Electronegativity provides the relationship between formal charge, oxidation state, and actual charge

IF 1.8 3区 化学 Q1 HISTORY & PHILOSOPHY OF SCIENCE Foundations of Chemistry Pub Date : 2022-10-29 DOI:10.1007/s10698-022-09447-6
Balakrishnan Viswanathan, M. Shajahan Gulam Razul
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Abstract

Formal charge and oxidation state are two means of estimating the charge of an atom in a molecule. Though these concepts have very different origins—formal charge is derived from the ball-and-hook model of bonding and oxidation state is based on the ionic approximation of molecules—they are used to predict reactivity and other molecular properties through their properties as charges. In this submission, it is shown that formal charge and oxidation state are two extreme descriptions of bonding: formal charge represents zero charge transfer between atoms while oxidation state represents complete charge transfer in each bond. These ‘localised electron approximations’ form an incomplete picture of atomic charge. Electronegativity measures the extent of polarity in real bonds; this concept can be introduced to polarise bonds relative to the ‘equal sharing model’. It is shown that the various electronegativity models are fundamentally related. We chose two models to demonstrate numerically that polar bonds yield charges intermediate between the localised electron approximations: Pauling and Mulliken. It is shown that probabilistic interpretation of the Pauling scale (‘scaled Pauling’ method) and use of asymmetric chemical potential (‘modified Mulliken’ method) lead to atomic charges that closely approximate experimental values using simple ‘back of the envelope’ calculations. It is seen that formal charge, oxidation state, and electronegativity-interpolated charge lie on a continuum and are mathematically related. It is therefore concluded that electronegativity introduces (quantum) delocalisation to the localised (classical) picture of electron bonding.

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电负性提供了形式电荷、氧化态和实际电荷之间的关系
形式电荷和氧化态是估计分子中原子电荷的两种方法。虽然这两个概念有着非常不同的起源——形式电荷来源于键合的球钩模型,而氧化态是基于分子的离子近似——但它们都被用来通过它们作为电荷的性质来预测反应性和其他分子性质。本文表明,形式电荷和氧化态是键的两种极端描述:形式电荷表示原子之间的零电荷转移,而氧化态表示每个键中完全的电荷转移。这些“局域电子近似”形成了原子电荷的不完整图像。电负性衡量的是真实键的极性程度;这个概念可以被引入到相对于“相等共享模型”的键极化中。结果表明,各种电负性模型是基本相关的。我们选择了两个模型来数值证明极性键产生的电荷介于局域电子近似之间:鲍林和穆里肯。结果表明,鲍林尺度的概率解释(“缩放鲍林”方法)和不对称化学势的使用(“改进的Mulliken”方法)导致原子电荷非常接近使用简单的“信封背面”计算的实验值。可见形式电荷、氧化态和电负性内插电荷在一个连续体上,并且在数学上是相关的。因此可以得出结论,电负性引入(量子)离域到局域(经典)电子成键图。
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Foundations of Chemistry
Foundations of Chemistry HISTORY & PHILOSOPHY OF SCIENCE-
自引率
22.20%
发文量
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期刊介绍: Foundations of Chemistry is an international journal which seeks to provide an interdisciplinary forum where chemists, biochemists, philosophers, historians, educators and sociologists with an interest in foundational issues can discuss conceptual and fundamental issues which relate to the `central science'' of chemistry. Such issues include the autonomous role of chemistry between physics and biology and the question of the reduction of chemistry to quantum mechanics. The journal will publish peer-reviewed academic articles on a wide range of subdisciplines, among others: chemical models, chemical language, metaphors, and theoretical terms; chemical evolution and artificial self-replication; industrial application, environmental concern, and the social and ethical aspects of chemistry''s professionalism; the nature of modeling and the role of instrumentation in chemistry; institutional studies and the nature of explanation in the chemical sciences; theoretical chemistry, molecular structure and chaos; the issue of realism; molecular biology, bio-inorganic chemistry; historical studies on ancient chemistry, medieval chemistry and alchemy; philosophical and historical articles; and material of a didactic nature relating to all topics in the chemical sciences. Foundations of Chemistry plans to feature special issues devoted to particular themes, and will contain book reviews and discussion notes. Audience: chemists, biochemists, philosophers, historians, chemical educators, sociologists, and other scientists with an interest in the foundational issues of science.
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