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Kinetics of Silver Dissolution in Nitric Acid from Ag-Au0.04 -Cu0.10 and Ag-Cu0.23 Scraps
S.K.Sadrnezhaad , E.Ahmadi and M.Mozammel
Center of Excellence for Advanced Processes of Production of Materials, Department of Materials Science and Engineering, Sharif University of Technology, Tehran, Iran
[Manuscript received September 27, 2005, in revised form January 30, 2006]

Kinetics of dissolution of silver present in precious metal scraps in HNO3 was studied in temperature range of 2685 C. Dissolution rate of silver was much faster than that of copper at all temperatures. Eects of particle size, stirring speed, acid concentration and temperature on the rate of dissolving of silver were evaluated. Dissolution rate decreases with particle size and increases with temperature. Dissolving was accelerated with acid concentrations less than 10 mol/L. Concentrations greater than 10 mol/L resulted in slowing down of the dissolution rate. Shrinking core model with internal diusion equation t/ =13(1x)2/3 +2(1x) could be used to explain the mechanism of the reaction. Silver extraction resulted in activation energies of 33.95 kJ/mol for Ag-Au0.04 -Cu0.10 and 68.87 kJ/mol for Ag-Cu0.23 particles. Inter-diusion of silver and nitrate ions through the porous region of the insoluble alloying layer was the main resistance to the dissolving process. Results were tangible for applications in recycling of the material from electronic silver-bearing scraps, dental alloys, jewelry, silverware and anodic slime precious metal recovery. KEY WORDS: Silver; Copper; Kinetics, Dissolution; Shrinking core model; Internal diusion

1. Introduction Silver is used as an alloying element, coating material, ornament, catalyst and biosensor[1,2] in medicine, battery and lm industry[2,3] . Silver nitrate has a wide application in electroplating, painting, xerography and chemical processing. Silver is produced directly from its ores or as a by-product of zinc, copper and lead[35] . The world consumption of silver exceeds its mine production rate. Silver containing articles must, therefore, be recycled in order to partly cover its consumption[6] . Recovery of the scrapped products plays an important role in fulllment of the increasing silver demand in a foreseeable future. A common process used in precious metals industry to separate silver from gold is nitric acid dissolution[712] . Alloys with high silver content can be directly treated with HNO3 to dissolve their silver content and to leave the undissolved elements as a separable solid phase[12] . This method is preferably used in small-scale processes like alloy renement when aqua regia dissolution is not a suitable treatment. Many investigations on silver/copper reaction with nitric acid solutions can be found in literature [710]. Schack and Clemmons[11] illustrated a high temperature treatment of silver scrap via smelting and cupellation. Martinez et al.[12] report on silver molar fraction that substantially aect on the rate of silver nitrate formation. With both high nitric acid activity and temperature, Martinez et al.[12] showed an outward diusion of nitrate molecules within the undissolved gold containing less than 0.65 mol fraction of silver[12] to control the dissolution rate. At 0.7 and more silver mole fraction, a solid-surface chemical mechanism with activation energy of 54.3 kJ/mol prevails. Jiang et al.[13] illustrated the leaching kine Prof., Ph.D., to whom correspondence should be addressed, E-mail: sadrnezh@sharif.edu; sadrnezh@yahoo.com.

tics of pyrolusite of Mn-Ag ores in presence of hydrogen peroxide. The activation energy obtained by them is 4.450.3 kJ/mol at 3060 C in nitrate[13] . Traditional recovery of precious metals from anode slime consists of fusion of sludge in presence of ux, cupellation, melting with-lead in a cupel and parting. Lead is oxidized by atmospheric oxygen and absorbed by the magnesite in the cupel. This leaves gold, silver and platinum group elements as a button, which can be weighed to determine the total content of the precious metals. This usually contains too much gold to be separated by nitric acid treatment. Kunda[14] applied an alternative hydrometallurgical silver extraction method, which consisted of (a) sulfuric acid leaching of the silver bearing materials, (b) dilution in water of the product, (c) dissolving in dilute ammonia of the precipitate and (d) reduction with hydrogen of the precipitate into silver[14] . Similar processes can be applied to the solid waste materials containing silver bearing substances. Ultrasound can help to increase the rate of the leaching process[15] . The precious metals such as gold, silver, selenium and tellurium can be recovered from the anodic slim by (a) nitric acid leaching, (b) liquid-liquid extraction and (c) direct reduction[16,17] . In comparison with the conventional pyrometallurgical processes, Wang et al.[16] claimed hydrometallurgical process to be economic, energy-saving and pollution-free. Demir et al.[18] determined a semi-empirical kinetic model for dissolution of metallic copper particles in HNO3 . Their results showed 18.81 kJ/mol of activation energy. Kinetics of reaction between metallic silver and nitric acid was investigated by Ozmetin et al.[19] in the concentration range of 7.2214.44 mol/L. Their results have shown a surface reaction control with activation energy of 57.66 kJ/mol. Literature lacks essential information on kinetics

