General acid-base theory

The photodecomposition and thermodecomposition of nitromethane have been extensively studied as model systems in combustion, explosion and atmosphere pollution processes[l]. On another hand, nitromethane was selected as a model solvent in experiments aimed at examining non hydrogen-bonded solvent effects in a general acid-base theory of organic molecules [2.3]. This selection is based on the electronic and structural characteristics of nitromethane that has a high dielectric constant, and at the same time cannot form hydrogen bonds with solute molecules. 

In 1923, Johannes Br nsted and his English counterpart Thomas Lowry independently developed a more general acid-base theory. According to the Br nsted-Lowry model, an acid is a proton (H+) donor and a base is a proton acceptor. Each proton donor (acid) has its pair (conjugate) proton acceptor (base). In an acid-base reaction, H (proton) is transferred from an acid to a base. For example ... 

In the early 1930s Gilbert Lewis, an American chemist, proposed a more general acid-base theory that is based on sharing electron pairs rather than... 

The distinction between amphoteric and amphiprotic will be clearer after reading Chapter 18. Lewis theory is a more general acid-base theory that includes all Brpnsted-Lowry acids and bases. 

General acid-base theory and non-aqueous solvents The general relationship,... 

The Usanovich theory is the most general of all acid-base theories. According to Usanovich (1939) any process leading to the formation of a salt is an acid-base reaction. The so-called positive-negative definition of Usanovich runs as follows. 

Rates of addition to carbonyls (or expulsion to regenerate a carbonyl) can be estimated by appropriate forms of Marcus Theory. " These reactions are often subject to general acid/base catalysis, so that it is commonly necessary to use Multidimensional Marcus Theory (MMT) - to allow for the variable importance of different proton transfer modes. This approach treats a concerted reaction as the result of several orthogonal processes, each of which has its own reaction coordinate and its own intrinsic barrier independent of the other coordinates. If an intrinsic barrier for the simple addition process is available then this is a satisfactory procedure. Intrinsic barriers are generally insensitive to the reactivity of the species, although for very reactive carbonyl compounds one finds that the intrinsic barrier becomes variable. ... 

This equation corresponds to today s general convention of expressing base strength also be means of pKa, where K is considered in the sense of the Bronsted acid-base theory as a protolysis constant of the following protolytic reactions for acids ... 

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). 

Enzymes are often considered to function by general acid-base catalysis or by covalent catalysis, but these considerations alone cannot account for the high efficiency of enzymes. Proximity and orientation effects may be partially responsible for the discrepancy, but even the inclusion of these effects does not resolve the disparity between observed and theoretically predicted rates. These and other aspects of the theories of enzyme catalysis are treated in the monographs by Jencks (33) and Bender (34). 

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. 

At about the same time that Bronsted proposed his acid-base theory, Lewis put forth a broader theory, A base in the Lewis theory is the same as in the Brpnsted one, namely, a compound with an available pair of electrons, either unshared or in a tt orbital. A Lewis acid, however, is any species with a vacant orbital.1115 In a Lewis acid-base reaction the unshared pair of the base forms a covalent bond with the vacant orbital of the acid, as represented by the general equation... 

These observations have been interpreted in terms of the hard-soft acid-base theory (77CJC4112), in which the salts of the harder cations, such as the Li+ ion, lead to C-alkylation, whilst the salts of the soft cations, such as the quaternary ammonium salts, are TV-alkylated. This interpretation is particularly relevant in understanding the reactivity of the heteroaryl-magnesium salts. The Mg2+ ion is a harder cation than the Li+ ion and, with the more strongly associated Grignard compounds, C-alkylation predominates. Generally, the pyrrole... 

The large differences seen in Cu(II) adsorption capacity for thiol- and amino-modified silicas does not occur for Pb(II) adsorption (Figure 7). While it is tempting to argue these differences in adsorption behavior based on hard-soft acid-base theory the hardness of Cu2+ and Pb2+ are very similar, both generally categorized as intermediate cases.18 It is more likely that Pb(II) adsorption behavior under the conditions of this study is dictated largely by solution behavior and speciation of Pb2+ in aqueous solution at pH 5. Indeed it was found that these solutions were unstable and prone to precipitation slowly over time under these conditions. Further work will be needed as a function of pH, surface functionality, and metal ion to determine the role of various factors on adsorption behavior of these systems. 

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 ... 

Usanovic acid-base theory — A general theory of acids and bases taking into consideration electron exchange processes (redox reactions) was proposed in 1939 by Usanovic. His definition is a symmetrical one and includes all concepts discussed above, i.e., an acid is defined as a substance which is able to liberate protons or other cations (cation donator) or to take up anions or electrons (anion acceptor, electron acceptor). A base is defined as a substance which is able to release anions or electrons (anion donator, electron donator) or to take up protons or other cations (cation acceptor). According to that theory, all chemical reactions (excluding reactions between radicals resulting in covalent bindings) can be considered as acid-base reactions. 

The chemistry of coordination compounds is a broad area of inorganic chemistry that has as its central theme the formation of coordinate bonds. A coordinate bond is one in which both of the electrons used to form the bond come from one of the atoms, rather than each atom contributing an electron to the bonding pair, particularly between metal atoms or ions and electron pair donors. Electron pair donation and acceptance result in the formation of a coordinate bond according to the Lewis acid-base theory (see Chapter 5). However, compounds such as H3N BC13 will not be considered as coordination compounds, even though a coordinate bond is present. The term molecular compound or adduct is appropriately used to describe these complexes that are formed by interaction of molecular Lewis acids and bases. The generally accepted use of the term coordination compound or coordination complex refers to the assembly that results when a metal ion or atom accepts pairs of electrons from a certain number of molecules or ions. Such assemblies commonly involve a transition metal, but there is no reason to restrict the term in that way because nontransition metals (Al3+, Be2+, etc.) also form coordination compounds. 

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 ... 

Several acid-base theories have been proposed to explain or classify acidic and basic properties of substances. You are probably most familiar with the Arrhenius theory, which is applicable only to water. Other theories are more general and are applicable to other solvents. We describe the common acid-base theories here. 

---