Leaching of gold in thiocyanate solutions—Part 1: chemistry and thermodynamics O. Barbosa-Filho and A. J. Monhemius Synopsis Fundamental aspects of the thiocyanate system are discussed with reference to the leaching of gold. The oxidation of thiocyanate is considered in terms of its ‘stable and metastable products and also in terms of the intermediate species involved—particularly the trithio- cyanate ion, (SCN);. Correlations between thermo- dynamic calculations and electrochemical results are used to demonstrate the participation of these inter- mediate species in the anodic dissolution of gold. The overall approach emphasizes the analogies between the chemical and electrochemical behaviours of SCN and ‘those of the halides (CI, Br and I). “The ability of thiocyanate to dissolve gold in the presence ofa suitable oxidizing agent was first reported by White in 1905." However, that pioneering work was forgotten during the following decades, which ssw the establishment of cyanida- tion as the predominant gold extraction process worldwide. Tt was moze than 60 yeas before the subject was revisited when, in 1986, Fleming” published the results of a investigation of the simultaneous extraction of gold and uranium from South ican acidic pyritic ores in suiphate-thiocyanate media using Fe(m) asthe oxidant ‘A theoretical analysis of the leaching of gold and silver in thiocyanate solutions was published in 1989 by the present authors,? who discussed in detail the chemistry of the thio- cyanate jon and the thermodynamics ofthe interactions of this, ligand with gold and silver. Distribution curves forthe scrics of complexes of Au!) and Au(it) with thiocyanate and Eh-pHT diagrams for the systems SCN-H,O and Au-SCN- 1,0 were presented. More recently, another stady of the speciation in the gold-thioeyanate system was published by Broadhurst and du Preez.* “The present series of three contributions describes the results of a detailed experimental investigation ofthe funda~ :entals ofthe disolution of gold in thioeyanate solutions. In Part further aspects of the chemistry and thermodynamics of the thiocyanate system are discussed, with emphasis on the intermediate species tihiocyanate, (SCN). In Part 2 the redox processes that occur in the Fe(it)-thoeyanate system, and which are responsible for the phenomenon known as autoreduction are discussed, tis shown that autoreduction leads to the formation ofthe intermediate thiocyanate species. ‘The significance ofthese species and thee important role in the leaching of god i considered inthe final contribution of the series. Thiocyanate ion and thiocyanic acid ‘The thiocyanate ion, SCN; has a linear structure with the carbon atom in the centre and has the ability to form covalent ‘Manuscript first received by the Institution of Mining and ‘Metallurgy on 7 Jane, 1993; revised manuscript received on 14 February, 1994, Paper published in Trans. son Min. Merall. (Sec. ©: Mineral Process. Bu. Metall), 103, May-August 1994. © The Institution of Mining and Metallurgy 1994. compounds and complexes. The free ion can be regarded as the combination of two resonance forms, “S-C-N and ‘S=C=N;, on which the linearity ofits structure is based. Thus, the thiocyanate ion is an ambidentate ligand that realizes its donor function via either the S atom or the N atom. This gives rise to two series of covalent complexes, the thiocyanates or S-thiocyanates (written as SCN*) and the isothiocyanates or Nethiocyanates (written as NCS). With homogeneous ‘complexes it is generally observed that soft metal ions form S-thiocyanates, whereas hard metal ions prefer the ‘N-thiocyanate coordination. The former are more frequently, though not exclusively, second- and third-row transition clements, including Au and Ag. The latter aze often first-row transition metals, such as Fe, Mn, Ni, Cu and Zn. Thiocyanate is a pseudohalide, which forms the pseudo- halogen thiocyanogen, (SCN), and the acid thiocyanic acid, HCN. Thiocyanic acid exists as two tautomeric forms, H-S-C_NandH-N=C=S, which are in equilibrium with each other. These result from protonation of the thiocyanate ion at the S or the N atom and are termed thiocyanic acid and