Reaction Mechanism and Kinetics of Enargite Oxidation

at Roasting Temperatures
RAFAEL PADILLA, ALVARO ARACENA, and MARIA C. RUIZ
Roasting of enargite (Cu
3
AsS
4
) in the temperature range of 648 K to 898 K (375 C to 625 C)
in atmospheres containing variable amounts of oxygen has been studied by thermogravimetric
methods. From the experimental results of weight loss/gain data and X-ray diraction (XRD)
analysis of partially reacted samples, the reaction mechanism of the enargite oxidation was
determined, which occurred in three sequential stages:
First stage: 4Cu
3
AsS
4
s + 13O
2
g = As
4
O
6
g + 6Cu
2
S s + 10SO
2
g
Second stage: 6Cu
2
S s + 9O
2
g = 6Cu
2
O s + 6SO
2
g
Third stage: 6Cu
2
O s + 3O
2
g = 12CuO s
The three reactions occurred sequentially, each with constant rate, and they were affected
significantly by temperature and partial pressure of oxygen. The kinetics of the first stage were
analyzed by using the model X = k
1
t. The first stage reaction was on the order of 0.9 with
respect to oxygen partial pressure and the activation energy was 44 kJ/mol for the temperature
range of 648 K to 898 K (375 C to 625 C).
DOI: 10.1007/s11663-012-9675-x
The Minerals, Metals & Materials Society and ASM International 2012
I. INTRODUCTION
ROASTING is a pyrometallurgical process used in
the metallurgical industry to transform sulde minerals
into oxides, sulfates, or other compounds more amena-
ble for subsequent treatment toward the production of
metals. In the case of copper concentrates, roasting is
commonly used for the elimination of toxic arsenic and
other deleterious elements through the gas phase, mainly
because copper concentrates containing high amounts of
arsenic are not apt for conventional smelting-converting
technology because of the high risk of ambient contam-
ination with arsenic compounds and the risk of produc-
ing nal copper with unacceptable high levels of arsenic.
Arsenic in copper concentrates is present primarily as
the enargite mineral (Cu
3
AsS
4
), and when these copper
concentrates contain appreciable amounts of enargite,
they must be pretreated to eliminate the arsenic before
smelting. Roasting is the preferred pretreatment pro-
cess,
[13]
where most of the deleterious arsenic is elimi-
nated through the gas phase inasmuch as arsenic
compounds (including oxides and suldes) have high
vapor pressures at relatively low temperatures. Thus, the
volatilization of arsenic at roasting temperatures should
occur rather easily, but in practice, appreciable amounts
of arsenic remain in the calcine as nonequilibrium
compounds depending on the processing circum-
stances.
[3,4]
Although, the arsenic elimination fromenarg-
ite by thermal decomposition in neutral atmospheres is
relatively well understood, the literature survey did not
show conclusive rate data or an indication of the
mechanismof arsenic eliminationfromenargite inoxygen
containing atmospheres. On this matter, Kusick and
Nadkarni
[5]
reported some data on the roasting of
enargite concentrates in nitrogen and carbon dioxide
atmospheres. These investigators focused mainly on the
production of arsenic sulde in the roasting as a nal
product anddiscussedthe results of some data obtainedin
rotary and electric arc reactors.
Smith and Paredes
[6]
reported some data on the
decomposition of enargite and volatilization of arsenic
as sulde in nitrogen atmosphere. The following chem-
ical reaction was proposed with the formation of two
copper suldes:
2Cu
3
AsS
4
s Cu
2
S s 4CuS s As
2
S
3
g 1
A somewhat dierent enargite decomposition reaction
in nitrogen atmosphere was reported by Yoshimura
[1]
as
given by Reaction [2].
2Cu
3
AsS
4
s 3Cu
2
S s As
2
S
3
g S
2
g 2
Seco et al.
[7]
studied the decomposition of enargite in
nitrogen and air, and they reported some inconclusive
results obtained from dierential thermal analysis mea-
surements and experiments carried out in a horizontal
tube furnace setup. Their data showed a very similar
behavior of enargite in both nitrogen and air atmo-
spheres, and they concluded that enargite decomposed in
nitrogen atmosphere according to Reaction [2] as well.
Later, Padilla et al.
[8]
carried out a more detailed
study for the same system in nitrogen atmosphere at
848 K to 973 K (575 C to 700 C) and proposed the
following overall enargite decomposition reaction:
RAFAEL PADILLA and MARIA C. RUIZ, Professors, and
ALVARO ARACENA, Graduate Student, are with the Department
of Metallurgical Engineering, University of Concepcion, Edmundo
Larenas 285, Concepcion, Chile. Contact e-mail: rpadilla@udec.cl
Manuscript submitted October 4, 2011.
Article published online May 15, 2012.
METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 43B, OCTOBER 20121119
4Cu
3
AsS
4
s 6Cu
2
S
1x
+ As
4
S
4
g 3 3x S
2
g
3
In Reaction [3], the arsenic gaseous species was
selected based on thermodynamic considerations, and
the copper sulde product Cu
2
S
1x
is a general formula
that included chalcocite (Cu
2
S), nonstoichiometric
djurleite (Cu
1.96
S), and digenite (Cu
1.8
S) in the solid
residues. Additionally, these investigators showed that
the decomposition of enargite in nitrogen atmosphere
proceeded in two consecutive stages through the forma-
tion of intermediate tennantite (Cu
12
As
4
S
13
) according
to the following reactions:
4Cu
3
AsS
4
= Cu
12
As
4
S
13
1:5S
2
g 4
Cu
12
As
4
S
13
6Cu
2
S
1x
As
4
S
4
g 1:5 3x S
2
g
5
Both stages of the reaction were found to follow rst-
order kinetics, and the determined activation energy
values were 125 and 236 kJ/mol for the rst and second
stages, respectively.
In an oxidizing atmosphere, Mihajlovic et al.
[9]
con-
ducted an oxidative roasting of a copper-arsenic mineral
with a signicant concentration of enargite in a hori-
zontal tube furnace at 673 K to 1073 K (400 C to
800 C). These investigators indicated that the maxi-
mum desulfurization was obtained at 1073 K (800 C)
after 30 minutes, and 81 pct of arsenic was also removed
at 1023 K (750 C) after 30 minutes. Yaozhong and
Smith
[10]
reported limited data on arsenic volatilization
obtained from roasting gold concentrate that contained
arsenic in the form of arsenopyrite (FeAsS). The
roasting was carried out in a tube furnace, which
simulated a rotary furnace, using coal gas produced in a
charcoal gas generator. These investigators concluded
that the removal of arsenic was greater than 95 pct in
the range of 923 K to 973 K (650 C to 700 C), with
coal gas with 15 to 16 pct CO
2
, and 30 to 40 minutes of
reaction time.
Considering the preceding data, it is clear that
fundamental research is needed to understand the
behavior of enargite in oxidizing atmosphere at roasting
temperatures. Thus, in this article, the mechanism and
kinetics of oxidation of enargite are discussed.
II. EXPERIMENTAL STUDY
A. Materials
The experimental work was carried out using enargite
mineral samples obtained from El Indio Mine (Barrick
Corporation, Chile). Pure enargite crystals were selected
for the experimental study, which were crushed, ground,
and classied by sieving into size fractions. The enargite
sample of 75 to +53 lm size fraction used in the
present research was acid digested and subjected to
chemical analysis by atomic absorption spectroscopy.
The result indicated that the sample had 18.6 pct As,
46.9 pct Cu, and 33.3 pct S, which is close to the
theoretical composition of pure enargite (19.03 pct As,
48.4 pct Cu, and 32.5 pct S). This analysis and the
microscopic mineralogical analysis, shown in Table I,
indicated that the enargite sample was essentially pure
and the major impurity was gangue.
In regard to the gases, high-purity nitrogen and
nitrogenoxygen gas mixtures (supplied by Indura, S.A.,
Santiago, Chile) were used to provide inert and oxidiz-
ing atmospheres.
B. Experimental Procedure
The oxidation experiments were carried out by the
method of weight loss measurement in a custom-built
thermogravimetric analysis apparatus. This apparatus
consisted basically of a vertical quartz tube reactor
(44 mm inside diameter) mounted in a vertical furnace
with programmable temperature controller, a Sartorius
microbalance model ME235P with sensitivity 0.00001 g
set on top of the tube furnace, a data acquisition system,
and a gas distribution system designed to provide
nitrogenoxygen atmospheres of various compositions.
The temperature prole of the tube reactor showed a
constant temperature region of approximately 150 mm
length, where the 1.3-mL sample crucible (11 mm inner
diameter [ID] 9 14 mm high [H]) was placed in the
experiments; thus, during the course of an experiment,
the temperature of the sample was measured continu-
ously by means of a calibrated chromelalumel thermo-
couple placed just below the crucible.
In most experiments, approximately 50 mg of the
enargite sample contained in the crucible was introduced
into the preheated reaction tube and suspended from the
balance by a quartz chain in the region of constant
temperature of the tube. To check the development of
local temperature changes caused by the heat of
reaction, few experiments were conducted with a ther-
mocouple placed inside the crucible in direct contact
with the reacting sample and with the thermocouple in
empty crucible. The results indicated that the dierence
in the temperature prole for both cases was negligible
for the small 50-mg sample used. Thus, during the
