Process metallurgy

Thermodynamics of antimony, arsenic, and tin in CaO-CaF 2 melts

Tomoo Isawa. Takashi Wakasugi. Kei Noguchi, and Nobuo Sano

In view of the importance of tramp element contamination of steel products through a large volume of scrap consumption in
the near future, the thermodynamic behaviour of Sb, As, Sn and Cu in CaO-CaFz melts under reducing conditions was studied
by examining the dependences of distribution of each element between Cu, Ag or Sn alloys and CaO-CaF z melts on the CaO
activity, oxygen partial pressure and temperature around 1500°C.
As a result, the reaction products on treatment by Ca compounds were demonstrated to be Ca3Sbz, Ca3AsZ, Ca-Sn and CaCu.
Experimentally obtained distributions were extrapolated to lower oxygen partial pressures less than 10 - 18 atm to estimate the
feasibility of removing those tramp elements from molten iron. It is thermodynamically indicated that if the prevailing oxygen
partial pressure of the environment is below 10 -Z3 atm, these impurities, except Cu. would be substantially removed from
molten steel.

Thermodynamik von Antimon, Arsen und Zinn in CaO-CaFrSchmelzen. Hinsichtlich der Bedeutung von Verunreinigungen
durch Spurenelemente, die durch den hohen Schrottverbrauch in Stahlerzeugnisse gelangen, wurde das thermodynamische
Verhalten von Sb. As, Sn und Cu in Ca-CaFTSchmelzen unter reduzierenden Bedingungen untersucht. Die Abhanqiqkeiten
der Elementverteilungen in Cu. Ag oder Sn-Legierungen und CaO-CaFTSchmelzen von der CaO-Aktivitat, dem Sauerstoffpar-
tialdruck und einer Temperatur von 1500°C wurde ermittelt. Als Ergebnis wurden die Reaktionsprodukte aus der Behandlung
mit Ca-Verbindungen als Ca3Sbz, Ca3AsZ, Ca-Sn und CaCu nachgewiesen. Die experimentell erreichten Verbindungen wurden
zu niedrigen Sauerstoffpartialdrucken unterhalb von 10- 18 atm extrapoliert, um die Moglichkeit abzuschiitzen, diese Spuren-
elemente aus flussiqem Eisen zu entfernen. Es ist thermodynamisch nachgewiesen, daB, bei einem Umgebungs-Sauerstoffpar-
tialdruck unterhalb von 10 -Z3 atm diese Verunreinigungen, mit Ausnahme von Cu. weitestgehend aus flussiqern Stahl entfernt
werden konnen,

When using scrap as a source of iron and chromium, con-

tamination of tramp elements such as copper, tin, antimony
and arsenic which are harmful for steel properties must be
taken into account. The conventional refining principle by
oxydation cannot be applied for the removal of these ele-
ments, because they are generally nobler than iron and espe-
cially chromium which would be preferentially oxidized on
the treatment. Although a new refining process under
strongly reducing conditions has been recently developed,
there are few thermodynamic data available for process out
analysis. Accordingly, in this investigation the thermody- @) ®
namic properties of tin, arsenic, antimony and copper in
CaO-CaF z melts under strongly reducing conditions were 1 su furic acid 4 Soda lime
measured at temperatures ranging from 1360 to 1550°C. 2 Gas mixer 5 Magnesium perchlorate
3 Magnesium turnings 6 SiC electric resistance furnace

Experimental procedures Figure 1. Schematic representation of the experimental system

