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1.
Enthalpies of solution in 2PbO · B2O3 at 981 K have been measured for glasses in the system albite-orthoclase-silica and along the join Na1.6Al1.6Si2.4O8-K1.6Al1.6Si2.4O8. The join KAlSi3O8-Si4O8 shows zero heat of mixing similar to that found previously for NaAlSi3O8-Si4O8 glasses. Albite-orthoclase glasses show negative heats of mixing symmetric about Ab50Or50 (Wn = ? 2.4 ± 0.8 kcal). Negative heats of (Na, K) mixing are also found at Ternary excess enthalpies of mixing in the glassy system Ab-Or-4Q are positive but rarely exceed 1 kcal mol?1.Using earlier studies of the thermodynamic properties of the crystals, the present calorimetric data and the “two-lattice” entropy model, the albite-orthoclase phase diagram is calculated in good agreement with experimental data. Attempts to calculate albite-silica and orthoclase-silica phase diagrams reveal complexities probably related to significant (but unknown) mutual solid solubility between cristobalite and alkali feldspar and to the very small heat and entropy of fusion of SiO2. 相似文献
2.
Richard L. Hervig Derry Scott Alexandra Navrotsky 《Geochimica et cosmochimica acta》1985,49(7):1497-1501
Enthalpies of solution in 2PbO · B2O3 at 974 K have been measured for glasses along the joins Ca2Si2O6 (Wo)-Mg2Si2O6 (En) and Mg2Si2O6-MgAl2SiO6 (MgTs). Heats of mixing are symmetric and negative for Wo-En with WH = ?31.0 ± 3.6 kJ mol?. Negative heats of mixing were also found for the En-MgTs glasses (WH = ?33.4 ± 3.7 kJ mol?).Enthalpies of vitrification of pyroxenes and pyroxenoids generally increase with decreasing alumina content and with decreasing basicity of the divalent cation.Heats of mixing along several glassy joins show systematic trends. When only non-tetrahedral cations mix (outside the aluminosilicate framework), small exothermic heats of mixing are seen. When both nontetrahedral and framework cations mix (on separate sublattices, presumably), the enthalpies of mixing are substantially more negative. Maximum enthalpy stabilization near compositions with Al/Si ≈ 1 is suggested. 相似文献
3.
Five hundred eighty-five viscosity measurements on 40 melt compositions from the ternary system CaMgSi2O6 (Di)-CaAl2Si2O8 (An)-NaAlSi3O8 (Ab) have been compiled to create an experimental database spanning a wide range of temperatures (660-2175°C). The melts within this ternary system show near-Arrhenian to strongly non-Arrhenian properties, and in this regard are comparable to natural melts. The database is used to produce a chemical model for the compositional and temperature dependence of melt viscosity in the Di-An-Ab system. We use the Vogel-Fulcher-Tammann equation (VFT: log η = A + B/(T − C)) to account for the temperature dependence of melt viscosity. We also assume that all silicate melts converge to a common viscosity at high temperature. Thus, A is independent of composition, and all compositional dependence resides in the parameters B and C. The best estimate for A is −5.06, which implies a high-temperature limit to viscosity of 10-5.06 Pa s. The compositional dependence of B and C is expressed by 12 coefficients (bi=1,2.6, cj=1,2..6) representing linear (e.g., bi=1:3) and higher order, nonlinear (e.g., bi=4:6) contributions. Our results suggest a near-linear compositional dependence for B (<10% nonlinear) and C (<7% nonlinear). We use the model to predict model VFT functions and to demonstrate the systematic variations in viscosity due to changes in melt composition. Despite the near linear compositional dependence of B and C, the model reproduces the pronounced nonlinearities shown by the original data, including the crossing of VFT functions for different melt compositions. We also calculate values of Tg for melts across the Di-An-Ab ternary system and show that intermediate melt compositions have Tg values that are depressed by up to 100°C relative to the end-members Di-An-Ab. Our non-Arrhenian viscosity model accurately reproduces the original database, allows for continuous variations in rheological properties, and has a demonstrated capacity for extrapolation beyond the original data. 相似文献
4.
