Minerals Engineering, Vol. 7, No. 10, pp.

1313-1325, 1994
Copyright~)1994 ElsevierScience Ltd
~ Pergamon Printed in GreatBritain. All rights reserved
0892-6875/94 $7.00+0.00
0892-6875(94)00069-7

THE CEMENTATION OF Ag(I) IONS FROM

AQUEOUS SODIUM CHLORIDE SOLUTIONS

G. PUVVADA and T. TRAN*

Centre for Minerals Engineering, The University of New South Wales
Kensington, N.S.W 2033, Australia
* to whom correspondence should be addressed
(Received 13 December 1993; accepted 28 April 1994)

ABSTRACT

The kinetics of cementation of sih,er chloro-complexes [Ag(1)] from sodium chloride

solutions onto copper and zinc was studied using a rotating disc system. The reduction
potentials for Ag(I)/Ag, Cu(I)/Cu and Zn(II)/Zn couples in chloride solutions were
measured and found to follow the Nernstian relationship. The speciation chemistry of
Ag(l), Cu(1) and Zn(ll) chloro-complexes in concentrated chloride solutions was studied
using CHEMIX computer programme. The cementation of Ag(1) ions, both onto copper
and zinc, was found to follow the first order Mnetics in a two-stage reaction. The
activation energies obtained for Ag(I)/Cu system (in the temperature range 283 - 348K)
were found to be 10.8 kJ/mole and 8.0 kJ/mole its 3M and 4M NaCI solutions,
respectively. Whereas, 30.5 kJ/mole and 22.0 kJ/mole were obtained for Ag(I)/Zn system
its 3M and 4M NaCI solutions, respectively.

Evans diagrams were conso~cted from the current-potential data obtained from the
electrochemical half-cell studies for the deposition of silver onto a glassy carbon electrode
and the dissolution of copper or zinc disc. The rate constants obtained for the Ag(1)/Cu
system were found to be close to the predicted values from Levich's equation, whereas,
higher rate constants were obtainedfor the Ag(l)/'-Znsystem. Scanning electron microscope
studies were conducted to evaluate the deposit mos~ohology on both substrates. The
cementation of Ag(l) ions (chloro-complexes) onto copper was found to be diffusion
controUed and to be both diffusional and smface controlled for zinc.

Keywords
Cementation, Chloride complexes, Reduction potentials, Rate constants, Limiting current
density, Levich equation, Diffusion coefficient and Deposit morphology.

INTRODUCTION

Cementation is the precipitation of a metal by a more electronegative one. These reactions are
electrochemical in nature and can be represented as:

M x" + x N o = XNy" . M o. (1)

Y Y

where M x+ and M o are the ionic and metallic forms of the noble metal and NY+ and N ° are tbr the less
noble metal. Cementation reactions are widely used in hydrometallurgical processing of solution streams
and in recovering precious and base metal values from pregnant leach solutions. In the Cuprex [1] process

1313
1314 G. PUVVADAand T. TRAN

co-developed by Technicas Reunidas and ICI, the recovery of silver from copper chloride leach liquors
was conducted via zinc cementation.

The kinetics of cementation of uncomplexed silver ions onto rotating discs of zinc and ferrous alloys was
studied by Mathes and Lawson [2]. They found that the rate of deposition of silver onto zinc was limited
by its diffusion to the zinc surface, whereas, the reaction of silver with ferrous alloys was found to be
controlled by both mass transfer and surface chemical processes. The apparent activation energies were
reported to be 15.5 kJ/mole and 17.6 kJ/mole for zinc and iron, respectively. Morrison et al [3] studied
the cementation of silver ions (chloro-complexes) onto rotating copper and lead discs and reported the
activation energies to be 10.0 kJ/mole and 19.2 kJ/mole for Cu and Pb discs, respectively.

