International Journal of Mineral Processing, 33 ( 1991 ) 275-290 275

Elsevier Science Publishers B.V., Amsterdam

Mechanisms of pyrite flotation with xanthates

Xiang-Huai Wang" and K.S. Eric Forssbergb

aDepartment of Mining Engineering, 230 Mining and Mineral Resources Building,
University of Kentucky, Lexington, KY 40506, USA
bDivision of Mineral Processing, Lule& University of Technology, S-951 87, Lule& Sweden
(Received April 10, 1990; accepted after revision April 26, 1991 )

ABSTRACT

Wang, X.H. and Forssberg, K.S.E., 1991. Mechanisms of pyrite flotation with xanthates. In: K.S.E.
Forssberg (Editor), Flotation of Sulphide Minerals. Int. J. Miner. Process., 33: 275-290.

Thermodynamic equilibrium calculations have been carried out for the Fe-S-X-CO]--H20
systems, where X denotes xanthates. The results were interpreted by means of dominance and
distribution diagrams to study the stability of Fe(III)-xanthate compounds under different
chemical conditions. Selected electrochemical studies on the pyrite/ethyl xanthate systems are
compared with the results obtained by flotation and infrared spectroscopic techniques, and are
correlated with the thermodynamic studies to elucidate the mechanisms involved in the flota-
tion of pyrite with xanthates as collectors. Contrary to previous studies, our studies show that
dixanthogen is not the sole species responsible for the flotation behavior of pyrite. The ther-
modynamic stability studies demonstrate that insoluble Fe(III)-xanthate compounds can be
formed under normal flotation conditions. The results of pyrite flotation with ethyl xanthate
indicate that the formation of ferric dihydroxy ethyl xanthate on pyrite surfaces can either im-
prove or deteriorate the floatability of pyrite, depending on the concentration of ethyl xanthate.
Good flotation can be obtained when ethyl xanthate ions and/or diethyl dixanthogen are co-
adsorbed on ferric dihydroxy ethyl xanthate sites. Electrochemical measurements in the pyrite/
ethyl xanthate systems show that the open-circuit potentials of pyrite electrodes in ethyl xan-
thate solutions are essentially independent of the solution pHs, and furthermore, are within the
stability regions of Fe(III)-ethyl xanthate compounds. This also indicates that the pyrite sur-
faces may be covered by Fe (III)-ethyl xanthate compounds. FTIR spectroscopic studies con-
firmed the formation of Fe (III)-xanthate compounds on the pyrite surfaces. The Fe (III)-xan-
thate compounds are strongly bonded to the pyrite surface. Above the Fe(III)-xanthate
compound layer, dixanthogens and xanthate ions are co-adsorbed probably as multiple layers.

INTRODUCTION

Pyrite is probably the most widely occurring sulfide mineral. It occurs in

association with other base-metal sulfide minerals as well as with coal. In most
cases, pyrite is a gangue mineral and should be removed from the associated
sulfides or coal to reduce its contamination of the valuable concentrate or to

0301-7516/91/$03.50 © 1991 Elsevier Science Publishers B.V. All rights reserved.

 ( H X X'~.XN(, .\NI } K S | t ¢ ~bISSBFR{ ;

reduce SOe emission to the atmosphere. The removal of pyrite has usually
been carried out by froth flotation. Pyrite is readily floatable with several types
of collectors: xanthates, dithiophosphates, fatty acids, etc. The xanthate type
is the most important and the most widely used collector of pyrite flotation.
Despite the importance of pyrite separation from other sulfides and coal, only
a comparatively modest amount of study has been devoted to the pyrite-xan-
thate flotation system in the absence of depressants and activators.
Mechanisms of adsorption of xanthate on pyrite surfaces have been the
subject of a number of studies. At present, a general conclusion is accepted,
namely dixanthogen is the only product of xanthate adsorption/reaction on
pyrite and is responsible for pyrite flotation, independent of solution and py-
rite surface conditions (Ball and Rickard, 1976: Finkelstein and Poling, 1977:
Woods, 1988). This extreme conclusion was based on the results of IR, UV,
flotation and rest-potential studies (Fuerstenau et al., 1968: Majima and Tak-
eda, 1968; Allison et al., 1972: Leppinen et al., 1988 ). The proposed process
is schematically shown in Fig. 1. It is generally believed that xanthate ions are
oxidized to dixanthogen through an electrochemical process via pyrite as a
catalyst.
However, the above theory cannot explain a number of phenomena ob-
served in the pyrite/xanthate flotation system. For example, a complete or
partial depression of pyrite flotation was observed at low xanthate concentra-
tions in the neutral pH range (Fuerstenau et al., 1968; Fuerstenau and Mishra,
1981 ); the surface charge of pyrite was reversed upon adsorbing xanthate spe-
A B

SpectroscopicTechniques:IR, FTIR, etc.