R.C. Newton T.V. Charlu P.A.M. Anderson O.J. Kleppa 《Geochimica et cosmochimica acta》1979,43(1):55-60
Enthalpies of solution of synthetic clinopyroxenes on the join CaMgSi2O6-Mg2Si2O6 have been measured in a melt of composition Pb2B2O5 at 970 K. Most of the measurements were made on samples crystallized at 1600°–1700°C and 30 kbar pressure, which covered the range 0–78 mole per cent Mg2Si2O6, and whose X-ray patterns could be satisfactorily indexed on the diopside (C2/c) structure. For the reaction: Mg2Si2O6→-Mg2Si2O6 enstatite diopside the present data, in conjunction with previous and new measurements on Mg2Si2O6 enstatite, determine ΔH° ~ 2 kcal and WH (regular solution parameter) ~ 7 kcal. These values are in good agreement with those deduced by Saxena and Nehru (1975) from a study of high temperature, high pressure phase equilibrium data under the assumption that the excess entropy of mixing is small, but, in light of the recent theoretical treatment of Navrotsky and Loucks (1977, Phys. Chem. Min.1, 109–127), the meanings of these parameters may be ambiguous.Heat of solution measurements on Ca-rich binary diopsides made by annealing glasses at 1358°C in air gave slighter higher values than the higher temperature high pressure samples. This may be evidence for some (Ca, Mg) disorder of the sort postulated by Navrotsky and Loucks (1977, Phys. Chem. Min.1, 109–127), although no differences in heat of solution dependent on synthesis temperature in the range 1350°–1700°C could be found in stoichiometric CaMgSi2O6. 相似文献
5.
Yannick Linard 《Geochimica et cosmochimica acta》2008,72(2):590-601
The enthalpies of solution of La2O3, TiO2, HfO2, NiO and CuO were measured in sodium silicate melts at high temperature. When the heat of fusion was available, we derived the corresponding liquid-liquid enthalpies of mixing. These data, combined with previously published work, provide insight into the speciation reactions in sodium silicate melts. The heat of solution of La2O3 in these silicate solvents is strongly exothermic and varies little with La2O3 concentration. The variation of heat of solution with composition of the liquid reflects the ability of La(III) to perturb the transient silicate framework and compete with other cations for oxygen. The enthalpy of solution of TiO2 is temperature-dependent and indicates that the formation of Na-O-Si species is favored over Na-O-Ti at low temperature. The speciation reactions can be interpreted in terms of recent spectroscopic studies of titanium-bearing melts which identify a dual role of Ti4+ as both a network-former end network-modifier. The heats of solution of oxides of transition elements (Ni and Cu) are endothermic, concentration-dependent and reach a maximum with concentration. These indicate a charge balanced substitution which diminishes the network modifying role of Na+ by addition of Ni2+ or Cu2+. The transition metal is believed to be in tetrahedral coordination, charge balanced by the sodium cation in the melts. 相似文献
6.
The short range distribution of interatomic distances in three feldspar glasses has been determined by X-ray radial distribution analysis. The resulting radial distribution functions (RDF's) are interpreted by comparison with RDF's calculated for various quasi-crystalline models of the glass structure.The experimental RDF's of the alkali feldspar glasses were found to be inconsistent with the four-membered rings of tetrahedra associated with crystalline feldspars; the structures of these glasses are probably based on interconnected six-membered rings of the type found in tridymite, nepheline, or kalsilite. In contrast, the RDF of calcic feldspar glass is consistent with a four-membered ring structure of the type found in crystalline anorthite. T-O bond lengths (T = Si,Al) increase from 1.60 Å in SiO2 glass [J. H. Konnert and J. Karle (1973) Acta Cryst.A29, 702–710] to 1.63 Å in the alkali feldspar glasses to 1.66 Å in the calcic feldspar glass due to the substitution of Al for Si in the tetrahedra] sites. The T-O-T bond angles inferred from the RDF peak positions are 151° in SiO2 glass (see reference above), 146° in the alkali feldspar glasses, and 143° in the calcic feldspar glass. Detail in the RDF at distances greater than 5 Å suggests that the alkali feldspar glasses have a higher degree of long range order than the calcic feldspar glasses.Assuming that the structural details of our feldspar glasses are similar to those of the melts, the observed structural differences between the alkali feldspar and calcic feldspar glasses helps explain the differences in crystallization kinetics of anhydrous feldspar composition melts. Structural interpretations of some thermodynamic and rheologic phenomena associated with feldspar melts are also presented based on these results. 相似文献
7.
