首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献，搜索用时 15 毫秒
1.
Reports of the high ion content of steam and low-density supercritical fluids date back to the work of Carlon [Carlon H. R. (1980) Ion content of air humidified by boiling water.J. Appl.Phys.51, 171-173], who invoked ion and neutral-water clustering as mechanism to explain why ions partition into the low-density aqueous phase. Mass spectrometric, vibrational spectroscopic measurements and quantum chemical calculations have refined this concept by proposing strongly bound ion-solvent aggregates and water clusters such as Eigen- and Zundel-type proton clusters H3O+·(H2O)m and the more weakly bound water oligomers (H2O)m. The extent to which these clusters affect fluid chemistry is determined by their abundance, however, little is known regarding the stability of such moieties in natural low-density high-temperature fluids. Here we report results from quantum chemical calculations using chemical-accuracy multi-level G3 (Curtiss-Pople) and CBS-Q theory (Peterson) to address this question. In particular, we have investigated the cluster structures and clustering equilibria for the ions and H3S+·(H2O)m(H2S)n, where m ? 6 and n ? 4, at 300-1000 K and 1 bar as well as under vapor-liquid equilibrium conditions between 300 and 646 K. We find that incremental hydration enthalpies and entropies derived from van’t Hoff analyses for the attachment of H2O and H2S onto H3O+, and H3S+ are in excellent agreement with experimental values and that the addition of water to all three ions is energetically more favorable than solvation by H2S. As clusters grow in size, the energetic trends of cluster hydration begin to reflect those for bulk H2O liquids, i.e. calculated hydration enthalpies and entropies approach values characteristic of the condensation of bulk water (ΔHo = −44.0 kJ mol−1, ΔSo = −118.8 J K mol−1). Water and hydrogen sulfide cluster calculations at higher temperatures indicate that a significant fraction of H3O+, and H3S+ ions exists as solvated moieties.  相似文献   

2.
We have studied thermochemistry of the first hydration steps for Cl−, Br−, and I− in the gas phase both experimentally using high-pressure mass spectrometry (HPMS) and theoretically using density functional theory (DFT) calculations. The highest hydration steps measured experimentally were n = 8 for Cl−, n = 7 for Br−, and n = 5 for I−, all of them being higher than previously reported. Both experimental and theoretical stepwise enthalpies and entropies of hydration for these halides exhibited non-monotonic behavior for successive hydration steps that was not reported in previous HPMS investigations of these reactions. This behavior can be successfully interpreted using halide water cluster geometries obtained from DFT calculations by considering the number of additional hydrogen bonds formed at each hydration step and simultaneous weakening of ion-solvent interaction with increasing cluster size. Results of DFT calculations for surface cluster geometries agree better with experimental results than do the results for interior cluster geometries. We conclude that predominantly surface clusters were observed in our experiments and that small surface clusters have larger number of possible isomers than the interior clusters of the same size. The results for enthalpies of hydration for the studied halide ions lead to the conclusion that ion-solvent interaction is stronger than solvent-solvent interaction for chloride-water clusters. The difference between the two types of interaction diminishes with increasing anion size. The ion-solvent and solvent-solvent interactions are of nearly equal magnitude for iodide.  相似文献   

3.
Understanding bacterial surface reactivity requires many different lines of investigation. Toward this end, we used isothermal titration calorimetry to measure heats of proton adsorption onto a Gram positive thermophile Bacillus licheniformis at 25, 37, 50, and 75 °C. Proton adsorption under all conditions exhibited exothermic heat production. Below pH 4.5, exothermic heats decreased as temperature increased above 37 °C; above pH 4.5, there was no significant difference in heats evolved at the temperatures investigated. Total proton uptake did not vary significantly with temperature. Site-specific enthalpies and entropies were calculated by applying a 4-site, non-electrostatic surface complexation model to the calorimetric data. Interpretation of site-specific enthalpies and entropies of proton adsorption for site L1, L2, and L4 are consistent with previous interpretations of phosphoryl, carboxyl, and hydroxyl/amine site-identities, respectively, and with previous calorimetric measurements of proton adsorption onto mesophilic species. Enthalpies and entropies for surface site L3 are not consistent with the commonly inferred phosphoryl site-identity and are more consistent with sulfhydryl functional groups. These results reveal intricacies of surface reactivity that are not detectable by other methods.  相似文献   