The rotating disc electrode system has been used widely in the investigation of cementation reactions. This
is not only due to the advantage of reproducible hydrodynamics, but also due to its simplicity, The
cementation of copper [4], cadmium [5], silver [6-8], gold [9-1 I] etc onto various substrate materials were
investigated using different techniques like rotating disc electrode system, rotating cylinder and zinc dust
cementation. In almost all cases these reactions were found to follow the first order reaction kinetics and
in most cases the initial reaction rate changed after an initial period. The first order rate expression[121
for the cementation of Ag(I) (Ag(I) denotes silver chloro-complexes) onto copper or zinc disc is given as:

In [Ag(I)], = _kcA t (2)

[AGO)]° Vo
where

[Ag(I)] o = Initial concentration of silver ions, mole/l

[Ag(I)] t = Concentration of silver at time t, mole/l
A = Surface area of the disc, cm 2
V o = Initial volume of the solution, cm 3
t = Time, see
k e = Cementation rate constant, cm/s

Under laminar flow conditions set up by the rotating disc, the cementation rate constant can be predicted
from the well known Levich equation [13] as:

kp = 0.62 D 2/3 w 1/6 ~1/2 exp {-Ea/R[I/T-1/298]} (3)

where

D = Diffusion coefficient of Ag(I) at 298 K, cm2/s

u = Kinematic viscosity of the solution at 298 K, cm2/s
co = Angular velocity, rad/s
R = Gas constant, J/K mole
T = Temperature, K
E a = Activation energy for the cementation process, kJ/mole

The kinetics of a cementation reaction can also be studied by measuring the changes in current with
respect to an applied potential on the two half-cells (cathodic and anodic) separately. Since cementation
reaction is considered a deposition (cathodic) process coupled with dissolution (anodic) process, it may
be evaluated by using Evans diagrams. The intersection of the two polarization curves on an Evans
diagram determines the cementation current density and the cementation potential. These diagrams
demonstrate clearly whether the cementation reaction is controlled by an electrochemical kinetic step (if
the intersection point is in the Tafel region) or by a mass transfer (diffusion) controlled mechanism (if the
intersection point is in the diffusion controlled region) [13]. The Levich equation [14,15] used to calculate
the limiting current density for a reduction reaction using a rotating disc electrode system is given a s :
 Cementation of Ag(I) ions 1315

IL=0.62 n F A D 2/3 v 1/6 co1/2 C (4)

where

IL = Limiting current, mA
A = Cathodic area, cm 2
n = Number of electrons involved
F = Faraday constant, 96,486 coulomb/mole
C = Concentration of the reducing species, mole/1

and the rest as explained before.

In this study the electrochemical half-cell reaction for Ag(I) reduction on to a glassy carbon electrode was
investigated at different temperatures, NaCI concentrations and rotation speeds. The limiting currents
obtained at different rotation speeds for each variable were plotted and the diffusion coefficients were
calculated from the slopes of such plots. The diffusion coefficients obtained at different temperatures and
NaCI concentrations are plotted (as Arrhenius plots) to calculate the diffusional activation energy Ea,
which in turn is used in Equation (3) in order to predict the cementation rate constants (kp).

EXPERIMENTAL METHOD

Reagents
A stock solution of 1000 ppm Ag(I) was prepared from analytical grade BDH AgNO 3, and 99% NaCI
was used for the preparation of the background electrolyte.

Apparatus
The reduction potentials for the couples Ag(I)/Ag, Cu(I)/Cu and Zn(II)/Zn were measured at different
concentrations in a 3M NaCI solution using the respective electrodes against a standard calomel electrode
(SCE).

The cementation of Ag(I) ions onto rotating copper or zinc discs (3 cm dia) was carried out in a 2 litre
glass reaction vessel which was immersed in a water bath to control the temperature. The disc was placed
in a bell shaped resin holder mounted on a rotating titanium shaft which could be rotated up to 2000 rpm.
The discs were polished at 600 and then 1200 grit before each experiment. The reaction vessel had a lexen
top through which a standard calomel electrode (SCE), sampling port, gas inlet, etc. were located. Before
the start of each experiment, the solution pH was adjusted to 2.0 and the solution was deoxygenated with
high purity nitrogen gas at a moderate pressure. The samples taken at different time intervals were
analysed for silver using a Varian AAS 20 atomic absorption spectrometer.

The half-cell reactions (Ag(I)/Ag, Cu(I)/Cu and Zn(II)/Zn) were studied using Pine Instrument RDE
system connected to a YEW 3086 XY recorder. The reduction of silver was studied using a glassy carbon
disc (0.7cm dia). A SCE and carbon electrodes were used as reference and counter electrodes,
respectively.

