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1.
The intra-crystalline cation partitioning over T- and M-sites in a synthetic Mg(Fe,Al)2O4 spinel sample has been determined as a function of temperature by Rietveld structure refinements from powder diffraction data, combining in situ high-temperature neutron powder diffraction (NPD; POLARIS diffractometer, at ISIS, Rutherford Appleton Laboratory, UK), to determine the Mg and Al occupancy factors, with in situ high-temperature X-ray powder diffraction, to fix the Fe3+ distribution. The results obtained agree with a two-stage reaction, in which an initial exchange between Fe3+ and Mg, the former leaving and the latter entering tetrahedral sites, is successively followed by a rearrangement involving also Al. The measured cation distribution has then been compared and discussed with that calculated by the Maximum Configuration Entropy principle, for which only NPD patterns have been used. The cation partitioning has finally been interpreted in the light of the configuration model of O’Neill and Navrotsky.  相似文献   

2.
Structural investigations at high temperature were carried out on natural columbite samples across the join Fe(Nb0.95Ta0.05)2O6–Mn(Nb0.95Ta0.05)2O6. The samples were preliminarily annealed to attain the complete cation-ordered state and avoid the superimposition of the effects of cation ordering during high-temperature studies. Unit-cell parameters of three columbites with different XFe content were measured at regular intervals in the temperature range 25–900 °C using single-crystal X-ray diffraction techniques. The crystal structures of completely ordered ferrocolumbite and manganocolumbite were also refined from intensity data collected at room temperature, 300 and 600 °C. Structural thermal expansion coefficients show positive, linear expansion of a, b, c lattice constants and cell volume. In general, slightly higher expansion occurs along a and c directions. However, anisotropy decreases sharply with decreasing Fe content. Reversibility of thermal expansion in the investigated temperature range was checked by high-temperature diffraction studies under heating-up and cooling-down conditions. Impurities do not play an important role in thermal expansion of columbites; expansion coefficients measured on two crystals of the same sample characterized by different Ti content are in fact almost identical. Structural changes with temperature essentially affect bond lengths: volumes of both A and B octahedral sites increase linearly with temperature, whereas interpolyhedral geometrical parameters do not vary significantly.  相似文献   

3.
Pumpellyite of the general formula W8X4Y8-Z12O56-n(OH)n contains Fe, Al and Mg in two crystallographically different octahedral sites. Three different pumpellyite samples covering the known compositional field from Al- to Fe-rich have been studied to determine the valence state and intracrystalline partitioning of the Fe cations between the two independent octahedral sites. Fe+2 and Fe+3 cation partitioning is interpreted on the basis of results obtained by 57Fe Mössbauer spectroscopy at 293 and 77 K and from Rietveld structure analysis performed on powder X-ray diffraction data. Pumpellyite from low-grade metamorphic rocks typically contains a majority of iron in the Fe+3 oxidation state, which is found in the smaller and less symmetrical octahedral Y-site. Fe+2 was also present in all pumpellyite samples studied and it is located in the larger and more symmetrical octahedral X-site.  相似文献   

4.
Samples of the eosphorite-childrenite [(Mn2+, Fe2+)AlPO4(OH)2H2O] series from Divino das Laranjeiras and Araçuaí (Minas Gerais State) and Parelhas (Rio Grande do Norte State) pegmatites have been investigated by X-ray diffraction, microprobe analysis and Mössbauer spectroscopy at 295 and 77 K. The Mössbauer spectra of ernstite [(Mn2+, Fe3+)AlPO4(OH)2-xOx] showed the existence of ferric ions in both A and B sites, whereas ferrous ions seem to be located exclusively in the A site. Nonoxidised samples show ferrous ions located in both sites, and no Fe3+ could be detected. The interpretation of the Mössbauer spectra of both, oxidised and nonoxidised samples, is difficult because the hyperfine parameters of these minerals are rather similar, rendering it difficult to make proper site assignments.  相似文献   

