Calorimetric study of olivine solid solutions in the system Mg2SiO4-Fe2SiO4     

H. Kojitani  M. Akaogi 《Physics and Chemistry of Minerals》1994,20(8):536-540

Solution enthalpies of synthetic olivine solid solutions in the system Mg₂SiO₄-Fe₂SiO₄ have been measured in molten 2PbO·B₂O₃ at 979 K. The enthalpy data show that olivine solid solutions have a positive enthalpy of mixing and the deviation from ideality is approximated as symmetric with respect to composition, in contrast to the previous study. Applying the symmetric regular solution model to the present enthalpy data, the interaction parameter of ethalpy (W_H) is estimated to be 5.3±1.7 kJ/mol (one cation site basis). Using this W_h and the published data on excess free energy of mixing, the nonideal parameter of entropy (W_s) of olivine solid solutions is estimated as 0.6±1.5 J/mol·K.  相似文献   

Calorimetric study on high-pressure transitions in KAlSi<Subscript>3</Subscript>O<Subscript>8</Subscript>   总被引：1，自引：1，他引：0  

M.?AkaogiEmail author  N.?Kamii  A.?Kishi  H.?Kojitani 《Physics and Chemistry of Minerals》2004,31(2):85-91

KAlSi₃O₈ sanidine dissociates into a mixture of K₂Si₄O₉ wadeite, Al₂SiO₅ kyanite and SiO₂ coesite, which further recombine into KAlSi₃O₈ hollandite with increasing pressure. Enthalpies of KAlSi₃O₈ sanidine and hollandite, K₂Si₄O₉ wadeite and Al₂SiO₅ kyanite were measured by high-temperature solution calorimetry. Using the data, enthalpies of transitions at 298 K were obtained as 65.1 ± 7.4 kJ mol^–1 for sanidine wadeite + kyanite + coesite and 99.3 ± 3.6 kJ mol^–1 for wadeite + kyanite + coesite hollandite. The isobaric heat capacity of KAlSi₃O₈ hollandite was measured at 160–700 K by differential scanning calorimetry, and was also calculated using the Kieffer model. Combination of both the results yielded a heat-capacity equation of KAlSi₃O₈ hollandite above 298 K as C_p=3.896 × 10²–1.823 × 10³T^–0.5–1.293 × 10⁷T^–2+1.631 × 10⁹T^–3 (C_p in J mol^–1 K^–1, T in K). The equilibrium transition boundaries were calculated using these new data on the transition enthalpies and heat capacity. The calculated transition boundaries are in general agreement with the phase relations experimentally determined previously. The calculated boundary for wadeite + kyanite + coesite hollandite intersects with the coesite–stishovite transition boundary, resulting in a stability field of the assemblage of wadeite + kyanite + stishovite below about 1273 K at about 8 GPa. Some phase–equilibrium experiments in the present study confirmed that sanidine transforms directly to wadeite + kyanite + coesite at 1373 K at about 6.3 GPa, without an intervening stability field of KAlSiO₄ kalsilite + coesite which was previously suggested. The transition boundaries in KAlSi₃O₈ determined in this study put some constraints on the stability range of KAlSi₃O₈ hollandite in the mantle and that of sanidine inclusions in kimberlitic diamonds.  相似文献   

Vibrational mode analysis and heat capacity calculation of K2SiSi3O9-wadeite     

Linlin Chang  Xi Liu  Hong Liu  Hiroshi Kojitani  Sicheng Wang 《Physics and Chemistry of Minerals》2013,40(7):563-574

The phonon dispersions and vibrational density of state (VDoS) of the K₂SiSi₃O₉-wadeite (Wd) have been calculated by the first-principles method using density functional perturbation theory. The vibrational frequencies at the Brillouin zone center are in good correspondence with the Raman and infrared experimental data. The calculated VDoS was then used in conjunction with a quasi-harmonic approximation to compute the isobaric heat capacity (C _P ) and vibrational entropy ( $S_{298}^{0}$ ), yielding C _P (T) = 469.4(6) ? 2.90(2) × 10³  T ^?0.5 ? 9.5(2) × 10⁶  T ^?2 + 1.36(3) × 10⁹  T ^?3 for the T range of 298–1,000 K and $S_{298}^{0}$  = 250.4 J mol^?1 K^?1. In comparison, these thermodynamic properties were calculated by a second method, the classic Kieffer’s lattice vibrational model. On the basis of the vibrational mode analysis facilitated by the first-principles simulation result, we developed a new Kieffer’s model for the Wd phase. This new Kieffer’s model yielded C _P (T) = 475.9(6) ? 3.15(2) × 10³  T ^?0.5 – 8.8(2) × 10⁶  T ^?2 + 1.31(3) × 10⁹  T ^?3 for the T range of 298–1,000 K and $S_{298}^{0}$  = 249.5(40) J mol^?1 K^?1, which are in good agreement both with the results from our first method containing the component of the first-principles calculation and with some calorimetric measurements in the literature.  相似文献   

