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1.
The heat capacity of natural chamosite (XFe=0.889) and clinochlore (XFe=0.116) were measured by differential scanning calorimetry (DSC). The samples were characterised by X-ray diffraction, microprobe analysis and Mössbauer spectroscopy. DSC measurements between 143 and 623?K were made following the procedure of Bosenick et?al. (1996). The fitted data for natural chamosite (CA) in J?mol?1?K?1 give: C p,CA = 1224.3–10.685?×?103?×?T ??0.5???6.4389?× 106?×T ??2?+?8.0279?×?108?×?T ??3 and for the natural clinochlore (CE): C p,CE = 1200.5–10.908?×?103?×T ??0.5?? 5.6941?×?106?×?T ??2?+?7.1166?×?108?×?T ??3. The corrected C p-polynomial for pure end-member chamosite (Fe5Al)[Si3AlO10](OH)8 is C p,CAcor = 1248.3–11.116?× 103?×?T ??0.5???5.1623?×?106?×?T ??2?+?7.1867?×?108×T ??3 and the corrected C p-polynomial for pure end-member clinochlore (Mg5Al)[Si3AlO10](OH)8 is C p,CEcor = 1191.3–10.665?×?103?×?T ??0.5???6.5136?×?106?×?T ??2?+ 7.7206?×?108?×?T ??3. The corrected C p-polynomial for clinochlore is in excellent agreement with that in the internally consistent data sets of Berman (1988) and Holland and Powell (1998). The derived C p-polynomial for chamosite (C p,CAcor) leads to a 4.4% higher heat capacity, at 300?K, compared to that estimated by Holland and Powell (1998) based on a summation method. The corrected C p-polynomial (C p,CAcor) is, however, in excellent agreement with the computed C p-polynomial given by Saccocia and Seyfried (1993), thus supporting the reliability of Berman and Brown's (1985) estimation method of heat capacities.  相似文献   

2.
The heat capacity of synthetic andradite garnet (Ca3Fe2Si3O12) was measured between 9.6 and 365.5 K by cryogenic adiabatic calorimetry and from 340 to 990 K by differential scanning calorimetry. At 298.15 K Cop,m and Som are 351.9 ± 0.7 and 316.4 ± 2.0 J/(mol·K), respectively.Andradite has a λ-peak in Cop,m with a maximum at 11.7 ± 0.2 K which is presumably associated with the antiferromagnetic ordering of the magnetic moments of the Fe3+ ions. The Gibbs free energy of formation, ΔfGom (298.15 K) of andradite is −5414.8 ± 5.5 kJ/mol and was obtained by combining our entropy and heat capacity data with the known breakdown of andradite to pseudowollastonite and hematite at ≈ 1410 to 1438 K. From a reexamination of the calcite + quartz = wollastonite equilibrium data we obtained ΔfHom (298.15 K) = − 1634.5 ± 1.8 kJ/mol for wollastonite.Between 300 and 1000 K the molar heat capacity of andradite can be represented by the equation Cop,m = 809.24 - 7.025 × 10−2T− 7.403 × 103T−0.5 − 6.789 × 105T−2. We have also used our thermochemical data for andradite to estimate the Gibbs free energy of formation of hedenbergite (CaFeSi2O6) for which we obtained ΔfGom (298.15 K) = −2674.3 ± 5.8 kJ/mol.  相似文献   

3.
Solubilities of silver chloride in aqueous hydrochloric acid solutions have been determined from 100 up to 350°C. From these measurements, the ionisation constant of HC1 has been evaluated up to 225°C. Evidence is presented to show that a protonated silver species, HAgCl20, exists at 275°C and above. Available experimental data up to 200°C have been firted to Pitzer's equation to generate an algorithm to calculate stoichiometric activity and osmotic coefficients of HCl up to 350°C and concentrations up to at least 3.0 m. Using the present results and those of Wrightet al. (1961), Pearsonet al. (1963) and Lukashowet al. (1976), the dissociation constant (Kd) of HCl as a function of temperature is described by the equation log10K = 2136.898 + 1.020349T−4.5045 × 10−4T2−50396.40/T−901.770 10g10T (Tin °K) which is valid in the range 25–350°C. Calculated enthalpy (ΔH0), entropy (ΔS0) and heat capacity change (ΔCp0) functions for HCl dissociation have been rationalized in terms of changing solute and solvent characteristics as temperature is raised.  相似文献   