iso- thiocyanic acid, respectively. Isothiocyanic acid generally pre- dominates over thiocyanic acid. Regardless of this structural distinction, however, an aqueous solution of the acid is usu- ally referred to as thiocyanic acid and is indicated as HSCN, a practice that is also adopted in the present contributions. Oxidation and anodic behaviour of thiocyanate It is well established that thiocyanate participates in three redox systems that lead to its oxidation to sulphate: SO} + CN-+8H"+ 6e" = SCN-+4H,0 © $0} +CNO-+ 10H" +8e"=SCN-+7H,0 SO} + CO}-+NH, + 11H" + Be" = SCN-+7H,0 @) ‘These systems have been extensively discussed by Gauguin? "and Eh-pH diagrams corresponding to the three redox systems have been published.” Reaction 1 is irrever- sible as CN and SO? cannot be reduced back to SCN either chemically or electrochemically7"* Reaction 2.can be seen as a further irreversible oxidation step leading to the production of cyanate, CNO™ or cyanic acid, HCNO, depending on the pH, Cyanate and eyanic acid, in turn, are ‘metastable oxidation products whose irreversible decom- position into carbon dioxide and ammonia, corresponding to reaction 3, has been reported by different researchers.2101 Cyanic acid, in particular, is very unstable in aqucous solution. According to Jolly? it can be regarded as an aquo- ammono-carbonic acid, easly decomposing into H,CO, and NH. Cyanic acid has a pK, of 3.91 and, thus, below pH 3.91 the very unstable HCNO predominates, resulting in rapid decomposition into NHj and CO,. At pH levels above 3.91 the predominant form is the cyanate ion, CNO™ which is more stable than cyanic acid and is usually considered to bbe the main oxidation product of cyanide in industrial 10spractice. CNO> is, however, metastable and, ultimately, decomposes into carbonate and ammonia. Early experimental observations showed thatthe potentials for the onset of the oxidation of thiocyanate were higher than chose expected from thermodynamic calcu- lations. These diserepancies led to the suggestion that the oxidation mechanism proceeds through the formation of intermediate species, the most plausible, according to Gauguin, >” being thiocyanogen, (SCN),. The existence of thiocyanogen had been proposed much earlier by Bjerrum and Kirschner,!? who determined the standard potential for the couple (SCN) (aq) + 2¢°= 28CN- ® B9 = 0.77 V (versus SHE) Once formed, thiocyanogen undergoes rapid hydrolysis according to the reaction®*? 3(SCN), + 41,0 = SSCN-+HCN+S02+7H" (5) ‘Thus, the overall thiocyanate oxidation process (reaction 1) results from the combination of reactions 4 and 5: 3(SCN),(aq) + 6" = 6SCN- ® 5SCN-+HCN+S0}+7H*=3(6CN), +4H,0 (5) SO} +HCN + 7H? + 6e" = SCN" +410 @ “The stoichiometry indicates the transfer of six electrons for cach thiocyanate ion that is oxidized. When cyanate is con- sidered as the oxidation product eight electrons are involved, as indicated by reaction 2. Eight electrons are also involved when the final oxidation products are carbonate, sulphate and ammonia, as shown by rection 3 ‘Subsequent investigations of the oxidation of alkali metal and ammonium thiocyanates by a variety of reagents in | E,V (Ag-AgCi) ecpicthS Fig. 1 Linear-sweep cyclic voltammograms on stationary gold electrode in aqueous solution containing 0.01 mol 1 KSCN and 041 mal" 1,80, C106 aqueous solution have repeatedly shown that cyanide (or cyanate) and sulphuric acid are the main products and are generated via mechanisms that involve several intermediate species, but, principally, thiocyanogen.'*22 In every case the overall oxidation process corresponds either to reaction 1 or to reaction 2 despite the greater thermodynamic stability of, the equilibrium represented by reaction 3. Electrochemical methods have provided useful infor- ‘mation on the response of thiocyanate to oxidation. The formation of (SCN), in the anodic oxidation of thiocyanate hhas been confirmed by voltammetric studies on platinum electrodes in both aqueous and organic media?