Figure 1 shows a whole experimental system which consists
of a gas mixer (Westhoff), gas cleaning units and a SiC re-
sistance furnace. The oxygen partial pressure of the system
was controlled by a mixture of CO and Ar, equilibrating the
reaction, CO = C + 1/2 Oz. Since the oxygen partial pressure
was very low, (Po,=10- 16_10- z 1 atm), the gas was cleaned
very carefully. Moisture in the gas was removed by sulphuric
acid and magnesium perchlorate. Similarly CO 2 in CO and
O 2 in Ar were removed by soda lime and magnesium turn-
ings, respectively. By this method the Po, in Ar was found to
be as low aSPo,=10- 14 atm.
Two thermoelectric couples (Pt/6% Rh-Pt/30% Rh) were
used, one for control and the other for temperature measure-
ment of the hot zone. The temperature was controlled by a
PI D controller as seen in figure 2 to ± 2°C in a zone of 6 em
long, over the experimental temperature range. A mullite
Tomoo lsawa, presently with Nippon Kokan, K. K.; Takashi Wakasuqi,
Nobuo Sano, Department of Metallurgy, University of Tokyo; Kei Nogu-
chi, with Nisshin Steel Corporation, Japan
Bild 1. Schematische Darstellung des Versuchsaufbaus
tube was set (50 mm o.d., 42 mm i.d. and 850 mm in length)
at the center of the furnace as a reaction tube, an alumina
porous tube (37 mm o.d. and 30 mm i.d.) being used for pro-
tection against thermal shock.
The specimen, two grams of CaO-CaFz mixture and two
grams of metal in a graphite crucible, was equilibrated un-
der a controlled flow of CO-Ar mixture for 18 hours, as
shown in figure 2. The reagent grade chemicals of CaO and
Ca F, were mixed and then premelted at about 1500°C to
prepare master slags.
As for a metal specimen, three alloys were prepared for ex-
periments on antimony, arsenic and tin, respectively. Name-
ly, for antimony, copper containing 5% antimony was used
because thermodynamic data of Cu-Sb alloys are available
in literature. For similar reasons, Ag-1% As alloy was used
for arsenic. For the case of tin, metallic tin was used because
otherwise the tin content in slags would be too low for

296 steel research 58 (1987) NO.7


10
4 the minimum oxygen partial pressure is likely to be within
Figure 2. Schematic sketch of the technique for equilibration between
molten metals and CaO-CaF, melts
1 mullite tube, 2 porous alumina tube, 3 gas inlet, 4 porous alumina
block, 5 graphite holder, 6 graphite crucible, 7 graphite lid, 8 thermo-
couple, 9 CaO-CaF, melt, 10 metal
Bild 2. Schematische Beschreibung der Gleichgewichtseinstellung
zwischen geschmolzenen Metallen und CaO-CaF,-Schmelzen
chemical analysis. These alloys were preliminarily melted
and provided for subsequent experiments.
After 18 hours' equilibration these samples were quickly
withdrawn from the hot zone and cooled down under Ar
flow. Immediately afterwards the sample was supplied for
chemical analysis to prevent the slag from hydration or from
oxidation. Concentrations of antimony, tin and copper were
determined by atomic absorption spectroscopy. For arsenic,
molybdenum blue colourimetric absorption was used. The
separation of species with negative valence from that with
positive valence was conducted for several samples contain-
ing antimony and arsenic. The method is described as fol- .
lows. The specimen was dissolved in 40 ml of 50% HCI un-
der argon. Gaseous SbH} or AsH} which was formed from
the compound such as Ca}Sb 2 or Ca3As2, was carried away
by Ar flow and was absorbed into an Ag-DDTC (silver-di-
ethildithiotetracarbamate) solution in a separate vessel while
oxidized compounds remained in an HCI solution. After
separation the concentration of Ca,Sb 2 or Ca3As2 was mea-
sured by colour change of the Ag-DDTC solution using col-
ourimetry.
For metal analysis, the antimony content in copper was de-
termined by atomic absorption spectroscopy and arsenic
content in silver was colourimetrically determined. The CaO
content in slags was determined by EDTA titration after
CaO was selectively dissolved in 25% acetic acid solution.
steel research 58 (1987) NO.7
Process metallurgy
Theoretical considerations
Determination of oxygen partial pressure. The oxygen partial
pressure of the system can be calculated by equation (2):
C(s)+ 1/202(g)=CO(g) (1)
t>Go= - 114300- 85.7 T [llmoW). (2)
In this investigation, the activity of carbon was fixed at uni-
ty, by using graphite as a container. As the ratio of COl
CO + Ar varies from 0.02 to 1 by changing the flow rate of
each gas, the partial pressure of oxygen varies from
7.96 x 10- 20 to 1.99 X 10- 16 atm at 1500°C. When the ratio
of COICO + Ar is very low, the following side reaction takes
place between CaO-CaF2 melts and the graphite crucible,
the minimum oxygen partial pressure being fixed at
8.47 x 10- 2 1 atm at CaO saturation:
CaO(s) + 2 C (s) = CaC 2 (s) + 112O 2 (g) (3)
t>Go= 579300- 134.7 T [Jz'mol]'). (4)
However, because there is a scatter of ± 3 kcal in literature,
5.64x 10- 2 1_1.27 x 10- 20 atm. According to Mitche1l2 ) , the
solubility of CaC 2 for the CaC 2 - C a F2 is reported as about
0.24 mole fraction. However, the concentration of CaC 2 in
present slag melts (CaO-CaF2 - C a C 2) at double saturation
of CaO and CaC 2 was found to be 6 mass % after equilibra-
tion, which is the maximum content under the experimental
conditions employed in this study. Since the CaC 2 content
ranges from 0.2 to 6 mass %, dependence of Pea and the
CaO activity is not likely to affect the CaO solubility in the
CaO-CaF 2 system, as is described in the next section.
Determination of the CaO activity. The CaO activity in
CaO-CaF 2 melts at I 500°C using a graphite crucible was
reported by Edmunds and Taylor"). At their partial pressure,
1.99 x 10- 2' atm, there seems to be little CaC 2 in slags so
that their data have been used for conversion from CaO con-
tent to its activity.
When the temperature dependence is studied in the present
investigation, the phase diagram of the CaO-CaF 2 system
is necessary to keep the activity of CaO at unity. However,
there is a great discrepancy among those reported by EiteI 4 ) ,
Ries and Schwerdtfeger"), Baak"), Mukerji'), Kor and Rich-
ardson") and Zhmoidin and Chatterjii"). Our solubility val-
ues of CaO after equilibration, using a CaO single crystal
together with slag melts, agree well with the data of Kor and
t
Richardson, see figure 3.
1600r----~------;-T--,-----,-----,--_--,---_----,
Ti'C) - - E i t e l
- R,es et al
-.---- Mukerji et aL
","
•••
- . - - - Kor et ol
1500 _ . - Zhmoidin et oL
• Present work
••
•
•i •
1400 -:--_
---~-
.. ·",1
.--.e----::.
1300~-----.?\------.5rc----2'n-~-~;c--------d
10 40 50
Figure 3. Solubilities of CaO into the CaO-CaF, system
Bild 3. l.oslichkeiten von CaO im CaO-CaF,-System
297
Process metallurgy