4.
The accuracy of differential scanning calorimetry (DSC) on a heat capacity measurement was evaluated using MgO. The result indicated that the deviation of the result in comparison to literature values was less than 0.4% at temperatures above 300 K and 2.1% below this temperature. Since this experiment proved the reliability of DSC, heat capacity, compressibility, and thermal expansion of ilmenite-type MgGeO3 were measured by means of DSC, a diamond anvil high pressure device, and a high-temperature X-ray camera, respectively. The heat capacity was approximated by C p = a + b·T + c·T ?2 at high temperatures and by the Debye function at low temperatures. The compressibility was well-represented by the Murnaghan-Birch equation of 2nd order. The thermal expansion coefficient was constant up to 1073 K.  相似文献   

5.
The low-temperature heat capacity of knorringite garnet (Mg3Cr2Si3O12) was measured between 2 and 300 K, and thermochemical functions were derived from the results. The measured heat capacity curves show a sharp lambda-shaped anomaly peaking at around 5.1 K. Magnetic susceptibility data show that the transition is caused by antiferromagnetic ordering. From the C p data, we suggest a standard entropy (298.15 K) of 301 ± 2.5 J mol?1 K?1 for Mg3Cr2Si3O12. The new data are also used in conjunction with previous experimental results to constrain ?H f ° for knorringite.  相似文献   

6.
The heat capacity of a natural monticellite (Ca1.00Mg.09Fe.91Mn.01Si0.99O3.99) measured between 9.6 and 343 K using intermittent-heating, adiabatic calorimetry yields Cp0(298) and S2980 of 123.64 ± 0.18 and 109.44 ± 0.16 J · mol−1K−1 respectively. Extrapolation of this entropy value to end-member monticellite results in an S0298 = 108.1 ± 0.2 J · mol−1K−1. High-temperature heat-capacity data were measured between 340–1000 K with a differential scanning calorimeter. The high-temperature data were combined with the 290–350 K adiabatic values, extrapolated to 1700 K, and integrated to yield the following entropy equation for end-member monticellite (298–1700 K): ST0(J · mol−1K−1) = S2980 + 164.79 In T + 15.337 · 10−3T + 22.791 · 105T−2 − 968.94. Phase equilibria in the CaO-MgO-SiO2 system were calculated from 973 to 1673 K and 0 to 12 kbar with these new data combined with existing data for akermanite (Ak), diopside (Di), forsterite (Fo), merwinite (Me) and wollastonite (Wo). The location of the calculated reactions involving the phases Mo and Fo is affected by their mutual solid solution. A best fit of the thermodynamically generated curves to all experiments is made when the S0298 of Me is 250.2 J · mol−1 K−1 less than the measured value of 253.2 J · mol−1 K−1.A best fit to the reversals for the solid-solid and decarbonation reactions in the CaO-MgO-SiO2-CO2 system was obtained with the ΔG0298 (kJ · mole−1) for the phases Ak(−3667), Di(−3025), Fo(−2051), Me(−4317) and Mo(−2133). The two invariant points − Wo and −Fo for the solid-solid reactions are located at 1008 ± 5 K and 6.3 ± 0.1 kbar, and 1361 ± 10 K and 10.2 ± 0.2 kbar respectively. The location of the thermodynamically generated curves is in excellent agreement with most experimental data on decarbonation equilibria involving these phases.  相似文献   

