The Fea-,S-PbS-ZnS phase system

J. E. DUTRIZAC
Metallurgical Chemistry Section, Mineral Sciences Laboratories, C A N M E T , Department of Energy, Mines and Resources,
Ottawa, Ont., Canada K I A 061
Received November 23, 1979
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J. E. DUTRIZAC. Can. J. Chem. 58,739 (1980).

Nigh temperature phase relationships have been determined for the binary systems FeS-PbS, Fe,,,,S-PbS, Fe,,,,S-ZnS, and
PbS-ZnS, and for the ternary system Fe,,,,S-PbS-ZnS. All the systems were ofthe eutectic-type with eutectic points being notedat
53 mol% FeS - 47 mol% PbS and 850°C, 53 mol% Fe,,,,S - 47 mol% PbS and 852"C, 90 mol% Fe,,,,S - 10 mol% ZnS and 1 178"C, 87
mol% FbS - 13 mol% ZnS and 1050°C, and at 46 mol% Fe,,,,S - 41 mol% PbS - 13 mol% ZnS and 850°C, respectively. Solid
solubilities were less than 1 mol% except for an appreciable solubility of Fe,-,S in ZnS.

J. E. DUTRIZAC. Can. J. Chem. 58,739 (1980).

On a determine les relations de phase a haute temperature des systemes binaires suivants: FeS-PbS, Fe,,,,S-PbS, Fe,.,,S-ZnS et
PbS-ZnS et du systeme ternaire Fe,,,,S-PbS-ZnS. Tous ces systemes f o m e n t des eutectiques. On a determine les points
eutectiques des systemes ayant respectivement les compositions molaires suivantes: FeS-PbS 53-47%: 850°C; Fe,,,,S-PbS
53-47%: 852°C; Fe,,,,S-ZnS 90-1%; 1178°C; Pbs-ZnS 87-13%: 1050°C et Fe,,,,S-PbS-ZnS 46-13%: 850°C. Les solubilites des
solides sont inferieures 1 mol% a l'exception de la solubilite non negligeable de Fe,-,S dans ZnS.
[Traduit par le journal]
Can. J. Chem. 1980.58:739-743.

