Lewis valency Definition

G. N. Lewis, Valence and the Structure of Atoms and Molecules, American Chemical Society Monograph, The Chemical Catalog Co., New York, 1923. Lewis also gave a definition equivalent to that of Bronsted at this time, but he considered the electron-pair definition to be more general. 

As we will learn later in this section, these processes are practically very important. The sites of highest catalytic reactivity are often the edged corner positions. The concentration of such sites is enhanced by Freund s adaption processes. The effective charges on the broken-bond surfaces are such that they induce Lewis acid- or Lewis basic-type reactivity features. The local charge excesses on an ionic surface, considered to exist as a series of point charges, can be estimated using Pauling s valency definitions 1 1. 

In 1923. Lewis published a classic book (later reprinted by Dover Publications) titled Valence and the Structure of Atoms and Molecules. Here, in Lewis s characteristically lucid style, we find many of the basic principles of covalent bonding discussed in this chapter. Included are electron-dot structures, the octet rule, and the concept of electronegativity. Here too is the Lewis definition of acids and bases (Chapter 15). That same year, Lewis published with Merle Randall a text called Thermodynamics and the Free Energy of Chemical Substances. Today, a revised edition of that text is still used in graduate courses in chemistry. 

It was G. N. Lewis who extended the definitions of acids and bases still further, the underlying concept being derived from the electronic theory of valence. It provided a much broader definition of acids and bases than that provided by the Lowry-Bronsted concept, as it furnished explanations not in terms of ionic reactions but in terms of bond formation. According to this theory, an acid is any species that is capable of accepting a pair of electrons to establish a coordinate bond, whilst a base is any species capable of donating a pair of electrons to form such a coordinate bond. A Lewis acid is an electron pair acceptor, while a Lewis base is an electron pair donor. These definitions of acids and bases fit the Lowry-Bronsted and Arrhenius theories, and cover many other substances which could not be classified as acids or bases in terms of proton transfer. 

Before studying some examples more closely, let us consider some cases which are not listed in Table 13. There are numerous compounds SnX2 which are definitely monomeric but are nevertheless no carbene analogs since their valence electron number at the tin atom is at least eight. These compounds contain chelating ligands which can stabilize the carbenoid tin atom due to intramolecular Lewis acid-base interactions as shown by structure A and B (see also Chapter 3). 

There is no clear rigorous definition of an atom in a molecule in conventional bonding models. In the Lewis model an atom in a molecule is defined as consisting of its core (nucleus and inner-shell electrons) and the valence shell electrons. But some of the valence shell electrons of each atom are considered to be shared with another atom, and how these electrons should be partitioned between the two atoms so as to describe the atoms as they exist in the molecule is not defined. 

Lewis defined a base as an electron pair donor and an acid as an electron pair acceptor. Lewis electron pair donor was the same as Bronsted-Lowry s proton acceptor, and therefore, was an equivalent way of defining a base. Lewis acids were defined as a substance with an empty valence shell that could accommodate a pair of electrons. This definition broadened the Bronsted-Lowry definition of an acid. The three definitions of acids and bases are summarized in Table 13.3. 

A Lewis acid is defined as a species that can accept a pair of electrons from a base. This is a very general definition of an acid proposed by G. N. Lewis in 1923 (LI). In the case of structure (I), the Al atom is not completely coordinated, i.e., it is bonded to three oxygen atoms instead of four. The aluminum atom thus has a total of six valence electrons instead... 

Since all proton acceptors have an unshared pair of electrons, and since all electron-pair donors can accept a proton, the Lewis and the Bronsted-Lowry definitions of a base are simply different ways of looking at the same property. All Lewis bases are Bronsted-Lowry bases, and all Bronsted-Lowry bases are Lewis bases. The Lewis definition of an acid, however, is considerably more general than the Bronsted-Lowry definition. Lewis acids include not only H+ but also other cations and neutral molecules having vacant valence orbitals that can accept a share in a pair of electrons donated by a Lewis base. 

