Hydrometallurgy 68 (2003) 23 – 31

www.elsevier.com/locate/hydromet

The solubility of copper sulfides under reducing conditions

Courtney A. Young, Eric J. Dahlgren, Robert G. Robins *
Department of Metallurgical and Materials Engineering, Montana Tech of The University of Montana, 215 ELC Building,
1300 West Park Street, Butte, MT, USA
Received 20 March 2002; received in revised form 30 July 2002; accepted 9 September 2002

Abstract

The formation of copper thio-complexes in sulfide solutions has been recognized for many years, and the measured
solubilities of certain copper sulfide minerals are attributed to these complexes. Attempts to model this system have proposed
either copper(I) or copper(II) thio-complexes. These species have been incorporated into computer programs for generating
stability diagrams for the copper – sulfur – water system in order to delineate the region where the reductive dissolution of copper
sulfide minerals is likely. In this paper, it is proposed that the dissolution of copper from both ore bodies and sulfide tailings can
be explained by the formation of the cupro-thio-complexes under anaerobic conditions. Stability diagrams are presented to
depict the region and extent of the solubility. It is concluded that the stability diagrams involving copper(I) thio-complexes
better represent the system.
D 2003 Elsevier Science B.V. All rights reserved.

Keywords: Copper Sulfides; Solubility; Bisulfide Complexes; EH – pH Diagrams; Thermodynamics

1. Introduction tions such as the NBS tables (Wagman et al., 1982).

It is well known that many metal thio-complexes
exist and that metal sulfide minerals are soluble (to
some extent) in sulfide solutions (Khodakovsky,
1966). Khodakovsky (1966) discussed the transport
of heavy metals in the form of hydrosulfides, giving
specific data for the solubilities of the sulfide minerals
of Fe, Zn, Pb, Ag, Cu, Co, Cd and Hg. The free
energy data in Table 1 originates from his work and is
taken from the Russian compilation by Naumov et al.
(1974) but is not available in more recent compila-
* Corresponding author.
E-mail address: bobrobins@bigpond.com.au (R.G. Robins).
The solubility of gold and silver in high-temperature
sulfide solutions has been widely investigated
recently to explain transport in ore-forming solutions.
A number of papers on the solubility of sulfide mi-
nerals in sulfide solution and the various thio-com-
plexes involved were published together in the 1989
edition of the journal Geochimica et Cosmochimica
Acta (Various authors, 1989). Although most of the
published work has been conducted at elevated tem-
perature, it has indicated that there is an appreciable
solubility of sulfide minerals in sulfide solutions at
ambient temperature. The influence of the polysulfide
ions S2x
on the solubilities has been considered to
be appreciable (Cloke, 1963), but the importance of
these complexes has also been questioned by later
workers.

0304-386X/03/$ - see front matter D 2003 Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 4 - 3 8 6 X ( 0 2 ) 0 0 1 6 6 - 4
24 C.A. Young et al. / Hydrometallurgy 68 (2003) 23–31

Table 1 per(I) complexes CuHS0, Cu(HS)2
and Cu2S(HS)22

Some metal thio-complexes and their free energies of formation which fit well with the low temperature data of Crerar
(Naumov et al., 1974)
0
and Barnes (1976).
Species DG298 (kcal/mol)
The solubility measurements reported in the above
0
AgHS + 2.1 publications (Romberger and Barnes, 1970; Snell-
Ag(HS)

1.0
2
grove and Barnes, 1974; Crerar and Barnes, 1976;
CdHS+
29.6
Cd(HS)02
35.4 Shea and Helz, 1988, 1989; Thompson and Helz,
Cd(HS)
3
35.5 1994; Mountain and Seward, 1995, 1999) can be seen
Cd(HS)24

35.6 to apply to a variety of copper sulfide assemblages
Co(HS)+
18.3 and, although pH measurements were reported in
Co(HS)02
19.6
most cases, there is no mention of potential. It is
Cu(HS)
3
11.1
Hg(HS)02
6.4 possible that the varying speciation models have been
HgS22
+ 10.0 influenced by the potential in the particular experi-
Pb(HS)02
20.9 ments which is discussed later.
Pb(HS)
3
19.8
Zn(HS)02
49.8
Zn(HS)
3
48.5
Fe(HS)02
28.5 2. Stability diagrams
Fe(HS)23

