Hydrometallurgy 178 (2018) 7–11

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Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

The kinetics of the dissolution of chrysocolla in acid solutions T

⁎
Michael J. Nicol , Chandrika Akilan
School of Engineering and Information Technology, Murdoch University, Perth, WA 6150, Australia

A R T I C LE I N FO A B S T R A C T

Keywords: The dissolution of liberated chrysocolla particles in dilute (0.033 to 0.15 mol L−1) sulfuric acid solutions has
Chrysocolla been shown to be relatively rapid and the kinetics of dissolution are consistent with rate-determining diffusion of
Leach acid through the silica layer that is formed around the particles from which the copper has been dissolved. The
Acid rate is inversely proportional to the square of the particle size and increases linearly with increasing acidity. The
Ash-layer
effect of the addition of chloride ions on the rate is negligible at concentrations below 70 g/L chloride. Addition
Diffusion
of sulphate ions results in reduced rates of dissolution due to complexation of the proton by sulphate ions. The
effect of temperature is relatively small as expected for a process for which the rate is controlled by diffusion.
The rate of dissolution in dilute acid is slower than malachite but faster than tenorite under the same con-
ditions. These results suggest that heap leaching of chrysocolla in dilute acid may be slow relative to malachite
but should present no chemical problems and that there is no advantage to be gained from the addition of
chloride ions. High sulphate concentrations (100 g/L) in the raffinate solution to the heap could reduce the rate
by up to one-half.

1. Introduction dissolution of relatively pure chrysocolla particles under conditions

Chrysocolla is a copper silicate mineral with the nominal formula
CuSiO3.xH2O although the actual formula is accepted to be
Cu8(Si4O10)2(OH)12.xH2O in which x is normally 8. It is considered to
be a gel-like substance with a disordered array of microcrystallites
(Pohlman and Olson, 1976). It has a very high surface area of greater
than 250 m2/g that reduces to below 25 m2/g after acid leaching
(Pohlman and Olson, 1976). Visual observation of a large particle
during dissolution showed that the pale blue surface changes to a white
hydrated silica outer layer (similar to silica gel) with the inner blue core
gradually decreasing in diameter as leaching progresses.
It is known to be easily soluble in dilute acids but very few studies
(Hsu and Murr, 1975; Pohlman and Olson, 1974) have focussed on the
kinetics of dissolution process and the dependence of the rate on par-
ticle size, temperature and acid and chloride concentrations while most
(Bryce et al., 1968) have used low grade ores with the resulting pro-
blems of mass transport to the mineral surfaces within larger ore par-
ticles.
Dissolution in acid occurs by the following reaction
CuSiO3 . xH2 O + 2H+ = Cu2 + + SiO2 . H2 O + xH2 O
in which hydrated silica forms as a product layer on the surface of the
mineral.
The following is a summary of a study of the kinetics of the
similar to those encountered during heap leaching of oxide or mixed
oxide/sulfide ores.
2. Thermodynamics
The species distribution for the dissolution of chrysocolla in acidic
sulfate solutions is shown in Fig. 1. This was obtained using HSC
Chemistry Roine (2015) with the free energy of formation of chryso-
colla (−1220.8 kJ mol−1 for CuSiO3·2H2O) obtained from the literature
(Wei et al., 2010).
It can be seen that chrysocolla is completely soluble at pH values
below about 3 and completely insoluble at pH values above about 6.
Thus, there are no thermodynamic restrictions on the dissolution of
chrysocolla under acidic conditions.
3. Experimental
Natural chrysocolla inevitably occurs as intergrowths with quartz
and it is difficult to obtain sufficient material of high grade. Small
lumps of chrysocolla from Arizona were sourced locally and XRD ana-
(1)
lysis provided little confirmatory evidence as expected from the lit-
erature (Pohlman and Olson, 1976) that reported either none or very
poor crystallinity or crystallinity of colloidal size. The XRD scan
obained with the present sample using Cu radiation is compared with a

⁎
Corresponding author.
E-mail address: m.nicol@murdoch.edu.au (M.J. Nicol).

