Syllabus

Electrochemistry
9. Fundamentals of Electrochemistry
Data treatment and analysis
10. Potentiometry
1. Errors in Chemical Analysis
11. Ion Selective Electrodes
2. Significance Tests
12. Voltammetry
3. Sampling and Calibration Methods
Separation science
4. Extraction Techniques
5. Introduction to Chromatography
6. Gas Chromatography
7. High Pressure Liquid
Chromatography
8. Electrophoresis

Nanoanalysis
13. Nanoanalysis
Equilibria
14. Chemical Equilibrium
15. Acid, Bases and Acid-Base
Equilibrium
16. Chemical Equilibrium for Complex
Systems
17. Chemical Equilibrium for Titrations

CM2142

Fundamentals of Electrochemistry
1.
2.
3.
4.
5.
6.
7.
8.
9.

Introduction
Oxidation Numbers
Balancing Redox Equations
Voltaic/Galvanic Cells
Cell Diagrams
Cell Potentials
Free Energy and Nernst Equations
Electrolytic Cells
2-Electrode and 3-Electrode Systems

CM2142

eLecture prepared by
Dr Emelyn Tan

What is Electrochemistry?
Electrochemistry involves chemical phenomena
associated with charge separation and charge transfer,
with applications ranging from fundamental studies and
research to industrial, environmental and clinical
applications.

Source: International Society of Electrochemistry

www.ise-online.org

CM2142

Terminology
Term

Units

Equation

Definition

Current (i)

Amperes (A)

A=C/s

Quantity of charge
flowing in a circuit per
second.

Potential (E)

Volts (V)

V=J/C

Measure of work needed

to move electric charge
from 1 point to another.

Resistance (R)

ohm ()

V=iR

Ohms Law

Electric charge (Q) Coulombs (C)

Q=nF=it

A charge of single
electron is 1.602 x 10-19
C.
1 mol of electron has
96485 C (Faradays
constant).

Work (w)

Joules (J)

w=nFE=QE

Power (P)

Watt (W) = 1 J / s P = w / t = i E
CM2142

Work done per unit time

4

A=C/s
V=J/C

Current

Potential
CM2142

Revision: Redox Reaction

Oxidation:
- Loss of electrons
- Increase in oxidation number
- Gain of oxygen
- Loss of hydrogen

Reduction:
- Gain of electrons
- Decrease in oxidation number
- Loss of oxygen
- Gain of hydrogen

Oxidising Agent:
- Species is reduced

Reducing Agent:
- Species is oxidised

Reduction (gaining electrons) cant happen without an

oxidation to provide the electrons.
You cant have 2 oxidations or 2 reductions in the same
equation. Reduction has to occur at the cost of oxidation.
Hence, redox reactions!
CM2142

Oxidation Numbers (O.N.)

In order to keep track of what
loses electrons and what gains
them, assign oxidation
numbers.
Zn is oxidised as it loses two
electrons to go from neutral Zn
(O.N. = 0) metal to the Zn2+
(O.N. = 2) ion.

Each of the H+ is reduced as it

gains an electron each to go
from H+ (O.N. = 1) ions to
combine to form H2 (O.N. = 0)
gas.

Assigning Oxidation Numbers

1.

Elements in their elemental form have an oxidation

number of 0. e.g. Hg (O.N. = 0)

2.

The oxidation number of a monoatomic ion is the same

as its charge. e.g. Cu2+ (O.N. = 2)

CM2142

Assigning Oxidation Numbers

3.

Non-metals 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 (e.g. in H2O2) in which it has an oxidation number of 1.

Hydrogen has an oxidation number of +1, except when bonded to a metal

as the hydride ion (e.g. in CaH2) in which it has an oxidation number of
1.

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. e.g. HClO4 (Cl O.N. = 7)
CM2142

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.

O.N of H in H2O2

O.N of l in lO65-

1 + x + 4(-2) = 0
x = +7

2x + 2(-1) = 0
x = +1

x + 6(-2) = -5
x = +7

O.N. of Mn is +7

O.N. of H is +1

O.N. of I is +7

O.N of Mn in CsMnO4

CM2142

10

Balancing Oxidation-Reduction
Equations
Perhaps the easiest way to balance the equation of an
oxidation-reduction reaction is via the half-reaction method.
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.
1 oxidation half reaction
+ 1 reduction half reaction
Overall reaction
CM2142

11

Half-Reaction Method
This must be done in sequential order.
1.