Introduction the same open cell technique observed the eutectic

The Fe,-$3-PbS-ZnS phase system is of con-
cern to pyrometaliurgists treating either iron and
zinc-rich lead concentrates or pyritic zinc-lead
sulphide ores and concentrates of the type found,
for example, in northeastern New Brunswick. Re-
gardless of whether the iron sulphide mineral pres-
ent in the ore is pyrrhotite (FeS-Fe7S,) or pyrite
(FeS,), an iron sulphide of approximate composi-
tion FeS will be formed on heating. Pyrite decom-
poses to pyrrhotite and sulphur vapour ( I atm) at
about 740°C (1, 2) and the pyrrhotite itself evolves
sulphur, approaching the stoichiomeeric compound
at elevated temperatures. Although Fe,,,,S melts
incongruently, the composition FeO.,$3was found
to melt congruently at about 1190°C (3).
The Fe,-,S-ZnS binary has been investigated
several times, but the melting relationships are still
not fully resolved. Friedrich (4) observed a
eutectic-type system with a eutectic at 5.5 mol%
ZnS and 1170- 1180°C; his experiments were car-
ried out in open cells. The eutectic behaviour was
confirmed by Kullentd ( 9 , who reported a eutectic
at 6 mol% ZnS and 1170"C, by Avetisyan and
Gnatyshenko (6), who found the eutectic at 6 mol%
ZnS and 1180°C and by Kerby (71, who noted the
point at 6 mol% ZnS and 1135°C. A11 workers are in
accord concerning the high solubility of FeS in ZnS
and that the liquidus temperature rises sharply on
the ZnS side of the eutectic.
The Fe,-,S-PbS system was first investigated
by Wiedrnann (8), who repofled a simple eutectic at
48 mol% FeS and 482°C. Later, Friedrich (9) using
We-4042/80/070739-05$01.00/0
@ 1980 National Research Council of Canada/Conseil national de recherches du Canada
at 51 mol% FeS and 863°C. Kopylov (10) reported a
eutectic at 52 mol% FeS and 860°C and Kerby (7)
observed the point at 52 mol% FeS and 835°C.
The PbS-ZnS binary was studied by Friedrich
(4) using open cells; he observed simple eutectic
behaviour with the eutectic at 13 mol% ZnS and
1045°C. Kerby (7) rerneasured this system with
sealed cells and reported a eutectic at 22 mol% ZnS
and 988°C.
The FeS-PbS-ZnS ternary has been studied
only by Avetisyan and Gnatyshenko ( 6 ) ,who used
open cells under a nitrogen atmosphere. They ob-
served a single ternary eutectic at 49.8 mol% FeS,
37.5 mol% PbS, and 12.9 mol% ZnS and 820°C. The
liquidus surface rose abruptly in the direction of
ZnS once the eutectic valley had been passed.
Because of the importance of this system in
pyrometallurgy, it was decided to re-evaluate the
Fe,-$3-PbS-ZnS phase diagram using sealed-
cell DTA techniques. This was effected by
measuring the bounding binaries and by determin-
ing several "cuts" across the ternary itself. The
results were checked by quenching-petrographic
methods and by X-ray diffraction and electron
microprobe techniques.
Lead sulphide (PbS) was obtained from Atomergic Chemetals
Ltd. and was 99.99W0 pure with respect to metallic impurities;
unlike some "pure" PbS materials examined, this was also low
in sulphate, hydroxide, etc. Zinc sulphide (ZnS) was purchased
from Electronic Space Roducts and was 99.9995% pure with
respect to metallic impurities; it was received in the wurtzite
 CAN. J . CHEM. VOL. 5 8 , 1980

TABLE1. Analytical data for the pure sulphides

Compound wt%Fe wt%Pb wt%Zn wt%S X-ray

Synthesized FeS FeS (troilite structure)
FeS (theoretical) -
Synthesized Fe,,,,S -
-
Fe,,,,S (theoretical)
Purchased PbS PbS (galena) plus faint
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trace of unknown compound

PbS (theoretical)
Purchased ZnS ZnS (sphalerite) plus
trace of ZnS (wurtzite)
ZnS (theoretical)

modification which was converted to the sphalerite structure by

heating in a vacuum sealed ampoule to 900°C for a few hours. -
The iron sulphides FeS and Fe,,,,S were synthesized using
established procedures (1 1). The various starting materials were
analyzed chemically and by Guinier X-ray diffraction analysis,
and the results are presented in Table 1. The X-ray data show
IMO
C FCS PbS
x-REFEREWE 6

the general absence of oxide lead compounds and the predomi-

nately sphalerite form of the ZnS. When the wurtzite modifica-
tion was used, data interpretation was greatly complicated be-
Can. J. Chem. 1980.58:739-743.

