Thermodynamics of Copper Matte Converting" Part III.

Steady-State Volatilization of Au, Ag, Pb, Zn, Ni, Se, Te,

Bi, Sb, and As from Slag, Matte, and Metallic Copper
M. NAGAMORI and P.C. CHAUBAL

A comprehensive compilation of various thermodynamic data required for a complete analysis of

copper matte converting reactions is presented. The data comprise estimated free energies of formation
for such gases as SeO, SeS, TeO, TeS, BiO, BiS, SbO, SbS, AsO, and AsS, as well as activity
coefficients in dilute copper alloys and vapor pressures of various elements and compounds. The
volatilization of minor elements in steady-state reactors comprising gas and several condensed phases
is mathematically formulated, and a parameter which governs the volatilization in such reactors is
defined and named volatilization constant. The vapor pressures of various volatile species are calcu-
lated thermodynamically for the Noranda Process reactor by assuming equilibrium conditions. The
volatilization constants of various minor elements are expressed explicitly as functions of oxygen and
sulfur activities.

I. INTRODUCTION of the Noranda Process, but to demonstrate a new computer-

THERMODYNAMIC models of copper-matte converting modeling concept and technique which can certainly
have been recently formulated. 1,2 As an example of the be applied in the analyses of many pyrometallurgical
application, the models were demonstrated to predict the process reactors where steady-state or equilibrium condi-
behavior of five major elements I (Cu, Fe, S, O, SiO2) and tions prevail.
also ten minor elements 2 in the condensed phases of the
Noranda Process. These models not only provide plausible
explanations for the commercial operation data, but also II. THERMODYNAMIC DATA
reveal many important fundamentals that are useful in con-
trolling the commercial process. The models were based on Some of the required basic free energy data were
the assumption that molten phases in the Noranda Process compiled elsewhere. 1.2 Table 13-32 provides additional ther-
reactor are in equilibrium with each other as well as with mochemical data for important gaseous species. Several
the reacted tuyere gas, or SOz-Nz gas. The remarkable suc- values of AH~98, S~98, and c o that are still missing in the
cess of these equilibrium modelings encouraged a further literature were estimated by the authors, and the details of
thermodynamic analysis of the process with the aims of the calculation are given in the Appendix A. Using the data
assessing the volatilization of the minor elements in the listed in Table I, the free energy (AG ~) data were calculated
reactor, and establishing eventually the overall performance by the relation:
of the reactor as to the ten minor elements.
The present work consists of three studies: the first is a
critical review and compilation of the related thermo-
AG~- = AH~98 + f;98
Ac~dT -- TASk98 - T f2TAcp
98 Z
dT

dynamic data (Part III), the second the derivation of a [201]

mathematical formula for steady-state volatilization (also The AG~ values were calculated at every 200 K from 300 to
Part III), and the third a demonstration of how to apply 1500 K, and the least squares method was then applied to
the steady-state reactor model to the commercial Noranda these values to obtain linear expressions, which are listed in
Process (Part IV). Table II. These linear expressions may be used up to 2000 K
The present model can provide a set of predictions for the without loss of accuracy.
overall reactions of minor elements as functions of process Selected activity coefficients of minor elements of
parameters. The predictions are presented in the form of binary Cu-M melts at infinite dilution ('),~) are summarized
tables (Part IV). This tabular method coupled with computer in Table III. 22-29 By definition,
techniques allows the analysis of a complex multi-
component system, which is practically impossible with aM = '~~ [202]
graphical methods. where aM refers to Raoultian activity and ArMto mole fraction
It will be self-evident in the course of the present of minor element M.
modeling that the ultimate purpose of the present study In copper matte converting, molten metallic copper
is not merely to explain the commercially observed data saturated with copper sulfide, or Cu2S, appears. Activity
M. NAGAMORI, formerly Associate Professor, Department of Metal- coefficients of minor elements in Cu2S-saturated copper,
lurgical Engineering, University of Utah, Salt Lake City, UT, is now with 3r'~, may be calculated on the basis of the relation:
Centre de Recherches Min6rales, Quebec Government, 2700 Einstein,
Ste-Foy, Quebec GIP 3W8, Canada. E C. CHAUBAL is Graduate In 3r~ = In y~ + e~Vs [203]
Student, Department of Metallurgical Engineering, University of Utah,
Salt Lake City, UT 84112. where e s refers to the Wagnerian interaction parameter.
Manuscript submitted September 8, 1981. Accordingly,
ISSN 0360-2141/82/0911-0319500.75/0
METALLURGICAL TRANSACTIONS B 9 1982 AMERICAN SOCIETY FOR METALS AND VOLUME 13B, SEPrEMBER 1982--319
THE METALLURGICAL SOCIETY OF AIME
 Table I. Selected and Estimated Standard Heats of Formation, Entropies,
and Molar Heat Capacities of Related Gases (See Appendix A for PWi)
A/-~29s ~gs cp = a + b x 10-3T + c x 10ST-s (cal/mole/deg)
Gas (kcal/mole) Reference (cal/mole 9 deg) Reference a b c Reference
O 59.55 3 38.47 16 4.98 0 0.24 17
02 0.0 -- 49.01 9 16 7.16 1.00 -0.40 17
S 66.4 3 40.09 16 4.96 0.10 0.60 17
$2 30.84 3 54.5 16 8.72 0.16 -0.90 17
Se 54.3 7 42.21 16 5.57 0.02 -0.52 17
Ses 34.12 3 60.2 16 8.73 0.32 -0.34 17
Se6 35.38 4 110 16 30.74 1.04 - 1.82 17
SeO 12.75 7,PW1 55.83 5 8.35 0.36 -0.88 17
SeO2 -26.2 5 62.74 5 13.12 0.41 -2.58 5
SeS 34 PW2 58.6 6,PW2 9 0 0 PW5
Te 47.02 7 43.64 7 4.64 0.44 0.18 17
Te2 40.2 7 64.1 7 8.94 0 -0.20 17
TeO 17.3 8 58.0 8 8.44 0.32 -0.83 17
TeO2 - 15.1 8 65.7 8 13.28 0.17 -2.47 8
TeS 47 PW2 60.4 6,PW2 9 0 0 PW5
As 69.0 4 41.61 16 4.92 0.06 0.02 17
Ass 48.0 4 57.2 16 8.93 0 -0.52 17
As, 34.5 4 75.6 16 19.84 0 - 1.20 17
AsO 4.8 9 55.6 16 9.74 -0.30 - 1.72 17
AsS 24.5 10 59.22 10 9 0 0 PW5
Sb 62.65 1t 43.06 16 4.97 0 0 17
Sb2 56.3 11 60.9 16 8.94 0 -0.22 17
Sb4 49.0 12 83.6 16 19.85 0 -0.44 17
SbO 14 PW3 57.0 16 8.47 0.84 -0.99 17
SbS 32.89 13 61.62 13 9 0 0 PW5
Bi 49.5 11 44.67 16 4.97 0 0 17
Bi2 52.5 11 65.4 16 8.94 0 -0.10 17
BiO 28 14 58.9 16 8.63 0.2 -0.79 17
BiS 44.5 15 64.0 PW4 9 0 0 PW5
1 cal = 4.19J

Table II. Free Energy Data and Equilibrium Constants. See Part II2 for the Reactions [1] through [20].