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of silver recovery from silver bearing waste materials such as electronic wastes, photographic lms, spent catalysts and jewelry scraps. Signicant amounts of these materials are created these days throughout the world[20,21] . This paper aims to elucidate the kinetics and mechanism of dissolution of silver present in Ag-Au0.04 -Cu0.10 and Ag-Cu0.23 scraps in nitric acid. The results are useable to improve recovery of precious metals from silver bearing scraps and wastes[22] . It is therefore of value to the newly growing materials recycling technologies[2022] . 2. Experimental Ag-Cu0.23 ingots were produced by melting and casting of analytical grade raw materials in alumina crucibles. Chemical composition of the samples is 85 wt pct Ag and 15 wt pct Cu. Pieces of metals (silver and copper) were weighted, charged and heated up to 1050 C for 15 min. Alloy lings were made of the ingot by hack sawing of the specimens. The empirical data obtained by Rubcuminintara and Tasaso[6] for Ag-Au0.04 -Cu0.10 jewelry scraps having 86.91 wt pct Ag and 5.89 wt pct Cu were also used for data verication and comparison purposes. The experimental conditions used in this research are similar to those. Dissolving experiments were carried out in a oneliter cylindrical container immersed into a thermostatically controlled water bath. Test temperatures were selected in the range of 26 to 85 C. After the container was warmed up to the required temperature, it was fed with 250 ml of aqueous HNO3 being stirred with a specied rate. The stirring rate remained constant during each test and one gram of lings was added to the container. At selected time intervals, 5 ml solution was sampled. The samples were diluted to the desired volume in a volumetric ask. The analysis of the diluted samples was made with an atomic absorption spectrophotometer (AAS). Dissolution kinetics was determined by analyzing the dissolved silver. Assuming that there exists a spontaneous reaction, fractional extraction can be dened as the ratio of the concentration of the metallic species present in the solution at time t divided by its total amount in the alloy. The apparatus was calibrated with a series of well known standard solutions. The uncertainties of the measurements were estimated with regression analysis procedure. The correlation coecient (R2 ) was found to be in the range of 0.980.99. 3. Results and Discussion Dierent mixing speeds were used to monitor the eect of stirring on the rate of dissolution of the silver. The rate of dissolution did not change with the speed of mixing. This nding was consistent with the data reported by previous authors[6] . Therefore, external transfer was not the controlling step for silver dissolution. Other inuential parameters were concentration, alloy particle size and temperature. Figure 1 shows the eect of nitric acid concentration on fractional dissolution of silver. It can be seen from Fig.1 that the dissolution rate increases with acid concentrations up to 10 mol/L HNO3 and then decreases beyond this
Fig.1 Eect of acid concentration on fractional dissolution of silver of Ag-Au0.04 -Cu0.10 alloy

