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1.
The thermodynamic stability of selected alkylated, dealkylated and rearranged 17α- and 17β-hopane isomers in the C27, C28, C29, C30 and C31 families were calculated using molecular mechanics (MM2) methods and, where possible, calculated equilibrium ratios of certain isomers were compared with observed ratios of isomers in thermally mature crude oil samples. Those calculated and observed ratios having similar values include: (1) the relative distributions among 17β(H)/17α(H) and 21β(H)/21α(H)-hopanes including the absence of the 17β(H),21β(H)- and 17α(H),21α(H)-hopanes; (2) the 22R/22S ratios in 30-methyl-17α-hopane and 30-methyl-17β-moretane; (3) the relative distributions among 17α(H)/17β(H)- and 21α(H)/21β(H)-28,30-bisnorhopanes and among 25,28,30-trisnorhopanes, including the relatively greater stability of 17β(H) isomers in contrast to the regular hopane series; and (4) the ratios of 28(18−17S)abeo hopanes with respect to their unrearranged counterparts including the C27 compounds, Ts/Tm.  相似文献   

2.
Fougerite is a new iron oxide, a mixed M(II)–M(III) hydroxide, a member of the green rust group. Its structure consists of a brucitic layer of Fe(III)–Fe(II)–Mg(II), where the excess of the positive charge due to Fe3+ is compensated in the interlayer by anions. The limits of composition are structurally and geochemically constrained, and the stabilities of the mineral and green rusts are obtained by a thermodynamic model of a regular solid solution, for different compensating anions and for any allowed composition of the brucitic layer.  相似文献   

3.
The thermodynamic stabilities of thirteen cholestane isomers have been computed using molecular mechanics. The calculated composition of a mixture of these isomers at thermodynamic equilibrium is in agreement with the composition of a cholestane isomerate. From the calculated stabilities the extent to which isomerisation reactions can proceed during maturation can be predicted. The GLC retention order on non-polar phases of 20R/S isomeric pairs has been estimated from the preferred geometries of the molecules which are also obtained by molecular mechanics.  相似文献   

4.
A tetradeuteriated cholestane was heated with kerogen isolated from the Messel oil shale at 350 °C for 25 different time periods (ranging from 0.5 to 80 h) in borosilicate vessels. Three isomers of tetradeuteriated dimethylperhydrophenanthrene were formed and one of these was the major saturated hydrocarbon product under most conditions. The stereochemistry for these isomers was unknown but if the stable 5α,8β,9α(H),10β(CH3) sterane configuration is inherited from the cholestane then there are four possible isomers namely: I and II [13β(H) and 13α(H) diastereomers, respectively, of 10,13-dimethylperhydrophenanthrene] as well as III and IV [14β(H) and 14α(H) diastereomers, respectively, of 10,14-dimethylperhydrophenanthrene]. Molecular mechanics revealed that I is the most stable form and therefore is the component that dominated the saturated hydrocarbon degradation products. The identification of only three isomers of deuteriated dimethylperhydrophenanthrene in the pyrolysis experiments is supported by the calculated stabilities (ΔΔG) as isomer IV is considerably more unstable (by 1.7 kcal/mol) than II which is the least stable of I, II and III. If these compounds can be detected in crude oils their distributions may be useful maturity indicators in oils that have been generated at high thermal maturity.  相似文献   

5.
A new thermodynamic model for multi-component spinel solid solutions has been developed which takes into account thermodynamic consequences of cation mixing in spinel sublattices. It has been applied to the evaluation of thermodynamic functions of cation mixing and thermodynamic properties of Fe3O4–FeCr2O4 spinels using intracrystalline cation distribution in magnetite, lattice parameters and activity-composition relations of magnetite–chromite solid solutions. According to the model, cation distribution in binary spinels, (Fe1-x2+ Fex3+)[Fex2+Fe2-2y-x3+Cr2y]O4, and their thermodynamic properties depend strongly on Fe2+–Cr3+ cation mixing. Mixing of Fe2+–Fe3+ and Fe3+–Cr3+ can be accepted as ideal. If Fe2+, Fe3+ and Cr are denoted as 1, 3 and 4 respectively, the equation of cation distribution is –RT ln(x2/((1–x)(2–2y–x)))= G13* + (1–2x)W13+y(W14–W13–W34) where G13* is the difference between the Gibbs energy of inverse and normal magnetite, Wij is a Margules parameter of cation mixing and G13*, J/mol =–23,000+13.4 T, W14=36 kJ/mol, W13=W34=0. The positive nonconfigurational Gibbs energy of mixing is the main reason for changing activity–composition relations with temperature. According to the model, the solvus in Fe3O4–FeCr2O4 spinel has a critical temperature close to 500°C, which is consistent with mineralogical data.  相似文献   

