hydrometallurgy

Hydrometallurgy42 (19%) 63-82

Thermodynamics of Cu-H,SO,-Cl--H,0 and

Cu-NH &l-H 2O based on predominance-existence
diagrams and Pourbaix-type diagrams
Carmen Nila, Ignacio Gonzilez *
Uniuersidad Authwma Metropolitana-lztapalapa, Departamento de Quimica, Apartado Postal 55-534, 09340,
Mixico, D.F. Mexico

Received 17 February 1995; accepted 8 July 1995

Abstract

A study of the thermodynamics of the systems copper(H)-sulfuric acid-chloride-water and

copper(ammonium chloride-water is presented based on the construction of the corresponding
predominance-existence diagrams and Pourbaix-type diagrams. These diagrams, besides elucidat-
ing the chemistry of the complexes involved in these systems, predict the optimum experimental
conditions and the factors that affect the leaching processes.
The existence of a relationship between the predominant species in solution and the species
observed at the interface during the electrochemical reduction of copper is established. The
predominance of a given species in solution depends on the following conditions: Cl- concentra-
tion, in the case of the system Cu(II)-H,SO,-Cl--H,O, and pH, in the CL@)-NH&Y-H,0
system.
The predominance of chemical species in solution and the existence of insoluble phases for
C&I) predicted by the diagrams are corroborated by UV-VIS and X-ray spectra. The Cu(I)
species predicted by the diagrams are only corroborated by voltammetric experiments.

1. Introduction

One of the methods for metal recovery (e.g., Cu, Zn, Ni, Co, Ag, Pb and Hg) from
complex minerals such as sulfides and oxides, is leaching followed by a separation step,
such as adsorption, electrowinning or solvent extraction. Leaching has recently been
done by means of the ammonium salts (NHJ,C03, (NH&SO, or NH&l [l-41. The

* Corresponding author.

0304-386X/96/$15.00 0 1996 Elsevier Science B.V. All rights reserved

SSDI 0304-386X(95)00073-9
64 C. Nila, I. Gonzdez/ Hydrometullurgy 42 (1996) 63-82

use of NH,Cl in the process presents advantages over the other salts. Mineral treatment
with Cl- only is useful because of the high solubility that its salts present, guaranteeing
(at high concentrations) the solubility of lead and silver. The control of sulfates in the
solution is achieved by the addition of calcium chloride [51. The importance of the
addition of NH: to the leaching process is that it produces a solubility increment of the
minerals, due to its ease of forming highly stable complexes with metals such as Cu*+,
Cu+, Zn*+, Ag+ and Ni2+; in addition, it generates a pH close to neutral, which favors
the recovery of metal ions with few impurities, in particular, iron remains as ferric
oxide.
In order to predict the chemical species that participate in the processes, to select the
optimum operation conditions and to find the factors that affect leaching, the potential-
pH diagrams are used. In particular for the copper system, the potential-pH diagrams in
water, sulfur and chloride media have been described by Winand [6], the log CUT-
potential-pH in ammonia by Luo [7], the potential-pH in ammonia oxalate and
ammonia sulfate for extraction systems with LIX 65N by Dyke et al. [8] and the
potential-pH, potential-log [Cul and potential-log [NH: + NH,] by Osseo-Asare et al.
[91.
The diagrams by Dyke et al. are applicable to oxide-reduction processes whose
validity is undeniable; nonetheless, the restriction is that they scarcely represent the real
systems. In general, in the leaching processes, besides the presence of a complexing
agent, there is an oxidizing species (Cu*+, 0,) Cl,, etc.). This medium makes the Cu(1)
and Cu(I1) oxidation states unstable in solution; for this reason, the recovery of metals
by extraction, proposed in their work, is not through these ions.
The three-dimensional diagrams log CUT-E-pH presented by Luo for the copper-
ammonia-water system, show an experimental application in the recovery of copper as a
function of the ratio ammonium ion-ammonia in the process of leaching.
The diagrams mentioned above use computational algorithms. As Luo, Osseo-Asare
and Brown describe them, there are several equations that have to be taken into account
when ammonia is put in the diagrams. In addition, the algorithm becomes even more
complicated if the addition of ammonia is through the salt NH&l, because Cl- (as well
as NH,) generates complexes with copper, and also, as described later, a mixed
precipitate appears in solution. Nonetheless, using the methodology presented in [lo- 161
for the construction of predominance-existence diagrams and the Pourbaix-type dia-
grams, a simplification of this system can be achieved.
Studies of the systems: copper-sulfuric acid-chloride-water and copper-ammonium
chloride-water, are presented in this work with only one degree of oxidation, as can be
seen in the corresponding predominance-existence diagrams; in addition, studies that
include the different oxidation states are shown in the corresponding Pourbaix-type
diagrams. The thermodynamic predictions are corroborated by spectroscopic studies for
Cu(I1) and by an electrochemical study for Cu(1).