The enthalpies of solution of several synthetic garnets on the join Mg3Al2Si3O12-Ca3Al2Si3O12 (pyrope-grossular) and of several synthetic clinopyroxenes on the join CaMgSi2O6-CaAl2SiO6 (diopside-Ca-Tschermak's molecule) were measured in a melt of composition 2PbO · B2O3 at 970 K. The determinations were made with sufficient precision so that thermochemical characterizations of the solid solutions could be achieved.The pyrope-grossular solutions show positive enthalpies of mixing. The non-ideality in the range 0–30 mole % grossular is relatively the largest and is in good agreement with the predictions of Ganguly and Kennedy (1974) based largely on cation partitioning of natural high grade metamorphic garnets with biotite, and with the deductions of Hensenet al. (1975) based on measurement of the compositions of synthetic pyrope-rich garnets equilibrated with anorthite, Al2SiO5 and quartz. However, the garnets show smaller excess enthalpies at higher grossular contents. This would lead to an asymmetric solvus with a critical temperature lower than predicted by the symmetrical regular solution model of Ganguly and Kennedy (1974). The composition-dependent non-ideality can be understood by simple ionic size considerations in solid substitution and is analogous to the situations for the calcite-dolomite and enstatite-diopside solvi.The heats of solution of pyropes crystallized in the range 1000–1500°C were all the same, within the precision of measurement, and thus we have found no evidence for temperature-dependent cation disordering as a possible explanation of the high entropy of pyrope, as suggested by Charluet al. (1975). Positional disorder of dodecahedral Mg is a more probable reason.The diopside-CaTs join is also non-ideal, with the larger positive enthalpy deviations near the diopside end. The calorimetric data in the magnesian range are consistemt with the model for completely disordered tetrahedral Si and Al which results from the free energy derivations of wood (1975) based on syntheses of diopside-rich aluminous pyroxenes in the presence of anorthite and quartz. At higher Al concentrations the calorimetric data seem more consistent with the ‘local charge-balance’ model of Wood (1975).No evidence for temperature-dependent disorder was found for either the diopside or CaTs end-members. 相似文献
8.
Alexandra Navrotsky Hans D Zimmermann Richard L Hervig 《Geochimica et cosmochimica acta》1983,47(8):1535-1538
High temperature solution calorimetry of glasses in the system CaMgSi2O6 (Di)-CaAl2SiO6 (CaTs) show them to have negative enthalpies of mixing with a regular enthalpy parameter, WH, of -11.4 ± 0.7 kcal. Negative heats of mixing between alumina-rich and alumina-poor glasses seem to be a general phenomenon in aluminosilicates and are not confined only to glassy systems containing anorthite as a component. The thermodynamic behavior of glasses in the system SiO2-Ca0.5;AlO2-CaMgO2 appears to vary in a smooth fashion, with small positive heats of mixing near SiO2 and substantial negative heats of mixing for other compositions. The exothermic behavior with increasing may be related to local charge balance of M2+ and Al3+. The negative heats of mixing in MgCaSi2O6-CaAl2SiO6, MgCaSi2O6-CaAl2Si2O8 and NaAlSi3O8-CaAl2Si2O8 glasses are in contrast to the positive heats of mixing found in MgCaSi2O6-CaAl2SiO6 (pyroxene) and NaAlSi3O8-CaAl2Si2O8 (high plagioclase) crystalline solid solutions. 相似文献
9.
