International Journal of Mineral Processing, 1 (1974) 141--149

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

S U L P H I D I Z I N G R E A C T I O N S IN T H E F L O T A T I O N O F O X I D I Z E D
C O P P E R M I N E R A L S , I. C H E M I C A L F A C T O R S IN T H E S U L P H I D I Z A T I O N
OF COPPER OXIDE

SERGIO CASTRO 1, JORGE GOLDFARB 1 and JANUSZ LASKOWSKI2

1Department of Physical Chemistry, University of Chile, Santiago (Chile)
2Laboratory of Mineral Processing, Department of Inorganic Chemistry and Metallurgy of
Rare Elements, Wroctaw Technical University, Wroclaw (Poland)*
(Accepted for publication October 25, 1973)

ABSTRACT

Castro, S., Goldfarb, J. and Laskowski, J., 1974. Sulphidizing reactions in the flotation of
oxidized copper minerals, I. Chemical factors in the sulphidization of copper oxide.
Int. J. Miner. Process., 1: 141--149.

The rate and extent of the heterogeneous reaction that takes place between dissolved
sodium sulphide and synthetic tenorite is studied for a wide range of sodium sulphide to
copper oxide ratios. Besidesthe sulphidization with the formation of a copper-sulphide
layer, a substantial oxidation of sulphide ions takes place at the surface of the solid. The
extent of both types of reactions is quantitized by combining specific analytical methods.
The results are discussed in terms of possible mechanisms and of their implications in
the sulphidization process applied in the flotation of oxidized copper ores.

INTRODUCTION

The activating effect o f soluble sulphides on oxidized minerals in the

x a n t h a t e f l o t a t i o n is o f i m p o r t a n c e because of its practical applications with
certain ores ( G l e m b o c k i et al., 1 9 6 3 ; Mitrofanov, 1967), especially with
oxidized lead (Fleming, 1 9 5 3 ) and c o p p e r (~er et al., 1 9 7 0 ) ores. In spite o f
its industrial i m p o r t a n c e , however, the n a t u r e o f the h e t e r o g e n e o u s reactions
t h a t m a y o c c u r b e t w e e n sulphide ions in solution and the surface o f oxidized
minerals has n o t y e t been established. This is especially true in the case o f
oxidized c o p p e r minerals where c o m p a r a t i v e l y little w o r k has been d o n e on
the s t u d y o f surface reactions, the f o r m a t i o n o f s e c o n d a r y p r o d u c t s and their
role in the f l o t a t i o n b e h a v i o u r o f these minerals (Wright and Prosser, 1 9 6 4 - -
1 9 6 5 ; A b r a m o v , 1 9 6 9 ; Castro et al., 1 9 7 2 ; S o t o and Laskowski, 1973). It is

*During this study Visiting Professor at the Department of Mining, University of Chile,
Santiago, Chile.
142

also known that when an excess of sulphides is added to puip, the activating
effect is lost (Fleming, 1953; Salam6 et al., 1972; Soto and Laskowski, 1973).
This is a serious drawback in the sulphidization process, since the optimum
dosage is highly dependent on the time of conditioning, procedures of mixing
and other variables, leading usually to poor reproducibility.
Extensive laboratory research appears to be needed in order to obtain
proper information concerning the mechanisms involved in the activation and
depression by soluble sulphides of oxidized copper minerals.
It was considered advisable to start with a pure and well-defined solid, so
as to avoid initially additional complexities arising from impurities and
peculiarities of natural minerals. In this context synthetic copper oxide presents
some advantages over malachite or chrysocolla. It may be easily obtained in a
chemically pure state, with a well-defined formula and crystalline structure
and also with a high specific surface, which facilitates adsorption measure-
ments. Moreover, since hydrated copper oxide is probably present on the
surface of copper carbonates, silicates and sulphides (Lekki and Laskowski,
1971), the conclusions obtained might be applicable to those substances.

EXPERIMENTAL METHODS

Materials

CuO of analar grade (Merck) was used throughout. X-ray examination has
shown that its crystalline structure corresponds to tenorite. The microscopic
photographs revealed that the sample contained fairly uniform particles. The
specific surface determined by means of the BET method yielded approxi-
mately 15 m2/g.

