Transactions

of theJapan Instituteof Metals,Vol. 24, No. 7 (1983),pp. 518to 528

Distribution Equilibria of Minor Elements

between Liquid Copper and Calcium Ferrite Slag

By Yoichi Takeda*, Shoji Ishiwata** and Akira Yazawa*

The distribution of Ag, Co, Ni, Zn, Sn, Pb, As, Sb and Bi between calcium ferrite slag and

liquid copper was measured at 1523 K under controlled CO-CO2 atmospheres. The distribution

ratios, defined by %X in slag/%X in metal, were plotted against the oxygen potential and compared

with those obtained for silicate slag. From the slopes of such plots, reasonable oxide forms dissolved
in slag, XOν, were estimated. The increasing content of CaO in ferrite slag results in increase in the

distribution ratio for As or Sb, but in decrease in the ratio for Pb. The effects of the composition

change in the alloy phase and the temperature dependence on the distribution ratios were evaluated

thermodynamically. It was proved that a mono-nuclear atom base expression is reasonable to

express the oxide form dissolved in slag, such as CuO0.5, AsO1.5 etc. Moreover, from the iron

contents in a Cu-X alloy, the interaction parameters between Fe and X in liquid copper were derived.

(Received February 21, 1983)

Keywords: ferrite slag, distribution equilibrium, impurity distribution, activity coefficient,

oxygen potential, equilibrium study, thermodynamic study, copper smelting, interaction
parameter

taming a minor element were brought into

Ⅰ. Introduction equilibrium in a lime, magnesia or silicacrucible
usually at 1523 K under a current of CO-CO2
Interesting features of calcium ferrite slag gas mixture. Most procedures were similar to
have recently been recognized(1), and ther- those describedin the previousreports(2)(3).
modynamic properties of the FeO-Fe2O3-CaO The chemical analysis for minor elements were

system were reported previously(2). Considering mostly carried out by the atomic absorption

the application of the ferrite slag to the copper method, but the photometric method by using

smelting, the equilibrium relations between the silver diethyl-dithiocarbamate pyridine solution

slag and liquid copper were also investigated by was used for arsenic.

the authors(3). In the present paper, the distri-

bution equilibria of Ag, Co, Ni, Zn, Sn, Pb, Ⅲ. Thermodynamic Expression

As, Sb and Bi between liquid copper and cal-

cium ferrite slag are described in comparison When the slag-metal distribution of a minor

with those obtained for iron silicate slag. A element X having the valence of 2ν is con-

considerable number of reports(4)-(15) are sidered, the equilibrium constant K for the

available for the distribution of minor ele- following reaction is expressed by the terms of

ments between iron silicate slag and liquid activities, and derived by free energy data,

copper, but the results do not necessarily ΔG°(16)(17).

agree with one another. Thus, the distribution X+ν/2O2=XOν (1)

measurements of Sb, Bi, Zn, Sn and Pb were
and
also carried out for the silicate slag system.
K=aXO ν/(aX・pν/2O2). (2)

Ⅱ. Experimental Procedure The distribution ratio of X between slag and

liquid copper will be described as follows:

Calcium ferrite slag and copper metal con-

* The Research Instituteof Mineral Dressing and (3)

Metallurgy (SENKEN), Tohoku University,
where () and [] denote the values in slag and
Sendai 980, Japan.
** Mitsubishi Metal Research Institute , Omiya, metal phases, respectively.As described in the
Saitama 330, Japan. previous paper(3),nT isthe totalmole number of
 Distribution Equilibria of Minor Elements between Liquid Copper and Calcium Ferrite Slag 519

constituents in 100 g of eaih phase.(nT) in the

present study is around 1.45 when all con-

stituents are expressed with the mono-nuclear

metal atom base such as FeO1 .5, CuO0.5 etc.

Considerable data are available for [γX] in the

plain Cu-X binary systems, and the values in

infinite dilute solution for X, [γoX](18)-(20), are
).K 3

summarized in Table 1 together with those for

251

ΔG° and log K. The values of p*o

2 in Table 1 are
(gal

derived from eq.(2) assuming aX and aXO ν are

sd

unity. The value of

(γXO ν) in eq.(3) can be de-
nareppocneewt

rived from distribution measurements, and the

value of ν may be estimated from the slope of

the plot of log LS/CuX versus log pO2.