4.
The hexa-aqua complexes [Fe(H2O)6−m−n(OH)n](2−n)+n = 0 → 3, m = 0 → 6 − n; [Fe(H2O)6−m−n(OH)n](3−n)+n = 0 → 4, m = 0 → 6 − n were investigated by ab-initio methods with the aim of determining their ground-state geometries, total energies and vibrational properties by treating their inner solvation shell as part of their gaseous precursor1 (or “hybrid approach”). After a gas-phase energy optimization within the Density Functional Theory (DFT), the molecules were surrounded by a dielectric representing the Reaction Field through an implicit Polarized Continuum Model (PCM). The exploration of several structural ligand arrangements allowed us to quantify the relative stabilities of the various ionic species and the role of the various forms of energy (solute-solvent electronic interaction, cavitation, dispersion, repulsion, liberation free energy) that contribute to stabilize the aqueous complexes. A comparison with experimental thermochemistries showed that ab-initio gas-phase + solvation energies are quite consistent with experimental evidence and allow the depiction of the most stable form in solution and the eventual configurational disorder of water/hydroxyl species around central cations. A vibrational analysis performed on the 54Fe, 56Fe, 57Fe and 58Fe isotopomers indicated important separative effects systematically affected by the extent of deprotonation. The role of the system’s redox state (fO2) and acidity (pH) on the isotopic imprinting of the aqueous species in solution was investigated by coupling the separative effects with speciation calculations. The observed systematics provided a tool of general utility in the interpretation of the iron isotopic signature of natural waters. Applications to the interpretation of isotopic fractionation in solution dictated by redox equilibria and to the significance of the Fe-isotopic imprinting of Banded Iron Formations are given.  相似文献   

5.
Molecular dynamics computer simulations of the molecular structure, diffusive dynamics and hydration energetics of water adsorbed on (0 0 1) surfaces of brucite Mg(OH)2, gibbsite Al(OH)3, hydrotalcite Mg2Al(OH)6Cl · 2H2O, muscovite KAl2(Si3Al)O10(OH)2, and talc Mg3Si4O10(OH)2 provide new insight into the relationships between the substrate structure and composition and the molecular-scale structure and properties of the interfacial water. For the three hydroxide phases studied here, the differences in the structural charge on the octahedral sheet, cation occupancies and distributions, and the orientations of OH groups all affect the surface water structure. The density profiles of water molecules perpendicular to the surface are very similar, due to the prevalent importance of H-bonding between the surface and the water and to their similar layered crystal structures. However, the predominant orientations of the surface water molecules and the detailed two-dimensional near-surface structure are quite different. The atomic density profiles and other structural characteristics of water at the two sheet silicate surfaces are very different, because the talc (0 0 1) surface is hydrophobic whereas the muscovite (0 0 1) surface is hydrophilic. At the hydrophilic and electrostatically neutral brucite and gibbsite (0 0 1) surfaces, both donating and accepting H-bonds from the H2O molecules are important for the development of a continuous hydrogen bonding network across the interfacial region. For the hydrophilic but charged hydrotalcite and muscovite (0 0 1) surfaces, only accepting or donating H-bonds from the water molecules contribute to the formation of the H-bonding network at the negatively and positively charged interfaces, respectively. For the hydrophobic talc (0 0 1) surface, H-bonds between water molecules and the surface sites are very weak, and the H-bonds among H2O molecules dominate the interfacial H-bonding network. For all the systems studied, the orientation of the interfacial water molecules in the first few layers is influenced by both the substrate surface charge and the ability by the surfaces to facilitate H-bond formation. The first layer of water molecules at all surfaces is well ordered in the xy plane (parallel to the surface) and the atomic density distributions reflect the substrate crystal structure. The enhanced ordering of water molecules at the interfaces indicates reduced orientational and translational entropy. In thin films, water molecules are more mobile parallel to the surface than perpendicular to it due to spatial constraints. At neutral, hydrophilic substrates, single-monolayer surface coverage stabilizes the adsorbed water molecules and results in a minimum of the surface hydration energy. In contrast, at the charged and hydrophilic muscovite surface, the hydration energy increases monotonically with increasing water coverage over the range of coverages studied. At the neutral and hydrophobic talc surface, the adsorption of H2O is unfavorable at all surface coverages, and the hydration energy decreases monotonically with increasing coverage.  相似文献   

