Leaching Kinetics of Copper from Natural

Chalcocite in Alkaline Na4EDTA Solutions

YASUHIRO KONISHI, MASAYA KATOH, and SATORU ASAI
The leaching behavior of copper from natural chalcocite (Cu2S) particles in alkaline Na4EDTA
solutions containing oxygen was examined at atmospheric pressure. The EDTA leaching process
took place with consecutive reactions, where the solid product of the first reaction, covellite
(CuS), became the reactant for the second. The copper leached into the alkaline solutions was
immediately consumed by the chelation of copper (II) with EDTA, and the mineral sulfur was
completely oxidized to sulfate ion. The experimental data for the leaching rate of copper were
analyzed with a familiar shrinking-particle model for reaction control. The conversion rate of
chalcocite to covellite was found to be about 10 times as high as the dissolution rate of covellite.
The time required for complete dissolution of covellite was directly proportional to the initial
particle size and was inversely proportional to the square root of the product of the hydroxide
ion concentration and the oxygen partial pressure, but it was independent of the Na4EDTA
concentration in the presence of excess Na4EDTA. The observed effects of the relevant operating
variables on the dissolution rate were consistent with a kinetic model for electrochemical reaction control. The kinetic model was developed by applying the Butler-Volmer equation to the
electrochemical process, in which the anodic reaction involves the oxidation of covellite to
copper (II) ion and sulfate ion and the cathodic reaction involves the reduction of oxygen in
alkaline solution. The rate equation allowed us to predict the time required for the complete
leaching of copper from chalcocite in the alkaline Na4EDTA solutions.

I.

INTRODUCTION

R E C E N T L Y , a number of reports have appeared on the

application of the chelating leachant ethylenediaminetetraacetic acid (EDTA) to various minerals: the leaching
of copper from carbonate-silicate ores, m the leaching of
nickel from lateritic ores, [2] the leaching of radium from
uranium mill railings, 131and the leaching of tungsten from
s c h e e l i t e o r e s . [4-7] These previous studies indicated that
the alkaline EDTA solutions could rapidly and selectively leach the valuable metals from the minerals even
at atmospheric pressure and temperatures up to 373 K,
and furthermore, that the EDTA could be regenerated for
the purpose of recycling. Although we have more recently reported the leaching kinetics of tungsten from
pure scheelite ore and low-grade scheelite ore, I6,71 little
work has been done to investigate the kinetics of EDTA
leaching processes.
This paper considers the kinetics of the dissolution of
sized natural chalcocite (Cu2S) in aqueous Na4EDTA solutions. A similar dissolution system was treated by Duda
and Bartecki, ~sl who studied experimentally the dissolution of synthetic polydispersive CUES particles in aqueous
EDTA solutions. T h e dissolution of synthetic CUES was
found to occur in two steps, with the formation of covellite (CuS) as an intermediate product, but their discussion on the reaction kinetics was nevertheless confined
to the initial dissolution rate of CuzS. In addition to the
copper dissolution, the problem of copper recovery from
EDTA leach solutions was addressed by Bauer and
Lindstrom. m They found that all of the copper leached
YASUHIRO KONISHI, Research Associate, MASAYA KATOH,
Graduate Student, and SATORU ASAI, Professor, are with the Department of Chemical Engineering, University of Osaka Prefecture,
Sakai, Osaka 591, Japan.
Manuscript submitted August 6, 1990.
METALLURGICAL TRANSACTIONS B

in EDTA solution could be precipitated as metal powder

of high purity (99 pct Cu) by using some reducing agents
such as formaldehyde, hydrogen, and carbon monoxide.
In order to consider the feasibility of the EDTA leaching
process, it is necessary to study quantitatively both problems of the leaching of copper from minerals and the
recovery of copper from the EDTA leach solution.
The objective of this paper is to examine the kinetics
of the leaching of copper from chalcocite ore in aqueous
Na4EDTA solutions. An electrochemical leaching mechanism consistent with the experimental data is proposed,
and the associated rate equation is formulated in terms
of relevant operating variables. The kinetic data are then
analyzed to determine the parameters in the rate equation.
II.

