arXiv subjects

Fabio La Mantia

Publications and source records attributed to Fabio La Mantia.

5 recordsLinked to original sources

arXiv2025

A toy model solved by statistical mechanics for teaching reaction kinetics beyond ideality

Chemical equilibrium is fully characterized by thermodynamics, while the rates of chemical reactions can be calculated for ideal solutions by using mass-action equations. The evaluation of the rates of reactions in a non-ideal system is instead much more complex, even at equilibrium, being dependent on the microscopic features of the interactions: no universal theory exist. Here we propose a toy model to help students understand such complexity. It is formulated by means of statistical mechanics and aims at the evaluation of the exchange reaction rate at equilibrium. The toy model can be solved by the students, with various types of interactions, as an exercise. The results prove that no general rule connects the reaction rates to the thermodynamic quantities, such as the activity coefficients, dramatically proving the complexity and richness of the field.

physics.chem-ph↗

arXiv2023

Modeling of electrochemical oxide film growth -- a PDM refinement

The Point Defect Model (PDM) is known for over 40 years and has brought deeper insight to the understanding of passivity. During the last decades it has seen several changes and refinements, and it has been widely used to analyze growth kinetics of different alloys. Nevertheless, the model has been based on still unconfirmed assumptions, as constant and potential independent electric field strength. To overcome this limitation, we introduce a Refined PDM (R-PDM) in which we replace those assumptions by using additional equations for charge distribution including new physically valid boundary conditions based on considering finite dimensions for the defects by introduction of two defect layer at the film boundaries and by calculating the potential drop at the surface of the film towards the solution over the compact double layer. The calculations by the R-PDM show that the original PDM assumptions are only valid for very specific parameter combinations of oxide film growth and vacancies transport and cannot generally be taken for granted. We believe our findings of electric field and potential drop dependency on the external potential to pave the way for a more realistic description of passive layer formation.

cond-mat.mtrl-sci↗

arXiv2023

Modeling of electrochemical oxide film growth -- impact of band-to-band tunneling

The Point Defect Model (PDM) describes the corrosion resistance properties of oxide films based on interfacial reactions and defect transport, which are affected by the electric field inside the oxide film. The PDM assumes a constant electric field strength due to band-to-band tunneling (BTBT) of electrons and the separation of electrons and holes by high electric fields. In this manuscript we present a more complex expansion of the common models to simulate steady state oxide films to test this assumption. The R-PDM was extended by including the transport of electrons and holes and BTBT. It could be shown that BTBT only occurs in very rare cases of narrow band gaps and high electric fields and the impact of electrons and holes does indeed lead to a buffering effect on the electric field, but does not lead to a constant electric field strength. Modeling the transport of electrons and holes on the oxide film allows to specifically estimate their potential impact on the film growth. Especially during modeling of oxide films with narrow band gap and/or electrochemical reactions at the film/solution interface the electrons and holes needs to be included to the model.

physics.chem-ph↗

arXiv2023

Electrochemical impedance spectroscopy beyond linearity and stationarity - a critical review

Electrochemical impedance spectroscopy (EIS) is a widely used experimental technique for characterising materials and electrode reactions by observing their frequency-dependent impedance. Classical EIS measurements require the electrochemical process to behave as a linear time-invariant system. However, electrochemical processes do not naturally satisfy this assumption: the relation between voltage and current is inherently nonlinear and evolves over time. Examples include the corrosion of metal substrates and the cycling of Li-ion batteries. As such, classical EIS only offers models linearised at specific operating points. During the last decade, solutions were developed for estimating nonlinear and time-varying impedances, contributing to more general models. In this paper, we review the concept of impedance beyond linearity and stationarity, and detail different methods to estimate this from measured current and voltage data, with emphasis on frequency domain approaches using multisine excitation. In addition to a mathematical discussion, we measure and provide examples demonstrating impedance estimation for a Li-ion battery, beyond linearity and stationarity, both while resting and while charging.

eess.SY↗

arXiv2019

Electro-Oxidation of p-Silicon in Fluoride-Containing Electrolyte: A Physical Model for the Regime of Negative Differential Resistance

When Si is anodically oxidized in a fluoride containing electrolyte, an oxide layer is grown. Simultaneously, the layer is etched by the fluoride containing electrolyte. The resulting stationary state exhibits a negative slope of the current-voltage characteristics in a certain range of applied voltage. We propose a physical model that reproduces this negative slope. In particular, our model assumes that the oxide layer consists of both partially and fully oxidized Si and that the etch rate depends on the effective degree of oxidation. Finally, we show that our simulations are in good agreement with measurements of the current-voltage characteristics, the oxide layer thickness, the dissolution valence, and the impedance spectra of the electrochemical system.

physics.chem-ph↗