28.4
The use of thermodynamics to calculate stability
diagrams in relation to an understanding of hydro-
Regarding the Cu –S – H2O system, the solubility of metallurgical processes has developed over a period
copper sulfide minerals in sulfide solutions has been of more than 40 years, mostly due to the publication
studied extensively (Romberger and Barnes, 1970; of the English language version of the Atlas of
Snellgrove and Barnes, 1974; Crerar and Barnes, Electrochemical Equilibria in Aqueous Solutions by
1976; Shea and Helz, 1988, 1989; Thompson and Pourbaix (1966). The utility of potential – pH dia-
Helz, 1994; Mountain and Seward, 1995, 1999). Rom- grams in the minerals geology field was promoted
berger and Barnes (1970) measured the solubility of by Garrels (1960) and Garrels and Christ (1965), and
covellite (CuS) in concentrated sulfide solutions in the these diagrams are now well known in hydrometallur-
pH range 3.5– 13.5 and 20 – 200 jC and proposed the gical circles. It is unfortunate that there is no up-to-
copper(II) species Cu(HS)3
and CuS(HS)33
to explain date and comprehensive treatise in the area of hydro-
the room temperature solubility. Later, Snellgrove and metallurgy, but perhaps, this is not necessary when,
Barnes (1974) claimed that on the basis of spectro- with a knowledge of fundamentals, we can now use
scopic evidence, the copper(I) complex Cu(HS)32
was the computer to generate stability diagrams for the
the only species likely to be present. Crerar and Barnes systems of interest at any time.
(1976) proposed two copper(I) complexes Cu(HS)2
During the last 40 years, there have been many
and Cu(HS)2(H2S)
when investigating the Cu0 – Cu2S hydrometallurgical papers published where stability
assemblage. Shea and Heltz (1988,1989) measured the diagrams have been used to illustrate process con-
solubility of CuS at 25 jC and interpreted their data in ditions as well as to provide a fundamental under-
terms of copper(II) complexes of the form CuS(HS)xx
. standing of the aqueous solutions involved. Halpern
Thompson and Helz (1994) chose a monomer –dimer (1957) used EH – pH diagrams to describe the physical
model or a trimer – tetramer model which depended on chemistry of hydrometallurgical systems. The poten-
the chosen activity for the solid copper sulfide in tial –pH diagram (EH vs. pH or pe vs. pH, where
chalcocite –djurleite (Cu2S – Cu1.96S) and anilite – cov- pe = F/2.303RTEH) is still the most widely presented,
ellite (Cu1.75S –CuS) assemblages. Mountain and Sew- but others such as log activity vs. pH, log activity vs.
ard (1995,1999) measured the solubility of synthetic log activity and log activity vs. pe + pH and others are
chalcocite (Cu2S) at 22 jC in the pH range 4 – 11.5 in a also common.
flow-through column, and reassessed the high-temper- Computer generation of stability diagrams in
ature data. They presented stability data for the cop- hydrometallurgy has evolved along with other com-
 C.A. Young et al. / Hydrometallurgy 68 (2003) 23–31
puter modeling work. Provided that the free energies
of formation for all species present in an aqueous
system are known and reliable, then a number of
computer codes can be used to minimize free energies
and show equilibrium conditions either in numerical
or graphical format. Some of these codes have been
reviewed by Waite (1989), but with emphasis on those
producing numerical output. A brief review of those
programs that can be used for generating stability
diagrams is included in the paper by Robins (1993a)
on the copper –sulfur– water system.
Stability diagrams for the Cu – S – H2O system
have been widely applied over many years to
explain the chemistry and stability regions in the
system, mostly in reference to hydrometallurgical
process solutions. However, in most of the published