Number Reaction AG ~ cal/mole Equilibrium Constant (1523 K)

21 Se2(g) = 2Se(g) 75,360 - 26.23 T K21 = 8.230 X 10 - 6
22 Te2(g) = 2Te(g) 54,320 - 24.29 T K22 = 3.253 x 10-3
23 As2(g) = 2As(g) 90,540 - 27.30 T K23 = 9.325 x 10 -g
24 Sbffg) = 2Sb(g) 69,490 - 26.36 T Kz, = 6.132 • 10 -5
25 Biffg) = 2Bi(g) 46,960 - 25.03 T Kss = 5.360 • 10 -2
26 Ass(g) = 89 -30,320 + 18.41 T K26 = 2.128
27 Sbdg) = 89 -31,360 + 18.08 T K27 = 3.546
28 Seffg) = 89 -21,690 + 22.07 T K2s = 1.944 • 10 -2
29 89 + -~Os(g) = SeO(g) - 4,300 - 1.23 T K29 = 7.698
30 89 + ~Ds(g) = TeO(g) - 2,780 - 1.48 T K3o = 5.273
31 89 + ~Ds(g) = AsO(g) -18,890 - 3.19 T K~I = 2.564 x 103
32 89 + 2~D2(g) = SbO(g) -13,990 - 2.37 T K32 = 3.360 • 10s
33 89 + ~O2(g) = BiO(g) 1,830 - 1.87 T K33 = 1.397
34 89 + O2(g) = SeO2(g) -43,110 + 16.10 T K~, = 4.667 • 102
35 89 + Oz(g) = TeOffg) -35,050 + 15.08 T K35 = 5.431 • 10
36 89 + 89 = SeS(g) 1,560 - 1.68 T K36 = 1.391
37 89 + 89 = TeS(g) 11,650 - 1.49 T K37 = 4.499 • 10 - s
38 89 + 89 = AsS(g) -14,740 - 3.83 T K3a = 9.013 x l0 s
39 89 + 89 = SbS(g) -10,540 - 4.31 T K39 = 2.854 • l0 s
40 89 + 89 = BiS(g) 2,970 - 4.41 T K4o = 3.452
41 2Cu(/) + 89 = CusSe(/) -31,200 + 8.50 T K41 = 4.2 x 102(pw, 12)
42 2Cu(/) + 89 = CusTe(/) -29,000 + 8.23 T K,s = 2.3 • 102(pw, 22)
1 cal = 4.19 J PW = present work

320--VOLUME 13B, SEPTEMBER 1982 METALLURGICALTRANSACTIONS B

 Table III. Raoultian Activity Coefficients in Dilute Cu-M Alloys
Element (M) Temperature Dependence y~ at 1523 K Reference
Ag(/) log y~,g = 850 T -I - 0.070 3.07 23
As(s) log y~s = -4,830 T -~ 6.75 • 10-a 24, 55, PW
Au(/) log y~, = -1,660 T -I 8.13 • 10_2 25, PW
Bi(/) log Y~i = 1,900 T -z - 0.885 2,30 26
Fe(s) log y~, = 4,430 T -~ - 1.41 3.15 • 10 27
Ni(s) log y~i = 1,430 T i _ 0.546 2.47 23
Pb(/) log y~,b = 2,670 T -j - 1.064 4.88 28, PW
Sb(/) log Y]b = -4,560 T -1 + 1.24 1.76 x 10_2 29, PW
Se(/) log yg~ = -3,770 T -~ + 0.25 5.95 X 10 _3 22, PW
Sn(/) log yg, = -1,300 T -l - 0.45 4.96 X 10 -2 25
Te(/) log 3~~ = -3,680 T -~ + 1.142 5.32 x 10-z 22, PW
Zn(/) log ~, = -1,230 T -~ 1.56 x 10-~ 23
PW = present work

Table IV. Raoultian Activity Coefficients (y*~) and Interaction Parameters (e s ) in Dilute Cu-S-M
Alloys Saturated with Cu2S(I). For example, N~ = 0.026 at 1250 ~ See Appendix A for PWi.
Minor Element 1523 K Note Reference
Ag(/) ~ = y.~g assuming eSgN~ --- 0; "flA~2swas2 calculated therefrom. 2, PW6
As(s) 3rL = )'~,s assuming eSsN~ = 0 PW
Au(/) 3r~u = 9.7 x 10 - 2 using eS, = 6.7 30
Bi(/) 3r~i = y~ assuming eSiN~ -- 0 PW
Fe(s) 3ri~ = 3.4 x 10 equivalent to eSe = 3.3; 31 cf. esF~ = -8-030 30, 31, PW7
Ni(s) 3r~i = 2.08 using eS~ = -29,800 T -~ + 13.0;23 3~2s was calculated therefrom 2 2, 23, PW6
Pb(/) ~ = 6.1 • l0 equivalent to es = 96 (?) 2, 32, PW8
Sb(/) 3r~b = Ygb assuming esdv~' = 0 PW
Se(/) Y'~e = 3'~ assuming eS~N~ = 0 PW
Te(/) 7~, = Y~, assuming eS,N~ --- 0 PW
Zn(/) 3r~. = 8.3 • 10 -~ equivalent to esz. = 64 (?) 2, 33, PW8
PW = present work

aM ~- '~MNM [204] L h = [M]c~ [206]

The activity coefficients of minor elements in the Cu2S-
saturated copper alloys are presented in Table IV. 24'3~ The
interactions between minor elements were considered to be
negligibly small in view of the low concentrations of minor
elements and sulfur in the metallic solutions.
Selected data on vapor pressure of various volatile species
are summarized in Table V. 2'12'34-37 Although some values
are extrapolated beyond the original temperature range,
errors involved in the extrapolation may be considered
mostly insignificant. Indeed, the original activity mea-
surements of certain species such as PbS, Zn, and As were
done on the same basis of extrapolated reference. The actual
use of these data will be demonstrated later in this paper
under the heading "Volatilization Constants". By definition,
the partial pressure of a species M can be calculated as
PM = P~aM
L~ = ~[M]c~ [207]
The distribution coefficients L ~ and L n have already been
given elsewhere. 2
Assume further that the concentration of minor elements
is sufficiently low that the sum of the partial pressures of all
the M-containing gases, pT, is proportional to the concen-
tration of M in the copper phase. Hence,
pT = kM[M]cu [208]
where kM is constant under given partial pressures of oxygen
and sulfur at constant temperature. When the condensed
phases are flushed with a very small volume of a neutral gas,
AVg, in such a way that the gas will be saturated with all the
[205]
M-containing gases, we have

AVM AVM [209]

III. VOLATILIZATION MODEL pT -- AVg -{- AVM = AV__.
~

where AVM refers to the total volume of M-containing gases.

