A CNDO/2 molecular orbital study of the silica polymorphs quartz,cristobalite, and coesite     

Meagher  E. P.  Tossell  J. A.  Gibbs  G. V. 《Physics and Chemistry of Minerals》1979,4(1):11-21

CNDO/2 MO calculations on H₁₂Si₅O₁₆ clusters modeling silicate tetrahedral linkage in the silica polymorphs show total energy minima at bent SiOSi angles and a correlation between the Si-O bond lengths, d(Si-O), used in the calculation and the minimum energy value of the SiOSi angle. Calculations on hydrogen saturated Si₅O₁₆ clusters isolated from the structures of low quartz, low cristobalite and coesite which were adjusted by DLS methods so that all d(Si-O) equal 1.61 Å and all _L OSiO equal 109.47° yield Mulliken bond overlap populations, n(Si-O), and Si-O two-center energies, E(Si-O), which correlate with observed bond lengths; shorter bonds involve larger n(Si-O) values and more negative E(Si-O) values.

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The tetrahedral framework in glasses and melts — inferences from molecular orbital calculations and implications for structure,thermodynamics, and physical properties     

A. Navrotsky  K. L. Geisinger  P. McMillan  G. V. Gibbs 《Physics and Chemistry of Minerals》1985,11(6):284-298

Results of ab initio molecular orbital (MO) calculations provide a basis for the interpretation of structural and thermodynamic properties of crystals, glasses, and melts containing tetrahedrally coordinated Si, Al, and B. Calculated and experimental tetrahedral atom-oxygen (TO) bond lengths are in good agreement and the observed average SiO and AlO bond lengths remain relatively constant in crystalline, glassy, and molten materials. The TOT framework geometry, which determines the major structural features, is governed largely by the local constraints of the strong TO bonds and its major features are modeled well by ab initio calculations on small clusters. Observed bond lengths for non-framework cations are not always in agreement with calculated values, and reasons for this are discussed in the text. The flexibility of SiOSi, SiOAl, and AlOAl angles is in accord with easy glass formation in silicates and aluminosilicates. The stronger constraints on tetrahedral BOB and BOSi angles, as evidenced by much deeper and steeper calculated potential energy versus angle curves, suggest much greater difficulty in substituting tetrahedral B than Al for Si. This is supported by the pattern of immiscibility in borosilicate glasses, although the occurrence of boron in trigonal coordination is an added complication. The limitations on glass formation in oxysulfide and oxynitride systems may be related to the angular requirements of SiSSi and Si(NH)Si groups. Although the SiO and AlO bonds are the strongest ones in silicates and aluminosilicates, they are perturbed by other cations. Increasing perturbation and weakening of the framework occurs with increasing ability of the other atom to compete with Si or Al for bonding to oxygen, that is, with increasing cation field strength. The perturbation of TOT groups, as evidenced by TO bond lengthening predicted by MO calculations and observed in ordered crystalline aluminosilicates, increases in the series Ca, Mg and K, Na, Li. This perturbation correlates strongly with thermochemical mixing properties of glasses in the systems SiO₂-M ₁ ^n/n+ AlO₂ and SiO₂-M ⁿ⁺O _n/2 (M=Li, Na, K, Rb, Cs, and Mg, Ca, Sr, Ba, Pb), with tendencies toward immiscibility in these systems, and with systematics in vibrational spectra. Trends in physical properties, including viscosity at atmospheric and high pressure, can also be correlated.  相似文献   

