In ternational Journal of Mineral Processing, 10 (1983 ) 113--129

113

Elsevier Scientific Publishing Company, Amsterdam -- Printed in The Netherlands

A KINETIC STUDY OF ENARGITE D I S S O L U T I O N I N A M M O N I A C A L

SOLUTIONS

S. GAJAM and S. RAGHAVAN

Department of Metallurgical Engineering, University of Arizona, Tucson, AZ 85721 (U.S.A.)

(Received July 7, 1982; accepted for publication August 25, 1982)

ABSTRACT

Gajam, S. and Raghavan, S., 1983. A kinetic study of enargite dissolution in ammoniacal
solutions. Int. J. Miner. Process., 10: 113--129.
The kinetics of dissolution of natural enargite in ammoniacal solution has been investigated. Unlike other copper sulfide minerals, the dissolution of copper from enargite is very
slow and only 60% of the copper is extracted after 24 hours. The rate of dissolution is
favored by high temperatures and high oxygen pressures. The experimental data seem to fit
an electrochemical mechanism.

INTRODUCTION
Many c o p p e r sulfide ores c o n t a i n arsenic in the f o r m o f the mineral enargite
(Cu3AsS4). P r e c o n c e n t r a t i o n o f ores c o n t a i n i n g enargite by f r o t h f l o t a t i o n
t e c h n i q u e s invariably c o n c e n t r a t e s enargite along with the o t h e r c o p p e r sulfides. H y d r o m e t a l l u r g i c a l t r e a t m e n t o f such c o p p e r c o n c e n t r a t e s f o r the rec o v e r y o f c o p p e r will be i n f l u e n c e d b y the relative dissolution rates o f the various c o p p e r sulfide minerals. Because available i n f o r m a t i o n on the h y d r o m e t a l lurgical t r e a t m e n t o f enargite is scarce, it was decided to investigate the dissolution o f enargite in a m m o n i a c a l solution u n d e r o x y g e n pressure. In particular,
this investigation was directed t o w a r d s elucidating the kinetics of dissolution
o f enargite in a m m o n i a c a l solutions and then suggest o p t i m a l c o n d i t i o n s for its
dissolution.
BACKGROUND AND LITERATURE REVIEW

Crystal structure o f enargite

Enargite (Cu3AsS 4) has an o r t h o r h o m b i c crystal s t r u c t u r e with each arsenic
or c o p p e r a t o m being s u r r o u n d e d b y f o u r sulfur a t o m s at the corners o f a
nearly regular t e t r a h e d r o n , and each sulfur a t o m being similarly s u r r o u n d e d
by a t e t r a h e d r o n of o n e arsenic a t o m and three c o p p e r a t o m s (Pauling and

0301-7516/83/$03.00

1983 Elsevier Science Publishers B.V.

114
Weinbaum, 1930). The AsS4 groups are discrete and do not share any sulfur
atoms with one another. The atomic arrangement for enargite is shown in
Fig. 1. The entropy and enthalpy of formation of enargite have been reported
to be 85.17 cal/deg and - 4 2 . 7 8 kcal/mole respectively (Knight, 1977).

aJ I

~c

Fig. 1. Crystal structure of enargite (after Pauling and Weinbaum, 1930).

Previous work on the hydrometallurgical processing of enargite

Hydrometallurgical treatment of enargite has not received much attention
do date. Ehrlich (1964) conducted a brief study of the bacterial leaching of
enargite. Dutrizac and MacDonald (1972) investigated the dissolution of synthetic enargite in acidified ferric sulfate solutions, which presumably takes
place according to the following equation:
Cu3AsS4 + 1 1 F e 3+ + 4 H 2 0

~ 3 C u 2+ + A s O ~ - + 4 S + 8 H + + 1 1 F e 2+ (1)

They found that copper and arsenic dissolve at approximately the same rate
and that the residual solid is not substantially depleted of either element.
From their experimental results they concluded that the dissolution process in
the temperature range 60--95C was controlled by a surface chemical reaction.
The rate of copper dissolution was found to increase with the 0.55 power of
the ferric ion concentration and 0.20 power of the hydrogen ion concentration.

