Thermodynamic mixing properties of sodium silicate liquids and

implications for liquidliquid immiscibility

Guy L. Hovis
a,
*
, Michael J. Toplis
b,1
, Pascal Richet
c
a
Department of Geology and Environmental Geosciences, Lafayette College, Easton, PA 18042-1708, USA
b
CRPG-CNRS, BP20, F-54501, Vandoeuvre-les-Nancy, France
c
Physique des Mineraux et des Magmas, UMR CNRS 7047, Institut de Physique du Globe, 4 place Jussieu, 75252 Paris Cedex 05, France
Received 20 December 2003; received in revised form 4 May 2004; accepted 31 August 2004
Abstract
Enthalpies of solution have been measured for synthetic glasses in the SiO
2
Na
2
O system from 0 to 50 mol% Na
2
O. The
positive enthalpies of mixing determined for the compositional range between 0 and 33.3 mol% Na
2
O, combined with entropies
for the same compositions based on ideal mixing involving Q
4
and Q
3
species, allowed us to calculate a liquidliquid solvus in
good agreement with the experimental data of Haller et al. [Haller, W., Blackburn, D.H., Simmons, J.H., 1974. Miscibility gaps
in alkalisilicate binariesdata and thermodynamic interpretation. J. Am. Ceram. Soc. 57, 120126]. This demonstrates a high
degree of compatibility among the data for entropy, enthalpy, and phase equilibrium and also confirms the requirement of
positive enthalpies of mixing for liquid immiscibility in the SiO
2
Na
2
O system.
D 2004 Elsevier B.V. All rights reserved.
Keywords: Sodium silicate liquids; Solution calorimetry; Excess enthalpy; Configurational entropy; Thermodynamic mixing; Solvus
1. Introduction
In view of their simple chemistry and relatively low
glass transition temperatures, sodium silicates have
long been used as a starting point for investigating the
relationships among the structure, chemical composi-
tion and physical properties of silicate glasses and
melts (e.g. Mysen, 1988). Liquidus phase relationships
in the system SiO
2
Na
2
O were determined as early as
1930 (Kracek, 1930) but it was almost 40 years later
that the existence of a metastable miscibility gap in the
liquid phase at SiO
2
-rich compositions was discovered
(Porai-Koshits and Averjanov, 1968; Haller et al.,
1974). This latter feature, common to many silica
metal oxide binary systems, is of interest as it implies
positive Gibbs free energies of mixing such that two
different liquid compositions have identical chemical
potentials of endmember components at the same
temperature. Therefore, although the assumption of
ideal mixing would appear to be sufficient to rationalize
0009-2541/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.chemgeo.2004.08.041
* Corresponding author.
E-mail addresses: hovisguy@lafayette.edu (G.L. Hovis)8
mtoplis@crpg.cnrs-nancy.fr (M. Toplis)8 richet@ipgp.jussieu.fr
(P. Richet).
1
Present address: DTP (UMR 5562), Observatoire Midi-
Pyrenees 14, Ave. Edouard Belin F-31400, Toulouse, France.
Chemical Geology 213 (2004) 173186
www.elsevier.com/locate/chemgeo
the liquidus phase relations in this system (e.g. Halter
and Mysen, 2004), it is clear that a complete
thermodynamic model of sodium silicate liquids must
take into account the presence of the miscibility gap.
Ideally, the assessment of such thermodynamic models
requires the possibility of separating the enthalpic and
entropic contributions to the Gibbs free energy of
mixing.
In this respect it is of note that within the
framework of the theory of structural relaxation in
viscous liquids proposed by Adam and Gibbs (1965),
configurational entropies of liquids can be estimated
from viscosity and heat capacity data (Richet, 1984).
For the system SiO
2
Na
2
O, such an analysis infers
strongly positive configurational entropies of mixing
in the silicic part of the system (Toplis, 2001). Thus, if
both entropies (S
ex
) and Gibbs free energies of mixing
( G
ex
) are positive, then enthalpies of mixing (H
ex
)
also must be positive for immiscibility to exist, owing
to the standard thermodynamic relationship G
ex
=
H
ex
TS
ex
, where T is absolute temperature.
Several studies have attempted to determine enthal-
pies of mixing from measurements of enthalpies of
solution of SiO
2
Na
2
O binary glasses either in hydro-
fluoric acid (HF) solutions near room temperature
(Hummel and Schweite, 1959; Tischer, 1969; Takaha-
shi and Yoshio, 1970) or in a molten salt near 970 K
(Rogez and Mathieu, 1985). None have concluded that
large positive heats of mixing exist for silicic compo-
sitions. However, none of the previous studies adjusted
data to calculate the isothermal variation of enthalpy as
a function of composition in the liquid state. This
essential step must be performed before attempting any
quantitative modeling of liquidliquid, or liquidsolid
phase equilibria because of the large difference in
fictive temperature of pure SiO
2
versus Na-bearing
compositions.
Anewcalorimetric investigation of sodium silicates
is reported in this paper. Because of their ready
dissolution, glasses in this system have been dissolved
in HF solution at 50 8C, where the measurements can
have high precision (Hovis et al., 1998). From these
experiments enthalpies of solution between SiO
2
and
Na
2
SiO
3
have been determined, with average standard
errors of F0.51 (2r) kJ/mol. After correction for the
fictive temperature we then assess to what extent the
results are consistent with the known miscibility gap in
this system. Furthermore, owing to the considerable
structural information available on sodium silicates,
our results may also be interpreted and discussed in
terms of the properties of the species that have been
identified in spectroscopic studies of melt structure.