Fig.2 Eect of particle size on fractional extraction of silver and copper at 26 C. Part of the data is obtained from literature [6]

concentration. A maximum is therefore observable at 10 mol/L nitric acid concentration. Martinez and Espiel[12] investigated the eect of nitric acid concentration on dissolution rate of silver in Ag-Au alloys and found that the reaction was rst order with 51.1 and 75.12 pct silver at 80 C and 3.87.10 mol/L nitric acid concentrations. For alloys with 51.1 pct silver and acid concentrations exceeding 6 mol/L, the reaction order dropped to zero. HNO3 reduced generally to NO2 at these concentrations. For leaching silver from copper anode slime, it was reported that there is an optimum nitric acid concentration of about 7 mol/L[23] . This value was lower than the acid concentrations corresponding to the maximum rate of extraction of silver in this investigation. According to Butts and Coxe[24] , the solubility of silver nitrate in water decreases considerably with the nitric acid concentration. The decrease in dissolution rate of the silver beyond 10 mol/L HNO3 concentration seems therefore to be due to this effect. The concentration for dissolution experiments was chosen 10.4 mol/L. Eect of particle size on fractional extraction of silver in the nitric acid solution is depicted in Fig.2. As is seen, the dissolution rate decreases with average size of the particles. The silver dissolution rate seems, therefore, to be sensitive to the internal (pore) mass diusion step. This contradicts with the conclusion mentioned by previous researchers, who claimed a single-step chemical control mechanism[6] . Figure 3 shows that the amount of copper extraction is much less than that of silver, especially at low temperatures. However, both rates increase dramatically with temperature. A much faster dissolution process was therefore observed at 85 C than at room temperature. A comparison of the extraction data for Ag-Cu0.23 and Ag-Au0.04 -Cu0.10 alloys given in Fig.4

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reactions[6,12] . 3Ag(s)+4HNO3 (aq) 3AgNO3 (l)+NO(g)+2H2 O(l) (1) Ag(s) + 2HNO3 (aq) AgNO3 (l) + NO2 (g) + H2 O(l) (2) With alloy compositions and nitric acid concentrations used in this investigation, Reactions (1) and (2) are spontaneous at room temperature. Sum of the two reactions is as follows: 4Ag(s) + 6HNO3 (aq) 4AgNO3 (l) + NO(g) + NO2 (g) + 3H2 O(l) (3) At high nitric acid concentrations, the following reactions may also become feasible[79] : 2Cu(s)+4HNO3 (aq) Cu(NO3 )2 (aq)+ Cu(NO2 )2 (aq) + 2H2 O(l) Cu(NO2 )2 (aq) + 2HNO3 (aq)
Fig.3 Eect of temperature on extraction: (a) silver and (b) copper from Ag-Cu0.23 alloy having a particle size of 75150 m with 10.4 mol/L HNO3 and a stirring rate of 250 r/min

(4) (5) (6) (7) (8) (9)

Cu(NO3 )2 (aq) + 2HNO2 (aq) Cu(s) + HNO3 (aq) + HNO2 (aq) Cu(NO2 )2 (aq) + H2 O(l) Cu(NO2 )2 (aq) + 2HNO3 (aq) Cu(NO3 )2 (aq) + 2HNO2 (aq) HNO2 (aq) + HNO3 (aq) 2NO2 (g) + H2 O(l) Cu(s)+4HNO3 (aq) Cu(NO3 )2 (aq)+ 2NO2 (g) + 2H2 O(l)

Fig.4 Eect of temperature on fractional extraction of silver from Ag-Cu0.23 and Ag-Au0.04 -Cu0.10 alloys leached with 10.4 mol/L HNO3 at 250 r/min. The data on ternary alloys are from literature [6]

Table 1 Thermodynamic properties of substances at 298 K and 105 Pa[27] Substance Ag(s) Cu(s) AgNO3 (l) Cu(NO3 )2 (aq) HNO2 (aq) HNO3 (aq) H2 O(l) NO(g) NO2 (g) Hf /(kJ/mol) 0 0 124.52 350 119 207 286 90.2 33.2 S /(J/molK) 42.68 33.14 140.92 193 46.1 53.5 69.95 211 240

indicates that the presence of gold in the scrap has an increasing eect on the rate of extraction of silver especially at lower temperatures. This implies a positive interaction parameter of gold on silver in AgAu0.04 -Cu0.10 alloys employed in this study[25] . The closest kinetic mechanism indicates the optimal condition for maximum recovery of silver from silver containing metallic objects. From thermodynamics, the spontaneity of the dissolution process can be predicted. The dissolution reaction of the impure alloys in nitric acid can be expressed by several typical

