The role of hydrogen bonding in the thermal expansion and dehydration of brushite,di-calcium phosphate dihydrate

The unit-cell and atomic parameters of perdeuterated brushite have been extracted from Rietveld analysis of neutron powder diffraction data within the temperature range 4.2 to 470 K. The thermal expansion of brushite is anisotropic, with the largest expansion along the b axis due principally to the effect of the O(1)···D(4) and O(3)···D(2) hydrogen bonds. Expansion along the c axis, influenced by the Ow1···D(5) interwater hydrogen bond, is also large. The high temperature limits for the expansion coefficients for the unit-cell edges a, b and c are 9.7(5) × 10^–6, 3.82(9) × 10^–5 and 5.54(5) × 10^–5 K^–1, respectively, and for the cell volume it is 9.7(1) × 10^–5 K^–1. The angle displays oscillatory variation, and empirical data analysis results in = 1.28(3) × 10^–6sin(0.0105 T) K^–1, within this temperature range. The evolution of the thermal expansion tensor of brushite has been calculated between 50 T 400 K. At 300 K the magnitudes of the principal axes are ₁₁ = 50(6) × 10^{–6 K–1}, ₂₂ = 26.7(7) × 10^–6 K^–1 and ₃₃ = 7.0(5) × 10^–6 K^–1. The intermediate axis, ₂₂, is parallel to b, and using IRE convention for the tensor orthonormal basis, the axes ₁₁ and ₃₃ have directions equal to (–0.228, 0, –0.974) and (–0.974, 0, 0.228) respectively. Under the conditions of these experiments, the onset of dehydration occurred at temperatures above 400 K. Bond valence analysis combined with assessments of the thermal evolution of the bonding within brushite suggests that dehydration is precipitated through instabilities in the chemical environment of the second water molecule.     

Single crystal X-ray diffraction study of MgSiO3 perovskite from 77 to 400 K

Single crystal X-ray diffraction study of MgSiO₃ perovskite has been completed from 77 to 400 K. The thermal expansion coefficient between 298 and 381 K is 2.2(8) × 10^-5 K^-1. Above 400 K, the single crystal becomes so multiply twinned that the cell parameters can no longer be determined.From 77 to 298 K, MgSiO₃ perovskite has an average thermal expansion coefficient of 1.45(9) × 10^-5 K^-1, which is consistent with theoretical models and perovskite systematics. The thermal expansion is anisotropic; the a axis shows the most expansion in this temperature range (_a = 8.4(9) × 10^-6 K^-1) followed by c(_c = 5.9(5) × 10^-6 K^-1) and then by b, which shows no significant change in this temperature range. In addition, the distortion (i.e., the tilting of the [SiO₆] octahedra) decreases with increasing temperature. We conclude that the behavior of MgSiO₃ perovskite with temperature mirrors its behavior under compression.     

Equation of state,structural behaviour and phase diagram of synthetic MgFe<Subscript>2</Subscript>O<Subscript>4</Subscript>, as a function of pressure and temperature

The behaviour of synthetic Mg-ferrite (MgFe₂O₄) has been investigated at high pressure (in situ high-pressure synchrotron radiation powder diffraction at ESRF) and at high temperature (in situ high-temperature X-ray powder diffraction) conditions. The elastic properties determined by the third-order Birch–Murnaghan equation of state result in K₀=181.5(± 1.3) GPa, K=6.32(± 0.14) and K= –0.0638 GPa^–1. The symmetry-independent coordinate of oxygen does not show significant sensitivity to pressure, and the structure shrinking is mainly attributable to the shortening of the cell edge (homogeneous strain). The lattice parameter thermal expansion is described by _a0+_a1*(T–298)+_a2/(T–298)², where _a0=9.1(1) 10^–6 K^–1, _a1=4.9(2) 10^–9 K^–2 and _a2= 5.1(5) 10^–2 K. The high-temperature cation-ordering reaction which MgFe-spinel undergoes has been interpreted by the ONeill model, whose parameters are = 22.2(± 1.8) kJ mol^–1 and =–17.6(± 1.2) kJ mol^–1. The elastic and thermal properties measured have then been used to model the phase diagram of MgFe₂O₄, which shows that the high-pressure transition from spinel to orthorombic CaMn₂O₄-like structure at T < 1700 K is preceded by a decomposition into MgO and Fe₂O₃.     

