ISIJ International, Vol. 34 (1 994), No. 3, pp.

265-269

Assessmentof Calcium-Oxygen Equilibrium in Liquid lron

Sung-WookCHOand Hideaki SUITO

Institute for AdvancedMaterials Processing, Tohoku University, Katahira, Aoba-ku, Sendai, Miyagi-ken, 980 Japan.
(Received on Novemberl7. 1993.• accepted in final form on December17. 1993)

)
(ega) and the second-order (rga rg•• o interaction parameters between calcium and oxygen
Thefirst-order
in liquid were determined at 1873 K by using the previous data obtained in slag-metal equilibrium
iron
experiments, on the basis of the reciprocal and conversion relationships between mass percent and mole
fraction scales. Thevalues for ega, rg• and rg•, o were obtained as -3 600, 5.7 x I 05 and 2.9 x I 06 jn the range
of {[masso/oCa] +2.51 [masso/oO]} and -990, 4.2x I 04 and 2.1 x I 05 jn the range of {[masso/oCa] +
}
2.51 [massoloO] ~: O.005, respectively, and the validity of these values was discussed.

KEYWORDS:
interaction parameter; equilibrium constant; calcium; deoxidation,

l. Introduction 2. Interaction Parameters between Calcium and Oxygen

Calcium treatment in ladle refining is of fundamental 2.1. Reciprocal and Conversion Relationships
importance to produce high-quality grade steels, and the The following reciprocal relationships amonginter-
calcium-oxygen equilibrium has been discussed based on action parameters were derived by Lupis and Elliott,i6)
the experimental resultsl~9) and thermodynamic con-
sideration.5,i0.11)
p~,i+8J!=2p;+8: ••••••••••(1)
However, the solubility product of •••••••

calcium and oxygen as well as the interaction parameter 8i=8} ••

••••••••••(2)

between calcium and oxygen are considerably different 8~ p;• (p~,i)

where and are the first-order and the
from one another. In particular, the values3~6) of the
deoxidation constant. Kc*, for the reaction: CaO(s) second-order interaction parameters, respectively, on
= mole fraction scale.
Ca+0 obtained experimentally at 1873 K are sig- For the conversion relationships between the interac-
nificantly greater than thoses,lo,11) calculated from the
tion parameters on mole fraction and masspercent scales,
reliablethermodynamic data.
the following equations were derived,16)
Using the data obtained in slag-metal equilibrium
experiments, Kimura and Suit09) estimated the value pJj 2.3 x 102/M~{ 102M~rJj+ Mj(MI Mj)e~}
for Kc* and the first-order interaction parameter eg* at
= ~
+ l/2{(MI ~ Mj)/M1}2 ...............................(3)

l 873 K. However, their value for eco' was obtained 102MjMirJj,i

= 2.3 x 102/M~{ + Mj(MI ~ Mi)e~
pJ,!,i
coupled with the Kc. value in three different ranges of
{[masso/o Ca] +2.51[masso/o O]}. Such a treatment for +Mi(MI -Mj)e;}+(MI ~Mj)(MI ~Mi)/M~ ••(4)

calcium deoxidation by using the first-order interaction

8i= 230Mj/Miei+ (MI
- Mj)/MI
(5)
parameter only seems to be uncompiicated and con- "-"--"
vinient in practical application for plant data. However, where e~ and r~ (rJj•i) are the first-order and the
when the equilibria such as calciurn-sulfur, magnesi- second-order interaction parameters, respectively, on
um-oxygen, etc. are considered in the presence of oxy- mass percent scale. The values of M1' Mi and Mj are
gen and calcium, their interaction parameters without the atornic weights of solvent, solute of i and solute of
coupling the corresponding equilibrium constants have j, respectively.
no thermodynamic meaning and are of limited use. To
solve this problem, therefore, the hlgher-order interac-
The value represented by exchanging i for
for 8j is

in Eq. (5). Substituting ej, and 8i given by Eq. (5) into

j
tion parameters are essential. Eq. (2), one obtains the reciprocal relationship between
In this work, based on the reciprocal and conversion e,J'
and e} as follows.
relationships with respect to the interaction parameters
ej.= Mj/MieJ!+0•434 x l0~2(Mi- Mj)/Mi ......(6)
on masspercent and mole fraction scales, the first-order
and the second-order interaction parameters between Using Eqs. (1) to (6), the following relations can be
calcium and oxygen were estimated at 1873 K by using derived (Appendix A and B).
the previous experimental data9'12~ 15) obtained by the
(Mj/Mi)2rJ,!
authors' group.
rj.
= + Mj/(2Mi)(r~,' - r},j)
+ Mj(Mi - Mj)/(200M~)e~ •••••,•••••••••••••(7)

