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1.
A new determination, using high temperature drop-solution calorimetry, of the enthalpy of transformation of MgSiO3 pyroxene to ilmenite gives H
298 = 59.03 ±4.26 kJ/mol. The heat capacity of the ilmenite and orthopyroxene phases has been measured by differential scanning calorimetry at 170–700 K; Cp of MgSiO3 ilmenite is 4–10 percent less than that of MgSiO3 pyroxene throughout the range studied. The heat capacity differences are consistent with lattice vibrational models proposed by McMillan and Ross (1987) and suggest an entropy change of -18 ± 3 J-K-1 ·mol-1, approximately independent of temperature, for the pyroxene-ilmenite transition. The unit cell parameters of MgSiO3 ilmenite were measured at 298–876 K and yield an average volume thermal expansion coefficient of 2.44 × 10-5 K-1. The thermochemical data are used to calculate phase relations involving pyroxene, -Mg2SiO4 plus stishovite, Mg2SiO4 spinel plus stishovite, and ilmenite in good agreement with the results of high pressure studies. 相似文献
2.
Olga B. Fabrichnaya 《Physics and Chemistry of Minerals》1995,22(5):323-332
Based on the available experimental data on phase equilibria in the FeO -MgO -SiO2 system the mixing properties of the solid solutions (olivine, β- and γ-spinel, pyroxene, majorite, ilmenite and perovskite and magnesiowustite), the enthalpies of FeO and fictive FeSiO3 phases with ilmenite and majorite structures have been assessed. The entropies, temperature dependance of heat capacities for fictive FeSiO3 end-members were estimated from structural analogies. The calculated phase diagrams for Mg2SiO4-Fe2SiO4 and MgSiO3 — FeSiO3 systems at pressures up to 30 GPa and temperatures between 1000 and 2100 K are quite consistent with the available experimental determinations except for the fine features of the phase diagram at 2073 K. 相似文献
3.
M. Akaogi H. Kojitani T. Morita H. Kawaji T. Atake 《Physics and Chemistry of Minerals》2008,35(5):287-297
Low-temperature isobaric heat capacities (C
p
) of MgSiO3 ilmenite and perovskite were measured in the temperature range of 1.9–302.4 K with a thermal relaxation method using the
Physical Properties Measurement System. The measured C
p
of perovskite was higher than that of ilmenite in the whole temperature range studied. From the measured C
p
, standard entropies at 298.15 K of MgSiO3 ilmenite and perovskite were determined to be 53.7 ± 0.4 and 57.9 ± 0.3 J/mol K, respectively. The positive entropy change
(4.2 ± 0.5 J/mol K) of the ilmenite–perovskite transition in MgSiO3 is compatible with structural change across the transition in which coordination of Mg atoms is changed from sixfold to eightfold.
Calculation of the ilmenite–perovskite transition boundary using the measured entropies and published enthalpy data gives
an equilibrium transition boundary at about 20–23 GPa at 1,000–2,000 K with a Clapeyron slope of −2.4 ± 0.4 MPa/K at 1,600 K.
The calculated boundary is almost consistent within the errors with those determined by high-pressure high-temperature in
situ X-ray diffraction experiments. 相似文献
4.
5.
Philippe Gillet François Guyot Geoffrey D. Price Benoit Tournerie Andrée Le Cleach 《Physics and Chemistry of Minerals》1993,20(3):159-170
The effect of pressure (up to 21 GPa at room temperature) and temperature (up to 1570 K at room pressure) on the Raman spectrum of CaTiO3 is presented. No significant changes, which could be attributed to a major structural change, are observed in the spectra up to 22 GPa. The pressure shifts of the Raman modes can be related to a significant compression of the Ti-O bond. Discontinuous changes in the spectra upon heating may be related to phase changes observed by calorimetry and X-ray diffraction. The important temperature shifts of some low-frequency modes can be related to an increase in the Ti-O-Ti angle in agreement with the X-ray data showing a decrease of the structural distortion with increasing temperature. These data are compared to those available for MgSiO3-perovskite and show that CaTiO3 is a good structural analogue for MgSiO3-perovskite. The present spectroscopic data are used to calculate the specific heat and entropy of CaTiO3. The role of the low frequency modes in the calculations is emphasized. Good agreement is observed between calculated and experimentally determined values in the 0–1300 K temperature range. A similarly defined model is proposed for MgSiO3-perovskite. It is found that the entropy lies between 57 and 64 J/mol/K at 298 K and between 190 and 200 J/mol/K at 1000 K in agreement with the values inferred from experimental equilibrium data. Finally we briefly discuss the values of the Grüneisen parameters of both perovskites inferred from macroscopic and microscopic data. 相似文献
6.