EXPERIMENTAL PROCEDURE

A. Materials

The chalcocite used in this study was obtained from

Arizona. The mineral was ground and then sieved to obtain four different size fractions, 20 to 25 /xm, 25 to
37 gm, 45 to 53 /xm, and 88 to 105 /xm. The X-ray
diffraction analysis of the ground particles showed high
purity of chalcocite with a small amount of SIO2. The
average chalcocite content was 92 pct in terms of Cu2S.
Test liquids were aqueous Na4EDTA solutions, and
their initial concentrations were 40, 60, 120, and
200 mol m -3, respectively. The pH of the solution was
adjusted to 12.7 to 13.5 with NaOH. The ionic strength
of the solution was held almost constant at 2400 mol m -3
by adding a neutral salt, Na2SO4. The gas phase was
pure 02 or mixtures of 02 and N2, which were saturated
with water vapor at the experimental temperature. The
concentration of dissolved oxygen in the leach solutions
was changed with the partial pressure of oxygen above
VOLUME 22B, JUNE 1991- 295

the solution. The mole fraction of 0 2 in the influent gas

was varied from 0.753 to 0.0859.

B. Apparatus and Procedure

The reactor used to perform the leaching experiments
was a flat-bottomed PYREX* flask of 1000 cm 3 capacity. The reactor was equipped with a stirrer, a thermometer, a reflux condenser, and a gas sparger. The liquid
stirrer was a TEFLON** paddle agitator of 6 cm in di*PYREX is a trademark of Coming Glass Works, Coming, NY.
**TEFLON is a trademark of E.I. Du Pont de Nemours, Inc.,
Wilmington, DE.
ameter, placed 1 cm above the bottom of the reactor and
driven at two constants speeds of 5.0 and 14.3 s -~. All
of the experiments were carried out at atmospheric pressure and at 338 to 367 K. The duration of experimental
runs varied from 360 to 480 minutes.
The reactor was operated continuously with respect to
the gas and batchwise with respect to the liquid. A
Na4EDTA solution of 500 cm 3 was first charged into the
reactor and then raised to the experimental temperature.
The gas mixture was continuously fed into the leach solution, and the gas was dispersed in the form of small
bubbles by the stirrer. The total feed rate of the gas ranged
from 16.7 to 33.3 cm 3 s -l. After that, 0.25 to 1.5 g of
chalcocite of the desired size was added to the NaaEDTA
solution, and this is taken as zero time. Solution sampies, 1 to 2 cm 3, were withdrawn periodically. The samples were diluted with deionized water and analyzed for
copper by atomic absorption spectrophotometry. The
leaching fraction X of copper was calculated from the
amount in the solution at any time, divided by the initial
content in the solid particles. In some runs, the solution
samples were analyzed for sulfate ions by EDTA-Ba
method. [91
The experimental conditions and the compositions of
the solutions used are given in Table I. Since the amounts
of NaaEDTA and O H - ion in the leach solutions were
Table I.

in large excess compared to the depletion due to leaching

reaction, the concentration of Na4EDTA and pH of the
solution remained almost constant during the experimental runs.
III.

EXPERIMENTAL RESULTS

A. Leaching Rate of Copper

Leaching curves obtained at various Na4EDTA concentrations [y4-] are shown in Figure 1, where the
leaching fractions X of copper are plotted against the time
t. It is evident that the leaching of copper in the alkaline
Na4EDTA solution readily occurs even at atmospheric
pressure and that, furthermore, the leaching fraction X
reaches close to 100 pct in 420 minutes. In the absence
of Na4EDTA as a chelating agent, however, the leaching
of copper does not occur in the alkaline solution of pH
13.5. Thus, it can be concluded that the chelating agent
EDTA plays an important role in the leaching of copper
from chalcocite, although the concentration of Na4EDTA
has no effect on the leaching rate of copper in the presence of excess EDTA.
Figure 2 shows the leaching fractions X measured by
varying both liquid-phase stirring speed nL and initial
particle size Dpo. The leaching rate is independent of the
stirring speeds covered in this work, indicating that the
leaching rate is not controlled by the mass transfer between the suspended solid particles and the liquid.
Therefore, the liquid-phase stirring speed was fixed at
14.3 s -~ in the subsequent experimental runs. It is also
clear that the leaching rate of copper increases with a
decrease in the initial particle size.
Figure 3 gives the leaching fractions X obtained at the
initial solid-liquid ratios Wo/V in the range of 0.5 to
3.0 kg m -3. The solid-liquid ratio Wo/V has no effect
on the leaching rate of copper. This result shows that the
buildup of reaction products in the leach solution makes
a negligible contribution to the leaching rate.
Figure 4 shows the leaching fractions X measured at

Experimental Conditions and Compositions of Solutions Used

Run
Number

Temperature,
T (K)

Liquid
Stirring
Speed,
nL (s -1)