cause in some experiments the wurtzite would, on heating,

convert to sphalerite which would revert to wurtzite on further
heating (>900"C) before the liquidus was reached. In other runs
the wurtzite would "melt" before any wurtzite sphalerite
reactions occurred.
The sulphides were mixed in suitabie proportions and were
vacuum sealed in 4 mm id silica glass DTA tubes; the sulphides
did not attack the silica glass although they seemed to promote
devitrification at the highest temperatures employed. For the
purpose of calculating mole percentages, the formula of the
congruently melting iron sulphide was expressed as Fe,,,S., The
samples were run on a Stone DTA System equipped wlth a
palladium holder and Pt-Pt: 10%Rh thermocouples. The sul-
phides were heated against a calcined alumina reference, and the
system was calibrated against the melting point ofgold (1063°C).
Programming rates of 5, 10, or 1S0C/minwere used depending on
the system response. and data were recorded on both heating 0 2 0 4 0 6 0 8 0 1 0 0
and cooling. Selected samples were analyzed microscopically FQS Wld % PbS Pb S
and by X-ray diffraction analysis after they had been heated and
cooled. FIG.1. High temperature portion of the FeS-PbS phase dia-
To estimate solid solubilities, suitable compositions were gram; eutectic temperature is 850°C.
melted in vacuum-sealed silica glass ampoules (8 mm id) and
the two systems are very similar. Both are of the
then annealed for 2 to 3 days at a temperature just below the
simple eutectic type with the eutectic composition
appropriate eutectic. Longer annealing times did not yield
significantly different results and it was assumed that equilib-
being at 53 mol% Fe,-,S and 47 mol% PbS; the
rium was fairly quickly attained in the fine eutectic structures
eutectic temperature was 850°C for FeS-PbS and
produced. The samples were then quenched in water and
852°C for Fe,,,,S-PbS. The eutectic composition is
examined microscopically and by electron microprobe analysis
to estimate the maximum extent of solid solubility. in essential agreement with earlier work (7, 9, 10).
The eutectic temperature is supported by the
Results and Discussion studies of Friedrich (91, 863"C, and Kopylov (101,
(a) Pel-,S-PbS 860°C, but is substantially higher than Kerby9s
The phase diagram for the FeS-PbS binary sys- value of 835°C; examination of his PbS suggested
tem is presented in Fig. 1 and the cowesponding oxide contamination which may have caused his
diagram for the Fe,.,,S-PbS system is given in Fig. lower melting temperatures. The x ' s marked on
2. PbS melted at 1115°C in agreement with the the FeS-PbS binary are Biquidus temperatures
reported value. FeS and Fe,,,,S fused at 1165°C taken from the ternary data of Avetisyan and
and 1190"C, respectively, and both these values are Gnaty shenko (61, and the agreement is acceptable.
in accord with the published data (3). Aside from The only phases identified by X-ray diffraction
the diEerent melting points for the iron sulphides, analysis of cooled samples were PbS (galena) and
 DUTRIZAC 741
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- FIG. 3. The Fe,,,,S-ZnS phase diagram showing the ap-

proximate range of F e , , S solubility in ZnS; eutectic tempera-
ture is 1178°C.
Can. J. Chem. 1980.58:739-743.

800
0 20 40 80 80 $00
F ~ o , ~ ~ S MOLE X PbS F.b.5

FIG. 2. High temperature portion of the Fe,,,,S-PbS phase

diagram; eutectic temperature is 852°C.

iron sulphides of the type Fe,-,S. Electron micro-

probe examination of various samples annealed at
840°C for 2-3 days and then quenched indicated
less than 0.5 wt% Fe in the primary PbS and less
than 0.5 wt% Pb in the primary Fe,-,S. Micro-
scopic examination likewise confirmed that solid
solubilities were considerably less than 1 wt% in
these binary systems.
(b) Feo,g2S-ZnS
The determined phase diagram for the
Fe,.,,S-ZnS binary system is presented in Fig. 3;
because of the steep liquidus on the ZnS side of the
eutectic, liquidus points were not usually detected
by the DTA apparatus. The liquidus falls from the
1190°C melting point of Fe,,,,S to the eutectic
which occurs at 90 mol% Fe,.,,S - 10 mol% ZnS
and 1178"C, and then rises sharply. The eutectic
temperature observed in this study is consistent
with previous work (4-6) except that of Kerby (7),
which appears low at 1135°C. The eutectic compo-
sition observed in the present study is slightly
richer in zinc than was previously observed.
The only phases detected in this system were
Fe,-,S and iron-rich sphalerite. Samples annealed
at 1165°C for 2-3 days and quenched indicated that
the iron sulphide contained less than 0.5 wt% Zn.
Since very fine ZnS inclusions could be seen in the
Fe,-,S phase, the amount of zinc actually in solu-
tion in %;el-,S might be lower than this amount.
ILY)
0 20 40 60 80 100
P ~ S W X Z n S Zn s
FIG. 4. The PbS-ZnS phase diagram; the eutectic tempera-
ture is 1050°C.
Barton and Toulmin (12) found the maximum Zn
content of Fe,-,S to be less than 0.24 atom%. The
ZnS phase dissolves considerable amounts of iron
sulphide at 1 165OC. Electron microprobe examina-
tion of the quenched samples indicated 26-27 wt%
Fe and this corresponds to about 43 mol% FeS in
the ZnS. The solubility of FeS in ZnS is somewhat
variable because the sulphur fugacity of the system
is not buffered. Kullemd (5) reported 45 mol% FeS
solubility at 1190°C; Barton and Toulmin (12) sb-
served a molar FeS solubility of 56% at 850°C and
52% at 580°C for (Zn,Fe)S in equilibrium with FeS
and metallic iron; lower solubilities were noted
 CAN. J. CHEM. VOL. 58, 1980
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1190.C 10 20 30 40 50 60 70 80 90 lll5*C
MOLE X PbS