A computer model for the cubic sodalite structure     

D. Taylor  C. M. B. Henderson 《Physics and Chemistry of Minerals》1978,2(4):325-336

A computer model for cubic sodalite structures, general formula M ₈(T ₁₂O₂₄)X ₂ where M, X and T are the cavity cation and anion and framework cation respectively, has been devised. It has been used to determine the effect of changing cavity cation and anion radii on the cell edge, tilt angle of the tetrahedra and T-O-T angle for the following sodalite frameworks: (Al₆Si₆O₂₄)^6?, (Be₆Si₆O₂₄)^12?, (Al₁₂O₂₄)^12?, and (B₁₂O₂₄)^12?. After fixing the T-O distance(s), the cavity cation-framework oxygen distance and taking a value of 1.4 Å for the radius of oxygen the model was used to calculate atomic coordinates and interatomic distances and angles for selected aluminosilicate-sodalites. The structure calculated for Na₈(Al₆Si₆O₂₄)Cl₂ agrees closely with that determined for natural sodalite (Löns and Schulz, 1967). The model is also applied to the estimation of the effective radii of the tetrahedrally-coordinated cavity anions which can be accommodated in natural and synthetic sodalites: OH^? 1.48–1.51, Cl^? 1.78, Br^? 1.93, I^? 2.14–2.17, SO ₄ ^2? 2.37–2.57, MoO ₄ ^2? 2.70 and WO ₄ ^2? 2.79 Å.  相似文献   

A method for calculating fractional s-character for bonds of tetrahedral oxyanions in crystals     

M. B. Boisen Jr.  G. V. Gibbs 《Physics and Chemistry of Minerals》1987,14(4):373-376

A method for calculating fractional s-character, f _s , for TO bonds has been devised to apply to TO₄ tetrahedral oxyanions in crystals. These f _s -values rank bond lengths with the better correlations obtained for T atoms associated with larger bond strengths and larger electronegativities. As a simple formula, it is found that 2cot²〈?〉₃ does a good job of estimating f _s where 〈?〉₃ is the triple angle average of the three angles common to a given bond.  相似文献   

Oxygen-exchange pathways in aluminum polyoxocations     

James R Rustad  John S Loring 《Geochimica et cosmochimica acta》2004,68(14):3011-3017

Using molecular dynamics simulations and electronic structure methods, we postulate a mechanism to explain the complicated reactivity trends that are observed for oxygen isotope exchange reactions between sites in aluminum polyoxocations of the ε-Keggin type and bulk solution. Experimentally, the molecules have four nonequivalent oxygens that differ considerably in reactivity both within a molecule, and between molecules in the series: Al₁₃, GaAl₁₂, and GeAl₁₂ [MO₄Al₁₂(OH)₂₄(H₂O)₁₂ⁿ⁺(aq); with M = Al(III) for Al₁₃, n = 7; M = Ga(III) for GaAl₁₂, n = 7; M = Ge(IV) for GeAl₁₂, n = 8]. We find that a partly dissociated, metastable intermediate molecule of expanded volume is necessary for exchange of both sets of μ₂-OH and that the steady-state concentration of this intermediate reflects the bond strengths between the central metal and the μ₄-O. Thus the central metal exerts extraordinary control over reactions at hydroxyl bridges, although these are three bonds away.This mechanism not only explains the reactivity trends for oxygen isotope exchange in μ₂-OH and η-OH₂ sites in the ε-Keggin aluminum molecules, but also explains the observation that the reactivities of minerals tend to reflect the presence of highly coordinated oxygens, such as the μ₄-O in boehmite, α-, and γ-Al₂O₃ and their Fe(III) analogs. The partial dissociation of these highly coordinated oxygens, coupled with simultaneous activation and displacement of neighboring metal centers, may be a fundamental process by which metals atoms undergo ligand exchanges at mineral surfaces.  相似文献   

XPS spectra of uranyl minerals and synthetic uranyl compounds. I: The U 4f spectrum     