265 C 1994 ISIJ

 ISIJ International, Vol. 34 (1994), No. 3
considered to be sufficiently small in comparison with
ri J,'
= -e,J!/lO0+2(MilMj)r} •••••••••••••••••(8)
the other terms. The second and the third terms in the
2.2. Estimation of the Values for Interaction Parameters right hand side of Eq. (7) can also be neglected, thus
Deoxidation equilibrium for calcium is represented by resulting in the simple relationship given by rg.
= (Mc./
Mo)2rg". The substitution of this relation into Eq. (1 l)
CaO(s)=~~+Q .......
..........(9)
yields the following equation.
Using the equilibrium constant Kc. of Eq. (9), the log K~+ ~e~.[masso/o i]
+ ~e~[massoloj] - Iog ac.o
apparent equilibrium constant, K~ = [masso/o Ca]
[masso/o O]}, and the respective interaction parameters,
{ '

=-
eg•{ [masso/o Ca]
+ (Mc./Mo)[masso/o O] }
rg•{[masso/o Ca]2 (Mc./Mo)2[masso/o O] 2
one can express the calclum deoxidation equilibrium as, - +
log K~+ ~ + ~e~[massoloj] - Iog ac.o
e~.[masso/o i] + 4Mc./. Mo[masso/oO] [masso/o Ca] }
eg.[masso/o
O] - eg•[masso/o Ca]
rco.[masso/o O]2 + (MO+ Mc.)/( IOOMo)eg•[masso/oCa] [masso/o O]
=- - +10gKc* """--"""""""""""""""-""',.............(12)
rg"[masso/o Ca] 2 (rg~c. rg, c.)
- Ca] +
- [masso/o O][masso/o
+10gKc* """""(lO) Since the third term in the right hand side of Eq. (12) is
x ""'
considered to be sufficiently small to be eliminated in
j
where i and represent the components other than O
and Ca, respectively. In the derivation of Eq. (lO), the
comparison with the first and the second terms, Eq. (12)
can be rewritten as,
terms with respect to the self-interaction parameters
and the second-order interaction parameters except those 10g K~+
~e~.[masso/o i]
+ ~e~[massoloj] - Iog ac.o
between calcium and oxygen are neglected.
By using Eqs. (6) to (8) derived in Sec. 2.1. Eq. (lO)
=- eg•{ [masso/o
Ca] + (Mc./Mo)[masso/o O]
c* {[masso/o
}
can be rewritten as - ro Ca] + (Mc./Mo)[masso/o O]}2
2rg"Mc./Mo[masso/o O][masso/o Ca] + Iog Kc. (1 3)
log K~+ ~e~*[masso/o i] + ~e~[massoloJ] - Iog ac*o - '

The values for e~l7) and ac*018) used in this study are
=-
eg•{ [masso/o Ca] (Mc./Mo)[masso/o O]
+
rg•{ [masso/o Ca] 2 (Mc./Mo)2 [masso/o O] 2}
} summarizedin Table I and Fig. l, respectively.
- + The relation between the left hand side of Eq. (1 3) and
Mc./(2Mo)(roc*, o ~rc.o, c* )[masso/o O]2 {[massoloCa] +2.51[massoloO]} is shown in Fig. 2,
-
Mc*)/(200Mg)eg•[masso/o O] 2 indicating a nonlinearity. As can be seen in Eq. (13),
- Mc.(Mo~ therefore, the terms with respect to the second-order
+ {(eco"
+ eco.)/lOO 2(Mo/Mc.rg. + Mc./Morg•)}
- interaction parameter rg* in Eq. (13) have to be taken
x [masso/o Ca][masso/o O] + Iog Kc. ""' """""
(1 l) into account for the calcium-oxygen equilibrium. Slag
where the second term of the right hand side of Eq. (6), compositions for the data used in Fig. are indicated 2
in
-0.0065, was neglected in Eq. (1 l). the CaO-AIO1.5-Si02 phase diagram in Fig. I .