diagrams for the Cu – S– H2O system, there has been
no account of the thio-complexes of copper, except
for the paper by Robins (1993a) which considers
only the copper(II) thio-complexes. In this paper, the
free energies of formation for the various species in
the system have again been reevaluated for consis-
tency, and both copper(I) and copper(II) thio-com-
plexes considered in generating potential – pH
diagrams using the program STABCAL (Huang,
1999).
Majima (1969) used a potential –pH diagram for
the Cu – Fe– S –H2O system at 25 jC to explain some
effects in flotation. Prior to this, Majima had produced
diagrams for Cu –S – H2O (unpublished). Peters and
Majima (1968) used a potential –pH diagram for the
Cu – Fe – S – H2O system in discussing the physical
chemistry of hydrometallurgy, and Peters (1973) used
a similar diagram for the same purpose. Similar
potential – pH diagrams were determined by Kwok
and Robins (1973) but also included diagrams at
elevated temperatures (100 and 200 jC) using ther-
modynamic data obtained with the Criss and Cobble
(1964) entropy correspondence principle. High-tem-
perature diagrams for the Cu – S –H2O system are also
presented in the thesis by Ferreira (1975). A poten-
tial –pH diagram for Cu – S– H2O at 25 jC appears in
the compilation of diagrams by Duby (1977) which
also included the ion-pair species CuSO4 (aq) not
previously considered.
Wadsworth (1979) used a potential –pH diagram
for the Cu – S– H2O system to illustrate some of the
electrochemical fundamentals involved in leaching
25
sulfide minerals. Jang and Wadsworth (1993) used a
potential – pH diagram for Cu – Fe– S –H2O at 200 jC
as a guide to hydrothermal oxidation of chalcopyrite
under conditions of controlled EH and pH. Linkson
(1982) has used a potential – pH diagram for the Cu –
S(IV) – H2O system to show the stability region for
Chevreul’s salt (a hydrated Cu(I) – Cu(II) sulfite). This
concept of incorporating ‘‘metastable’’ species such as
sulfite into ‘‘stability’’ diagrams is not new and has
been used widely, particularly in systems where
kinetics can be slow and/or controlling. In their case,
the other component (i.e., copper) was included in all
oxidation states.
The potential – pH diagrams for Cu – S –H2O have
remained much the same over the years. One im-
portant improvement has been the consideration of
solid sulfide species other than CuS (covellite) and
Cu2S (chalcocite). Baratin (1980) included copper –
iron sulfide minerals and Young (1987) and Woods et
al. (1987) considered non-stoichiometric stable sul-
fides including Cu1.75S (anilite) and Cu1.96S (djur-
leite) as well as metastable sulfides including Cu1.93S,
Cu1.83S, Cu1.67S and Cu1.38S, all in the presence of
unprotonated polysulfide ions. Some unusual activ-
ity– distribution diagrams for the system Cu – S –H2O
were presented by El-Demerdash and El-Raghy
(1993). The only consideration of aqueous copper
thio-complexes in any of the published potential –
pH diagrams for this system was by Robins (1993a)
who used data for copper(II) thio-complexes taken
from Shea and Helz (1988,1989) and Romberger and
Barnes (1970).
3. Objectives and procedures
In this paper, the Cu – S – H2O system is reex-
amined in terms of potential– pH diagrams with con-
sideration for the first of copper(I) thio-complexes
proposed by Mountain and Seward (1999). The free
energy data for those species used in generating the
diagrams are shown in Table 2 and originate from the
literature that is cited. Some of the data has been
adjusted with the computer program CONSIST (Rob-
ins, unpublished), and the diagrams were then gen-
erated with the computer program STABCAL
developed by Huang (1999). Note the similarity in
free energies of formation of the copper(II) thio-
26 C.A. Young et al. / Hydrometallurgy 68 (2003) 23–31