115
Kuhn et al. (1974) investigated the dissolution of copper concentrates containing different copper sulfides in ammoniacal solutions under conditions of
intense agitation. This process, known as the Arbiter process, was designed to
improve the extraction rates by removing the surface products that might
form during the leaching reaction. They found that in ammoniacal solutions
under low oxygen pressure (5 psi), enargite exhibits the slowest reaction in
comparison to other copper sulfides. The extractability of copper from different sulfides was found to follow the order:

Cu2S > CuS > CusFeS4 > CuFeS2 > CuaAsS4

Enargite leachingin ammoniacalsolutions can be represented by the following equation:
Cu3AsS4 + 13NHa + 8.75 02 + 2.5 H20 ~ 3Cu(NHa)~+ + NH4H2AsO4 +
+ 4SO~- + 2H+

(2)

According to eq. 2, enargite dissolutionin ammoniacalsolutions will result in

substantial arsenic accumulationin the pregnant solution. This important
feature must be borne in mind in devisingschemes for the recovery of copper
from pregnant solutions obtained from an enargite leachingprocess.
EXPERIMENTAL MATERIALS AND METHODS

Experimental materials
The enargite sample used in the investigations was donated by Hussein
Salek of the Anaconda Research Center in Tucson. The enargite sample was
crushed and ground in a porcelain m or t a r and pestle and sieved into various
sized fractions, The chemical analysis of the different size fractions used in the
investigation is tabulated in Table I.
The p u r ity of the enargite sample was tested using an X-ray diffractometer.
The peaks obtained in the X-ray diffraction pattern are summarized in Table II
The data in this table indicates the presence of arsenopyrite and chalcocite in
the sample.
Reagent grade (NH4)2SO4 and NH4OH (58%) were used to make the leach
solutions. Sodium h y d r o x i d e and sulfuric acid were used for pH adjustment.
TABLE I
Chemical analysis of different size fractions of enargite
Particle size (mesh)

Cu (%)

As (%)

Fe (%)

Ag (oz/ton)

100 150
150 270
270 400

15.82
28.15
30.07

10.5
13.12
17.2

15.5
12.2
15.0

0.72
1.23
1.63

116
T A B L E II
X-ray d i f f r a c t i o n analysis o f t h e enargite s a m p l e
d (A)

Expected mineral

3.3510
3.2090
3.0686
2.8400
2.7063
2.2116
1.8519
1.7277
1.6079

Cu=S
Cu3AsS 4 a n d CusS
Cu3AsS" a n d Cu2S
FeAsS a n d Cu3AsS 4
F e A s S a n d Cu=S
Cu3AsS 4 a n d Cu=S
Cu3AsS 4 a n d FeS=
Cu3AsS 4
Cu3AsS ,

Experimental methods
The leaching reactions were conducted in a 1-gallon stainless steel reactor
made by the Bench Scale Equipment Company. The speed of the reactor
shaft was measured with a frequency counter. Temperatures higher than the
ambient temperature were obtained by: {1) a heating jacket surrounding the
reactor; and (2) an internal coil through which water at a given temperature
can be circulated. The water to the cooling coil was supplied by a Forma
scientific, 7-gallon, constant-temperature bath.

= variable speed drive

F1

= inside filter

F2

outside filter

M
Q

= thermometer

= reactor

TB

= torque

meter

- constant

temperature

bath

= venting valve

= heating jacket

TB
iv . . . .

Fig. 2. S c h e m a t i c diagram of t h e r e a c t o r set-up.

117

A schematic sketch of the reactor setup is shown in Fig. 2. In a typical experimental run, the reactor was charged with 2000 cm 3 of a solution containing NH4OH and (NH4)2SO4 in a predetermined ratio. The reactor was then
sealed and heated to the required temperature. Once the required temperature
was reached, 1 gram of a given size fraction of enargite was added to the leach
solution and the system pressurized to the required value. Agitation was then
started and samples were taken at regular time intervals for copper and arsenic
analysis by atomic absorption spectrophotometry.
EXPERIMENTAL RESULTS AND DISCUSSION

