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正1 Introduction China has very abundant liquid mineral resources.Especially,the brine resources in the west of Sichuan Basin are pushed into the first place in China,whose K and B contents are unusually high.These rare liquid mineral resources have very good exploitation prospect(Lin,2001;2006).Generally speaking,phase equilibrium 相似文献
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Kirsten Linnow Michael Steiger Christine Lemster Hilde De Clercq Maja Jovanović 《Environmental Earth Sciences》2013,69(5):1609-1620
Several double salts have been detected in building materials and most of these salts are incongruently soluble compounds. In contrast to single salts, however, no systematic investigations of the crystallization behavior and deleterious effects of incongruently soluble double salts exist. To assess the damage potential of these salts, a systematic investigation of their highly complex behavior is desirable. This paper deals with the crystallization behavior of various solids in the ternary mixed NaNO3–Na2SO4 system including the formation of the double salt darapskite, Na3NO3SO4·H2O. The crystallization sequence during droplet evaporation experiments at room conditions was determined using Raman and polarization microscopy. The basic idea of this research is to use deviations of the crystallization sequence of a salt or a mixed salt solution from the equilibrium pathway as an indicator to detect the degree of supersaturation. The observed crystallization pathway includes the formation of the metastable phases Na2SO4(III), Na2SO4(V) and darapskite. The experimental observations are discussed on the basis of the NaNO3–Na2SO4–H2O phase diagram and the results provide evidence for crystal growth from highly supersaturated solutions in both systems. If the crystals growing under these conditions are confined, these supersaturations result in substantial crystallization pressures. 相似文献
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We report on the crystallization behavior and the salt weathering potential of Na2SO4, MgSO4 and an equimolar mixture of these salts in natural rock and porous stone. Geochemical modeling of the phase diagram of the ternary Na2SO4–MgSO4–H2O system was used to determine the equilibrium pathways during wetting (or deliquescence) of incongruently soluble minerals and evaporation of mixed electrolyte solutions. Model calculations include stable and metastable solubilities of the various hydrated states of the single salts and the double salts Na2Mg(SO4)2·4H2O (bloedite), Na2Mg(SO4)2·5H2O (konyaite), Na12Mg7(SO4)13·15H2O (loeweite) and Na6Mg(SO4)4 (vanthoffite). In situ Raman spectroscopy was used to study the phase transformations during wetting of pure MgSO4·H2O (kieserite) and of the incongruently soluble salts bloedite and konyaite. Dissolution of kieserite leads to high supersaturation resulting in crystallization of higher hydrated phases, i.e. MgSO4·7H2O (epsomite) and MgSO4·6H2O (hexahydrite). This confirms the high damage potential of magnesium sulfate in salt damage of building materials. The dissolution of the incongruently soluble double salts leads to supersaturation with respect to Na2SO4·10H2O (mirabilite). However, the supersaturation was insufficient for mirabilite nucleation. The damage potential of the two single salts and an equimolar salt mixture was tested in wetting–drying experiments with porous sandstone. While the high damage potential of the single salts is confirmed, it appears that the supersaturation achieved during wetting of the double salts at room temperature is not sufficient to generate high crystallization pressures. In contrast, very high damage potentials of the double salts were found in experiments at low temperature under high salt load.1 相似文献