6.
Molecular mechanics calculations of rearranged cholestenes revealed that diacholest-13(17)-enes with 10α stereochemistry are more stable than their 10β counterparts and that a partly rearranged sterene with a Δ8 double bond and 10β, 14β stereochemistry (compound 7) is relatively stable at thermodynamic equilibrium. The calculated data are in good agreement with sedimentary and experimental data and thus reinforce recent propositions for early-stage diagenesis of steroids.  相似文献   

7.
40Ar/39Ar dating on muscovites, performed on leucogranitic intrusions of Charroux–Civray plutonic complex, points out the existence of two peraluminous magmatic activities, whose equivalents are known in the Limousin: (1) garnet-bearing leucogranitic veins at ca. 340 Ma; (2) a specialised leucogranite associated with W ± Sn deposits at ca 310 Ma. However, available 40Ar/39Ar data do not allow us to provide further data concerning the age and the geometry at depth of a large leucogranitic body identified by geophysics. To cite this article: P. Alexandre et al., C. R. Geoscience 334 (2002) 1141–1148.  相似文献   

8.
Multi-equilibrium thermobarometry shows that low-grade metapelites (Cubito-Moura schists) from the Ossa–Morena Zone underwent HP–LT metamorphism from 340–370 °C at 1.0–0.9 GPa to 400–450 °C at 0.8–0.7 GPa. These HP–LT equilibriums were reached by parageneses including white K mica, chlorite and chloritoid, which define the earliest schistosity (S1) in these rocks. The main foliation in the schists is a crenulation cleavage (S2), which developed during decompression from 0.8–0.7 to 0.4–0.3 GPa at increasing temperatures from 400–450 °C to 440–465 °C. Fe3+ in chlorite decreased greatly during prograde metamorphism from molar fractions of 0.4 determined in syn-S1 chlorites down to 0.1 in syn-S2 chlorites. These new data add to previous findings of eclogites in the Moura schists indicating that a pile of allochtonous rocks situated next to the Beja-Acebuches oceanic amphibolites underwent HP–LT metamorphism during the Variscan orogeny. To cite this article: G. Booth-Rea et al., C. R. Geoscience 338 (2006).  相似文献   

9.
The P–T partition function in statistical thermodynamics can be used to derive semi-empirical formulations of the Gibbs free energy G for minerals and fluids. Parameterization of these equations includes simultaneous regression of experimental heat capacity and molar volume data, allowing fitting, appraisal and optimization of various data sources, as required in the construction of internally consistent petrological data bases. This approach can also be extended to minerals with -transitions and to fluids by considering the Gibbs free energy as a function of pressure P, temperature T and an ordering parameter X, so that accurate modelled representation and extrapolation of the thermodynamic properties of large numbers of petrologically significant minerals and coexisting fluids can be attained. The ordering parameter is chosen to denote the equilibrium mole fraction (thermodynamic probability) of ordered clusters (structural units) in a substance when G(T,P, X)=min. The procedure is tested on existing experimental data for the system MgO–SiO2–H2O. The proposed Gibbs free energy formulation permits thermodynamic properties of minerals, fluids and phase equilibria to be described and extrapolated over a wide range of pressure (0–800 kbar) and temperature (20–3000 K), thus allowing effective use in thermodynamic data bases of petrological interest.  相似文献   