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16

367
358
358
358
358
358
358
358
358
358
358
358
358
358
348
338

14.3
14.3
5.0
14.3
14.3
14.3
14.3
14.3
14.3
14.3
14.3
14.3
14.3
14.3
14.3
14.3

Concentration
of Na4EDTA,
[y4-] (mol m -3)

pH of
Solution

Partial
Pressure
of 02,
Po2 (kPa)

200
200
200
200
200
40*
60*
120"
200
200
200
200
200
200
200
200

13.5
13.5
13.5
13.5
13.5
13.5
13.5
13.5
12.9
12.7
13.5
13.5
13.5
13.5
13.5
13.5

19.9
43.5
43.5
43.5
43.5
43.5
43.5
43.5
43.5
43.5
26.1
8.7
43.5
43.5
62.8
76.3

Initial
Particle Size,

Deo X
20
20
20
25
25
25
25
25
45
45
25
25
45
88
20
20

10 6 (m)

to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to

25
25
25
37
37
37
37
37
53
53
37
37
53
105
25
25

Initial
Solid-Liquid
Ratio,
Wo/V (kg m -3)
1.0
1.0
1.0
1.0
3.0
0.5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0

*Addition of a neutral salt Na2SO4.

296--VOLUME22B, JUNE 1991

METALLURGICALTRANSACTIONSB

1.0

1.0

0.8

i.

0.6

~<

0.4

0.8

!
X

Key
9

0.2

=~ ....

x....

60
120
200
0

-.y,-

x- --

I
200

0.4

[y4-], mol m -3

o
x

0.6

0.2

4O0

I
0

I
200

Fig. 1 - - F r a c t i o n X of copper leached at 358 K; pH = 13.5; oxygen

partial pressure Po2 = 43.5 kPa; initial particle size D~o = 25 to
37/~m; initial solid-liquid ratio Wo/V = 1.0 kg m-3; and liquid stirring
speed nL = 14.0 s -s (effect of Na4EDTA concentration [y4-]). Solid
lines are predicted from Eqs. [10] and [11], using the ~'~ and ~'2 values
given in Table lI.

40
200
200
I
400

I
600

T i m e (mi n)

600

Ti m e (rain)

[ Y mol
, m -3

Key WolV, kg m-3

9
0.5
o
1.0
1>
3.0

Fig. 3 - - F r a c t i o n X of copper leached at 358 K; pH = 13.5; oxygen

partial pressure Po2 = 43.5 kPa; and initial particle size De0 = 25 to
3 7 / x m (effect of initial solid-liquid ratio Wo/V). Solid lines are pred i c t e d from Eqs. [10] and [11], using the Zl and ~'2 values given in
Table II.

1-0
1.0

0.8

0.8

0.6

0.6

0.4

0.4
1

20

n
r=
9

0.2

25

0.2
0

I
0

I
200

I
400

200

I
400

I
600

Time(min)

I
600

Time(rain)
Fig. 2 - - F r a c t i o n X of copper leached at 358 K; Na4EDTA concentration [y4-] = 200 mol m 3; pH = 13.5; oxygen partial pressure
Po2 = 43.5 kPa; and initial solid-liquid ratio Wo/V = 1.0 kg m -3 (effect of liquid stirring speed nL and initial particle size Dp0). Solid lines
are predicted from Eqs. [10] and [11], using the rl and ~'2 values given
in Table II.

different pH levels of the Na4EDTA solution: pH = 12.7,

12.9, and 13.5. It is evident that the leaching rate of
copper is affected by the pH of the solution.
Figure 5 represents the leaching fractions X obtained
at various oxygen partial pressures: Poz = 8.7, 26.1, and
43.5 kPa. The partial pressure Po2 of oxygen was corrected by subtracting the vapor pressure of water from
the total pressure. The leaching rate is found to depend
METALLURGICAL TRANSACTIONS B

I
0

13.5
12.9
12.?

Fig. 4 - - F r a c t i o n X of copper leached at 358 K; Na4EDTA concentration [y4-] = 200 mol m-3; oxygen partial pressure Po2 = 43.5 kPa;
initial particle size Deo = 45 to 53 /zm; and initial solid-liquid ratio
Wo/V = 1.0 kg m -3 (effect of pH of solution). Solid lines are predicted from Eqs. [10] and [11], using the ~'1 and r2 values given in
Table II.