Unpolarized infrared (IR) reflectance spectra for MgSiO3 ilmenite taken from a single-crystal and from a densly packed polycrystalline sample possessed all eight peaks mandated by symmetry between 337 and 850 cm?1. Polarizations were inferred from intensity differences between the two samples. IR peak positions differ by up to 250 cm?1 from recent calculations, but on average are within 11%. Heat capacity C p calculated from these data by using a Kieffer-type model are within the experimental uncertainty of calorimetric measurements from 170 to 700 K. Outside this range, calculated C p is probably accurate within a few percent, based on recent results for garnets. Calculated entropy is only slightly less accurate, giving S 0 (298.15 K) as 54.1 ±0.5 J/ mol-K, which is 10% lower than recent estimates based on phase equilibria. The slope of the phase boundary between ilmenite and perovskite is used to predict S 0 (298.15 K) of perovskite as 58.7 ±1.4 J/mol-K, which is 10% lower than previous values. 相似文献
7.
8.
M. Akaogi H. Yusa E. Ito T. Yagi K. Suito J. T. Iiyama 《Physics and Chemistry of Minerals》1990,17(1):17-23
ZnSiO3 clinopyroxene stable above 3 GPa transforms to ilmenite at 10–12 GPa, which further decomposes into ZnO (rock salt) plus
stishovite at 20–30 GPa. The enthalpy of the clinopyroxene-ilmenite transition was measured by high-temperature solution calorimetry,
giving ΔH0=51.71 ±3.18 kJ/mol at 298 K. The heat capacities of clinopyroxene and ilmenite were measured by differential scanning calorimetry
at 343–733 and 343–633 K, respectively. The C
p of ilmenite is 3–5% smaller than that of clinopyroxene. The entropy of transition was calculated using the measured enthalpy
and the free energy calculated from the phase equilibrium data. The enthalpy, entropy and volume changes of the pyroxene-ilmenite
transition in ZnSiO3 are similar in magnitude to those in MgSiO3. The present thermochemical data are used to calculate the phase boundary of the ZnSiO3 clinopyroxene-ilmenite transition. The calculated boundary,
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相似文献
9.
High-pressure phase transformations were investigated for two silicates, MgSiO3 and ZnSiO3; six germanates, MGeO3 and six titanates, MTiO3 (M=Ni, Mg, Co, Zn, Fe, and Mn) at about 1,000°C and pressures up to ca. 30 GPa. CoGeO3 was found to assume the ilmenite form. The ilmenite phases were confirmed to transform in the following schemes: to perovskite in MgSiO3 and MnGeO3, to corundum in MgGeO3 and ZnGeO3, to rocksalt plus rutile in ZnSiO3 and CoGeO3 and to rocksalt plus TiO2 (possibly of some denser structure) in NiTiO3, MgTiO3, CoTiO3, ZnTiO3 and FeTiO3. In the case of FeTiO3, the corundum form appeared as an intermediate phase. The possibility that the corundum type MnTiO3 might transform to some denser modification could not be excluded. The compound NiGeO3 was nonexistent throughout the pressure range studied. High-pressure phases of ABO3 (A=Ni, Mg, Co, Zn, Fe, and Mn; B=Si, Ge and Ti) are summarized, and those stabilized at pressures higher than 20 GPa are discussed. 相似文献
10.