High-temperature enthalpy at the orientational order-disorder transition in calcite: implications for the calcite/aragonite phase equilibrium

The enthalpy of calcite has been measured directly between 973 K and 1325 K by transposed-temperature- drop calorimetry. The excess enthalpy has been analysed in terms of Landau theory for this tricritical phase transition. The zero-point enthalpy and entropy allow estimates of the parameters a and C in the Landau expansion for free energy which expresses excess free energy G as a function of the order parameter Q and temperature T: G 1/2a(T _2c–T)Q ²+1/6CQ ⁶ with a=24 J·K·mol^-1, C = 30 kJ·mol^– T _c = 1260 ±5 K. The entropy of disorder below the transition has been formulated as a function of temperature allowing the calculation of the calcite/aragonite phase boundary when taking this extra entropy into account. There is remarkable agreement between the calculated equilibrium curve and previous experimental observations. The Landau theory predicts behaviour which fully accounts for the change in slope of the calcite/aragonite phase boundary, which is thus wholly due to the R¯3c –R¯3m transition in calcite.     

Thermal expansion of gehlenite, Ca2Al[AlSiO7], and the related aluminates LnCaAl[Al2O7] with Ln=Tb, Sm

The thermal expansion of gehlenite, Ca₂Al[AlSiO₇], (up to T=830 K), TbCaAl[Al₂O₇] (up to T=1,100 K) and SmCaAl[Al₂O₇] (up to T=1,024 K) has been determined. All compounds are of the melilite structure type with space group Thermal expansion data was obtained from in situ X-ray powder diffraction experiments in-house and at HASYLAB at the Deutsches Elektronen Synchrotron (DESY) in Hamburg (Germany). The thermal expansion coefficients for gehlenite were found to be: α₁=7.2(4)×10⁻⁶ K⁻¹+3.6(7)×10⁻⁹ΔT K⁻² and α₃=15.0(1)×10⁻⁶ K⁻¹. For TbCaAl[Al₂O₇] the respective values are: α₁=7.0(2)×10⁻⁶ K⁻¹+2.0(2)×10⁻⁹ΔT K⁻² and α₃=8.5(2)×10⁻⁶ K⁻¹+2.0(3)×10⁻⁹ΔT K⁻², and the thermal expansion coefficients for SmCaAl[Al₂O₇] are: α₁=6.9(2)× 10⁻⁶ K⁻¹+1.7(2)×10⁻⁹ΔT K⁻² and α₃=9.344(5)×10⁻⁶ K⁻¹. The expansion-mechanisms of the three compounds are explained in terms of structural trends obtained from Rietveld refinements of the crystal structures of the compounds against the powder diffraction patterns. No structural phase transitions have been observed. While gehlenite behaves like a ’proper’ layer structure, the aluminates show increased framework structure behaviour. This is most probably explained by stronger coulombic interactions between the tetrahedral conformation and the layer-bridging cations due to the coupled substitution (Ca²⁺+Si⁴⁺)-(Ln ³⁺+Al³⁺) in the melilite-type structure. Electronic Supplementary Material Supplementary material is available for this article at     

P - V - T equation of state of stishovite to the mantle transition zone conditions

In-situ synchrotron X-ray diffraction experiments were conducted using the SPEED-1500 multi-anvil press of SPring-8 on stishovite SiO₂ and pressure-volume-temperature data were collected at up to 22.5 GPa and 1,073 K, which corresponds to the pressure conditions of the base of the mantle transition zone. The analysis of room-temperature data yielded V₀=46.56(1) ų, K_{T 0}=296(5) GPa and K _T =4.2(4), and these properties were consistent with the subsequent thermal equation of state (EOS) analyses. A fit of the present data to high-temperature Birch-Murnaghan EOS yielded (K_T /T) _P =–0.046(5) GPa K^–1 and = a + bT with values of a =1.26(11)×10^–5 K^–1 and b =1.29(17)×10^–8 K^–2. A fit to the thermal pressure EOS gives ₀=1.62(9)×10^–5 K^–1, ( K _T / T) _V =–0.027(4) GPa K^–1 and (²P /T ²) _V =27(5)×10^–7 GPa K^–2. The lattice dynamical approach by Mie-Grüneisen-Debye EOS yielded ₀=1.33(6), q =6.1(8) and ₀=1160(120) K. The strong volume dependence of the thermal pressure of stishovite was revealed by the analysis of present data, which was not detectable by the previous high-temperature data at lower pressures, and this yields ( K _T / T) _V 0 and q 1. The analyses for the fictive volume for a and c axes show that relative stiffness of c axis to a axis is similar both on compression and thermal expansion. Present EOS enables the accurate estimate of density of SiO₂ in the deep mantle conditions.     