on the oxygen partial pressure, which can be related to

the liquid-phase concentration of oxygen through Henry's
law.
Figure 6 indicates the leaching fractions X measured
at temperatures T of 338 to 367 K. The leaching rate is
slightly enhanced by an increase in temperature. As the
temperature changes from 338 to 367 K, the oxygen partial pressure Po2 above the solution markedly decreases
from 76.3 to 19.9 kPa, because the vapor pressure of
water increases with temperature. The significant effect
of temperature on the leaching rate is presumably offset
VOLUME 22B, JUNE 1991--297

0.8

Z O.6

><

0.2
r
00

43.5
8.7

"
I

I
200

I
400

I
600

Time (min)

vellite formed is considered to be further leached with

NaaEDTA, because the leaching fraction of copper can
reach close to 100 pct, exceeding 50 pct, as demonstrated by Figures 1 through 6.
For the alkaline leach solutions, the identification of
the complex of copper (II) with free EDTA ligand, Y,
was performed with a spectrophotometer. The qualitative analysis revealed that the chelate compound is a
hydroxycomplex, Cu(OH)Y 3-. Furthermore, the content
of sulfate ions in the solution after the leaching runs was
analyzed quantitatively and found to be equal to half the
content of leached copper. This indicates that the leaching of copper and sulfur from chalcocite proceeds
stoichiometrically, and that the mineral sulfur is completely oxidized to sulfate ions in the alkaline Na+EDTA
solutions. Thus, the overall dissolution reaction can be
written as
CuzS + 2Y 4- + 5 / 2 0 2 + H20 ~ 2Cu(OH)Y 3- + SO42-

Fig. 5 - - F r a c t i o n X of copper leached at 358 K; Na4EDTA concentration [y4-] = 200 mol m-3; pH = 13.5; initial particle size D m =
25 to 37/zm; and initial solid-liquid ratio Wo/V = 1.0 kg m -3 (effect
of oxygen partial pressure Po2)- Solid lines are predicted from
Eqs. [10] and [11], using the 71 and ~'2 values given in Table II.

[1]
which is the same as reaction reported by Duda and
Bartecki. ml

IV.

THEORETICAL

APPROACH

A. Application of Shrinking-Particle Model

1.0

When insoluble product is not formed, as in the EDTA

leaching processes of chalcocite and covellite, the reacting particles are likely to shrink during reaction. The
EDTA leaching behavior is illustrated in Figure 7. The
unreacted chalcocite core, which is surrounded by covellite formed, shrinks and finally disappears. The time
for complete disappearance of chalcocite is denoted as
~'1. The covellite particle also disappears by dissolution
at t = ~2. The two dissolution reactions occur simultaneously until t = rl. Thus, the leaching fraction X of
copper based on the original mineral is comprised of the
contributions of the two leaching processes for chalcocite and covellite:

0-8
T0,6
X

0-4
II

0.2t0

3 67

34B

kPa
19.9

62.0

for 0 < t < 'T1,

200

400
Time (rain)

600

Fig. 6 - - F r a c t i o n X of copper leached at Na4EDTA concentration

[y4-] = 200 tool m-a; pH = 13.5; initial particle size Dpo = 20 to
25 /zm; and initial solid-liquid ratio Wo/V = 1.0 kg m -3 (effect of
temperature T). Solid lines are predicted from Eqs. [10] and [1l],
using the r~ and z2 values given in Table II.

by a decrease in the oxygen partial pressure with respect

to temperature.

X = 0.5(a, + a2)

[21

X = 0.5(1 + c~2)

[3]

for r~ < t < ~'z,

In these equations, the fractional conversion t~ of chalcocite to covellite and the fractional conversion tx2 of

~CuzS

~,CuS

(~

Eq.[6]

t='E1
= ~;: 1
Eq.[7]
,~-

B. Identification of Reaction Products

X-ray diffraction patterns were observed for leach residues. The analytical result showed that the original
chalcocite (Cu2S) was converted to covellite (CuS) as an
intermediate product. This observation for the natural
chalcocite is consistent with the previous results for synthetic chalcocite in EDTA leaching, m] ferric sulfate
leaching, [t~ and oxygen pressure leaching. ["j The co298--VOLUME 22B, JUNE 1991

t=o
~1:0 ~
~2= 0
X : 0-

Eq.[!O]

t = "1:2
Cf.2 =

Eq.['I1]

~X=l

Fig. 7 - - S c h e m a t i c diagram for the leaching behavior of Cu2S particle in aqueous Na4EDTA solution.
METALLURGICAL TRANSACTIONS B