-1

P02=1.99x10-'8atm •• 4
. . ~.
0C
1500

••
-1
,.......
•
-
./\
••
,h •
/~
-2

/
'." /. CaO-CaF2 system
/
./

L}
1500·C
=
PO z 1.99xlO-18 atm

2
-3 -3
o 10 20 30 -1 o
(wt%CaO) log 0 Coo
Figure 5. Dependence of Sb distribution between Cu and CaO-CaF 2
melts on the CaO activity
Figure 4. Effect of CaO content on Sb distribution ratio Bild 5. Abhiingigkeit der Sb-Verteilung zwischen Cu und CaO-CaF2 -
Bild 4. Einflul1. des CaO-Gehalts auf das Sb-Verteilungsverhiiltnis Schmelzen von der CaO-Aktivitiit

Identification of chemical reactions and determination of ther- ologLM )

(9)
modynamic properties. When a CaO-CaF2 slag is used, the X = ( ologacao Pm.Temp.
reaction for M, representing metal in general, is expressed
by equation (5): OIOg LM)
y= ( 01 (10)
ogPo (lCaO,Tcmp.
2
M +xCaO+ y02=Ca,MOx+2, (5)
From the van't Hoff equation, the standard enthalpy change
where x and yare coefficients, and the sign of y is either of equation (5) is expressed as equation (11):
positive or negative. That is, when y is negative, the third
term in the left moves to the right and equation (5) can be I'1W= -R ( oinK) (11)
rewritten as equation (5'): o(lIT) a c ao.l'm

M+xCaO=Ca,M+xI20 z (y= -xl2) (5') Since the CO partial pressure is kept constant in this study
while the temperature varies, the obtained I'1Ho is for equa-
For equation (5), the equilibrium constant K is written as tion (12), where the heat of the solution of Ca,MOd 2 , into
equation (6): CaO-CaF2 melts is included: .