Dissolution reaction of silver depends on the nitric acid concentration. With a dilute acid, Eq.(1) is applicable. With a concentrated one, Eq.(2) proceeds further. For simplicity, we chose Eq.(3), which is a combination of two reactions. With nitric acid, HNO2 has a catalytic eect on dissolution of copper. Nitrogen dioxide can react with water to form nitric acid (compare Eqs.(8) and (9)). We have, therefore, chosen Eq.(9) for our evaluations. The standard Gibbs free energy change (G ) in Reactions (1)(9) can be determined from Hf and S data of compounds and elements (see Table 1). Standard Gibbs free energies in Reactions (3) and (9) are, thus, obtained to be 209.06 and 196.20 kJ/mol at 298 K and 105 Pa, respectively. If all activities are considered unity, the reactions seem spontaneous at room conditions. Figure 3 shows that Reaction (3) is more favorable than Reaction (9) under the experimental conditions used in this research. Therefore, it is logically reasonable to assume the activity of silver greater than that of copper and gold. Reactions (1)(3) require NO /Ag+ ion trans3 port between the reaction-site and the bulk-liquid phase. The experimental data obtained in this research were used to check the dierent kinetic models available for solid-uid reactions[26] . Since copper and gold do not favor reaction with HNO3 at room temperature, a porous metallic layer composed of Cu (and Au) remains on the surface of the un-reacted AgCu0.23 (or Ag-Au0.04 -Cu0.10 ) core. The radius of the scrap grains does not, therefore, considerably change with advancement of the reaction. Pore diusion control with constant particle-size gave the best answer with correlation coecients

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greater than 0.96. For spherical particles having the average initial radius of R0 , the total conversion time is dened by the following equation. =
2 a R0 6bDe cA

(10)

where a is the molar density of the alloy; b is the stoichiometric coecient of the reaction (3/4, 1/2 and 2/3 for Eqs.(1), (2) and (3), respectively); De is the coecient of inter-diusion of Ag+ and NO ions through 3 the porous metallic layer and cA is the concentration of HNO3 in the bulk solution. Reactant and product ions, i.e. NO and Ag+ ions, must diuse through3 out the pores in order to obtain an on-going reaction. De is the inter-diusion coecient of NO and Ag+ 3 indicating ion transfer within the porous region. The reaction between silver and nitric acid is of electrochemical nature. Because of considerable conductivity of the metallic layer, there is no resistance to charge transfer through the solid region. The only remaining resistance is thus related to the NO and 3 Ag+ ion transfer through the aqueous electrolyte that lls the porous region of the solid phase. This resistance is considered by the inter-diusion coecient De in the present system. The dimensionless conversion time relevant to the pore diusion mechanism can be obtained by the following equation: t = 1 3(1 x)2/3 + 2(1 x) (11)

Fig.5 Internal diusion plot for silver dissolution: (a) Ag-Cu0.23 alloy at dierent temperatures and (b) Ag-Au0.04 -Cu0.10 particles at dierent acid concentrations

Silver dissolution plot on the right side of Eq.(11) is depicted against time in Fig.5. Regression analyses of the data indicated correlation values of 0.99 at different temperatures. Other model correlations were plotted against time. No cases gave better straight lines than those in Fig.5. The data plotted in Fig.2 conrms the above conclusion. As it is seen, the size of the alloy particles has a substantial eect on the extraction rate of the silver. In order to assess the quantitative relationship between the total conversion time and the average size of the particles, the slopes of the curves shown in 2 Fig.5 were plotted vs R0 , as shown in Fig.6. The straight line regression equation was found to have a correlation factor of 0.98. It was, therefore, assessed once more that the silver dissolution from the alloys into the nitric acid was controlled by diusion. The eective internal diusion coecient De was estimated from Eq.(10). The density of the AgAu0.04 -Cu0.10 scrap is nearly 11.03 g/cm3 while that of Ag-Cu0.23 is about 10.25 g/cm3 (estimated from densities of pure elements with an ideal solution model). The average initial size of the lings was used from the sieve analyses data. The results obtained was De =7.59107 cm2 /s for Ag-Au0.04 -Cu0.10 and 5.76107 cm2 /s for Ag-Cu0.23 scrap at room temperature. The radius of Ag+ ions (0.113 nm) is smaller than that of Ag atoms (0.144 nm). On the contrary, the radius of NO ions (0.200 nm) is larger. Consider3 ing geometry of the system, it may be concluded that the pore diusion for Ag+ /NO ions is not easy for 3 their transfer within the bulk phase. Porosity and