Thermal expansion of gehlenite, Ca2Al[AlSiO7], and the related aluminates LnCaAl[Al2O7] with Ln = Tb, Sm

The thermal expansion of gehlenite, Ca₂Al[AlSiO₇], (up to T=830 K), TbCaAl[Al₂O₇] (up to T=1100 K) and SmCaAl[Al₂O₇] (up to T=1024 K) has been determined. All compounds are of the melilite structure type with space group Thermal expansion data were obtained from in situ X-ray powder diffraction experiments in-house and at HASYLAB at the Deutsches Elektronen Synchrotron (DESY) in Hamburg (Germany). The thermal expansion coefficients for gehlenite were found to be: α₁=7.2(4)×10⁻⁶×K⁻¹+3.6(7)×10⁻⁹ΔT×K⁻² and α₃=15.0(1)×10⁻⁶×K⁻¹. For TbCaAl[Al₂O₇] the respective values are: α₁=7.0(2)×10⁻⁶×K⁻¹+2.0(2)×10⁻⁹ΔT×K⁻² and α₃=8.5(2)×10⁻⁶×K⁻¹+2.0(3)×10⁻⁹ΔT×K⁻², and the thermal expansion coefficients for SmCaAl[Al₂O₇] are: α₁=6.9(2)×10⁻⁶×K⁻¹+1.7(2)×10⁻⁹ΔT×K⁻² and α₃=9.344(5)×10⁻⁶×K⁻¹. The expansion mechanisms of the three compounds are explained in terms of structural trends obtained from Rietveld refinements of the crystal structures of the compounds against the powder diffraction patterns. No structural phase transitions have been observed. While gehlenite behaves like a ‘proper’ layer structure, the aluminates show increased framework structure behavior. This is most probably explained by stronger coulombic interactions between the tetrahedral conformation and the layer-bridging cations due to the coupled substitution (Ca²⁺+Si⁴⁺)–(Ln ³⁺+Al³⁺) in the melilite-type structure. This article has been mistakenly published twice. The first and original version of it is available at .     

MgSiO3 ilmenite: Heat capacity,thermal expansivity,and enthalpy of transformation

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; C_p 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.     

Cation distribution in pentlandites (Fe,Ni)9S8: Dependence on pressure and temperature and kinetics of the cation exchange reaction

This paper describes the distribution of Fe and Ni between the octahedral and tetrahedral sites in pentlandite (Fe,Ni)₉S₈. The dependence of the distribution on pressure and temperature and the activation energy of the cation exchange reaction were determined through annealing experiments. Synthetic crystals were annealed at 433–723 K and pressures up to 4 GPa, and natural crystals were annealed at 423, 448 and 473 K in evacuated silica capillary tubes for various durations. The cation distributions in the synthetic crystals were determined with an X-ray powder method employing the anomalous dispersion effect of CuK. and FeK radiations, while those of natural crystals were calculated from the cell dimensions. The values of U, S and V for the Fe/Ni exchange reaction are –6818 J mol^–1, 20.52 J K^–1 mol^–1, and 6.99 × 10^–6 m³ mol^–1, respectively. The dependence of the Fe/Ni distribution on pressure (Pa) and temperature (Kelvin) was determined as lnK = 2.47+8.20 × 10² T ^–1+8.41 x 10^–7 T ^–1 P, where K = (Fe/Ni)_octahedral /(Fe/Ni)_tetrahedral. The activation energy of the cation exchange reaction was 185 kJ mol^–1.     

