American Mineralogist, Volume 86, pages 448–455, 2001

Thermochemical study of calcium zeolites—heulandite and stilbite

I. KISELEVA,1 A. NAVROTSKY,*,2 I. BELITSKY,3 AND B. FURSENKO3

1
Department of Geology, Moscow State University, Vorobyevy Gory, Moscow 119899, Russia
2
Thermochemistry Facility, Department of Chemical Engineering and Materials Science,
University of California at Davis, Davis, California 95616, U.S.A.
3
Institute of Mineralogy and Petrography, Academy of Sciences, Novosibirsk 630090, Russia

ABSTRACT
Calorimetric measurements were made on natural samples of heulandite having the composition
Ca0.86Na0.37K0.06Al2.14Si6.86O18.6.1H2O and stilbite Ca1.01Na0.12Al2.12Si6.88O18.7.27H2O both from the same
locality (Nidym River, E. Siberia, Russia). Enthalpies of formation and hydration were studied by
calorimetry in lead borate solvent at 975 K. The enthalpies of formation from oxides and elements at
298 K of heulandite are: -238.7 ± 4.9 kJ/mol, and –10656.3 ± 8.6 kJ/mol, and of stilbite are –232.0
± 8.3 kJ/mol and –11017.9 ± 10.9 kJ/mol respectively. The integral hydration enthalpies including
the enthalpies of phase transitions during heulandite and stilbite dehydration are –209.4 ± 5.9 kJ/mol
and –229.2 ± 7.4 kJ/mol at 298 K, respectively. The molar Gibbs free energies of formation for
idealized calcium-sodium and pure calcium heulandites and stilbites were calculated by combining
these new calorimetric data with thermodynamic quantities from the literature. Equilibrium tem-
peratures for the reaction: Ca-stilbite = Ca-heulandite + H2O, calculated on the basis of these ther-
modynamic data, agree with experimental phase equilibria.

INTRODUCTION parameters, and the measured densities were investigated by

Calcium-rich high-silica zeolites, heulandite (CaNa0.25
Al 2.25 Si 6.75 O 18 ·6H 2 O) and stilbite (CaNa 0.25 Al 2.25 Si 6.75 O 18 ·
7.5H2O), occur worldwide as major constituents of submarine
volcanic sediments and as alteration products of volcanic glass
in low-grade meta-volcanics and metaclastics. These zeolites
are also formed in the progressive sequence of diagenesis and
zeolite facies metamorphism (Coombs et al. 1959). For a long
time, many authors called “stilbite” the mineral we now name
heulandite, using the name “desmine” for stilbite. Heulandite
is distinctly monoclinic; stilbite too is monoclinic, but nearer
to orthorhombic symmetry than heulandite (Gottardi and Galli
1985). A serious problem encountered in investigations of these
minerals is the wide variability in their chemical compositions
with respect to Si/Al ratio and cation and water contents. Natu-
ral heulandite exhibits continuous solid solution between
h e u l a n d i t e C a ( N a , K ) 0 . 2 5 ( A l 2 . 2 5 S i 6 . 7 5 O 1 8 ) ·6 H 2 O a n d
clinoptilolite (Na,K) 1.5 (Al 1.5 Si 7.5O 18 )·5H 2O (Gottardi and
Galli 1985). The Si/Al and Ca/(Na + K) ratios of different
samples vary significantly.
The wide variability in the chemical compositions of natu-
ral stilbites, the possible correlations of chemical data with cell
* E-mail: anavrotsky@ucdavis.edu
0003-004X/01/0004–448$05.00
Passaglia et al. (1978). According to this work, natural stilbites
have the formula (Na,K)k(Ca,Mg)1+mAl2+k+2mSi7-k-2mO18⋅7H2O,
with k < 1.22 and –0.56 < m <+0.08. Natural stilbite may be
regarded as a member of a continuous stilbite-stellerite (Ca-
member) solid solution series in which Ca/(Na + K) ratios vary
significantly.
Reliable thermodynamic properties for these minerals will
assist in the interpretation of physical and chemical conditions
of their occurrences. Previously the thermodynamic properties
of natural heulandite-Ca were studied by Johnson et al. (1985,
1989, 1992) and Petrova (1997). Low-temperature heat capaci-
ties and enthalpy increments to 475 K were measured by adia-
batic and drop-calorimetry, the standard enthalpy of formation
of heulandite at 298 K was determined by HF-solution calo-
rimetry for Sr-Ba-bearing heulandite-Ca (Johnson et al. 1985,
1989). However later these authors recalculated the enthalpy
of formation and Gibbs free energy of heulandite using new
data for the enthalpy of formation of gibbsite, Al(OH)3, and
recommended new values (Johnson et al. 1992). The enthalpy
of formation of natural heulandite-Ca was also determined by
oxide melt solution calorimetry (Petrova 1997), but the value
obtained differs significantly from that of Johnson et al. (1992).
Enthalpy of formation data for the natural heulandite obtained
by acid and oxide melt calorimetry can be compared with a
value for theoretical pure calcium heulandite from experimen-
448
 KISELEVA ET AL.: THERMOCHEMISTRY OF HEULANDITE AND STILBITE 449

