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1.
The electron paramagnetic resonance (EPR) spectra of Fe3+ in a well cristallized kaolinite from Decazeville in France are well resolved. It is shown that in this sample there are mainly two slightly different spectra, well separated at low temperature and characterized at -150° C by the constants B 2 0 = 0.112 cm?1, B 2 2 = 0.0688 cm?1 for one and B 2 0 = 0.116 cm?1, B 2 2 = 0.0766 cm?1 for the second. These two spectra arise from Fe3+ substituted for Al3+ at the two octahedral positions in equal amounts. The temperature dependence of EPR spectra was studied and was explained by a modification of the octahedral sites.  相似文献   

2.
Electron paramagnetic resonance (EPR) of Fe3+ in SnO2 has been realized in a natural single crystal of cassiterite at 9.55 GHz (X-band) and at 34.40 GHz (Q-band). Spectra show the simultaneous presence of four groups of independent signals, each one typical of the immediate environment of a specific paramagnetic iron. Fe3+ always substitutes Sn4+ in an octahedral site. The four paramagnetic centers are due to four different charge compensation mechanisms. The spin Hamiltonian constant values for the SN center and I1 center confirm the former results of the authors about for these two centers. SN and I1 present a weak deviation from axial symmetry. The first preserves the crystallographic local symmetry of the tin site and the second shows a symmetry deviation of 0.6° probably due to the presence of an OH group in the coordination polyhedron. On the other hand, for the Sd1 center and mostly for the Sd2 center, never previously subjected to single crystal EPR measurements, the study of spectra symmetry and the determination of B 2 0 and B 2 2 constants produced new data. The Sd1 center could be due to a relaxation of the lattice together with a non local charge compensation mechanism. The Sd2 center presents a strong deviation from axial symmetry with mm local symmetry coordination due to coupling of Fe3+ and Nb5+. This coupling is proven by EPR studies of synthetic cassiterites doped with iron and niobium.  相似文献   

3.
Electron paramagnetic resonance (EPR) measurements of natural anhydrite CaSO4, celestite SrSO4 and barite BaSO4 have revealed the presence of PO 3 2? and SO 3 ? radicals. Hyperfine structure from33S has been detected and measured for the first time. Low-symmetry effects, which are manifested in noncoincidence of g and hyperfine axes, were observed for SO 3 ? . The dynamics of one of the two SO 3 ? types in anhydrite has been investigated. Variations of spin Hamiltonian parameters with temperature have been attributed to thermally induced jumps between the two magnetically inequivalent sites of this center.  相似文献   

4.
57Fe Mössbauer spectra are presented for synthetic cation-deficient Fe2TiO4 and FeCr2O4 spinel particles (<1μm) at various temperatures. The spectra of ferrimagnetic cation-deficient Fe2TiO4 show characteristic features due to relaxation because of superparamagnetism and spin relaxation in the temperature range 5–294 K. At 5 K and 78 K, a superposition of at least two sextets is observed which appear to arise from Fe3+ onA-sites (Fe A 3+ andB-sites (Fe B 3+ ) of the spinal lattice with magnetic hyperfine fields at 5 K ofB hf ((Fe B 3+ )≈47.5 T andB hf (Fe B 3+ )≈51.0 T, respectively. Cation-deficient FeCr2O4 particles reveal at 78 K a fieldB hf (Fe3+)≈46.9 T and exhibit relaxation spectra as a consequence of superparamagnetism in the temperature range 80 K - ～300 K. At 294 K, quadrupole splitting Δ(Fe A 3+ )=0.92 mm/s and isomer shift δ(Fe A 3+ )=0.29 mm/s (relative to metallic Fe) are measured. For both compounds the magnetic hyperfine fieldsB hf are discussed in terms of supertransferred hyperfine fields involving vacancies and in the case of cation-deficient Fe2TiO4 also diamagnetic Ti4+ neighbours of the Fe ions.  相似文献   

