Electrochemistry

Outline (2 lectures, 1 tutorial)

Reactions at electrodes
Half equations
Electrode Potentials
Electrolytic and Galvanic cells
Cell emf
The Standard Hydrogen Electrode (SHE)
Standard Electrode Potential, SEP (E0)

Outline
The Nernst Equation
Relationship between Eo, Gibbs Free Energy (G) and

equilibrium Constants (K).

Measurement of pH.

Electrochemistry
Is the interchange between electricity and materials

that may involve charge (electron) or ion transfer.

Electron Transfer reactions (Redox)

The exchange of charge in reactions is not always easy to

see, so the concept of oxidation number was devised.

Example
2 Mg(s) + O2(g) MgO(s)
Mg is oxidized:
2 Mg(s) 2 Mg2+(aq) + 4eO2 is reduced:
O2(g) + 4e- 2O2-(aq)
Oxidation : loss of electrons
Reduction: Gain in electrons
OIL
RIG
Oxidation Is Loss
Reduction Is Gain

Electrochemistry

Observations:
- a spontaneous reaction occurs (G is ve) &

equilibrium.

Redox Reaction

will continue until it reaches

Gradually a grayish white deposit forms on the copper

The solution becomes pale blue as hydrated Cu2+ ions enter the solution.
Cu0(s) Cu2+(aq) and Ag+(aq) Ag0(s)
Overall reaction : Cu(s) + Ag+(aq) Cu2+(aq) + Ag(s)

Redox Reaction (Electron Transfer)

Half equations
Oxidation

Cu0(s) Cu2+(aq)+ 2e-

Reduction

Ag+(aq) + e- Ag0(s)

Electrochemistry
It would be useful to be able to convert this chemical

energy to electrical energy instead of heat energy.

This is done by an electrochemical cell.
An Electrochemical Cell - is a device used to convert

chemical energy (produced in a redox reaction) into

electrical energy.

Galvanic or Voltaic Cell

Electrochemical Cells are also known as Galvanic or

Voltaic Cells.

Named after Luigi Galvani( 1737-1798) an Italian

anatomist who discovered that electricity can cause the

contraction of muscles.

Also called voltaic cells after another Italian scientist

Alessandro Volta (1745-1827), the inventor of the battery.

Galvanic cell is one in which the energy released in a

spontaneous redox reaction is used to perform electrical

work (drive e-s through an external circuit).

Example of an Early Galvanic Cell

Daniell Cell (Porous Pot)
.

Galvanic cells are formed when we separate the

sites where oxidation and reduction in a
spontaneous reaction occur.
Higher electrode potential

How does the Daniell Cell work?

- the copper strip attracts electrons from the zinc strip.
- these electrons pass through the wires of our external circuit.
- As the copper electrode receives electrons, free positive ions in the solution arrive
to equalize the charges.
- Positive Cu2+ are attracted to the charged copper electrode where they receive two
electrons and become neutral and deposit on the electrode in metallic form.
- The use of a porous barrier allows SO42- to move from right to left (to balance eflow in circuit) but prevents the Cu2+ and Zn2+ from moving between electrodes.
-For each copper atom that is deposited on the copper electrode, a zinc atom goes
into solution, giving up two electrons to the zinc electrode.

Electromotive Force (emf)

The electromotive force is the maximum

potential difference between two electrodes of a

galvanic or voltaic cell. (the energy converted into
electrical energy when unit charge passes through
the source)

It measures the pulling tendency of the two

electrodes.

That is the tendency to acquire (i.e. gain) or release

(loss) electrons.

Daniell Cell
The maximum potential between Zn and Cu of the Daniell cell

has been measured to be 1.10 V, but this is not observed in

practice.

Factors that affect the measured potential in a cell (e.g. Daniell Cell)?
1.
2.
3.