2. Experimental procedures
2.1. Solution calorimetry
The hydrofluoric acid (HF) solution calorimetric
system utilized in this investigation has been described
by Hovis and Roux (1993) and Hovis et al. (1998). This
system has the potential to produce highly precise data
on small samples (Hovis et al., 1998), although in the
present study no dissolutions were performed on
samples smaller than 39 mg. Each calorimetric experi-
ment took place in 910.1 g (about 1liter) of 20.1 wt.%
HF at 50 8C under isoperibolic conditions (i.e. the
temperature of the mediumsurrounding the calorimeter
was held constant) using an internal sample container
(Waldbaum and Robie, 1970). Either one or two
experiments were performed in each liter of acid.
Multiple experiments in the same solution had no
detectable effect on the data, the result of the high
dilution of dissolved ions in the acid. Experiments were
conducted on materials ranging from lightly crushed to
more highly ground materials. The effects of grain size
are discussed below.
2.2. Sample synthesis
The SiO
2
glass was the same high-purity sample as
that investigated by Richet et al. (1982) by drop
calorimetry. To investigate samples with different
fictive temperatures, 700 mg of coarse powders were
annealed in a light Pt cup at 1387, 1441 and 1526 K for
70, 7 and 0.3 h, respectively, after having being rinsed
for a few minutes in a fresh HF solution. The samples
then were quenched rapidly by dipping the bottom of
the cup into water. The annealing temperatures were
measured with a newly prepared PtRh
6
PtRh
30
thermocouple placed in contact with the samples in
the electric muffle furnace.
Sodium silicate samples were synthesized from
reagent grade sodium carbonate and silica as described
by Richet et al. (1984). The Na
2
SiO
3
sample was
from the batch investigated in the latter study. Other
G.L. Hovis et al. / Chemical Geology 213 (2004) 173186 174
glasses were those investigated by Jarry and Richet
(2001). For these new samples, chemical homoge-
neity was ensured by stirring of the fluid melts. After
synthesis, all except the two most sodic glasses were
ground (by request of GH), then sent by express mail
delivery to Lafayette College, where upon receipt
they were placed in desiccators. All samples were
dried at 125 8C for periods ranging from hours to
days prior to the solution calorimetric dissolutions.
The glass compositions reported in this paper are the
nominal compositions.
3. Results
3.1. Calorimetric data
Calorimetric results for the original samples of this
study are recorded in Table 1 and shown as squares in
Fig. 1, where data are reported as the negatives of the
heats of solution (for which concave down curvature
indicates positive enthalpies of mixing). In general, the
initial solution calorimetric experiments, many of
which were made on finely ground glasses, produced
unsatisfactory data. Calorimetric reproducibility for
individual samples was as poor as 1%, in contrast to
numerous previous studies in which precision typically
has been 0.1% to 0.3%. Furthermore, it was difficult to
make sense of the variation of data with chemical
composition, particularly for Na-rich samples.
After these initial calorimetric experiments were
conducted, it was discovered that the most finely
ground samples, those with compositions from 25
through 40 mol% Na
2
O, had developed NaOH on
the glass surfaces from exposure to air during
shipping. The NaOH in turn reacted with airborne
CO
2
to form Na carbonate, a phenomenon that is
common in Na silicate glasses. Indeed, tests with
dilute HCl on these samples produced vigorous
bubbling. Simple drying at 125 8C would not have
eliminated contamination of the samples. The initial
calorimetric results on fine-grained sodic samples
therefore suffered from at least three factors: An
unwanted heat component from the dissolution of Na
carbonate, inaccurate sample weights for the glasses
themselves due to the added presence of Na
carbonate, and loss of heat during the calorimetric
experiments due to the escape of carbon dioxide
from the calorimeter during HF dissolution of the Na
carbonate.
To resolve these problems, a new glass sample
(0202) at 40 mol% Na
2
O was synthesized at CRPG-
CNRS in Nancy, France. A portion of the resulting
glass was transported to the US as a single 7.15 g
specimen, stored in a desiccator, then crushed (not
ground) just prior to calorimetric dissolution. The
resulting calorimetric data differed substantially from
those of the original 40 mol% Na
2
O sample (0017).
Therefore, sample 0017 was remelted (1450 8C, 10
min, air quench, producing sample 0301) and
dissolved anew. The resulting calorimetric data for
the remelted sample were indistinguishable from
those of 0202 (Fig. 2). The new calorimetric data
confirmed the aforementioned problems with the
original specimens. The results also indicated, how-
ever, that the Na-bearing glasses could be restored to
their original carbonate-free condition by simple
remelting for a short period of time.
Thus, all other glasses were remelted at 1450 8C.
To minimize high-temperature loss of Na, most
specimens were heated for just 10 min, although
the higher viscosity glasses at 15 and 20 mol% Na
2
O
needed remelting periods of 3045 min. The glasses
were quenched in air, then immediately placed in
desiccators. The initial calorimetric dissolution on
each remelted glass was conducted within hours of
the remelting. Grain sizes for these dissolutions were
either fine chips or somewhat larger pieces (several
millimeters in diameter), but in no case powders.