The enthalpies of solution of petrologically important phases in the system MgO-Al2O3-SiO 2 were measured in a melt of composition 2PbO · B2O3 at 970 ± 2K. The substances investigated included synthetic and natural (meteoritic) enstatite (MgSiO3), synthetic aluminous enstatite (MgSiO30.9Al2O30.1), synthetic and natural cordierite (Mg2Al4Si5O18), synthetic and natural sapphirine (approx. 7MgO·9Al2O3 · 3SiO2), synthetic spinel (MgAl2O4), natural sillimanite (Al2SiO5), synthetic forsterite (Mg2SiO4), synthetic pyrope (Mg3Al2Si3O12), natural quartz (SiO2), synthetic periclase (MgO) and corundum (Al2O3). Improvement in standardization of the calorimeter solvent made possible greater precision in this study than obtainable in former work in this laboratory on some of the same substances.The enthalpies of formation of enstatite, synthetic cordierite, forsterite and spinel are in reasonable agreement with values previously determined by solution calorimetry. The enthalpy of formation of enstatite is about 0.7 kcal less negative than the value for clinoenstatite resulting from the HF calorimetry of Torgesen and Sahama (J. Amer. Chem. Soc.70. 2156–2160, 1948), and is in accord with predictions based on analysis of published pyroxene equilibrium work. Aluminous enstatite with 10 wt.% Al2O3 shows an enthalpy of solution markedly lower than pure MgSiO3: the measurements lead to an estimate of the enthalpy of formation at 970 K for MgAl2SiO6 (Mg-Tschermak) orthopyroxene of + 9.4 ± 1.5 kcal/mole from MgSiO3 and Al2O3.Comparison of the enthalpies of formation of synthetic cordierite and anhydrous natural low-iron cordierite shows that they are energetically quite similar and that the synthetic cordierite is not likely to have large amounts of (Al, Si) tetrahedral disorder. Comparison of the enthalpies of formation of synthetic sapphirine and natural low-iron sapphirine shows, on the other hand, that the former is not a good stability model for the latter. The lower enthalpy of formation of the high-temperature synthetic sample is undoubtedly a consequence of cation disordering.The enthalpy of formation of natural sillimanite is considerably less negative than given by the tables of Robie andWaldbaum (U.S. Geol. Surv. Bull.1259 1968).The measured enthalpy of formation of synthetic pyrope is consistent with that deduced from published equilibrium diagrams in conjunction with the present measured enthalpy of formation of aluminous enstatite. Calculation of the entropy of synthetic pyrope from the present data yields surprisingly high values and suggests that synthetic pyrope is not a good stability model for natural pyrope-rich garnets. Hence, considerable doubt exists about the direct quantitative application of experimental diagrams involving pyropic garnet to discussions of the garnet stability field in the Earth's outer regions. 相似文献
10.
Robert G. Berman 《Geochimica et cosmochimica acta》1984,48(4):661-678
A thermodynamic model is proposed for calculation of liquidus relations in multicomponent systems of geologic interest. In this formulation of mineral-melt equilibria, reactions are written in terms of the liquid oxide components, and balanced on the stoichiometry of liquidus phases. In order to account for non-ideality in the liquid, a ‘Margules solution’ is derived in a generalized form which can be extended to systems of any number of components and for polynomials of any degree. Equations are presented for calculation of both the excess Gibbs free energy of a solution and the component activity coefficients.Application to the system CaO-Al2O3-SiO2 at one atmosphere pressure is achieved using linear programming. Thermodynamic properties of liquidus minerals and the melt are determined which are consistent with adopted error brackets for available calorimetric and phase equilibrium data. Constraints are derived from liquidus relations, the CaO-SiO2 binary liquid immiscibility gap, solid-solid reactions, and measured standard state entropies, enthalpies, and volumes of minerals in this system.Binary and ternary liquidus diagrams are recalculated by computer programs which trace cotectic boundaries and isothermal sections while checking each point on a curve for metastability. The maximum differences between calculated and experimentally determined invariant points involving stoichiometric minerals are 17°C and 1.5 oxide weight per cent. Because no solid solution models have been incorporated, deviations are larger for invariant points which involve non-stoichiometric minerals.Calculated heats of fusion, silica activities in the melt, and heats of mixing of liquids compare favorably with experimental data, and suggest that this model can be used to supplement the limited amount of available data on melt properties. 相似文献
11.
