共查询到20条相似文献，搜索用时 31 毫秒
1.
Molecular simulation of the magnetite-water interface 总被引：1，自引：0，他引：1
This paper reports molecular dynamics simulations of the magnetite (001)-water interface, both in pure water and in the presence of a 2.3 molal solution of NaClO4. The simulations are carried out using a potential model designed to allow the protonation states of the surface functional groups to evolve dynamically through the molecular dynamics trajectory. The primary structural quantities investigated are the populations of the surface functional groups, the distribution of electrolyte in the solution, and the surface hydrogen bonding relationships. The surface protonation states are dominated by extensive hydrolysis of interfacial water molecules, giving rise to a dipolar surface dominated by FeOH2+-OH2-OH− arrangements. Triply coordinated, more deeply buried, surface sites are inert, probably due to the relative lack of solvent in their vicinity. The electrolyte distribution is oscillatory, arranging preferentially in layers defined by the solvating water molecules. The presence of electrolyte has a negligible effect on the protonation states of the surface functional groups. Steady-state behavior is obtained for the protonation states of the surface functional groups and hydrogen-bonding network. Although the overall structure of the electrolyte distribution is fairly well established, the electrolyte distribution has not fully equilibrated, as evidenced by the asymmetry in the distribution from the top to the bottom of the slab. 相似文献
2.
3.
The structure and dynamics of water on muscovite mica (0 0 1) surfaces have been investigated by molecular dynamics simulations. X-ray reflectivity profiles highly reflecting the interfacial structure are directly calculated and compared with those of experiments. The direct comparison has validated the usefulness of MD simulations to understand the real interfacial structure of the mica−water system. We observed five distinguished peaks in the density profile of oxygen present in water, and these peaks are attributable to the water molecules directly adsorbed on mica, hydrated to the K+ ions on the mica surface, and ordered due to hydrogen bonds between hydrated K+ ions. The hydrated K+ ions make an inner-sphere complex and have an explicit first hydration shell with a radius of 3.6 Å and a hydration number of 2.9. The change of the viscosity of water located above 1 nm apart from the mica surface was not observed. This feature is in good agreement with a recent experimental study in which the shear measurement was conducted using a surface forces apparatus. The increase of the viscosity by a factor of ca. 2-3 relative to that of the bulk water was observed at water located within 1 nm from the isolated mica surface. 相似文献
4.
Jianwei Wang Andrey G. Kalinichev R. James Kirkpatrick 《Geochimica et cosmochimica acta》2006,70(3):562-582
Molecular dynamics computer simulations of the molecular structure, diffusive dynamics and hydration energetics of water adsorbed on (0 0 1) surfaces of brucite Mg(OH)2, gibbsite Al(OH)3, hydrotalcite Mg2Al(OH)6Cl · 2H2O, muscovite KAl2(Si3Al)O10(OH)2, and talc Mg3Si4O10(OH)2 provide new insight into the relationships between the substrate structure and composition and the molecular-scale structure and properties of the interfacial water. For the three hydroxide phases studied here, the differences in the structural charge on the octahedral sheet, cation occupancies and distributions, and the orientations of OH groups all affect the surface water structure. The density profiles of water molecules perpendicular to the surface are very similar, due to the prevalent importance of H-bonding between the surface and the water and to their similar layered crystal structures. However, the predominant orientations of the surface water molecules and the detailed two-dimensional near-surface structure are quite different. The atomic density profiles and other structural characteristics of water at the two sheet silicate surfaces are very different, because the talc (0 0 1) surface is hydrophobic whereas the muscovite (0 0 1) surface is hydrophilic. At the hydrophilic and electrostatically neutral brucite and gibbsite (0 0 1) surfaces, both donating and accepting H-bonds from the H2O molecules are important for the development of a continuous hydrogen bonding network across the interfacial region. For the hydrophilic but charged hydrotalcite and muscovite (0 0 1) surfaces, only accepting or donating H-bonds from the water molecules contribute to the formation of the H-bonding network at the negatively and positively charged interfaces, respectively. For the hydrophobic talc (0 0 1) surface, H-bonds between water molecules and the surface sites are very weak, and the H-bonds among H2O molecules dominate the interfacial H-bonding network. For all the systems studied, the orientation of the interfacial water molecules in the first few layers is influenced by both the substrate surface charge and the ability by the surfaces to facilitate H-bond formation. The first layer of water molecules at all surfaces is well ordered in the xy plane (parallel to the surface) and the atomic density distributions reflect the substrate crystal structure. The enhanced ordering of water molecules at the interfaces indicates reduced orientational and translational entropy. In thin films, water molecules are more mobile parallel to the surface than perpendicular to it due to spatial constraints. At neutral, hydrophilic substrates, single-monolayer surface coverage stabilizes the adsorbed water molecules and results in a minimum of the surface hydration energy. In contrast, at the charged and hydrophilic muscovite surface, the hydration energy increases monotonically with increasing water coverage over the range of coverages studied. At the neutral and hydrophobic talc surface, the adsorption of H2O is unfavorable at all surface coverages, and the hydration energy decreases monotonically with increasing coverage. 相似文献
5.
