Hydrometallurgy 77 (2005) 183 190

www.elsevier.com/locate/hydromet

Dissolution kinetics of metallic copper with CuSO4NaClHCl

Osvaldo Herrerosa,T, Roberto Quiroza, Ambrosio Restovicb, Joan Vinalsc
a

Departamento Ingeniera Minas, Universidad de Antofagasta, Casilla 170, Antofagasta, Chile

b
Departamento de Qumica, Universidad de Antofagasta, Chile
c
Departamento de Ingeniera Qumica y Metalurgia, Universidad de Barcelona, Spain

Received 4 May 2004; received in revised form 10 November 2004; accepted 21 November 2004

Abstract
A study was made on the dissolution kinetics of metallic copper flat packs using solutions of Cu(II) in a chloride medium
which was obtained via reaction between copper sulfate and sodium chloride. The effect of stirring, chloride and Cu(II)
concentrations, distribution of Cu(II) chlorocomplexes and temperature were investigated.
The leaching data showed the reaction to be under chemical kinetics control, with an activation energy of 28 kJ/mol (7 kcal/
mol). Leaching occurred at an apparent order of
1 with respect to the total chloride concentration and an apparent first order
with respect to the total copper concentration. The Cu(II) ion was the main active species based on calculation of copper species
distribution and the solution kinetics may be interpreted as rate=k[Cu2+]. For ratios of C Cl/C Cu2+ of less than about 8, a layer of
CuCl(s) formed which impeded the solubilization process.
D 2005 Elsevier B.V. All rights reserved.
Keywords: Copper; Leaching; Chlorides; Chlorocomplexes

1. Introduction
Processes for the leaching of metallic copper in
chloride media have been based primarily on the
action of cupric copper in the presence of sodium
chloride. Important references on this topic include
the studies of Lin et al. (1992) and Tolley et al. (1977),
which report on the thermodynamics of the equilibrium involved as well as on kinetic data in the Cu/
T Corresponding author.
E-mail address: oherreros@uantof.cl (O. Herreros).
0304-386X/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2004.11.010

Cl
system. Lin et al. report a copper leaching rate

consistent with the following expression:

1=2
2
Cl 
1
rate k Cu2
The order of this in reference to [Cu2+] is 0.5, which is
in agreement with that reported by Tolley et al.
(1977), who leached copper beads with CuCl2 in a
stirred reactor.
The study carried out by Herreros et al. (1999)
on the dissolution of copper flat packs by aqueous
Cl2/Cl
media (0.510
21.910
2 M Cl2, 0.51.4
M Cltot), reported that the most significant effects

184

O. Herreros et al. / Hydrometallurgy 77 (2005) 183190

Cu0

CuCl

Cu + CuCl+ + Cl-

Cu2+ or
CuCl+

CuCl+

2 CuCl
Cu2+

Cu + Cu

2+

+ 2Cl

2 CuCl

CuCl + Cl-

CuCl2-

Fig. 1. Scheme of the possible steps in the leaching of metallic copper with Cu(II) in chloride media.

were those related to the concentrations of chlorine

and chloride, and that the aqueous chlorine was the
reagent that made possible the dissolution of the
copper, with chloride contributing a negative effect.
The chloride inhibited the dissolution, probably due
to the formation of a superficial layer of CuCl.
When working with excess chlorine, however, the
dissolution of this solid CuCl was increased. In this
case the kinetic control was affected by the transfer
of mass in the film, with activation energy of 18 kJ/
mol (4.3 kcal/mol). The apparent order of reaction
with respect to chlorine was 1.0 and
0.17 for the
chloride.
On the other hand, the literature describes a process
for copper recovery from bronze scrap in which
leaching is obtained using 0.28 M CuCl2 and 4.8 M
NaCl at a temperature of 75 8C (Langer et al., 1977).
The CLEAR process, dating from the 1970s (Copper
Leach, Electrolysis and Regeneration) also uses cupric
chloride together with a solution of 4.4 M NaCl and 2.4
M KCl, although in this case, the objective was the
leaching of chalcopyrite (Atwood and Livingston,
1980).
In contrast with results from the preceding brief
literature review, the objective of the present research
was to study the dissolution of metallic copper with
cupric chlorocomplexes generated in situ by reacting
copper sulfate with sodium chloride in a hydrochloric acid medium, and then determining if the
CuCl+ complex is the main active species in the
leaching of the metallic copper by having a
sufficiently oxidative potential for obtaining the
solubilization. This kinetic study may be applicable

