Reaction Mechanism and Kinetics of Enargite Oxidation

at Roasting Temperatures
RAFAEL PADILLA, ALVARO ARACENA, and MARIA C. RUIZ

Roasting of enargite (Cu3AsS4) 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 diffraction (XRD)
analysis of partially reacted samples, the reaction mechanism of the enargite oxidation was
determined, which occurred in three sequential stages:
First stage: 4Cu3 AsS4 ðsÞ + 13O2 ðgÞ = As4 O6 ðgÞ + 6Cu2 SðsÞ + 10SO2 ðgÞ
Second stage: 6Cu2 SðsÞ + 9O2 ðgÞ = 6Cu2 OðsÞ + 6SO2 ðgÞ
Third stage: 6Cu2 OðsÞ + 3O2 ðgÞ = 12CuOðsÞ
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 = k1t. 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
Ó The Minerals, Metals & Materials Society and ASM International 2012

I. INTRODUCTION relatively well understood, the literature survey did not

ROASTING is a pyrometallurgical process used in
the metallurgical industry to transform sulfide 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 final copper with unacceptable high levels of arsenic.
Arsenic in copper concentrates is present primarily as
the enargite mineral (Cu3AsS4), 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,[1–3] where most of the deleterious arsenic is elimi-
nated through the gas phase inasmuch as arsenic
compounds (including oxides and sulfides) 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 from enarg-
ite by thermal decomposition in neutral atmospheres is
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.
show conclusive rate data or an indication of the
mechanism of arsenic elimination from enargite in oxygen
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 sulfide in the roasting as a final
product and discussed the results of some data obtained in
rotary and electric arc reactors.
Smith and Paredes[6] reported some data on the
decomposition of enargite and volatilization of arsenic
as sulfide in nitrogen atmosphere. The following chem-
ical reaction was proposed with the formation of two
copper sulfides:
2Cu3 AsS4 ðsÞ ¼ Cu2 SðsÞ þ 4CuSðsÞ þ As2 S3 ðgÞ ½1
A somewhat different enargite decomposition reaction
in nitrogen atmosphere was reported by Yoshimura[1] as
given by Reaction [2].
2Cu3 AsS4 ðsÞ ¼ 3Cu2 SðsÞ þ As2 S3 ðgÞ þ S2 ðgÞ ½2
Seco et al.[7] studied the decomposition of enargite in
nitrogen and air, and they reported some inconclusive
results obtained from differential 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:

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 43B, OCTOBER 2012—1119

4Cu3 AsS4 ðsÞ ¼ 6Cu2 S1x + As4 S4 ðgÞ þ ð3  3xÞS2 ðgÞ
½3
In Reaction [3], the arsenic gaseous species was
selected based on thermodynamic considerations, and
the copper sulfide product Cu2S1–x is a general formula
that included chalcocite (Cu2S), nonstoichiometric
djurleite (Cu1.96S), and digenite (Cu1.8S) 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 (Cu12As4S13) according
to the following reactions:
4Cu3 AsS4 = Cu12 As4 S13 þ 1:5S2 ðgÞ ½4
Cu12 As4 S13 ¼ 6Cu2 S1þx þ As4 S4 ðgÞ þ ð1:5  3xÞS2 ðgÞ
½5
Both stages of the reaction were found to follow first-
order kinetics, and the determined activation energy
values were 125 and 236 kJ/mol for the first and second
stages, respectively.
In an oxidizing atmosphere, Mihajlovic et al.[9] con-
ducted an oxidative roasting of a copper-arsenic mineral
with a significant 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 CO2, 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 classified 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.
1120—VOLUME 43B, OCTOBER 2012
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
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
nitrogen–oxygen 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
nitrogen–oxygen atmospheres of various compositions.
The temperature profile 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 chromel–alumel 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 difference
in the temperature profile 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 final and interme-
diate compounds formed by the reaction of the sample
METALLURGICAL AND MATERIALS TRANSACTIONS B
was done by means of X-ray diffraction (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 final cooling and
weighing. In general, the experiments were conducted
isothermally until no weight change of the sample was
observed.
III.
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
figure, 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 (Wo – W)/Wo, where Wo is
the initial weight of the sample and W is the weight at
time t.
We can observe in this figure that the weight loss
curves for enargite samples heated under different
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
first 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.
0.6
0.5
773 K, 10.1 kPa O2
Fraction of weight loss
0.4
0.3
0.2
0.1
0.0
0 2000
Fig. 1—Thermal behavior of enargite in N2-O2 atmospheres at vari-
ous experimental conditions.
METALLURGICAL AND MATERIALS TRANSACTIONS B
Experiments were also done to determine the condi-
tions in which the external and internal mass transfer
processes do not affect the enargite oxidation rate.
Because the first stage has the fastest rate, this stage is
the most likely to be affected by such processes.
Therefore, focusing on this stage, experiments were
carried out varying the gas flow 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 flat
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 different gas
flow rate conditions and the type of sample holder had a
negligible effect on the oxidation rate. Therefore, these
results indicate that mass-transfer resistances were not
important under the experimental conditions of this
RESULTS work. Thus, the subsequent experiments were done
using the crucible mainly because of the convenience in
handling the samples and the gas flow rate of 1 L/min
was used as standard in the experiments.
B. Effect of Temperature on the Enargite Oxidation
The effect 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
effect on the oxidation of enargite. When the tempera-
ture augmented, the rates of the three sequential stages
of enargite oxidation increased significantly. 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
0.5
T = 873 K
PO = 5.07 kPa
2
0.4
Fraction of weight loss
873 K, 1.01 kPa O2
0.3
798 K, 5.07 kPa O2
0.2 Flow rate Sample holder
1 L/min Crucible
0.6 L/min Flat holder
0.1 1 L/min Flat holder
1.5 L/min Flat holder
1.5 L/min Crucible
0.0
4000 6000 8000 10000 0 200 400 600 800 1000 1200 1400
Time, s Time, s
Fig. 2—Results of experiments showing the negligible effect of mass
transfer during oxidation of enargite.
VOLUME 43B, OCTOBER 2012—1121
 0.6 35000 (A)
* Enargite
PO = 5.07 kPa 873 K * + * + Tenantite
2 30000 o Chalcocite
0.5 150 s
Fraction of weight loss