10.
Examination of schorlomite from ijolite at Magnet Cove (USA) and silicocarbonatite at Afrikanda (Russia), using electron-microprobe and hydrogen analyses, X-ray diffraction and Mössbauer spectroscopy, shows the complexity of substitution mechanisms operating in Ti-rich garnets. These substitutions involve incorporation of Na in the eightfold-coordinated X site, Fe2+ and Mg in the octahedrally coordinated Y site, and Fe3+, Al and Fe2+ in the tetrahedrally coordinated Z site. Substitutions Ti4+Fe3+Fe3+–1Si–1 and Ti4+Al3+Fe3+–1Si–1 are of major significance to the crystal chemistry of schorlomite, whereas Fe2+ enters the Z site in relatively minor quantities (<3% Fe). There is no evidence (either structural or indirect, such as discrepancies between the measured and calculated Fe2+ contents) for the presence of [6]Ti3+ or [4]Ti4+ in schorlomite. The simplified general formula of schorlomite can be written as Ca3Ti4+2[Si3-x(Fe3+,Al,Fe2+)xO12], keeping in mind that the notion of end-member composition is inapplicable to this mineral. In the published analyses of schorlomite with low to moderate Zr contents, x ranges from 0.6 to 1.0, i.e. Ti4+ in the Y site is <2 and accompanied by appreciable amounts of lower-charged cations (in particular, Fe3+, Fe2+ and Mg). For classification purposes, the mole percentage of schorlomite can be determined as the amount of [6]Ti4+, balanced by substitutions in the Z site, relative to the total occupancy in the Y site: ([6]Ti4+–[6]Fe2+–[6]Mg2+– [8]Na+)/2. In addition to the predominant schorlomite component, the crystals examined in this work contain significant (>15 mol.%) proportions of andradite (Ca3Fe3+2Si3O12), morimotoite (Ca3Fe2+TiSi3O12), and Ca3MgTiSi3O12. The importance of accurate quantitative determination and assignment of Fe, Ti and other cations to the crystallographic sites for petrogenetic studies is discussed.
A. R. ChakhmouradianEmail: Phone: +1-204-4747278Fax: +1-204-4747623
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11.
The vibrational spectrum of calcite (CaCO3) is evaluated at an ab initio periodic quantum-mechanical level by using the CRYSTAL package. A localized basis set of Gaussian-type functions and the B3LYP hybrid Hamiltonian are adopted. The dynamical matrix is obtained by differentiating numerically the analytical first derivatives of the energy. The accuracy with respect to all computational parameters is documented. The calculated frequencies are compared with available IR and RAMAN data (16 and 5 peaks, respectively), the mean absolute error being less than 12 cm–1 (frequencies range from 100 to 1600 cm–1). Overall, the agreement with experiment is very satisfactory, and shows that simulation can produce at a relatively low cost the full spectra of crystalline compounds of mineralogical interest.  相似文献   

12.
Monomeric palladium(II) chloro aqua complexes of the form PdClr(H2O)4-r2-r (r = [0,4]) were studied both experimentally and theoretically to gain insight on both the stabilities and the nature of palladium-chloride interactions.The thermodynamic stabilities of these complexes were studied in aqueous solutions from 5 to 125°C with UV-vis spectrophotometry using a quartz flow-through cell. Tentative measurements up to 200°C were also carried out in pressurised titanium and gold-lined optical cells but revealed important losses in soluble palladium. The strong ligand-to-metal charge transfer bands of the palladium complexes below 350 nm were used to constrain the stepwise thermodynamic formation constants at each temperature, using results of singular value decompositions of the spectra over a broad range of palladium:chloride ratios and wavelengths. The temperature-dependent constants were used to obtain changes in enthalpy and in entropy for each reaction. The thermodynamic stabilities of PdCl(H2O)3+, PdCl2(H2O)20, and PdCl3(H2O)- are larger at higher temperatures, whilst the one of PdCl42- is smaller. All changes in entropies are positive for the former three species, but negative for the latter, presumably due to a larger solvent reorganisation around the doubly charged PdCl42- species. The room temperature thermodynamic values derived from this study are also in agreement with previously published calorimetric data.Theoretical calculations on the intramolecular distributions of electrons in the different palladium(II) chloro aqua complexes, using the methods of atoms in molecules and of the electron localisation function, showed Pd-Cl and Pd-OH2 interactions to be of largely closed-shell/ionic nature. These interactions induce an important distortion of the outer core shell electrons of Pd, as well as stable accumulations of electrons between adjacent Pd-Cl and Pd-OH2 bonds known as ligand opposed core charge concentrations.  相似文献   