5.
The partitioning of Fe and Mn between the large M(4) site and the octahedral sites, M(1,2,3) in the amphibole structure has been investigated in two natural manganogrunerites of compositions Ca0.1Mn1.9 Mg1.25Fe2+ 3.56Fe3+ 0.38Si7.81O22(OH)2 and Ca0.24Mn1.57 Mg2.27 Fe2+ 2.76Fe3+ 0.32Si7.84O22(OH)2. The long-range cation distribution in the two samples has been elucidated by in situ neutron powder diffraction revealing that Mn is preferentially ordered onto M(4) ? M(2) >M(1) >M(3) in both samples. Partitioning of Mn from M(4) into the octahedral sites begins at 350 °C, with site exchange energies of ?16.6 kJ mol?1 and ?14.9 kJ mol?1, in samples containing 1.90 and 1.57 Mn apfu, respectively. Mössbauer and infrared spectroscopy have been used to study the samples at room temperature, and Mössbauer data agree well with the diffraction results, confirming that high-temperature cation distributions are retained during cooling. The fine structure in the hydroxyl-stretching region of the IR absorption spectra has been used to discuss qualitatively the site occupancies of the coordinating M(1)M(3)M(1) triplet, linked by O(3). On the basis of such modelling, we conclude that a degree of local clustering is present in both samples.  相似文献   

6.
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   

7.
Synthetic almandine garnet, Fe3Al2Si3O12, has been studied by temperature — dependent single crystal X-ray diffraction and57Fe Mössbauer spectroscopy. The Fe2+ doublet in almandine is characterized by a small asymmetry between the high and low-velocity peaks that decreases in magnitude with decreasing temperature from 420 to 15 K. The X-ray results show that the Fe2+ cation is dynamically disordered with an anisotropic motion within the eight-coordinated site in garnet. The magnitudes of the X-ray determined mean-square-vibrational amplitudes of this motion parallel,x ∥, and perpendicular,x ⊥, to the principle axes of the electric field gradient give a calculated angular dependence of the electric quadrupole interaction of theI 1/2 toI 3/2 transitions that agree with the experimentally measured peak ratios. This is the first recognition of anisotropic recoil free fraction of57Fe in silicates.  相似文献   

8.
We have prepared aqueous MgSO4 solutions doped with various divalent metal cations (Ni2+, Zn2+, Mn2+, Cu2+, Fe2+, and Co2+) in proportions up to and including the pure end-members. These liquids have been solidified into fine-grained polycrystalline blocks of metal sulfate hydrate + ice by rapid quenching in liquid nitrogen. In a companion paper (Fortes et al., in Phys Chem Min 39) we reported the identification of various phases using X-ray powder diffraction, including meridianiite-structured undecahydrates, melanterite- and epsomite-structured heptahydrates, novel enneahydrates and a new octahydrate. In this work we report the changes in unit-cell parameters of these crystalline products where they exist over sufficient dopant concentrations. We find that there is a linear relationship between the rate of change in unit-cell volume as a function of dopant concentration and the ionic radius of the dopant cation; large ions such as Mn2+ produce a substantial inflation of the hydrates’ unit-cell volume, whereas smaller ions such as Ni2+ produce a modest reduction in unit-cell volume. Indeed, when the data for all hydrates are normalised (i.e., divided by the number of formula units per unit-cell, Z, and the hydration number, n), we find a quantitatively similar relationship for different values of n. Conversely, there is no relationship between the degree of unit-cell inflation or deflation and the limit to which a given cation will substitute into a certain hydrate structure; for example, Co2+ and Zn2+ affect the unit-cell volume of MgSO4·11H2O to a very similar degree, yet the solubility limits inferred in our companion paper are >60 mol. % Co2+ and <30 mol. % Zn2+.  相似文献   

9.
As a contribution to the systematic study of iron oxide thermodynamics, this work reports enthalpies of formation of green rust, a double layered (FeII, FeIII) hydroxide with the ideal stoichiometry , with sulfate as the anion in the interlayer. Samples were characterized by X-ray powder diffraction, thermogravimetric analysis, infrared spectroscopy, and Mössbauer spectroscopy. Full chemical analysis was performed. Contents of FeII, FeIII, water, and sulfate were obtained. We report standard enthalpies of formation for green rust with different FeII/FeIII ratios. Enthalpies of formation from single cation compounds, namely, Fe(OH)2, Fe(OH)3, FeSO4 and H2O show reasonable agreement with Gibbs free energies of formation from single cation compounds recalculated from the reported literature values. These values show that green rust has little stabilization over a mechanical mixture of these single cation compounds and there is no thermodynamic preference for any particular FeII/FeIII ratio.  相似文献   