ElectrochemicalTechniques:CV, Rest Potential,etc.
ElectrokineticTechniques:Zeta-Potential
FlotationTechniques
Fig. I. Schematic presentation of the classical model of pyrite flotation with xanthates as
collectors.
MECHANISMS OF PYRITE FLOTATION WITH XANTHATES 277

cies (Fuerstenau, 1981; Fuerstenau and Mishra, 1981 ); and pyrite was well
floated at redox potentials far below the formation of dixanthogen (Trahar,
1983 ). These results suggest that there are some other reactions taking place
on the pyrite/aqueous interface and species other than dixanthogen might
have been formed/adsorbed on the pyrite surface.
A review of the published studies on the mechanisms of pyrite flotation
impressed upon us that some of the results should be regarded with great cau-
tion. First of all, as shown by Sheikh (1972) and Sheikh and Leja (1977),
the IR spectra of dixanthogen and ferric xanthates are quite similar. Purifi-
cation of ferric xanthate free of dixanthogen has been shown to be very diffi-
cult. Great care must be exercised in order to obtain pure ferric xanthate sam-
pies. However, it appeared that previous investigators (e.g., Fuerstenau et al.,
1968; Majima and Takeda, 1968; Allison et al., 1972; Leppinen et al., 1988)
made no attempts to characterize the IR spectra of true ferric xanthates when
IR techniques were used to study the product (s) of xanthate adsorption on
pyrite surfaces. Secondly, Fuerstenau et al. ( 1968 ) reported in their earlier
study that most of the pyrite particles strongly flocculated in the presence of
xanthate; the zeta potentials were thus measured on those panicles which re-
mained dispersed in the pulp. It is possible that these particles were least ac-
tive and no significant adsorption of xanthate occurred on their surfaces. Fi-
nally, on applying the "rest-potential theory", previous investigators (e.g.,
Allison et al., 1972 ) merely compared the open-circuit potential of pyrite with
the reversible potential of the xanthate/dixanthogen couple. Fe(III)-xan-
thate compounds in the systems were completely excluded from the system.
Some investigators went as far as stating that "the formation of ferric xan-
thate is not possible, unlike that of the other systems such as lead and copper
xanthates" (Finkelstein and Poling, 1977). These points could have been
misleading in studying the mechanisms of pyrite flotation with xanthates.
In this view, it is useful to investigate the pyrite/xanthate flotation system
in detail. An extensive study on the mechanisms of pyrite flotation with xan-
thate has thus been carried out using various techniques, including thermo-
dynamic stability calculations, FTIR, and electrochemical studies. In a pre-
vious paper, the stability of iron xanthate compounds in aqueous solutions
has been studied (Wang et al., 1989). It was found that Fe(III) xanthate
compounds play important roles in controlling the flotation behavior of py-
rite. In the present paper, the stabilities of the Fe (III)-xanthates in systems
containing carbonate and sulfur components have been studied. The prod-
ucts formed at the pyrite/xanthate interface have been determined by electro-
chemical and FTIR spectroscopic techniques. The possible mechanisms of
pyrite flotation with xanthates are discussed.
THERMODYNAMICEQUILIBRIUMCALCULATIONS
The thermodynamic equilibrium calculations were performed with the help
278 tI.X '/VAN(; 4,N[,~K.S.! I-:~)RSSBER(~

of the computer program SOLGASWATER (Eriksson, 1979 ). Except for the

amyl xanthate-bearing compounds, the stability constants of the species con-
sidered in this study have been presented in the previous papers (Wang et al..
1989; Wang and Forssberg, 1990). For the amyl xanthate compounds, the
stability constants were taken from the following references: Critchley and
Hunter ( 1986 ), Majima and Takeda ( 1968 ), Majima ( 1961 ), and Hamilton
and Woods ( 1981 ). The estimated solubility products for Fe (AX) 3( s ) and
FeOH(AX)2(s) (Wang, 1989) have been used in the present study, since no
determined solubility product values are available for the two compounds. In
this regard, the stabilities of Fe (AX) 3(s) and FeOH (AX) 2(s) established in
the present study cannot be considered as absolutely reliable. However, it was
found that the established stability diagrams are of great guiding value in pre-
paring the Fe(IIl)-amyl xanthate compounds. The calculation results were
presented in terms of dominant stability (pe-pH) diagrams and distribution
[log (concentration) vs. pe ] diagrams, where pe = - log (electron activity ).
The pe gives (hypothetical) electron activity at equilibrium and measures the
relative tendency of a solution accept or transfer electrons. High positive pe
values indicate a relatively strong tendency for oxidation, while high negative
pe value means strong tendency for reduction. The pe is related to the redox
potential, Eh vs. SHE, by the following equation:
EhF f Eh(mV) )
Pe=2.~~- 59 , at T = 2 9 8 . 1 5 K

where R---gas constant, T= temperature (K), F = Faraday constant.

