共查询到20条相似文献，搜索用时 31 毫秒
1.
《Geochimica et cosmochimica acta》1993,57(16):3847-3853
Ab initio, molecular orbital calculations at the 6-31G1 level including second-order Møller-Plesset electron correlation predict that the species [Si(OH)5]1− is dynamically stable in a distorted trigonal bipyramid configuration. Reaction pathways for Si(OH)4 + (OH)− → [Si(OH)5]1− → [(OH)3SiO]1−—H2O are also calculated. The first reaction represents the formation of pentacoordinate Si from orthosilicic acid and hydroxide. The activation energy for adding a fifth Si-(OH)− bond to the Si(OH)4 molecule is ≈0.1 eV /molec (≈10kJ/mol). The second reaction is the deprotonation of the Si(OH)4 which forms as a hydroxyl group leaves the [Si(OH)5]1− molecule. Removal of a bond from this complex requires 0.9 eV/molecule (≈85 kJ/mol). Lengthening the Si—OH2 distance results in the isolated molecules [(OH)3SiO]1− + H2O. This represents dehydration of the deprotonated orthosilicic acid.[Si(OH)5]1− and [(OH)3SiO]1−- H2O have the same energetic stability within the accuracy of these calculations. The potential energies of the isolated molecular systems [(OH)3SiO]1−+ H2O and Si(OH)4 + (OH)− are considerably higher. These results suggest that [Si(OH)5]1− may be a stable species or reaction intermediate in dissolution of silicate minerals in basic aqueous solutions. 相似文献
2.
We discuss the experimental results of silicon and oxygen self-diffusion coefficients in forsterite and iron-bearing olivine from the perspective of defect chemistry. Silicon diffusion is dominated by VO ··-associated VSi″″, whereas oxygen diffusion is dominated by hopping of VO ·· under anhydrous conditions, and by (OH)O · under hydrous conditions. By considering the charge neutrality condition of [(OH)O ·] = 2[VMe″] in hydrous forsterite and iron-bearing olivine, we get D Si ∝ (\(C_{{{\text{H}}_{2} {\text{O}}}}\))1/3 and D O ∝ (\(C_{{{\text{H}}_{2} {\text{O}}}}\))0, which explains the experimental results of water effects on oxygen and silicon self-diffusion rates (Fei et al. in Nature 498:213–215, 2013; J Geophys Res 119:7598–7606, 2014). The \(C_{{{\text{H}}_{2} {\text{O}}}}\) dependence of creep rate in the Earth’s mantle should be close to that given by Si and O self-diffusion coefficients obtained under water unsaturated conditions. 相似文献
3.
Sulfur-35 was used to monitor the non-steady-state tracer diffusion of the free sulfate ion and sulfate ion-pairs in aqueous solutions of MgSO4 and Na2SO4. Diffusion coefficients were derived from radiotracer flux measurements taken over ionic strengths ranging from 0.001 to 0.7. The experimental tracer diffusion coefficient is a function of the diffusion coefficients of the free sulfate ion and the sulfate ion-pairs as well as the ion pair equilibrium constant. The free sulfate ion tracer diffusion coefficient was determined independently from both the MgSO4 and Na2SO4, experiments and found to be 1.11 and 1.08 (in units of 10-5cm2sec-1, ± 10%, respectively. These values closely agree with that calculated from the Nernst expression, 1.07 sx 10-5cm2sec-1. The tracer diffusion coefficients of MgSO40 and NaSO4- were determined to be 0.85 and 1.23 sx 10-5cm2sec-1, respectively. These numbers are in reasonable agreement with the earlier work on mutual diffusion coefficients by Rard and Miller (1979b) (DMgSO4o = 0.65, Dnaso4- = 1.19) and Harned and Hudson (1951)DMgSO40 = (0.70). A modified version of the theoretical equation developed by Pikal (1971) is proposed for predicting the tracer diffusion coefficients of many ion-pairs relevant to seawater. Many of these predicted values are found to be within 10–20% of the empirical values extracted from mutual diffusion data. The experimental and theoretical diffusion coefficient data are used to calculate revised coupled diffusion coefficients, Dg, according to the model of Lasaga (1979). 相似文献
4.