The possibility of mass transfer through the boundary layer around particles being the rate-controlling step in the leaching reaction was first investigated by conducting experiments at different degrees of agitation. Three different agitation speeds, namely, 1000, 750, and 500 rpm were chosen for the
investigations. The conditions and results of these experiments are displayed
in Fig. 3. It can be concluded from the data in this figure that increasing the
speed of rotation within the range investigated produces no significant improvement in the rate of extraction.
Valuable information on the leaching reaction can be obtained by changing
the reaction temperature and by calculating the activation energies from the
leaching data. The leaching of 150 X 270-mesh enargite was investigated at
60

E~RG I TE
TEMPERATL~I
82 c'
OXYGEN I~5~JRIE* 50 PSIG
TOTAL AMMONIA CO~I 0.]04a MOLES

50

PHt

1o

PARTICLE SIZEI 150X270 I~E~,,H

SI~EED

40

Z~
o

,b,
o

1000 RPM

500 R ~

/
_ /

750 ~

c
o
L
~

30

CZ

D-

2O

1,

2.0

30

40
Time,

50

60

70

80

9.0

HRS

Fig. 3. Leaching of 150 270 mesh enargite at different agitation speeds.

118
60
56

ENARGITE
OXYGEN P~S~z
50 P S I G
T O T A L API~C]~QIA CC)NCz 0 . 3 0 4 ~

52

PHI

MOLES

10

S,PEED~ 1o00 ~ M
PARTICLE SIZE: 150X2Z0 N'II:SH
TEMPERATURE
O 0
3 0 C"
D ~'~
55 c"

48

44

A~ .~.

7oc"

-4~-@--- 82 C"

36

5_
u~ 32
x

28

~ 24
0
U
2O

16
12

10

20

30

40

SO

60

70

80

90

100

110

120

Time, HRS

Fig. 4. Leaching of 150 x 270 mesh enargite at different temperatures.

temperatures of 30, 55, 70 and 82C at a rotation speed o f 1 0 0 0 rpm, an
o x y g e n pressure of 50 psi, and a pH value o f 10. The results obtained are
s h o w n in Fig. 4. A striking observation that can be made from Fig. 4 is that
the rate of extraction o f copper from enargite increases significantly with an
increase in temperature. From the extraction versus time data obtained at
these four temperatures, calculation of activation energy for the leaching reaction was made using the f o l l o w i n g equation:
d(ln k)
dT

E
RT 2

where k is the initial reaction rate, E is the activation energy, T is a reaction

temperature, and R is the gas constant. A plot of log k vs. ( l / T ) is s h o w n in
Fig. 5. The activation energy calculated from the slope of the plot is approximately 4.5 kcal/mole. It s h o u l d be m e n t i o n e d at this p o i n t that this value for
activation energy is considered l o w w h e n a chemical reaction is the ratecontrolling step in the leaching process.
If the times for 24% extraction are used for the rate calculations, the activation energy is a p p r o x i m a t e l y 14 kcal/mole. This probably indicates that the

119

~Tf
I

2.5Lo
23!-

,e

\,

E =45

21 L

Kcal / m o l e

\
19~

17

1.5

\
13 - - - 28

I
29

__._ I
30

__
I/T

_A
31
32
x 103 (K -1)

__~J~J~
33

34

Fig. 5. Arrhenius plot for enargite dissolution.

copper release during initial and later stages may be from two different
minerals. Since chalcocite is known to dissolve quite readily and rapidly in
ammoniacal solutions, the initial rate may be slightly influenced by the rate
of copper release from chalcocite.
The oxidative dissolution of enargite in ammoniacal solutions takes place
by transfer o f arsenic from the lattice to the solution as arsenate and the
transfer of sulfur from the lattice to solution as sulfate. As depicted in eq. 2,
oxygen is essential to the leaching reaction. Hence, it was decided to investigate the role o f oxygen pressure in the kinetics of the leaching reaction. The
oxygen pressure was varied between 5 and 50 psi during the leaching of
150 X 270-mesh enargite particles at a t em p erat ure of 82C and a pH of 10.
The results obtained are shown in Fig. 6. It can be discerned from this figure
that the rate o f dissolution increases with an increase in oxygen pressure. The
data in Fig. 6 are replotted in Fig. 7 as (initial) rate of extraction versus square
r o o t of partial pressure of oxygen. The slope of this plot is close to one, indicating th at the rate of leaching reaction is proportional to the square r o o t of
oxygen partial pressure. As will be discussed later, this feature strongly indicates that the leaching takes place by an electrochemical mechanism.
The leaching process is likely to depend on n o t 0nly the total ammonia concentration but also on the ammonia-ammonium ion ratio (and hence the pH)
of the leach solution. Experiments were carried out at pH values of 8.5, 9.4,
10, and 11, with the total ammonia concent rat i on maintained at a fixed value
of 0.3044 moles. The results of these experiments, which are given in Fig. 8,
show that a pH value of 10 yields the best extraction. Increasing the pH above
10 decreases the extraction of copper from enargite.