Assign oxidation numbers to determine what is oxidised and

what is reduced.

2.

Write the oxidation and reduction half-reactions.

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.

CM2142

12

Half-Reaction Method
4.

Multiply the half-reactions by integers so that the electrons

lost and gained are the same for oxidation and reduction,
respectively.

5.

Add the half-reactions, subtracting things that appear on both

sides.

6.

Check that the equation is balanced on both sides according

to elements present. Conservation of mass

7.

Check that the equation is balanced on both sides according

to charge. Conservation of charge
CM2142

13

Consider the reaction between MnO4 (permanganate) and C2O42 (oxalate):

+7

+3

+2

+4

MnO4(aq) + C2O42(aq) Mn2+(aq) + CO2(aq)

Manganese is reduced.
Carbon is oxidised.
10
5 C2O42 2 CO2
2 MnO4 + 8H+ + 5e16
10

10
+ 2e-

Mn2+ + 4H2O
2
8

X5
X2

2MnO4 + 5C2O42 + 16H+ 2Mn2+ + 10CO2 + 8H2O

Balancing
+ 16OH-(aq)
+ 16OH-(aq)
in Basic
Solution: 2MnO + 5C O 2 + 16H O 2Mn2+ + 10CO + 8H O + 16OH4
2 4
2
2
2
2MnO4 + 5C2O42 + 8H2O 2Mn2+ + 10CO2 + 16OHCM2142

14

Figure 21.3
Silberberg

General characteristics of voltaic and electrolytic cells.

VOLTAIC CELL

ELECTROLYTIC CELL

Energy is released from

spontaneous redox reaction

Energy is absorbed to drive a nonspontaneous redox reaction

Oxidation half-reaction
X
X+ + e- from electrode

Oxidation half-reaction
AA + e- in solution

Reduction half-reaction
at electrode Y++ eY

Reduction half-reaction
in solution B++ eB

Overall (cell) reaction

X + Y+
X+ + Y; G < 0

Overall (cell) reaction

A- + B+
A + B; G > 0

Inert
electrodes

Voltaic vs. Electrolytic Cells

Cells

Ecell

Electrode
name

Process at Sign of
electrode electrode

Voltaic/
Galvanic

>0
Spontaneous

Anode
Cathode

Ox.
Red.

- (e- source) Redox

process
+
involves
electrodes

Electrolytic

Tunable,
Nonspontaneous

Anode
Cathode

Ox.
Red.

+ (anions)
- (cations)

CM2142

Electrodes

Electrodes
are (usually)
inert

16

Voltaic Cells
In spontaneous oxidationreduction (redox) reactions,
electrons are transferred and
energy is released.
The energy can be used to do
electrical work when the
electrons are channeled
through an external device =>
voltaic cell.

CM2142

17

Voltaic Cells

Separate the species

(i.e. Zn and Cu) into two
compartments. One for
oxidation other for
reduction.

Connect electrodes by a
wire/voltmeter.

Connect solutions by a
salt bridge.

-ve
+ve

Ox.

Red.

CM2142

18

Salt Bridge

Once even just 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. (right half cell will be -ve, preventing further electron flow)

Therefore, a salt bridge is used, usually a U-shaped tube that contains a salt
solution, to keep the charges balanced.
Left half cell: net + ve charge in solution so anions move toward the anode.
Right half cell: net - ve charge in solution so cations move toward the
cathode.

Migration of ions out of the salt bridge is higher than into the salt bridge.
Diffusion from high to low ion concentration.

Besides NaNO3, other usual choices for the electrolyte in the salt bridge are
KCl or KNO3.
CM2142

19

Cell Diagrams

Cell diagram: Zn(s) I Zn2+(aq) II Cu2+(aq) I Cu(s)

Phase boundary

Ox. first then red.

Salt bridge

If both ox. and red. species are ions, then use Pt (or graphite) as
the electrode. e.g Zn(s) I Zn2+(aq) II Fe3+(aq), Fe2+ (aq) I Pt(s)
Cannot dip wire into solution, need an electrode.
CM2142

20

Electromotive Force (emf)

CM2142

Water only spontaneously

flows one way in a
waterfall.

