首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献，搜索用时 31 毫秒
1.
The thermal expansion of cubic pyrochlore Ce2Zr2O7 has been measured from room temperature to 898 K on polycrystalline material in conjunction with structural analyses using neutron diffraction. This compound has a thermal expansion coefficient in line with the other comparable lanthanoide pyrochlore oxides. The coefficient can be expressed as α(T) = 8.418 × 10−6 + 0.9861 × 10−9 × T. The structural refinements performed for each measured temperature showed a comparable linear evolution of the Ce–O/Zr–O distances (within 0.57%).  相似文献   

2.
Phengite samples (2M 1 and 3T politypes) and a synthetic end-member muscovite specimen were studied by in situ high-temperature synchrotron radiation X-ray diffraction. The measured volume thermal expansion of 2M 1 phengite (<α V> ≈ 36.6 × 10−6 K−1) was systematically greater than <α V> of the 3T polytype (≈33.3 × 10−6 K−1). A positive linear correlation between the average thermal expansion on (001) plane and the mean tetrahedral rotation angle at ambient condition is proposed on the ground of new measurements and literature data. Dehydroxylation processes were observed in 2M 1, starting at 1,000 K in 3T at 800 and 945 K in synthetic muscovite. Rietveld refinements allowed a determination of structural variations upon heating of phengite samples and their dehydroxylate phases. The phengite structure expands by regularizing the tetrahedral sheet and by reducing the bond length differences between the outer and inner coordination shell of the interlayer site. The dehydroxylate phase derived from 2M 1 is characterized by fivefold polyhedra in the low temperature form as a consequence of two OH groups reacting to form H2O + O (residual). The dehydroxylate exhibits an increase of the cation–cation distances along the M–Or–M bonds with respect to low-temperature phengite structures. For the 3T phase, we were unable to achieve completion of dehydroxylation. The refined structural model of the dehydroxylate phase shows two hydroxyl sites, but at a short distance from one another. This result suggests that the dehydroxylation reaction did not proceed to completion. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

3.
The Heihe River Basin is a typical arid inland river basin for examining stress on groundwater resources in northwest China. The basin is composed of large volumes of unconsolidated Quaternary sediments of widely differing grain size, and during the past half century, rapid socio-economic development has created an increased demand for groundwater resources. Understanding the hydrogeochemical processes of groundwater and water quality is important for sustainable development and effective management of groundwater resources in the Heihe River basin. To this end, a total of 30 representative groundwater samples were collected from different wells to monitor the water chemistry of various ions and its quality for irrigation. Chemical analysis shows that water presents a large spatial variability of chemical facies (SO4 2−–HCO3−, SO4 2−–Cl−, and Cl−–SO4 2−) as groundwater flow from recharge area to discharge area. The ionic ratio indicates positive correlation between the flowing pairs of parameters: Cl− and Na+(r = 0.95), SO4 2− and Na+ (r = 0.84), HCO3 − and Mg2+(r = 0.86), and SO4 2− and Ca2+ (r = 0.91). Dissolution of minerals, such as halite, gypsum, dolomite, silicate, and Mirabilite (Na2SO4·10H2O) in the sediments results in the Cl−, SO4 2−, HCO3 −, Na+, Ca2+ and Mg2+ content in the groundwater. Other reactions, such as evaporation, ion exchange, and deposition also influence the water composition. The suitability of the groundwater for irrigation was assessed based on the US Salinity Laboratory salinity classification and the Wilcox diagram. The results show that most of the groundwater samples are suitable for irrigation uses barring a few locations in the dessert region in the northern sub-basin.  相似文献   