M. Schindler  F.C. Hawthorne  P.C. Burns 《Geochimica et cosmochimica acta》2009,73(9):2471-7290

The occurrence and binding energies of the U⁶⁺, U⁵⁺ and U⁴⁺ bands in the U 4f_7/2 peak of 19 uranyl minerals of different composition and structure were measured by XPS. The results suggest that these minerals can be divided into the following four groups: (1) Uranyl-hydroxy-hydrate compounds with no or monovalent interstitial cations; (2) Uranyl-hydroxy-hydrate minerals with divalent interstitial cations; (3) Uranyl-oxysalt minerals with (TO_n) groups (T = Si, P, and C) in which all equatorial O-atoms of the uranyl-polyhedra are shared with (TO_n) groups; (4) Uranyl-oxysalt minerals with (TO_n) groups (T = S and Se), in which some equatorial O-atoms are shared only between uranyl polyhedra. The average binding energies of the U⁶⁺and U⁴⁺ bands shift to lower values with (1) incorporation of divalent cations and (2) increase in the Lewis basicity of the anion group bonded to U. The first observation is a consequence of an increase in the bond-valence transfer from the interstitial species (cations, H₂O) groups to the O-atoms of the uranyl-groups, which results in an electron transfer from O to U⁶⁺. The second trend correlates with an increase in the covalency of the UO bonds with increase in Lewis basicity of the anion group, which results in a shift of the electron density from O to U. The presence of U⁴⁺ on the surface of uranyl minerals can be detected by the shape of the U 4f_7/2 peak, and the occurrence of the U 5f peak and satellite peaks belonging to the U 4f_5/2 peak. The presence of U⁴⁺ in some of the uranyl minerals and synthetics examined may be related to the conditions during their formation. A charge-balance mechanism is proposed for the incorporation of lower-valence U in the structure of uranyl minerals. Exposure of a Na-substituted metaschoepite crystal in air and to Ultra-High Vacuum results in dehydration of its surface structure associated with a shift of the U⁶⁺ bands to higher binding energies. The latter observation indicates a shift in electron density from U to O, which must be related to structural changes inside the upper surface layers of Na-substituted metaschoepite.  相似文献   

Ab initio calculated geometries and charge distributions for H4SiO4 and H6Si2O7 compared with experimental values for silicates and siloxanes     

M. D. Newton  G. V. Gibbs 《Physics and Chemistry of Minerals》1980,6(3):221-246

Ab initio STO-3G molecular orbital theory has been used to calculate energy-optimized Si-O bond lengths and angles for molecular orthosilicic and pyrosilicic acids. The resulting bond length for orthosilicic acid and the nonbridging bonds for pyrosilicic acid compare well with Si-OH bonds observed for a number of hydrated silicate minerals. Minimum energy Si-O bond lengths to the bridging oxygen of the pyrosilicic molecule show a close correspondence with bridging bond length data observed for the silica polymorphs and for gas phase and molecular crystal siloxanes when plotted against the SiOSi angle. In addition, the calculations show that the mean Si-O bond length of a silicate tetrahedron increases slightly as the SiOSi angle narrows. The close correspondence between the Si-O bond length and angle variations calculated for pyrosilicic acid and those observed for the silica polymorphs and siloxanes substantiates the suggestion that local bonding forces in solids are not very different from those in molecules and clusters consisting of the same atoms with the same coordination numbers. An extended basis calculation for H₄SiO₄ implies that there are about 0.6 electrons in the 3d-orbitals on Si. An analysis of bond overlap populations obtained from STO-3G* calculations for H₆Si₂O₇ indicates that Si-O bond length and SiOSi angle correlations may be ascribed to changes in the hybridization state of the bridging oxygen and (d – p) π-bonding involving all five of the 3d AO's of Si and the lone-pair AO's of the oxygen. Theoretical density difference maps calculated for H₆Si₂O₇ show a build-up of charge density between Si and O, with the peak-height charge densities of the nonbridging bonds exceeding those of the bridging bonds by about 0.05 e Å^?3. In addition, atomic charges (+1.3 and ?0.65) calculated for Si and O in a SiO₂ moiety of the low quartz structure conform reasonably well with the electroneutrality postulate and with experimental charges obtained from monopole and radial refinements of diffraction data recorded for low quartz and coesite.  相似文献   

A bond-topological approach to theoretical mineralogy: crystal structure, chemical composition and chemical reactions     

