Cargando…

Relationship between the Atomic Structure and Electrochemistry. 1. Electric Force, Standard Reduction Potential E°, and Standard Reaction Gibbs Free Energy ΔG°

[Image: see text] The relationship among the standard reaction Gibbs free energy ΔG°, the standard reduction potential E°, and the atomic structure parameters of radius, nuclear charge, and isoelectronic orbitals nl is accomplished through the attraction electric force F(elec). In relationship with...

Descripción completa

Detalles Bibliográficos
Autores principales: Campero, Antonio, Díaz Ponce, Javier Alejandro
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2020
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7271030/
https://www.ncbi.nlm.nih.gov/pubmed/32548383
http://dx.doi.org/10.1021/acsomega.0c00257
Descripción
Sumario:[Image: see text] The relationship among the standard reaction Gibbs free energy ΔG°, the standard reduction potential E°, and the atomic structure parameters of radius, nuclear charge, and isoelectronic orbitals nl is accomplished through the attraction electric force F(elec). In relationship with E°, it was necessary to define two new reference scales: E(0)(°) with a final state of E° in the element, which allowed to have a parabolic trend of ΔG° versus F(elec), and E(°,0) whose final state is the ion with a more negative charge (e.g., −1, –2, −3). The relationship with ΔG° is related to the concept of chemical stability, and the relationship with E(°,0) is more related to the concept of electronegativity. In relationship with ΔG°, it was necessary to predict the values of possible new cations and noncommon cations in order to find a better trend of ΔG° versus F(elec), whose stability is analyzed by Frost diagrams of the isoelectronic series. This dependence of ΔG° on F(elec) is split into two terms. The first term indicates the behavior of the minimum of ΔG° for each isoelectronic orbital nl, while the second term deals with the parabolic trend of this orbital. For the minima of the configuration np(6), a hysteresis behavior of the minima of ΔG° is found: an exponential behavior from periods 1 and 2 and a sigmoidal behavior from periods 5 and 4 to interpolate period 3. It is also found that the proximity of unfilled np or (n + 1)s orbitals induces instability of the ion in configurations ns(2)/nd(2)/4f(2) and nd(10)/nd(8)(n + 1)s(2), respectively. On the contrary, the stability of the orbitals np(6) does not depend on the neighboring empty (n + 1)s(0) orbitals. Both phenomena can be explained by the stability of the configuration of noble gas np(6) and the nd(10)(n + 1)s(2) configuration. We have also found that it is possible to increase the reduction potential E(°,0) (macroscopic electronegativity), although the electric force F(elec) decreases because the orbital overlap influences the electronegativity.