7.
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   

8.
The thermodynamic properties of the copper carbonates malachite and azurite have been studied by adiabatic calorimetry, by heat-flux Calvet Calorimetry, by differential thermal analysis (DTA) and by thermogravimetrie (TGA) analysis. The heat capacities, C p 0 of natural malachite and azurite have been measured between 3.8 and 300 K by low-temperature adiabatic calorimetry. The heat capacity of azurite exhibits anomalous behavior at low temperatures. At 298.15 K the molar heat capacities C p 0 and the third law entropies S 298.15 0 are 228.5±1.4 and 254.4±3.8 J mol?1 K?1 for azurite and 154.3±0.93 and 166.3±2.5 J mol?1 K?1 for malachite. Enthalpies of solution at 973 K in lead borate 2PbO·B2O3 have been measured for heat treated malachite and azurite. The enthalpies of decomposition are 105.1±5.8 for azurite and 66.1±5.0 kJ mol? for malachite. The enthalpies of formation from oxides of azurite and malachite determined by oxide melt solution calorimetry, are ?84.7±7.4 and ?52.5±5.9 kJ mol?1, respectively. On the basis of the thermodynamic data obtained, phase relations of azurite and malachite in the system Cu2+-H2O-CO2 at 25 and 75 °C have been studied.  相似文献   

9.
Relative-enthalpy measurements have been made on the hexagonal, tetragonal, glass and liquid phases of GeO2. The glass transition is very sensitive to the impurity content, with a T g ranging from 980 K for a pure product to 780 K for a Li-doped sample with 0.06 mol % Li. The relative C p change at T g of about 5% increases with the impurity content as a result of lower glass transition temperatures. Above 298 K the derived heat capacities are similar for all forms, with slightly higher values for the amorphous phases and two C p cross-overs at 400 and 1000 K between the hexagonal and tetragonal modifications. For both GeO2 and SiO2 the coordination state markedly affects C p and the entropy below 300 K, where the properties are much lower for the tetragonal than for the hexagonal modifications, i.e., S 298 = 39.7 vs 55.3 J/mole K and 27.8 vs 41.4 J/ mole K for GeO2 and SiO2, respectively. The high-temperature C p's of coesite and stishovite are likely similar to those of the low-pressure SiO2 forms. Finally, these results, low-temperature C p data and enthalpy-of-solution measurements have been used to derive a consistent set of thermodynamic properties for the GeO2 modifications.  相似文献   

10.
One hundred and fifty new measurements of the solubility of witherite were used to evaluate the equilibrium constant of the reaction BaCO3(cr) = Ba2+(aq) + CO32−(aq) between 0 and 90°C and 1 atm total pressure. The temperature dependence of the equilibrium constant is given by logK = 607.642 + 0.121098T − 20011.25/T − 236.4948 logT where T is in degrees Kelvin. The logK of BaCO3(cr), the Gibbs energy, the enthalpy and entropy of the reaction at 298.15 K are −8.562, 48.87 kJ · mol−1, 2.94 kJ · mol−1 and −154.0 J · mol−1 · K−1, respectively. The equilibrium constants are consistent with an aqueous model that includes the ion pairs BaHCO3+(aq) and BaCO30(aq) Three different methods were used to evaluate the association constant of BaHCO3+(aq), and all yielded similar results. The temperature dependence of the association constant for the reaction Ba2+(aq) + HCO3−(aq) = BaHCO3+(aq) is given by logKBaHCO3+ = −3.0938 + 0.013669T.The log of the association constant, the Gibbs energy, the enthalpy and entropy of the reaction at 298.15°K are 0.982, −5.606 kJ · mol−1, 23.26 kJ · mol−1 and 96.8 J · mol−1 · K−1, respectively. The temperature dependence of the equilibrium constant for the reaction Ba2+(aq) + CO2−3(aq) = BaCO03(aq) is given by logKBaCO30 = 0.113 + 0.008721T.The log of the association constant, the Gibbs energy, the enthalpy and entropy of the reaction at 298.15° K are 2.71, −15.49 kJ · mol−1, 14.84 kJ · mol−1 and 101.7 J· mol−1 · K−1.The above model leads to reliable calculations of the aqueous speciation and solubility of witherite in the system BaCO3-CO2-H2O from 0 to more than 90°C. Literature data on witherite solubility were re-evaluated and compared with the results of this study.Problems in the thennodynamic selections of Ba compounds are considered. Newer data require the revision of ΔfH° and ΔfG° of Ba2+(aq) to −532.5 and −555.36 kJ · mol−1, respectively, for agreement with solubility data.  相似文献   