Porosity of the pot

Cleanliness of the electrodes
Electrical Resistance of the Measuring Device

Minimize

Make pot as porous as possible without allowing solutions to mix

Electrodes clean
High Resistance Voltmeter

Internal Resistance {there is build up of charges inside pot }

Liquid Junction Potential (LJP) {difference in ion mobility}

Liquid Junction Potential (LJP)

The liquid junction, porous pot, is also a source of lost potential
Why is this?
Build-up of charge results from the difference in mobility of the

ions as they move across the wall of the porous pot to neutralize
the charge.
Potential difference exists between the inner & outer surfaces of

the wall of the porous pot .

This potential that results is called a LIQUID JUNCTION

POTENTIAL

How do we overcome the liquid junction potential?

We need to provide a good conducting path

Use a salt bridge with ions of similar mobilities to reduce the

effect of liquid junction potentials (i.e. potentials which arise
because of the difference in mobilities of the ions).

Once these precautions are taken the emf of the cell depends

solely on the concentrations of the solutions & the metals

used as the electrodes.

Salt Bridge

Or No electrical
current could be
produced by the
cell

For a galvanic cell to work, the solution in both half cells

must remain electrically neutral (charge must be

balance).
Therefore ions must be permitted to enter and leave the
solutions.
Salt Bridge: a tube filled with an electrolyte
solution(viscous), such as KNO3 or KCl and fitted with a
porous plug at each end or simply a strip of filter paper
soaked in saturated KNO3.
Function:
- Maintains electrolytic contact (w/o mixing solutions)
- Completes the circuit
- Reduces liquid junction potential (LJP)

Cu2+ a better
oxidizing agent
than Zn2+

Daniell Cell Salt Bridge

Galvanic or Voltaic Cell

Electrochemical Cell
Each half-cell has a characteristic voltage.
Different choices of substances for each half-cell give

different potential differences.

Each reaction is undergoing an equilibrium reaction

between different oxidation states of the ionswhen

equilibrium is reached the cell cannot provide
further voltage.

The spontaneous reaction that drives the Daniell cell is:

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

Galvanic or Voltaic Cell

0.46V

Oxidation

Reduction
Ag

- Ag+ has a greater tendency to pull electrons than Cu2+

- Ag+ is a better oxidizing agent than Cu2+

The spontaneous reaction: Cu + 2Ag+

Cu2+ + Ag

Electrolytic Cell
An electrochemical cells which uses energy from other

source (e.g. DC) to induce redox reactions and in which

electrical energy converts into chemical energy.

Electrolytic vs Galvanic Cell

NOTE: It is the nature of the chemical change and

not the electrical charge that determines whether we

label an electrode as cathode or anode.
Electrolytic Cell

Galvanic Cell

Cathode is negative (reduction)

Cathode is positive (reduction)

Anode is positive (oxidation)

Anode is negative (oxidation)

Electrode (Cell) Potential

What is potential (E)?
Potential is the amount of work required to bring one unit

of charge from infinity to a fixed distance in space.

Electrode Potential or Cell Potential (emf or

electromotive force) : is the difference in

potential between two half-reactions or electrodes.
i.e. Ecell = E= Ecathode Eanode = Eoxidation + Ereduction
Ecell is expressed in Volts.
Potential is a relative quantity and a standard state needs

to be defined.

Electrode Potential & Half Cells

Each electrode, i.e. the ion & its neutral atom

Contributes a characteristic potential to the overall cell potential

Independent of the other electrode in the pair

Cu | Cu2+ half cell has a characteristic potential

Zn | Zn2+ half cell has a characteristic potential

Ag | Ag+ half cell has a characteristic potential

To assign a potential to each half cell one must assign an

electrode as a standard electrode & measure each

electrode relative to this standard electrode.

Standard Hydrogen Electrode (SHE)

The standard to which all electrodes

are compared is the Standard

Hydrogen Electrode

Its characteristic potential is ZERO at

ALL temperatures

The SHE is represented as:

Pt(s) | H2(g) | H+(aq)
H2+ 2e- 2H+
E0 = 0.0Volts

Potentials measured against the SHE

are called Reduction Potentials and
are represented by Eo in Volts

Standard Electrode Potentials

Standard potentials are

measured with the test

electrode on the right hand
side

The measured potential is +ve

if the electrode has a greater

tendency to pull electrons
than the H2 electrode (SHE)
and ve if it has a lower
tendency

