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Hydrometallurgy 76 (2005) 193 205 www.elsevier.

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The effect of cyanide and lead ions on the cementation rate, stoichiometry and morphology of silver in cementation from cyanide solutions with zinc powder
G. Viramontes Gamboaa, M. Medina Noyolaa, A. Lo pez Valdiviesob,*
Instituto de F sica bManuel Sandoval VallartaQ, Universidad Auto noma de San Luis Potos , Av. Manuel Nava 6. San Luis Potos , S.L.P. 78210, Mexico b Instituto de Metalurgia, Universidad Auto noma de San Luis Potos , Av. Sierra Leona 550 San Luis Potos , S.L.P., Me xico, 78210, Mexico Received 3 October 2003; received in revised form 3 August 2004; accepted 3 November 2004
a

Abstract The cementation of silver on zinc powder from solutions with a wide concentration range of cyanide has been investigated in the absence and presence of lead ions through stirred reactor batch tests and scanning electron microscopy studies on the cementation product. The concentration of cyanide ions affected the morphology of the product, the nature of cementation reaction and the cementation kinetics. Three cyanide-dependent concentration regimes have been identified: a low cyanide concentration regime in which silver cementation followed an ion-exchange type reaction taking place at the zinc/aqueous solution interface, and the silver deposited around the zinc particle in a uniform growth; a high cyanide concentration regime, as in plant practices, in which the cementation of silver followed an overall chemical reaction involving the evolution of hydrogen and a one-to-one molar silver-to-zinc stoichiometry (In this regime, both the anodic oxidation and the cathodic reduction reactions occurred at distinct interfaces and the silver deposited in a dense-branching morphology.), and an intermediate cyanide concentration regime which is a transition between the two previous regimes. In the low and intermediate regimes, lead and cyanide ions did not affect the morphology of the cemented silver, but increased the silver cementation kinetics owing to Zn(OH)2 instability. Within the high cyanide concentration regime, lead ions did not appreciably change the cementation kinetics. They modified the pattern of the silver deposit from a dense-branching to a dendritic morphology. D 2005 Elsevier B.V. All rights reserved.
Keywords: Cementation rate; Silver recovery; Zinc cementation; Lead effect; Cyanide solutions

1. Introduction
* Corresponding author. Tel.: +52 444 825 5004; fax: +52 444 825 4326. E-mail address: alopez@uaslp.mx (A. L. Valdivieso). 0304-386X/$ - see front matter D 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.hydromet.2004.11.005

The Merrill-Crowe process to recover gold and silver from cyanide-leach liquors has been widely used around the world since its introduction at the end

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of 19th century. Although the chemistry of the process is in general well understood, there are some related questions not answered yet or at least not sufficiently understood such as the origin of the different effects of lead ions in the cementation process. Nowadays there is no consensus on the mechanisms by which lead ions not only perform catalytic effects, but also induce morphological transitions and depolarization effects. In the case of gold cementation, when lead ions are adequately added a considerable number of effects has been reported, such as an increase in the cementation rate (Miller et al., 1990), displacement in the overpotential for the evolution of hydrogen (Kirk and Foulkes, 1984; Nicol et al., 1979; Oo and Tran, 1991; Parga, 1987), inhibition to the passivation of the zinc particles due to the formation of Zn(OH)2 (Miller et al., 1990; Oo and Tran, 1991; Parga, 1987), and a change to a more highly porous deposit (Oo and Tran, 1991). The main beneficial effects of lead ions in silver cementation have been reported to be on the catalysis of the cementation rate (Miller et al., 1988; Parga, 1987; Parga et al., 1988), the increase in the zinc solubility (Chi et al., 1997), and the formation of dendritic morphologies (Miller et al., 1988; Parga, 1987; Parga et al., 1988). The first improvement to the Merril-Crowe process was the addition of lead salts to the pregnant solution in 1894 (Leblanc, 1942), even before the change of zinc shavings to zinc powder in 1897. Most of the research work in the literature related to the effects caused by lead ions on precious metal recovery is devoted to the gold system (Chi et al., 1997; Dorr and Bosqui, 1950; Finkelstein, 1972; Flemming, 1992; Hamilton, 1950; Kirk and Foulkes, 1984; Lawson, 1985; Leblanc, 1942; McIntyre and Peck, 1976; Miller et al., 1988, 1990; Nicol et al., 1979; Oo and Tran, 1991; Parga, 1987; Paul, 1986; Paul and Howarth, 1986). The beneficial role of lead ions has been associated to different causes. The first refers to the formation of zinclead galvanic couples. As lead ions can be reduced at the zinc surface, it is thought that they form cathodically charged areas of metallic lead where gold and silver cyanide species are reduced preferentially. This prevents the entire surface of zinc from becoming completely coated by non-porous silver or gold (Chi et al., 1997; Dorr and Bosqui, 1950; Finkelstein, 1972; Oo and Tran, 1991).