Calorimetric experiments on remelted samples
(Table 1) reproduced original data for samples at 15
and 20 mol% Na
2
O (see Fig. 2). This can be
attributed to minimal carbonate formation in the
original samples due to their low Na content. In
fact, even after months of storage the powders of
the latter samples did not produce a visible reaction
with dilute HCl. The new experiments also repro-
duced original data on samples at 45 and 50 mol%
Na
2
O, most likely due to the coarse grain size and
small surface area of the original calorimetric
samples. Glasses with compositions between 25
and 40 mol% Na
2
O, however, for which early
results were based on finely ground samples, gave
very different data from initial results. Moreover,
the data for glasses with higher contents of Na
2
O
display greater differences from data on original
G.L. Hovis et al. / Chemical Geology 213 (2004) 173186 175
Table 1
Calorimetric data
Sample number
and T
g
Nominal
mole
fraction
Na
2
O
Gram
formula
weight
(g/mol)
a
Calorimetric
experiment
no.
Sample
weight
(g)
Calorimeter Cp
before and after
dissolution (J/deg)
DT during
dissolution
(8C)
Heats of solution
based on Cp I
and II (kJ/mol)
DH
a
adjustment
to heats of solution
for T
r
of 1000 K
(kJ/mol)
Pure-silica glasses
S 1387/1387 K 0.000 60.0848 895 0.07438 3870.28 3870.20 0.046607 145.425 145.421 3.57
S 1387/1387 K 0.000 60.0848 898
b
0.07821 3865.68 3866.27 0.044939 146.393 146.414 3.57
S 1387/1387 K 0.000 60.0848 900
b
0.07414 3865.81 3866.31 0.046669 145.917 145.938 3.57
S 1387/1387 K 0.000 60.0848 901 0.07703 3870.79 3871.16 0.047982 144.581 144.598 3.57
S 1441/1441 K 0.000 60.0848 904 0.09947 3870.12 3870.74 0.062652 146.172 146.197 4.01
S 1441/1441 K 0.000 60.0848 905
b
0.09778 3867.82 3868.07 0.061963 146.974 146.986 4.01
S 1441/1441 K 0.000 60.0848 906 0.09927 3870.41 3870.41 0.062680 146.540 146.540 4.01
S 1441/1441 K 0.000 60.0848 907
b
0.09856 3866.10 3866.43 0.062452 146.899 146.911 4.01
S 1526/1526 K 0.000 60.0848 896
b
0.07667 3866.43 3866.52 0.048062 145.337 145.341 4.68
S 1526/1526 K 0.000 60.0848 897 0.07377 3869.57 3869.49 0.046782 147.149 147.145 4.68
S 1526/1526 K 0.000 60.0848 899 0.07590 3870.62 3869.57 0.048193 147.375 147.329 4.68
S 1526/1526 K 0.000 60.0848 902
b
0.07309 3866.77 3866.60 0.046253 146.732 146.723 4.68
Original Na-silicate glasses
0005/782 K 0.100 60.2742 930 0.11402 3871.12 3869.87 0.072571 148.210 148.160 2.57
0005/782 K 0.100 60.2742 940 0.10291 3871.46 3871.04 0.065298 147.767 147.751 2.57
0007/771 K 0.150 60.3689 929
b
0.10038 3865.81 3865.76 0.064018 148.536 148.536 2.67
0007/771 K 0.150 60.3689 933
b
0.09991 3867.44 3867.56 0.063542 148.189 148.193 2.67
0011/751 K 0.200 60.4636 925
b
0.09896 3868.07 3867.44 0.064000 150.953 150.928 2.88
0011/751 K 0.200 60.4636 931
b
0.10384 3867.86 3866.89 0.066946 150.469 150.435 2.88
0013/736 K 0.250 60.5584 927
b
0.10326 3867.10 3868.19 0.066385 150.256 150.298 3.03
0013/736 K 0.250 60.5584 939
b
0.10059 3867.69 3867.02 0.064476 149.830 149.805 3.03
0014/731 K 0.300 60.6531 926 0.09513 3870.37 3870.03 0.059909 147.542 147.529 3.03
0014/731 K 0.300 60.6531 935
b
0.10241 3866.35 3867.10 0.064546 147.504 147.533 3.03
0015/716 K 0.350 60.7478 934 0.10481 3870.53 3870.95 0.064436 144.264 144.281 3.17
0015/716 K 0.350 60.7478 937
b
0.10283 3867.61 3867.35 0.062598 142.740 142.731 3.17
0016/716 K 0.350 60.7478 928 0.10240 3872.00 3869.74 0.060849 139.491 139.408 3.17
0016/716 K 0.350 60.7478 932 0.09786 3871.25 3871.25 0.058057 139.241 139.241 3.17
0029/706 K 0.375 60.7951 951 0.25806 3871.37 3871.62 0.164544 149.772 149.780 3.28
0029/706 K 0.375 60.7951 952
b
0.25020 3868.69 3870.16 0.157155 147.437 147.492 3.28
0017/695 K 0.400 60.8425 924 0.10161 3870.07 3869.41 0.064776 149.809 149.780 3.40
0017/695 K 0.400 60.8425 936 0.10373 3870.62 3871.41 0.058293 132.079 132.104 3.40
0017/695 K 0.400 60.8425 938 0.10700 3870.58 3870.03 0.059551 130.806 130.785 3.40
0017/695 K 0.400 60.8425 946 0.19537 3870.99 3871.20 0.108411 130.430 130.451 3.40