Table II. Evaluated Time r Required for

Complete Disappearance of Chalcocite Core
and Time r Required for Complete Dissolution
of Covellite at Present Experimental Conditions

covellite to Cu 2+ based on the initial particle diameter

Dpo are defined as
Ol1 = 1 -

(Op,/Dpo) 3

[4]

and

Run

a2 = 1 - (DpE/Dpo) 3

Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16

[5]

where Dpl and Op2 are the shrinking diameters of unreacted chalcocite and covellite, respectively. Applying
a shrinking-particle model for chemical reaction control tiE] yields the conversion-time expression for chalcocite:
a, = 1 - (1

t/7.,)3

[6]

As will be shown later, the conversion rate of chalcocite

to covellite is much higher than the dissolution rate of
covellite. It is thus considered that the volume of formed
covellite is much larger than that of unreacted chalcocite
core during the dissolution process of covellite, except
the very short period after chalcocite begins to dissolve.
In this case, the conversion-time expression for covellite
is given by applying the shrinking-particle model:
a 2 =

1 -- (1

t/T2) 3

----

3 p M , D p o / ( ~),Rc, )

T2 (min)
756
735
735
858
855
873
886
851
2672
3625
1256
2498
1562
3603
804
1030

r2/zl ( - )
12.4
11.1
11.3
9.5
11.1
9.2
10.6
8.8
12.1
10.7
7.6
8.1
7.5
7.8
9.1
9.7

[7]

The times % and r required for complete disappearance of chalcocite and covellite are given as
7",

~'1 (min)
61
66
65
90
77
95
84
97
220
338
165
308
209
461
88
106

[8]

of the shrinking-particle model further, some representative data for r, < t < 7.2 given in Figures 1 and 2 are
plotted in Figure 8, according to the rearrangement of
Eq. [11] which gives:
for 7., < t < 7.2,

and
7.z = 3pu2D pO/ ( qb2Rc2)

where PM is the molar density of solid particle, 4, is the

specific shape factor, and Rcl and Rc2 are the dissolution
rates of chalcocite and covellite per unit area of dissolving surface, respectively. The dissolution rates Rcl and
Rc2 can be considered constant under the present experimental conditions, since the concentrations of reactants in the leach solutions are unchanged during the
dissolution processes. Substituting Eqs. [6] and [7] into
Eqs. [2] and [3] gives the expressions for the timevariation of the leaching fraction X of copper based on
the original mineral:
for0<t<

1 - (2 - 2X//3 = t/z2

[91

[12]

0.8
Key
v
o
n

Dpo, p.m
20- 25
25-3?
45- 53

0.6

1"

X ~

0.4

X = 1 - 0.5(1

t/7.,) 3 - 0.5(1 - t/7.2) 3

[10]

for 7., < t < 7.'/'2,

X = 1 - 0.5(1

t/7.2) 3

[11]

Equation [ 10] indicates that graphical methods can not

be employed for evaluating the values of 7., and 7.2. Thus,
a nonlinear least-square method was used to find the 7.,
and 7.z values for each run, which gave the best fit with
the leaching fraction X-time data shown in Figures 1
through 6. During the early stages of leaching (X < 0.5),
a rapid increase in the leaching fraction X might lead to
an error in the evaluation of ~-, from only a few experimental points. Table II lists the evaluated values of 7.,
and ~'2 for various experimental runs. With the 7", and 7.2
values, the solid curves in Figures 1 through 6 were generated from Eqs. [10] and [11]. Good agreement between the calculated curves and the experimental data
can be seen from these figures. To test the applicability
METALLURGICAL TRANSACTIONS B

v
I

0.2

I
0

I
200

I
z.o0

600

T i m e (rain)
Fig. 8 - - P l o t of experimental data for ~'t < t < r according to
Eq. [12]. Experimental points are obtained at 358 K; Na~EDTA concentration ]y4-] = 200 mol m-3; pH = 13.5; oxygen partial pressure
Po2 = 43.5 kPa; initial particle size D m = 25 to 37 ~ m ; and initial
solid-liquid ratio W o / V = 1 kg m 3. Solid lines are predicted f r o m
Eq. [12], using the ~'1 and r values given in Table II.
VOLUME 22B, JUNE 1991 - - 299

For each of the initial particle sizes, the data points obtained for rl < t < r2 agree well with the straight line
representing the model predictions, which was calculated from Eq. [12] using the ~'1 and ~'2 values given in
Table II. This supports that the chalcocite particles do
not break up into a new size range and that the dissolution of covellite occurs in a shrinking particle fashion.
Table II demonstrates that for all of the experimental
runs, the evaluated values of r2 are greater by one order
of magnitude than those of rl. This indicates that the
conversion of chalcocite to covellite is rapidly completed, whereas the dissolution of formed covellite proceeds much slowly. Furthermore, it explains why the
leaching curves in Figures 1 through 6 increase remarkably up to about 50 pct of the leaching fraction. For the
practical leaching operation of chalcocite, therefore, it
is more significant to make a detailed kinetic study on
the leaching of the intermediate product, covellite, rather
than the leaching of the original mineral. In what follows, the leaching kinetics of covellite in aqueous
NaaEDTA solution will be considered in detail.