A. Basic Model The weight of element M, AUM g, contained in volume
Assume that a system consisting of copper, matte, and AVM l (STP) is given by
slag phases is under equilibrium conditions. The concen-
AUM = AMAVM/22.4 [210]
trations of a m i n o r element M in the three melts are
interrelated as 2 where AM refers to atomic weight of element M.

METALLURGICALTRANSACTIONSB VOLUME 13B, SEPTEMBER1982--321

 T a b l e V. Vapor Pressures of Pure Solids and Liquids

Temperature
Condensed Phase Vapor Pressure, P~ atm. P~, 1523 K Range, K Reference
Ag(/) log P~g = -14,400 T -~ + 8.82 - 0.85 log T 4.57 x 10-4 1234 to 2473 12
As(s) log P~,s, = - 6,160 T -~ + 6.94 7.86 x 102 600 to 900 12
Au(/) log P~,, = -19,280 T -~ + 9.50 - 1.01 log T 4.23 X 10 -7 1336 to 3223 12
Bi(/) log P~ = -10,400 T -~ + 9.47 - 1.26 log T 4.28 x 10 -2 544 to 1953 12
Cu(/) log P~, = -17,520 T -~ + 10.33 - 1.21 log T 9.45 • 10 -6 1356 to 2843 12
Fe(s) log P~:~ = -19,710 T -~ + 10.39 - 1.27 log T 2.55 x 10-7 298 to 1809 12
FeS(s) log P~s = -10,850 T -) + 1.28 1.43 x 10-6 1077 to 1279 34
Ni(s) log P~ = -22,500 T -~ + 10.72 - 0.96 log T 7.78 x 10-8 298 to 1718 12
NiO(s) log P~,o = -24,480 T -) + 8.438 2.31 x 10-8 1438 to 1566 4
NiS(s) l o g P~is = - 9,213 T -X + 2.96 8.14 • 10-4 877 to 1077 34
Pb(/) log P~,u = -10,130 T -~ + 8.28 - 0.985 log T 3.12 x 10 -2 597 to 2013 12
PbO(I) log P~,bO = --10,598 T -~ + 6.012 1.13 x 10-~ 1159to 1745 4
PbS(s) log popbs = -11,700 T- + 7.50 6.59 X 10-~ -- 52
Se(/) log P~r = - 5,540 T -~ + 5.57 8.55 x 10 970 to 1650 35, PW
Sb(/) log P~b2 = --11,170 T -~ + 15.66 - 3.02 log T 5.18 x 10-2 900 to 1910 12
Sn(/) log P~, = -15,500 T -~ + 5.35 1.49 x 10-5 505 to 3023 12
SnS(s) log P~.s = -10,470 T ~+ 7.088 1.63 950 to 1075 4
Te(/) log P~r = - 5,900 T -j + 4.64 5.83 980 to 1780 36, PW
Zn(/) log P ~ = - 6,620 T -~ + 9.46 - 1.255 log T 1.32 x 10 693 to 1180 12
ZnO(s) log P~.o = - 8,930 T -1 + 2.02 1.44 x 10-4 1473 to 1573 37, PW
ZnS(s) log P~ns = -13,500 T -~ + 7.07 1.61 x 10.2 1000 to 1250 4
1 arm = 101.3 kPa P W = present work

Let us assume a closed system consisting o f gas, copper, ( = f i n a l ) the volatilization, respectively. The basic concept
matte, and slag phases, undergoing the volatilization reac- of Eq. [213] is due to R u d d l e ) s The value k* is a constant
tion, which brings about a weight increase of AUM in the gas which governs the volatilization of element M, and is called
phase, accompanied by a concentration change of A[M]c~ in volatilization constant in this paper. Eq. [213] may be re-
the copper phase, A [ M ] M t in the matte phase, and A[M]sl in written as
the slag phase. The difference in the mass balances of ele-
[M]~u = CM[M~, [215]
ment M before and after the volatilization of AUM may be
expressed as and

AUM = -- 0.01A[M]cuWcu-0.01A[M]MtWM,
- 0.01A[M]slWsl CM
WM, Wsl
0.224 Wcu + L--~-M+
WMt Ws,) [2111
= - 0.01A[M]c~ Wc. + L--~M + L~J
V~ can be any gas flushing the melts. In the case of the
where Wc., WM. and Ws~ refer to the weights of the copper, Noranda Process, V~ = VN, + VsO, and the sample values
matte, and slag phases, respectively. F r o m Eqs. [208] of Vg have been given elsewhere 1 as a function of feed
through [211], we have composition and other process variables.
By converting [M]cu into [M]M, or [M]sj by means of
AVg - -0.224 Wc~ + -WMt
- + Ws:] A[M]c~ [212] Eqs. [206] and [207], we may apply Eqs. [213] and [215]
kMAM LI L~,I [M]co to cases where one or two of the three phases is absent
insofar as one phase is saturated with the others. In other
Replacing • 1 7 7 with dVg/d[M]c., and integrating
words, Eq. [213] is valid even if one or two of Wcu, WM,, and
Eq. [212] from the initial conditions of [M]~. at Vs = 0 to
Ws~ is zero. Knowing the concentration of a minor element
the final conditions of [M]tc. at Vg = V~, we have
M in a phase, therefore, the concentration after gaseous
flushing can be calculated.
f[ -0.224 /
Wco+L
WM~ Ws)~ d[M]c~
+ L~] [M]c, Eqs. [213] and [215] are valid originally for an in-
finitesimally small batch volatilization where weights of the
fe -0.224 ( WM, wq major elements in the phases involved may be regarded as
= k aM Wcu+ L--h + L~] d In[M]c, remaining constant. However, the validity can be extended
to a continuous operation by incorporating these relations
0.224 ( WM, Wsj'~ [M]8,
In - - [213] into a steady-state reactor model, as will be shown next.
- k* Weu + L--iM-
M + L~] [M]rc.
B. Steady-state Volatilization in the Copper-making
and k~ = kMAM [214] Noranda Process
where [M]~, and [M]tcu refer to the concentration of a minor In both c o p p e r - m a k i n g and m a t t e - m a k i n g N o r a n d a
element M in the copper phase before ( = i n i t i a l ) and after Processes, the reactor always retains more or less constant