FIG. 5. The Fe,,,2S-PbS-ZnS ternary phase diagram.

when Fe,-,S was used. Neuhaus and Cemic (13) ZnS

reported a value of 51 mol% FeS at 900°C and 5

kbars pressure.
( c )PbS-ZnS
Figure 4 illustrates the liquidus relationships in
Can. J. Chem. 1980.58:739-743.

the PbS-ZnS binary system. The eutectic was ob-

served at about 13 mol% ZnS and 1050"C,in general
agreement with Friedrich (4) who reported a eutec-
tic at 13 mol% ZnS and 1045°C. Neither study
agrees with the recent work of Kerby (7), but it is
felt that his purchased lead sulphide was badly
oxidized. The slight curvature in the liquidus on the
PbS side of the system was also noted by Friedrich 30

(4). Microscopic examination of solidified melts in

80
the vicinity of the eutectic composition indicated 20
80 m 60 50 40 30 20 10
that the eutectic contained more than 12 mol% ZnS MOLE r FOo , z ~
but less than 15 mol% of this component. FIG. 6. The solubility of Fe,-,S in solid ZnS as a function of
Electron microprobe study of samples annealed total composition in the Fe, ,,s-P~S-Z~Sternary system.
just below the eutectic temperature and then
quenched suggested that solid rather gradually from either Fe0.92S or PbS, but rise
were less
than 0.5 mol% at either end of the phase diagram; $teeply on the ZnS-rich side of the figure. The steep
the zinc sulphide contained 0.4 wt% ~b and the lead ZnS liquidus combined with the location of the
sulphide assayed 0.2 wt% Zn. ternary eutectic close to the Fe,,,,S-PbS binary
causes ZnS to be a difficult impurity in the pro-
(d) FeO,,,S-PbS-ZnS cessing of iron and/or lead mattes.
Liquidus relationships in the Feo,,,S-PbS-ZnS (e) Ternary Solid Solutions
ternary were elucidated by measuring seven Study of the bounding binary systems revealed
pseudobinary cuts across the system. In the inter- that solid solubilities were low except for Fe,-,S in
est of brevity, the seven pseudobinaries are not ZnS. To test for solid solubilities in the ternary
presented but are available from the author on de- system, nine ternary compositions were prepared
mand. The various binary and pseudobinary sys- and heated to 1200°C in vacuum sealed tubes for 2
tems were then used to construct the ternary phase to 4 h. The tubes were then cooled to 1040°C and
diagram shown in Fig. 5. The ternary is of the held at that temperature for 2 to ? days. After water
simple eutectic type with the ternary eutectic point quenching, the samples were examined micro-
at 46 mol% Feo,,,S - 41 mol% PbS - 13 mol% ZnS scopically and by the electron microprobe to
and 850°C. The ternary eutectic composition is evaluate the extent of solid solubility. Solubilities
similar to that of Avetisyan and Gnatyshenko (6), in Fe0.,,S and PbS were always less than I%, in
49.8 mol% FeS - 37.5 mol% PbS - 12.4 mol% ZnS, agreement with the binary data. Extensive Fe,-,S
although those authors noted the ternary eutectic solubility in ZnS as well as the possibility of trace
temperature at 820°C. The liquidus surfaces fall PbS solid solubility was indicated.
 DUTRIZAC 743

