Electrochemistry

Thermodynamics at the electrode

Learning objectives

You will be able to:

Identify main components of an electrochemical cell
Write shorthand description of electrochemical cell
Calculate cell voltage using standard reduction potentials
Apply Nernst equation to determine free energy change
Apply Nernst equation to determine pH
Calculate K from electrode potentials
Calculate amount of material deposited in electrolysis

Energy in or energy out

Galvanic (or voltaic) cell relies on
spontaneous process to generate a
potential capable of performing work
energy out
Electrolytic cell performs chemical reactions
through application of a potential energy
in

Redox Review
Oxidation is...
Loss of electrons

Reduction is...
Gain of electrons

Oxidizing agents oxidize and are reduced

Reducing agents reduce and are oxidized

Redox at the heart of the matter

Zn displaces Cu from CuSO4(aq)
In direct contact the enthalpy of reaction is
dispersed as heat, and no useful work is done
Redox process:
Zn is the reducing agent
Cu2+ is the oxidizing agent
2

Zn( s ) Zn (aq ) 2e
2

Cu (aq ) 2e Cu ( s )

Separating the combatants

Each metal in touch with a solution of its own ions

External circuit carries electrons transferred during the redox process
A salt bridge containing neutral ions completes the internal circuit.
With no current flowing, a potential develops the potential for work
Unlike the reaction in the beaker, the energy released by the reaction
in the cell can perform useful work like lighting a bulb

Labelling the parts

Odes to a galvanic cell

Cathode
Where reduction occurs
Where electrons are
consumed
Where positive ions
migrate to
Has positive sign

Anode
Where oxidation occurs
Where electrons are
generated
Where negative ions
migrate to
Has negative sign

The role of inert electrodes

Not all cells start with elements as the redox
agents
Consider the cell
Fe( s ) 2 Fe3 (aq) 3Fe 2 (aq)

Fe can be the anode but Fe3+ cannot be the

cathode.
Use the Fe3+ ions in solution as the
cathode with an inert metal such as Pt

Anode

Cathod
e

Oxidati
on

Reduct
ion

Cell notation

Anode on left, cathode on right

Electrons flow from left to right
Oxidation on left, reduction on right
Single vertical = electrode/electrolyte boundary
Double vertical = salt bridge
Anode:
Zn Zn2+ +
2e

Cathode:
Cu2+ + 2e
Cu

Vertical denotes different phase

Fe(s)Fe2+(aq)Fe3+(aq),Fe2+(aq)Pt(s)
Cu(s)Cu2+(aq)Cl2(g)Cl-(aq)C(s)

Connections: cell potential and free

energy
The cell in open circuit generates an
electromotive force (emf) or potential or
voltage. This is the potential to perform
work
Energy is charge moving under applied
voltage

1J 1C 1V

Relating free energy and cell

potential
The Faraday:
F = 96 485 C/mol e

G nFE
Standard conditions (1 M, 1 atm, 25 C)

G nFE

Standard Reduction Potentials

The total cell potential is the sum of the potentials
for the two half reactions at each electrode
Ecell = Ecath + Ean
From the cell voltage we cannot determine the
values of either we must know one to get the
other
Enter the standard hydrogen electrode (SHE)
All potentials are referenced to the SHE (=0 V)

Unpacking the SHE

The SHE consists of a Pt electrode in contact with
H2(g) at 1 atm in a solution of 1 M H+(aq).
The voltage of this half-cell is defined to be 0 V
An experimental cell containing the SHE half-cell
with other half-cell gives voltages which are the
standard potentials for those half-cells
Ecell = 0 + Ehalf-cell

Zinc half-cell with SHE

Cell measures 0.76 V
Standard potential for Zn(s) = Zn2+(aq) + 2e = 0.76
V

Where there is no SHE

In this cell there is no SHE and the
measured voltage is 1.10 V
2

Zn Zn (aq ) C u (aq) Cu
2

Zn( s ) Cu (aq ) Zn (aq ) Cu ( s )

2

Zn( s ) Zn (aq ) 2e, E 0.76V

2

Cu (aq) 2e Cu ( s ), E 0.34V
o

Standard reduction potentials

Any half reaction can be written in two ways:
Oxidation:
M = M+ + e (+V)
Reduction:
M+ + e = M (-V)
Listed potentials are standard reduction
potentials

Applying standard reduction

potentials
Consider the reaction

Zn( s ) 2 Ag (aq ) Zn 2 (aq ) 2 Ag ( s )

What is the cell potential?

The half reactions are:
2
Zn
(
s
)

Zn
(aq ) 2e
Ag (aq ) e Ag ( s )
E = 0.80 V (-0.76 V) = 1.56 V
NOTE: Although there are 2 moles of Ag
reduced for each mole of Zn oxidized, we do not
multiply the potential by 2.