《Chemical Geology》2004,203(1-2):139-151
Aragonite is precipitated by a new CO2-diffusion technique from a Ca2+–Mg2+–Cl− solution between 10 and 50 °C. Crystallisation of aragonite instead of calcite occurs by maintaining a [Mg2+]/[Ca2+] ratio of 2 in the fluid. The dissolved inorganic carbon (DIC) is received by diffusion of CO2 through a polyethylene membrane (diffusion coefficient: DCO2=10−6.4 cm2 s−1 at 19 °C). It is suggested that significant amounts of DIC may be transferred by diffusion of CO2 in natural systems if the CO2 gradient is high. The CO2-diffusion technique is used as a kind of simple mixed flow reactor for the co-precipitation of barium and strontium with aragonite. The distribution coefficients of Ba2+ and Sr2+ decrease from 10 to 50 °C according to DBa,a*=2.42−0.03595T (°C) and DSr,a*=1.32−0.005091T (°C). At 25 °C, the distribution coefficients are DBa,a*=1.5±0.1 and DSr,a*=1.19±0.03. The effect of temperature on DBa,a* is about one order of magnitude higher versus that on DSr,a*. Thus, Ba2+ may be a potential paleotemperature indicator if the composition of the solution is known. 相似文献
5.
《Applied Geochemistry》2001,16(5):559-570
Fe(II)–Fe(III) layered double hydroxysalt green rusts, GRs, are very reactive compounds with the general formula, [FeII(1−x) FeIIIx (OH)2]x+·[(x/n) An−·(m/n) H2O]x−, where x is the ratio FeIII/Fetot, and reflects the structure in which brucite-like layers alternate with interlayers of anions An− and water molecules. Two types of crystal structure for GRs, GR1 and GR2, represented by the hydroxychloride GR1(Cl−) and the hydroxysulphate GR2(SO42−) are distinguished by X-ray diffraction due to different stacking. By analogy with GR1(Cl−) the structure of the fougerite GR mineral, [FeII(1−x) FeIIIx (OH)2]x+·[x OH−·(1−x) H2O]x- Fe(OH)(2+x)·(1−x) H2O, is proposed displaying interlayers made of OH− ions and water molecules (in situ deprotonation of water molecules is necessary for explaining the flexibility of its composition). The space group of mineral GR1(OH−) would be R3̄m, with lattice parameters a≅0.32 and c≅2.25 nm. Stability conditions and the Eh-pH diagram of Fe(OH)(2+x) (the water molecules are omitted) are determined from hydromorphic soil solution equilibria with GR mineral in Brittany (France). Computed Gibbs free energies of formation from soil solution/mineral equilibrium fit well with a regular solid solution model: μ°[Fe(OH)(2+x)]=(1−x) μ°[Fe(OH)2]+x μ°[Fe(OH)3]+RT [(1−x) ln (1−x)+x ln x]+A0 x (1−x), where μ°[Fe(OH)2]=−492.5 kJ mol−1, μ°[Fe(OH)3]=−641 kJ mol−1 and A0=−243.9 kJ mol−1 at the average temperature of 9±1°C. The upper limit of occurrence of GR mineral at x=2/3, i.e. Fe3(OH)8, is explained by its unstability vs. α-FeOOH and/or magnetite; Fe(OH)3 is thus a hypothetical compound with a GR structure which cannot be observed. These thermodynamic data and Eh-pH diagrams of Fe(OH)(2+x) can be used most importantly to predict the possibility that GR minerals reduce some anions in contaminated soils. The cases of NO3−, Se(VI) or Cr(VI) are fully illustrated. 相似文献
6.