Rate and e x t e n t of the reaction

The heterogenous reaction was followed by a chemical analysis of the ions

remaining in solution after a given time of contact with copper oxide.
Known weights of copper oxide were placed in contact with standardized
sodium-sulphide solutions in glass stoppered flasks at room temperature
(15--18°C). The air inside the flasks was displaced by nitrogen. The contents
were mixed manually, so as to homogenize the system, and then left in
contact w i t h o u t stirring, unless otherwise indicated.
After given times of contact, the contents were filtered through Whatman
paper No.32 and the aliquotes of the filtrate were analyzed by one of the
following techniques.

Iodometric m e t h o d
The usual iodometric technique with iodine and thiosulphate was performed
by weighing the titrating solutions. In this way the accuracy could be increased
up to an error of less than 1% for 10 -4 normality.
 143

Colorimetric method
The methods of Fogo and Popowsky (1949) and Johnson and Hideo (1952)
for sulphide analysis was used. This involves the conversion of HS- (or H2S)
into methylene blue by coupling with p-dimethylaminoaniline. The blue color
was read in a 1-cm path Spectronic 20, Bausch and Lomb spectrophotometer
at 670 mp wave-length.
The method is reported to be specific for sulphide ions; it was found, how-
ever, that the presence of $2 032- or SO32- ions increased the time needed for
the appearance of the blue color. Accordingly all the readings were taken
60 min after the addition of reactives, since it had been found that in this
way the other ions did not interfere.

Thiosulphate ions
The thiosulphate present in solution was analysed by converting it into
thiocyanate (SSrbo, 1957) with a further addition of ferric ions. Ferric thio-
cyanate was analysed spectrophotometrically at 460 mp.

RESULTS

When the sulphidization reaction is studied by means of the iodometric

technique, the obtained results followed the pattern of the two examples
shown in Fig.1. It may be seen from this figure that after some time the
concentration of reducing ions is very low and it then increases with time
until it approaches a limiting value dependent on the initial concentration of
sulphide.

I
3o I
~o ci= g'10-3 N

1O:
u

O .4 8 12 !6 2Q 24 2B
Time, h

Fig.1. C o n c e n t r a t i o n of r e d u c i n g ions ( e x p r e s s e d as HS ) m e a s u r e d b y i o d o m e t r y as a
f u n c t i o n of t i m e o f c o n t a c t for various initial c o n c e n t r a t i o n s o f Na2S. E x p e r i m e n t a l
c o n d i t i o n s : 1 g of CuO in 50 ml of s o l u t i o n .

If curves such as those of Fig.1 were described in terms of a simple uptake

or adsorption by a solid, they would appear clearly anomalous. A large
portion of the sulphide ions would be initially adsorbed by the solid and
 144

afterwards the same ions would be given up or "desorbed" back into the
solution.
When the same solutions are analysed by means of the colorimetric
technique already described, no sulphide ions can be detected. Some typical
results, plotted in the form of adsorption kinetics, are shown in Fig.2. It may
be seen that the uptake or adsorption of HS- (or S 2-) ions is completed
(100%) in the first few minutes, as revealed by the colorimetric technique
(curve 1) and that no desorption is apparent. On the other hand, in the case
of the iodometric technique, the initial uptake is high but not complete and
decreases with time (curve 2); if the system is stirred continuously (curve 3),
the decrease in adsorption is much greater.

©
o.4o~
¢0 0.71

oJ

-o-2
E 035
i " E '~ Calorimetry ,,/l°d°metry
wl
I

~_ 0.30
_~ 0.2 ,>/z"

01~
t!
0.25 0 i'
0 20 40 60 80 100 120 140 '0 5 10 ~5 20
Time, rnin Final concentration of HS-, Cf.~O4N

Fig.2. Effect of t i m e on uptake of sulphide ions on CuO. Curve 1 : c o n c e n t r a t i o n s

measured b y the colorimetric m e t h o d ; curve 2: c o n c e n t r a t i o n s measured by the i o d o m e t r i c
m e t h o d ; curve 3: c o n c e n t r a t i o n s measured by the i o d o m e t r i c m e t h o d with mild c o n t i n u o u s
stirring. Initial c o n c e n t r a t i o n o f Na2S was 8 "10-3N.

Fig.3. Uptake o f sulphide ions on CuO versus final c o n c e n t r a t i o n in solution after 1 h o f

contact. Range o f initial c o n c e n t r a t i o n of Na2S was from 1 0 - 2 N to 1 0 - 3 N .