tal phase equilibria in the system CaAl2Si2O8-SiO2-H2O (Cho TABLE 1. Chemical analyses (wt%) and formulas of zeolites stud-
et al. 1987). However, calcium heulandite having the composi- ied (Siberia, Russia)
tion CaAl2Si7O18.6H2O like that of the synthetic material does Heulandite Stilbite
not exist in nature. The standard molar enthalpy and entropy of SiO2 59.73 58.03
Al2O3 15.80 15.16
pure calcium heulandite were estimated from the experimental CaO 7.00 7.93
brackets of the upper stability of heulandite studied by Cho et Na2O 1.64 0.53
K 2O 0.40 –
al. (1987). The large difference between the enthalpy of for- H 2O 15.85 18.39
mation values obtained for natural Ca-Na heulandite from calo- Total 100.42 100.04
rimetry and for synthetic pure calcium heulandite from phase Cations and H2O molecules per unit cell
A B A B
equilibrium data may in part be due to different compositions. Si 27.44 6.86 27.51 6.88
Thermodynamic properties of natural stilbite with compo- Al 8.56 2.14 8.47 2.12
sition Ca1.019Na0.136K0.006Al2.180Si6.820O18⋅7.33H2O were investi- Ca 3.44 0.86 4.03 1.01
Na 1.48 0.37 0.49 0.12
gated by Howell et al. (1990) using different calorimetric K 0.24 0.06 – –
methods: acid solution calorimetry to obtain the enthalpy of H2 O 24.4 6.1 29.09 7.27
formation, adiabatic calorimetry to measure the low-tempera- A = Cell contents based on 72 framework O atoms.
B = Idealized composition (18 framework O atoms) used for calculation
ture heat capacity from 5 to 350 K, and enthalpy increments to of molar thermodynamic properties.
500 K.
The present study of heulandite and stilbite thermochemis-
try is part of a series of calorimetric measurements of the ther- with previous studies of Gottardi and Galli (1985). No impu-
modynamic properties of natural calcium zeolites: laumontite, rity phases were detected by optical examination or diffrac-
leonhardite, wairakite, yugawaralite (Kiseleva et al. 1996a, tion.
1996b). Here we use drop solution calorimetry in molten High-temperature behavior of heulandite and stilbite was
2PbO·B2O3 to measure the enthalpies of formation of heulan- studied using a Derivatograph Q-1500 D (Hungary) between
dite and stilbite. The enthalpy of hydration was studied by trans- 293 K and 1273 K. DTA, TG and DTG curves of the samples
posed temperature drop calorimetry. Combining our enthalpy studied are typical for these minerals (Gottardi and Galli 1985).
data with entropy data from the literature, provides standard mo- Heulandite shows two dehydration peaks, the first broad peak
lar Gibbs free energy of formation for the idealized composition from 323 to 533 K corresponds to the loss of nearly 13 H2O
of calcium-sodium heulandite (CaNa0.25Al2.25Si6.75O18·6H2O) and molecules, the second sharp peak at 603 K corresponds to the
stilbite (CaNa0.25Al2.25Si6.75O18·7.5H2O) and pure calcium heulan- loss of 9 H2O; the remaining 2 H2O are lost gradually at higher
dite and stilbite. Using our new thermochemical data, we calcu- T up to 1173 K. The thermal behavior of stilbite is similar to
late stilbite-heulandite equilibrium. heulandite, with three main water losses, the smallest one at
ZEOLITE CHARACTERIZATION 343 K, the largest at 448 K, and a medium one at 523 K; there
is also a much smaller fourth water loss at 773 K.
Heulandite and stilbite are both from Nidym River, left tribu-
tary of the Nizhnyaya Tunguska River, Siberia, Russia. We se- CALORIMETRY
lected colorless transparent or white, prismatic crystals up to All calorimetric measurements were made using a Tian-
1-2 cm in length. Calvet high-temperature heat-flux microcalorimeter described
Chemical analyses (Table 1) were done by X-ray fluores- in detail by Navrotsky (1977, 1997). The enthalpy of forma-
cence (Carl Zeiss VRA 20R) and electron microprobe (Camebax tion was measured by dropping the samples from room tem-
Micro). Water content was determined by measuring the weight perature into molten 2PbO·B2O3 at 975 K. Most calorimetric
loss after heating to 975 K for 24 h in air. The weight fluctua- experiments were performed using pressed pellets about 3 mm
tion of the heulandite sample was about ±0.1% at room tem- in diameter, 0.5-1 mm in height, and 10-25 mg in mass. The
perature during two weeks in the calorimetry lab, indicating heat of drop solution was the sum of the heat of solution
only very small change in hydration state with small variations (∆H0sol,975) in the melt plus the heat content (H0975-H0298).
in ambient temperature and humidity. Ambient conditions were Heat of dehydration and heat contents were obtained using
controlled to be 23.5 ± 0.5 °C and 55 ± 5% relative humidity in transposed temperature drop calorimetry (sample dropped into
the calorimetry lab. Thus the hydration state of the zeolites
were well characterized and did not vary significantly during
the course of calorimetry. The compositions of heulandite and TABLE 2. Lattice parameters of heulandite and stilbite studied
stilbite are very close to the idealized compositions given by
a (Å) b (Å) c (Å) β (°)
Gottardi and Galli (1985) and Coombs et al. (1997). The ther-
modynamic properties of heulandite and stilbite calculated for Heulandite* 17.697 (9) 17.839 (7) 7.419 (2) 116°31′ (2)
Heulandite† 17.70 17.94 7.42 116°241
18 atoms O in the framework are based on ideal formulae for
Na-Ca-heulandite, CaNa0.25Al2.25Si6.75O18·6H2O, and stilbite, Stilbite* 13.591 (7) 18.243 (6) 11.27 (1) 127°421 (1)
CaNa0.25Al2.25Si6.75O18·7.5H2O, and pure calcium heulandite, Stilbite† 13.61 18.24 11.27 127°51′
CaAl2Si7O18·6H2O, and stilbite, CaAl2Si7O18·7H2O. Notes: For unit cells on the basis of 72 framework O atoms. Values in
parentheses represent confidence interval (for 95% probability).
Lattice parameters were measured using a DRON-3 pow- * This work.
der diffractometer with Cu Ka radiation. The data (Table 2) agree † Gottardi and Galli (1985).
450 KISELEVA ET AL.: THERMOCHEMISTRY OF HEULANDITE AND STILBITE
an empty platinum crucible equilibrated in the calorimeter).