4.
The thermoelastic behavior of a natural clintonite-1M [with composition: Ca1.01(Mg2.29Al0.59Fe0.12)Σ3.00(Si1.20Al2.80)Σ4.00O10(OH)2] has been investigated up to 10 GPa (at room temperature) and up to 960°C (at room pressure) by means of in situ synchrotron single-crystal and powder diffraction, respectively. No evidence of phase transition has been observed within the pressure and temperature range investigated. P–V data fitted with an isothermal third-order Birch–Murnaghan equation of state (BM-EoS) give V 0 = 457.1(2) ?3, K T0 = 76(3)GPa, and K′ = 10.6(15). The evolution of the “Eulerian finite strain” versus “normalized stress” shows a linear positive trend. The linear regression yields Fe(0) = 76(3) GPa as intercept value, and the slope of the regression line leads to a K′ value of 10.6(8). The evolution of the lattice parameters with pressure is significantly anisotropic [β(a) = 1/3K T0(a) = 0.0023(1) GPa−1; β(b) = 1/3K T0(b) = 0.0018(1) GPa−1; β(c) = 1/K T0(c) = 0.0072(3) GPa−1]. The β-angle increases in response to the applied P, with: βP = β0 + 0.033(4)P (P in GPa). The structure refinements of clintonite up to 10.1 GPa show that, under hydrostatic pressure, the structure rearranges by compressing mainly isotropically the inter-layer Ca-polyhedron. The bulk modulus of the Ca-polyhedron, described using a second-order BM-EoS, is K T0(Ca-polyhedron) = 41(2) GPa. The compression of the bond distances between calcium and the basal oxygens of the tetrahedral sheet leads, in turn, to an increase in the ditrigonal distortion of the tetrahedral ring, with ∂α/∂P ≈ 0.1°/GPa within the P-range investigated. The Mg-rich octahedra appear to compress in response to the applied pressure, whereas the tetrahedron appears to behave as a rigid unit. The evolution of axial and volume thermal expansion coefficient α with temperature was described by the polynomial α(T) = α0 + α1 T −1/2. The refined parameters for clintonite are as follows: α0 = 2.78(4) 10−5°C−1 and α1 = −4.4(6) 10−5°C1/2 for the unit-cell volume; α0(a) = 1.01(2) 10−5°C−1 and α1(a) = −1.8(3) 10−5°C1/2 for the a-axis; α0(b) = 1.07(1) 10−5°C−1 and α1(b) = −2.3(2) 10−5°C1/2 for the b-axis; and α0(c) = 0.64(2) 10−5°C−1 and α1(c) = −7.3(30) 10−6°C1/2for the c-axis. The β-angle appears to be almost constant within the given T-range. No structure collapsing in response to the T-induced dehydroxylation was found up to 960°C. The HP- and HT-data of this study show that in clintonite, the most and the less expandable directions do not correspond to the most and the less compressible directions, respectively. A comparison between the thermoelastic parameters of clintonite and those of true micas was carried out.  相似文献   

5.
The synthetic LiGaSi2O6 clinopyroxene is monoclinic C2/c at room-T. Its experimental electron density, ρ(r), has been derived starting from accurate room-T single-crystal diffraction data. Topological analysis confirms an intermediate ionic-covalent character for Si–O bonding, as found by previous electron-density studies on other silicates such as diopside, coesite and stishovite. The non-bridging Si–O bonds have more covalent character than the bridging ones. The Ga–O bonds have different bonding characters, the Ga–O2 bond being more covalent than the two Ga–O1 bonds. Li–O bonds are classified as pure closed-shell ionic interactions. Similar to spodumene (LiAlSi2O6), Li has sixfold coordination, but the bond critical points associated to the two longest bonds are characterized by very low electron density values. Similar to what previously found in spodumene and diopside, O···O interactions were detected from the topological analysis of ρ(r), and indicate a cooperative interaction among the lone pairs of neighbouring oxygen atoms. In particular, this kind of interaction has been obtained for the O1···O1 edge shared between two Ga octahedra. Integration over the atomic basins gives net charges of −1.39(10), 2.82(10), 1.91(10) and 0.82(8) e for O (averaged), Si, Ga and Li atoms, respectively. Periodic Hartree–Fock and DFT calculations confirm the results obtained by multipole refinement of the experimental data. Moreover, the theoretical topological properties of the electron density distribution on the Si2O6 group are very similar to those calculated for spodumene. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