isothermal experiments, the instantaneous weight of the
sample was recorded as a function of time. The total
pressure of the system was the atmospheric pressure
(101.3 kPa).
The fraction of weight loss at any time was deter-
mined from the initial and the instantaneous weight of
the sample. The determination of the nal and interme-
diate compounds formed by the reaction of the sample
Table I. Mineralogical Composition of the Enargite Sample
Mineral Weight Pct
Enargite 93.55
Covellite 0.40
Pyrite 0.06
Gangue 5.99
Total 100
1120VOLUME 43B, OCTOBER 2012 METALLURGICAL AND MATERIALS TRANSACTIONS B
was done by means of X-ray diraction (XRD) spec-
troscopy by using a Rigaku model Geiger Flex, cop-
per anode spectrometer (Rigaku Corporation, The
Woodlands, TX). The partially reacted samples for the
XRD analysis were prepared by allowing the reaction of
a sample to proceed for a predetermined length of time;
then, the crucible with the sample was rapidly raised to
the upper end of the reaction tube where it was
quenched under a stream of nitrogen gas for approxi-
mately 15 seconds. Subsequently, the sample was rap-
idly removed to a desiccator for nal cooling and
weighing. In general, the experiments were conducted
isothermally until no weight change of the sample was
observed.
III. RESULTS
A. Preliminary Experiments
Preliminary experiments of oxidation of enargite were
carried out to study the thermal behavior in an
atmosphere that contained various concentrations of
oxygen. Figure 1 shows typical results of the isothermal
behavior of enargite in an oxidizing atmosphere. In this
gure, the results are plotted as the fractional weight
loss of the sample versus time for various experimental
conditions of temperature and partial pressure of
oxygen. The fractional weight loss (or weight gain) of
the sample was calculated as (W
o
W)/W
o
, where W
o
is
the initial weight of the sample and W is the weight at
time t.
We can observe in this gure that the weight loss
curves for enargite samples heated under dierent
experimental conditions show a similar behavior to
each other. In all cases, the curves are composed by a
sequence of three essentially straight lines with sudden
changes in the slopes indicating that the overall oxida-
tion of enargite takes place in three distinct stages. In the
rst stage, the samples lose weight at a fast rate. In the
second stage, the samples also lose weight but at a
slower rate, whereas in the third stage, a weight gain
occurred.
Experiments were also done to determine the condi-
tions in which the external and internal mass transfer
processes do not aect the enargite oxidation rate.
Because the rst stage has the fastest rate, this stage is
the most likely to be aected by such processes.
Therefore, focusing on this stage, experiments were
carried out varying the gas ow rate (from 0.6 to 1.5 L/
min) using 50-mg samples contained in two sample
holders: a crucible (11 mm ID 9 14 mm H) and a at
sample holder (13 mm ID 9 1 mm H) where the solids
were distributed forming a thin layer. The results are
shown in Figure 2 where it is clear that the dierent gas
ow rate conditions and the type of sample holder had a
negligible eect on the oxidation rate. Therefore, these
results indicate that mass-transfer resistances were not
important under the experimental conditions of this
work. Thus, the subsequent experiments were done
using the crucible mainly because of the convenience in
handling the samples and the gas ow rate of 1 L/min
was used as standard in the experiments.
B. Effect of Temperature on the Enargite Oxidation
The eect of temperature on the overall oxidation of
enargite in mixtures of nitrogen-oxygen atmospheres
was investigated in the range of 648 K to 898 K (375 C
to 625 C). This temperature range was considered
appropriate to avoid the formation of liquid phases in
the system because enargite and related tennantite have
melting points of 960 K and 930 K (687 C and 657 C),
respectively. All the roasting experiments were isother-
mal at constant partial pressure of oxygen.
Some of the results are presented in Figure 3, where
the rate of oxidation of enargite is shown again as the
fraction of weight loss of the sample versus reaction
time. We can see that temperature has a pronounced
eect on the oxidation of enargite. When the tempera-
ture augmented, the rates of the three sequential stages
of enargite oxidation increased signicantly. It can also
be observed that the maximum weight loss experienced
by the samples was about 0.45 for all the temperatures
studied. It is interesting to note that for temperatures
0 2000 4000 6000 8000 10000
0.0
0.1
0.2
0.3
0.4
0.5
0.6
F
r
a
c
t
i
o
n