Frank C. Hawthorne 《Physics and Chemistry of Minerals》2012,39(10):841-874

Here, I describe a theoretical approach to the structure and chemical composition of minerals based on their bond topology. This approach allows consideration of many aspects of minerals and mineral behaviour that cannot be addressed by current theoretical methods. It consists of combining the bond topology of the structure with aspects of graph theory and bond-valence theory (both long range and short range), and using the moments approach to the electronic energy density-of-states to interpret topological aspects of crystal structures. The structure hierarchy hypothesis states that higher bond-valence polyhedra polymerize to form the (usually anionic) structural unit, the excess charge of which is balanced by the interstitial complex (usually consisting of large low-valence cations and (H₂O) groups). This hypothesis may be justified within the framework of bond topology and bond-valence theory, and may be used to hierarchically classify oxysalt minerals. It is the weak interaction between the structural unit and the interstitial complex that controls the stability of the structural arrangement. The principle of correspondence of Lewis acidity–basicity states that stable structures will form when the Lewis-acid strength of the interstitial complex closely matches the Lewis-base strength of the structural unit, and allows us to examine the factors that control the chemical composition and aspects of the structural arrangements of minerals. It also provides a connection between a structure, the speciation of its constituents in aqueous solution and its mechanism of crystallization. The moments approach to the electronic energy density-of-states provides a link between the bond topology of a structure and its thermodynamic properties, as indicated by correlations between average anion coordination number and reduced enthalpy of formation from the oxides for ^[6]Mg _m ^[4] Si _n O_(m+2n) and MgSO₄(H₂O) _n .  相似文献   

57Fe mössbauer study of clinopyroxenes in the join CaFe3+ AlSiO6 - CaTiAl2O6     

Masahide Akasaka 《Physics and Chemistry of Minerals》1983,9(5):205-211

Synthetic clinopyroxenes of compositions between CaFe³⁺AlSiO₆ and CaFe _0.85 ³⁺ Ti_0.15Al_1.15Si_0.85O₆ have been studied by ⁵⁷Fe Mössbauer spectroscopy. The spectra consist of two doublets assigned to Fe³⁺ in M1 and T sites. From the area ratios of the doublets the site occupancies of Fe³⁺ and Al were determined. Si decreases from 1.00 to 0.85 and Al+Fe³⁺ increases from 1.00 to 1.15 per formula unit with increasing CaTiAl₂O₆ component of the clinopyroxene. The atomic ratio of Fe³⁺(T)/Fe³⁺(total) is 0.11–0.16; 4.5–7.5 percent of the T sites are occupied by Fe³⁺. Thus the presence of Si-O-Fe³⁺, Al-O-Fe³⁺, and Fe³⁺-O-Fe³⁺ bonds is expected in addition to Si-O-Si, Si-O-Al and Al-O-Al bonds. However, the possibility of the former bonds being present would be small, because the amount of Fe³⁺(T) is far less than that of Si and Al. The isomer shift of Fe³⁺(T) is one of the largest in the values found previously for Fe³⁺(T) in silicates. It increases with increasing CaTiAl₂O₆ component and seems to be correlated to the ionic character of the cation — anion bonds calculated from electronegativity. The quadrupole splittings of Fe³⁺(M1) and Fe³⁺(T) decrease with the substitution of Fe³⁺?Ti⁴⁺ in the M1 and of Si?Al in the T sites.  相似文献   

Climatic and hydrologic variability during the past millennium in the eastern Rocky Mountains and northern Great Plains of western Canada   总被引：1，自引：0，他引：1  

Thomas W.D. Edwards  S. Jean Birks  Glen M. MacDonald 《Quaternary Research》2008,70(2):188-197

