Role of partial molar enthalpy of oxides on Soret effect in high-temperature CaO-SiO2 melts.
ABSTRACT: The Soret effect or thermodiffusion is the temperature-gradient driven diffusion in a multicomponent system. Two important conclusions have been obtained for the Soret effect in multicomponent silicate melts: first, the SiO2 component concentrates in the hot region; and second, heavier isotopes concentrate in the cold region more than lighter isotopes. For the second point, the isotope fractionation can be explained by the classical mechanical collisions between pairs of particles. However, as for the first point, no physical model has been reported to answer why the SiO2 component concentrates in the hot region. We try to address this issue by simulating the composition dependence of the Soret effect in CaO-SiO2 melts with nonequilibrium molecular dynamics and determining through a comparison of the results with those calculated from the Kempers model that partial molar enthalpy is one of the dominant factors in this phenomenon.
Project description:Molecules drift along temperature gradients, an effect called thermophoresis, the Soret effect, or thermodiffusion. In liquids, its theoretical foundation is the subject of a long-standing debate. By using an all-optical microfluidic fluorescence method, we present experimental results for DNA and polystyrene beads over a large range of particle sizes, salt concentrations, and temperatures. The data support a unifying theory based on solvation entropy. Stated in simple terms, the Soret coefficient is given by the negative solvation entropy, divided by kT. The theory predicts the thermodiffusion of polystyrene beads and DNA without any free parameters. We assume a local thermodynamic equilibrium of the solvent molecules around the molecule. This assumption is fulfilled for moderate temperature gradients below a fluctuation criterion. For both DNA and polystyrene beads, thermophoretic motion changes sign at lower temperatures. This thermophilicity toward lower temperatures is attributed to an increasing positive entropy of hydration, whereas the generally dominating thermophobicity is explained by the negative entropy of ionic shielding. The understanding of thermodiffusion sets the stage for detailed probing of solvation properties of colloids and biomolecules. For example, we successfully determine the effective charge of DNA and beads over a size range that is not accessible with electrophoresis.
Project description:Thermal gradients induce concentration gradients in alkali halide solutions, and the salt migrates towards hot or cold regions depending on the average temperature of the solution. This effect has been interpreted using the heat of transport, which provides a route to rationalize thermophoretic phenomena. Early theories provide estimates of the heat of transport at infinite dilution. These values are used to interpret thermodiffusion (Soret) and thermoelectric (Seebeck) effects. However, accessing heats of transport of individual ions at finite concentration remains an outstanding question both theoretically and experimentally. Here we discuss a computational approach to calculate heats of transport of aqueous solutions at finite concentrations, and apply our method to study lithium chloride solutions at concentrations >0.5?M. The heats of transport are significantly different for Li+ and Cl- ions, unlike what is expected at infinite dilution. We find theoretical evidence for the existence of minima in the Soret coefficient of LiCl, where the magnitude of the heat of transport is maximized. The Seebeck coefficient obtained from the ionic heats of transport varies significantly with temperature and concentration. We identify thermodynamic conditions leading to a maximization of the thermoelectric response of aqueous solutions.
Project description:Thermophoresis is an efficient process for the manipulation of molecules and nanoparticles due to the strong force it generates on the nanoscale. Thermophoresis is characterized by the Soret coefficient. Conventionally, the Soret coefficient of nanosized species is obtained by fitting the concentration profile under a temperature gradient at the steady state to a continuous phase model. However, when the number density of the target is ultralow and the dispersed species cannot be treated as a continuous phase, the bulk concentration fluctuates spatially, preventing extraction of temperature-gradient induced concentration profile. The present work demonstrates a strategy to tackle this problem by superimposing snapshots of nanoparticle distribution. The resulting image is suitable for the extraction of the Soret coefficient through the conventional data fitting method. The strategy is first tested through a discrete phase model that illustrates the spatial fluctuation of the nanoparticle concentration in a dilute suspension in response to the temperature gradient. By superimposing snapshots of the stochastic distribution, a thermophoretic depletion profile with low standard error is constructed, indicative of the Soret coefficient. Next, confocal analysis of nanoparticle distribution in response to a temperature gradient is performed using polystyrene nanobeads down to 1e-5% (v/v). The experimental results also reveal that superimposing enhances the accuracy of extracted Soret coefficient. The critical particle number density in the superimposed image for predicting the Soret coefficient is hypothesized to depend on the spatial resolution of the image. This study also demonstrates that the discrete phase model is an effective tool to study particle migration under thermophoresis in the liquid phase.