《Applied Geochemistry》2000,15(8):1203-1218
Ca6[Al(OH)6]2(CrO4)3·26H2O, the chromate analog of the sulfate mineral ettringite, was synthesized and characterized by X-ray diffraction, Fourier transform infra-red spectroscopy, thermogravimetric analyses, energy dispersive X-ray spectrometry, and bulk chemical analyses. The solubility of the synthesized solid was measured in a series of dissolution and precipitation experiments conducted at 5–75°C and at initial pH values between 10.5 and 12.5. The ion activity product (IAP) for the reaction Ca6[Al(OH)6]2(CrO4)3·26H2O⇌6Ca2++2Al(OH)−4+3CrO2−4+4OH−+26H2O varies with pH unless a CaCrO4(aq) complex is included in the speciation model. The log K for the formation of this complex by the reaction Ca2++CrO2−4=CaCrO4(aq) was obtained by minimizing the variance in the IAP for Ca6[Al(OH)6]2(CrO4)3·26H2O. There is no significant trend in the formation constant with temperature and the average log K is 2.77±0.16 over the temperature range 5–75°C. The log solubility product (log KSP) of Ca6[Al(OH)6]2(CrO4)3·26H2O at 25°C is −41.46±0.30. The temperature dependence of the log KSP is log KSP=A−B/T+D log(T) where A=498.94±48.99, B=27,499±2257, and D=−181.11±16.74. The values of ΔG0r,298 and ΔH0r,298 for the dissolution reaction are 236.6±3.9 and 77.5±2.4 kJ mol−1. the values of ΔC0P,r,298 and ΔS0r,298 are −1506±140 and −534±83 J mol−1 K−1. Using these values and published standard state partial molal quantities for constituent ions, ΔG0f,298=−15,131±19 kJ mol−1, ΔH0f,298=−17,330±8.6 kJ mol−1, ΔS0298=2.19±0.10 kJ mol−1 K−1, and ΔC0Pf,298=2.12±0.53 kJ mol−1 K−1, were calculated. 相似文献
7.
《Applied Geochemistry》2000,15(4):425-438
The dissolution of silica and diffusion of reactive dissolved Si in the porewaters of river sediments are investigated using sediments of different physical and chemical properties. Three sediments are considered: (a) from sectioned cores taken from a river-bed, (b) fine organic-rich surface sediment (<5 cm depth) installed in a fluvarium channel and, (c) coarse river sediment of low organic matter content also installed in a fluvarium channel. Dissolution rates of silica are measured at 10°C using batches of suspended material. The derived dissolution rate constants show large differences between the sediments. The river bed-sediment cores had vertical concentration profiles of dissolved Si that are consistent with the diffusion and dissolution of biogenic silica. Experiments in a fluvarium channel enabled Si fluxes to be calculated from a mass-balance of the overlying solution. The results are consistent with the attainment of a steady-state concentration profile of dissolved Si in the sediment. There are no discernible effects of water velocity over the sediment between 5 and 11 cm s−1. However, at 20 cm s−1, the flux increases as a result of either entrainment of fine particles at the surface or advective effects in the surface sediment. A fluvarium experiment with the fine sediment (<125 μm) over 61 days, produced a concentration profile with the highest concentration of 1025 μmol dm−3 at a depth of 4–5 cm in the sediment. A FORTRAN program is used to model the results of the increase in dissolved Si in the overlying water and development of a concentration profile in the porewater. This leads to a sediment diffusion coefficient of 1.21×10−9 m2 s−1 at 8.8°C at the beginning of the experiment and rate constant k=13.1×10−7 s−1 at pH=7.82 and average temperature of 7.6°C for the entire experiment. Fluxes measured at the sediment–surface interface and calculated assuming steady-state profiles had developed are typically 0.01–0.04 μmol m−2 (of river bed) s−1. The approach enables the efflux of dissolved Si from bottom-sediments to be estimated from dissolution rates measured using suspensions of bed-sediment. 相似文献
8.
