METE 215 MATERIALS PROCESSING

Experiment 6:

LEACHING AND ELECTROWINNING

Prepared by: Prof.Dr. İshak Karakaya

THEORY
Leaching is the process of extracting a soluble constituent from a solid by means of a solvent. It
is the process of dissolving certain constituents from an ore, concentrate, or from metallurgical
products such as calcines, mattes, etc.

Leaching processes have been used for many years as a parallel treatment method to
pyrometallurgy in treating some metals such as zinc. Leaching of zinc concentrates followed by
electrowinning is rapidly increasing in popularity for its cleaner environmental operations,
energy saving possibilities and ability to treat lower grade and complex ores.

The relations between chemical change and electrical energy have theoretical as well as
practical importance. Chemical reactions can be used to produce electrical energy (voltaic or
galvanic cells). Electrical energy can be used to bring about chemical transformations
(electrolytic cells).

Electrowinning is important for the very reactive light metals (Al, Mg) which are produced by
electrolysis of fused salts. For other metals such as Cu and Zn, electrowinning from aqueous
solutions represent an alternative to pyrometallurgical processes.

Electrowinning (electrolytic deposition) is used for extraction, particularly from acid leach
solutions where the form of the leach solution makes a satisfactory aqueous solution to be used
as an electrolyte. The calcine is leached in dilute sulphuric acid solution according to:

ZnO(s) + H2SO4(aq) = ZnSO4(aq) + H2O(l) (1)

Where ZnSO4(aq) exists as Zn++ and SO4= ions in aqueous solution.

When current is passed to cause decomposition of this solution, zinc is precipitated by

electrolysis. The main cathodic reaction is:

Zn++ + 2 e- = Zn eo(cathode) = -0.76 V (2)

The following reaction occurs at the anode:

H2O(l) = ½ O2(g) + 2 H+ + 2 e- eo(anode) = -1.23 V (3)

The solution becomes more acidic during electrolysis and can be recycled as a leaching agent.
This solution is called spent electrolyte and it could be used to leach new concentrate or calcine
(ZnO).

The metallic zinc will be deposited at the cathode and can be stripped from there after sufficient
metal buildup has occurred. The deposited metal is relatively pure and needs only to be melted
and cast into slabs or ingots for commercial use or sale.

The cathodes can be either a pure metal starting sheet of the same metal (zinc in this case) to
be deposited or they can be a different metal (aluminum in this case) from which deposited
layer will be stripped at regular intervals. The anodes are merely insoluble electrical conductors,
such as sheet lead or a lead-1% silver alloy. The cell will have one more anode than cathodes. A
typical industrial cell will have 46 anodes and 45 cathodes.

Cell temperature is important and is generally held at 35 to 45 °C. Heat generated during
electrolysis is dissipated by circulating cool water through lead coils immersed in the cell. High
temperature can increase deposition but also intensifies the effect of impurities in the cell.

The decomposition of zinc sulfate solution takes place according to reaction:

ZnSO4(aq) + H2O(l) = Zn(s) + H2SO4(aq) + ½ O2(g) (4)

Since ZnSO4(aq) is Zn++ and SO4=, similarly H2SO4(aq) is 2H+ and SO4=; reaction (4) can also be
written as:

Zn++ + SO4= + H2O(l) = Zn(s) + 2H+ + SO4= + ½ O2(g) (5)

This is the summation of cathodic and anodic reactions given in equations (2) and (3)
respectively. Then, the theoretical standard decomposition voltage of zinc sulfate is:

Eo = eo(anode) + eo(cathode) = -1.99 volts. (6)

Theoretically 1.99 volts of potential should be applied between the electrodes for the
electrolysis of a zinc sulfate solution under standard conditions. Under electrolysis conditions,
the theoretical voltage required for the electrolysis of a zinc sulfate solution is 2.35 volts, but in
actual practice voltages higher than this are used. In practical electrolysis, there will be
additional potentials. These are the voltage drop due to ohmic resistance in the electrolyte,
voltage drop due to ohmic resistance in the electrode leads and electrodes and voltage drop
due to overvoltage, η, of the cell. The overvoltage is caused either by the reactants not being
supplied to the electrodes as fast as they are removed or by the reaction products not being
removed as fast as they are supplied. Thus, the total applied voltage may be expressed as:
 V = - E + ( Re+ Rl ) I + η (7)

