Electrochemistry

Relating electricity and chemical reactions

ELECTROCHEMISTRY Transfer of electrons

Chemical reaction Electricity applied

occurs to produce to produce
electricity chemical reaction
CHAPTER 20

Study of redox Recall

reactions Oxidation LOSS of electrons
Manufacturing Batteries Reduction GAIN of electrons
of chemicals Fuel cells
Oxidation number
Applications of For a monatomic ion the oxidation no. = the
Electrochemistry actual charge of the atom
Study and
Electroplating control for or it is the hypothetical charge assigned to the
and refining corrosion atom using a set of rules.
of metals Bioelectrochemistry: Make sure YOU know how to assign oxidation
study of electron numbers!!!!
transfer in biological
regulations of Oxidation occurs at the ANODE
organisms Reduction occurs at the CATHODE

Oxidising agent/oxidant The substance that How do we know if a chemical

causes oxidation of another substance and
hence it is reduced. reaction is a REDOX reaction?
Reducing agent/reductant The substance that
Look to see if there is a change in oxidation
cause reduction of another substance and
numbers of elements.
hence it is oxidised.
Zn(s) + 2H+ Zn2+(aq) + H2(g)
ELECTRIC CURRENT = transfer of charge

METALLIC CONDUCTION = flow of electrons

with no movement of the atoms of the metal
ELECTROLYTIC (IONIC) CONDUCTION =
electric current by movement of ions through a
solution or pure liquid
Both oxidation and reduction must occur.
Electrons lost by one component is gained
by another.

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Example:
A nickel
nickelcadmium battery (NiCad) is a
rechargeable dry cell
cell that uses the following
redox reaction to generate electricity
Cd(s) + NiO2(s) +2H2O(l) Cd(OH)2(s) + Ni(OH)2(s)
Cd(s)
Identify the substances oxidised & reduced and
the oxidising & reducing agents.
Balancing Redox Reactions
In acidic solutions:
1. Write the 2 half-reactions
2. Balance elements other than O and H
3. Balance O by adding H2O
4. Balance H by adding H+
5. Balance electrons
6. Multiply half-reactions by integer so that no.
of electrons in both are equal
7. Add the 2 half-reactions

EXAMPLE: 5. Balance electrons

Mn2+(aq) + NaBiO3(s) Bi3+ + MnO4-(aq)

1. Write the 2 half-reactions

6. Multiply half-reactions by integer so that no. of

electrons in both are equal
2. Balance elements other than O and H

3. Balance O by adding H2O

7. Add the 2 half-reactions

4. Balance H by adding H+

In basic solutions: EXAMPLE:

Mn2+(aq) + NaBiO3(s) Bi3+ + MnO4-(aq)
1. Write the 2 half-reactions
1-4. Same as before
2. Balance elements other than O and H
Mn2+ + 4H2O MnO4- + 8H+
3. Balance O by adding H2O NaBiO3 + 6H+ Bi3+ + Na+ + 3H2O
4. Balance H by adding H+ 5. Add an equal number of OH- to both sides of the
5. Add an equal number of OH- to both sides of reaction so that all H+ is neutralised
the reaction so that all H+ is neutralised
Recall: H+ + OH- H2O
6. Balance electrons 6-8. Same as before
7. Multiply half-reactions by integer so that no.
of electrons in both are equal
8. Add the 2 half-reactions

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For you to do!
Voltaic/Galvanic Cells
A spontaneous redox reaction produces energy
following:
Balance the following: which can do electrical work.
Example:
MnO4-(aq) + C2O42-(aq) Mn2+(aq) + CO2(g) Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
Spontaneous reaction!

2MnO4- + 5C2O42- + 16H+ 2Mn2+ + 10CO2 + 8H2O Half-reactions:

in acidic solution
Zn(s) Zn2+(aq) + 2e-

2MnO4- + 5C2O42- + 8H2O 2Mn2+ + 10CO2 + 16OH- Cu2+(aq) + 2e- Cu(s)

in basic solution
Electrons lost by Zn are gained by Cu2+.

Molecular view:

Cu2+ ion must collide with The Zn2+ ion formed

the Zn strip for electron enters the solution and
Zn strip inserted into Zn(s) Zn2+(aq) + 2e- transfer to occur. the Cuo is deposited on
CuSO4 solution the Zn strip.
Cu2+(aq) + 2e- Cu(s)

In a galvanic/voltaic cell the transfer of Reaction at anode = Reaction at cathode =

Oxidation: Reduction:
electrons takes place through an external
Zn(s) Zn2+(aq) + 2e- Cu2+(aq) + 2e- Cu(s)
circuit rather than directly between reactants.

