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Phase Equilibria and Thermodynamic Properties of the

Cu2O-CaO-Na2O System in Equilibrium with Copper
PASCAL COURSOL, ARTHUR D. PELTON, and MANUEL ZAMALLOA

The liquidus surfaces of the Cu2O-CaO, Cu2O-Na2O, and Cu2O-CaO-Na2O phase diagrams in equilibrium
with metallic Cu were measured by thermal analysis at compositions varying from approximately 0 to
35 wt pct Na2O and 0 to 15 wt pct CaO. Solubilities in the solid binary terminal solutions were also
measured by wavelength dispersive X-ray spectrometer analysis. Copper oxide activities in binary
liquid slags were determined from the measured oxygen content of the metallic copper equilibrated
with the slags. The ternary system is a simple eutectic system. No ternary compounds were observed.
The Cu2O-CaO binary eutectic was measured at 1140 °C
10 °C at 10
1 wt pct CaO and the
Cu2O-Na2O binary eutectic was measured at 803 °C
15 °C at 28
2 wt pct Na2O. The liquid slag
was thermodynamically modeled with the modified quasi-chemical model, while the solid Cu2O-rich
solution was treated as Henrian ideal. All data from the present work and from the literature (phase
diagrams and activities) for the binary systems were evaluated simultaneously by least-squares
optimization in order to obtain the best model parameters. With only these binary parameters, the
calculated ternary liquidus surface is in very good agreement with the measurements. Finally, using
the model, the liquidus projection of the Cu2O-CaO-Na2O system in equilibrium with Cu was calculated
as well as the oxygen content of the equilibrated Cu as a function of slag composition.

I. INTRODUCTION used. In the thermal analysis experiments, the reference cru-

BASIC fluxes are commonly used to reduce the concen-
trations of certain minor elements in blister copper. Despite
the proven effectiveness of Na2CO3-CaO fluxes in removing
As and Sb,[1–4] various thermochemical aspects of the slag
produced industrially are not fully understood. As described
by Riveros et al.[5], Na2CO3 and Cu2O are not fully miscible.
Depending upon the overall composition and the oxygen con-
tent of the copper, the slag formed during fluxing may con-
sist of two liquid phases, one rich in Na2CO3 and one rich in
Cu2O. An understanding of the phase equilibria and thermo-
dynamics of this system is essential for process simulation
and control. Kuxmann and Kurre[6] studied the solubility of
CaO in liquid Cu2O in the presence of metallic copper. Oishi
et al.[7] have studied the partial pressure of O2 in equilibrium
with liquid copper and CaO-Cu2O liquid solutions at 1300
°C. Thermodynamic modeling of the Cu-CuO-Cu2O-CaO sub-
system was done by Ranniko[8] using the association model.
No other literature data were found. In the present article,
we report our measurements and thermodynamic modeling
of the Cu2O-CaO-Na2O system in equilibrium with copper.
II. EXPERIMENTAL
A. Thermal Analysis and Differential Thermal Analysis
The DTA apparatus is shown in Figure 1. Recrystallized
Al2O3 crucibles of 99.8 pct purity (Vesuvius McDanel) were
PASCAL COURSOL, Process Scientist, is with the Alcan Research and
Development Centre, P.O. Box 1250, Jonquiere, PQ G7S 4K8, Canada.
ARTHUR D. PELTON, Professor, is with the Centre de Recherche en Calcul
Thermochimique, Ecole Polytechnique de Montreal, Montreal, PQ, Canada
H3C 3A7. Contact e-mail: apelton@polymtl.ca MANUEL ZAMALLOA,
Senior Scientist, is with the Noranda Technology Center, Pte. Claire, PQ
H9R 1G5, Canada.
Manuscript submitted September 10, 2002.
cible was not used. The entire assembly was enclosed in a
covered SiC crucible and purged with Ar at 6 l/min. The
assembly was vibrated to reduce undercooling by attaching
the thermocouple supports to a motor oscillating at 30 Hz.