The heat effect contained two contributions, the enthalpy of
dehydration at 975 K (∆H0deh,975) and the heat content of the
mineral (H0975-H0298). In addition, the solid decomposition prod-
ucts were dropped into the calorimeter, allowing measurement
of the heat content of the dehydrated heulandite.
The calorimeter was calibrated using pellets of α-Al2O3 of
weight comparable to that of the zeolite samples (Kiseleva et
al. 1996). All experiments were performed under a flowing at-
mosphere of dry air at rates of 30–40 cm3/min (Navrotsky et
al. 1994).
For calculations of the enthalpy of formation of heulandite
and stilbite containing potassium, sodium, and calcium, we need
the heat of drop solution of all constituent oxides under the
same calorimetric conditions. We used data from our earlier
work (Kiseleva et al. 1996a, 1996b). Potassium, sodium, and
calcium carbonates were used as reference materials. Chai and
Navrotsky (1993) and Navrotsky et al. (1994) showed that
CaCO3 could be used reliably for drop-solution calorimetry
under a flowing-gas atmosphere at 975 K. Because Na2CO3
and especially K2CO3 are hygroscopic, we checked the forma-
tion of hydration products using room and high-temperature
X-ray diffraction. These experimental procedures and sample
preparation were described in detail in our earlier work
(Kiseleva et al. 1996b).
CALORIMETRIC RESULTS
Five to eighteen enthalpy measurements were made for each
substance. The statistical errors reported in Table 3 (two stan-
dard deviations of the mean) are 1% or better, indicating that
variation of water content at ambient conditions was not sig-
nificant and that problem-free dissolution occurred. An uncer-
tainty of about ±0.5% was obtained for calibrations.
The enthalpy values for Al2O3, SiO2, and Na, K, and Ca
carbonates were discussed in our earlier papers (Kiseleva et al.
1996a, 1996b). The heats of drop solution of Na2O and K2O
are essential for calculation of the enthalpy of formation of
sodium and potassium-containing minerals and we discussed
these data in our earlier work (Kiseleva et al. 1996b). The heat
of drop solution of Na2O in the present work was recalculated
using our experimental data (Table 3) and the enthalpy of for-
mation at 298 K of Na2CO3 from the newer tabulation of Robie
and Hemingway (1995) to be –111.8 ± 0.8 kJ/mol. This value
of drop solution enthalpy of Na2O is preferable rather than
–113.1 ± 0.8 kJ/mol obtained previously for the same Na2CO3
drop solution calorimetric data (Kiseleva et al. 1996b), where
∆f H0 of Na2CO3 has been taken from JANAF (1986). We cal-
culated the heat of solution of Na2O from the enthalpy of drop
solution using the heat content of Na2O at 975 K from Robie
and Hemingway (1995) to be –169.5 ± 0.9 kJ/mol. This is in
good agreement with the previous data: –172.2 ± 4.3 kJ/mol
(Zygan et al. 1978), but has significantly less error.
ENTHALPY OF HYDRATION
The enthalpy of hydration of zeolites studied may be calcu-
lated from our experimental data (Table 3) using the following
thermochemical cycle:
Dehydrated zeolite (xtl, 298 K) + n H 2O(l,298 K) =
zeolite·H2O (xtl, 298K) (1)
Zeolite·H2O (xtl, 298 K) = Dehydrated Zeolite (xtl, 975 K)+n
H2O(g, 975 K) (2)
Dehydrated Zeolite (xtl, 298 K) = Dehydrated Zeolite (xtl,
975 K) (3)
n H2O(l, 298 K) = n H2O(g, 975 K) (4)
The enthalpy of hydration of the zeolite according to reac-
tion 1 is :
∆H1 = – ∆H2 + ∆H3 + ∆H4, (5)
where ∆H2 is the measured (Table 3) enthalpy of dehydration
and heat content of zeolite [(H0975 – H0298) + ∆H0deh,975], the en-
thalpy of reaction 3 (∆H3) is the measured heat content of the
dehydrated zeolite (H0975 – H0298), the enthalpy of reaction 4
(∆H4) is the heat content of H2O (Robie and Hemingway 1995).
Thus, the calculated value of integral hydration en-
thalpy at 298 K of heulandite having the composition
Ca 0.86 Na 0.37 K 0.06 Al 2.14 Si 6.86 O 18 ·6.1H 2 O is –209.4 ± 5.9 kJ/
mol and of stilbite having the composition
Ca 1.01 Na 0.12 Al 2.12 Si 6.88 O 18 ·7.27H 2 O is –229.2 ± 7.4 kJ/mol.
These values of integral hydration enthalpies also include the
enthalpies of phase transitions during heulandite and stilbite
dehydration. At about 503-520 K heulandite undergoes a tran-
sition to a new phase, heulandite B, with a significant contrac-
tion of the lattice (15% of the cell volume, 8% of the parameter
“ b”) (Gottardi and Galli 1985). Stilbite also undergoes a tran-
sition at about 420 K, changing the symmetry from monoclinic
to the orthorhombic phase B (Gruciani et al. 1997). Dehydra-
tion of the heulandite we studied (Nidym River, Siberia) was
previously investigated by thermogravimetry, thermal analy-
sis, and DSC methods (Drebushak 1990; Dementiev and
Drebushak 1992). According to these authors, the phase tran-
sition is connected with dehydration and starts when the water
content is about 10 molecules per unit cell (dehydrated from a
maximum content of 24 molecules). About 2.5 molecules of
water (or 0.63 molecules for a formula with 18 atoms O) are
lost during the phase transition. The enthalpy of this reaction
(heulandite – heulandite B + 2.5 H2O) obtained by Drebushak
(1990) is about 296 ± 37 kJ/mol at 513-523 K for a formula
with 72 atom O (or 74 ± 9 kJ/mol for a formula with 18 atom
O). We recalculated this value to 298 K and a liquid water ref-
erence state using H0518-H0298 for water (Robie and Hemingway
1995) and obtained 41.7 kJ/mol. This value of the enthalpy of
phase transition of heulandite includes 0.63 moles water loss
(for a formula with 18 atoms O) as well as the structural transi-
tion during dehydration. Thus the transition enthalpy contribu-
tion is about 25% of the integral hydration enthalpy obtained
by us (–209.4 ± 5.9 kJ/mol). If we subtract the enthalpy of
phase transition from the integral hydration enthalpy we can
estimate the average enthalpy of hydration per mole of H2O,
for water not associated with the phase transition (relative to
 KISELEVA ET AL.: THERMOCHEMISTRY OF HEULANDITE AND STILBITE 451

