Introduction

Dr. Neil V. Rees

School of Chemical Engineering
[email protected]

Introduction to Electrochemistry
21-25 October 2013
 Why electrochemistry?

a) It’s the name of the module, stoopid

b) It’s the most fun you can have (legally)

c) Scientific importance

d) Industrially relevant
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 Chloralkali Industry

• Electrolysis of Brine to form chlorine

2NaCl(aq) + 2H2O(l) → Cl2(g) + H2(g) + 2NaOH(aq)

• Worldwide production of chlorine [1]:

– 55 × 106 tonnes pa
– 500 producers
– 650 sites

[1] World Chlorine Council

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 Aluminium extraction
• Al is produced via electrolysis of molten cryolite
(Na3AlF6) at 950˚C
• E.g. an Alcoa plant in Iceland produces 322,000 tons
of Al per year, but a 630 MW hydropower station had
to be constructed nearby to provide the power!
Al3+ + 3e → Al(s)
• Annual production:
– 46,000 tonnes

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 Nylon manufacture

• 4 × 106 tonnes of nylon is produced pa

• The industrial synthesis of nylon 6-6, starts with the
following electrolysis
2 H2C=CHCN + 2H+ + 2e- → NC(CH2)4CN
• Half of the hexanedinitrile is then hydrogenated to
give hexamethylenediamine, and the other half is
hydrolyzed to give adipic acid. A salt is then formed
from these two components, and then subsequent
dehydration leads to the polymerisation process.
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•
Glucose Meters for Diabetics

• Most glucose meters use an electrochemical method to measure

the amount of glucose present.
• The test strips contain a capillary that sucks up a small amount of
blood and an enzyme electrode containing glucose oxidase, which
oxidizes the glucose to gluconic acid.
Glucose + O2 → Gluconic acid + H2O2
• The hydrogen peroxide produced is then oxidised at a platinum
surface.
H2O2 → O2 + 2H+ + 2e-
• The total charge passing through the electrode is measured and is
proportional to the concentration of glucose in the blood.
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 Electrochemical Gas Sensors

• Respond to concentration not partial pressure

• Dry out?

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 Electroanalysis
• Heavy metal determination in natural waters,
etc
– Cd, As, Hg, Sb, etc

• Limits of detection (LoD) often in ppb range

(or better)
• Nanoparticle pollution

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 Fuel Cells
• These use the energy derived from a chemical reaction
to produce electricity.
• In hydrogen fuel cells, hydrogen provides the fuel and
oxygen is the oxidant. This cell has the benefit that the
only waste product is water, and so there are no carbon
dioxide emissions.

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 Some basics
• Electrochemistry concerns charge transfer
processes at interfaces or in solution
– Can include chemical reactions occurring
before/after the charge transfer
• These are often termed redox processes
– “red”=reduction (i.e. gain of electrons)
– “ox” = oxidation (loss of electrons)

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 Electrochemistry

Faradaic processes Galvanic processes

Applying a potential difference An electrochemical reaction
generates an electrochemical creates a potential difference
reaction
e.g. batteries, fuel cells
e.g. electrolysis, electrodeposition

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 Galvanic Processes

• Named after Luigi Galvani

• Frog’s leg expts (1771)

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 Equilibrium electrochemistry

• Principle of batteries
– E.g. Daniell Cell
• Half-cell reactions
– Anode (-)
Zn2+(aq) + 2e→ Zn(s)
– Cathode (+)
Cu2+(aq) + 2e→ Cu(s)
– Overall cell reaction
Zn(s) + Cu2+(aq) → Zn2+ (aq) + Cu(s)
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 Basics of electrochemistry
• If a Pt wire is dipped into a solution containing
Fe2+ and Fe3+ ions (and X- counterions), what
happens?
Pt wire

Fe2+
Fe3+
X-
H2O

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 How do the ions move?
Mass transport
• Ions, molecules etc move under 3 methods:
– Diffusion (along concentration gradients)
– Migration (along electric field gradients)
– Convection
• Natural (along temperature gradients)
• Forced (stirring, shaking, flow)

• Some may be augmented/diminished if

desired by choice of experimental methods
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 Equilibrium Electrochemistry
Questions
• Half reactions always written as reductions
• Standard reduction potentials (E0) given in
tables
• Why is it useful?
– (relatively) simple way to access thermodynamic
information
– E0 related to G0 via G0 = -nFE0
• Can derive Keqm, H0, and S0

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 Theories of electron transfer
• Separate into macroscopic and microscopic
theories
– Butler-Volmer
– Marcus & variants
• Both have pros & cons:
– Butler-Volmer is easy to use, but not easy to relate
to molecule
– Marcus is more difficult to use, but give physical
insight at the molecular level
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 Fuel Cells

Effectively batteries in
which the reactants are
continually fed into the
cell from outside.

Chemical energy is
converted into electrical
energy

Batteries are closed

systems; fuel cells are
open systems.
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 Mines

Mines are a key part of naval warfare, and an easy

way to detonate them is electrochemically.
In the lead acid battery in mines, a different way is used
to activate the battery. This time no reaction can happen
until the battery is activated by the addition of H 2SO4
e-
I

Add

H2SO4

Pb PbO2
PbSO4 PbSO4
H2SO4

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Mines are designed to detonate when the ship hits the mine.
The impact causes horns on the outside of the mine to bend.
This breaks glass cylinders of sulphuric acid inside the horns.
The acid flows into the circuit of the mine and acts as an
electrolyte for the lead acid battery. This produces a voltage
which can detonate the TNT or other form of explosive in the
mine.

Glass vial of Horn

H2SO4
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They were used on a huge scale in the World Wars
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The force of detonation can be extremely powerful…

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 Course Details
• 10-4pm in G35
• Problems sheet issued daily: please attempt
for next morning tutorial session
• Sign up for lab sessions (21/22/28/29 Nov)
• Assessment
– 75% on written exam
– 25% on write up from lab session

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 Time Monday 21/10 Tuesday 22/10 Wednesday 23/10 Thursday 24/10 Friday 25/10

Lecture 1:
10:00 – 11:15 Tutorial Tutorial Tutorial Tutorial
Introduction

11:15 - 11:30 Break

Lecture 2: Lecture 8:
Lecture 5: Lecture 9: Lecture 12:
11:30 – 12:45 Equilibrium Mechanistic
Electrode Processes II Shortening the timescale I Selected Applications
electrochemistry I Electrochemistry

12:45 - 13:30 Lunch

Lecture 3:
Lecture 6: Lecture 10: Lecture 13:
13:30 – 14:45 Equilibrium
Electrode Processes III Shortening the timescale II Selected Applications
electrochemistry II

14:45 – 15:00 Break Free Break

Lecture 7: Lecture 11:

Lecture 4: Lecture 14:
15:00 – 16:15 Theories of Electron Nanoparticles and
Electrode Processes I Course Review
Transfer catalysts

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 Assessment
• Exam (75%)
– 2 hour written paper
• Lab session (25%)
– 4 hours to work through 4 stations in groups
– Report to be submitted 2 weeks from lab date

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 Suggested Reading
• Electrode Potentials, RG Compton & GHW Sanders, OCP
#41, OUP. 1996
• Fuel Cell Systems Explained, J Larminie & A Dicks
• Electrochemistry, CH Hamann, A Hamnett, W Vielstich
• Understanding voltammetry (& Problems book) RG
Compton & CE Banks

For heroes:
• Electrochemical Methods: Fundamentals & Applications, AJ
Bard & LR Faulkner.
• Analytical & Physical Electrochemistry, HH Girault
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