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1.
Hitoshi Yusa Masaki Akaogi Nagayoshi Sata Hiroshi Kojitani Ryo Yamamoto Yasuo Ohishi 《Physics and Chemistry of Minerals》2006,33(3):217-226
In-situ X-ray powder diffraction measurements conducted under high pressure confirmed the existence of an unquenchable orthorhombic perovskite in ZnGeO3. ZnGeO3 ilmenite transformed into perovskite at 30.0 GPa and 1300±150 K in a laser-heated diamond anvil cell. After releasing the pressure, the lithium niobate phase was recovered as a quenched product. The perovskite was also obtained by recompression of the lithium niobate phase at room temperature under a lower pressure than the equilibrium phase boundary of the ilmenite–perovskite transition. Bulk moduli of ilmenite, lithium niobate, and perovskite phases were calculated on the basis of the refined X-ray diffraction data. The structural relations among these phases are considered in terms of the rotation of GeO6 octahedra. A slight rotation of the octahedra plays an important role for the transition from lithium niobate to perovskite at ambient temperature. On the other hand, high temperature is needed to rearrange GeO6 octahedra in the ilmenite–perovskite transition. The correlation of quenchability with rotation angle of GeO6 octahedra for other germanate perovskites is also discussed. 相似文献
2.
The stable polymorph of MnTiO3 at room temperature and pressure has the ilmenite structure. At high temperatures and pressures, MnTiO3 ilmenite transforms to a LiNbO3 structure through a cation reordering process (Ko and Prewitt 1988). Single crystals of both phases have been studied with X-ray diffraction to 5.0 GPa. We have obtained the first experimental verification of the close relationship between the LiNbO3 and perovskite structures, first postulated by Megaw (1968). MnTiO3 with the LiNbO3 structure (MnTiO3 II) transforms directly to an orthorhombic perovskite structure (MnTiO3 III) between 2.0 and 3.0 GPa. The transition involves a change of volume of -5%, is reversible and has pronounced hysteresis. Only pressure is required to drive the transition because it involves no breaking of bonds; it simply involves rotation of the [TiO6] octahedra about their triad axes accompanied by displacement of the Mn cations to the distorted twelve-coordinated sites formed by the rotations. An unusual aspect of this transition is that twinned MnTiO3 II crystals transform to untwinned MnTiO3 III crystals with increasing pressure. The twin plane of MnTiO3 II,
, corresponds to the (001) mirror plane of the orthorhombic perovskite structure. MnTiO3 III examined at 4.5 GPa is very distorted from the ideal cubic perovskite structure. The O(2)-O(2)-O(2) angle describing the tilting in the ab plane is 133.3(7)°, in contrast to 180° for a cubic perovskite and the O(2)-O(2)-O(2) angle describing the tilting in the ac plane is 109.3(4)°, as opposed to 90° in a cubic perovskite. 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.
Daisuke Yamazaki Eiji Ito Yoshinori Tange Takashi Yoshino Shuangmeng Zhai Hiroshi Fukui Anton Shatskiy Tomoo Katsura Ken-ichi Funakoshi 《Physics and Chemistry of Minerals》2007,34(4):269-273
In situ X-ray observations of the phase transition from ilmenite to perovskite structure in MnGeO3 were carried out in a Kawai-type high-pressure apparatus interfaced with synchrotron radiation. The phase boundary between
the ilmenite and perovskite structures in the temperature range of 700–1,400°C was determined to be P (GPa) = 16.5(±0.6) − 0.0034(±0.0006)T (°C) based on Anderson’s gold pressure scale. The Clapeyron slope, dP/dT, determined in this study is consistent with that for the transition boundary between the ilmenite and the perovskite structure
in MgSiO3. 相似文献
5.