TABLE 3. Results of calorimetric experiments at 975 K

Mineral and formula Observed enthalpy
(H0975–H0298) (H0975 – H0298+∆H0deh975) (H0975 –H0298) + ∆H0s0l975
(J/g) (kJ/mol) (J/g) (kJ/mol) (J/g) (kJ/mol)
Heulandite 1506.2 ± 7.8(5) 1044.7 ± 5.4(5)† 1444.0 ± 6.1(8) 1001.6 ± 4.2(8)
Ca0.86Na0.37K0.06Al2.14Si6.86O18·H2O 999.5 ± 4.2‡
F.W.* = 693.61 991.6 ± 4.2§
Dehydrated heulandite 710.1 ± 3.9(6) 414.5 ± 2.3(6)
Ca0.86Na0.37K0.06Al2.14Si6.86O18
F.W. = 583.72
Stilbite 1603.0 ± 10.1(6) 1142.4 ± 7.1(6) 1533.0 ± 11.1(8) 1092.5 ± 7.9(8)
Ca1.01Na0.12Al2.12Si6.88O18·7.27H2O 1102.6 ± 8.0||
F.W. = 712.63 1080.4 ± 7.8#
Dehydrated stilbite 707.7 ± 3.2(5) 411.7 ± 1.9(5)
Ca1.01Na0.12Al2.12Si6.88O18
F.W. = 581.66
Corundum 1058.6 ± 9.6(8)** 107.9 ± 1.0(8)
Al2O3
F.W. = 101.96
Quartz 715.0 ± 5.3(12)** 43.0 ± 0.3(12) 551.3 ± 5.2(9)** 39.1 ± 0.3(9)
SiO2
F.W. = 60.08
Calcite 1931.8 ± 6.8(10)** 193.4 ± 0.7(10)
CaCO3
F.W. =100.09
Potassium carbonate 1696.0 ± 8.0(18)†† 234.4 ± 1.1(18)
K2CO3
F.W. =138.21
Sodium carbonate 2275.7 ± 7.5(10)†† 241.2 ± 0.8(10)
Na2CO3
F.W. =105.99
* F.W.= gram formula weight
† Uncertainty is two standard deviations of mean; number in parentheses is number of experiments.
‡—# Corrected for ideal stoichiometry:
‡ for calcium-sodium heulandite.
§ for pure calcium heulandite.
|| for calcium-sodium stilbite.
# for pure calcium stilbite.
** From Kiseleva et al. (1996a).
†† From Kiseleva et al. (1996b).

