Gaudin Lecture Sulfide and metal leaching reactions “for his creative efforts in explaining the electro: chemistry of sulfide mineral leaching systems. MLE. Wadsworth Abstract - Leaching reactions that occur during he dissolution of selected base metal sulfides and metals are considered in terms of surface reactions and the influence of intermediate or final products formed, These products may be solid layers, requiring solld phase diffusion for the reaction to proceed, or ions in solution that can influence the kinetics by ontrolling the mized potential of the solid. Three general types of reactions are proposed to explain observed rates of reaction. Examples are presented for non-ozidative and oxidative leaching of galena (PbS), anodic dissolution and oxidative leaching of molybdenite (MoS,) and cyanidation of silver and gold. Introduction Reactions representing the dissolution of metal sulfides and metals may often be characterized by one ‘or more of the following types of surface reactions: solld-1 + ions, (aq) = tons, (aq) w solid-1 + ons, (aq) # solid-2 + ionsp(aq) (2) solld-1¥ solid-2= tons (aq) @) 1 ig Reactions (1) and (2) represent a solid in contact with reactant ions (ions,) and product ions (ions) in solution, However, reactant ions (ions,) may not be required for the reaction to proceed. Also, solid-1 may react with the solvent (HzO). Reaction (2) represents the case where a porous solid-? forms, permitting ‘access of solution to solid-1. Examples of reactions (1) and (2) are! direct (non-oxidative) dissolution of galena. PDS + 8HCI(aq) = PbCIj(aq) +H *(aq) + HS (4) anodle dissolution of galena. PbS = Pb?*(ag) + 8° +207 6) anodie dissolution of gold. ‘Au® + 2CN~(ag) 2 AUCN3(aq) + e~ 6) In reactions (4) and (6), the surface is not protected by products of reaction and leaching is expected to follow linear kinetics. Elemental sulfur formed by reaction (5) is porous permitting continued anodic Gissolution, In this case, linear kinetics would not be expected since pore diffusion would become rate limit- {ng as the sulfur layer grows. Reactions (4) to (6) are overall reactions representing a summation of events ‘These may include adsorption, desorption, and forma tion of defect surface layers as well as various inter- mediate ionic species. Reaction (3) represents the case where a new protective solid layer (solid-2) forms, requiring lattice iffusion of ions between boundaries I and II for the reaction to proceed. Solid-2 may be viewed as a solid electrolyte with oxidation-reductlon reactions occur- ring at boundaries I and II. Charge transfer between solld-2 and the solution occurs at boundary II. Multiple solid layers may form in the course of the leaching reaction. Reaction (8), under a variety of conditions, can account for most kinetic rate laws observed during Teaching. If solld-2 grows continuously in thickness, the Fick diffusion rate law, including particle size and ape, will apply. If very large voltage drops occur at boundary I, logarithmic kinetics may result. If solid.2 grows to a thickness for which net mass transfer at boundaries I and IT become equal, then boundaries I and II will move at the same constant velocity result: ing in linear kinetics, If this condition is met for very MLE. Wadsworth, member SME, Is dean of the College of Mines and Mineral industries, Unversity of Utah, Salt Lake City, UT Presented at the SMEVAIME Annual Mooting, New York, NY, Feb. 24-28, 1985,thin films, linear kinetics will be observed during the entire reaction, The transition from parabolic to linear kinetics results in paralinear kinetics. The low voltage reaction of molybdenite in acidic solutions results in paralinear kineties by forming a MoIV oxy-sulfide Intermediate layer: low voltageanodie reaction of molybdenite. MoS; + 5xH,0 * Mo0,S:.x Oxi *(aq) + Sxe™ o ‘The oxy-sulfide reacts electrochemically with the solution forming molybdate and sulfate ions in solution, Mo00,S2.x + (12-5x)H,O = HMoO;(aq) + 