode concentration cell
The potential difference is developed between two like
electrodes at different concentrations dipped in the same
solution of the electrolyte.
For example, two hydrogen electrodes at different pressure
in the same solution of hydrogen ions constitute a cell of
this type.
Pt,H2 (Pressure p1)) |H+ ||H+, H2 (Pressure p2)Pt

In the amalgam cells, two amalgams of the same metal at

two different concentrations are inserted in the same
electrolyte solution.
27

Liquid Junction Potentials, Elj

Electrolyte concentration cells always
have a liquid junction, electrode
concentration cells do not.
In a cell with two different electrolyte
solutions in contact, there is an
additional source of potential difference
across the interface of the two
electrolytes, and this potential is known
as the liquid junction potential.

The contribution of the liquid junction to the potential can be reduced by

joining the electrolyte compartments through a salt bridge.
The salt bridge which is an inverted tube consist of concentrated salt
solution in jelly, has two opposing liquid junction potentials at both ends
that almost cancel.
28

Cell Potential, V
- The potential difference between two electrodes.

- Measured in volts (V) (1V = 1JC-1s)

- As long as cell has not reached chemical

equilibrium, it can do work as reaction drives

electrons through external circuit
- A cell which has reached equilibrium can do no
work. The cell potential = 0.

29

Gibbs energy change in a cell

Given we = non expansion work
eg. Electrical work of pushing e through a circuit
If change occurs at constant P and T
dwerev = dG (Tp = constant)
But the process is reversible, the work done must have max
value. For a measurable change
wmax = dG (Tp = constant)
For a spontaneous process, max electrical work by cell =
wmax = G

30

Relation between E and G

wmax = G
For this equation to be valid, cell must be operating
reversibly at specific constant composition.
Measure the cell potential when it is balanced by
exactly opposing source of potential.
This results in zero current cell potential or E,
electromotive force of the cell.
-nFE = G
n = no of mole
F= Faradays constant = 96500 C mol-1
E = cell potential.
31

Voltmeter
A voltmeter is an instrument used for

32

measuring electrical potential difference

between two points in an electric circuit.
Analog voltmeters move a pointer across a
scale in proportion to the voltage of the
circuit;
digital voltmeters give a numerical display of
voltage by use of an analog to digital
converter.
The maximum possible voltage to be
measured is called the electromotive force
(emf).
The emf of a cell under standard conditions
is E0

Multimeter

Voltmeter

The Nernst Equation

The reaction of Gibbs energy is related to the composition of
reaction mixture by
G = Go + RT lnQ
(At equilibrium, Q = Keq and G = 0.

Go = - RT lnQ )

Substituting above equation by: -nFE = G

And dividing each by nF
E = -Go - RT lnQ
nF
nF
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The Nernst Equation

E = -Go - RT lnQ
nF
nF
Given Go = - nFEo
E = Eo - RT lnQ
or E = Eo 2.303 RT logQ
nF
nF
at 25oC RT = 0.0257V
F
E = Eo 0.0257 lnQ or E = Eo 0.0592 logQ
n
n

34

Standard Potentials
Define a potential of one electrodes as having zero
potentials, then assign values to others on that
basis.
SHE (LH) Standard Hydrogen Electrode.
Pt | H2(g)|H+(aq) E0= 0 at all temperatures
Example:
The standard potential of Cu2+/Cu couple (RH
electrode)
Pt | H2(g)|H+(aq) || Cu2+|Cu
E0 (Cu2+/Cu)=0.337V
35

Standard Electrode Potentials

Standard Reduction Potentials
(Eo)
is the voltage associated with
a reduction reaction at an
electrode when all solutes are
1M and all gases are at 1 atm.
Reduction reaction:
2H+(1M) + 2e- H2(1 atm)
Eo = 0
36

1 atm

Standard Electrode Potentials

Zn(s)|Zn2+(1M) |H+(1M)| H2(1 atm)| Pt(s)
(LH electrode)
Eocell = Eocathode - Eoanode
Eocell = EoH+/H2 - EoZn2+/Zn
0.76 = 0 - EoZn2+/Zn
EoZn2+/Zn = - 0.76
Zn2+(1M) + 2e Zn

Eo = - 0.76

Anode: Zn(s) Zn2+(1M) + 2e

Cathode: 2H+(1M) + 2e H2(1 atm)
Zn(s) + 2H+(1M) Zn2+(1M)+ H2(1 atm)

37

Eocell = 0.76 V

Standard Electrode Potentials

Eocell = 0.34V
Pt(s)|H
H2(1 atm) 2H+(1 M)
+ 2(1 atm) |H+(1M)|Cu2+(1M) |Cu(s)

Eocell = Eocathode - Eoanode

Eocell = EoCu2+/Cu - EoH+/H2
0.34 = EoCu2+/Cu - 0
EoCu2+/Cu = 0.34
Cu2+(1M) + 2e Cu(s) Eo = 0.34
Anode: H2(1 atm) 2H+(1 M) + 2e
Cathode: Cu2+(1M) + 2e Cu(s)
H2(1 atm) + Cu2+(1M) Cu(s) + 2H+(1 M)

38

Standard Reduction Potential Table

39

Increasing strength in reducing agent

Increasing strength in oxidising agent

Half cell reactions are

only in the form of

reduction reactions.
The more positive Eo

the greater the

tendency for substance
to be reduced

Standard Reduction Potential Table

Half cell reactions are

reversible
The sign Eo changes

when the reaction is

reversed
Changing stoichio-

metric coefficients of
half cell reaction does
not change value of Eo
40

Example
Consider the following reaction:
Cu2+(aq) + Zn(s) Cu(s) + Zn2+(aq)
Determine the emf of the cell given the
concentration of Cu2+ and Zn2+ are 5.0M and
0.050M respectively at 298K.