liquid water) at 298 K to be –30.6 kJ/mol of water. The en-
thalpy represents the average strength of the bonding interac-
tion of water with the heulandite framework. These results may
be compared to other studies of calcium zeolites hydration en-
ergetics. The enthalpies of hydration (relative to liquid water)
are generally between –20 and –35 kJ/mol of water, even for
different zeolite structures (Shim et al. 1999). Carey and Bish
(1996, 1997) determined the energetics of clinoptilolite hydra-
tion by both water equilibration and by immersion calorim-
etry. Their calorimetric data for clinoptilolite showed a linear
dependence of the partial molar enthalpy of hydration on wa-
ter content. The partial molar enthalpy of hydration of
clinoptilolite becomes less exothermic with increasing water
content. The average enthalpies of hydration for clinoptilolite-
Ca is –30.3 ± 2.0 kJ/mol of liquid water (Carey and Bish 1997).
A recent study of Ca clinoptilolite energetics (Yang et al. 2000)
gives an average enthalpy of hydration of –27.3 ± 1.2 kJ/mol
of H2O. The average enthalpy of hydration of chabazites with
different Al-contents ranges from –21 to –34 kJ/mol of liquid
water (Shim et al. 1999). The enthalpy associated with the phase
transition may be conceptually divided into two parts: that aris-
ing from water loss and that from lattice contraction. For a
formula containing 18 O atoms and losing 0.63 moles of wa-
ter, the enthalpy change at 298 K is 41.7 kJ/mol. As a crude
approximation, we assume that the enthalpy associated with
H2O loss is the average enthalpy found above, 30.6 kJ/mol, or
19.3 kJ for 0.63 moles. Then the enthalpy associated with the
lattice is 22.4 kJ (per 18 oxygen mole). This value would be
the order of 12 kJ/mol per TO2 unit, which is comparable to the
value for enthalpy of differences among various zeolite frame-
works (Petrovic et al. 1993; Navrotsky and Tian 2000).
There are no data on the enthalpy of phase transition dur-
ing dehydration of stilbite. As our study shows, the integral
hydration enthalpy at 298 K of stilbite having 7.27 H2O is
–229.2 ± 7.4 kJ/mol and the average enthalpy of hydration of
stilbite including the enthalpy of phase transition is –31.5 ±
1.0 kJ/mol of liquid water at 298 K. We can expect that with-
out the enthalpy of phase transition the enthalpy of hydration
of stilbite per mole of water is slightly less than this value and
than the enthalpy of hydration of heulandite.
ENTHALPY AND GIBBS FREE ENERGY OF FORMATION
OF HEULANDITE AND STILBITE
The enthalpies of formation of the zeolites from the oxides
at 298 K were calculated from the calorimetric data (Table 3)
using:
∆f H0ox,298 zeol. = ∑νi[ ∆H0sol,975 + (H0975 -H0298 )]ox + n(H0975 -
H )H2O – [∆H0sol,975 + (H0975 -H0298)] zeol
0
298 (6)
where νi are the stoichiometric coefficients in the formation
reaction of the minerals from the oxides, and n is the number
452 KISELEVA ET AL.: THERMOCHEMISTRY OF HEULANDITE AND STILBITE

of H2O molecules. water molecules in heulandite estimated by Johnson et al. (1985)

Thus, the enthalpies of formation from the oxides of
natural heulandite having the composition
Ca 0.86Na 0.37 K 0.06 Al 2.14Si 6.86 O 18 . 6.1H 2 O at 298 K were calcu-
lated from the enthalpies of drop solution to be –238.7 ±
4.9 kJ/mol, and of natural stilbite with composition
Ca 1.01 Na 0.12 Al 2.12 Si 6.88 O 18 ·7.27H 2O to be –232.0 ± 8.3 kJ/
mol.
The standard molar enthalpies of formation from the ele-
ments of the zeolites studied were calculated from the thermo-
dynamic values for the constituent oxides taken from Robie
and Hemingway (1995) and the molar enthalpy of formation
from the oxides obtained in this study to be ∆ f H0298 = -10656.3
± 8.6 kJ/mol for heulandite (Table 4) and ∆f H0298 = -11017.9 ±
10.9 kJ/mol for stilbite (Table 5).
For Gibbs free energy calculations we used entropy data
from the literature. The standard entropy of natural stilbite at
298 K, calorimetrically determined by Howell et al. (1990), is
805.54 ± 1.61 J/(mol-K). The compositions of stilbite studied
by us and by Howell et al. (1990) are similar. Using the en-
tropy value [805.54 ± 1.61 J/(mol-K)] and thermodynamic data
from the compilation of Robie and Hemingway (1995), we
calculated the standard entropy of formation and Gibbs free
energy of formation of stilbite from the elements at 298 K: ∆f
S0 = -2976.5 ± 1.9 J/(mol-K). and ∆f G0 = -10130.9 ± 10.9 kJ/
mol, respectively.
The standard entropy of natural Sr-Ba-bearing heulandite
at 298 K, calorimetrically determined by Johnson et al. (1985),
is 767.18 ± 0.77 J/(mol-K). The standard entropy of pure cal-
cium heulandite is estimated from the oxide sum method by
Helgeson et al. (1978) as 763.2 J/(mol-K) and from the experi-
mental P-T brackets by Cho et al. (1987) as 783.7 ± 16 J/(mol-
K). We calculated the standard entropy of the heulandite studied
from calorimetric data (Johnson et al. 1985) for natural Sr-Ba-
bearing heulandite [767.18 ± 0.77 J/(mol-K)] with corrections
for compositional differences. Small amounts of Sr, Ba, Na, K,
and other components were considered as constituent oxides.
The entropy contribution derived from the compositional dif-
ferences was estimated by addition of the entropies of oxides
taken from Robie and Hemingway (1995). The entropy contri-
bution derived from differences of water content in heulan-
dites was calculated from the entropy contributions of zeolitic
at 298 K as 50.5 J/(mol-K) per mole of H2O. The standard en-
tropy of heulandite was thus estimated to be 765.0 ± 2.2 J/
(mol-K). Using this entropy value, the enthalpy of formation
obtained in this work, and the thermodynamic data from Robie
and Hemingway (1995), we calculated the standard entropy of
formation ∆fS0 and Gibbs free energy of formation of heulan-
dite from the elements at 298 K: ∆ f S 0 =
–2753.6 ± 2.5 J/(mol-K) and ∆fG0 = –9835.7 ± 8.6 kJ/mol.
DISCUSSION
The standard enthalpy of formation of natural sample of Sr-
Ba -bearing heulandite-Ca having the composition
Ba0.065Sr0.175Ca0.585Na0.383K0.132 Al2.165Si6.835O18⋅6H2O was previ-
ously measured by acid solution calorimetry (Johnson et al.
1985, 1989). Their value –10594.6 ± 10.2 kJ/mol differs from
our data (-10656.3 ± 8.6 kJ/mol). Later Johnson et al. (1992)
revised and recalculated their data, using new values of the
enthalpy of formation of gibbsite, Al(OH)3. Their recommended
new value for the enthalpy of formation of heulandite was
–10622.5 ± 10.2 kJ/mol (Table 4). This revised value is some-
what closer to our value. Compositional differences almost
certainly account for the remaining difference. Petrova (1997)
reported the enthalpy of formation of several zeolites, including
natural heulandite having the composition Ca0.75Sr0.10Na0.41K0.04Al2.28
Fe0.01Si6.75O18⋅6.11H2O, by oxide melt solution calorimetry. Its
enthalpy of formation from the elements (18 oxygen basis) was
–10776.8 ± 19.6 kJ/mol. This value is substantially more exo-
thermic than our value for heulandite with similar composition
(–10656.3 ± 8.6 kJ/mol ) and Johnson et al.’s (1992) data
(–10622.5 ± 10.2 kJ/mol). The enthalpy of formation of
chabazite-Ca from the oxides (–617.0 ± 13.8 kJ/mol, 24 oxy-
gen basis) determined in the same work by Petrova (1997) is
also more exothermic than the values for chabazite–Ca with
similar Si/Al ratios, –300 to –350 kJ/mol (Shim et al. 1999).
These authors explain such differences by possible difficulties
in Petrova’s (1997) calorimetric experiments. The enthalpy of
formation of natural heulandite (Table 4) obtained by calori-
metric methods can be compared with a value (–10524.3 ± 9.6
kJ/mol) for synthetic pure calcium heulandite from experimental
equilibria studied by Cho et al. (1987). The large difference
between calorimetry and phase equilibrium data is probably