6.
The thermo-elastic behavior of a natural epidote [Ca1.925 Fe0.745Al2.265Ti0.004Si3.037O12(OH)] has been investigated up to 1,200 K (at 0.0001 GPa) and 10 GPa (at 298 K) by means of in situ synchrotron powder diffraction. No phase transition has been observed within the temperature and pressure range investigated. P–V data fitted with a third-order Birch–Murnaghan equation of state (BM-EoS) give V 0 = 458.8(1)Å3, K T0 = 111(3) GPa, and K′ = 7.6(7). The confidence ellipse from the variance–covariance matrix of K T0 and K′ from the least-square procedure is strongly elongated with negative slope. The evolution of the “Eulerian finite strain” vs “normalized stress” yields Fe(0) = 114(1) GPa as intercept values, and the slope of the regression line gives K′ = 7.0(4). The evolution of the lattice parameters with pressure is slightly anisotropic. The elastic parameters calculated with a linearized BM-EoS are: a 0 = 8.8877(7) Å, K T0(a) = 117(2) GPa, and K′(a) = 3.7(4) for the a-axis; b 0 = 5.6271(7) Å, K T0(b) = 126(3) GPa, and K′(b) = 12(1) for the b-axis; and c 0 = 10.1527(7) Å, K T0(c) = 90(1) GPa, and K’(c) = 8.1(4) for the c-axis [K T0(a):K T0(b):K T0(c) = 1.30:1.40:1]. The β angle decreases with pressure, βP(°) = βP0 −0.0286(9)P +0.00134(9)P 2 (P in GPa). The evolution of axial and volume thermal expansion coefficient, α, with T was described by the polynomial function: α(T) = α0 + α1 T −1/2. The refined parameters for epidote are: α0 = 5.1(2) × 10−5 K−1 and α1 = −5.1(6) × 10−4 K1/2 for the unit-cell volume, α0(a) = 1.21(7) × 10−5 K−1 and α1(a) = −1.2(2) × 10−4 K1/2 for the a-axis, α0(b) = 1.88(7) × 10−5 K−1 and α1(b) = −1.7(2) × 10−4 K1/2 for the b-axis, and α0(c) = 2.14(9) × 10−5 K−1 and α1(c) = −2.0(2) × 10−4 K1/2 for the c-axis. The thermo-elastic anisotropy can be described, at a first approximation, by α0(a): α0(b): α0(c) = 1 : 1.55 : 1.77. The β angle increases continuously with T, with βT(°) = βT0 + 2.5(1) × 10−4 T + 1.3(7) × 10−8 T 2. A comparison between the thermo-elastic parameters of epidote and clinozoisite is carried out.  相似文献   

7.
Sulfide Inhibition of Nitrate Removal in Coastal Sediments   总被引：1，自引：0，他引：1  
Microbial nitrate (NO3−) removal via denitrification (DNF) at high sulfide (H2S) concentrations was compared in sediment from a coastal freshwater pond in a developed area that receives salt-water influx during storm events, and a saline pond proximal to an undeveloped estuary. Sediments were incubated with added SO42− (1,000 μg per gram dry weight basis (gdw)) to determine whether acid volatile sulfides (AVS) were formed. DNF in the sediments was measured with NO3–N (300 μg gdw−1) alone, and with NO3–N and H2S (1,000 μg S2− gdw−1). SO42− addition to the freshwater sediments resulted in AVS formation (970 ± 307 μg S gdw−1) similar to the wetland with no added SO42− (986 ± 156 μg S gdw−1). DNF rates measured with no added H2S were greater in the freshwater than the wetland site (10.6 ± 0.6 vs. 6.4 ± 0.1 μg N2O–N gdw−1 h−1, respectively). High H2S concentrations retained NH4–N in the undeveloped wetland and retained NO3–N in the developed freshwater site, suggesting that potential salt-water influx may reduce the ability of the freshwater sediments to remove NO3–N.  相似文献   

8.
The thermal expansion of gehlenite, Ca2Al[AlSiO7], (up to T=830 K), TbCaAl[Al2O7] (up to T=1100 K) and SmCaAl[Al2O7] (up to T=1024 K) has been determined. All compounds are of the melilite structure type with space group Thermal expansion data were obtained from in situ X-ray powder diffraction experiments in-house and at HASYLAB at the Deutsches Elektronen Synchrotron (DESY) in Hamburg (Germany). The thermal expansion coefficients for gehlenite were found to be: α1=7.2(4)×10−6×K−1+3.6(7)×10−9ΔT×K−2 and α3=15.0(1)×10−6×K−1. For TbCaAl[Al2O7] the respective values are: α1=7.0(2)×10−6×K−1+2.0(2)×10−9ΔT×K−2 and α3=8.5(2)×10−6×K−1+2.0(3)×10−9ΔT×K−2, and the thermal expansion coefficients for SmCaAl[Al2O7] are: α1=6.9(2)×10−6×K−1+1.7(2)×10−9ΔT×K−2 and α3=9.344(5)×10−6×K−1. The expansion mechanisms of the three compounds are explained in terms of structural trends obtained from Rietveld refinements of the crystal structures of the compounds against the powder diffraction patterns. No structural phase transitions have been observed. While gehlenite behaves like a ‘proper’ layer structure, the aluminates show increased framework structure behavior. This is most probably explained by stronger coulombic interactions between the tetrahedral conformation and the layer-bridging cations due to the coupled substitution (Ca2++Si4+)–(Ln 3++Al3+) in the melilite-type structure. This article has been mistakenly published twice. The first and original version of it is available at .  相似文献   