41

Answer
Cu2+(aq) + 2e- Cu(s) EoCu2+/Cu = +0.34 V
Zn2+(aq) + 2e- Zn(s)
EoZn2+/Zn = - 0.76 V
Cu2+(aq) + Zn(s) Cu(s) + Zn2+(aq) Eocell = ?

Eocell = Eocathode - Eoanode

= EoCu2+/Cu - EoZn2+/Zn
= 0.34 (-0.76)
= 1.10 V

42

Answer(cont)
Using Nernst equation:

E cell = Eocell 0.0592 logQ

n
E cell = Eocell 0.0592 log[Zn2+]
n
[Cu2+]
= 1.10 - 0.0592 log [0.050]
2
[5.0]
= 1.16 V
Cell reaction becomes more spontaneous
since [reactant]>[product] -- E cell > Eocell
43

Example
Consider the following reaction:
Cr2O72- (aq) + 14H+ (aq) + 6I- (aq) 2Cr3+(aq)
3I2(s) + 7H2O(l)
Determine the emf of the cell given the
concentration:
[Cr2O72-]= 2M, [H+] =1M, [I-] = 1M and
[Cr3+] = 1.0 x 10-5M

44

Answer
Cr2O72- (aq) + 14H+ (aq) + 6I- (aq) 2Cr3+(aq) 3I2(s) +
7H2O(l)
Eocell = Eocathode - Eoanode
= EoCr2O72-/Cr3+ - EoI2/I= 1.33 0.53
= 0.8 V

45

Answer
Cr2O72- (aq) + 14H+ (aq) + 6e 2Cr3+(aq) +7H2O(l)
6I- (aq) 3I2(s) + 6e
n=6
Using Nernst equation:
E cell= Eocell 0.0592 logQ = Eocell 0.0592 log[Cr3+]2
n
n
[Cr2O72-][H+]14[I-]6
= 0.8 - 0.0592 log (1.0 x 10-5) 2
6
[2] [1]14[1]6
= 0.8 - 0.0592 log 5 x 10-11
6
= 0.8 (- 0.10) = 0.90 V
Since [reactant]>[product] -- E cell > Eocell
46 If value of Q increases -- value of E cell decreases.

Concentration Cell
Cell Notation:
M(s)|M+(aq, L) M+(aq, R)| M(s)
[R] > [L], E 0
Positive potential arises because positive ions tend to
be reduced , withdrawing electrons from the electrode.
This occur in the right hand electrode compartment
which is more concentrated
M+ (m2) + e M
The reaction at the left hand electrode is:
M M+(m1) + e
Overall reaction:
M+ (m2) M+ (m1)
47

Overall reaction:
M+ (m2) M+ (m1)
If m2 > m1 the reaction is a forward direction, positive
emf is produced.
If m2 < m1 electrons flow from right to left electrode,
negative emf is produced.
G associated with transfer of M+ ions from M+ (m1)
M+ (m1) is given by:
G = RT ln m1
m2
Since no. of mol of e- = 1,
E = RT ln m2
E is positive if m2 > m1
F
m1
Go = 0 and Eo = 0 since a cell cannot drive a current
through a circuit with 2 identical electrode
compartment.
48

Example:
Calculate the emf at 25oC of a concentration cell of
this type in which the molalities are 0.2m and
3.0m.

E = RT ln m2
F
m1

49

at 25oC

E = 0.0257 ln m2
m1
= 0.0257 ln 3.0
0.2
= 0.0696 V

Concentration Cell
Calculate the emf of the
cell in the diagram at
25oC

E = 0.0592 log 1.00

2
= 0.0888 V

50

1.00 x 10-3

Cell Equlibrium
When a cell has reached equilibrium, then Q = K,
while E = 0 since chemical reaction at equilibrium do no work
and generates 0 potential difference between the electrodes
of the cell.

