Estimating the activation energy of bond hydrolysis by time-resolved weighing of dissolving crystals

Bond-breaking activation energy EB is nowadays a key parameter for understanding and modeling crystal dissolution processes. However, a methodology to estimate EB based on classical dissolution experiments still does not exist. We developed a new method based on the calibration of a Kossel type dissolution model on measured dissolution rates obtained by mass (or volume) variations over time. The dissolution model does not depend on the geometry of the crystal surface but only on the density of the different types of sites (kink, step, terrace, bulk). The calibration method was applied to different experimental setups (flow through and batch) with different ways of estimating the dissolution rates (solute concentration in the fluid, surface topography) for calcite crystals. Despite the variety of experimental conditions, the estimated bond-breaking activation energies were very close to each other (between 31 and 35 kJ/mol) and in good agreement with ab initio calculations.

Time-resolved dissolution elucidates the mechanism of zeolite MFI crystallization

Zeolite crystal growth mechanisms are not fully elucidated owing to their complexity wherein the formation of a particular zeolite can occur by more than one crystallization pathway. Here, we have conducted time-resolved dissolution experiments of MFI-type zeolite crystals in ammonium fluoride medium where detailed structural analysis allowed us to extrapolate and elucidate the possible mechanism of nucleation and crystal growth. A combination of electron and scanning probe microscopy shows that dissolution initiates preferentially at lattice defects and progressively removes defect zones to reveal a mosaic structure of crystalline domains within each zeolite crystal. This mosaic architecture evolves during the growth process, reflecting the changing conditions of zeolite formation that can be retroactively assessed during zeolite crystal dissolution. Moreover, a more general implication of this study is the establishment that dissolution can be used successfully as an ex situ technique to uncover details about crystal growth features inaccessible by other methods.

Technical note: Analytical protocols and performance for apatite and zircon (U–Th) ∕ He analysis on quadrupole and magnetic sector mass spectrometer systems between 2007 and 2020

Apatite and zircon (U–Th) / He thermochronological data are obtained through a combination of crystal selection, He content measurement by crystal heating with analysis using noble gas mass spectrometry, and measurement of U, Th, and Sm contents by crystal dissolution as well as solution analysis using inductively coupled plasma mass spectrometry (ICP-MS). This contribution documents the methods for helium thermochronology used at the GEOPS laboratory, Paris-Saclay University, between 2007 and the present that allow apatite and zircon (U–Th) / He data to be obtained with precision. More specifically, we show that the He content can be determined with precision (at 5 %) and accuracy using a calibration of the He sensitivity based on the Durango apatite, and its use also appears crucial to check for He and U–Th–Sm analytical problems. The Durango apatite used as a standard is therefore a suitable mineral to perform precise He calibration and yields (U–Th) / He ages of 31.1 ± 1.4 Ma with an analytical error of less than 5 % (1σ). The (U–Th) / He ages for the Fish Canyon Tuff zircon standard yield a dispersion of about 9 % (1σ) with a mean age of 27.0 ± 2.6 Ma, which is comparable to other laboratories. For the long-term quality control of the (U–Th) / He data, attention is paid to evaluating the drift of He sensitivity and blanks through time as well as that of (U–Th) / He ages and Th / U ratios (with Sm / Th when possible), all relying on the use of Durango apatite and Fish Canyon Tuff zircon as standards.

Complete chiral resolution in a continuous flow crystallizer with recycle stream

Repeated temperature cycling of crystals from a conglomerate forming chiral substance suspended in their saturated solution has shown to be effective in converting a mixture of both enantiomers into an enantiomerically pure state. While by now a large number of different setups has been demonstrated, here we show for the first time how a continuous flow temperature cycler with recycle stream is capable of establishing enantiopurity while converting a racemic starting suspension. By capturing the most significant parameters influencing the process kinetics a competitive productivity could be achieved. We show, that fast crystal dissolution at high undersaturations and fast crystal growth at high supersaturations are speeding up the process as long as nucleation can be kept to a minimum or avoided at all. Temperature cycling has shown to result in a shift towards larger sizes for the particle size distribution of the crystals suspended, which is detrimental to the present process governed by size-dependent solubility. By implementing an ultrasound unit recycled material was comminuted, resulting in nearly stable deracemization rates. Graphical abstract

Improvement the InAs, InSb, GaAs and GaSb surface state by nanoscale wet etching

Various experimental approaches of the wet nanoscale treatment have been proposed to account for features of the InAs, InSb and GaAs, GaSb semiconductor dissolution process in the (NH4)2Cr2O7–HBr–EG etching solution. Etching kinetics data showed that a crystal dissolution has diffusion-determined nature. The lowering of the solvent concentration from 80 to 0 vol.% in the solution was accompanied by a significant increase in the semiconductor etching speed. Depending on the solution composition, we have studied two types of crystal surface morphology, polished and passivated by the film, which was formed after chemical-dynamic (CDP) and/or chemical-mechanic polishing (CMP) in the solution, saturated by solvent and by oxidant, accordingly. It was found that in the polished etchants both CDP and CMP procedures lead to the formation of the mirror-like and super-smooth surface with nanoscale roughness less than 1 nm. The obtained results of surface state indicate that the (NH4)2Cr2O7–HBr–EG etchants could be used successfully for controllable CDP and CMP treatment of III–V semiconductors and formation of super-smooth surface.

Microstructure Investigation of Oil-Bearing Rhyolites: A Case Study from the Hailar Basin, NE China

Understanding the microstructure of rhyolites may greatly promote exploration efforts on rhyolitic hydrocarbon reservoirs; however, related studies are sparse. In this contribution, the microstructure and related porosity of oil-bearing rhyolitic lavas from the Hailar Basin (NE China) were investigated using a combination of optical microscopy, fluorescence image analysis, and scanning electron microscopy. The direct visual and quantitative analyses show that the rhyolites are heterogeneous and porous rocks and have complex microstructures. Phenocryst-rich rhyolitic lava, perlitic lava, and spherulitic rhyolite may be favorable targets for rhyolitic hydrocarbon exploration. For the phenocryst-rich rhyolitic lavas, embayment pores, cleavages, cavitational and shear fractures, and intracrystalline sieve pores are commonly observed in the phenocrysts; while flow-parallel laminar and micropores are ubiquitous in the groundmass. Perlitic lavas are characterized by the occurrence of numerous perlitic fractures which can also be produced in the glassy groundmass of other lavas. Spherulitic rhyolites mainly consist of small-sized (<1 mm) clustered or large-sized (>1 mm) isolated spherulites. Clustered spherulites are characterized by the development of interspherulite pores. Isolated spherulites contain numerous radiating micropores. Both types of spherulites may have water expulsion pores formed in the spherulite–glass border. The formation of the microstructure and related porosity of rhyolites is controlled by pre-, syn- (e.g., deuteric crystal dissolution, cavitation, ductile–brittle deformation, and high-T devitrification), and post-volcanic (e.g., hydration and low-T devitrification) processes. Although pores with diameters > 50 μm are often observed, small pores dominate in pore-size distribution. Small (<15 μm) and large (>300 μm) pores give the most volumetric contribution in most cases. Medium-sized pores with diameters ranging from ~150–300 μm are the least developed and contribute the least to the total volume. The results of this paper can be beneficial to further the understanding of the microstructure and pore system of rhyolites and may be applied to rhyolitic lava hydrocarbon reservoirs elsewhere.