322--VOLUME 13B, SEPTEMBER 1982 METALLURGICALTRANSACTIONS B

weights of copper, matte, and slag, the compositions of
which are also constant as long as reactor feed composition
remains constant. Let Qc,, QMt, and Qs~ be the weights
of copper, matte, and slag phases in the reactor under
steady-state operation. An example may be given as
Qc, = 50 x 106 g , aMt = 500 • 106 g, and QsJ = 100 x
10 6 g.39
When I00 g of concentrate is fed to the reactor together
with V~ l of tuyere air to convert the feed, which is equiva-
lent to Vg l of washing gas, there are produced AWc, g of
copper, AWM, g of matte, and AWs~ g of slag. Assume that
after a cycle of the feeding, converting, and tapping-out, the
weight and composition of each phase remain the same
as before the cycle. The actual copper-making Noranda
Process does not produce matte as such, but matte must be
taken into consideration to account for the physically en-
trained mattes in tapped copper and slag. The weight of a
minor element M fed to the reactor together with 100 g
concentrate* is given by
*If M is fed in forms other than concentrate, it must be included in the
concentrate in this model. For example, if the flux for 100 g concentrate
(0.080 pct Ag) carries 20.0 mg Ag, the adjusted value is [Ag]c = 0.100.
WM = [MJc [217]
Let [M]cu, [M]Mt, and [M]sl be the respective minor ele-
ment concentration of the subscripted phases before the feed
addition, and A[M]cu, AIM]Mr, andA[M]sj be the increase of
minor element concentration in the subscripted phases after
the feed addition of WM, assuming that the condensed phases
first absorb all of the minor element in the feed prior to the
volatilization. Then, the temporary mass balance after the
absorption but before any volatilization of the minor element
may be expressed as
IOOWM + [M]cuQc, + [M]M,QMt + [M]s,Qs,
= ([M]c. + A[M]c0Wc. + ([M],, + A[M]M,)WM,
+ ([M]st + A[M]s,)Ws, [218]
where Wcu, WMt, and Wsl are given by
Wco= Qc~ + AWc~ [219]
WMt = QMt + AWMt [220]
Ws~ -- Osl + AWs, [221]
Since the three melts are always in equilibrium with
each other, the constancy of the distribution coefficients
prevails, namely
_ [M]cu _ [M]cu + A[M]c. [222]
Lh [M]M, [M]M, + A[M]M,
L~ - [S]c~ _ [M]cu + A[m]c. [223]
[M]s, [MJs, + A[M]s,
Using Eqs. [222] and [223], Eq. [218] can be rewritten as
QMt+ Qs,'~
WM + 0.01[M]c, Qc~ + L--~M L--~M]
Ws,
= O.Ol([M]cu + A[M]cu) Wcu + L-SM-
~ + L~J [224]
The concentration [M]c~ is the initial minor element level
prior to the addition of a feed, but can also be regarded as
METALLURGICALTRANSACTIONS B
the ultimate level of the minor element that can be estab-
lished when a continuous reactor reaches a steady-state
with a feed of constant composition. Thus, Eq. [224] repre-
sents the temporary mass balance before volatilization.
Owing to the volatilization accompanied with gaseous
washing by the volume Vg, which results from the oxidation
of the added feed, the minor element concentration
decreases from the initial level of [M]cu + A[M]c, to the
final level of [M]c,. Accordingly, under the steady-state
volatilization, the following relations should prevail; com-
paring Eq. [215],
[M]cu ~ [M]rcu [225]
[M]co + A[M]cu =-- [M]~, [226]
Inserting Eqs. [225] and [226] into Eq. [224], and rear-
ranging it with the use of Eq. [215], we have
100WM
[M]rc, - [227]
CMWT -- QT
where
WMt Wsl
WT m Wc~ + C--~-M+ L--~ [228]
QM--2+ ----2
LQ~ [229]
Qv -= Qcu + L~
Eq. [227] is the very heart of the present model dealing with
the steady-state volatilization of minor elements in con-
tinuous reactors.
C. Steady-state Volatilization in the Matte-making
Noranda Process
Assume that 100 g concentrate is added to the steady-state
system consisting of matte and slag, whose weights are QM,
and Qs~, respectively. The typical weights of the matte and
slag retained always in the commercial reactor may be
quoted as QMt = 500 X 106 g and Qsl = 100 • 106 g. The
addition of the concentrate accompanied with flux results in
the production of new matte and slag, whose weights are
given by AWM,and AWsb respectively. Hence, for the matte-
making process, we have
WM, = QM, + AWM, [230]
Ws~ = Qs~ + AWs~ [231]
Equations [230] and [231 ] are the counterparts of Eqs. [219]
to [221] for the copper-making process. Insofar as both
matte and slag phases are in equilibrium, the distribution
coefficients govern the concentration ratio of minor ele-
ments, such that
L~ - [M]M~ _ [M]M, + A[M]M, [232]
[M]s, [M]s, + A[M]s,
It is difficult to establish activity-composition relationships
for a minor element in copper-unsaturated mattes, and the
available data are limited to iron and volatile elements such
as zinc and lead. However, the only difference between
copper-saturated and copper-unsaturated mattes is due to the
small variation in sulfur concentration (less than 2 pct S). It
is most unlikely that this small variation in sulfur content
can cause a large difference in activity coefficients of minor
VOLUME 13B, SEPTEMBER 1982--323
elements. Accordingly, the definition of L ~may be extended
to higher sulfur potentials by assuming a metastable metallic
copper phase that may coexist with mattes having a high
sulfur potential. This assumption is equivalent to stating that
L I is independent of ps.,, or that the values of L j, t n, and L m
are interchangeable.
The generalized interchangeability among L ~, L H, and L m
enables a metastable value of [M]c, to be calculated irre-
spective of whether or not an actual metallic copper phase
exists in the system. Thus, when the concentration of a
minor element in the matte or slag phase is known, the
corresponding concentration in the metallic copper phase
can be calculated by
[M]c~ = L~[M]Mt [233]
[M]c~ = L~[M]s~ [234]
Then, the calculated values of [M]c, may be converted to aM
by virtue of 3/~ or 3r'~, which are already known. Under these
assumptions, therefore, the following relations can be de-
rived for the volatilization in the matte-making process:
[MYMt - 100WM [235]
cMw-r - q'r
where
WsI
wT = WMt + - - [236]
qr ~- QMt + L~ [237]
It is evident that Eq. [235] is identical with Eq. [227] on
insertion of Wc, = 0 and Qc, = 0 in Eq. [227], and the
value of c~ for the matte-making process can readily be
calculated by inserting Wco = 0 in Eq. [216].
Even if a reactor operates in a steady state rather than
under strict equilibrium conditions, Eqs. [227] and [235]
are still valid provided the volatilization constant k* can
be calculated for such a steady state. Thus, the composi-
tion change due to volatilization, such as formulated by
Eqs. [227] and [235], can be employed as they are for
analyzing the behavior of minor elements in a steady-state
continuous reactor.
The foregoing equations permit the minor element distri-
bution in the Noranda Process to be assessed from minor
element concentrations in the feed (WM), constantly retained
weights of melts (Qi), weights of produced melts (AW~), and
the parameter cM that is defined in Eq. [216].
The values of Q~ have already been specified in the
examples. The parameter cM contains the quantities: Vg, k*,
and AW~. The volume of washing gas (Vg) has already been
expressed elsewhere as a function of the process variables. J
Consequently, the only remaining unknowns are volatili-
zation constant k~ and respective weights of produced melts
AW~. While the general expressions for AW~ will be derived
in the Part IV, the next section is devoted to expressing
explicitly the volatilization constants.
IV. V O L A T I L I Z A T I O N CONSTANTS UNDER
EQUILIBRIUM CONDITIONS
The volatilization constant as defined earlier does not
have to be the equilibrium value. It can well be a constant
324--VOLUME 13B, SEPTEMBER 1982
inherent in a steady state. However, as established in the
Parts I and II,~'2 when the steady state is established in the
commercial Noranda Process reactor, the phases there
are also in equilibrium with one another because of very
fast reaction rates at the high temperature. It is then pos-
sible to calculate a p r i o r i the volatilization constants
thermodynamically.
The volatile species considered here are oxides and sul-
fides as well as elemental monomers and polymers. All the
possible gaseous species must be enumerated, and their
partial pressures must be evaluated under the conditions of
interest prior to the selection of relevant species for each
minor element.
A gas having a small partial pressure relative to the other
gases of the same element may be neglected in the final
expression of the volatilization constant of the element.
However, in order to choose the principal gaseous species of
each minor element, the partial pressures of the possible
gaseous species are calculated under the typical partial pres-
sures of oxygen and sulfur which prevail in the copper-matte
converting. The results are shown in Table VI.
Equation [208] is valid for an element that has no stable
gaseous molecules containing two or more atoms of the
element, such as M2 or M203. The volatilization constant
then is a concentration-independent constant, and with the
use of Eq. [214], may be rewritten as
- [238]
[M]cu
For an element that indicates a considerable partial pres-
sure of such gaseous molecules as M2 or MuOv, the follow-
ing Eq. [239] must be used:
P ~ = PM + 2PM2 + upMuo, + . . . . .
= k2[M]cu + k2[M]~u + k3[M]~u + . . . . . [239]
where ki's are functions of temperature, Po_, and Ps2. In this
case, the integration of Eq. [212] can only be carried out
numerically. Fortunately, the simpler relationship Eq. [238]
remains valid for most minor elements within the dilute
solution ranges to be discussed in the present study.
The values of [M]cu to be inserted in Eq. [238] may be
calculated based on the interchangeability among L x, L n, and
L HI for both copper-making and matte-making processes,
provided the minor element concentration in either copper,
matte, or slag phase is known.
While the values of L I are assumed to be independent of
the partial pressures of sulfur and oxygen as well as the iron
concentration in the matte, the values of L I~for most minor
elements depend on the partial pressures of sulfur and oxy-
gen, as were already shown elsewhere. 2 The partial pres-
sures of volatile sulfides and oxides are dependent upon the
partial pressures of sulfur and oxygen, which have been
calculated for any given set of smelting conditions as func-
tions of temperature, SO2 pressure, magnetite activity, and
matte grade. ~'2 The equilibrium constants, activity coeffi-
cients, and vapor pressures to be used in the following have
been given in Tables II, IV, and V.
A. Au
When Au concentration in metallic copper phase is
known, the Au activity can be calculated by
METALLURGICAL TRANSACTIONS B
 Table VI. Partial Pressures of Various Volatile Species at 1250 *C. Conditions for Cu-make:
p~z2 = 1.49 x 10 -s and p ~ = 4.91 x 1 0 - 4 Corresponding to Blowing with Air (21 Pct O2). Conditions
for Mt-make: p ~ = 6.31 x 10 -2 and p ~ = 7.35 x 10 -s Corresponding to Producing 60 Pet
Cu Matte with Air (21 Pct O2). See Also References 1 and 2. One atm = 101.3 kPa.