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Liquid–liquid immiscibility has crucial influences on geological processes, such as magma degassing and formation of ore deposits. Sulfate, as an important component, associates with many kinds of deposits. Two types of immiscibility, including (i) fluid–melt immiscibility between an aqueous solution and a sulfate melt, and (ii) fluid–fluid immiscibility between two aqueous fluids with different sulfate concentrations, have been identified for sulfate–water systems. In this study, we investigated the immiscibility behaviors of a sulfate- and quartz-saturated Na2SO4–SiO2–H2O system at elevated temperature, to explore the phase relationships involving both types of immiscibility. The fluid–melt immiscibility appeared first when the Na2SO4–SiO2–H2O sample was heated to ~270°C, and then fluid–fluid immiscibility emerged while the sample was further heated to ~450°C. At this stage, the coexistence of one water-saturated sulfate melt and two aqueous fluids with distinct sulfate concentrations was observed. The three immiscible phases remain stable over a wide pressure–temperature range, and the appearance temperature of the fluid–fluid immiscibility increases with the increased pressure. Considering that sulfate components occur extensively in carbonatite-related deposits, the fluid–fluid immiscibility can result in significant sulfate fractionation and provides implications for understanding the formation of carbonatite-related rare earth deposits. 相似文献
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We report on the crystallization behavior and the salt weathering potential in natural rock and porous stone of single salts (NaNO3, Na2SO4) and salt mixtures in the ternary NaNO3–Na2SO4–H2O system. Geochemical modeling of the phase diagram of the ternary NaNO3–Na2SO4–H2O system was used to determine the equilibrium pathways during wetting (or deliquescence) of incongruently soluble minerals and evaporation of mixed electrolyte solutions. Experiments were carried out in order to study the phase changes during dissolution either induced by deliquescence or by the addition of liquid water. In situ Raman spectroscopy was used to study the phase transformations during wetting of pure Na2SO4 (thenardite) and of Na3NO3SO4·H2O (darapskite). In both experiments crystallization of Na2SO4·10H2O (mirabilite) from highly supersaturated solutions is demonstrated confirming the high salt weathering potential of thenardite and darapskite wetting. In order to study the damage potential of darapskite experimentally, wetting–drying experiments with porous sandstone with the two single salts (Na2SO4, NaNO3) and two NaNO3–Na2SO4 salt mixtures were carried out. Different destructive and non-destructive techniques were tested for damage monitoring. NaNO3 was found to be the least damaging salt and Na2SO4 is the most damaging one. The classification of the two salt mixtures was less obvious. 相似文献
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This work aims to quantify sulfate ion concentrations in the system Na2SO4-H2O using Raman micro-spectroscopy.Raman spectra of sodium sulfate solutions with known concentrations were collected at ambient temperature（293 K） and in the 500 cm1-4000 cm-1 spectral region.The results indicate that the intensity of the SO42- band increases with increasing concentrations of sulfate ion.A linear correlation was found between the concentration of SO42-（c） and parameter I1,which represents the ratio of the area of the SO42- band to that of the O-H stretching band of water（As/Aw）:I1=-0.00102+0.01538 c.Furthermore,we deconvoluted the O-H stretching band of water(2800 cm-1-3800 cm-1) at 3232 and 3430 cm-1 into two sub-Gaussian bands,and then defined Raman intensity of the two sub-bands as ABi(3232 cm-1) and AB2(3430 cm-1),defined the full width of half maximum（FWHM） of the two sub-bands as WB1(3232 cm-1) and WB2(3430 cm-1).A linear correlation between the concentration of SO42-（c） and parameter I2,which represents the ratio of Raman intensity of SO42-（As）(in 981 cm-1) to(AB1+AB2),was also established:I2=-0.0111+0.3653 c.However,no correlations were found between concentration of SO42-（c） and FWHM ratios,which includes the ratio of FWHM of SO42-（Ws） to WB1 WB2 and WB1+B2(the sum of WB1 and WB2),suggesting that FWHM is not suitable for quantitative studies of sulfate solutions with Raman spectroscopy.A comparison of Raman spectroscopic studies of mixed Na2SO4 and NaCI solutions with a constant SO42- concentration and variable CI- concentrations suggest that the I\ parameter is affected by CI-,whereas the I2 parameter was not.Therefore,even if the solution is not purely Na2SO4-H2O,SO42- concentrations can still be calculated from the Raman spectra if the H2O band is deconvoluted into two sub-bands,making this method potentially applicable to analysis of natural fluid inclusions. 相似文献