6.
《Applied Geochemistry》2001,16(2):161-181
Thermodynamic properties of water, in various families of hydroxides, oxihydroxides and hydrates (chlorides, chlorates, sulfates and sulfites …), have been calculated by using a large number of data available in the literature. A phase diagram of water has been used to find the first complete set of thermodynamic properties at 298 K, 1 bar of 8 ice polymorphs, from Ih (hexagonal ice, the common polymorph) to IX (very low temperature and high pressure polymorph). These results are used to illustrate the concept of ‘ice-like water’ available for a very large number of hydrated phases (noted X.H2O) in which water is attached to the corresponding anhydrous substrate (noted X) within a large spectrum of different enthalpies (ΔfH°) or Gibbs free energies (ΔfG°), but within a relatively small range of others properties. Heat capacity (Cp°), entropy (S°), and volume (V°) of hydration water (X.H2O−X=H2O) appeared to be very close to those characterizing ice polymorphs such as ice II or ice VIII. This concept allows the authors to propose a classification of minerals in terms of affinity for water and to predict the relative stability of hydrated and dehydrated phases under climatic variations.  相似文献   

7.
  相似文献   

8.
The mechanism and rate of hydration of rhyolitic glass during weathering were studied. Doubly polished thin sections of two rhyolites with different duration of weathering (Ohsawa lava: 26,000 yr, Awanomikoto lava: 52,000 yr) were prepared. Optical microscope observation showed that altered layers had developed along the glass surfaces. IR spectral line profile analysis was conducted on the glass sections from the surface to the interior for a length of 250 μm and the contents of molecular H2O (H2Om), OH species (OH) and total water (H2Ot) were determined. The diffusion profile of H2Om in Ohsawa lava extends beyond the layer observed by optical microscope. The content of H2Om in the hydrated region is much higher than that of OH species. Thus, the reaction from H2Om to OH appears to be little and H2Om is the dominant water species moving into the glass during weathering. Based on the concentration profiles, the diffusion coefficients of H2Om(DH2Om) and H2Ot(DH2Ot) were determined to be 2.8 × 10−10 and 3.4 × 10−10 μm2 s−1 for Ohsawa lava, and 5.2 × 10−11 and 4.1 × 10−11 μm2 s−1 for Awanomikoto lava, respectively. The obtained DH2Om during weathering are more than 2-3 orders of magnitude larger than the diffusion coefficient at ∼20 °C that is extrapolated from the diffusivity data for >400 °C. This might suggest that the mechanism of water transport is different at weathering conditions and >400 °C.  相似文献   

9.
Equilibrium in the chabazite-H2O system was investigated by isothermal thermogravimetric analysis over a large range of temperatures (from 23 to 315°C) and H2O-vapor pressures (from 0.03 to 28 mbar). Thermodynamic analysis of the phase-equilibrium data revealed the existence of three energetically distinct types of H2O, referred to as S-1, S-2, and S-3. At 23°C and 26 mbar of H2O-vapor pressure, chabazite has maximum H2O occupancies of 8.2, 11.1, and 3.1 wt.% for S-1, S-2, and S-3, respectively. During dehydration, S-1 H2O is lost first, followed by S-2 H2O and then S-3 H2O, with significant overlap for S-1 and S-2 as well as S-2 and S-3. The thermodynamics of chabazite-H2O were modeled using three independent equilibrium formulations for S-1, S-2, and S-3. These formulations yielded standard-state molar Gibbs free energy of hydration of −21.8 ± 0.6, −52.1 ± 1.8, and −111.7 ± 6.7 kJ/mol for S-1, S-2, and S-3. Standard-state molar enthalpies of hydration for each type of H2O are −65.6 ± 0.5, −100.1 ± 1.6, and −156.9 ± 6.2 kJ/mol, respectively. Integral molar values for the Gibbs free energy of hydration for each type of H2O are −19.0 ± 0.7, −40.1 ± 2.1, and −76.9 ± 9.6 kJ/mol, respectively. Integral molar values for the enthalpy of hydration for each type of H2O are −62.8 ± 0.6, −88.1 ± 1.9, and −122.2 ± 9.3 kJ/mol, respectively. Integration of the predicted total partial molar enthalpy of hydration for all three types of H2O over the full H2O content of chabazite gave an integral molar enthalpy of −39.65 ± 9.3 kJ/mol relative to liquid water. The thermodynamic data obtained for the hydration of natural chabazite were used to predict the hydration state of chemically similar chabazites under various temperatures and PH2O, ranging from 25 to 400°C and from 10−5 to 104 bars.  相似文献   