Molecular dynamics (MD) computer simulations of liquid water held in one-dimensional nano-confinement by two parallel, electrostatically neutral but hydrophilic surfaces of brucite, Mg(OH)2, provide greatly increased, atomistically detailed understanding of surface-related effects on the spatial variation in the structural ordering, hydrogen bond (H-bond) organization, and local density of H2O molecules at this important model hydroxide surface. NVT-ensemble MD simulations (i.e., at constant number of atoms, volume and temperature) were performed for a series of model systems consisting of 3 to 30 Å-thick water layers (containing 35 to 360 H2O molecules) confined between two 19 Å-thick brucite substrate layers. The results show that the hydrophilic substrate significantly influences the near-surface water structure, with both H-bond donation to the surface oxygen atoms and H-bond acceptance from the surface hydrogen atoms in the first surface layer of H2O molecules playing key roles. Profiles of oxygen and hydrogen atomic density and H2O dipole orientation show significant deviation from the corresponding structural properties of bulk water to distances as large as 15 Å (∼5 molecular water layers) from the surface, with the local structural environment varying significantly with the distance from the surface. The water molecules in the first layer at about 2.45 Å from the surface have a two-dimensional hexagonal arrangement parallel to brucite layers, reflecting the brucite surface structure, have total nearest neighbor coordinations of 5 or 6, and are significantly limited in their position and orientation. The greatest degree of the tetrahedral (ice-like) ordering occurs at about 4 Å from the surface. The translational and orientational ordering of H2O molecules in layers further from the surface become progressively more similar to those of bulk liquid water. A quantitative statistical analysis of the MD-generated instantaneous molecular configurations in terms of local density, molecular orientation, nearest neighbor coordination, and the structural details of the H-bonding network shows that the local structure of interfacial water at the brucite surface results from a combination of “hard wall” (geometric and confinement) effects, highly directional H-bonding, and thermal motion. This structure does not resemble that of bulk water at ambient conditions or at elevated or reduced temperature, but shares some similarities with that of water under higher pressure. 相似文献
6.
Phase transformation and crystal growth in nanoparticles may happen via mechanisms distinct from those in bulk materials. We combine experimental studies of as-synthesized and hydrothermally coarsened
titania (TiO2) and zinc sulfide (ZnS) with thermodynamic analysis, kinetic modeling and molecular dynamics (MD) simulations. The samples
were characterized by transmission electron microscopy, X-ray diffraction, synchrotron X-ray absorption and scattering, and
UV-vis spectroscopy. At low temperatures, phase transformation in titania nanoparticles occurs predominantly via interface nucleation at particle–particle contacts. Coarsening and crystal growth of titania nanoparticles can be described
using the Smoluchowski equation. Oriented attachment-based crystal growth was common in both hydrothermal solutions and under
dry conditions. MD simulations predict large structural perturbations within very fine particles, and are consistent with
experimental results showing that ligand binding and change in aggregation state can cause phase transformation without particle
coarsening. Such phenomena affect surface reactivity, thus may have important roles in geochemical cycling. 相似文献
7.