13.
We have investigated the effect of Fe on the stabilities of carbonate (carb) in lherzolite assemblages by determining the partitioning of Fe and Mg between silicate (olivine; ol) and carbonates (magnesite, dolomite, magnesian calcite) at high pressures and temperatures. Fe enters olivine preferentially relative to magnesite and ordered dolomite, but Fe and Mg partition almost equally between disordered calcic carbonate and olivine. Measurement of K d (X Fe carb X Mg ol /X Fe ol X Mg carb ) as a function of Fe/ Mg ratio indicates that Fe–Mg carbonates deviate only slightly from ideality. Using the regular solution parameter for olivine W FeMg ol of 3.7±0.8 kJ/mol (Wiser and Wood 1991) we obtain for (FeMg)CO3 a W FeMg carb of 3.05±1.50 kJ/mol. The effect of Ca–Mg–Fe disordering is to raise K d substantially enabling us to calculate W CaMg carb -W CaFe carb of 5.3±2.2 kJ/mol. The activity-composition relationships and partitioning data have been used to calculate the effect of Fe/Mg ratio on mantle decarbonation and exchange reactions. We find that carbonate (dolomite and magnesian calcite) is stable to slightly lower pressures (by 1 kbar) in mantle lherzolitic assemblages than in the CaO–MgO–SiO2(CMS)–CO2 system. The high pressure breakdown of dolomite + orthopyroxene to magnesite + clinopyroxene is displaced to higher pressures (by 2 kbar) in natural compositions relative to CMS. CO2. We also find a stability field of magnesian calcite in lherzolite at 15–25 kbar and 750–1000°C.  相似文献   

14.
Crystals of hydronium jarosite were synthesized by hydrothermal treatment of Fe(III)–SO4 solutions. Single-crystal XRD refinement with R1=0.0232 for the unique observed reflections (|Fo| > 4F) and wR2=0.0451 for all data gave a=7.3559(8) Å, c=17.019(3) Å, Vo=160.11(4) cm3, and fractional positions for all atoms except the H in the H3O groups. The chemical composition of this sample is described by the formula (H3O)0.91Fe2.91(SO4)2[(OH)5.64(H2O)0.18]. The enthalpy of formation (Hof) is –3694.5 ± 4.6 kJ mol–1, calculated from acid (5.0 N HCl) solution calorimetry data for hydronium jarosite, -FeOOH, MgO, H2O, and -MgSO4. The entropy at standard temperature and pressure (So) is 438.9±0.7 J mol–1 K–1, calculated from adiabatic and semi-adiabatic calorimetry data. The heat capacity (Cp) data between 273 and 400 K were fitted to a Maier-Kelley polynomial Cp(T in K)=280.6 + 0.6149T–3199700T–2. The Gibbs free energy of formation is –3162.2 ± 4.6 kJ mol–1. Speciation and activity calculations for Fe(III)–SO4 solutions show that these new thermodynamic data reproduce the results of solubility experiments with hydronium jarosite. A spin-glass freezing transition was manifested as a broad anomaly in the Cp data, and as a broad maximum in the zero-field-cooled magnetic susceptibility data at 16.5 K. Another anomaly in Cp, below 0.7 K, has been tentatively attributed to spin cluster tunneling. A set of thermodynamic values for an ideal composition end member (H3O)Fe3(SO4)2(OH)6 was estimated: Gof= –3226.4 ± 4.6 kJ mol–1, Hof=–3770.2 ± 4.6 kJ mol–1, So=448.2 ± 0.7 J mol–1 K–1, Cp (T in K)=287.2 + 0.6281T–3286000T–2 (between 273 and 400 K).  相似文献   

15.
On the mechanism of tectonic transport in zones of oblique subduction   总被引：2，自引：0，他引：2  
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16.
The interaction of water and sulfide minerals yields dissolved species which can be utilized to trace back the presence of sulfide minerals and associated minerals. Computer modeling and laboratory and field results show that the most characteristic dissolved species are hydrogen sulfide (H2S, HS−), polysulfide ions (Sn2−) and thiosulfate (S2O32−), derived from the hydrolysis of sulfide minerals. Typical concentration ranges are: 10−5 – 10−7 mole/l for hydrogen sulfide, 10−6 – 10−9 mole/l for polysulfides and 10−5 – 10−8 mole/l for thiosulfate. The chemical reactivity of these species at contact with air makes them difficult to assess unless determined immediately after sampling.These sulfur species can be determined rapidly and accurately in field conditions by simultaneous titration with mercuric chloride employing an Ag/Ag2S electrode for the determination of the end points.The application to ore exploration is exemplified by the results of the research on roll-type uranium deposits in the southwest of France.  相似文献   