The third and the fourth terms in the right hand side The values for eco" and rg• in Eq. (1 3) determined
were
of Eq. (1 1), which correspond to the second and the third by using the contents of calcium, oxygen and other
terms in the right hand side of Eq. (7), respectively, are components obtained in previous equilibrium exper-
iments,9'12 ~ 15) the respective Interaction parametersl7)
Table l. Interaction parameters at 1873 Ki7) used in the given in Table l, the values for ac*018) and the Kca
present work. value. The value of logKc* was obtained as
- l0.22 at
e~ (ri)
l K
873 by using the thermodynarnic data for the reac-
tions: CaO(s)=Ca(1)+11202 (AG'=434.5kJ/moll9))
and ll202=Q (AG'= I17OOO 2.9T J/g atoml 7))
Al Al 0.045 - -
and the free energy for calcium dissolution in liquid iron
'

O Al
-
3.9 (1.7)
Si -0.131 Ca(1) ~~ (AG'
= = 121 OOO- 35.5 TJ/g
estimated based on the solubility
atom), which was
data20) by assuming
'

Ca Al
- 0.072
Si
- 0.097 regular solution. It should be noted that the values for
eco* and rg• cannot be obtained from the plot of Fig. 2,

acaO SiO 2
( )
S2A6
cs 4O
(0.013)

C3S
C2S AIO1.5
CAS9 Acs2
80 (0.106) (o cn3) 20
CAS5
0.35 Acs4 CA12 Fig. l.
(o,045)
CaO cAs8 CA4 Activities of CaO(s)18) and slag compositions plotted in
(1.0 the CaO-AIOI5-Si02 phase diagram at 1873 K.
20 CA 60 AC 80 AIOI .5
CaO (1.0) (O 11)
(mol "/.)

C 1994 ISIJ 266

 ISIJ International. Vo]. 34 (1994). No. 3
-4
~~e

-2 [ppm Ca] + 2.51 [ppm O] 50 1873 K

O ~~~ X~ xAx
a)
~l
~ V>~Z~~
'~)~~~(~:~_~)
VV
+ -6 + +v ++ ;/~;~~::O~i)~:~
I~~
O
~~:s) -4 ~:~
~
[1 .'
\
\
O AC
[] CA
O
o [1 / t
~::~)

-o
p~l
/
+ -8 /
/ A CS eJ) -6
O(I~
/ x ACS-2
/
u V ACS-4
cls / ~> CAS-5

~ /
// 1873
K [1 CAS-8
-8 Thermo. calc.
I / + CAS-9
_~ -1O [o/. Al] O.3 aCaO= O.11 OAC :
~,~ -F ["/. Si
J 1.0
Thermo calc
eJ) _~ acaO= I A CA
-10
O O O(]2 OOO4 O006 {] 008 (1.OIO 0.012 -6 -5 -4 -3 -2 -1

[% Ca] + 2.51 [% O] lOg [% Ca]

Fig. 2. Relation between the left hand side of Eq. (13) and Fig. 3.
A plot for the relation between oxygen and calcium
{[mass"/* Ca] + 2.51 [mass"/* O]} term. contents in logarithmic form calculated by the itera-
tive method using the interaction parameters given in
Table 2. Estimated values for interaction parameters Table 2. Only the solid lines satisfy the condition of
between calcium and oxygen at 1873 K. + 1
{[masso/o Ca] 2.5 [masso/o O]} Previous ex-
perimental data9'12] are also indicated.
["/oCa] + 2.5 1["loO] i j e t
J'

r j
i*

0,005 O Ca - 3600 5.7 x 105 2.9 x 106

-2
[ppm Ca] + 2.51 [ppm O] ~: 50 1873 K
Ca O - 9ooo 3.6 x 106 2.9 x 106
~: 0.005 O Ca - 990 4.2 x 104 2,1 x 105
Ca O - 2500 2.6 x 105 2,1 x 105 ,r
-4