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Gennaro Ventruti Fernando Scordari Giancarlo Della Ventura Fabio Bellatreccia Alessandro F. Gualtieri Andrea Lausi 《Physics and Chemistry of Minerals》2013,40(8):659-670
The thermal stability of sideronatrite, ideally Na2Fe3+(SO4)2(OH)·3(H2O), and its decomposition products were investigated by combining thermogravimetric and differential thermal analysis, in situ high-temperature X-ray powder diffraction (HT-XRPD) and Fourier transform infrared spectroscopy (HT-FTIR). The data show that for increasing temperature there are four main dehydration/transformation steps in sideronatrite: (a) between 30 and 40 °C sideronatrite transforms into metasideronatrite after the loss of two water molecules; both XRD and FTIR suggest that this transformation occurs via minor adjustments in the building block. (b) between 120 and 300 °C metasideronatrite transforms into metasideronatrite II, a still poorly characterized phase with possible orthorhombic symmetry, consequently to the loss of an additional water molecule; X-ray diffraction data suggest that metasideronatrite disappears from the assemblage above 175 °C. (c) between 315 and 415 °C metasideronatrite II transforms into the anhydrous Na3Fe(SO4)3 compound. This step occurs via the loss of hydroxyl groups that involves the breakdown of the [Fe3+(SO4)2(OH)] ∞ 2? chains and the formation of an intermediate transient amorphous phase precursor of Na3Fe(SO4)3. (d) for T > 500 °C, the Na3Fe(SO4)3 compound is replaced by the Na-sulfate thenardite, Na2SO4, plus Fe-oxides, according to the Na3Fe3+(SO4)3 → 3/2 Na2(SO4) + 1/2 Fe2O3 + SOx reaction products. The Na–Fe sulfate disappears around 540 °C. For higher temperatures, the Na-sulfates decomposes and only hematite survives in the final product. The understanding of the thermal behavior of minerals such as sideronatrite and related sulfates is important both from an environmental point of view, due to the presence of these phases in evaporitic deposits, soils and sediments including extraterrestrial occurrences, and from the technological point of view, due to the use of these materials in many industrial applications. 相似文献
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含NaCl和Na2SO4双组分盐渍土的水盐相变温度研究 总被引：1，自引：0，他引：1
盐渍土相变温度是判断土体中水分冻结与融化、盐分结晶与溶解的重要参数。不同盐分含量相变温度的差异,给盐渍土在降温过程中的水盐迁移过程及变形规律的模拟带来极大的不确定性。通过降温试验,研究了降温过程中氯盐和硫酸盐综合作用盐渍土中水盐相变温度的变化情况。结果表明：全盐量相同时,盐结晶温度随NaCl和Na2SO4比例的不同而不同。随NaCl的加入,在Na+同离子效应的影响下,Na2SO4更容易结晶,但土体的冰和芒硝共晶点温度下降,使得冰含量显著减少,从而降低了孔隙溶液中固相的产生比例,起到抑制Na2SO4盐渍土盐冻胀变形的作用。当土中只含Na2SO4盐时,随Na2SO4浓度的增加,冰和芒硝共晶点的温度先上升而后缓慢下降,二次相变前冰盐的累积量是导致冰和芒硝共晶点产生这种变化的主要原因。盐渍土三相共晶点温度随NaCl含量的增加呈现上升趋势,这是因为随着NaCl的加入,在发生三相共晶前,孔隙溶液发生相变的固相含量减少,从而使孔隙结构对三相共晶点的影响减小。此外,含有NaCl与Na2SO4双组分的盐渍土,水分和盐分可能以单固相、双固相以及三固相状态析出。研究结果可为深入认识盐渍土的相变规律及物理性质提供理论支撑。 相似文献
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The configurational heat capacity, shear modulus and shear viscosity of a series of Na2O–Fe2O3–Al2O3–SiO2 melts have been determined as a function of composition. A change in composition dependence of each of the physical properties
is observed as Na2O/(Na2O + Al2O3) is decreased, and the peralkaline melts become peraluminous and a new charge-balanced Al-structure appears in the melts.
Of special interest are the frequency dependent (1 mHz–1 Hz) measurements of the shear modulus. These forced oscillation measurements
determine the lifetimes of Si–O bonds and Na–O bonds in the melt. The lifetime of the Al–O bonds could not, however, be resolved
from the mechanical spectrum. Therefore, it appears that the lifetime of Al–O bonds in these melts is similar to that of Si–O
bonds with the Al–O relaxation peak being subsumed by the Si–O relaxation peak. The appearance of a new Al-structure in the
peraluminous melts also cannot be resolved from the mechanical spectra, although a change in elastic shear modulus is determined
as a function of composition. The structural shear-relaxation time of some of these melts is not that which is predicted by
the Maxwell equation, but up to 1.5 orders of magnitude faster. Although the configurational heat capacity, density and shear
modulus of the melts show a change in trend as a function of composition at the boundary between peralkaline and peraluminous,
the deviation in relaxation time from the Maxwell equation occurs in the peralkaline regime. The measured relaxation times
for both the very peralkaline melts and the peraluminous melts are identical with the calculated Maxwell relaxation time.
