Electrometallurgy

Objective
• For students to know the basic principles
governing electrometallurgical operations.
 Electro winning and refining
• Electro winning is the commercial deposition
of a metal from its solution onto an inert
electrode.
• Electro refining is the refining of the metal
from its anode to obtain the cathode metal in
its purest form under certain conditions.
 Factors affecting the process of
electrolysis
• 1- Current density: This directly affects the
variations of the electrode potential both at the
anode and cathode. Example of Cu or Au , this
prevents the possible dissolution of the plated
copper and avoiding deposition of other metals in
the electrolyte.
• 2-Electrolyte composition
With Cu for example, concentrations of about
42-43 g/l are necessary
2+
to meet the preferential
discharge of Cu ions.
• Should the concentration go down and that of
nickel go up for example, then there are
chances that nickel will deposit as well onto
the cathode.
• Insufficient circulation of electrolyte and
crystallization may lead to the formation of a
concentration gradient in the electrolytic cell
leading to unwanted deposition of other
metals like Ni for example.
• Temperature
This affects the mobility of the electrolyte.
Higher temperatures result in reduced
electrolyte resistance and therefore less
current for electron and ion mobility.
This leads however to higher heat
requirement to warm up the electrolyte.
 Electrolysis of silver
• Electro refining of silver
• During electro refining of silver, the impure
silver is used as the anode, and refined silver
as the cathode.
• The electrolyte is an aqueous solution of silver
nitrate with nitric acid.
• The system can be represented as follows
• Ag(cathode)/AgNO₃ , HNO₃, H₂O,
impurities/Ag with impurities(anode)
• Possible cathode reactions:
Ag+ + e Ag
+
2H + 2e H₂(gas)
+
2NO₃⁻ + 10 H + 8e N₂O(gas) + 5H₂O
+
NO₃⁻ + 4 H + 3e NO(gas) + 2H₂O
• Possible anode reactions
+
Ag - e Ag
+
2H₂O - 4e 4H + O₂
4 NO₃ - 4e 2N₂O₅(gas) + O₂
+
N₂O₅ + H₂O 2H + 2NO₃⁻
• Silver is a very electro positive metal, its
standard electrode potential is 0.799V.
• The velocity of silver ion discharge is very high.
• Therefore even though the current densities are
quite high, discharge of impurities is minimal.
• Evolution of hydrogen at the cathode
theoretically , is possible only when the
electrolyte is very dilute, which in practice does
not happen.
• The discharge of NO₃⁻ is negligible, therefore the
cathodic process favours the reduction of silver.
• At the anode silver dissolves and impurities as
well, whose potential is more electronegative
than that of silver.
• Elements with electropositive potentials
precipitate as sludge.
• Liberation of oxygen at the anode practically is
impossible because the standard potential of
oxygen (+1.23V) is higher than that of silver.
• For this reason at the anode there is no oxidation
of NO₃⁻ ions.
• Function of the nitric acid in this system, is to increase
the electro conductivity of the electrolyte.
• Excess nitric acid concentration is not desirable
because the process of chemical dissolution of silver
deposited on the cathode is accelerated; which
reduces the cathodic efficiency , increasing the
consumption of nitric acid and results in the evolution
of nitrous oxide gases, posing a health hazard.
• There is considerable passage of platinum and
palladium into solution resulting in the co-deposition
of these elements with silver at the cathode thereby
reducing its purity.
 Applications of electrochemistry to
electrometallurgy
• Coulomb(C)
• Because a current of electricity is the flow of
electrons through a conductor ( an electrolyte), a
unit quantity of electricity is the number of
electrons that pass through the circuit.
• The standard unit quantity is the coulomb, C
• Ampere
• One ampere A, is a measure of the rate of flow of
electrons,
• One ampere is the flow of one coulomb per
second through a conductor
1
A = C.S⁻ or C= A.s
• The unit of electric potential or voltage is the
volt.
• Volt (v) is defined as the potential necessary
to produce one joule of electric energy, per
second at a current flow of one ampere.
• V= J.A⁻1 .s 1
• Because the coulomb has dimensions of
amperes x seconds we see that
1
• V= J.C⁻
• Faraday’s law
• The whereby a current of electricity is used to
bring about redox reactions is called
electrolysis
• The amount of chemical change produced by
an electric current is directly proportional to
the quantity of electricity passed. This was
postulated by Michael Faraday(1834)
• Definition: During electrolysis, the passage of
1 faraday through the circuit brings about the
oxidation of one equivalent weight of a
substance at one electrode and the reduction
of one equivalent weight at the other.
• Equivalent weights, stated simply are the
weights of substances that are equivalent to
one another in chemical reactions.
• Equivalent weights are always obtained with
reference to specific reactions.
• Example consider the following redox reaction
0 0 +3 (-)3
2Al + 3Cl₂ 2AlCl₃
• We can divide this redox reaction into two half
reactions:
0 3+
Oxidation: Al Al + 3e
0
Reduction: Cl₂ + 2e 2Cl⁻
• For each mole of the reducing agent , 3+
aluminium, that undergoes oxidation to Al , 3
moles of electrons are lost.
• The amount of aluminium required to lose 1
mole of electrons is 26.98g/3= 8.99
 3+
• 1/3 Al 1/3Al + e
1/3 mol 8.99g 1/3 mol 8.99 + 1 mol
• For each mole of the oxidising agent , chlorine,
that undergoes reduction to Cl⁻, 2 moles of
electrons are gained.
• The amount of chlorine required to gain 1 mole
of electrons is 70.906g/2 = 35.453 g
-1
½ Cl₂ + e Cl
½ mol, 35.453g+ 1mol ½ mol, 35.453g
• Therefore the equivalent weight of an
oxidizing or reducing agent is the weight of
the substance required to gain or lose 1 mole
of electrons.
• In the previous example the equivalent weight
of Al is 8.99g, the equivalent weight of Cl₂ is
35.453g.
• As mentioned, the standard unit quantity of
electricity that expresses the number of electrons
that have passed through an electrolyte is the
coulomb.
• On the basis of the change of one electron, it is
calculated that 96500 C( more precisely) 96487 C)
corresponds to the passage of 1 mole of
electrons. This quantity is called a faraday.
4
• 1 faraday= 1 mol of electrons= 9.65 x10 C.