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1.
Ions and water molecules mobilities were studied by the 7Li, 23Na, 1H nuclear magnetic resonance in the framework aluminosilicate mineral analcime and in its cation-exchanged (lithium) form. It has been found that cation exchange as well as dehydration alter radically dynamics of particles interposed in channels of the zeolite framework. The highest mobility of alkali cations with the diffusion activation energy of 0.52 eV was detected in hydrated Li-analcime. The ion diffusion increase with temperature is accompanied by an increase in the dynamic orientational disordering of water sublattice. The energy of formation of structural defects responsible for ion diffusion and water disordering was deduced to be 0.2 eV. As a possible defect, the occupation of water positions by cations is discussed (model of bridging-type ion diffusion).  相似文献   

2.
 The heat capacity of paranatrolite and tetranatrolite with a disordered distribution of Al and Si atoms has been measured in the temperature range of 6–309 K using the adiabatic calorimetry technique. The composition of the samples is represented with the formula (Na1.90K0.22Ca0.06)[Al2.24Si2.76O10]·nH2O, where n=3.10 for paranatrolite and n=2.31 for tetranatrolite. For both zeolites, thermodynamic functions (vibrational entropy, enthalpy, and free energy function) have been calculated. At T=298.15 K, the values of the heat capacity and entropy are 425.1 ± 0.8 and 419.1 ±0.8 J K−1 mol−1 for paranatrolite and 381.0 ± 0.7 and 383.2 ± 0.7 J K−1 mol−1 for tetranatrolite. Thermodynamic functions for tetranatrolite and paranatrolite with compositions corrected for the amount of extraframework cations and water molecules have also been calculated. The calculation for tetranatrolite with two water molecules and two extraframework cations per formula yields: C p (298.15)=359.1 J K−1 mol−1, S(298.15) −S(0)=362.8 J K−1 mol−1. Comparing these values with the literature data for the (Al,Si)-ordered natrolite, we can conclude that the order in tetrahedral atoms does not affect the heat capacity. The analysis of derivatives dC/dT for natrolite, paranatrolite, and tetranatrolite has indicated that the water- cations subsystem within the highly hydrated zeolite may become unstable at temperatures above 200 K. Received: 30 July 2001 / Accepted: 15 November 2001  相似文献   

3.
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   

4.
Sedimentary biogenic silica from Redeyef in Gafsa basin (southern Tunisia) was analysed for its 29Si and 27Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectra and complemented by X-ray diffraction and SEM observations. The 29Si MAS NMR spectrum is characterized by the abundance of hydroxylated silicon, displayed in resonance intensities and reflects a clear tendency towards dissolution of diatomaceous amorphous silica and the occurrence of the hydrated silica, which is the main component that ensures the diagenetic transition via the mechanism of dissolution–precipitation to other more crystalline silica phases, after the lost of its hydroxyls groups (water) by heating (burial). 27Al MAS NMR reveals two coordinations of Al; the octahedrally coordinated Al suggests the presence of clay relics trapped during crystal growth or a microcrystalline zeolite (clinoptilolite detected by SEM observations), while the tetrahedrally coordinated Al suggests the presence of minor quantities of minerals with tetrahedral Al, such as an Al-rich fluid and/or minerals such as feldspars.  相似文献   