Ⅳ. Experimental Results and Discussion

ebs
tnemel

1. Distribution of silver and copper

er

Calcium ferrite slag containing around 25

oni

per cent CaO was brought to an equilibrium in

mf

a magnesia crucible with liquid copper contain-

oai

ing 1 or 5 per cent silver. The distribution ratios

r

of copper and silver are plotted against the oxy-

bi
liuqeno

gen potential in Fig. 1 with half-closed circles

and squares. Because silver is very difficult to be
oxidized, the distribution ratio is so small that
itubi

the order of magnitude is between 10-4 and

1el
baT rtsi
dht
iw gni
tal
erat
adci
manydomr
ehT

Fig. 1 Distributionratiosof copper and silverplotted

againstoxygen potentialat 1523 K.
520 Yoichi Takeda, Shoji Ishiwata and Akira Yazawa

10-3,buttheslopeforlogpO2isapproximately
1/4,similar
to thatforcopper,suggesting that
bothofcopperand silver dissolveinslaginthe
mono-valent oxideform,CuO0 .5and AgO0.5.
Richardsonetal.(22) and Kashima etal.(8)
investigated
thedissolution of silver
in silicate
slagbut didnot observeany appreciable de-
pendenceon the oxygenpotential, and esti-
mated the dissolution in a metallic form.
However,when theregionofoxygenpotential
investigated
wasnotwideenough,theprecision
of chemicalanalysis fora minuteamount of
silvermight not be so high to confirma
gentleslope.Moreover,dissolution of silver
asthesulphide may alsobe expected intheex-
perimentof Kashima etal.(8), becausethree
liquidphasesof slag, whitemetaland copper
wereincoexistence.
To clarify
thedissolution formsofcopperand
silver,
calciumferrite slagwas broughtto an Fig. 2 Distribution ratiosof lead and zinc plotted
equilibrium
withsilver metalcontaining around againstoxygen potentialat 1523 K.
1 percentcopperundera current ofCO-CO2,
CO2, airor pureoxygen.The obtained distri-the solid magnetite separation, the dotted lines
butionratiosofcopperandsilver areillustrated are limited to around -7 of log pO2. In a general
in Fig.1withmarksof opencircles and open trend, zinc dissolves mainly into slag but lead
squares.Althoughthepossibility of predomi- into the copper phase. However, the distribu-
nant existence of metallicsilver in slagcan tion ratios of zinc and lead are much larger in
not be deniedin the loweroxygenpotentialsilicate slag than in forrite slag. As reported(3),
region,thepredominant dissolved speciesmay copper represents a similar tendency, and the
be of the monovalentoxideform,thatis, results are reproduced also in Fig. 2. The ratios
CuO0 .5 and AgO0.5.In the higheroxygen of LS/CuX in ferrite slag to silicate slag, LS/CuX
potentialregion,possible existence of the (ferrite)/LS/CuX(silicate), are also listed in Table 1.
divalentoxideof copper,CuO, may alsobe Judging from the slope of each line in Fig. 2,
suggested
fromthevariation oftheslope. zinc and lead in slag are believed to exist in the
Itisunderstood fromeq.(3)thatthediffer-divalent form, ZnO and PbO.
ence betweenLS/CuCu and LS/AsCu,
or LS/CuAgand The significant differences in the distribution
LS/AgAg, observed in Fig. 1, can be ascribed to the ratios between ferrite and silicate slags are

values of [γX]. The difference between LS/MCu and hardly observed for cobalt, nickel and bismuth,

LS/MAg in Fig. 1 is around two in the order of as illustrated in Fig. 3. Similar tendencies are

magnitude, and is mainly ascribed to the differ- also expected for silver and iron, although iron

ence in the equilibrium constants as shown in is not a minor element. Cobalt tends to dis-
Table 1. solve into slag, beiause it has a strong affinity
with oxygen and [γCO] in copper is more than 10.
2. Distribution of various minor elements
Dissolution as the divalent oxide is clearly ex-