K= aca",~O'+2'1
M+xCaO+2yCO=Ca,MO'+2,+2yC (12)
(6)
aM·aCaO·po,
I'1H o= -R ( oInK). (13)
In the present investigation, only the concentrations of M in o(lIT) "c,o.Pca

slags and metal, (%M) and [% M], respectively, were deter-
mined. Using the distribution ratio which is defined as
L M == (% M)/[% M], equation (6) is rewritten as equation (7):
10gL M=xlogac,o+ ylogpo, +
+ 10gf'lf+ 10gK
where a, is the activity of species i, f is the Henrian activity
coefficient of compound, Ca,MO'+2n and f~ is also the
Henrian activity coefficient of M in metal. The distribution
ratio can be described as a function of four variables, name-
ly, the activity of CaO, the oxygen partial pressure of the
system, the ratio of activity coefficients of M in metal and
slag and the equilibrium constant K, i. e. temperature. On
the assumption that the third term of equation (7), f' If, does
not vary widely over the range of experimental temperatures
and of CaO content in slag, equation (7) becomes equation
(8):
10gL M = xlogacao+ ylogPo 2 + C
where C is a constant. The coefficients, x and y, are calcu-
lated by partial differentiation as follows:
I'1Ho of equation (5) or equation (5') can be calculated by
using equation (2).
(7)
Results and discussion
Dependence of impurity distributions on the activity of CaO.
Figure 4 shows the antimony distribution between
Cu-5%Sb and CaO-CaF2 melts as a function ofCaO con-
tent in slags. Experiments were conducted under the follow-
ing conditions:
temperature: I 500°C
atmosphere: Po, = 1.99 x 10- 18 atm.
As CaO content in slags increases, the antimony distribution
ratio, L S b , between metals and slags increases. The distribu-
tion ratio reaches maximum at around 22 mass % of CaO
beyond which it levels off. On the other hand, the phase di-
(8)
agram shows that the solubility of CaO in CaO-CaF2 melts
is 20.8 mass % at 1500°C 8 ) . This agrees with experimental
findings mentioned above. If equation (5) holds as the reac-

298 steel research 58 (1987) No.7

 Process metallurgy

CoO-CoF 2 system
1500 0C
P0 2 =1.9 9 X1O- 18 otl 1500 0 C
CaO-CaF2
Po2 = 4.98xl0- 19 atm

0
.'
,•
0

••
<
en
..J
OJ
0
...J
.}. 3
,....
(J)
v:
'-'"

-'
c

Cl
0

-1 ~2_~
•

-1
•1--
/ 2

-1 o - 2 L..-_L.- .....J
log 0coo -1 log OCaO o
Figure 6. Dependence of As distribution between Ag and CaO-CaF 2 Figure 7. Dependence of Sn content in CaO-CaF2 melts on the CaO
melts on the Ca0 activity activity
Bild 6. Abhiingigkeit der As-Verteilung zwischen Ag und CaO-CaF,- Bild 7. Abhiingigkeit des Sn-Gehalts in CaO-CaF 2-Schmelzen von der
Schmelzen von der CaO-Aktivitiit CaO-Aktivitiit

tion of deantimonization, the distribution ratio will increase (16)

linearly as the CaO activity increases, when they are plotted
on a log scale. Using the relationship between the activity
and the content of CaO in CaO-CaF 2 system:'), figure 4
was replotted as figure 5. The slope of the line in figure 5 is
calculated as + 1.2. On the assumption that the value of f' If
in equation (7) changes insignificantly, this means that the
coefficient, x in equation (7), is equal to + 1.2. Considering
that the stable valence of antimony under reducing condi-
tions is - 3, x is presumed to be equal to + 1.5. The experi-
mental value of x, + 1.2, is in fair agreement with the theor-
etical prediction. This suggests that the reaction product is
Ca}Sb 2 , and the reaction of deantimonization is expressed
by equation (14) for one mole of antimony:
Sb+3I2CaO =Ca15Sb + 3/40 2 (14)
Dependence of impurity distributions on the oxygen partial
pressure. Measurements of distribution were made at
I 500°C with slags having the same activity of CaO. The
oxygen partial pressure was varied by changing the COl
CO + Ar ratio, as described before, down to that at double
saturation with CaO and CaC 2 • The solid CaO activity in
slags was kept at unity, except for the case of tin, by letting a
chunk of CaO single crystal coexist with slag melts. In the
latter, the CaO activity in slags was fixed at 0.62.
The results on antimony, arsenic and tin are shown in fig-
ures 8, 9 and 10, respectively. The slope of each line was

