Yeditepe University
Materials Science and Nanotechnology Engineering Department
MSN 316 – Materials Laboratory Course, Experiment Booklets
Published Version Number / Date Page Numbers
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LEACHING AND CEMENTATION
İlayda ÖZBAĞ TOĞAÇAR, Mustafa TEKİN
1. OBJECTIVES AND SCOPE
The purpose of this experiment is primarily to leach ores containing the metals desired to be recovered
(malachite: Cu2CO3(OH)2, azurite: Cu3(CO3)2(OH)2 etc.) by using suitable solutions and to transfer the
metals they contain to solution. In the second stage of the experimental studies, sampling of
electrochemical reduction (cementation) without current with the help of ion – metal pairs (Cu2+ - Fe
and Cu2+ - Zn) where there is sufficient difference between standard electrode potentials and solution
pH value, mixing speed, ion concentration etc. It is aimed to examine the effects of the parameters on
the cementation rate.
2. TECHNICAL BACKGROUND
2.1. Leaching and Precipitation
Reactions between solid compounds and liquid phase are heterogeneous reactions and do not differ from
carbon gasification and metal oxide reduction. The reaction rate can be controlled by atomic diffusion
from or to the surface, reactions occurring at the surface, or both. In the first case, the dissolution rate
can be increased by mixing the liquid. In the second case, the motion of the liquid has no effect on the
dissolution rate. In both cases, increasing the amount of reactant in the solvent increases the rate of
dissolution [1].
The main subject of hydrometallurgy is the leaching (solution) of the valuable part in the ores. Generally,
in these cases, the valuable part is dispersed into the unwanted part in the ore called gangue (or gangue
minerals). To make the mineral accessible to the solvent, the ore must be crushed and grinded to very
low average particle sizes until particle liberation of minerals (or metals if it is in native form e.g., gold)
is achieved. In fact, precious metals or their compounds between small pores in gangue minerals should
be leached by diffusion. In this case, the leaching process cannot be controlled by agitation [1].
Intermediate products and by-products can be formed during leaching processes. An example of this is
the formation of elemental sulphur as a result of acid leaching of sulphide ores. This sulphur layer is
porous below the melting point and does not prevent the diffusion of the solvent into the ore. However,
the sulphur layer melts above 120 °C and covers the mineral particles, reducing the speed of the leaching
process [1].
Chemically, leaching reactions are of two types.
1. Leaching of copper oxide in acid or ammonia:
CuO + 2H+ → Cu2+ + H2O (1)
CuO + 2H+ + 4NH3 → Cu(NH3)42+ + H2O (2)
These reactions have varying rates according to the oxide type and the reactions are diffusion controlled.
For example, when copper-nickel matte, subjected to total oxidation roasting, is dissolved in sulfuric
acid, copper oxide dissolves faster than nickel oxide, and thus separation is possible [1].
LEACHING AND CEMENTATION
Yeditepe University
Materials Science and Nanotechnology Engineering Department
MSN 316 – Materials Laboratory Course, Experiment Booklets
Published Version Number / Date Page Numbers
24.Nov.2021 2 / 30.Jan.2025 2/7
2: Oxygen composition of acid leaching of copper oxide or copper sulphide or metallic copper with
ammonia:
2Cu2O + 8H+ + O2 ↔ 4Cu2+ + 4H2O (3)
2Cu2S + 4H+ + 5O2 ↔ 4Cu2+ + 2SO42- + 2H2O (4)
2Cu + 2H2O + 8NH3 + O2 ↔ 2Cu(NH3)42+ + 4OH- (5)
At low reactant ion concentrations, diffusion of ions to or from the interface can control reaction rates.
At high concentrations, the amount of oxygen is the reaction controlling step. The reaction rate can then
be increased by increasing the oxygen pressure. In addition, when the amount of iron in the solution
increases, the reaction rate of oxygen also increases. When iron reacts with air, it is oxidized to Fe3+ and
acts as an oxidizing agent for copper sulphide [1].
Some routes to precipitate metals (in metallic state or in the form of their salts) are given below.
1. Hydroxide precipitation without changing the oxygen potential by changing the pH,
2. Insoluble compounds and salt precipitation by adding chemical agents or by cooling,
3. Precipitation by reduction or oxidation [1].
The precipitation of Ca(OH)2 and Mg(OH)2 from sea water is an example of Type (1) precipitation. CuS
precipitation from Cu+ solution is an example of Type (2). Precipitating Cu by reducing the Cu+2 ion
solution with iron or hydrogen can be given as an example of the Type (3) [1].
Precipitation of metals from solutions using less noble metals is widely used in industry and, it is called
‘‘cementation’’. A typical example of this is copper cementation using ferrous scrap. Although this
reaction is very fast, the reaction rate is determined by the solution diffusion into the ferrous scrap or
the ferrous scrap. Therefore, the reaction rate can be increased by mixing (agitation) and by removing
the metallic copper accumulated in / on the iron [1].