5.
 The presence of zeolitic water, with a reversible hydration behaviour, was determined by structural and kinetic studies on synthetic mixite BiCu6(OH)6(AsO4)3·nH2O (n≤3). X-ray diffraction and infrared-spectroscopic investigations were performed on single crystals. Isothermal thermogravimetric experiments were carried out to determine the reaction kinetics of the de- and rehydration processes. The single-crystal structure refinement of a fully hydrated crystal yielded five partially occupied Ow positions (Ow=oxygen atom of a H2O molecule) within the tube-like channels of the hexagonal [BiCu6(OH)6(AsO4)3] framework. For the partially dehydrated form, with n≈1, at least two of these sites were found to be occupied significantly. In addition, the structural investigations allowed two different intra-framework hydrogen bonds to be distinguished that are independent of the extra-framework water distribution and are responsible for the stability of the self-supporting framework. The kinetic analysis of the rate data in the 298–343K temperature range shows that the dehydration behaviour obeys a diffusion-controlled reaction mechanism with an empirical activation energy of E a dehyd=54±4 kJ mol–1. A two-stage process controls rehydration of which the individual steps were attributed to an initial surface-controlled (E a hyd-I=6±1 kJ mol–1) and subsequent diffusion-controlled reaction mechanism (E a hyd-II=12±1 kJ mol–1). The estimated hydration enthalpy of 42±5 kJ mol–1 supports the distribution model of molecular water within the channels based on a purely hydrogen-bonded network. Received June 26, 1996 / Revised, accepted November 11, 1996  相似文献   

6.
The enthalpy of formation of petalite, LiAlSi4O10, has been measured using high-temperature solution calorimetry. The measurements were carried out in a Calvet-type twin micro calorimeter at 728?°C. A 2PbO?·?B2O3 melt was used as a solvent. Tabulated heats of formation of the components and tabulated heat capacities of the reactants and the product (Robie and Hemingway 1995) were used to calculate the standard heat of formation of petalite from the measured heats of solution. The calculations yielded a mean value of Δ f H pet 298.15=?4872±5.4 kJ mol?1. This value may be compared to the heat of formation of Δ f H pet 298.15= ?4886.5±6.3 kJ mol?1 determined by the HF solution calorimetry by Bennington et?al. (1980). Faßhauer et?al. (1998) combined thermodynamic data with phase-equilibrium results to obtain best-fit thermodynamic results using the Bayes method, in order to derive an internally consistent dataset for phases in the NaAlSiO4– LiAlSiO4–Al2O3–SiO2–H2O system. They determined ?4865.6?±?0.8?kJ?mol?1 as the enthalpy of formation of petalite, a value that is appreciably closer to the enthalpy found in this work.  相似文献   

7.
High-temperature oxide-melt calorimetry and Rietveld refinement of powder X-ray diffraction patterns were used to investigate the energetics and structure of the hematite–corundum solid solution and ternary phase FeAlO3 (with FeGaO3 structure). The mixing enthalpies in the solid solution can be described by a polynomial ΔHmix=WX hem(1?X hem) with W=116 ± 10 kJ mol?1. The excess mixing enthalpies are too positive to reproduce the experimental phase diagram, and excess entropies in the solid solution should be considered. The hematite–corundum solvus can be approximately reproduced by a symmetric, regular-like solution model with ΔG excess=(W H ?TW S )X hem X cor, where W H= 116 ± 10 kJ mol?1 and W S =32 ± 4 J mol?1 K?1. In this model, short-range order (SRO) of Fe/Al is neglected because SRO probably becomes important only at intermediate compositions close to Fe:Al=1:1 but these compositions cannot be synthesized. The volume of mixing is positive for Al-hematite but almost ideal for Fe-corundum. Moreover, the degree of deviation from Vegard's law for Al-hematite depends on the history of the samples. Introduction of Al into the hematite structure causes varying distortion of the hexagonal network of oxygen ions while the position of the metal ions remains intact. Distortion of the hexagonal network of oxygen ions attains a minimum at the composition (Fe0.95Al0.05)2O3. The enthalpy of formation of FeAlO3 from oxides at 298 K is 27.9 ± 1.8 kJ mol?1. Its estimated standard entropy (including configurational entropy due to disorder of Fe/Al) is 98.9 J mol?1 K?1, giving the standard free energy of formation at 298 K from oxides and elements as +19.1 ± 1.8 and ?1144.2 ± 2.0 kJ mol?1, respectively. The heat capacity of FeAlO3 is approximated as C p (T in K)= 175.8 ? 0.002472T ? (1.958 × 106)/T 2? 917.3/T 0.5+(7.546 × 10?6) T 2 between 298 and 1550 K, based on differential scanning calorimetric measurements. No ferrous iron was detected in FeAlO3 by Mössbauer spectroscopy. The ternary phase is entropy stabilized and is predicted to be stable above about 1730 ± 70 K, in good agreement with the experiment. Static lattice calculations show that the LiNbO3-, FeGaO3-, FeTiO3-, and disordered corundum-like FeAlO3 structures are less stable (in the order in which they are listed) than a mechanical mixture of corundum and hematite. At high temperatures, the FeGaO3-like structure is favored by its entropy, and its stability field appears on the phase diagram.  相似文献   