5.
Room temperature X-irradiation of some natural beryls produced several new absorption lines in the electron paramagnetic resonance (EPR) spectrum, a known series of optical absorption lines in the 500–700 nm range, and a shift of the absorption edge to lower energies. Several of the new EPR lines and part of the irradiation-induced shift of the absorption edge disappeared after a few days at room temperature, and were not examined in detail. However, three of the paramagnetic centres responsible for the new EPR lines were stable at room temperature and two of these have previously been identified as atomic hydrogen and the methyl radical, CH3. These species were stable to ～150 and ～450°C respectively. The third stable species, hitherto unreported, showed a single-line EPR spectrum of axial symmetry, with g∥=2.0051 and g⊥=2.0152. This spectrum was found to be intensity-correlated with the series of optical bands in the 500–700 nm range, after thermal bleaching at 175°C. The EPR and optical spectra are therefore assigned to the same species. It is argued that this species is the CO 3 ? molecular ion, located in the widest part of the structural channel and aligned with the plane of the molecule perpendicular to the c axis. The EPR spectrum is consistent with a 2 A′2 ground state of a CO 3 ? molecule with trigonal symmetry, and this requires that the optical transition has a 2 A′2 → 2 E′ character. Most of the features in the optical spectrum can be assigned to coupling of a totally symmetric mode of frequency ～1020 cm?1 onto a zero-phonon line at 14,490 cm?1 and a second weaker line at 16,020 cm?1. However, both of these two fundamental lines are structured, and the two components show strong temperature-dependent derivative-shaped magnetic circular dichroism (MCD). Furthermore, the overall sign of the MCD for the line at 16,020 cm?1 is opposite to that at 14,490 cm?1. The separation (～120 cm?1) of the two components of the 14,490 cm?1 line is much larger than that expected from spin-orbit interaction, and the origin of this splitting is not yet understood.  相似文献   

6.
In order to obtain a better understanding of fluorite deposits, rare earth impurities have been analyzed for a large number of samples taken from cross-sections of several low temperature hydrothermal veins. Two types of measurements have been used: Electron Paramagnetic Resonance (EPR) and Neutron Activation Analysis (NAA). For Gd, the ratio of spin concentrations to total concentration [Gd3+]/[Gdtotal] is close to 1 in all the samples; on the other hand, the ratios [Eu2+]/[Eutotal] and [Ce3+ -F ? i ]/[Cetotal] exhibit large variations. The first result suggests that the major part of the lanthanides in the samples is incorporated in the crystal lattice and that clustering of lanthanides ions is not important. The behaviour of Eu and Ce is ascribed to charge state changes and symmetry state changes respectively.  相似文献   

7.
Absorption bands are determined in polarized optical spectra of vivianite Fe3(PO4)2·8H2O, recorded at room and low temperatures. These bands are caused by spin-allowed d-d transitions in structurally nonequivalent Fe A 2+ (～11000 cm-1 (γ-polarization) (and) ～12000 cm-1 (β-polarization)) (and) Fe B 2+ (～8400 cm-1 (γ, α-polarization) and ～11200 cm-1 (α-polarization)) ions. A charge transfer band (CTB) Fe B 2+ +Fe B 3+ →Fe B 2+ +Fe B 2+ (～15000 cm-1) also determined, has polarizing features giving evidence of a change in the Fe B 2+ -Fe B 3+ bond direction, when compared with Fe B 2+ -Fe B 2+ . Bands of exchange-coupled Fe3+-Fe3+ pairs (～19400, ～20400, ～21300 and ～21700 cm-1) which appear on oxidation of Fe2+ in paired Fe B octahedra are also characterized.  相似文献   