Using the same method, the distribution of arsenic was mea- 1 I

CoO-CoF 2 system
sured. Figure 6 shows the relationship between arsenic dis- CoO sotd.
tribution and the CaO activity. The slope of the line is ob- 1500 0C
tained as + 1.6, which indicates the valence of arsenic under 0
strongly reducing conditions is equal to - 3, as estimated
from the existence of a stable arsenide compound such as
.,
AsH}. Consequently, the reaction of dearsenization is pro- III
.-l -1
posed as equation (15), similarly to antimony which is a 01
member of the V-b group in the periodic table together with 3
N, P, As and Bi:
As+3I2CaO = Ca1.5As +3/40 2 , (IS) -2

As for tin, similar measurements were made and the results

are shown in figure 7. From the slope of the straight line
+ 2.I was obtained as the coefficient, x, of equation (7) on -20 -19 -18 -17 -16
detinization. Tin belongs to the IV-b group and is consid- log P0 2 (ctm)
ered to have the valence of - 4 under strongly reducing con-
Figure 8. Dependence of Sb distribution between Cu and CaO-CaF2
ditions. In fact, gaseous SnH 4 is reported to exist. Accord- melts on oxygen partial pressure
ingly, the equation of detinization can be expressed as fol- Bild 8. Abhiingigkeit der Sb-Verteilung zwischen Cu und CaO-CaF,-
lows: Schmelzen vom Sauerstoffpartialdruck

steel research 58 (1987) No 7 299

 Process metallurgy

I I Sn under reducing conditions as equations (14), (15)

~
•
CoO-CoF, ",',m
CoO sotd.
and (16).
Kohler, Engel1 and Janke 10) reported the copper distribution
f- - 1 5 0 0 oC
to be a function of the calcium activity in molten iron. They
observed that the slope of the straight line expressing the
• relationship between log Leu and logaeu is approximately

I~ •
unity. In order to identify the reaction of decopperization,
.,

3~·'·~
-<
-l 0 the relationship between copper distribution and the oxygen
Cl partial pressure with samples used for antimony measure-
.3
ments is demonstrated in figure 11. The reaction of decop-

~.
perization under strongly reducing conditions, therefore, is
suggested as equation (17) from the fact that the value of the
4 slope of the straight line in figure 11 is - 0.42:
-1
" Cu+CaO=CaCu+ 1120 2 , (17)
-19 -18 -17 -16
log POz (atm) Since a compound CaCu exists according to the phase dia-
Figure 9. Dependence of As distribution between Ag and CaO-CaF 2 gram of the Ca-Cu system 11), this may be reasonable as a
melts on oxygen partial pressure reaction for decopperization.
Bild 9. Abhangigkeit der As-Verteilung zwischen Ag und CaO-CaF2 -
Schmelzen vom Sauerstoffpartialdruck
Dependence of impurity distributions on temperature. For
equations (14), (15) and (16), the standard free enthalpy
o changes, sn: were measured by using the relation of equa-
tion (13). The temperature dependence of impurity distribu-

-. I CoO-CoF z system
1500 0 C
tion at CaO saturation with constant Pea is shown for anti-
mony, arsenic, tin and copper in figures 12 to 15, respective-

~\t•
'2 ly. The standard free enthalpy change, fl,.Ho, of Ca3Sb2 in-
(/)
~-1
Cl -r
•
cluding the heat of solution into a CaO-CaF 2 melt was ob-
tained as -795 kJ/mo!. Kubaschewski and Villa IZ) reported

.~ /.~.
.3 it as - 729 kJ/mol by calorimetric measurement.