Die Struktur des Tief-K2Li[AIF6] und ihre Beziehung zu Elpasolith,K2Na[AlF6] und anderen Strukturen

Zusammenfassung Die Struktur von Kristallen der Tieftemperaturmodifikation des K₂Li[AlF₆] wurden untersucht. Es ergaben sich folgende Daten: Kristallklasse –3m–D _3d: ditrigonal-skalenoedrisch; rhomboedrisches Translationsgitter; RaumgruppeR –3m–D _3d (5). Hexagonale Aufstellung:a ₀=5,574 Åc ₀=13,648 Å ;c/a=2,4485. Inhalt der Zelle 3 · K₂LiAlF₆. Rhomboedrische Aufstellung: _R = 5,573 Å;=60° 01; Inhalt dieser Zelle 1 · K₂LiAlF₆;D _x = 3,066. Die vollständige Struktur wird mitgeteilt und mit der sehr ähnlichen Struktur des kubischen Minerals Elpasolith, K₂Na[AIF₆], verglichen; es besteht zwischen beiden Strukturen Homöotypie, Außerdem werden die optischen Daten und die Spaltbarkeit dieser beiden Kristallarten miteinander verglichen und die Unterschiede qualitativ auf Grund der Kristallstrukturen erklärt. Weitere Homöotypiebeziehungen werden aufgezeigt.     

The P-T-fO 2 stability of deerite,Fe 12 2+ Fe 6 3+ [Si12O40](OH)10

New equilibrium experiments have been performed in the 20–27 kbar range to determine the upper thermal stability limit of endmember deerite, Fe ₁₂ ²⁺ Fe ₆ ³⁺ [Si₁₂O₄₀](OH)₁₀. In this pressure range, the maximum thermal stability limit is represented by the oxygen-conserving reaction: deerite(De)=9 ferrosilite(Fs)+3 magnetite(Mag)+3 quartz(Qtz)+5 H₂O(W) (1). Under the oxygen fugacities of the Ni-NiO buffer the breakdown-reduction reaction: De=12 Fs+2 Mag+5 W+1/2 O₂ (10) takes place at lower temperatures (e.g. T=63° at 27 kbar). The experimental brackets can be fitted using thermodynamic data for ferrosilite, magnetite and quartz from Berman (1988) and the following 1 bar, 298 K data for deerite (per gfw): V^o=55.74 J.bar^-1, S^o=1670 J.K^-1, H _f ^o =-18334 kJ, =2.5x10^-5K^-1, =-0.18x10^-5 bar^-1. Using these data in conjunction with literature data on coesite, grunerite, minnesotaite, and greenalite, the P-T stability field of endmember deerite has been calculated for P _s=P _{H 2}O. This field is limited by 6 univariant oxygenconserving dehydration curves, from which three have positive dP/dT slopes, the other three negative slopes. The lower pressure end of the stability field of endmember deerite is thus located at an invariant point at 250±70°C and 10+-1.5 kbar. Deerite rich in the endmember can thus appear only in environments with geothermal gradients lower than 10°C/km and at pressures higher than about 10 kbar, which is in agreement with 4 out of 5 independent P-T estimates for known occurrences. The presence of such deerite places good constraints on minimum pressure and maximum temperature conditions. From log f _{O 2}-T diagrams constructed with the same data base at different pressures, it appears that endmember deerite is, at temperatures near those of its upper stability limit, stable only over a narrow range of oxygen fugacities within the magnetite field. With decreasing temperatures, deerite becomes stable towards slightly higher oxygen fugacities but reaches the hematite field only at temperatures more than 200°C lower than the upper stability limit. This practically precludes the coexistence deerite-hematite with near-endmember deerite in natural environments.     