RESULTS AND DISCUSSION

ThermodynamicStudy
Cementation is the precipitation of cations of a more noble metal onto a relatively less noble metal
precipitant. Prior to the kinetic study of the cementation reaction it was necessary to conduct

ME 7-10-1t
1316 G. PUVVADA and T. TRAN

thermodynamic study to establish the potential differences between the two half cells involved in the
process. According to Power and Ritchie [ 14], a minimum potential difference (AE) of 0.36V is required
for a cementation reaction to be diffusion controlled. Since silver, copper or zinc are present in the
aqueous chloride solutions as chloro-complexes, the predominant species are modelled using CHEMIX
[16], a computer software which determines the stability of a particular system based on the minimisation
of the total free energy of the system.

Effect of Metal Ion Concentration on the Reduction Potentials

The reduction potentials for Ag(I)/Ag, Cu(I)/Cu and Zn(II)/Zn couples were measured in a 3M NaCI
solution, 20°C and pH 2.0 at different metal ion concentrations. The potentials measured for the Ag(I)/Ag
system were found to shift from + 0.009V to + 0.068V by increasing the concentration of Ag(I) from 20.0
ppm to 150.0 ppm. Whereas, the shift was observed from -0.219V to -0.147V and from -1.028V to -
0.990V, respectively, for copper and zinc redox couples by increasing the Cu(I) or Zn(II) concentration
from 1.0 g/1 to 20.0 g/l. The measured reduction potentials are plotted with the predicted values (Figure
1) showing that the three systems follow close to the Nerstian relationship. The AE values obtained for
Ag(I)/Cu and Ag(I)/Zn systems consisting of 30 ppm Ag(I) and 1.0 g/l Cu(I) or Zn(II) in a 3M NaCI
solution at 20 ° C were found to be 0.225V and 1.052V, respectively.

200

0
Ag(I)/Ag
-200
Cu(I)/Cu
L) -400

-600
@ Measured
-800
O Predicted

-1000
3M NaC1
Temp = 20 C Zn(II)/Zn
-1200 pH = 2.0

-1400 . . . . . . . . i . . . . . . . i . . . . . . . . i . . . . . . . .

10 100 1000 10000 100000

Concentration (ppm)

Fig. 1 Measured electrode potentials of various redox couples

vs predicted values from Nernst equation

The reactions considered in predicting the reduction potentials using the Nernst equation for the Ag(I)/Ag,
Cu(I)/Cu and Zn(II)/Zn couples are given below:

AgCI32" + e'=Ag + 3C1- (5)

CUC132- + e-=Cu + 3C1" (6)

ZnCI 3" + 2e'=Zn + 3C1- (7)

and the Nemst equation used in calculating the theoretical values for the above three reactions is given
below:

E = E ° - 2.303 RT/nF {log [oxidant]/[reductant]} (8)

 Cementation of Ag(I) ions 1317

where

[ ] = activity
E = emf of the cell
E ° = standard reduction potential
R = gas constant, 8.314 J/mole
T = temperature, K
n = number of electrons involved
F = Faraday constant, 96486 coulomb/mole

Modelling of Speciation Chemistry using CHEMIX

The concentration profile of various chloro-complexes of silver, copper and zinc at different CI-
concentrations was modelled using the CHEMIX [16] computer programme. The distribution of silver,
copper and zinc chloro-complexes at different chloride concentrations are given in Figures 2, 3 and 4,
which are modelled at 11.2 mg/1 of 02 and 5.6 mg/l of N 2 levels in the gaseous phase of the systems.
Table 1 summarizes the free energy data (from NBS Thermodynamic Data) of major silver species for
the modelling. Others are extracted from data files from CHEMIX.

100 "
[Ag(I)] = 102.58 p p m X AgCI (aq)
90-
O AgCI2 (aq)
80" • AgCI ~" (aq)
70- + AgCI 3- (aq)
• AgCI (s)
60"

50'
et)
.<
40'

30"

20'

10"

0 1 2 3 4 5 6
[CI" ] M

Fig.2 Equilibrium concentration profiles of silver chloro-complexes at different CI" concentrations

at room temperature, 02 = 11.2 mg/l, [Ag(I)] = 102.58 ppm

100'
[Cu(1)] = 1016.8 ppm + Cu (II)(aq)
90" Temp = 25 C; O 2 = 11.2 rng/l O CuCI + (aq)
80" • CuCI2 (aq)
70" El CuCI ~" (aq)
• CuCI~" (aq)
60'

50.