8.
The energy levels of MnO 6 9? clusters, with D 4h approximated and C 2v actual symmetry of the M 1 site of Mn3+-bearing andalusite, are calculated using the multiple scattering method. The energies of the electronic d-d transition of Mn3+ in the clusters with D 4h symmetry are calculated to be 6,000–7,000 cm?1 (5 B 1g → 5 A 1g ), ～18,000 cm?1 (5 B 1g → 5 B 2g ) and ～19,000 cm?1 (5 B 1g → 5 E g ). Apart from a splitting of the 5 E g -level into two levels separated by 300–350 cm?1, no significant changes of these transition energies are noted for the corresponding cluster with C 2v symmetry. The calculated transition energies give a good fit to the structure of the optical absorption spectra of Mn3+-bearing andalusites and support recent assignments of the major absorption bands observed in these spectra.  相似文献   

9.
In this study, the physicochemical parameters (Conductivity, pH, Cl?, HCO 3 ? , PO 4 3? , SO 4 2? , NO 3 ? , NO 2 ? , F?, TH, Ca2+, K+, Mg2+, Na+, and DS) were determined for 41 samples collected from fourteen places in Algeria. The temperature of the thermal water samples at collection sites varied from 26°C to 86°C. pH values varied from 6.5 to 8.5 (i.e., from slightly acidic to moderately alkaline); 90.24% of the samples exhibited relatively high salinity (DS?=?550–5,500 mg L?1). Total hardness measurements indicated these waters to be moderately hard. Forty-six percent of the samples are Na–Cl in character. The ratios Na+/Ca2+, Na+/Mg2+, and (Na+ + K+)/(Ca2+ + Mg2+) were high in 90.24% of the samples. This indicates the ion exchange process is important, which indicates that most of the Algerian thermal waters had developed over a long period at a depth sufficient to react with the rock. Statistical analyses of the physicochemical data gave positive correlation values, thereby enabling good interpretation of the results and revealing the composition of ions present in the thermal waters, as well as some information about their origin. The therapeutic properties associated with thermal waters encourage people at spas to drink the water they bathe in. Therefore, we examined the drinkability of these thermal waters. World Health Organization (WHO 1993) standards were used to evaluate the thermal water quality for drinking. With respect to hardness, the samples were classified as moderately hard (58.54% of the samples), very hard (36.58% of the samples), and soft (4.88% of the samples). The drinkability study shows that only 16 samples of the investigated waters were drinkable and thus could be consumed without special precaution.  相似文献   

10.
The temperature dependence of the lattice parameters of pure anorthite with high Al/Si order reveals the predicted tricritical behaviour of the \(I\bar 1 \leftrightarrow P\bar 1\) phase transition at T c * =510 K. The spontaneous strain couples to the order parameter Q° as x i∝S xQ i Q°2 with S xQ 1 =4.166×10?3, S xQ 2 =0.771×10?3, S xQ 3 =?7.223×10?3 for the diagonal elements. The temperature dependence of Q° is $$Q^{\text{o}} = \left( {1 - \frac{T}{{510}}} \right)^\beta ,{\text{ }}\beta = \tfrac{{\text{1}}}{{\text{4}}}$$ A strong dependence of T c * , S xQ i and β is predicted for Al/Si disordered anorthite.  相似文献   

11.
Assessment of groundwater quality is essential to ensure sustainable use of it for drinking, agricultural, and industrial purposes. The chemical quality of groundwater of Gaya region has been studied in detail in this work to delineate the potable groundwater zones. A total of 30 groundwater samples and 2 surface water samples were collected in and around Gaya district of Bihar. The major cations follow the trend: Ca2+?>?Mg2+?>?Na+?>?K+. The domination of calcium ions in the groundwater is due to weathering of rocks. The K+ ranged between 0.2 and 47.95 ppm, suggesting its abundance the below desired limit; but some samples were found to be above permissible limit. K+ weathering of potash silicate and the use of potash fertilizer could be the source. The major anions abundance followed the order HCO 3 ? ?>?Cl??>?SO 4 2? ?>?NO 3 ? ?>?PO 4 3? . Dissolution of carbonates and reaction of silicates with carbonic acid accounts for the addition of HCO 3 ? to the groundwater and oxidation of sulphite may be the source of SO 4 2? . Principal component analysis was utilized to reflect those chemical data with the greatest correlation and seven major principal components (PCs) representing >80 % of cumulative variance were able to interpret the most information contained in the data. PC1, PC2 and PC3 reflect the hydrogeochemical processes like mineral dissolution, weathering and anthropogenic sources. PC4, PC5, PC6 and PC7 show monotonic, random and independent relationships.  相似文献   