Thermodynamic data from redox reactions at high temperatures. III. Activity-composition relations in Ni-Pd alloys from EMF measurements at 850–1250 K,and calibration of the NiO+Ni-Pd assemblage as a redox sensor

The assemblage NiO+Ni-Pd alloy has been calibrated as a precise oxygen fugacity sensor in the temperature range 850–1250 K at 1 bar, using an electrochemical technique with oxygen-specific CSZ electrolytes, and Ni+NiO and Cu+Cu₂O as the reference electrodes. Nine compositions were studied, ranging from 0.12 to 0.83 X _Ni ^alloy . Steady EMFs, implying equilibrium, were rapidly achieved in all cells, and were found to be reversible on increasing and decreasing temperature with a precision approaching 0.1 mV. The estimated accuracy of the measurements on each cell is ±0.2 mV (1, corresponding to ±0.003 log-bar units in fo₂ at 1273 K). Compositions of the Ni-Pd alloys were measured after each run by electron microprobe, and these compositions were then checked for internal consistency by measuring the lattice parameter by X-ray diffraction. Nickel-rich alloys show positive deviations from ideality and endothermic enthalpies of mixing, but palladium-rich compositions have exothermic enthalpies of mixing and strong negative deviations from ideality. The excess entropies of mixing are positive for all compositions, and correlate approximately with the excess volumes of mixing. The highly asymmetrical deviations from ideality are well described by a polynomial expression of the Redlich-Kister form, with three terms for the enthalpies, and two for the excess entropies and volumes of mixing. The experimental data from this study have been used to re-formulate the Ni-Pd oxygen fugacity sensor to give an expression; _O2 ^ss = _O2 ^NNO – 2RT ln X _Ni ^alloy – [2 · (1 – X _Ni ^alloy )² · [(–2165–7.958 · T) + (9409 – 0.888 · T) · (4 X _Ni ^alloy – 1) + 2089 · (6 X _Ni ^alloy – 1) · (2 X _Ni ^alloy – 1)]](850<T<1300) where _O2 ^ss is in J mol^-1, T is in kelvins, and the expression for _O2 ^NNO is that given by O'Neill and Pownceby (1993). Values in terms of log fo₂ may be obtained from the above by dividing by RT ln 10. The estimated standard error in _O2 ^ss is on the order of ±200 J mol^-1, which is approximately ±0.01 log-bar units in fo₂ at 1273 K.     

Thermal expansion of Neapolitan Yellow Tuff

Summary In saturated rocks and soils it is possible to define different coefficients of thermal expansion depending on the drainage conditions. This topic is first examined from the theoretical point of view with regard to an ideal isotropic thermo-elastic porous medium. Some special features of the behaviour of natural soils and rocks during thermal expansion tests are subsequently discussed. An experimental evaluation of some of these coefficients is presented in the second part of the paper. The material investigated is a pyroclastic rock, the so-called Neapolitan Yellow Tuff. Thermal expansion coefficient in drairend conditions has been evaluated, when this material is saturated with water. The e pressure increase induced by heating has been measured in undrained tes temperatures investigated range between room temperature up to 225°C.Different types of apparatus have been used and, when possible, a comparison between the results has been proposed. The results obtained in undrained thermal expansion tests are in agreement with theoretical predictions. This research is part of an on-going study of the complex phenomena known as Bradyseism, which is occurring in a volcanic area a few kilometers from Naples (Italy). Some considerations on this phenomenon are drawn in the last paragraph of the paper.List of Symbols _l linear thermal expansion coefficient - _s volumetric thermal expansion coefficient of the solid phase - _ss volumetric drained thermal expansion coefficient of the solid skeleton - _st volumetric drained thermal expansion coefficient that takes into account variations of porosity induced by heating - _t volumetric drained thermal expansion coefficient of the whole system - _u volumetric undrained thermal expansion coefficient of the whole system - _v volumetric thermal expansion coefficient - _w volumetric thermal expansion coefficient of the water - _l ^* volumetric thermal expansion coefficient of the distilled water - Biot's coefficient - _d dry specific gravity - _s specific gravity of the solid phase - _r ^' uniaxial compressive strength - _r ^' yield stress in isotropic compression - B _T parameter relating undrained thermally generated pore pressure with temperature change - d ₀ maximum uplift during Bradyseismic crises - d _f residual uplift during Bradyseismic crises - K _s compressibility modulus of the solid phase - K _ss compressibility modulus of the solid skeleton - K _w compressibility modulus of the water - n porosity - T temperature - T ₀ initial temperature in thermal expansion, tests performed in thermal expansion cell - T _m temperature at which the volume of waterV _Eexpelled from thermal expansion cell. is measured - V volume of the solid skeleton - V _E volume expelled from thermal expansion cell - V ₀ volume of the expansion cell at temperatureT ₀ - V _s volume of the solid phase     