EXPERIMENTAL

Electrochemical measurements

The open-circuit potentials of the pyrite/ethyl xanthate systems were mea-

sured in 0.1 M NaCIO4 solution using a pyrite electrode. The method of elec-
trode preparation, the chemical compositions of the pyrite electrode, and the
experimental set-up were described in detail elsewhere (Ahlberg et al., 1990 ).
No pH buffer was used in the present study in order to avoid possible com-
plications. The solution was purged with high purity nitrogen gas for 90 rain
before measurements were started. The potentials were measured against a
saturated calomel reference electrode (SCE) which potential is 0.245 V vs.
SHE. The potentials were reported with respect to SHE.
Potassium xanthates were purified as follows: xanthate was first dissolved
in acetone and the solution was filtered through 0.8/tm filter paper using a
Millipore apparatus. Diethyl ether was added into the filtrate solution to re-
crystallize xanthate. The solution was filtered and potassium xanthate was
MECHANISMS OF PYRITE FLOTATION WITH XANTHATES 279

obtained. This was repeated three times. The final purified xanthate was dried
and stored in a vacuum desiccator. All other chemicals were of AR grade.

Zeta potential measurements

100 mg of the fine pyrite fraction ( - 20/~m) was conditioned in a 100 ml

de-oxygenated solution for 15 min. The suspension was then left for 5 min to
allow coarse particles to sediment. The top suspension was then taken for zeta
potential measurements using a syringe. The zeta potential measurements were
effected with a Laser Zee Zeta-meter (Model 501, Penkem, Inc. ).

RESULTS AND DISCUSSION

Figure 2 shows the stability diagram of the dominant Fe-species in the Fe-
EX-H20 system at total concentrations of [ F e ] x = [ E X ] x = l . 0 × 10-3 M,
where the subscript T denotes total. The results are the same as presented
elsewhere (Wang et al., 1989). It can be seen that there is a considerably large
area in which Fe (III) ethyl xanthate compounds are stable. Ferric ethyl xan-
thate is stable and dominates in the acidic pH range of 2-5. Upon increasing
the pH value, the xanthate groups are gradually replaced by hydroxy groups.
In the weakly acidic pH range, ferric monohydroxo ethyl xanthate is formed,
while in neutral to weakly alkaline pH solutions, ferric dihydroxy ethyl xan-
thate is stable. Note that all these Fe (III) ethyl xanthate compounds are sta-
ble at potentials below and above the reversible potential of the E X - / X 2
couple.
10 590

5 295

03

-295 I.~
(o.),(-)

-10 4 10 12 -590
-Sg
pH
Fig. 2. pe-pH stability diagram of Fe-species for the Fe-EX-H20 system at
[Fe]x= [EX ]x= 1.0X 10-3 tool l-t.
 ~11 } I.X V~ \ N ( i ~,",i [ ) K . S . I , ~:( ) R S S B E R ( 3

The Fe-dominant stability diagram for the Fe-EX-CO3~ - H 2 0 system at total

concentrations of [ Fe ]-r = [ EX ]~ = [COq, ]~ = 1.0 × 10 ) ~1 is shown in Fig.
3. It can be seen that ferrous carbonate precipitates in weakh acidic to alka-
line pH solutions under reducing redox potentials. The stability of the Fe( III)
ethyl xanthate compounds is essentially not affected. These results suggest
that the presence of carbonate in the pyrite-xanthate flotation system will
have no profound influence on the flotation behavior of pyrite. However, this
is true only for a closed system. For an open system which is in equilibrium
with the atmosphere, the total carbonate concentration will be very high in
alkaline solutions. It has been shown that for an open-to-atmosphere system,
the total carbonate concentration is higher than 1.0 × 10- ' / I only when the
pH is above 8.5 ( S t u m m and Morgan, 1982). Therefore, it can be expected
that the stability area of ferric dihydroxy xanthate above pit 8.5 will be re-
duced. However, as shown in the previous paper (Wang et al., 1989), the
floatability of pyrite in the highly alkaline pH range is also determined by
dixanthogen, therefore it can still be concluded that pyrite flotation with xan-
thates will not be greatly affected by the presence of carbonate. This suggests
that in commercial pyrite flotation, adjusting pH by sodium hydroxide or by
soda ash will give no significant difference.
The dominant Fe-containing compounds for the Fe-EX-S-H20 and Fe-AX-
S-H20 systems are shown in Fig, 4 and Fig. 5, respectively. In constructing
Figs. 4 and 5, no "kinetic restriction" or "destabilization" was imposed on
sulfate or any other sulfoxy species. The systems are therefore considered as
thermodynamically stable systems. The results show that the stability of
Fe(III ) ethyl xanthate compounds is essentially not affected by the presence

t0- 590

FeZ-C--~ Fe(OH)3(s)

5 29s ~-
&
m

~_ o. o

-295 ILl

-10 --590
4 6 8 10 12
pH
Fig. 3. p e - p H stability diagram of Fe-species for the Fe-EX-CO3-H20 system at
[Fe]-r = [ E X ] T = [CO3]T = 1.0× 10 -3 mol 1-~ .
MECHANISMSOF PYRITEFLOTATIONWITHXANTHATES 281
lO 590

F."
F$(OH)eEX(s) 295

II) i,i
o o "I-
F_-S. u -~a tJ )

~ FeS=(s)
-5 ~ -,^..,,- -2~5 ~

-,o -o,o
10 12
pH
This Study: e EX'-O M • EX--1.0 mM
Ahmed (1978): EX-mO
Im M • EX--1.0 mM
Allison et o! (1972): ¢ EX--0.65 rnM
Mojirno & Tokedo (1968): • EX'-I.0 rnM to 10 rnM
PoUio & Bockris (1984): AEX--1,0 rnM and 10 rnM
Buckley et ol (1988): O EX-=0 bl

Fig. 4. pe-pH stability diagram of Fe-species for the Fe-EX-S-H20 system at

[FelT= [EXIT= [S]T= 1.0× 10 -3 mol 1-t, and open-circuit potentials of pyrite electrodes in
the presence of different concentrations of ethyl xanthate.

