Transactions of the Japan Institute of Metals, Vol. 25, No. 12 (1984), pp.

879 to 884

Thermodynamic Activity of Na2O

n Na2O-SiO2-Al2O3 Melt*i

By Hideaki Itoh** and Toshio Yokokawa***

The relative partial molar quantities of Na2O in the ternary mixture were determined from elec-
tromotive force measurements of a concentration cell. Over the composition range studied aluminium
oxide functions as a weaker acid than silica. The basicity of the ternary system was discussed from the
results. The basicities of binary melts were reviewed on a new scale.
ReceivedJuly 9, 1984) (

Keywords: thermodynamic activity, sodium oxide-silicon oxide-aluminum oxide melt, basicity

of oxide melt, electromotive force, oxide network

reported. This melt is one of the most impor-

Ⅰ.Introduction tant metallurgical slags. The binary melts
studied previously were also reviewed, based
In previous studies the thermodynamic ac- on the present data on the Na2O-SiO2 binary
tivities of Na2O in various binary melts as well melt.
as in two ternary melts, Na2O-B2O3-Al2O3 and
Na2O-B2O3-SiO2, have been measured(1)-(4). Ⅱ
. Experimental
The results were interpreted in terms of the
basicity and the network structures. The basici- Concentration cells of the type
ty, defined by pO=-log αNa2o, was found to
O2(Pt)￨Na2O-SiO2(ref.)￨β-Al2O3￨
vary widely as a function of composition and
N a2O-SiO2-Al2O3￨O2(Pt)
to be a significant measure describing the ther-
modynamic state of the oxide ion. This ion is were constructed. Details of the cell and the ex-
obviously the most important component of perimental procedures have been described
the melts and plays a decisive role in controll- elsewhere(2). The electromotive force of the cell
ing various physico-chemical properties of the is related to the activity of Na2O as follows:
melts, depending upon the composition of the
(1)
counter cations. However, the thermodynamic
requirement does not permit the discussion in where αNa2o and αoNa2o are the activities of
terms of the chemical potential of a charged NaaO in the sample and reference melts, respec-

particle independent of the counter ion. The tively, and F is Faraday constant.

activity of Na2O seems the best choice, when

Na2O is the only one highly basic component . Results and Discussion
in the melts under consideration.
In the present paper the experimental results (1) Experimental results. Raw data of the
on the Na2O-SiO2-Al2O3 ternary melts are measurement are summarizd in Table 1. At
every composition, the temperature de-
* Emf Measurement of Molten Oxide Mixture IX . pendence of the emf value was found linear,
Presented at the Autumn Meeting of Japan Institute giving a constant value of ΔS(Na2O)over
of Metals, Nov., 1983. the temperature range studied. ΔG(Na2O),
** Graduate Student
, Hokkaido University. Present ad- ΔH(Na2O), and ΔS(Na2O)referred to the cor-
dress: The Japan Steel Works, Ltd., Muroran 051,
Japan.
responding quantities in the reference melt are
*** Department of Chemistry
, Faculty of Science, Hok- tabulated at 1400 K in Table 2.
kaido University, Sapporo 060, Japan. (2) The partial molar free energy of Na2O

Ⅲ
880 Hideaki Itoh and Toshio Yokokawa

Table 1 Emf value of Na2O-SiO2-Al2O3 system, referring to 40Na2O・60SiO2 melt.

 Thermodynamic Activity of Na2O in Na2O-SiO2 A12O3 Melt 881

Table 2 Relative partial molar quantities of Na2O in Na2O-SiO2-Al2O3 system at 1400 K, referring

to 40Na2O・60SiO2 melt.

referred to pure Na2O at the same tem- ΔG*(Na2O), if ΔG*(SiO2)is known. It happens

perature. The electromotive to be the case, since the present measurement

force was meas-
ured referring to 40Na2O・60SiO2 for the ex- allows evaluation of the latter by means of
perimental convenience. A more meaningful Gibbs-Duhem integration.
quantity will be derived, if it refers to pure Measurements of Na2O-SiO2 binary system
Na2O. The procedure is as follows. The free have been carried out before(6). However, con-
energy of the reaction to form Na20・2SiO2 sidering the easier cell operation in the present
from its mother oxides is known to be study, the data of the present study seem much
more reliable. The integration of the data in
Table 1 from XNa2o=0.33 to SiO2 end (actually
(2)
XNa2o=0.214 of tridymite solubility limit)
leads to
This is equivalent to the description,
log α*sio2=-0.43, referring to tridymite,
0.33ΔG*(Na20)+0.67ΔG*(SiO2)
at XNa2o=0.33 and a 1300 K, (4)
=-81 .5kJ/mol, (3)
where logα*sio2 is equal to ΔG*(SiO2)
where ΔG*(MO)is the partial molar free
(2.303RT). ÷
energy of MO referring to pure MO. When this value is substituted for eq. (3), we
Therefore, we may be able to calculate get
882 Hideaki Itoh and Toshio Yokokawa

Al2O3 on ΔG(Na2O)inNa2O-SiO2 is shown in

logα*Na2o=-9.0, referring to pure(solid)
Fig. 2, where the partial molar free energy of
Na2O, at XNa2o=0.33 and at 1300K. (5)
Na2O is plotted referring to that in 40Na2O
The relative activities of Na2O in various 60SiO2. Over the whole composition range
binary systems referring to that in Na2O・ Al2O3 regularly neutralizes the base Na2O・.