10.
Ilvaite samples from six different localities in Japan are found to be members of a solid-solution series varying from Ca(Fe2+,Fe3+)2Fe2+(OH)O Si2O7 to approaximately Ca(Fe2+,Fe3+)2Fe 0.5 2+ Mn 0.5 2+ (OH)O Si2O7, and have been studied by Mössbauer spectrometry and magnetic measurements. The variation in intensity of Mössbauer doublets confirms that Mn substitutes for Fe2+ in the M(B) cation site. An temperatures decreasing from 300 K to 4K, an abrupt change in the reciprocal mass magnetic susceptibility, 1/x g, occurs about 120 K; 1/x g depends linearly upon temperature above 120 K. This change, which is characterized by an unusual mode of decrease in 1/x g, has been interpreted based on Mössbauer spectra at 80 K: the spectra of Fe2+ and Fe3+ in the M(A) site show Zeeman splitting, whereas those of Fe2+ in the M(B) site do not show the effect. This Mössbauer evidence suggests that magnetic spins of Fe in M(A) are in an ordered state, very likely of antiparallel coupling, whereas those of Fe in M(B) are randomly oriented, showing that below 120 K ilvaite has two different magnetic states for Fe ions. As there is a line of evidence that the spins of Fe in M(B) would take an ordered state at extremely low temperatures, ilvaite magnetism may be regarded as basically antiferromagnetic. The magnetic spins of Fe in M(A) and M(B) undergo magnetic transitions at different specific temperatures, thus giving as a whole unusual features of magnetism.  相似文献   

11.
Summary Synthesis of Mn-bearing ilvaites, CaFe 2–x 2+ MnxFe3+ [Si2O7/O/(OH)], with 0 x 0.19, have been performed under hydrothermal conditions at 2 and 3 kbars, T = 300 -400°C and at oxygen fugacities defined by the Fe2O3/Fe3O4 - and the Ni/NiO -buffer. As shown by X-ray diffraction, the substitution of Fe2+ by Mn2+ decreases the monoclinic angle and causes a phase transition from monoclinic to orthorhombic at x = 0.19. The Fe-distribution has been determined by Mössbauer spectroscopy.
Synthese und Charakterisierung von Mn-haltigem Ilvait CaFe 2–x 2+ MnxFe3+ [Si2O7/O/(OH)]
Zusammenfassung Mn-haltiger Ilvait CaFe 2–x 2+ Mnx Fe3+ [Si2O7/O/(OH)] wurde unter hydrothermalen Bedingungen bei Drucken von 2 und 3 kbar, Temperaturen zwischen 300 und 400°C und bei Sauerstoff Fugazitäten, die durch Festkörperpuffer (Fe2O3/Fe3O4 und Ni/NiO) kontrolliert wurden, hergestellt. Röntgenbeugungsuntersuchungen zeigen, daß mit steigendem Mn-Einbau der monokline Winkel kleiner wird, und daß bei x = 0.19 ein Phasenübergang von der monoklinen zur orthorhombischen Struktur erfolgt. Die Fe-Verteilung wurde mit Mössbauer-Spektroskopie bestimmt.

With 4 Figures  相似文献   

12.
The dependence of the electronic and the crystallographic structure on temperature of synthetic Mnbearing ilvaites CaFe2+ 2-xMn2+ xFe3+ [Si2O7/O/OH] with 0≤x≤0.19 has been investigated. The change of the electronic structure was studied by 57Fe Mössbauer spectroscopy. The spectra show an increasing valence fluctuation rate between Fe2+ and Fe3+ in the double chain of edge-sharing octahedra with increasing temperature resulting in a mixed valent state of iron. The valence fluctuation rate is distinctly increased by the Mnsubstitution. The temperature of the crystallographic phase transition T x as studied by a high temperature Guinier method is distinctly lowered by the Mn-substitution (x = 0.0, T x=390K; x = 0.12, T x =370K; x = 0.19, T x=295K). The reasons for this behaviour are discussed in terms of Fe2 +, Fe3 + cation order-disorder, electronic relaxation rate, and relaxation of the lattice. In the monoclinic phase there is electron hopping between Fe2 +, Fe3 + pairs whereas in the orthorhombic phase there is extended electron delocalization via a narrow, d-band mechanism.  相似文献   