*#° Linear potential sweeps show that the anodic currents corres- ponding to the oxidation of thiocyanate become significant only at potentials above 700 mV (versus SHE), which are considerably higher than those estimated thermo- dynamically, ‘The electrode reaction that is responsible for the overpotentials was ascribed to the formation of (SCN). ‘This becomes particularly clear when the anodic oxidation of thiocyanate is caried out in organic media, which prevents interference caused by the rapid hydrolysis of the (SCN), that is formed in the electrode reaction.242528 ‘Similar results are obtained when gold electrodes are used instead of platinum electrodes. ‘This is illustrated by the voltammograms shown in Figs. 1 and 2, which were obtained in the course of the present work, The current densities that are observed with gold anodes are considerably higher than those observed with platinum anodes, which indicates a marked tendency of the thiocyanate ion to adsorb at and react with the surface of metallic gold. The anodic currents in Figs. 1 and 2 become significant only at potentials around 6660 mV (versus SHE)—again showing that there is a consi- ws iy (Ag-Agc), Fig.2 Lincar-sweep cyclic voltammogram on stationary gold tlectrode in aqueous solution containing 0.1 mol 1! KSCN, Supporting electrolyte: 0.1 mot I! H,S0, and 0.2 mol I! KHSO, Sweep rate, 2 mV!Au(Scniy AUOHS(s =] Aulseny, ‘AUlOHIG(=) [Paauos 40 60 80 100 120 140 @ Fe Fig. 3 Bh-pH diagrams for Au-SCN-H,0 system at 25°C, Activities of gold species, 107m. Activites of xe SCN~ or HSCN: (a) 10! t and (8) 10? erable overpotential relative to the values expected on thermodynamic grounds Ttabashi??* used spectroelectrochemical techniques to demonstrate that the anodic currents that are observed during the anodic oxidation of thiocyanate at gold electrodes correspond mainly to the production of the trthiocyanate jon, (SCN). This is currently regarded as the main inter- ‘mediate species responsible for the overpotentials that are ‘observed in the oxidation of thiocyanate on gold.2”-%° The standard potential (versus SHE) was estimated? for the redox couple (SCN)3-SCN* (SCN)5 +26" =38CN- © £9 =0.68V ‘The small cathodic peaks in the voltammograms of Figs. 1 and 2 correspond to the reduction of the (SCN); that is produced in the anodic sweeps. A comparison of these voltammograms with the Eh-pH diagrams for the Au-SCN-H,O system shown in Fig. 3 indicates that the dissolution of gold as the auric complex Au(SCN); should ‘occur at potentials at which the oxidation of the thiccyanate ion to (SCN); is also taking place. Furthermore, the potential range that corresponds to the formation of the aurous complex Au(SCN); is also partly located in the region of formation of (SCN)5. These observations show that it is plausible to hypothesize that (SCN); participates in the mechanism of gold dissolution. Species such as (SCN); and (SCN), act both as oxidants and, on reduction to SCN, as complexants of gold. Experimental evidence for the involvement of these species is provided by the interpretation fof results from experiments on gold leaching by Fe(sn)- thiocyanate solutions that have been reported elsewhere”? and are discussed further in Parts 2 and 3.312 20 00 20 40 60 60 100 120 140 © me 5 § = ott zp +m Fou) concentration, mol Fig 4 Effect of Fe(t) concentration on potential readings in feshly prepared thiocyanate solutions at pH 2 and 3. Lowes readings at pH13 reflect precipitation of Fe(it) due to hydro! ‘Thioeyanate concentration: 0.10 mol I! (as KSCN); temperature, 23°C ‘Mechanistic aspects of leaching of gold by thiocyanate ‘The pseudohalide character of thiocyanate is highlighted by the similarities between the Eh-pH diggram for the AuSCN-H,O. system (Fig.3) and those for. the Au-ClH,O, Au-Br-H,O and Au-I-H,O systems.333435 ‘The dithiocyano-aurous and tetrathiocyano-auric complexes Au(SCN)3 and Au(SCN);, respectively, are the most important since they are the only such species to appear in the predominance-area diagrams. Thermodynamic consi- erations suggest that gold should dissolve as Au(SCN)3 at C107potentials around 600 mV or higher and as Au(SCN); at potentials above ca 680 mV. ‘An important feature of the Au-SCN-H,O system is that gold can be dissolved in the pH range 1-2, which allows the use of several oxidizing agents that are suitable for acidic ‘media—particularly Fe(m). At