2. Experimental

The electrochemical study was done using 0.01 M Cu(I1) solutions prepared with
CuSO, .5H,O (R.A. Baker) and 0.73 M H,SO, (R.A. Baker) or 1 M NH&l (R.A.
 C. Nilu, I. Gon.@ilez./ Hydromerallurgy 42 (1996) 63-82 65

Quimica Dinamica). In order to analyze the influence of chlorides, NaCl was added
(R.A. Merck) and solid NaOH (R. A. Baker) was used to vary the pH, which was
measured with a Corning 240 pH Meter.
A simple, three-electrode cell was used: a saturated mercurous sulfate electrode
(SMSE) or a saturated calomel electrode (SCE) as reference, a vitreous carbon rod in a
separate compartment as an auxiliary electrode and a working electrode, which was a
vitreous carbon disk (Lorraine Carbon), mirror polished with 0.3 km alumina and rinsed
with diluted HNO,. The electrochemical experiments were carried out under a nitrogen
atmosphere.
The UV-VIS spectra were obtained with a Perkin-Elmer, Lambda 7 UV-VIS
spectrophotometer and the X-ray diffraction patterns with a Siemens X-ray diffractome-
ter.
A PAR 17.5 Universal Programmer fitted with a PAR 273 Potentiostat-Galvanostat
and a 7090A Hewlett-Packard recorder were used for the voltammetric experiments.

3. Results and discussion

The data used in the calculations for the construction of the predominance-existence
diagrams (PED) and the Pourbaix-type diagrams (PTD) are taken from Smith and
Martell and Bard et al. [17,18] and are shown in Table 1. The equations that represent
the lines of the PED and PTD are described by the expressions shown in Appendix A.

3.1. Predominance-existence diagram of the system CdU-H, SO,-Cl --Hz 0

Fig. 1 shows the PED, pCl_ versus pSO> for the system 0.01 M Cu(I1) in 0.73 M
H,SO, (corresponding to a pH of 0.09). The continuous lines that separate two soluble
species indicate equal concentrations. The difference between the continuous and
non-continuous lines is only the exchanged ligand; that is, while, for the continuous line,
the exchanged ligands are Cl-, for the non-continuous lines these are generalized
sulfates (HSO;, SO:-). From this figure it is possible to determine graphically and
quickly the predominant species of Cu(I1) at defined concentrations of chloride and
sulfate. In this diagram it is observed that at pSOI, < -0.06 the soluble species CuSO,
appears.
It is considered in this study that the concentration of sulfate does not change (since it
is buffered, pSok = 0.14) and so the predominance of the chemical species in Fig. 1 is
simplified to a one-dimensional PED:

t
CUCI C”*+
I
> PC1 (1)
-0.06
66 C. Nilu, I. Gonzcilez / Hydrometallurgy 42 (1996) 63-82

Table 1
Thermodynamic data used for the construction of diagrams of the systems Cu(II)/Cu(I)-H,SO,-Cl--H,0
and Cu(II)/Cu(I)-NH&%H,O at 25°C [ 17,181
Ion Equilibrium Stability constant log K

L = cl-
cu+ ML,,, /M.L 7.38
ML/M. L 2.70
ML, /M.L* 6
ML, /M.L3 6
M,L,/M’.L4 13.1

cu*+ M(OH),,SL,.SW /M.(OH)‘.5.L0.5 17.16

ML/M.L -0.06a, 0.4b

L=soi-
HL/H.L 1.1
cu*+ M(OH),,5L0,25(sj /M(OH)‘.5, Lo.25 16.86
ML/M.L 0.95

L=OH-
cu+ (M,O)$/M.L 14.7

cu*+ ML/M.L 6.3

ML, /M.L* 12.8
ML,/M.L3 14.5
ML,/M.L4 15.6
ML,(,) /M. Lz 18.9

L=NH,
HL/H.L 9.4
ctl+ ML/M.L 5.93
ML, /M.L* 10.58

cl?+ ML/M.L 4.12

ML, /M.L* 7.63
ML,/M.L’ 10.51
ML,/M.L4 12.6
ML, /M.L5 12.43
MLOH/M .L . OH 14.9
ML(OH), /M.L.(OH)3 16.3
ML,(OH), /M.L*.(OH)* 15.7

Equilibrium E”/mV vs NHE

Cu& + le- ti Cu$,, 159
Cuf,,) + le- F? CucSj 520

aThis value is used for the construction of diagrams involving sulfate. bThis value is used for the construction
of diagrams involving ammonia.

The pCl- shown here indicates the predominance zone limits and corresponds to a
point in Fig. 1; it represents the conditional formation constant of the complex CuCl+.
The predominance zone diagram (1) shows that, for pCl- < - 0.06 the predominant
 C. Nila, I. Gonzrilez/ Hydrometallurgy 42 (1996) 63-82 67

10
I
l
pa-
I
I

. ’
4_ $ 1
cd+
6 1
I

_,i,--

-2 4 3

pso;
Fig. 1. Two-dimensional predominance-existence diagram (pCl- -SO’,) of Cu(IlY’ species at pH 0.09 buffered
condition (0.73 M H,SO,) and -log [Cu(II)I= 2. SOL represents the generalized sulfate concentration
(HSO; + SO;- 1.

species in solution is CuCl+ (its fraction is greater than 0.5) and for pCl_> - 0.06 it is
CL?+.
Fig. 2 shows the UV-VIS absorbance spectra (A) as a function of wavelength (A) for
0.01 M Cu(I1) in 0.73 M H2S0, without and with various chloride ion concentrations,

a 1

Fig. 2. UV-VIS spectra of absorbance (A) as a function of the wavelength (A) for 0.01 M Cu(I1) in 0.73 M
H,SO, without and with different choride ion concentrations [Cl- ] (with the addition of NaCI): * = 0 M;
0 = 0.01 M, gray triangle = 1 M; ??= 2.5 M.
68 C. Nila, I. Gonza’lez/Hydrometallur~y 42 (1996) 63-82