10 59o

5 295 ~'

5. ~ ~. -295L d

-,o , ~, , , , ~ , ~,~ . . . . . ,~," , -3,0

2 4 6 8 10 12
pH

Fig. 5. pe-pH stability diagram of Fe-species for the Fc-AX-S-H20 system at

[Fe]T= [AX]T-~- I S ] T = 1.0~( 10--3 mol 1-1.
2~-~ t t x , W'ANG ~NI) K.SE. Ff}RSSBERG

of a sulfur component. In the acidic pH range, both ferric ethyl xanthate and
pyrite are stable. Increasing the length of the hydrocarbon chain of xanthate
also increases the stability of Fe( llI) xanthates, as shown in Fig. 5. However,
the upper boundaries of the stability area of ferric amyl xanthates do not ex-
pand. This is because the equilibrium potential of xanthate/dixanthogen re-
dox reaction decreases linearly with increasing the length of the hydrocarbon
chain.
The above calculations demonstrate that the presence of carbonate a n d / o r
sulfur exerts insignificant effect on the stability of the xanthate-containing
compounds, therefore the following distribution diagrams for xanthate com-
pounds have been calculated for the Fe-EX-H20 system. Figures 6 and 7 show
the distribution of ethyl xanthate-bearing species as a function of pe (i.e. re-
dox potential) at total concentration of [ F e ] T = I . 0 X I 0 -~ M and
[ E X ] v = 2 . 5 × 10 `-5 M at pH 6, 8 and 9. It can be seen that at pH 6 and 8,
ferric dihydroxy ethyl xanthate is formed in the moderate oxidizing potential
range, while at pH 9, no ferric dihydroxy ethyl xanthate is formed at this xan-
thate concentration. However, if the ethyl xanthate concentration is in-
creased to 1,0 X 10- 3 M, then ferric dihydroxy ethyl xanthate is formed at pH
9, as shown in Fig 8. In all cases, the formation of diethyl dixanthogen is
favored only at fairly high potentials.
It is interesting to notice that the quantity distribution of ethyl xanthate ion
is different at different pH values under potential ranges where ferric dihy-
droxy ethyl xanthate is formed. The concentration of ethyl xanthate ion at pH
6 and 7 is much lower than that at pH 8 and 9. Similar results were obtained
(Wang et al., 1989). The formation of ferric dihydroxy ethyl xanthate and
distribution of ethyl xanthate ion are well correlated to the pyrite flotation
recovery. Ferric dihydroxy ethyl xanthate plays a dual role in pyrite flotation.
On one hand, ferric dihydroxy ethyl xanthate is not strongly hydrophobic and
so formation of such a compound on the pyrite surfaces will not render pyrite
hydrophobic. On the other hand, ferric dihydroxy ethyl xanthate could act as
good contact site for the attachment of ethyl xanthate ions a n d / o r diethyl
dixanthogen molecules to the surfaces of pyrite. If a significant amount of
xanthate ions or dixanthogen molecules are co-adsorbed, then good flotation
can still be obtained. The neutral pH depression/flotation p h e n o m e n o n re-
ported by Fuerstenau et al. (1968) and Fuerstenau and Mishra ( 1981 ) can
be well explained by the above proposed mechanisms.
Trahar ( 1983 ) conducted studies of pyrite flotation as a function of redox
potential at pH 8 in the presence of about 2.5 × 10 -5 M ethyl xanthate. The
results are presented in Fig. 7. It can be seen that pyrite flotation commences
at a potential which is much more negative than the reversible potential of
ethyl xanthate oxidation to diethyl dixanthogen. Thus, the flotation cannot
be attributed solely to adsorption of diethyl dixanthogen. Comparing the flo-
tation results with the distribution diagram of ethyl xanthate species, we can
MECHANISMS OF PYRITE FLOTATION WITH XANTHATES 283

O-
(a)
pH=6
EXt.¢=2.5* 10-~1
F e ~ - 1.0.10-~I

0
E -4- EX- Fe(OH)zEX(s) (EX)t(oq)
h/-----"
(~),0)
-6-
0
C.)
~n
0
HEX

-10 , , , , = ., ih ......
-10 -5 0 10
pe

O-
(b)
pH-9
-2' Fe~= 1.0.10"~1
E'X~=2-5*10 -=M
_~ -
0
~ -4- EX- (EX)~(aq)

d (EX),O)