Where;
V: The total applied voltage Rl: Resistance of leads
E: Decomposition Voltage I: Current
Re: Resistance of electrolyte η: Overvoltage

The decomposition voltage of zinc sulfate is above that of hydrogen, and normally it would be
expected that hydrogen evolve instead of zinc being deposited. However, the hydrogen
overvoltage, which is the voltage actually required to evolve hydrogen in excess of theoretical
decomposition voltage, with respect to zinc in an acid solution is high enough to let the zinc
plate out of a zinc sulfate solution without the evolution of a great amount of hydrogen at the
cathode.

Most plants operate with current density of 220 to 450 amperes per square meter of cathode
area, with the choice of the current density for each particular plant adjusted against the
voltage used per cell, the acid strength of the electrolyte, the volume and temperature of the
cooling water, and the volume and metal content of the solution, to give the maximum
deposition of metal in each case.

OBJECTIVE
A series of tests on leaching and electrowinning of metal values from aqueous solutions will be
performed to analyze various principles involved.

APPARATUS
1. D.C power supply
2. Ampermeters
3. 150 ml. beakers
4. aluminum cathodes
5. lead anodes
6. Zinc sulfate
7. Sulfuric acid
8. Balance and weights
PROCEDURE
1. Dissolve proper amount of ZnSO4 in a 150 ml beaker (as instructed) by using distilled
water to prepare 100 ml electrolyte with desired concentration. Find your group number
and corresponding Zn concentration from the table below.
2. Add proper amount of H2SO4 given for your group in the table below.

ZnSO4 (g/lt) H2SO4 (ml/lt) Cathode Area, cm²

Group 1 100 5 4.0 (2x2)
Group 2 110 5 4.0 (2x2)
Group 3 120 5 4.0 (2x2)
Group 4 130 5 4.0 (2x2)
Group 5 100 8 4.0 (2x2)
Group 6 110 8 4.0 (2x2)
Group 7 120 8 4.0 (2x2)
Group 8 130 8 4.0 (2x2)
Group 9 140 8 4.0 (2x2)

3. Weigh the cathode and record the weight.

4. Place the electrodes in the electrolyte and position them so that the anode and cathode
are parallel to each other (see Fig. 1). Place spacers on the bus bars to keep the
electrode distance uniform and constant (about 2 cm). (Do not let the hooks supporting
the electrodes touch the electrolyte or they will dissolve.)
5. Connect anode bus bar to the (+) source and cathode bus bar to the (-) source and adjust
the voltage to 3.3 volts. During the course of the experiment make adjustments to
maintain this voltage if necessary.
6. Measure current passing through the cell every 5 minutes (every minute at the
beginning) and record them.
7. After one hour remove the electrodes, rinse in water, dry them, then weigh the cathode
and record its weight change.
8. Weight the deposited zinc metal, if possible, as an alternative.

QUESTIONS
1. Calculate the current density in amperes per square meter of cathode surface.
2. Draw power consumption and current density vs. time graphs.
3. Calculate the percent current and energy efficiencies and energy consumptions for zinc
deposition.
4. Discuss and draw conclusions from the data obtained based on your observations.
5. Discuss the importance of e.m.f. series in electrowinning.
SUGGESTED READINGS

1. J. O’ M. Bockris and A.K.N. Reddy, “Modern Electrochemistry”, Vol. 1 and 2,

Plenum/Rosetta Ed., 1970.
2. C.L. Mantell, “Electrochemical Engineering” , McGraw-Hill, New York, 1960.
3. H. H. Kellog, Energy Use in Zinc Extraction, “Lead-Zinc-Tin ‘80”, TMS-AIME World
Symposium on Metallurgy and Environmental Control, Editors: J. M. Cigan, T. S. Mackey
and T. J. O’ Keefe, 28-47 (1979).