[Cl-]. In these spectra, the maximum at approximately 850 nm is associated with the
species Cu(H,O)t+ [19-211 and is in agreement with that indicated in diagram (1).
At pH = 0.09 (corresponding to 0.73 M H, SO,) the soluble and insoluble Cu(OH)t- i
(i 2 1) species do not predominate and species of the type CI_I(SO,)~-~~(j 2 2) do not
appear, because data for them is not reported in the literature. Rice et al. associate the
decrease in copper recovery in the presence of high concentrations of (NH4)2S0,, with
the appearance of copper complexes with sulfates [22].
Two additional maxima appear in the UV zone: one at 250 nm and another at 300
nm; these are attributed to the appearance of Cu(I1) with Cl- ligands [21]. According to
the predominance zone diagram (1) this species corresponds to CuCl+. Thus, the
thermodynamic prediction is confirmed.

3.2. Predominance-existence diagram of the system G(I)-H, SO,-Cl --Hz 0

Fig. 3 shows the PED, pCl- versus pSOi, for the system 0.01 A4 Cu(1) in 0.73 M
H, SO, (corresponding to pH = 0.09). As in the Cu(I1) diagram, the species C&SO,);- k
(k 2 1) reported in the literature do not exist. The continuous lines that separate a
soluble from an insoluble species indicate coexistence of these species. In this case, the
precipitate CuCl,,, coexists in the interval 0.62 < pH < 5.38.
When extracting the DEP at pSok = 0.14 (corresponding to 0.73 M H,SO,) the
diagram is:

c& cuc1; , C”C’[s] , cu’+ (2)

I I I
>pcl-
0 0.62 5.38

Diagram (2) shows that the species CuCl:- predominates for pCl-< 0, CuCl, in the
interval 0 < pCl- < 0.062; and Cu2+ predominates at pCl-> 5.38. The instability of
Cu(I), in the presence of oxygen makes it difficult to obtain UV-VIS spectra and so
they were not taken.
The PED of Figs. 1 and 3 show the Cu(I1) and Cu(1) systems separately; these
diagrams are useful when the separation processes of these metals involve the extraction
and precipitation - among other processes - of recovery in non-redox leaching baths.
The need for the PTD is only when the recovery processes involve redox charge
transfer, which is generally through electrolytic processes.

3.3. Pourbaix-type diagram of the Cu(II)-G(I)--H, SO,--Cl --Hz 0 system

The construction of PTD, where one plots the biconditional potential versus pCl-
(i.e. E”-pCl-) is d one using diagrams (1) and (2) and the Nernst equations shown in
Appendix A. Fig. 4 shows the PTD obtained this way. In Fig. 4, predominant and
existent species of Cu(IIy’ and Cu(1)” are indicated (where the double prime indicates
double buffering at pH = 0.09 and pS0: = 0.14) depending on E” and pCl-. The
 C. Nilu, 1. Gonz~lez/HydrometaNur~y 42 (1996) 63-82 69

Fig. 3. Two-dimensional predominance-existence diagram (pCI_ -SO&) of Cu(I)” species at pH = 0.09

buffered condition (0.73 M H,SO,) and -log [Cu(I)I = 2. SO& represents the generalized sulfate concentra-
tion.

0 4 pCT

Fig. 4. Pourbaix-type diagram of biconditional potential as a function of the pCl- (E”-pCl- ) for the
cu(II)-cuW-cu(o)-cI- -so:, system, calculated from thermodynamic data. Tbe diagram is constructed
using: [Cu(II)l = [Cu(I)l= 0.01 M, pH =0.09 and pSO’, = 0.14 buffered conditions (0.73 M H,SO,).
Temperature = 25°C.
70 C. Nila, I. Gonza’lez/ Hydromerallurgy 42 (1996) 63-82

continuous lines correspond to the biconditional potential and the pCl- where there is
the same concentration of Cu(IIj” and Cu(Ij”, when these are soluble; and their
coexistence, if any species is insoluble. In this case the lines are drawn for a total copper
concentration of 0.01 M. The non-continuous lines correspond to pCl- values where
there are the same concentrations of the complex species with the same oxidation state
or else to the appearance of a precipitate, given the case that, at this boundary, one solid
is present.
This diagram shows that in 0.73 M H,SO, the stabilization of Cu(1) depends on the
amount of chloride present in solution. At pCl-> 3.32 the reduction of C&I) involves
only one stage that interchanges two electrons, while at pCl- < 3.32 two monoelectronic
stages appear, due to the formation of soluble or insoluble Cu(1) species. In the zone

m
a 1

u
E

L
-660
c
-200
I
E/mV vs SMSE E/mV vs SMSE

-800 -400 0 E/mV w SMSE

Vnvvs SMSE

v=+
-700 -300 100
10

I
-000 -250
I

E/mV w SMSE E/mVvs SM SE

Fig. 5. Linear sweep voltammograms at v = 100 mV/s for copper reduction on vitreous carbon in solutions of
0.01 M C&II) in 0.73 M H,SO,, in the presence of different concentrations of NaCI: (a) 0 M; (b) 0.01 M;
(c) 0.02 M; (d) 0.11 M; (e) 1 M; and (f) 2.5 M. The reference electrode used is a saturated mercurous sulfate
electrode, SMSE.
 C. Nilu, 1. Gonz~lez/HydrometaNurgy 42 (1996) 63-82 71