2.2. Cementation
Cementation is an electrochemical displacement reaction based on the principle that the metal ion in the
solution is reduced into the metallic state of the more noble one by adding a more basic metal than that
metal to the solution in elemental form. In other words, the precipitation of a metal from its aqueous
solution with the help of another metal more basic than itself is called “cementation”. In the cementation
system, the more basic metal added to the solution is called “cementator”, and the more noble metal
reduced from the solution is called “cement”. The precipitated metal is usually cemented onto the added
metal [2].
In the cementation method, which is widely used in hydrometallurgical applications, metal added to the
solution as powder, granule, shaving or scrap sheet [2];
MeI → MeIn+ + ne- (6)
the electrons it liberates while passing into the solution in accordance with its anodic reaction;
MeIIn+ + ne- → MeII (7)
LEACHING AND CEMENTATION
Yeditepe University
Materials Science and Nanotechnology Engineering Department
MSN 316 – Materials Laboratory Course, Experiment Booklets
Published Version Number / Date Page Numbers
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reduction is carried out by the ions of the more noble metal in the dissolved state, according to the
cathodic Reaction (7). The total reaction between the basic metal and the more noble metal is [2];
MeIIn+ + MeI → MeII + MeIn+ (8)
expressed by reaction equation. For this redox reaction to proceed at a sufficient speed and efficiency,
a sufficient standard potential difference is required between the metals in question and the difference
amounts are given in the Electromotive Force (EMF) Series given in Figure 1. Metals at the top of the
EMF series are noble (electropositive). The basicity of metals increases towards the bottom of the table
(electronegative) [2].
Figure 1. Electromotive Force (EMF) Series.
The most common metal couple in the industrial applications of cementation process is Cu-Fe couple.
In cases where the copper concentration of the obtained solution is not suitable for electrolytic recovery,
copper reduction from solutions is carried out by adding scrap iron to them. Although the technological
use of cementation reactions varies widely, the main areas in which they are generally used are as
follows [2, 3];
1. In the recovery or removal of a metal from its aqueous solutions,
Cu++ + Fe → Fe++ + Cu (9)
2. In the recovery of a metal from a suspension of insoluble salts,
LEACHING AND CEMENTATION
Yeditepe University
Materials Science and Nanotechnology Engineering Department
MSN 316 – Materials Laboratory Course, Experiment Booklets
Published Version Number / Date Page Numbers
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2AgCl + Fe → 2Ag + FeCl2 (10)
3. In removing unwanted impurities from metal solutions,
Cu++ + Zn → Zn++ + Cu (11)
4. In the separation of two metals in solution, for example in the separation of cobalt, in the separation
of Cu-Co,
Cu++ + Co → Co++ + Cu (12)
5. In coating without using current: fastener, paper clip etc. coating of materials with copper for
decorative and anti-corrosion purposes, copper coating of steel wires used in the production of
automobile tires to increase adhesion with rubber-based matrix,
Cu++ + Fe → Fe++ + Cu (13)
6. In the preparation of the alloy of two metals that have little or no solubility in each other: to prepare
the PbCa alloys, which are very frequently used in the battery industry and cannot be produced by
conventional alloying, first of all, PbNa alloy is prepared and this alloy in liquid form is poured onto
molten CaCl2 to form a PbCa alloy with the help of cementation.
Pb(Na) + CaCl2 → Pb(Ca) + 2NaCl (14)
In industrial practice, the copper solution is passed over heaps of scrap iron or iron shavings and the
copper is deposited on the iron. Cemented copper, which generally settles in powder form, contains 85-
90% Cu, 0.2-2% Fe, 0.5% SiO2+Al2O3 and variable amounts of oxygen and other impurities from the
ore. Therefore, cemented copper needs to be refined. The most used methods are to refining this
intermediate or returning it to converters. Although rare, there are also processes that dissolve cemented
copper and purify it by reducing it with pressurized hydrogen [3]. The cementation units used on an
industrial scale are shown in Figure 2.
Figure 2. Industrial type cementation units; (A) Drum type, (B) cone type [4].
LEACHING AND CEMENTATION
Yeditepe University
Materials Science and Nanotechnology Engineering Department
MSN 316 – Materials Laboratory Course, Experiment Booklets
Published Version Number / Date Page Numbers
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Cementation can also be considered as a corrosion process because the basic metal added to the solution
is corroded. Initially, when the cementator is immersed in the metal solution, minor differences in
potential begin to develop across the cementator metal surface. Regions of more negative potential
become anodic and tend to go into solution. Other sites become cathodic and many cathodic reactions
are possible [2];
O2 + 4H+ + 4e- → 2H2O (15)
2H+ + 2e- → H2 (16)
Men+ + ne- → MeCathode (17)
The reduction reaction of oxygen (15) has a high positive potential in acidic solutions and occurs
preferentially in many metal ion reduction reactions where oxygen is dissolved in solution and may not
be considered in the cementation efficiency arithmetic [2].