TABLE 4. Thermodynamic properties at 298 K of heulandite obtained in this study and from the literature
Formula F.W.* S0, [J/(mol.K)] ∆H0hyd298 (kJ/mol) ∆f H0298 (kJ/mol) ∆f G0298 (kJ/mol) References
Ca0.86Na0.37K0.06Al2.14Si6.86O18·6.1H2O 693.61 765.0 ± 2.2† –209.4 ± 5.9 –10656.3 ± 8.6 –9835.7 ± 8.6 c
Ba0.065Sr0.175Ca0.585Na0.383K0.132Al2.165Si6.835O18 ⋅6H2O 708.13 767.18 ± 0.77 –10622.5 ± 10.2 –9807.0 ± 10.2 d
Ca0.75 Sr0.10Na0.41K0.04Al2.28Fe0.01Si6.75O18 ⋅6.11H2O 699.48 –10776.8 ± 19.6 e
CaAl2Si7O18·6H2O 686.72 783.7 ± 16 –10524.3 ± 9.6 –9722.3 ± 6.3 f
Notes: References and methods are as follows: c = this work (calorimetry); d = Johnson et al. (1985, 1989, 1992) (calorimetry); e = Petrova 1997
(calorimetry); f = Cho et al. (1987) (phase equilibrium).
* F.W.= gram formula weight.
† Estimated from experimental data of Johnson et al. (1985) for corresponding stoichiometry.

TABLE 5. Thermodynamic properties at 298 K of stilbite

Mineral and formula F.W*. S0, [J/(mol.K)] ∆H0hyd298 (kJ/mol) ∆f H0298 (kJ/mol) ∆f G0298 (kJ/mol) Notes
Ca1.01Na0.12Al2.12Si6.88O18·7.27H2O 712.63 – –229.2 ± 7.4 –11017.9 ± 10.9 –10130.9 ± 10.9† a
Ca1.019Na0.136K0.006Al2.180Si6.820O18 ·7.33H2O 714.61 805.54 ± 1.61 – –11033.6 ± 6.6 –10142.0 ± 6.6 b
Note: References are as follows: a = this work; b = Howell et al. (1990). Both used calorimetric methods.
* F.W.= gram formula weight.
† Calculated with entropy from Howell et al. (1990).
 KISELEVA ET AL.: THERMOCHEMISTRY OF HEULANDITE AND STILBITE 453