pH levels around 3 Fe(t) is precipitated by hydrolysis, with a consequent decrease in solution potentials, as shown in Fig. 4. On the other hand, at pH values below 1 the dissolution of gold is expected to decrease owing to the reduction in the activity of SCN> that is caused by its protonation to HSCN. The protonation ‘causes the changes in slope at low pH of the lines that limit the predominance areas uf the complexes Au(SCN)3 and ‘Au(SCN); in the Eh-pH diagrams in Fig 3 ‘The pseudohalide character of thiocyanate is made evident by the many analogies with the halide systems. The following equilibria are found both in organic and in aqueous acide media:?7** ch =a, +cr @ Bey = Be, + Be ® 4 ® A similar equilibrium occurs with thiocyanate in organic ‘media, as was demonstrated by Cauquis and Pierre:°° (SCN); = (SCN), + SCN’ ao K=@4)x107 ‘This equilibrium, however, is not attained in aqueous solution. Reactions 7, 8 and 9 differ from reaction 10 in that the thiocyanate species (SCN), and (SCN); are not stable in acidic aqueous solution, unlike the halide species X, and X; (& = Gl, Br or D. As already discussed, the thiocyanate species undergo 2 complex process of hydrolysis that yields the final oxidation products indicated by reactions 1, 2 and 3. Experimental observations have shown, however, that (SCN)} is considerably more stable than (SCN),, probably Table 1 Standard potentials for halide and thiocyanate redox couples in aqueous solution at 25°C Reaction BAY Reference 0.621 38, 44 0.536 38, 44 (SCN), (ag) +2e"= 28CN-(09) o27 13,45 (SCN); (aq) + 25° = 3SCN (aq) 0.68 a Brg(aq) +22 Lost 38,44 1.0503 38, 44 1.396 ry aise “4 ‘owing to the formation of jon pairs with H* or with other cations in solution 27 The standard potentials of the relevant halide redox couples, given in Table 1, show that thiocyanogen lies between bromine and jodine in its halogenic character. In fact, thiocyanogen is capable of oxidizing I” to L,, whereas Bra, in turn, is capable of oxidizing SCN to (SCN),. A. broader analogy between thiocyanate and the halides is demonstrated by the Eh-pH diagrams shown in Fig. 5 for the SCN-H0 system, which are analogous to those for the BrH,O and I-H,0 systems found in the literarure.?7® However, it must be recognized that the diagrams in Fig. 5 do not correspond to equilibrium situations as only unstable intermediate species have been included in the calculations. ‘The classification of thiocyanate between bromine and iodine also relates to the abilities of the ions to complex with gold and to the process of gold dissolution. The stability constants of the complexes of Au(i) and Au(t) with SCN’ lie between those with Brand T', as shown in Table 2. ‘Theoretically, the dissolution of gold by thiocyanate occurs, at potential values that are lower than those for the bromine system and above those for the iodine system, as can be seen, from a comparison of the diagrams in Fig. 3 with those for the Au-Br-H,O and Au-I-H,O systems published by other authors. 333435 2 20 10 Eh 00} oo 20-40 BOBO ae Ao to 20 40 60 80 OD ho aH pH @ ® Fig. 5 Eh-pH diagrams for SCN-H,O system at 25°C considering only intermediate species in oxidation of thiocyanate (metastable and stable oxidation products were disregarded in calculations) C108Table 2 Stability constants of halide and thiocyanate complexes with gold Gold ‘Complex Lo 8, oxidation Aud Auly 2118 AuSCN(@@) 15.27 AUu(SCN)5 19.16 AuBry 1455 AuCl; 1137 auch); 38.89 Aucuy Auk 48.06 AiG, 4.66 AUS 48.62 Au(SCN)} 43.67 ANB, 33.48 AuCh, 26.34 *Calculated from AG® data given by Hiskey and Attu? {Calculated from AG° data given by Berd and co-workers. 