--10~
--10
, , , , i
--5
. . . .

pe
i
0
/., 5

Fig. 6. log[conc]-pe distribution diagrams of EX-species in the Fe-EX-HzOsystem at

10

[FelT= 10.0× 10 - 3 mol 1-~ and [EX]T=2.5X 10-5 mol 1-t. (a) pH=5.0, and (b) pH=9.0.

clearly see that there is a very good agreement between the commencement of
pyrite flotation and the formation of ferric dihydroxy ethyl xanthate. There-
fore, the floatability at potentials lower than that of diethyl dixanthogen for-
mation might be due to the formation of ferric dihydroxy ethyl xanthate and
the co-adsorption of ethyl xanthate ions.
To verify if ferric xanthate compounds are formed on pyrite surfaces, elec-
trochemical studies were carried out. In the electrochemical studies, the open-
circuit potentials of a pyrite electrode were measured at pH 4, 7 and 11 in the
presence and absence of 1.0 × 10-3 M ethyl xanthate, respectively. It was found
that the open-circuit potentials of a freshly polished pyrite electrode shift neg-
 ,'-;4 II.X '~, ~.N~ ; , \ N ! ) K S . I Fq )RtqSBER(i

VVC'0 D L AvV N ~ Y ;~ "E:

t:
pH 8 Ii,
10 r"g KE: ~'
PPG L00 ~1, t
7:/~
Trahc~r [1983 j /
Z
- f},,3} t
z ]
~~ ",oiL tl

2 ~
$3

-500
I t ~__[__
L00 -300 -200 --100 0 100 200 300
I I I
~00 500
PULP PO'fENTIAL (mY vs SHE }

P. EX-
Fe(OH)2EX{s} (EX)2(aq)

.. { E X ) 2 ( I . ) ..
Ig

(D

~ 8
I

-lo .2_
[ .l__
-10 8 10
pe

Fig. 7. log [conc. ]-pe distribution diagram of EX-species for the Fe-EX-H20 system at pH = 8,
[ Fe ] V= 1.0 X 10- 3 mol 1- ~and [ EX ] V= 2.5 X 10- ~mol 1- ~, compared with the flotation recov-
cry of pyrite as a function of redox potential (Trahar, 1983 ).

atively and reach a steady state value in about five to ten minutes, depending
on the solution pH. The reproducibility was fairly good under the experimen-
tal conditions. The results are shown in Fig. 4. For comparison, the results
reported by Majima and Takeda ( 1 9 6 8 ) , Allison et al. (19721, A h m e d
( 1 9 7 8 ) , Bockris and Pillai ( 1 9 8 4 ) , and Buckley et al. ( 1 9 8 4 ) for the same
system have also been plotted in the diagram. In the absence of xanthate, the
open-circuit potentials obtained in the present study are considerably lower
than that reported by A h m e d ( 1978 ) but are fairly close to that o f Hamilton
and Woods ( 1981 ). The measured open circuit potentials of the pyrite elec-
MECHANISMS OF PYRITE FLOTATION WITH XANTHATES 285

pH=7
o7 EX~= 1.0.10"~
(a)

E:X- Fe(OH),~X(,) (Ex),(O

0
E (EX)t(aq)

-6-
0
.
cr~
o -s- H~

-10 , , , i , ,
-10 -5 0
pe
O- pH=9
Ib)
Fe~= 1.0.10-'~
EX~= 1.0.10-~

Ex- Fe(OH),EX(,) (E~)=(t)

-6
E -4.
ZX),(aq)

0
-6- \
0
v
E~
0
-- -8
\
-10 ,
-10 ' ' '25 ' ' ' 6 ' '~' 'ib
pe
Fig. 8. log[conc.]-pe distribution diagrams of EX-species for the Fe-EX-H20 system at
[Fe]T= 1.0× 10 -3 mol 1-~ and [EXIT= 1.0× 10 -3 mol 1-~. (a) p H = 7 and (b) pH=9.

trode are considerably more positive than the thermodynamic potentials,

which is in good agreement with previous studies (Chander, 1985). It was
observed that a thin iron hydroxide film is formed on the surfaces of the py-
rite electrode and the thickness of the film greatly influences the open-circuit
potentials of the system (Ahlberg et al., 1990; Buckley et al., 1988 ). In the
presence of 1.0 × 10-3 M ethyl xanthate, the open circuit potentials of pyrite
electrode fall into the stability regions of Fe(III) ethyl xanthates. Ahmed
( 1978 ) studied the open circuit potentials of pyrite electrode in the presence
of 2.0 × 10-3 M ethyl xanthate in an oxygen or nitrogen atmosphere. It is in-
teresting to notice that, in the absence of ethyl xanthate the open circuit po-
256 l-t.X WANG ANDK.S.E FORSSBERG