Enthalpies of drop solution (ΔH
drop-sol) of CaGeO3, Ca(Si0.1Ge0.9)O3, Ca(Si0.2Ge0.8)O3, Ca(Si0.3Ge0.7)O3 perovskite solid solutions and CaSiO3 wollastonite were measured by high-temperature calorimetry using molten 2PbO · B2O3 solvent at 974 K. The obtained values were extrapolated linearly to the CaSiO3 end member to give ΔH
drop-sol of CaSiO3 perovskite of 0.2 ± 4.4 kJ mol−1. The difference in ΔH
drop-sol between CaSiO3, wollastonite, and perovskite gives a transformation enthalpy (wo → pv) of 104.4 ± 4.4 kJ mol−1. The formation enthalpy of CaSiO3 perovskite was determined as 14.8 ± 4.4 kJ mol−1 from lime + quartz or −22.2 ± 4.5 kJ mol−1 from lime + stishovite. A comparison of lattice energies among A2+B4+O3 perovskites suggests that amorphization during decompression may be due to the destabilizing effect on CaSiO3 perovskite from a large nonelectrostatic energy (repulsion energy) at atmospheric pressure. By using the formation enthalpy
for CaSiO3 perovskite, phase boundaries between β-Ca2SiO4 + CaSi2O5 and CaSiO3 perovskite were calculated thermodynamically utilizing two different reference points [where ΔG(P,T )=0] as the measured phase boundary. The calculations suggest that the phase equilibrium boundary occurs between 11.5 and
12.5 GPa around 1500 K. Its slope is still not well constrained.
Received: 20 September 2000 / Accepted: 17 January 2001 相似文献
6.
Hugh S. C. O'Neill 《Contributions to Mineralogy and Petrology》1998,133(3):284-296
The partitioning of Fe2+ and Mn2+ between (Fe, Mn)TiO3 and (Fe, Mn)2SiO4 solid solutions in the system FeO-MnO-TiO2-SiO2 has been experimentally investigated at 1100 ∘C and pressures of 1 bar and 25 kbar, over a wide range of Fe/Mn ratios, using electron microprobe analysis of quenched run
products. The ilmenite solid solution in this system is within analytical uncertainty a simple binary between FeTiO3 and MnTiO3, but the olivine solid solution appears to contain up to 2.5 wt% TiO2. The Fe-Mn partitioning results constrain precisely the difference in the thermodynamic mixing properties of the two solid
solutions. If the mixing properties of (Fe, Mn)2SiO4 solid solutions are assumed to be ideal, as experimentally determined by Schwerdtfeger and Muan (1966), then the ilmenite
is a regular, symmetric solution with W
ilm
Fe-Mn=1.8±0.1 kJ mol−1. The quoted uncertainty does not include the contribution from the uncertainty in the mixing properties of the olivine solution,
which is estimated to be ±1.8 kJ mol−1, and which therefore dominates the uncertainty in the present results. Nevertheless, this result is in good agreement with
the previous experimental study of O'Neill et al. (1989), who obtained W
ilm
Fe-Mn=2.2±0.3 kJ mol−1 from an independent method. The results provide another item of empirical evidence supporting the proposition that solid
solutions between isostructural end-members, in which order-disorder effects are not important, generally have simple thermodynamic
mixing properties, with little asymmetry, modest excess entropies, and excess enthalpies approximately proportional to the
difference in the molar volumes of the end-members.
Received: 11 February 1998 / Accepted: 29 June 1998 相似文献
7.
Tibor Gasparik 《Contributions to Mineralogy and Petrology》1996,124(2):139-153
Melting relations on the enstatite−diopside (En, Mg2Si2O6−Di, CaMgSi2O6) join, including the compositions of crystalline phases and melts coexisting along the solidi, were experimentally determined
in the pressure range 70–224 kbar with a split-sphere anvil apparatus (USSA-2000). Melting is peritectic in enstatite-rich
compositions at 70–124 kbar (1840–2100° C) and eutectic at higher pressures, while the diopside-rich clinopyroxene melts azeotropically
at 70–165 kbar and up to 300° C lower temperatures than the eutectic. Orthopyroxene is replaced with enstatite-rich clinopyroxene
at 120 kbar and 2090°C. First garnet with 17 mol% Di forms on the solidus at 158 kbar and 2100° C. Two garnets coexist on
the solidus at 165–183 kbar and 2100° C, garnet coexists with CaSiO3 perovskite at 183–224 kbar (2100–2230° C) and two coexisting perovskites are stable at higher pressures. The melting curve
of diopside was determined at 80–170 kbar; the slope becomes negative at 140 kbar and 2155° C. At 170 kbar and 2100° C, diopside
with 96% Di breaks down to garnet with 89% Di and CaSiO3 perovskite. The new data were used to calculate an improved temperature-pressure phase diagram for the CMAS system, which
can be useful for estimating the mineralogy of the Earth's upper mantle.