Project description:Pressure-induced changes in properties of multicomponent silicate melts in magma oceans controlled chemical differentiation of the silicate earth and the composition of partial melts that might have formed hidden reservoirs. Although melt properties show complex pressure dependences, the melt structures at high pressure and the atomistic origins of these changes are largely unknown because of their complex pressure–composition dependence, intrinsic to multicomponent magmatic melts. Chemical constraints such as the nonbridging oxygen (NBO) content at 1 atm, rather than the structural parameters for melt polymerization, are commonly used to account for pressure-induced changes in the melt properties. Here, we show that the pressure-induced NBO fraction in diverse silicate melts show a simple and general trend where all the reported experimental NBO fractions at high pressure converge into a single decaying function. The pressure-induced changes in the NBO fraction account for and predict the silica content, nonlinear variations in entropy, and the transport properties of silicate melts in Earth’s mantle. The melt properties at high pressure are largely different from what can be predicted for silicate melts with a fixed NBO fraction at 1 atm. The current results with simplicity in melt polymerization at high pressure provide a molecular link to the chemical differentiation, possibly missing Si content in primary mantle through formation of hidden Si-rich mantle reservoirs.
Project description:Platinum-bearing chromitites in mafic-ultramafic intrusions such as the Bushveld Complex are key repositories of strategically important metals for human society. Basaltic melts saturated in chromite alone are crucial to their generation, but the origin of such melts is controversial. One concept holds that they are produced by processes operating within the magma chamber, whereas another argues that melts entering the chamber were already saturated in chromite. Here we address the problem by examining the pressure-related changes in the topology of a Mg2SiO4-CaAl2Si2O8-SiO2-MgCr2O4 quaternary system and by thermodynamic modelling of crystallisation sequences of basaltic melts at 1-10 kbar pressures. We show that basaltic melts located adjacent to a so-called chromite topological trough in deep-seated reservoirs become saturated in chromite alone upon their ascent towards the Earth's surface and subsequent cooling in shallow-level chambers. Large volumes of these chromite-only-saturated melts replenishing these chambers are responsible for monomineralic layers of massive chromitites with associated platinum-group elements.
Project description:The effect of the ZrO2 loading was studied on spherical SiO2@ZrO2-CaO structures synthetized by a simple route that combines the Stöber and sol-gel methods. The texture of these materials was determined using SBET by N2 adsorption, where the increment in SiO2 spheres' surface areas was reached with the incorporation of ZrO2. Combined the characterization techniques of using different alcoholic dissolutions of zirconium (VI) butoxide 0.04 M, 0.06 M, and 0.08 M, we obtained SiO2@ZrO2 materials with 5.7, 20.2, and 25.2 wt % of Zr. Transmission electron microscopy (TEM) analysis also uncovered the shape and reproducibility of the SiO2 spheres. The presence of Zr and Ca in the core-shell was also determined by TEM. X-ray diffraction (XRD) profiles showed that the c-ZrO2 phase changed in to m-ZrO2 by incorporating calcium, which was confirmed by Raman spectroscopy. The purity of the SiO2 spheres, as well as the presence of Zr and Ca in the core-shell, was assessed by the Fourier transform infrared (FTIR) method. CO2 temperature programmed desorption (TPD-CO2) measurements confirmed the increment in the amount of the basic sites and strength of these basic sites due to calcium incorporation. The catalyst reuse in FAME production from canola oil transesterification allowed confirmation that these calcium core@shell catalysts turn out to be actives and stables for this reaction.