Modelling of tree-ring δ¹³C and δ¹⁸O data from the Columbia Icefield area in the eastern Rocky Mountains of western Canada provides fuller understanding of climatic and hydrologic variability over the past 1000 yr in this region, based on reconstruction of changes in growth season atmospheric relative humidity (RH_grs), winter temperature (T_win) and the precipitation δ¹⁸O-T_win relation. The Little Ice Age (~ AD 1530s-1890s) is marked by low RH_grs and T_win and a δ¹⁸O-T_win relation offset from that of the present, reflecting enhanced meridional circulation and persistent influence of Arctic air masses. Independent proxy hydrologic evidence suggests that snowmelt sustained relatively abundant streamflow at this time in rivers draining the eastern Rockies. In contrast, the early millennium was marked by higher RH_grs and T_win and a δ¹⁸O-T_win relation like that of the 20th century, consistent with pervasive influence of Pacific air masses because of strong zonal circulation. Especially mild conditions prevailed during the “Medieval Climate Anomaly” ~ AD 1100-1250, corresponding with evidence for reduced discharge in rivers draining the eastern Rockies and extensive hydrological drought in neighbouring western USA.  相似文献   

Solubility and complexing of Ni in the system NiO-H2O-HCl     

Saulwood Lin  Robert K. Popp 《Geochimica et cosmochimica acta》1984,48(12):2713-2722

The solubility of bunsenite (NiO) in Cl-bearing fluids in the range of 450°–700°C, 1–2 kbar was determined using the Ag + AgCl acid buffer technique. Based on the results of the experiments, it is concluded that the associated NiCl⁰₂ complex is the dominant Ni species in the fluid over the entire temperature-pressure range investigated. The temperature dependence of the equilibrium constant for the reaction NiO(s) + 2HCl⁰(aq) = NiCl⁰₂(aq) + H₂O is given by logK = ?4.17(±0.55) + 4629(±464)/T(K) at 1 kbar, and logK = ?4.75(±0.91) + 5933(±756)/T(K) at 2 kbar. The calculated difference in standard state Gibbs free energy of formation between NiCl⁰₂ and 2HCl⁰ in kcal is G⁰(NiCl⁰₂) ? 2G⁰(HCl⁰) = ?20.77(±2.22) + 0.03264(±0.0026)T(K), at 1 kbar and G⁰(NiCl⁰₂) ? 2G⁰(HCl⁰) = ?25.01(±1.35) + 0.03264(±0.0016)T(K) at 2 kbar. Comparison of the solubilities of Ni end-member minerals with those of Ca, Mn, Fe, and Mg indicates that nickel minerals generally are the least soluble at a given temperature and pressure. The relatively low solubility of Ni end-member minerals, combined with the relatively low concentration of Ni in most rocks, should result in a quite low mobility of Ni in hydrothermal fluids.  相似文献   

The SiO bond and electron density distributions     

G. V. Gibbs  F. C. Hill  M. B. Boisen Jr. 《Physics and Chemistry of Minerals》1997,24(3):167-178

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Structural variation of babingtonite depending on cation distribution at the octahedral sites     

Mariko Nagashima  Keiko Mitani  Masahide Akasaka 《Mineralogy and Petrology》2014,108(2):287-301

Babingtonite, Ca₂Fe²⁺Fe³⁺[Si₅O₁₄(OH)] (Z?=?2, space group $ P\overline{1} $ ) from Yakuki mine (Japan), Grönsjöberget (Sweden), Kandivali Quarry (India), Baveno Quarry (Italy), Bråstad Mine (Norway), and Kouragahana (Japan), and manganbabingtonite, Ca₂(Mn²⁺, Fe²⁺)Fe³⁺[Si₅O₁₄(OH)], from Iron Cap mine (USA) were studied using electron-microprobe analysis (EMPA), ⁵⁷Fe Mössbauer analysis and single-crystal X-ray diffraction methods to determine the cation distribution at M1 and M2 and to analyze its effect on the crystal structure of babingtonite. Although all studied babingtonite crystals are relatively homogeneous, chemical zonation due to mainly Fe ? Mn substitution is observed in manganbabingtonite. Mössbauer spectra consist of two doublets with isomer shift (I.S.)?=?1.16–1.22 mm/s and quadrupole splitting (Q.S.)?=?2.33–2.50 mm/s and with I.S.?=?0.38–0.42 mm/s and Q.S.?=?0.82–0.90 mm/s, assigned to Fe²⁺ and Fe³⁺ at the M1 and M2 octahedral sites, respectively. The determined ratio of Fe²⁺/total Fe in manganbabingtonite (0.26) was smaller than that in the others (0.35–0.44) because of high Mn²⁺ content instead of Fe²⁺. The unit-cell parameters of babingtonite are a?=?7.466–7.478, b?=?11.624–11.642, c?=?6.681–6.690 Å, α?=?91.53–91.59, β?=?93.86–93.94, γ?=?104.20–104.34º, and V?=?560.2–562.3 Å³, and those of manganbabingtonite are a?=?7.4967(3), b?=?11.6632(4), c?=?6.7014(2) Å, α?=?91.602(2), β?=?93.989(2), γ?=?104.574(3)º, and V =565.09(5) ų. Structural refinements converged to R ₁ values of 1.64–3.16 %. The <M1-O> distance was lengthened due to the substitution of large octahedral cations such as Mn²⁺ for Fe²⁺. The increase of the M1-O8, M1-O8’ and M1-O13 lengths with mean ionic radii is slightly more pronounced than of the other M1-Oi lengths. The lengthened M1-O13 distance leads the positive correlation between Si5-O15-Si1 angle and M1-O13 distance. The increase of Si2-O3-Si1 and Si5-O12-Si4 angles due to the increase of mean ionic radius of M2 is also observed.  相似文献   