10.
The solubility of molybdenum trioxide in liquid-undersaturated water vapour has been investigated experimentally at 300, 320, and 360 °C and 39-154 bars. Results of these experiments show that the solubility of MoO3 in water vapour is between 1 and 29 ppm, which is 19-20 orders of magnitude higher than the vapour pressure of MoO3(g). Molybdenum solubility increases exponentially with fH2O, suggesting the formation of a gaseous hydrated complex of the type MoO3·nH2O by the reaction:
(A.1)  相似文献   

11.
Thermodynamic mixing properties and subsolidus phase relations of the rhombohedral carbonate system, (1 − x) · CaCO3 − x · MgCO3, were modelled in the temperature range of 623-2023 K with static structure energy calculations based on well-parameterised empirical interatomic potentials. Relaxed static structure energies of a large set of randomly varied structures in a 4 × 4 × 1 supercell of calcite (a = 19.952 Å, c = 17.061 Å) were calculated with the General Utility Lattice Program (GULP). These energies were cluster expanded in a basis set of 12 pair-wise effective interactions. Temperature-dependent enthalpies of mixing were calculated by the Monte Carlo method. Free energies of mixing were obtained by thermodynamic integration of the Monte Carlo results. The calculated phase diagram is in good agreement with experimental phase boundaries.  相似文献   

12.
Complexation of (trace) elements in fluids plays a critical role in determining element mobility in subduction zones, but to date, the atomic-scale processes controlling elemental solubilities are poorly understood. As a first step towards computer simulation of element complexation in subduction zone fluids, a thermodynamic cycle was developed to investigate the hydration environment and energetics of lanthanide complexes using density functional theory. The first solvation shell is explicitly defined and the remaining part of the aqueous fluid is modelled using a polarisable continuum model, which allows extrapolation to a broad pressure and temperature range.We illustrate our method by comparing solvation of lanthanide series elements in H2O in the presence of fluoride or chloride for conditions relevant to subduction zones. The energetics of lanthanide- and lanthanide-fluoride/chloride hydration complexes were determined computationally. Calculated hydration free energies for trivalent lanthanides with explicit eight- and nine-fold coordinated first hydration shells show good agreement with literature data at room pressure and temperature. The hydration free energy is more negative for smaller complexes (heavy lanthanides) relative to larger complexes (light lanthanides), with the difference between La and Lu in water amounting to 361 kJ mol−1. The hydration free energy of all lanthanide ions becomes less negative with increasing pressure (p) and temperature (T) up to 2.5 GPa and 1000 K (typical conditions in the upper part of subducting slabs). The free energy difference between light- and heavy-lanthanides remains essentially unchanged at elevated (p, T) conditions. There are minor geometrical differences in local hydration environment between light lanthanide-chloride (La-Nd) and heavy lanthanide-chloride (Pm-Lu) hydrated complexes, without a distinguishable energy difference. Complexation with fluoride is energetically more favourable than with chloride by 206 ± 4 kJ mol−1 across the entire lanthanide series. The association of fluoride-water and chloride-water fragments with lanthanide-water complexes is energetically more favourable for aqueous lanthanide complexes surrounded by fewer first hydration shell water molecules.The methods developed in this study, in conjunction with simulation of the energetics of trace element incorporation into minerals, open the possibility to use molecular modelling to constrain elemental behaviour in subduction zones.  相似文献   

13.
  相似文献   

14.
Computer modelling techniques were used to elucidate the hydration behaviour of three iron (hydr)oxide minerals at the atomic level: white rust, goethite and hematite. A potential model was first adapted and tested against the bulk structures and properties of eight different iron oxides, oxyhydroxides and hydroxides, followed by surface simulations of Fe(OH)2, α-FeO(OH) and α-Fe2O3. The major interaction between the adsorbing water molecules and the surface is through interaction of their oxygen ions with surface iron ions, followed by hydrogen-bonding to surface oxygen ions. The energies released upon the associative adsorption of water range from 1 to 17 kJ mol−1 for Fe(OH)2, 26 to 80 kJ mol−1 for goethite and 40 to 85 kJ mol−1 for hematite, reflecting the increasing oxidation of the iron mineral. Dissociative adsorption at goethite and hematite surfaces releases larger hydration energies, ranging from 120 to 208 kJ mol−1 for goethite and 76 to 190 kJ mol−1 for hematite.The thermodynamic morphologies of the minerals, based on the calculated surface energies, agree well with experimental morphologies, where these are available. When the partial pressures required for adsorption of water from the gas phase are plotted against temperature for the goethite and hematite surfaces, taking into account experimental entropies for water, it appears that these minerals may well be instrumental in the retention of water during the cyclic variations in the atmosphere of Mars.  相似文献   