E= Eo - RT lnQ
nF
0 = Eo - RT lnK

(x nF

nF
0 = nFEo RTlnK

nFEo = RT lnK

ln K = nFEo

RT
51

E= 0
and Q = K)

Example:
Calculate the equilibrium constant at 25oC for the
reaction occurring in the Daniell cell, if the
standard emf is 1.10V.
Answer:
ln K = nFEo
RT = 0.0257
RT
F
ln K = 2 x 1.10 = 85.6
0.0257
K = e85.6 = 1.50 x 1037
For spontaneous process, Go <0, Eo > 0 and K > 1
52

Example
A reaction important in an acidic environment:
Fe(s) + 2H+(aq) + O2 (g) Fe2+ (aq) + H2O(l)
Does the equilibrium constant favour the formation of
Fe2+ (aq)?
Reduction half reaction:
Fe2+ + 2e Fe(s)
Eo = - 0.44 V
(anode)
2H+(aq) + O2 (g) + 2e H2O(l) Eo = +1.23 V
(cathode)
Eo cell = Eocathode Eoanode = 1.23 (-0.44)= 1.67 V
Since Eo cell > 1, the reaction has K>1
Favour the formation of Fe2+
53

The composition dependence of

individual potentials
1.

54

Metal electrode
-potential of an Ag+/Ag electrode is given by:
Electrode half reaction:
Ag+(aq) + e Ag(s) n = 1
E Ag+/Ag = EoAg+/Ag RT ln 1
F
(Ag+)

2.

Gas using platinum as electrode.

- eg, chlorine gas is bubbled over a platinum
electrode dipping aqueous sodium chloride at
298 K. Calculate the change in potential of
electrode when the chlorine pressure is
increased from 1.0 atm to 2.0 atm.
Electrode half reaction:
Cl2(g) + 2e 2Cl-(aq)
Q = (Cl-)2
F

55

n=2

Electrolysis
- is a chemical process that uses

electricity to cause a non-spontaneous

redox to occur.
- Take place in electrolytic cell made up

of two electrodes connected to a battery

and immersed in an electrolyte.

56

Electrolytic cell
Battery function as a
source of direct current
- Forces electrons out
of anode
- Pushes electrons
towards the
cathode.
Yn- Y + ne
(oxidation)
Cathode: Xn+ + ne X
(reduction)
Anode:

57

Electrolysis of Molten Salt

Cathode: 2Na+(l) + 2e 2 Na(l)
Anode: 2Cl-(l) Cl2(g) + 2e
Overall: 2Na+(l) + 2Cl-(l) 2 Na(l) + Cl2(g)

58

Electrolysis of Aqueous solutions

- Solution contain cations and anions from the salt

and water molecules.

- Water is an electro-active substance can be
oxidized or reduced depending on condition of
electrolysis.
Reduction: 2H2O(l) + 2e H2(g) + 2OH- E=-0.83V
Oxidation: 2H2O(l) O2(g) + 4H+ + 4e
E=-1.23V

59

Example: Electrolysis of aqueous

solution of NaCl
At cathode:
Na+(aq) + e Na(s)
2H2O(l) + 2e H2(g) + 2OH-(aq)
At anode:
2Cl-(l) Cl2(g) + 2e
2H2O(l) O2(g) + 4H+ + 4e

60

Eo = - 2.71V
Eo = - 0.83V
Eo = -1.36V
Eo = -1.23V

61

Corrosion

62

Corrosion
Corrosion is the gradual (spontaneous)

destruction of material, usually metals, by

chemical reaction with its environment.
Electrochemical oxidation of metals in reaction
with an oxidant such as oxygen.
Example - Rusting, the formation of iron oxides,
is a well-known example of electrochemical
corrosion.
Occur on the exposed surface

63

Figure 21.20

The corrosion of iron.

(1)

Fe( s) Fe 2 (aq) 2e (anodicregion;oxidation) 2

(2)

O2 ( g ) 4 H (aq) 4e 2 H 2O(l ) (cathodicregion;reduction)

Total 2 Fe( s) O2 ( g ) 4 H (aq) 2 Fe 2 (aq) 2 H 2O(l )

(3)

64

1
2 Fe 2 (aq) O2 ( g ) (2 n) H 2O(l ) Fe2O3 .nH 2O( s) 4 H (aq)
2

3
Overall 2 Fe( s) O2 ( g ) nH 2O(l ) Fe2O3 nH 2O( s)
2

Figure 21.22

The effect of metal-metal contact on the corrosion of iron.

faster corrosion

65

cathodic protection

Protection from corrosion

Surface coating plating with a thin layer of other

metal, painting, enamel, grease, varnish

Anodizing eg aluminium oxide (oxide as the
protective outer coating)
Cathode protection surface as cathode
(connecting metal to a more electropositive metal)
eg steel, water, and fuel pipelines and tanks;
steel pier piles, ships, and offshore oil platforms.
Anodic protection - impresses anodic current on
the structure to be protected (opposite to the
cathodic protection)
66

Figure 21.23

The use of sacrificial anodes to prevent iron corrosion.

67

Quantitative aspect of electrolysis

First Law of electrolysis

- the quantity of a substance formed at an

electrode is directly proportional to the quantity of
electric charge that has flowed through the circuit
Second Law of electrolysis
- for a given electric charge, the amount of any
metal formed at the electrode is proportional to its
equivalent weight. (relative mass/charge on the
metal of the ion)

68

Quantity of electric charge:

Q = It
Q = electric charge in couloumbs (C)
I = current in Amperes (A)
t = time in seconds (s)
The amount of substance formed at the electrodes
may be calculated from stoichiometric of
equations, and knowing the charge on one mole
of electrons is one Faraday (F)
1 F = 96500 C
69