8.
The effect of γ-irradiation on the structure, phase composition and kinetics of isothermal decomposition of natural textural brucite Mg(OH)2 has been investigated by Mn2+ electron paramagnetic resonance (EPR), proton magnetic resonance (PMR), X-ray diffraction (XRD) and weight loss methods. Starting from a 106-Gy dose, γ-irradiation (60Co, 13.8 Gys?1) is found to stimulate the formation of a new phase in the brucite structure, namely basic magnesium carbonate. The carbonate phase is assumed to form in brucite under γ-irradiation accordingly to the scheme \(\) (in the brucite structure). There is also a possibility that γ-irradiation forms particles with high reaction ability, CO?2 radicals and/or CO molecules, which can react with the brucite structure. Preliminary γ-irradiation (9.75 × 107 Gy) slows down the subsequent isothermal dehydroxylation of natural brucite, which can be explained by the formation of the new carbonate phase in the Mg(OH)2 structure. Dehydroxylation kinetics of both original and irradiated samples are interpreted by a two-stage nucleation model at 623, 648, 673, 698 and 723 K. The reaction rate is limited by the first nucleation stage rate (proton transition from an OH group near the reaction interface on a freed vacant orbital of an oxygen ion of the OH group in the nearest elementary cell, i.e., formation of a structured water molecule). The second-stage rate (water molecule removal from the structure and proton migration from the residual hydroxyl inside the structure) is about 1 order of magnitude higher. The activation energy of the limiting stage is 194 and 163 kJ mol?1 for the original and irradiated samples, respectively. Non-linear Arrhenius dependencies for the first-stage rate constants are related to the potential barrier reduction due to thermal fluctuations of large structural zones (with radii of about 20 and 81 Å in original and irradiated samples, respectively), whose ions form this barrier.  相似文献   

9.
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   

10.
Infrared absorption spectra (400–4000 cm?1) were measured on dehydrated and partially dehydrated powder of the zeolite harmotome Ba2[(AlO2)4(SiO2)12]·12H2O. Whereas the disappearance of the bending mode at ～1640 cm?1 proved the absence of water molecules after dehydration, the O-H stretching mode at 3200 cm?1 showed the presence of hydroxyl groups. The vibrational modes of the framework are only slightly influenced by dehydration.  相似文献   

11.
The dissolution kinetics of three stoichiometric dolomite specimens (hydrothermal single crystal, microcrystalline sedimentary rock, coarse-grained marble) were studied in aqueous carbonate solutions. Hydrodynamic conditions were controlled through use of a rotating dolomite disk in which one face was exposed to solution and fluid flow regime was defined by spinning rate. The resulting mass transfer properties were uniform across the disk surface. The dissolution experiments were begun at an initially undersaturated condition set by CO2 at ~ 1 atm dissolved in deionized water. The reaction was followed by measuring concentrations of Ca2+, Mg2+, HCO3?, and pH over time in a free-drift type of experiment at 0, 15, and 25°C.Dissolution rates for all three samples were similar in form and value; grain size effects were insignificant. Ca/Mg was constant throughout each run at 0.81–0.96. From initial conditions, the dissolution rate decreased as the solution became more saturated. At solution conditions still far from equilibrium (ion activity product = 10?19), rate dropped off sharply to a very low value. Surface morphology, determined by SEM, showed deep narrow holes in the single crystal, while the rocks dissolved along grain boundaries. These features suggested preferential dissolution of energetically favored sites and surface reaction rate control. Initial rates were used to calculate an apparent activation energy of 32 kJ mol?1 (sedimentary dolomite) and 27 kJ mol?1 (single crystal).Initial dissolution rates at 25°C and pH ~ 4 for all samples varied with spinning speed and ranged from 1–3 μmol m?2 s?1 for laminar flow conditions to almost 3–6 μmol m?2 s?1 as the transition to turbulence began. At lower temperatures, the rate was lower, and increasing spinning velocity had less effect. The strongest spinning rate dependence occurred far from equilibrium, and it became a less important factor as the saturation state increased.  相似文献   