High-pressure phase relations in the system CaAl4Si2O11–NaAl3Si3O11 with implication for Na-rich CAS phase in shocked Martian meteorites     

M. Akaogi  M. Haraguchi  K. Nakanishi  H. Ajiro  H. Kojitani 《Earth and Planetary Science Letters》2010,289(3-4):503-508

High-pressure phase relations in the system NaAl₃Si₃O₁₁–CaAl₄Si₂O₁₁ were examined at 13–23 GPa and 1600–1900 °C, using a multianvil apparatus. A Ca-aluminosilicate with CaAl₄Si₂O₁₁ composition, designated CAS phase, is stable above about 13 GPa at 1600 °C. In the system NaAl₃Si₃O₁₁–CaAl₄Si₂O₁₁, the CAS phase dissolving NaAl₃Si₃O₁₁ component coexists with jadeite, corundum and stishovite below 22 GPa, above which the CAS phase coexists with Na-rich calcium ferrite, corundum and stishovite. At 1600 °C, the solubility of NaAl₃Si₃O₁₁ component in the CAS solid solution increases with increasing pressure up to about 50 mol% at about 22 GPa, above which the solubility decreases with pressure. The maximum solubility of NaAl₃Si₃O₁₁ component in the CAS phase increases with temperature up to around 70 mol% at 1900 °C at 22 GPa. The dissociation of NaAlSi₂O₆ jadeite to NaAlSiO₄ calcium ferrite plus stishovite occurs at about 22 GPa. Lattice parameters of the CAS phase with the hexagonal Ba-ferrite structure change with increase of the NaAl₃Si₃O₁₁ component: a-axis decreases and c-axis slightly increases, resulting in decrease of molar volume. Enthalpies of the CAS solid solutions were measured by high-temperature drop-solution calorimetry techniques. The results show that enthalpy of hypothetical NaAl₃Si₃O₁₁ CAS phase is much higher than the mixture of NaAlSi₂O₆ jadeite, corundum and stishovite and is close to that of the mixture of NaAlSiO₄ calcium ferrite, corundum and stishovite. When we adopt the Na:Ca ratio of 75:25 of the natural Na-rich CAS phase in a shocked Martian meteorite, Zagami, the phase relations determined above suggest that the natural CAS phase crystallized from melt at pressure around 22 GPa and temperature close to or higher than 2000–2200 °C. The inferred P, T conditions are consistent with those estimated using other high-pressure minerals in the shocked meteorite.  相似文献   

Raman spectroscopy and heat capacity measurement of calcium ferrite type MgAl2O4 and CaAl2O4     

Kojitani  H.  Nishimura  K.  Kubo  A.  Sakashita  M.  Aoki  K.  Akaogi  M. 《Physics and Chemistry of Minerals》2003,30(7):409-415

Raman spectroscopy of calcium ferrite type MgAl₂O₄ and CaAl₂O₄ and heat capacity measurement of CaAl₂O₄ calcium ferrite were performed. The heat-capacity of CaAl₂O₄ calcium ferrite measured by a differential scanning calorimeter (DSC) was represented as C_P(T)=190.6–1.116 × 10⁷T^–2 + 1.491 × 10⁹T^–3 above 250 K (T in K). The obtained Raman spectra were applied to lattice dynamics calculation of heat capacity using the Kieffer model. The calculated heat capacity for CaAl₂O₄ calcium ferrite showed good agreement with that by the DSC measurement. A Kieffer model calculation for MgAl₂O₄ calcium ferrite similar to that for CaAl₂O₄ calcium ferrite was made to estimate the heat capacity of the former. The heat capacity of MgAl₂O₄ calcium ferrite was represented as C_P(T)=223.4–1352T ^–0.5 – 4.181 × 10⁶T ^–2 + 4.300 × 10⁸T ^–3 above 250 K. The calculation also gave approximated vibrational entropies at 298 K of calcium ferrite type MgAl₂O₄ and CaAl₂O₄ as 97.6 and 114.9 J mol^–1 K^–1, respectively.  相似文献   

