Campero Antonio, Díaz Ponce Javier Alejandro
Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa. Av. San Rafael Atlixco 186, Col. Vicentina, Mexico City C.P. 09340, Mexico.
Departamento de Física, Universidad Autónoma Metropolitana-Iztapalapa. Av. San Rafael Atlixco 186, Col. Vicentina, Mexico City C.P. 09340, Mexico.
ACS Omega. 2020 May 18;5(21):12046-12056. doi: 10.1021/acsomega.0c00257. eCollection 2020 Jun 2.
The relationship among the standard reaction Gibbs free energy Δ°, the standard reduction potential °, and the atomic structure parameters of radius, nuclear charge, and isoelectronic orbitals l is accomplished through the attraction electric force . In relationship with °, it was necessary to define two new reference scales: with a final state of ° in the element, which allowed to have a parabolic trend of Δ° versus , and whose final state is the ion with a more negative charge (e.g., -1, -2, -3). The relationship with Δ° is related to the concept of chemical stability, and the relationship with is more related to the concept of electronegativity. In relationship with Δ°, it was necessary to predict the values of possible new cations and noncommon cations in order to find a better trend of Δ° versus , whose stability is analyzed by Frost diagrams of the isoelectronic series. This dependence of Δ° on is split into two terms. The first term indicates the behavior of the minimum of Δ° for each isoelectronic orbital l, while the second term deals with the parabolic trend of this orbital. For the minima of the configuration p, a hysteresis behavior of the minima of Δ° 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 p or ( + 1)s orbitals induces instability of the ion in configurations s/d/4f and d/d( + 1)s, respectively. On the contrary, the stability of the orbitals p does not depend on the neighboring empty ( + 1)s orbitals. Both phenomena can be explained by the stability of the configuration of noble gas p and the d( + 1)s configuration. We have also found that it is possible to increase the reduction potential (macroscopic electronegativity), although the electric force decreases because the orbital overlap influences the electronegativity.
标准反应吉布斯自由能Δ°、标准还原电势°与半径、核电荷和等电子轨道l的原子结构参数之间的关系是通过吸引电力来实现的。与°相关，有必要定义两个新的参考标度：一个是元素中°处于最终状态的标度，这使得Δ°与呈现抛物线趋势；另一个是最终状态为带更负电荷离子（如-1、-2、-3）的标度。与Δ°的关系涉及化学稳定性概念，与的关系则更多地与电负性概念相关。与Δ°相关时，有必要预测可能的新阳离子和非常见阳离子的值，以便找到Δ°与更好的趋势，其稳定性通过等电子系列的弗罗斯特图进行分析。Δ°对的这种依赖性分为两项。第一项表示每个等电子轨道l的Δ°最小值的行为，而第二项处理该轨道的抛物线趋势。对于p构型的最小值，发现了Δ°最小值的滞后行为：第1和第2周期呈指数行为，第5和第4周期到第3周期呈S形行为。还发现未填充的p或( + 1)s轨道的接近分别会导致s/d/4f和d/d( + 1)s构型中离子的不稳定性。相反，p轨道的稳定性不依赖于相邻的空( + 1)s轨道。这两种现象都可以用稀有气体p构型和d( + 1)s构型的稳定性来解释。我们还发现，尽管电力减小，但由于轨道重叠会影响电负性，所以有可能提高还原电势（宏观电负性）。