11.
《Applied Geochemistry》2000,15(8):1203-1218
Ca6[Al(OH)6]2(CrO4)3·26H2O, the chromate analog of the sulfate mineral ettringite, was synthesized and characterized by X-ray diffraction, Fourier transform infra-red spectroscopy, thermogravimetric analyses, energy dispersive X-ray spectrometry, and bulk chemical analyses. The solubility of the synthesized solid was measured in a series of dissolution and precipitation experiments conducted at 5–75°C and at initial pH values between 10.5 and 12.5. The ion activity product (IAP) for the reaction Ca6[Al(OH)6]2(CrO4)3·26H2O⇌6Ca2++2Al(OH)−4+3CrO2−4+4OH−+26H2O varies with pH unless a CaCrO4(aq) complex is included in the speciation model. The log K for the formation of this complex by the reaction Ca2++CrO2−4=CaCrO4(aq) was obtained by minimizing the variance in the IAP for Ca6[Al(OH)6]2(CrO4)3·26H2O. There is no significant trend in the formation constant with temperature and the average log K is 2.77±0.16 over the temperature range 5–75°C. The log solubility product (log KSP) of Ca6[Al(OH)6]2(CrO4)3·26H2O at 25°C is −41.46±0.30. The temperature dependence of the log KSP is log KSP=A−B/T+D log(T) where A=498.94±48.99, B=27,499±2257, and D=−181.11±16.74. The values of ΔG0r,298 and ΔH0r,298 for the dissolution reaction are 236.6±3.9 and 77.5±2.4 kJ mol−1. the values of ΔC0P,r,298 and ΔS0r,298 are −1506±140 and −534±83 J mol−1 K−1. Using these values and published standard state partial molal quantities for constituent ions, ΔG0f,298=−15,131±19 kJ mol−1, ΔH0f,298=−17,330±8.6 kJ mol−1, ΔS0298=2.19±0.10 kJ mol−1 K−1, and ΔC0Pf,298=2.12±0.53 kJ mol−1 K−1, were calculated.  相似文献   