Reaction at anode = Reaction at cathode =

Oxidation: Reduction:
Zn(s) Zn2+(aq) + 2e- Cu2+(aq) + 2e- Cu(s)

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 Molecular view:
Salt bridge: The 2e-s move through the circuit to the Cu strip.
2
Completes the circuit.
Maintains electrical neutrality in the two
compartments by migration of ions
through the porous material.
No further redox reaction will take place if
electrical neutrality is not maintained.
Prevents mixing of the electrode solutions.

1 3
On the Zn strip, a Zn atom When the Cu2+ ions collide with
looses 2e-s to form Zn2+ the Cu strip, 2e-s are
which moves into solution. transferred to form Cuo

Cell Notation: Cell EMF

Oxidation at anode Reduction at cathode Why do electrons flow in the direction they do?
Due to the potential difference between the 2
Separate Salt Separate
phases bridge phases
electrodes (or difference in potential energy)
electrode in soln in soln electrode
Electrons at the anode have a higher potential
Zn(s) | Zn2+(1 M) | | Cu2+(1 M) | Cu(s)
energy than the electrons at the cathode
electrons spontaneously flow from
anode to cathode

The potential difference is the driving force that

pushes electrons through the circuit
= electromotive force = EMF
= cell voltage
= cell potential = Ecell

Ecell depends on: Standard Reduction Potentials

the reactions that occur at the electrodes
the concentrations of reactants and products
temperature (assume 25oC unless otherwise stated)
Ecell > 0 for a SPONTANEOUS cell reaction!
Eocell = standard cell potential By convention
Standard conditions:
1 M concentration for reactants & products
1 atm pressure for gases
Recall: the cell potential is the difference
between 2 electrode potentials (the anode and
the cathode)
Eocell = Eored(cathode) - Eored(anode)
Table of Standard Reduction Potentials
Potentials all measured relative to the
standard hydrogen electrode (SHE)

Zn(s) + Cu2+(aq,1M) Zn2+(aq,1M) + Cu(s) 2H+(aq, 1M) + 2e- H2(g, 1atm) Eo = 0 V

Eocell = +1.10 V

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 Standard hydrogen electrode (SHE)

2H+(aq, 1M) + 2e- H2(g, 1atm) Eo(Cath) = 0 V

H2(g, 1atm) 2H+(aq, 1M) + 2e- Eo(An) = 0 V

The more positive the value for Eored, the Example:

stronger the driving force for reduction. List according to increasing strength of
reducing agent:
Note: Ag(s), Zn(s), Cu(s)
Since electrical potential measures potential
energy per electrical charge, the standard
reduction potential is a intensive property. Ag+(aq) + e- Ag(s) Eo = +0.80 V
Cu2+(aq) + 2e- Cu(s) Eo = +0.34 V
1V=1J 1C
Zn2+(aq) + 2e- Zn(s) Eo = -0.76 V
changing a stoichiometric coefficient in a
half-reaction does NOT affect the value of the
standard reduction potential.
Which is the weakest oxidising agent:
Zn2+(aq, 1M) + 2e- Zn(s) Eo = -0.76 V Ag+, Zn2+, Cu2+?
2Zn2+(aq, 1M) + 4e- 2Zn(s) Eo = -0.76 V

Spontaneity of Redox Reactions

So far we know:
Eocell = Eored(cathode) - Eored(anode)

AND
From the standard reduction potentials table:
Eored(cathode) > Eored(anode)
for a spontaneous reaction

THEREFORE

Eocell > 0 for a SPONTANEOUS cell reaction!

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 Example:
We also know that:
Use standard reduction potentials to calculate standard
G < 0 spontaneous reaction free energy change for the following reaction:
4Ag(s) + O2(g) + 4H+(aq) 4Ag+(aq) + 2H2O(l)
Relationship between EMF and free energy
change: From the table:
G = -nFE O2(g) + 4H+(aq) + 4e- 2H2O(l) Eo = 1.23 V

where n = no. of e-s transferred Ag+(aq) + e- Ag(s) Eo = 0.80 V

F = Faradays constant
= 96 500 C mol-1 96 500 J V-1 mol-1

For reactants and products in their standard

state:
Go = -nFEo

Cat: O2(g) + 4H+(aq) + 4e- 2H2O(l) Eo = 1.23 V

Effect of concentration
An: 4Ag+(aq) + 4e- 4Ag(s) Eo = 0.80 V
Recall:
Eocell = Eored(cathode) - Eored(anode)
G = Go + RT ln Q
Eo cell = Since Go = -nFEo and G = -nFE
Go = -nFEo RT
E = Eo ln Q Nernst equation
nF
2.303RT
E = Eo log Q
nF
0.05916
Repeat for:
2Ag(s) + 1/2O2(g) + 2H+(aq) 2Ag+(aq) + H2O(l)
E = Eo log Q at 25oC
Ans: -83 kJ mol-1
n