12.
The dehydration kinetics of serpentine was investigated using in situ high-temperature infrared microspectroscopy. The analyzed antigorite samples at room temperature show relatively sharp bands at around 3,655–3,660 cm?1 (band 1), 3,570–3,595 cm?1 (band 2), and 3,450–3,510 cm?1 (band 3). Band 1 corresponds to the Mg–OH bond, and bands 2 and 3 correspond to OH associated with the substitution of Al for Si. Isothermal kinetic heating experiments at temperatures ranging from 625 to 700 °C showed a systematic decrease of the OH band absorbance with heating duration. The one-dimensional diffusion was found to provide the best fit to the experimental data, and diffusion coefficients were determined with activation energies of 219 ± 37 kJ mol?1 for the total water band area, 245 ± 46 kJ mol?1 for band 1, 243 ± 57 kJ mol?1 for band 2, and 256 ± 53 kJ mol?1 for band 3. The results indicate that the dehydration process is controlled by one-dimensional diffusion through the tetrahedral geometry of serpentine. Fluid production rates during antigorite dehydration were calculated from kinetic data and range from 3 × 10?4 to 3 × 10?5  $ {\text{m}}_{\text{fluid}}^{ 3} \,{\text{m}}_{\text{rock}}^{ - 3} \,{\text{s}}^{ - 1} $ . The rates are high enough to provoke hydraulic rupture, since the relaxation rates of rocks are much lower than these values. The results suggest that the rapid dehydration of antigorite can trigger an intermediate-depth earthquake associated with a subducting slab.  相似文献   

13.
Isothermal thermogravimetric experiments have been carried out to determine the reaction kinetics of the dehydration processes in fuller's earth, a natural Ca-montmorillonite. Dehydration in swelling clays is a complex reaction, and analysis of the thermogravimetric data using empirical rate equations and time-transformation analysis reveals that the nature of the rate controlling mechanism is dependent upon both the temperature regime of the sample as well as the extent of reaction. For fuller's earth, we find that the dehydration kinetics are dominated by a nucleation and growth mechanism at low temperatures and fractions transformed (stage I), but above 90 °C the last stages of the reaction are diffusion controlled (stage II). The activation energy for dehydration during stage I is around 35 kJ · mol−1, whereas the removal of water during stage II requires an activation energy of around 50 kJ · mol−1. These two stages of dehydration are associated with primary collapse of the interlayer (stage I) and movement of water that is hydrated to cations within the interlayer (stage II). Received: 28 August 1998 / Revised, accepted: 27 January 1999  相似文献   

