Berichte der Bunsengesellschaft fiir physikalische Chemie (friiher Zeitschrift fitr Elektrochemie) Band 67, Heft 4, 1963 (Seite 402-406) Kinetics and Mechanism of Copper Dissolution in Aqueous Ammonia By Fathi Habashi Verlag Chem GmbH, Weinheim/Bergstr.|8 F. Habashi: Kinetics and Mechanism of Copper Dissolution in Aqueous Ammonia Kinetics and Mechanism of Copper Dissolution in Aqueous Ammonia By FATHI HABASHI NRC Research Fellows, Department of Mines and Technical Surveys, Extraction Metallurgy Division, ‘Ottawa, Canada (Eingegangen am 26. September 1962) ‘The disolution of copper in aqueous solutions of ammonia isa corrosion proces in which the cathodic reaction ir the reduction of oxygen atthe strface ofthe metal according t0 ¥,0,+ 1,0 +2€° 2087 andthe anodic reaction isthe oxidation of copper according to Cu + 4NH, + Cu(NH,)f* + 2¢7 Superimposed with these reactions ithe cuprous-cupic equilibrium: (Cu(NH,)j" + Cu 2Cu(NH,)} Ca(NHgy + 2H, + Cu(NHye + ‘Atheoretcal derivation of the velocity equation of the distoltion proces has ben obtained, which describes “qwanttatively the experimental facts. The equation i 3s follows: 2k ke A[O,)[NHg]} ‘2k, [O.) + BINH) where ys fas he and fare constants, isthe suriceateaof the metal in contact with the aqueous phase and [G41 INI] and [Cu] ae oxygen, ammonia and cupric ion concentrations respecuvely. Rat + by A[Cum]"* — J (NH) Die Aufllsung von Kupfer in wBriger Ammoniaklisung ist ein KorrosionsprozeB, bei dem als kathodische eaktion die Reduktion von Sauerstoff an der MetalloberBiche gemi0: 1YOy+ H,O + 2¢° + 208° sufirite, wahrend die anodische Reaktion in der Oxydation des Kupfers besteht: (Cu + 4NH, + Cu(NHi* + 26° Diesen Reaktionen ist das Gleichgewicht zwisehen Cu(I)/Cu(D)tonen diberlagert CUNY + Cu e 2CuNHDE (CuNHi)t + 2NH, + CNH) + Es wird eine cheoretsche Ableitung einer Geschwindigheitsgleichung fUr die Kupferauflisung gegeben, die Beret de Biengselhat ‘quantieativ die experimentellen Erfahrungen wiedergibt. Die Gleichung lautet Geschwindigheit = 2k by A[Og] [NH] 2k,[Od + keINF] Es bedeuten: ly, yy ky und f Konstanten, A die Metalloberfliche in Kontakt mit der w: + kA Coty" — J (NEG) igen Phase sowie TOs}, [NE] und [Cut] die Konzentrationen der betrefenden Stoffe Introduction ‘The solubility of metallic copper in aqueous ammonia solutions was known since 1858 by Peligot!). The blue solution obtained from this reaction was used extensively 0 dissolve cellulose to manufacture the cuprammonium sayon, Schweizer?) In the ammonia synthesis industry, this blue solution is used universally 4) E.Peligot,C.R. hebd.Seénces Acad. Sci. 47,1034 (1858), 4) E Schweizer, J. prakt. Chem. 76, 344 (1859) to purify the synthesis gas from carbon monoxide, which otherwise would poison the catalyst. ‘The action of aqueous ammonia on metallic copper also received attention in extractive metallurgy, and ic ‘was suggested as a possible process for recovering copper from ores, Benedict?) In the USA this process was applied successfully to leach native copper from tailings to0 low in copper (0.4% Cu as metal) to be effectively 9) CH. Benedict, U. S. Patent 1,131,986 (1915)By. recovered _by other process, Benedict and Kenny). Similar processes were also applied to recover nickel INCO staff) and cobalt Caron) from ores after a simple reduction treatment to the metallic state, ‘A knowledge of the mechanism of these leaching processes is therefore of interest to the chemical as well as the metallurgical industries. In this paper, the mecha- nisms previously suggested are criticized and a new mechanism is discussed which overcomes their draw- backs. The similarity between this reaction and the ceyanidation of gold and silver is noted. Chemistry of Dissolution ‘twas realised since the discovery ofthis reaction that no dissolution takes place in the absence of air, Schwei- es), The reaction was formulated as follows: Cu + ANH, +0, + HO + CulNHF + 20H". (1) ‘There is evidence that some nitrite is formed during the dissolution; copper acting as a catalyst for the oxidation of ammonia, Schénbein’): 2NHygq) + 30,4 20H" + 2NOz + 41,0. Q) No other oxidation-reduction products such as HO, 6 cuprous ions were detected in solution, Halpern’) Ammoaium ion alone does not dissolve copper; but when added to NH, solutions it increases the rate, Schweizer?). This was confirmed by Fisher and Halpern’), who found further that beyond a certain NH{/NH, ratio