Electrochemistry

Pre-seminar Material

Speaker: Prof. Kwok Yin WONG

The Hong Kong Polytechnic University
 Curriculum Link
This seminar builds on knowledge learnt in the
DSE curriculum:
•Chemistry: Topic VII
•Combined Science (Chemistry): Topic VI

Image source: EN Wikipedia

Electrochemistry and Redox Reactions
• In electrochemistry, reactions involving transfer of
electrons (redox reactions) are studied.
• All redox reactions can be considered as consisting
of two half reactions, one of which is oxidation
and the other is reduction.

e.g. The redox reaction: Fe + Cu2+  Fe2+ + Cu

can be considered as consisting of the following
two half reactions:

Fe  Fe2+ + 2e- (oxidation)

Cu2+ + 2e-  Cu (reduction)
 Electrochemical Cells
Zn Zn2+ + 2e- 1.10 V Cu2+ + 2e-  Cu
e- 
Voltmeter

Zn Cu

Salt bridge

Zn2+ Cu2+
1.000M 1.000M

If two electrochemical half cells with different electrode potential

are connected together, electrons flow from anode (zinc
electrode) to cathode (copper electrode). Therefore, cell
potential is developed across the electrodes.
 Standard Reduction Potential
• Each half reaction is associated with an
electrode potential.
• The electrode potential cannot be measured
without a reference, so a standard hydrogen
electrode (SHE) is used as a standard.
• Conventionally, the half reaction is often written
in the form of reduction.
• The electrode potential of the reduction under
standard conditions is known as standard reduction
potential (E).
Cu2+ (aq) + 2e-  Cu(s)
Standard conditions:
concentration of all solutions = 1.000 M
temperature = 25C
pressure = 1.000 atm (atmosphere)
 Standard Hydrogen Electrode
• A standard hydrogen electrode (SHE) consists
of a platinum-black electrode immersed in a
1.000 M H+(aq) in contact with H2(g) at
1.000 atm pressure.

2 H+ (aq) + 2 e- H2 (g) Eo = 0.000 V

• By convention, the standard electrode

potential of SHE is defined as 0.000V.

• SHE is used as a standard in measuring the

standard reduction potentials of other half
reactions.
Standard Hydrogen Electrode
Conducting wire
 Electrochemical Cell
at Equilibrium
Electrode 1 Electrode 2
V

1. With very high resistance

=> current ～ 0
2. Charge distribution (around
electrode) can attain equilibrium
and virtually does not change
during the measurement



M’n+ + ne-  M’(s)
Mn+ + ne-  M(s) porous partition

If there is no net current from one electrode to the other, the

electrochemical system is at equilibrium.
 Electromotive Force (EMF)
Electrode 1 Electrode 2
V

Half cell With very high resistance Half cell

=> current ～ 0


M’n+ + ne-  M’(s)
Mn+ + ne-  M(s) porous partition

The potential difference between the two electrodes of an

electrochemical cell measured at equilibrium is specifically called
the EMF of the cell. It is the maximum potential difference
between the two electrodes that the electrochemical cell can attain.
 Electrode Potentials
• The standard electrode potentials of all half
reactions are measured with reference to the
standard hydrogen electrode (SHE).

e.g. Cu2+(aq) + 2e- → Cu(s) Eo = +0.34 V

• Thus +0.34 V refers to the standard reduction

potential of the above half reaction.
 Electrochemical Series
• The electrochemical series is the arrangement
of half reactions for the reduction in
increasing order of Eo.
 Electrochemical Cell
NOT at Equilibrium
Electron flow
Electron flow → Electrode 2
Electrode 1
A
Ammeter Charge distribution deviates from the
equilibrium situation.

porous partition

If the current flow in the electrochemical system is not zero, the

electrode system does not attain equilibrium and it suffers from
voltage drop due to the charge distribution deviating from the
equilibrium conditions.
 Applications: Primary and
Secondary Cells
• Primary cells refer to electrochemical cells
which are not rechargeable, while secondary
cell can be recharged.

zinc-carbon cells lead-acid accumulator lithium ion battery

(Primary cell) (Secondary cell) (Secondary cell)
 Applications: Fuel cells
• A fuel cell is a device which converts the
chemical energy in a fuel into electricity.

2H2  4H+ + 4e-

Proton O2 + 4H+ + 4e-  2H2O
exchange
(Platinum) membrane
(Platinum)

Image source: Electrochemistry Encyclopedia

(http://electrochem.cwru.edu/encycl/art-f04-fuel-cells-pem.htm)
This seminar covers the following areas in
electrochemistry:
•Concepts and misconceptions in
electrochemistry
•Primary and secondary cells
•Safety and environmental issues relating to the
use of batteries
•Fuel Cells
•The future of electrochemistry
 Glossary (詞彙)
Electrohemistry 電化學
Standard reduction potential 標準還原電勢
Standard hydrogen electrode 標準氫電極
Electrochemical series 電化序
Dynamic equilibrium 動態平衡
Over potential 過電壓
Memory effect 記憶效應
Direct methanol fuel cell (DMFC) 直接甲醇燃料電池
Proton-exchange membrane (PEM) 質子交換膜
Hybrid-powered vehicles 混能車輛
Current density 電流密度
 EDB Glossary
• The link to EDB Glossary (Chinese/English) is
http://www.edb.gov.hk/tc/curriculum-
development/kla/science-edu/ref-and-
resources/glossary.html