High-pressure phase behaviors of ZnTiO3: ilmenite–perovskite transition,decomposition of perovskite into constituent oxides,and perovskite–lithium niobate transition     

M. Akaogi  K. Abe  H. Yusa  H. Kojitani  D. Mori  Y. Inaguma 《Physics and Chemistry of Minerals》2015,42(6):421-429

  相似文献   

High-pressure transitions and thermochemistry of MGeO3 (M=Mg, Zn and Sr) and Sr-silicates: systematics in enthalpies of formation of A2+B4+O3 perovskites     

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   

Phase relations on the diopside-jadeite-hedenbergite join up to 24 GPa and stability of Na-bearing majoritic garnet   总被引：1，自引：0，他引：1  

Andrey V. Bobrov  Hiroshi Kojitani  Yuriy A. Litvin 《Geochimica et cosmochimica acta》2008,72(9):2392-2408

Phase relations on the diopside (Di)-hedenbergite (Hd)-jadeite (Jd) system modeling mineral associations of natural eclogites were studied for the compositions (mol %) Di₇₀Jd₃₀, Di₅₀Jd₅₀, Di₃₀Jd₇₀, Di₂₀Hd₈₀, and Di₄₀Hd₁₀Jd₅₀ using a toroidal anvil-with-hole (7 GPa) and a Kawai-type 6-8 multianvil apparatus (12-24 GPa). We established that Di, Hd, and Jd form complete series of solid solutions at 7 GPa, and melting temperatures of pure Di (1980 °C) and Jd (1870 °C) for that pressure were estimated experimentally. The melting temperature for the Di₅₀Jd₅₀ composition at 15.5 GPa is 2270 °C. The appearance of garnet is clearly dependent on initial clinopyroxene composition: at 1600 °C the first garnet crystals are observed at 13.5 GPa in the jadeite-rich part of the system (Di₃₀Jd₇₀), whereas diopside-rich starting material (Di₇₀Jd₃₀) produces garnet only above 17 GPa. The proportion of garnet increases rapidly above 18 GPa as pyroxene dissolves in the garnet structure and pyroxene-free garnetites are produced from diopside-rich starting materials. In all experiments, garnet coexists with stishovite (St). At a pressure above 18 GPa, pyroxene is completely replaced by an assemblage of majorite (Maj) + St + CaSiO₃-perovskite (Ca-Pv) in Ca-rich systems, whereas Maj is associated with almost pure Jd up to a pressure of 21.5 GPa. Above ∼22 GPa, Maj, and St are associated with NaAlSiO₄ with calcium ferrite structure (Cf). We established that an Hd component also spreads the range of pyroxene stability up to 20 GPa. In the Di₇₀Jd₃₀ system at 24 GPa an assemblage of Maj + Ca-Pv + MgSiO₃ with ilmenite structure (Mg-Il) was obtained. The experimentally established correlation between Na, Si, and Al contents in Maj and pressure in Grt(Maj)-pyroxene assemblages, may be the basis for a “majorite” geobarometer. The results of our experiments are applicable to the upper mantle and the transition zone of the Earth (400-670 km), and demonstrate a wide range of transformations from eclogite to perovskite-bearing garnetite. In addition, the mineral associations obtained from the experiments allowed us to simulate parageneses of inclusions in diamonds formed under the conditions of the transition zone and the lower mantle.  相似文献   

Low-temperature heat capacities,entropies and enthalpies of Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript> polymorphs,and α−β−γ and post-spinel phase relations at high pressure     