14.
High temperature infrared spectra of hydrous microcrystalline quartz   总被引：1，自引：0，他引：1  
A series of in-situ high temperature infrared (IR) measurements of water in an agate sample and in a milky quartz has been conducted in order to understand the nature of water in silica at high temperatures (50–700?°C) and the dehydration behavior. IR absorption bands of water molecules trapped in the milky quartz showed a systematic decrease in intensities and a shift from 3425?cm?1 at 50?°C toward 3590?cm?1 at 700?°C without any loss of water. This indicates a change in IR absorption coefficients corresponding to different polymeric states of water at different temperatures. The broad 3430?cm?1 band in the agate sample also showed a systematic decrease in IR intensity and a band shift toward higher frequency with increasing temperature (～700?°C). This indicates that the agate sample also contains fluid inclusion-like water. For this agate sample, a dehydration of loosely hydrogen-bonded molecular water occurred at lower temperatures (<200?°C). At higher temperatures (>400?°C), sharp bands around 3660 and 3725?cm?1 (3740?cm?1 at 50?°C) due to surface silanols, appeared. This indicates dehydration of H2O molecules that are hydrogen bonded to surface silanols. SiOH species in the agate are divided into three groups, namely SiOH group located at structural defects, surface silanols hydrogen bonded to each other and free surface silanols. Former two dehydrate below 700?°C and the dehydration rate of the SiOH at structural defects is faster than the other. IR spectra show that SiOH species decrease continuously even after the dehydration of most of H2O molecules. All these results provide realistic bases for the change in physicochemical states of different OH species in silica at high temperatures.  相似文献   

15.
The local structural response of Ca/Mg substitution and the energetic effects associated with dodecahedral ordering in the pyrope-grossular garnet solid solution are derived from a combination of static lattice energy calculations and Monte Carlo simulations. We start with a thorough analysis of the goodness of the empirical potential models used for the modelling of aluminosilicate garnets. The degree of polyhedral distortion was found to be a sensitive indicator for the quality of the model and, by comparison with experimental data, was used to select the best of several available empirical potentials. The Ca/Mg substitution on the dodecahedral site in garnet was found to produce strong local distortions in the surrounding tetrahedral and octahedral polyhedra. This arises from the absence of rigid unit modes (RUMS) in the garnet structure, because local rotations of otherwise rigid SiO4 tetrahedra and AlO6 octahedra cannot occur in order to accommodate different-sized divalent cations in the dodecahedral sites. Strain effects, therefore, mainly govern the dodecahedral substitution, and the corresponding strain field around a dodecahedral site has a minimum radius of 5?Å. Pyrope-grossular solid solution compositions were modelled using a supercell approach. For several garnet compositions many different configurations representing individual disordered arrangements were relaxed. The resulting energies were analyzed in terms of different-neighbour interactions to determine the parameters of a model Hamiltonian. The corresponding interaction energies were found to be virtually independent of composition. Surprisingly, the nearest-neighbour interaction between edge-sharing dodecahedra is of no particular significance in the garnets. Instead, the strongest interaction is only via the third-nearest neighbours, i.e. dodecahedra that are edge-shared to a common SiO4 tetrahedron. This cannot lead to dodecahedral long-range order in garnets, but can produce significant amounts of short-range order. Monte Carlo simulations were performed on several compositions to determine the macroscopic effects such as NMR-based cluster occupancy, ordering energy and configurational entropy of the short-range ordering process. As expected, the samples tend to random disorder at high temperatures, and at low temperatures it is compositions nearer Py50Gr50 that depart most strongly from random mixing. For example, a maximum reduction of 3.5?J?mol?1?K?1 is predicted for Py75Gr25 and ～10?J?mol?1?K?1 for Py50Gr50. A comparison of NMR cluster occupancy with experimental 29Si MAS NMR resonance intensity is partly successful. However, the changes in NMR cluster occupancy are relatively low (～5%) compared to changes in configurational entropy (～30%), implying that it might be difficult to estimate exact entropy data from 29Si MAS NMR line intensities.  相似文献   

16.
天然沸石降氟作用的初步探讨   总被引：2，自引：0，他引：2       下载免费PDF全文
韩成 《地质科学》1986,(3):268-275
为了探讨有关天然沸石降低水溶液中氟含量方面实际应用的可能性及其机理,笔者自1979年春到1982年冬断断续续开展了些试验。实验中也用雪硅钙石(建筑上加气砖废料)对笔者的观点作了进一步验证。  相似文献   