40"

30'

20"

10"

1 2 3 4 5 6
1C1"] M

Fig.3 Equilibrium concentration profiles of copper species (chloro-complexes) at different

CI- concentrarions at room temperature, 02 = 11.2 rag/l, [Cu(I)] = 1016.8 ppm
1318 G. PUVVADA and T. TRAN

100
+ Zn(ll) (aq)
[Zn(II)] = 1000.31 ppm
90 0 2 = 11.2 mg/1 0 ZnCI + (aq)

80 ZnCI 2 (aq)
[] ZnCI 3 (aq)
70
2-
ZnCI 4 (aq)
60
50
N
40
30 ¸
20"
10-
I w w v m
w ~ -- __ _ _

0 I i i | •

0 1 2 3 4 5
[CI-IM

Fig.4 Equilibrium concentration profiles of zinc species (chloro-compleses at different CI-

concentrations at room temperature, O 2 = 11.2 mg/1, [Zn(II)] = 1000ppm

T A B L E 1 Free energy data used in the modelling study.

Species AG°f (k J/
mole)
Ag+aq 77.107
AgClaq -72.8
AgCl2-aq -215.2
AgC132-aq -349.16
AgC143- -472.92
AgOH -92.0
Ag(OH) 2- -260.20
AgCl(s) -109.79

As shown in Figure 2, the weight percentages of silver chloro-complexes with respect to an initial Ag(I)
concentration of 102.6 ppm are plotted against the chloride concentration ranging from 1M to 5M. At 1M
chloride concentration, 85 % of silver was found to be insoluble in the form of AgC1 solid, 10 % was found
to exist as AgCI32-, 4% as AgCI 2- and 1% as AgCI43-. Increasing the chloride concentration to 2.5M
resulted in an increase in the weight percentage of AgCI32- to 70 %, whereas, AgCI 2- and AgCI43" are
found to be 7.5% each. At 3M CI- concentration AgC1 solid was found to be completely soluble, out of
which 82% was found to be AgC132-. At 5M CI" the weight percentage of AgCI43- increases to 17%.

The percent distribution of Cu(I) in chloride solutions is modelled at an initial input of 1017 ppm as
shown in Figure 3. The Cu(I) was found to exist predominantly as CUC132-, and its weight percentage
increased from 71% to 80% by increasing the chloride concentration from 1M to 5M. And the second
major component was found to be CuCI +, which is around 15 %. The presence of CuCI 2- was found to
decrease from 10% to 1% by an increase in chloride concentration from 1M to 5M.

The distribution of Zn(II) in chloride solutions is modelled at an initial input of 1000 ppm. At 1M chloride
concentration ZnCI 3- and Zn(II) are found to present at 40% each, and ZnCI + is at 12% with minor
 Cementation of Ag(I) ions 1319

amounts of ZnCI 2 and ZnCI42-. Increasing CI" concentration to 2.5M increased ZnCI 3- weight percentage
from 40 % to 75 %, with a decrease in Zn(II) weight percentage from 40 % to 5 %. The weight percentage
of ZnCI42" increased from 4% to 30% by increasing CI concentration from 1M to 5M. However, ZnCl 3-
was found to be the most predominant in concentrated chloride solutions as shown in Figure 4. Therefore,
the cementation reaction between Ag(I)/Cu and Ag(I)/Zn systems in concentrated chloride solutions can
be represented as:

AgC132- + Cu=Ag + CuCI32- (9)

AgC132- + Zn= Ag + ZnCI 3- (10)

Kinetic Study

Effect of Temperature

Experiments were conducted at different temperatures ranging from 10°C to 75°C at 30 ppm initial Ag(I)
concentration, 800 rpm, initial pH 2.0, both in 3M and 4M NaCI solutions using copper and zinc discs.
The reaction was found to follow the first order kinetics as shown in Figure 5, for both substrates with
an increase in rate as the temperature is increased. At all temperatures, the reaction rate was found to
increase after an initial period (45 mins for copper and 30 mins for zinc). Therefore, the initial and final
rates are said to be stage 1 and stage 2 rates of the cementation reaction, respectively. At 10°C the stage
2 rate constants obtained on copper are found to be lower than the respective stage 1 rate constants due
to change in deposit morphology to be discussed later.