where Cu(1) is stable, the biconditional potential is anodically displaced in the reduction
process of C&I) to Cu(I), when the pCl_ decreases, and cathodically in the process of
Cu(1) to Cu(0).
Fig. 5 shows the triangular potential scan obtained on a vitreous carbon electrode in
0.01 M C&I) solutions in 0.73 M H,SO, without and with different [Cl-], for the
same scan rate, V. These plots show that, for the system without Cl- (Fig. 5a), there is a
reduction peak and an oxidation peak, in contrast at [Cl-] 2 0.02 M two reduction
peaks (I:,II’,) and two oxidation peaks <IL, II:) appear.
For [Cl-] = 0.01 M two cathodic and one anodic peak appear, demonstrating that
there is a minimum limit of [Cl-] for the appearance of the two monoelectronic stages
during reduction as well as oxidation. In this case, since [Cl-] is not buffered
([Cl-] = 0.01 M = [Cu2+]) the reduction process differs from the oxidation process.
The corresponding voltammogram without Cl- shows that the anodic peak is sharp
and the cathodic peak is wide; the anodic peak current magnitude (lip,]) is larger than the
cathodic peak current magnitude (lip,]). This difference is due to the fact that the first
involves the reduction of a soluble species and the latter the oxidation of an insoluble
species. In this case the mechanism is simple: the soluble species corresponds to CL?+
and the insoluble to Cu(O), as the Pourbaix-type diagram predicts.
In the voltammograms of the solutions where the interval is 0.02 M < [Cl-] I 0.11
M (1.7 2 pCl_ 2 0.96) (Fig. 5c,d), the cathodic peak I’, and the anodic peak 1: also
present the relationship lip,,,:1 < lipa,,:l.
Thus, the process I’, indicates that a soluble species of Cu(I1)” is reduced and the
anodic process I’, that an insoluble species of Cu(1)’ is oxidized. The same is concluded
by comparing the current magnitudes of the cathodic processes 1: and III,. According to
the Pourbaix-type diagram for this condition of pCl_, the thermodynamically stable
species are Cu*+ and CuCl(,,, concordant with the voltammetric results mentioned
above.
For the voltammograms obtained in the solutions that involve [Cl-] 2 1M (pCl_< 0)
(Fig. 5e,f), the relationship lip, ,’I z lip,,,,:1 is ob tained; this leads to the prediction that
the Cu(I1) species that is oxid&d and the Cu(1) that is reduced at the interface are
soluble. This prediction agrees well with the diagram’s prediction; that is, in this
condition of pCl- the species Cu(IIY’and Cu(Iy’ are soluble. This is also concluded by
comparing the current magnitudes of the cathodic peaks I’, and III,.

3.4. Predominance-existence diagram of the system Cu(II)-NH, Cl-H, 0

Fig. 6 shows the PED, pCl- as a function of pH, for the system 0.01 M Cu(I1) in 1
M NH&l (corresponding to pNH> = 0, where ’ indicates the total ammonia without
complexing, NH, + NH:). This diagram shows the zones that limit the predominance
of soluble species and the existence of insoluble C&I). The non-continuous lines
indicate ligand exchange related to protons, ammonia and hydroxide ions; the continu-
ous lines interchange of chlorides. The formation of higher complexes of C&I) with
ammonium ligands allows the dissolution of the precipitate Cu(OH),. It can be seen in
this diagram that a mixed precipitate, Cu(OH),,,Cl,,(,,, appears in two zones; neverthe-
less, it is only possible experimentally to reach the pCl- in the acid zone, because in the
72 C. Nila, I. Gonzcilez/ Hydromerallurgy 42 (1996) 63-82

PH
Fig. 6. Two-dimensional predominance-existence diagram (pCl_-pH) of C&I)” species at pNH\ = 0
buffered condition (1 M NH&l) and -log [Cu(II)l = 2. NH; represents the generalized ammonia concentra-
tion (NH: +NH,).

basic zone the pCl-z - 2 (100 A4 ), which by no means represents a real case; it is
only presented in order to complete the diagram.
Even though the mixed precipitate has been mentioned in the literature, there is still
controversy concerning its existence [23-251. This diagram shows that the idea of the
disappearance of metallic hydroxides in the zone is incorrect, because this depends on
the buffering conditions, since under certain conditions such a precipitate is formed. For
pH > 11.85 the precipitate Cu(OH), exists, in spite of the large amount of chloride and
ammonia present in the solution.
From the diagram in Fig. 6 the predominance existence zones for a pCl- = 0 (the one
corresponding to 1 M Cl-) are extracted:

CUCI+ CuPi], .5CI o.51sl ‘WNH3 I ‘4 ‘WW21sl

(3)
>PH
I I I
4.16 7.66 11.85

The predominance existence zones in diagram (3) indicate that, in a 1 M NH&l

solution (pNH> = 0 and pCl-= 0) the Cu(I1)’ appears in the interval 4.16 < pH < 7.66
as a mixed precipitate Cu(OH),,,ClO,,(,, and at pH > 11.85 as Cu(OH),(,,. For pH < 4.16
the species CuCl+ predominates and its concentration does not change with pH, because
the ligand involved (the Cl-), does not exchange protons. In the interval 7.66 < pH <
11.85 the species Cu(NH,):+ predominates and, as this contains the ammonia ligand,
its concentration depends on pH because NH, does exchange protons.
 C. Nila, I. Gonzcilez/ Hydrometallurgy 42 (1996) 63-82

0.8

0.8

0.2

0
150 350 550 750 950
hlnm

Fig. 7. UV-VIS spectra of absorbance (A) as a function of the wavelength (h) for 0.01 M C&I) in I M
NH&I and different pH values (with the addition of NaOH):+ = 3.74;gray square = 4.23;gray triangle=
7.82; X = 9.01; * = 10.23.

