The Use of the Legendre Transform in Chemical Thermodynamics: A Powerful Tool

This article highlights the importance of the Legendre transform (LT) in thermodynamics, demonstrating its role in replacing nonmeasurable variables, such as entropy, with experimentally accessible coordinates. Despite its essential nature, the LT is rarely covered in Physical Chemistry textbooks, a gap noted in the literature as well. The article clarifies the LT, applies it in detail to Thermodynamics, discusses its connection to the extensiveness of internal energy, and proposes a mnemonic rule for obtaining the differential forms of thermodynamic potentials from the Gibbs equation. It is also shown that the total LT of an extensive function is zero, which leads to Euler's relation and reinforces the relevance of including the topic in teaching materials.

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Publication Details

Journal
Israel Journal of Chemistry
Published
2026-03-01
DOI
https://doi.org/10.1002/ijch.70010
Primary Topic
Complex Systems and Dynamics
Type
article
Field-Weighted Citation Impact
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article

The Use of the Legendre Transform in Chemical Thermodynamics: A Powerful Tool

Luiz Daniel Alves Rios, Norberto de Kássio Vieira Monteiro, Renato Veríssimo de Oliveira
Israel Journal of Chemistry
Complex Systems and Dynamics
article

The Use of the Legendre Transform in Chemical Thermodynamics: A Powerful Tool

Luiz Daniel Alves Rios, Norberto de Kássio Vieira Monteiro, Renato Veríssimo de Oliveira
article en

Abstract

This article highlights the importance of the Legendre transform (LT) in thermodynamics, demonstrating its role in replacing nonmeasurable variables, such as entropy, with experimentally accessible coordinates. Despite its essential nature, the LT is rarely covered in Physical Chemistry textbooks, a gap noted in the literature as well. The article clarifies the LT, applies it in detail to Thermodynamics, discusses its connection to the extensiveness of internal energy, and proposes a mnemonic rule for obtaining the differential forms of thermodynamic potentials from the Gibbs equation. It is also shown that the total LT of an extensive function is zero, which leads to Euler's relation and reinforces the relevance of including the topic in teaching materials.

Israel Journal of ChemistryVol. 66(2)
Universidade Federal do Ceará (BR), State University of Vale do Acaraú (BR)
Openalex Percentile: Top 4%
Complex Systems and Dynamics
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