Boom Clay is studied as a potential host formation for the disposal of high-and intermediate level long-lived radioactive waste in Belgium. In such a geological repository, generation of gases (mainly H2 from anaerobic corrosion) will be unavoidable. In order to make a good evaluation of the balance between gas generation vs. gas dissipation for a particular waste form and/or disposal concept, good estimates for gas diffusion coefficients of dissolved gases are essential. In order to obtain an accurate diffusion coefficient for dissolved hydrogen in saturated Boom Clay, diffusion experiments were performed with a recently developed through-diffusion set-up for dissolved gases. Due to microbial activity in the test set-up, conversion of hydrogen into methane was observed within several experiments. A complex sterilisation procedure was therefore developed in order to eliminate microbiological disturbances. Only by a combination of heat sterilisation, gamma irradiation and the use of a microbial inhibitor, reliable, reproducible and accurate H2(g) diffusion coefficients (measured at 21 °C) for samples oriented parallel (Deff = 7.25 × 10−10 m2/s and Deff = 5.51 × 10−10 m2/s) and perpendicular (Deff = 2.64 × 10−10 m2/s) to the bedding plane were obtained. 相似文献
9.
Crystals of sodium trisilicate (Na2Si3O7) have been grown in the presence of melt at 9 GPa, 1200 °C using the MA6/8 superpress at Edmonton, and the X-ray structure determined at room pressure (R=2.0%). Na2Si3O7 is monoclinic with a=8.922(2) Å, b= 4.8490(5) Å, c=11.567(1) Å, β=102.64(1)° (C2/c), D x = 3.295 g·cm-3. Silicon occurs in both tetrahedral and octahedral coordination ([6]Si∶[4]Si = l∶2). The SiO4 tetrahedra form a diorthosilicate [Si2O7] group and are linked by the isolated SiO6 octahedra via shared corners into a framework of 6-membered ([4]Si-[4]Si-[6]Si[4]Si-[4] Si-[6]Si) and 4-membered ([4]Si-[6]Si-[4]Sr-[6]Si) rings: 〈[6]Si-O〉=1.789 Å, 〈[4]Si-O〉= 1.625 Å, [4]Si-O-[4]Si=132.9° and the bridging oxygen is overbonded (s = 2.22). Channels parallel to b-axis and [110] accommodate Na in irregular 6-fold coordination: 〈Na-O〉 = 2.511 Å. 相似文献
10.
Experimentally reversed quartz solubilities at 250°C and at 250, 500 and 1000 bars yield values of the logarithm of the molality of aqueous silica of ?2.126, ?2.087 and ?2.038, respectively. Extrapolation of quartz solubility to the saturation pressure of water at 250°C results in a log molality of aqueous silica of-2.168. These solubility determinations and analyses of fluid pressures in geothermal systems indicate that pressure is significant when calculating quartz equilibrium temperatures from silica concentrations in waters of deep thermal reservoirs.The results of this investigation, combined with other reported quartz solubility measurements, yielded a pressure-sensitive “silica geothermometer” for fluids that have undergone adiabatic steam loss of where P is the fluid pressure in bars and mSi(OH)4 · 2H2O represents the molality of aqueous silica measured in surface samples. The geothermometer is applicable to solutions in equilibrium with quartz from 180°C to 340°C and fluid pressures from H2O saturation to 500 bars. 相似文献
11.