in the leaching of copper precipitates, which in Chile

have varying degrees of surface oxidation, as well as
in treatment of discarded cathodes from the electrowinning process.
Our study determined the effects of the stirring,
temperature, as well as the concentrations of total
Cu(II), total chloride, and copper chlorocomplexes for
postulating the possible controlling stage or stages of
the dissolution, and modeling a kinetic expression for
the leaching rate.
1.1. Criteria for the application of kinetic models
It is broadly recognized in the literature that in the
case of dissolution of pure species without formation
of insoluble products in surface layers, the only
controlling steps can be the mass transfer through
the fluid film and the specific chemical reaction
(Levenspiel, 1979; Sohn and Wadsworth, 1986). In
the case of leaching of Cu with Cu(II) in a Cl

medium, competition may exist between a bsolidQ
intermediate formed on the surface of the metallic
copper, probably CuCl, which would tend to dissolve,
whereupon the leaching reagent would advance to the
reaction surface.
A diagram of the possible steps is presented as Fig.
1. The reactions of this process would be
Cu Cu2 2Cl
2CuCls

Cu CuCl Cl
2CuCls

2CuCls 2Cl
2CuCl2

O. Herreros et al. / Hydrometallurgy 77 (2005) 183190

The overall reaction from combining Eqs. 3 and 4 is:

Cu CuCl 3Cl
2CuCl

2

E0 0:538V

E 0 0:137V

1.3. Distribution of chloride species

When chloride ion and cupric ion share an aqueous
system, the composition of the resulting solution is
governed by the following equilibria (Duby, 1977):
Cu2 Cl
CuCl

and the Cu(I)Cu(0) reduction as:

CuCl e
Cu Cl

solution, n=reaction order, k r=rate constant (cm

min
1, for n=1) and e 0=flat pack thickness (cm).

Following data from tables of standard potentials

(Software HSC Chemistry; Duby, 1977), the equilibrium of Cu(II)Cu(I) in chloride solutions is shown as
Cu2 Cl
e
CuCl

185

K1 100:46

12

CuCl Cl
CuCl2Aq

K2 10
0:27

13

Using these data, the solution of copper by cupric

chloride may be written as:

CuCl2Aq Cl
CuCl

3

K3 10
2:48

14

Cu Cu2 2Cl
2CuCl

Reaction (8) has E cel=0.401 V and free energy of

formation=
38.7 kJ/mol (
9.25 kcal/mol).
The cuprous chloride is only slightly soluble under
these standard conditions, but its solubility increases
with increase in the chloride concentration due to the
successive formation of CuCl2
and CuCl32
ion
complexes. Also, the solubility increases with temperature (Jackson, 1986).

2

CuCl

3 Cl CuCl4

K4 10
2:30

For determination of the different species of the

copper chlorocomplexes in the initial solution, the
following material balance is used:




C Cl Cl
 CuCl  2 CuCl2Aq 3 CuCl

3


4 CuCl2

16
4
and
CCl CNaCl CHCl

1.2. Kinetic model utilized

The geometry of the particles used to carry out the
present leaching experiments was of small flat-packs,
and the conversion model used is described below
(Levenspiel, 1979; Sohn and Wadsworth, 1986):
a

2bkr
CAO n t
qB e0

or also
a kexp t

10

15

17




 

C Cu Cu2 CuCl  CuCl2Aq CuCl

3


18
CuCl2

4
where C Cl , C NaCl, C HCl and C Cu are total concentrations (mol/L), and [i] are concentrations of the
different species. If C Cl and C Cu are known, the
concentrations of the remaining species are defined if
it is assumed that the activity coefficients are near unity.
According to values for the formation of chlorocomplexes, the predominant species in this Cu2+/Cl

system are Cu2+, CuCl+ and CuCl2(Aq).