15.
《Chemical Geology》2006,225(3-4):373-387
Rock-forming zeolites often exhibit complex solid solutions reflecting isomorphous substitutions between Si and Al in tetrahedral framework sites, between charge-balancing extraframework cations, and between water molecules and vacancies. Although the number of moles of charge on extraframework cations in a zeolite must equal the moles of Al in order to maintain charge balance, the relationships between Si–Al and extraframework substitutions vary considerably across this mineral group. Review of available compositional data suggests that there are three main modes of Si–Al substitution in zeolites: 1) coupled CaAl–NaSi substitution; 2) coupled substitution of a single extraframework cation plus Al for Si; and 3) completely uncoupled substitution among extraframework cations and Si and Al on tetrahedral sites. Among zeolites that exhibit the latter two modes of solid solution, Si–Al substitution can be described by an SiO2 (± H2O) compositional exchange vector from a hypothetical, pure-silica endmember composition. Recent calorimetric, structural, and theoretical investigations suggest that Si–Al substitution follows a non-ideal, athermal solution model characterized by no excess enthalpies of mixing and negative excess entropies of mixing. Because Si–Al exchange in these minerals can be explicitly or implicitly described by exchange of an SiO2 component, the Si/Al ratio in their framework can be predicted solely as a function of temperature, pressure, and the chemical potential of SiO2. Application of this model leads to calculated Si/Al ratios in stilbite (coexisting with albite), analcime, and chabazite consistent with observed mineral compositions and parageneses in very low-grade metamorphic environments. Coexistence of silica polymorphs with zeolites containing SiO2·nH2O exchange vectors potentially provides a means of performing thermobarometric calculations in very low-grade metamorphic and diagenetic environments.  相似文献   

16.
Experimental studies on the stability of several Mg-sulfate hydrates including epsomite (MgSO4·7H2O), hexahydrite (MgSO4·6H2O), starkeyite (MgSO4·4H2O), and kieserite (MgSO4·H2O) as a function of temperature and relative humidity are in poor agreement with calculations based on thermodynamic properties of these substances taken from the literature. Therefore, we synthesized four different MgSO4 hydrates and measured their enthalpies of formation by solution calorimetry at T = 298.15 K. The resulting enthalpies of formation from the elements are:
•
ΔfH0298 (epsomite) = −3387.7 ± 1.3 kJmol−1
•
ΔfH0298 (hexahydrite) = −3088.1 ± 1.1 kJmol−1
•
ΔfH0298 (sanderite, MgSO4·2H2O) = −1894.9 ± 1.3 kJmol−1
•
ΔfH0298 (kieserite) = −1612.4 ± 1.3 kJmol−1
Using mathematical programming (MAP) techniques, standard thermodynamic values consistent both with our calorimetric data and previously published humidity brackets could be derived:
•
Epsomite: ΔfH0298 = −3388.7 kJmol−1, S0298 = 371.3 Jmol−1 K−1, ΔfG0298 = −2871.0 kJmol−1
•
Hexahydrite: ΔfH0298 = −3087.3 kJmol−1, S0298 = 348.5 Jmol−1 K−1, ΔfG0298 = −2632.3 kJmol−1
•
Starkeyite: ΔfH0298 = −2496.1 kJmol−1, S0298 = 259.9 Jmol−1 K−1, ΔfG0298 = −2153.8 kJmol−1
•
Kieserite: ΔfH0298 = −1611.5 kJmol−1, S0298 = 126.0 Jmol−1 K−1, ΔfG0298 = −1437.9 kJmol−1
Additionally, heat capacity measurements and standard entropy determinations of several magnesium sulfate hydrate minerals from the literature are analyzed and judged against estimates obtained from a linear combination of the heat capacities of MgSO4 and hexagonal ice. The results of the MAP analysis are compared to these estimates to conclude that heat capacity and entropy correlate well with the number of waters of hydration. However, even the good correlation is not good enough to capture the fine variations in these properties. Consequently, their experimental measurement is inevitable if reliable thermodynamic data are sought. Our MAP thermodynamic data show that epsomite, hexahydrite, and kieserite have stability fields in the T-%RH space. Starkeyite is metastable. Although no MAP data could have been derived for pentahydrite (MgSO4·5H2O) and sanderite, their transient existence suggest that both of them are metastable as well.  相似文献   