The hydrogen ion discharge reaction (16) depends on the potential of the metal system (17), the pH of
the solution, and the hydrogen overvoltage on the precipitating metal. In some cases, an increase in the
pH value, that is, a decrease in the hydrogen ion concentration, is helpful, but hydrolysis should be
avoided because the cementation rate may decrease rapidly due to the hydroxide layer that will form on
the surface due to the increase in the solution pH value. In solutions at low pH, hydrogen escape occurs
easily with the decrease of the concentration of cemented metal ions, resulting in an inert consumption
of the cementator and reducing the yield [2, 3].
In the early stages of cementation, the metal reduction rate is low, but when the dissolved oxygen in the
solution decreases and some cement metal is formed in the system, a galvanic cell will form between
the cementator and the cemented metal as shown in Figure 3. In this case, the corrosion of the cementator
metal will no longer depend on the potential differences created by the anodic and cathodic regions on
its surface, and almost the entire surface in electrical contact with the cementum metal will be of anodic
character. As cementation progresses, the size of the cathodic regions will increase according to the
amount of cemented metal deposition, and as a result, the cementation rate of the entire system will
increase [2].
Figure 3. Changes occurring in the early stages of cementation, (a) at first (b) after some accumulation
[2].
LEACHING AND CEMENTATION
Yeditepe University
Materials Science and Nanotechnology Engineering Department
MSN 316 – Materials Laboratory Course, Experiment Booklets
Published Version Number / Date Page Numbers
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Cementation reactions are generally diffusion-controlled reactions and the progression of the reaction
involves 6 simplified basic steps that take place at the phase boundary. In Figure 4, the basic steps
occurring at the phase boundary during the cementation reaction are shown schematically [2].
Figure 4. The basic reaction steps in the cementation process [2].
These steps are listed below [2];
1. The transport of metal ions in the solution from the solution to the reaction surface by passing the
diffusion layer,
2. The flow of electrons into the cemented metal,
3. The structuring of the reduced atoms in the crystal lattice,
4. Transition of cementator ions from cement metal to solution,
5. Transfer of cementator ions to the reaction interface,
6. Transport of cementator ions to the solution by passing through the diffusion layer.
The chemical driving force of the cementation reaction is the difference between the standard potentials
of the two elements being exchanged. For the system considered in this experiment, the final
concentrations that will occur at equilibrium are calculated as follows [3].
ECu = EFe (18)
E0Cu+(RT/nF)ln[Cu+2] = E0Fe+(RT/nF)ln[Fe+2] (19)
0.340 + 0.0295log [Cu+2] = -0.444 + 0.0295 log[Fe2+] (20)
26.57 = log[Fe+2 ]/[Cu+2] (21)
[Fe+2]/[Cu+2] = 1027/1 (22)
From this, it can be seen that when metallic iron is added to a copper solution, one copper ion can remain
unreduced for 1027 iron ions in that solution [3].
According to the Reaction (13), 1 mole of iron (55.85 g) completely cements 1 mole of copper (63.54
g). In practice, several times the stoichiometric amount of iron is used. This is due to some kinetic factors
that slow down or prevent the reaction, such as covering the surface of the reactant (cementator) with
LEACHING AND CEMENTATION
Yeditepe University
Materials Science and Nanotechnology Engineering Department
MSN 316 – Materials Laboratory Course, Experiment Booklets
Published Version Number / Date Page Numbers
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the reaction product. Material consumption and reaction time can be shortened by activating the solution
and adding the precipitating metal as powder or shavings [3].
3. EXPERIMENTAL PROCEDURE
A certain amount of azurite [Cu3(CO3)2(OH)2] or malachite [Cu2CO3(OH)2] ore will be leached by using
a magnetic stirrer in an H2SO4 solution of appropriate molarity. Parameters such as leaching time,
stirring speed, solid/liquid ratio and molarity may differ for each experiment. At the end of the leaching
operation, solid-liquid separation will be carried out by filtration. Then, cemented copper will be
produced from the copper-saturated leaching solution (leachate, pregnant solution) by the addition of
metallic iron in powder form, and recovery efficiencies from the ore will be calculated.
References
[1] Habashi, F., Principle of Extractive Metallurgy Volume 2, Science Publishers, Paris, 1980.
[2] Metalurji Laboratuarı Deney Föyü, İstanbul Teknik Üniversitesi Metalurji ve Malzeme Mühendisliği
Bölümü.
[3] F.Y. Bor, O. Addemir, İ. Duman, J. U. Fischer, E. Açma, K. Şeşen, İ. Öz, O. Yücel, K. Keskin,
Üretim Metalurjisi Laboratuvarı El Kitabı, İTÜ Kimya-Metalurji Fakültesi Ofset Atölyesi-İstanbul,
1986.
[4] F. Y. Bor, Ekstraktif Metalurji Prensipleri, Kısım II, Teknik Üniversite Matbaası, İstanbul, 1989.
LEACHING AND CEMENTATION