o
f

w
e
i
g
h
t

l
o
s
s
Time, s
873 K, 1.01 kPa O
2
798 K, 5.07 kPa O
2
773 K, 10.1 kPa O
2
Fig. 1Thermal behavior of enargite in N
2
-O
2
atmospheres at vari-
ous experimental conditions.
0 200 400 600 800 1000 1200 1400
0.0
0.1
0.2
0.3
0.4
0.5
F
r
a
c
t
i
o
n

o
f

w
e
i
g
h
t

l
o
s
s
Time, s
Flow rate Sample holder
1 L/min Crucible
0.6 L/min Flat holder
1 L/min Flat holder
1.5 L/min Flat holder
1.5 L/min Crucible
T = 873 K
P
O
2
= 5.07 kPa
Fig. 2Results of experiments showing the negligible eect of mass
transfer during oxidation of enargite.
METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 43B, OCTOBER 20121121
lower than 723 K (450 C) the second and third stages
of enargite oxidation do not occur appreciably, as
shown by the attening o of the curves at approxi-
mately 0.4 value.
C. Effect of Oxygen Concentration
The experimental results concerning the eect of
partial pressure of oxygen on the oxidation of enargite
at 773 K (500 C) is shown in Figure 4. It can be
observed in this gure that a higher oxygen concentra-
tion in the gas phase produced a signicant increase on
the rate of weight loss of enargite; a similar eect was
found in experiments at other temperatures studied. It
can be noted in Figure 4 that the weight loss rate is very
rapid at an oxygen partial pressure of 21.3 kPa even at
this relatively low temperature of 773 K (500 C).
D. Reaction Mechanism
To determine the reaction mechanism and intermedi-
ate compounds through which the oxidation of enargite
proceeds, partially reacted samples were analyzed by
XRD to identify the reaction products. The results are
shown in Figures 5 and 6. Figure 5 shows two XRD
spectrums A and B obtained at 873 K (600 C) and
1.01 kPa of oxygen for reaction times corresponding to
the rst stage. Spectrum A (for 150 seconds) shows
strong diraction peaks for enargite and tennantite and
very weak peaks for chalcocite, whereas spectrum B (for
1400 seconds, time near the end of the rst stage)
shows peaks for tennantite and chalcocite. In contrast,
Figure 6 shows also two spectrums C and D corre-
sponding to samples taken at 873 K (600 C), 1.01 kPa
O
2
, and 2700 seconds, and 898 K (625 C), 21.3 kPa O
2
,
and 900 seconds, respectively. Spectrum C corresponding
to a sample in the second stage of oxidation shows
diraction lines for Cu
2
S and Cu
2
O, whereas spectrum D
indicates the formation of CuO and basic copper sulfate
(CuO*CuSO
4
) in the third stage.
These results suggest that in the rst stage of reaction,
the oxidation of enargite (Cu
3
AsS
4
) proceeds through
the formation of tennantite (Cu
12
AsS
13
) as an interme-
diate compound that subsequently forms solid chalco-
cite (Cu
2
S). The absence of condensed arsenic
compounds other than tennantite in the rst stage
indicates that arsenic is eliminated by the formation of
volatile arsenic compounds. Afterward, in the second
stage, the newly formed chalcocite is oxidized to cuprite
0 1000 2000 3000 4000 5000 6000 7000 8000
0.0
0.1
0.2
0.3
0.4
0.5
0.6
F
r
a
c
t
i
o
n