tentials of pyrite electrode in oxygen, air and nitrogen atmosphere are consid-
erably different, but in the presence of xanthate the open circuit potentials
are almost the same in nitrogen and oxygen atmosphere for all pH levels stud-
ied. Furthermore, there is almost no pH dependence of the open-circuit po-
tential of pyrite electrode in the presence of xanthate. Majima and Takeda
( 1968 ) studied the open-circuit potential of a pyrite electrode at pH 9 in the
presence of 1.0× 10 - 3 M to 5.0× 10 2 M ethyl xanthate. The open-circuit
potential decreases with increasing the xanthate concentration. As shown in
Fig. 4, the potentials are all within the stability region of Fe(OH)2EX(s).
Similarly, the mixed-potentials of pyrite/ethyl xanthate system reported by
Bockris and PiUai (1984) are quite close to that reported by Majima and
Takeda ( 1968 ) and Ahmed ( 1978 ). Allison et at. ( 1972 ) reported a value of
0.22 v vs. SHE for the "rest-potential" of the pyrite electrode at pH 7 in the
presence of 6.25 × 10 -4 M ethyl xanthate. This value, although much higher
than that reported by all other investigators, is still under the stability poten-
tials of ferric dihydroxy xanthate. Except for pH 11, the measured open cir-
cuit potentials of pyrite electrode in the presence of ethyl xanthate are within
the stability region of the Fe (III)-ethyl xanthate compounds. Furthermore,
all the measured open circuit potentials of pyrite electrode are lower than the
boundary potential above which liquid dixanthogen dominates. Therefore,
these electrochemical studies demonstrate that under normal flotation con-
ditions, the surfaces of pyrite are covered by an Fe (III) xanthate compound.
The formation of surface/bulk iron xanthates compounds on pyrite will
change the surface electrical properties. Zeta potential measurements were
thus performed to study the pyrite/xanthate system. However, it was found
that in the presence of 1.0 × 10-4 M or 1.0 × 10-3 M ethyl xanthate, the pyrite
particles were very strongly flocculated. This made the zeta-potential mea-
surement very difficult. Using sodium silicate to disperse the pyrite particles
was also unsuccessful. No illustrative results were obtained in the present
study. However, it was reported by Fuerstenau ( 1981 ) and Fuerstenau and
Mishra ( 1981 ) that the zeta-potentials of pyrite surfaces change from posi-
tive to negative in the presence of ethyl xanthates. These results indicate that
some products other than dixanthogen have been formed on pyrite surface.
From the present study, the surface compounds can be identified as Fe (III)-
ethyl xanthate compounds.
The above techniques used for studying the pyrite/xanthate interface are
indirect techniques. These techniques can tell if reactions have occurred.
However, identification of the exact nature of the reaction (s) and product (s)
using these techniques alone is very difficult, if possible. Therefore, it is useful
to use direct surface analytical techniques. FTIR is one of easily accessible
surface analytical techniques and has been used to investigate the pyrite/xan-
thate systems. The experimental methods and results will be described in de-
tail later elsewhere (Wang and Parekh, 1991 ). It has been found from the
MECHANISMS OF PYRITE FLOTATION WITH XANTHATES 287

FTIR studies that both dixanthogens and Fe(III)-xanthate compounds are

adsorbed/formed on the surfaces of the xanthate-reacted pyrite particles. The
quantity of dixanthogens is much greater than that of ferric xanthates. After
washing the pyrite surface with organic solvent such as carbon tetrachloride,
all the dixanthogens and some ferric xanthate compounds were removed from
the pyrite surfaces. However, some xanthate compounds still remained on the
pyrite surface after washing, with their IR spectra resembling to that of
Fe (III)-xanthates. These results demonstrate that some Fe (III)-xanthate
compounds, are strongly bonded to the pyrite surfaces. The quantity of this
layer is probably around one monolayer. Above this strongly bonded xanthate
layer, dixanthogen could be adsorbed as multiple layers. Similar results were
reported recently by Mielczarski (1986) and Fozo et al. (1989). The FTIR
studies have therefore proved the mechanisms proposed on the basis of ther-
modynamic stability and flotation studies.
However, it must still be stressed that the practical processes of pyrite flota-
tion with xanthate can be more complex. It was shown by Wang (1989) and
Ahlberg et al. (1990) that the initial oxidation of pyrite can be described by
the following reaction:
Fes2 + O H - ~ F e S 2 (OH)ads + e ( 1)
Therefore, adsorption of ethyl xanthate may take place by the following
reaction:
FeS2 ( OH ) ads + EX-,--,FeS2 ( EX ) aas + O H - (2 )
This process is similar to the "ion-exchange" model of Sutherland and Wark
(1955 ). It was also shown by several investigators (e.g., Bockris and Pillai,
1984; Ahlberg and Elfstrom, 1988 ) that the formation of diethyl dixanthogen
takes place on sulfide minerals through the following steps:
EX -,--,EX~s ~EXaas + e ( 3a )
EX-,--,EX~ds + e ( 3b )
EXads + EX~s,-~'EX2aas + e (3c)
2EX~ds~--*EX2,d~ (3d)
Here dixanthogen can be chemically or physically adsorbed. More impor-
tantly, the above reactions suggest that dixanthogen can be produced at an
underpotential on the pyrite electrode. From their recent electrochemical
studies on the pyrrhotite-xanthate flotation system, Hodgson and Agar ( 1988 )
found that the formation of Fe (III) surface sites is essential for the establish-
ment of hydrophobicity on the pyrrhotite surfaces. They suggested that xan-
thate ions are electrostatically adsorbed, probably through some reactions as
follows:
2~S ttIN ~,~,k x { . \NI) Ix,S.E I{}RSSBER(i