The silicon isotopic composition of dissolved silicon and suspended particulate matter (SPM) were systematically investigated in water samples from the mainstem of the Yellow River and 4 major tributaries. The SPM content of the Yellow River varied from 1.4 to 38,560 mg/L, averaging 3568 mg/L, and the δ30Si of suspended particulate matter (δ30SiSPM) varied from 0.3‰ to −0.4‰, averaging −0.02‰. The major factors affecting the SPM content and the δ30SiSPM values in the Yellow River were inferred to be the mineralogical, chemical and isotopic characteristics of the sediments from the Loess Plateau and a combination of the climate and the flow discharge of the river.The major ions in the Yellow River water were Na+, Ca2+, Mg2+, HCO3−, SO42− and Cl−. High salt concentration was observed in samples from the middle and lower reaches, likely reflecting the effects of evaporation and irrigation because the Na+, Mg2+, SO42− and K+ concentrations were correlated with the Cl− concentration. The dissolved Si concentration (DSi) increased downstream, varying from 0.016 to 0.323 mM. The δ30Si of dissolved Si (δ30SiDiss) varied from 0.4‰ to 2.5‰, averaging 1.28‰. The major processes controlling the DSi and δ30SiDiss of the Yellow River are (a) the weathering of silicate rocks, (b) the formation of phytoliths in plants, (c) the evaporation of water from and the addition of meteoric water to the river system, which only affects concentrations, (d) the adsorption and desorption of aqueous monosilicic acid on iron oxide, and (e) the dissolution of phytoliths in soils.The DSi and δ30SiDiss values of global rivers vary spatially and temporally in response to changes in climate, chemical weathering intensity and biological activity. The moderately positive δ30SiDiss values observed in the Yellow River may be attributed to the higher rates of chemical weathering and biological activities that have been observed in this catchment in comparison with those of other previously studied catchments, excluding the Yangtze River. Human activities may also potentially influence chemical weathering and biological activities and affect the DSi and δ30SiDiss values of the major rivers of the world. Further river studies should be performed to gain a better understanding of the global Si isotope budget. 相似文献
12.
Si+4 Content of natural phengites 总被引：2，自引：0，他引：2
B. Velde 《Contributions to Mineralogy and Petrology》1967,14(3):250-258
The chemical compositions of white micas separated from adjacent rocks of glaucophane and greenschist facies are compared with respect to their Si+4 content. The micas are predominantly phengitic, i.e. between muscovite, K[Al2Si3AlO10(OH)2] and celadonite, K[(R+2R+3)Si4O10(OH)2] in composition. Constancy of Si content in micas coming from rocks of different bulk chemical composition but closely similar physical conditions indicates that the silica content of a potassic dioctahedral mica can be used to indicate the pressure and temperature conditions of its formation. This conclusion is in part based upon previous experimental data obtained for synthetic phengites. 相似文献
13.
By using a specially designed and constructed isopiestic apparatus, we measured the osmotic coefficients at 313.2 K for the NaOH-NaAl(OH)4-H2O system with the total alkali molality, mNaOHT (mNaOH + mNaAl[OH]4), from 0.05 mol/kg H2O to 12 mol/kg H2O and αK (mNaOHT/mNaAl(OH)4) from 1.64 to 5.53. The mean standard deviation of the measurements is 0.0038. Several sets of the Pitzer model parameters for NaOH-NaAl(OH)4-H2O system were then obtained by regressing the measured osmotic coefficients with the Pitzer model and the Pitzer model parameters for NaOH(aq). One set of the results is as follows: β(0)NaOH: 0.08669, β(1)NaOH: 0.31446, β(2)NaOH: −0.00007367, CΦNaOH: 0.003180, β(0)NaAl(OH)4: 0.03507, β(1)NaAl(OH)4: 0.02401, CΦNaAl(OH)4: −0.001066, θOH−Al(OH)4−: 0.08177, ΨNa+OH−Al(OH)4−: −0.01162. The mean standard difference between the calculated and the measured osmotic coefficients is 0.0088. With the obtained Pitzer model parameters, we calculated the values of K = (γNaAl(OH)4,cal2 · mAl(OH)4−,exp)/(γNaOH,cal2 · mOH−,exp) for the gibbsite solubility. The results show that the obtained Pitzer model parameters are reliable, and the relative error of the calculated activity coefficients should be < 2.1%. We also compared the calculated gibbsite solubility data among several activity coefficients models over a range of mNaOHT at various temperatures. The comparison indicates that our activity coefficients model may be approximately applied in the ranges of temperature from 298.2 to 323.2 K and mNaOHT from 0 to 8 mol/kg H2O. We also calculated the stoichiometric activity coefficients of NaOH and NaAl(OH)4 and the activity of H2O for the NaOH-NaAl(OH)4-H2O system, and these calculations establish their variations with mNaOHT and αK. These variations imply that the strengths of the repulsive interactions among various anions are in the following sequence: Al(OH)4−-Al(OH)4− < Al(OH)4−-OH− < OH−-OH−, and the attractive interaction between Al(OH)4− and H2O is weaker than that between OH− and H2O. 相似文献
14.