0.0
'gg8 •
14 o o
Q
o o o
-0.1
• g
-0.2

"-6 -0.3
v
-0.4

,,- -0.5

< -0.6
o 10CCu
,.d -0.7 • 10CZn
-0.8 [] 45CCu
I 3M NaCI I
-0.9 • 45CZn 800 rpm

-1.0 . . . . , . . . . , . . . .
0 50 100 150
Time (rain)
Fig.5 Variation of log {[Ag(I)]t/[Ag(I)]o} ratio with time for copper and zinc
discs at different temperatures in a 3M NaC1 solution

The cementation rate constants (ke) of stage 1 obtained from the slopes of the first order kinetic plots
(Figure 5) using equation 2 are plotted against 1000/T (K) as shown in Figure 6. The activation energies
obtained from the slopes of the Arrhenius plots are found to be 10.8 kJ/mole and 8.0 kJ/mole for
Ag(I)/Cu system in 3M and 4M NaCI solutions, respectively. Whereas, 30.5 kJ/mole and 22.0 kJ/mole
are obtained for Ag(1)/Zn system in 3M and 4M NaCI solutions, respectively. The reaction rate constants
and the activation energies are found to decrease with an increase in NaCI concentration for both the
systems.
1320 G . PUVVADA a n d T. TRAN

-1.0

O 3M NaCICu
• 3M NaCIZn
-1.5' I"1 4M NaCICu

-2.0"

-2.5"

-3.0 , , ,
2.8 3.0 3.2 3.4 3.6
1000IT

Fig.6 Arrhenius plot showing the effect of temperature on the stage 1 cementation rate constant 1%(I)
for copper and zinc discs, (30 ppm Ag(I), 800 rpm)

According to Miller [17] the activation energy for a diffusion controlled reaction is from 8.4 kJ/mole to
25.1 kJ/mole. The activation energies obtained for both systems are within the range for a diffusion
controlled reaction, except at 3M NaC1 for the Ag(I)/Zn system, which is slightly higher. The rate
constants obtained for the Ag(I)/Zn system are found to be higher than the rate constants for the Ag(I)/Cu
system at moderate and higher temperatures. However, at lower temperatures (10°C) the rate constants
obtained for the Ag(I)/Zn system are found to be lower than for the Ag(I)/Cu system. These differences
will be explained later in surface studies.

Effect of Disc Rotation Speed

A convenient way to express whether a heterogeneous reaction is mass transfer controlled is to observe
the change in the reaction rate as the disc rotation speed is changed. Experiments were conducted at
different disc rotation speeds ranging from 200 to 1500 rpm (i. e., 20.9 to 157.1 rad/s) at 30 ppm initial
Ag(I) concentration, 30°C and 3M NaCI for both the systems. The rate constants of stage 1 and stage 2
obtained are plotted against the square root of angular velocity w, along with the theoretical values as
shown in Figures 7 and 8.

0.04"
3M NaC1
30 ppm Ag(I)
30C
0.03' ..... Theoretical O

stage 2
E
0.02"

stage 1 •
0.01" O

•4 .... g
0.013
4 6 8 10 12 14
1/2 1/2
CO ( r a d / s )

Fig.7 Effect of rotation speed on the cementation rate constants stage 1 and stage 2, Ag(I)/Cu
 Cementation of Ag(I) ions 1321

0.05
3M NaCI stage 2
30 ppm Ag(I) O
30 C O
0.04
.... Theoretical
A

E
0.03
E o •
stage 1
0.02
v

0.01
• __j_--v--'"
.-."1-

0.00 . . . .
4 6 8 10 12 14
1/2 1/2
co (rad/s)

Fig.8 Effect of rotation speed on the cementation rate constants stage 1 and stage 2, Ag(I)/Zn

The theoretical values were calculated from the limiting current densities obtained for Ag(I) reduction
from the electrochemical half-cell studies using Equations 3 and 4. The initial rate constants (stage 1) were
found to follow closely the predicted values for the Ag(I)/Cu system (Figure 7), whereas, the Ag(I)Zn
system followed the predicted values up to 800 rpm indicating a mass transfer controlled mechanism and
significantly higher rate constants than the predicted values were obtained at 1000 and 1500 rpm (Figure
8). These higher values obtained at higher rotation speeds could be attributed to the changes in the initial
deposit morphology at these speeds. The stage 1 and stage 2 rate constants obtained using zinc are found
to be higher than copper.