17.
The effects that Al3+ and benzene interactions exhibit on a model fulvic acid were investigated. Energy minimizations of the structures mimicking the interactions of Al3+-Suwannee fulvic acid (SFA), benzene-SFA and Al3+-benzene-SFA were run with a solvation sphere of 60 H2O molecules with the semi-empirical methods PM3 and PM5. The semi-empirical method PM3 was run with Gaussian 98 and CAChe Workstation Pro 6.1.1 to compare the results of the energy minimization algorithms in the two programs. PM5 calculations were run with CAChe Workstation Pro 6.1.1. Molecular dynamics (MD) simulations were run in Cerius2 (Accelrys Inc., San Diego, CA) using the Universal Force Field (UFF) 1.02 [Rappé A. K., Casewit C., Colwell K., Goddard W., and Skiff W. (1992) UFF, a full periodic-table force-field for molecular mechanics and molecular dynamics simulations. J. Am. Chem. Soc.114(25), 10024-10035] and COMPASS force field [Sun H. (1998) COMPASS: an ab initio force-field optimized for condensed-phase applications—overview with details on alkane and benzene compounds. J. Phys. Chem. B102, 7338-7364]. Single point calculations were run on the minimized structures at the B3LYP/6-31G(d) level to obtain more accurate estimates of the energy on the minimized structures derived from the PM3, PM5, and UFF methods and to normalize energies to the same reference state. This methodology was used as the standard of comparison for all the models to assess whether or not a given configuration was reasonably stable.The PM3/G03 energy minimizations predicted the lowest B3LYP/6-31G(d) potential energies of the methodologies examined in this study. Thus, this method is considered the most reliable of those tested. The PM3/G03 method predicted that there would be aromatic-aromatic interactions between benzene and SFA. The presence of Al3+ was predicted not to interfere with aromatic-aromatic interactions between benzene and SFA, but benzene may influence the location of metal complexation to SFA.  相似文献   

18.
Column experiments, simulating the behavior of passive treatment systems for acid mine drainage, have been performed. Acid solutions (HCl or H2SO4, pH 2), with initial concentrations of Fe(III) ranging from 250 to 1500 mg L−1, were injected into column reactors packed with calcite grains at a constant flow rate. The composition of the solutions was monitored during the experiments. At the end of the experiments (passivation of the columns), the composition and structure of the solids were measured. The dissolution of calcite in the columns caused an increase in pH and the release of Ca into the solution, leading to the precipitation of gypsum and Fe–oxyhydroxysulfates (Fe(III)–SO4–H+ solutions) or Fe–oxyhydroxychlorides (Fe(III)–Cl–H+ solutions). The columns worked as an efficient barrier for some time, increasing the pH of the circulating solutions from 2 to 6–7 and removing its metal content. However, after some time (several weeks, depending on the conditions), the columns became chemically inert. The results showed that passivation time increased with decreasing anion and metal content of the solutions. Gypsum was the phase responsible for the passivation of calcite in the experiments with Fe(III)–SO4–H+ solutions. Schwertmannite and goethite appeared as the Fe(III) secondary phases in those experiments. Akaganeite was the phase responsible for the passivation of the system in the experiments with Fe(III)–Cl–H+ solutions.  相似文献   

19.
The authors report a redox profile based on Mössbauer data of spinel and garnet to a depth of 210 km from mantle xenoliths of the northern (N) and southeastern (SE) Slave craton (northern Canada). The profile transects three depth facies of peridotites that form segments of different bulk composition, represented by spinel peridotite, spinel–garnet peridotite, low-temperature garnet peridotite, high-temperature garnet peridotite, and pyroxenite. The shallow, more depleted N Slave spinel peridotite records lower oxygen fugacities compared to the deeper, less depleted N Slave spinel–garnet peridotite, consistent with their different spinel Fe3+ concentrations. Garnet peridotites show a general reduction in log fO2 (FMQ)s with depth, where values for garnet peridotites are lower than those for spinel–garnet peridotites. There is a strong correlation between depletion and oxygen fugacity in the spinel peridotite facies, but little correlation in the garnet peridotite facies. The strong decrease in log fO2 (FMQ) with depth that arises from the smaller partial molar volume of Fe3+ in garnet, and the observation of distinct slopes of log fO2 (FMQ) with depth for spinel peridotite compared to spinel–garnet peridotite strongly suggest that oxygen fugacity in the cratonic peridotitic mantle is intrinsically controlled by iron equilibria involving garnet and spinel.
C. McCammonEmail: Phone: +49-921-553709Fax: +49-921-553769
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20.
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