because the left hand side of Eq. (13) is not a function O

~~~)
'
l!
'

of {[masso/o Ca] + 2.5 1[masso/o O]}. Therefore, the mul- eJ)o ~6

tiple regression analysis fixing the value of log Kc*
=
10.22 was used to determine the values for eg" and
-
rg", which
were obtained as - 3600 and 5.7 x 105 in the -8 Thermo. calc.
range of {[masso/oCa]+2.51[masso/oO]} and ac:lO = 11
O•

990 and 4.2 x 104 in the range of {[masso/o Ca] + 2.51 1

-
[masso/oO]};Z0.005, respectively.
aGIO=
The values for the -lo
reverse interaction parameters eg* and rg* were obtain- -6 -5 -4 -3 -2 -1

ed by the reciprocal relationship given by Eq. (6) and

the relation of rj•=(Mj/Mi)2r,Ji
log [% Ca]
deduced from Eq. (7).
The values for rg•,o and rg~c* calcuiated by using were Fig. 4.
A plot for the relation between oxygen and calcium

Eq. (8). The results are summarized in Table 2. The contents in logarithmic form calculated by the itera-
tive method using the interaction parameters given in
curved lines indicated in Fig. 2 will be explained later. Table 2. Only the solid lines satisfy the condition of
The relations between oxygen and calcium contents
were calculated by the iterative method, using the inter-
{ [mass"/~ Ca] + 2.5 1[mass"/. O]} ~: 0.005.

action parameters given in Table 2. The results, which and calcium calculated for ac*o = were used to draw I
were calculated without taking into account the effect of the lines in Fig. 2
in order to neglect the effects of the
aluminumon oxygen, are shownin Figs. 3and 4for the components other than Ca and O. Although two or
ranges of {[masso/oCa]+2.51[masso/oO]} and three oxygen contents were obtained at a given calcium
~ O.005, respectively. for Experimental results9'i2)
AC content as shownin Figs. 3and 4, these oxygen contents
(ac*o =0.1 and (ac*o
= 1)
CA
slags ar6 also indicated l) fall
on the sameline in Fig. 2. The reason for the devia-
in Fig. 3. Only the solid lines in these figures represent tion of the data points from the calculated lines in Fig.
the relations betweenoxygen and calcium contents which 2is not clear and more detailed studies are required.(9).
satisfy the respective conditions of {[masso/o Ca] + The following relation can be written from Eq.
2.51 [masso/o O]}. It is not clear at present that which of
logKc*+10gac.o~loga0=10gac* "-"""'(14)
the oxygen contents in two or three is real for a given
calcium content. The relations given by Eq. (14) are plotted in Figs. 5
The lines in Fig. 2were obtained by using the contents and 6, inwhich the interaction parameters given in Table
of oxygen and calcium calculated in the respective ranges 2and experimental data in respective ranges shownin
the
of {[masso/o Ca] +2.51[masso/o O]} as shown in Figs. 3 Fig. were used to calculate the values for ao and ac.'
2
and 4. It should be noted that only the contents of oxygen Data obtained by other investigators2~4,6) are als~o

267 C 1994 ISIJ

 ISIJ International, Vol. 34 (1994), No. 3
-2
CI
~
~~c)
I] -lO o
~
~~
~~0 []
C]

~l []
~ -4 ~>
1873 K
cf)
+ (~)
-12 Cl
OO oo
+ 1873 K
o
~;]
O AC ~
~ o
(J -6
~>
[]
[] C] CA clS AC CA
'-O oC]
ccf

eO
~>:
~D>
[> V
D>
ACS-4
CAS-5
a)
~l
cf)
~
Cl CAS-8
+
OI
c~f
-8 O + cAS-9
+
~:~~)
~
~~o
~~~+
~ V
+
["/~ Al] 0.3
without slag e) ~
~~~~
-12
C~oo
oo
o
~ Gustafss'on ~~ o [][] O
["/~ Si]
1 & Mellberg c\i []
-1O
[ppm Ca] + 251 [ppm OJ 50 ~ Ototani et al +
~~
~
(50 ~14

eo c~
-10 -8 -6 -4 -2 Q +
log
o 0.1 0.2 0.3 0.4 0.5
aca
2[% O] + 1.78[% AI]
Fig. 5.
Aplot forthe relation expressed by Eq.(14) inth range
of {[masso/. Ca] + 2.5 1[masso/o O]
} 0.005. Fig. 7. A plot for the retation expressed by Eq. (17).

j
where i and represent the components other than O
and Al, respectively. The values of eJj used in this study
-3
1873K are given in Table I
~
~1 ~> The authorsl5)
.

previously estimated the values for

~ _5 ~l 10gK15 and e~1 by using Eq. (16) as 13.3~0.59 and
+
o(Q
- ~
6.83 O.07, respectively, without taking into considera-
tion the effect of calcium on oxygen. As mentioned in
(J
x ACS-2
~~~~ the previous report,15) the positive deviation from the
(Is
_7 V ACS-4
~ A CS line in a piot of the left hand side of Eq. (16) vs.
{2[masso/oO]+1.78[masso/oAl]} term was observed
+ without slag
ol vvA z~ Gustafsson for the data obtained in CaO-saturated slags. This
cv ~ 9
&
Mel]berg indicates that the effect of calcium on oxygen cannot be
~ ["/~ Al] O3
~)
Haneta].
Ototani et al.
neglected.
["/. Si]
l Considering the first-order
-1
1 [ppm Ca] + 2.51 [ppm O] ~ 50 C] Miyashita and the second-order in-
& Nishikawa teraction parameters between calcium and oxygen, one
-1
1 -c) _7 _5 _3 _ 1 can write instead of Eq. (16) as,
10g aCa log K'I
5+ 2~
e~l[masso/o i]
+ 3~e~[massoloj]
Fig. 6.
A plot for the relation expressed by Eq. (14) in the
+ 3~r~[masso/o k]2 + 3rco"' o[masso/o O] [masso/o Ca]
Iog
range of {[masso/* Caj + 2.5 1[mass"/o O]} ~: 0.005.
- aAl'o,
e~l{2[masso/o O] I .78[masso/o Al]}
=- + - Iog K15 7)
indicated in Figs. 5
and 6. The results in these figures 1
.(