due to different compositions of natural and synthetic samples.
The standard molar enthalpy of formation of stilbite obtained
in this work (–11017.9 ± 10.9 kJ/mol) may be compared with the
value (–11033.6 ± 6.6 kJ/mol) determined from HF solution calo-
rimetry by Howell et al. (1990) for natural stilbite with compo-
sition Ca1.019Na0.136K0.006Al2.180Si6.820O18⋅7.33H2O. The enthalpy of
formation from oxides calculated by us from this value and
reference data (Robie and Hemingway 1995) is –224.0 ± 9.7
kJ/mol, with our value being –232.0 ± 8.3 kJ/mol. Thus values
of the enthalpies of formation of stilbite obtained by different
calorimetric methods are in reasonable agreement for natural
stilbite of similar composition.
The wide variability in the chemical composition of natural
heulandites and stilbites with respect to Si/Al ratio, exchange-
able cations, and water content are likely sources of various
inconsistencies among the thermodynamic data. Phase equi-
librium and thermochemical studies are performed on materi-
als of different composition. The natural heulandite and stilbite
contain mainly Ca, but their Na or K contents can be rather
different. Phase equilibrium studies (Liou 1971; Cho et al. 1987)
used natural Na-Ca zeolites as starting materials and seeds for
zeolite growth. For example, the heulandite starting material
used in Cho et al.’s experiments had a composition nearly iden-
tical to our sample. However the compositions of the reaction
products were not given and the thermodynamic data are cal-
culated for pure calcium heulandite. Variations in exchange-
able cations can affect the position of the reversal brackets. It
is unreasonable to expect that the thermodynamic data obtained
by different investigators on widely different materials will be
consistent. The greatest inconsistencies may be expected be-
tween the thermodynamic data obtained by calorimetry for
natural samples and by P-T phase equilibria studies for pure
calcium samples.
The compositions of heulandite and stilbite studied in this
work are very close to the ideal stoichiometry given by Gottardi
and Galli (1978). Compositions of stilbite studied by us and by
HF-calorimetry (Howell et al. 1990) are very similar and the
enthalpy of formation agrees within experimental errors in both
these investigations. Our heulandite thermochemical data dif-
fer more significantly from acid calorimetry results obtained
by Johnson et al. (1992) on Sr-Ba bearing heulandite-Ca.
It may be useful to estimate the thermodynamic properties
of the idealized composition heulandites and stilbites for evalu-
ation of zeolite stability. According to Gottardi and Galli (1978)
natural heulandite and stilbite have the idealized formulas
CaNa0.25Al2.25Si6.75O18·6H2O and CaNa0.25Al2.25Si6.75O18·7.5H2O,
respectively. Our calorimetric experiments show that small
(<2%) compositional differences of natural minerals have a
negligible effect on the enthalpy of drop solution (in J/g). For
correction of the actual measurements to the end-member com-
positions, we calculated the enthalpies of drop solution of the
idealized compositions from the specific experimental values
and ideal formula weight. The heats of drop solution corrected
for the idealized compositions of Ca-Na and pure Ca-heulan-
dites and stilbites (Table 3). These values were used to calcu-
late the standard molar enthalpies of formation for the
stoichiometric heulandites and stilbites (Table 6).
The standard entropies for stoichiometric Ca-Na heulandite
and stilbite were estimated from adiabatic calorimetric data
(Johnson et al. 1985) for natural Sr-Ba-bearing heulandite
[767.18 ± 0.77 J/(mol-K)] and from Howell et al. (1990) for
natural stilbite [805.54 ± 1.61 J/(mol-K)] taking into account
their compositional variations (components were considered
as constituent oxides, Robie and Hemingway 1995). The stan-
dard entropy of pure calcium heulandite, CaAl2Si7O18·6 H2O,
(783.7 ± 16 J/(mol-K) was taken from phase equilibrium data
of Cho et al. (1987). The standard entropy of pure calcium stil-
bite, CaAl2Si7O18·7H2O, was estimated from calorimetric data
[803.99 ± 0.80 J/(mol-K)] for natural pure calcium stellerite
having very similar composition, Ca1.06Al2.05Si6..93O18·7.08 H2O
(Paukov et al. 1997). The entropy contribution derived from
very small compositional differences was estimated by addi-
tion of the entropies of the constituent oxides. The standard
entropy of calcium stilbite was estimated as 799 J/(mol-K).
By combining our enthalpy of formation data with the en-
tropy values we estimated the standard molar Gibbs free en-
ergy of formation for the stoichiometric zeolites (Table 6).
The new thermodynamic data for pure Ca-heulandite and
stilbite in Table 6 allowed calculations of reactions among heu-
landite and stilbite in the system CaAl2Si2O8-SiO2-H2O. Phase
equilibrium study of such low-temperature zeolite reactions is
rather difficult because these reactions have slow reaction rates.
The univariant reaction governing the upper stability of Ca-
heulandite:
heulandite = laumontite + 3quartz + 2H2O (7)
was studied by Cho et al. (1987). The equilibrium temperature
of this reaction is about 15 K higher than the metastable equi-
librium temperature of the reaction
stilbite = laumontite + 3quartz + 2H2O (8)
at 2000 bars studied by Liou (1971). The intersection of the