On the entropy of glaucophane Na2Mg3Al2Si8O22(OH)2

The heat capacity of glaucophane from the Sesia-Lanza region of Italy having the approximate composition (Na_1.93Ca_0.05Fe_0.02) (Mg_2.60Fe_0.41) (Al_1.83Fe_0.15Cr_0.01) (Si_7.92Al_0.08)O₂₂(OH)₂ was measured by adiabatic calorimetry between 4.6 and 359.4 K. After correcting the C _p ⁰ data to values for ideal glaucophane, Na₂Mg₃Al₂Si₈O₂₂(OH)₂ the third-law entropy S ₂₉₈ ⁰ -S ₀ ⁰ was calculated to be 541.2±3.0 J·mol^-1·K^-1. Our value for S ₂₉₈ ⁰ -S ₀ ⁰ is 12.0 J·mol^-1·K^-1 (2.2%) smaller than the value of Likhoydov et al. (1982), 553.2±3.0, is within 6.2 J·mol^-1·K^-1 of the value estimated by Holland (1988), and agrees remarkably well with the value calculated by Gillet et al. (1989) from spectroscopic data, 539 J·mol^-1·K^-1.     

Determination of Sr and Ba partition coefficients between apatite and water from 5°C to 60°C: a potential new thermometer for aquatic paleoenvironments

Apparent partition coefficients of Sr and Ba between calcium phosphate and water were measured experimentally for temperature ranging from 5°C to 60°C. Calcium phosphates were precipitated from an aqueous mixture of Na₂HPO₄ · 2H₂O (10⁻² M) and CaCl₂ · 2H₂O (10⁻² M). Spiked solutions of Sr or Ba were introduced into the CaCl₂ · 2H₂O solution at Sr/Ca and Ba/Ca ratios of 0.1. The experiment consisted in sampling the liquid and solid phases after 1, 6, 48, and 96 h of interaction. The amorphous calcium phosphate (ACP) precipitated early in the experiment was progressively replaced by hydroxylapatite (HAP), except at 5°C where brushite (di-calcium phosphate di-hydrate or DCPD) was formed. We observed that the crystallinity of the solid phase increased with time for a given temperature and increased with temperature for a given time of reaction. With the exception of the experiment at 5°C, yield (R%) and apparent partition coefficients (K_a-w^Sr/Ca and K_a-w^Ba/Ca) both decreased with increasing reaction time. After 96 h, R%, K_a-w^Sr/Ca and K_a-w^Ba/Ca were observed to be constant, suggesting that the solid phases were at steady-state with respect to the aqueous solutions. The thermodependence of Sr and Ba partitioning between apatite and water at low temperature could therefore be calculated:

     

Static compression and H disorder in brucite,Mg(OH)2, to 11 GPa: a powder neutron diffraction study

Neutron diffraction data suitable for Rietveld refinements were collected on a powder sample of synthetic Mg(OH)₂ by the Polaris time-of-flight spectrometer (ISIS spallation source, U.K.) at 10^-4 7.8(3) and 10.9(6) GPa. The Paris-Edinburgh high-pressure cell with WC anvils was used. Pressure calibration and equation-ofstate results were attained by separate runs with an NaCl internal standard. Interpolation of p(V) data by the fourth-order Birch-Murnaghan e.o.s. yields K ₀=41(2) GPa, K₀=4(2) and K₀=1.1(9) GPa^-1. The bulk modulus obtained is smaller than previously reported results. Rietveld refinements (R _prof =1.45% and 2.02% at 10^-4 and 10.9 GPa) show that H lies on the threefold axis (1/3, 2/3, z) up to 10.9 GPa, where a model with H disordered in (x, 2x, z) can be refined. In the latter case, a hydrogen bond with O-H=0.902(7), H..O=2.026(8) Å and <>=145.9 (7)° is observed. Differences with previous results for deuterated brucite are discussed. The onset of H disorder, and a jump of the c/a ratio vs. pressure at 6–7 GPa, may be related to a second-order phase transition consistent with recently reported Raman spectroscopic results.     