Example:
0.05916 Consider the reaction:
E=E o
log Q Zn(s) + Cu2+(aq) Zn2+ (aq) + Cu(s)
n Calculate the cell emf when:
[Cu2+] = 5.0 M and [Zn2+] = 0.5 M

Use the Nernst equation to:

- find the EMF produced by a cell under non-
standard conditions.
- determine the concentration of reactant or
product by measuring the EMF of the cell.

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Since emf depends on concentration, a voltaic cell with Anode: Ni(s) Ni2+(aq) + 2e- Eored = -0.28V
a non-zero emf can exist using the same species in both
Cathode: Ni2+(aq) + 2e- Ni(s) Eored = -0.28V
the anode and cathode compartments.

Eocell = Eored(cathode) - Eored(anode)

CONCENTRATION CELL = (-0.28 V) (-0.28 V) = 0V

But the cell is operating under non-standard conditions

since concentrations are 1 M.

Driving force of cell due to the difference in

concentration tries to equalise
concentrations in both compartments.
Anode: Ni(s) Ni2+(aq, dil) + 2e-
Cathode: Ni2+(aq, conc) + 2e- Ni(s)
Ni2+(aq, conc) Ni2+(aq, dil)

Ni(s) Ni2+(aq, dil) + 2e-

Anode:
EMF and Equilibrium
Cathode: Ni2+(aq, conc) + 2e- Ni(s)
Why does the emf drop as a voltaic cell
Ni2+(aq, conc) Ni2+(aq, dil) discharges?
0.05916 [Ni2+ ] 0.05916
Look at Nernst equation: E = E
o
log Q
E = Eo log 2+ dil n
n [Ni ]conc
0.05916 (1.00 10 3 ) As reactants are converted to products, Q
E = (0 V ) log increases.
2 (1.00)
Eventually E = 0 V.
E = 0.0887 V
Since G = -nFE, G = 0 kJ/mol
NOTE:
equilibrium!
When the concentrations in the 2 compartments
become equal, i.e. when E = 0 V, equilibrium
Q = 1 and E = 0 V. no net reaction

The equilibrium constant can be calculated for BATTERIES

a redox reaction as follows: A battery is a portable , self contained
electrochemical power source that consist of
At equilibrium: one or more voltaic cells.
E = 0 V and Q = K
Greater voltages can be achieved if cells are
0.05916 placed in series e.g. in a torch.
E=E o
log Q
n
0.05916 Cathode = + Anode = -
0 = Eo log K
n
nEo Separate anode and cathode compartments
log K =
0.05916 with a porous barrier

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 Lead-
Lead-acid battery
Cell emf depends on the substances that are
oxidised and reduced. Used in cars
12 V = 6 x 2 V cells

Cell life depends on the quantities of the

substances. Anode = Pb
Cathode = PbO2 packed on metal grid
Primary cell cannot be recharged Electrolyte = H2SO4
Secondary cell can be recharged Spacers prevent cathode and anode from touching.

Cathode: PbO2 + 4H+ + SO42- + 2e- PbSO4 + 2H2O

Anode: Pb + SO42- PbSO4 + 2e-
Overall: PbO2 + Pb + 4H+ + 2SO42- 2PbSO4 + 2H2O

Eocell = (+1.685)-(-0.356) = +2.041 V

Solid products and reactants

not appear in expression for Q
maintain relatively constant emf while discharging
variation due to [H2SO4] decreases during discharge

Can be recharged since PbSO4 adheres to the electrode

surface.
External source of power = alternator (generator) driven
by the engine.