https://doi.org/10.1016/j.hydromet.2018.04.001
Received 9 January 2018; Received in revised form 22 March 2018; Accepted 1 April 2018
Available online 04 April 2018
0304-386X/ © 2018 Elsevier B.V. All rights reserved.
M.J. Nicol, C. Akilan
Fig. 1. Species distribution for chrysocolla in acidic sulfate solutions at 25 °C.
Fig. 2. Photograph of a group of particles from the +500–710 μm size fraction
before and after leaching.
published scan in Appendix A. The only impurity detected by XRD was
quartz. The lumps were hand-crushed in a pestle and mortar and sev-
eral size fractions from 180 μm to 850 μm obtained by dry screening the
crushed material. Fig. 2 shows a number of such particles from the
+500 to 710 μm size fraction.
Examination of the particles shows that the chrysocolla (pale blue/
green) is generally liberated from the quartz (colourless) and other
minor dark gangue minerals. The composition in terms of chrysocolla
content increased with decreasing particle size due to preferential
crushing of the softer copper mineral. The copper content decreased
from 17.8% to 11.7% from the finest to coarsest fraction.
After leaching, the converted chrysocolla appears as amorphous
cloudy, white particles easily distinguished visually from the original
crystalline quartz. There does not appear to be a noticeable size change
during dissolution.
The leach tests were conducted in a stirred, temperature-controlled
baffled reactor as described previously (L Velásquez-Yévenes et al.,
2010). A small glass tube heat exchanger was fitted to the reactor
through which chilled water from a low-temperature water bath was
circulated. Most experiments were conducted at 25 °C at a stirring rate
of 580 rev min−1. Agitation at 400 rev min−1 was found to be required
to maintain the particles in suspension. Unless stated otherwise, 600 mL
of a leach solution of the appropriate composition was added to the
reactor and, after the temperature had stabilized, 1 g of the desired size
fraction was added to the reactor. 2 mL samples were periodically re-
moved after allowing the suspension to settle for 20 s before sampling
the solution.
The solution samples were added to 5 mL of 2 M ammonium
chloride.ammonium hydroxide at pH 10 and the volume made up to
10 mL. The absorbance of the solution at 615 nm was measure in a
20 mm quartz cell using a Shimadzu spectrophotometer. A standard
solution of copper was used for calibration. This method is more rapid
8
Hydrometallurgy 178 (2018) 7–11
and accurate than AA or ICP analysis at these concentrations.
4. Results
As will be demonstrated below, the rate of the dissolution of chry-
socolla particles can be very well described in terms of rate-determining
diffusion of protons through the amorphous silica product layer.
This well known “ash layer” model (Prosser, 1996) for the dis-
solution of a particle with a product layer results in the following ex-
pression for the extent of dissolution(X) as a function of time(t)
t/(3τ) = 1 − 2X/3 − (1 − X)2/3 (2)
in which τ is the time for complete dissolution.
τ = ρR2/(6bCD) (3)
in which b is a stoichiometric factor (in this case 1 mol copper dis-
solved/mol sulfuric acid consumed), C is the concentration
(mole cm−3) of the species diffusing into or out of the product layer and
D is the diffusion coefficient (cm2 s−1) in the product layer.
Fig. 3 shows the dissolution curves for various size fractions in
0.1 mol L−1 sulfuric acid.
It is obvious that the initial dissolution rate is rapid but it slows
noticeably after about 60% dissolution and that the rate decreases as
the particle size increases. Also shown (as square points and right axis)
are the corresponding plots according to Eq. (2). The good linearity of
the plots up to 80% extraction suggests that the data is consistent with
the assumed rate-determining step.
As a further test of the rate equation, the values of 3 x slope (=1/τ)
of these lines are plotted in Fig. 4 as a function of the reciprocal of the
square of the geometric mean diameter (d) of the screen sizes defining
each size fraction as per Eq. (3).
Again, the adequate linearity (except for the point for the smallest
size) confirms the applicability of the leaching model. From the slope of
the line in Fig. 4, the diffusion coefficient of the proton in the hydrated
silica layer (density 2.21 g cm−3) can be estimated as
7.8 × 10−6 cm2 s−1 that is remarkably similar to the measured diffu-
sion coefficient of HCl in silica gel of 8.5 × 10−6 cm2 s−1 (Patrick and
Allan, 1934). These values are about an order of magnitude lower than
the value in the solution phase (9.3 × 10−5 cm2 s−1 at infinite dilution)
(Cussler, 2011), confirming that diffusion in the product layer is rate-
determining.
The results (in terms of the time for complete dissolution) as ob-
tained from plots similar to those shown in Fig. 3 for experiments on the
effect of the acid concentration on the rate of dissolution of the
+250–355 μm size fraction at 25 °C are summarized in Fig. 5.
It can be seen that the rate increases linearly with increasing acidity
as would be required for diffusion (a first-order process) as the rate
controlling step.
The effect of the addition of chloride (as sodium chloride) on the
rate was studied using the +355–500 μm size fraction in a solution of
0.1 mol L−1 acid at 25 °C. The results are summarized in Table 1.
It is apparent that the rate is independent of the chloride con-
centration in the range studied as could be expected if the rate is con-
trolled by the diffusion of acid within the silica product layer.
Addition of excess sulfate ions (as magnesium sulfate) could be
expected to reduce the rate due to the formation of hydrogen sulfate
ions thereby reducing the proton concentration. The results of such
experiments with the +250–355 μm size fraction in 0.1 mol L−1 acid at
25 °C are shown in Table 2.
These results confirm the above expectation and also shown in
Table 2 are the calculated proton concentrations using thermodynamic
data (Martell and Smith, 2004) for the protonation of sulfate and the
formation of magesium sulfate ion-pairs at various ionic strengths. The
approximate correlation between the rate of dissolution and the proton
concentration is consistent with the rate-determining step being the
diffusion of protons through the product layer. It is likely that
M.J. Nicol, C. Akilan Hydrometallurgy 178 (2018) 7–11

Fig. 3. Effect of particle size on the dissolution of chrysocolla in 0.1 mol L−1 acid at 25 °C.