12.
The specific heat capacity (C p) of six variably hydrated (~3.5 wt% H2O) iron-bearing Etna trachybasaltic glasses and liquids has been measured using differential scanning calorimetry from room temperature across the glass transition region. These data are compared to heat capacity measurements on thirteen melt compositions in the iron-free anorthite (An)–diopside (Di) system over a similar range of H2O contents. These data extend considerably the published C p measurements for hydrous melts and glasses. The results for the Etna trachybasalts show nonlinear variations in, both, the heat capacity of the glass at the onset of the glass transition (i.e., C p g ) and the fully relaxed liquid (i.e., C p l ) with increasing H2O content. Similarly, the “configurational heat capacity” (i.e., C p c  = C p l  ? C p g ) varies nonlinearly with H2O content. The An–Di hydrous compositions investigated show similar trends, with C p values varying as a function of melt composition and H2O content. The results show that values in hydrous C p g , C p l and C p c in the depolymerized glasses and liquids are substantially different from those observed for more polymerized hydrous albitic, leucogranitic, trachytic and phonolitic multicomponent compositions previously investigated. Polymerized melts have lower C p l and C p c and higher C p g with respect to more depolymerized compositions. The covariation between C p values and the degree of polymerization in glasses and melts is well described in terms of SMhydrous and NBO/T hydrous. Values of C p c increase sharply with increasing depolymerization up to SMhydrous ~ 30–35 mol% (NBO/T hydrous ~ 0.5) and then stabilize to an almost constant value. The partial molar heat capacity of H2O for both glasses (\( C_{{{\text{p}}\;{\text{H}}_{2} {\text{O}}}}^{\text{g}} \)) and liquids (\( C_{{{\text{p}}\;{\text{H}}_{2} {\text{O}}}}^{\text{l}} \)) appears to be independent of composition and, assuming ideal mixing, we obtain a value for \( C_{{{\text{p}}\;{\text{H}}_{2} {\text{O}}}}^{\text{l}} \) of 79 J mol?1 K?1. However, we note that a range of values for \( C_{{{\text{p}}\;{\text{H}}_{2} {\text{O}}}}^{\text{l}} \) (i.e., ~78–87 J mol?1 K?1) proposed by previous workers will reproduce the extended data to within experimental uncertainty. Our analysis suggests that more data are required in order to ascribe a compositional dependence (i.e., nonideal mixing) to \( C_{{{\text{p}}\;{\text{H}}_{2} {\text{O}}}}^{\text{l}} \).  相似文献   

13.
The Gibbs free energies of formation of RuO 2, OsO 2 and IrO 2 have been determined by measuring the chemical potentials of oxygen (μO 2) defined by the reactions M +O 2 = MO 2,whereM =Ru, Os. or Ir, using an electrochemical method with calcia-stabilized zirconia (CSZ) solid electrolytes. Measurements were attempted in the temperature ranges from ∼870 K to 1620, 1270, and 1415 K for the Ru, Os, and Ir equilibria, respectively, but inspection of the results reveals that equilibrium could not be established below ∼930 K for all three reactions. For Ru + RuO 2, the highest temperature data (above 1520 K) may be systematically affected by the onset of significant electronic conduction in the CSZ electrolyte, while the attempted measurements of the Os + OsO 2 equilibrium above 1190 K are obscured by the disproportionation of OsO 2 to gaseous Os oxides.The high temperature heat capacities at constant pressure (Cp) of RuO 2 and IrO 2 were determined from 370 to 1070 K by differential scanning calorimetry. These data were combined with heat content measurements and low-temperature heat capacities from the literature, and fitted to an extended Maier-Kelley equation. The calorimetric data for RuO 2 and IrO 2, together with assessed data for Ru, Os, and Ir metals and estimated data for OsO 2, were used in a third law analysis of the electrochemical measurements.The values of μO 2 of the three equilibria were smoothed and filtered by the third-law analysis to yield the following equations which can be extrapolated to lower and higher temperatures as indicated: μO 2 (Ru + RuO 2) = −324563 + 344.151 T−22.1155 TlnT (700 ⩽ T ⩽ 1800) μO 2 (Os + OsO 2) = −300399 + 307.639 T−17.4819 TlnT (700 ⩽ T ⩽ 1500) μO 2 (Ir + IrO 2) = −256518 + 295.854 T−15.2368 TlnT (700 ⩽ T ⩽ 1500) where μO 2 is in J mol −1, T is in K, the reference pressure for O 2 is 1 bar (10 5 Pa), and estimated accuracies are approximately 200 to 400 J mol −1. For Ru + RuO 2, the drift in the measurements relative to the calorimetric data deduced from the third-law evaluation is 0.7 J K −1 mol −1, and for Ir + IrO 2 is 1.6 J K −1 mol −1. The analogous third-law evaluation of the Os + OsO 2 data gives S° 298K = 54.8 ± 0.7J K −1mol −1 and Δ /tfH° 298K = −291.8 ± 0.6 kJ mol −1 for OsO 2.  相似文献   