Concentration (Pct) in Partial Pressure (atm) in

Minor Element Copper Matte Gas Cu-make Mt-make Remark
Au 0.01 5.8 • 10 -5 Au 1.3 • 10 ~2 1.3 • 10 -~2
Ag 0.1 4.2 x 10 -2 Ag 8.3 x 10 7 8.3 • 10 -~
Pb 0.1 6.7 • 10 -2 Pb 1.3 • 10 -4 1.3 • 10 -4
PbO 4.9 x 10 -5 7.3 X 10 - 6
PbS 6.7 • 10 -5 2.9 x 10 -3
Zn 0.001 7.4 x 10 -4 Zn 1.1 • 10 4 1.1 x 10 -4
ZnO 4.5 x 10 -6 6.7 x 10 -7
ZnS 1,8 X 10 - 6 7.5 • 10 -5
Ni 0. I 3.4 x 10 -2 Ni 1.7 • I0 -~~ 1.7 • 10 -~~ negligible
NiO 4.5 • 10 - ~ 6.7 x 10 -~2 negligible
NiS 9.5 • 10 -8 4.0 • 10 -6
Se 0.01 9.1 x 10 -2 Se 1.3 • 10 -8 1.3 x 10 -8
Se2 2.0 x 10-" 2.0 x 10 - ~ negligible
Se6 5.5 • 10 3s 5.5 X 10 -3s negligible
SeO 1.7 • 10 -8 2.6 X 10 - 9
Se02 5.0 • 10 -~~ 1,1 x 10 -H
SeS 9.3 x 10 -9 3.9 x 10 -7
Te 0.01 4.4 • 10 -z Te 3.6 x 10 -7 3.6 x 10 -7
Te 2 4.1 • 10 -H 4.1 x 10 - ~ negligible
TeO 1.7 x 10 -8 2.5 x 10 -9
TeO2 8.4 x 10 - ~ 1.9 x 10 -~2 negligible
TeS 4.3 x 10 -I~ 1.8 • 10 -s
Bi 0.01 1.5 • 10 -3 Bi 3.0 X 10 - 6 3.0 X 10 - 6
Bi2 1.7 X 10 - 1 ~ 1.7 • 10 -~~ negligible
BiO 8.9 X 10 - 9 1.3 • 10 -9 negligible
BiS 6.7 • 10 -8 2.8 x 10 -6
Sb 0.1 6.7 x 10 -3 Sb 1.6 x 10 -s 1.6 x 10 -s negligible
Sb2 4.4 • 10 -12 4.4 x 10 -1~ negligible
SbO 3.5 • 10 -7 5.2 • 10 -s
SbS 8.9 • 10 -7 3.8 • 10 -s
As 1.0 4.6 x 10 -2 As 6.3 X 10 - 9 6.3 X 10 - 9 negligible
As2 4.3 x 10 -~~ 4.3 • 10 -~~ negligible
As4 8.4 x 10 -19 8.4 x 10 -19 negligible
AsO 2.6 • 10 -5 3.9 x 10 -6
AsS 2.8 x 10 -5 1.2 X 10 - 3