ELECTROWINNING CELL

D.C. Voltage source

bus
+ bars
-

Solution level

Aluminum
cathode

Lead anode

150 ml
Fig. 1: Schematic representation of experimental electrowinning cell
APPENDIX
Faraday’s Laws:

Faraday showed that the amount of chemical substance liberated at an electrode is directly
proportional to the amount of current passed through the cell. Also, he found that 96500
coulombs is required to deposit or dissolve 1 gm-equivalent substance, where

𝑎𝑡𝑜𝑚𝑖𝑐 𝑤𝑒𝑖𝑔ℎ𝑡
1 𝑔𝑚 − 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 =
𝑣𝑎𝑙𝑒𝑛𝑐𝑦

The theoretical weight of substance dissolution or deposition after a certain electrolysis time
can be expressed as;
𝑀𝑊∗𝐼∗𝑡
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 𝑑𝑒𝑝𝑜𝑠𝑖𝑡𝑒𝑑 in gm (theor.) =
𝑛∗ 𝐹

Where:
MW: Atomic or Molecular Weight n: Valency
I: Current (ampere) F: Faraday’s constant
t: Time (sec)
Due to deposition of unwanted products, electronic conductivity in the electrolyte, chemical
and electrical short-circuiting in actual cases substance deposition is less than theoretical value.
The ratio between the weight of actually deposited and theoretically deposited substance is
called current efficiency;

𝑊𝑡 𝐴𝑐𝑡𝑢𝑎𝑙 𝑑𝑒𝑝𝑜𝑠𝑖𝑡𝑒𝑑
𝐶. 𝐸. =
𝑊𝑡 𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑑𝑒𝑝𝑜𝑠𝑖𝑡𝑒𝑑

Decomposition Potentials:

If an electrochemical reaction is carried out reversibly i.e at infinitely low current density, the
cell voltage is denoted E and is called electromotive force (e.m.f) of the cell. We have;

∆G = -n E F

Where ∆G is the change in Gibbs energy, n is the number of electrons transferred (valency), and
F is Faraday’s number (96500 coulombs). If in a cell reaction all components are present in their
standard states the Gibbs energy change is denoted as ∆G° and the corresponding e.m.f. as E°. If
for a reaction “AX = A + X” the components are present with activities aAX, aX and aA, then we
have:
𝑎𝐴 𝑎𝑋
∆G = ∆G° + RT ln [ ]
𝑎𝐴𝑋
and
𝑎 𝑎
E = E° - 𝑅𝑇/𝑛𝐹 𝑙𝑛 [ 𝑎𝐴 𝑋]
𝐴𝑋

ENERGY CONSUMPTION:

The energy consumption per unit mass of metal produced is an important factor in assessing
and comparing the economics of electrolytic processes. It is generally expressed in unit of
kW.h/kg of metal deposited, and is given by;

Energy consumption = (V* I* t)/(W*3600*1000)

Where V is the applied potential in volts, I is the current passing through the circuit in amperes,
t is the time of deposition in seconds, and W is the actual weight of deposition in kilograms.

ENERGY EFFICIENCY:

It is also an important factor in the electrolytic processes. Because, it combines two factors:
energy consumption and current efficiency. It is given by formula of;

Energy Efficiency = (Vt/Va) * C.E.

Where Vt is the theoretical cell voltage in volts (Vt of zinc electrowinning cell is 2.35 volts), Va is
the applied voltage in volts, and C.E. is the current efficiency of process.

OHMIC RESISTANCE:

Resistance of electrolyte affects the rate of electrolytic processes. Therefore, it is also an

important parameter in the electrowinning. It may be calculated from equation;

Resistance of electrolyte= R =  (L/A)

Where L is the distance between electrodes, A is the electrode area, and  is the resistivity of
electrolyte.