Electrochemical Half-Cell Studies

The two half cell reactions involved in the cementation of Ag(I) ions onto copper or zinc (i. e., the
reduction of Ag(I) ions and the oxidation of copper or zinc) were studied separately using rotating disc
systems. The current-potential data obtained from the polarization curves for both Ag(I) reduction and
copper or zinc oxidation were used to construct Evans diagrams. The effect of NaCI concentration and
temperature on the reduction of Ag(I) ions are studied. The limiting currents obtained at different disc
rotation speeds on a glassy carbon electrode ranging from 100 to 1200 rpm are plotted against the square
root of angular velocity w and the slopes obtained were used in Equation (3) inorder to calculate the
diffusion coefficient (D) values.

Thus obtained D values are plotted in an Arrhenius plot as shown in Figure 9, from which slopes the
diffusional activation energies (Ea) were calculated. The diffusional activation energies obtained in 3M
and 4M NaCI solutions are found to be 20. I U/mole and 22.1 U/mole, respectively. The diffusion
coefficients were found to increase with an increase in temperature and decrease with an increase in NaCI
concentration.

Using the diffusion coefficients (D) and the diffusional activation energies (Ea) from Equation (3) the
predicted cementation rate constants (kp) were calculated and plotted against the experimental rate
constants 1% (stage 1) as shown in Figure 10, (also given in Table 2). The Ag(I)/Cu system was found
to be close to the predicted values, whereas, for the Ag(I)/Zn system it was found that at moderate
temperatures and disc rotation Speeds the predicted rate constants are close to the experimental values.
At higher temperatures and disc rotation speeds the k¢ values are found to be higher than the k_ values.
This is due to the structural changes in the deposit morphology at these conditions affecting tee initial
rates.
 1322 G. PUVVADA and T. TRAN

-4.6

-4.8'

-5.0'

0
,.d

-5.2

-5.4
2.9 3.0 3.1 3.2 3.3 3.4 3.5
1000IT
Fig.9 Arrhenius plot showinf the effect of temperature on the diffusion coefficient
of silver chloro-complexes at different NaCI concentrations

0.05

0.04' o

"" 0.03'

ta ° °

0.02

° 0 0 - - _ _

0.01

~ l • • copper

0.00 I I I I

0.00 0.01 0.02 0.03 0.04 0.05

K p (cm/s)

Fig. 10 Cementation rate constants Measured vs Predicted (kc vs kp)

for copper and zinc discs at different variables

The Evans diagrams constructed from the polarization curves obtained for Ag(I) reduction onto a glassy
carbon electrode and for the oxidation of copper or zinc at different temperatures in a 4M NaCI solution
is shown in Figure 11. Increasing temperature resulted in an increase in the limiting current density for
Ag(I) reduction and little effect on the dissolution of copper or zinc was found. However, the oxidation
rest potentials were found to shift negatively from -310V to -420V by increasing the temperature from
20°C to 40°C for Cu(I)/Cu couple and for Zn(II)/Zn couple the shift was found to be minimal. The rest
potentials obtained in this study are in agreement with the measured reduction potentials as shown in
Figure 1. It is evident from this figure that the polarization curves for the Ag(I)/Cu system intersect in
the diffusion control region for Ag reaction and for the Ag(I)/Zn system they intersect in the hydrogen
evolution region.
 Cementation of Ag(I) ions 1323

T A B L E 2 Rate constants determined from cementation experiments (kc at 30 rains)

and as predicted from electrochemical measurements (kp) at 3M NaCI.

Sl. No [Ag(I)] Rotation Temp k¢ × 10-~ k e × 10-~ kp x 10-3

(ppm) speed (rpm) (K) (era/s), Cu (era/s), Zn (cm/s)
1 30 200 303 2.'77 6.13 3.10
2 30 500 303 3.26 6.84 4.91
3 30 800 303 5.59 7.22 6.21
4 30 1000 303 9.01 11.9 6.94
5 30 1500 303 10.9 25.5 8.50
6 30 800 283 4.67 3.31 2.80
7 30 800 303 5.59 7.22 4.92
8 30 800 318 7.44 15.00 7.17
9 30 800 333 9.28 19.30 10.10
10 30 800 348 10.5 40.20 13.80

0 20.0 C
-200 Ag(I)+e = Ag • • 30.0 C

[] 40.0 C
-400 • 51.0C
Cu = Cu(I)+e ooom
t~
-600 ~0 •
oo[]m
-800
W,'- •
O@ []
-1000
_ A A
¢~ [] ~ ~ _,~.r~ -~..