13.
Summary Phosphates of compositions (Na1–xLix)1.5Mn1.5Fe1.5(PO4)3 were synthesized by solid state reactions in air, and pure alluaudite-type compounds were obtained for x=0.00, 0.25, and 0.50. Rietveld refinements of X-ray powder diffraction data indicate the occurrence of Mn2+ in the M(1) site, and of Fe3+ and Mn2+ in the M(2) site. For x=0.25 and 0.50, A(1) is occupied by Li+ and Na+, whereas A(2) is occupied by Na+ and vacancies. A careful examination of the number of electrons occurring in the A sites of the alluaudite-type compounds (Na1–xLix)MnFe2(PO4)3 and (Na1–xLix) CdIn2(PO4)3 confirms that lithium occupies only the A(1) crystallographic site of the alluaudite structure.  相似文献   

14.
Structural and compositional data as well as 57Fe Mössbauer parameters were determined on a natural Mn-rich monoclinic ilvaite crystal (ideal composition CaFe 2 2+ Fe3+Si2O8(OH)) which was used for electrical conductivity and thermopower measurements (part 2 of this paper). A zonar structure was found by electron microprobe analysis with a strong decrease in Mn concentration from the rim to the centre of the crystal in a plane perpendicular to the [001] direction. X-ray powder diffraction analysis of the most Mn-rich composition was performed. Mn2+ cations populate preferentially M2 sites of the ilvaite unit cell (space group P21/a), to a lower extent they reside on M1 and a reduced part is on Ca sites. The monoclinic angle was determined to β=90.178(4)°. The structural results are compared to literature data for other natural Mn-rich as well as low-impurity ilvaites; this concerns in particular the lattice b parameter and the undecided issue of the varying β angle. In the literature, the order parameter σ, which describes the varying degree of ordering of Fe2+–Fe3+ pairs on M11 and M12 sites in chains running parallel to the [001] direction, and structural defects are thought to be related to β. The interrelationship between β and σ with respect to a possible twin domain structure is discussed. Various 57Fe Mössbauer spectra were recorded between 151 K and 327 K. Mössbauer parameters and Fe2+/Fe3+ concentration ratios were determined from the fits to the spectra. Fitting of subspectra was accomplished with the idea to find assignments of Fe2+ and Fe3+ doublets in agreement with X-ray results. The fraction of Mn2+ substituting Fe2+ on M1 sites could be estimated.  相似文献   

15.
Using a conventional high-T furnace, the solid solutions between magnesiochromite and manganochromite, (Mg1−x Mn x )Cr2O4 with x = 0.00, 0.19, 0.44, 0.61, 0.77 and 1.00, were synthesized at 1,473 K for 48 h in open air. The ambient powder X-ray diffraction data suggest that the V–x relationship of the spinels does not show significant deviation from the Vegard’s law. In situ high-T powder X-ray diffraction measurements were taken up to 1,273 K at ambient pressure. For the investigated temperature range, the unit-cell parameters of the spinels increase smoothly with temperature increment, indicating no sign of cation redistribution between the tetrahedral and octahedral sites. The V–T data were fitted with a polynomial expression for the volumetric thermal expansion coefficient (aT = a0 + a1 T + a2 T - 2 \alpha_{T} = a_{0} + a_{1} T + a_{2} T^{ - 2} ), which yielded insignificant a 2 values. The effect of the composition on a 0 is adequately described by the equation a 0 = [17.7(8) − 2.4(1) × x] 10−6 K−1, whereas that on a 1 by the equation a 1 = [8.6(9) + 2.1(11) × x] 10−9 K−2.  相似文献   