ago - ')g~uNAu = O.Ol(Acu/AAu)y~,[Au]co [240] Pug = 8.3 x 10 -7 a t m . T h e partial p r e s s u r e o f A g 2 S ( g ) , if

it exists, m a y b e d e t e r m i n e d b y
S i n c e g a s e o u s m o n o m e r A u is the o n l y i m p o r t a n t v o l a t i l e
species in the a b s e n c e o f h a l o g e n s , 2 the s u m m e d partial PAg2S
= ,x
t " 161
o o Ag2SUAg~S
~2 ~l/z
2
[246]
p r e s s u r e is g i v e n b y
T h e v a p o r p r e s s u r e o f m o l t e n p u r e Ag2S m a y b e r o u g h l y
P~. = PAu -----~AuaAu [241] e s t i m a t e d to b e o f t h e o r d e r o f 10 -6 a t m at 1250 ~
U s i n g the v a l u e p l ~ = 1.49 x l 0 -2 for a t y p i c a l c o p p e r -
I n s e r t i n g Eq. [ 2 4 0 ] into Eq. [241], a n d a p p l y i n g Eq. [ 2 3 8 ] ,
m a k i n g p r o c e s s , 2 w e find PAg2S = 6 • l 0 -~4. O n t h e o t h e r
the v o l a t i l i z a t i o n c o n s t a n t k* is g i v e n as
h a n d , u s i n g the v a l u e psi:22 --- 6.31 • 10 -2 f o r a t y p i c a l
T matte-making process with 60 pct Cu matte, 2 we find
pAuAAu
k~, [Au]cu = 0.01Ac~y~u~A~ [242] PAgeS = 2 X t 0 -Jz. T h u s , the s p e c i e s A g 2 S ( g ) a l w a y s re-
m a i n s n e g l i g i b l e c o m p a r e d to A g ( g ) .

B. A g
C. P b
B y a m a n n e r s i m i l a r to t h e c a s e o f A u , w e h a v e
F o r P b , Z n , a n d N i , it is c o n v e n i e n t to e x p r e s s activities
aAg = O.Ol(Ac,/AAg)y~g[Ag]cu [243] o f M - c o n t a i n i n g s p e c i e s in t e r m s o f [M]Mt r a t h e r t h a n [M]c~.
T h e c o n v e r s i o n c a n r e a d i l y b e d o n e t h r o u g h L ~.
pTg -- PAg = ~Agagg [244]
F o r a g i v e n v a l u e o f [Pb]M,, the P b activity is calcu-
k~g = 0.01Ac~Y~g~Ag [245] lated b y

A s s u m i n g 0.1 pct A g in c o p p e r p h a s e , for e x a m p l e , w e find apb = O.Ol(Acu2s/Apb)K~o'~bs[Pb]MtPs2~/2 [247]

METALLURGICAL TRANSACTIONS B VOLUME 13B, SEPTEMBER 1982--325

Using this apb, the activities of the oxides and sulfides are E. Ni
calculated as
From the definition of activity coefficient for Ni2S, 2
apbo = K 9r162
~ ~1/2 [248]
aN~,S = (Y~2sNN~2S)2 [263]
apbS = K,0avao~/~ [249] Using Eq. [263], for a given Ni concentration in high
Consequently, the partial pressures of Pb-containing gases grade mattes,
can be expressed as aNi = O.Ol(Acu2s/2ANi)K~3'~z')PNizs[Ni]MtP~ TM [264]
PPb = ~bapb [250] r. 1/2 [265]
aNiO --'~ /~14aNiPo2

PP60 = ~bOapbo [251] aNi s = 91 1~2

/~IsON~OS2 [266]
PPbS = P~.bsapbs [252] The partial pressures of Ni-bearing gases are given as
AS shown in Table VI, all the three species of Pb, PbO, and PNi = P~qiaNi [267]
PbS should be taken into consideration under the copper-
making conditions, whereas the species PbO may be PNiO = ~
PNioaNiO [268]
neglected under the matte-making conditions. However, as
the general expression, PNiS = PNiSaNiS [269]
AS shown in the examples in Table VI, the only important
PPTb= PPb + PPbo + PPbS [253]
gas is NiS as two other gases of Ni and NiO remain always
Calculating Eq. [238], we have negligibly low. Accordingly, we have

kg -
0'0 I'~bsAcu2 s
~
o
(Peb + /k9t'pbOP02
.... 1,2 + /~lot'pbsPs2
.... ,/2,) pTi = PNiS [270]