For copper extraction in the presence of (NH&SO,, Nathsarma and Bhaskara [2]
and Rao and Sahoo [3] found that it is affected by pH. Nathsarma and Bhaskara argue
that, in this medium, as pH increases, copper-ammonia complexes are formed and they
are not extracted by the organic phase. Rao and Sahoo associate this phenomenon with
the formation of copper-hydroxide complexes. This diagram demonstrates that probably
both reasonings are incorrect, since it seems as if the appearance of a precipitate,
Cu(OH),sCl0.,(,,~ on the interface of the leached mineral, could be responsible for the
decrease in the extraction of copper.
Fig. 7 shows the UV-VIS spectra for 0.1 M Cu(I1) solutions in 1 M NH,Cl at
various pH values (with the addition of NaOH). For pH 5 4.23, three maxima appear, at
approximately 850 nm, 300 nm and 250 nm, whose absorbance does not vary with pH;
indicating that the predominant species does not contain ligands that exchange protons,
just as diagram (3) predicts. In this system, the peaks present in the UV region
correspond to the species CuCl+, as well as for the system C&I)--H,SO,-Cl--H,0
(Fig. 2a), as predicted in diagram (3).
In the spectra for pH r 7.82 the three peaks mentioned before disappear and one
appears whose absorbance maximum is at 600 nm. The absorbance changes with pH,
and thus the predominant species has a ligand which exchanges protons. According to
the literature, a maximum at 600 nm corresponds to the complex Cu(NH,)t+ [14,161,
which is predicted in diagram (3).
74 C. Nila, I. Gonz~lez/Hydrometallurgy42 (1996) 63-82

8 20 32 44 58
28

Fig. 8. X-ray diffraction patterns. Bold line = (a) green, (b) blue and (c) black precipitates, together with the
standards (fine line) from the corresponding references: (a) Cu,(OH),CI [26]; (b) Cu(OH), [27]; and (c) 010
[=I.

At 4.62 < pH < 7.66, a green precipitate forms which has slow appearance kinetics
(about 7 days). This is probably why few authors give importance to its presence. For
pH > 11.85 a blue precipitate appeared in the solution and became black with time.
Fig. 8 presents the X-ray diffraction patterns of the green, blue and black precipitates,
together with the standards attributed by the corresponding references [26-281. The
comparison of such X-ray diffraction patterns allows verification of the existence of the
precipitates predicted by the diagram: the green one corresponds to the mixed com-
pound, Cu(OH),.,Cl,.,, the blue precipitate corresponds to Cu(OH), and the black to
CuO. Thus, experimentally, the hydroxide is formed first, and this, with time, is
dehydrated to form the oxide.
The spectroscopic studies verify the validity of the method used for the construction
of the FTD of Cu(II), since it adequately predicts what occurs in the solution.
When NH&l is used as the leaching medium, copper forms the mixed precipitate
Cu(OH),.Jlo.S, in the pH interval mentioned above. This fact explains the low recovery
efficiency of this metal. In a similar way, in (NH,),SO, or NH,N03 solutions, the
 C. Nila, I. Gonzcilez/ Hydrometallurgy 42 (1996) 63-82 75

PH
Fig. 9. Two-dimensional predominance-existence diagram (pC- -pH) of h(I) species at pNH> = 0 buffered
condition (1 M NH&l) and -log [MI)] = 2. NH> represent the generalized ammonia concentration
(NH: +NH,).

corresponding mixtures Cu(OH),~,(SO,),,, and Cu(OH),.,(NO,),,, are probably formed,

since these are also reported in the literature [29].

3.5. Predominance-existence diagram of the system Cu(I)-NH, Cl-H, 0

Fig. 9 shows the PED, pCl- versus pH, for 0.01 A4 Cu(1) in 1 M NH,Cl
(corresponding to pNH\ = 0). In this diagram the appearance of CuCl(,, and Cu,O(,,
precipitates is observed in acidic conditions, whose pH value depends on pCl-. While
CuCl(,, is mentioned in the literature at these pH conditions [30], Cu,O(,) is generally
reported in neutral or slightly alkaline media [31].
When extracting the predominance-existence diagram, for pCl- = 0 (corresponding to
1 A4 Cl-) one obtains from Fig. 9:

cuci; , CuINH& 1 cup0 bl

>PH (4)
I I
7.11 11.88

This diagram indicates that, in a 1 M NH&l solution (pNI-I\ = 0 and pCl_= O), Cu(I)
is insoluble at pH > 11.88.