F e S + H e O ~ F e ( O H ) [S] * + H ~ +2e (4a)

Fe(OH)[S] ,+Ex ~Fe(OH)[S]EX (4b)
2EX-*--*EX3 +2e (4c)
Fe(OH ) [S ] E X + EX2*--~Fe(OH) [S ]EX . . . . . . EX2 (4d)
where [S] represents the surface polysulfide sites. The exact nature of the
product is unknown, however. Probably, the product is a surface Fe (Ill) xan-
thate compound as discussed in the present paper.
Finally, several other published works should also be reviewed. It was re-
ported by Harris and Finkelstein ( 1975 ) that monothiocarbonate was formed
on pyrite through an adsorbed species analogue to Fe(OH)2EX or
FeOH (EX) 2. Winter ( 1973 ) showed that S (II)-xanthates are stable xan-
thate compounds. The possibility of formation of such compounds on pyrite
cannot be ignored. In fact, Kihlstedt et al. (1976) reported that sulfur-xan-
thate like compounds were identified on pyrite surfaces by the IR technique.
These observations suggest that more extensive work should be devoted to
elucidate the mechanisms of pyrite flotation with xanthates.

CONCLUSIONS

The surface chemistry of the pyrite/xanthate flotation systems has been

studied by electrochemical and FTIR spectroscopic techniques in combina-
tion with thermodynamic stability calculations. The thermodynamic stability
studies showed that Fe (III) xanthates are stable under normal flotation con-
ditions and their stability is essentially not influenced by the presence of car-
bonate a n d / o r sulfur components. The open-circuit potentials of pyrite elec-
trodes coincide with the potentials under which Fe (III) xanthates are formed,
The formation of Fe(III) xanthate compounds on pyrite surfaces may play
an important role in controlling the pyrite floatability. FTIR spectroscopic
studies have confirmed that Fe (III) xanthate compounds are strongly bonded
to the surface of pyrite. Dixanthogen and xanthate ions are co-adsorbed on
pyrite surfaces.

REFERENCES

Ahlberg,E. and Elfstrom,A., 1988. Electrochemicaloxidation and adsorption of ethylxanthate

in connectionwith flotation. In: P.E. Richardsonand R. Woods (Editors), Electrochemistry
in Mineraland Metal ProcessingII. AES,Pennington,N J, pp. 36-48.
Ahlberg, E., Forssberg, K.S.E. and Wang, X,H., 1990. Surfaceoxidation of pyrite in alkaline
solutions. J. AppliedElectrochem.,20: 1033-1039.
Ahmed, S.M., 1978. Electrochemicalstudies of sulfides, 1: The electrocatalyticactivityof gal-
MECHANISMS OF PYRITE FLOTATION WITH XANTHATES 289