A qualitative molecular orbital study of the stability of polyanions in mineral structures     

J. A. Tossell 《Physics and Chemistry of Minerals》1983,9(3-4):115-123

The existence and structures of various polyanion species, A _k ^n? ,occurring in inorganic compounds and minerals are rationalized using qualitative molecular orbital (MO) theory. Polyanions which may be stabilized by high pressure or lattice defects are discussed and compounds likely to show such species are identified. Previously observed high pressure properties of Fe riebeckite and MgO are interpreted in terms of O - O bond formation at high pressure.  相似文献   

High-pressure crystal chemistry of phenakite (Be2SiO4) and bertrandite (Be4Si2O7(OH)2)     

Robert M. Hazen  Andrew Y. Au 《Physics and Chemistry of Minerals》1986,13(2):69-78

Compressibilities and high-pressure crystal structures have been determined by X-ray methods at several pressures for phenakite and bertrandite. Phenakite (hexagonal, space group R \(\bar 3\) ) has nearly isotropic compressibility with β=1.60±0.03×10^?4 kbar^?1 and β=1.45±0.07×10^?4 kbar^?1. The bulk modulus and its pressure derivative, based on a second-order Birch-Murnaghan equation of state, are 2.01±0.08 Mbar and 2±4, respectively. Bertrandite (orthorhombic, space group Cmc2₁) has anisotropic compression, with β _a =3.61±0.08, β _b =5.78±0.13 and β _c =3.19±0.01 (all ×10^?4 kbar^?1). The bulk modulus and its pressure derivative are calculated to be 0.70±0.03 Mbar and 5.3±1.5, respectively. Both minerals are composed of frameworks of beryllium and silicon tetrahedra, all of which have tetrahedral bulk moduli of approximately 2 Mbar. The significant differences in linear compressibilities of the two structures are a consequence of different degrees of T-O-T bending.  相似文献   

Complex formation of Cm(III) with formate studied by time-resolved laser fluorescence spectroscopy     

