Of the concepts that chemists use to make sense of chemical transformations, ideas about acids and bases are among the most fruitful. Nearly all of the heterolytic reactions that we shall be considering can be thought of as acid-base precosses; it is therefore appropriate to begin our discussion of the chemical properties of organic compounds with a review of these ideas and of their applications in organic chemistry. Definition of bronsted acids and bases. Acids and bases have been known for centuries, but the definitions in common use today are of comparatively recent origin. In 1923 J.N. Bronsted proposed the following definitions: Ana cid is a proton donor. A base is a proton acceptor. Ana cid HA is thus any substance that reacts according to Equation 3.1, and a base B is any substance that reacts according to Equation 3.2:
Equations 3.1 and 3.2 are oversimplified as descriptions of acid-base
chemistry in the liquid phase. The proton, H+, does not exist free to any apreciable extent in solution but is always solvated by one or more molecules of some other species. Bonding to one solvent molecule would produce in water H3O+; in ammonia NH4+; in alcohols, ROH2+. In general, in solvent S, cordination of a proton to solvent yields SH+, referred to as the lyonium ion of the solvent. Event these formulations are oversimplifications, because the lyonium ion, once formed, will itself be solvated by close association with more solvent molecules, the number and strength of binding depending on the solvent. It has proved posible to study by mass spectrometry the binding in the gas phase of protons to watr molecules and to molecules of various other basic species. The binding of the first wter molecules and to yield H3O+ is about 165 Kcal mol-1 exothermic; coordination of the second wter molecule releases 36 kcal mol -1. Addition of subsequent wter molecules up to at least the eighth releases decreasing but still significant amounts of energy. Kebarle and co.workers are of the opinin thet exothermicity on adding more wter molecules to thecluster indicates that the proton is bound equally to several wter molecules, as would be indicated by the formula H+(H2O)n, rather that being coordinated more tightly to one,
as would be indicated by H3=+(H2O)m. Gas-`hace ninding of the
proton to CH3OH, (CH3)2, H2S, HCN, and CH3CN have also been investigated. The small size and consequent large electrostatic field of the proton makes it seem very likely that in solution association of H+ with a base is a general phenomenon. Although it is clear that the proton in aqueous solution is solvated by a number of water molecules as yet not precisely determined but certainly greater than one, the shorthand designations H3O+ or even more simply H+, where the remaining solvation is understood, are commonly used. The H3O+ formulation emphasizes an important symmetry of bronsted acid-base reactions, illustrated en Equation 3.3 for the dissociation of acetic acid en water. Here the acid donates a proton and base accepts it; this chemical change constitutes an acidbase reaction in the bronsted sense. In this reaction, note that the reverse process un as acid- base reaction just as the forward process is. The acetate ion us a base that can accept a proton from the acid H3O+. This reciprocal relationship is emphasized by the terminology. Acetate ion is called the conjugate base of the acid CH3COOH, and H3O+ is called the conjugate acid of the base H2O.
In considering an acid- base reaction, it is important to realiza that the
choice of which acid is to be called the conjugate acid is completely arbitrary. In Equation 3.3 we could just as well have decided to call H2O the conjugate base of the acid H3O and CH3COOH the conjugate acid of the base CH3COO-. Note that acid-base reaction can be of a variety of charge types; a general representation is Where m and n can each be a positive or negative integer or zero.
We must also recognize that many molecules that we ordinarily think
of as exhibiting neither acidic nor basic behavior are in fact acids or bases, or, frequently, both. For example, acetone, which is neutral in water solution, reacts as a base in sulfuric acid according to the equilibrium in 3.5; and in dimethylsulfoxide containing sodium methoxide, acetone is an acid (Equation 3.6).
Logical extensin of these ideas leads to the conclusion that acetic
acid is a base as well as an acid, and that aniline, a substance ordinarily considered as a base, can also act as an acid (Equations 3.7 and 3.8).
Indeed, one may conclude that any molecule containing hydrogen is a
potential Bronsted acid, whereas any molecule at all is a potential Bronsted base.
Acid and base strength
For acids that can be studied in aqueous solution, we measure the strength by the magnitude of the equilibrium constant for dissociation, Ka. This quantity is defined by first writing the equilibrium constant Ka for Reaction 3.9, using activities, and then converting to the form given in Equation 3.11 by incorporating the water activity, which is essentially constant in dilute solution when water is the solvent, into the equilibrium constant.
Because we will be considering acid dissociation in various solvents,
and in recognition of the fact that the degree of solvation of H+ is imprecisely known and varies from solvent to solvent, we will simplify the nomenclature by referring to the proton henceforth simply as H+; it is to be understood that this symbol represents the proton in a state of solvation as it exists in the mdium under consideration. With this simplification, Equation 3.11 becomes 3.12, which can also be written in terms of activity coefficients (Equation 3.13).
The standard state is defined as the hypothetical state that would
exist if the solute were at a concentration of 1M, but with the molecules experiencing the environment of an extremely dilute solution; with this estndar state, activity coefficients approach unity with increasing dilution. For electrolytes in dilute solution in water, the departure of the coefficients from unity can be calculated from Debye.Huckel limiting law. It is possible to define another equilibrium constant, Kc (Equation 3.14), which does not include the activity coefficients and hence will not be a true constant except in very dilute solution, where it
approaches the thermodynamic Ka that we have been considering so
fer. The constant Kc is often used for convenience, but it is not satisfactory for careful work, nor where comparisons between different solvents must be made.
Base strengths can be defined similarly by the equlibrium constant for