With the same method, the sn: of CajAs, was calculated as

-2 -741 kJ/mol and fl,.Ho of Ca-Sn as -490 kJ/mo!. The
-19 -18 -17 -16 -15 value of the latter agrees fairly wel1 with -354 kJ/mol,
log POz (atm) which was obtained by Min and Sano 13) by the chemical
Figure 10. Dependence of Sn content in CaO-CaF 2 melts on oxygen equilibration, rather than - 134 kJ/mol in literature. On the
partial pressure other hand, the fl,.Ho of CaCu, + 118 kJ/mol is positive. The
Bild 10. Abhanqiqkeit des Sn-Gehalts in CaO-CaF,.Schmelzen vom
Sauerstoffpartialdruck

.
3

~I-
I
1500 0 C 1600 1550 1500 1450 1400 1360 (oC)

o
s CoO satd.
~
(J
E
a. I CoO-CoF 2 ( CoO sotd.)
~2 Pco=O.1 otm

'~-I -
Cl
.3

-19 -18 -17

-1:'
-16 15
-1 ""--~-
log P0 2 (atm) D
<J1
<,
Figure 11. Dependence of Cu content in CaO-CaF 2 melts on oxygen
partial pressure
Bird 11. Abhangigkeit des Cu-Gehalts in CaO-CaF,.Schmelzen vom
--'
01
o <,
Sauerstoffpartialdruck -2 -1'<-
obtained by linear regression, yielding - 0.52, - 0.63 and
- 0.99 for antimony, arsenic and tin, respectively. According
to equations (14), (15) and (16) the values of these slopes are
predicted as - 0.75 for antimony and arsenic and - 1.00 for -3
5.3 5.4 5.5 5.6 5.7 5.8 5.9 6.0 6.1
tin. Those experimentally obtained are in good agreement
with the prediction, especial1y for the case of tin. l!TXlO' [K-1)

Figure 12. Dependence of Sb distribution between Cu and CaO-CaF2

Thus, the experimental results with both the oxygen partial melts on temperature
pressure dependence and the CaO activity dependence can Bird 12. Abhanqiqkeit der Sb-Verteilung zwischen Cu und CaO-CaF 2 -
consistently express the reactions of removal of Sb, As and Schmelzen von der Temperatur

300 steel research 58 (1987) No.7

 Process metallurgy

1550 1500 1450 1400 (OC) 1500 1450 1400 ('C)

r,
CaO-CaF2 system
CaO satd. COO-COF2 system
Pca = 1110 atm CaD snt d,

• • Pco = 1120 atm

01---+---- '2
(/)
0
e---."",
-,
'ill.
Ul
< • ~
+-

...J

s'" • ~
Ol

• -1
.",
5.4 5.5 5.6 5.7 5.8 5.9 6.0 6.1 I I

5.5 5.6 5.7 5.8 5.9 6.0 6.1

lITxl0· (K-')
1/T x 10' rK-']
Figure 13. Dependence of As distribution between Ag and CaO-CaF 2 Figure 14. Dependence of Sn content in CaO-CaF2 melts on temper-
melts on temperature ature
Bild 13. Abhangigkeit der As-Verteilung zwischen Ag und CaO-CaF2 - Bild 14. Abhangigkeit des Sn-Gehalts in CaO-CaF,-Schmelzen von
Schmelzen von der Temperatur der Temperatur

heat of formation of CaCu, which is deduced by substract- 1550 1500 1450 1400 (OC)

ing its heat of solution into CaO-CaF2 melts from this val-
ue, would be slightly negative. This indicates that CaCu 3 ~.1
does not seem to be a very stable compound.
.~ Pca = 1110 atm

CaO satd.
Judging from figure 8 which represents the distribution de-
•
~
pendence on the oxygen partial pressure, the oxygen partial so
pressure below 10- 16 atm is low enough for antimony to [2
.e