Reduction Potentials

Cu2+ + 2e- Cu
Zn2+ + 2e- Zn
Ag+ + e- Ag
Pb2+ + 2e- Pb
Pb4+ + 2e- Pb2+

E = + 0.34V
E = - 0.76V
E = + 0.80V
E = - 0.13V
E = + 1.67V

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The standard-state cell potentials for some

common half-reactions
More ve E

Half-Reaction

Eored/V

K+ + e- K
Ba2+ + 2 e- Ba
Ca2+ + 2 e- Ca
Na+ + e- Na
Mg2+ + 2 e- Mg
H2 + 2 e - 2 H Al3+ + 3 e- Al
Mn2+ + 2 e- Mn
Zn2+ + 2 e- Zn
Cr3+ + 3 e- Cr
S + 2 e- S2CO2 + 2 H+ + 2 e- H2C2O4
Cr3+ + e- Cr2+
Fe2+ + 2 e- Fe
Co2+ + 2 e- Co
Ni2+ + 2 e- Ni
Sn2+ + 2 e- Sn
Pb2+ + 2 e- Pb
Fe3+ + 3 e- Fe
2H+ + 2 e- H2

-2.924
-2.90
-2.76
-2.7109
-2.375
-2.23
-1.706
-1.04
-0.7628
-0.74
-0.5082
-0.49
-0.41
-0.409
-0.28
-0.23
-0.1364
-0.1263
-0.036
0.0000

Species at the top

of the series are
more readily
oxidized
Zn2+ is oxidized
when paired with
the hydrogen
electrode

ECell
1.Measured against SHE
2.Concentration 1 Molar
3.Pressure 1 atmosphere
4.Temperature 25C

The standard-state cell potentials for some

Copper is
common half-reactions

Increasing oxidizing strength

S4O62- + 2 e- 2S2O3 2Sn4+ + 2 e- Sn2+

Cu2+ + e- Cu+
Cu2+ + 2 e- Cu
O2 + 2 H2O + 4 e- 4 OH0.401
Cu+ + e- Cu
I3- + 2 e- 3 IMnO4- + 2 H2O + 3 e- MnO2 + 4OHO2 + 2 H+ + 2 e- H2O2
Fe3+ + e- Fe2+
Hg22+ + 2 e- Hg
Ag+ + e- Ag
Hg2+ + 2 e- Hg
H2O2 + 2 e- 2 OHHNO3 + 3 H+ + 3 e- NO + 2 H2O
Br2(aq) + 2 e- 2 BrIO3- + 12 H+ + 10 e- I2 + 6 H2O
CrO42- + 8 H+ + 3 e- Cr3+ + 4 H2O 1.195

0.0895
0.15
0.158
0.3402
0.522
0.5338
0.588
0.682
0.770
0.7961
0.7996
0.851
0.88
0.96
1.0872
1.19

*The more positive the Eo value for a half-reaction, the greater the
tendency for that reaction to occur as written.

reduced when
paired with
hydrogen

More
+ve E0
More easily
reduced

Standard Cell Notation for Galvanic Cell

A s a matter of convenience chemists have devised a

shorthand way of representing a galvanic cell.

For example the copper-silver cell is represented as follows.
Salt bridge

Cu(s) Cu2+(aq)

Ag+(aq) Ag(s)

Phase
boundary

By convention anode half cell is specified on left

Exercise : Write the anode and cathode half reactions for the

following galvanic cell.

Al(s) Al3+(aq) Pb2+(aq) Pb(s)

Al(s)

Al3+(aq)+ 3e-

Pb2+(aq) + 2e-

Pb(s)

Daniell Cell - Cell Notation

Daniell Cell can be written as

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

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

Cell Potential - Calculating E0 of Cells

To calculate voltages for any two electrochemical cell we

can do the following:

Daniell Cell:
Zn(s) | Zn2+ (aq) || Cu2+ (aq) | Cu(s)
a) Locate the two half cells reactions in the table of

standard reduction potentials.

1.
2.