The beneficial effect of lead ions has also been related to zinc solubility, which has been reported to depend considerably on the lead ion concentration in the cyanide solution. Chi et al. (1997) have shown that zinc solubility has a maximum when lead nitrate is added at 1015 mg/l in the cyanide concentration range of 0.1 to 0.3 g/l NaCN. They found that lead ion reduction on the zinc surface enhances zinc dissolution, thus promoting the kinetics of precious metal recovery. These authors ascribed the detrimental effect of excess lead ion addition to the excessive coating of zinc particles by metallic lead. Parga (1987) has shown that lead ions affect mainly the anodic dissolution of zinc without any appreciable changes to the cathodic reduction of silver. On the other hand, Oo and Tran (1991) reported that lead ions affect only slightly the zinc dissolution rate at different gold concentrations. Another well-known beneficial effect of lead ions that has been reported is their ability to prevent the passivation of the zinc surface due to the formation of Zn(OH)2 at low cyanide concentrations, mainly in the gold case. Miller et al. (1990) have explained that the presence of lead ions and their adsorption at the zinc surface may reduce the surface concentration of zinc in the anodic interfacial region and decrease proton reduction. Thus, reducing the tendency for zinc hydroxide to form. Finally, the role of lead ions has been associated with their effect on the overpotential for the reduction reactions of both gold and water. It has been found that in the absence of lead ions, both reduction reactions occur simultaneously (Barin et al., 1980; Dorr and Bosqui, 1950; Kirk and Foulkes, 1984; Nicol et al., 1979; Oo and Tran, 1991; Parga, 1987). Oo and Tran (1991) reported that the addition of lead ions up to 3 mg/l drastically shifted the kineticcontrolled region of cathodic gold deposition to a more anodic direction. Above this lead ion concentration, no further changes were observed in the region of gold deposition. Understanding the origin of the effects of lead ions has been a highly involved subject for optimizing the Merril-Crowe process. In their comprehensive study on gold recovery from cyanide solution, Nicol et al. (1979) have shown that the addition of about 5 mg/l lead nitrate to a gold-bearing solution having 5 mg/l gold increases the cementation rate by approximately

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30%. If lead nitrate is added to gold-bearing solutions with 0.02 to 0.55 mg/l, it inhibits the cementation reaction, however. Paul (1986) has stressed that with barren solutions having gold concentrations higher than 15 mg/l, lead nitrate addition is unnecessary, and for solutions of a few hundred mg/l gold only slight improvement in gold recovery was observed with lead additions of 6 mg/l at 50 8C (Paul and Howarth, 1986). These results show that it is difficult to make a proper estimation a priori about the pertinent lead ion concentration to be used in a plant operation. Studies on the cementation of silver on zinc powder from cyanide solutions are less abundant than for the gold case (Parga, 1987). In some aspects, the two systems behave similarly. For example, the catalytic and depolarization effect caused by lead ions turn out to be quite similar. Some differences have been observed, however. The addition of lead ions induces silver to cement as complex branched or dendritic structures, which does not happen to gold cementation. Electrochemical reduction of Au(CN)2 ions is usually coupled with the evolution of hydrogen (Barin et al., 1980; Dorr and Bosqui, 1950; Kirk and Foulkes, 1984; Nicol et al., 1979; Oo and Tran, 1991; Parga, 1987), which has not been detected for the case of silver (Parga, 1987). Particle aggregation at the scale of millimeters has been observed in the gold system by Miller et al. (Miller et al., 1988; Parga, 1987), whereas this occur only for a small number of particles in the silver system. The presence of lead ions in silver liquors has been found to affect the structure and morphology of cemented silver in plant operation; lead addition increases the porosity of the silver cake and the pressure across the plate-and-frame filter press drops. It is also believed that there is a decrease in the retention time of the liquor in the filter press due to the ability of lead ions to enhance the cementation reaction kinetics and to affect the cake porosity (Parga et al., 1988). With regards to the effects of cyanide ions on silver and gold cementation, the main difference between the two systems is that for gold, the cementation kinetics increases as the cyanide ion concentration increases. In the silver system, increasing the cyanide concentration beyond a certain value decreases the cementation rate, which has been explained to be due to the stability and