o
f

w
e
i
g
h
t

l
o
s
s
Time, s
648 K
673 K
723 K
773 K
823 K
848 K
873 K
898 K
P
O
2
= 5.07 kPa
Fig. 3Inuence of temperature on the rate of enargite oxidation.
0 500 1000 1500 2000 2500 3000 3500 4000
0.0
0.1
0.2
0.3
0.4
0.5
F
r
a
c
t
i
o
n

o
f

w
e
i
g
h
t

l
o
s
s
Time, s
21.3 kPa
1.01 kPa
5.07 kPa
10.13 kPa
T = 773 K
Fig. 4Inuence of partial pressure of oxygen on the rate of enarg-
ite oxidation.
20 30 40 50 60
0
5000
10000
15000
20000
25000
30000
35000
o Chalcocite
+ Tenantite
o Chalcocite
*
Enargite
o
o
o o
+ Tenantite
+
+
+
+
+
+
+
*
*
*
*
*
C
p
s
,

a
r
b
i
t
r
a
r
y
2 Theta, deg
*
+
o
(A)
873 K
150 s
(B)
873 K
1400 s
Fig. 5XRD results obtained for samples corresponding to the rst
stage of enargite oxidation at 873 K (600 C) and 1.01 kPa partial
pressure of oxygen.
10 20 30 40 50 60 70
0
2000
4000
6000
8000
10000
12000
14000
16000
(D)
898 K, 900 s
21.3 kPa

+
+
+
+
o
o o
o
*
*
*
c
p
s
,

a
r
b
i
t
r
a
r
y
2Theta, deg
* Cu
2
O
Cu
2
S
o
+CuO*CuSO
4
CuO
(C)
873 K, 2700s
1.01 kPa O
2
Fig. 6XRD results obtained for samples corresponding to the sec-
ond and third stages of enargite oxidation.
1122VOLUME 43B, OCTOBER 2012 METALLURGICAL AND MATERIALS TRANSACTIONS B
(Cu
2
O), a process that ends at the time corresponding to
the maximum of the weight loss curve. Finally, the XRD
results indicated that in the third stage, further oxida-
tion of Cu
2
O occurred to produce tenorite (CuO), or
mixtures of CuO and CuO*CuSO
4
, which resulted in a
weight gain of the samples. The latter basic copper
sulfate has been found consistently at 898 K (625 C),
which is in accordance with thermodynamic predictions.
From these results, the following sequential reactions
can be written for the behavior of enargite in oxygen
containing atmosphere at the studied temperatures:
First stage: 4Cu
3
AsS
4
s 13O
2
g
6Cu
2
S s As
4
O
6
g 10SO
2
g 6
Second stage: 6Cu
2
S g 9O
2
g
6Cu
2
O s 6SO
2
g 7
Third stage: 6Cu
2
O s 3O
2
g 12CuO s 8a
A small fraction of the Cu
2
O oxidizes to basic copper
sulfate by the following alternative reaction:
6Cu
2
O s 6SO
2
g 6O
2
g 6CuO CuSO
4
s
8b
The main overall reaction is the sum of Reactions [6]
through [8] given as Reaction [9]:
4Cu
3
AsS
4
s 25O
2
g 12CuO s + As
4
O
6
g
16SO
2
g 9
This reaction mechanism is consistent with the results
of the XRD analysis and also with the experimental
weight loss fractions observed for the rst and second
stages and the weight gain fraction of the third stage.
Hence, in the rst stage, the theoretical weight loss
fraction is 0.39 according to the stoichiometry of
Reaction [6], which is in agreement with the experimental
weight loss fraction value of 0.39 to 0.40, where the rst
change in the slope of the curves occurred, as shown in
Figures 1, 3, and 4. If we consider the overall oxidation
of enargite to Cu
2
O (rst plus second stages), then the
theoretical weight loss fraction is 0.45, which again
agrees well with the experimental maximum weight loss
value of approximately 0.45, conrming the stoichiom-
etry of the reactions. In the range 723 K to 898 K
(450 C to 625 C), the nal weight loss experienced by
the samples at the end of the tests (which included the
weight gain of the third stage) showed some variation,
which can be attributed to the formation of small
amounts of CuO*CuSO
4
by the alternative Reaction [8b]
in addition to copper oxide. At temperatures lower than
723 K (450 C), only the rst stage of reaction occurs, as
evidenced by the plateau of the fractional weight loss
value at approximately 0.39 to 0.40.
It should be pointed out that because tennantite and
chalcocite were identied during the rst stage of
reaction, the enargite particles must decompose to
tennantite rst with the release of sulfur, which diuses
as a gas to the surface of each of the particles where
oxidizes to SO
2
. Subsequently, tennantite reacts to
chalcocite, releasing arsenic and sulfur (presumably as
arsenic trisulde), which oxidizes and is evolved as
As
4
O
6
, because this arsenic species has been reported to
predominate at low temperatures in oxidizing condi-
tions.
[3]
The elementary reactions that occurred in this
stage cannot be discerned solely from the weight loss
data of the reacting sample.
The formation of tennantite as an intermediate
compound during the thermal decomposition of enarg-
ite to chalcocite in nitrogen has been reported previously
by Padilla et al.
[8]
As discussed, the decomposition
reaction proceeded in two consecutive steps: (1) enargite
to tennantite and (2) tennantite to chalcocite. This
sequential decomposition of enargite could be clearly
visualized in the temperature range of 848 K to 898 K
(575 C to 625 C) by a noticeable change in the slope of
the conversion curves because of a much faster decom-
position of enargite to tennantite than the subsequent
decomposition of tennantite to chalcocite in that tem-
perature range. At higher temperatures, the change in
slope was not noticeable because the dierence in the
rates of both decomposition stages became smaller.
To verify the decomposition behavior of enargite,
experiments were conducted in pure nitrogen atmo-
sphere to compare with the results obtained in oxygen-
containing atmospheres. The results are shown in
Figure 7, where the weight loss curves for enargite
heated in nitrogen at 773 K and 873 K are compared to
data obtained in an atmosphere with 5.07 kPa P
O
2
for
the same temperatures. As expected, at 873 K (600 C)
in nitrogen atmosphere, there is a noticeable change in
the slope of the curve for a fractional weight loss value
at approximately 0.08, indicating the rapid decomposi-
tion of enargite to tennantite followed by the slower
decomposition of tennantite to chalcocite. At 773 K
(500 C) in nitrogen atmosphere, the rate of the decom-
position of enargite is very slow, and as shown in the
gure, the transformation of enargite to tennantite was
incomplete at the end of the experiment at this low
temperature. In contrast, in an oxidizing atmosphere at
0 500 1000 1500 2000 2500 3000 3500 4000
0.0
0.1
0.2
0.3
0.4
0.5
O
2
, 873 K
N
2
, 873 K
O
2
, 773 K
F
r
a
c
t
i
o
n