The distribution ratios of zinc and lead pected for cobalt, and probably also for nickel
between calcium ferrite slag and liquid copper although the slope is intermediate between XO

are illustrated in Fig. 2 with open marks and and XO0 .5.
solid lines. The distribution ratios between iron On the contrary, the dissolution ratios for tin,

silicate slag and liquid copper are also shown arsenic and antimony are much larger for the

with closed marks and dotted lines. Because of ferrite slag, as illustrated in Fig. 4 and in
 Distribution Equilibria of Minor Elements between Liquid Copper and Calcium Ferrite Slag 521

Table 1. Thus, ferrite slag is more convenient

for oxidation removal of these elements from

liquid copper. It is understood that basic ferrite

slag is convenient to fix acidic oxides. On the

other hand, acidic silicate slag may be superior

to remove lead or zinc as basic oxides. How-

ever, judging from the low distribution ratios of

arsenic, antimony and bismuth, especially in the

low oxygen potential, removal of these ele-

ments from copper is not very easy.

Although the slopes for arsenic, antimony

and bismuth are located between XO and

XO1 .5, the predominant dissolved species of
these elements seem to be of the trivalent oxide

form, AsO1 .5, SbO1.5 and BiO1.5. It is inter-

esting that divalent SnO may be predominant

under a usual condition, but tetra-valent SnO2

is expected at a higher oxygen potential.

Nagamori et al.(5) and See and Rankin(13)

did not confirm any dependence of the distribu-

tion ratios of arsenic, antimony and bismuth

on the oxygen potential and assumed the neu-

tral dissolution forms, As and Sb. However,
Fig. 3 Distributionratiosof cobalt,nickel,bismuth
judging from their precision of chemical analy-
and silverplottedagainstoxygen potentialat1523 K.
sis and the region of oxygen potential investi-

gated, their conclusion is not necessarily

reasonable. The oxide dissolution of these ele-
ments is supported by Goto et al.(11).

In a practical operation of Mitsubishi con-

tinuous converting furnace, calcium ferrite slag

is in coexistence with liquid copper at around

-5 .5 of log pO2. The practical distribution
ratios(23) for As, Sb and Pb agree in general

with the data obtained in the present work,

but that for Bi is much higher than that shown

in Fig.3.

3. Activity coefficients of dissolved oxides

Based upon the distribution ratios described

above, the activity coefficients of the minor

oxide components in slag can be derived from

eq.(3). However, it should be noted that under

an extremely low or high oxygen potential the

constancy of [γX] may not necessarily be guar-

anteed because of the dissolution of iron or

oxygen in liquid copper. Thus, (γXO ν) is derived

based upon eq.(3) in the region of log pO2

Fig.4 Distributionratiosof tin,arsenic and anti- from -11 to -6, illustrated in Figs.5 and 6,
mony plottedagainstoxygen potentialat 1523 K. and also summarized in Table 1. Approximately

horizontal lines are observed for the oxides of

522 Yoichi Takeda, Shoji Ishiwata and Akira Yazawa
Fig. 5 Activitycoefficients
of divalentoxides in slag
plottedagainstoxygen potential.
Fig. 6 Activitycoefficientsof mono-and
oxides in slag plottedagainstoxygen potential.
which the valencesare estimatedobviously,but
the dependence on the oxygen potentialmight
be too bigforthe activity
coefficients
of AsO1 .5,
SbO1 .5 (ferrite),BiO1.5 (ferrite)and NiO
(ferrite).
4. Effectsof CaO contentin ferrite
slag
The distributionratiosof nickel,arsenicand
antimony between calcium ferriteslagand liq-
uid copper were determined at a fixedoxygen
potentialat 1523 K under varying content of
CaO in slag.As shown in Fig.7, the distribu-
tionratioof nickeldoes not show any appreci-
able change with variationof the CaO content.
Similarbehaviourwas confirmed for copper(3).
On the other hand, the distribution ratiosof
arsenic and antimony which tend to form
acidicoxidesincreasegraduallywith increasing
CaO contentin the slag.
The activitycoefficientsof these oxides are
plottedagainstCaO contentintheslagas shown
in Fig.8. The linefor PbO which was a basic
oxide was estimatedbased upon unpublished
data(24),and representsjust an oppositetend-
ency to thosefor arsenicand antimony.
5. Effectsof metalphase compositionson
distribution
behaviour
At the fixedoxygen potentialat 1523 K, the
distribution
ratiosof X between slagand liquid
Cu-X alloy were investigatedunder varying
tri-valent
Fig.7 Effectof CaO contents in slagon distribution
ratiosat 1523 K.
 Distribution Equilibria of Minor Elements between Liquid Copper and Calcium Ferrite Slag 523