12.
The lattice parameters of anorthites An98Ab2 and An100 have been measured from 22 to 1100 K. The spontaneous strain arising from the \(I\overline 1 - P\overline 1\) displacive transition in An98 follows second order Landau behaviour. The spontaneous strain (? s) couples quadratically to the order parameter (Q 0) with ? s∝Q 02∝(T c * ?T) and T c * =530 K in An98. This is in contrast to the tricritical behaviour observed in pure anorthite. These observations are consistent with a Landau model for the free energy of Ca-rich plagioclases in which Al/Si order and Na content renormalize the fourth order coefficient.  相似文献   

13.
Electric dipole polarizabilities have been calculated from first principles of quantum mechanics for the BO 3 3? , CO 3 2? , NO 3 ? series and for NO 2 ? and LiNO3(g). Calculated trends in average polarizability and polarizability anisotropy in the BO 3 3? -NO 3 ? series are in agreement with experiment and can be qualitatively interpreted in terms of the varying energies of the a1′, a2″ and e′ symmetry unoccupied MO's of the oxyanions. Embedding a CO 3 2? ion in a D3h symmetry array of divalent cations reduces both the average polarizability and its anisotropy, particularly when diffuse s and p functions are included in the calculation. Calculations on the gas phase LiNO3 molecule and on the free NO 3 ? ion in the distorted geometry found in LiNO3(g) allow us to separate polarizability contributions internal to the NO 3 ? and Li+ ions from those which arise from the Li+-NO 3 ? interaction. The Li+-NO 3 ? interaction term so obtained is much smaller than the NO 3 ? contribution but is in turn larger than the Li+ contribution, suggesting that the inclusion of this interaction term is essential for obtaining accurate results for ion pairs. Although static polarizabilities are in reasonable agreement with experiment for NO 3 ? the wavelength dispersion of the polarizability is underestimated by about a factor of two, apparently as a result of inadequacies in the quantum mechanical method. Calculated values are also presented for 14N NMR shieldings in the nitrogen oxyanions but these are in only qualitative agreement with the experimental values. Similarly, calculated values of magnetic susceptibility are in only qualitative agreement with experiment although trends along the BO 3 3? -NO 3 ? series are properly reproduced.  相似文献   

14.
We investigated the high-pressure behaviour of Fe3+-bearing hydrous phase-X, (K1.307Na0.015)(Mg1.504Fe 0.373 3+ Al0.053Ti 0.004 4+ )Si2O7H0.36, up to 34?GPa at room temperature by synchrotron X-ray powder diffraction. The lattice parameters behave anisotropically, with the [001] direction stiffer than [100]. In the 10?4 to 22?GPa pressure range, the axial bulk moduli are K 0a ?=?112(3) GPa and K′?=?4, and K 0c ?=?158(2) GPa and K′?=?4, and the anisotropy of the lattice parameters is β0c :β0a ?=?0.71:1. The cell volumes are fitted by a second-order Birch–Murnaghan equation of state giving a bulk modulus of K 0?=?127(1) GPa and K′?=?4 in the same pressure range. After 22?GPa, a discontinuity in volume and lattice parameters can be recognized. Sample did not become amorphous up to 34?GPa. The coupled substitution K?+?Mg?=?[]?+?Fe3+ has only a limited influence on the bulk modulus and structural stability of phase-X.  相似文献   