0021/692 K 0.425 60.8898 949 0.25030 3870.33 3870.99 0.155510 146.122 146.151 3.41
0021/692 K 0.425 60.8898 950
b
0.24886 3868.02 3868.94 0.154319 145.759 145.792 3.41
0018/689 K 0.450 60.9372 942 0.21572 3872.71 3872.38 0.148649 162.294 162.278 3.41
0018/689 K 0.450 60.9372 943 0.47607 3870.87 3871.71 0.327042 161.714 161.751 3.41
0019/675K 0.500 61.0319 944
b
0.21354 3869.61 3868.99 0.150542 166.161 166.136 3.54
0019/675K 0.500 61.0319 945 0.22096 3872.75 3872.12 0.154384 164.816 164.787 3.54
CRPG-CNRS Na-silicate glass
0202/695 K 0.400 60.8425 987 0.52739 3877.40 3880.49 0.356183 159.008 159.133 3.40
0202/695 K 0.400 60.8425 988 0.47664 3870.33 3868.86 0.322320 158.920 158.862 3.40
0202/695 K 0.400 60.8425 1002 0.13254 3869.28 3867.19 0.089005 157.776 157.689 3.40
Remelted Na-silicate glasses
0317/771 K 0.150 60.3689 1033
b
0.04948 3864.97 3863.21 0.031740 149.371 149.300 2.67
0317/771 K 0.150 60.3689 1034 0.04604 3867.02 3865.01 0.029302 148.281 147.905 2.67
G.L. Hovis et al. / Chemical Geology 213 (2004) 173186 176
samples (see Fig. 2), just as one might expect from
surface contamination that is a function of Na
content. Note that data on the remelted specimens
display much-improved systematic behavior with
composition.
3.2. Comparison with previous studies
The results obtained in previous studies are
included in Fig. 3. Hummel and Schweite (1959)
performed solution calorimetric dissolutions in 39%
Table 1 (continued)
Sample number
and T
g
Nominal
mole
fraction
Na
2
O
Gram
formula
weight
(g/mol)
a
Calorimetric
experiment
no.
Sample
weight
(g)
Calorimeter Cp
before and after
dissolution (J/deg)
DT during
dissolution
(8C)
Heats of solution
based on Cp I
and II (kJ/mol)
DH
a
adjustment
to heats of solution
for T
r
of 1000 K
(kJ/mol)
Remelted Na-silicate glasses
0310/751 K 0.200 60.4636 1027 0.04550 3868.94 3864.80 0.029404 150.870 150.711 2.88
0310/751 K 0.200 60.4636 1030 0.05467 3869.78 3866.94 0.035197 150.335 150.227 2.88
0307/736 K 0.250 60.5584 1024 0.05586 3867.15 3866.73 0.036310 151.922 151.905 3.03
0307/736 K 0.250 60.5584 1035
b
0.04993 3865.56 3863.25 0.032532 152.218 152.127 3.03
0304/731 K 0.300 60.6531 1023 0.07483 3867.90 3867.35 0.048614 152.106 152.081 3.03
0304/731 K 0.300 60.6531 1025 0.07115 3869.99 3867.61 0.046451 152.937 152.845 3.03
0302/716 K 0.350 60.7478 1022 0.09283 3873.25 3866.77 0.061332 155.146 154.887 3.17
0302/716 K 0.350 60.7478 1036 0.10028 3868.15 3864.55 0.065959 154.252 154.106 3.17
0301/695 K 0.400 60.8425 1021 0.10877 3864.64 3862.96 0.072838 157.142 157.075 3.40
0312/689 K 0.450 60.9372 1028
b
0.06424 3865.18 3862.71 0.044652 163.384 163.284 3.41
0312/689 K 0.450 60.9372 1032 0.05024 3867.94 3865.10 0.034697 162.457 162.336 3.41
0309/675 K 0.500 61.0319 1026
b
0.05612 3867.73 3866.14 0.038762 162.716 162.649 3.54
0315/675 K 0.500 61.0319 1031
b
0.04973 3866.73 3863.97 0.034724 164.453 164.336 3.54
a
A mole is defined as one mole of oxides.
b
Calorimetric dissolution performed in acid of preceding experiment.
Fig. 1. Calorimetric data for the initial glass specimens, some of which were contaminated by Na carbonate. Note the disagreement among
various experiments for the specimen at 0.4 mol fraction Na
2
O. The two clusters of data at 0.3 mol fraction Na
2
O are for two different
specimens at that composition. The scatter of data for pure silica results from three specimens with three different fictive temperatures.
G.L. Hovis et al. / Chemical Geology 213 (2004) 173186 177
Fig. 2. Calorimetric data adjusted to a fictive temperature of 1000 K (values in Table 1). Final data selection is represented by larger symbols
with crosses: squares for original specimens, circles for sample 0202 synthesized at CRPG-CNRS (Nancy), and diamonds for remelted
specimens. Data at mol fractions of 0.15 and 0.20 Na
2
O for original and remelted samples are essentially superimposed. Note the agreement
between data for new sample 0202 and for remelted sample 0301 at the same composition, both of which are different from initial results.