Alkaline battery
Most common primary battery Cathode: 2MnO2 +2H2O + 2e- 2MnO(OH) + 2OH-
Anode = Zn powder immobilised in gel surrounded by Anode: Zn + 2OH- Zn(OH)2 + 2e-
electrolyte Overall: 2MnO2 + Zn + 2H2O 2MnO(OH) + Zn(OH)2
Cathode = MnO2 + graphite
Electrolyte = conc. solution of KOH Eocell = +1.55 V
Separator = porous fabric

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 Dry cell or Zinc carbon battery
Cathode: 2MnO2 + 2NH4+ + 2e- 2Mn2O3 + 2NH3 + H2O Nickel-
Nickel-cadmium, Nickel-
Nickel-metal-
metal-
Anode: Zn Zn2+ + 2e- hydride and Lithium-
Lithium-ion batteries
Overall: 2MnO2 + Zn + 2NH4+ 2Mn2O3 + Zn2+ +2NH3 + H2O

Eocell = +1.55 V Used in high-power-demand portable devices

e.g. cellphones, PCs etc
Lightweight and readily rechargeable

Alkaline batteries better performance than the old dry

cells which are also based on MnO2 and Zn.

NiCad batteries: NiMH batteries:

Cathode: 2NiO(OH) + 2H2O + 2e- 2Ni(OH)2 + 2OH-
Anode: Cd + 2OH- Cd(OH)2 + 2e- Same cathode reaction as in NiCad batteries.

Overall: 2NiO(OH) + Cd + 2H2O 2Ni(OH)2 + Cd(OH)2 Anode reaction different.

Eocell = = 1.30 V use cells in series

Anode = metal alloy (eg ZrNi2) that has the ability to
absorb hydrogen atoms

-Solid adheres to electrodes rechargeable During oxidation process H-atoms are released
-Disadvantage:
Cd = toxic heavy metal
increases mass of battery
+ environmental hazard

Solid electrolyte used.

Li-ion batteries:
Based on ability of Li+ ions to insert themselves into
Advantages: certain layers solids.
- Li has the most negative standard reduction potential,
thus makes a good anode.
- Li is a lightweight metal.
- Cell emf can be as high a 3 V.

Disadvantages:
- Batteries do not yet have high reliability and long
lifetime

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 Fuel cells
Unlike batteries, fuel cells do not store chemical
Thermal energy released during combustion of energy. Reactants must be constantly supplied
fuels is converted to electrical energy. and products removed from the fuel cell.

This process is only about 40% efficient.

Example: The hydrogen fuel cell
Because combustion reactions are redox Cathode: O2 + 2H2O + 4e- 4OH-
reactions, the process can be carried out Anode: 2H2 + 4OH- 4H2O + 4e-
electrochemically
Overall: 2H2 + O2 2H2O
found efficiency is almost doubled

2H2 + O2 2H2O
CORROSION

The deterioration of metals by an

electrochemical process.

Examples of corrosion: Oxidation of Aluminium

- rust on iron
Expect Al to be readily oxidised
- tarnish on silver
Al3+ + 3e- Al Eo = -1.66 V
- green patina on copper and brass
However, we find it is exceptionally stable in air.
For almost all metals oxidation is a
WHY?
thermodynamically favourable process at room
temperature.
A thin protective layer of a hydrated form of
Al2O3 forms on the surface of the metal.
Can be extremely destructive
or can form a protective oxide layer. This oxide layer is then impermeable to O2 and
H2O, thus protecting the underlying metal from
further corrosion.

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Corrosion of Iron
Rusting
Need both O2 and H2O.
Cathode: O2(g) + 4H+(aq) + 4e- 2H2O(l)
Anode: Fe(s) Fe2+(aq) + 4e-
Fe + O2 + 4H+ Fe2+ + 2H2O
Need H+ for corrosion
above pH 9 Fe does not corrode
Preventing the corrosion of iron
Covering of iron with e.g. paint or tin
- Prevents O2 and H2O from reaching surface.
- Coating damaged corrosion
Cathode: O2(g) + 4H+(aq) + 4e- 2H2O(l)
Anode: Fe(s) Fe2+(aq) + 4e-
Fe + O2 + 4H+ Fe2+ + 2H2O
Further oxidation of Fe2+ to Fe3+:
4Fe2+ + O2 + (4+2x)H2O 2Fe2O3.xH2O + 8H+
Eored = 1.23 V Rust
Eored = -0.44 V
Part of the Fe surface is the anode at which
oxidation occurs.
e-s migrate through the Fe metal to another
part of the Fe surface, the cathode, where O2 is
reduced.
Other factors can accelerate rusting:
- pH of the soln
(lower pH faster corrosion)
- presence of salts
(improves conductivity of electrolyte)
- contact with metals more difficult to oxidise
than Fe
- stress on Fe
Galvanised iron coated with layer of zinc
- Protects Fe by electrochemical means even
after coating is damaged
Easier to oxidise Zn (anode) than Fe (cathode)
Zn rather corrodes
Cathodic protection Zn = sacrificial anode
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 ELECTROLYSIS
Cathodic protection is used for e.g. the
protection of iron pipelines or storage tanks Use electrical energy to
cause non-spontaneous
redox reaction to occur
- Takes place in electrolytic
cells
- Need an external DC source
e.g. a battery
= electron pump
Reduction occurs at the
cathode (negative) and
Mg is the sacrificial anode for the Fe tank. oxidation occurs at the
anode (positive)