Project description:Findings of coesite and microdiamond in metamorphic rocks of supracrustal protolith led to the recognition of continental subduction to mantle depths. The crust-mantle interaction is expected to take place during subduction of the continental crust beneath the subcontinental lithospheric mantle wedge. This is recorded by postcollisional mafic igneous rocks in the Dabie-Sulu orogenic belt and its adjacent continental margin in the North China Block. These rocks exhibit the geochemical inheritance of whole-rock trace elements and Sr-Nd-Pb isotopes as well as zircon U-Pb ages and Hf-O isotopes from felsic melts derived from the subducted continental crust. Reaction of such melts with the overlying wedge peridotite would transfer the crustal signatures to the mantle sources for postcollisional mafic magmatism. Therefore, postcollisonal mafic igneous rocks above continental subduction zones are an analog to arc volcanics above oceanic subduction zones, providing an additional laboratory for the study of crust-mantle interaction at convergent plate margins.
Project description:Crustal pathways connecting deep sources of melt and the active volcanoes they supply are poorly understood. Beneath Mounts St. Helens, Adams, and Rainier these pathways connect subduction-induced ascending melts to shallow magma reservoirs. Petrogenetic modeling predicts that when these melts are emplaced as a succession of sills into the lower crust they generate deep crustal hot zones. While these zones are increasingly recognized as a primary site for silicic differentiation at a range of volcanic settings globally, imaging them remains challenging. Near Mount Rainier, ascending melt has previously been imaged ~28?km northwest of the volcano, while to the south, the volcano lies on the margin of a broad conductive region in the deep crust. Using 3D full-waveform tomography, we reveal an expansive low-velocity zone, which we interpret as a possible hot zone, linking ascending melts and shallow reservoirs. This hot zone may supply evolved magmas to Mounts St. Helens and Adams, and possibly Rainier, and could contain approximately twice the melt volume as the total eruptive products of all three volcanoes combined. Hot zones like this may be the primary reservoirs for arc volcanism, influencing compositional variations and spatial-segmentation along the entire 1100?km-long Cascades Arc.
Project description:The composition and origin of Earth's early crust remains hotly debated. Here we use partition coefficients to invert the trace element composition of 4.3-3.3 Gyr Jack Hills zircons to calculate the composition of the melts from which they crystallised. Using this approach, the average SiO2 content of these melts was 59?±?6 wt. % with Th/Nb, Dy/Yb and Sr/Y ratios of 2.7?±?1.9, 0.9?±?0.2 and 1.6?±?0.7, respectively. Such features strongly indicate that the protolith for the Jack Hills zircons was not an intra-plate mafic rock, nor a TTG (tondjhemite-tonalite-granodiorite) or a Sudbury-like impact melt. Instead, the inferred equilibrium melts are much more similar to andesites formed in modern subduction settings. We find no evidence for any secular variation between 4.3 and 3.3 Gyr implying little change in the composition or tectonic affinity of the Earth's early crust from the Hadean to Mesoarchaean.
Project description:The origin of iron oxide-apatite deposits is controversial. Silicate liquid immiscibility and separation of an iron-rich melt has been invoked, but Fe-Ca-P-rich and Si-poor melts similar in composition to the ore have never been observed in natural or synthetic magmatic systems. Here we report experiments on intermediate magmas that develop liquid immiscibility at 100?MPa, 1000-1040?°C, and oxygen fugacity conditions (fO2) of ?FMQ?=?0.5-3.3 (FMQ?=?fayalite-magnetite-quartz equilibrium). Some of the immiscible melts are highly enriched in iron and phosphorous?±?calcium, and strongly depleted in silicon (<5?wt.% SiO2). These Si-poor melts are in equilibrium with a rhyolitic conjugate and are produced under oxidized conditions (~FMQ?+?3.3), high water activity (aH2O???0.7), and in fluorine-bearing systems (1?wt.%). Our results show that increasing aH2O and fO2 enlarges the two-liquid field thus allowing the Fe-Ca-P melt to separate easily from host silicic magma and produce iron oxide-apatite ores.