120
60
56
ENARGITE
TE~PERATLIREI 82 C
TOTAL AMIMC)NIA COb~21 0 . 3 0 4 4 NIUI_ES

52

PHI

1o

SPEEDz i000 RPM

PARTICLE S I Z E I 1 5 0 x 2 7 0 MESH
OXYGEN PRESSURE

48

44

5O PSIG

--

5 PSIG

4o

X
c 3~
_o
u

~ 32

o
u 24
20

10

20

30

40

50

6,O

70

8.0

90

10.0

110

120

T i m e , HRS

Fig. 6. Leaching of 1 5 0 x 270 mesh enargite at different o x y g e n pressures.

03~ /

ENAR6 I TE

03

150 ~< 2]0 MESH

2 C
IJH = 113

025
V

o2

z ~

011 j J

......
"
- J

005
10

20

_ J
30

40
~/~'

r__

50

60

70

, P SIG 1/2

Fig. 7. D e p e n d e n c e of rate o f extraction o f copper from 150 x 270 mesh enargite on

square root of o x y g e n pressure.

121
60
56

ENARGITE
TEMPERATLJREz 82 C"
OXYGEN PRESSUREI 50 PSIG
TOTAL AMMONIA COI~CI O.30G4 MOLES
SI:'EED= i000 RPM
PARTICLE SIZE~ 150X270 MESH
PH
O O
10

52
48

44

4C

s5

E 3e
v
L

~a 3~

o 2~

c.

~ 24
aa 20
0
O
16

10

20

40

60

70

90

10.0

11.0 120

Ti m e , HRS

Fig. 8. L e a c h i n g o f 1 5 0 x 2 7 0 m e s h e n a r g i t e a t d i f f e r e n t p H v a l u e s .

Free ammonia and a m m o n i u m ions are consumed during the leaching process by conversion of Cu to copper ammine complexes. Hence, it is likely that
the rate of leaching reaction, if chemically controlled, would depend on the
total ammonia concentration. To investigate this, experiments were carried
out with 150 X 270-mesh samples at total ammonia concentrations of
0.1522 moles, 0.3044 moles and 0.6088 moles. The results of these tests are
presented in Fig. 9. This figure indicates that increasing the total ammonia concentration above a value of 0.3044 moles does not improve the rate or the extent of extraction. However, a decrease in the total ammonia to a value below
0.3044 moles decreases the rate as well as the e x t e n t of extraction of copper
from enargite. It should be pointed out that most of the experiments were conducted at a total ammonia concentration of 0.3044 moles.
Particle size plays a key role in the rate of dissolution of particulates. The
rate of dissolution of c oppe r from enargite was investigated with enargite
samples o f 100 X 150 mesh, 150 X 270 mesh, and 270 X 400 mesh. The results o f experiments carried out with these three samples are presented in
Fig. 10. As is obvious from these data, a decrease in particle size enhances the
rate and e x t e n t of extraction of copper from enargite. For example, at the end

122
56

52

ENARGITE

TEMPERATUREI 82 C"
OXYGEN PRESSL.FRE: 50 PSIG
PH: 1o
SPEED= 1ooo R P M
PARTICLE SIZE~ 150X270 MESH
TOTAL AMMONIA CDNC
[~ O
0.6088 MOLES
O
O
o, 30~4 MOLES
~
0, 1522 MOLES

48
44

4c
Y
E
o
~'
u

3e
32

(_

2~

X 24

o
(J

2C

16

10'

2 i0

3 ~0

4 I0

5'0

. . 8. 0 .
7.0

6 I0

90

10,0

11'0

90

100

110

120

T i m e , HRS
60
ENARGITE

56

TEMPERATURE: 82 C'
OXYGEN PRESgJRE: SO PSIG
TOTAL. AMMONIA CONC: 0.3044 MOLES

52

PHI ]o
SPEEDI 1000 RPM
MESH SIZE
~-(~4~
CU (27ox~oo)

48

co.......