Fig. 5. Effect of acidity on the rate of dissolution of the +250–355 μm size

Fig. 4. Effect of particle size on the slopes of the lines in Fig. 2.
fraction of chrysocolla at 25 °C.

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M.J. Nicol, C. Akilan Hydrometallurgy 178 (2018) 7–11

Table 1
Effect of chloride on the rate of dissolution.
[NaCl] M 1/τ min−1

0 0.0049
0.2 0.0055
0.5 0.0051
2 0.0051

Table 2
Effect of sulfate on the rate of dissolution.
[Sulfate] mol L−1 1/τ min−1 [H+] calc mol L−1

0.1 0.0102 0.046

0.3 0.0086 0.034 Fig. 6. Effect of temperature on the rate of dissolution of the +355–500 um
0.5 0.0063 0.028 fraction in 0.1 mol L−1 H2SO4.

Table 4
Table 3 Initial rates of dissolution in 0.1 mol L−1 H2SO4 at 25 °C.
Effect of temperature on the rate of dissolution. Mineral Initial rate mol cm−2 min−1
° −1
Temp C 1/τ min
Malachite 2.4 × 10−6
20 0.0042 Chrysocolla 1.3 × 10−6
25 0.0049 Tenoritea 2.5 × 10−7
30 0.0056
35 0.0068
a
0.2 M H2SO4 – rotating disk.

These results confirm unpublished reports that the rate of chrysocolla

dissolution will occur by reaction with the HSO4− ion as well as the
proton. However, the diffusion coefficient of the bisulfate ion is an
order of magnitude less than that of the proton and the contribution of
bisulfate to the dissolution will be comparable to that of the proton only
at low proton concentrations.
The effect of temperature was studied using the +355–500 μm size
fraction in 0.1 mol L−1 acid and the results shown in Table 3 and as an
Arrhenius plot in Fig. 6.
The activation energy calculated from the slope of the plot is
23.4 kJ mol−1. This low value is as expected for a diffusion controlled
reaction (Cussler, 2011).
It is interesting to compare the rate of dissolution of chrysocolla
with that of malachite (Cu2(OH)2CO3) (Nicol, 2018) and tenorite (CuO)
(Majima et al., 1980) for which the rate-determining step is the rate of
the chemical reaction on the surface of the minerals (no product layer is
formed in the case of malachite or tenorite). Previously obtained data
for the dissolution of malachite under identical conditions showed that
the time for complete dissolution is less for malachite than chrysocolla.
The relative rates are compared in Table 4.
Note that, in the case of chrysocolla, the initial rate using Eq. (3) is
infinite but will actually be the rate of the chemical reaction in the
absence of diffusion limitations. An arbitrary choice of X = 0.1 has
been chosen to estimate this rate of the chemical reaction.
As a result of the difference in the form of the rate equations, the
rate of chrysocolla dissolution decreases more rapidly at high extents of
reaction than does that for malachite or tenorite. Thus, the time for 80%
dissolution under these conditions is 3.5 times longer for chrysocolla
than malachite although it is only 2.1 times longer for 50% dissolution.
leaching in heaps is slower than that of malachite. The absence of
significant quantities of tenorite in most copper ores is fortunate in that
the rate of leaching could be expected to be an order of magnitude
slower than the other copper “oxide” minerals.
5. Conclusions
The dissolution of screened samples of liberated chrysocolla parti-
cles in dilute (0.033 to 0.15 mol L−1) sulfuric acid solutions has been
shown to be relatively rapid and the kinetics of dissolution are con-
sistent with rate-determining diffusion of acid through the silica layer
that is formed around the particles from which the copper has been
dissolved. The rate is inversely proportional to the square of the particle
size and increases linearly with increasing acidity. The effect of the
addition of chloride ions on the rate is negligible at concentrations
below 70 g/L chloride. Addition of sulphate ions (as magnesium sul-
phate) results in reduced rates of dissolution due to complexation of the
proton by sulphate ions. The effect of temperature is relatively small as
expected for a process for which the rate is controlled by diffusion.
The rate of dissolution in dilute acid is slower than malachite but
faster than tenorite under the same conditions. These results suggest
that heap leaching of chrysocolla in dilute acid may be slow relative to
malachite but should present no chemical problems and that there is no
advantage to be gained from the addition of chloride ions. High sul-
phate concentrations (100 g/L) in the raffinate solution to the heap will
reduce the rate by up to one-half.

Appendix A. Appendix

A published (University of Arizona, 2018) XRD scan of chrysocolla (Fig. A.1) is compared to that obtained with the sample used in this study (Fig.
A.2). The former was characterized as having broad, low peaks with weak lines often diffuse. The pattern is fairly characteristic. The similarity in
terms of very broad lines for the present sample provides confirmatory identification of the present sample as chrysocolla. Note the sharp peaks in the
present sample (Fig. A.2) due to quartz as an impurity.

10
M.J. Nicol, C. Akilan
Fig. A.1. XRD scan of chrysocolla courtesy of RRUFF project at University of Arizona (2018)
Fig. A.2. XRD scan for the sample of chrysocolla used in the present study.
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