21-9x)H* (aq) + (18-8x)e (8) At higher voltages, molybdenite forms the MoVI oxide, MoOs, on the surface: high voltage anodic reaction of molybdenite. MoS; + 11H,0 2 Mo0s + 2HSOj(aq) + 20H *(aq) +18 () ‘The MoO; surface reacts rapidly with the solution forming molybdate ions in solution. Thin transitory layers of MoO, result and linear kinetics are observed essentially from the beginning of the reaction. Once elther reaction, (7) or (8), enters the region of linear Kinetics, the overall stoichiometry observed is, MoS, + 19H,0 7 HMo0;(aq) + 2HSO;(aq) + 21H * (ag) + 18" a0) Galena Leaching Chioride solution chemistry is of special interest to lead hydrometallurgy because of the high solubility of PbCl, at elevated temperatures. Galena will react anodieally, as illustrated by the half cell reaction, equation (2). This reaction may be promoted by the ‘coupled cathodic reduction of ferric chloride FeCls(aq) +e” 2 FeCla(ag) + Cl“(aa) a) resulting in the overall stoichiometry PDS + 2FeCIy(aq) * PbClo(aq) + 2FeCl;(aq) +8° a2) ‘The lead released to the solution forms a series of lead chloride complex ions, PbCly'27), depending on the ‘amount of exeess Cl” in solution. Palmer et al. (1983) land Dutrizae (1985) have shown the reaction kinetics follow Fick's diffusion equation for isometric particles. = (2/8) a~ (1-0)? = (Iep/42)t (as) where ais the traction of lead leached, dis the initial particle diameter, t is time, and ky is the normalized ate in em? sec), Figure 1 illustrates the correlation of observed @ values? plotted according to equation (13) for four FeCl; concentrations in 4 M NaCl solu tions. The value of kp increased in a complex fashion with FeCl, concentration becoming independent of FeCl, concentration above 0.2 M. ‘Dufrizac (1985) has shown a similar shift in rate control, finding ky to be independent of FeCl for con. centrations greater than 0.1 M in the absence of added NaCl. In the higher FeCl; concentration range, ky decreased linearly with increased PbCl, concentration (Dutrizae, 1985). These results suggest the rate con- trolling step 1s the Inward pore diffusion of ferric chloride through the growing sulfur product layer at low rates of reaction and outward pore diffusion of lead chloride at high rates of reaction. For the latter, the calculated activation energy was 16 kJ/mol (4 keal per mol) consistent with the pore diffusion model. ° 02 o20 F Fig. 1 — Data of Palmer otal. (198 showing correlation using the diffusion equation for isometric particles for four FeCly Concentrations {monosized galene, 35 x 48 mosh, 4.0 M NaCl, 328° 60"C)) Direct acid dissolution of galena, reaction (4), has two modest advantages when compared to FeCls leaching. The reaction is faster, following linear xineties (Scott and Nicol, 1978; Awakura, Kamei, and Majima, 1980), and the process can be carried out in low iron solutions. A more important advantage is improved selectivity for galena in the presence of other sulfide minerals, A major disadvantage 1s the formation of HS. Han (1985) has taken advantage of the direct leaching reaction by continuous removal of H,8 using saturated SO, solutions. The well known Claus reaction 2H,8 + 802 8° + H,0 aay proceeds more rapidly than the dissolution reaction, effectively removing the HS as rapidly as it is formed. The overall leaching reaction is PbS + 2HCl (aq) + 0.580;(g) = PbClz(aq) + $° + H,0 (as) Sulfur produced by reaction (15) is nonprotective, forming spherical clusters loosely attached to the surface. Figure 2 illustrates results obtained for a rotating disk of galena and compares rates of reaction at four separate temperatures. The rate is somewhat faster with SO, since removal of H,S limits the back reaction. Galena is unique in that the rate of leaching can readily be changed from: one kinetic region to another by controlling the concentration of HCI in Solution. Han has shown that the direct leachingno reaction involves an lon-pair mechanism in that the rate of leaching 1s proportional to