Acid-base concepts Lewis theory

For a monograph on Lewis acid-base theory, see Jensen, W.B. The Lewis Acid-Base Concept Wiley NY, 1980. For a discussion of the definitions of Lewis acid and base, see Jensen, W.B. Chem. Rev, 1978, 78, 1. 

Resonance such as (5.28a)-(5.28c) is inherently a quantal phenomenon, with no classical counterpart. In NBO language, each of the resonance interactions (5.28a)-(5.28c) corresponds to a donor-acceptor interaction between a nominally filled (donor Lewis-type) and unfilled (acceptor non-Lewis-type) orbital, the orbital counterpart of G. N. Lewis s general acid-base concept. As mentioned above, Lewis and Werner (among others) had well recognized the presence of such valence-like forces in the dative or coordinative binding of free molecular species. Thus, the advent of quantum mechanics and Pauling s resonance theory served to secure and justify chemical concepts that had previously been established on the basis of compelling chemical evidence. 

I. Definition of Basicity A. General Comments on the Acid-base Concept The current general definition of the acid-base concept is based on the definitions by Bronsted and Lewis. According to Bronsted s theory (1923) an acid-base interaction can be described by the general relation (1) ... 

Empirically measured parameters are additional solvent properties, which have been developed through the efforts of physical chemists and physical organic chemists in somewhat different, but to some extent related, directions. They have been based largely on the Lewis acid base concept, which was defined by G. N. Lewis. The concept originally involved the theory of chemical bonding which stated that a chemical bond must involve a shared electron pair. Thus, an atom in a molecule or ion which had an incomplete octet in the early theory, or a vacant orbital in quantum mechanical terms, would act as an electron pair acceptor (an acid) from an atom in a molecule or ion which had a complete octet or a lone pair of electrons (a base). Further developments have included the concepts of partial electron transfer and a continuum of bonding from the purely electrostatic bonds of ion-ion interactions to the purely covalent bonds of atoms and molecules. The development of the concept has been extensively described (see Ref. 11 for details). 

Lewis acid-base theory— To describe reactions where no proton transfer occurs, - Lewis has proposed a more general acid-base concept where an acid is a molecule or an ion with an incomplete outer electron sphere, i.e., an acceptor of electron pairs. A base is a molecule or an ion having a free electron pair, i.e., an electron pair donor. A neutralization reaction is characterized by the formation of a coordination or covalent bond. The following reactions illustrate the Lewis-definition ... 

Refs. [i] Finston H, Rychtman AC (1982) A new view of current acid-base theories. Wiley, New York [ii] Hand CW, BlewittHL (1986) Acid-base chemistry. Macmillan, New York [iii] )ensen WB (1980) The Lewis acid-base concepts. Wiley, New York [iv] Tanabe K (1989) New solid acids and bases. Elsevier, Amsterdam... 

R, Robinson, Outline of an Electrochemical (Electronic) Theory of the Course of Organic Reactions, Institute of Chemistry, London, 1932, pp. 12-15 W. B. Jensen, The Lewis Acid-Base Concepts, Wiley-Interscience, New York, 1980, pp. 58-59. 

W. B. Jensen, The Lewis Acid-Base Concepts An Overview, Wiley-Interscience, New York, 1980, and H. L Finston and Allen C. Rychtman, A New View of Current Acid-Base Theories, John Wiley Sons, New York, 1982, provide good overviews of the history of acid-base theories and critical discussions of the different theories. R. G. Pearson s Hard and Soft Acids and Bases, Dowden, Hutchinson, Ross, Stroudsburg, PA, 1973, is a review by one of the leading exponents of HSAB. For other viewpoints, the references provided in this chapter should be consulted. 

A history of acid-base theories was given by Jensen, W. B. The Lewis Acid-Base Concepts An Overview Wiley-Interscience New York, 1980. 

The acid-base concept, either in the limited interpretation of the Bronsted-Lowry theory or in the more general sense of the Lewis theory, is one of the most useful classification schemes in chemistry and a tool for systematizing the relationship between structure and reactivity. In this section we examine how this general concept can be applied to solid surfaces [29], From the most general (Lewis) point of view, a surface is classified as acidic (electron acceptor) or basic (electron donor) according to the direction of net electron transfer that results in the formation of new chemical bonds with an adsorbed molecule. 

Acid-base concepts share some features with seemingly different types of interactions complexing, precipitation, and even redox. Comparison of these through theories of Bronsted, Lewis, Usanovich, and Lux-Flood extends our use of the electronic interpretations of... 

In the previous section, we presented ideas about the molecular structures of acids and bases. In 1923, G. N. Lewis proposed an acid-base theory closely related to bonding and structure. The Lewis acid-base theory is not limited to reactions involving H and OH It extends acid-base concepts to reactions in gases and in solids. It is especially important in describing certain reactions between organic molecules. 

The Arrhenius definition of an acid and a base attributed acidity to the presence of H" (aq), and alkalinity to OH (aq). Br0nsted-Lowry theory generalizes the acid-base concept by focusing on proton transfer, rather than on particular aqueous ions. Here, we discuss an attempt to generalize it further by focusing on the changes in electronic structure that occur when acid-base reactions take place, ideas introduced by G. N. Lewis. 

This theory was advanced by G. N. Lewis (1916, 1923, 1938) as a more general concept. In his classic monograph of 1923 he considered and rejected both the protonic and solvent system theories as too restrictive. An acid-base reaction in the Lewis sense means the completion of the stable electronic configuration of the acceptor atom of the acid by an electron pair from the base. Thus ... 

Electrophilicity — (1) The property of being - electrophilic (see -> electrophile). (2) The relative reactivity of an electrophilic reagent. (It is also sometimes referred to as electrophilic power ) Qualitatively, the concept is related to Lewis acidity (- acid-base theories). However, whereas Lewis acidity is measured by relative - equilibrium constants, electrophilicity is measured by relative -> rate constants for reactions of different electrophilic... 

There were some attempts to estimate acid-base properties for oxide compounds, both solids and melts. The most popular of them is Lux-Flood s acid-base theory.2,3 This concept seems to be more effective for estimating the acid-base characteristics of anhydrous borates and of some promising solvents for the flux growth of borate crystals. According to Lewis-Lux s equation,... 

E. Concepts of Acids and Bases — Brpnsted-Lowry approaches, Lewis theory, solvent system approaches... 

Arrhenius in 1887 was the first person to give a definition of an acid and a base. According to him, an acid is one that gives rise to excess of in aqueous solution, whereas a base gives rise to excess of OH in solution. This was modified by Bronsted-Lowry in 1923 such that a proton donor was defined as an acid and a proton acceptor as a base. They also introduced the familiar concept of the conjugate acid-base pair. The final refinement to the acid-base theory was completed by Lewis in 1923, who extended the concept that acid is an acceptor of electron pairs while base is a donor of electron pairs. 

In the simple theory based on Lewis concepts exemplified above, the key aspects are an empty orbital on one atom and a filled orbital (with a pair of electrons present, the lone pair) on the other. Many of the ligand species providing the lone pair are considered bases in the classical Brpnsted-Lowry concept of acids and bases (which has as its focus the transfer... 

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