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

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

E0 = + 0.34V
E0 = - 0.76V

Cell Potential - Calculating E0 of Cells

b) The half reaction that has the higher reduction
potential will reduce and can be written as you find it in
the table.
1. Cu2+ + 2e- Cu

E = + 0.34V

c) The half reaction that has the lower reduction

potential must be reversed and written as an oxidation.
(The sign of the Eo value of the lower half reaction is
changed ).
Reverse Eqn. 2

Zn Zn2+ + 2e-

E = + 0.76V

Cell Potential - Calculating E0 of Cells

d) The two half reactions are balanced for the number

of electrons exchanged but the value of each Eo

remains unchanged.
Cu2+ + 2e- Cu
E = + 0.34V

Zn Zn2+ + 2e

E0oxi= - E0red

E = + 0.76V

Cell Potential - Calculating E0 of Cells

g) The two half reactions are then added together and
so are the Eo values. ( This value will always be
positive for an electrochemical cell).
Cu2+ + 2e- Cu
E0 = + 0.34V

Zn Zn2+ + 2eE0 = + 0.76V

Overall eqn. Cu2+ + Zn Zn2+ + Cu

Overall Ecell0= E0oxi + E0red= 0.34 +0.76 = 1.10V

When E0 is +ve the reaction is spontaneous

(thermodynamically favourable) in the direction written.

Cell Potential -Exercise

Determine the cell potential for a galvanic cell based on the

redox reaction.

Cu(s) + Fe3+ (aq) Cu2+ (aq) + Fe2+ (aq)

Fe3+ (aq) + e- Fe2+ (aq)

E = 0.77 V

Cu2+ (aq)+2e- Cu(s) E = 0.34 V

2Fe3+ (aq) + 2e- 2Fe2+ (aq)
Cu(s) Cu2+ (aq)+2e-

E = 0.77 V
E = -0.34 V

Overall eqn. Cu(s) + 2Fe3+ (aq) Cu2+ (aq) + 2Fe2+ (aq)

Ecello = E0xi + Ered V

Free Energy and Electrode Potentials

The cell potential of a voltaic cell is a measure of the

maximum amount of energy per unit charge which is

available to do work when charge is transferred through
an external circuit.

This maximum work is equal to the change in Gibbs free

energy, G, in the reaction.

Maximum work = G = -nFEcell
n= number of electrons transferred per mole of reactant
(after balancing)
F = Faradays constant (96485 Cmol-1)
Ecell= standard cell potential

Free Energy and Electrode Potentials

Consider the historic Daniell cell in which zinc and

copper were used as electrodes.

Cathode (Reduction) Half-Rxn

Standard Potential E (volts)

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

-0.76

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

+0.34

Ecell = 1.1 Volts

n= 2 electrons are transferred per mole of reactant.
G = -nFEcell = -2 x 96,485 Cmol-1 x 1.10 JC-1 = -212 kJ
Voltage is defined as the work done per unit charge.
(1V = 1JC-1)

Gibb's Free Energy

The Gibb's free energy G is the negative value of maximum

electric work,
G = - W
= - q E
W = maximum electric work is the product of charge q in Coulomb
(C), and the potential E in Volt (= J/C)
A redox reaction equation represents definite amounts of reactants
in the formation of also definite amounts of products.
The number (n) of electrons in such a reaction equation, is related
to the amount of charge transferred when the reaction is completed.
Since each mole of electron has a charge of 96485 C (known as the
Faraday's constant, F),
q = n F
and, G = - n F E
At standard conditions,
G = - n F E

G0& E0 - Spontaneity
G0 = -n F E0

When E0 is +ve, G0is -ve = reaction is spontaneous

When E0 is -ve, G0 is +ve = reaction is not spontaneous

Nernst Equation
As a voltaic cell is discharged, its emf falls until E = 0, at which

point we say that the cell is dead.

Studies show that the emf depends on the concentrations of the

reactants and products in the cell reaction.

Increasing the [reactants] will increase the cell emf.

Increasing the [products] will decrease the cell emf.
The emf generated under nonstandard conditions can be

calculated by using an equation first derived by Walther

Hermann Nernst (1864 - 1941).