o
f


w
e
i
g
h
t

l
o
s
s
Time, s
N
2
, 773 K
Fig. 7Comparison of enargite behavior in pure nitrogen atmo-
sphere and nitrogen-oxygen atmosphere (5.07 kPa O
2
).
METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 43B, OCTOBER 20121123
both temperatures, the weight loss of the sample
occurred at much faster rates than in a nitrogen
atmosphere. In addition, in the oxidizing atmosphere,
the weight loss occurs at a constant rate throughout the
rst stage of oxidation without a change in the slope of
the lines. Therefore, even though the oxidation of
enargite also produces tennantite as an intermediate
product, the oxidation of enargite to tennantite and
tennantite to chalcocite apparently occur with compa-
rable rates to give a constant slope line. From these
results, the following reactions can be written for this
rst stage:
4Cu
3
AsS
4
s 3O
2
g Cu
12
As
4
S
13
s 3SO
2
g
10
Cu
12
As
4
S
13
s + 10O
2
g
= 6Cu
2
S s + As
4
O
6
g + 7SO
2
g 11
4Cu
3
AsS
4
s + 13O
2
g 6Cu
2
S s As
4
O
6
g
10SO
2
g 6
Reaction [6] proposed for the rst stage of enargite
oxidation is the sum of Reactions [10] and [11]. This
reaction accounts for the arsenic elimination from
enargite by oxidation/volatilization producing chalco-
cite as the sole solid product.
According to Figure 7, the arsenic elimination from
enargite by oxidizing roasting is signicantly faster
compared with the elimination in nitrogen atmosphere
at 773 K and 873 K (500 C to 600 C) . From the
results discussed regarding Figures 3 and 4, it is clear
that temperature and partial pressure of oxygen in the
gas phase are equally important for the arsenic elimi-
nation from enargite because both aect drastically the
rate of oxidation. Furthermore, for ecient elimination
of arsenic in oxidizing atmosphere, the advancement of
Reactions [7] and [8] should be prevented because they
do not contribute to arsenic elimination and they are
undesirable if the arsenic free calcines are to be treated
by conventional smelting/converting. Therefore, to pro-
duce a copper sulde calcine, roasting of enargite
concentrate should be carried out at temperatures below
723 K (450 C) in an atmosphere with oxygen partial
pressures around or less than 5.07 kPa. Under these
conditions, arsenic elimination from enargite is rapid
and chalcocite is the nal solid product. In contrast, in
nitrogen atmosphere the elimination of arsenic is very
slow at these low temperatures (less than 723 K
[450 C]).
E. Oxidation Kinetics
As discussed, the rst stage reaction (Reaction [6]) is
the relevant reaction for the elimination of the toxic
arsenic from enargite. Because the rst stage reaction
occurs at a constant rate, the kinetics can be analyzed by
the following rate equation:
0 1000 2000 3000 4000 5000 6000 7000
0.0
0.2
0.4
0.6
0.8
1.0
F
r
a
c
t
i
o
n
a
l