Philip N Froelich Gordon A Hambrick Lisa W Kaul James T Byrd Odile Lecointe 《Geochimica et cosmochimica acta》1985,49(2):519-524
Eleven monthly estuarine profiles of dissolved inorganic germanium (Gei) and silica (Si) in a natural, pristine river/bay system demonstrate that Ge-removal and -input parallel the seasonal silica cycle, reflecting Ge-uptake by and -dissolution from diatoms. The Ge/Si atom ratio of the river is 0.6 ± 0.15 × 10?6, which is near the average value for continental granites and for uncontaminated, remote, natural rivers (0.7 ± 0.3 × 10?6). The ratio escaping this estuary to the ocean is 0.8 × 10?6, reflecting some estuarine enhancement of the fluvial Ge-flux, probably due to release of Gei from fluvial particulates. Nevertheless, the post-estuarine ratio is not significantly different from the continental crustal ratio but is very different from the ratio in sea-floor hot springs and mid-ocean ridge hydrothermal plumes (4 ± 2 × 10?6) and in oceanic basalts (2.6 × 10?6). Thus natural estuarine processes do not obscure the contrasting signatures entering the ocean from dissolution of continental and sea-floor silicates. 相似文献
15.
In order to gain insight into the correlations between 29Si, 17O and 1H NMR properties (chemical shift and quadrupolar coupling parameters) and local structures in silicates, ab initio self-consistent
field Hartree-Fock molecular orbital calculations have been carried out on silicate clusters of various polymerizations and
intertetrahedral (Si-O-Si) angles. These include Si(OH)4 monomers (isolated as well as interacting), Si2O(OH)6 dimers (C2 symmetry) with the Si-O-Si angle fixed at 5° intervals from 120° to 180°, Si3O2(OH)8 linear trimers (C2 symmetry) with varying Si-O-Si angles, Si3O3(OH)6 three-membered rings (D3 and C1 symmetries), Si4O4(OH)8 four-membered ring (C4 symmetry) and Si8O12(OH)8 octamer (D4 symmetry). The calculated 29Si, 17O and 1H isotropic chemical shifts (δi
Si, δi
O and δi
H) for these clusters are all close to experimental NMR data for similar local structures in crystalline silicates. The calculated
17O quadrupolar coupling constants (QCC) of the bridging oxygens (Si-O-Si) are also in good agreement with experimental data. The calculated 17O QCC of silanols (Si-O-H) are much larger than those of the bridging oxygens, but unfortunately there are no experimental data
for similar groups in well-characterized crystalline phases for comparison. There is a good correlation between δi
Si and the mean Si-O-Si angle for both Q
1 and Q
2, where Q
n
denotes Si with n other tetrahedral Si next-nearest neighbors. Both the δ
i
O and the 17O electric field gradient asymmetry parameter, η of the bridging oxygens have been found to depend strongly on the O site
symmetry, in addition to the Si-O-Si angle. On the other hand, the 17O QCC seems to be influenced little by structural parameters other than the Si-O-Si angle, and is thus expected to be the most
reliable 17O NMR parameter that can be used to decipher Si-O-Si angle distribution information. Both the 17O QCC and the 2H QCC of silanols decrease with decreasing length of hydrogen bond to a second O atom (Si-O-H···O), and the δ
i
H increase with the same parameter.
Received: 18 July 1997 / Revised, accepted: 23 February 1998 相似文献
16.