Nernst Equation
The dependence of the cell emf on concentration can be

obtained from the dependence of the G on concentration.

Recall:
Gat any stage of rxn = Go + RT ln Qrxn .. .eqn. 1
where R = Universal gas constant, T = temperature
and for a generalized equation of the form:
cC + bB+..
mM+ nN+

At equilibrium, Ecell = 0 hence G = 0 and Qrxn corresponds to Keq.

Activity

Activity- effective
concentration of
species.

Some of the species that take part in these electrode

reactions are pure solid compounds and pure liquid

compounds. In dilute aqueous solutions, water can be
treated as a pure liquid.
For pure solid compounds or pure liquid compounds,
activities are constant and their values are considered to
be unity. i.e. a= 1
The activities of gases are usually taken as their partial
pressures and the activities (ai) of solutes such as ions are
the product of the molar concentration and the activity
coefficient of each chemical species :
ai = [i]i [i]

Nernst Equation
Substituting G = -nFEcell into eqn. 1 gives:

-nFEcell = -nFEocell + RT ln Q
Solving this equation for E gives the Nernst equation:

The equation is usually written in term of common logarithms:

Nernst Equation
At 298 K the quantity

2.303RT / F = 0.0592 V,
- so at 298 K a simplified form of the Nernst equation is:

Non-standard Conditions
The SEP values refer to standard conditions i.e. 1 Molar concentrations at

25C and atmospheric pressure.

If these conditions change then so does the electrode potential.
For example, according to standard electrode potentials, MnO 2 will not
react spontaneously with HCl, however this is the standard preparation of
chlorine in the laboratory.
MnO2(s) + 4H+(aq) + 2e- Mn2+ + 2H2O(l)
E = 1.23 V
Cl2(g) + 2e2Cl-(aq)
E = 1.36V
Predicting spontaneity, E = Ered + Eox = 1.23 +(- 1.36 ) Eocell = - 0.13V
Negative value therefore no reaction!!
In the lab preparation the MnO2 is heated with the concentrated HCl - these
are not standard conditions, the temperature >>25C and [HCl] >>1 mol
dm-3.
Under these new conditions the reaction becomes spontaneous and
proceeds at a comfortable rate to collect the chlorine gas produced.
MnO2(s) + 4H+(aq) + 2Cl-(aq)
Mn2+ (aq) + 2H2O(l) + Cl2(g)

Worked Example

Nernst Equation
If we have a Cu2+/Cu electrode in one half & the SHE in

the other
Pt(s) | H2(g) | H+(aq) || Cu2+(aq) | Cu(s)

E0 = + 0.34V

Cu2+ + 2e- Cu
2H+ + 2e- H2
(E0xi + Ered) Cu2+(aq) + H2(g)

E0 = + 0.34 V
E0 = 0.00 V
Cu(s) + 2H+(aq) E0 = + 0.34 V

Q = [aH+]2 [aCu]/[aH2][aCu2+]
Q = [1.00]2 [1]/[1.0][1.00] = 1
45

Nernst Equation - pH
When H+ concentration is NOT 1.00 M but everything remains the same.

log10Q, for pH measurements, can be expressed in terms of the

hydrogen ion activity by :-log10aH+ which is the pH of a solution and the
equation becomes:

The measured potential is related to the activity/ concentration of H + and

E0 of the cell

pH can be measured electrically

E.g. pH meter

46

Nernst Equation - pH
Take for example:
MnO4- + 5e- + 8H+ Mn2+ + 4H2O

E0 = 1.51V

Here the potential depends not only on the

concentrations of the manganese species but also

on the pH of the solution.
8

Applications
Widespread applications of electrochemistry.
In the industry important chemical : liquid

bleach(NaOCl) and lye (NaOH) are manufactured by

electrochemical reactions.
Batteries (galvanic cells) which produce electrical energy
by means of chemical reactions are used to power toys,
flashlights, calculators, laptop computers, cellphones,
clocks, watches, remote controllers etc. (Dry Cells)
Wet cells : lead acid batteries in some cars.
Fuel Cells e.g. hydrogen fuel cell

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