In general, undercooling was less than 5 °C. Samples were
held at 1260 °C for 1 hour before cooling at 4 °C/min.
Heating curves were also obtained when appropriate, for
example, to determine eutectic temperatures more accurately.
The deviation of the measured liquidus temperatures from
the true values is estimated as
10 °C when Cu2O is the
primary solid phase. When CaO is the primary solid phase,
the error with this technique is about
20 °C because the
CaO liquidus is very steep. These errors are the combined
effects of undercooling, contamination, thermocouple accu-
racy, and data treatment.
B. Measurement of Cu2O Activity by Slag/Metal
Equilibration
Activities of Cu2O in the slag were measured by
equilibration with liquid copper followed by quenching and
analysis of the Cu phase for dissolved oxygen. Since the
activity of oxygen in molten Cu as a function of concentra-
tion is known from the literature,[12,13] the activity of Cu2O
can then be determined.
Samples of
40 g slag and
5 g Cu were held in cov-
ered Al2O3 crucibles (of the same type as in Figure 1) in a
flowing Ar atmosphere for 3 hours at 1200 °C and were then
quenched in water. The water did not come into contact with
the slag.
The quenched copper was analyzed for oxygen by a com-
bustion technique. Samples of
1.0 g were weighed, heated
in a graphite crucible under Ar at 1175 °C for 1 hour, and
cooled under Ar in the furnace. After combustion, the
graphite crucible was not wetted by the copper, hence all
the metallic copper could be completely separated from the

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Fig. 1—Differential thermal analysis apparatus.
crucible. The dissolved oxygen content was then calculated
from the weight loss. Because the dissolved oxygen content
was high (0.1 to 2.5 wt pct), this method permitted precise
measurements to be made. For each equilibration run, the
average of three analyses was taken. Some samples were
also analyzed with a LECO* oxygen analyzer. Results
* LECO is a trademark of LECO Corporation, St. Joseph, MI.
obtained by the two methods were in good agreement. The
error of the measured oxygen contents is estimated to be
5
pct of the measured value.
For the reaction,
2Cu (liquid)  1/2O2(gas)  Cu2O (liquid)
the equilibrium constant at 1200 °C is
aCu2O
K1200 °C  1  119.9
Po/22 aCu2
where aCu2O is the activity of Cu2O in the liquid slag at
1200 °C relative to the pure liquid (metastable) Cu2O as
standard state, aCu is the activity of liquid copper, and PO2
is the equilibrium oxygen potential. The value of K1200  119.9
in Eq. [2] was calculated from the Gibbs energies of Cu
(liquid), O2 (gas), and Cu2O (solid) from the FactSage
5.1 database,[9] and from the following Gibbs energy of
fusion of Cu2O:
Cu2O (solid)  Cu2O (liquid)

G0fusion  G0Cu2O (liquid)  G0Cu2O (Solid)
 64,200  42.739 T (J/mol)
632—VOLUME 34B, OCTOBER 2003
which was obtained by combining the enthalpy of fusion
of 64,200 (J/mol) reported by Mah et al.[10] with the melting
point of 1229 °C reported by Neumann et al.[11] under the
assumption that Cp  0 (such that Sfusion
o
 64,200/(1229
 273.15)  42.739 (J/mol K)).
Oxygen activities in liquid Cu were taken from the critical
evaluation of Sigworth and Elliott.[12] These are very close
to the values given in the compilation of Oishi and Ono.[13]
The following equation for PO2 and aCu as a function of
the oxygen mole fraction XO in liquid Cu was obtained by
using the parameters given by Sigworth and Elliott[12] in the
unified interaction parameter formalism.[14]
10,266
O2 (bar)  Xo exp c a
P1/2  5.44b
T
[4]
X2o
 a7.80  b aXo  b d
24,000
T 2
1
aCu  (1  Xo) exp c a7.80  b X2o d
24,000
[5]
2 T
From the measured values of XO, one can calculate PO2 and
aCu from Eqs. [4] and [5]. Substitution into Eq. [2] then gives
aCu2O relative to pure (metastable) liquid Cu2O as standard state.