Received: 15 October 1994 / Accepted: 15 October 1995 相似文献
8.
The exchange equilibrium
was studied by reversal experiments as a function of temperature (650 ≤ T ≤ 1000 °C), pressure (10 ≤ P ≤ 20 kbar), and chemical composition. Experiments were performed in a piston-cylinder apparatus using starting mixtures consisting
of 95% garnet and 5% ilmenite. At the lower temperatures, 3–5% PbO flux was added to the reactants. The PbO was reduced to
metallic lead by the graphite of the capsules. The EMP analysis shows that ilmenite is essentially a solid solution of FeTiO3 and MnTiO3 with up to 4.5 mol% Fe2O3 (for Fe-rich compositions). Garnet is compositionally close to (Fe,Mn)3 Al2Si3O12 but apparently contains up to 1.0 wt% TiO2. As garnet was usually analyzed within 5–15 μm distance from ilmenite grains, the Ti measured in garnet appears to be largely
an analytical artifact (due to secondary fluorescence). This was confirmed by analyzing profiles across a couple constructed
from ilmenite and Ti-free garnet. The more than 100 exchange runs indicate that the distribution coefficient KD [=(X
Mn
gnt·X
Fe
ilm)/(X
Fe
gnt·X
Mn
ilm)] is essentially independent of P and decreases with T. With a few exceptions at Mn-rich compositions, the present results are consistent with previous studies on the Fe-Mn partitioning
between garnet and ilmenite. Contrary to previous studies, however, the narrow experimental brackets obtained during the present
calibration constrain that, at constant T, KD is larger for Mn-rich compositions than for Fe-rich ones. This compositional dependence of KD will complicate garnet-ilmenite geothermometry. Mutually consistent activity models for Fe-Mn garnet and ilmenite, based
on a thermodynamic analysis of the present results and other phase equilibria studies in the system Fe-MnO-Al2O3-TiO2-SiO2-O2, will be presented in a following contribution (M. Engi and A. Feenstra, in preparation).
Received: 12 September 1996 / Accepted: 11 December 1997 相似文献
9.
Using lattice dynamic modelling of pure MgSiO3 clinopyroxenes, we have be able to simulate the properties of both the low-clino (P21/c) and a high-density-clino (C2/c) phases and our results are comparable with the high pressure (HP) X-ray study of these
phases (Angel et al. 1992). The transition between the two phases is predicted to occur at 6GPa. The volume variation with
pressure for both phases is described by a third-order Birch-Murnaghan equation of state with the parameters V
0
low=31.122 cm3·mol−1, K
T0
low= 107.42 GPa, K′
T0
low=5.96, V
0
high=30.142 cm3·mol–1, K
T0
high102.54 GPa and K′
T0
high=8.21. The change in entropy between the two modelled phases at 6GPa is ΔS
6
Gpa=−1.335 J·mol−1·K−1 and the equivalent change in volume is ΔV
6
GPa=−0.92 cm3·mol−1, from which the gradient of the phase boundary δP/δT is 0.0014 GPa·K−1. The variation of the bulk modulus with pressure was also determined from the modelled elastic constants and compares very
well with the EOS data. The reported Lehmann discontinuity, ∼220 km depth and pressure of 7.11Gpa, has an increase in the
seismic compressional wave velocity, v
p
, of 7.14% using the data given for PREM (Anderson 1989). At a pressure of 7GPa any phase transition of MgSiO3 pyroxene would be between ortho (Pbca) and high-clino. We find the value of v
p
at 7GPa, for modelled orthoenstatite (Pbca), is 8.41 km·sec−1 and that for the modelled high-clino phase at 7GPa is 8.93 km·sec−1, giving a dv
p
/v
p
of 6.18%.