16.
We define and calibrate a new model of molar volume as a function of pressure, temperature, ordering state, and composition for spinels in the supersystem (Mg, Fe2+)(Al, Cr, Fe3+)2O4 ? (Mg, Fe2+)2TiO4. We use 832 X-ray and neutron diffraction measurements performed on spinels at ambient and in situ high-P, T conditions to calibrate end-member equations of state and an excess volume model for this system. The effect on molar volume of cation ordering over the octahedral and tetrahedral sites is captured with linear dependence on Mg2+, Al3+, and Fe3+ site occupancy terms. We allow standard-state volumes and coefficients of thermal expansion of the end members to vary within their uncertainties during extraction of the mixing properties, in order to achieve the best fit. Published equations of state of the various spinel end members are analyzed to obtain optimal values of the bulk modulus and its pressure derivative, for each explicit end member. For any spinel composition in the supersystem, the model molar volume is obtained by adding excess volume and cation order-dependent terms to a linear combination of the five end-member volumes, estimated at pressure and temperature using the high-T Vinet equation of state. The preferred model has a total of 9 excess volume and order-dependent parameters and fits nearly all experiments to within 0.02 J/bar/mol, or better than 0.5 % in volume. The model is compared to the current MELTS spinel model with a demonstration of the impact of the model difference on the estimated spinel-garnet lherzolite transition pressure.  相似文献   

17.
Cordierite has the ideal formula (Mg,Fe)2Al4Si5O18 .x(H2O,CO2), but it must contain some Fe3+ to account for its blue color and strong pleochroism. The site occupation and concentration of Fe3+ in two Mg-rich natural cordierites have been investigated by EPR and 57Fe Mössbauer spectroscopy. In addition, powder IR spectroscopy, X-ray diffraction, and TEM examination were used to characterize the samples. Single-crystal and powder EPR spectra indicate that Fe3+ is located on T11 in natural cordierites and not in the channels. The amount in Mg-rich cordierites is very small with an upper limit set by Mössbauer spectroscopy giving less than 0.004 cations per formula unit (pfu). Fe3+ in cordierite can, therefore, be considered insignificant for most petrologic calculations. Heat-treating cordierite in air at 1,000?°C for 2?days causes an oxidation and/or loss of Fe2+ on T11, together with an expulsion of Na+ from the channels, whereas heating at the Fe–FeO buffer produces little Fe3+ in cordierite. Heating at 1,000?°C removes all class I H2O, but small amounts of class II H2O remain as shown by the IR measurements. No evidence for channel Fe2+ or Fe3+ in the heat-treated samples was found. The blue color in cordierite arises from a broad absorption band (E//b and weaker with E//a) around 18,000?cm?1 originating from charge-transfer between Fe2+ in the octahedron and Fe3+ in the edge-shared T11 tetrahedron. It therefore appears that all natural cordierites contain some tetrahedral Fe3+. The brown color of samples heated in air may be due to the formation of very small amounts of submicroscopic magnetite and possibly hematite. These inclusions in cordierite can only be identified through TEM study.  相似文献   

18.
The cation distribution of natural and heated ferromagnesian olivine with chemical composition, Fo67Fa33, from metagabbro was examined by X-ray diffraction. Heating and quenching experiments were made by a newly devised apparatus which enables us to obtain very fast quenching speed in comparison with the usual technique. The distribution constants, K D=(Fe+2/Mg) M1/(Fe+2/Mg) M2, of the natural samples were less than 1.07, and those of heat-treated samples were more than 1.15, indicating that cation ordering takes place with temperature. The distribution of Fe+2 and Mg is nearly random at low temperatures, whereas Fe+2 shows a slight but significant preference for a smaller M1 site at high temperatures. The change of the distribution constant was observed on specimens which were heated for a short period of time (6–1,060 s) and quenched within 10 ms. Thus the rate of the cation reordering reaction is a very fast process. The lattice parameters b and c decrease whereas a increases with the increase of distribution constant. The overall effect on unit cell volume is a decrease with the increasing distribution constant, suggesting the presence of significant pressure dependence of the cation distribution towards the ordering of Fe at M1 site in ferromagnesian olivine.  相似文献   

