Kinetic concepts for quantitative prediction of fluid-solid interactions

Lüttge, Andreas; Arvidson, Rolf S.; Fischer, Cornelius; Kurganskaya, Inna

doi:10.1016/j.chemgeo.2018.11.016

Cited by 47 publications

(56 citation statements)

References 154 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Anisotropic surface kinetics related to different crystal faces and grain size have been demonstrated in kinetic modeling studies [41][42][43]. This interplay between dissolution steps generated at grain edges (or grain boundaries) and steps generated from crystal defects in the middle of grains (e.g., point or screw dislocations) has been previously discussed and demonstrated via kMC modelling [16]. At grain edges, reactive curvilinear steps constantly form supplying the grain with kink sites.…”

Section: Inter-pore Variability Of Rates Versus Grain Sizementioning

confidence: 80%

“…Currently, a normalization approach using concepts of specific surface area and reactive surface area is implemented in models involving pore scale processes. This has been discussed at length elsewhere ( [16] and references within). Both parameters serve as a crude approximation for dissolution processes at the microscopic scale and have a number of pitfalls.…”

Section: Introductionmentioning

confidence: 84%

“…The associated method error is constrained by its spatial and temporal resolution. Due to the dynamic surface changes that occur during the ongoing of a dissolution process, the local dissolution rates seen at the nano to macroscale can effectively vary in time ( [16], and references therein). Generally, the method captures variations at the nano to micron-scales relevant to pore-scale processes.…”

Section: Intra-variability Of Ratesmentioning

confidence: 99%

“…Calcite dissolution rates measured at similar experimental conditions can vary within several orders of magnitude [12]. This is due to both crystallographic and microstructural factors intrinsic to the mineral itself (e.g., crystallinity, crystal orientation, number and distribution of crystal defects) that result in a heterogeneous evolution of the dissolving surface, hence of reaction rates [13][14][15][16]. Inter-dataset disagreement can also occur due to the contrast between non-site-specific observations (e.g., in a powder) versus site-specific variations within a domain or field of view (e.g., AFM or VSI frame).…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

A Statistical Approach for Analysis of Dissolution Rates Including Surface Morphology

2019

Self Cite

View full text Add to dashboard Cite

Understanding mineral dissolution is relevant for natural and industrial processes that involve the interaction of crystalline solids and fluids. The dissolution of slow dissolving minerals is typically surface controlled as opposed to diffusion/transport controlled. At these conditions, the dissolution rate is no longer constant in time or space, an outcome observed in rate maps and correspondent rate spectra. The contribution and statistical prevalence of different dissolution mechanisms is not known. Aiming to contribute to close this gap, we present a statistical analysis of the variability of calcite dissolution rates at the nano- to micrometer scale. A calcite-cemented sandstone was used to perform flow experiments. Dissolution of the calcite-filled rock pores was measured using vertical scanning interferometry. The resultant types of surface morphologies influenced the outcome of dissolution. We provide a statistical description of these morphologies and show their temporal evolution as an alternative to the lack of rate spatial variability in rate constants. Crystal size impacts dissolution rates most probably due to the contribution of the crystal edges. We propose a new methodology to analyze the highest rates (tales of rate spectra) that represent the formation of deeper etch pits. These results have application to the parametrization and upscaling of geochemical kinetic models, the characterization of industrial solid materials and the fundamental understanding of crystal dissolution.

show abstract

Section: Inter-pore Variability Of Rates Versus Grain Sizementioning

confidence: 80%

Section: Introductionmentioning

confidence: 84%

Section: Intra-variability Of Ratesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

A Statistical Approach for Analysis of Dissolution Rates Including Surface Morphology

2019

Self Cite

View full text Add to dashboard Cite

show abstract

“…[16,17] The characterization of crystals after the immersion in solvents, made by optical interferometry, [18] electronic microscopy [19] and diffraction, [20] showed that dissolution can be rapid or slow depending on driving effects on the surface. More recently, scanning probe microscopies (SPM), such as atomic force microscopy (AFM), [21][22][23][24][25][26][27] have been exploited to study the local morphology of crystals and their dissolution kinetics. Moreover, SPM offers the possibility to immerse the tip inside the solution, to observe in real time the in-situ evolution of the surface.…”

Section: Introductionmentioning

confidence: 99%

Reactive Dissolution of Organic Nanocrystals at Controlled pH

et al. 2020

View full text Add to dashboard Cite

The development of novel protocols and techniques for waste treatment represents the state of the art in the so‐called “green conversion”. Chemical wastes deriving from industrial and power‐station processes, which involve organic crystals, can be very hazardous for the environment. Studying their dissolution mechanism, both theoretically and experimentally, represents a mandatory step in the critical task of their disposal. Surprisingly, most of the studies are focused on millimeter scale length, from which one could estimate the crystal dissolution rate. In these studies, where no information about the dissolution mechanism on a molecular scale is provided, etch‐pit formation is recognized as the ultimate mechanism of crystal dissolution. In this work, we show the morphological evolution of organic nanocrystals on the sub‐micrometer scale range in a reactive dissolution process controlled by pH. This approach allows us to explore ranges of high undersaturation, whereby crystal dissolution occurs even though etch‐pit formation is suppressed. Adopting different surface and bulk‐sensitive techniques (atomic force microscopy, time‐of‐flight secondary ion mass spectroscopy and X‐ray/electron diffraction, Raman spectroscopy, respectively), we investigate the dissolution process of porphyrin thin films deposited on the basal plane of highly oriented pyrolytic graphite, proving that such films constitute a model system to unveil the dissolution mechanism of organic nanocrystals.

show abstract

Variability of Radionuclide Sorption Efficiency on Muscovite Cleavage Planes

Schabernack,

Oliveira,

Heine

et al. 2023

Advcd Theory and Sims

Self Cite

View full text Add to dashboard Cite

In deep geological repositories for nuclear waste, the surrounding rock formation serves as an important barrier against radionuclide migration. Multiple potential host rocks contain phyllosilicates, which have shown high efficiency in radionuclide sorption. Recent experimental studies report a heterogeneous distribution of adsorbed radionuclides on nanotopographic mineral surfaces. In this study, the energetic differences of surface sorption sites available at nanotopographic structures such as steps, pits, and terraces are investigated. Eleven important surface sites are selected and the energies of ad‐ and desorption reactions are obtained from density functional theory calculations. The adsorption energies are then used for the parameterization of a kinetic Monte Carlo model simulating the distribution of adsorbed europium on a typical nanotopographic muscovite surface. On muscovite, silicon step sites are favorable for europium sorption and lead to an increased adsorption in regions with high step concentrations. Under identical chemical conditions, sorption on typical nanotopographic surfaces is increased by a factor of three compared to atomically flat surfaces. Desorption occurs preferentially at terrace sites, leading to an overall 2.5 times increased retention at nanotopographic structures. This study provides a mechanistic explanation for heterogeneous sorption on nanotopographic mineral surfaces due to the availability of energetically favorable sorption sites.

show abstract

Kinetic concepts for quantitative prediction of fluid-solid interactions

Cited by 47 publications

References 154 publications

A Statistical Approach for Analysis of Dissolution Rates Including Surface Morphology

A Statistical Approach for Analysis of Dissolution Rates Including Surface Morphology

Reactive Dissolution of Organic Nanocrystals at Controlled pH

Variability of Radionuclide Sorption Efficiency on Muscovite Cleavage Planes

Contact Info

Product

Resources

About