Solubility of CaO in liquid Cu2O
A very similar technique was used to measure the solubil-
ity of CaO in molten Cu2O (i.e., the liquidus). The technique
and results are described in Section IV–A–1
C. Solubilities in Solid Solutions
The mutual solubilities of CaO, Cu2O, and Na2O in the
terminal solid solutions are, at most, a few percent. Slag samples
of
40 g were held in covered Al2O3 crucibles under flow-
ing Ar for 1 hour at a temperature where the slag was liquid.
They were then cooled to the measurement temperature and
held for 3 hours in order to attain equilibrium and to permit
the growth of solid particles large enough for analysis. The
samples were then quenched in water (avoiding contact between
the slag and the water) and dry polished. The primary particles
[1] were subsequently analyzed with a JEOL* 8900 electron micro-
JEOL is a trademark of Japan Electron Optics Ltd., Tokyo.
scope equipped with a wavelength dispersive X-ray spectro-
[2] meter. For analysis of Na, Ca, and Cu, the following standards
were used, respectively, Na2Al2Si6O16, CaMgSi2O6, and Cu2O.
The errors in the measured CaO, Cu2O, and Na2O contents
are estimated as
10 pct of the measured values as long as
Na2O was not the main component of the solid solution (i.e.,
not in the Na2O-rich terminal solid solution). When Na2O was
the solvent, results were erratic, probably because of hydration
or oxidation, and percentage errors are estimated as
50 pct.
D. Starting Materials
Metallic Cu of 99.99 pct purity from Noranda Inc. (Pte.
Claire, Quebec) and CaO of 99.95 pct purity from Alfa Aesar
(Ward Hill, MA) were used. The Cu2O was produced by Alfa
[3]
Aesar by oxidation of high-purity Cu.
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The Na2O was purchased from Alfa Aesar who supplied
the following analysis: 87 wt pct Na2O, 12 wt pct Na2O2, and
1 wt pct Na2CO3. At the high temperatures of the experiments,
it was assumed that all Na2O2 is decomposed to Na2O and
O2 and all Na2CO3 is decomposed to Na2O and CO2.
E. Use of Al2O3 Crucibles
Preliminary tests with MgO crucibles showed a large
penetration of the slags into the crucible walls. With recrys-
tallized Al2O3 crucibles (99.8 pct, Vesuvius McDanel (Beaver
Falls, PA)), no such penetration was observed. With Cu2O-CaO
slags, a dense passivating layer of calcium aluminate rapidly
forms on the crucible surface (Figure 2), which was shown by
energy dispersive X-ray spectroscopy analysis to be of the
approximate composition Ca3Al2O6. From measurements of
the thickness of this layer (
20 m), and assuming that the
layer is Ca3Al2O6 (which is the calcium aluminate that has the
highest density and highest CaO content), we calculate, in the
worst-case scenario, that CaO losses in the slag are less than
0.25 wt pct, which can be neglected. With Cu2O-Na2O slags,
a passivating layer was also observed, although a successful
analysis of this layer was not obtained. Analysis of the melt
by inductively coupled plasma mass spectroscopy (ICPMS)
after the test showed that the Na2O losses were negligible
(within the experimental error of the ICPMS analysis).
The slags were also analyzed for Al2O3 by ICPMS.
Alumina contents of less than 1 wt pct were observed in the
slags after the tests. This indicates that contamination from
the alumina crucibles was negligible.
III. SOLUBILITY OF Cu0 and Cu2 IN
THE MOLTEN OXIDE
From the Cu-Cu2O phase diagram[11] in Figure 3, it can be
seen that the solubility of Cu in pure molten Cu2O is high.
However, with small additions of CaO or Na2O, this solubility
decreases markedly. Oishi et al.[7] equilibrated Cu2O-CaO
melts with liquid copper followed by quenching and analysis.