Hydrated mineral surfaces play an important role in many processes in biological, geological, and industrial applications. An energy force field was developed for molecular mechanics and molecular dynamics simulations of hydrated carbonate minerals and was applied to investigate the behavior of water on the calcite surface. The force field is a significant development for large-scale molecular simulations of these systems, and provides good agreement with experimental and previous modeling results. Simulations indicate that water molecules are significantly ordered near the calcite surface. The predominant surface configuration (75-80%) results from coordination of a water molecule with a single calcium cation-carbonate anion pair, while the less common situation involves water coordination with two ion pairs. Surface restructuring and variation in coordination in the water layers results in distinct distances for water oxygens above the calcite surface—a two-component first monolayer (2.3 and 3.0 Å) and a secondary monolayer (5.0 Å). The different coordinations also alter lateral displacement, hydrogen bonding, and surface-normal orientation of the water molecules. The ordering of water molecules and the formation of a unique hydrogen bonding network at the calcite surface influence the physical properties of the interfacial water. Surface exchange of water molecules is observed by molecular dynamics simulation to occur at a rate of one exchange per 10 ps. Diffusion coefficients derived from mean square displacement analysis of atomic trajectories indicate a dependence of water transport based on the distance of the water molecules from the calcite surface. 相似文献
8.
The distribution and dynamics of water molecules and monovalent cations (Li+, Na+, K+, Cs+, and H3O+) on muscovite surfaces were investigated by molecular dynamics (MD) simulations. The direct comparison of calculated X-ray reflectivity profiles and electron density profiles with experiments revealed the precise structure at the aqueous monovalent electrolyte solutions/muscovite interface. To explain the experimentally observed electron density profiles for the CsCl solution-muscovite interface, the co-adsorption of Cs+ and Cl− ion pairs would be necessary. Two types of inner-sphere complexes and one type of outer-sphere complex were observed for hydrated Li+ ions near the muscovite surface. For Na+, K+, Cs+, and H3O+ ions, the inner-sphere complexes were stable on the muscovite surface. The density oscillation of water molecules was observed to approximately 1.5 nm from the muscovite surface. The number of peaks and the locations for the density of water oxygen atoms were almost similar among the water molecules coordinated to Li+, Na+, K+, and H3O+ ions adsorbed on the muscovite surfaces. The water molecules around Cs+ ions that were adsorbed to muscovite surfaces seemed to avoid coordinating with Cs+ ions on the surface, and the density of water oxygen near the muscovite surface decreased relative to that in a bulk state. There was no significant difference in self-diffusion, viscosity, retention time, and reorientation time of water molecules among different cations adsorbed to muscovite surfaces. These translational and rotational motions of water molecules located at less than 1 nm from the muscovite surfaces were slower than those in a bulk state. A significant difference was observed for the exchange times of water molecules around monovalent cations. The exchange time of water molecules was long around Li+ ions and decreased with an increase in the ionic radius. 相似文献
9.
Sebastien Kerisit Chongxuan Liu Eugene S. Ilton 《Geochimica et cosmochimica acta》2008,72(6):1481-1497
Molecular dynamics simulations of water in contact with the (0 0 1) and (0 1 0) surfaces of orthoclase (KAlSi3O8) were carried out to investigate the structure and dynamics of the feldspar-water interface, contrast the intrinsic structural properties of the two surfaces, and provide a basis for future work on the diffusion of ions and molecules in microscopic mineral fractures. Electron density profiles were computed from the molecular dynamics trajectories and compared with those derived experimentally from high-resolution X-ray reflectivity measurements by Fenter and co-workers [Fenter P., Cheng L., Park C., Zhang H. and Sturchio N. C. (2003a) Structure of the orthoclase (0 0 1)- and (0 1 0)-water interfaces by high-resolution X-ray reflectivity. Geochim. Cosmochim. Acta67, 4267-4275]. For each surface, three scenarios were considered whereby the interfacial species is potassium, water, or a hydronium ion. Excellent agreement was obtained for the (0 0 1) surface when potassium is the predominant interfacial species; however, some discrepancies in the position of the interfacial peaks were obtained for the (0 1 0) surface. The two surfaces showed similarities in the extent of water ordering at the interface, the activation energies for water and potassium desorption, and the adsorption localization of interfacial species. However, there are also important differences between the two surfaces in the coordination of a given adsorbed species, adsorption site densities, and the propensity for water molecules in surface cavities and those in the first hydration layer to coordinate to surface bridging oxygen atoms. These differences may have implications for the extent of dissolution in the low-pH regime since hydrolysis of Si(Al)OSi(Al) bonds is a major dissolution mechanism. 相似文献
10.