C
o
n
v
e
r
s
i
o
n
Time, s
Experimental data
648 K
673 K
723 K
773 K
823 K
873 K
898 K
Linear fit
P
O
2
= 5.07 kPa
Fig. 8Kinetics of the enargite oxidation in oxidizing atmosphere.
dX
1
dt

1
W
1stg
dW
dt
k
1
12
or
X
1
k
1
t 13
with
X
1
W
o
W =W
1stg
14
In these equations, X
1
is the fractional conversion for
the rst stage, k
1
is the apparent rate constant, W
o
is the
initial weight of the enargite sample, W
1stg
is the
theoretical weight loss of the rst stage according to
the stoichiometry of Reaction [6], and W is the weight at
time t. The dependence of the rate constant on the
partial pressure of oxygen and temperature is given by
k
1
k
o
e
Ea
RT

P
O
2

m
15
where k
o
is the preexponential factor, E
a
is the activa-
tion energy, R is the gas constant, T is the absolute
temperature, and m is the order of reaction with respect
to oxygen partial pressure P
O
2
.
Therefore, according to Eq. [13], a plot of fractional
conversion vs time should give a straight line with the
rate constant k
1
as the slope of the line. The data shown
in Figure 3 were plotted accordingly, and the results are
shown in Figure 8. The rate constants obtained from
this gure are shown in Table II. A similar approach
was followed for the experimental results concerning the
eect of partial pressure of oxygen. The resulting
conversion-time plot for the data at 773 K (500 C) is
shown in Figure 9.
Figure 10 shows the dependence of the rate constant
on the oxygen concentration in the gas phase as ln k vs
lnP
O
2
. A linear relationship can be observed between
them with a slope of 0.9, indicating that the reaction is
of 0.9 order with respect to the oxygen partial pressure.
The determination of the activation energy was done by
constructing an Arrhenius plot by using the rate
constants given in Table II; such a plot is shown in
1124VOLUME 43B, OCTOBER 2012 METALLURGICAL AND MATERIALS TRANSACTIONS B
Figure 11, from which the activation energy for the
temperature range of 648 K to 898 K (375 C to 625 C)
was determined as 44 kJ/mol.
IV. CONCLUSIONS
The behavior of enargite in the temperature range of
648 K to 898 K (375 C to 625 C) in atmospheres
containing variable amounts of oxygen has been studied
by thermogravimetric methods. The results can be
summarized as follows:
Based on the experimental weight loss/gain curves
and XRD analysis of partially reacted samples, it was
concluded that enargite oxidation occurred in three
sequential stages according to the following reactions:
First stage: 4Cu
3
AsS
4
s + 13O
2
g
= 6Cu
2
S s + As
4
O
6
g + 10SO
2
g
Second stage: 6Cu
2
S g + 9O
2
g
= 6Cu
2
O s + 6SO
2
g
Third stage: 6Cu
2
O s + 3O
2
g = 12CuO s
Thus, the rst stage corresponds to the elimination of
arsenic and the formation of chalcocite, the second stage
corresponds to the oxidation of chalcocite to cuprite
(Cu
2
O), and the third stage corresponds to the oxidation
of cuprite to tenorite (CuO). The three sequential
reaction stages occurred with constant rates that were
aected signicantly by temperature and partial pressure
of oxygen. The kinetics of the rst stage was analyzed by
using the model X
1
= k
1
t, which permitted the determi-
nation of the temperature dependence of the rate as well
as the dependence of the rate on the partial pressure of
oxygen. A value of 0.9 was found for the reaction order
with respect to oxygen partial pressure, and the activa-
tion energy determined was 44 kJ/mol for the tempera-
ture range of 648 K to 898 K (375 C to 625 C).
Overall, the oxidizing roasting requires a lower
temperature than inert roasting for a comparable rate
of arsenic elimination. A low partial pressure of oxygen
(5.07 kPa or lower) and a temperature of approximately
723 K (450 C) are advisable for ecient elimination of
arsenic while avoiding the production of a calcine
containing copper oxides.
ACKNOWLEDGMENTS
This work was supported by the National Fund for
Scientic and Technological Development (FONDECYT)
of Chile under Project No. 1080296.
Table II. Rate Constants for the First Stage of Enargite
Oxidation
T [K (C)] 1000/T (1/K) k
1
ln k
1
648 (375) 1.543 1.67E04 8.697
673 (400) 1.486 2.59E04 8.259
723 (450) 1.383 4.61E04 7.681
773 (500) 1.294 8.00E04 7.130
823 (550) 1.215 1.15E03 6.768
873 (600) 1.145 1.42E03 6.557
0 500 1000 1500 2000 2500 3000 3500 4000
0.0
0.2
0.4
0.6
0.8
1.0
l
n