2 low diffusion coefficient of Ag(CN)3 complexes at high cyanide concentrations (Miller et al., 1988, 1990; Parga, 1987). This work is aimed at looking at the effects of both lead and cyanide ion concentration on the cementation of silver from cyanide solutions using zinc powder in order to shed more light on the underlying mechanisms of silver cementation in the Merrill-Crowe Process. Novel results relating lead and cyanide concentration with the morphological, kinetics, and chemical aspects of the cementation process are reported.

2. Experimental The cementation tests were carried out in a 2.5 l glass reaction vessel immersed in a temperature controlled water bath. The vessel had openings to introduce a dispersion tube for highly purified nitrogen, pH and dissolved O2 electrodes, a funnel to pour zinc powder or withdraw solution samples, and a central opening used to fix a screwed propeller to stir the solution at a controlled speed of 500 rpm. All experiments were performed at 25 8C. Analytical grade AgNO3, NaCN and Pb(NO3)2 reagents were used to prepare all solutions in deionized water. Dilute NaOH and HNO3 solutions were used to fix the initial pH at the desired value of 10.8. The silvercyanide solutions were purged with oxygen-free highly pure N2 to remove oxygen from the solution. The nitrogen was passed through a pyrogallol solution before it was bubbled into the solution. Most experiments were carried out using an initial silver concentration of 0.927 mM and a zinc powder with a BET surface area of 0.1494 m2/g. A given amount of zinc powder was added once the oxygen level in the solution was below 0.2 mg/l. Any other silver or zinc concentration will be explicitly indicated in the text when necessary. As cementation took place, the pH was continuously monitored and 10 ml samples were withdrawn from the reactor at different times. These samples were filtered using a 0.22 Am pore size filter, titrated for free cyanide, and assayed for zinc, silver and lead using an atomic absorption spectrophotometer. At the end of the cementation tests, the products were collected through filtration, observed and analyzed using a Phillips XL

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30 scanning electron microscope with accessories for chemical analysis.

3. Results and discussion The effect of cyanide ion concentration on the cementation of silver on zinc is discussed first, followed by that due to the addition of lead nitrate. In the text below, the various cyanide concentrations are indicated as [NaCN]0 /[Ag]0 , where [NaCN]0 and [Ag]0 are the total initial cyanide and silver concentration in mol/l, respectively. The initial silver concentration was fixed at 0.927 mM, while that of cyanide was varied so that a wide range of [NaCN]0 / [Ag]0 ratios could be studied by increasing the cyanide concentration. Three cyanide concentration regimes have been characterized as will become clear below. A low cyanide concentration regime given by [NaCN]0 /[Ag]0 ratios slightly larger than 2, where free cyanide ions are beginning to be significant in solution; a high cyanide concentration regime occurring at [NaCN]0 /[Ag]0 ratios larger than 8; and finally, an intermediate cyanide concentration regime at ratios between 2 and 8. These values represent adequate approximations to distinguish diffuse limits between the different mechanisms that have been identified for the cementation of silver. With regards to the cemented silver distinct morphologies have been observed and for a clearer discussion it has been necessary to classify them as: (1) a uniform growth,