Cps, arbitrary
25000 * + +
0.4 * + o * o *
648 K 20000
0.3 673 K (B) + Tenantite
723 K 15000 873 K + o Chalcocite
1400 s
773 K +
0.2 10000
823 K
848 K o
0.1 5000 o +
873 K + o
898 K 0
0.0 20 30 40 50 60
0 1000 2000 3000 4000 5000 6000 7000 8000
2 Theta, deg
Time, s
Fig. 5—XRD results obtained for samples corresponding to the first
Fig. 3—Influence of temperature on the rate of enargite oxidation. stage of enargite oxidation at 873 K (600 °C) and 1.01 kPa partial
pressure of oxygen.

16000
0.5 (C) * * Cu2O
21.3 kPa 10.13 kPa 14000 873 K, 2700s o Cu2S
1.01 kPa O2
Fraction of weight loss

0.4 5.07 kPa 12000

cps, arbitrary
10000 * *
0.3 o o o
o
8000
Δ
1.01 kPa (D) Δ
0.2 6000 Δ CuO
898 K, 900 s + CuO*CuSO4
4000 21.3 kPa
0.1 + + + Δ
2000 Δ + Δ Δ
T = 773 K ΔΔ

0.0 0
10 20 30 40 50 60 70
0 500 1000 1500 2000 2500 3000 3500 4000
2Theta, deg
Time, s
Fig. 6—XRD results obtained for samples corresponding to the sec-
Fig. 4—Influence of partial pressure of oxygen on the rate of enarg- ond and third stages of enargite oxidation.
ite oxidation.

shown in Figures 5 and 6. Figure 5 shows two XRD

lower than 723 K (450 °C) the second and third stages
of enargite oxidation do not occur appreciably, as
shown by the flattening off of the curves at approxi-
mately 0.4 value.
C. Effect of Oxygen Concentration
The experimental results concerning the effect 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 figure that a higher oxygen concentra-
tion in the gas phase produced a significant increase on
the rate of weight loss of enargite; a similar effect 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
spectrums A and B obtained at 873 K (600 °C) and
1.01 kPa of oxygen for reaction times corresponding to
the first stage. Spectrum A (for 150 seconds) shows
strong diffraction peaks for enargite and tennantite and
very weak peaks for chalcocite, whereas spectrum B (for
1400 seconds, time near the end of the first 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
O2, and 2700 seconds, and 898 K (625 °C), 21.3 kPa O2,
and 900 seconds, respectively. Spectrum C corresponding
to a sample in the second stage of oxidation shows
diffraction lines for Cu2S and Cu2O, whereas spectrum D
indicates the formation of CuO and basic copper sulfate
(CuO*CuSO4) in the third stage.
These results suggest that in the first stage of reaction,
the oxidation of enargite (Cu3AsS4) proceeds through
the formation of tennantite (Cu12AsS13) as an interme-
diate compound that subsequently forms solid chalco-
cite (Cu2S). The absence of condensed arsenic
compounds other than tennantite in the first 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

