ELECTROMETALLURGY

General Characteristics
 Reversible electrode potential of a reaction:
¨ 

An+ + ne à Ao
May be calculated using the Nernst equation:
E = Eo – RT/nF ln(aAo/aAn+)

Using this general relationship, potential difference of

two electrodes (EI and EII) can be calculated.
¨  In case of self-driving electrochemical reactions, (EI
–EII) defines maximum differences in potentials
¨  In case of reaction require external potential to

drive electrochemical reactions, (EI-EII) defines the

minimum cell voltage that must be applied
Butler-Volmer equation
¨  Reaction rate where rates of electrochemical
reactions are limited by reactions at the electrode/
electrolyte interface, the current flow:

J = current density across electrode/electrolyte interface (Am-2)

Jo = exchange current density (Am-2)
β= constant dependent the electrolyte & electrode
η = overpotential of electrode (V)
F = Faraday’s constant = 96847 C/mol.electron
¨  U = Eo + η
¨  Overpotensial of an electrode defined as the

difference between applied potential (U) and

equilibrium potential (Eo)
¨  β à related to transfer of ions across layer

between electrode & electrolyte

à sensitive to species & concentration
 Generalised Butler-Volmer correlation
(Tafel plot)

Anodic: Ao à An+ + ne
Cathodic: Bm+ + me à Bo
Positive over potential à
cathode
Negative overpotential à
anode

At U = equilibrium reversible
electrode potential, net current
density = 0

At increasing current density,

increasing overpotential à
increasing overall reaction

Fig 1. Generalised Butler-Volmer relationships (V vs log j) for externally

driven electrochemical reaction
Generalised Butler-Volmer correlation

Anodic: Ao à An+ + ne
Cathodic: Bm+ + me à Bo

At the equilibrium potential,

log J = o

à  Current density ~ 1 (low)

Increasing net current density

à lowering potential of
cathode & increase of anode
potential --> lowering
resistance

Fig 2. Generalised Butler-Volmer relationships (V vs log j) for self-driving

electrochemical reaction
¨  Fig 1 & 2 deals only reactions involving addition &
removal of electrons at the interface

¨  Effect of mass transfer??

¨  Transport of species?

¨  At high current densities, transport of species can be

limiting factor
Generalised Butler-Volmer correlation
involving mass transport limitation
Anodic: Ao à An+ + ne
Cathodic: Bm+ + me à Bo
With increasing current density,
Supply of oins / removal of ions
from electrode becomes
increasingly difficult.

At V limit, no increase in current

density is obtained

Fig 3. Generalised Butler-Volmer relationships (V vs log j) for externally

driven electrochemical reaction involving mass transport limitation
Generalised Butler-Volmer correlation
involving mass transport limitation
Anodic: Ao à An+ + ne
Cathodic: Bm+ + me à Bo

Fig 4. Generalised Butler-Volmer relationships (V vs log j) for self driving

electrochemical reaction involving mass transport limitation
¨  With increasing current density, limiting current
density is reached
¨  à no advantage to add more applied potential
Effect of Concentration
¨  Concentration (/activities) determined:
¤  Equilibrium reversible potentials
¤  Exchange current densities

¤  Limiting current densities

¨  à Altering concentrations can have significant

effect on Tafel plot
Effect of reactant concentration
Anodic: Ao à An+ + ne
Cathodic: Bm+ + me à Bo

Fig 5. Generalised Butler-Volmer relationships (V vs log j) for externally

driven electrochemical reaction showing effect of reactants
Effect of reactant concentration
Anodic: Ao à An+ + ne
Cathodic: Bm+ + me à Bo

Fig 6. Generalised Butler-Volmer relationships (V vs log j) for self driving

electrochemical reaction involving mass transport limitation
¨  Decreasing concentration of ions in the cathode à
decreasing potential à decrease in limiting current
density at cathode
¨  Effect of production rate?

¨  Power = U x I
Effect of Mass Transfer
Anodic: Ao à An+ + ne
Cathodic: Bm+ + me à Bo

Effect of mass transfer :

Increasing mass transfer à affect the
Limiting current densities in the cell

Fig 7. Generalised Butler-Volmer relationships (V vs log j) for externally

driven electrochemical reaction, effect of increasing mass transfer
Effect of Mass Transfer

Fig 8. Generalised Butler-Volmer relationships (V vs log j) for externally

driven electrochemical reaction, effect of increasing mass transfer
Effect of Electrode
¨  Electrode determines :
¤  the mechanism of reactions at electrode interface,
¤  Influence exchange current density

¤  Tafel slope (effect of β)

¨  Example: Figure 9

Example: Tafel lines for electrochemical
reduction of oxygen on series of
electrodes at 0,5 M H2SO4 at 25 C
¨  At the anode, the greater bulk concentration of B+
ions à the lower driving force for transfer from the
electrode surface into bulk electrolyte
+
¨  Increasing B ions concentration, lowering the

limiting current density at the anode

Effect of side reactions
¨  In reality, there may be a number of reactions
simultaneously at the electrode
¨  à Electrode characteristics become prime

importance
¨  Although a number of products are

thermodynamically stable, by manipulation of

kinetics of electrode reactions, it is possible to
selectively produce a high purity product
Effect of Electrode kinetics on the
products of electrochemical reactions
Conclusions
¨  To determiner the relationship between potentials of
electrodes in electrochemical cell & current densities,
it is necessary to define :
¤  ….

¤  ….
¤  ….

¤  ….
Factors Affecting the Design of Electrochemical
Reactors
¨  Electrodes
¤  Good electrical conductors
¤  Low Tafel slope

¤  Should not become passivated

¨  Electrolytes
¤  High ionic conductivity
¤  High chemical stability

¤  High solubility

¨  General factors affecting cell design & optimisation

Processes Aimed at Separation
¨  Example: electro-dissolution of metal sulphides
¨  (Hayes page 334)
Compound Formation
¨  Example: Chloroalkali cell (page 336 Hayes)
Metal Production
¨  Example: Aluminium production (hayes page 341)
¨  Example: electrolytic zinc production (Hayes page

347
TUGAS 4
¨  Buat rangkuman dari halaman 334 & 336
mengenai contoh aplikasi elektometalurgi:
¤  Pelarutan logam sulfida secara elektrometalurgi
¤  Chloroalkali cell untuk produksi NaOH dan Cl2
¤  Produksi Zn melalui elektrolisis

¤  Tugas ditulis tangan, dikumpulkan tanggal 24 April

2015
Economic Characteristics of
Electrometallurgy
¨  Capital intensive operation
¨  Direct Operating cost: electric power

¨  For any given metal, cost of electrorefining will be

less that for metal production

¨  Electrochemical processes are expensive to run,

need much care in both operation & maintenance

¨  Value: least loss of value
¨  Need high purity raw materials à heavy cost of

feed purification
¨  Further consequence for Al & Zn (has negative

electrode potential) à high power consumption

¨  à desirable where cheap power available
Summary
¨  Reaction system:
¨  Reactants are able to exist in charged state

¨  Electron is transferred by electrical conductor

(electrolyte)
¨  There is potential between anode & cathode

¨  Electrochemical reactions: ideal for high purity

metal/materials