Smaller open squares are discarded data for contaminated samples; note that differences between data for remelted samples and initial results
generally increase for samples with compositions from 0.25 to 0.40 mol fraction Na
2
O. Solid curve corresponds to the fourth-order fit to the
final selected data set (Eq. (2)); the dashed curve represents the fourth-order fit to heats of mixing (Eq. (3), Fig. 3) after addition to enthalpies of
solution along the line of ideal mixing.
Fig. 3. Comparison of present calorimetric data adjusted to a fictive temperature of 1000 K with data of previous workers, all of which are
unadjusted for fictive temperature. The data point of Takahashi and Yoshio (1970) for pure silica is hidden by data points from the present study.
Note the changes in slope of data from previous workers at Na
2
ON0.3.
G.L. Hovis et al. / Chemical Geology 213 (2004) 173186 178
HF at 26.5 8C on glasses whose thermal history is
unknown. Later, Tischer (1969) performed HF dis-
solutions with a Bunsen calorimeter in 39% HF at
26.91 8C on brapidly quenchedQ glasses using 1-g
samples enclosed in gelatin capsules introduced into
80 ml of acid. Note that the acid quantity and
concentration of these two studies are very different
from those of the present work. Enthalpies of solution
in both studies can be described by two linear
segments with a break in slope at approximately 33
mol% Na
2
O. However, in neither case were adjust-
ments made to account for the fact that glass transition
temperatures for each composition are different, an
essential consideration when calculating isothermal
enthalpies of mixing, as discussed below. Similar
measurements have also been made either in 5% HF
solutions and in pure water by Takahashi and Yoshio
(1970).
Other measurements have been reported only in a
graphical form at higher temperatures for composi-
tions from pure-silica to 50% Na
2
O by Rogez and
Mathieu (1985). Because dissolutions were made in
molten lead borate at 876 K, all samples but pure
SiO
2
were supercooled liquids. When referenced to
pure silica and 50% Na
2
O end members, their data
show approximately ideal thermodynamic behavior
at silicic compositions, but strongly negative enthal-
pies of mixing between about 20 and 50 mol%
Na
2
O.
3.3. Adjustments for fictive temperature
Application of the data presented here to thermody-
namic calculations relative to the liquid state (e.g. the
solvus, as discussed below) is not immediate because
our solution calorimetry measurements have been
made on glasses. Although effects of thermal history
of glasses on enthalpies of mixing of liquids have long
been discussed (Richet and Bottinga, 1984), this
essential step in the treatment of data warrants some
discussion.
To convert measured heats of solution to those of
liquids under isothermal conditions, one must take
into account the fact that the temperature at which
the glass becomes a liquid (the glass transition
temperature, T
g
) is different for each composition.
As previously discussed (Richet and Bottinga, 1984,
1986), relative enthalpies at a common reference
temperature in the liquid state may be calculated by
adjusting measured values of the enthalpy of glasses
with enthalpies of annealing given by:
DH
a

Z
T
r
T
g
Cp
l
Cp
g

dT 1
where DH
a
is the correction to be applied, Cp
l
and
Cp
g
are the heat capacities of the liquid and glass,
respectively, T
g
is the glass transition temperature
and T
r
is an arbitrary reference temperature.
Application of Eq. (1) is complicated by the fact
that even at fixed composition the glass transition
temperature is not uniquely defined, but rather a
function of the thermal history of the sample (with
the consequence that the enthalpy of a glass
depends on its thermal history, as illustrated by
the experiments of Tischer, 1969). In the simplest
case one may work on samples which have been
annealed at a known temperature for a sufficient
length of time that structural relaxation is complete,
then cooled sufficiently quickly that no further
structural changes occur. This is the approach which
has been employed for our SiO
2
samples. Sodium
silicate samples have not been annealed, but for
these samples we make use of the fact that, even
for liquids continuously cooled across the glass
transition range, one may define a temperature
(called the fictive temperature) at which the actual
configuration of the glass would be the equilibrium
configuration of the supercooled liquid. For a given
cooling rate, the viscosity of liquids at the fictive
temperature is constant, thus this temperature may
be simply calculated if one knows the viscosity of
the liquid as a function of temperature and the
cooling rate (e.g. see equation and discussion in
Toplis et al., 2001). However, although the cooling
rates of our liquids are not known exactly, they are
similar for all sodium-bearing samples. Thus, we
have chosen to define the fictive temperature of all
Na-bearing glasses as the temperature at which the
viscosity is 10
12
Pa s (values shown in Table 1),
using viscosities as determined by Jarry and Richet
(2001). We note too that as demonstrated by the
experiments of Sipp et al. (1997) T
g
is affected only
1020 8C by typical laboratory cooling rates,
representing a second order effect relative to that
of changing composition, and one that would affect
G.L. Hovis et al. / Chemical Geology 213 (2004) 173186 179
adjustment of the calorimetric data for T
g
by a few
tenths of a kJ/mol at most.
Eq. (1) has been applied to our calorimetric
measurements assuming a reference temperature of
1000 K. Heat capacities of each composition were
calculated from values of partial molar heat capacity
of SiO
2
and Na
2
O components given by Richet (1987)
and Richet et al. (1984) for glasses and liquids,
respectively. The resulting adjustments to DH
a
from
Eq. (1) are slightly greater for the pure-SiO
2
samples,
whose fictive temperatures are in the range 1387
1526 K, and of opposite sign to those of Na-bearing
glasses whose fictive temperatures are generally
between 700 and 800 K. The good agreement of
adjusted data for remelted samples at 15, 20, 45, and
50 mol%, and those for original samples at the same
compositions, confirms that any cooling rate depend-
ence of T
g
for Na-bearing samples is not significant
relative to the precision of the data. The enthalpies
obtained from Eq. (1) have been included in Table 1
and subtracted from the measured enthalpies of
solution to yield isothermal enthalpy values (last
column, Table 1).