Received: July 26, 1996 / Revised, accepted: September 27, 1996 相似文献
10.
Tomoo Katsura Sho Yokoshi Kazuyuki Kawabe Anton Shatskiy Maki Okube Hiroshi Fukui Eiji Ito Akifumi Nozawa Ken-ichi Funakoshi 《Physics and Chemistry of Minerals》2007,34(4):249-255
The electrical conductivity of (Mg0.93Fe0.07)SiO3 ilmenite was measured at temperatures of 500–1,200 K and pressures of 25–35 GPa in a Kawai-type multi-anvil apparatus equipped
with sintered diamond anvils. In order to verify the reliability of this study, the electrical conductivity of (Mg0.93Fe0.07)SiO3 perovskite was also measured at temperatures of 500–1,400 K and pressures of 30–35 GPa. The pressure calibration was carried
out using in situ X-ray diffraction of MgO as pressure marker. The oxidation conditions of the samples were controlled by
the Fe disk. The activation energy at zero pressure and activation volume for ilmenite are 0.82(6) eV and −1.5(2) cm3/mol, respectively. Those for perovskite were 0.5(1) eV and −0.4(4) cm3/mol, respectively, which are in agreement with the experimental results reported previously. It is concluded that ilmenite
conductivity has a large pressure dependence in the investigated P–T range. 相似文献
11.
M. Akaogi H. Kojitani H. Yusa R. Yamamoto M. Kido K. Koyama 《Physics and Chemistry of Minerals》2005,32(8-9):603-613
Phase transitions in MgGeO3 and ZnGeO3 were examined up to 26 GPa and 2,073 K to determine ilmenite–perovskite transition boundaries. In both systems, the perovskite
phases were converted to lithium niobate structure on release of pressure. The ilmenite–perovskite boundaries have negative
slopes and are expressed as P(GPa)=38.4–0.0082T(K) and P(GPa)=27.4−0.0032T(K), respectively, for MgGeO3 and ZnGeO3. Enthalpies of SrGeO3 polymorphs were measured by high-temperature calorimetry. The enthalpies of SrGeO3 pseudowollasonite–walstromite and walstromite–perovskite transitions at 298 K were determined to be 6.0±8.6 and 48.9±5.8 kJ/mol,
respectively. The calculated transition boundaries of SrGeO3, using the measured enthalpy data, were consistent with the boundaries determined by previous high-pressure experiments.
Enthalpy of formation (ΔH
f°) of SrGeO3 perovskite from the constituent oxides at 298 K was determined to be −73.6±5.6 kJ/mol by calorimetric measurements. Thermodynamic
analysis of the ilmenite–perovskite transition boundaries in MgGeO3 and ZnGeO3 and the boundary of formation of SrSiO3 perovskite provided transition enthalpies that were used to estimate enthalpies of formation of the perovskites. The ΔH
f° of MgGeO3, ZnGeO3 and SrSiO3 perovskites from constituent oxides were 10.2±4.5, 33.8±7.2 and −3.0±2.2 kJ/mol, respectively. The present data on enthalpies
of formation of the above high-pressure perovskites were combined with published data for A2+B4+O3 perovskites stable at both atmospheric and high pressures to explore the relationship between ΔH
f° and ionic radii of eightfold coordinated A2+ (R
A) and sixfold coordinated B4+ (R
B) cations. The results show that enthalpy of formation of A2+B4+O3 perovskite increases with decreasing R
A and R
B. The relationship between the enthalpy of formation and tolerance factor (
R
o: O2− radius) is not straightforward; however, a linear relationship was found between the enthalpy of formation and the sum of
squares of deviations of A2+ and B4+ radii from ideal sizes in the perovskite structure. A diagram showing enthalpy of formation of perovskite as a function of
A2+ and B4+ radii indicates a systematic change with equienthalpy curves. These relationships of ΔH
f° with R
A and R
B can be used to estimate enthalpies of formation of perovskites, which have not yet been synthesized. 相似文献
12.
