Cementation

Or contact reduction
 Definition
• Precipitation of a metal from an aqueous solution of its
salts by another metal.
• Since precipitation generally occurs on the surface of
the added metal, it is called cementation.
• The process can be predicted in terms of electrode
potentials.
• The metal with more positive oxidation potential of the
electromotive series will pass into solution and displace
a metal with a less positive potential.
• The basic mechanism is electrochemical in nature.
 Brief mechanism
• The overall phenomenon would comprise of
several steps including non-electrochemical
phenomena such as diffusion processes and
sequential chemical reactions.
• So far as the overall stoichiometry is concerned
the process can be complex;
• Because the reducible ion may be present as
hydrated cations e.g. Cu(H2o2)62+ or complex ions
e.g. Ni(NH3)n2+ , Au(CN)2- etc.
 Electrode Potential and Cementation
• Assuming that the reducing ion is a simple ion(M1Z1+) the
general process for reduction by a metal M 2 is written as
M1Z1+ + z1/z2 x M2 = M1 + z1/z2 x M2z2+ (1)
• The appropriate Nernst equations for the electrode
potentials of metals M1 and M2 respectively are as follows:
E1 = E10 + RT/z1F x lnC10
E2 = E20 + RT/z2F x lnC20
• Where E01 and E02 denote the standard
electrode potentials of M1 and M2 , respectively,
and C10 and C20 denote, respectively, the bulk
concentrations of species M1Z1+ and M2z2+ .
• If E1 is higher than E2 then reaction (1) will be
thermodynamically feasible.
 Electrochemical Mechanism
• Equation(1) , the overall reaction, is actually a summation
of two reactions, viz cathodic and anodic.
• Cathodic reaction: M1Z1+ + z1e- = M1
Anodic reaction : z1/z2x M2 = z1/z2 x M2z2+ + z1e-
• Due to continuous flow of electrons from an ‘anodic’ area
to a cathodic area, the system has a unique electrode
potential E which is less than the equilibrium potential of
the cathode, Ec but greater than the equilibrium
potential of the anode, Ea . E is known as the
compromise potential.
Electrochemical mechanism (cont)
• If the overall reaction is controlled by the slow
cathodic process, then the anode will be essentially
at equilibrium.
• In such a situation , the compromise potential will be
equal to Ea and there will be negligible overpotential
at the anode.
• This is indeed the case in most contact processes.
• Therefore, a better driving force is obtained by using
a reactive metal which would allow a high value of E.
 Practical problems
• Example, in the traditional process zinc is used
to precipitate gold from cyanide solutions.
• The cemented gold contains some zinc which is
easily removed by volatilization.
• Aluminium, although it is placed higher than
zinc in then electrochemical series, is not
preferred due to difficulty in removing
entrapped aluminium.
 Kinetics of Cementation
• Cementation may be mass transfer controlled or chemically
controlled.
• For reaction (1) the rate of reaction is given by the equation
x/V = kc AvC1s
Where kc = Chemical rate constant
Av = Specific interfacial area per unit vol. of interface
C1s = the concentration of M1z+ ions at the interface .
At the steady state per unit volume of solution,
• Rate of mass transfer = Rate of chemical
reaction at the interface hence,
x/V = Av C10 x kc.km /(kc + km)
where km is mass transfer coefficient
 Example
• A copper solution containing 30 kg of Cu/m3 is
being treated by scrap iron to precipitate
copper at room temperature(250C). The
residual solution after copper recovery
contains iron to the extent of 0.5kg/m3 .
Estimate percentage copper recovery.
 Solution
• The cementation reaction is written as
Cu2+ (aq) + Fe = Cu + Fe2+(aq) (2)
At equilibrium
EFe/Fe2+ = ECu/Cu2+ (3)
From Eqs. 2 and 3 and in accordance with Eq.
E1 = E10 +lnC10 x RT/z1..F therefore,
E0Fe/Fe2+ - 1.984 x 10-4 T/2 x log (aFe2+) +
E0Cu/Cu2+ 1.984x 10-4/2 x log (aCu2+)
 Or
0.441- 0.0296logaFe2+ = -0.337- 0.0296logaCu2+

Or
log {aFe2+ / aCu2+ } = 0.778/0.296 = 26.284

i.e.
(aFe2+ / aCu2+) 1026
• This shows that concentration of Cu2+ in the
residual solution is negligibly small and copper
recovery should be almost complete.
(Answer)
 Next lecture

Gaseous reduction of metals from aqueous

solution