07 06 oo as Potential, mV versus SHE os LNGhaad GauaeOh al FEA wal DD + log [SCN] Fig. 6 Eh versus log(SCN'] lines showing potential zones of predominance of Au(SCN)3 (above line 4), Auw(SCN); (above line B) and (SCN); (above line ©) considering total activity of gold in solution as 10-9 at, equal activities of gold complexes and activity of (SCN)j as 1% ofthat of foe SCN Species such as X3 and X, (X= Cl, Br or T) are regarded 1s good oxidants for gold.39-42 The work reported in Parts 2 and 3°42? Jeads to the conclusion that the same is true of (SCN); and (SCN), and that the participation of these species in the mechanism of gold dissolution is similar to that ‘of the homologous halide species. ‘The formation of Au(SCN)3, Au(SCN); and (SCN); ‘can be compared by plotting together the straight lines corresponding to equations 11, 13 and 15; this has been done in Fig. 6, where line A represents Au(SCN); +°= Aus) + 28CN- ap = 0.3952 -0.1182og[SCN*] a2 line B represents Au(SCN); +26" = Au(SCN)3 + 2SCN- a3) B= 0.6433 ~ 0,0591 log{SCN'] ay Conditions Reference Temp., Tonic strength, °C uw 25 ° + 25 30 46,47 25 ° t 25 ° t 25 ° t 25 ° t 25 ° . 25 ° t 25 ° t 25 ° t 25 ° t 5 ° t and line C represents (SCN)5 + 2e" = 3SCN- as) E=0.6209 ~ 0.0591 log[SCN] a6) ‘The plot in Fig.6 was calculated from data given elsewhere™® and on the assumption of a total activity of gold in solution of 10° xt and an activity of (SCN); equal to 19 ‘of that of free SCN~, This valuc is typical of that found in the leaching of gold with Fe(a1)-thioeyanate solutions.2912 ‘The aurous complex Au(SCN); is formed at potentials at which SCN predominates in the area bounded by lines A and C (Fig. 6). The same aurous complex is also formed in the area bounded by lines B and C, where the predominant thiocyanate species is (SCN);. The auric complex Au(SCN), in tur, is formed above line B, where (SCN); predominates. The predominance of the aurie complex Au(SCN); at mixed potentials above line B of Fig, 6 was frst demonstrated experimentally by Bjerrum and Kirschner!? and, much later, by Pouradier and Gadet.* The above calculations have proved to be useful in the interpretation of the results of experiments on gold leaching by Fe(tn)-thiocyanate solutions. The mixed potentials in such solutions decrease spontaneously with time owing to the autoreduction of the Fe(m)-thiocyanate complexes. Leaching experiments with a rotating gold disk revealed that initially Ge. during the first minutes) the mixed potentials correspond to the formation of Au(SCN);, whereas later the formation of Au(SCN); predominates, a gradual transition ‘occurring between the two conditions.299%2 Conclusions ‘The thermodynamic analysis presented here suggests that gold can be leached by thiocyanate at potentials around, 600-700 mV (versus SHE). The system can operate at PH levels between 1 and 3, which allows the use of Fe(ai) as the oxidant. Gold is expected to dissolve mainly as the complexes Au(SCN)3 and Au(SCN);. Electrochemical measurements indicate that the dis- solution of gold occurs at potentials at which the oxidation of thiocyanate also takes place. The experimental data show that considerable overpotentials are associated with the oxidation of thiocyanate, which proceeds through the 109formation of several intermediate species, the main intermediates being (SCN); end (SCN),. These species can, act both as oxidants and, on reduction, as complexants for gold. They are postulated to be the primary oxidizing agents, in the mechanism of dissolution of gold. AAs far as the chemical, electrochemical and mechanistic aspects are concerned, marked analogies are observed between the thiocyanate and the halide systems, such species ‘as X5 and X, (X= SCN, Cl, Br or D playing important roles, in the mechanism of gold dissolution, Acknowledgement ‘One of the authors (O.B-F.) is grateful to the Brazilian ‘Research Council (CNP9) for the award of a scholarship and to the Catholic University of Rio de Janeiro and Per6xidos do Brasil, Ltda, for other financial support. References 1. White H.A. The solubility of gold in thiosulphates and thioeyanates.j. Chom. Metall Min. Soc. S. Afca, 6, 1905, 109-11, 2,” Fleming C. A. A process for simultancous recovery of gold and. ‘uranium from South Afican ore. In Gold 100—Proc. Inert. conf ‘on gold. Vol 2: Extractioe mezalurgy of gold. 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Smith RM, and Martell A. E. Crisial sabilcycontants—Vol 4: Inorganic complexes. (New York: Plenum Press, 1976), 257. 47, Riehl C. Bestimmung der Subilitskonstanten yon in ‘wiseriger Losing exitieenden Komplesverbindungen awischen Gold (1+) und Rhodanidionen. Z, Ps. Chem. (Leipzig), 232, 1966, 380-00. Biographies of the autor appear on page C125.