further addition of NH; has no effet; apparently due to a buffering action. Halpesa et al") found Further that when NaOH is added to the solution, the rate decreases. This leads us to atteibute the accel. crating effect of NH} to be two-fold; frst increasing the conceateation of free ammonia, and secondly decreasing the OH" concentration as given by the following wo reactions NH, + H,0 <*NHt + OH” e NHj + 1,0 ==NH, + HO" ® A thermodynamical study of the reaction was pres- ented by Halpern), Mechanisms suggested 1, The autonateytic mechani ‘The dissolution was assumed to take place in thee steps ) Formation of cuprous-ammine complex 2Cu + ANH, + 1,0, + HO» 2CuNH)! +208". 6) ©) GH Benedict and C,H. Kenny, Trans, Amer, Inst Mining Metallurg. Engr. 70, 95 (1924), ') The International Nickel Company Staf, Canad. Mining Metallang. Ball. 59, 201 (1956), *) MLH.Caron, ‘Trans. Amer. Inst. Mining Metallurg. Eng. 188, 67 (1950). 3) C.F Schénbein, Her. Akad. 580 (1856) and later papers. I. Halpern, J. electrochem. Soe. 100, 421 (1953). 8) EL Fischer and J. Halpern, J. electrochem. Soc. 103, 282 (1956), %) J. Halpern, H. Milants and D.R. Wiles, J. electro chem, Soc. 105, 647 (1959). 1) J. Halpern, J. Metals 9, 280 (1957). [ Habashi: Kinetice and Mechanism of Copper Dissolution in Aqueous Ammonia b) Oxidation of the cuprous-ammine to cupric~ ammine by oxygen: CHOSE + ANH, + 1,0, + YO —+ ColNHAE + 20H. © ©) The reduction of the cupric-ammine to cuprous by copper: Cun) + Cu #2 CoN 0 It is apparent from this mechanism that the cuprous teupric equilibrium plays the role of a catalyst. Supporters of this mechanism were: Yamasakilt), Zeretskii and Akimov"), and Lu and Graydon"). 2. The copper-oniecflm mechanism In this mechanism the dissolution of copper was believed to follow the following steps: 4) Adsorption of dissolved oxygen onto the copper surface cu + 4,0, 8 cu-0 ® ) Reaction of an NH, molecule oxygen complex with the copper Ni Ca 0+ Nig FH ca HOH cu + 2087 Ko ae Co(NH,)* + NH, —+ CuNE % ‘This mechanism was originally suggested by Lane and MeDonald'§)") who thought that CuO was formed, and later modified by Halpeen*) who stressed that oxygen was only adsorbed on the copper surface. This view was maintained by Fisher and Halpern’), Halpern et al.!®), and Sircar and Wiles"). The last two studies wore concerned with complexing agents other than ammonia ‘The first mechanism was criticized by Halpern) on. the following grounds: 1) No cuprous ions were detected in solution. 2) The addition of cupric ion did not affect the rate. ‘The first point is not strong enough, because if the rate of oxidation of Cu’ to Cu** is faster than its rate of formation, as would be expected since it is a homo- ‘geneous reaction, then no Cu* would be detected. The answer to the second point was clarified by Lu and Graydon"), who found that in order to observe catalytic action, the cupric ion must be added in large amounts; (they did not however mention how large), and the oxygen concentration should be low as compared ‘with the ammonia concentration. 38) E, Yamasaki, Sei. Rep. Tohoku Imp. Univ. Ser. 1,9, 169 (1920), '8) E. Zeretskii and G. Akimow, Zhur. peikl. Khimil 11, 1161 (1938), ¥)'B.C, Y. Lu and W. F. Graydon, J. Amer. chem. Soc. 77,6136 (1955), 8) RW. Lane and H.J.MeDonald, Corrosion & Material Protection 2 (5), 17 (1945);2 (6), 15 (1945). ™) R.W.Lane and H.J. McDonald, J. Amer. chem. Soc. 68, 1699 (1946). ) $.C. Sircar and D.R, Wiles, J. clectrochem. Soe, 107, 164 (1960),‘The second mechanism in our opinion, is not likely to take place because one would expect that cupric oxide would dissolve more rapidly than copper, which is not the case. If copper is covered by any form of oxide or adsorbed oxygen, dissolution will be inhibited, Schwei- zee’), Yamasakil®), In this paper a new mechanism is diseussed which overcomes all these difficulties and at the same time is in complete agreement with the experimental data ‘The Electrochemical Nature of Dissolution ‘The generally accepted theory of corrosion of a metal, Evanslf, is that when a metal comes into contact with an aqueous salt solution to which oxygen is accessible, oxygen takes up electrons at one part of the susface (the cathodic zone) while the metal gives them up at another (the anodic zone). In this way the attack of metal proceeds at an appreciable rate at room temperature. ‘These principles are well established and