the product (H-) (CI?) This is illustrated in Fig. 8 where the linear rate is plotted versus (H*) (CI*) Fig. 2 — Data of Han (1985) for dissolution of galena in SO2 lustrating linear kinetics at various temperatures (rotating disk sample, 1500 rpm, 1 M HCI, 1 aim. pressure SO; ‘ng model proposed by The non.oxidative lea‘ Awakura, Kamel, and Majima (1980) includes H adsorption followed by a surface reaction. The ion-pair version of the model Pps + H* = PDS+H aa as) PDS-H* agg + Cl” = PCL 1) followed by the formation of PbC xe depending on the solution composition. Molybdenite Leaching Molybdenite 1s unusual because its electronic and electrochemical properties are highly directional. The electrical conductivity perpendicular to the c axis is about 10 times that parallel to the c axis. Recently shnaswamy and Fuerstenau (1962) demonstrated the influence of crystal orientation and photo-induced enhancement on the anodic dissolution of n-type molybdenite, Ahn and Wadsworth (1984) identified passive and transpassive oxidation in low voltage and high voltage regions as Indicated by reactions (7) to (9) with the same overall stoichiometry, reaction (10). Figure 4 illustrates potentiodynamic curves obtained for a synthetic MoS; electrode for three HCI concen: trations. From the rest potential (0.2 to 0.28 V versus fo about 0.7 V, slow, diffusion kinetics were observed. Above 0.7 V, the Feaction proceeds rapidly and follows linear kineties. A surface oxide product formed in the high voltage region was identified by ESCA analysis to contain MoVI and oxygen and is assumed to be MoO;. On the reverse scan (Fig. 4), the high voltage surface product was observed to have a rest potential in the region 0.58 00.57 V J 7 2 346 10 caf) (01) (mote Fig. 3 — Rate of dissolution of galena in SO, showing correla: tion of the rate with the (H*) (Cl-) product (Han, 1986) (rotating disk sample, 1500 rpm, 1 atm. SO,, $83°K (60°C) Fig. 4 Polarization curves of pressed electrodes of synthet MoSp at three concentrations illustrating the low voltage ‘anodic region, V < 0.7, and the high voltage anodle region, V>07 (Ain, 1984)In the low voltage region, the reaction proceeds as noted earlier according to reactions (7) and (8). The proposed diffusion boundary, consisting of a MoIV oxy-sulfide layer with oxygen substitution for sulfur, was confirmed by ESCA analysis. Figure 6 illustrates potentiostatic Q (coulombs) versus time (hr) curves obtained at four voltages in the low voltage region. The kinetics initially are parabolic becoming linear when a fixed thickness of the diffusion boundary layer is attained for each voltage. At this point, boundaries T and I, reaetion (3), are moving at the same constant velocity. If kp is the parabolic rate constant for the ‘diffusion process and k, the linear rate constant for the boundary II surface reaction, the paralinear rate equation may be presented as ee = o Bei | me Ss ‘The solid lines of Fig. 6 are calculated curves, accord- ing to equation (18). Both diffusion and boundary I surface reaction rate constants were voltage depen: dent. The linear, kj, voltage dependence is consistent with the oxidation of MoIV to MoVI at boundary II, according to reaction (8). Tine (ho) Fig. 5 — Potentlostatlc @ (coulombs) versus time curves for the anodie dissolution of MoS, at four fixed voltages in the low voltage region (Ahn, 1984). Solid curves calculated using paralinear rate equation (1). It is apparent that molybdenite will dissolve anod. {cally very rapidly if its potential is maintained more positive than 0.7 V (SCE). The standard half-cell potential for chlorine discharge in acid solutions, Cl +28” = 2C1"(aq) a) is 111 V (SCE). In the presence of chlorine, MoS, would be expected to have a mixed potential greater than 0.7 V (SCE). This condition would result if the rate of MoS, dissolution is controlled predominantly by the anodie reaction, In this circumstance, the mixed potential would be near the chlorine half-cell