3.6. Pourbaix-type diagram for the system Cu(Il)-Cu(l)-NH,Cl-H, 0

Fig. 10 shows the Pourbaix-type diagram (E”-pH) constructed from diagrams (3) and
(41 for the species Cu(IIY’and CuW’, respectively, and from the corresponding Nernst
16 C. Nila, I. Gonza’lez/Hydrometallurgy42 (1996) 63-82

-0.4 I

0 7 14
PH
Fig. 10. Pourbaix-type diagram, biconditional potential as a function of the pH (E” -pH) for the Cu(II)-
h(I)-h(O)-Cl--NH\ system, calculated from thermodynamic data. The diagram is constructed using:
[Cu(II)I = [Cu(I)l= 0.01 M, pNH\ = 0 and pCl- = 0 buffered conditions (1 M NH&l). Temperature = 25°C.

equations. For the system Cu(I)/Cu(O) a total copper concentration of 0.01 M is

considered. From this Pourbaix-type diagram it is possible to determine that, in a 1 M
NH&l solution, Cu(1) is stable for any pH, and the reduction of Cu(I1) occurs through
two monoelectronic processes. The appearance of the mixed precipitate Cu(OH),,,Cl,,,~,,,
present in the solution in the theoretical interval 4.16 < pH < 7.66 (experimentally
observed at 4.62 < pH < 7.66 and whose appearance kinetics are slow), limits the
efficiency of the copper deposition. It is also observed that the biconditional potentials
do not vary at acidic pH values and are cathodically displaced at pH < 9.4, when the pH
increases in the basic zone.
 C. Nila, I. Gonzn’lez/ Hydrometallurgy 42 (1996) 63-82 77

- 6bO b 60”

E/mV vs SCE ElmV r~s SCE

I
-900 150 6W

ElmV vs SCE
Fig. 1 I. Linear sweep voltammograms at Y = 100 mV/s for copper reduction on vitreous carbon, in solutions
of 0.01 M Cu(I1) in 1 M NH&I, at different pH values (with the addition of NaOH): (a) 3.72; (b) 4.62; (cl
8.80; (d) 9.04; and (e) 10.55. The reference electrode used is a saturated calomel electrode, SCE.

Fig. 11 shows the triangular potential scans in 0.01 M Cu(I1) solutions in 1 M

NH,Cl at different pH values (set with the addition of NaOH) for the same scan rate, v.
At the different pH values shown here, two cathodic peaks (I,, II,) and two anodic
peaks (I,, II,> are observed. This leads us to conclude that, in these media, Cu(1) is
always stable, as the Pourbaix-type diagram of Fig. 10 predicts.
78 C. Nila, I. Gonza’lez/ Hydrometallurgy 42 (1996) 63-82

Three wide peaks are shown in these voltammograms: I,, I, and II, and the sharp
peak IIa; here, the values of the corresponding currents fulfil the following relationships:
li~a.i,l= li~c,,~i and lipa,,& li~,,,,~(. This behavior indicates that the reduction pro-
cesses of C&I) and of Cu(I), as well as the oxidation of Cu(I), involve soluble species
and the oxidation of Cu(0) involves an insoluble species (the dissolution of the metallic
deposit).
At pH I 4.62 the peak potentials of the reduction and oxidation processes practically
do not change with pH, indicating that the species of Cu(I1) and Cu(1) have a ligand that
does not exchange protons. In contrast, these potentials in the basic zone (pH 2 8.80) are
cathodically displaced with pH, which implies the involvement of copper species that
have ligands that exchange protons.
Such variation in the cathodic and anodic potentials shows the same trend as the
biconditional potentials of the Pourbaix-type diagram of Fig. 10. In this diagram, the
predominant species of Cu(I1)” as well as of Cu(1)” are (for pH I 4.02) species with Cl-
ligands (CuCl+ and CuCl;) and for pCl-> 7.66, they are species with NH, ligands
(Cu(NH$+ and Cu(NH,);).

4. Conclusions

The thermodynamic study of the PED and the PTD allow one to select the chemical
conditions in which a given species predominates in the system.
There is a relationship between the predominant species in solution and the one
observed at the interface in the electrochemical reduction of copper(I1). The predominant
species in solution depends on the concentration of Cl- in the case of the system
Cu(II)-H,SO,-Cl--H,0 and on pH in the system Cu(II)-NH&l-H,O.
The use of 1 M NH&l in the solution at various pH values, for copper recovery, is
limited by the appearance of the mixed precipitate Cu(OH),,&l,,,. This medium can
only be used at pH < 4.62 or at pH > 7.66.
The electrochemical study of the electrodeposition mechanism of Cu(I1) in 0.73 M
H,SO, at different [Cl-] allows one to establish that only for pCl-< 3.32 in 0.01 A4
Cu(I1) does the reduction occur through two monoelectronic stages. In contrast, in 1 M
NH&l at different pH values, the reduction of Cu(I1) always occurs in two monoelec-
tronic stages.

Acknowledgements

We are grateful for the financial support from CONACYT and the English translation
of the manuscript made by L.T. Velasco and J.G. Ib%ez. C. Nila thanks CONACYT for
a scholarship. The X-ray diffractograms were kindly obtained by Dr. P. Bosch and V.H.
Lara.
 C. Nila, I. Gonzcilez/ Hydrometallurgy 42 (1996) 63-82

Appendix A. Thermodynamic equations

A. I. Chemical reactions

A.1 .l. Copper(U)-chloride-sulfare-water systems

CuCl+ + HSO, P CuSO, + Cl- f H+ pCl- = pS0; (Al)
Cu’++Cl-eCuCl+ pCl-= -0.06 (A2)

A.l.2. CopperiIbchloride-sulfate-water systems

cu+ + cl- * CuCl,,, pc1- = 5.38

CuCl; P CuCl,, + Cl- pCl-= 0.62

cuc1; + Cl-P cuc12,- pc1- = 0

A.2. Electrochemical equations

A.2.1. Copper-chloride-sulfate-water systems

Cu2+ + 2e- P CL+,) E/mV = 280 646)
Cu2+ + Cl- + le- + CuClc,, E/mV = 476 - 59 pCl- (A71