Electrolysis of molten NaCl

Electrolysis of aqueous solutions

Need high temps to produce molten salts.

Can also produce ions by dissolving salts in
water at room temp.

Problem:
Electrolysis of aqueous salts complicated
by the presence of water.

Example: Electrolysis of aqueous NaF solution 2 possible anode reactions:

2F-(aq) F2(g) + 2e- Eored = +2.78 V

2 possible cathode reactions: 2H2O(l) O2(g) + 4H+(aq) + 4e- Eored = +1.23 V

Na+(aq) + e- Na(s) Eored = -2.71 V Favoured oxidation reaction

2H2O(l) + 2e- H2(g) + 2OH-(aq) Eored = -0.83 V more -ve or less +ve Eored
2H2O(l) O2(g) + 4H+(aq) + 4e-
Favoured reduction reaction
more +ve or less ve Eored
In fact it is easier still to oxidise OH-(aq) that is
Cathode: 2H2O(l) + 2e- H2(g) + 2OH-(aq)
produced at the cathode:
Anode: 4OH-(aq) O2(g) + 2H2O(l) + 4e- Eored = +0.40 V

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 Example: Electrolysis of aqueous NaCl solution
Cathode reactions as in previous example.
2 possible anode reactions:
2Cl-(aq) Cl2(g) + 2e- Eored = +1.36 V
2H2O(l) O2(g) + 4H+(aq) + 4e- Eored = +1.23 V
Expect favoured reaction to be:
2H2O(l) O2(g) + 4H+(aq) + 4e-
Electrolysis with active electrodes
Inert electrodes do not undergo reaction but
only act as a surface where oxidation and
reduction occurs.
Active electrodes participate in the
electrolysis process
E.g. electroplating

HOWEVER, in experiments Cl- is oxidised.

Activation energy is lower for Cl- oxidation, so it

is kinetically favoured.

Example: Ni electroplating
Quantitative aspects of electrolysis
Find the favoured reaction to be: The stoichiometry of a half-reaction shows us
Cathode (steel strip): how many electrons needed in electrolysis.
Ni2+(aq) + 2e- Ni(s) Pic of
cell E.g. Na+ + e- Na
Anode (nickel strip):
Ni(s) Ni2+(aq) + 2e- 1 mol e-s will plate out 1 mol Na metal
Or 2 mol e-s will plate out 2 mol Na metal

Overall reaction: transferring Ni atoms from E.g. Ni2+ + 2e- Ni

the anode to form a thin layer on the steel
2 mol e-s will plate out 1 mol Ni metal
cathode.

Recall:
FARADAY`S LAW
The amount of substance that undergoes
oxidation or reduction at each electrode is
directly proportional to the amount of electricity
that passes through the cell.
Unit of charge (Q) = coulomb (C)
The charge in 1 mole of electrons = 96 500 C
Example:
Calculate the mass of aluminium produced in 1.0 hour
by the electrolysis of molten AlCl3 if the electrical
current is 20 A.
Where does the Al come from?
1 Calculate the amount of charge transferred:
2 Calculate the no. of moles of e-s transferred:
3 Relate no. of moles of e-s to no. of moles of Al formed:

1 F = 96 500 C/mol (F = Faraday)

4 Convert moles to grams:
Q = It (Current in A, time in s)

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 Electrical work
For an electrolytic cell, work has to be done on
Recall: the system for the reaction to occur,
w = nFEext
G < 0 and Ecell > 0 spontaneous process
where Eext = external potential applied.
G = -nFE
G = wmax Electrical power is the rate of energy
expenditure.
Thus the maximum useful work obtainable from Unit: Watt (W) = J/s
a voltaic cell is:
wmax = -nFE
1 kWh = 3.6x106 J

Example:
Calculate the number of kWh of electricity required to
produce 1.0x103 kg of aluminium by electrolysis of Al3+
if the applied emf is 4.50 V.

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