potential resulting in rapid linear kinetics of dissolu- tion, Measured values of mixed potential were near 0.9V (SCE). Figure 6 illustrates the fraction reacted versus time data of Say and Wadsworth (1985) for four sized fractions of high grade Amax MoS, at room tempera- ture and Pq, = 0.143 atm. Very rapid dissolution occurs even “at room temperature. Mass balance ‘measurements confirmed the overall reaction MoS; + 9Cly(g) + 8H,0 = MoClg(aq) + 12C1“(aq) 280,* (aq) + 16H * (aq) (20) Also, the rate was observed to increase directly with Ci; partial pressure. If the reaction occurs predom- inantly on MoS. crystallite edges, the kinetics should reflect cylindrical geometry resulting in the rate expression 1 - (1a) = (KP cg/do)t @ where a is the fraction reacted, k is the linear rate constant, d, is the initial diameter, and t is time. Figure 7 illustrates the data of Fig. 6 plotted according to equation (20). Particles €0 My in diameter react 98% in less than 50 minutes at room temperature for Pay, = 0.5 atm. The observed kinetics are sensitive to the’ degree of agitation, insensitive to changes in temperature, and match rates expected for mass transfer of Cl, through a liquid boundary layer at the crystallite surface, Fig. 6 — Data of Say (1986) showing fraction reacted versus time results for four monosized fractions of MoS, In acid-Cly solutions at room temperature (aa) Wr “Sauer 08 ©0032 one a 2 0.060 ia | TIME (mis) Fig. 7 — Correlation of data using cylindrical geometry (Say, 41985) (room temperature, Pej, = 0.143 atm)rrr Metals Leaching Metals leaching is the primary means for the recovery of precious metals from ore. Hydrometallurzy ‘also represents an alternative for the recovery of metals from industrial metallic waste for purposes of recycle, For 100 years, cyanidation has been the principle method for gold (Au) and silver (Ag) extrac tion worldwide, The leaching mechanism was recog- nized by early investigators to be electrochemical in nature, Also, dissolution rates have been observed to @isplay unique kinetic characteristics, shifting from one kinetic regime to another with only slight varia. tions in concentration of oxidant or complexing agent {in solution, In the case of conventional Au and Ag extraction recovery, O2 in air is the oxidant and CN~ the complexing agent. Copper, nickel, and cobalt may be leached by oxygen in ammoniacal solutions and NHpis the complexing agent forming soluble ammines n basic solutions. ‘Kudryk and Kellogg (1954) published an important fundamental paper establishing the electrochemical nature of gold cyanidation and explained the abrupt shift in kinetic regimes on the basis of mixed pote’ tials. The open and closed circles of Fig. 8 represent a few of the experimental voltage-current data points measured by these investigators. Cylindrical speci ‘mens of gold were rotated at various rpm. The anodic curves, displaying increasing current with increasing Voltage, represent anodie dissolution of Au in solutions of various KCN concentration. The cathodic branch for oxygen discharge (air) on a gold electrode is also shown, ‘In the plateau regions, the current is independent of voltage, indicative of solution boundary layer diffu- sion. The plateau values at 0.005%, 0.019, and 0.0175% KCN are controlled kinetically by CN” diffusion. The plateau region of the cathodic branch is a region where oxygen diffusion is rate controlling. The mixed poten: flal is the potential a solid metallic particle will assuime when exposed to the leaching solution and, for 2 given solution composition, corresponds to the point of intersection of the anodic and cathodic branches. ‘The mixed potential and its assoclated mixed current establish the rate of leaching, It is apparent from Fig. 8 that, as KCN Is in. creased, the rate of reaction moves from CN~ diffusion control to O, diffusion control. Kudryk and Kellogg also showed the reverse to be true for a fixed %KCN and changing %03. The kinetics are well described