14.
《Geochimica et cosmochimica acta》1999,63(19-20):3105-3119
A comprehensive low-temperature thermodynamic model for the geochemically important Na2CO3−MgCO3−CaCO3−H2O system is presented. The model is based on calorimetrically determined ΔfH°298 values, S°298 values and C°p(T) functions taken from the literature as well as on μ°298 values of solids derived in this work from solubility measurements obtained in our laboratories or by others. When these thermodynamic quantities were combined with temperature-dependent Pitzer parameters taken from the literature, solubilities calculated for a wide range of conditions agree well with experimental data. The results for several subsystems were summarized by depicting the respective phase diagrams. For the MgO−CO2−H2O subsystem, it was found that the commonly believed stability relations must be revised, i.e., in the temperature range covered, nesquehonite never becomes more stable than hydromagnesite at pCO2 ≤ 1 atm. Although the recommended set of thermodynamic data on sparingly soluble solids was derived from experimental results on mainly NaClO4 systems, it can be incorporated in databanks containing additional Pitzer parameters for modeling more complex fresh- or seawater systems.  相似文献   

15.
The heat capacity of synthetic ferrosilite, Fe2Si2O6, was measured between 2 and 820 K. The physical properties measurement system (PPMS, Quantum Design®) was used in the low-temperature region between 2 and 303 K. In the temperature region between 340 and 820 K measurements were performed using differential scanning calorimetry (DSC). The C p data show two transitions, a sharp λ-type at 38.7 K and a small shoulder near 9 K. The λ-type transition can be related to collinear antiferromagnetic ordering of the Fe2+ spin moments and the shoulder at 10 K to a change from a collinear to a canted-spin structure or to a Schottky anomaly related to an electronic transition. The C p data in the temperature region between 145 and 830 K are described by the polynomial $C_{p} {\left[ {\hbox{J\,mol}^{{ - 1}}\,{\hbox{K}}^{{ - 1}} } \right]} = 371.75 - 3219.2T^{{ - 1/2}} - 15.199 \times 10^{5} T^{{ - 2}} + 2.070 \times 10^{7} T^{{ - 3}} $ The heat content [H 298 – H 0] and the standard molar entropy [S 298 – S 0] are 28.6 ± 0.1 kJ mol?1 and 186.5 ± 0.5 J mol?1 K?1, respectively. The vibrational part of the heat capacitiy was calculated using an elastic Debye temperature of 541 K. The results of the calculations are in good agreement with the maximum theoretical magnetic entropy of 26.8 J mol?1 K?1 as calculated from the relationship 2*Rln5.  相似文献   

16.
Thermochemical properties have been either measured or estimated for synthetic monazite, LaPO4, and dissakisite, CaLaMgAl2(SiO4)3OH, the Mg-equivalent of allanite. A dissakisite formation enthalpy of ?6,976.5 ± 10.0 kJ mol?1 was derived from high-temperature drop-solution measurements in lead borate at 975 K. A third-law entropy value of 104.9 ± 1.6 J mol?1 K?1 was retrieved from low-temperature heat capacity (C p) measured on synthetic LaPO4 with an adiabatic calorimeter in the 30–300 K range. The C p values of lanthanum phases were measured in the 143–723 K range by differential scanning calorimetry. In this study, La(OH)3 appeared as suitable for drop solution in lead borate and represents an attractive alternative to La2O3. Pseudo-sections were calculated with the THERIAK-DOMINO software using the thermochemical data retrieved here for a simplified metapelitic composition (La = ∑REE + Y) and considering monazite and Fe-free epidotes along the dissakisite-clinozoïsite join, as the only REE-bearing minerals. Calculation shows a stability window for dissakisite-clinozoïsite epidotes (T between 250 and 550°C and P between 1 and 16 kbar), included in a wide monazite field. The P–T extension of this stability window depends on the bulk-rock Ca-content. Assuming that synthetic LaPO4 and dissakisite-(La) are good analogues of natural monazite and allanite, these results are consistent with the REE-mineralogy sequence observed in metapelites, where (1) monazite is found to be stable below 250°C, (2) around 250–450°C, depending on the pressure, allanite forms at the expense of monazite and (3) towards amphibolite conditions, monazite reappears at the expense of allanite.  相似文献   