and
kexp

2bkr
CAO n
qB e0

2. Materials and experimental procedure

11

where a=fraction reacted, k exp=experimental rate

constant (min
1), t=time (min), b=stoichiometric
factor (mol solid dissolved/mol leaching reagent),
q B=molar density of solid (mol solid dm
3), [C AO]=
molar concentration of leaching species in the bulk

2.1. Materials
Metallic copper of about 99.99% purity was used in
all experimentation. Copper flat packs of about 11
mm and 0.105 mm in thickness cut from electrolytic
copper sheets were used in the kinetic experiments. The

O. Herreros et al. / Hydrometallurgy 77 (2005) 183190

reagents, copper sulfate pentahydrate, sodium chloride

and hydrochloric acid, were of analytical grade.
2.2. Reactor
A conventional leaching apparatus was used,
consisting of a 1200-cm3 triple-neck spherical glass
reactor submerged in a thermostatic bath, and fitted
with motor-driven stirring using a Teflon-coated
agitator (propeller of 5 cm diameter). The solution
potential was continuously measured with a platinum
electrode and a AgCl/Ag (KClsat) reference electrode,
connected to a high impedance potentiometer. Temperature was also continuously monitored and the
progress of reaction, copper concentrations and the
pH were measured by removing samples for measurement at specified times. The reactor was operated
under closed conditions.
2.3. Leaching reagent
The experiments were designed so that the
concentration of both the total chloride as well as
total cupric ion could be determined initially.
The solutions used in each experiment were
obtained by the following methods: a given volume
of distilled water was placed in the reactor, followed
by given masses of copper sulfate pentahydrate and
sodium chloride, and the pH was adjusted with
concentrated HCl to the desired value. The system
was then made up to 1000 cm3, and the initial
concentration of copper and pH were determined.
The kinetic experiments were initiated once the
solution was prepared. Here 2 g of copper flat packs
was added at t=0, and the progress of the leaching was
determined by taking 5-ml samples of the liquid for
copper analysis using atomic absorption spectrometry
(AA). Selected samples of attacked copper in the different conditions were examined by SEM/EDS in order
to detect possible layers of solid reaction products.

concentration of C Cu at 1.3810
1 (M), C Cl at

1.43 (M) and temperature of 24 8C. Under these
experimental conditions and according to the distribution of species (Eqs. (13)(19)), it was found
that [Cl
]=1.3 M, [Cu2+ ]=0.019 M, [CuCl+]=0.070
M, [CuCl2]=0.049 M, [CuCl3
]=2.1 10
4 M and
[CuCl4
]=1.4 10
6 M.
The experimental results are presented graphically in Fig. 2. In Fig. 2 it is seen that the fraction
reacted, a, increases as the stirring increases,
becoming essentially constant at stirrings above
350 rpm, which ensure full particle suspension.
This suggests that chemical or electrochemical
reaction control dominates at high agitations levels.
No formation of CuCl(s) was observed in this set of
experiments.
3.2. Effect of total copper concentration
Leaching experiments were carried out by varying
the initial copper concentration in the system to
determine the effect produced by this reactant on the
dissolution kinetics of the copper flat packs in order to
subsequently determine the apparent order of reaction
(350 rpm, 24 8C, C Cl=1.43 M). The calculated
distribution of species for these experimental conditions is shown in Table 1.
Fig. 3 presents the experimental leaching results
in graphical form. Fig. 3 shows that the experimental data fit the flat packs model well for up to
1520 min of leaching. By linear regression of a

0.7

Fraction reacted

186

0.6
0.5
0.4
0.3
0.2
0.1
0

3. Results and discussion

3.1. Effect of stirring
The effect of stirring on the dissolution kinetics of
the copper flat packs was carried out fixing the initial

20

40

60

80

Time (min)
180 rpm

300 rpm

350 rpm

400 rpm

Fig. 2. Dissolution of copper flat packs over time as a function of

the stirring speed (24 8C, C Cu=1.3810
1 M, C Cl=1.43 M).