Water structure at hematite-water interfaces 总被引：1，自引：0，他引：1
Sebastien Kerisit 《Geochimica et cosmochimica acta》2011,75(8):2043-17045
The atomic-level structure of water at mineral surfaces is an important controlling factor in interfacial reactions such as foreign ion incorporation, crystal growth and dissolution, and redox reactions. Molecular dynamics simulations with four different models based on interatomic potentials have been carried out to determine the atomic-level structure of three hematite-water interfaces. In addition, for each of the three surfaces, different terminations or protonation schemes were considered. The availability of surface X-ray scattering data for the surfaces considered here allowed for an extensive comparison with experimental data. Qualitatively, with the exception of one termination with one model, all models predict the correct arrangement of water molecules at the interface. Quantitatively, the agreement with experimental positions, distances, and layer occupancies is good to excellent, especially given the range of values reported in published experimental studies. Therefore, this study provides further evidence that interatomic potential models can be used to reliably predict the structure of mineral-water interfaces. In addition, molecular simulations are a valuable source of information to complement surface X-ray scattering experiments owing to their ability to directly determine the position of hydrogen atoms and to yield three-dimensional predicted structures at no added cost, as demonstrated in this work. Indeed, the molecular dynamics trajectories were analyzed to determine the surface structural controls on the interfacial water structure. Each of the three surface functional groups present at the surfaces considered in this work, namely, triply-coordinated oxo, doubly-coordinated hydroxo, and singly-coordinated aquo groups, was found to form similar hydrogen bond configurations with adsorbed water molecules at all surfaces. Oxo groups accept long-lasting and linear hydrogen bonds from adsorbed water molecules; hydroxo groups can form hydrogen bonds with other surface functional groups as well as with adsorbed water molecules; and aquo groups normally only donate hydrogen bonds to other surface groups or adsorbed water molecules. Additionally, the majority of adsorbed water molecules were found to adopt multiple configurations and orientations. This information was used to evaluate three-dimensional structural models of the interfaces, which were previously derived experimentally from one-dimensional electron density profiles and steric considerations. 相似文献
11.
Reduction of crystalline iron(III) oxyhydroxides using hydroquinone: Influence of phase and particle size 总被引：1，自引：0，他引：1
Iron oxides and oxyhydroxides are common and important materials in the environment, and they strongly impact the biogeochemical
cycle of iron and other species at the Earth's surface. These materials commonly occur as nanoparticles in the 3–10 nm size
range. This paper presents quantitative results demonstrating that iron oxide reactivity is particle size dependent. The rate
and extent of the reductive dissolution of iron oxyhydroxide nanoparticles by hydroquinone in batch experiments were measured
as a function of particle identity, particle loading, and hydroquinone concentration. Rates were normalized to surface areas
determined by both transmission electron microscopy and Braunauer-Emmett-Teller surface. Results show that surface-area-normalized
rates of reductive dissolution are fastest (by as much as 100 times) in experiments using six-line ferrihydrite versus goethite.
Furthermore, the surface-area-normalized rates for 4 nm ferrihydrite nanoparticles are up to 20 times faster than the rates
for 6 nm ferrihydrite nanoparticles, and the surface-area-normalized rates for 5 × 64 nm goethite nanoparticles are up to
two times faster than the rates for 22 × 367 nm goethite nanoparticles. 相似文献
12.
13.