1122—VOLUME 43B, OCTOBER 2012 METALLURGICAL AND MATERIALS TRANSACTIONS B

(Cu2O), 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 Cu2O occurred to produce tenorite (CuO), or
mixtures of CuO and CuO*CuSO4, 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: 4Cu3 AsS4 ðsÞ þ 13O2 ðgÞ
¼ 6Cu2 SðsÞ þ As4 O6 ðgÞ þ 10SO2 ðgÞ ½6
Second stage: 6Cu2 SðgÞ þ 9O2 ðgÞ
¼ 6Cu2 OðsÞ þ 6SO2 ðgÞ ½7
Third stage: 6Cu2 OðsÞ þ 3O2 ðgÞ ¼ 12CuOðsÞ ½8a
A small fraction of the Cu2O oxidizes to basic copper
sulfate by the following alternative reaction:
6Cu2 OðsÞ þ 6SO2 ðgÞ þ 6O2 ðgÞ ¼ 6CuO  CuSO4 ðsÞ
½8b
The main overall reaction is the sum of Reactions [6]
through [8] given as Reaction [9]:
4Cu3 AsS4 ðsÞ þ 25O2 ðgÞ ¼12CuOðsÞ + As4 O6 ðgÞ
þ 16SO2 ðgÞ ½9
This reaction mechanism is consistent with the results
of the XRD analysis and also with the experimental
weight loss fractions observed for the first and second
stages and the weight gain fraction of the third stage.
Hence, in the first 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 first
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 Cu2O (first 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, confirming the stoichiom-
etry of the reactions. In the range 723 K to 898 K
(450 °C to 625 °C), the final 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*CuSO4 by the alternative Reaction [8b]
in addition to copper oxide. At temperatures lower than
723 K (450 °C), only the first 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 identified during the first stage of
reaction, the enargite particles must decompose to
METALLURGICAL AND MATERIALS TRANSACTIONS B
tennantite first with the release of sulfur, which diffuses
as a gas to the surface of each of the particles where
oxidizes to SO2. Subsequently, tennantite reacts to
chalcocite, releasing arsenic and sulfur (presumably as
arsenic trisulfide), which oxidizes and is evolved as
As4O6, 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 difference 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 PO2 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
figure, 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
0.5
O2, 873 K
Fraction of weight loss
0.4
0.3 O2, 773 K
N2, 873 K
0.2
0.1 N2, 773 K
0.0
0 500 1000 1500 2000 2500 3000 3500 4000
Time, s
Fig. 7—Comparison of enargite behavior in pure nitrogen atmo-
sphere and nitrogen-oxygen atmosphere (5.07 kPa O2).
VOLUME 43B, OCTOBER 2012—1123
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
first 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
first stage:
4Cu3 AsS4 ðsÞ þ 3O2 ðgÞ ¼ Cu12 As4 S13 ðsÞ þ 3SO2 ðgÞ
½10
Cu12 As4 S13 ðsÞ + 10O2 ðgÞ
= 6Cu2 SðsÞ + As4 O6 ðgÞ + 7SO2 ðgÞ ½11
4Cu3 AsS4 ðsÞ + 13O2 ðgÞ ¼ 6Cu2 SðsÞ þ As4 O6 ðgÞ
þ 10SO2 ðgÞ ½6
Reaction [6] proposed for the first 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 significantly 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 affect drastically the
rate of oxidation. Furthermore, for efficient 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 sulfide 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
dX1 1 dW
¼ ¼ k1 ½12
dt W1stg dt
or
X1 ¼ k1 t ½13
with
X1 ¼ ðWo  WÞ=W1stg ½14
In these equations, X1 is the fractional conversion for
the first stage, k1 is the apparent rate constant, Wo is the
initial weight of the enargite sample, W1stg is the
theoretical weight loss of the first 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
Ea
k1 ¼ ko eð RT Þ ðPO2 Þm ½15
where ko is the preexponential factor, Ea 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 PO2 .
Therefore, according to Eq. [13], a plot of fractional
conversion vs time should give a straight line with the
rate constant k1 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 figure are shown in Table II. A similar approach
was followed for the experimental results concerning the
effect 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
lnPO2 . 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
1.0
Fractional Conversion

0.8
and chalcocite is the final solid product. In contrast, in
PO = 5.07 kPa
nitrogen atmosphere the elimination of arsenic is very 2
0.6 Experimental data
slow at these low temperatures (less than 723 K 648 K
[450 °C]). 673 K
0.4 723 K
773 K
823 K
0.2 873 K
E. Oxidation Kinetics 898 K
As discussed, the first stage reaction (Reaction [6]) is Linear fit
0.0
the relevant reaction for the elimination of the toxic 0 1000 2000 3000 4000 5000 6000 7000
arsenic from enargite. Because the first stage reaction Time, s
occurs at a constant rate, the kinetics can be analyzed by
the following rate equation: Fig. 8—Kinetics of the enargite oxidation in oxidizing atmosphere.