Table 1
Calculated distribution of species as a function of the total copper
concentration
Cl total
(M)

Cu total
(M)

Cl

(M)

Cu2+
(M)

CuCl+
(M)

CuCl2
(M)

1.43
1.43
1.43
1.43

0.0352
0.0442
0.0641
0.0820

1.386
1.375
1.351
1.329

0.0044
0.0056
0.0083
0.0108

0.0176
0.0222
0.0323
0.0415

0.013
0.016
0.024
0.030

K exp (1/min)

O. Herreros et al. / Hydrometallurgy 77 (2005) 183190

187

0.045
0.04
0.035
0.03
0.025
0.02
0.015
0.01
0.005
0
0

0.02

0.04

0.06

0.08

0.1

Copper species concentration (mole/L)

vs. t, the experimental rate constant, k exp, is

obtained. Fig. 4 illustrates the rate constant in
relation to the total copper concentration, Cu2+,
CuCl+ and CuCl2. It can be seen that the reaction
rate increases in proportion to the total copper
concentration. However, when the concentration of
chloride is maintained constant, an increase in the
total copper concentration brings an almost proportional increase in concentrations of the various Cu
species present. At this stage, the active species
responsible for the dissolution of the copper cannot
be clearly resolved from this effect.
3.3. Effect of total chloride concentration

Fraction reacted

Leaching experiments were carried out varying the

initial chloride concentration of the system to determine the effect produced by this reactant on the
dissolution kinetics of copper flat packs and to
determine the apparent order of reaction (350 rpm,
24 8C, C Cu=3.3910
2 M).The calculated distribution of species for these experimental conditions is
shown in Table 2.

1
0.8

CuCl+

Cu2+

Cu tot

CuCl2

Fig. 4. Dependence of the k exp on the concentrations of Cu2+,

CuCl+, CuCl2 and C Cu.(350 rpm, 24 8C, C Cl=1.43 M).

The experimental results of the leaching are shown

in graphic form in Fig. 5. Fig. 5 shows that the
experimental leaching data fit the flat-packs model
well up to a time of 1520 min. Over longer time
periods, lowering of the total Cu2+ concentration, as
consequence of the reaction progress, produces
curvature of the plots. No formation of a CuCl layer
was observed in this set of experiments. The experiment rate constant (k exp ) was obtained by considering
only the straight portion of the curve of linear
regression of a vs. t.
Fig. 6 shows the dependence of k exp on the
concentrations of Cl
and C Cl. The apparent order
of the reaction for both C Cl and free chloride was

1.1, based on the linear regression data of Fig. 6.
This dependency may be due to the fact that the
chloride ion shows a real (chemical or electrochemical) order of about
1, although this order
may only be apparent, i.e., increase in the chloride
concentration may decrease the concentrations of
active oxidants.

0.6
0.4
0.2

Table 2
Calculated distribution of species as a function of total chloride

0
0

20

40

60

80

Time (min)
0.035 M

0.044 M

0.064 M

0.082 M

Fig. 3. Fraction reacted vs. time, as a function of total copper

concentration (350 RPM, 24 8C, C Cl=1.43M).

Cl total
(M)

Cu total
(M)

Cl

(M)

Cu2+
(M)

CuCl+
(M)

CuCl2
(M)

0.56
0.74
0.91
1.43

0.034
0.034
0.034
0.034

0.53
0.71
0.87
1.39

0.0115
0.0089
0.0073
0.0043

0.0175
0.0182
0.0182
0.0171

0.0049
0.0068
0.0084
0.0126

O. Herreros et al. / Hydrometallurgy 77 (2005) 183190

0.5
0.45
0.4
0.35
0.3
0.25
0.2
0.15
0.1
0.05
0

K exp (1/min)

Fraction reacted

188

0.002

0.004

0.006

0.008

0.01

0.012

Cu2+ concentration (M)

0

20

40

60

80

Time (min)
0.56 M

0.74 M

Fig. 7. Dependence of k exp as a function of the calculated Cu2+

concentration (350 rpm, 24 8C, C Cu=3.3910
2 M).