2~

u
e 44
L

CU (loox15o)
As ( 27ox4oo )

" 40

8
L

36

32

(3-

~- 2 a
u
24

20

16

12

10

20

30

40

50

6.0

T i m e , HRS

70

80

120

123
of 8 hours o f leaching time, o n l y 24% o f the c o p p e r is e x t r a c t e d f r o m the
100 X 150 mesh sample, whereas almost 51% o f the c o p p e r is e x t r a c t e d f r o m
the 270 X 400 mesh sample.
DISCUSSION
A r e c a p i t u l a t i o n o f some o f the results is p e r t i n e n t at this stage. These are:
(1) the rate o f the leaching reaction is p r o p o r t i o n a l t o the square r o o t o f
o x y g e n partial pressure; (2) the activation energy is a b o u t 4.50 k c a l / m o l e ;
and (3) the leaching rate is a f u n c t i o n o f particle size.
It is well k n o w n t h a t m a n y metal sulfides dissolve in o x y g e n a t e d ammoniacal solutions by an e l e c t r o c h e m i c a l m e c h a n i s m (Wadsworth and Miller,
1979). Hence, an i n t e r p r e t a t i o n o f the e x p e r i m e n t a l results will n o w be m a d e
in terms o f an e l e c t r o c h e m i c a l model. S o m e s u p p o r t for the e l e c t r o c h e m i c a l
m e c h a n i s m in this system exists in the finding t h a t the r e a c t i o n rate is prop o r t i o n a l to the square r o o t o f o x y g e n partial pressure.
Electrochemical mechanism for enargite leaching
The a m m o n i a o x i d a t i o n leaching o f enargite can be c o n s i d e r e d to take place
by t w o e l e c t r o c h e m i c a l reactions:
(1) Cu3AsS4 + 39 O H - ~ 3 Cu 2 + 19 H 2 0 + H A s O ~ - + 4 S O ~ - + 3 5 e -

(3)

( A n o d i c reaction)
(2) O2 + 2 H 2 0 + 4e- ~ 4 OH-

(4)

(Cathodic reaction)
T h e B u t l e r - V o l m e r e q u a t i o n can be used f o r the i n t e r p r e t a t i o n o f the kinetic data u n d e r these conditions. T h e general B u t l e r - V o l m e r c u r r e n t density equation for a half-cell r e a c t i o n is:
i = n F k c e x p ( [ 3 Z F E / R T ) - n F k c exp [ - ( 1 - [3)ZFE/RT]
where
F
k, k'
Z
T
E

is the F a r a d a y c o n s t a n t ,
are the rates for the anodic and c a t h o d i c directions, respectively, in the
absence o f a potential,
is the n u m b e r o f electrons transferred in the r a t e - d e t e r m i n i n g step,
is the transfer coefficient, or s y m m e t r y factor,
is the absolute t e m p e r a t u r e ,
is the m i x e d p o t e n t i a l o f the overall reaction,

Fig. 9. Leaching of 150 270 mesh enargite at various total ammonia concentrations.
Fig. 10. Effect of particle size on the kinetics of copper extraction from enargite.

124
R
--> <.._ is the gas constant,
= concentrations of the reacting species for the anodic and cathodic
C, C
directions,
= number of electrons.
n
Applying this equation to the anodic and cathodic reactions on enargite,
the following expressions can be written for the anodic current density (ia)
and the cathodic current density (ic).*
[/3aFE 1 _

ia = 35 F (OH-) ka exp L RT J

35 F (CU 2+) (HAsO~-) (SO~-) ka exp

ic = 4 F (OH-) kc exp

7-

LRT

[ - ( 1 - ~a) FE ]

(5)

RT

4 F (O2) kc exp

(6)

RT

If ia = -ie and assuming that both ia and ie fall within their corresponding
Tafel region, it can be shown that:
35F(OH-)kaexp

[----~

=4F(O2)keexp

RT

(7)