With the addition of
3 wt pct CaO to Cu2O, the Cu solubility
at 1300 °C was reduced from
14 wt pct (Figure 4) to

2 wt pct, due to the high electropositivity of Ca relative to
Fig. 2—Inner surface of alumina crucible showing calcium aluminate pas-
sivation layer (layer became detached during cooling).
METALLURGICAL AND MATERIALS TRANSACTIONS B
Cu. A similar large decrease in the solubility of Cu in Cu2O
is expected with the addition of Na2O. Indeed, when we cooled
Cu2O that was equilibrated with liquid Cu, we observed
significant precipitation of Cu from the oxide. However, if

3 wt pct CaO or Na2O was added to the Cu2O, the amount
of Cu precipitate observed was negligible.
The order of magnitude of the Cu2 concentration in
Cu2O in equilibrium with metallic Cu can be calculated by
considering the equilibrium
Cu (liquid)  CuO (liquid)  Cu2O (liquid) [6]
aCu2O
K  [7]
aCuOaCu
Since no data for the Gibbs energy of fusion of CuO are
available, we have estimated K as being approximately equal
to K for the corresponding reaction among Cu (liquid), CuO
(solid), and Cu2O (solid). At 1200 °C, K  15.39.[9] Setting
aCu  1 and aCu2O  1 in Eq. [7] gives aCu2O  0.065. If
Cu and Cu ions are assumed to form an approximately
ideal (Temkin) mixture, then the ratio of Cu to Cu ions
in the melt is of the order of Cu/Cu
0.065.
IV. RESULTS
A. Cu2O-CaO System
1. Phase diagram
The phase diagram of the Cu2O-CaO system equilibrated
with metallic copper is shown in Figure 4. The Cu2O
liquidus points shown on Figure 4 were measured by
thermal analysis (cooling curves) as were the eutectic
temperatures (heating curves). The melting point of Cu2O
in equilibrium with metallic Cu was measured at 1219 °C,
which may be compared with the value of 1223 °C [11]
shown in Figure 3.
For measuring the steep CaO-liquidus, thermal analysis
is too imprecise. Hence, the following technique was used.
Eleven samples containing different concentrations of CaO,
either in the single-phase liquid or two-phase (liquid  CaO)
region, were equilibrated with Cu at 1235 °C for 2 hours and
quenched, as described in Section II–B. The oxygen content
Fig. 3—Phase diagram[11] of the Cu-Cu2O system.
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of the Cu phase was subsequently analyzed and plotted vs
the CaO content of the slag, as shown in Figure 5.
In the two-phase region, the oxygen potential is inde-
pendent of composition. Hence, from Figure 5, it can be seen
that the liquidus composition at 1235 °C occurs at
(11
1) wt pct CaO. This point is plotted in Figure 4.
Measurements of the solubility of CaO were also
performed by Kuxmann and Kurre[6] who used CaO
crucibles. After quenching, the slag and metal phase were
both analyzed. As can be seen from Figure 4, there is good
agreement between the results of Kuxmann and Kurre and
the present study.
Mutual solid solubilities of Cu2O and CaO were measured
as described in Section II. C. An equimolar mixture of Cu2O
and CaO was equilibrated at 1235 °C and quenched, and the
solid primary lime particles were analyzed for Cu2O. The
copper oxide (either CuO or Cu2O) solubility in solid CaO
(solidus composition) at 1235 °C was measured as 1.5 wt. pct.
To measure the solubility of CaO in solid Cu2O, a ternary
mixture (80 wt pct Cu2O, 5 wt pct CaO, 15 wt pct Na2O)
was heated to 1260 °C, cooled slowly to 780 °C (20 °C below
the ternary eutectic temperature), held at 780 °C for 3 hours
and quenched. The Cu2O-rich phase of the eutectic was
Fig.4—Cu2O-CaO-(Cu) phase diagram in equilibrium with Cu (solubili-
ties in terminal solid solutions  0.1 wt pct).
Fig. 5—Measurement of solubility of CaO in liquid Cu2O in equilibrium
with Cu at 1235 °C.