1.43 M

0.91 M

Fig. 5. Fraction reacted vs. time, as a function of C Cl (350 rpm, 24

8C, C Cu 3.410
2 M).

Fig. 7 shows the approximately proportional dependence of the rate constant on the calculated Cu2+
concentration; the fact that the curve passes practically through the origin strongly suggests that Cu2+
may be the active species in the copper leaching.
On the other hand, similar plots of rate constant
with respect to the calculated CuCl+ and CuCl2
concentrations do not show significant correlation.
Thus, the effect of chloride concentration on the
leaching kinetics should be only apparent, since
variation of [Cl
] markedly varies the distribution of
calculated Cu(II) species. Among these, the only one
that shows a significant effect is Cu2+, which proportionally increases the reaction rate. Increases in the

concentrations of the other species do not lead to

significant changes in the reaction rate which lead to
the conclusion that the Cu2+ is the main active species
under these conditions. The rate for the investigated
interval is:
rate k

Cl  100:46 10
0:27 Cl
2

19

Experimental results of the effect of temperature

on the dissolution kinetics of copper flat packs are
presented in Fig. 8. The experimental constants
based on the data of Fig. 8 were obtained by linear
regression. An Arrhenius plot is presented in Fig. 9.
An activation energy of 28 kJ/mol (aprox. 7 kcal/

Fraction reacted

- log K (min-1)

1 10

0.7

2.3
2.2
2.1
2

0.6
0.5
0.4
0.3
0.2
0.1

1.9

1.8
-0.1

CCu
0:46

3.4. Effect of temperature

2.4

-0.2

0.016
0.014
0.012
0.01
0.008
0.006
0.004
0.002
0

0
0

0.1

0.2

10

20

0.

30

40

Time (min)

- log [i] (mole/L)

Cl total

Cl-

Fig. 6. Dependence of k exp on the C Cl and Cl
concentrations (350

rpm, 24 8C, C Cu=3.410
2 M).

9C

15C

24C

37C

47C

Fig. 8. Fraction reacted vs. time as a function of temperature: (350

rpm, C Cu 1.3710
1 M, C Cl 1.43 M).

O. Herreros et al. / Hydrometallurgy 77 (2005) 183190

189

- ln Kexp (min-1)

7
6
5
4
3
2
1
0

3.4

3.8

4.2

1000/T (1/K)

Fig. 9. Arrhenius plot of the experimental rate constants (350 rpm,

C Cu 1.3710
1 M, C Cl 1.43 M).

mol) was obtained, which is indicative of chemical

or electrochemical reaction control.

4. Surface study
Copper surfaces attacked with different concentrations of Cu(II) and chloride were studied by
scanning electron microscopy (SEM) coupled by
energy dispersive microanalysis (EDS). Samples
were carbon coated. Observation was performed by
secondary electron signal and EDS spectra were
recorded at 20 kV. For ratios C Cl/C CuN8, no
formation of CuCl(s) on the copper was found. Fig.
10 is an example of corrosion texture observed for
this concentration ratio.
However, for ratios C Cl/C Cub8, formation of
CuCl(s) was found on the surface. Fig. 11 shows the
surface of metallic copper attacked for 5 min by NaCl

Fig. 11. SEM image of metallic copper attacked by NaCl=0.56 M,

HCl 0.06 M and total Cu of 0.08 M.

0.56M, HCl 0.06 M and total Cu of 0.08 M. Here, a

continuous layer of tetrahedric crystals of CuCl is
observed. The attack was rapid at 0.08 M Cu but the
concentration of the Cl
is not very high, and thus, the
dissolution of the CuCl is slow in this case. Fig. 12
shows the corresponding EDS spectrum of CuCl from
Fig. 11.
Based on the kinetics results, the species distribution calculations and the surface studies, it is

X-RAY:
Live:
Real:

0 20 keV
Preset:
100s
15s
25% Dead
20s

Remaining:

85s

C
u

C
l
C
u

C
u

< .4
5.480 keV
FS= 1K
ch 284=
MEM1:CL 0.62 CU 0.08 5MIN
Fig. 10. SEM image of metallic copper attacked by NaCl 1.43 M,
HCl 0.06 M and total Cu of 0.034 M.