Lin-Gun Liu 《Geochimica et cosmochimica acta》1977,41(9):1355-1361
Complete solid solutions with the ilmenite structure from pure MgSiO3 to 75% MgSiO3·25% Al2O3 have been synthesized in the pressure region between 240 and 300 kbar at 1000–1400°C in a diamond-anvil cell coupled with laser heating. The results suggest that complete solid solutions with the ilmenite structure might be formed between MgSiO3 and Al2O3 under high pressure-high temperature conditions. The lattice parameters for the ilmenite solid solutions between MgSiO3 and Al2O3 deviate from ideality in the same manner as those found by Berry and Combs along the FeVO3–Fe2O3 join. For the ordered A2+ B4+O3 ilmenite-type compounds, co is determined primarily by the size of the relatively large A2+ cation, whereas ao depends strongly on the radii of both A2+ and B4+ cations. Such systematics might account for the fact that co and ao for the ilmenite-type MgSiO3 are respectively smaller and larger than those for Al2O3. The lattice parameters ao and molar volumes for the A23+O3 corundum-type compounds and the disordered A2+B4+O3 ilmenites follow a different trend and are, therefore, readily distinguished from the ordered A2+B4+O3 ilmenites. 相似文献
11.
Anne M. Hofmeister 《Physics and Chemistry of Minerals》2014,41(5):361-371
Thermal diffusivity (D) was measured up to ~1,800 K of refractory materials using laser-flash analysis, which lacks radiative transfer gains and contact losses. The focus is on single-crystal MgO and Al2O3. These data are needed to benchmark theoretical models and thereby improve understanding of deep mantle processes. Measurements of AlN, Mg(OH)2, and isostructural BeO show that the power law (D = AT ?B ) where T is temperature holds for simple structures. Results for more structurally complicated corundum Al2O3 with and without impurity atoms are best fit by CT d + ET f where d ~ ?1 and f ~ ?4, whereas for isostructural Fe2O3, f is near +3 and multiphase ilmenite Fe1.12Ti0.88O3 is fit by the above power law. The positive temperature response for hematite is attributed to diffusive radiative transfer arising from electronic–vibronic coupling. We find good agreement of k and D data on single-crystal and non-porous ceramic Al2O3. For the corundum structure, D is nearly independent of T at high T. Although D at 298 K depends strongly on chemical composition, at high temperature, these differences are reduced. Thermal conductivity provided for MgO and Al2O3, using LFA data and literature values of density and heat capacity, differs from contact measurements which include systematic errors. The effect of pressure is discussed, along with implications for the deepest mantle. 相似文献
12.
Guillaume Fiquet Philippe Gillet Pascal Richet 《Physics and Chemistry of Minerals》1992,18(7):469-479
Drop-calorimetry determinations of the isobaric heat capacity (CP) of Mg2GeO4, Ca2GeO4 and CaMgGeO4 have been made up to 1700 K. The thermal expansion coefficient (α) of these olivine germanates has been determined from high-temperature X-ray measurements up to 1500 K. From these measurements and available compressibility data, one calculates that the isochoric heat capacity (CV) exceeds the harmonic limit of Dulong and Petit above 1000–1200 K. Such an intrinsic anharmonic behaviour can be accounted for by introducing anharmonic parameters ai=(? ln v i/?T)V in vibrational modelling of CV. These parameters are calculated from pressure and temperature shifts of the vibrational frequencies as measured by Raman spectroscopy up to 10 GPa at room temperature and up to 1300 K at 1 bar. A comparison of the Raman spectra of the three germanates with those of natural olivines justifies once again the use of germanates as silicate analogues. Extensive Ca,Mg disordering likely takes place in CaMgGeO4, beginning at about 1100 K and leading to unusually high increases of the heat capacity and thermal expansion coefficient. 相似文献
13.
Variations of Raman spectra of MgSiO3·10% Al2O3-perovskite were investigated up to about 270 kbar at room temperature and in the range 108–425 °K at atmospheric pressure. Like MgSiO3-perovskite, the Raman frequencies of MgSiO3·10% Al2O3-perovskite increase nonlinearly with increasing pressure and decrease linearly with increasing temperature within the experimental uncertainties and the range investigated. A comparison of these data with those of MgSiO3-perovskite suggests that MgSiO3·10% Al2O3-perovskite is slightly more compressible than MgSiO3-perovskite, and that the volume thermal expansion for MgSiO3·10% Al2O3-perovskite is also slightly greater than that for MgSiO3-perovskite. 相似文献
14.