Likewise, electrons only

spontaneously flow one
way in a redox reaction.

Which species gives

(anode) and which takes
(cathode)?

21

Appendix 5 Skoog

Standard Reduction Potentials (Ered)

Higher red.
potential, more
easily reduced,
half-cell will be
the cathode.
Strong oxidising
agents.

Standard:
g = 1 atm
aq = 1 molL-1
a=1

Lower red.
potential, more
easily oxidised,
half-cell will be the
anode.
Strong reducing
agents.

CM2142

22

Standard Hydrogen Electrode:

the other half-cell

Their values are referenced to a standard hydrogen electrode

(SHE).

By definition, the standard reduction potential (Ered) for the

hydrogen ion is 0 V:
2H+ (aq, 1 M) + 2e H2 (g, 1 atm)

aq = 1 molL-1
i.e. pH = 0

CM2142

23

Standard Hydrogen Electrode

by definition, Ered of SHE = 0

Potential
readings can
be negative.

o
Ered
0V

Cu2+ is more readily

reduced cf. H+
Ered (Cu2+) > 0

CM2142

H+ is more readily
reduced cf. Zn2+
Ered (Zn2+) < 0 24

Standard Cell Potentials

Referenced against the SHE, all species with Ered > 0 were
reduced and all species with Ered < 0 were oxidised.
After a half-cell is referenced against the SHE, its Ered can be
compared against other half-cells.
For a given voltaic cell, the cell potential at standard conditions
can be written as this equation:
Standard reduction potentials

= Ered
(cathode) Ered
(anode)
Ecell
Larger Ered,
Reduction process
CM2142

Smaller Ered,
Oxidation process
25

Cell Potentials
For the oxidation (anode) in this cell,
= 0.76 V
Ered

For the reduction (cathode),

= +0.34 V
Ered

Ecell

(cathode) Ered
(anode)
= Ered
= +0.34 V (0.76 V)
= +1.10 V
CM2142

26

Consider the following two electrode reactions and their standard

electrode potentials:

Al3+(aq) + 3e- Al(s)

Cd2+(aq) + 2e- Cd(s)

E0 = -1.66 V
E0 = -0.40 V

Write the cell reaction for a voltaic cell based on these two
electrodes, and calculate the standard cell potential, Eocell.
Indicate which is the positive and negative electrode.
Al is oxidised at the anode. In voltaic cells, anode is negative.
Cd2+ is reduced at the cathode. In voltaic cells, cathode is positive.
2Al(s) + 3Cd2+(aq) 2Al3+(aq) + 3Cd(s)

Eocell = -0.40 (-1.66) = 1.26 V

CM2142

V=J/C
27

Free Energy
Go for a redox reaction under standard conditions, can be
written as the equation:
Go = total charge x Eocell = -RT ln K
Go = nF x Eo
Go = nFEo = wmax For redox reaction to be

spontaneous, G < 0, so E > 0.

w < 0, work is done by the system.

where:
n is the number of moles of electrons transferred per mole of
reaction
F is the Faraday constant (1 F = 96,485 Cmol-1)
Eo is in V = J/C
CM2142

28

Nernst Equation
Recall that G = G + RT ln Q
then nFE = nFE + RT ln Q
By dividing both sides of nFE = nFE + RT ln Q by nF,
we obtain the Nernst equation:
At 298 K,
RT
Ecell = Ecell
nF
In

x 2.303

ln Q

Ecell = Ecell 0.059 log Q

n

log

x ln 10
CM2142

29

A voltaic cell consists of Mn/Mn2+ and Cd/Cd2+ half-cells with

concentrations [Mn2+] = 0.75 M and [Cd2+] = 0.15 M. Use the
Nernst equation to calculate the cell potential, Ecell, at 25 oC.
(F = 96485 Cmol-1)
Data: Cd2+(aq) + 2e- Cd(s) Eo = -0.40 V
Mn2+(aq) + 2e- Mn(s) Eo = -1.18 V
From Ered, Cd2+ undergoes reduction and Mn oxidation.
Overall: Cd2+ + Mn Cd + Mn2+
Ecell = -0.40 (-1.18) = 0.78 V

