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Standard Electrode Potentials

Standard Electrode Potentials

On comparing the reactivity of silver and lead, it is observed that the two ionic species, Ag+ (aq) and Pb2+ (aq), show a difference in their redox reactivity towards copper: the silver ion undergoes spontaneous reduction, while the lead ion does not. This relative redox activity can be easily quantified in electrochemical cells by a property called cell potential. This property is commonly known as cell voltage in electrochemistry, and it is a measure of the energy which accompanies the charge...

Potentiometry: Types of Electrodes

Potentiometry: Types of Electrodes

Reference electrodes serve as a stable reference point for potentiometric measurements, while indicator and working electrodes react to variations in the composition of a solution.
The Standard Hydrogen Electrode (SHE) is a widely used reference electrode that maintains zero potential across all temperatures. However, its need for a continuous hydrogen gas supply renders it impractical for everyday use.
An alternative to SHE is the Saturated Calomel Electrode (SCE). This electrode features an...

Ladder Diagrams: Redox Equilibria

Ladder Diagrams: Redox Equilibria

Ladder diagrams are useful tools for understanding redox equilibrium reactions, especially the effects of concentration changes on the electrochemical potential of the reaction. The vertical axis in the redox ladder diagrams represents the electrochemical potential, E. The area of predominance is demarcated using the Nernst equation.
Consider the Fe3+/Fe2+ half-reaction, which has a standard-state potential of +0.771 V. At potentials more positive than +0.771 V, Fe3+ predominates, whereas Fe2+...

Electrodes: Overview

Electrodes: Overview

Electrochemical measurements are conducted in an electrochemical cell composed of various components that control and measure the current and potential. One fundamental component is electrodes, conductive materials that enable electron transfer reactions at their surfaces.
There are two main types of electrodes in electrochemical cells. The first type, known as the working or indicator electrode, has a potential that is sensitive to the analyte's concentration and reacts to changes in the...

Redox Reactions

Redox Reactions

Oxidation-reduction or redox reactions involve the transfer of electrons from one molecule or atom to another. When an atom gains an electron, another atom must lose an electron, meaning oxidation and reduction must occur together. Since the redox occurs in pairs, the atom that gets oxidized is also called the reducing agent or reductant, and the atom that is reduced is also called the oxidizing agent or oxidant. A straightforward way to remember the definitions of oxidation and reduction is...

Redox Reactions

Redox Reactions

Redox reactions are vital biochemical processes that underpin energy metabolism in cells. These reactions involve the transfer of electrons between molecules, occurring in tandem as oxidation and reduction. Oxidation refers to the loss of electrons, while reduction denotes their gain. This coupling ensures the seamless flow of electrons through metabolic pathways. For example, in bacterial metabolism, glucose undergoes oxidation to carbon dioxide, while oxygen is simultaneously reduced to...

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Related Experiment Video

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Simple Methods for the Preparation of Non-noble Metal Bulk-electrodes for Electrocatalytic Applications

Simple Methods for the Preparation of Non-noble Metal Bulk-electrodes for Electrocatalytic Applications

Published on: June 21, 2017

Consistent scheme for computing standard hydrogen electrode and redox potentials.

Toru Matsui¹, Yasutaka Kitagawa, Mitsutaka Okumura

¹Department of Chemistry, Graduate School of Science, Osaka University, 1-1 Machikaneyama, Toyonaka, Osaka 560-0043, Japan. matsui@chem.sci.osaka-u.ac.jp

Journal of Computational Chemistry

|August 29, 2012

Summary

A new computational method accurately calculates the standard hydrogen electrode (SHE) potential using experimental pKa values. This approach precisely determines proton Gibbs energy, validating its use for redox potential calculations in aqueous solutions.

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Area of Science:

Computational Chemistry
Electrochemistry
Physical Chemistry

Background:

The standard hydrogen electrode (SHE) is a crucial reference point in electrochemistry.
Accurate determination of SHE potential is essential for understanding redox reactions.
Existing methods for SHE potential calculation can be computationally intensive or rely on experimental data.

Purpose of the Study:

To develop and validate a novel computational procedure for determining the standard hydrogen electrode (SHE) potential in aqueous solutions.
To assess the accuracy of this new scheme by comparing calculated values with experimental data.
To evaluate the performance of different computational methods within the developed scheme.

Main Methods:

A new computational procedure was developed to calculate the Gibbs energy of a proton in aqueous solution.
This procedure utilizes experimental pKa values and Gibbs energy changes from deprotonation reactions of neutral alcohol molecules.
High-level computational methods, including CCSD(T)/aug-cc-pVDZ and B3LYP, were employed.

Main Results:

The CCSD(T)/aug-cc-pVDZ method, using the new scheme, yielded a SHE potential of 4.52 V, closely matching experimental values.
The computational scheme accurately reproduced redox potentials for several typical reactions within approximately 0.1 V.
The B3LYP method also demonstrated excellent accuracy for redox potential calculations using this scheme.

Conclusions:

The developed computational procedure provides a reliable method for calculating the SHE potential.
This approach offers a viable alternative for determining proton Gibbs energy and redox potentials.
Both CCSD(T)/aug-cc-pVDZ and B3LYP methods are suitable for use within this computational scheme.