-1200 t Zn = Zn(II) + 2e

-1400 ! . . . . . . . . ! . . . . . . . . | . . . . . . . .

.01 .1 1 10
Current density (mA/cm 2 )
Fig. 11 Evans diagram showing the effect of temperature on the polarization curves
for Ag(I)/Cu and Ag(I)/Zn systems, (lAg(I)] = 75 ppm, 4M NaCI, 800rpm)

Surface Studies

Scanning electron microscope studies were conducted to evaluate the morphology of silver on copper and
zinc discs. The two stage deposit morphology is evident on both substrates. Photomicrographs shown in
Figure 12, were taken at 3M NaC1, 800 rpm, 30 ppm initial Ag(I) for both copper and zinc substrates
at two different temperatures. Photomicrographs (a) and (b) are taken at 10°C and 45°C, respectively,
for copper, where, initial smooth, coherent deposit followed by minor growth of dendrites is evident at
10°C, resulting in a decreased rate during stage 2. At 45°C the dendritic growth is found to be more
predominant with tree-like structure, causing an increased cathodic surface area and thereby, resulting in
an enhanced stage 2 rate constant.

Photomicrographs (c) and (d) were taken at 10°C and 45°C, respectively for zinc. At 10°C the initial
deposit is found to be loose and less coherent in nature with some minor secondary dendritic formation.
At these conditions the rate constants obtained for the Ag(I)/Zn system are lower compared to those of
the Ag(I)/Cu system. At 45°C, the loose secondary dendritic formation is found to be predominant,
1324 G. PUVVADA and T. TRAN

spreading across the disc surface and these differences in the deposit morphology between copper and zinc
discs are the cause for the differences in the cementation rate constants. Therefore, a prediction of
cementation rate constants using the electrochemical model is valid at certain conditions only.

a b

c d
Fig. 12 Photomicrographs taken by scanning electron microscope showing the effect of temperature on
silver cementation onto copper and zinc surface, Ag(I)/Cu, (a) 10°C, (b) 45°C, at 3M NaCI, 800 rpm,
30 ppm initial Ag(I); Ag(I)/Zn, (c) 10°C, (d) 45°C at 3M NaC1, 800 rpm, 30 ppm initial Ag(I)

CONCLUSIONS

The reduction potentials measured tbr Ag(I)/Ag, Cu(1)/Cu and Zn(II)/Zn couples in concentrated chloride
solutions were found to tbllow the Nerstian relationship and the predominant species of Ag(I), Cu(I) and
Zn(II) in concentrated chloride solutions are found to be AgCI32-, CUC132- and ZnC13-, respectively.

The cementation reaction for the Ag(I)/Cu and the Ag(I)/Zn systems is found to follow first order kinetics
with a two stage reaction at all conditions. At moderate temperatures and rotation speeds the rate constants
obtained using zinc are found to be higher than for copper, but at lower temperatures zinc resulted in
lower rate constants compared to copper. The activation energies obtained for the Ag(I)/Cu system for
both 3M and 4M NaC1 solutions are found to be within the diffusion controlled region. The activation
energy obtained tbr the Ag(I)/Zn system at 4M NaCI was found to be within the diffusion controlled
region, but at 3M NaC1 a slightly higher activation energy was obtained.
 Cementation of Ag(I) ions 1325

On Evans diagrams, polarization curves obtained for the deposition of silver and the dissolution of copper
or zinc in 4M NaCI solution were found to intersect in the diffusion control region for the Ag(I)/Cu
system and in the hydrogen evolution region for the Ag(I)/Zn system. The cementation rate constants
predicted from the electrochemical half-cell studies are found to be close to the real system only at
moderate temperatures and rotation speeds, which is due to the influence of the deposit morphology on
the cementation rate constants, both inhibiting and enhancing depending on the experimental conditions.
Based on the results obtained from this study it is conclusive that the cementation of Ag(I) ions onto
copper from chloride solutions is found to be diffusion controlled and onto zinc is both diffusional and
surface controlled.

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