which means that silver has grown outward in an approximately spherical form around the zinc particle; (2) a dense-branching morphology, which means that silver has grown outward, in a branched fashion like the tip-splitting dynamics process as has been described for a two-dimensional case by Ben-Jacob and Garik (1989), a characteristic of this morphology is that it results from diffusion-limited growth and asymptotically has a 3D Euclidian behavior (BenJacob and Garik, 1989); (3) a dendritic morphology, which means a feather-like main trunk with side branches that grow outward; a characteristic of this morphology is its fractal property that results mainly from microscopic anisotropies (Ben-Jacob and Garik, 1989). 3.1. Effect of cyanide concentration Fig. 1 shows the cemented silver to dissolved zinc molar ratio as a function of initial cyanide concentration for the cementation process. Below [NaCN]0 / [Ag]0=2 cementation does not occur because the cyanide ions are complexed as Ag(CN)2 and the concentration of free cyanide ions is not significant. At the onset of the low cyanide concentration regime, the cementation stoichiometry abruptly jumps from 0 to 2 mol of recovered silver per mol of dissolved zinc. At the intermediate cyanide concentration regime, the recovery stoichiometry decreases gradually from 2 to 1. Finally, at the high cyanide concentration regime, 1 mol of silver is cemented by 1 mol of zinc. Under

Cemented Ag/Dissolved Zn molar ratio

1 [Ag]0 = 0.927 mM T = 25C Zn = 7.43 mg/l rpm = 500 pH0 = 10.8 0 0 2 4 6 8 10 12 14 16

Initial [NaCN]0 /[Ag]0 ratio


Fig. 1. Molar ratio of cemented silver/dissolved zinc as a function of the initial cyanide concentration given by the [NaCN ]0/[Ag ]0 ratio.

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0.0

197

conditions of low cyanide concentration, the two electrons arising from the anodic dissolution of one zinc atom reduce cathodically two silver atoms. In contrast, at the high cyanide concentration regime, only one of the two electrons resulting from the zinc oxidation reduces one silver atom and the other one is lost in collateral reactions. Fig. 2 shows the change in pH in the cementation solution as a function of time for various [NaCN]0 / [Ag]0 ratios. At low cyanide concentrations, even though the recovery of silver is 80%, the pH remains essentially constant, close to its initial value. At high cyanide concentrations, there is an increase in pH with time, which is higher the larger the [NaCN]0 /[Ag]0 ratio. This can be accounted for by the reduction of water as has been reported elsewhere (Dorr and Bosqui, 1950; Flemming, 1992; Parga, 1987): H2 O e YOH 1=2H2 1

Ln([Ag]t /[Ag]0 )

-0.2

-0.4 Initial [NaCN]0/[Ag]0 ratio -0.6 2 5 12 0 3 6 4 8

10

Cementation time (min.)


Fig. 3. Silver concentration disappearance in solution as a function of time in cementation of silver using zinc powder at various initial cyanide concentrations given by the [NaCN]0/[Ag]0 ratio.

The effect of initial cyanide ion concentration on silver cementation kinetics is shown in Fig. 3. It is noted that by increasing the [NaCN]0 /[Ag]0 ratio up to 8, the silver cementation kinetics increases. This behavior can be related to the observations reported by Chi et al. (1997) in that there is an increase in the stability of zinc-cyano complexes over that of Zn(OH)2 as the concentration of cyanide is increased. In gold cementation, zinc hydroxide has been reported to passivate the zinc surface, lowering the cementation rate (VilchisCarbajal, 2000).

Above the [NaCN]0 /[Ag]0 ratio of 8, the cementation kinetics tends to decrease, which is in agreement with the work by Parga (1987) and Miller et al. (1988). They have attributed this to the increase in the stability 2 of Ag(CN)3 species over that of Ag(CN)2 species at high cyanide concentration; the species with the highest molecular weight are more difficult to discharge and have a smaller diffusion coefficient. The speciation diagram for silver-cyano complexes as a function of [NaCN]0/[Ag]0 ratio is presented in Fig. 4. It can be seen that the predominant species are Ag(CN)2 ions and the increase in concentration of 2 Ag(CN)3 ions is less than 2% in the [NaCN]0 /[Ag]0

11.0

10.9

pH
10.8 Initial [NaCN]0 /[Ag]0 ratio 3 4 8 16 10.7 0 10 20 30 40 50 60

Cementation time (min.)


Fig. 2. pH evolution in solution as a function of time in the cementation of silver using zinc powder at various initial cyanide concentrations given by the [NaCN]0 /[Ag]0 ratio.