It has been reported that the leaching reactions of synthetic chalcocite were electrochemical in acidic solutions
containing an oxidizing agent, tH,~31 Wadsworth [~31 proposed an electrochemical model for ferric sulfate leaching, in which the leaching process is accompanied by a
cathodic half-cell reaction (reduction of Fe 3+ ion) and a
two-stage anodic half-cell reaction (oxidation of Cu2S to
Cu 2 ion through CuS). It was indicated that the first
stage represents a galvanic couple where two electrical
conductors, Cu2S and CuS, are in contact with each other,
and that the second stage represents a corrosion couple
where an electrical conductor, CuS, is surrounded by elemental sulfur. Mao and Peters I1~] studied the sulfuric
acid leaching under autoclave pressure with oxygen. They
considered the oxygen pressure leaching to be similar to
the ferric sulfate leaching, except that the cathodic reaction is replaced with the direct reduction of oxygen in
acid solution.
The leaching of chalcocite with Na4EDTA, which is
the subject of this work, is accompanied by the formation of covellite. The formed covellite, which is capable
of conducting electron, is exposed to the alkaline
Na4EDTA solution containing oxygen as an oxidizing
agent. Under such alkaline conditions, the electrochemical dissolution reaction may be expressed as
ka

Cu2+

+SO42- + 4 H 2 0 +

8e

[13]

The O H - ion is required in the anodic half-cell reaction,

because the mineral sulfur must be completely oxidized
to sulfate ion. The standard potential of Reaction [13] is
equal to - 0 . 4 1 V at 25 ~ The value of potential was
calculated using thermodynamic data for Gibbs free energy. [141In a chemical leaching system, the anodic halfcell reaction must be coupled with a cathodic reaction.
Since oxygen is the only available oxidant, the reduction
of oxygen in alkaline solution is
k~
O2 + 2H20 + 4e ~ 40H300--VOLUME 22B, JUNE 1991

CuS + 02 + 4 O H - --~ Cu 2 + SO42- + 2H20 + 4e

[15]
The standard electrode potential of Reaction [ 15] is equal
to 0.81 V. The value was calculated from the standard
potentials of Reactions [13] and [14]. The positive potential for Reaction [15] indicates that even in alkaline
solutions, covellite has a tendency to corrode by being
oxidized.
Under the alkaline conditions, the free Cu 2+ ion liberated by the electrochemical reaction is presumably
hydrolyzed in the absence of EDTA. It is inferred that
in EDTA-free solution, the formed hydrolytic products
adhere on the anodic site, and then further dissolution is
prevented. In the presence of EDTA, however, the
9
Cu 2+ 1on
leached by electrochemical Reaction [ 15] is immediately consumed through the following chelation:
Cu2+ + y4- + OH----> Cu(OH)Y 3-

B. Electrochemical Dissolution Mechanism of the

Intermediate Product, Covellite

CuS+80H-

The standard potential of the cathodic Reaction [14] is

0.40 V at 25 ~ [141The overall reaction can be expressed
in terms of the sum of half-cell Reactions [13] and [14]:

[14]

[16]

because it is widely accepted that the chelation of heavy

metal ions with EDTA takes place instantaneously and
irreversibly. In this case, the concentration of free Cu 2+
ion in the leach solution is always extremely small, and
the dissolution of covellite proceeds irreversibly.
Since the formation rate of Cu-EDTA complex is very
high in the presence of excess EDTA, the electrochemical process may be regarded as the slowest step in
the EDTA leaching process, i.e., the rate-controlling step.
According to the electrochemical reaction scheme described above, the formation rate, Rc2, of Cu 2+ ions per
unit surface area of covellite can be related to the anodic
current density, ia:

Rc2 --- iaAa/ (ZaFA)

[17]

with

= A a -4-

Ac

[18]

where A a and Ac are areas of anodic and cathodic sites.