those for ferrite slag containing around 25 per

cent CaO. Because the distribution ratios in

Fig. 9 are considerably lower than unity, the

contents of XOν in the slag are rather small,

though the contents of X in the copper alloy is

considerable, and thus, the composition of the

slag does not change significantly. Accordingly,

it is expected that the activity coefficients of

oxide of X in slag,(γXO ν), are not very much

influenced by the copper alloy composition.

This is proved by the derived activity coeffi-

cients of XOν, as illustrated in Fig. 10.

When the temperature, the oxygen potential

and the slag composition are kept constant, the

distribution ratios are controlled by the activity

of X in the alloy, [γX], as suggested by eq.(3).

In the binary alloy system of which the activities

exhibit a positive deviation, [γX] tends to de-

Fig. 8 Effect of CaO contents in slag on activity co- crease with increasing X content in the alloy,
efficients of oxides. and results in decreasing distribution ratio.

Thus, the distribution ratios of lead, silver,

bismuth and nickel in Fig. 9 decrease with in-

creasing contents of these metals in the alloys.

On the contrary, an inverse tendency is ob-

served for antimony and arsenic.

The distribution equilibria were also deter-

mined in the whole composition range of Cu-

Ag and Cu-Pb binary alloys. Figure 11 shows

results for the Cu-Ag system at pOt=10-8 and

10-11, and reflecting

the positivedeviation

Fig.9 Effects
of copperalloycompositions
on the
distribution
ratiosat1523K.

composition of the copper alloy phase, and

resultsobtained are plottedagainstthe con-
centrationof X in the Cu-X alloy in Fig.9.
Dotted lineswith closedmarks are the data for Fig. 10 Effects of copper alloy compositions on
iron silicate
slag,and allother solidlinesare activitycoefficients
of oxides.
524 Yoichi Takeda, Shoji Ishiwata and Akira Yazawa

Fig. 12 Variationsof distributionratios and activity

coefficientsof oxides plotted against equilibrating
Cu-Pb alloycomposition.

ratio of copper is considerable, but that of lead

is much smaller than that expected. This is
ascribed to a great difference in the atomic
weights between copper and lead; i.e., in eq.
(3), increasing lead content in the alloy results
in decrease in [γPb], but at the same time brings
about decrease in [nT] to cancel the variation of

LS/MPb. On the contrary, variation of LS/MCu is

accelerated by both of [γCu] and [nT]. The activity

coefficients of copper and lead oxides are also

constant, as shown in Fig. 12, suggesting that
the evaluation of the distribution behaviour
Fig. 11 Variations of distribution ratios, activity co- will be easily realized in such a case based upon
efficients and iron content in alloy plotted against eq. (3).
equilibrating Cu-Ag alloy composition.
6. Temperature dependence of distribution
behaviour of activities in this binary alloy, as ratios
explained above, increasing silver content in the The temperature dependence of the distribu-
alloy results in decreasing distribution ratio of tion ratios between ferrite slag containing 25
silver and also increasing distribution ratio of per cent CaO and liquid copper at PO2=10-8 is
copper. As has been described, both of these summarized in Fig. 13. The results for nickel
elements dissolve into slag in the monovalent and cobalt are similar to those reported for iron
oxide form, and the activity coefficients of the silicate slag(4)(6)
oxides are not influenced by the alloy composi- . When the regular solution behaviour is pos-
tion, as shown in the top of Fig. 11. tulated for both of the slag and copper metal
The distribution ratios between ferrite slag phases under a given slag composition and oxy-
and the Cu-Pb alloy are illustrated in Fig. 12. gen potential, the temperature dependence of
Because the positive deviation of activity curves the distribution ratio may be expressed as
in the Cu-Pb system is more significant than in follows based upon eq. (3):
the Cu-Ag system, variation of the distribution
 Distribution Equilibria of Minor Elements between Liquid Copper and Calcium Ferrite Slag 525