15.
Laihuite reported in the present paper is a new iron silicate mineral found in China with the following characteristics:
  1. This mineral occurs in a metamorphic iron deposit, associated with fayalite, hypersthene, quartz, magnetitc, etc.
  2. The mineral is opaque, black in colour, thickly tabular in shape with luster metallic to sub-metallic, two perfect cleavages and specific gravity of 3.92.
  3. Its main chemical components are Fe and Si with Fe3+>Fe2+. The analysis gave the formula of Fe Fe 1.00 3+ ·Fe 0.58 2+ ·Mg 0.03 2+ ·Si0.96O4.
  4. Its DTA curve shows an exothermic peak at 713°C.
  5. The mineral has its own infrared spectrum distinctive from that of other minerals.
  6. This mineral is of orthorhombic system; space group:C 2h /5 ?P21/c; unit cell:α=5.813ű0.005,b=4.812ű0.005,c=10.211ű0.005,β=90.87°.
  7. The Mössbauer spectrum of this mineral is given, too.
  相似文献   

16.
An experimental study of the particulars of the solubility and crystallization of brushite Ca(HPO4) · 2H2O from aqueous solution in conditions of a variable pH (6.0–3.0) and the contents of impurity ions (K+, Na+, NH 4 + , Mg2+, SO 4 2? , CO 3 2? ) has been conducted. It is established that brushite solubility markedly rises with a decrease in pH from 6 to 3 and slightly rises with an increase in Mg2+ and SO 4 2? concentrations. The enrichment in K+, Na+, and NH 4 + does not affect brushite solubility. The changeable chemistry of the medium results in variation of the synthetic crystal habit, from rhombic tabular to thickened prismatic crystals.  相似文献   

17.
Violet, non-pleochroic and greenish-blue, pleochroic chromium-substituted sapphirines were found in corundum-bearing spinel-websterite xenolites from the Yakutian kimberlite pipes Noyabrskaya (N) and Sludyanka (Sl), respectively. The crystallochemical formulae of sapphirine crystals from such xenolites were determined by EMP to be (Mg3.40Fe0.23Al3.25Cr0.16)[6] Al 1.00 [6] [O2/Al4.53Si1.47O18] (N) and (Mg2.53Fe0.55 Mn0.04Ti 0.03 4+ Al3.55Cr 0.08 3+ )[6]Al 1.00 [16] [O2/Al4.28Si1.73O18] (Sl). Single crystal spectra in the range 35000–6000 cm1- showed a slightly polarization dependent absorption edge near 3200 cm1- (N) or 30000 cm1- (Sl) and unpolarized bands at 25300 and 17300 cm1-, typical of spin-allowed transitions, derived from 4A2g→4T1g and 4A2g→4T2g, of Cr3+ in octahedral sites, with point symmetry C1, of the structure. Another weak band at 23000 cm?1 in the sapphirine-N spectra is attributed to low symmetry splitting of the excited 4T1 (F)-State of Cr3+. These assignments lead to crystal field parameters Dq=1730cm?1 and B= 685cm?1 of Cr3+ in sapphirine. Crystallochemical and spectroscopic arguments suggest that Cr3+ subsitutes for Al in the M(1) or M(8) sites of the sapphirine structure. In addition to Cr3+-transitions, spectra of Sl exhibit weak dd-bands of Fe2+ at 10000 and 7700 cm1-, which are unpolarized in consistency with the C1 site symmetry of the octahedra in the structure. Spectra of Sl show also prominent, broad bands (Δv1/2～-5000 cm1-) at 15000 and 11000 cm1-, which occur in E//Y(//b) and E//Z(//c=12°) only and exhibit an intensity ratio αY∶αz close to 1∶3. This result, the large half width, as well as band energy — MM distance considerations suggest that these bands originate from Fe2+[6]-Fe3+[6] charge-transfer transitions in wall octahedra M(1)M(2), M(6)M(7) etc., forming MM vectors of 30° with the c-axis. The lack of Fe2+-Fe3+ charge-transfer bands in sapphirine N might indicate a lower oxygen fugacity during the formation of the websterite from the Noyabrskaya pipe compared to that from the Sludyanka pipe.  相似文献   