Table 2 4. Updated copper– sulfur – water system

Cu – S – H2O species and their free energies of formation which were
adjusted to be consistent with key values from Wagman et al. (1982)*
0
In order to update the Cu – S – H2O system, all
Species DG298 (kcal/mol)
available free energy in the literature was critically
Copper species* evaluated, not just the copper thio-complexes. A
Cu (s) 0.0
review of all of the data here is not appropriate, but
Cu+ 12.0
Cu2 + 15.7 the more important source references are given in
CuOH+
31.0 Table 2. In addition, the data was subjected to the
Cu(OH)2
(aq)
74.0 computer consistency manipulation procedure men-
Cu(OH)3
118.6 tioned previously. Some data such as for metastable
Cu(OH)24

157.3
species have not been used in the particular stability
CuO (s)
32.0
Cu2O (s)
35.4 diagrams shown in this paper but have been consid-
ered in the overall assessment of the system. Data for
Stable sulfur species* the hydrolysis complexes of copper(I), namely, CuO-
S (s, rhombic) 0.00 H(aq) and Cu(OH)2
, which were used by Beverskog
H2S (aq)
6.66
and Puigdomenech (1997), are not used since the
H2S (g)
8.02
HS
2.88 values were obtained from experimental solubility of
SO24

177.94 CuO at elevated temperatures.
HSO
4
180.68 The free energy data for the solid copper sulfides,
CuS (covellite), Cu1.75S (anilite), Cu1.96S (djurleite)
Copper sulfate species*
and Cu2S (chalcocite), were taken initially from the
CuSO4 (aq)
165.43
CuSO42Cu(OH)2 (s)
345.75 work by Potter (1977) as used by Young (1987) and
CuSO43Cu(OH)2 (s)
434.44 Woods et al. (1987) but with consideration given to
CuSO45H2O (s)
449.30 data in Robie et al. (1994) and then manipulated to
maintain consistency. Surprisingly, there are still var-
Water*
iations in the data for these compounds (minerals) in
H2O (l)
56.69
the various data compilations, and some of these can
Copper sulfide solids** be attributed to a variation in the key values, but some
CuS (covellite)
12.8 due to the extrapolation of high-temperature (non-
Cu1.75S (anilite)
18.7 aqueous) data to 25 jC (298 K). The variations in data
Cu1.96S (djurleite)
20.1
values do not significantly affect the stability dia-
Cu2S (chalcocite)
20.4
grams that are shown here.
Copper(II) thio-complexes§ Potential –pH diagrams shown in this paper were
Cu(HS)

3
11.94 selected firstly in order to update the previously
CuS(HS)33

0.85 published work. In that respect, there is perhaps
little change except for that caused by the introduc-
Copper(I) Thio-complexesy
Cu(HS)

2
5.68 tion of the copper(I) thio-complexes. Fig. 1 is a
Cu2S(HS)22

8.11 potential –pH (EH – pH) diagram for the Cu – S– H2O
CuHS0
2.85 system that considers only copper(I) thio-complexes.
** Data calculated from Wagman et al. (1982), Robie et al. Fig. 2 is a diagram with the copper(II) thio-com-
(1994), Koch and McIntyre (1976) and Potter (1977) using the plexes and Fig. 3 considers both copper(I) and
CONSIST program. copper(II) thio-complexes together. All of the dia-
§
Data calculated from Shea and Helz (1988,1989) and
grams were calculated for unit activity of the sum of
Romberger and Barnes (1970) using the CONSIST program.
y
Data calculated from Mountain and Seward (1999). sulfur species and 10
5 activity of the sum of
copper species using the STABCAL program. It
complex, Cu(HS)3
, in Tables 1 and 2. The concen- can be seen that in all diagrams, the region of the
trations of copper and sulfur were set at 0.00001 and solubility gap is similar, and it can be shown that
1.0 M, respectively, for all diagrams. the highest solubility is at pH = 7. Numbers in
 C.A. Young et al. / Hydrometallurgy 68 (2003) 23–31 27

Fig. 1. EH – pH diagram for the Cu – S – H2O system that considers copper(I) thio-complexes. Copper = 0.00001 M and sulfur = 1.0 M.