The apparent differences between heats of mixing determined by solution calorimetric measurements on quenched samples in the system NaAlSi3O8-KAlSi3O8 and heats of mixing determined at high temperatures by Knudsen cell mass spectrometry are caused by thermal effects related to the glass transition. When these effects are allowed for, the calorimetric data and Knudsen cell measurements are in good agreement. 相似文献
12.
A drop calorimetric study, between 900 and 1800 K, of amorphous SiO2, NaAlSi3O8, NaAlSi2O6, NaAlSiO4 and KAlSi3O8 shows the increase in heat capacity which results from glass transitions. For these glasses, the fictive temperature has a negligible effect on the heat capacity above room temperature, but it has an important influence on the enthalpy of formation as obtained from solution calorimetry. From these results and published Cp and enthalpy of solution data, several properties have been calculated: the enthalpies of fusion of high albite, nepheline, Jadeite and high sanidine, the thermodynamic functions of amorphous NaAlSi3O8 and KAlSi3O8 between 0 and 2000 K, and some mixing properties of liquids along the join SiO2-NaAlSi3O8. The latter data suggest that these liquids behave more closely as athermal solutions than as regular solutions. 相似文献
13.
Guy L. Hovis 《Geochimica et cosmochimica acta》1984,48(3):523-525
Glasses in the systems NaAlSi3O8-KAlSi3O8 and NaAlSi3O8-Si4O8 have been studied by means of hydrofluoric acid solution calorimetry at 50°C. Results indicate small negative enthalpies of mixing in the former system and small positive departures from ideality in the latter. 相似文献
14.
J. F. Stebbins D. F. Weill I. S. E. Carmichael L. K. Moret 《Contributions to Mineralogy and Petrology》1982,80(3):276-284
Enthalpies and heat capacities of glasses and of stable liquids in the system NaAlSi3O8-CaAl2Si2O8 have been measured by drop and differential scanning calorimetry. Within experimental error, values of C
p and of H
T
300 of three intermediate compositions fall on straight line interpolations between the end members for both liquids and glasses, indicating that excesses in true and in mean heat capacities [(H
T
–H
300)/(T–300)] are small or absent. A value for the heat capacity of the An100 liquid component can therefore be derived, and is probably a better estimate than that based on measurements on the pure substance alone. On the assumption of zero excess heat capacity in this system, heats of mixing in the stable liquids are equal to those measured in the glasses by solution calorimetry, and can be as negative as -2 kcal mol–1.Heat capacities of solids and glasses in the Ab-An system are similar and do not vary greatly with composition. The C
P's of the liquids, however, increase strongly with An content, suggesting major structural changes take place across the binary. 相似文献
15.
16.
Nico de Koker 《Geochimica et cosmochimica acta》2010,74(19):5657-470
We have performed first-principles molecular dynamics simulations of CaAl2Si2O8 (anorthite) liquid at pressures up to 120 GPa and temperatures of 3000, 4000 and 6000 K. At the lowest degrees of compression the liquid is seen to accommodate changes in density through decreasing the abundance of 3- and 4-membered rings, while increases in coordination of network forming cations take effect at somewhat higher degrees of compression. Results are fit to a fundamental thermodynamic relation with 4th order finite strain and 1st order thermal variable expansions. Upon compression by a factor of two, the Grüneisen parameter (γ) is found to increase continuously from 0.35 to 1.10. Weak temperature dependence in γ is thermodynamically consistent with a slight decrease in isochoric heat capacity (CV), for which values of between 4.4 and 5.2 NkB are obtained, depending on the temperature. Pressure and temperature dependence of self-diffusivities is found to be well represented by an Arrhenius relation, except at 3000 K and pressures lower than 5 GPa, where self-diffusivities of Si, Al, and O increase with pressure. Analysis of the lifetimes of individual coordination species reveals that this phenomenon arises due to the disproportionately high stability of 4-fold coordinated Si, and to a lesser extent 4-fold coordinated Al. Our results represent a marked improvement in accuracy and reliability in describing the physics of CaAl2Si2O8 liquid at deep mantle pressures, pointing the way to a general thermodynamic model of melts at extreme pressures and temperatures relevant to planetary-scale magma oceans and deep mantle partial melting. 相似文献
17.