Variation in ferrous iron-magnesium distribution coefficients of metamorphic pyroxenes from Quairading,Western Australia

Distribution coefficients (K _D·Fe ⁺⁺ _–Mg) calculated for orthopyroxene-clinopyroxene pairs from 12 basic granulites of the Quairading district, Western Australia, range from 1.87 for magnesian pyroxenes (Opx Mg value=78.1) to 1.70 for iron-rich varieties (Opx Mg value 37.7). Field and petrographic evidence indicates that these pyroxenes have probably reached equilibrium within a narrow temperature range. In order to account for the observed variation of K _D values it is suggested that one (or both) of the pyroxene structures is not the ideal Fe⁺⁺-Mg solution proposed in the thermodynamic model of the pyroxene equilibrium exchange. After consideration of the geometry of the pyroxene cation sites, the relative bond energies of each site (especially crystal field stabilization energy) and structural ordering a model is proposed to explain the non-ideal behaviour of Fe⁺⁺-Mg in the pyroxene system. The distribution pattern in low-iron pyroxenes will probably show Fe⁺⁺ favouring the M _2·Opx site; competing unfavourably with Mg⁺⁺ for the M _1·Cpxsite; and probably excluded by Mg⁺⁺ from the M _1·Opxsite. As the iron content of the system increases the M _2·Opxsite will begin to become saturated with Fe⁺⁺ and this ion will enter the M _1·Opx site. Further increases in the iron content of the system will cause the Fe⁺⁺-Mg distribution to depend increasingly on the relative attraction of the M ₁ sites of both pyroxenes. Of these sites Fe⁺⁺ should show preference to the more distorted M _1·Cpxsite. The distribution coefficient reflects this swing towards a relative enrichment of Fe⁺⁺ in the clinopyroxene by decreasing regularly with increasing iron content. It is likely that this downward trend will not become evident until the iron content of the M _2·Opx site reaches saturation. This would explain why the K _D values for the magnesian pyroxenes remain practically unchanged until the orthopyroxene Mg value is approximately 60; from here on the iron-rich pyroxenes show a rapid decrease in K _D value with increasing iron content.The Ca content of the pyroxenes is also significant since the Quairading pyroxenes show a marked increase in mutual solubility with increasing iron content. Calcium taken into the orthopyroxene structure will enter the M ₂ site ahead of Fe⁺⁺ so that this site will reach Fe⁺⁺ saturation at a lower iron content than when the orthopyroxene is Ca-free.The application of K _D values to the regional study of basic granulites, particularly when establishing relative temperature zones on the basis of K _D variation, should only be attempted when pyroxenes which extend over a wide range of Fe-Mg content are available.     

Heat capacity of minerals in the system Na2O-K2O-CaO-MgO-FeO-Fe2O3-Al2O3-SiO2-TiO2-H2O-CO2: representation,estimation, and high temperature extrapolation

A revised equation is proposed to represent and extrapolate the heat capacity of minerals as a function of temperature: C _P=k₀+k₁ T ^–0.5+k₂ T ^–2+k₃ T ^–3 (where k₁, k₂0).This equation reproduces calorimetric data within the estimated precision of the measurements, and results in residuals for most minerals that are randomly distributed as a function of temperature. Regression residuals are generally slightly greater than those calculated with the five parameter equation proposed by Haas and Fisher (1976), but are significantly lower than those calculated with the three parameter equation of Maier and Kelley (1932).The revised equation ensures that heat capacity approaches the high temperature limit predicted by lattice vibrational theory (C _P=3R+²VT/). For 16 minerals for which and have been measured, the average C _Pat 3,000 K calculated with the theoretically derived equation ranges from 26.8±0.8 to 29.3±1.9 J/(afu·K) (afu = atoms per formula unit), depending on the assumed temperature dependence of . For 91 minerals for which calorimetric data above 400 K are available, the average C _Pat 3,000 K calculated with our equation is 28.3±2.0 J/(afu·K). This agreement suggests that heat capacity extrapolations should be reliable to considerably higher temperatures than those at which calorimetric data are available, so that thermodynamic calculations can be applied with confidence to a variety of high temperature petrologic problems.Available calorimetric data above 250 K are fit with the revised equation, and derived coefficients are presented for 99 minerals of geologic interest. The heat capacity of other minerals can be estimated (generally within 2%) by summation of tabulated oxide component C _Pcoefficients which were obtained by least squares regression of this data base.     

