ISIJ International, Vol. 52 (2012), No. 12, pp.

23032304

i. Hence, the log CS2 will be directly proportional to the

log X O2 , if the second term in Eq. (3) would not be significantly changed by silicate composition at a fixed temperature.
The sulfide capacity of the CaOSiO2MnO slag measured by Abraham et al.4) and Park et al.5,6) is shown in Fig.
1 as a function of the concentration of free oxygen ions
obtained in previous study.1) Here, the relationship between
the sulfide capacity and the content of free oxygen in the
CaOSiO2 binary slag at 1 773 and 1 923 K is also compared.7) There is a good linear relationship with a slope of
about 0.9 which is close to the ideal value of unity from Eq.
(3) between log CS2 and log X O2 as given in Eq. (4) in the
CaOSiO2 (MnO) slags, indicating that the log ( O2 fS2 )
ratio is not significantly affected by slag composition within
experimental uncertainty at temperatures from 1 773 to
1 873 K.

Note

Sulfide Capacity and Excess Free Energy of CaO

SiO2MnO Slag Derived from Structural Analysis
of Raman Spectra
Joo Hyun PARK*
School of Materials Science and Engineering, University of Ulsan,
Ulsan, 680-749 Korea.
(Received on May 7, 2012; accepted on August 8, 2012)

KEY WORDS: silicate structure; Raman spectroscopy; sulfide capacity; excess free energy of mixing; Q3/Q2 ratio;
degree of polymerization; free oxygen; bridging oxygen;
non-bridging oxygen.

log CS2 = 0.87(0.05) log X O2 1.75(0.09) (r 2 = 0.96)

.......................................... (4)

In a previous article,1) the structure of molten CaOSiO2

MnO slag was systematically analyzed using micro-Raman
spectroscopic data obtained from a melt-quenched glass
samples. Various thermophysical properties such as viscosity, density (molar volume), and electrical conductivity
(resistivity) of the CaOSiO2MnO slag was strongly
dependent of a degree of polymerization defined as Q3/Q2
ratio. Furthermore, the speciation of free oxygen, bridging
oxygen and non-bridging oxygen was also quantitatively
derived from a novel approach based on a mass balance of
oxygen and silicon atoms in discrete silicate anionic units,
viz. Qn (n = 0, 1, 2, and 3). In the present note, the thermochemical properties such as sulfide capacity and excess
free energy of mixing of oxide components which are
important properties in metallurgical slags are evaluated
using a concentration of free oxygen as well as a degree of
polymerization of silicate melts, i.e. Q3/Q2 ratio.
The capability of molten slags absorbing sulfide ions is
quantified as the sulfide capacity ( CS2 ) which is given in
Eq. (2) deduced from Eq. (1).2,3) Here, Eq. (1) indicates the
gas-slag equilibrium reaction for sulfur dissolution into the
slag phase with a reference state of sulfur and oxygen to
gaseous state.

(Temperature: 1 773 to 1 873 K)

However, the sulfide capacity of the CaOSiO2 binary
slag at 1 923 K is above Eq. (4) at a given O2 content, which
probably results from the effect of temperature not only on
the value of K(1) but also on the O2 fS2 ratio. Consequently,
it is concluded that the sulfur dissolution behavior into the
silicate melts at high temperatures can be understood more
quantitatively by considering not only the effect of concentration (or activity) of free oxygen ions, viz. basicity but also
the effect of structural modification behaviour on the stability of oxygen and sulfide ions in silicate melts.5,6,8) In previous works of the present author,1,5,6,8) it was found that, in
the relatively acidic region of which silica content is greater
than about 30(5) mass%, the large amounts of Ca2+ ions are
consumed to modify the silica networks due to a large ionic
potential, resulting in a stabilization of S2 ions not by Ca2+
but mainly by Mn2+ ions. However, in the relatively basic
region of which silica content is lower than about 30(5)
mass%, Ca2+ and Mn2+ ions competitively react with S2
ions because Ca2+ ions are relatively free from a network
modifying role, resulting in a stabilization of S2 ions mainly