634—VOLUME 34B, OCTOBER 2003
analyzed for CaO. The solubility was found to be less than
0.1 wt pct CaO in solid Cu2O at 780 °C.
The phase boundaries drawn on Figure 4 were calculated
from the model, as discussed in Section V. The experimental
points of the present study are systematically approximately
5 °C below the calculated boundaries. We believe that this
probably reflects a real systematic error due to undercool-
ing and to contamination by dissolved alumina.
2. Activity of Cu2O in the slag
The activity of Cu2O in molten Cu2O-CaO slags equili-
brated with Cu was measured at 1235 °C, as described in
Section II–B. Results are shown in Figure 6. A slight neg-
ative deviation from ideal solution behavior of the activity
of CuO1/2 (aCuO1/2  aCu2O1/2) is seen when plotted vs mole
fraction in the CuO1/2-CaO system, thereby indicating a
small negative deviation from ideal (Temkin) random mixing
of Cu and Ca ions.
These same results are also plotted as equilibrium oxygen
pressure (calculated from Eq. [4]) vs composition in Figure 7,
where the results of Oishi et al.[7] at 1300 °C are also plotted.
These authors measured PO2 using CaO-ZrO2 solid electrolytes
with Ni/NiO reference electrodes.
Fig. 6—Activity of CuO1/2 (liquid standard state) in CuO1/2-CaO slags equi-
librated with Cu at 1235 °C.
Fig. 7—Equilibrium oxygen partial pressure of Cu2O-CaO slags equili-
brated with copper.
METALLURGICAL AND MATERIALS TRANSACTIONS B
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B. Cu2O-Na2O System
1. Phase diagram
Results of differential thermal analyses are presented in
Figure 8. After the experiments, several slag samples were
analyzed. Within error limits, the compositions were the
same as the original weighed-in compositions, indicating
that sodium losses by volatilization were negligible.
A ternary mixture (80 wt pct Cu2O, 5 wt pct CaO, and
15 wt pct Na2O) was heated to 1260 °C, cooled slowly to
780 °C, held at 780 °C for 3 hours, and quenched. The Na2O
content of the solid Cu2O was found to be 5
1 wt pct, as
shown in Figure 8.
As discussed in Section II–C, it was very difficult to
measure the Cu2O content of the solid Na2O. In general,
however, the results suggest a solubility of 1 wt pct or less.
2. Activity of Cu2O in the slag
The activity of Cu 2 O in molten Cu 2 O-Na 2 O slags
equilibrated with Cu was measured at 1200 °C, as
described in Section II–B. Results are shown in Figure 9.
A slight negative deviation of aCuO1/2 from ideal mixing
behavior is seen. The same results are plotted as equi-
librium oxygen pressure (calculated from Eq. [4]) vs com-
position in Figure 10.
Fig. 8—Cu2O-Na2O-(Cu) phase diagram in equilibrium with Cu.
Fig. 9—Activity of CuO1/2 (liquid standard state) in CuO1/2-NaO1/2 slags
equilibrated with Cu at 1200 °C.
METALLURGICAL AND MATERIALS TRANSACTIONS B
C. Cu2O-CaO-Na2O System
The DTA measurements were performed at constant
Cu2O compositions of 70, 80, and 90 wt pct (which is the com-
position range of most practical interest) in the Cu2O-CaO-Na2O
system in equilibrium with Cu. Results are presented in
Figures 11 through 13. Due to its steepness, measurements of
the CaO liquidus are less precise.
V. THERMODYNAMIC MODELING
The phase diagrams and the thermodynamic properties
are related by the equation
RT ln ai (liquidus)  RT ln ai (solidus)  
g0fusion(i) [8]
where ai (liquidus) and ai (solidus) are the activities of
component i at equilibrium on the liquidus and solidus (relative
to the liquid and solid standard states, respectively) and
gfusion(i)
0
is the Gibbs energy of fusion of component i at
temperature T. The Gibbs energy of fusion of Cu2O was given
in Eq. [3]. Those of Na2O and CaO were calculated by taking
Fig. 10—Equilibrium oxygen partial pressure of Cu2O-Na2O slags equili-
brated with copper at 1200 °C.