2SiO2 melt have been measured previously(1). The However, the effect is smaller than that of
data were replotted in Fig.1 with a new activity SiO2, as the lines of the ternary systems lie
scale,-pO=logα*Na2o=ΔG*(Na2O)÷(2.303RT) above the binary at common Na2O contents.
as derived above, instead of the measured elec- The partial molar entropy of Na2O is plotted in
tromotive force. As for Na2O-B2O3 the com- Fig. 3. Here, no appreciable dependence on the
position dependence was measured in more Al2O3/SiO2 ratio is observed.
detail in a recent work(2). The curve for this Most of previous investigators (11)(12)
of glass
system was drawn in Fig. 1, based on this and melt of this system agree on the notion
work. Similarly the present data of Na2O-SiO2 that all aluminium atoms coordinate 4 oxygen
were used for the pO vs. XNa2ocurve, when the atoms in the composition range of Al/Na<1,
origin was so shifted that -p0 value is equal
to 9 at XNa2o=0.33. In Fig. 1 are also shown a
value measured referring to Na2WO4 by
Neudorf and Elliott(7), another one measured
referring to the Na2CO3-CO2 system by
Yamaguchi et al.(8) and a third one measured
referring to the Na2O-C-Na-CO equilibrium
by Sano and Tsukihashi(9). The agreement
among them is satisfactory considering their in-
dependent references. In passing, the activity
of the Na2O in Na2O-P2O5 system measured by
Yamaguchi et al.(10) also reproduces our data
quite well, as is shown in Fig. 1.
(3) Na2O-SiO2-Al2O3 system. The effect of
Fig.2 Partial molar free energy of Na2O in Na2O-SiO2-

Al2O3 melts, referring to that in 40Na2O・60SiO2 at

1400K.

Fig. 1 Basicity of various binary melts containing Na20 Fig.3 Partial molar entrolsy of Na2O in Na2O-SiO2-

as functions of composition of the latter. (see text for Al2O3 melts, referring to that in 40Na2O・60SiO2 at

solid and dot-dash lines)   1400K.

 Thermodynamic Activity of Na2O in Na2O-SiO2-Al2O3 Melt 883

as was covered in the present measurement. sator but the free energy of Na2O is not much
Thus, on mixing three component oxides a decreased by that process. Thus, the activity of
part of Na2O is consumed for the reaction Na2O is rather high compared with the SiO2-
Na2O binary system, and ΔS(Na2O)behaves
Na2O+Al2O3=2[AlO2]-Na+, (6)
just in a similar way to in the SiO2-Na2O
to prepare AlO4 unit in the network. The system. In other words, Na-Al pairing as
remaining part of Na2O is consumed for Na+AlO2 in the composition range of
modifying Si-O-Si (and Si-O-Al) bond. Al/Na<1 seems essential, but its influence on
the activity of Na2O is not so strong.
Na2O+Si-O-Si=2Si-O-+2Na+. (7)
It may be interesting to quote that AlKα and

This point of view seems to be supported by Si Kα X-ray  fluorescence spectra shift in this

the thermal expansion coefficient of this melt system(13). While Si Kα of this glass referring to
measured by Rieblingt(11).
Figure 4 shows iso-ex- that in quartz decreases with the alkali content
pansivity lines based on his data. The most (the effective charge on a Si atom decreases),
important character is that the minimum, Al Kα does not much change with the basicity
denoted zero, runs along Na2O/Al2O3 equi- and stays near the value in NaAlO2 crystal.
molar line, where silica network seems not Figure 5 shows the optical basicity measured
much changed by alkali oxide but only replac- by Yanagase and Morinaga(14) and pO derived
ed by AlO4 unit. The expansivity increases from ΔG*(Na2O). The general tendency is in
sharply on the Al2O3 rich side of the line, good agreement. However, the isobasicity lines
where octahedrally coordinated Al atoms scatter wider than those of the iso optical
presumably starts to appear. basicity line with increase of Al2O3 content. In
It looks puzzling to say that alumina is a other words, the optical basicity gets a wider
weaker acid than silica while the reaction (6) range of values with increasing Al2O3 content.
proceeds quantitatively before the reaction (7) It is not clear whether the discrepancy comes
starts. These two theses will become consistent from the difference in the definition or from
with each other, when in the SiO2 network an that in the temperature of the measurements.
Al atom tends to locate itself in a tetrahedral The activity of CaO in CaO-SiO2-Al2O3
site and Na+ ion helps it as a charge compen- measured by Rein and Chipman(15) shows
much the same trend as that in the present
system. The wider liquid range in the present
system over the CaO slag seems one reason of
recent popularity of soda slags.
Finally, it is worthy of comment of
ΔS(Na2O)of the three systems. Figure 3 shows

that it decreases with the Na2O content more

steeply than the ideal entropy, -RT In XNa2o,
ammounts. However, in Na2O-B2O3-Al2O3 the
reverse was found. The latter was interpreted
in conjunction with the BO4 as well as the AlO4
network reinforcement with Na2O addition, in
contrast with the network modification in
silicate melts. Na2O-B2O3-SiO2 is quite in-
teresting.ΔS(Na2O)in Na2O-B2O3 decreases

first with SiO2, and then the dependence on

Na2O becomes reversed at an intermediate com-
position, where the network starts to be
modified. The effect of Al2O3 seems different
between Na2O-B2O3-Al2O3 and Na2O-SiO2-
Fig. 4 Iso-expansivity lines in Na2O-SiO2-Al2O3 melts(11). Al2O3. Although the network propagation with
884 Hideaki Itoh and Toshio Yokokawa

Fig. 5 Optical basicity(14) (left) compared with the present thermodynamic basicity (right).

AlO4 does occur in both systems,ΔS(Na2O)is Thermodynamics, 11 (1979), 547.

kept quite low in B2O3 solvent, and it is not so
in SiO2 solvent. This suggests that the in-
dividuality of each acid oxide persists in ter-
nary systems so strongly that the basicity alone
may not describe the system effectively.
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