9.
  相似文献   

10.
 Cordierite precursors were prepared by a sol-gel process using tetraethoxysilane, aluminum sec.-butoxide, and Mg metal flakes as starting materials. The precursors were treated by 15-h heating steps in intervals of 100 °C from 200 to 900 °C; they show a continuous decrease in the analytical water content with increasing preheating temperatures. The presence of H2O and (Si,Al)–OH combination modes in the FTIR powder spectra prove the presence of both H2O molecules and OH groups as structural components, with invariable OH concentrations up to preheating temperatures of 500 °C. The deconvolution of the absorptions in the (H2O,OH)-stretching vibrational region into four bands centred at 3584, 3415, 3216 and 3047 cm−1 reveals non-bridging and bridging H2O molecules and OH groups. The precursor powders remain X-ray amorphous up to preheating temperatures of 800 °C. Above this temperature the precursors crystallize to μ-cordierite; at 1000 °C the structure transforms to α-cordierite. Close similarities exist in the pattern of the 1400–400 cm−1 lattice vibrational region for precursors preheated up to 600 °C. Striking differences are evident at preheating temperatures of 800 °C, where the spectrum of the precursor powder corresponds to that of conventional cordierite glass. Bands centred in the “as-prepared” precursor at 1137 and 1020 cm−1 are assigned to Si–O-stretching vibrations. A weak absorption at 872 cm−1 is assigned to stretching modes of AlO4 tetrahedral units and the same assignment holds for a band at 783 cm−1 which appears in precursors preheated at 600 °C. With increasing temperatures, these bands show a significant shift to higher wavenumbers and the Al–O stretching modes display a strong increase in their intensities. (Si,Al)–O–(Si,Al)-bending modes occur at 710 cm−1 and the band at 572 cm−1 is assigned to stretching vibrations of AlO6 octahedral units. A strong band around 440 cm−1 is essentially attributed to Mg–O-stretching vibrations. The strongly increasing intensity of the 872 and 783 cm−1 bands demonstrates a clear preference of Al for a fourfold-coordinated structural position in the precursors preheated at high temperatures. The observed band shift is a strong indication for increasing tetrahedral network condensation along with changes in the Si–O and Al–O distances to tetrahedra dimensions similar to those occurring in crystalline cordierite. These structural changes are correlated to the dehydration process starting essentially above 500 °C, clearly demonstrating the inhibiting role of H2O molecules and especially of OH groups. Received: 1 March 2002 / Accepted: 26 June 2002  相似文献   

11.
Thermal behaviour and kinetics of dehydration of gypsum in air have been investigated using in situ real-time laboratory parallel-beam X-ray powder diffraction data evaluated by the Rietveld method. Thermal expansion has been analysed from 298 to 373 K. The high-temperature limits for the cell edges and for the cell volume, calculated using the Einstein equation, are 4.29 × 10−6, 4.94 × 10−5, 2.97 × 10−5, and 8.21 × 10−5. Thermal expansion of gypsum is strongly anisotropic being larger along the b axis mainly due to the weakening of hydrogen bond. Dehydration of gypsum has been investigated in isothermal conditions within the 348–403 K range with a temperature increase of 5 K. Dehydration proceeds through the CaSO4·2H2O → CaSO4·0.5H2O → γ-CaSO4 steps. Experimental data have been fitted with the Avrami equation to calculate the empirical activation energy of the process. No change in transformation mechanism has been observed within the analysed temperature range and the corresponding E a is 109(12) kJ/mol.  相似文献   