suggest that the present interaction parameters are than O

reasonably well-estimated.
and Al, respectively.
j
where i and represent the components other

Figure 7 shows the relation between the left hand

3. Aluminum-OxygenEquilibrium in the Presence of
side of Eq. (17) and {2[massoloO]+ 1.78[masso/oAl]}
Calcium
term, by using the contents of oxygen, aluminum and
Deoxidation equilibrium for aluminum in liquid iron the other componentsobtained in previous equilibrium
is given by experiments9'12) for ACand CAslags, the respective
interaction parameters and the values of aAl'o, = 0.33
2A1+ 3Q=Al203(s) ..........(15)
........ (AC) and 0.0048 (CA) reported by Rein and Chipman.18)
From the equilibrium constant K15 of Eq. (15), the The effect of calcium on oxygen is excluded in the upper
apparent equilibriurn constant, K'I5{=[masso/o Al]2. diagrarn of Fig. 7, whereas in the lower diagram the
[masso/o O]3}, and the first-order interaction parameters, interaction parameters between calcium and oxygen are
the following relation is derived, considered for all the data points, which are in the
range of {[masso/oCa]+2.51[masso/oO]} The
10g Kj
5+ 2 ~e~l[masso/o e~~{2[masso/o
i]
+ 3~e~[massoloj] line in the
upper diagram is the
same in Fig. I in Ref.
O]
- Iog aAl'o, = ~ l 5), which was determined by using the data not only
+ I .78[masso/o Al] }- Iog K1
5
for the CaO-Al203slags but also for the CaO-A1203-

C 1994 ISIJ 268

 ISIJ International. Vol. 34 (1 994), No. 3
Si02 and the CaO-Al203-MgO slags. The line in the (i by j) in Eq. (5). These four values of pj., p;•,j, 8; and 8~

lower diagram in Fig. 7was drawn with the sameslope along with those for p~ and p~" given by Eqs. (3)
an~
of the line in the upper diagram. (4), respectively, are substituted into Eq. (A-1). Com-
The value for the equilibrium constant log K15 = 13.80, bining this result with Eq. (6), one obtains the follow-
which was obtained from the intercept of the line shown ing equation after arrangement.
in the lower diagram by using the data except one point
= (Mj/Mi)2ri + Mj/(2Mi)(r~" -
rj. r},j)
I
(2[masso/o O] + .78[masso/o Al]
= 0.425), agrees with the
previous value of 13.3~0.59 by the present authors.15) + Mj(Mi - Mj)/(200M?)eJ,i - Mj/(200Mi)(e - ; ej)
It
can be seen from Fig. 7
that the linearity becomes + (Mi- Mj)/(4.6 x 104Mi) ..............................(A-2)
better by considering the interaction between calcium
and oxygen, although the data points still scatter Since the fourth and the fifth terms in the right hand
significantly. side of Eq. (A-2) are negligibly small, Eq. (7) is deduced.