As the Maxwell equation was created to describe the timescale of flow of a mono-structure material, a deviation from the prediction
would indicate that the structure of the melt is too complex to be described by this simple flow equation. One possibility
is that Al-rich channels form and then disappear with decreasing Si/Al, and that the flow is dominated by the lifetime of
Si–O bonds in the Al-poor peralkaline melts, and by the lifetime of Al–O bonds in the relatively Si-poor peralkaline and peraluminous
melts with a complex flow mechanism occurring in the mid-compositions. This anomalous deviation from the calculated relaxation
time appears to be independent of the change in structure expected to occur at the peralkaline/peraluminous boundary due to
the lack of charge-balancing cations for the Al-tetrahedra. 相似文献
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正1 Introduction The underground brine resources distributing widely in Sichuan Basin,China have drawn worldwide attention due to their unusual element abundance and excellent quality. 相似文献
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Helen E. A. Brand A. Dominic Fortes Ian G. Wood Lidunka Vočadlo 《Physics and Chemistry of Minerals》2010,37(5):265-282
We have carried out ab initio calculations using density functional theory to determine the bulk elastic properties of mirabilite, Na2SO4·10H2O, and to obtain information on structural trends caused by the application of high pressure up to ~60 GPa. We have found that there are substantial isosymmetric discontinuous structural re-organisations at ~7.7 and ~20 GPa caused by changes in the manner in which the sodium cations are coordinated by water molecules. The low-pressure and intermediate-pressure phases both have sodium in sixfold coordination but in the high-pressure phase the coordination changes from sixfold to sevenfold. These coordination changes force a re-arrangement of the hydrogen-bond network in the crystal. The trend is towards a reduction in the number of hydrogen bonds donated to the sulphate group (from twelve down to six over the range 0–60 GPa) and an increase in hydrogen bonding amongst the Na-coordinated water molecules and the two interstitial water molecules. Ultimately, we observe proton transfers from the interstitial waters (forming OH? ions) to two of the Na-coordinated waters (forming a pair of H3O+ ions). The equation of state in the athermal limit of the low-pressure phase of mirabilite, parameterised by fitting an integrated form of the third-order Birch-Murnaghan expression to the calculated energy as a function of unit-cell volume, yields the zero-pressure unit-cell volume, V 0 = 1468.6(9) Å3, the incompressibility, K 0 = 22.21(9) GPa, and the first pressure derivative K 0′ = (?K/?P)0 = 5.6(1). 相似文献
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An equation of state (EOS) explicit in Helmholtz free energy has been improved to calculate the PVTx and vapor–liquid phase equilibrium properties of CH4–CO2 fluid mixture. This EOS, where four mixing parameters are used, is based on highly accurate EOSs recommended by NIST for pure components (CH4 and CO2) and contains a simple generalized departure function presented by Lemmon and Jacobsen (1999). Comparison with experimental data available indicates that the EOS can calculate both vapor–liquid phase equilibrium and volumetric properties of this binary fluid system with accuracy close to that of experimental data up to high temperature and pressure within full range of composition. The EOS of CH4–CO2 fluid, together with the updated Gibbs free energy model of solid CO2 (dry ice), is applied to calculate the CH4 content (xCH4) and molar volume (Vm) of the CH4–CO2 fluid inclusion based on the assumption that the volume of an inclusion keeps constant during heating and cooling. diagrams are presented, which describe phase transitions involving vapor, liquid and CO2 solid phases of CH4–CO2 fluid inclusions. Isochores of CH4–CO2 inclusions at given and Vm can be easily calculated from the improved EOS. 相似文献
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Tonči Balić-Žunić 《Mineralogy and Petrology》2014,108(4):479-486