A series of compositions consisting of 50 mol%
ZnS and various amounts of Feo,,,S and PbS were
prepared and annealed at 1160°C; i.e., just below
the Fe,-,S-ZnS binary eutectic temperature.
These compositions are indicated (A1-H') on Fig.
6, and the corresponding compositions of the solid
zinc sulphide phases are given by A-H, respec-
tively. The solubility of lead in the ZnS phase was
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mol% FeO.,,S - 41 mol% PbS - 13 mol% ZnS and
850"C, respectively. Solid solubilities were less
than 1 mol% except near the Fe,-,S-ZnS binary
where an appreciable solubility of Fe,-,S in ZnS
was observed.
The assistance of 0. Dinardo with the experi-
mental program and D. R. Owens with the electron

always less than 1 wt%; at 1160°C and 5 mol% PbS

in the charge, the ZnS phase assayed 0.25 wt% Pb; microprobe analyses is recognized.
the corresponding value for a charge containing 40
1. P. TOULMIN and P. B. BARTON.Geochim. Cosmochim.
mol% PbS was 0.76 wt% Pb. The iron concentra- Acta, 28,641 (1964).
tion of the ZnS phase depends strongly on the ac- 2. R. G. ARNOLD.Econ. Geol. 57,72 (1962).
tivity of FeS in the associated melt. This value was 3. E. JENSON. Am. J. Sci. 240,695 (1942).
6 mol% FeS in ZnS when the charge contained 4. K . FRIEDRICH. Metallurgie, 5, 114(1908).
10 mol% FeS, and 43 mol% FeS along the 5. G. KULLERUD. Norsk. Geol. Tidsskr. 32,61(1953).
6. K. K. AVETISYAN A N D G. I. GNATYSHENKO. IZV. Akad.
Fe,.,,S-ZnS binary (Fig. 6). Nauk Kaz. SSR, Ser. Gorn. Dela Met. Stroit. it Stroim. 6,
11 (1956).
Conclusions 7. R. C. KERBY.Mines Branch Report IR 73-49, Department
High temperature phase relationships have been of Energy, Mines and Resources, Ottawa, Ont., Canada
KlAOGl.
determined for the binary systems FeS-PbS, 8. N.WIEDMANN.
Can. J. Chem. 1980.58:739-743.

Metallurgie, 3,660 (1906).

Feo.,,S-PbS, Fe0,,,S-ZnS, and PbS-ZnS, and for 9. K. FRIEDRICH. Metallurgie, 4,479 (1907).
the ternary system Fe0,,,S-PbS-ZnS. All the sys- 10. N . I. KOPYLOV. Russ. J. Inorg. Chem. 12(E0), 1494 (1967).
tems were of the eutectic-type with eutectic points 11. J. E. DUTRIZACand R. J. C. MACDONALD. Mater. Res.
being noted at 53 mol% FeS - 47 mol% PbS and Bull. 8(8), 961 (1973).
12. P. B. BARTONand P. TOULMIN.Econ. Geol. 61(5), 815
850"C, 53 mol% Fe0.,,S - 47 mol% PbS and 852"C, (1966).
90 mol% Fe0.,,S - 10 mol% ZnS and 1178"C, 87 13. A . NEUHAUSand L. CEMIC.Naturwissenschaften, 57(7),
mol% PbS - 13 mol% ZnS and 1050"C, and at 46 354 (1970).