The electrical charge conservation principle necessitates
that the anodic current is equal to the negative of the
cathodic current:

iaAa = -icAc

[19]

The current densities ia and ic for the anodic and cathodic

half-cell reactions can be expressed using the ButlerVolmer equation. For simplicity, it is usually assumed
that anodic and cathodic transfer coefficients are 0.5 and
that the rate-controlling step is the transfer of a single
electron. Moreover, each of Reactions [13] and [14] is
assumed to be an irreversible reaction of a finite rate
with a first-order kinetics for each reacting species. Under
these assumptions, the current densities are given by the
Butler-Volmer equation:

ia = ZaFka[OH-] exp [FEu/2RT]

[20]

ic = -Z~Fkc[O2] exp [-FEM/2RT]

[21]

and

where EM is the mixed potential. Substituting Eqs. [20]

METALLURGICAL TRANSACTIONS B

1 - (I - a2) w3 = t/z2

and [21] into Eq. [19] and rearranging gives the following relation:
exp L2RT]

\ ~ l

with

[~

',2

[O~

92 = [3pM2/(kqb2)] De0(Po2[OH ])

[22]

Po~ = H[O2]

[23]

Combining Eqs. [17], [18], [20], [22], and [23] gives

the expression for the formation rate of Cu 2 ions:

Rc~ = k(Po2[OH-]) 1/2

[24]

with
+

(Ac/Ao)]

[25]
It is evident that when electrochemical Reactions [13]
and [14] are rate-controlling steps, the leaching rate of
copper is dependent on Po2 and [OH-] but independent
of the Na4EDTA concentration [ y 4 - ] . These effects predicted by Eq. [24] are consistent with the experimentally
observed behavior given in Figures 1, 4, and 5.
When the dissolution of the covellite particles, in which
the rate is electrochemically controlled, occurs in a
shrinking particle fashion, the leaching rate of copper is
expressed in terms of the diameter, Dp2, of shrinking
covellite:

-Rc2Dp22 = (PM2/qb2) d(Dp23)/dt

-1/2

[29]

for the case where the parameter ~'2 is assumed to be

constant during the dissolution process. Equation [28],
which is a rearrangement of Eq. [7], represents the familiar kinetic expression based on the shrinking-particle
model.
The validity of our kinetic model was tested for the
present experimental results by confirming the relation
of parameter ~'2 to the relevant operating variables. If a
given set of experimental data obeys our kinetic model,
the observed value of ~'2 should be of the same mathematical form as Eq. [29]. In Figure 9, the observed values of ~2 are shown as a function of the initial particle
size, Dpo, the oxygen partial pressure, Po2, the OH- ion
concentration, [OH-], and the Na4EDTA concentration,
[ y 4 - ] . It is evident that the observed effects of the Dpo,
Po~, [OH-], and [ y 4 - ] values on the parameter r2 are the
same as the theoretical predictions from Eq. [29]. These
agreements justify the validity of the assumed kinetic
model for the covellite-Na4EDTA solution system.
Figure 10 shows the temperature dependency of the
parameter r2 as an Arrhenius plot. The ordinate was
modified by multiplying ~2 by the square root of the oxygen partial pressure Po2. Parameter ~'2 is inversely proportional to the apparent reaction rate constant as judged
from Eq. [29], so the activation energy of electrochemical reaction was evaluated as 38.3 kJ mo1-1 from
the reciprocal of the slope of a straight line in Figure 10.
The activation energy of about 40 kJ mol-' suggests that
the dissolution rate of covellite is chemically controlled.
The equation correlating the parameter 22, which is in
line with Eqs. [25] and [29], was obtained as follows:

As regards the oxygen concentration, the liquid-phase

concentration [02] can be related to the partial pressure
Po: in the gas phase through Henry's law:

k = (kakJ/2(Zc/Za) '/2 I-I-'/2(Ac/Ao)'/2/[(I

[28]

[26]

Combining Eqs. [5], [24], and [26] gives

da2/dt = (k~b2/PM2) (1/Dpo) (eo2[OH-])'/2(1 - a2) 2/3

[27]

~'2 = 9.08 103 Dpo/(Po~[OH-]) 1/2 exp (38,300/RT)

Integration of Eq. [27] subject to the initial condition of

(~2 = 0 a t t = 0gives

[30]

I0 ~

6
4

2A

e"

E 10 3
r

P'

4
200

z0

I , I

40 60

D~ x ~os (m)

, I I

20

40

Po2(kPa)

, I I

40 60 mo

400

[OH-] (rno[ rn"3)

Fig. 9 - - P a r a m e t e r ~2 as a function of initial particle size Dp0, oxygen partial pressure Po2, OH
centration [y4 ]. The symbols are the same as in Figs. 2 through 5.
METALLURGICAL TRANSACTIONS B