Fig. 2. EH – pH diagram for the Cu – S – H2O system that considers copper(II) thio-complexes. Copper = 0.00001 M and sulfur = 1.0 M.
28 C.A. Young et al. / Hydrometallurgy 68 (2003) 23–31

Fig. 3. EH – pH diagram for the Cu – S – H2O system that considers copper(I) and copper(II) thio-complexes. Copper = 0.00001 M and
sulfur = 1.0 M.

parentheses correspond to the proposed reactions CuS þ HS
þ Hþ þ e
¼ CuðHSÞ

2 ð5Þ
discussed next.
2CuðHSÞ
2


2 ¼ Cu2 SðHSÞ2 þ HS þ H
þ
ð6Þ
5. Reaction equations
2Cu0 þ 3HS
¼ Cu2 SðHSÞ2
þ
2 þ H þ 2e


ð7Þ
Chemical reaction equations can be written for
each of the equilibria represented by the numbers in
2CuS þ HS
þ Hþ þ 2e
¼ Cu2 SðHSÞ2

2 ð8Þ
parenthesis in the figures. However, these equations
represent only the predominant species involved,
þ
2

whereas in the computer generation of the diagrams, Cu2 S þ 2SO2

4 þ 18H þ 16e ¼ Cu2 SðHSÞ2
all species in relevant areas were considered. þ 8H2 O ð9Þ
Reactions that yield copper(I) thio-complexes:
Reactions that yield copper(II) thio-complexes:
Cu0 þ 2HS
¼ CuðHSÞ

2 þe


ð1Þ
Cu2 S þ 5HS
þ Hþ ¼ 2CuðHSÞ

3 þ 2e


ð10Þ
Cu0 þ 2H2 S ¼ CuðHSÞ
þ
2 þ 2H þ e


ð2Þ

Cu2 S þ 3HS
þ Hþ ¼ 2CuðHSÞ
ð3Þ Cu2 S þ 5H2 S ¼ 2CuðHSÞ
þ

3 þ 4H þ 2e


ð11Þ
2

CuS þ H2 S þ e
¼ CuðHSÞ

2 ð4Þ CuS þ 2H2 S ¼ CuðHSÞ

3 þH
þ
ð12Þ
 C.A. Young et al. / Hydrometallurgy 68 (2003) 23–31 29

CuS þ 2SO2
þ

waters, and claims that there is an apparent increase in

4 þ 19H þ 16e ¼ CuðHSÞ3 þ 8H2 O
the solubility product with depth. This has been
ð13Þ explained by Robins (1993b) to be due to the possible
formation of the well-known iron(II) thio-complexes.
CuðHSÞ

3

3 þ HS ¼ CuSðHSÞ3 þ H
þ
ð14Þ Robins also suggests that there is evidence for reduc-
tive dissolution of other metals, including copper, in
Cu2 S þ 7HS
¼ 2CuSðHSÞ3
þ
3 þ H þ 2e


ð15Þ the results from a very thorough study of the Ana-
conda Tailings in Montana, USA.
þ
3
In the case of the copper sulfide minerals, the
Cu2 S þ 7SO2

4 þ 62H þ 42e ¼ 2CuSðHSÞ3
formation of either copper(I) or copper(II) thio-com-
þ 28H2 O ð16Þ plexes would have a similar effect of causing solu-
bility in a region of potential that could be expected at
Reactions that yield copper(II) thio-complexes
the bottom of a tailings heap, below an orebody, or
from copper(I) thio-complexes:
even in an anaerobic treatment wetlands as suggested
CuðHSÞ

þ
by Gammons and Frandsen (2001). There are also
2 þ H2 S ¼ CuðHSÞ3 þ H þ e ð17Þ
implications in considering more carefully the chem-
CuðHSÞ