they were successfully demonstrated in many cases, e.g. the dissolution of zine in sodium chloride solution in contact with air, or gold in cyanide solution saturated with ait, Thompson") ‘The same mechanism is supposed to take place during the dissolution of copper in ammonia solutions saturated with air. Two simultaneous reactions are believed to take place, (Fig. 1): rem core © | sewers sua Ne = Big.1 Schematic representation of the electrochemical dissolution ‘process of copper in ammonia solution 1) The eathodie reduction of oxygen at the surface of copper Myx + HO + 20° io) 2) The anodic dissolution of copper in the presence of the complexing agent: Ca + ANH, CuNH)g + 26 ‘The overall reaction will be equation (1). +208" ay ¥) U.R. Evans, The Corrosion and Oxidation of Metals ‘Amold, London (1960), ™) BE Thompson, Trans, clectrochem. Soc. 9f, 41 (a9s7) , Habashi: Kinetics and Mechanism of Copper Dissolution in Aqueous Ammonia esc dee Bimengoctienat ‘There is no doubt that superimposed. with these reactions isthe cupric-cuprous equilibrium which causes mote copper to dissolve Cu + CoNHY =*2Cu(NH, o Cu(NH)$ + 2NH,—> CuNHQ +e. (12) It is apparent that these last two reactions arc of importance only at high cupric ion concenteation. Let us consider the simple case when the concen- tration of Cu** is negligible, We make two assumptions, ‘whose validity will be proved later, These assumptions 1) The cathodic reaction is a diffusion-controlled PD The anodic reaction is a chemicaly-contoled from the fst asumption it follows thatthe ste of oxygen diffusion through the Nernst boundary layer will be given by: 410) _ Da, Fr = FT AillO] = (041) (3) where Do, = the diffsion coefficient of disolved oxygen 3°" dhe thickness ofthe boundary layer ‘A = the surface area at which the cathodic reaction takes place .] = oxygen concentration inthe bulk of the solution [Oj], = oxygen concentration atthe surface of the metal Since diffusion is the controlling factor, then the rate of oxygen reduction at the surface is very rapid as compared with the rate at which it diffuses, i.e, oxygen is consumed as soon as it reaches the surface, or [O,], = 0. Therefore, 40) _ Do, Sar Ft A1Oal 14) From equation (1), two equivalents of copper are dissolved when one mole of oxygen is consumed, therefore, Rat of copper dalton = 22409 = 2k, A, [0,] a5) where D . 4-3 co) From the second assumption it follows that the rate ‘of chemical reaction between ammonia and copper is much slower than the rate at which NH, diffuses 10 the sueface of the metal through the boundary layer, since the chemical reaction in this ease is rate-controlling, This can be expressed approximately*) as follows: Rate of copper dissolution = &,A,INH,] (17) ©) The curved brackets () represent moles, while [] re- present moles/liter. ‘**) The dependence of the rate of dissolution on ammonia ‘concentration is not exactly lines, due to a side reaction, zamely, the oxidation of ammonia by oxygen leading to nitritewhere ty = velocity constant of the chemical reaction (expected fo be much lower than the diffusional velocity constant) y= the surfice area at which the anodic reaction takes place [NH] ~ the concentration of fre ammonia Ae the steady state, the rate of cathodic reaction (diffusion of oxygen) = the rate of anodic reaction (chemical attack by ammonia) i.e. 2, A [Og] = yg NF (8) An Aye Ay 9) where A is the total surface area of the metal in contact ‘with the solution, therefore Bat since 2k A[OJINI mire hisey °° From equation 20) it is seen that at low oxygen concentration and high ammonia concentration, the term 2k, (O,} can be neglected in the denominator, and the velocity equation becomes: Rate = 24, 4(0,] ey (ie) the rate of copper dissolution under these con- ditions depends only on the oxygen partial pressure. Rate of copper distolution — Zion = £ _— 30 £ Za 3 ase Sn as s 1. | o ca oa 1, PRESSE Fig. 2 ‘ Eifect of oxygen pressure and ammonia concentration on the rate of dissolution of copper in ammonia solution, Halpern*) Tele f Elect of Speed of Stirring and Temperature (Activation Energy) on the Rate of Dissolution of Copper in 0.5 mol/l Se te th «70 ae ] a | 26 7 *) Region of low oxygen pressure and high ammonia con coe ena Es “oat pees meee ae ae te con coo ee SO ee F, Habashi: Kinetics and Mechanism of Copper Dissolution in Aqueous Ammonia ‘This is in agreement with experiments as shown in Fig. 