For a cell reaction, Ecell = Ecell

RT ln products
reactants
nF

Ecell = 0.78 [(8.314 x 298)/(2 x 96485)] In (0.75/0.15) = 0.76 V

CM2142

30

Discharge of Voltaic Cell

Ecell = Ecell

RT
nF

ln Q

Cu(s) I Cu2+(aq, 1 M) II Ag+(aq, 1 M) I Ag(s)

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

[Cu2 ] 1
Q
2 1
2
[Ag ] 1

E (Cu2+/Cu) = 0.34 V and E (Ag+/Ag) = 0.80 V

Figure 18-5
Skoog

The cell potential is initially 0.46 V, Q = 1.

As the reaction proceeds, the potential
decreases continuously until it approaches zero,
as the overall reaction approaches equilibrium.

At the end, when Ecell = 0, Q = K, K = 3.6 x 1015

CM2142

31

Concentration Cells

Ni

Ecell = Ecell

RT
nF

ln Q

Ni

Notice that the Nernst equation implies that a cell could be created
that has the same substance at both electrodes.
For such a cell, Ecell would be zero, but Q would not.
Therefore, as long as the concentrations are different, Ecell
will not be 0.
CM2142

32

Given the following cell: Fe(s) I Fe2+(aq, 2 x 10-2 M) II Fe2+(aq, 1 M) I Fe(s)

and that the standard reduction potential of Fe2+(aq) to Fe(s) is -0.44 V,
calculate Ecell.
Oxidation: Fe(s) Fe2+(2 x 10-2 M) + 2eReduction: Fe2+(1 M) + 2e- Fe(s)
Overall: Fe2+(1 M) Fe2+(2 x 10-2 M)
Ecell = Eocell RT/nF In Q
Ecell = 0 RT/nF In (2 x 10-2 / 1)
Ecell = 0.05 V

CM2142

33

Multiplying a cell reaction by any

number does not change Ecell
Cu(s) Cu2+(aq) + 2e-

5Cu(s) 5Cu2+(aq) + 10e-

2Ag+(aq) + 2e- 2Ag(s)

10Ag+(aq) + 10e- 10Ag(s)

Cu(s) + 2Ag+ Cu2+ + 2Ag(s)

5Cu(s) + 10Ag+ 5Cu2+ + 10Ag(s)

RT [Cu2 ]
E E
ln
2F [Ag ]2

V=J/C
CM2142

RT [Cu2 ]5
E E
ln
10F [Ag ]10
RT
E E
(ln[Cu 2 ]5 - ln[Ag ]10 )
10F
RT
E E
(5ln[Cu 2 ] - 10ln[Ag ])
10F
RT
E E
5(ln[Cu 2 ] - 2ln[Ag ])
10F
RT
E E
(ln[Cu 2 ] - ln[Ag ]2 )
2F
RT [Cu2 ]
E E
ln
2F [Ag ]2
34

Ered values are T dependent

Go = -nFEo = -RT ln K
Ecell values are T dependent, since K is T dependent according to
the vant Hoff equation:

In (K2/K1) = (-H/R)(1/T2 1/T1)

Ered (Ag+/Ag) = 0.80 V at 298 K

At 298 K, K = 3.39 x 1013

Hf (Ag+(aq)) = +105.6 kJmol-1

Ered (Ag+/Ag) = 0.795 V at 303 K

CM2142

At 303 K, K = 1.68 x 1013

35

Why is Ered (Ag+/Ag) = 0.80 V but

Ered (AgCl/Ag) = 0.22 V?
Ag+(aq) + e- Ag(s)
E Ag /Ag E

o
Ag /Ag

0.059
1

log
1
[Ag ]

[Ag ] depends on K sp of AgCl(s).