《Applied Geochemistry》1998,13(4):509-520
A gravity-fed, battery-powered, portable continuously-stirred tank reactor has been developed to directly measure aqueous reaction rates in the field. Dye and tracer experiments indicate the reactor is well-mixed. Rates of Fe2+ oxidation at untreated and passively treated coal mine drainage sites in Pennsylvania were measured under ambient conditions and with the addition of either O2 gas or NaOH solutions. Rates at 5 sites ranged from below the detection limit for this technique (approximately 10−9 mol L−1 s−1) to 3.27±0.01×10−6 mol L−1 s−1. Uncertainties in rates ranged from 70% near the lower limit of measurement to as little as 1% at higher rates of reaction. Multiple linear regressions showed no universal correlations of rates to Fe2+, dissolved O2, and pH (Thiobacillus populations were not measured), although data for two more acidic sites were found to fit well for the model log rate=log K+a log [Fe2+]+b log [OH−]+c log [O2]. Field rates of Fe oxidation from this and other studies vary by 4 orders of magnitude. A model using the ambient field rate of Fe oxidation from this study successfully reproduced independently-measured Fe2+ concentrations observed in a passive wetland treatment facility. 相似文献
17.
D. J. Cherniak 《Physics and Chemistry of Minerals》2008,35(4):179-187
Self-diffusion of Si under anhydrous conditions at 1 atm has been measured in natural zircon. The source of diffusant for
experiments was a mixture of ZrO2 and 30Si-enriched SiO2 in 1:1 molar proportions; experiments were run in crimped Pt capsules in 1-atm furnaces. 30Si profiles were measured with both Rutherford backscattering spectrometry (RBS) and nuclear reaction analysis with the resonant
nuclear reaction 30Si(p,γ)31P. For Si diffusion normal to c over the temperature range 1,350–1,550°C, we obtain an Arrhenius relation D = 5.8 exp(−702 ± 54 kJ mol−1/RT) m2 s−1 for the NRA measurements, which agrees within uncertainty with an Arrhenius relation determined from the RBS measurements
[62 exp(−738 ± 61 kJ mol−1/RT) m2 s−1]. Diffusion of Si parallel to c appears slightly faster, but agrees within experimental uncertainty at most temperatures
with diffusivities for Si normal to c. Diffusion of Si in zircon is similar to that of Ti, but about an order of magnitude faster than diffusion of Hf and two
orders of magnitude faster than diffusion of U and Th. Si diffusion is, however, many orders of magnitude slower than oxygen
diffusion under both dry and hydrothermal conditions, with the difference increasing with decreasing temperature because of
the larger activation energy for Si diffusion. If we consider Hf as a proxy for Zr, given its similar charge and size, we
can rank the diffusivities of the major constituents in zircon as follows: D
Zr < D
Si << D
O, dry < D
O, ‘wet’. 相似文献
18.
《Geochimica et cosmochimica acta》2001,65(16):2691-2708
The concentration and transport of metals in hydrothermal solutions depend on how metals ions combine with ligands to form complexes, and experimental methods are necessary to identify the important complexes. UV-Vis-NIR spectrophotometry was used to study the formation of Cu(II)-chloride complexes in LiCl brines up to very high chlorinities (18 m LiCl), at temperatures between 25°C and 90°C. The number of Cu(II)-chloride complexes necessary to account for the variation in spectra with varying chloride molality at each temperature was estimated using principal component analysis. The molar absorptivity coefficients and concentrations of each complex were then determined using a “model-free” analysis, which does not require any assumption about the chemistry of the system, other than the number of absorbing species present. Subsequently, the results from the “model-free” analysis were integrated with independent experimental evidence to develop a thermodynamic speciation model, where the logarithms of the equilibrium constants for Cu(II)-chloride formation reactions were fitted to the data using a non-linear least-squares approach. Maps of the residual function were used to estimate uncertainties in the fitted equilibrium constants.The results of this study are similar to published properties of distorted octahedral [CuCl(OH2)5]+ and [CuCl2(OH2)4]0 at all temperatures, but diverge for [CuCl3(OH2)3]− and distorted tetrahedral [CuCl4]2−. Moreover, the data suggest the presence of [CuCl5]3−, probably with D3h point group, at very high salt concentration. This study demonstrates that it is possible to determine apparent thermodynamic equilibrium constants for the formation of complexes of trace amount of metals in highly concentrated brines, such as those associated with many ore deposits. The results are dependent on the choice of activity coefficients for charged and neutral aqueous complexes, but this influence is relatively small compared with the experimental uncertainty. This study shows that Cu2+ chloro-complexes, predominantly [CuCl2(OH2)4]0 and [CuCl4]2−, will play a dominant role in nature where free oxygen is available (near-surface), and where chloride activities are very high (evaporitic basins; hypersaline soils). 相似文献
19.