《Applied Geochemistry》2015

Pore waters of natural clays, which are investigated as potential host rock formations for high-level nuclear waste, are known to contain large amounts of low-molecular weight organic compounds. These small organic ligands might impact the aqueous geochemistry of the stored radionuclides and, thus, their migration behavior. In the present work, the complexation of Cm(III) with formate in aqueous NaCl solution is investigated by time-resolved laser fluorescence spectroscopy (TRLFS) as a function of the ionic strength (0.5–3.0 mol/kg), the ligand concentration (0–0.2 mol/kg) and the temperature (20–90 °C). The Cm(III) speciation is determined by deconvolution of the emission spectra. The obtained distribution of Cm(III) species is used to calculate the conditional stability constants (log K′(T)) at a given temperature and ionic strength which are extrapolated to zero ionic strength by using the specific ion interaction theory (SIT). Thus, the thermodynamic log K⁰_n(T) values for the formation of [Cm(Form)_n]⁽³⁻ⁿ⁾⁺ (n = 1, 2) and the ion interaction coefficients (ε(i,k)) for [Cm(Form)_n]⁽³⁻ⁿ⁾⁺ (n = 1, 2) with Cl⁻ are obtained. The log K⁰₁(T) (2.11 (20 °C)–2.49 (90 °C)) and log K⁰₂(T) values (1.17 (30 °C–2.01 (90 °C)) increase continuously with increasing temperature. The log K⁰_n(T) values are used to derive the standard reaction enthalpies and entropies (Δ_rH⁰_m, Δ_rS⁰_m) of the respective complexation reactions according to the Van’t Hoff equation. In all cases, positive Δ_rH⁰_m and Δ_rS⁰_m values are obtained. Thus, both complexation steps are endothermic and entropy-driven.  相似文献   

Hydrogen isotope fractionation between OH-bearing minerals and water     

Tetsuro Suzuoki  Samuel Epstein 《Geochimica et cosmochimica acta》1976,40(10):1229-1240

Hydrogen isotope fractionation factors between hydroxyl-bearing minerals and water were determined at temperatures ranging between 400 and 850°C. The hydrogen isotope exchange rates for the mineral-water pairs examined were very slow. In most cases it was necessary to use an interpolation method for the determination of the hydrogen isotope equilibrium fractionation factor, α_e.For the temperature range of 450–850°C the hydrogen isotope fractionation factors for the mica-water and amphibole-water systems are simply expressed as a function of temperature and the molar fractions of the six-fold coordinated cations in the crystal, regardless of mineral species, as follows: 10³ In α_{e(mineral-water)} = ? 22.4 (10⁶T^?2) + 28.2 + (2X_Al ? 4X_Mg ? 68X_Fe), where X is the molar fraction of the cations. As the equation indicates, for any specific composition of the OH-bearing minerals, the change of α_e with temperature, over the temperature range investigated, is the same for all minerals studied. Thus for any specified values of X_Al, X_Mg, and X_Fe for these minerals, the relationship between α_e and T is 10³ In α_e = αT^?2 + k. Consequently, hydrogen isotope fractionation among coexisting minerals is temperature independent and cannot be used as a hydrogen isotope geothermometer.Some exceptions to the above general observations exist for minerals such as boehmite and kaolinite. In these minerals hydrogen bonding modifies the equilibrium hydrogen isotopic fractionation between mineral and water.  相似文献   

Distance least squares modelling of the cubic sodalite structure and of the thermal expansion of Na8(Al6Si6O24)I2     

M. J. Dempsey  D. Taylor 《Physics and Chemistry of Minerals》1980,6(3):197-208

The Distance Least Squares (DLS) structure modelling technique is used to determine the room-temperature structures of the sodalites Li₈(Al₆Si₆O₂₄)Cl₂, Na₈(Al₆Si₆O₂₄)Cl₂, K₈(Al₆Si₆O₂₄)Cl₂, Na₈(Al₆Si₆O₂₄)Br₂, and Na₈(Al₆Si₆O₂₄)I₂. The technique is also used to calculate the thermal expansion behaviour of Na₈(Al₆Si₆O₂₄)I₂ assuming that the discontinuity in its thermal expansion curve occurred either when the ideal fully-expanded state was achieved (case 1) or when the x-coordinate of the sodium atom became 0.25 (case 2). The results are given as plots of bond lengths and bond angles as a function of temperature. Case 2 was preferred and analysis of the results implied that the driving force for the untwisting of the partially-collapsed sodalite framework was in the framework bonds with the cavity ion bonds resisting the untwisting. Best estimates indicate that the expansion of the Na-O and Na-I bonds are 9% and 27.4% respectively, between room temperature and 810° C, and there is an apparent shortening of the framework bond distances of about 1.5%.  相似文献   