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1.0
Ag(CN)2
-

0.8

[Species]/[Ag]0

0.6

0.4
Ag
+

0.2
Ag(CN)

Ag(CN)3

2-

Ag(CN)4

3-

0.0 0 2 4 6 8 10 12 14 16

[NaCN]0 /[Ag]0
Fig. 4. Diagram of species in thermodynamic equilibrium for the system AgCNH2O at pH 10.8. In the abscissa, the [NaCN]0 /[Ag]0 molar ratio, [Ag]0=9.27104 M; in the ordinates the molar concentration of species normalized with [Ag]0 .

ratio range of 8 to 12. Thus there is not a good correspondence between the decrease in the cementation kinetics and the increase in the concentration of 2 Ag(CN)3 . In addition, this role attributed to the 2 Ag(CN)3 species does not fully explain the transition in the cementation stoichiometry nor the change in morphology of the cemented silver taking place at the high [NaCN]0 /[Ag]0 ratio, which are observed in this study and occurred together with the decrease in the cementation kinetics. The morphology of the cemented silver was affected by the [NaCN]0 /[Ag]0 ratios as shown in Fig. 5. At the [NaCN]0 /[Ag]0 ratio of 3 (Fig. 5a), which is a condition of low cyanide concentration, the cemented product is composed of two-phase particles, a zinc core with a tightly bound metallic silver shell. This structure is typical of a shrinkingcore cementation process, where the cementation front advances towards the center of the cementing metal and diffusion of ions takes place through the product layer. At a [NaCN]0 /[Ag]0 ratio of 8 (Fig. 5b), a layer of Zn(OH)2 is observed around the zinc particle and the cemented silver is not attached to this layer nor to the zinc particle. There is a tendency for a hollow shell to form between the zinc particle covered by Zn(OH)2 and the layer of cemented silver. It is evident that the cementation of silver is not towards the center of the zinc particle, but towards the aqueous solution in a uniform growth. With increase in the [NaCN]0 /[Ag]0 ratio up to 16 (Fig. 5c), it is seen that the cementation front

advanced towards the aqueous solution and a cavity resulted from the dissolution of the zinc particle. Finally, at [NaCN]0 /[Ag]0 ratio of 30 (Fig. 5d), silver cemented towards the aqueous solution in a dense-branching like morphology, which is a characteristic of a diffusion-controlled process (BenJacob and Garik, 1989). It is noted that a cavity resulted from the zinc dissolution. Under these conditions of high cyanide concentration, Zn(OH)2 was not detected in the cementation product. Accordingly, the initial cyanide ion concentration determines not only the cementation reaction and the cementation kinetics, but also the morphology pattern of the cemented silver. At low cyanide ion concentrations, 2 mol of silver are cemented by 1 mol of zinc, the solution pH does not change appreciably, the cementation front advances toward the center of the zinc particle, zinc hydroxide forms in the system and the cemented silver is bound to the zinc particle. All this can be explained by the overall cementation reaction that has been proposed elsewhere (Dorr and Bosqui, 1950; Nicol et al., 1979; Parga, 1987; VilchisCarbajal, 1992):
2 2AgCN 2 ZnY2Ag ZnCN4

which at high pH values is well known to occur via the formation of Zn(OH)2 as follows: ZnYZn2 2e Zn2 2OH YZnOH2 3a 3b

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Fig. 5. Scanning electron micrographs of particles in cementation products recovered from the cementation of silver using zinc powder at different initial cyanide concentrations given by the [NaCN]0 /[Ag]0 ratio; [Ag]0 is the initial silver concentration equal to 0.927 mM. (a) [NaCN]0 /[Ag]0 ratio of 3, (b) [NaCN]0 /[Ag]0 ratio of 8, (c) [NaCN]0 /[Ag]0 ratio of 16 and (d) [NaCN]0 /[Ag]0 ratio of 30.

in equilibrium with the complexation reactions between zinc and cyanide ions: Zn2 2CN ZnCN2 Zn2 3CN ZnCN 3 Zn
2

4a 4b 4c

cavity resulted in the cementation product from the zinc dissolution. The cementation stoichiometry can be accounted for by the overall chemical reaction proposed by Barin et al. (1980) for gold, which for the cementation of silver can be expressed by:
Zn AgCN 2 H2 O 2CN 2 YAg ZnCN4 OH 1=2H2

4CN

ZnCN2 4

At low cyanide concentrations, zinc hydroxide is very stable and forms around the zinc particle as can be seen in Fig. 5b. The silver-cyano species diffuse through the product layer and silver is cemented as follows:
AgCN 2 e YAg 2CN