k~ i
= -
0.01mcu~sgl3
- 1/2
gls'~i,s
- poN i s P 1/? I
s,/2LNi [271]
[254]
In actual smelting, the gaseous molecule NiS is readily
All the terms in the right-hand side of Eq. [254] are known, oxidized above the melt surface upon contact with a more
and therefore the volatilization constant k* can be calculated. oxidizing atmosphere, and therefore what is observed in the
As shown in Table VI, the partial pressure of PbS which effluent gas is, in fact, oxidized or sulfatized dust particles.
is the most volatile Pb-bearing species is some 40 times
higher under typical matte-making conditions than under E Se
typical copper-making conditions for a given Pb concen-
For a given Se concentration in molten copper, the Se
tration in matte. Based on this difference, it follows that
activity can be calculated as
the matte-making process greatly favors the volatilization
of lead. asc = O.Ol(Acu/Zsr [272]
From the definition, the partial pressure of dimer Se2 is
D. Zn
given by
By a manner similar to the case of Pb, the following = o 9
Psc2 Ps~2age [273]
relations may be derived.
Using the partial pressure of the dimer as welt as the equi-
az, = O.Ol(Acu2s/Az.)K?~z,s[Zn]Md)S,_ ''2 [255] librium constants listed in Table II, we can calculate the
r. I/2 [256] partial pressures of various other Se-containing gases.
azn O = /~12aznPO2
Pse
= K 21
''2-v2
]JSe 2
[274]
azn S = .- I/2
/'-kllaznps 2 [257]
Psi6 = K~sp~_~ [275]
Pz, = P~~ [258]
PSeo
= K 29Po2Pse2
1,2 1~2 [276]
Pz.o = Pznoazno
o [259]
PSe02= K 34)02PSe2
I,'2 [277]
PZnS = P},saz,s [260]
As shown in Table VI, three gases of Zn, ZnO, and ZnS PSeS = K36p~22P~'~_ [278]
should be considered under the copper-making conditions, As shown in the examples in Table VI, the partial pressures
while only Zn and ZnS are important gases under the matte- of Se2 and Se6 are normally negligibly small, and therefore
making conditions. The general expression for the summed
partial pressure is psrc = Pse + Pseo + PScO2 + PSeS [279]
1~'~ I7 rl 1/2
p~z. = pz. + pz~ + pz,s [261] k~'~ = 0.01Acoy~'e(Ws~_,) -(K21- + ~20Po2 + K34Po2 + K36p~/2)
[280]
0 " 0 1 ~znsAcu2s " p ~ /t 12rznoPo ~ +
_ /kl IrZnSPS2 ) It is to be noted that the three most volatile gases are SeO,
Se, and SeS in the copper-making process, whereas in the
[262] matte-making process, SeS is the only important species.
All the terms in the right-hand side of Eq. [262] are al- Literature data on the gaseous species SeO, SeO2, and SeS
ready known. are rather scant.
3 2 6 - - V O L U M E 13B, SEPTEMBER 1982 METALLURGICAL TRANSACTIONS B
 G. Te ash = O.Ol(Acu/Asb)3r~b[Sb]co [296]
For a given Te content of molten copper, the Te activity Using this Sb activity, the vapor pressure of dimer Sb2 is
can be calculated by given as
ate = O . O l ( A c u / a T , ) 3 G [ T e ] c u [281] PSb2 = P~sb2azb [297]
The partial pressure of dimer Te2 is then given by Using this Sb2 partial pressure, the partial pressures of the
o 2 other volatile Sb-containing species may be expressed as
PTe 2 = PTezaTe [282]
= K1/2 I12
from which the partial pressures of the other gases can PSb 24Psb2 [298]
be calculated: rl 112 I/2
psbo = a32Po2Psb~ [299]
PTe = K~I2P~ [283] r~ 1/2 1.'2
Psbs = /~39Ps2Psb2 [300]
1/2 I/2
PTeO =
rT
/K30Po2PTe2 [284] As shown in Table VI, dimer Sb2 is always negligible,
= rz 1/2 whereas the partial pressure of monomer Sb remains lower
PTeO2 /'k 35Po2PTe2 [285]
than 2 pet of the total partial pressure. Accordingly, taking
rl 1/2 1/2 only SbO and SbS into account, we have
PTeS ----- / ~ 3 7 P s 2 P T e 2 [286]
As shown in Table VI, the partial pressures of T e 2 and TeO 2 pTb ----- Ps~ + PSbS [301]
are small enough to be neglected, and therefore
k~b = 0.01acu~b(Psb2)~~/2(K32Po2~.:+ K39P~/2) [302]
pT = PT~ + PT~O + PT~S [287]
While SbS is the sole predominant Sb-containing gas under
k~r = O.OIAcu3~e(P~2)"2(K~2 2 + ^30Po2
" ,/2 + K37P~/~) [288] the matte-making conditions, the partial pressure of SbO
also becomes significant under the copper-making condi-
As in the case of SeS, literature data on TeS gas are scarce. tions. The species 56203 remains negligible under normal
smelting conditions, since its partial pressure is proportional
H. Bi to the square of the already small concentration of Sb in the
The Bi activity is related to the Bi content of the copper Cu-Sb alloy, thus becoming geometrically smaller as the
phase by concentration decreases. The high temperature thermo-
dynamic data for Sb203(g) remain still unknown.
aBi = O.Ol(Acu/ABi)'Y~i[Bi]cu [289]
The vapor pressures of various species are then given as
J. As
PBi = P~iam [290]
For a given As content of molten copper, the As activity
PB~, = K;s~p~ [291] may be calculated by
T~
PBio = ^~3Po,PBi,_
1/2 1/2
[292] aA~ = O.Ol(Acu/AAs)y~s[As]c~ [303]
r~ 1/2 I/2 Using this aA~, the partial pressures of As4 and As2 can be
PBiS = /~40Ps2PBi2 [293] calculated as
As shown in Table VI, dimer Bi2 and oxide BiO can be o 4
PAs4 = PAs4aAs [304]
neglected relative to the sum of monomer Bi and sulfide
BiS. Accordingly, PAs2
= r l I 1/2
/~26PA84 [305]
pTi = P B i + PBiS [294] Using Eq. [305], the partial pressures of the other gases can
be calculated:
k~ = 0.01Ac, yt~P~(1 + a25~'-~/2"~,40Ps2'/2') [295]
rTl/2 1/2
The species BiS is negligible under the copper-making con- PAs = /~23PAs 2 [306]
ditions, but becomes as important as the monomer Bi under PAsO = ^31Po2PAs2
rl 1/2 1/2
[307]
the matte-making conditions. It has been known long since
that bismuth volatilization proceeds well from mattes until PA~S = K 3 8 p ~ p ~ [308]
metallic copper is formed in the mattes. Based on this obser- As shown in Table VI, the major As-containing gases are
vation, several converting methods have been developed in AsO and AsS, and all the other gases may be neglected.
which tuyere blowing is conducted in such a way as to delay
Consequently, we have
the formation of metallic copper phase in the converterf1-44
Such converting methods should also favor the elimination P~s = PAsO + PAsS [309]
by volatilization of antimony and arsenic, since these ele- k*s = 0.01AcuK26
ments of V-A subgroup tend to form stable volatile sulfides
- 1/2 o I/4
~As(PAs,~) (K31Po,_
i/2 rl 1/2x
+ /~38Ps21 [310]
in the absence of metallic copper phase, as demonstrated in The two rather unknown gases, AsO and AsS, are the pre-
the examples in Table VI. dominant As-containing gases in copper smelting. In par-
I. Sb ticular under the matte-making conditions, AsS is the only
important gas as the other gases remain at a negligibly low
The Sb content in metallic copper phase may be related to level. The high temperature thermodynamic data for
the Sb activity by As203(g) are still missing from the literature.