Fig. 11—Isopleth of the Cu2O-CaO-Na2O-(Cu) system at 70 wt pct Cu2O
(equilibrated with copper).
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Fig. 12—Isopleth of the Cu2O-CaO-Na2O-(Cu) system at 80 wt pct Cu2O
(equilibrated with copper).
the enthalpies and temperatures of fusion from the FactSage
5.1 database[9] and assuming Cp(fusion)  0. This gives
Na2O (solid)  Na2O (liquid) [9]

g0fusion  47,698  33.95T J/mol
CaO (solid)  CaO (liquid) [10]

g0fusion  79,496  27.94T J/mol
As shown in Sections IV–A–2 and B–2, the liquid phase
is close to an ideal (Temkin) solution of Cu,Ca, and Na
ions on cation sites. That is, the Gibbs energy of mixing is
close to

gideal  RT (XCuO1/2ln XCuO1/2 [11]
 XCaO ln XCaO  XNaO1/2 ln XNaO1/2)
where the Xi are the mole fractions of the components CuO1/2,
CaO, and NaO1/2. As shown in Section III, the concentra-
tion of Cu is small and the concentration of Cu0 is small
as long as the content of (CaO  Na2O) is above
3 wt pct.
Hence, in the model, it is assumed that all copper in the slag
is present as Cu.
The liquid was modeled with the modified quasi-chemical
model described elsewhere,[15] which takes into account the
small degree of short range ordering that must occur. This
model requires “cation-cation” coordination numbers, which
were chosen as ZCa  2ZNa  2ZCu  2.7548 in order to be
consistent with earlier optimizations of other slag systems,
thereby allowing the eventual incorporation of the present
model for Cu2O-Na2O-CaO slags into our larger database
for multicomponent slags.[9]
“Equivalent fractions” Yi are also defined as
YCaO  2XCaO /(2XCaO  XCuO1/2  XNaO1/2) [12]
YCuO1/2  XCuO1/2 /(2XCaO  XCuO1/2  XNaO1/2) [13]
YNaO1/2  XNaO1/2 /(2XCaO  XCuO1/2  XNaO1/2) [14]
The parameters of the modified quasi-chemical model
are the Gibbs energies gAB of the second-nearest-neighbor
pair-exchange reactions:
[A  A]  [B  B]  2[A  B]
gAB [15]
where A, B  Cu, Na, or Ca.
636—VOLUME 34B, OCTOBER 2003
Fig. 13—Isopleth of the Cu2O-CaO-Na2O-(Cu) system at 90 wt pct Cu2O
(equilibrated with copper).
By simultaneous least-squares optimization of all the data
(phase diagram and activities) for the Cu2O-CaO and Cu2O-
Na2O binary systems, the following expressions were obtain
for the model parameters:

gCuCa  (44,296  19T)  34,984 (YCaO  YCuO1/2)
 26,236(YCaO  YCuO1/2)2 (J/mol)
[16]

gCuNa  18,229  22,906 (YNaO1/2  YCuO1/2)
 21,745(YNaO1/2  YCuO1/2)2 [17]
 8083 (YNaO1/2  YCuO1/2)3 (J/mol)
The Cu2O-rich terminal solid solution was modeled as a
Henrian ideal solution of NaO1/2 and CuO1/2 with the
following activity coefficient, independent of composition
at a given temperature:
21,000(J/mol)
ln gNaO1/2  [18]
RT
All lines shown in Figures 4 through 13 were back-calculated
from the model equations. The model gives a melting point
of Cu2O of 1229 °C rather than 1223 °C because of the neglect
of Cu0 dissolution in the slag.
