Reciprocal Derivative Chronopotentiometry with Programmed Current: Influence of the Reversibility

Molina, Á.; González, Joaquı́n; Moreno, Marién M.

doi:10.1002/1521-4109(200202)14:4<281::aid-elan281>3.0.co;2-9

Cited by 13 publications

(10 citation statements)

References 27 publications

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“…Although earlier pioneering reports on the derivative approach in electrochemistry are found in the reference sections in our previous reports in electronalyticalchemistry [11][12][13][14][15], the approach with derivatives is not only limited to electrochemical methods but also have extended to other various fields of science and engineering [23][24][25][26][27]33]. These reviews and earlier articles introduces basics of the method and techniques of signal processing [2-4, 28, 34], as applied to spectroscopic and spectrophotometric data [2][3][4][5][6][7][8][9]34], electrochemical data [10][11][12][13][14][15][16][17][18][19][20][21], and other signals from seismic data [23] and data from biomechanics measurements [24][25][26][27]33]. Several group [3,6] extended the derivatives to as high as fourth order for enhanced peak resolutions.…”

Section: Backgroundsmentioning

confidence: 99%

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Advances in Derivative Voltammetry - A Search for Diagnostic Criteria of Several Electrochemical Reaction Mechanisms

Kim¹

2021

Analytical Chemistry - Advancement, Perspectives and Applications

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New methods for analysis of current-potential curves in terms of their derivatives are presented for studying various types of electrode processes – such as simple electron transfer reactions (reversible, quasi-reversible, and irreversible electron transfer) as well as chemically coupled electron transfer reactions along with a diagnostic scheme for differentiating these various types of electrochemical reaction mechanisms. Expressions for first- and higher order derivatives are derived from theoretical analytical solutions for currents for the different types of electrode mechanisms. The derivative curves are analyzed in terms of various parameters which characterize peak shape or peak symmetry with an emphasis on the second derivatives with well-defined anodic and cathodic peaks. Second derivatives can yield, in a simpler manner, the symmetry ratios; i.e., a ratio of anodic to cathodic peak-currents (ipa/ipc), and a ratio of anodic to cathodic peak-widths (Wpa/wpc) and a ratio of anodic to cathodic peak potential differences (ΔEpa/ΔEpc) or a peak separation (Epa-Epc) are evaluated, and these ratio can be related to kinetic parameters associated with a particular types of electrode mechanisms. Peaks are found to be symmetrical for a simple reversible electron transfer process (Er). However, peaks become asymmetrical when the electron transfer become slower (namely, irreversible, Eirr) or e− transfer reaction is coupled with homogeneous chemical reactions such as a prior reaction (CEr) or a follower-up reaction (ECr). From measured values of such symmetry ratios above, one can gain insight to the nature of the electrochemical systems enabling us to determine various kinetic parameters associated with a system. A diagnostic criteria for assigning an electrode mechanism is devised based on the values of asymmetry parameters measured, which are unity for a simple reversible electron transfer process.

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Section: Backgroundsmentioning

confidence: 99%

“…In the field of electrochemical analysis, the derivative approach has been applied to potentiometric [10,16] as well as to voltammetric measurements [10][11][12][13][14][15][16][17][18][19][20][21][22] with the enhanced resolution and better signal-to-noise (S/N) ratios.…”

Section: Backgroundsmentioning

confidence: 99%

Advances in Derivative Voltammetry - A Search for Diagnostic Criteria of Several Electrochemical Reaction Mechanisms

Kim¹

2021

Analytical Chemistry - Advancement, Perspectives and Applications

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“…(T1.7), (T1.8), (3) and (4)) [1,2,[13][14][15][16][17], such that for the system of a single polarized interface we have the following expressions…”

Section: > > ;mentioning

confidence: 99%

“…For the first system, a transposition of the theory already existent for charge transfer processes at electrode/solution interfaces has been made, whereas for the second the complete theory is developed here, pointing out that both uptake and stripping transition times are independent of whether the system has one or two polarized interfaces. In RCP and CRDCP techniques, a constant or variable with time current flux is applied and then reversed when the corresponding transition time is reached with no re-establishing of the equilibrium, and the E-t and dt/dE-E curves corresponding to the direct and reverse charge transfer processes are plotted vs the potential [11][12][13][14][15][16][17].…”

Section: Introductionmentioning

confidence: 99%

“…Thus, it provides the same information as CV, but the mathematical treatment is simpler. It allows the evaluation of thermodynamic, kinetic and analytical parameters for both direct and reverse processes from the peak coordinates and, furthermore, the ratio of heights and half-peak widths for both direct and reverse processes provide very simple and reliable criteria to analyze the reversibility [13][14][15][16][17].…”

Section: Introductionmentioning

confidence: 99%

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Study of ion transfer through liquid membrane systems by Current Reversal Chronopotentiometric techniques

Torralba

Molina

Ortuño

et al. 2011

Journal of Electroanalytical Chemistry

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Electrochemistry of Cadmium

Stroka

Maksymiuk

Galus

2006

Encyclopedia of Electrochemistry

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The sections in this article are Double‐layer Properties of Cadmium Electrodes Electrochemical Properties and Kinetics of the Cd ( II )/ Cd ( Hg ) Systems Electrochemistry in Aqueous Solutions Kinetics of Simple Ions Influence of a Catalyst Influence of Inhibitors Electrochemistry in Mixed and Nonaqueous Solvents Electrochemical Properties of the Cadmium Complexes Determination of Stability Constants Electrochemical Preparation of Cadmium Complexes Preparation and Electrochemical Properties of Cadmium Chalcogenides CdS CdSe Cd Te Properties of Cadmium Intermetallic Compounds Cadmium Underpotential Deposition and Electrodeposition on Solid Electrodes Deposition of Cd on Cadmium Electrode Electrodeposition of Cd on Other Solid Substrates Gold Platinum Silver Copper Silicon Other Substrates Passivation and Corrosion of Cadmium Passivation of Cadmium Electrode Corrosion of Cadmium Applied Electrochemistry Batteries Cadmium–Mercuric Oxide Primary Cells Cadmium–Nickel Oxide ( Ni – Cd ) Secondary Cells Cadmium–Silver Oxide Secondary Cells Application in Electrochemical Sensors Potentiometric Sensors Amperometric‐voltammetric Sensors

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Reciprocal Derivative Chronopotentiometry with Programmed Current: Influence of the Reversibility

Cited by 13 publications

References 27 publications

Advances in Derivative Voltammetry - A Search for Diagnostic Criteria of Several Electrochemical Reaction Mechanisms

Advances in Derivative Voltammetry - A Search for Diagnostic Criteria of Several Electrochemical Reaction Mechanisms

Study of ion transfer through liquid membrane systems by Current Reversal Chronopotentiometric techniques

Electrochemistry of Cadmium

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