Apurva Mehta Kurt Leinenweber Alexandra Navrotsky Masaki Akaogi 《Physics and Chemistry of Minerals》1994,21(4):207-212
A calorimetric study of the ilmenite and lithium niobate polymorphs of FeTiO3 was undertaken to assess the high-pressure stabilities of these phases. Ilmenite is known to be the stable phase at ambient pressure, but the lithium niobate form may be a quench phase from a perovskite form which has been previously observed in situ at high pressure.In this study, the lithium niobate phase of FeTiO3 was synthesized from an ilmenite starting material at 15– 16 GPa and 1473 K, using a uniaxial split-sphere high-pressure apparatus (USSA 2000). The energetics of the ilmenite to lithium niobate transformation were investigated through transposed-temperature drop calorimetry. The heat of back-transformation of lithium niobate to ilmenite was measured by dropping the sample in argon from ambient conditions to a temperature where the transformation occurs spontaneously. In drops made at 977 K, an intermediate x-ray amorphous phase was encountered. At 1273 K, the transformation went to completion. A value of -13.5±1.2 kJ/mol was obtained for the heat of transformation. 相似文献
13.
V. M. Gurevich M. A. Ryumin A. V. Tyurin L. N. Komissarova 《Geochemistry International》2012,50(8):702-710
The heat capacity of gadolinium orthophosphate (GdPO4) measured in the temperature range 11.15–344.11 K by adiabatic calorimetry and available literature data were used to calculate its thermodynamic functions at 0–1600 K. At 298.15 K, these functions are as follows: C p 0(298.15 K) = 101.85 ± 0.05 J K−1 mol−1, S 0(298.15 K) = 123.82 ± 0.18 J K−1 mol−1, H 0(298.15 K)–H 0(0) = 17.250 ± 0.012 kJ mol−1, and Φ 0(298.15 K) = 65.97 ± 0.18 J K−1 mol−1 The calculated Gibbs free energy of formation from the elements of GdPO4 is Δ f G 0 (298.15 K) = −1844.3 ± 4.7 kJ mol−1. 相似文献
14.
Márian Urban Rainer Thomas Vratislav Hurai Patrik Koneèný Martin Chovan 《Mineralium Deposita》2006,40(8):867-873
CO2 inclusions with density up to 1,197 kg m−3 occur in quartz–stibnite veins hosted in the low-grade Palaeozoic basement of the Gemericum tectonic unit in the Western Carpathians. Raman microanalysis corroborated CO2 as dominant gas species accompanied by small amounts of nitrogen (<7.3 mol%) and methane (<2.5 mol%). The superdense CO2 phase exsolved from an aqueous bulk fluid at temperatures of 183–237°C and pressures between 1.6 and 3.5 kbar, possibly up to 4.5 kbar. Low thermal gradients (∼12–13°C km−1) and the CO2–CH4–N2 fluid composition rule out a genetic link with the subjacent Permian granites and indicate an external, either metamorphogenic (oxidation of siderite, dedolomitization) or lower crustal/mantle, source of the ore-forming fluids.According to microprobe U–Pb–Th dating of monazite, the stibnite-bearing veins formed during early Cretaceous thrusting of the Gemeric basement over the adjacent Veporic unit. The 15- to 18-km depth of burial estimated from the fluid inclusion trapping PT parameters indicates a 8- to 11-km-thick Upper Palaeozoic–Jurassic accretionary complex overlying the Gemeric basement and its Permo-Triassic autochthonous cover. 相似文献
15.
