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Recent Advances in Voltammetry.

Batchelor-McAuley C, Kätelhön E, Barnes EO, Compton RG, Laborda E, Molina A - ChemistryOpen (2015)

Bottom Line: The transformation over the last decade of the level of modelling and simulation of experiments has realised major advances such that electrochemical techniques can be fully developed and applied to real chemical problems of distinct complexity.This review focuses on the topic areas of: multistep electrochemical processes, voltammetry in ionic liquids, the development and interpretation of theories of electron transfer (Butler-Volmer and Marcus-Hush), advances in voltammetric pulse techniques, stochastic random walk models of diffusion, the influence of migration under conditions of low support, voltammetry at rough and porous electrodes, and nanoparticle electrochemistry.The review of the latter field encompasses both the study of nanoparticle-modified electrodes, including stripping voltammetry and the new technique of 'nano-impacts'.

View Article: PubMed Central - PubMed

Affiliation: Department of Chemistry, Physical and Theoretical Chemistry Laboratory, University of Oxford South Parks Road, Oxford, OX1 3QZ, UK.

ABSTRACT
Recent progress in the theory and practice of voltammetry is surveyed and evaluated. The transformation over the last decade of the level of modelling and simulation of experiments has realised major advances such that electrochemical techniques can be fully developed and applied to real chemical problems of distinct complexity. This review focuses on the topic areas of: multistep electrochemical processes, voltammetry in ionic liquids, the development and interpretation of theories of electron transfer (Butler-Volmer and Marcus-Hush), advances in voltammetric pulse techniques, stochastic random walk models of diffusion, the influence of migration under conditions of low support, voltammetry at rough and porous electrodes, and nanoparticle electrochemistry. The review of the latter field encompasses both the study of nanoparticle-modified electrodes, including stripping voltammetry and the new technique of 'nano-impacts'.

No MeSH data available.


Related in: MedlinePlus

Examples of two different definitions of boundary conditions in a random walk simulation. The grid in (B) is displaced relative to the boundary.
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fig14: Examples of two different definitions of boundary conditions in a random walk simulation. The grid in (B) is displaced relative to the boundary.

Mentions: To illustrate this problem, we focus on the common case of a random walker on a one-dimensional grid in between two reflecting boundaries; the approach is, however, equally applicable to three dimensions. In the one-dimensional case, the boundary condition at a boundary can be formulated in multiple ways; the most common definition can be seen in Figure 14 A). The closest grid point to the boundary is separated from it by and, during each temporal step dt, the random walker may either remain on this position or perform a step away from the boundary. In this case, the reflection at the boundary has to be divided into two independent first passage problems: the diffusive movement to the boundary surface and the movement back to the initial position of this step. Mathematically, however, the expected time of such a reflection, dt0, does not equal the time, dt, as it is presumed in the formulation of the boundary condition. Using Equation 43, we obtain:48


Recent Advances in Voltammetry.

Batchelor-McAuley C, Kätelhön E, Barnes EO, Compton RG, Laborda E, Molina A - ChemistryOpen (2015)

Examples of two different definitions of boundary conditions in a random walk simulation. The grid in (B) is displaced relative to the boundary.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4522172&req=5

fig14: Examples of two different definitions of boundary conditions in a random walk simulation. The grid in (B) is displaced relative to the boundary.
Mentions: To illustrate this problem, we focus on the common case of a random walker on a one-dimensional grid in between two reflecting boundaries; the approach is, however, equally applicable to three dimensions. In the one-dimensional case, the boundary condition at a boundary can be formulated in multiple ways; the most common definition can be seen in Figure 14 A). The closest grid point to the boundary is separated from it by and, during each temporal step dt, the random walker may either remain on this position or perform a step away from the boundary. In this case, the reflection at the boundary has to be divided into two independent first passage problems: the diffusive movement to the boundary surface and the movement back to the initial position of this step. Mathematically, however, the expected time of such a reflection, dt0, does not equal the time, dt, as it is presumed in the formulation of the boundary condition. Using Equation 43, we obtain:48

Bottom Line: The transformation over the last decade of the level of modelling and simulation of experiments has realised major advances such that electrochemical techniques can be fully developed and applied to real chemical problems of distinct complexity.This review focuses on the topic areas of: multistep electrochemical processes, voltammetry in ionic liquids, the development and interpretation of theories of electron transfer (Butler-Volmer and Marcus-Hush), advances in voltammetric pulse techniques, stochastic random walk models of diffusion, the influence of migration under conditions of low support, voltammetry at rough and porous electrodes, and nanoparticle electrochemistry.The review of the latter field encompasses both the study of nanoparticle-modified electrodes, including stripping voltammetry and the new technique of 'nano-impacts'.

View Article: PubMed Central - PubMed

Affiliation: Department of Chemistry, Physical and Theoretical Chemistry Laboratory, University of Oxford South Parks Road, Oxford, OX1 3QZ, UK.

ABSTRACT
Recent progress in the theory and practice of voltammetry is surveyed and evaluated. The transformation over the last decade of the level of modelling and simulation of experiments has realised major advances such that electrochemical techniques can be fully developed and applied to real chemical problems of distinct complexity. This review focuses on the topic areas of: multistep electrochemical processes, voltammetry in ionic liquids, the development and interpretation of theories of electron transfer (Butler-Volmer and Marcus-Hush), advances in voltammetric pulse techniques, stochastic random walk models of diffusion, the influence of migration under conditions of low support, voltammetry at rough and porous electrodes, and nanoparticle electrochemistry. The review of the latter field encompasses both the study of nanoparticle-modified electrodes, including stripping voltammetry and the new technique of 'nano-impacts'.

No MeSH data available.


Related in: MedlinePlus