Fig.6 Eect of initial radius on the total extraction time of silver from Ag-Au0.04 -Cu0.10 alloy

tortuosity are two important factors that aect the amount of the diusion coecient in porous regions. De = D(Ag+ /NO )
3

(12)

where DAg+ /NO is bulk inter-diusion coecient; 3 is porosity and is the tortuosity coecient of the porous region. Bulk diusion coecient of AgNO3 in aqueous HNO3 media is reported to be 1.71105 cm2 /s at room temperature[28] . The inter-diusion coecients obtained in this research are mush smaller than this. Considerable dierence between these coecients indicates signicant inuence of the electrochemical and geometrical characteristics of the present porous system. AgNO3 has lower solubility at higher acid concentrations (cHNO3 10 mol/L). Solid precipitate may thus partially block the reaction front at cHNO3 10 mol/L. Rate controlling mechanism can hence locally change from pore diusion into transfer in solid phase. The reaction rate is therefore reduced due to lowering of De inside the porous layer. The frequency factor and the activation energy of dissolution of silver are thus determined using the Arrhenius law. De = D0 eQ/RT (13)

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Table 2 Activation energies and frequency factors evaluated from application of the silver dissolution data to the mathematical model developed for internal transfer of silver into nitric acid solution Alloy Ag-Au0.04 -Cu0.10 Ag-Cu0.23 Q/(kJ/mol) 33.95 68.87 D0 /(cm2 /s) 0.73 2.27106

REFERENCES [1 ] A.Vaskelis, A.Jagminiene, L.T.Tamasiunaite and R.Juskenas: Electrochim. Acta, 2005, 50, 4586. [2 ] T.W.H.Oates, L.Ryves, M.M.M.Bilek and D.R.McKenzie: Sensors and Actuators B, 2005, 109, 146. [3 ] M.S.Oncel, M.Ince and M.Bayramoglu: Ultrasonics Sonochem., 2005, 12, 237. [4 ] R.Raghavan, P.K.Mohanan and S.C.Patnaik: Hydrometallurgy, 1998, 48, 225. [5 ] M.Wang, Y.Zhang, T.Deng and K.Wang: Miner. Eng., 2004, 17, 943. [6 ] T.Rubcuminintara and P.Tasaso: www.cape.canterbury. ac.nz (Cited at June 15, 2005). [7 ] F.M.El-Cheikh, S.A.Khalil, M.A.El-Manguch and A.O.Hadi: J. Chem. Edu., 1985, 62(9), 761. [8 ] R.A.Stairs, W.D.Hill and F.M.El-Cheikh: J. Chem. Edu., 1987, 64, 1069. [9 ] J.D.Carr, W.D.Hill, F.M.El-Cheikh: J. Chem. Edu., 1990, 67(2), 183. [10] C.Ozmetin, M.Copur, A.Yarta,s and M.M.Kocakerim: y Chem. Eng. Tech., 2000, 23(8), 707. [11] C.H.Schack and B.H.Clemmons: Extractive Processes: Silver, Economics, Metallurgy and Use, D.Van Nostrand Company, Inc., Princeton, New Jersey, 1967, 57. [12] L.L.Martinez, M.Segarra, M.Fernandez and F.Espiel: Metall. Trans. B, 1993, 24, 827. [13] T.Jiang, Y.Yang, B.Zhang, Z.Huang and G.Qiu: Hydrometallurgy, 2004, 72, 129. [14] W.Kunda: in Proc. the Third Conf. on Precious Metal, Sponsored by the International Precious Metals Institute, Inc.: Chicago, Illinois, 1972. [15] M.Salim Oncel, M.Ince and M.Bayramoglu: Ultrasonics Sonochem., 2005, 12, 237. [16] W.Wang, Y.C.Hoh, W.S.Chuang and I.S.Shaw: U.S. Patent 4293332, October 6, 1981. [17] A.M.Amer: Waste Manage., 2003, 23, 763. [18] H.Demir, C.Ozmetin, M.M.Kocakerim, S.Yartasi and M.Copur: Chem. Eng. Processing, 2004, 43, 1095. [19] C.Ozmetin, M.Copur, A.Yartasi and M.M.Kocakerim: Ind. Eng. Chem. Res., 1998, 37, 4641. [20] H.E.Hilliard: U.S. Geological Survey, Version 1.0, U.S. Department of the Interior, Reston, Virginia, 2003, N1. [21] M.Harper and J.M.Siegel: Air & Waste Manage. Assoc, 53, 434. [22] A.Gherrou, H.Kerdjoudj, R.Molinari and E.Drioli: Desalination, 2001, 139, 317. [23] Y.C.Hoh, I.S.Shaw and W.K.Wang: in Proceeding at 72nd AIChE Annual Meeting, San Francisco, USA, 1979 (Cited by 6). [24] A.Butts and C.D.Coxe: Silver-Economics: Metallurgy and Use, R.E.Krieger Publ. Comp., Huntington, USA, 1975 (Cited by 6). [25] C.H.P.Lupis and J.F.Elliot: Acta Met., 1966, 14, 529 and 1019. [26] O.Levenspiel: Chemical Reaction Engineering, John Wiley and Sons, New York, 1972, 578. [27] http://www.ualbrta.ca/ jplampec/che/data/index.htm (Cited at August 29, 2005). [28] A.James and M.Lord: Index of Chemical and Physical Data, Van Nostrand Reinhold, NY, USA, 1992, 98.