Cu2++2C1-+le-eCuC1; E/mV=513-118pCl- (A81

Cu2++ 3Cl-+ led* CuCl;- E/mV = 513 - 177pCl- (A91
CuCl++ 2Cl-+ le-* CuCl:- E/mV = 516 - 118pCl- (‘410)
CuClc,, + le- F1 Cucsj + Cl- E/mV = 84 + 59 pCl- (All)
CuCl; + le-@ Cuoj + 2Cl- E/mV = 48 + 118pCl- (A121
CuCli- + le-* Cu(,) + 3Cl- E/mV = 48 + 117pCl- (A131

A.3. Chemical reactions

A.3.1. Copper(U)-chloride-ammonia-water systems

Cu2++C1-~cuCl+ pc1-=0.4 (A14
Cu(W 1.5C10.*(s)+ 1.5H+ 8 Cu2+ + l.5H20 + 0.5Cl-

pCl-= - 11.68 + 3pH (A151

Cu(OH) LsClo.s(s) +0.5Cl-+ 1.5H+eCuCl++ 1.5H20

pCl-= 12.48 - 3pH (A161

80 C. Nilu, I. GonzLilez/ Hydromerullur,gy 42 (1996) 63-82

WOW l.SC~O.5(s) + NH; + OSH+e CuNH:+ + 0.5C1- + 1 SH,O

pCl-= - 1.12 + pH

Cu(OH) I.5%(s) -I- 0.5H,O * CUB + 0.5Cl- + 0.5H+

pCl- = 10.52 - pH

Cu(OH),,,Cl,,,~,, + 3NH1; FI Cu(NH,);+ + 0.5Cl- + 1.5H+ + 1.5H,O

pCl-= 23.7 - 3pH

Cu(OH) 1.5C1OS(s) + 4NH; F? Cu(NH,);+ + 0.5Cl- + 2.5H+ + 1.5H,O

pCl-= 38.32 - 5pH

Cu(OH) I sC*os(s) + 4NH, + 1.5H+F’, Cu(NH&+ + 0.5Cl- + 1.5H,O

pCl-= -36.88 + 3pH

A.3.2. CopperfIbchloride-ammonia-water systems

CUCl~,, Ft cu++ cl- pc1-= 5.38

CuClc,, + Cl-e CuCl, pCl-= 0.62

CuCl, + cl- P cucq pc1- = 0

CuC+,, + 0.5H,O + 0.5Cu,0c,, + Cl- + H+ pCl- = 6.68 - pH

CuCl, + 0.5H,O + 0.5Cu,0c,, + 2Cl- + H+ pCl-= 3.65 - 0.5 pH

cuc1; + 2NH; # Cu(NH,); + 2C1- + 2H+ pCl-= 7.11 - pH

CuCl;- + 2NH: &u(NH,); +3Cl-+2H+ pCl-=4.74-$pH

CuCl;- + 2NH, F? Cu(NH,); + 3Cl- pCl-= - 1.527

CuC12,- + 0.5H,O e 0.5Cu,O,,, + 3C1- + H+ pCl- = 2.43 - f pH

A.4. Electrochemical equations

A.4.1. Copper-chloride-ammonia-water systems

CuCl++ Cl-+ le-z$ CuCI; E/mV = 489

Cu(OH) 1sCl0s(n) + 1.5Cl- + 1 .5Hf + le-z$ CuCl; + 1.5H,O

E/mV = 858 - 88.5 pH

Cu(OH)1.5clo.5(s)+ 2NH: + le-P Cu(NH,): + 0.5Hf+ 0.5Cl-+ 1.5H,O

E/mV = 19 + 29.5 pH (‘433)

 C. Nila, 1. Gonza’lez/ Hydrometallurgy 42 (1996) 63-82 81

Cu(NH,):+ +2H++le_tiCu(NH,): +2NHI E/mV= 1149- 118pH

(A34)

Cu(NlG+ + le-# Cu(NH,): + 2NH, E/mV = 39.8 (A35)

CUE + 2NH, + 2H++ le-ti Cu(NH,)l + 2H,O

E/mV= 1438 - 118pH (A36)

CUE + H++ le- e 0.5Cu,O,,, + 1SH,O E/mV = 737 - 59 pH (A37)

CuCl; + le-* Cuts) + 2Cl- E/mV = 48 (A38)

Cu(NH,)l + 2H++ le-F? Cy,) + 2NHi E/mV = 887 - 118pH (A39)

Cu(NH,)l + le-e Cq,) + 2NH, E/mV = 222 (A40)

0.5Cu,0c,, + H++ le-F? CUE,)+ 0.5H,O E/mV = 479 - 59pH (A41)