The same overall reaction has been found to explain the results of Vilchis-Carbajal (1992) in that 1 mol of silver is cemented by 1 mol of zinc. In the gold system, Barin et al. (1980) suggested that H2 evolution takes place as follows:
1=2ZnOH2 e Y1=2ZnO2 2 1=2 H 2 : 1=2ZnO2 2 H2 OY1=2 ZnOH2 OH

7a 7b

At the high cyanide ion concentration regime, which in fact represents conditions in plant practice, 1 mol of zinc cemented 1 mol of silver, the solution pH increased as the cementation proceeded, the cementation front advanced towards the aqueous solution away from the center of the zinc particle, zinc hydroxide was not detected in the system, and a

7c H2 O e YOH 1=2H2 An interesting feature to note in the mechanism proposed by Barin et al. (1980) is that of the two electrons resulting from the zinc oxidation, one is

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for the reduction of the metal-cyano complex species and the other one is for the reduction of water. Thermodynamically this is unlikely due to a distinct free energy change for the two reduction reactions. In addition, the mechanism pictures the cementation as a process occurring at the zinc particle surface through the formation of Zn(OH)2; if this were true, silver reduction and the zinc oxidation reactions would occur at the zinc/aqueous solution interface. Such a mechanism explains well the increase in pH and the cementation stoichiometry. But the reaction steps considered in the mechanism do not explain various other phenomena observed in this study such as the cavity in the interior of the particles of the cementation product, the growth of silver in a dense-branching like morphology and the growth of silver towards the aqueous solution. Figs. 5c and d show that the cemented product at high cyanide concentrations is made of particles with a hollow space nearly spherical in shape, which is surrounded by silver with a uniform growth or densebranching like morphology. It is clear that three interfaces appear in the cementation process, an inner-particle zinc/aqueous solution interface, an inner-particle silver/aqueous solution interface and an outer-particle silver/aqueous solution interface. Comparing the texture of the surface of silver at the inner-particle silver/aqueous solution interface to that of the zinc particle that was used in the cementation tests, it can be noted that the textures are very similar (see Figs. 6a and b). This leads to suggest that the hollow space in the particles appears from the beginning of the cementation process. It is then obvious that silver-cyano species did not diffuse from the bulk solution to this interface nor to the interior of the hollow space. The silver-cyano complexes are reduced at the outer-particle silver/aqueous solution interface giving rise to an outward growing of silver. So the anodic dissolution of zinc occurred in an environment free of silver-cyano species at the innerparticle zinc/aqueous solution interface, giving rise to the cavity in the cementation product. These steps in the mechanisms of silver reduction and zinc dissolution differ from those proposed for gold by Barin et al. (1980) in that they take place at distinct interfaces, even though at the end the overall cementation reaction is identical for both systems.

Fig. 6. Scanning electron microphotographs showing (a) the inside surface of the silver shells cemented on zinc particles and (b) the outside surface of the zinc particle used in the cementation [NaCN]0 /[Ag]0 =30 , [Ag]0= 0.927 mM, pH 10.5.

At the intermediate cyanide concentration regime, a transition between the scenarios for low and high cyanide conditions is suggested to take place. The increase in the cementation kinetics in the lowintermediate cyanide ion concentration regime can be ascribed to the decrease in the stability of zinc hydroxide at the inner-particle zinc/aqueous solution interface, whereas the decrease in the cementation kinetics from the low-intermediate to the high cyanide ion concentration regime can be accounted for by the transition of the cementation reactions from Eqs. (2) to (6) rather than for the low diffusion 2 rate of Ag(CN)3 as has been suggested by Parga (1987). 3.2. Effect of lead ions Several studies have been carried out to determine the role of lead ions in the cementation of gold and