17.
The Newtonian viscosity of synthetic rhyolitic liquids with 0.15-5.24 wt% dissolved water was determined in the interval between 580 and 1640 °C and pressures of 1 atm and 5-25 kbar. Measurements were performed by combining static and accelerated (up to 1000g) falling sphere experiments on water-bearing samples, with high temperature concentric cylinder experiments on 0.15 wt% H2O melts. These methods allowed viscosity determinations between 102 and 107 Pa s, and cover the complete range of naturally occurring magmatic temperatures, pressures, and H2O-contents for rhyolites.Our viscosity data, combined with those from previous studies, were modeled by an expression based on the empirical Vogel-Fulcher-Tammann equation, which describes viscosities and derivative properties (glass transition temperature Tg, fragility m, and activation volume of viscous flow Va) of silicic liquids as a function of P-T-X(H2O). The fitted expressions do not account for composition-dependent parameters other than X(H2O) and reproduce the entire viscosity database for silicic liquids to within 3.0% average relative error on log η (i.e. std. error of estimate of 0.26 log units).The results yield the expected strong decrease of viscosity with temperature and water content, but show variable pressure dependencies. Viscosity results to be strongly affected by pressure at low pressures; an effect amplified at low temperatures and water contents. Fragility, as a measure for the deviation from Arrhenian behavior, decreases with H2O-content but is insensitive to pressure. Activation volumes are always largely negative (e.g., less than −10 cm3/mol) and increase strongly with H2O-content. Variations in melt structure that may account for the observed property variations are discussed.  相似文献   

18.
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   

19.
The internal energies and entropies of 21 well-known minerals were calculated using the density functional theory (DFT), viz. kyanite, sillimanite, andalusite, albite, microcline, forsterite, fayalite, diopside, jadeite, hedenbergite, pyrope, grossular, talc, pyrophyllite, phlogopite, annite, muscovite, brucite, portlandite, tremolite, and CaTiO3–perovskite. These thermodynamic quantities were then transformed into standard enthalpies of formation from the elements and standard entropies enabling a direct comparison with tabulated values. The deviations from reference enthalpy and entropy values are in the order of several kJ/mol and several J/mol/K, respectively, from which the former is more relevant. In the case of phase transitions, the DFT-computed thermodynamic data of involved phases turned out to be accurate and using them in phase diagram calculations yields reasonable results. This is shown for the Al2SiO5 polymorphs. The DFT-based phase boundaries are comparable to those derived from internally consistent thermodynamic data sets. They even suggest an improvement, because they agree with petrological observations concerning the coexistence of kyanite?+?quartz?+?corundum in high-grade metamorphic rocks, which are not reproduced correctly using internally consistent data sets. The DFT-derived thermodynamic data are also accurate enough for computing the P–T positions of reactions that are characterized by relatively large reaction enthalpies (>?100 kJ/mol), i.e., dehydration reactions. For reactions with small reaction enthalpies (a few kJ/mol), the DFT errors are too large. They, however, are still far better than enthalpy and entropy values obtained from estimation methods.  相似文献   

20.
Solid phases of silicon dioxide react with water vapor with the formation of hydroxides and oxyhydroxides of silica. Recent transpiration and mass-spectrometric studies convincingly demonstrate that H4SiO4 is the predominant form of silica in vapor phase at water pressure in excess of 10−2 MPa. Available literature transpiration and solubility data for the reactions of solid SiO2 phases and low-density water, extending from 424 to 1661 K, are employed for the determination of ΔfG0, ΔfH0 and S0 of H4SiO4 in the ideal gas state at 298.15 K, 0.1 MPa. In total, there are 102 data points from seven literature sources. The resulting values of the thermodynamic functions of H4SiO4(g) are: ΔfG0 = −1238.51 ± 3.0 kJ mol−1, ΔfH0 = −1340.68 ± 3.5 kJ mol−1 and S0 = 347.78 ± 6.2 J K−1 mol−1. These values agree quantitatively with one set of ab initio calculations. The relatively large uncertainties are mainly due to conflicting data for H4SiO4(g) from various sources, and new determinations of would be helpful. The thermodynamic properties of this species, H4SiO4(g), are necessary for realistic modeling of silica transport in a low-density water phase. Applications of this analysis may include the processes of silicates condensation in the primordial solar nebula, the precipitation of silica in steam-rich geothermal systems and the corrosion of SiO2-containing alloys and ceramics in moist environments.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号