Thermodynamic equilibrium and kinetic fundamentals of oxide dissolution in aqueous solution

Wang, Jianwei

doi:10.1557/jmr.2020.81

Cited by 11 publications

(17 citation statements)

References 170 publications

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“…If the nucleation and growth of a stable alteration layer is fast, secondary crystalline phases may directly form through a dissolution-coupled in situ reprecipitation mechanism. 245 This section will describe advances in the mechanistic understanding and performance prediction of the corrosion process of crystalline ceramics, which can be distinguished from the traditional trial-and-error approach. Figure 20 presents an overview of the activities.…”

Section: Such Oxyanions Include [Clomentioning

confidence: 99%

“…The collapse of the structural framework transformed the Ti-enriched alteration layer into crystalline titanium oxide phases (rutile and/or brookite). 245 In Cs-hollandite (Cs 0.8 Ba 0.4 Ti 8 O 16 ) subjected to nitric acid solution (pH = 1.0), which is a highly oxidizing condition, the removal of Cs from the titanate framework was dependent not only on H + but also on redox chemistry. The release of Cs as well as the highly oxidizing environment accelerated the oxidation of Ti 3+ to Ti 4+ to maintain charge neutrality.…”

Section: Passivation Film Formation and Breakdownmentioning

confidence: 99%

“…Knowledge of the corrosion mechanisms and kinetics of ceramics in aqueous solutions is critically important in the understanding of the chemical durability of nuclear waste forms and the prediction of the long-term dissolution rate. , A number of phenomena are involved, including surface adsorption, hydrolysis, ion exchange, solid-state transformation, and electron-transfer reactions if redox-active elements are present. In general, the complex corrosion reactions consist of parallel and sequential elementary steps, but not all are critical in determining the overall dissolution rate.…”

Section: Corrosion Of Crystalline Ceramics In Aqueous Environmentsmentioning

confidence: 99%

“…Different theories have been developed to describe the corrosion mechanisms and kinetics in understanding the chemical durability. Qualitatively, the composition of oxides has been used to predict the relative chemical durability. , For instance, halogen and alkaline ions such as chloride and sodium ions are soluble in aqueous solutions and occupy large areas in their Eh–pH diagram under the conditions that commonly occur in most geological environments. They are singly charged ionic species and often exist as dissolved species in solutions.…”

Section: Corrosion Of Crystalline Ceramics In Aqueous Environmentsmentioning

confidence: 99%

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Recent Advances in Corrosion Science Applicable To Disposal of High-Level Nuclear Waste

et al. 2021

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High-level radioactive waste is accumulating at temporary storage locations around the world and will eventually be placed in deep geological repositories. The waste forms and containers will be constructed from glass, crystalline ceramic, and metallic materials, which will eventually come into contact with water, considering that the period of performance required to allow sufficient decay of dangerous radionuclides is on the order of 105–106 years. Corrosion of the containers and waste forms in the aqueous repository environment is therefore a concern. This Review describes the recent advances of the field of materials corrosion that are relevant to fundamental materials science issues associated with the long-term performance assessment and the design of materials with improved performance, where performance is defined as resistance to aqueous corrosion. Glass, crystalline ceramics, and metals are discussed separately, and the near-field interactions of these different material classes are also briefly addressed. Finally, recommendations for future directions of study are provided.

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Section: Such Oxyanions Include [Clomentioning

confidence: 99%

Section: Passivation Film Formation and Breakdownmentioning

confidence: 99%

Section: Corrosion Of Crystalline Ceramics In Aqueous Environmentsmentioning

confidence: 99%

Section: Corrosion Of Crystalline Ceramics In Aqueous Environmentsmentioning

confidence: 99%

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Recent Advances in Corrosion Science Applicable To Disposal of High-Level Nuclear Waste

et al. 2021

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“…The description of crystal dissolution kinetics in water as a function of undersaturation is a long-standing fundamental problem. − Theory of crystal dissolution involves the traditional physical chemistry approach for calculations of equilibrium constants and solubility products . Theory of mineral dissolution kinetics relates dissolution rates to aqueous solution composition and equilibrium constants/solubility products. − The laws providing dissolution rates as a function of concentrations are typically provided as closed-form functions of Δ G calculated from concentrations/activities and the equilibrium constant/solubility product.…”

Section: Introductionmentioning

confidence: 99%

Mineral Dissolution Kinetics: Pathways to Equilibrium

Kurganskaya

Lüttge

2021

ACS Earth Space Chem.

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Dependence of dissolution rate from undersaturation is a fundamental problem that has been traditionally approached from thermodynamic arguments and empirical observations. Commonly used rate laws predicting dissolution kinetics are constructed based on these considerations. A persistent issue is the poor reproducibility of some kinetic parameters in the experimental measurements with 2−3 orders of magnitude in their parameter value variance. Some puzzling functional dependencies of rates on reaction Gibbs free energies became a subject of debate during the last two decades. In the present paper, we have derived new generic rate laws based on statistical mechanics considerations. These rate laws are implemented into a kinetic Monte Carlo model for calcium carbonate (calcite) dissolution at fixed concentrations of the dissolved ions. The saturation state was gradually changed from far-from-equilibrium towards equilibrium conditions. We showed how different kinetic pathways can be easily generated for systems with different types and amounts of lattice defects. The analysis of these pathways showed that a reactive system never repeats the same pathway when it enters a saturation state visited previously. This behavior reflects intrinsic mineral−water interface kinetics incorporated into the new rate laws including reactive site population statistics. We discuss the underlying theoretical issues in rate law definitions, leading to large rate variances and uncertain ΔG-dependencies. We also discuss the physical meaning of n in the (1 − Ω) n term arising from experimental and field studies. An alternative way to treat mineral−fluid kinetics is offered.

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Imaging the Footprint of Nanoscale Electrochemical Reactions for Assessing Synergistic Hydrogen Evolution

et al. 2023

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This work proposes a novel method for measuring the intrinsic activity of single metal-based nanoparticles towards water reduction in neutral media at industrially relevant current densities. Instead of using gas nanobubbles as proxy, the method uses optical microscopy to track the local footprint of the reaction through the precipitation of metal hydroxide, which is associated to the local pH increase during electrocatalysis. The results show the electrocatalytic activities of different types of metal nanoparticles and bifunctionnal core-shell nanostructures made of Ni and Pt, and demonstrate the importance of metal hydroxide nanoshells in enhancing electrocatalysis. This method should be generalizable to any electrocatalytic reaction involving pH changes such as nitrate or CO 2 reduction.

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Thermodynamic equilibrium and kinetic fundamentals of oxide dissolution in aqueous solution

Abstract: Abstract

Cited by 11 publications

References 170 publications

Recent Advances in Corrosion Science Applicable To Disposal of High-Level Nuclear Waste

Recent Advances in Corrosion Science Applicable To Disposal of High-Level Nuclear Waste

Mineral Dissolution Kinetics: Pathways to Equilibrium

Imaging the Footprint of Nanoscale Electrochemical Reactions for Assessing Synergistic Hydrogen Evolution

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