[ . - ( 1 - ~ c ) FE]

4F
exp k R T J

35 F (OH-) k a

(8)

By raising the two parts of (8) to the mth power where m = fla/(1 + ~a - Pc):

[[JaFE] m :
[ HaRE] =
J

exp e - ~ - -

[ 3~002i~_]--.~-k)~;
a

4(02)kc
k3~kaJ

~-~

(9)

]m
(9a)

Hence,

ia = 3

4(O2)kc

]m

F(OH-)ka [ 35-(-0-H -ka 2

(10)

or

ia = F ( 3 5 ( O H - ) k a } 1-m (4(O:)kc} m

(10a)

*Here it is assumed that reactions (3) and (4) are single-electron transfer reactions, i.e.

Z=I.

125
The rate of leaching is:
-dnMs
dt

ia
35F

(11)

where nMS is the number of moles of metal sulfide. For the special case of
the above equation reduces to:

Ha = ~c = 0 . 5 ,

-dnMs

2
_ _ [kakc(OH-)(O2 )]o.s
x/35

dt

(12)

If the proposed mechanism is valid, a plot of rate of leaching against: (1) (02)1~
at constant pH and (2) ( O H - ) 1~ at constant oxygen pressure should yield
straight lines. The plots for case (1) and (2) are shown in Figs. 7 and 11, respectively. The straight-line nature of these plots yields strong support for the
electrochemical mechanism.
03

025

0.2

T
0~5

01

0.0 E

/
i

?'
i

0 008

0016

0024

0032

0 040

O~H~

0048

~ M o l e 1/2 Lit - y 2

Fig. 11. Plot o f rate o f e x t r a c t i o n versus square r o o t o f h y d r o x i d e ion c o n c e n t r a t i o n at

c o n s t a n t o x y g e n pressure.

Leaching models
An attempt will be made at this stage to explain the role of particle size in
the leaching kinetics. The classical solid-fluid reaction model, namely the
shrinking-core model, can be invoked to explain the experimental data. The

126

shrinking-core model can be applied to particles of unchanging size as well as

to particles of decreasing size. The dependence of time needed to achieve the
same fractional conversion for particles of different but unchanging sizes on
particle size (r0) can be summarized as follows (Levenspiel, 1972):
(1) Time for a given percent of extraction ~ r0 1 . s to 2.0 for film diffusion
control.
(2) Time for a given percent of extraction ~ r02.0 for product layer control.
(3) Time for a given percent of extraction ~ r0 for chemical reaction
control.
For particles (> 10 pm) that change in size during the leaching process the
following relationships hold (Levenspiel, 1972):
(4) Time for a given percent of extraction = r03/2 for film diffusion control.
(5) Time for a given percent of extraction ~ r0 for chemical reaction control.
The above sets of relationships can be used to decipher the rate-controlling
step in the leaching process. It should be noted that the time for conversion
versus radius relationship is of the same functional form for a chemical reaction-controlled process. During the ammoniacal leaching of enargite, the
particle size is likely to decrease since copper, sulfur and arsenic go into solution.
10
100X150)
MESH

09

(150X200)

08

SLOPE = 1 . o

07

3
J
O6

05
7ox4oo1

MESH

0Z

03

i
17

1.6

i
1.8

i
19
Log

D ~ ~

Particle

i
2 0

i
21

2 2

D ;1':

saze

Fig. 12. Plot of t i m e for 25% c o p p e r e x t r a c t i o n versus particle size.

127
In Fig. 12 a p l o t o f t i m e f o r 25% c o p p e r e x t r a c t i o n f r o m particles of differe n t sizes is p l o t t e d as a f u n c t i o n o f particle size on a log-log scale. T h e slope of
this p l o t is v e r y close to o n e w h i c h strongly suggests t h a t a surface c h e m i c a l rea c t i o n is the r a t e - c o n t r o l l i n g step.
T h e r e is s o m e d i s c r e p a n c y b e t w e e n t h e A s / C u r a t i o in t h e p r e g n a n t s o l u t i o n
and the A s / C u r a t i o in t h e solid. F o r e x a m p l e t h e As/Cu ratio in the 270 X
4 0 0 m e s h size f r a c t i o n is 0 . 5 7 2 and t h e As/Cu ratio in the p r e g n a n t s o l u t i o n
o b t a i n e d b y leaching this solid is 0.24 as s h o w n in T a b l e III. R e m e m b e r i n g
t h a t t h e A s / C u r a t i o in p u r e enargite is 0.39 t w o c o m m e n t s can be m a d e
a b o u t the d i s c r e p a n c y .