where D0 is the frequency factor and Q is the activation energy of the diusion. R is the universal gas constant and T is the absolute temperature of the solution. The results is illustrated in Table 2. The values evaluated for the activation energies of the silver supported the porous metallic layer diusion. Considerable reduction in frequency factor of silver due to presence of gold in the alloy implies the signicant interaction between the two species of the system. This could be the matter of further investigation. 4. Conclusions (1) Based on the data presented in this paper, the rate of reaction with nitric acid of the silver contained in jewelry scrap, silver-copper and silver-copper-gold alloys are inuenced by particle size, acid concentration and temperature. Insertion of the empirical data into dierent solid-uid kinetic models indicated a shrinking core internal diusion equation explaining the mechanism of the reaction. The kinetic data showed a linear relation of 13(1x)2/3 +2(1x) with time. The apparent activation energies obtained depend on the chemical species present in the scrap phase. (2) An eective inter-diusion coecient, De , of 7.59107 cm2 /s for Ag-Au0.04 -Cu0.10 and 5.76107 cm2 /s for Ag-Cu0.23 scrap was obtained for ion transfer through the porous silver-less layer formed at exterior of the particles because of dissolution of silver at room temperature. The maximum rate of dissolution occurs between 7.9 and 10.4 mol/L acid concentration. This is due to lower water solubility for AgNO3 in presence of nitric acid at 26 C. Previous investigators have recognized the AgAu0.04 -Cu0.10 grains size eects on the rate of silver dissolution[6] . This nding is also backed-up by our further measurements (Fig.2). The extraction rate decreases, for example, by increasing of the size of the particles dissolving in the nitric acid solution as shown in Fig.2. This result is in obvious contradiction with chemical reaction mechanism reported by previous authors[6] .
Acknowledgements The authors would like to express their appreciation to Ms. A.Ruhani Mashhadi for AAS tests, Mr. P.Abdollahi for technical assistance and Mr. S.M.M.Sadrnezhad for his help in mathematical calculations.

Nomenclatures b: stoichiometric coecient (dimensionless) cA : concentration of H+ ion in the bulk solution (mol/L) De : eective diusion coecient of ions in porous medium (cm2 /s) a : molar density of the alloy R0 : initial radius of particles (microns) t: time (s) : time for complete conversion (s) T : temperature (K) x: fraction extracted