《Applied Geochemistry》2006,21(2):269-288
Reliable quantification of mineral weathering rates is a key to assess many environmental problems. In this study, the authors address the applicability of pure mineral laboratory rate laws for dissolution of mill tailings samples. Mass-normalised sulfide and aluminosilicate mineral dissolution rates, determined in oxygenated batch experiments, were found to be different between two samples from the same ∼50-year-old, carbonate-depleted mill tailings deposit. Consideration of difference in particle surface area and mineralogy between the samples resolved most of this discrepancy in rates. While the mineral surface area normalised dissolution rates of pyrite in a freshly crushed pure pyrite specimen and a sulfide concentrate derived from the tailings were within the range of abiotic literature rates of oxidation by dissolved molecular O2, as were rates of sphalerite and chalcopyrite dissolution in the tailings, dissolution rates of pyrite and aluminosilicates in the tailings generally differed from literature values. This discrepancy, obtained using a consistent experimental method and scale, is suggested to be related to difficulties in quantifying individual mineral reactive surface area in a mixture of minerals of greatly varying particle size, possibly due to factors such as dependence of surface area-normalised mineral dissolution rates on particle size and time, or to non-proportionality between rates and BET surface area. 相似文献
14.
Potential-based molecular dynamics simulations of aqueous uranyl carbonate species (MxUO2(CO3)y2+2x−2y with M = Mg, Ca, or Sr) were carried out to gain molecular-level insight into the hydration properties of these species. The simulation results were used to estimate the self-diffusion coefficients of these uranyl carbonate species, which often dominate uranyl speciation in groundwater systems. The diffusion coefficients obtained for the monoatomic alkaline-earth cations and polyatomic ions (uranyl, carbonate, and uranyl tri-carbonate) were compared with those calculated from the Stokes-Einstein (SE) equation and its variant formulation by Impey et al. (1983). Our results show that the equation of Impey et al. (1983), originally formulated for monovalent monoatomic ions, can be extended to divalent monoatomic ions, with some success in reproducing the absolute values and the overall trend determined from the molecular dynamics simulations, but not to polyatomic ions, for which the hydration shell is not spherically symmetrical. Despite the quantitative failure of both SE formulations, a plot of the diffusion coefficients of the uranyl carbonate complexes as a function of the inverse of the equivalent spherical radius showed that a general linear dependence is observed for these complexes as expected from the SE equation. The nature of the alkaline-earth cation in the uranyl carbonate complexes was not found to have a significant effect on the ion’s diffusion coefficient, which suggests that the use of a single diffusion coefficient for different alkaline-earth uranyl carbonate complexes in microscopic diffusion models is appropriate.The potential model reproduced well published quantum mechanical and experimental data of and of the individual constituent ions, and therefore is expected to offer reliable predictions of the structure of magnesium and strontium uranyl carbonate aqueous species, for which there is no structural data available to date. In addition, the interatomic distances reported for could help with the refinement of the interpretation of EXAFS data of these species, which is made difficult by the similar uranium-distant carbonate oxygen and uranium-calcium distances.An analysis of the dynamics of water exchange around the alkaline-earth cations revealed that the presence of the uranyl tri-carbonate molecule has a strong influence on the geometry of the cation’s first hydration shell, which, in turn, can considerably affect the water exchange kinetics depending on whether the imposed geometry matches that around the isolated alkaline-earth cation. This result shows that the alkaline-earth uranyl carbonate complexes have distinct water exchange dynamics, which may lead to different reactivities. Finally, significant changes in water residence time were also predicted when replacing carbonate for water ligands in the uranyl coordination shell. 相似文献
15.
Jeffrey G. Catalano Paul Fenter Changyong Park 《Geochimica et cosmochimica acta》2007,71(22):5313-5324
Many geochemical reactions that control the composition of natural waters, contaminant fate and transport, and biogeochemical element cycling take place at the interface between minerals and aqueous solutions. A fundamental understanding of these important processes requires knowledge of the structure of mineral-water interfaces. High-resolution specular X-ray reflectivity was used to determine the structure of the hematite (0 1 2)-water interface. Relaxation of the surface was observed to be minor, and water was found to order near the hematite surface. Two sites of adsorbed water are inferred to be ordered laterally, one bridging between triply coordinated functional groups and the other bridging between the singly coordinated functional groups on the surface, as steric constraints limit the possible arrangements of water molecules occurring at the observed heights above the hematite surface. Relaxations of the hematite and corundum (0 1 2) surfaces, which are isostructural, are similar and limited primarily to the top most layer of the structures. No significant changes to the interfacial stoichiometry (i.e., partial occupancy of surface species) are observed in either case. The structure of interfacial water is similar on the hematite and corundum (0 1 2) surfaces as well, although water appeared to be less well ordered on the hematite surface. This may be due to expected differences in the oxygen exchange rates from surface functional groups or the apparent better matching of the corundum oxygen lattice to the natural structural ordering in water, and suggests that the dielectric constant gradients of interfacial water may differ on the two surfaces. Similar charging behavior is expected for these surfaces as similar types of surface functional groups are exposed. Although generally similar, subtle differences in the reactivity of hematite and corundum (0 1 2) surfaces to arsenate adsorption, and possibly the adsorption of other species, may be related to the difference in ordering of interfacial water observed in this study. 相似文献
16.