Six polymorphs of MgSiO3 have been studied using molecular dynamic (MD) simulation techniques, based on the empirical potential (MAMOK), which is composed of terms to describe pairwise additive Coulomb, van der Waals attraction, and repulsive interactions. Crystal structures, bulk moduli, volume thermal expansivities, and enthalpies were simulated for the known MgSiO3 polymorphs; orthoenstatite, clinoenstatite, protoenstatite, garnet, ilmenite, and perovskite. The simulated values compare very well with the available experimental data, and the results are quite satisfactory in view of the diversity of the crystal structures of the six polymorphs, the wide range of simulated properties, and the simplicity of the MAMOK potential. MD simulation was further successfully used to study the possibile existence of a post-protoenstatite phase at high temperature, and a C2/c phase at high pressure, both phases being suggested or inferred previously from experimental works. 相似文献
15.
The Raman spectra of geikielite (MgTiO3-ilmenite) have been recorded at high pressure (up to 27 GPa) and at high temperature (up to 1820 K). No phase transitions could be evidenced in both cases. In particular, no cation disordering can be evidenced from the high temperature spectra. The observed Raman wavenumber shifts with pressure and with temperature are used to calculate the intrinsic mode anharmonic parameters. The low absolute values of these parameters indicate that geikielite has a nearly quasi-harmonic behaviour, at least to moderate temperatures. However, systematics and the temperature evolution of Raman linewidths suggest that the absolute values of the anharmonic parameters increase at high temperatures. Anharmonic corrections are applied to Kieffer modelling of the constant volume heat capacity of geikielite. They amount to +4 J · mol-1 · K-1 at 1800 K, i.e. are much lower than those inferred for, for instance, olivine and garnet structures. These results are used to discuss some implications on the phase relations of the high-pressure MgSiO3-ilmenite, and the factors controlling the occurence of order-disorder transitions in ilmenite structures. 相似文献
16.
Ph. D'Arco G. Sandrone R. Dovesi E. Aprà V. R. Saunders 《Physics and Chemistry of Minerals》1994,21(5):285-293
The relative stability of MgSiO3-ilmenite, MgSiO3-perovskite and (periclase+stishovite) assemblage phases as a function of the pressure is investigated with the periodic quantum mechanical ab initio HartreeFock program CRYSTAL. For the first time, the structure of MgSiO3-ilmenite is fully optimized. Basis set effects are explored. It turns out that relatively small basis sets reproduce correctly experimental geometries. However, larger basis sets (triple zeta quality, plus polarization d functions) are needed to yield significant thermochemical results. All contributions to the 0 K enthalpy are discussed. On the basis of the present highest level calculations, it appears that in the explored range of pressure (0P< 60=" gpa)=" the=" mineralogical=" assemblage=" periclase+stishovite=" has=" higher=" enthalpy=" than=">3-ilmenite or perovskite, and that ilmenite transforms to orthorhombic perovskite around to 29.4 GPa in good agreement with experimental data extrapolated down to 0 K. 相似文献
17.
Luca Bindi Ekaterina A. Sirotkina Andrey V. Bobrov Tetsuo Irifune 《Physics and Chemistry of Minerals》2014,41(7):519-526
The crystal structure and chemical composition of crystals of (Mg1?x Cr x )(Si1?x Cr x )O3 ilmenite (with x = 0.015, 0.023 and 0.038) synthesized in the model system Mg3Cr2Si3O12–Mg4Si4O12 at 18–19 GPa and 1,600 °C have been investigated. Chromium was found as substitute for both Mg at the octahedral X site and Si at the octahedral Y site, according to the reaction Mg2+ + Si4+ = 2Cr3+. Such substitutions cause a shortening of the <X–O> and a lengthening of the <Y–O> distances with respect to the values typically observed for pure MgSiO3 ilmenite and eskolaite Cr2O3. Although no high Cr contents are considered in the pyrolite model, Cr-bearing ilmenite may be the host for chromium in the Earth’s transition zone. The successful synthesis of ilmenite with high Cr contents and its structural characterization are of key importance because the study of its thermodynamic constants combined with the data on phase relations in the lower-mantle systems can help in the understanding of the seismic velocity and density profiles of the transition zone and the constraining composition and mineralogy of pyrolite in this area of the Earth. 相似文献
18.