The crystal structure of bøgvadite, Na2SrBa2Al4F20, has been solved and refined to a R1 factor of 4.4 % from single-crystal data (MoKα X-ray diffraction, CCD area detector) on a sample from the cryolite deposit at Ivittuut, SW Greenland. Bøgvadite is monoclinic, P21/n space group, with unit cell parameters a?=?7.134(1), b?=?19.996(3) and c?=?5.3440(8) Å, β?=?90.02(1)o. A close proximity of the crystal structure to an orthorhombic symmetry and the presence of the two twin components in a nearly 1:1 ratio suggest that the investigated bøgvadite crystal has originally formed as a high-temperature orthorhombic polymorph which on cooling transformed to the stable low temperature monoclinic structure. The bøgvadite crystal structure has groupings of cation-fluoride coordination polyhedra similar to those found in the crystal structures of the genetically closely associated minerals jarlite and jørgensenite. However, its structure type is different from the latter two. The fluoridoaluminate framework of bøgvadite consists of infinite zig-zag chains of cis-connected AlF6 coordination octahedra. The 1 ∞[AlF5] chains are interconnected by infinite chains of Na-F coordination polyhedra which extend in the same direction. Na is coordinated by nine F atoms if its full surrounding is taken in consideration, but makes significant chemical bonds only to closest five. The chains of AlF6 and NaF9 coordination polyhedra form double layers. In the centre of layers, relatively large voids in the form of pentagonal antiprisms are occupied by Sr atoms which make chemical bonds with the closest six F atoms. Between the SrF10 coordinations in the centre of layers run empty channels. The double layers are interconnected by Ba atoms which are coordinated by eight F atoms and fill the spaces between the layers. Bøgvadite belongs to the group of fluoridoaluminates with infinite chains of cis-connected AlF6 coordination octahedra, alike those found in the crystal structures of Ba-fluoridoaluminates. 相似文献
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Thomas Pichler 《Environmental Geology》2005,47(2):215-224
The application of sulfur isotope (34S) values of sulfate in groundwater provided the information necessary to evaluate the source, transport and fate of battery acid and associated contaminants at the Gulf Coast Recycling (GCR) facility. The chemical and isotopic composition of groundwater beneath the (GCR) property, a battery recycling facility in east Tampa, Florida, varies more than expected for an area of comparable size. Sulfate (SO42–) values, for example, range from 1.2 to 11,500 mg/L and oxygen and hydrogen isotopes do not attenuate towards the weighted annual mean. Those samples that are high in sulfate generally have a low pH, which immediately indicates battery acid (H2SO4) contamination as a potential source for the sulfate. The low pH and high reactivity of the sulfuric acid groundwater cause the formation of hydrogeological microenvironments due to preferential dissolution of carbonate minerals, which in turn causes enhanced recharge and groundwater flow in certain areas; thus, the extreme scatter in the data set. Because of the difficult hydrogeology it is not straightforward to delineate the point-sources of contamination and up to five potential scenarios have to be evaluated: (1) seawater intrusion, (2) upwelling of high-sulfate groundwater, (3) local dissolution of gypsum, (4) an up-gradient contaminant source to the northeast of the GCR property and (5) battery acid contamination. 相似文献
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Two synthetic series of spinels, MgCr2O4–Fe2+Cr2O4 and MgCr2O4–MgFe2 3+O4 have been studied by Raman spectroscopy to investigate the effects of Fe2+ and Fe3+ on their structure. In the first case, where Fe2+ substitutes Mg within the tetrahedral site, there is a continuous and monotonic shift of the Raman modes A1g and Eg toward lower wavenumbers with the increase of the chromite component into the spinel, while the F2g modes remain nearly in the same position. In the second series, for low Mg-ferrite content, Fe3+ substitutes for Cr in the octahedral site; when the Mg-ferrite content nears 40 %, a drastic change in the Raman spectra occurs as Fe3+ starts entering the tetrahedral site as well, consequently pushing Mg to occupy the octahedral one. The Raman spectral region between 620 and 700 cm?1 is associated to the octahedral site, where three peaks are present and it is possible to observe the Cr–Fe3+ substitution and the effects of order–disorder in the tetrahedral site. The spectral range at 500–620 cm?1 region shows that there is a shift of modes toward lower values with the increase of the Mg-ferrite content. The peaks in the region at 200–500 cm?1, when observed, show little or negligible Raman shift. 相似文献