Spherical calcium dioleate particles (∼ 10 μm in diameter) were used as AFM (atomic force microscope) probes to measure interaction forces of the collector colloid with calcite and fluorite surfaces. The attractive AFM force between the calcium dioleate sphere and the fluorite surface is strong and has a longer range than the DLVO (Derjaguin–Landau–Verwey–Overbeek) prediction. The repulsive AFM force between the calcium dioleate sphere and the fluorite surface does not agree with the DLVO prediction. Consideration of non-DLVO forces, including the attractive hydrophobic force, was necessary to explain the experimental results. The non-DLVO interactions considered were justified by the different interfacial water structures at fluorite– and calcite–water interfaces as revealed by the numerical computation experiments using molecular dynamics simulation. The density of interfacial water at the fluorite surface is low and the fluorite surface is not strongly wetted by water molecules. In contrast to the water at the fluorite surface, water molecules at the calcite surface form tightly packed monolayer structures and the calcite surface is extensively hydrated by water molecules. The interfacial water structure agrees with the AFM force measurements and the flotation recovery data. The strong attraction between the calcium dioleate colloid and the fluorite surface, and the moderately wetted fluorite surface by water molecules explain the better flotation response of fluorite with the oleate collector colloid. 相似文献
17.
Sergey V. Churakov 《Geochimica et cosmochimica acta》2007,71(5):1130-1144
Edge sites of clay minerals play a key role for pH dependent sorption of ions from solutions of electrolytes. Pyrophyllite, Al2[Si4O10](OH)2, is an important structural prototype for a variety of 2:1 dioctahedral phyllosilicates but in contrast to the other clays has no permanent structural charge. The structure of thin water films confined between most common edges of 1Tc pyrophyllite: (0 1 0), (1 1 0) and (1 0 0), was analyzed by means of ab initio molecular dynamic simulations. The system setup allowed for a full flexibility of the interfaces and a proton exchange between the edges of pyrophyllite and water molecules in solution. The structure of hydrated surfaces is compared with the recent predictions of static geometry optimizations for edge-vacuum interfaces. All surfaces studied reveal a strong hydrophilic character of edge similar to the hydrated silica surface and the facets of simple layered hydroxides. Spontaneous proton transfer between different surface sites were observed in molecular dynamics simulations of the (0 1 0) interface. The proton bound to the SiOH site was found to exchange with the AlOH group by the mechanism . The direction of the proton transfer agrees with the scale of relative proton affinities for surface sites obtained from the static calculations. Alternatively, the proton attached to the AlOH2 site exchanges with the AlOH group. In both reactions, the protons are transferred through the chains of hydrogen bonds formed between water molecules in the solution and the surface sites. The observed mechanisms might be one of the basic schemes for the surface proton diffusion in compacted clays. Kinetics of the proton transfer at edge sites is limited by the rate of rearrangements of the water molecules near interface. 相似文献
18.