Fig. 14 Calculated temperature dependency of dis-

Fig. 13 Experimentai results of temperature de-
tribution ratios at log pO2=-8 under assumption
pendency of distributionratiosat logpO2=-8.
of regular solution behaviour.

theory, from the data of[γoX] listed in Table 1

and also of (γXO ν) illustrated in Figs. 5 and 6:

ΔH=RTlnγ. (5)

The distribution ratios thus evaluated at

log pO2=-8 are plotted against 1/T, as illus-

(4) trated in Fig. 14. The results generally agree

with those shown in Fig. 13, but small differ-

where ΔH° and ΔS° are standard enthalpy and ences may be ascribed to various reasons such
entropy changes for the oxidation reaction of as accuracy of thermodynamic data including
eq.(1), and the values are tabulated in Table 1. ΔH°, ΔS° and γ, estimation of valence 2ν,
The partial molar enthalpy of X in the Cu-X postulation of regular solution, and also ex-
alloy, ΔH[X], and the partial molar enthalpy of perimental error.
XOν in slag, ΔH(XO The temperature dependence itself is pre-
ν),are derived, based upon
the following equation of the regular solution dominantly influenced by ΔH°, and the absolute
 526 Yoichi Takeda, Shoji Ishiwata and Akira Yazawa

value of ΔH° increases with inireasillg affinity

for oxygen and also increasing value of ν.

Accordingly, the temperature dependence of the

distribution ratio increases in the order of

XO0 .5, XO and XO1.5, and is greater for Fe or

Zn than for Pb even at the same oxide form of

XO. An extream case would be observed for

phosphorus which has the high valence and the

affinity for oxygen. The distribution ratio of

phosphorus is illustrated in Fig.13 based upon

the data obtained by Kuxmann et al.(25).

7. Representation of oxide species in slag

It was reported in our previous report(3) that

the representation of oxidic species with the

mono-nuclear atom base was very convenient,

because the total mole number of constituents

in 100 g of slag (nT) could be taken as a fixed

value. It was observed in the present study that

this way of expression is also reasonable from

the theoretical standpoint, although the similar

conclusions were already described by a few

reseaxihers(26)-(28).

In Fig.15, the activity coefficients of oxidic

species are plotted against mole fractions of the

oxides in the slag phase. In the top figure, the Fig.15 Activitycoefficients
of oxidesplottedagainst
oxidic species are expressed with one cation mole fractionof oxidesinslagat 1523K.
base such as CuO0 .5, SbO1.5, etc., and fixed Top figure:Under assumption of mono-nuclear
values of the activity coefficients are observed, metal atom oxides.
Bottom figure:Under assumptionof multi-nuclear
though the concentrations of these oxides are
metal atom oxides.
considerably varied; that is, Henry's law is

valid in this way of expression. However, when

(NXOn/m)=1.56(NxmOn) (7)
the oxides having the odd number valence are
and
represented With the form of XmOn suih as

Cu2O, Sb2O3, as shown in the bottom figure in (γXmOn)=2.43(γXOn/m)2(NXmOn). (8)

Fig.15, the activity coefficients of these oxides In this equation, if(γXO n/m) is a fixed value as
never show definite values against the con- shown in the top figure in Fig.15, (γXmOa) must
centration. be a function of (NX mOn), as shown in the bot-
The following equation is valid between these tom figure, and it tends to become zero in the
two expressions: infinite dilue solution of XmOn. This is ther-

modynamically unreasonable.
(γXmOn)=(γXOn/m)m(NXOn/m)m/(NXmOn). (6)
It should be noted that the mono-nuclear

When the mono-nuclear atom base expression is atom base expression is also indispensable to
used for the present ferrite slag, i.e., FeO- discuss the temperature dependence of the
FeO1 .5-CuO0.5-CaO-MgO-XOn/m system, (nT) distribution ratios described above.