Fig. 12. EDS spectrum of the CuCl.

10.6 >
33
cts

190

O. Herreros et al. / Hydrometallurgy 77 (2005) 183190

suggested that the dissolution of copper with Cu(II) in

chloride media occurs in the following steps:

Cus Cu2
aq 2Cuads

20

Cu
ads 2Claq CuCl2

21

With a high Cl/Cu(II) ratio, reaction (20) would be a

slow and overall controlling process. In contrast, at
low Cl/Cu(II) ratios, reaction (21) would not occur,
forming CuCl(s) in accordance with:


Cu
ads Claq CuCls

22

inhibiting the reaction. If the chloride concentration

reached zero, there would be no attack on the metallic
copper as experimentally shown when exposing the
copper flat packs to solutions of Cu2+ in the absence
of chloride. It is thus clear that chloride is necessary in
the leaching process, although high concentrations of
the chloride decrease the reaction rate. Species
distribution calculations suggest that this is due to
decreasing the concentration of the active Cu2+
species.

5. Conclusions
(1) The dissolution of metallic copper using solutions of Cu(II) in Cl
media is relatively
insensitive to stirring when the particles are well
suspended. The activation energy of the process
is 28 kJ/mol (7 kcal/mol) which suggests
chemical-type control.
(2) The leaching rate of copper has an apparent
order of
1 with respect to the total chloride
concentration and an apparent order of unity (1)
with respect to the copper concentration.
(3) The correlation of rate constants with the
calculated distribution of copper species in
solution indicates that the Cu(II) ion is the main
active species. Within the interval studied, the
equation for the rate is:
rate k

CCu
1 10

0:46

Cl  100:46 10
0:27 Cl
2

(4) For total chloride/total copper ratios of approximately less than 8, a layer of cuprous chloride is
formed on the copper surface, which inhibits the
leaching process.

Acknowledgements
The authors thank the National Fund for Scientific
and Technological Research (FONDECYT) for support of the present study (FONDECYT project no.
1030046). The support of the bServeis CientficoTe`cnics de la Universitat de BarcelonaQ in the surface
studies is also gratefully acknowledged.

References
Atwood, G.E., Livingston, R.W., 1980. The CLEAR process, a
Duval Corporation development. Erzmetall 33, 251 255.
Duby, P., 1977. Incra Monograph IV, The Metallurgy of Copper,
Library of Congress, Catalogue Card number 77-71709,
National Bureau of Standards, USA. pp. 3031.
Herreros, O., Quiroz, R., Vinals, J., 1999. Dissolution kinetics of
copper, white metal and natural chalcocite in Cl
/Cl2 media.
Hydrometallurgy 51, 345 357.
Jackson, E., 1986. Hydrometallurgical Extraction and Reclamation,
Ellis Horwood Series in Industrial Metals. J. Wiley and Sons,
New York.
Langer, S.H., Kaun, T.D., Nametz, M.A., Anderson, J.H., 1977. The
application of the cupric chloride process to copper recovery
from scrap and ore. Chloride Hydrometallurgy Proc., (Int.
Benelux Metall., Brussels, Belgium), p. 134.
Levenspiel, O., 1979. Ingeniera de las reacciones qumicas.
Editorial Reverte, Barcelona.
Lin, H.K., Wu, X.J., Rao, P.D., 1992. The electrowinning of cooper
from a cupric chloride solution. J. Metals 43 (8), 60 65.
Software HSC Chemistry, ver 1.12 copyright Outokumpu Research
Oy, Pori, Finland.
Sohn, H.Y., Wadsworth, M.E., 1986. Cinetica de los procesos de la
metalurgia extractiva. Trillas, Mexico D.F.
Tolley, W.K., Young, H.H., Miller, J.D., 1977. Reaction kinetics
involved in cupric chloride leaching of metallic cooper spheres
in a stirred reactor. Chloride Hydrometallurgy Proc., (Int.
Benelux Metall., Brussels, Belgium), pp. 96 113.