We have calculated the compressional, vibrational, and thermodynamic properties of Ni3S2 heazlewoodite and the high-pressure orthorhombic phase (with Cmcm symmetry) using the generalized gradient approximation
to the density functional theory in conjunction with the quasi-harmonic approximation. The predicted Raman frequencies of
heazlewoodite are in good agreement with room-temperature measurements. The calculated thermodynamic properties of heazlewoodite
at room conditions agree very well with experiments, but at high temperatures (especially above 500 K) the heat capacity data
from experiments are significantly larger than the quasi-harmonic results, indicating that heazlewoodite is anharmonic. On
the other hand, the obtained vibrational density of states of the orthorhombic phase at 20 GPa reveals a group of low-frequency
vibrational modes which are absent in heazlewoodite. These low-frequency modes contribute substantially to thermal expansivity,
heat capacity, entropy, and Grüneisen parameter of the orthorhombic phase. The calculated phase boundary between heazlewoodite
and the orthorhombic phase is consistent with high-pressure experiments; the predicted transition pressure is 17.9 GPa at
300 K with a negative Clapeyron slope of −8.5 MPa/K. 相似文献
19.
Gary K. Jacobs Derrill M. Kerrick Kenneth M. Krupka 《Physics and Chemistry of Minerals》1981,7(2):55-59
The heat capacity (C P) of a natural sample of calcite (CaCO3) has been measured from 350 to 775 K by differential scanning calorimetry (DSC). Heat capacities determined for a powdered sample and a single-crystal disc are in close agreement and have a total uncertainty of ±1 percent. The following equation for the heat capacity of calcite from 298 to 775 K was fit by least squares to the experimental data and constrained to join smoothly with the low-temperature heat capacity data of Staveley and Linford (1969) (C P in J mol?1 K?1, T in K): $$\begin{gathered} C_p = - 184.79 + 0.32322T - 3,688,200T^{ - 2} \hfill \\ {\text{ }} - (1.2974{\text{ }} \times {\text{ 10}}^{ - {\text{4}}} )T^2 + 3,883.5T^{ - 1/2} \hfill \\ \end{gathered} $$ Combining this equation with the S 298 0 value from Staveley and Linford (1969), entropies for calcite are calculated and presented to 775 K. A simple method of extrapolating the heat capacity function of calcite above 775 K is presented. This method provides accurate entropies of calcite for high-temperature thermodynamic calculations, as evidenced by calculation of the equilibrium: CaCO3 (s)=CaO(s)+CO2 (s). 相似文献
20.
Crystals of a high-pressure phase of MnTiO3 have been synthesized at pressures of 60 kbar using the SAM-85 cubic-anvil high pressure apparatus. Although all crystals examined were twinned on (10 \(\bar 1\) \(\bar 2\) ), a set of diffraction intensities that are essentially unaffected by the twinning were obtained. Three possible structure models were considered: (1) the corundum (completely disordered Mn and Ti), (2) the partially-disordered ilmenite, and (3) the LiNbO3 structures. The R factors of the corundum and the disordered ilmenite models were much larger than that of LiNbO3. Using structure factors unaffected by twinning, the final LiNbO3-type refinement gave R w=0.037 and R=0.034. The averaged bond lengths for Mn-O and Ti-O were consistent with ones calculated using Shannon and Prewitt's (1969) radii. The study concludes that MnTiO3 II actually has an ordered LiNbO3-type structure rather than the disordered one as reported previously. From the analysis of the two MnTiO3 structures, the transition can be related to a cation reordering process, in which half of the cations participate, accompanied by the rotation of oxygens to accommodate the cations. 相似文献
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