Fig. 2 shows the final selected data, all adjusted
for fictive temperature, but excluding inaccurate data
from contaminated samples. Included are data for
both original and remelted specimens at 15, 20, 45,
and 50 mol% Na
2
O, data for original specimens at
0% and 10% Na
2
O, and data for remelted specimens
(only) at compositions from 25 through 40 mol%
Na
2
O.
The negatives of the resulting enthalpies of
solution (H
soln
) are expressed well by a fourth-order
polynomial:
H
soln
kJ=mol 142:2 138:9X
Na
757X
2
Na
1984X
3
Na
1632X
4
Na
2
where X
Na
is mole fraction of Na
2
O in the glass.
One sees that the enthalpies of solution vary in an
essentially linear fashion for compositions between
50 and 30 mol% Na
2
O. However, distinct curvature
is found in the compositional region between 0 and
30 mol% Na
2
O, inferring the existence of excess
enthalpies of mixing in this range, as discussed
below.
4. Thermodynamic mixing properties for
SiO
2
Na
2
O liquids
4.1. The choice of mixing units
The enthalpy of mixing (H
ex
) is defined as the
difference between the measured enthalpy of a given
composition and that of an isochemical mechanical
mixture of relevant endmember compositions. For the
data presented here derivation of enthalpies of mixing
between pure SiO
2
and Na
2
SiO
3
would result in
complex variations of excess enthalpies across the
system. In light of the general form of heats of
solution shown in Fig. 2, and because there is
particular interest in accurate characterization of
relations at silica-rich compositions, three endmember
compositions at 0, 33.3 and 50 mol% Na
2
O are here
defined. These components effectively divide the
system into two binary subsystems. These compo-
nents correspond to Q
4
, Q
3
and Q
2
species defined
from NMR spectroscopic studies (silica tetrahedra
surrounded by 0, 1 and 2 non-bridging oxygens,
respectively). This fact therefore provides a physical
basis for this choice of components, as well as
justification for considering data in the range 0 to
33 mol% Na
2
O separately from that between 33 and
50 mol% Na
2
O.
Using these three endmembers, then, excess
enthalpies clearly exist in the range 033 mol%
Na
2
O. On the other hand, the heats of solution
between 33 and 50 mol% Na
2
O are nearly linear
with respect to composition, requiring little or no
excess heat related to mixing. Indeed, the change in
slope of the heats of solution near 33 mol% Na
2
O
could be ascribed to the fact that, in the range 033
mol% Na
2
O, addition of sodium predominantly
(although not exclusively) leads to creation of Q
3
-
species, while in the range 3350 mol% Na
2
O
additions of sodium predominantly lead to the
creation of Q
2
-species.
4.2. Enthalpies of mixing between 0 and 33 mol%
Na
2
O
Heats of mixing between 0 and 33 mol% Na
2
O
have been computed by subtracting heats of solution
along a line of bideal mixingQ from the observed en-
thalpies of solution, after adjustment to a Tr of 1000 K.
G.L. Hovis et al. / Chemical Geology 213 (2004) 173186 180
This line was defined as: H
soln,ideal
(kJ/mol)=
142.20+44.23X
Na
extending from the calorimetric
data for pure silica (142.2 kJ/mol, the average of
12 measurements made on three SiO
2
samples) to
the result for the 33.3 mol% Na
2
O composition
(taken to be 156.9 kJ/mol, a value that lies along
a line connecting calorimetric data for 30 and 35
mol% Na
2
O glasses). The resulting positive values
of H
ex
are compositionally asymmetric, displaying a
maximum value of about 4 kJ/mol (Fig. 3) at 10
mol% Na
2
O. A fourth-order polynomial fitted to
H
ex
values for samples with compositions from 0
through 35 mol% Na
2
O, and constrained to have
H
ex
equal zero for the 0 and 33.3 mol% Na
2
O
endmembers, is given by:
H
ex
kJ=mol 89:334X
Na
770:4X
2
Na
2454:7X
3
Na
2842:5X
4
Na
3
Alternative bstandardQ formalisms may be used to
describe excess enthalpies or free energies, the
simplest being a compositionally symmetric regular
solution model having only one Margules (or
interaction) adjustable parameter. In light of the
pronounced asymmetry of the calorimetric data
(Fig. 2), however, this formalism is clearly inappro-
priate in the present case. Still, the compositional
axis may be altered through choice of endmembers
selected to make the data symmetric with respect to
composition (a technique employed by Haller et al.,
1974); in such a case a regular solution model may
be applied. Fig. 4 shows such fits that pair a
Na
2
SiO
3
endmember with silica endmembers having
stoichiometries of SiO
2
/0.5 and SiO
2
/0.45. The
effects of these choices will be discussed below in
connection with solvus calculations.