Extensive v intensive
Free energy is extensive property so need to
multiply by no of moles involved

G nFE

But to convert to E we need to divide by no of

electrons involved

E G

E is an intensive property

nF

The Nernst equation

Working in nonstandard conditions

G G RT ln Q

nFE nFE RT ln Q

E E RT

nF

ln Q

E E 0.0592 log Q
n

Electrode potentials and pH

For the cell reaction

H 2 ( g ) 2 H (aq ) 2e

The Nernst equation

EH

2 2 H

EH

2 2 H

H 2 2 H

0.06V

log H

pH 2

0.06V

log H
n

Half-cell potential is proportional to pH

The pH meter is an electrochemical cell

Overall cell potential is proportional to pH
Ecell 0.06V pH Eref

pH

Ecell Eref
0.06V

In practice, a hydrogen electrode is

impractical

Calomel reference electrodes

The potential of the calomel electrode is known vs
the SHE. This is used as the reference electrode
in the measurement of pH

Hg 2Cl2 ( s ) 2e 2 Hg (l ) 2Cl

The other electrode in a pH probe is a glass

electrode which has a Ag wire coated with AgCl
dipped in HCl(aq). A thin membrane separates the
HCl from the test solution

Cell potentials and equilibrium

G nFE
Lest we forget

G RT ln K

So then

nFE RT ln K

and E RT

2.303RT
ln K
log10 K
nF
nF

Cell potential a convenient way to

measure K

Many pathways to one ending

Measurement of K from different
experiments
c
d
Concentration data

C D
a
b
A B

Thermochemical data
Electrochemical data

G RT ln K

nFE RT ln K

Batteries
The most important application of galvanic
cells
Several factors influence the choice of
materials

Voltage
Weight
Capacity
Current density
Rechargeability

Running in reverse
Recharging a battery requires to run the
process in reverse by applying a voltage
In principle any reaction can be reversed
In practice it will depend upon many factors
Reversibility depends on kinetics and not
thermodynamics
Cell reactions that involve minimal structural
rearrangement will be the easiest to reverse

Lithium batteries

Lightweight (Molar mass Li = 6.94 g)

High voltage
Reversible process

Fuel cells a battery with a

difference
Reactants are not contained within a sealed
container but are supplied from outside
sources
anode : 2 H 2 ( g ) 4OH (aq ) 4 H 2O(l ) 4e

cathode : O2 ( g ) 2 H 2O(l ) 4e 4OH (aq )

overall : 2 H 2 ( g ) O2 ( g ) 2 H 2O(l )

Store up not treasures on earth

where moth and rust
An electrochemical mechanism for corrosion of iron. The metal and a surface
water droplet constitute a tiny galvanic cell in which iron is oxidized to Fe 2+ in
a region of the surface (anode region) remote from atmospheric O 2, and O2 is
reduced near the edge of the droplet at another region of the surface
(cathode region). Electrons flow from anode to cathode through the metal,
while ions flow through the water droplet. Dissolved O 2 oxidizes Fe2+ further to
Fe3+ before it is deposited as rust (Fe 2O3H2O).

Mechanisms
Why does salt enhance rusting?
Improves conductivity of electrolyte

Standard reduction potentials indicate which

metals will rust
Aluminium should corrode readily. It
doesnt. Is thermodynamics wrong?
No, the Al2O3 provides an impenetrable barrier

No greater gift than to give up your

life for your friend
A layer of zinc protects iron from oxidation, even when the
zinc layer becomes scratched. The zinc (anode), iron
(cathode), and water droplet (electrolyte) constitute a tiny
galvanic cell. Oxygen is reduced at the cathode, and zinc is
oxidized at the anode, thus protecting the iron from
oxidation.

Electrolysis

Electrolysis of a molten salt using inert electrodes

Signs of electrodes:
In electrolysis, anode is positive because electrons are removed
from it by the battery
In a galvanic cell, the anode is negative because is supplies
electrons to the external circuit

Anode : 2Cl (l ) Cl2 ( g ) 2e

Cathode : 2 Na (l ) 2e 2 Na (l )

Overall : 2 Na (l ) 2Cl (l ) 2 Na (l ) Cl2 ( g )

Electrolysis in aqueous solutions a

choice of process
There are (potentially)
competing processes
in the electrolysis of an
aqueous solution
Cathode Cathode : 2 Na (l ) 2e 2 Na (l )...E 2.71V

Cathode : 2 H 2O(l ) 2e H 2 ( g ) 2OH (aq )...E 0.83V

Anode

Anode : 2Cl (l ) Cl2 ( g ) 2e...E 1.36V

Anode : 2 H 2O(l ) O2 ( g ) 4 H 4e...E 1.23V

Thermodynamics or kinetics?
On the basis of thermodynamics we choose
the processes which are favoured
energetically
Anode : 2 H 2O(l ) O2 ( g ) 4 H 4e...E 1.23V

Cathode : 2 H 2O(l ) 2e H 2 ( g ) 2OH (aq )...E 0.83V

Butchlorine is evolved at the anode

The role of overpotentials

Thermodynamic quantities prevail only at
equilibrium no current flowing
When current flows, kinetic considerations
come into play
Overpotential represents the additional
voltage that must be applied to drive the
process

 In the NaCl(aq) solution the overpotential for

evolution of oxygen is greater than that for
chlorine, and so chlorine is evolved
preferentially
Overpotential will depend on the electrolyte
and electrode. By suitable choices,
overpotentials can be minimized but are never
eliminated
The limiting process in electrolysis is usually
diffusion of the ions in the electrolyte (but not
always)
Driving the cell at the least current will give
rise to the smallest overpotential

Electrolysis of water
In aqueous solutions of
most salts or acids or
bases the products will
be O2 and H2
Cathode : 2 H 2O(l ) 2e H 2 ( g ) 2OH (aq )...E 0.83V

Anode : 2 H 2O(l ) O2 ( g ) 4 H 4e...E 1.23V

Quantitative aspects of electrolysis

Quantitative analysis
uses the current
flowing as a measure
of the amount of
material
Charge = current x
time
Moles =
charge/Faraday