18.
The carbonate (CO 3 ?2 ) produced by Sporosarcina pasteurii was injected electrokinetically to enhance the mechanical properties of soft clay soils. In this method the Ca2+ was injected into the anode chamber and moved towards the cathode by electromigration and electroosmotic flow. Then the released CO 3 ?2 from a blend of bacteria and urea was injected into the cathode chamber. The CO 3 ?2 ions were moved from the cathode to the anode under electromigration mechanism. The CaCO3 was precipitated in the presence of calcium in porous medium of the soil, and consequently increased the shear strength of the soil. The polarity reversal was applied to have a homogeneous distribution of CaCO3.  相似文献   

19.
Despite a large number of studies of iron spin state in silicate perovskite at high pressure and high temperature, there is still disagreement regarding the type and P–T conditions of the transition, and whether Fe2+ or Fe3+ or both iron cations are involved. Recently, our group published results of a Mössbauer spectroscopy study of the iron behaviour in (Mg,Fe)(Si,Al)O3 perovskite at pressures up to 110 GPa (McCammon et al. 2008), where we suggested stabilization of the intermediate spin state for 8- to 12-fold coordinated ferrous iron ([8–12]Fe2+) in silicate perovskite above 30 GPa. In order to explore the behaviour in related systems, we performed a comparative Mössbauer spectroscopic study of silicate perovskite (Fe0.12Mg0.88SiO3) and majorite (with two compositions—Fe0.18Mg0.82SiO3 and Fe0.11Mg0.88SiO3) at pressures up to 81 GPa in the temperature range 296–800 K, which was mainly motivated by the fact that the oxygen environment of ferrous iron in majorite is quite similar to that in silicate perovskite. The [8–12]Fe2+ component, dominating the Mössbauer spectra of majorites, shows high quadrupole splitting (QS) values, about 3.6 mm s?1, in the entire studied P–T region (pressures to 58 GPa and 296–800 K). Decrease of the QS of this component with temperature at constant pressure can be described by the Huggins model with the energy splitting between low-energy e g levels of [8–12]Fe2+ equal to 1,500 (50) cm?1 for Fe0.18Mg0.82SiO3 and to 1,680 (70) cm?1 for Fe0.11Mg0.88SiO3. In contrast, for the silicate perovskite dominating Mössbauer component associated with [8–12]Fe2+ suggests the gradual change of the electronic properties. Namely, an additional spectral component with central shift close to that for high-spin [8–12]Fe2+ and QS about 3.7 mm s?1 appeared at ~35 (2) GPa, and the amount of the component increases with both pressure and temperature. The temperature dependence of QS of the component cannot be described in the framework of the Huggins model. Observed differences in the high-pressure high-temperature behaviour of [8–12]Fe2+ in the silicate perovskite and majorite phases provide additional arguments in favour of the gradual high-spin—intermediate-spin crossover in lower mantle perovskite, previously reported by McCammon et al. (2008) and Lin et al. (2008).  相似文献   

20.
The polarized (E‖a′, E‖b and E‖c) electronic absorption spectra of five natural chromium-containing clinopyroxenes with compositions close to chromdiopside, omphacite, ureyite-jadeite (12.8% Cr2O3), jadeite, and spodumene (hiddenite) were studied. The polarization dependence of the intensities of the Cr3+ bands in the clinopyroxene spectra cannot be explained by the selection rules for the point groups C 2 or C 2v but can be accounted for satisfactorily with the help of the higher order pseudosymmetry model, i.e. with selection rules for the point symmetry group C 3v. The trigonal axis of the pseudosymmetry crystal field forms an angle of 20.5° with the crystallographic direction c in the (010) plane. D q increases from diopside (1542 cm?1) through omphacite (1552 cm?1), jadeite (1574 cm?1) to spodumene (1592 cm?1). The parameter B which is a measure of covalency for Cr3+-O bonds at M1 sites in clinopyroxene depends on the Cr3+ concentration and the cations at M2 sites.  相似文献   

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