METALLURGICAL T R A N S A C T I O N S B V O L U M E 13B, SEPTEMBER 1 9 8 2 - - 3 2 7

 It is to be noted that the partial pressure of AszO3(g) is not SeS(g) and TeS(g) are compared with those estimated
proportional to the As concentration in the Cu-As alloy, but from the mass spectroscopic works by Korenev et a l 2~
to its square, and therefore there always is a low concen- and Karasev et al; z~
tration range where As203(g) is negligibly low as compared SeS(g) Present work
to AsS and AsO. Since the arsenic concentrations discussed AG~ K) = - 0 . 2 kcal/mole
here are well within the range of dilute Cu-As solutions, Korenev et a l
where the As activity is lower than 1 0 - 6 , the probability of AG~ K) = - 0 . 2 -- 0.8
forming poly-arsenic species such as As203 was considered TeS(g) Present work
to be negligibly small at the matte-smelting temperatures. AG~ K) = 10.3
Karasev et a l
AG~ K) = - 1 . 6 -- 1.5
V. STEADY-STATE V O L A T I L I Z A T I O N IN PW3: A smooth interpolation between AH~'98(PO)=
INDUSTRIAL R E A C T O R S - - 5 . 5 , 4 ~td-/~98(AsO ) = 4 . 8 , 9 and ~ld-/~98(BiO) = 2814

The application of Eq. [227] is demonstrated in the
Part IV 56 by quoting the commercial Noranda Process reac-
tor as an example. The comparison of the present model
with the actual operating data and the conclusion of the
present paper will be given in the Part IV, 56 where the sum-
mary of the symbols used here is also found.
APPENDIX A. NOTES TO TABLES I A N D IV
PWI: The dissociation energy of SeO(g) calculated by
Barrow et a/~8'49's~ is D~98 = I01 +- 15 kcal/mole,
whereas a more recent value calculated by Piacente
et al 5~ is 119.5 + 9 kcal/mole. Using these values,
we have
~d-/~98(SeO) = z~'/~98(Se) + z~r-/~98(O) - O~98(SeO) [All
The value by Barrow et a l leads to z~r-~298(SeO) =
13 +- 15 k c a l / m o l e , whereas that by Piacente
e t a l leads t o z~/--/~98(SeO ) = - 5 - 9 kcal/mole.
The p r e s e n t value 12.75 k c a l / m o l e is f r o m
Wagman et al. 7
PW2: According to the Barrow-Cousins model, 6 the inter-
molecular distance (r.~) in the ground states of gas-
eous diatomic sulfides may be estimated from that of
the oxide. Namely,
rMs = 0.237 + 1.116 rMo [A2]
Using rs~o = 1.640,~ 18 and rT~o = 1.825~, 19 one
finds rs,s = 2.067A and rv~s -- 2.274/~,. The mo-
ments of inertia I are therefore given as I(SeS) =
1.617 • 10-38andl(TeS)= 2.199 x 10-3gg 9 cm 2.
Accordingly, the rotational entropies are ~(SeS) =
16.14 and ~(TeS) = 16.76. The translational (~),
vibrational (S~ and electronic (S~) entropies were
estimated as S~'(SeS) = 40.03, ~(SeS) = 0.2, and
S~ = 2.18; S~'(TeS) = 41.11, S~ = 0.3,
and S~ = 2.18. Consequently, one finds
S~'98(SeS) = 58.55 and Sz~ = 60.35 c a l /
mole 9 deg. The dissociation energy of TeS(g) was
estimated by Drowart et a l 5~ to be 80 kcal/mole,
whereas 66 kcal/mole by Hauge e t al. s3 The former
value leads to A/-/~98(TeS) = 33 kcal/mole, while
the latter to 47 kcal/mole, which was preferred in the
present compilation. A value of 2.8 --+ 3.6 kcal/
mole was obtained by Huang e t a154 a s the heat of
reaction at 298 K for the reaction: Se2(g) + S2(g) =
2SeS(g), whence the present value of 34 kcal/mole
for SeS(g). The free energy values thus calculated for
suggests a much smaller value than z ~ k n ~ 9 8 ( S b O ) =
47.67 suggested by Wagman e t al. 7 The present
value 14 ( c a l / m o l e ) was e s t i m a t e d based on
the interpolation.
PW4: Estimated based on an extrapolation of S ~ 9 8 ( A s S ) and
S~298(5b5).
PW5: Estimated based on the model of Kubaschewski
et al. 12
PW6: When 3'~ and e s are known, y'~ can be calculated by
Eq. [203]. Accordingly, ~Ag,S and 3'~,s can be calcu-
lated by 2
~Ag2S = 2(Acu/Acu2s)g16LAg)r'~gPs2
I/2 [ I/4 [A3]
~Ni2S = 2(Acu/Acu2s)Kj3LNi3,~Os2
I/2 I I/4 [A4]
where the values of Ps, can be calculated I from
Eq. [11], insofar as silver and nickel concentrations
are low in the mattes.
PW7: With the use ~of Eqs. [8] and [13], the.activity coef-
ficient of iron in the CuzS-saturated copper at
1250 ~ may be expressed by
y~ = 2.0(aFc/acu)(1 + 0.5N~)/(O.183Kap~n2) [A5]
or neglecting the dissolved sulfur, by
3r~r = 2 . 0 ( a v ~ / a c u ) / ( O . 183K4pl~) [A6]
where the values ofps, have been given I by Eq. [ll].
Knowing N~' = 0.026in the Cu2S-saturated copper 46
at 1250 ~ and using the value of y~o given in
Table III, we obtain eSc through
e s = 2.303(Iog y~ - log ~)/N~ [A7]
PW8: For low concentrations of Pb and Zn in the
CuzS-saturated copper, the activity coefficients of Pb
and Zn may be given as
')/~b = (Acu2s/Acu)Y~bs/(KloLpbPs2
l 1/2) [A8I
,)t.~n = ( A c u , s / A c , ) ~ z , s / ( K 1 1 L z .lp s 21/2
) [A9I
where the values of Ps_, can be calculated ~ from
Eq. [ 11]. The interaction parameters between Pb and
S or Zn and S can then be calculated by Eq. [A7].
Since sulfur activity deviates considerably from lin-
earity in the Cu-S alloys even in dilute solution
range, 47 the above-calculated e values may therefore
be subject to error. While no experimental data are
available as yet for the present systems, the use of
such higher order interaction parameters as intro-
duced by Lupis and Elliott 48 may be necessary for
improved accuracy,

328--VOLUME 13B, SEPTEMBER 1982 METALLURGICAL TRANSACTIONS B

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pp. 567-79.
3. K.S. Pitzer and L. Brewer: Thermodynamics, by G.N. Lewis and
M. Randall (revised edition), McGraw-Hill, New York, NY, 1961.
4. J. E Elliott, M. Gleiser, and V. Ramakrishna: Thermochemistry for
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