Whatever model is used for H
ex
, it should be noted
that the calculated enthalpies of mixing in this system
are independent of temperature, as there is no excess
heat capacity in the system for compositions between
0 and 50 mol% Na
2
O. This is evidenced by the fact
that the heat capacities (Cp) of sodium silicate liquids,
measured over temperature intervals that could reach
900 K, extrapolate linearly to the heat capacity value
of pure SiO
2
liquid (Richet et al., 1984). This also
implies that the partial molar heat capacity of 81.37 J/
mol K measured for SiO
2
liquid is valid over a
Fig. 4. Enthalpies of mixing relative to the line of ideal mixing in Fig. 2 as discussed in the text. The solid curve is a fourth-order fit to the H
ex
values as described in the text and expressed by Eq. (3). The dotted curve represents Eq. (4) using the SiO
2
/(0.50) model discussed in the text,
and the dashed curve represents Eq. (5) for the SiO
2
/(0.45) model.
G.L. Hovis et al. / Chemical Geology 213 (2004) 173186 181
temperature range much wider than that actually
investigated in the liquid state by Richet et al. (1982).
4.3. The origin of heats of mixing between 0 and 33
mol% Na
2
O
The microscopic basis for immiscibility in binary
silicates has long been the subject of debate in the
literature (e.g. Levin, 1967). One of the most
convincing arguments is an electrostatic origin due
to coulombic repulsion of cations that are poorly
shielded from each other (McGahay and Tomozawa,
1989; Hess, 1995; Hudon and Baker, 2002a,b). As
discussed by McGahay and Tomozawa (1989) this
phenomenon lends itself to predictions of the critical
temperature of miscibility gaps in a number of binary
silicate systems containing cations of variable charge
and radius. Hess (1995) suggested that such repulsion
occurs because bridging oxygens, which are necessa-
rily used to coordinate Na in the melt at low
concentrations of Na, provide insufficient electrostatic
shielding. Conversely, non-bridging oxygens would
provide much more efficient shielding, thus explain-
ing why melts richer in Na are more stable. The same
argument may be used to explain the asymmetry of
the observed heats of mixing.
5. Solvus calculations from thermodynamic data
5.1. Generalities
From a thermodynamic point of view equilibrium
liquidliquid immiscibility can occur only if the
compositional dependence of the Gibbs free energy
for the liquid is such that the free energy of a
mechanical mixture of two different liquids is lower
than that of a single liquid of identical bulk compo-
sition. Therefore, assessment of the existence of
immiscibility and calculation of the solvus requires a
mathematical expression for the excess Gibbs free
energy ( G
ex
) that in turn is associated with expressions
for the excess enthalpies and entropies of mixing.
5.2. Choices for enthalpies and entropies of mixing
Enthalpies of mixing will be considered relative to
0 and 33.3 mol% Na
2
O endmembers (Eq. (3)), using
the fourth order polynomial presented above, as well
as the SiO
2
/(0.50) and SiO
2
/(0.45) models discussed
above. In the case of the latter two fits to the data,
variation of the enthalpy of mixing may be described
by the following fourth order polynomials:
H
ex
0:5 kJ=mol 72:342X
Na
526:13X
2
Na
1408:8X
3
Na
1446:0X
4
Na
4
and
H
ex
0:45 kJ=mol 80:172X
Na
627:54X
2
Na
1807:9X
3
Na
1942:9X
4
Na
5
both of which are shown in Fig. 3.
For the entropies of mixing, the simplest model is
to assume ideal mixing of the same endmember
components as defined for the enthalpy data such that
S
mix
R4 xlnx 1 x ln 1 x 6
where R is the gas constant and x=3*(1X
SiO
2
). In this
case the entropies of mixing are positive and symmetric
between SiO
2
and Na
0.66
Si
0.66
O
1.66
, reaching a max-
imum value of 5.8 J/mol K. This choice of functional
form is somewhat arbitrary, but we may assess its
validity by comparing these theoretical values with
those estimated within the framework of the Adam and
Gibbs theory (Richet, 1984). Configurational entropies
of sodium silicate liquids at the glass transition have
been calculated in this way by Toplis (2001) using
viscosity measurements of Knoche et al. (1994). Here
those data have been complemented with values
determined from the viscosity data of Poole (1948),
which cover a wider temperature range than those of
Knoche et al. (1994) and, in particular, reach viscosities
greater than 10
12
Pa s, thus maximizing the precision of
calculated values of entropy at the glass transition.
Comparison with the values derived from the viscos-
ities of Knoche et al. (1994) shows excellent general
agreement, with the exception of data at 40 mol%
Na
2
O. The origin of this discrepancy is unknown, but
we note that this has no bearing on consideration of
values in the range 033 mol% Na
2
O of interest here.
The only other discrepancy is at 20 mol% Na
2
O, where
G.L. Hovis et al. / Chemical Geology 213 (2004) 173186 182
one measurement of Knoche et al. (1994) is at odds
with the data of Poole (1948) and Sipp and Richet
(2002). This has the consequence that at this compo-
sition the calculated value of entropy at the glass
transition changes from 4.5 to 6.2 J/mol K.
