The Thermodynamic Activity of ZnO in Silicate Melts

R.A. REYES and D. R. GASKELL

The activity of ZnO in ZnO-SiO2 and Ca0-Zn0-Si02 melts has been measured at 1560 C using a transpiration
technique with C0-C02 mixtures as the carrier gas. The activities of ZnO in dilute solu- tion in 42 wt pct Si02-
38 wt pct Ca0-20 wt pct A1203 in the range 1400 to 1550 C and in 62 wt pct Si02-23.3 wt pct Ca-14.7 wt
pct A120, at 1550 C have also been measured. The measured free energies of formation of Zn0-Si02 melts are
significantly more negative than published estimated vales and this, together with the behavior observed in
the system Ca0-Al203-Si02, indcate that ZnO is a relatively basic oxide. The results are discussed in terms of
the polymerization model of binary silicate melts and ideal silicate mixing in temary silicate melts. The
behavior of ZnO in dilute solution in Ca0-Al203-Si02 melts is discussed in terms of the possibility of the fluxing
of ZnO by iron blast furnace slags.

I. INTRODUCTION
ZINC is unusual in that, in its oxide and crystalline silicates, Zn 2+ is tetrahedrally-coordinated with oxygen.
The only oxycompounds of zinc known to contain Zn 2+ in octahedral coordination are ZnCO3 and the high-
pressure modification of ZnO. ~ In this respect zinc contravenes the normal rules of crystal chemistry, and
hence it is of interest to determine whether or not the factors which determine the peculiar crystal chemistry
of ZnO and ZneSiO4 cause any unusual properties in silicate melts containing ZnO.
Experimental studies of the activity of ZnO in silicate melts have been confined to Fe-saturated FeO-
CaOA1203- SIO2 melts containing 1 to 2 wt pct ZnO at 1200 ~ 2 and up to 10 wt pct ZnO at 1250 ~ 3 These
studies were specifically concerned with conditions in zinc smelting operations. In addition, calculations of
the activity of ZnO in lead blast furnace slags containing up to 25 wt pct
ZnO have been made from analyses of operating plant data# The only published data for binary zinc silicates
are estimations of the activities of the component oxides 5 and the free energies of formation 6 of the melts at
1600 ~ The present study is concerned with the experimental measurement of the activity of ZnO in zinc
silicate and calcium zinc silicate melts.
II. EXPERIMENTAL DETAILS
The equilibrium
ZnOw + CO = Znw + C02 [1]
was measured using a transpiration technique in which a C0-C02 gas mixture was passed over the melt
containing ZnO at 1560 C. The transpiration cell, which is shown in Figure 1, was fabricated from an alumina
crucible of 1.8 cm diameter and 6 cm height with a 0.953 cm hole drilled in the center of its base, into which
was cemented a 76 cm length of 0.953 cm O.D. x 0.635 cm I.D. alumina tube. The open end of the crucible
was provided with a cap fabricated from a 3.8 cm length of 2.54 cm O.D. x 1.91 cm I.D. alumina tube which
was closed at one end by a 2.54 cm diameter alumina disk containing a 0.08 cm diameter hole.
The melts were contained in boats, 5 cm in length and 1.2 cm deep, fabricated by cold-pressing 0.045 cm thick platinum sheet, and
the experimental runs were conducted in a horizontally-mounted molybdenum wire resistance furnace.
Reagent grade CaO, Si02, A1203, and ZnO were used and master compositions 2Zn0-Si02, 3Zn0-2Si02, Zn0-Si02, 3Ca0-2Si02, Ca0-
Si02, 2Ca0-Zn0-2Si02, 24 mole pct ZnO-33 mole pct Si02-43 mole pct CaO, 42 wt pct Si02-38 wt pct Ca0-20 wt pct A1203, and 62 wt
pct Si02-23.3 wt pct CaO-14.7 wt pct A1203 were prepared by pelletizing and sintering. Weighed mixtures of the predried reagent
oxides were isostatically pressed into rods which were fired ovemight in air at 1000 C. The master compositions were then ground to
200 mesh and stored in desiccators.
In an experimental run 8 to 9 g of the appropriate mixture of master compositions were placed in the Pt boat
and held in the experimental furnace for 30 to 35 minutes to allow formation of a homogeneous melt. The
boat was then removed from the furnace, cooled, weighed, replaced in the alumina cell, and retumed to the
furnace. When the cell had reached the furnace temperature, the furnace was sealed and a C0-C02 gas
mixture was passed through the cell. The composition of the gas was determined and controlled by calibrated
capillary flow meters, and the volume of gas flowing was measured by a wet test meter. When the desired
volume of carrier gas had been passed, the C0-C02 mixture was replaced by air and the cell was removed
from the furnace. The boat and its contents were again weighed to determine the mass of ZnO reduced from
the melt.