References

[l] Limpo, J.L., Figueiredo, J.M., Amer, S. and Luis A., The CENIM-LNETI process: a new process for the
hydrometallurgical treatment of complex sulphides in ammonium choride solutions. Hydrometallurgy, 28
(1992): 149-161.
[2] Nathsarma, K.C. and Bhaskara Sarma, P.V.R., Processing of ammoniacal solutions containing copper,
nickel and cobalt for metal separation. Hydrometallurgy, 33 (1993): 197-210.
[3] Rao, K.S. and Sahoo, P.K., Effect of ammonium salts on the extraction of copper using Hostarex DK- 16.
Hydrometallurgy, 33 (1993): 211-218.
[4] Boyadzhiev, L. and Alexandrova, S., Recovery of copper from ammoniacal solutions by rotating film
pertraction. Hydrometallurgy, 35 (1994): 109- 121.
[5] Dutrizac, J.E., The leaching of sulphide minerals in choride media. Hydrometallurgy, 29 (1992): l-45.
[6] Winand, R., Choride hydrometallurgy. Hydrometallurgy, 27 (1991): 285-3 16.
[7] Luo Rutie, Overall equilibrium diagrams for hydrometallurgical systems: copper ammonia-water system.
Hydrometallurgy, 17 (1987): 177- 199.
[8] Dyke, J.T., Fernando, Q. and Zeitlin, H., The application of potential-pH diagrams to solvent extraction
systems. Hydrometallurgy, 6 (1980): 49-62.
[9] Osseo-Asare, K. and Brown, T.H., A numerical method for computing hydrometallurgical activity-activ-
ity diagrams. Hydrometallurgy, 4 (1979): 217-232.
[lo] Rojas, A. and Gonzalez, I., Relationship of two-dimensional predomiance-zone diagrams with conditional
constants for complexation equilibria. Anal. Chim. Acta, 187 (1986): 279-285.
[l 11 Rojas-Hemandez, A., Ramirez, M.T., Ib%iez, J.G. and Gonzalez, I., Construction of multicomponent
Pourbaix diagrams using generalized species. J. Electrochem Sot., 138 (199 1): 365-37 1.
[12] Rojas-Hemandez, A., Ramimz, M.T., Ib&iez, J.G. and Gonzalez, I., Relationship of multidimensional
predominance-zone diagrams with multiconditional constants for complexation equilibria. Anal. Chim.
Acta, 246 (1991): 435-442.
(131 Rojas-Hemandez, A., Ramirez, M.T., Gonzalez, 1. and Ib&iez, J.G., Multidimensional predominance-zone
diagrams for polynuclear chemical species. Anal. Chim. Acta, 259 (1992): 95-104.
[14] Rojas-Hemtlndez, A., Ramirez, M.T. and Gonzalez, I., Equilibria among condensed phases and a
multi-component solution using the concept of generalized species. I Systems with mixed species. Anal.
Chim. Acta, 278 (1993): 321-333.
82 C. Nila, I. Gonza’lez/ Hydrnmetallurgy 42 (1996) 63-82

[I51 Rojas-Hemtkidez, A., Ramirez, M.T. and Gonzalez, I., Equilibria among condensed phases and a
multi-component solution using the concept of generalized species. II Systems with polynuclear species.
Anal. Chim. Acta, 278 (1993): 335-347.
[16] Rojas-Hem&ndez, A., Ramirez, M.T., Gonzalez, 1. and Ib%iez, J.G., Predominance zone diagrams in
solution chemistry dismutation processes in two-component systems (M-L). J. Chem. Educ., in press.
[17] Smith, R.M. and Martell, A.E., Critical Stability Constants. Plenum Press, New York, Vol. 4 (1976).
[18] Bard, A.J., Parsons, R. and Jordan, J., Standard Potentials in Aqueous Solution. Marcel Dekker, New
York (198.5).
[ 191 Cotton, F.A. and Wilkinson, G., Advanced Inorganic Chemistry. Wiley, New York (1972).
[20] Figgis, B.N., Introduction to Ligand Fields. Interscience, New York (19661.
[Zl] Lever, A.B.P., Inorganic Electronic Spectroscopy. Elsevier, Amsterdam (1984).
[22] Rice, N.M., Nedved, M. and Ritcey, G.M., The extraction of nickel from ammoniacal media and its
separation from copper, cobalt and zinc usin, 0 hydroxyoxime extractants. Hydrometallurgy, 3 (19781:
35-54.
[23] Crousier, J., Pardessus, L. and Crousier, J.P., Voltammetry study of copper in choride solution.
Electrochim. Acta, 33 (1988): 1039- 1042.
[24] Moreau, A., Frayret, J.P., Del Rey, F. and Pointeau, R., Interpretation des courbes de polarisation
cathodique du cuivre dans Ies solutions chIorur&s acides desaerees: etude simultane6 de la corrosion du
cuivre et de la reduction des iones H’. Electrochim. Acta, 30 (1985): 649-651.
[25] Moreau, A., Etude du mecanisme d’oxydo-reduction du cuivre dans les solutions chorurees acides-II.
Systemes Cu-CuCl-CuCl; et Cu-CU,(OH)~CI-CUC~+ Cu’+. Electrochim. Acta, 26 (1981): 1609-1616.
[26] Larson, T., U.S. Geol. Surv. TEI Rep. 507,800b (1972): 119.
[27] Jaggi, O., Acta Crystallogr., 14 (1961): 1041.
[28] Swanson, T., Natl. Bur. Standards Circ. 539,149 (1953).
[29] Nls’tien, R. and Tamminen, V., The equilibria of cupric hydroxysalts in mixed aqueous solutions of
cupric and alkali salts at 25”. J. Am. Chem. kc., 71 (1949): 1994-1998.
[30] Stankovic, Z.D., The effect of Cl(I)- ions on kinetics and mechanism of anodic dissolution and cathodic
deposition of copper. Electrochim. Acta, 29 (1984): 407-409.
[31] Gorbunova, I.V., Lyamina, L.I. and Gorbunova, K.M., Some kinetics on cathodic solid-phase reduction
of copper (I) oxide. Sov. Electrochem., 23 (1987): 1027-1033.