12.
A natural datolite CaBSiO4(OH) (Bergen Hill, NJ, USA), before and after gamma-ray irradiation (up to ~70 kGy), has been investigated by single-crystal and powder electron paramagnetic resonance (EPR) spectroscopy from 10 to 295 K. EPR spectra of gamma-ray-irradiated datolite show the presence of a boron-associated oxygen hole center (BOHC) and an atomic hydrogen center (H0), both of which grow with increasing radiation dose. The principal g and A(11B) values of the BOHC at 10 K are: g 1 = 2.04817(3), g 2 = 2.01179(2), g 3 = 2.00310(2), A 1 = −0.401(7) mT, A 2 = −0.906(2) mT, A 3 = −0.985(2) mT, with the orientations of the g 1 and A 1 axes approximately along the B–OH bond direction. These experimental results suggest that the BOHC represents hole trapping on the hydroxyl oxygen atom after the removal of the proton (i.e. a [BO4]0 center): via a reaction O3BOH → O3BO· + H0, where · denotes the unpaired electron. Density functional theory (DFT) calculations (CRYSTAL06, B3PW, all-electron basis sets, and 1 × 2 × 2 supercell) support the proposed structural model and yield the following 11B hyperfine coupling constants: A 1 = −0.429 mT, A 2 = −0.901 mT, A 3 = −0.954 mT, in excellent agreement with the experimental results. The [BO4]0 center undergoes the onset of thermal decay at ~200°C and is completely annealed out at 375°C but can be restored readily by gamma-ray irradiation. Isothermal annealing experiments show that the [BO4]0 center exhibits a second-order thermal decay with an activation energy of 0.96 eV. The confirmation of the [BO4]0 center (and its formation from the O3BOH precursor) in datolite has implications for not only understanding of BOHCs in alkali borosilicate glasses but also their applications to nuclear waste disposal.  相似文献   

13.
The experiments of the dissolution kinetics of fluorite were performed in aqueous HCl solutions over the temperature range of 25–100 °C using a flow-through experimental apparatus. With a constant input of aqueous HCl solution through the reactor, output concentrations of the dissolved species Ca, F, Cl vary with flow rate, as well as with the surface compositions. Measured output concentrations of dissolved species and the pH can be used to determine a rate law for fluorite dissolution. Fluorite dissolution rates are found to be pH dependent. Usually, dissolution rates of fluorite decreases with increasing dissolved Ca in the output solution at 25 and 100 °C. Dissolution rate can be expressed as
(1a)
where k is the rate constant and α is the order with respect to the hydrogen ion activity vs. the activity of dissolved Ca. The α was obtained from kinetic experiments. For the fluorite sample passed through 18–35 mesh, α =1.198 at 100 °C and k = 10−0.983, while fluorite dissolved in HCl–H2O solution at pH 2.57 of input solution. Adsorption of a proton and Cl−1onto the fluorite surface, surface cation exchange and the formation of the surface complex Ca(F, Cl)2 and/or (H2x, Ca1−x)(F, Cl)2 control dissolution rates. Investigation of the fluorite surface before and after dissolution by using X-ray photoelectron spectroscopy (XPS) indicate that surface modifications affect reaction rates.  相似文献   

14.
Summary Low-temperature phase transitions of leonite-type compounds, K2Me2+(SO4)2 · 4H2O (Me = Mg, Mn, Fe), are investigated by temperature dependent measurements of single-crystal X-ray reflection intensities and lattice parameters. The transition temperatures and the progress of the transitions are determined by birefringence data and differential scanning calorimetry. The cause for the phase transitions of leonite-type compounds is a dynamic disorder of sulphate groups at room temperature (C2/m), that freezes in to an ordered structure (I2/a) at −4(1) °C in leonite, K2Mg(SO4)2 · 4H2O. At −153(1) °C the crystal structure switches to another ordered phase (P21/a). The Mn analogue shows the same succession with transition temperatures at −68(1) °C and −104(1) °C. The disordered room temperature structure of the isotypic mineral mereiterite, K2Fe(SO4)2 · 4H2O, transforms directly to the ordered P21/a structure at 3(2) °C. Analysis of X-ray intensities and of excess birefringence reveals that the displacive I2/a ⇔ P21/a phase transition of leonite and Mn-leonite is first order. According to Landau theory the C2/m ⇔ I2/a (leonite, Mn-leonite) and C2/m ⇔ P21/a (mereiterite) order-disorder transitions are almost tricritical. Received March 7, 2001; revised version accepted June 27, 2001  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.
The thermal expansion of gehlenite, Ca2Al[AlSiO7], (up to T=830 K), TbCaAl[Al2O7] (up to T=1,100 K) and SmCaAl[Al2O7] (up to T=1,024 K) has been determined. All compounds are of the melilite structure type with space group Thermal expansion data was obtained from in situ X-ray powder diffraction experiments in-house and at HASYLAB at the Deutsches Elektronen Synchrotron (DESY) in Hamburg (Germany). The thermal expansion coefficients for gehlenite were found to be: α1=7.2(4)×10−6 K−1+3.6(7)×10−9ΔT K−2 and α3=15.0(1)×10−6 K−1. For TbCaAl[Al2O7] the respective values are: α1=7.0(2)×10−6 K−1+2.0(2)×10−9ΔT K−2 and α3=8.5(2)×10−6 K−1+2.0(3)×10−9ΔT K−2, and the thermal expansion coefficients for SmCaAl[Al2O7] are: α1=6.9(2)× 10−6 K−1+1.7(2)×10−9ΔT K−2 and α3=9.344(5)×10−6 K−1. The expansion-mechanisms of the three compounds are explained in terms of structural trends obtained from Rietveld refinements of the crystal structures of the compounds against the powder diffraction patterns. No structural phase transitions have been observed. While gehlenite behaves like a ’proper’ layer structure, the aluminates show increased framework structure behaviour. This is most probably explained by stronger coulombic interactions between the tetrahedral conformation and the layer-bridging cations due to the coupled substitution (Ca2++Si4+)-(Ln 3++Al3+) in the melilite-type structure. Electronic Supplementary Material Supplementary material is available for this article at  相似文献   