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silver from cyanide solutions using zinc powder (Chi et al., 1997; Dorr and Bosqui, 1950; Flemming, 1992; Kirk and Foulkes, 1984; Leblanc, 1942; McIntyre and Peck, 1976; Miller et al., 1988, 1990; Nicol et al., 1979; Oo and Tran, 1991; Parga, 1987; Parga et al., 1988; Paul, 1986; Paul and Howarth, 1986). With regard to the catalytic effect of lead ions, Miller et al. (1988) and Parga (1987) have suggested that the kinetic changes in the cementation of silver are a consequence of a dendritic morphology of the cemented silver induced by lead ions. They have claimed that the dendritic structure of the surface deposit is sufficient to extend the cathodic surface area to such an extent that two-stage enhanced reaction kinetics take place. In this work, studies of the effect of lead ion addition on the cementation of silver have been undertaken in order to determine their role at the distinct cyanide concentration regimes. The initial silver ion concentration was kept constant at 0.92 mM while that of cyanide ions varied in order to have different ratios of [NaCN]0/[Ag]0. Fig. 7a depicts the moles of cemented silver as a function of the moles of dissolved zinc at the intermediate cyanide concentration given by a [NaCN]0/[Ag]0 of 4 using various lead ion additions. Fig. 7b shows the corresponding results for conditions of high cyanide ion concentration given by a [NaCN]0/ [Ag]0 of 16. The initial slopes of the data shown in the figures indicate the stoichiometry of the cementation reaction. In both cases, the cementation stoichiometry was not affected by the presence of lead ions, meaning that the cementation reactions (2) and (6) still hold. When the ratio [NaCN]0/[Ag]0 is 4, 1.5 mol of silver is cemented by 1 mol of zinc, which means that the two cementation reactions take place at this transition region. The deviation of the data from linearity, seen in Fig. 7a, is due to the continued dissolution of zinc after complete cementation of silver ions. At the ratio of [NaCN]0/[Ag]0 of 16, 1 mol of silver is cemented by 1 mol of zinc, which is an indication that the overall cementation reaction (6) prevailed. The addition of lead ions has been found to affect the cementation kinetics of silver (Miller et al., 1988; Parga, 1987; Parga et al., 1988). Figs. 8a and b show the cementation kinetics of silver in the absence and presence of various additions of lead ions at the

Fig. 7. Moles of cemented silver from solution as a function of moles of dissolved zinc at various additions of lead ions using two different initial cyanide concentrations [Ag]0 = 0.927 mM; (a) [NaCN]0 /[Ag]0 =4, and (b) [NaCN]0 /[Ag]0 =16.

intermediate and high [NaCN]0/[Ag]0 ratios of 4 and 16, respectively. The addition of lead ions up to 10 mg/l increases the cementation kinetics in the two cases. Further increase in the lead ion concentration diminishes the cementation kinetics, which is in agreement with the results reported by Chi et al. (1997). They have attributed this behavior to the passivation of the zinc surface by metallic lead. It can be noted in Figs. 8a and b and also in Fig. 3 that there is a smooth transition between two firstorder reaction kinetics for all cyanide and lead concentrations, which is independent of the final morphology of the product. Sedzimir (2000) has explained this transition as arising from an interplay

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a)

0.0 -0.2

Ln([Ag]t /[Ag]0 )

-0.4 -0.6 [NaCN]0 /[Ag]0 = 4 -0.8 -1.0 0 Added Pb (mg/l) 0 2.5 10 15 2 4 6 8 10


2+

Cementation time (min.)

b)

0.0

-0.4

Ln([Ag]t /[Ag]0 )

-0.8 [NaCN]0 /[Ag]0 = 16 Added Pb (mg/l) 0 5 10 15 20 0 5 10 15 20 25


2+

-1.2

-1.6

Cementation time (min.)


Fig. 8. Silver concentration disappearance in solution as a function of time at various additions of lead ions with two different initial cyanide concentrations and [Ag]0 = 0.927 mM: (a) [NaCN]0 /[Ag]0 = 4 and (b) [NaCN]0 /[Ag]0 =16.

between the electrical current of the cementation reaction and the changes in the cementation surface area as is the case in the cementation of silver on zinc. On the other hand, heterogeneous reactions controlled by diffusion through the boundary layer, such as the cementation at the high cyanide regime (Miller et al., 1988, 1990; Parga, 1987; Parga et al., 1988; Sedzimir, 2000), follow long time first-order kinetics. Thus, the long time behavior of the experiments in Figs. 8a and b has been fitted to the first-order kinetics equation dAgt kexp Agt dt 8

where t is the cementation time, k exp is the experimental rate constant, and [Ag]t is the molar silver concentration in solution at time t . The values of k exp were determined for the [NaCN]0/[Ag]0 ratios of 4, 10