17.
The electrical conductivity and polarization properties of calcite single crystals with three orientations, namely, a (00.1) plane perpendicular to the crystallographic c axis (10.0) plane parallel to the crystallographic c axis, and a (10.4) cleavage plane, were studied by both complex impedance and thermally stimulated depolarization current (TSDC) measurements. Conductivities for (00.1)-, (10.0)-, and (10.4)-oriented single calcite crystals at 400–600?°C were 1.16?×?10?7?–?1.05?×?10?5, 7.40?×?10?8?–?4.27?×?10?6, and 4.27?×?10?7?–?2.86?×?10?5 Ω?1 m?1, respectively, and the activation energies for conduction were 112, 103, and 101?kJ?mol?1, respectively. The TSDC spectra verified the electrical polarizability of calcite crystals. The activation energy for depolarization, estimated from TSDC spectra, of the (00.1)-, (10.0)-, and (10.4)-oriented calcite substrates were 112, 119, and 114?kJ?mol?1, respectively. Considering the correlation between the processes of conduction and electric polarization, we proposed the mechanisms of conduction and polarization in calcite on the assumption of oxide ion transport.  相似文献   

18.
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19.
Interdiffusion coefficients of Al + Al vs. Mg + Si in the gehlenite–åkermanite system of melilite were determined by coupled annealing of synthesized end-member single crystals. The observed diffusion coefficients for a couple-annealed sample vary for about 2 orders of magnitude, showing strong dependence on the gehlenite–åkermanite composition: diffusion coefficient observed at 1350 °C, for example, is 3 × 10?13 cm2 s?1 at 5 mol% åkermanite composition (Ak5), increases to 2 × 10?11 cm2 s?1 at Ak80, and then decreases to 1 × 10?12 cm2 s?1 at Ak95. The diffusion coefficient–temperature relation indicates high activation energy of diffusion of about 420 kJ mol?1 for gehlenite-rich melilite. The observed diffusion coefficient–composition relation may be explained by a combination of (1) the diffusion coefficient–melting temperature relation (Flynn's rule) and (2) the feasibility of local charge compensation, which can possibly be maintained more easily in the intermediate chemical composition. The high activation energy value for gehlenitic melilite appears to correspond to the complex diffusion mechanism. The observed highly variable diffusion coefficients suggest that gehlenite–åkermanite zoning in the melilite crystals in Ca, Al-rich inclusions in the carbonaceous meteorites may provide a sensitive indicator for the thermal history of the inclusions.  相似文献   

20.
A computational study of oxygen diffusion in olivine   总被引：1，自引：1，他引：0  
Atomistic modelling techniques are used to study the rate-determining steps that limit diffusion of oxygen in forsterite. The activation energies for diffusion parallel to all three crystallographic axes by the vacancy and interstitial mechanisms are calculated. The activation energy for extrinsic vacancy diffusion is predicted to be isotropic with a barrier height of 119 kJ mol–1. Conversely, in the interstitial case it is found to be anisotropic, with extrinsic activation energies that range between 94 and 178 kJ mol–1. The effect of intrinsic defects and two typical impurities, iron and hydrogen, upon diffusion is also considered. We find that the migration energy is slightly higher in iron-rich fayalite compared with forsterite and that the presence of hydrogen defects will not affect the diffusion mechanism. These observations lead us to reinterpret existing experimental results on oxygen diffusion in natural olivine. We suggest that at low oxygen partial pressure the mechanism observed is a vacancy mechanism, while at high oxygen partial pressure the mechanism is interstitial. We believe that this change in mechanism is mediated by iron redox reactions. Taking this process into account, we derive activation energies in excellent agreement with those found experimentally in natural samples of olivine. The anisotropy of activation barriers and hence the change in diffusion rates with temperature could be used to distinguish between the two mechanisms in future experimental work.  相似文献   

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