Solvent system acid-base definition

An example of the different points of view and different tastes in the matter of acid-base definitions was provided to one of the authors in graduate school while attending lectures on acid-base chemistry from two professors. One Felt that the solvent system was very useful, but that the Lewis concept went too far because it included coordination chemistry. The second used Lewis concepts in all of his work, but felt uncomfortable with the Usanovich definition because it included redox chemistry To the latter s credit, however, he realized that the separation was an artificial one, and he suggested the pyridine oxide example given above. 

For each of the following reactions identify the acid and the base. Also indicate which acid-base definition (Lewis, solvent system, Brpnsted) applies. In some cases, more than one definition may apply. 

Use the genendized definition of acids and bases to explain the examples given for the BrOnsicd-Lowry. Lux-Flood, solvent system, and Lewis definitions (Eqs. 9.1-9.4. 9.5-9.S. 9.9-9.36 9.37-9.40). 

Systems defined by the Arrhenius description, solvent system, Lux-Flood and proton acid-base definitions... 

By a further extension of the solvent-system concept, the definitions of acid and base may be extended to molten salts. Thus the tetra-... 

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. 

Almost all of the reactions that the practicing inotganic chemist observes in the laboratory take place in solution. Although water is the best-known solvent, it is not the only one of importance to the chemist. The organic chemist often uses nonpolar solvents sud) as carbon tetrachloride and benzene to dissolve nonpolar compounds. These are also of interest to Ihe inoiganic chemist and, in addition, polar solvents such as liquid ammonia, sulfuric acid, glacial acetic acid, sulfur dioxide, and various nonmctal halides have been studied extensively. The study of solution chemistry is intimately connected with acid-base theory, and the separation of this material into a separate chapter is merely a matter of convenience. For example, nonaqueous solvents are often interpreted in terms of the solvent system concept, the formation of solvates involve acid-base interactions, and even redox reactions may be included within the (Jsanovich definition of acid-base reactions. 

Such an equilibrium system is termed a conjugate (or corresponding) acid-base system. A and B are termed a conjugate acid-base pair. It is important to realize that the symbol H+ in this definition represents the bare proton (unsolvated hydrogen ion), and hence the new definition is in no way connected to any solvent. The equation expresses a hypothetical scheme for defining the acid and base - it can be regarded as a half reaction which takes place only if the proton, released by the acid, is taken up by another base. 

Their unique relation to water systems favors the inclusion of acid-base reactions in deuterium oxide with aqueous acid-base equilibria, even though some aspects of the chemistry suggest inclusion with nonaqueous solvents. In studies such as those of deuterium isotope effects, it is desirable to be able to measure pD as an index of acidity in heavy water. Glass electrodes respond in a nemstian way to changes in deuterium ion concentration, and therefore the usual combination of glass and calomel electrodes can form the basis of an operational definition of pD ... 

Aprotic nonaqueous solutions require a similar approach, but with a different definition of acid and base. The solvent system definition applies to any solvent that can dissociate into a cation and an anion (autodissociation), where the cation resulting from autodissociation of the solvent is the acid and the anion is the base. Solutes that increase the concentration of the cation of the solvent are considered acids and solutes that increase the concentration of the anion are considered bases. 

Lewis defined a base as an electron-pair donor and an acid as an electron-pair acceptor. This definition further expands the list to include metal ions and other electron pair acceptors as acids and provides a handy framework for nonaqueous reactions. Most of the acid-base descriptions in this book will use the Lewis definition, which encompasses the Brpnsted-Lowry and solvent system definitions. In addition to all the reactions discussed previously, the Lewis definition includes reactions such as... 

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