k
a
p
p
Time, s
T = 773 K
1.01 kPa O
2
5.07 kPa
10.13 kPa
21.28 kPa
Fig. 9Dependence of the enargite oxidation rate on the partial
pressure of oxygen.
0 1 2 3
9
8
7
6
5
l
n

k
1
ln P
O
2
Slope = 0.9
Fig. 10Rate constants for the oxidation of enargite as a function
of the partial pressure of oxygen.
1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7
10
9
8
7
6
5
l
n

k
1
1000/T, K
1
E
a
= 44 kJ/mol
Fig. 11Arrhenius plot for the arsenic elimination from enargite.
METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 43B, OCTOBER 20121125
REFERENCES
1. Z. Yoshimura: Bull. Inst. Min. Metall. Jpn., 1962, vol. 78, pp. 447
53.
2. N. Chakraborti and D.C. Lynch: Metall. Trans. B, 1983, vol. 14B,
pp. 23951.
3. S. Nakasawa, A. Yazawa, and F.R.A. Jorgensen: Metall. Mater.
Trans. A, 1999, vol. 30A, pp. 393401.
4. A. Jokilaakso and S. Stromberg: Waste Characterization and
Treatment, W. Petruk, eds., SME, Littleton, CO, 1988, pp. 3548.
5. C.L. Kusick and R.M. Nadkarni: Arsenic Metallurgy: Funda-
mentals and Applications, R.G. Reddy, ed., TMS, Warrendale, PA,
1988, pp. 37349.
6. E.H. Smith and E. Paredes: Arsenic Metallurgy: Fundamentals and
Applications, R.G. Reddy, ed., TMS, Warrendale, PA, 1988,
pp. 14560.
7. A.C. Seco, G. Riveros, and A. Luraschi: Copper 87, vol. 4,
C. Diaz, C. Landolt, and A. Luraschi, eds., FCFM, University of
Chile, Santiago, Chile, 1988, pp. 22535.
8. R. Padilla, Y. Fan, and I. Wilkomirsky: Can. Metall. Q., 2001,
vol. 40, pp. 33542.
9. I. Mihajlovic, N. Strbac, Z. Zivkovic, R. Kovacevic, and M.
Stehernik: Miner. Eng., 2007, vol. 20, pp. 2633.
10. L. Yaozhong and R.W. Smith: Miner. Process. Extractive Metall.,
2004, vol. 113, pp. C18991.
1126VOLUME 43B, OCTOBER 2012 METALLURGICAL AND MATERIALS TRANSACTIONS B