B. Derivation of rJi"i eJi', e;

as a Function of and r'j
4. Conclusrons for p;
The values and e; deduced from Eqs. (3) and
along with those for p~,i and 8Jj given by Eqs.
Calcium-oxygen equilibrium in liquid iron was as- (5) (4) and
sessed by using both first-order and second-order in- (5) are substituted into Eq. (1) in order to derive the ri,i

teraction parameters and the equilibrium constant for value as a function of and eJj,
By coupling with e; rj.

calcium deoxidation. The following conclusions are Eq. (6), one obtains the following relationship.
derived:
= - ei/lOO + 2(Mi/Mj)rj.
r~,i
(1) Based on the reciprocal and conversion relation-
ships with respect to the interaction parameters on mass +e /100+(M M)/(2 3x 104M) .......
(B-1)

percent and mole fraction scales, the relation between Since the third and the fourth terms in the right hand
the second-order interaction parameters ri and rj• was side of Eq. (B-1) are sufficiently small to be neglected,
derived. Furthermore, the value for rJj,i was expressed as Eq. (8) is deduced.
a function of other interaction parameters.
(2) By using previous equilibrium data, the values REFERENCES
1 K
for eg•, rg• and rg",o at 873 were obtained as -3 600, l) s. Kobayashi,Y. omori and K. Sanbongi: Trans. Iron Steel Insl.
5.7 x 105 and 2.9 x 106 in the range of {[masso/o Ca] + Jpn., Il (1971), 260.
2.51 [masso/o O]} and -990, 4.2 x 104 and 2.1 x 2) Y. Miyashita and K. Nishikawa: Tetsu-to-Hagan~, 57 (1971),
l05 in the range of {[masso/oCa]+2.51[masso/oO]} ;~ l 969 .

3) T. Ototani, Y. Kataura and T. Degawa: Trans. Iron Stee/ Inst.

0.005, respectively. The values for eg., rg. and rco~c. were
Jpn., 16 (1976), 275.
also estimated from the reciprocal relationships.
between calcium and
4) S. Gustafsson and P-O. Mellberg: Scand. J. Metall., (1980) 9
(3) The equilibrium relation lll.

oxygen contents in calcium deoxidized liquid iron was 5) M, Nadifand C. Gatellier: Rev. Metallurgie-CIT, 83 1986), 377.
Q, Han, X. Zhang, D. Chenand P. Wang:Metal/. Trans. B, 19B
(
described by using the present values for the interac- 6)
(1988), 617.
tion parameters and equilibriurn constant.
7) M. Hillert andM. Selleby: Scand. J. Metall., 19 (1990), 23.
(4) By taking into consideratlon the first-order and 8) M. Tano, H Fujiwara and E. Ichise: Proc, the 8th Japan-Germany
the second-order interaction parameters between calci-
.

Seminar. ISIJ, Tokyo, (1993), I 13.

umand oxygen, the aluminum deoxidation equilibriurn 9) T. Kimura and H. Suito: Metal/. Trans. B, 25B (1994). Feb.
in liquird iron can be satisfactorily explained. lO) I. S. Kulikov: Izv. Akad. NaukSSSR,Metally, (1985), No. 6, 9.
ll) E. T. Turkdogan: Stee! Res., 62 (1991), 379.

Appendix l 2) H. Suito, H. Inoue and R. Inoue: ISIJ Int., 31 (1991), 1381.

l 3) R. Inoue and H. Suito: Meta!!. Trans. B, 23B (1992), 613.
A. Reciprocal Relationship between r~ and r~ l4) F, Tamuraand H. Suito: Metall. Trans. B, 24B (1993), 121.

Subtracting Eq. (1) from the equation obtained frorn

l 5) S. W. Cho and H. Suito: ISIJ Inl., 34 (1994), 177.

16) C. H. P. Lupis and J. F. E1liott: Acta Metall., 14 (1966), 529.

replacing i by
j j
and by i in Eq. (1) and using the
relationshlp given by Eq. (2), one obtains
l 7) G
l 8)
K. Sigworth and J. F. Elliott: Mel. Sci., 8 (1974), 298.
R. H. Rein and J. Chipman: Trans. Metal!. Soc. AIME, 233
(1965), 415.
pj•=pJ,!+ l/2(pJj•i-pj•,j)- l/2(8;-8i) ••••••••(A-1)
l 9) M. W. Chase, Jr., C. A. Davies, J. R. Downey,Jr., D. J. Frurip,
R. A. McDonaldand A. N. Syverud: J. Phys. Chem. Ref. Data,
The values for and pj•,j can be obtained by replacing
pj•
14 (1985), Suppl. l, 688, 71 l.
i j j (8j)
by and by i in Eqs. (3)and (4), respectively. The 20) D. L. Sponseller and R. A. Flinn:
(1964), 876.
Trans. Met. Soc. AIME, 230
can also be obtained by replacingj by i
value for e;

269 C 1994 ISIJ