17.
Jarosite phases are common minerals in acidic, sulfate-rich environments. Here, we report heat capacities (C p) and standard entropies (S°) for a number of jarosite samples. Most samples are close to the nominal composition AFe3(SO4)2(OH)6, where A = K, Na, Rb, and NH4. One of the samples has a significant number of defects on the Fe sites and is called the defect jarosite; others are referred to as A-jarosite. The samples, their compositions, and the entropies at T = 298.15 K are:
Sample Chemical composition S o/(J mol−1 K−1)
K-jarosite K0.92(H3O)0.08Fe2.97(SO4)2(OH)5.90(H2O)0.10 427.4 ± 0.7
Na-jarosite Na0.95(H3O)0.05Fe3.00(SO4)2(OH)6.00 436.4 ± 4.4
Rb-jarosite RbFe2.98(SO4)2(OH)5.95(H2O)0.05 411.9 ± 4.1
NH4-jarosite (NH4)0.87(H3O)0.13Fe3.00(SO4)2(OH)6.00 447.2 ± 4.5
Defect jarosite K0.94(H3O)0.06Fe2.34(SO4)2(OH)4.01(H2O)1.99 412.7 ± 4.1
There are additional configurational entropies of 13.14 and 8.23 J mol−1 K−1 in defect and NH4-jarosite, respectively. A detailed analysis of the synchrotron X-ray diffraction patterns showed a large anisotropic peak broadening for defect and NH4-jarosite. The fits to the low-temperature (approx. <12 K) C p data showed that our samples can be divided into two groups. The first group is populated by the K-, Na-, Rb-, and NH4-jarosite samples, antiferromagnetic at low temperatures. The second group contains the H3O-jarosite (studied previously) and the defect jarosite. H3O- and defect jarosite are spin glasses and their low-T C p was fit with the expression C p = γT + ΣB j T j , where j = (3, 5, 7, 9). The linear term is typical for spin glasses and the sum represents the lattice contribution to C p. Surprisingly, the C p of the K-, Na-, Rb-, and NH4-jarosite samples, which are usually considered to be antiferromagnetic at low temperatures, also contains a large linear term. This finding suggests that even these phases do not order completely, but have a partial spin-glass character below their Néel transition temperature.  相似文献   