V. M. Gurevich O. L. Kuskov N. N. Smirnova K. S. Gavrichev A. V. Markin 《Geochemistry International》2009,47(12):1170-1179
The heat capacity of eskolaite Cr2O3(c) was determined by adiabatic vacuum calorimetry at 11.99–355.83 K and by differential calorimetry at 320–480 K. Experimental
data of the authors and data compiled from the literature were applied to calculate the heat capacity, entropy, and the enthalpy
change of Cr2O3 within the temperature range of 0–1800 K. These functions have the following values at 298.15 K: C
p
0 (298.15) = 121.5 ± 0.2 J K−1mol−1, S
0(298.15) = 80.95 ± 0.14 J K−1mol−1, and H
0(298.15)-H
0(0) = 15.30±0.02 kJ mol−1. Data were obtained on the transitions from the antiferromagnetic to paramagnetic states at 228–457 K; it was determined
that this transition has the following parameters: Neel temperature T
N
= 307 K, Δ
tr
S = 6.11 ± 0.12 J K−1mol−1 and δ
tr
H = 1.87 ± 0.04 kJ mol−1. 相似文献
16.
Three reactions limiting the stability field of the di-trioctahedral chlorite cookeite in the presence of quartz, in the system
Li2O−Al2O3−SiO2−H2O (LASH) have been reversed in the range 290–480°C, 0.8–14 kbar, using natural material close to the end member composition.
Combining our results with known and estimated thermodynamic properties of the other minerals belonging to the LASH system,
the enthalpy (-8512200 J/mol) and the entropy (504.8 J/mol*K) of cookeite are calculated by a feasible solution space approach. The knowledge of these values allowed us to draw the
first P−T phase diagram involving both the hydrated Li-aluminosilicates cookeite and bikitaite, which is applicable to a large
variety of natural rock systems. The low thermal extent of the stability field of cookeite+quartz (260–480°C) makes cookeite
a valuable indicator of low temperature conditions within a wide range of pressure (1–14 kbar). 相似文献
17.
I. E. Paukov N. K. Moroz Yu. A. Kovalevskaya I. A. Belitsky 《Physics and Chemistry of Minerals》2002,29(4):300-306
The heat capacity of paranatrolite and tetranatrolite with a disordered distribution of Al and Si atoms has been measured
in the temperature range of 6–309 K using the adiabatic calorimetry technique. The composition of the samples is represented
with the formula (Na1.90K0.22Ca0.06)[Al2.24Si2.76O10]·nH2O, where n=3.10 for paranatrolite and n=2.31 for tetranatrolite. For both zeolites, thermodynamic functions (vibrational entropy, enthalpy, and free energy function)
have been calculated. At T=298.15 K, the values of the heat capacity and entropy are 425.1 ± 0.8 and 419.1 ±0.8 J K−1 mol−1 for paranatrolite and 381.0 ± 0.7 and 383.2 ± 0.7 J K−1 mol−1 for tetranatrolite.
Thermodynamic functions for tetranatrolite and paranatrolite with compositions corrected for the amount of extraframework
cations and water molecules have also been calculated. The calculation for tetranatrolite with two water molecules and two
extraframework cations per formula yields: C
p
(298.15)=359.1 J K−1 mol−1, S(298.15) −S(0)=362.8 J K−1 mol−1. Comparing these values with the literature data for the (Al,Si)-ordered natrolite, we can conclude that the order in tetrahedral
atoms does not affect the heat capacity. The analysis of derivatives dC/dT for natrolite, paranatrolite, and tetranatrolite has indicated that the water- cations subsystem within the highly hydrated
zeolite may become unstable at temperatures above 200 K.
Received: 30 July 2001 / Accepted: 15 November 2001 相似文献
18.
The heat capacity (C
p
) of dmitryivanovite synthesized with a cubic press was measured in the temperature range of 5–664 K using the heat capacity
option of a physical properties measurement system and a differential scanning calorimeter. The entropy of dmitryivanovite
at standard temperature and pressure (STP) was calculated to be 110.1 ± 1.6 J mol−1 K−1 from the measured C
p
data. With the help of new phase equilibrium experiments done at 1.5 GPa, the phase transition boundary between krotite and
dmitryivanovite was best represented by the equation: P (GPa) = −2.1825 + 0.0025 T (K). From the temperature intercept of this phase boundary and other available thermodynamic data
for krotite and dmitryivanovite, the enthalpy of formation and Gibbs free energy of formation of dmitryivanovite at STP were
calculated to be −2326.7 ± 2.1 and −2,208.1 ± 2.1 kJ mol−1, respectively. It is also inferred that dmitryivanovite is the stable CaAl2O4 phase at STP and has a wide stability field at high pressures whereas the stability field of krotite is located at high temperatures
and relatively low pressures. This conclusion is consistent with natural occurrences (in Ca–Al-rich inclusions) of dmitryivanovite
and krotite, where the former is interpreted as the shock metamorphic product of originally present krotite. 相似文献
19.