1
1
S2 ( g ) + (O2 ) = (S2 ) + O2 ( g ) ............... (1)
2
2
CS2 =

K (1) aO2
fS2

= (mass%S)

log CS2 = log X O2 + log

O2
fS2

pO2
pS2

............. (2)

+ log K (1) ........... (3)

where K(1), aO2 , X O2 , O2 , fS2 and pi indicate, respectively,

the equilibrium constant of Eq. (1), the activity, mole fraction
and activity coefficient of free oxygen ions as a reference to
Raoultian standard state, the Henrian activity coefficient of
sulfide ions, and the partial pressure of gaseous component
Fig. 1.

* Corresponding author: E-mail: basicity@mail.ulsan.ac.kr

DOI: http://dx.doi.org/10.2355/isijinternational.52.2303

2303

Relationship between the sulfide capacity and the concentration of free oxygen in the CaOMnOSiO2 slag at high
temperatures.

2012 ISIJ

ISIJ International, Vol. 52 (2012), No. 12

by Ca2+ ions due to an interaction between Ca2+ and S2 ionic

pair which is stronger than Mn2+ and S2 pair. The more details
on this discussion are available in Refs. 1), 5), 6) and 8).
The partial molar excess free energy is of importance in
view of phase equilibria, mixing phenomena, and any other
thermochemical properties of molten silicates and it is
defined as follows.912)

indicates that the stability of CaO and MnO increases as the

ln (Q3/Q2) increases and the stability of CaO is larger than that
of MnO at a given degree of polymerization. Consequently,
the relative stability of oxide components in multicomponent
silicate melts is strongly dependent on a degree of polymerization.
In summary, the thermochemical properties such as sulfide capacity and excess free energy of mixing for each slag
component in the CaOSiO2MnO slag was estimated as a
linear function of concentration of free oxygen and a degree
of polymerization, i.e. Q3/Q2 ratio, respectively, derived
from a quantitative Raman spectroscopic analysis. This
methodology is believed to be widely extended to various
slag systems and compositions in ferrous and nonferrous
metallurgical communities.

GiEx = RT ln i ............................ (5)

In the present study, the activity coefficients of oxide components CaO, MnO and SiO2 was calculated using a commercial thermochemical computing software, FactSageTM6.2
with FToxid database, which has been successfully applied
in computation of thermochemical properties of multicomponent oxide melts.5,6,8,1323) Especially, the thermodynamic
database for the CaOSiO2MnO system was fully optimized by Kang et al.24) Also, from the previous works by
the present author,5,6,8,18,19) the activity calculation in the
present CaOSiO2MnO system was in good consistency
with other thermochemical properties such as carbide capacity, sulfide capacity, etc.
In order to elucidate the effect of structural modification
on thermochemical properties of silicate melts, the relationship between the partial molar excess free energy of mixing
of CaO, MnO and SiO2 and a degree of polymerization, ln
(Q3/Q2) in the CaOSiO2MnO slag at 1 873 K is shown in
Fig. 2. The excess free energy of mixing for each oxide
3
2
should be deleted linearly changes as a function of ln (Q /Q ),
Ex
Ex
Ex
i.e. the GCaO and GMnO linearly decreases and GSiO2 linearly increases by increasing the value of ln (Q3/Q2). This

Fig. 2.

Acknowledgment
The author expresses his sincere appreciation to Prof. Em.
K. C. Mills, Imperial College London, UK and Prof. Y.
Sasaki, Graduate Institute of Ferrous Technology, POSTECH,
Korea for their helpful discussion on this topic.
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Relationship between the partial molar excess free energy

of mixing of CaO, MnO and SiO2, and the Q3/Q2 ratio in the
CaOMnOSiO2 slag at 1 873 K.

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