黏性土中细粒表面水膜是影响其物理力学性质的内在因素。经典土力学一般将土粒表面水膜分为强结合水和弱结合水,即所谓双电层模型,弱结合水的存在是土具有可塑性的原因,强弱结合水的界限含水率为塑限,该模型很好地解释了黏性土的稠度变化及其有关的物理力学行为。然而,通过等温吸附试验发现,土粒表面还存在吸附水膜,对非饱和土高吸力段的物理力学特性有重要影响。为此,本文将黄土颗粒表面水膜分为单层吸附水、多层吸附水、强结合水、弱结合水和自由水5种类型。取甘肃正宁Q2最顶层的L2黄土试样,采用等温吸附和液限、塑限测试,对该黄土样和其中的单矿物颗粒各水膜之间的界限含水率进行了定量表征,并测试黄土试样的土水特征曲线（SWCC）,在SWCC上界定了这些界限含水率与基质吸力的关系。当水汽压很低时,土粒表面的吸力来自水的偶极分子与颗粒表面离子间的静电引力,形成单层吸附水,水膜厚度为1个水分子直径;离颗粒表面超出水分子直径的地方,吸力来自范德华力,水的偶极子相互靠拢呈定向排列,形成了多层吸附水;当土粒周围水分增加,颗粒表面未平衡掉的分子引力又可吸引更多的极化水分子,此时在吸附水的周围形成结合水,结合水又分为强结合水和弱结... 相似文献
19.
With previous two-dimensional (2D) simulations based on surface-specific feldspar dissolution succeeding in relating the macroscopic feldspar kinetics to the molecular-scale surface reactions of Si and Al atoms (
[Zhang and Lüttge, 2008] and [Zhang and Lüttge, 2009]), we extended our modeling effort to three-dimensional (3D) feldspar particle dissolution simulations. Bearing on the same theoretical basis, the 3D feldspar particle dissolution simulations have verified the anisotropic surface kinetics observed in the 2D surface-specific simulations. The combined effect of saturation state, pH, and temperature on the surface kinetics anisotropy has been subsequently evaluated, found offering diverse options for morphological evolution of dissolving feldspar nanoparticles with varying grain sizes and starting shapes. Among the three primary faces on the simulated feldspar surface, the (1 0 0) face has the biggest dissolution rate across an extensively wide saturation state range and thus acquires a higher percentage of the surface area upon dissolution. The slowest dissolution occurs to either (0 0 1) or (0 1 0) faces depending on the bond energies of Si-(O)-Si (ΦSi-O-Si/kT) and Al-(O)-Si (ΦAl-O-Si/kT). When the ratio of ΦSi-O-Si/kT to ΦAl-O-Si/kT changes from 6:3 to 7:5, the dissolution rates of three primary faces change from the trend of (1 0 0) > (0 1 0) > (0 0 1) to the trend of (1 0 0) > (0 0 1) > (0 1 0). The rate difference between faces becomes more distinct and accordingly edge rounding becomes more significant. Feldspar nanoparticles also experience an increasing degree of edge rounding from far-from-equilibrium to close-to-equilibrium. Furthermore, we assessed the connection between the continuous morphological modification and the variation in the bulk dissolution rate during the dissolution of a single feldspar particle. Different normalization treatments equivalent to the commonly used mass, cube assumption, sphere assumption, geometric surface area, and reactive surface area normalizations have been used to normalize the bulk dissolution rate. For each of the treatments, time consistence and grain size dependence of the normalized dissolution rate have been evaluated and the results revealed significant dependences on the magnitude of surface kinetic anisotropy under differing environmental conditions. In general, the normalized dissolution rates are strongly dependent on grain size. Time-consistent normalization treatment varies with the investigated condition. The modeling results suggest that the sphere-, cube-, and BET-normalized dissolution rates are appropriate under the far-from-equilibrium conditions at low pH where these normalizations are time-consistent and are slightly dependent on grain size. 相似文献
20.
High-resolution in situ X-ray specular reflectivity was used to measure the structures of orthoclase (001) and (010) cleavage surfaces in contact with deionized water at 25°C. X-ray reflectivity data demonstrate a high degree of structural similarity between these two orthoclase-water interfaces. Both interfacial structures include cleavage along the plane of minimal bond breakage resulting in surfaces terminated by non-bridging oxygens; structured water within 5 Å of the orthoclase surface (consisting of adsorbed species at the surface and layered water above the surface), with a featureless water profile beyond 5 Å; substitution of outermost K+ ions by an oxygen containing species (presumably H3O+); and small structural displacements of the near surface atoms. The interfacial water structure, in comparison with recent results for other mineral-water interfaces, is intermediate between the minimal structure found at calcite-, barite-, and quartz-water interfaces and the more extensive structure found at the muscovite-water interface. 相似文献