In the Cu2O-Na2O system, the model indicates that the
enthalpy of liquid-liquid mixing is slightly negative in Cu2O-
rich solutions and nearly zero or slightly positive in Na2O-
rich solutions. This gives rise to the prediction of a very flat
Na2O-liquidus in Na2O-rich solutions, as shown by the
dashed line in Figure 8. The model predicts similar behav-
ior in the Cu2O-CaO system, with a negative enthalpy of
mixing in Cu2O-rich solutions, becoming nearly zero or
positive in CaO-rich solutions. Hence, also in this system,
a flat CaO-liquidus is predicted.
Since the deviations from ideal solution behavior in the
liquid are small, the degree of short-range ordering is small.
Hence, as discussed by Pelton et al.,[15] the thermodynamic
properties of the binary liquids can be calculated approxi-
mately by taking the sum of gideal from Eq. [11] and an
excess Gibbs energy term equal to
ZCu XCuO1/2  ZCa XCaO
gE  a b YCuO1/2 YCaO
gCuCa [19]
2
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in the CuO1/2-CaO system, and
ZCu XCuO1/2  ZNa XNaO1/2
gE  a b YCuO1/2 YNaO1/2
gCuNa [20]
2
in the CuO1/2-NaO1/2 system.
The thermodynamic properties of the ternary liquid
Cu2O-Na2O-CaO solution were predicted from the binary
model parameters of Eqs. [16] and [17] using the “sym-
metric approximation,” as discussed by Pelton and Char-
trand. [16] No additional ternary parameters were used.
(Ideality was assumed in the CaO-NaO1/2 binary liquid
solution.) The calculated (predicted) phase boundaries
shown in Figures 11 through 13 agree well with the
measurements, except for the CaO-liquidus, where, as dis-
cussed in Section IV–A–1, the experimental points are
probably too low. Some of the thermal arrests at the 795 °C
invariant exhibited double differential thermal analy-
sis peaks, as shown in Figures 12 and 13. This remains
unexplained.
The model may be used to calculate various thermo-
dynamic properties and phase equilibria. For example, the
entire calculated liquidus surface of the Cu2O-Na2O-CaO
system in equilibrium with Cu is shown in Figure 14, and
the calculated oxygen content of liquid Cu in equilibrium
with the slag as a function of slag composition is shown on
Figure 15 (where Eqs. [4] and [5] were used for the copper
and oxygen activities in molten Cu).
VI. DISCUSSION
Industrially, the effectiveness of impurity removal from
blister copper by oxidation under a layer of soda slag
(Na2CO3-CaO) is highly dependent on oxygen potential.
Although this may be accomplished by injecting air/O2 mix-
Fig.14—Calculated liquidus of the Cu2O-Na2O-CaO-(Cu) system (equili-
brated with copper).
METALLURGICAL AND MATERIALS TRANSACTIONS B
tures into the molten copper, the eventual formation of excess
Cu2O must be taken into account. For example, Riveros et
al.[5] have shown that at 1250 °C, the solubility of copper
in Na2CO3 is very low when the oxygen potential PO2 is
below 106 bar, but above PO2  105 bar, the formation of
a Cu2O-rich slag takes place. As shown in Figure 8, Na2O
lowers the melting point of Cu2O, leading to the eventual
formation of a eutectic at 800 °C and approximately 28 wt
pct Na2O. Since Na2CO3 is stable as a carbonate melt, con-
ditions leading to its decomposition must be taken into
account (e.g., (1) level of impurities such as As and Sb, (2)
presence of other oxides such as SiO2 and FeOx, or (3)
control of PCO2 by adjusting the furnace draft or burner func-
tions). In general, depending on the process requirements,
the engineer may envisage alternative conditions and use
these systems to limit or promote the presence of immis-
cible layers. In fact, the concept of two immiscible layers
of slag for copper fire refining was recently used by Zamal-
loa et al.[17] in a process where a slag layer of Cu2O combined
with CaO or Na2O coexists with a molten (Na2SO4-CaSO4)
layer containing AsOx and SbOx. The present model for
Cu2O-CaO-Na2O equilibrated with molten copper may be
considered as the base system for the slag layer (copper
oxide–rich phase) in both soda-lime-fluxing and sulfate-
refining[17] processes.
