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Electrometallurgy PDF

Electrometallurgy uses electrochemical principles and reactions to extract and refine metals. The Nernst equation and Butler-Volmer equation describe the relationships between electrode potentials, current densities, concentrations, and overpotentials in electrochemical cells. Factors that influence these relationships include reactant concentrations, mass transfer rates, electrode materials, and the presence of side reactions. Common industrial applications of electrometallurgy include metal production via electrolysis and separation processes like the chloralkali process.

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Jeremy Putra
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374 views

Electrometallurgy PDF

Electrometallurgy uses electrochemical principles and reactions to extract and refine metals. The Nernst equation and Butler-Volmer equation describe the relationships between electrode potentials, current densities, concentrations, and overpotentials in electrochemical cells. Factors that influence these relationships include reactant concentrations, mass transfer rates, electrode materials, and the presence of side reactions. Common industrial applications of electrometallurgy include metal production via electrolysis and separation processes like the chloralkali process.

Uploaded by

Jeremy Putra
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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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

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