19Y502 – NON FERROUS EXTRACTIVE
METALLURGY
PARKE’S PROCESS
BY
AVANTHIKAA SRI M
22Y105
BE METALLURGY
PARKES PROCESS
The Parkes process for desilverization of liquid lead with zinc involves the removal of an
alloying element by precipitation of an intermetallic compound, in a manner similar to
deoxidation.
Zinc combines with silver to form a zinc-silver intermetallic compound that is highly insoluble
in liquid lead.
This process is carried out by adding a sufficient amount of zinc (up to 2 wt%) to lead bullion at
about 550°C.
The liquid lead is agitated and allowed to cool slightly, which causes a crust rich in silver to form
on the surface of the lead bath.
The crust contains up to 70% lead, along with silver and zinc.
In industrial practice, a two-stage desilverization is often conducted:
Zinc is added in two batches.
The first stage produces a crust that is fairly rich in silver.
The second crust contains excess zinc and is used to remove as much silver as possible.
The zinc-rich crust formed in the second stage is used as a source of zinc for the first stage of the
Parkes process on a fresh kettle of lead bullion.
Desilverization of lead bullion with zinc can also be done in a continuous
manner, as in the Williams continuous process.
Some lead bullions contain gold, which has a stronger affinity for zinc than
silver does.
A two-step refining process can be carried out:
A small addition of zinc is made to separate the gold.
A second addition of zinc removes the silver.
Thermodynamically, the process can be complex due to the possibility of the
crust forming a ternary alloy of lead, silver, and zinc, rather than just the
intermetallic silver-zinc compound plus entrained lead.
KINETICS OF NUCLEATION OF A SEPARATING PHASE
● The rate of nucleation of a separating phase is often the principal barrier to
reaching equilibrium.
● This is particularly noticeable in crystallization processes, where large
degrees of supercooling are frequently observed.
● In addition to the difference in free energies of the bulk phases, the surface
energy between the precipitate and the solution must also be considered,
especially for solids.
● For homogeneous nucleation of spherical particles, the total free energy
change is expressed as:
● ΔG = (4π/3) r³ ΔGv + 4πr² γ
● ΔGv is the bulk free energy change per unit volume.
● γ is the surface energy of a unit area of interface between the parent liquid
and the crystal nucleus.
● r is the radius of a spherical particle.
KINETICS OF NUCLEATION OF A SEPARATING PHASE(CONTD..)
● These terms vary with the specific geometry of the nucleus,
introducing a size effect into the problem.
● When nuclei are small, the positive surface energy term
predominates, causing the free energy to increase with increasing
size.
● As nuclei grow larger, the negative bulk free energy term
predominates, causing the free energy to decrease with increasing
size.
● The free energy curve (as shown in Fig. 1) rises to a maximum as
the size increases, reaching a critical nucleus size (r*).
● A nucleus is stable if its size is larger than the critical nucleus size
since the free energy decreases as the size grows.
● The free energy change for the formation of a nucleus of critical
KINETICS OF NUCLEATION OF A SEPARATING PHASE(CONTD..)
● The nucleus of critical size (r* ) is in unstable equilibrium with the parent phase
because any change in its size results in a decrease in free energy and a
tendency either to grow or disappear.
● The work of formation is determined by r*, which may be evaluated by
maximizing ΔG with respect to r:∂(ΔG)/∂r = 4πr²ΔGv + 8πrγ = 0
● Solving for the critical radius r*:r* = - (2γ) / ΔGv
● Substituting r* into the equation for ΔG gives the work of nucleus formation:
● ΔG* = ΔG(r*) = (4/3)πr*³ΔGv + 4πr*²γ
● Simplifying, we get:ΔG* = (16πγ³) / (3ΔGv²)
● The coefficient in the expression for ΔG* is for a sphere.
● If the nucleus were a cube, the coefficient would be 32, where r is the cube edge.
KINETICS OF NUCLEATION OF A SEPARATING PHASE(CONTD..)
● The value of ΔG*, which corresponds to the critical size, represents an energy
barrier that must be overcome by a nucleus before it becomes stable.
● The energy required can come only from momentary local fluctuations of both
concentration and energy.
● The energy fluctuations are statistical in nature and are of the usual kinetic type
that give rise to homogeneous reactions.
● The concentration fluctuations require movement of the requisite number of
molecules close enough to one another by molecular diffusion to form a nucleus
large enough to exceed the critical size.
KINETICS OF NUCLEATION OF A SEPARATING PHASE(CONTD..)
● Becker proposed the following equation for the nucleation rate:
● dN/dt = c * e^(-q / kT) * e^(-ΔG* / kT)
● dN/dt is the nucleation rate, the number of nuclei formed per unit volume per unit
time.
● q is the activation energy for diffusion.
● A(T) is the work required to form a nucleus.
● T is the absolute temperature.
● c is a constant.
● k is Boltzmann's constant.
FROM PHASE DIAGRAMS
Pb-Ag Phase Diagram (Lead-Silver System):
● Lead and silver form a simple eutectic system, with limited mutual solubility at
high temperatures.
● In the molten state, silver has a limited solubility in lead, and vice versa.
● This limited solubility is beneficial for the Parkes process because it means that
silver doesn’t dissolve uniformly in lead, making it feasible to separate silver by
adding zinc.
● At lower temperatures, the solubility of silver in solid lead decreases, which
further aids in silver separation when the alloy is allowed to cool.
FROM PHASE DIAGRAMS
Ag-Zn Phase Diagram (Silver-Zinc System):
● Silver and zinc form a eutectic system with significant solubility in each other in
the molten state.
● Zinc has a high solubility for silver, so adding zinc to molten lead with dissolved
silver results in the formation of a Zn-Ag liquid phase, which floats on the surface
of the lead due to its lower density.
● The phase diagram shows that at certain compositions, zinc can dissolve
substantial amounts of silver, enabling efficient extraction of silver from lead in
this alloy.
LIQUATION:
Liquation: Process of liquid phase separation in metallic systems.
Involves:Liquid immiscibility ,Melting point difference
Example: Separation of lead solders from steel by heating to below steel’s melting
point.
LEAD SILVER SYSTEM:
Pattinson Process (Lead-Silver System):Lead-
silver alloy cooled to separate high-purity lead
.Eutectic point at 304°[Link] phase enriched
in silver separated from pure lead.
LEAD-COPPER SYSTEM AND DROSSING
Lead-Copper Phase Diagram:Low melting
point [Link] in equilibrium with solid
copper.
Drossing Process:Slow cooling from 450°C to
350°[Link]-rich dross forms on molten
lead surface.
REFERENCES
● Unit process of Extractive metallurgy by Robert D. Phelke
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