The discrepancy between the results obtained by the two techniques and
the anomalous shape of the adsorption curves 2 and 3 may be accounted for
by the type of ionic species detected by both these methods. The colorimetric
method is specific for sulphide ions, whereas the iodometric technique detects
also a number of other species, like $2032-, SO32-, thionates etc. On this
basis, the results of Fig.2 may be described in terms of a complete removal of
HS- and S 2- ions from the solution (curve 1) and of their conversion into
other oxidized sulphur ions which are given back to the solution at a rate
which is dependent on the agitation of the system (curves 2 and 3).
The same picture is obtained when the results given by both methods at a
 145

fixed time of contact (10 min) and varying initial concentrations of sodium
sulphide are plotted in the form of adsorption isotherms, as in Fig.3. It may
be seen that the concentration of HS- ions (and S2-) as detected by means of
the colorimetric method is always zero for this range of initial concentrations,
whereas in the case of the iodometric technique appreciable concentrations
of sulphur-bearing ions are present in the system.
Although attempts have been made to identify and to quantitate the
sulphur ions that may be present in the system, a satisfactory method was
found only for the case of $2032-. The results obtained by using the method
described in the Experimental Section are presented in Fig.4. The results are
plotted in the form of the amounts of $2032- found in solution for various
ratios of sodium sulphide against the weights of CuO. It can be seen that for
1 h of contact the amounts of $2032- are linearly related to the initial
sulphide/CuO ratio; moreover, since in these experiments the concentration
of Na2S was kept constant whereas the amounts of CuO varied, it results that
the extent of the conversion of HS- to $2032- is proportional to the amounts
of CuO present (or to its surface area). For 24 h of contact, the amounts of
$2032- are much larger, the difference being greater for higher HS- to CuO
ratios. In experiments which were performed in the absence of CuO, but
otherwise in similar conditions, no detectable amounts of $2032- could be
found even after 24 h.
The data presented in Fig.5 include a large number of experiments per-
formed with various initial concentrations of sodium sulphide and weights of
CuO, so that the proportions between the amounts of HS- and CuO are
changed in a very broad range up to a hundredfold. The points obtained with
the colorimetric method after 24 h of contact lay on a straight line with a 45 °
slope, indicating that all the sulphide ions are consumed by the solid up to
doses of 4 meq HS-/g CuO. The curve obtained with the iodometric method
after 24 h shows lower slopes than the former one and diverges increasingly
from it for high HS-/CuO ratios. For each ratio the difference between the

0 12

~o
6-

u
g
0.5 1.0 1.5 2.0 2.5 3.0
Initial concentration of HS~ meq/g CuO

Fig.4. E f f e c t of t i m e of c o n t a c t o n t h e a m o u n t of t h i o s u l p h a t e ions f o r m e d in a d s o r p t i o n
of Na2S o n CuO. Initial c o n c e n t r a t i o n of Na2S was 7.58 "10-3N.
146

c, 2

3-

E 2

Imtlal concentration of meq HS-/g CuO

Fig.5. Change in uptake of sulphide ions on CuO upon ratio of sulphide added to weights
of CuO. Curve 1 : points obtained by the iodometric method after 1 h of contact; curve 2:
points obtained by the iodometric method after 24 h of contact; curve 3: points obtained
by the colorimetric method after 24 h of contact.

two curves would r e p r e s e n t the a m o u n t s of sulphur ions o t h e r t h a n sulphide

which are present in the solution. The points o b t a i n e d with the i o d o m e t r i c
m e t h o d after 1 h o f c o n t a c t lie o n the same line as those o f 24 h f o r low HS-/
CuO ratios. A f t e r a ratio value o f 1.6, the curve flattens d o w n a b r u p t l y ,
indicating some sort o f saturation point. F o r ratios higher t h a n 1.6, sulphide
ions c o u l d be d e t e c t e d b y means o f the c o l o r i m e t r i c m e t h o d a f t e r 1 h o f
c o n t a c t . The change in slope m a y t h e n be ascribed to the presence o f excess
HS- ions which are neither adsorbed n o r oxidized in o n e hour.
At ratios higher t h a n 1.6, a brownish c o l o r a t i o n c o u l d be seen in t h e
solutions, which t h e n s h o w e d a m a r k e d T y n d a l l effect. When the solutions
were left standing for longer times, b o t h the color and the T y n d a l l e f f e c t
disappeared and a brownish s e d i m e n t a p p e a r e d in the flasks. This evidence,
t o g e t h e r with separate e x p e r i m e n t s which will be r e p o r t e d later (S. Garshva
and J. G o l d f a r b , u n p u b l i s h e d results, 1972), seem to indicate t h a t the brown-
ish c o l o r c o r r e s p o n d s to the f o r m a t i o n o f colloidal c o p p e r sulphide which is
p e p t i z e d in the solution.
T h a t CuS is f o r m e d in the system was c o n f i r m e d by X-ray d i f f r a c t i o n .
S o m e samples o f CuO were left in c o n t a c t with sulphide solutions with a ratio
greater t h a n t w o for 60 min. The solid was filtered o f f and t h e n washed,
dried in a v a c u u m and e x a m i n e d b y X-rays. The p a t t e r n s clearly s h o w e d the
presence o f CuS with a covellite structure.