200

I 11

40 60 mo

I
200

[y 4-] (mot m-3)

ion concentration [OH-], and Na4EDTA con-

VOLUME 22B, JUNE 1991--301

data on the variation of the leaching fraction with time

were analyzed to determine the kinetic parameters appearing in the rate equations based on the shrinkingparticle model (Eqs. [10] and [11]). The disappearance
times listed in Table II indicate that the conversion rate
of chalcocite into covellite was about 10 times as high
as the dissolution rate of covellite. The kinetic data on
the dissolution of covellite were explained by the rate
expressions (Eqs. [28] and [30]), which were derived by
applying the Butler-Volmer equation to anodic and cathodic Reactions [13] and [14]. Equation [30] permits us
to calculate the time required for the complete leaching
of copper from chalcocite in the EDTA leaching process.

2
m

10 4

"=
r

"~

4
o

2
I
2.6

10a

10001T

I
2.0

I
3.0

NOMENCLATURE

(K -~)

Fig. 1 0 - - P a r a m e t e r r: as a function of temperature T. The symbols

are the same as in Figs. 2 and 6.

Figure 11 compares all of the observed r2 values with

the established correlation (Eq. [30]) on a log-log scale.
In accordance with the relation predicted by Eq. [30],
the observed ~'2 values vary as Dpo/(Po2[OH-]) 1/2 and can
be correlated well on a straight line with the slope of
unity.
V.

A
A,,, Ac

Dpo

E~
F
H
ia, ic

CONCLUSIONS

The leaching of copper from natural chalcocite particles in the alkaline Na4EDTA solutions containing oxygen was accompanied by the formation of covellite as
an intermediate product. The formed covellite was oxidized to copper (II) ion and sulfate ion, and then the
leached copper (II) ion was immediately consumed by
the formation of Cu-EDTA complex. The experimental

ka, kc
nL

Po~
R

Rc
T

t
V

6000

Wo
X

Za, Z~
[]

total surface area of covellite particle (m E)

surface areas of anode and cathode,
respectively (m 2)
initial diameter of solid particle (m)
diameter of solid particle (m)
mixed potential (V = J A -1 s -1)
Faraday constant (C mo1-1 = A s mol -~)
Henry's law constant (kPa m 3 mol -~)
anodic and cathodic current densities,
respectively (A m -2)
apparent reaction rate constant defined by
Eq. [25] (mol 1/2 s -l kPa -1/2 m -1/2)
rate constants for anodic and cathodic
Reactions [13] and [14] (m s -~)
liquid-phase stirring speed (s -~)
partial pressure of oxygen (kPa)
gas constant (J mo1-1 K -~)
formation rate of Cu E+ ion per unit surface
area of solid particle (mol m - 2 S - 1 )
thermodynamic temperature (K)
time (min)
volume of solution (m 3)
initial weight of solid particle (kg)
leaching fraction of copper, based on the
original mineral (CUES) ( - )
free EDTA ligand
total charge transferred at anode and
cathode, respectively ( - )
concentration in solution (mol m -3)

Greek Letters
a~
1000

aE

PM
r~

r2
400

J ~ i ~l
0.06
0.1

I
2

Dpo(Poz[OH-] )'t'Zexp(38300/RT)

J
4

J
0.6

~b

fractional conversion of chalcocite to

covellite, defined by Eq. [4] ( - )
fractional conversion of covellite to Cu(II)
ion, defined by Eq. [5] ( - )
molar density of solid particle (mol m -3)
time required for complete disappearance of
chalcocite core (min)
time required for complete dissolution of
covellite (min)
specific surface shape factor ( - )

(m 512 kl~U2mol-U2)

Subscripts
Fig. l 1 - - Comparison of experimental data with proposed correlation
for parameter rE. The symbols are the same as in Figs. 1 through 6.
Solid line is predicted from Eq. [30].
302--VOLUME 22B, JUNE 1991

1
2

chalcocite
covellite
METALLURGICAL TRANSACTIONS B

ACKNOWLEDGMENT

The authors are indebted to Mr. Hiroshi Doi, Japan

New Metals Co., Ltd., Osaka, Japan, for the X-ray diffraction analysis.

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METALLURGICAL TRANSACTIONS B

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vol. 18B, pp. 331-37.
7. Y. Konishi, H. Katada, and S. Asai: Hydrometallurgy, 1990,
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VOLUME 22B, JUNE 1991- 303