is always approximately 1.45, while (nT) is

8. Behaviour of iron in liquid copper phase
around 1.13 at ρO2=10-8 and (%CaO)∼25 if

the multi-nuclear atom base expression such as Relating the experimental studies shown in
FeO-Fe2O3-Cu2O-CaO-MgO-XmOn is adopt- Figs. 9, 10 and 11, the iron contents in liquid
ed. Thus, copper alloy were also determined. Results
 Distribution Equilibria of Minor Elements between Liquid Copper and Calcium Ferrite Slag 527

Fig. 17 Effects of alloy compositions on the activity

coefficient of iron in liquid copper at 1523 K.

Table 2 Interaction parameter between Fe and X in

liquid copper alloy (1523 K).

Fig. 16 Iron contents in liquid copper alloy plotted

against alloy composition at 1523 K.
in Table 2, although the accuracy of these values
may be not so high because of the derivation
obtained for the Cu-Ag alloy are illustrated in procedures including various assumptions and
Fig. 11, and reflecting the immiscible character experimental errors.
between iron and silver, iron contents decrease
remarkably with increasing silver content in the Ⅴ. Summary
alloy phase.
Variations of the iron contents in various The distribution equilibria of Ag, Co, Ni,
alloys rich in copper are summarized in Fig. 16. Zn, Sn, Pb, As, Sb and Bi between calcium fer-
The iron contents increase with increasing rite slag and liquid copper, and also of Zn, Sn,
nickel or arsenic content in liquid copper, but Pb, Sb and Bi between iron silicate slag and
decrease with increasing silver, bismuth or lead liquid copper were determined. From the re-
content. Because these alloying elements do not lations between the distribution ratio and the
dissolve so much into the slag phase, a definite oxygen potential the predominant oxide forms
composition of slag may be assumed under a of minor elements dissolved in slag were
given temperature and oxygen potential, and estimated to be CuO0.5, AgO0.5, CoO, ZnO,
thus, a definite activity value of iron, aFe, is NiO, SnO, PbO, AsO1.5, SbO1 .5 and BiO1.5.
also postulated. Using the literature value(18) The proportions of the distribution ratios for
of the activity coefficient of infinite dilution of ferrite slag to those for silicate slag, LS/CuX
iron in liquid iopper at 1523 K,[γoFe(1)]=17.5, (ferrite)/LS/CuX
(silicate), are around 8 to 10 for
the activity coefficients of iron derived from the As, 6 to 10 for Sb, 2 for Sn, 1 to 2 for Ni, 1 for
data of Fig.16 are plotted against the mole Bi, Co and Ag, 0.7 for Cu, 0.25 for Zn, and 0.1
fraction of X in the alloy as shown in Fig.17. for Pb.
From the slopes obtained in Fig.17, the inter- The distribution ratios for As and Sb of
action parameters εXFeare derived and tabulated which the oxides are acidic increase with in-
 528 Yoichi Takeda, Shoji Ishiwata and Akira Yazawa