by the Fick diffusion equation when the mixed potential falls within either the CN~ or O, plateau regions. To explain the kinetic results in the transition region, the electrokinetic reactions that establish the anodic and cathodic branches for all concentrations must be Getermined. Tt can be shown that the experimental curves measured by Kudryk and Kellogg are not totally diffusion overpotential limited, but require mixed diffusion plus surface charge transfer kinetics toexplain the shape of the curves. Equation (6) describes the overall anodie dissolutior of Aut in cyanide solutions. The anodic curves of Fig. § fare well described by coupled diffusion, plus surface charge transfer according to the reactions Dew Bayes ee (CN) (23) 23) ail where Dow is the aiff {s the bulk solution concentration, (CN concentration \¥ is the diffusion boundary thickness F is the Faraday constant, a, is the transfei cient, and E, the voltage for the anodic rea Assuming steady state conditions, equations (23) may be combined giving 14 (kq/k,) exp (-B,E,) where ky = DcyF/2 6 and By = agF/RT. The constan ka was evaluated from average plateau values for the 0.006, 0.01, and 0.0175 %KCN anodic curves. In this region, the current density is the_limiting current density, 1gq, and is equal to k4(CN"), providing a means to evaluate k,. The value of B, was determined from one point on the rising portion of the 0.0175 %KCN curve. The dashed curves of Fig. § were calculated using the same K, and B, valu Fig. 8 — Kudryk and Kellogg (1954) electrochemical cata for anodic dissolution of Au and cathodic discharge of oxygen. Dashed curves calculated using mixed kinetics model. Oxygen discharge is known to proceed through a series of reactions including peroxide intermediates. In baste solutions, simplified steps may be presented by 0g + 2H,0 + 2¢ & Hy0» + 20H 25) H,0, + 2e = 20H (28) the total reaction being 0g + 2H,0 + 4e = 40H C3) In the cyanidation process, the effective transfer of electrons will fall in the range of two to four electrons per mole of Oz, depending on the net rate of reaction “The cathodic O, discharge curves of Kudryk and Kellogg are also adequately described by a mixed fe (02) ky exp samme (29)where 1, 1s the anodic current density, Do, is the Giffusion coefficient for oxygen, and n is the effective number of electrons trat ‘4, Equations (28) and (29) may be combined to give PACH (kek) exp (BeHe) where ke = DoF /éand B, = agF/RT. The da curve shown in Fig. 8 was calculated using equation ‘The mixed potential E and current 1 correspond to the conditions B, = Ey = Bandi, = ip = 1. Equations (24) and (30) may be combined to give BAB [: as | =D ay 2- BIE] eS and may be determined from the electrochemical data. The rate of reaction R (mg em” hr-) is directly proportional to the mixed current density such that equation (31) becomes. 1-R/Ra] [1-R/Re | Babe =D 33) B/Rea BIR where R gq and R.ge are the limiting rates of dissolution corresponding to the limiting curren: densities igs and ige- Ideally, D and B,/B, values may be determined from the electrochemical data alone. A good cot tion is obtained for the electrochemical data of Kudryk and Kellogg. Measured rates of dissolution fall some what below those predicted from anodie and cathodic polarization data alone. This may be attributed in part to the oxidation of CN- in the presence of oxygen. Normally dissolution data, rather than electrochem: ical data, wil be available and used to evaluate D and B,/B,, The solid curves of Fig. 9 were calculated using ‘equation (38) and are compared to the measured rates, of dissolution, Dissolution kinetics for other metals, where both oxidation and complex formation oceur, have been found to follow a similar mixed kinetics model (Wadsworth, 1985). i oe Fig. 9 — Rate of dissolution of Au at various KCN concent tions for three Oz/N, gas mixtures showing correlation of neasured (Kudryk and Kellogg, 1964) and calculated (Wads- worth, 1985) rates References