istry of supergene ore formation.
2 þ HS ¼ CuðHSÞ3 þ e ð18Þ

CuðHSÞ

3
þ
2 þ 2HS ¼ CuSðHSÞ3 þ H þ e


ð19Þ 7. Discussion and conclusions

Cu2 SðHSÞ2

3
þ
2 þ 5HS ¼ 2CuSðHSÞ3 þ H þ 2e


ð20Þ
Other chemical equations involving the non-stoi-
chiometric minerals djurleite (Cu1.96S) and anilite
(Cu1.75S) have been omitted for brevity.
6. Sulfide tailings and orebodies
In a sulfide tailings heap ,it is considered that there
is an oxidized zone and a reduced zone. The reactions
leading to the oxidized have been widely discussed in
the literature (Murr, 1980), but the reactions in the
reduced zone have not been considered in the various
models for determining the chemical stability of
tailings. At the interface of the two zones, there will
be interactions between dissolved oxygen and dis-
solved sulfide, and these interactions can be mediated
by microorganisms. Jorgensen and Revsbech (1983)
have shown the influence of sulfur bacteria at the
oxygen –sulfide interface in sediments. This interface
was shown to exhibit very sharp oxygen and sulfide
gradients above and below it, and it is likely that the
same general conditions will exist in sulfide tailings.
Davidson (1980) has reviewed what has been reported
as measured solubilities of ferrous sulfide in natural
It has been said on many occasions that stability
diagrams for inorganic– aqueous systems provide a
very useful tool for hydrometallurgists to better under-
stand process and effluent solutions. In the past, these
diagrams have been tediously hand calculated, but
with the advent of computer modeling of aqueous
systems, codes have been developed which will gen-
erate the diagrams. There is a variety of other useful
x – y stability diagrams that can be generated by
computer to further elucidate this copper – sulfur –
water system, but only potential – pH diagrams are
presented in this paper.
Potential – pH diagrams presented in this paper are
specifically aimed at a consideration of the effects of
the existence of copper thio-complexes. Well-docu-
mented solubility data in the literature gives evidence
for both copper(I) and copper(II) complexes, but in
the experimental work that is reported, there has
apparently been no measurement or control of reduc-
tion potential (EH). The diagrams have been generated
for the Cu –S – H2O system with only copper(I) thio-
complexes considered (Fig. 1), with only the cop-
per(II) thio-complexes considered (Fig. 2) and with
both copper(I) and copper(II) thio-complexes included
(Fig. 3). An examination of these diagrams leads to
the conclusion that the copper(I) thio-complexes alone
could explain the solubility measurements for CuS
30 C.A. Young et al. / Hydrometallurgy 68 (2003) 23–31
and Cu2S, as well as the assemblages containing
Cu1.75S, Cu1.96S and more importantly, Cu. For the
same reasoning, it is unlikely that the copper(II) thio-
complexes exist. Therefore, Fig. 1 must correctly
predict the Cu – S –H2O system, that Reactions 1 –9
occur, whereas Reactions 10 – 20 do not, and that the
conclusions offered by Snellgrove and Barnes (1974),
Crerar and Barnes (1976) and, in particular, Mountain
and Seward (1999) are correct.
However, the absence of measurements of reduc-
tion potential in the experimental work of these and
other earlier workers (Romberger and Barnes, 1970;
Shea and Helz, 1988, 1989; Thompson and Helz,
1994; Mountain and Seward, 1995), leads to some
uncertainty as to the actual conditions that existed in
the system apart from the pH and concentrations of
copper and sulfide. An examination of Fig. 1, for
example, reveals that, in this case, the potential could
be anywhere around the top and left side of the
solubility gap. The potential could be controlled by
either of the possible assemblages: Cu + Cu 2 S,
Cu2S + Cu1.96S, Cu1.96S + Cu1.75S, or Cu1.75S + CuS.
Another control could be hydrogen, which appears on
the diagram through the stability region for Cu1.96S,
and if this is really the case, then more accurate data
for djurleite could possibly be obtained.
The data used here for both Cu1.96S and Cu1.75S
has originated mainly from the work of Potter (1977)
who used electrochemical cells in which the sulfide
electrodes (and a copper reference) were maintained
in solutions of CuSO4 or CuCl which were not
necessarily at the equilibrium potential –pH. It seems
that electrochemical cells in a sulfide system would
lead to reliable data.
The proposition that dissolution of copper sulfide
minerals from the bottom of tailings heaps or copper
sulfide orebodies could be enhanced by the formation
of soluble copper thio-complexes is supported by
solubility data that has been reported by Mountain
and Seward (1999) and others. The potential – pH
diagrams presented in this paper depict the regions in
which that enhanced solubility is most likely to occur.
Acknowledgements
Many thanks are extended to Dr. H.H. Huang for
the use of his STABCAL program.
The initial development of stability diagrams for
aqueous systems is due to the lifetime dedication of
Marcel Pourbaix. His contribution is sans égale.
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