19.
Infrared reflectance (IR) and Raman spectra were collected on small (ca. 500 micron) single crystals of 5 natural garnets with nearly end-member compositions: pyrope (98% Mg3Al2Si3O12), almandine (83% Fe3Al2Si3O12), spessartine (98% Mn3Al2Si3O12), grossular (97% Ca3Al2Si3O12), and andradite (99% Ca3Fe2Si3O12). Frequencies and symmetry assignments were determined for all 17 IR modes and all 25 Raman modes. By using factor group analysis and by correlating the bands by their intensities, bands were assigned to either one of the SiO4 internal motions, as a rotation, or to a type of translation. The assignments are supported by (1) the distinct trends of frequencies with cell size and cation masses for each of the different types of motion, (2) the similarity of garnet energies for each of the different types of motion to those of olivine with the same cation, and (3) the closeness of the T 1 u IR frequencies to the T 2 g Raman frequencies. Mode mixing appears to be weak. Correlations between frequencies and structural parameters suggests a direct dependence of force constants on lattice parameter. This relationship arises from bond lengths in the garnet structure being constrained by the size and compressibility of adjacent polyhedra through edge-sharing. Comparison of our endmember data with previous powder IR studies of intermediate garnets indicates that dodecahedral (X) and octahedral (Y) sites alone exhibit two-mode behavior for those solid solutions involving two ions with considerably different masses. However, for solid solutions involving cations of much different ionic radii, two-mode behavior is found for the translations of SiO4 groups. This is the first report of two-mode behavior that is unrelated to mass, and instead is due to significantly different force constants in the pyralspites compared to the ugrandites.Anomalies in mixing volumes are linked to two-mode behavior of the SiO4 translations, which leads to the suggestion that the mixing volume behavior is caused by the resistance of the Si-O bond to expansion and compression, as well as to changes in the dodecahedral site. Crystal-field effects may also play an important role within the ugrandite series. Deviation of molar volume dependence on composition from a linear to a asymmetric, non-linear (sometimes sigmoidal) dependence can be linked to solid solutions that possess slightly non-equivalent cation sites.  相似文献   

20.
The local structural heterogeneity and energetic properties of 22 natural Mg–Fe cordierites, ideal formula (Mg,Fe)2Al4Si5O18·x(H2O,CO2), were investigated at length scales given by powder infrared spectroscopy (IR) and also by published electronic absorption spectra. The studied samples have iron mole fractions from XFe = 0.06 to 0.82 and cover most of the Mg–Fe cordierite binary. Variations in wavenumbers and line widths of the IR bands were determined as a function of composition. Most modes shift linearly to lower wavenumbers with increasing XFe, except those at high wavenumbers located between 900 and 1,200 cm-1. They are vibrations that have a large internal (Si,Al)O4 character and are not greatly affected by Mg–Fe exchange on the octahedral site. The lower wavenumber modes can be best characterized as lattice vibrations having mixed character. The systematics of the wavenumber shifts suggest small continuous variations in the "average" cordierite structure with Mg–Fe exchange and are consistent with an ideal volume of mixing, Vmix= 0, behavior (Boberski and Schreyer 1990). IR line broadening was measured using the autocorrelation function for three wavenumber regions in order to determine the range of structural heterogeneity between roughly 2 and 100 Å (0.2–10.0 nm) in the solid solution. In order to do this, an empirical correction was first made to account for the effect that small amounts of channel Na have on the phonon systematics. The results show that between 1,200 and 540 cm-1 the line widths of the IR bands broaden slightly and linearly with increasing XFe. Between 350 and 125 cm-1 nonlinear behavior was observed and it may be related to dynamic effects. These results suggest minimal excess elastic enthalpies of mixing for Mg–Fe cordierite solid solutions. Channel Na should affect measurably the thermodynamic properties of natural cordierites as evidenced by variations in the IR spectra of Na-containing samples. Occluded H2O (Class I) and CO2 should have little interaction with the framework and can be considered nearly "free" molecules. They should not give rise to measurable structural heterogeneity in the framework. The contribution of the crystal field stabilization energy (CFSE) of octahedral Fe2+ to the energetics of Mg–Fe cordierites was also investigated using published electronic absorption spectra (Khomenko et al. 2001). Two bands are observed between 8,000 and 10,500 cm-1 and they represent electronic dd-excitations of octahedral Fe2+ derived from the 5T2g 5Eg transition. They shift to higher wavenumbers with increasing XMg in cordierite. An analysis gives slightly asymmetric excess -CFSE across the Mg–Fe cordierite join with a maximum of about –550 J/mole towards iron-rich compositions.Editorial responsibility: J. Hoefs  相似文献   

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