1124—VOLUME 43B, OCTOBER 2012 METALLURGICAL AND MATERIALS TRANSACTIONS B

 Table II. Rate Constants for the First Stage of Enargite –5
Oxidation
–6
T [K (°C)] 1000/T (1/K) k1 –ln k1
648 (375) 1.543 1.67E04 8.697
–7
673 (400) 1.486 2.59E04 8.259 Ea = 44 kJ/mol
723 (450) 1.383 4.61E04 7.681

ln k1
773 (500) 1.294 8.00E04 7.130 –8
823 (550) 1.215 1.15E03 6.768
873 (600) 1.145 1.42E03 6.557
–9

1.0 5.07 kPa –10

1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7
–1
1000/T, K
0.8 10.13 kPa
Fig. 11—Arrhenius plot for the arsenic elimination from enargite.
0.6 1.01 kPa O2
ln kapp

21.28 kPa
0.4 Based on the experimental weight loss/gain curves
and XRD analysis of partially reacted samples, it was
0.2 concluded that enargite oxidation occurred in three
sequential stages according to the following reactions:
T = 773 K
0.0 First stage: 4Cu3 AsS4 ðsÞ + 13O2 ðgÞ
0 500 1000 1500 2000 2500 3000 3500 4000
Time, s = 6Cu2 SðsÞ + As4 O6 ðgÞ + 10SO2 ðgÞ

Fig. 9—Dependence of the enargite oxidation rate on the partial

pressure of oxygen. Second stage: 6Cu2 SðgÞ + 9O2 ðgÞ
= 6Cu2 OðsÞ + 6SO2 ðgÞ
–5

Third stage: 6Cu2 OðsÞ + 3O2 ðgÞ = 12CuOðsÞ

–6
Thus, the first stage corresponds to the elimination of
arsenic and the formation of chalcocite, the second stage
Slope = 0.9
corresponds to the oxidation of chalcocite to cuprite
ln k1

–7
(Cu2O), and the third stage corresponds to the oxidation
of cuprite to tenorite (CuO). The three sequential
–8 reaction stages occurred with constant rates that were
affected significantly by temperature and partial pressure
of oxygen. The kinetics of the first stage was analyzed by
–9
using the model X1 = k1t, which permitted the determi-
0 1 2 3 nation of the temperature dependence of the rate as well
ln PO2 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-
Fig. 10—Rate constants for the oxidation of enargite as a function
of the partial pressure of oxygen.
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
Figure 11, from which the activation energy for the temperature than inert roasting for a comparable rate
temperature range of 648 K to 898 K (375 °C to 625 °C) of arsenic elimination. A low partial pressure of oxygen
was determined as 44 kJ/mol. (5.07 kPa or lower) and a temperature of approximately
723 K (450 °C) are advisable for efficient elimination of
arsenic while avoiding the production of a calcine
containing copper oxides.
IV. CONCLUSIONS
The behavior of enargite in the temperature range of
ACKNOWLEDGMENTS
648 K to 898 K (375 °C to 625 °C) in atmospheres
containing variable amounts of oxygen has been studied This work was supported by the National Fund for
by thermogravimetric methods. The results can be Scientific and Technological Development (FONDECYT)
summarized as follows: of Chile under Project No. 1080296.

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 43B, OCTOBER 2012—1125

 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. 239–51.
3. S. Nakasawa, A. Yazawa, and F.R.A. Jorgensen: Metall. Mater.
Trans. A, 1999, vol. 30A, pp. 393–401.
4. A. Jokilaakso and S. Stromberg: Waste Characterization and
Treatment, W. Petruk, eds., SME, Littleton, CO, 1988, pp. 35–48.
5. C.L. Kusick and R.M. Nadkarni: Arsenic Metallurgy: Funda-
mentals and Applications, R.G. Reddy, ed., TMS, Warrendale, PA,
1988, pp. 37–349.
1126—VOLUME 43B, OCTOBER 2012
6. E.H. Smith and E. Paredes: Arsenic Metallurgy: Fundamentals and
Applications, R.G. Reddy, ed., TMS, Warrendale, PA, 1988,
pp. 145–60.
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. 225–35.
8. R. Padilla, Y. Fan, and I. Wilkomirsky: Can. Metall. Q., 2001,
vol. 40, pp. 335–42.
9. I. Mihajlovic, N. Strbac, Z. Zivkovic, R. Kovacevic, and M.
Stehernik: Miner. Eng., 2007, vol. 20, pp. 26–33.
10. L. Yaozhong and R.W. Smith: Miner. Process. Extractive Metall.,
2004, vol. 113, pp. C189–91.
METALLURGICAL AND MATERIALS TRANSACTIONS B