M. Akaogi  H. Takayama  H. Kojitani  H. Kawaji  T. Atake 《Physics and Chemistry of Minerals》2007,34(3):169-183

The low-temperature isobaric heat capacities (C _p) of β- and γ-Mg₂SiO₄ were measured at the range of 1.8–304.7 K with a thermal relaxation method using the Physical Property Measurement System. The obtained standard entropies (S°₂₉₈) of β- and γ-Mg₂SiO₄ are 86.4 ± 0.4 and 82.7 ± 0.5 J/mol K, respectively. Enthalpies of transitions among α-, β- and γ-Mg₂SiO₄ were measured by high-temperature drop-solution calorimetry with gas-bubbling technique. The enthalpies of the α−β and β−γ transitions at 298 K (ΔH°₂₉₈) in Mg₂SiO₄ are 27.2 ± 3.6 and 12.9 ± 3.3 kJ/mol, respectively. Calculated α−β and β−γ transition boundaries were generally consistent with those determined by high-pressure experiments within the errors. Combining the measured ΔH°₂₉₈ and ΔS°₂₉₈ with selected data of in situ X-ray diffraction experiments at high pressure, the ΔH°₂₉₈ and ΔS°₂₉₈ of the α−β and β−γ transitions were optimized. Calculation using the optimized data tightly constrained the α−β and β−γ transition boundaries in the P, T space. The slope of α−β transition boundary is 3.1 MPa/K at 13.4 GPa and 1,400 K, and that of β−γ boundary 5.2 MPa/K at 18.7 GPa and 1,600 K. The post-spinel transition boundary of γ-Mg₂SiO₄ to MgSiO₃ perovskite plus MgO was also calculated, using the optimized data on γ-Mg₂SiO₄ and available enthalpy and entropy data on MgSiO₃ perovskite and MgO. The calculated post-spinel boundary with a Clapeyron slope of −2.6 ± 0.2 MPa/K is located at pressure consistent with the 660 km discontinuity, considering the error of the thermodynamic data.  相似文献   

Aluminum substitution mechanisms in perovskite-type MgSiO<Subscript>3</Subscript>: an investigation by Rietveld analysis     

Hiroshi Kojitani  Tomoo Katsura  Masaki Akaogi 《Physics and Chemistry of Minerals》2007,34(4):257-267

Al-containing MgSiO₃ perovskites of four different compositions were synthesized at 27 GPa and 1,873 K using a Kawai-type high-pressure apparatus: stoichiometric compositions of Mg_0.975Si_0.975Al_0.05O₃ and Mg_0.95Si_0.95Al_0.10O₃ considering only coupled substitution Mg²⁺ + Si⁴⁺ = 2Al³⁺, and nonstoichiometric compositions of Mg_0.99Si_0.96Al_0.05O_2.985 and Mg_0.97Si_0.93Al_0.10O_2.98 taking account of not only the coupled substitution but also oxygen vacancy substitution 2Si⁴⁺ = 2Al³⁺ + V_O¨. Using the X-ray diffraction profiles, Rietveld analyses were performed, and the results were compared between the stoichiometric and nonstoichiometric perovskites. Lattice parameter–composition relations, in space group Pbnm, were obtained as follows. The a parameters of both of the stoichiometric and nonstoichiometric perovskites are almost constant in the X _Al range of 0–0.05, where X _Al is Al number on the basis of total cation of two (X _Al = 2Al/(Mg + Si + Al)), and decrease with further increasing X _Al. The b and c parameters of the stoichiometric perovskites increase linearly with increasing Al content. The change in the b parameter of the nonstoichiometric perovskites with Al content is the same as that of the stoichiometric perovskites within the uncertainties. The c parameter of the nonstoichiometric perovskites is slightly smaller than that of the stoichiometric perovskites at X _Al of 0.10, though they are the same as each other at X _Al of 0.05. The Si(Al)–O1 distance, Si(Al)–O1–Si(Al) angle and minimum Mg(Al)–O distance of the nonstoichiometric perovskites keep almost constant up to X _Al of 0.05, and then the Si(Al)–O1 increases and both of the Si(Al)–O1–Si(Al) angle and minimum Mg(Al)–O decrease with further Al substitution. These results suggest that the oxygen vacancy substitution may be superior to the coupled substitution up to X _Al of about 0.05 and that more Al could be substituted only by the coupled substitution at 27 GPa. The Si(Al)–O1 distance and one of two independent Si(Al)–O2 distances in Si(Al)O₆ octahedra in the nonstoichiometric perovskites are always shorter than those in the stoichiometric perovskite at the same Al content. These results imply that oxygen defects may exist in the nonstoichiometric perovskites and distribute randomly.  相似文献