DISCUSSION

The results p r e s e n t e d here m a y be discussed in t e r m s of the h e t e r o g e n o u s

r e a c t i o n taking place b e t w e e n sulphide ions in solution and solid c o p p e r
 147

oxide. The heterogenous reaction appears quite complex and various parallel
processes seem to take place in the system. At least three steps may be
distinguished, namely (1) adsorption of sulphide ions with the formation of
copper sulphide, (2) sulphide oxidation, and (3) desorption of oxidized
compounds according to the ion-exchange mechanism.
The adsorption of sulphide ions appears to be a very fast process. As
reported in the experimental section, in most cases the sulphide ions disappear
from the solution in the first three minutes; shorter times could not be
studied because of the time needed for homogenization, filtering off the CuO
and adding the reactants. The high rate of adsorption is probably due to the
high specific area of the solid used (about 15 m2/g). Very high rates of the
oxidation of sodium sulphide in the presence of galena have also been
reported by Mitrofanov (1967) and Plaksin and Eliseev (1967).
Subsequently to physical adsorption the sulphide ions may react with CuO
to form a copper-sulphide layer. The formation of a layer of copper sulphide
is of great importance in the activation by sodium sulphide in the xanthate
flotation of oxidized copper ores (Bowdish and Stahmann, 1967; Mitrofanov,
1967; Abramov, 1969; Castro, 1972b; Castro et al., 1972; Salam~ et al., 1972;
Soto and Laskowski, 1973).
As reported in the Experimental Section, covellite could be found in the
sulphidized solid by X-ray diffraction. The formation of copper sulphide
appears to be the main path of reaction at least for HS-/CuO ratios smaller
than 1.6, since about 80% of the added sulphide is not found in an oxidized
form in the solution. The process may not be a mere surface reaction, but it
could involve inner layers of the solid. On the basis of the BET specific surface
and 10 A 2 per HS- ion, the values of the number of monolayers of copper
sulphide may be estimated. For an uptake of 1.5 meq HS- per gram of CuO,
i.e., at the inflection point in Fig.5, a value of approximately 10 monolayers
has been found.
The process of sulphide oxidation may take place either through oxidation
of physically adsorbed HS- ions or through oxidation of the copper sulphide
layer formed as described above. Copper sulphide, as well as other sulphides,
is subject to surface oxidation when dispersed in water (Alferova and Titova,
1969; Oestereicher and McGlashan, 1972; Soto and Laskowski, 1973). On
the other hand, a d s o r b e d H S - ions may be oxidized either by atomic oxygen,
produced in the reduction of cupric to cuprous oxide or through the reduction
of Cu ~ surface sites. The latter is thermodynamically possible as judged from
the oxidation potentials (Latimer, 1952).
In the present state of the problem little can be said about which of the
two is the favored path of reaction. Additional experiments on the rate of
oxidation of dissolved sulphide by covellite and chalcocite (Castro, 1972a;
S. Garshva and J. Goldfarb, unpublished results, 1972) are expected to yield
more information concerning the possible mechanisms.
Of the oxidized sulphur ions that may be formed in this process, only
$203 z- was detected and quantitized (Fig.4). Since the formed quantities
 148

amount only to a fraction of iodometric values, it must be assumed that

other sulphur anions like sulphite, polythionates, etc. may be present in the
system.
The sulphide oxidation process may be of considerable importance in flota-
tion with sulphidization because of two reasons.
(1) Since the excess HS- ions present in a solution act as a depressor, not
only for sulphide minerals but also for sulphidized ones, the oxidation process
may be a way of converting excess HS- ions into other species with a smaller
depressing activity as shown for the flotation of malachite (Soto and
Laskowski, 1973). Since in actual flotation systems the times of conditioning
are necessarily short, a fast rate of oxidation will be beneficial for the process,
whereas a slow rate will allow time for the depressing effect of sulphide ions.
(2) In the experiments reported here it may be seen that oxidation products
appear in the solution in the first few minutes of contact, especially so in
systems under agitation (Fig.2). In flotation conditions where air is bubled
through and the pulp is stirred, the oxidation of excess sulphide ions should
take place at higher rates.
The oxidized sulphur ions thus formed may have effects of their own in
the flotation process. Since, with the exception of sulphates, the other anions
are reducing agents, they might play a part, for instance, in the inhibition of
xanthate oxidation to dixanthogen. These and other effects are studied in
the second part of this report in relation with the flotation of malachite and
chrysocolla.

