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Voltammetry: Factors Affecting Measurements

Voltammetry: Factors Affecting Measurements

A current produced due to the redox reactions of the analyte at the working and auxiliary electrodes is called a faradaic current. The reaction can be divided into two types. The current generated due to the reduction of the analyte is called cathodic current, and it carries a positive charge. In contrast, the current produced by analyte oxidation is known as an anodic current, and it has a negative charge. The applied potential at the working electrode determines the faradaic current flow, and...

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Polarography is a classical voltammetric technique used to analyze electrochemical reactions. This method applies a linear potential sweep to a dropping mercury electrode (DME), and the resulting current is measured. A dropping mercury electrode is commonly used as the working electrode in polarography. It consists of a capillary tube filled with mercury, where the tiny droplet forms at the tip. This droplet continuously drops from the capillary, creating a new electrode surface for each...

Voltammograms: Overview

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Voltammograms are current plots as a function of applied potential, offering insights into electrochemical systems. The shape of a voltammogram depends on how the current is measured and whether convection (heat transfer by fluid movement) is present or absent.
Shapes of Voltammograms

Voltammetry: Overview

Voltammetry: Overview

Voltammetry is an electroanalytical technique in which the current flowing through an electrochemical cell is measured as a function of applied potential, typically under conditions of concentration polarization. The technique provides valuable information about redox-active species, and the current response is plotted as a voltammogram.
A voltammetric cell uses three electrodes: a working electrode, a reference electrode, and an auxiliary electrode. The redox reactions occur in the working...

Voltammetric Techniques: Pulse Voltammetry

Voltammetric Techniques: Pulse Voltammetry

Differential-pulse voltammetry (DPV) is a type of voltammetry that involves applying a series of voltage pulses to an electrochemical cell while measuring the resulting current. In DPV, the differential pulse or small potential pulses are superimposed on a linear potential sweep. The magnitude of these pulses is typically small, often in the millivolt range. Each voltage pulse lasts a short duration, usually in the order of a few milliseconds, and is applied at regular intervals along the...

Voltammetric Techniques: Cyclic Voltammetry

Voltammetric Techniques: Cyclic Voltammetry

Cyclic voltammetry (CV) is an electrochemical technique used to investigate the redox properties of a chemical species. It involves measuring the current response of an electrochemical cell as a function of the applied potential. The setup for cyclic voltammetry typically consists of a working electrode, a reference electrode, and a counter electrode—all immersed in an electrolyte solution. The working electrode is where the redox reaction of interest occurs, while the reference electrode...

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Related Experiment Video

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Precise Electrochemical Sizing of Individual Electro-Inactive Particles

Precise Electrochemical Sizing of Individual Electro-Inactive Particles

Published on: August 4, 2023

Migration and diffusion coupled with a fast preceding reaction. Voltammetry at a microelectrode.

A Jaworski¹, M Donten, Z Stojek

¹Department of Chemistry, University of Warsaw, ul. Pasteura 1, 02-093 Warsaw, Poland.

Analytical Chemistry

|June 14, 2011

Summary

This study models hydrogen ion voltammetry, considering chemical reactions and ion transport. The mathematical model accurately predicts experimental results for both strong and weak acids.

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Area of Science:

Electrochemistry
Chemical kinetics
Mathematical modeling

Background:

Voltammetry is a key electrochemical technique.
The hydrogen couple (H+/H2) presents complex electrochemical behavior.
Preceding chemical reactions and ion transport influence voltammetric signals.

Purpose of the Study:

To develop a mathematical model for simulating voltammetry.
To account for fast preceding reactions and mixed ion transport.
To validate the model against experimental data for acids.

Main Methods:

A simulation-based mathematical model was developed.
The model incorporates fast preceding chemical reactions.
It also accounts for mixed diffusional and migrational transport of ions.

Main Results:

Computed voltammograms align with experimental data.
The model successfully simulates the hydrogen couple.
Acid reduction at platinum microelectrodes was accurately modeled.

Conclusions:

The mathematical model effectively describes voltammetry.
It handles preceding reactions and mixed ion transport.
The model's assumption of anion-independent hydrogen ion flux is validated.