<,
form Ca3Sb2 in CaO-CaF2 melts. On the other hand, the
oxygen partial pressure to form Ca2Sn must be less than '"
~
10 -17 atm, above which tin and CaO may produce CaSn0 2
as indicated in figure 10.
.",
Because the critical oxygen partial pressure at which the 5.5 6.0
sign of valence of arsenic changes could not be determined
experimentally, it was calculated by using thermodynamic
Figure 15. Dependence of Cu content in CaO-CaF 2 melts on temper-
data of some arsenic compounds, as follows. Combining the ature
free energies of formation for Ca3As20 3 CaO . AS20 3 and Bild 15. Abhanpiqkeit des Cu-Gehalts in CaO-CaF,-Schmelzen von
CaO, expressed by equations (18), (19) and (20), respective- der Temperatur
ly, the free energy change for the critical oxygen partial pres-
sure to be determined is given by equation (21):
3 CaO . AS20 3(s) = 3 CaO (s) + AS 2 (g) + 3/2 O 2 (g),
using available thermodynamic data of alloys 19t23), together
AGo=934000-421.0 T[J/mol)14) 15), (18) with those for phosphorus/").
Ca3As2(s) = AS 2(g) + 3 Ca(g),
In figure 16, 10gL M for Sb, As and Sn is shown as a function
AGo=681 000-118.3 T[J/molj'6), (19) of log Po, and logaca, where ac" denotes the activity ofCa in
iron.
Ca(g)+ II20 2(g)=CaO(s),
AG()= -789000+ 195.7 T[J/moW), (20) The distributions obtained by the present investigation are
one or two orders of magnitude higher than those of Kohler
3CaO· AS203(s)=Ca3As2(s)+302(g),
and Engell 17 ) in terms of ac" which is represented by a) in
AG()=2647000-889.6T[J/molj. (21) the horizontal axis, when equation (20) is used to calculate
This gives 3.11 x 10- 11 atm to the critical oxygen partial aCa- However, Kay, Subramanian and Kumar 'S) have re-
cently reported that the free energy formation of CaO ex-
pressure to determine the stability of Ca3As2 and
pressed by equation (20) is questionable and modified as
CaO· AS 20 3 at I 500°C. Obviously the oxygen partial pres-
follows:
sure used in the present investigation is in the range where
Ca3As2 is stable. AGO= -720119+ 193.92 T [J/molj. (22)

Since foregoing experiments were carried out using different
metals suitable for each impurity, the results were extrapo-
lated to lower oxygen partial pressures in order to compare
with direct measurements for distribution of each element
L M between molten iron and CaO-CaF2 melts at 1500°C,
On the contrary, if we take this modified version as indi-
cated by (b) in the axis, the situation entirely changes and
our values will be one order of magnitude smaller than those
of Kohler et al. at the same aCa- Thus, the fair comparison
with other investigations would depend on the accuracy of

steel research 58 (1987) No.7 301

Process metallurgy

@ log QCo, tigation may be eliminated from molten iron except copper
0, -1, -2, -3, -4, using the CaO-CaF2 system as a flux.
@ log QCa
0, -,1 -2 !

4 Conclusions

The following reactions were identified for removing Sb, As,

Sn and Cu under strongly reducing conditions at around
1500°C with CaO-CaF2 melts:
Sb + 312CaO = 1/2Ca3Sb2 +3/40 2 ,
Ol
As + 312 CaO = 1/2 Ca3As2+ 3/4 O 2,
.2 0 Sn + 2 CaO = Ca2Sn + O 2,
Cu+CaO=CaCu+ 1/20 2 ,

Their standard enthalpy changes for formation, including

-2 heats of solution into CaO-CaF 2 melts were obtained as
follows:
-26 -24 -22 -20 -18 Ca3As2: -741 kJ/mol,
log P02(atm) Ca3Sb z: -795 kJ/mol,
Figure 16. Estimated distributions of various impurity elements be- Ca 2Sn: -490 kJ/mol,
tween molten iron and CaO-saturated CaF2 melts at 1500°C as a func- CaCu: + 118 kJ/mol.
tion of the calcium activity or oxygen partial pressure
Bild 16. Geschiitzte Verteilungen verschiedener Verunreinigungsele- Extrapolating the dependence of impurity distributions on
mente zwischen flussiqern Eisen und CaO-gesiittigten CaF2-Schmel-
zen bei 1500°C als Funktion der Calciumaktivitiit bzw. des Sauerstoff-
the oxygen partial pressure in the present work to lower
partialdrucks Po,s, we obtained fairly good agreement with direct measur-
ements with molten iron, although there remains the need to
improve the accuracy of the thermodynamic property of
llG~ao, unexpectedly. Nevertheless, figure 16 thermody- CaO.
namically demonstrates that if Po, is lower than 10 ~ 24 atm, (A 00099; received: 5. January 1987;
the tramp elements which were studied in the present inves- in revised form: 25. March 1987)

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302 steel research 58 (1987) NO.7