2. Further, the term ky is a diffasion velocity coefficient which therefore should depend markedly on the rate of stirring of the solution and only slightly on the temperature, (i. the activation energy is low). ‘This is in agreement with the expesimental results shown in “Table 1, thus verifying the first assumption. Similaely, at high oxygen pressure and low ammonia ‘concentration the term ky [NF] can be neglected in the denominator and the velocity equation becomes: Rate =f, A(NH) 2) which is also in agreement with Fig. 2. Here, the con- stant fy is a true chemical reaction velocity constant, therefore it should be expected that the, rate is ine dependent of the speed of stiering and the activation energy should be higher than 4 Keal. This is in agree- ‘ment with experimental results shown in Table 1, thus verifying the second assumption, (On the other hand, when 2h [Og] ~ fy NE] %) the velocity equation becomes: Ratejig, = Y2Rahe AO)" NHI" @ ‘This represents the critical points shown in Fig. 2 when the curve changes its slope. Under these condi- tions it is seen that INH] (Ol Table 2 gives the values of ammonia and oxygen ‘concentration at the critical points from which itis seen that the ratio [NH,]/[O,] is actually constant and equals 2s constant i 25) Table 2 [NH,]/[O4] Ratio at Limiting Rate of Dissolution of Copper at Different Ammonia and Oxygen Concentrations. Caleulated from data by Halp Deeresctdin INE) rc) Mole OrSolubiley | OIE | TO 02 | os | 90 | 09.10% | 290 os | 17 136 | 7104 | 306 om | 33 2300) shtos | 20. to | 3a | Be | abu | ats Average ratio 280 1) Escimated from data given in A, Seidell, Solubiltes of Inorganic Compounds, Volume h p. 1588, Van Nostrand, New York 1953, for the Soluiley of ‘Oxygen in Aqueous NaOH Solations. 280"). Thus supporting the mechanism suggested. Since the value of Do, is known (= 2.79. 10-Sem# sec?) thea the thickness of che boundary layer 3 can be %) Halpern ct al. obtained curves similar to those shown in Fig. 2 for the dissolution of copper in aqueous solutions of ‘ethylenediamine solutions. From these curves we found also that there is a constant ratio between the amine and oxygen concentration at which the limiting velocity occur ([Bthylenediamine) mS406 caleulated from equation (21) (ky = Do,/8). Using: Hal pemn’s data), we calculated) = 1.1" 10-8 em, from which ky = 2.54. 10-4 em sce, Therefore 2h, 2 ‘The value of by s0 obtained is much smaller than a Gut +e Cur + 2NH, — CuNHS Gui 5 ANH, + Gut * Cu(NH)g + 2NH, > CufNHP + CuNH) + Cust 2CuNH): ‘At high oxygen and ammonia concentsation the overall reaction can be expressed as follows: Cu + 4NH, + 1),0, + H,0 = Cu(NHj* + 208° ‘The dissolution process is similar to a corrosion prom cess in which minute parts ofthe metal acts as acathodic region where oxygen is reduced to OH” ions, and anodic regions where the liberated Cut or Cu®* ions react with the complexing agent. "The velocity equation of dissolution was derived on the basis of this model, as follows: 2.4, AO4] [NI ene Roe FET © vray MAI ‘The second term (the autocatalytic term) can be neglected at high oxygen and ammonia concentrations, while at high ammonia and very low oxygen concentra- tion, it becomes predominant. ‘Maximum rate of dissolution occurs when the ratio —AUNHAD. oes _ Te (a ce [NH,] > 280[0,] the dissolution will be contzolled only by the rate at which dissolved oxygen will difuse to the surface of the boundary layer i [NHL] « 280[0,] the dissolution will be controlled by the rate of chemical interaction of free NH molecules with the metal. This is consistent with kinetic measurements ‘There is a close similarity between this velocity cquation and that for the dissolution of gold and silver in eyanide solution, Habashi®): 2 ADex- Do, |CNH104) 5 [Dey CNT + #Do, (Oa) ~ ~ Flog {OH} with the exception that in the case of gold, both the anodic and cathodic reactions are difusion-controlled. Te is also possible that the dissolution of nickel and cobalt in aqueous solution of ammonia follow similar mechanism. Rate og [CN“) Aadenowregments This study was carried out during a Fellowship awarded to the author by the National Research Council of Canada £0 ‘which the author wishes to extend his thanks. ®) FHabashi, Kinetics and Mechanism of Gold and Silver Dissolution in Cyanide Solution. Paper presented atthe ALM.E. Symposium on Unit Processes in Hydrometallurgy. Dalls, Texas, USA. February 1963.