K.-D. Grevel A. Navrotsky W. A. Kahl D. W. Fasshauer J. Majzlan 《Physics and Chemistry of Minerals》2001,28(7):475-487
Calorimetric and P–V–T data for the high-pressure phase Mg5Al5Si6O21(OH)7 (Mg-sursassite) have been obtained. The enthalpy of drop solution of three different samples was measured by high-temperature
oxide melt calorimetry in two laboratories (UC Davis, California, and Ruhr University Bochum, Germany) using lead borate (2PbO·B2O3) at T=700 ∘C as solvent. The resulting values were used to calculate the enthalpy of formation from different thermodynamic datasets;
they range from −221.1 to −259.4 kJ mol−1 (formation from the oxides) respectively −13892.2 to −13927.9 kJ mol−1 (formation from the elements). The heat capacity of Mg5Al5Si6O21(OH)7 has been measured from T=50 ∘C to T=500 ∘C by differential scanning calorimetry in step-scanning mode. A Berman and Brown (1985)-type four-term equation represents
the heat capacity over the entire temperature range to within the experimental uncertainty: C
P
(Mg-sursassite) =(1571.104 −10560.89×T
−0.5−26217890.0 ×T
−2+1798861000.0×T
−3) J K−1 mol−1 (T in K). The P
V
T behaviour of Mg-sursassite has been determined under high pressures and high temperatures up to 8 GPa and 800 ∘C using a MAX 80 cubic anvil high-pressure apparatus. The samples were mixed with Vaseline to ensure hydrostatic pressure-transmitting
conditions, NaCl served as an internal standard for pressure calibration. By fitting a Birch-Murnaghan EOS to the data, the
bulk modulus was determined as 116.0±1.3 GPa, (K
′=4), V
T,0
=446.49 3 exp[∫(0.33±0.05) × 10−4 + (0.65±0.85)×10−8
T dT], (K
T/T)
P
= −0.011± 0.004 GPa K−1. The thermodynamic data obtained for Mg-sursassite are consistent with phase equilibrium data reported recently (Fockenberg
1998); the best agreement was obtained with Δf
H
0
298 (Mg-sursassite) = −13901.33 kJ mol−1, and S
0
298 (Mg-sursassite) = 614.61 J K−1 mol−1.
Received: 21 September 2000 / Accepted: 26 February 2001 相似文献
20.
The low-temperature heat capacity (C
P) of stishovite (SiO2) synthesized with a multi-anvil device was measured over the range of 5–303 K using the heat capacity option of a physical
properties measurement system (PPMS) and around ambient temperature using a differential scanning calorimeter (DSC). The entropy
of stishovite at standard temperature and pressure calculated from DSC-corrected PPMS data is 24.94 J mol−1 K−1, which is considerably smaller (by 2.86 J mol−1 K−1) than that determined from adiabatic calorimetry (Holm et al. in Geochimica et Cosmochimica Acta 31:2289–2307, 1967) and about 4% larger than the recently reported value (Akaogi et al. in Am Mineral 96:1325–1330, 2011). The coesite–stishovite phase transition boundary calculated using the newly determined entropy value of stishovite agrees
reasonably well with the previous experimental results by Zhang et al. (Phys Chem Miner 23:1–10, 1996). The calculated phase boundary of kyanite decomposition reaction is most comparable with the experimental study by Irifune
et al. (Earth Planet Sci Lett 77:245–256, 1995) at low temperatures around 1,400 K, and the calculated slope in this temperature range is mostly consistent with that determined
by in situ X-ray diffraction experiments (Ono et al. in Am Mineral 92:1624–1629, 2007). 相似文献