According to the Lewis definition, an acid is an electron pair acceptor and a base is an electron pair donor. All Bronsted-Lowry bases are also Lewis bases. However, Lewis acids include many species that are not proton acids instead of H+, they have some other electron-deficient species that acts as the electron pair acceptor. An example of a Lewis acid-base reaction is provided by the following equation. In this reaction the boron of BF3 is electron/deficient (it has only six electrons in its valence shell). The oxygen of the ether is a Lewis base and uses a pair of electrons to form a bond to the boron, thus completing boron s octet. 

If hypervalent literally means exceeding the lowest chemical valence, then even NH4+ is hypervalent, despite the fact that the Lewis-Langmuir theory easily accounts for its stability. Furthermore, if the definition of hypervalency is restricted to Groups 15-18, then this artificially excludes species such as SiFs and SiFe, which are isoelectronic and isostructural with PF5 and SFe, respectively. The ambiguities in the original definition have led to several changes. Today, no one would regard NH4+ as hypervalent, while those that consider PF5 and SFe hypervalent would classify SiFs" and SiFe in the same way. 

F 2p character than F 2s character and is also bonding with respect to the FI orbital. This set of orbitals (2cr, 3a) illustrates a central feature of the MO approach. Whereas a simple Lewis structure or valence picture would draw a localized electron pair interaction between two orbitals, the MO picture attributes some bonding character to two separate molecular orbitals. This simple MO diagram illustrates the difficulty of determining a meaningful definition for bond order in a polyatomic molecule. No single MO completely represents the bonding between two atoms. 

The fact that a Lewis acid must be able to accept an electron pair means that it must have either a vacant, low-energy orbital or a polar bond to hydrogen so it can donate H" which has an empty Is orbital). Thus, the Lewis definition of acidity is much broader than the Bronsted-Lowry definition and includes many other species in addition to H. For example, various metal cations such as are Lewis acids because they accept a pair of electrons when they form a bond to a base. In the same way, compounds of group 3A elements such as BF3 and AlCln are Lewis acids because they have unfilled valence orbitals and can accept electron pairs from Lewis bases, as shown in Figure 2.5. Similarly, many transition-metal compounds, such as TiCU, FeCla, ZnCl, and SnCl4, are Lewis acids. 

The final acid-base theory that we shall consider was proposed by chemist Gilbert Lewis in the early 1920s. The Lewis Theory is the most general, including more substances under its definitions than the other theories of acids and bases. A Lewis acid is a substance that accepts a pair of electrons to form a covalent bond. A Lewis base is a substance that provides a pair of electrons to form a covalent bond. In order for a substance to act as a Lewis base, it must have a pair of unshared electrons in its valence shell. An example of this is seen when a hydrogen ion attaches to the unpaired electrons of oxygen in a water molecule, as shown here ... 

The particular virtue of these definitions is that the Lewis acid and the Lewis base strengths are both estimates of the valence of the bond that links the cation with the anion. The most effective bonds will therefore occur between a cation whose Lewis acid strength (Sg) is close to the Lewis base strength (Sb) of the anion. This is known as the Valence Matching Principle. Compounds between badly matched ions, i.e. Be (Sa = 0.5 v.u.) and ClO j" (Sb = 0.08 v.u.), are difficult if not impossible to form as both the cation and the anion will be forced into unusual coordination. If they... 

The final acid-base concept we consider was developed by Gilbert N. Lewis, whose contribution to understanding the importance of valence electron pairs in molecular bonding we discussed in Chapter 9. Whereas the Brpnsted-Lowry concept focuses on the proton in defining a species as an acid or a base, the Lewis concept highlights the role of the electron pair. The Lewis acid-base definition holds that... 

According to the Lewis acid base definition, an acid is an electron pair acceptor. Any compound that has an unfilled valence orbital is a potential Lewis acid. 

The Bronsted acidT)ase definition differs somewhat from the Lewis definition. Rather than focusing on electron acceptors and donors, the Bronsted definition deals with donating or accepting H+ atoms (protons) in chemical reactions. A Bronsted acid is a species that tends to donate protons in a chemical reaction, while a Bronsted base is a species that tends to accept those protons. To accept protons, a Bronsted base must typically have at least one pair of nonbonding valence electrons. 

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