The shear viscosity of 66 liquids in the systems CaO-Al2O3-SiO2 (CAS) and MgO-Al2O3-SiO2 (MAS) have been measured in the ranges 1-104 Pa s and 108-1012 Pa s. Liquids belong to series, nominally at 50, 67, and 75 mol.% SiO2, with atomic M2+/(M2++2Al) typically in the range 0.60 to 0.40 for each isopleth. In the system CAS at 1600°C, viscosity passes through a maximum at all silica contents. The maxima are clearly centered in the peraluminous field, but the exact composition at which viscosity is a maximum is poorly defined. Similar features are observed at 900°C. In contrast, data for the system MAS at 1600°C show that viscosity decreases with decreasing Mg/(Mg + 2Al) at all silica contents, but that a maximum in viscosity must occur in the field where Mg/2Al >1. On the other hand, the viscosity at 850°C increases with decreasing Mg/(Mg + 2Al) and shows no sign of reaching a maximum, even for the most peraluminous composition studied. The data from both systems at 1600°C have been analysed assuming that shear viscosity is proportional to average bond strength and considering the equilibrium:
Al[4]-(Mg,Ca)0.5⇔(Mg,Ca)0.5-NBO+AlXS 相似文献
18.
Calorimetric measurements of fusion enthalpies for Ni2SiO4 and Co2SiO4 olivines were carried out using a high-temperature calorimeter, and Ni and Co partitioning between olivine and silicate liquid was analyzed using the measured heats of fusion. The fusion enthalpy of Co2SiO4 olivine measured by transposed-temperature drop calorimetry was 103 ± 15 kJ/mol at melting point (1688 K). The fusion enthalpy of Ni2SiO4 olivine was calculated based on the enthalpies of liquids in the system An50Di50-Ni2SiO4 measured by transposed-temperature drop calorimetry at 1773 K, and was 221 ± 26 kJ/mol at its metastable melting point (1923 K). The fusion enthalpy of Ni2SiO4 is the largest among those of olivine group, this is caused by the large crystal field stabilization energy of six-coordinated Ni2+ in olivine. The larger fusion enthalpy of Ni2SiO4 can account for the large and variable partition coefficient of Ni between olivine and silicate liquid. Based on the comparison between partition coefficients calculated from thermodynamic data and those observed in partition experiments, it is considered that the magnitude of partition coefficients is primarily dependent on the heats of fusion of the components. Furthermore, the activity coefficients for Ni-, Co- and Mn-bearing components in magmatic liquid are nearly of the same magnitude. 相似文献
19.
An end member of the tourmaline series with a structural formula □(Mg2Al)Al6(BO3)3[Si6O18](OH)4 has been synthesized in the system MgO-Al2O3-B2O3-SiO2-H2O where it represents the only phase with a tourmaline structure. Our experiments provide no evidence for the substitutions Al → Mg + H, Mg → 2H, B + H → Si, and AlAl → MgSi and we were not able to synthesize a phase “Mg-aluminobuergerite” characterized by Mg in the (3a)-site and a strong (OH)-deficiency reported by Rosenberg and Foit (1975). The alkali-free tourmaline has a vacant (3a)-site and is related to dravite by the □ + Al for Na + Mg substitution. It is stable from at least 300°C to about 800°C at low fluid pressures and 100% excess B2O3, and can be synthesized up to a pressure of 20 kbars. At higher temperatures the tourmaline decomposes into grandidierite or a boron-bearing phase possibly related to mullite (“B-mullite”), quartz, and unidentified solid phases, or the tourmaline melts incongruently into corundum + liquid, depending on pressure. In the absence of excess B2O3 tourmaline stability is lowered by about 60°C. Tourmaline may coexist with the other MgO-Al2O3-B2O3-SiO2-H2O phases forsterite, enstatite, chlorite, talc, quartz, grandidierite, corundum, spinel, “B-mullite,” cordierite, and sinhalite depending on the prevailing PTX-conditions.The (3a)-vacant tourmaline has the space group R3m with , , and . However, these values vary at room temperature with the pressure-temperature conditions of synthesis by , , and , probably as a result of MgAl order/disorder relations in the octahedral positions. Despite these variations intensity calculations support the assumed structural formula. Refractive indices are no = 1.631(2), nE = 1.610(2), Δn = 0.021. The infrared spectrum is intermediate between those of dravite and elbaite. The common alkali and calcium deficiencies of natural tourmalines may at least partly be explained by miscibilities towards (3a)-vacant end members. The apparent absence of (3a)-vacant tourmaline in nature is probably due to the lack of fluids that carry boron but no Na or Ca. 相似文献
20.