ena, pyrite, and cobalt sulfide for oxygen reduction in relation to xanthate adsorption and
flotation. Int. J. Miner. Process., 5:163-174.
Allison, S.A., Gold, L.A., Nicol, M. and Granvill, A., 1972. A determination of the products of
the reaction between various sulfide minerals and aqueous xanthate solution and a correla-
tion of the products with electrode rest potentials. Metal. Trans., 3:2613-2618.
Ball, B. and Rickard, R.S., 1976. The chemistry of pyrite flotation and depression. In: M.C.
Fuerstenau (Editor), Flotation - A.M. Gaudin Memorial Volume, Vol. 1. AIME, New York,
NY, pp. 458-484.
Bockris, J.O.M. and Pillai, K., 1984. Studies of the electro-chemical mechanisms of flotation.
In: P.E. Richardson and R. Woods (Editors), Electrochemistry in Mineral and Metal Pro-
cessing I. Pennington, N J, pp. 112-131.
Buckley, A.N., Hamilton, I.C. and Woods, R., 1988. Studies of the surface oxidation of pyrite
and pyrrhotite using X-ray photoelectron spectroscopy and linear potential sweep voltam-
metry. In: P.E. Richardson and R. Woods (Editors), Electrochemistry in Mineral and Metal
Processing 1I. Pennington, N J, pp. 234-246.
Chander, S., 1985. Oxidation/reduction effect in depression of sulfide minerals - A review.
Miner. Metall. Process., 2: 26-35.
Critchley, J.K. and Hunter, C.J., 1986. Solubility products of ferric xanthates. Trans. IMM, Sect
C: Miner. Process. Extra. Metall., 95:173-175.
Eriksson, G.A., 1979. An algorithm for the computation of aqueous multicomponent, multiple
phase equilibria. Anal. Chem. Acta, 112: 375-383.
Finkelstein, N.P. and Poling, G.W., 1977. The role ofdithiolates in flotation of sulfide minerals.
Miner. Sci. Eng. 9: 177-197.
Fozo, S., Persson, I. and Persson, P., 1989. Ytf6reningar pfi pyrit i samband med xanthatflota-
tion. STU Rep., 1988:11-17 (text in Swedish).
Fuerstenau, D.W. and Mishra, B.K., 1981. On the mechanism of pyrite notation with xanthate
as collectors. In: M.H. Jones (Editor), Complex Sulfides. IMM, London, pp. 271-278.
Fuerstenau, M.C., 1981. Adsorption ofsulphydryl collectors. In: R.P. King (Editor), Principles
of Flotation. pp. 91-108.
Fuerstenau, M.C., Kuhn, M.C. and Elgillani, D.A., 1968. The role of dixanthogen in xanthate
flotation of pyrite. Trans. AIME, 241: 148-156.
Hamilton, I.C. and Woods, R., 1979, The effect of alkyl chain length on the aqueous solubility
and redox properties of symmetrical dixanthogen. Aust. J. Chem., 32:2171-2179.
Hamilton, I.C. and Woods, R., 1981. An investigation of surface oxidation of pyrite and pyr-
rhotite by linear potential sweep voltammetry. J. Electroanal. Chem., 118: 327-343.
Harris, P.J. and Finkelstein, N.P., 1975. Interaction between sulfide minerals and xanthate. I:
the formation of monothiocarbonate at galena and pyrite surface. Int. J. Miner. Process., 2:
77-100.
Hodgson, M. and Agar, G.E., 1988. Modelling of mineral electrochemical interaction in INCO
SO2-air process and their effect on hydrophobicity selectivity. In: P.E. Richardson and R.
Woods (Editors), Electrochemistry in Mineral and Metal Processing II. AES, Pennington,
NJ, pp. 150-169.
Kihlstedt, P.G., Siirak, J. and Eriksson, K., 1976. IR-studier av j~irn-svavelf'6reningars samlar-
reaktion. STU Rep. No. 74-3865, 42 pp. (text in Swedish).
Leppinen, J.O., Basilio, C.I. and Yoon, R.H., 1988. In situ FTIR spectroscopic study of
ethylxanthate electrosorption on sulfide minerals. In: P.E. Richardson and R. Woods (Edi-
tors), Electrochemistry in Mineral and Metal Processing II. AES, Pennington, N J, pp. 49-
65.
Majima, H., 1961. Fundamental studies of the collection of sulfide minerals with xanthic acids.
I: On the dissociation and decomposition ofxanthic acids. Sci. Rep. Res. Inst., Tohoku Univ.
Ser. A, 13: 183-197.
Majima, H. and Takeda, M., 1968. Electrochemical studies ofxanthate-dixanthogen systems of
pyrite. Trans. AIME, 244:431-436.
29(I H x . WANG ANI~ KS.f-. F()RSSBER(I

Mielczarski, J., 1986. In situ ATR-IR spectroscopic study of xanthate adsorption on marcasite.
Colloids Surfaces, 17:251-271.
Sheikh, N., 1972. The Chemical Stability of the Heavy Metal Xanthatcs. Ph.D. Thesis. (!niver-
sity of British Columbia, Vancouver, BC, 154 pp.
Sheikh, N. and Eeja, J., 1977. Mossbauer spectroscopy of Fe-xanthates. Separation Sci., 12:
529-540.
Stumm, W. and Morgan, L.L., 1982. Aquatic Chemistry., 2nd ed. Wiley lnterscience, New York,
NY.
Sutherland, K.L. and Wark, I.W., 1955. Principles of Flotation. Aus. IMM, Melbourne, Vic.
Trahar, W.J, 1983. The influence of pulp potential on sulfide flotation. In: M.H. Jones and J.T.
Woodcock (Editors), Principles of Mineral Flotation, The Wark Symposium. Aus. IMM,
pp. 117-135.
Wang, X.H., 1989. The Chemistry of Flotation, Activation and Depression of Iron-Containing
Sulfide Minerals. Ph.D. Thesis, Lule~. University of Technology, Lule~, 540 p.
Wang, X.H. and Forssberg, K.S.E., 1990. The chemistry of cyanide-metal complexes in relation
to hydrometallurgical processes of precious metals. Miner. Process. Extra. Metall. Review.,
6: 81-125.
Wang, X.H. and Parekh, B.K., 1991. J. Colloid Interface Sci., (accepted).
Wang, X.H., Forssberg, K.S.E. and Bolin, N.J., 1989. Thermodynamic calculations on iron-
containing sulfide mineral flotation systems, I. The stability of iron xanthates. Int. J. Miner.
Process., 27: 1-19.
Winter, G., 1973. Xanthates of sulfur: their possible role in flotation. Inorg. Nucl. Chem. Lett.,
11:113-118.
Woods, R., 1988. Flotation of Sulfide Minerals. In: P. Somasundaran and B. Moudgil (Edi-
tors), Reagents in Mineral Technology. Marcel Dekker, New York, NY, pp, 39-77.