TABLE 6. Thermodynamic properties at 298 K of stoichiometric heulandites and stilbites estimated in this work
Mineral Formula F.W*. S0, [J/(mol.K)] ∆f H0298 (kJ/mol) ∆f G0298 (kJ/mol)
Heulandite CaNa0.25Al2.25Si6.75O18·6H2O 692.19 756† –10665.9 ± 8.5 –9850
Heulandite CaAl2Si7O18 6H2O 686.72 783.7 ± 16‡ –10614.1 ± 7.5 –9812
Stilbite CaNa0.25Al2.25Si6.75O18·7.5H2O 719.22 813.8§ –11094.2 ± 11.0 –10191.7
Stilbite Ca Al2Si7 O18·7H2O 704.74 799|| –10919.7 ± 11.0 –10052
* F.W.= gram formula weight.
† Estimated from experimental data of Johnson et al. (1985) for corresponding stoichiometry.
‡ From Cho et al. (1987).
§ Estimated from experimental data of Howell et al. (1990) for corresponding stoichiometry.
|| Estimated from experimental data of Paukov et al. (1997) for Ca-stellerite.
454 KISELEVA ET AL.: THERMOCHEMISTRY OF HEULANDITE AND STILBITE

experimentally determined curves for these reactions defines

an invariant point at which a third reaction

stilbite = heulandite + H2O (9)

meets. The invariant point is located, as suggested by Cho et

al. (1987), at approximately 600 bar and 413 K. However, re-
action 9 has not been experimentally investigated, but it was
located by combining the experimental data on the upper sta-
bility of the heulandite and stilbite reactions (Cho et al. 1987).
Thus, based on our new thermodynamic data, we calculated
the curve of the pure calcium stilbite–heulandite equilibrium:

CaAl2Si7O18 ⋅ 7H2O (stilbite) = CaAl2Si7O18 ⋅ 6H2O (heulan-

dite) + H2O (10)

Using the experimental values of drop solution enthalpy

corrected to the ideal stoichiometry of Ca-heulandite and Ca-
stilbite (Table 3) and the thermodynamic data for water taken
from Robie and Hemingway (1995) we calculated the enthalpy
of the stilbite-heulandite equlibrium using the equation:

∆H0r, 298 = [∆H0sol,975 + (H0975 -H0298)] st. –
[∆H0sol,975 + (H0975 -H0298)] he. – (H0975 – H0298) H2O (11)
The enthalpy of reaction at 298 K is ∆H0r = 19.8 ± 8.8 kJ/mol.
Using the entropy estimation of Ca-stilbite and Ca-heulan-
dite, we calculated that the standard Gibbs free energy of the
stilbite-heulandite reaction at 298 K: ∆G0r, 298 is near zero (2.9 ±
9.0 kJ/mol). This value is consistent with the Cho et al. (1987)
observations. We also estimated P-T curves of the stilbite-heu-
landite equilibrium at conditions PH2O = Ptotal and PH2O < Ptotal
(the last condition is more typical for natural environments).
For calculation of the Gibbs free energy of reaction (10) at T
and P we assume as a first approximation that ∆CP for the reac-
tion is zero and that ∆V of the solid phases is constant. These
assumptions are reasonable at the low-P and low-T conditions
of formation of these minerals. We used values of the molar
volumes of zeolites and standard entropy and enthalpy of H2O
from Robie and Hemingway (1995). Thermodynamic proper-
ties of H2O at P and T were taken from Burnham et al. (1969).
The calculated curves of stilbite-heulandite equilibrium at con-
ditions PH2O = 1 kbar and 2 kbar have positive slope (Fig. 1).
At conditions PH2O = Ptotal the calculated curve has a steep slope
and the equilibrium temperature of the reaction at 1–5 kbar is
in the range 390-410 K. This agrees reasonably with an invari-
ant point near approximately 600 bar and 413 K and supports
the topology of the stilbite-heulandite-laumontite phase dia-
gram suggested by Cho et al. (1987).
The actual compositions of heulandite and stilbite that co-
exist in natural equilibria might differ significantly from the
idealized compositions of zeolites with a fixed water contents.
As shown by Carey and Bish (1996) the zeolite equilibria are
not univariant but at least divariant because of the variable water
content of the phases. They illustrated how partial dehydration
stabilizes clinoptilolite relative to the assumption of a fixed
H2O contents. The assumption of a fixed H2O content results
in a reasonable approximation at temperatures below 423 K
FIGURE 1. P-T diagram, showing the relations among stilbite (S),
heulandite (H) and laumontite (L). The solid curve represents the stilbite
= heulandite + H2O equilibrium calculated from thermochemical data
at Ptotal = PH2O. Dashed lines are for kbar and 2 kbar (as labeled). The
light line represents the heulandite = laumontite + 3 quartz reaction
determined by Cho et al. (1987): the metastable extension is shown as
a dashed curve. The solid curve with symbols is the stilbite = laumontite
+ 3 quartz + H2O equilibrium determined by Liou (1971). The point
“I” refers to the invariant point (Cho et al. 1987).
but differs from the Na-clinoptilolite –H2O curve by 10 bars at
523 K. The zeolite stability curves are a function of the H2O
content and the thermodynamics of hydration (Carey and Bish
1996). Substitutions of Ca for Na or K in natural zeolites would
expand their stability field and displace the stilbite-heulandite
equilibrium toward higher temperatures that are consistent with
natural parageneses in low-grade metamorphic rocks.
ACKNOWLEDGMENTS
This work was supported by the U.S. Department of Energy (Grant
DEFGO3-97SF14789) (for calorimetry), the U.S. national Science Foundation
(Grant DMR-97) (for later data analysis), and the RFFI of the Academy of Sci-
ences, Russia (no. 98-05-64219). We thank W. Carey and F. Neuhoff for helpful
reviews.
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