TABLE III
Arsenic/copper ratio in solution from the dissolution of enargite. Conditions:
270 x 400 mesh enargite, pH = 10, temperature = 82C
Time (hr)

Cu (ppm)

As (ppm)

As/Cu solution

0:20
0:40
1:00
1:30
2:00
2:30
3:00
3:30
4:00
5:00
6:00
7:00
8:00
9:00

13
15
18
25
31
37
40
45
50
60
69
80
88
97

3
4
5
6
7
9
10
11
13
14
16
18
20
24

0.231
0.27
0.28
0.24
0.28
0.24
0.25
0.244
0.25
0.233
0.232
0.23
0.23
0.25

(1) T h e high As/Cu ratio in the solid indicates t h a t enargite is n o t the o n l y

a r s e n i c - c o n t a i n i n g m i n e r a l in the solid.
(2) T h e l o w value o f t h e As/Cu r a t i o in s o l u t i o n m a y arise f r o m t w o factors:
(a) Part o f t h e c o p p e r in s o l u t i o n c o u l d be f r o m a n o t h e r c o p p e r m i n e r a l in the
solid. This c o p p e r m i n e r a l is m o s t likely CusS, which is k n o w n to dissolve
readily in a m m o n i a c a l solutions. (b) T h e a r s e n a t e in s o l u t i o n m a y p r e c i p i t a t e
with iron f r o m i r o n - b e a r i n g sulfides f o r m i n g ferric arsenate, which will cause a
decrease in the r a t i o o f As t o Cu. K u h n et al. ( 1 9 7 4 ) o b s e r v e d t h a t if c h a l c o p y r ite is l e a c h e d a l o n g with enargite the level o f a q u e o u s arsenic r e p o r t i n g to the
p r e g n a n t s o l u t i o n can be m i n i m i z e d .
T h e sensitivity o f t h e leaching process t o s o l u t i o n p H deserves a c o m m e n t .
The E h - p H d i a g r a m f o r e n a r g i t e - N H 3 - w a t e r s y s t e m at 75 is given in Fig. 13.

128
1.8

1.8
ENARGITE/AMMONIA / WATER

14

75C

aCu(NH3)2+ , OCu++ = I

l aNH3

-...

,.0

~" ~l .~..~"
Cu+'|
~

06

SYSTEM

14

ONH4+ = l
1.0

kQS04-- = 0 . 5 ,

~" "
CuO

~"o.~m~"~,.

~
~- ~.

O6

Cu(NH3) 2

/..f ^~

0.2

q,.'?'~. ~ . r - - . .

oo ~

O0
-0.2

-06
-I.0

-I.0

-IN.

I0

12

14

16

1.4

pH

Fig. 13. Eh-pH diagram for the enargite-ammonia-water system at 75C.

It is interesting to note from this diagram that the only copper amine complex
that is stable at 75 is the cuprous diammine complex. This complex has a
very narrow stability region in the pH range 7--9. The experimental finding
that the best copper extraction occurs in the vicinity of pH 10 is a little hard
to explain from the Eh-pH diagram.

SUMMARY AND CONCLUSIONS

The oxidative dissolution of enargite in ammoniacal solutions exhibits a

half-order dependence on both the oxygen concentration and hydroxide concentration. The rate of dissolution increases with increase of temperature,
oxygen pressure, and a decrease in particle size. The apparent activation
energy for the leaching reaction is approximately 4.5 kcal/mole. Dissolution
is independent of stirring Speed in the range of 500--1000 rpm but is pHdependent. The optimum pH for dissolution is around 10. In the range of the
experimental conditions used only 60% of copper can be extracted from
enargite. The experimental data seem to fit an electrochemical model.

ACKNOWLEDGEMENT

S. Gajam wishes to acknowledge the financial support provided by the

University of Tripoli, Libya during the course of the work.

129
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