Arrhenius Lewis

This chapter sets the stage for all of the others by reminding us that the relationship between structure and properties is what chemistry is all about It begins with a review of Lewis structures moves to a discussion of the Arrhenius Brpnsted-Lowry and Lewis pictures of acids and bases and the effects of structure on acidity and basicity... 

The Lewis definitions of acids and bases provide for a more general view of acid-base reactions than either the Arrhenius or Br0nsted-Lowry pic ture A Lewis acid is an electron pair acceptor A Lewis base is an electron pair donor The Lewis approach incorporates the Br0nsted-Lowry approach as a subcategory m which the atom that accepts the electron pair m the Lewis acid is a proton... 

Achiral (Section 7 1) Opposite of chiral An achiral object is supenmposable on its mirror image Acid According to the Arrhenius definition (Section 1 12) a substance that ionizes in water to produce protons Accord mg to the Br0nsted-Lowry definition (Section 1 13) a sub stance that donates a proton to some other substance According to the Lewis definition (Section 1 17) an electron pair acceptor... 

A note on good practice The entities that are regarded as acids and bases are different in each theory. In the Lewis theory, the proton is an acid in the Bronsted theory, the species that supplies the proton is the acid. In both the Lewis and Bronsted theories, the species that accepts a proton is a base in the Arrhenius theory, the species that supplies the proton acceptor is the base (Fig. 10.61. 

Since Arrhenius, definitions have extended the scope of what we mean by acids and bases. These theories include the proton transfer definition of Bronsted-Lowry (Bronsted, 1923 Lowry, 1923a,b), the solvent system concept (Day Selbin, 1969), the Lux-Flood theory for oxide melts, the electron pair donor and acceptor definition of Lewis (1923, 1938) and the broad theory of Usanovich (1939). These theories are described in more detail below. 

The various acid-base definitions are summarized in the Venn diagram (Fig. 2.1). From this it can be seen that the Usanovich definition subsumes the Lewis definition, which in turn subsumes all other definitions (i.e. Arrhenius, Bronsted-Lowry, Germann-Cady-Elsey, Lux-Flood). 

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. 

A) In addition to the more modem Bronsted and Lewis theories, it is important not to forget the classic Arrhenius theory in its modern form, the so-called solvents theory, where it can be applied, i.e., with solvents that undergo self-dissociation in this form it was originally formulated in 1949 by Jander3 in Germany and is illustrated by the following reaction equations ... 

From our previous treatment of the Arrhenius, Bransted and Lewis acid-base theories, the importance of the choice between the divergent solvent types clearly appeared if we now confine ourselves to solvents to which the proton theory in general is applicable, this leads to a classification of eight classes as already proposed by Bronsted35,36 (Table 4.3). 

Acid-base reactions concepts of Arrhenius, Brpnstcd-Lowry, and Lewis coordination complexes, amphoterism... 

Thus, Lewis s definition is a much broader definition that includes coordination compound formation as acid-base reactions, besides Arrhenius and Lowry-Bronsted acids and bases. Examples ... 

Unlike Arrhenius, Lowiy-Bronsted and Lewis acids and bases, the Usanovich s concept in a much broader sense includes all the oxidizing agents as acids and the reducing agents as bases, e.g.,... 

The effect of ring substituents on the rate constants, deuterium kinetic isotope effects and Arrhenius parameters for ene-additions of acetone to 1,1-diphenylsilane have been explained in terms of a mechanism involving fast, reversible formation of a zwitterionic silene-ketone complex, followed by a rate-limiting proton transfer between the a-carbonyl and silenic carbon. A study of the thermal and Lewis acid-catalysed intramolecular ene reactions of allenylsilanes with a variety of... 

Although many other acid-base definitions have been proposed and have been useful in particular types of reactions, only a few have been widely adopted for general use. Among them are those attributed to Arrhenius (based on hydrogen and hydroxide ion formation), Br0nsted-Lowry (hydrogen ion donors and acceptors), and Lewis (electron pair donors and acceptors) [6,67-70]. 

Each of the three definitions expands our concept of acids and bases. Arrhenius basic definition is adequate for understanding many of the properties of acids and bases. It is important to recognize, though, that acids and bases are not fixed labels that can be applied to a substance. Bronsted-Lowry and Lewis showed that acid-base characteristics are dependent on the reactions that take place between substances. A... 

In practice, it s much simpler to use the Arrhenius or Bronsted-Lowry definition of acid and base, but you ll need to use the Lewis definition when hydrogen ions aren t being exchanged. You can pick and choose among the definitions when you re asked to identify the acid and base in a reaction. 

According to A. A. Noyes (1907), the degree of ionization decreases with a rise of temp. G. N. Lewis and G. A. Linhart have compared the degrees of ionization calculated by thermochemical data and by the ratio A/A. S. Arrhenius gives for the heat Of ionization at 35°, with W-soln., LiCl, —399 cals. NaCl, —454 cals. and KC1, —362 cals. 

Another way of applying the same test is to find E from the Arrhenius equation and then using this value to calculate k and compare it with the experimentally determined value. Lewis adopts this latter course. 

Arrhenius Arrhenius Bronsted-Lowry Bronsted- Lowry Lewis Lewis... 

Even more general is the Lewis concept of acids and bases a Lewis base has a lone pair available for formation of a coordinate bond, and a Lewis acid has a vacant acceptor orbital handy. This concept is applicable to reactions in the gas phase or in inert solvents (as discussed in the previous section) as well as to complex formation in solution and the acid/ base phenomena studied by Arrhenius, Br0nsted and Lowry. 

---