and 16, and graphed as a function of the concentration of lead ions in Fig. 9. As seen, the effect of lead ions on the silver cementation kinetics is higher when the cyanide ion concentration is lowest. It is noteworthy that, although the cementation kinetics is significantly affected by the presence of lead ions at low cyanide concentrations, both the morphology of the cemented silver and the shrinkingcore behavior of the cementation process do not change, as can be seen in Figs. 10a and b. These figures show microphotographs of particles similar in morphology as those presented in Fig. 4a for cementation at low cyanide concentration without lead ions. Thus, lead ions did not induce dendritic growth at any addition under conditions of low cyanide concentration. Accordingly, the increase in the silver cementation rate is not due to morphological

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203

Kinetic rate constant, Kexp. (min. )

-1

0.12 0.10 0.08 0.06 0.04 0.02 0.00 0 2 4 6 8


2+

Initial [NaCN]0 /[Ag]0 ratio 4 10 10 16 12 14 16

Added Pb (mg/l)
Fig. 9. Experimental rate constants for silver cementation as a function of addition of lead ions at various initial cyanide concentrations given by the [NaCN]0 /[Ag]0 ratio, at [Ag]0 = 0.927 mM and pH 10.8.

changes. Following Chi et al. (1997), this increase in the cementation rate can be accounted for by the reduction of lead ions on the zinc surface, which

enhances zinc dissolution in alkaline solutions and decreases the surface passivation of zinc due to zinc hydroxide.

Fig. 10. Scanning electron micrographs of the product collected in the cementation of silver at [NaCN]0/[Ag]0 =4, [Ag]0 = 0.927 mM, and pH 10.8 at two different additions of lead ions: (a) 2.5 mg/l and (b) 15 mg/l.

Fig. 11. Scanning electron micrographs of the products collected in the cementation of silver at [NaCN]0/[Ag]0 =30, [Ag]0 =0.927 mM, and pH 10.8: (a) in the absence of lead ions, and (b) with the addition of 10 mg/l lead ions.

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At high cyanide ion concentration, given by the [NaCN]0/[Ag]0 ratios of 16 and 30, the cementation rate slightly increases with the addition of lead ions. SEM studies on the products show that the addition of lead ions induced the silver to deposit in a dendritic-like morphology as can be seen in Fig. 11. Comparing this figure with Fig. 4d, it can be noted that there was a change in the morphology of the product from a densebranching to a dendritic-like morphology. The two morphologies have a branched nature so that their surface areas should be quite similar. Furthermore, these morphologies are characteristic of a process controlled by diffusion through boundary layer, in which lead ions are unlikely to have any significant effect on the diffusion rate of silver-cyano complex species. Accordingly the silver cementation rate is not appreciably affected by lead ions under conditions of high cyanide concentrations. The transition in the morphology of the silver deposit by lead ions may be related to their ability to change the electron discharge resistance of the crystallographic planes of silver, giving rise to microscopic anisotropies as has been reported for the electrocrystallization of copper ions in the presence of chloride ions (Oberholtzer et al., 1998).

affect the cementation kinetics only at low cyanide concentrations.

Acknowledgements The authors thank Centro de Investigacion y Desarrollo Tecnologico de Servicios Industriales Pen oles for financial support in the form of a scholarship to Gonzalo Viramontes Gamboa to pursue PhD studies and to carry out this investigation. References
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4. Conclusions Two distinct overall cementation reactions that depend on the initial cyanide concentration have been identified in the cementation of silver from cyanide solutions using zinc powder. At low cyanide ion concentration, the formation of zinc hydroxide on the surface of zinc determined that the cementation process followed a shrinking-core pattern; the cementation reactions took place at the surface of zinc and 2 mol of silver were cemented by 1 mol of dissolved zinc. At high cyanide ion concentrations, which represent conditions used in plant practice, zinc hydroxide is not stable and the cementation mechanisms differed from those occurring at low cyanide concentration. Silver cemented towards the aqueous solutions in a morphology that varied from a uniform layer to dense-branching around a hollow space resulting from zinc dissolution. The cathodic reduction reaction of silver-cyano complexes and the anodic oxidation reaction of zinc occurred at distinct interfaces appearing in the zinc particle. Lead ions

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