creasing CaO content in slag, on the contrary, (6)J.R. Taylor and J.H.E. Jeffes : Trans. Inst. Min.
the dissolution of Pb in slag decreases as the Met., 85 (1976), C136.
content of CaO in slag increases. However, (7)M. Nagamori and P.J. Mackey: Met. Trans.,
8B (1977), 39.
there are essentially no influences on the distri-
(8)M. Kashima, M. Eguchi and A. Yazawa: Trans.
bution ratios for Cu and Ni with increasing Japan Inst. Metals, 19 (1978), 152.
CaO content in slag. (9)S. Goto, O. Ogawa, Y. Inoue and H. Ohara: J.
When the content of minor element to be Min. Metall. Inst. Japan, 95 (1979), 205.
investigated increases in the copper alloy (10)M. Kashima, Y. Nishikawa, M. Eguchi and A.
Yazawa: J. Min. Metall. Inst. Japan, 96 (1980),
phase, the variation in the distribution ratio can 907.
be ascribed to the activity behaviour of this (11)S. Goto, O. Ogawa and I. Jimbo: Australia/Japan
element in the copper alloy. Extractive Metallurgy Symposium 1980, The
The temperature dependence of the distribu- Australasian Inst. Min. Metall, (1980), 127.
tion ratio of element X is determined by the ex- (12)D.C. Lynch and K.W. Schwartze: Can. Met.
Quart., 20 (1981), 269.
periment and also estimated by using ther- (13)J.B. See and W.J. Rankin: Randburg, National
modynamic data Because the predominant role Institute for Metallurgy, Report No. 2099, (1981),
is played by ΔH°, the element having a large (South Africa).
valence and a large affinity for oxygen repre- (14)M.G. Park, S. Nakazawa and A. Yazawa: Bull.
Res. Inst. Mineral Dress. Metall., Tohoku Univ.,
sents large ΔH° and temperature dependence of
38 (1982), 21.
the distribution ratio.
(15)A. Yazawa, M. Oida and Y. Nishikawa: J. Min.
As to the oxidic species dissolved in slag, the Metall. Inst. Japan, 98 (1982), 963.
expression with the mono-nuclear metal atom (16)A. Yazawa (ed.): Nonferrous Extractive Metal-
base seems to be reasonable from both theoreti- lurgy, Japan Inst. Metals, (1982), p. 315.
cal and practical standpoints. The multi- (17)M. Hino and T. Azakami: J. Min. Metall. Inst.
Japan, 96 (1980), 159.
nuclear atom base expression such as AS2O3,
(18)R. Hultgren, P.D. Desai, D.T. Hawkins, M.
Sb2O3, Cu2O0 etc. can not prove a reasonable Gleiser and K.K. Kelley: Selective Values for the
value for the activity coefficient under varying Thermodynamic Properties of Binary Alloys,
concentration of such an oxide in slag. (1973), Am. Soc. Metals, (Ohio).
The iron content in the copper alloy was (19)T. Azakami and A. Yazawa: Can. Met. Quart.,
15 (1976), 1.
determined under various Cu-X alloy composi-
(20)Estimated by the authors based upon the present
tions, and the interaction parameters between experimental date combining with those in (10),
Fe and X in liquid copper were derived. (17) and following paper: K. Itagaki, M. Hino
and A. Yazawa: Erzmetall, 36 (1983), 59.
Acknowledgement (21)S. Arac and G.H. Geiger: Met. Trans., 12B
(1981), 569.
The present investigation was supported
(22)F.D. Richardson and J.C. Billington: Trans.
partly by the Grant-in-Aids for Scientific Re- Inst. Min. Met., 65 (1956), 293.
search from the Ministry of Education, Science (23)T. Yanagida, M. Goto, S. Kawakita, T. Echigoya
and Culture, Japan. and N. Kikumoto: The paper presented in the
112th AIME Annual Meeting, Feb. 1983,
Atlanta.
REFERENCES
(24)Y. Takeda, M. Uekawa and A. Yazawa: unpub-
(1)A. Yazawa, Y. Takeda and Y. Waseda: Can. lished data.
Met. Quart., 20 (1981), 129. (25)U. Kuxmann and P. Volzing: Erzmetall, 22 (1969),
(2)Y. Takeda, S. Nakazawa and A. Yazawa: Can. 261.
Met. Quart., 19 (1980), 297. (26)J. Lumsden: Physical Chemistry of Process Metal-
(3)A. Yazawa and Y. Takeda: Trans. Japan Inst. lurgy, ed. by G.R. St. Pierre, AIME Conferences
Metals, 23 (1982), 328. Vol. 7, Interscience, (1959), p. 165.
(4)S.S. Wang, A.J. Kurtis and J.M. Toguri: Can. (27)R. Altman and H.H. Kellogg: Trans. Inst. Min.
Met. Quart., 12 (1973), 383. Met., 81 (1972), C163.
(5)M. Nagamori, P.J. Mackey and P. Tarasoff: (28)N. Fukatsu, Y. Shimoda, Z. Kozuka: J. Min.
Met. Trans.. 6B (1975). 295. Metall. Inst. Japan, 92 (1976), 357.