Carbon Dioxide in igneous petrogenesis: I     

Frank J. Spera  Steven C. Bergman 《Contributions to Mineralogy and Petrology》1980,74(1):55-66

A number of experimental CO₂ solubility data for silicate and aluminosilicate melts at a variety of P- T conditions are consistent with solution of CO₂ in the melt by polymer condensation reactions such as SiO _4(m ^4? +CO_2(v)+Si _n O _3n+1(m) ⁽²ⁿ⁺¹⁾ ?Si _n+1O _3n+4(m) ^(2n+4)? +CO _3(m ^)2? . For various metalsilicate systems the relative solubility of CO₂ should depend markedly on the relative Gibbs free change of reaction. Experimental solubility data for the systems Li₂O-SiO₂, Na₂O-SiO₂, K₂O-SiO₂, CaO-SiO₂, MgO-SiO₂ and other aluminosilicate melts are in complete accord with predictions based on Gibbs Free energies of model polycondesation reactions. A rigorous thermodynamic treatment of published P- T-wt.% CO₂ solubility data for a number of mineral and natural melts suggests that for the reaction CO_2(m) ? CO_2(v)

1. CO₂-melt mixing may be considered ideal (i.e., { \(a_{{\text{CO}}_{\text{2}} }^m = X_{{\text{CO}}_{\text{2}} }^m \) );
2. \(\bar V_{{\text{CO}}_{\text{2}} }^m \) , the partial molal volume of CO₂ in the melt, is approximately equal to 30 cm³ mole^?1 and independent of P and T;
3. Δ C _p ⁰ is approximately equal to zero in the T range 1,400° to 1,650 °C and
4. enthalpies and entropies of the dissolution reaction depend on the ratio of network modifiers to network builders in the melt. Analytic expressions which relate the CO₂ content of a melt to P, T, and \(f_{{\text{CO}}_{\text{2}} } \) for andesite, tholeiite and olivine melilite melts of the form

$$\ln X_{{\text{CO}}_{\text{2}} }^m = \ln f_{{\text{CO}}_{\text{2}} } - \frac{A}{T} - B - \frac{C}{T}(P - 1)$$ have been determined. Regression parameters are (A, B, C): andesite (3.419, 11.164, 0.408), tholeiite (14.040, 5.440,0.393), melilite (9.226, 7.860, 0.352). The solubility equations are believed to be accurate in the range 3<P<30 kbar and 1,100°<T<1,650 °C. A series of CO₂ isopleth diagrams for a wide range of T and P are drawn for andesitic, tholeiitic and alkalic melts.  相似文献   

Si,Al ordering in leucite by high-resolution 27Al MAS NMR spectroscopy     

Brian L. Phillips  R. James Kirkpatrick  Andrew Putnis 《Physics and Chemistry of Minerals》1989,16(6):591-598

High-resolution ²⁷Al MAS NMR spectra of natural leucite recorded at H ₀=11.7T contain three resolvable resonances at ²⁷Al δ _i = 69.2, 64.7, and 61.0±0.5 ppm. These three resonances are assigned to the three inequivalent framework positions of leucite: T3, T2, and T1, respectively. Fitting the observed spectra yields a Si,Al distribution for leucite in which approximately one-half of the Al is in T1 and one-quarter in each of T2 and T3. This Si,Al distribution differs substantially from those obtained by previous workers using ²⁹Si NMR spectroscopy and X-ray diffraction. New ²⁹Si NMR spectra and revision of previously reported ²⁹Si NMR peak assignments, however, make the ²⁷Al and ²⁹Si NMR results consistent. The ²⁷Al δ _i correlate linearly with the mean T-O-T′ bond angles of the average structure, which allows the peak assignments to be made. However, this correlation lies distinctly toward higher frequency and larger bond angles than correlations for Si,Al ordered aluminosilicates, suggesting that the mean T(Al)-O-T′(Si) bond angle for each site in leucite is smaller than the mean bond angle of the average structure, which is averaged over T(Al)-O-T′(Si) and T(Si)-OT′(Si,Al) angles.  相似文献