K sp 1.8 x 10-10

K sp

1
[Cl ]
[Ag ][Cl ]

[Ag ] K sp

E AgCl/Ag E
KCl + AgNO3 AgCl + KNO3
Figure 18-9
Skoog

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

AgCl(s) Ag+(aq) + Cl-(aq)
K sp [Ag ][Cl ] 1.8 x 10-10

o
Ag /Ag

EoAgCl/Ag 0.80

0.059
[Cl ]

log
1
K sp
0.059
1
log
1
1.8 x 10 -10

EoAgCl/Ag 0.22 V
36

Calculate the electrode potential vs. SHE of a silver electrode

immersed in a 0.05 M solution of NaCl and AgCl (s) using Eored
(Ag+/Ag) = 0.80 V. Ksp (AgCl) = 1.8 x 10-10.

Ag+(aq) + e- Ag(s)
E Ag /Ag EoAg /Ag

E AgCl/Ag E

o
Ag /Ag

0.059
1
log
1
[Ag ]

0.059
[Cl ]

log
1
K sp

E AgCl/Ag 0.80

0.059
0.05
log
1
1.8 x 10-10

E AgCl/Ag 0.30 V

CM2142

37

H2(g, 1 atm) 2H+(aq, 1 M) + 2e

2Ag+(aq) + 2e- 2Ag(s)

H2(g, 1 atm) + 2Ag+(aq) 2H+(aq, 1 M) + 2Ag(s)
0.059
[H ]2

log
2
[Ag ]2 [H2 ]

Ecell E

o
cell

Ecell E

o
Ag /Ag

Ecell E

o
Ag /Ag

0.059
1
0.059
[H ]2
o

log
EH /H
log
2
2
2
[Ag ]
2
[H2 ]

o
H /H2

0.059
1
[H ]2

(log
log
)
2
2
[Ag ]
[H2 ]

SHE, 0 V
Ecell E

o
Ag /Ag

0.059
1

log
1
[Ag ]

WE

CM2142

RE
38

In an ELECTROLYTIC CELL an external source of energy is

required to force the non-spontaneous reaction to proceed. An
application of an electrolytic cell is electroplating.
A technician is plating a faucet with 0.86 g of Cr from an electrolytic bath
containing aqueous Cr2(SO4)3. If 12.5 min is allowed for the plating, what
current is needed?
Q = nF = i t
1 A = 1 Cs-1 Current = Charge per sec
Cr3+(aq) + 3e-

mass of Cr needed

Cr(s)

divide by M
mol of Cr needed
3 mol e-/mol Cr
mol of e- transferred

0.86g

x 3 mol e-

= 0.050 mol e-

52.00 gmol-1
0.050 mol e- (96485 Cmol-1 e-) = 4787 C

96485 Cmol-1 e4787 C

charge (C)

12.5 min x 60 s

divide by time
current (A)

CM2142

= 6.4 A
39

Components involved in
Electrolytic Cells
Component

Electrolyte

Chemical system capable of conducting current e.g. 0.1 M

KNO3.

Electrochemical Solution

Solution in which electrolyte and analyte are dissolved.

Electrodes:
- Working electrode (WE)

Electrode at which redox process of interest occurs,

potential is applied to WE.

- Reference electrode (RE)

Potential is referenced against RE.

- Counter/Secondary/Auxiliary
electrode (CE)

Counters the current at the WE by allowing current to flow

through it and then the electrolyte.

CM2142

40

Potentiostat
i

Working
Electrode
(WE)

Counter
Electrode
(CE)

Pt wire

Satd AgCl

Ag wire

Au wire

Reference
Electrode
(RE)

Salt
bridge

Electrochemical Solution
Analyte, Electrolyte, Solvent

CM2142

41

Polarized vs. Non-polarizable Electrodes

Ideal polarized electrode

Ideal non-polarizable electrode

V = J/C

A = C/s

No analyte

e.g. noble metals (resistant to

corrosion) e.g. Au, carbon, Hg.
=> WE
Wide potential range that has
minimal current.

e.g. reference electrodes such

as SCE, Ag/satd AgCl and
counter electrodes such as Pt
wire.
=> RE, CE
Potential unchanged upon
passage of current.

CM2142

42

2-Electrode System vs. 3-Electrode System

Measures V or i

2 electrodes system
- Voltaic cells
- Small currents, no CE
- Small V = iRsolution

Applies V or i and
measures the other.

3 Electrode system
- Electrolytic cells
- Large currents
- Large V = iRsolution (e.g. in
non-aqueous solvents)
CM2142

43