Charles A. Geiger Edgar Dachs Gilberto Artioli 《Geochimica et cosmochimica acta》2010,74(18):5202-5215
Armenite, ideal formula BaCa2Al6Si9O30·2H2O, and its dehydrated analog BaCa2Al6Si9O30 and epididymite, ideal formula Na2Be2Si6O15·H2O, and its dehydrated analog Na2Be2Si6O15 were studied by low-temperature relaxation calorimetry between 5 and 300 K to determine the heat capacity, Cp, behavior of their confined H2O. Differential thermal analysis and thermogravimetry measurements, FTIR spectroscopy, electron microprobe analysis and powder Rietveld refinements were undertaken to characterize the phases and the local environment around the H2O molecule.The determined structural formula for armenite is Ba0.88(0.01)Ca1.99(0.02)Na0.04(0.01)Al5.89(0.03)Si9.12(0.02)O30·2H2O and for epididymite Na1.88(0.03)K0.05(0.004)Na0.01(0.004)Be2.02(0.008)Si6.00(0.01)O15·H2O. The infrared (IR) spectra give information on the nature of the H2O molecules in the natural phases via their H2O stretching and bending vibrations, which in the case of epididymite only could be assigned. The powder X-ray diffraction data show that armenite and its dehydrated analog have similar structures, whereas in the case of epididymite there are structural differences between the natural and dehydrated phases. This is also reflected in the lattice IR mode behavior, as observed for the natural phases and the H2O-free phases. The standard entropy at 298 K for armenite is S° = 795.7 ± 6.2 J/mol K and its dehydrated analog is S° = 737.0 ± 6.2 J/mol K. For epididymite S° = 425.7 ± 4.1 J/mol K was obtained and its dehydrated analog has S° = 372.5 ± 5.0 J/mol K. The heat capacity and entropy of dehydration at 298 K are Δ = 3.4 J/mol K and ΔSrxn = 319.1 J/mol K and Δ = −14.3 J/mol K and ΔSrxn = 135.7 J/mol K for armenite and epididymite, respectively. The H2O molecules in both phases appear to be ordered. They are held in place via an ion-dipole interaction between the H2O molecule and a Ca cation in the case of armenite and a Na cation in epididymite and through hydrogen-bonding between the H2O molecule and oxygen atoms of the respective silicate frameworks. Of the three different H2O phases ice, liquid water and steam, the Cp behavior of confined H2O in both armenite and epididymite is most similar to that of ice, but there are differences between the two silicates and from the Cp behavior of ice. Hydrogen-bonding behavior and its relation to the entropy of confined H2O at 298 K is analyzed for various microporous silicates.The entropy of confined H2O at 298 K in various silicates increases approximately linearly with increasing average wavenumber of the OH-stretching vibrations. The interpretation is that decreased hydrogen-bonding strength between a H2O molecule and the silicate framework, as well as weak ion-dipole interactions, results in increased entropy of H2O. This results in increased amplitudes of external H2O vibrations, especially translations of the molecule, and they contribute strongly to the entropy of confined H2O at T < 298 K. 相似文献