《Geochimica et cosmochimica acta》1999,63(13-14):1969-1980
The solubility of ettringite (Ca6[Al(OH)6]2(SO4)3 · 26H2O) was measured in a series of dissolution and precipitation experiments at 5–75°C and at pH between 10.5 and 13.0 using synthesized material. Equilibrium was established within 4 to 6 days, with samples collected between 10 and 36 days. The log KSP for the reaction Ca6[Al(OH)6]2(SO4)3 · 26H2O ⇌ 6Ca2+ + 2Al(OH)4− + 3SO42− + 4OH− + 26H2O at 25°C calculated for dissolution experiments (−45.0 ± 0.2) is not significantly different from the log KSP calculated for precipitation experiments (−44.8 ± 0.4) at the 95% confidence level. There is no apparent trend in log KSP with pH and the mean log KSP,298 is −44.9 ± 0.3. The solubility product decreased linearly with the inverse of temperature indicating a constant enthalpy of reaction from 5 to 75°C. The enthalpy and entropy of reaction ΔH°r and ΔS°r, were determined from the linear regression to be 204.6 ± 0.6 kJ mol−1 and 170 ± 38 J mol−1 K−1. Using our values for log KSP, ΔH°r, and ΔS°r and published partial molal quantities for the constituent ions, we calculated the free energy of formation ΔG°f,298, the enthalpy of formation ΔH°f,298, and the entropy of formation ΔS°f,298 to be −15211 ± 20, −17550 ± 16 kJ mol−1, and 1867 ± 59 J mol−1 K−1. Assuming ΔCP,r is zero, the heat capacity of ettringite is 590 ± 140 J mol−1 K−1. 相似文献
20.
《Geochimica et cosmochimica acta》1999,63(19-20):3407-3416
The apparent solubilities of schwertmannite and ferrihydrite were estimated from the H+, OH−, Fe3+, and SO42− activities of the natural stream waters in Korea and mine drainage in Ohio, USA. Both chemical composition of the stream waters and the mineralogy of the precipitates were determined for samples from two streams polluted by coal mine drainage. This study combines these new results with previous data from Ohio, USA to redetermine solubilities. The activities of the dissolved species necessary for the solubility determinations were calculated from the chemical compositions of the waters with the WATEQ4F computer code.Laboratory analyses of precipitates indicated that the main minerals present in Imgok and Osheep creek were schwertmannite and ferrihydrite, respectively. The schwertmannite from Imgok creek had a variable chemical formula of Fe8O8(OH)8−2x(SO4)x· nH2O, where 1.74 ≤ x ≤ 1.86 and 8.17 ≤ n ≤ 8.62. The chemical formula of ferrihydrite was Fe2O3· 1.6H2O. With known mineralogy of the precipitates from each stream, the activities of H+, OH−, Fe3+, and SO42− in the waters were plotted on logarithmic activity-activity diagrams to determine apparent solubilities of schwertmannite and ferrihydrite. The best estimate for the logarithm of the solubility product of schwertmannite, logKs, was 10.5 ± 2.5 around 15°C. This value of logKs constrains the logarithm of the solubility product of ferrihydrite, logKf, to be 4.3 ± 0.5 to maintain the stability boundary with schwertmannite observed in natural waters. 相似文献