All values of entropy at the glass transition
temperature were then adjusted to a common
temperature of 1000 K, shown in Fig. 5, using the
appropriate liquid heat capacities. Once adjusted to
1000 K the excess configurational entropies (Fig. 6)
were defined as the difference between the calcu-
lated values and a linear base-line connecting data at
0 and 33.3 mol% Na
2
O. Note that, as for excess
enthalpy discussed above, the choice of reference
temperature has no effect on calculated values of
excess entropy. When these values are compared
with the form of Eq. (6) (Fig. 6), there is general
agreement with positive entropies of mixing of the
correct order of magnitude. In detail, the agreement
with the theoretical form is not perfect, but the values
of excess entropy derived from viscosity data have
large uncertainties due not only to entropies of
intermediate compositions that have uncertainties on
the order of 0.75 J/mol K, but to endmember
compositions that have uncertainties of the same
order of magnitude. An additional point of note is
that viscosity and heat capacity measurements on
liquids at 15 mol% Na
2
O have been interpreted to
suggest that liquidliquid unmixing occurs on the
(relatively long) timescale of those measurements
(Jarry and Richet, 2001). If this is also the case during
the measurements of Poole (1948) and Knoche et al.
(1994), then the configurational entropy derived from
those determinations may be compromised. In the
absence of a theoretically more justifiable functional
form to describe the entropy of mixing, it is assumed
that Eq. (6) is a reasonable model for entropies in this
system. As an aside, we note that the rapidly
quenched samples at both 10 and 15 mol% Na
2
O
used for the calorimetric measurements presented here
were clear and transparent, and that there is no reason
to suspect that our enthalpy determinations are
affected by immiscibility.
5.3. Calculation of the solvus
The SiO
2
Na
2
O liquidliquid solvus has been
calculated from the ideal entropies of mixing
Fig. 5. Calculated configurational entropies discussed in the text. Data are based on the work of Poole (1948) (partially filled squares), Richet
(1984) (squares with Xs), and Knoche et al. (1994) (open circles).
G.L. Hovis et al. / Chemical Geology 213 (2004) 173186 183
between Q
4
and Q
3
species represented by Eq. (6)
used in conjunction with each of Eqs. (3)(5) for the
enthalpies of mixing. In detail, the critical temperature
(T
c
) and critical composition (X
c
) of the solvus can be
determined for each set of G
ex
by finding the lowest
temperature for which the second derivative of G
ex
equals zero at a single composition. At temperatures
above T
c
, the second derivative of G
ex
is positive (no
immiscibility), whereas at temperatures below T
c
pairs
of coexisting compositions satisfy the condition that
Fig. 6. Configurational entropies of mixing calculated as described in the text.
Fig. 7. Calculated liquidliquid solvi for the SiO
2
Na
2
O system based on various models discussed in the text along with the directly measured
data of Haller et al. (1974).
G.L. Hovis et al. / Chemical Geology 213 (2004) 173186 184
B
2
G
ex
/B
2
x=0 (a series of coordinates which define the
spinodal). The solvus has been located at each
temperature by finding the coexisting compositions
that have identical chemical potentials of SiO
2
,
defined as the extrapolation to pure SiO
2
of the local
tangent to the G
ex
curve. Despite the similarity of the
three equations for excess enthalpy, the critical
compositions and temperatures of the solvus vary
from 10.2 mol% Na
2
O at 993 K [using H
ex
(0.5)] to
6.3 mol% Na
2
O at 1166 K [using H
ex
(4th order)].
The various calculated solvi are shown in Fig. 7. To
illustrate further the sensitivity of the solvus calcu-
lations, we have calculated the variation of the critical
temperature in response to multiplying values of H
ex
by F10% around their original values (Fig. 8). This
shows that for each of the three equations for H
ex
a
1% change in H
ex
results in a change of calculated
critical temperature on the order of 10K. In view of
this sensitivity, one can appreciate that our calculated
solvi for the SiO
2
Na
2
O system are not far from the
experimentally determined solvus of Haller et al.
(1974), which has a critical temperature of 837 8C
(1110 K) and a critical composition of 8 mol% Na
2
O
(Fig. 7). Indeed, one can generate a good match of
modeled and experimental data by using the
H
ex
(0.45) model discussed above, adjusted by just
4.2% (i.e. H
ex
multiplied by a constant value of
1.042; see Fig. 7).
6. Conclusions
Our calorimetric data on sodium silicate glasses
provide clear evidence for positive enthalpies of
mixing in the liquid state for the compositional range
between 0 and 33.3 mol% Na
2
O. When combined
with estimates of entropy based upon ideal mixing of
Q
4
and Q
3
species in the liquid we calculate the
presence of a miscibility gap in this system. Values
of the critical temperature and composition at the
crest of the solvus are shown to be very sensitive to
small variations in H
ex
, but despite this sensitivity,
the critical temperature and shape of the experimen-
tally determined solvus (Haller et al., 1974) are
perfectly consistent with our measurements. This
demonstrates a high degree of compatibility among
the data for entropy, enthalpy, and phase equilibrium
and also confirms the requirement of positive
enthalpies of mixing for liquid immiscibility in the
SiO
2
Na
2
O system.
Fig. 8. Effect of variation in the heats of mixing on critical temperature.
G.L. Hovis et al. / Chemical Geology 213 (2004) 173186 185
Acknowledgements
We thank Philippe Jarry for the synthesis of many
of the glasses utilized in this study. GLH thanks the
U.S. National Science Foundation for support of this
research via grant EAR-0000523. We extend our
thanks to Pavel Hrma (Pacific Northwest National
Laboratory) for information concerning the reaction of
Na silicate glasses with water and carbon dioxide, and
also to Emmanuelle Bourgue for related information
on K silicate glasses. Joyce Hovis kindly helped with
proof reading. [RR]
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