17.
The elastic moduli of a single-crystal calcium oxide, CaO, are measured in the temperature range from 300 to 1200 K (1.8 times of the Debye temperature) by the resonant sphere technique (RST). The lowest 18 modes are identified in the frequency range from 0.6 to 1.4 MHz for the vibrating spherical specimen, which is 5.6564 mm in diameter and 3.3493 g/cm3 in density at room temperature, and the resonant frequencies are traced as a function of temperature. The adiabatic elastic moduli are determined in the present temperature range from the observed frequencies by inversion calculations. Most of the elastic moduli, except forC 12 modulus, decrease as temperature increases. The temperature curves ofC s andC 44 moduli cross at 372 K. This means that the CaO specimen has an isotropic elasticity at the temperature. The temperature derivatives (?C 11/?T) P and (?C s/?T) P become slightly less negative with temperature increase and (?C s /?T) P and (?C 44/?T) P are almost constant. Combining the present elastic data with thermal expansion and specimen heat capacity data of CaO, we present the temperature dependence of thermodynamic parameters important in the studies of earth's interior.  相似文献   

18.
《Geochimica et cosmochimica acta》1999,63(13-14):1969-1980
The solubility of ettringite (Ca6[Al(OH)6]2(SO4)3 · 26H2O) was measured in a series of dissolution and precipitation experiments at 5–75°C and at pH between 10.5 and 13.0 using synthesized material. Equilibrium was established within 4 to 6 days, with samples collected between 10 and 36 days. The log KSP for the reaction Ca6[Al(OH)6]2(SO4)3 · 26H2O ⇌ 6Ca2+ + 2Al(OH)4− + 3SO42− + 4OH− + 26H2O at 25°C calculated for dissolution experiments (−45.0 ± 0.2) is not significantly different from the log KSP calculated for precipitation experiments (−44.8 ± 0.4) at the 95% confidence level. There is no apparent trend in log KSP with pH and the mean log KSP,298 is −44.9 ± 0.3. The solubility product decreased linearly with the inverse of temperature indicating a constant enthalpy of reaction from 5 to 75°C. The enthalpy and entropy of reaction ΔH°r and ΔS°r, were determined from the linear regression to be 204.6 ± 0.6 kJ mol−1 and 170 ± 38 J mol−1 K−1. Using our values for log KSP, ΔH°r, and ΔS°r and published partial molal quantities for the constituent ions, we calculated the free energy of formation ΔG°f,298, the enthalpy of formation ΔH°f,298, and the entropy of formation ΔS°f,298 to be −15211 ± 20, −17550 ± 16 kJ mol−1, and 1867 ± 59 J mol−1 K−1. Assuming ΔCP,r is zero, the heat capacity of ettringite is 590 ± 140 J mol−1 K−1.  相似文献   

19.
Fluids at crustal pressures and temperatures   总被引：1，自引：0，他引：1  
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20.
The heat capacity (Cp) of two synthetic spessartine samples (Sps) was measured on 20-30 mg-size samples in the temperature range 2-864 K by relaxation calorimetry (RC) and differential scanning calorimetry (DSC). The polycrystalline spessartine samples were synthesized in two different laboratories at high pressures and temperatures from glass and oxide-mixture starting materials and characterized by X-ray powder diffraction and electron-microprobe analysis. The low-temperature heat capacity data show a prominent lambda transition with a peak at 6.2 K, which is interpreted to be the result of a paramagnetic-antiferromagnetic phase transition. The DSC data around ambient T agree excellently with the RC data and can be represented by the Cp polynomial for T > 250 K:
  相似文献   

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