The thermal expansion of synthetic aluminosilicate-sodalites,M 8(Al6Si6O24)X 2

Thermal expansion data, determined by powder X-ray diffraction methods are presented for 11 members of the (Li,Na,K,Rb)₈(Al₆Si₆O₂₄)Cl₂ solid solution series, 3 members of the (Na,K)₈(Al₆Si₆O₂₄)Br₂ solid solution series and Na₈(Al₆Si₆O₂₄)I₂. Only the latter showed a discontinuity in its expansion curve at 810° C wigh a mean linear expansion coefficient of 22.0×10^?6 °C^?1 below and 7.7×10^?6 °C^?1 above the discontinuity. The mean expansion coefficients from 0° to 500° C decrease gradually over the range of room temperature cell edges from 8.4 to 8.89 Å, then increase up to a cell edge of 9.01 Å above which they decrease sharply and extrapolate to a zero coefficient at 9.4 Å. These variations may be related to the expansion characteristics of the bonds between the cavity cations and cavity anions in different sodalites. The aluminosilicate-sodalites which show a discontinuity in their thermal expansion curves are those with large cavity anions, I^? or SO ₄ ^2? ; the discontinuity is believed to occur at the point when the x-coordinate of the cavity cation becomes 0.25.     

Admontit,ein neues Boratmineral aus der Gipslagerstätte Schildmauer bei Admont in der Steiermark (Österreich)

Zusammenfassung Admontit ist ein neues Magnesiumborat, das in der Gipslagerstätte Schildmauer bei Admont in der Steiermark (Österreich) in Vergesellschaftung mit drei weiteren neuen borhaltigen Mineralien sowie Gips, Anhydrit, Hexahydrit, Löweit, Quarz und Pyrit auftritt.Das Mineral bildet undeutlich ausgebildete farblose Kristalle von monokliner Symmetrie, die zum Teil nachc gestreckt und tafelig nach {100} sind. Keine Spaltbarkeit, Bruch muschelig, Härte wahrscheinlich 2–3,D _gem .=1,82,D _x =1,875g·cm^–3;n =1,442±0,002,n =1,504±0,002, 2V 30°,r. AE(010),n c auf (010) ca. 45°. a ₀=12,68,b ₀=10,07,c ₀=11,32 Å (alle Werte±0,02 Å),=109,68° (±0,1°),Z=2, RaumgruppeP2₁/c. Stärkste Linien des Pulverdiagramms: 12,08(9), 7,60(10), 3,93(8), 2,68(9). Formel: 2 MgO·6 B₂O₃·15 H₂O. In Wasser wird Admontit langsam zersetzt. Erhitzungsversuche zeigten, daß das Gitter zwischen 100 und 200°C zerstört wird. Ein Teil des Wassers entweicht schon unterhalb 100°C, der Rest zwischen 150 und 350°C.

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Admontite, a new borate mineral from the gypsum deposit Schildmauer near Admont in Styria (Austria)

Summary Admontite is a new magnesium borate found in the gypsum deposit of Schildmauer near Admont in Styria (Austria) in association with three other new borium-containing minerals and with gypsum, anhydrite, hexahydrite, löweite, quartz and pyrite.The mineral occurs in poorly developed colourless crystals of monoclinic symmetry, which in part are elongated along thec axis and flattened on {100}. No cleavage, fracture conchoidal, hardness probably 2–3,D _meas .=1.82,D _x =1.875g·cm^–3.n =1.442±0.002,n =1.504±0.002, 2V 30°,r. AE(010),n c on (010) about 45°.a ₀=12.68,b ₀=10.07,c ₀=11.32 Å (all±0.02 Å), =109.68° (±0.1°),Z=2,space groupP2₁/c. Strongest lines of the powder pattern: 12.08(9), 7.60(10), 3.93(8), 2.68(9). Chemical composition: 2 MgO·6 B₂O₃·15 H₂O. Admontite is slowly decomposed in water. Investigations of the thermal behaviour show that the lattice breaks down between 100 and 200°C. Part of the water escapes already under 100°C, the rest between 150 and 350°C.

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Herrn Univ. Prof. Dr.H. Meixner zum 70. Geburtstag gewidmet.