18.
The heat capacity at constant pressure, C p, of chlorapatite [Ca5(PO4)3Cl – ClAp], and fluorapatite [Ca5(PO4)3F – FAp], as well as of 12 compositions along the chlorapatite–fluorapatite join have been measured using relaxation calorimetry [heat capacity option of the physical properties measurement system (PPMS)] and differential scanning calorimetry (DSC) in the temperature range 5–764 K. The chlor-fluorapatites were synthesized at 1,375–1,220°C from Ca3(PO4)2 using the CaF2–CaCl2 flux method. Most of the chlor-fluorapatite compositions could be measured directly as single crystals using the PPMS such that they were attached to the sample platform of the calorimeter by a crystal face. However, the crystals were too small for the crystal face to be polished. In such cases, where the sample coupling was not optimal, an empirical procedure was developed to smoothly connect the PPMS to the DSC heat capacities around ambient T. The heat capacity of the end-members above 298 K can be represented by the polynomials: C pClAp = 613.21 − 2,313.90T −0.5 − 1.87964 × 107 T −2 + 2.79925 × 109 T −3 and C pFAp = 681.24 − 4,621.73 × T −0.5 − 6.38134 × 106 T −2 + 7.38088 × 108 T −3 (units, J mol−1 K−1). Their standard third-law entropy, derived from the low-temperature heat capacity measurements, is S° = 400.6 ± 1.6 J mol−1 K−1 for chlorapatite and S° = 383.2 ± 1.5 J mol−1 K−1 for fluorapatite. Positive excess heat capacities of mixing, ΔC pex, occur in the chlorapatite–fluorapatite solid solution around 80 K (and to a lesser degree at 200 K) and are asymmetrically distributed over the join reaching a maximum of 1.3 ± 0.3 J mol−1 K−1 for F-rich compositions. They are significant at these conditions exceeding the 2σ-uncertainty of the data. The excess entropy of mixing, ΔS ex, at 298 K reaches positive values of 3–4 J mol−1 K−1 in the F-rich portion of the binary, is, however, not significantly different from zero across the join within its 2σ-uncertainty.  相似文献   

19.
The Zhangye Basin, located in arid northwest China, is an important agricultural and industrial center. In recent years rapid development has created an increased demand for water, which is increasingly being fulfilled by groundwater abstraction. Detailed knowledge of the geochemical evolution of groundwater and water quality can enhance understanding of the hydrochemical system, promoting sustainable development and effective management of groundwater resources. To this end, a hydrochemical investigation was conducted in the Zhangye Basin. Types of shallow groundwater in the Zhangye Basin were found to be HCO3 −, HCO3 −–SO4 2−, SO4 2−–HCO3 −, SO4 2−–Cl−, Cl−–SO4 2− and Cl− . The deep aquifer groundwater type was found to be HCO3−–SO42− throughout the entire area. Ionic ratio and saturation index calculations suggest that silicate rock weathering and evaporation deposition are the main processes that determine the ionic composition in the study area. The suitability of the groundwater for irrigation was assessed based on the US Salinity Laboratory salinity classification and the Wilcox diagram. In the study area, the compositions of the stable isotopes δ18O and δD in groundwater samples were found to range from −4.00 to −9.28‰ and from −34.0 to −65.0‰, respectively. These values indicate that precipitation is the main recharge source for the groundwater system; some local values indicate high levels of evaporation. Tritium analysis was used to estimate the ages of the different groundwaters; the tritium values of the groundwater samples varied from 3.13 to 36.62 TU. The age of the groundwater at depths of less than 30 m is about 5–10 years. The age of the groundwater at depths of 30–50 m is about 10–23 years. The age of the groundwater at depths of 50–100 m is about 12–29 years. For groundwater samples at depths of greater than 100 m, the renewal time is about 40 years.  相似文献   

20.
The H2O content of wadsleyite were measured in a wide pressure (13–20 GPa) and temperature range (1,200–1,900°C) using FTIR method. We confirmed significant decrease of the H2O content of wadsleyite with increasing temperature and reported first systematic data for temperature interval of 1,400–1,900°C. Wadsleyite contains 0.37–0.55 wt% H2O at 1,600°C, which may be close to its water storage capacity along average mantle geotherm in the transition zone. Accordingly, water storage capacity of the average mantle in the transition zone may be estimated as 0.2–0.3 wt% H2O. The H2O contents of wadsleyite at 1,800–1,900°C are 0.22–0.39 wt%, indicating that it can store significant amount of water even under the hot mantle environments. Temperature dependence of the H2O content of wadsleyite can be described by exponential equation C\textH2 \textO = 6 3 7.0 7 \texte - 0.00 4 8T , C_{{{\text{H}}_{2} {\text{O}}}} = 6 3 7.0 7 {\text{e}}^{ - 0.00 4 8T} , where T is in °C. This equation is valid for temperature range 1,200–2,100°C with the coefficient of determination R 2 = 0.954. Temperature dependence of H2O partition coefficient between wadsleyite and forsterite (D wd/fo) is complex. According to our data apparent Dwd/fo decreases with increasing temperature from D wd/fo = 4–5 at 1,200°C, reaches a minimum of D wd/fo = 2.0 at 1,400–1,500°C, and then again increases to D wd/fo = 4–6 at 1,700–1,900°C.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号