REFERENCES

Abramov, A.A., 1969. Role of sulphidizing agent in flotation of oxidized minerals.

Tsvetn. Metall., Izv. Vyssh. Uchebn. Zaved., 12(5): 7--13 (in Russian).
Alferova, L.A. and Titova, G.A., 1969. Study of the reaction rate and mechanism for the
oxidation of hydrogen sulphide, sodium hydrosulphide and the sulphides of sodium,
iron and copper in aqueous solutions by atmosphere oxygen. Zh. Prikl. Khim., 42:
192--196 (in Russian).
Bowdish, F.W. and Stahmann, W.S., 1967. A chemical mechanism for sulphidization of
chrysocolla. Trans. SME/AIME, 238 : 118--120.
Castro, S., 1972a. Thesis, University of Chile, Santiago.
Castro, S., 1972b. Adsorcion de xantatos sobre CuO. Minerales, Rev. Inst. Ing. Minas
Chile, 27(118): 12--16.
Castro, S., Leppe, A. and Goldfarb, J., 1972. Sulfidizacion de CuO en medio acuoso.
Minerales, Rev. Inst. Ing. Minas Chile, 27(118): 17--22.
Fleming, M.G., 1953. Effects of soluble sulphide in the flotation of secondary lead
minerals. In: Recent Development in Mineral Dressing. Inst. Min. Metall., Lond., p.521.
Fogo, J.K. and Popowsky, M., 1949. Spectrophotometric determination of hydrogen
sulphide. Anal. Chem., 21: 732--734.
Glembocki, V.A., Klassen, V.I. and Plaksin, I.N., 1963. Flotation. Primary Sources, New
York, Part VI, Ch. 4 (translated from Russian).
Johnson, C.M. and Hideo, N., 1952. Microestimation of sulfur. Anal. Chem., 24: 736--742.
Latimer, W.M., 1952. Oxidation Potentials. Prentice-Hall, Englewood Cliffs, N.J., 2nd ed.,
392 pp.
 149

Lekki, J. and Laskowski, J., 1971. On the chalcocite/solution interface at alkaline pH.
22nd Meet. CITCE, Dubrovnik.
Mitrofano~,, S.I., 1967. Differencial flotation. Izd. Nedra, Moscow, 2nd ed.
p p . 1 4 1 - - 1 4 2 , 4 6 3 - - 4 7 4 (in Russian).
Ostereicher, C.A. and McGlashan, D.W., 1972. Surface oxidation of chalcocite. AIME Ann.
Meet., San Francisco (preprint).
Plaksin, I.N. and Eliseev, N.I., 1967. Effect of non-sulphide minerals on the kinetics of
galenite flotation from sodium sulphide solutions. Tsvetnye Metally, 40(9): 35--38.
Salami, N., Goldfarb, J., Leppe, A. and Laskowski, J., 1972. Estudios de flotacion de
malaquita por sulphidizacion en medio acuoso. Minerales, Rev. Inst. Ing. Minas Chile,
27(118): 23--30.
~er, F., MacDonald, I.D., Whyte, R.M. and Hillary, J.E., 1970. Sulphydric flotation of
previously sulphidized oxide copper minerals of Nchanga Consolidated Copper Mines
Ltd. Rudy (Prague), 18: 167--174.
SSrbo, B., 1957. A colorimetric method for the determination of thiosulphate. Biochim.
Biophys. Acta, 23: 412--416.
Soto, H. and Laskowski, J., 1973. Redox conditions in the flotation of malachite with
sulphidizing agent. Trans. Inst. Min. Metall., Sect. C, 82: C153--C157.
Wright, A.J. and Prosser, A.P., 1964--1965. Study of the reactions and flotation of
chrysocolla with alkali xanthates and sulphides. Trans. Inst. Min. Metall., 74: 259--279.