VII. CONCLUSIONS
Based upon the present measurements, the Cu2O-CaO-
Na2O system in equilibrium with Cu has been modeled
thermodynamically at compositions from approximately
0 to 35 wt pct Na2O and 0 to 15 wt pct CaO. The para-
meters of the model are stored in the database of the
FactSage[9] system and can be used along with the other
FactSage databases and Gibbs energy minimization software
to calculate phase equilibria and all thermodynamic
Fig. 15—Calculated content of oxygen in liquid copper equilibrated with
Cu2O-CaO-Na2O slags at 1200 °C.
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properties of this system. For example, the liquidus
projection, as well as the oxygen content of the equilibrium
liquid copper phase as a function of slag composition, has
been calculated.
ACKNOWLEDGMENTS
Constructive discussions with Dr. P. Chartrand during the
entire course of this project are much appreciated. Financial
support from the Noranda Technology Center and from the
Natural Sciences and Engineering Research Council of
Canada is gratefully acknowledged.
REFERENCES
1. C.T. Eddy: Trans. AIME, 1931, vol. 96, p. 104.
2. W.J. Hillendbrand, B.K. Poule, and H.C. Kenny: Trans. AIME, 1933,
vol. 100, p. 483.
3. Q. Jiao, E. Carissimi, and D. Poggi: Proc. Copper 91-Cobre 91 Int’l. Sym-
posium, Ottawa, 1991, vol. 4, pp. 341-357, Pergamon Press, Elmsford, NY.
4. U.C. Rojas and J.C. Gomez: Proc. Howard Worner Symp. on
Injection in Pyrometallurgy, TMS-AIME, Warrendale, PA, 1996,
pp. 275-87.
638—VOLUME 34B, OCTOBER 2003
5. G. Riveros, Y.J. Park, Y. Takeda, and A. Yazawa: J. Min. Metall. Inst.
Jpn, 1986, vol. 102, pp. 415-22.
6. J. Kuxmann and K. Kurre: Erzmetallurgy, 1968, vol. 21, pp. 199-209.
7. T. Oishi, Y. Kondo, and K. Ono: Trans. Jpn. Inst. Met., 1986,
vol. 27. (12), pp. 976-80.
8. H. Ranniko: Acta Polytech. Scan., 1995, Chem. Technol. Ser., vol. 229,
pp. 1-78.
9. C.W. Bale, A.D. Pelton, and W.T. Thompson: F*A*C*T (Facility for
the Analysis of Chemical Thermodynamics), Ecole Polytechnique, Mon-
treal (http://www.crct.polymtl.ca), 2002.
10. A.D. Mah, L.B. Pankratz, W.W. Weller, and E.G. King: Report of
Investigation 7026, U.S. Bureau of Mines, United States Government
Printing Office, Washington, DC, 1967.
11. J.P. Neumann, T. Zhong, and Y. Chan: Phase Diagram of Binary Cop-
per Alloys, ASM INTERNATIONAL, Material Park, OH, 1994,
pp. 288-93.
12. G.K. Sigworth and J.F. Elliott: Can. Metall. Q., 1974, vol. 13 (3),
pp. 455-62.
13. T. Oishi and K. Ono: Trans. Jpn. Inst. Met., 1986, vol. 25 (4),
pp. 291-300.
14. A.D. Pelton: Metall. Mater. Trans. B, 1997, vol. 28B, pp. 869-77.
15. A.D. Pelton, S.A. Degterov, G. Eriksson, C. Robelin, and
Y. Dessureault: Metall. Mater. Trans. B, 2000, vol. 31B, pp. 651-60.
16. A.D. Pelton and P. Chartrand: Metall. Mater. Trans. A, 2001, vol. 32A,
pp. 1355-60.
17. M. Zamalloa, Y. Tremblay, P. Coursol, and E. Carissimi: U.S Patent
No. 6, 395, 059 B1, 2001.
METALLURGICAL AND MATERIALS TRANSACTIONS B