Proton Conjugate base

Ionisations 2, 3 and 5 are complete ionisations so that in water HCI and HNO3 are completely ionised and H2SO4 is completely ionised as a monobasic acid. Since this is so, all these acids in water really exist as the solvated proton known as the hydrogen ion, and as far as their acid properties are concerned they are the same conjugate acid species (with different conjugate bases). Such acids are termed strong acids or more correctly strong acids in water. (In ethanol as solvent, equilibria such as 1 would be the result for all the acids quoted above.) Ionisations 4 and 6 do not proceed to completion... 

A sufficient concentration of base B is necessary for the removal of a proton of the CH, group. In a first step, the equilibrium in Scheme 20 results, in which the monomeric anhydrobase Bi constitutes the conjugated base of the quaternary salt A,. As has been shown for other rings (24). the equilibrium depends upon the concentration of the different species and the relative strength of the bases B and Bj, and depends also upon the nature of X. 

Its conjugate base A base and its conjugate acid always differ by a single proton Like wise an acid and its conjugate base always differ by a single proton... 

Conjugate acid (Section 1 13) The species formed from a Brpnsted base after it has accepted a proton Conjugate addition (Sections 1010 and 1812) Addition reaction in which the reagent adds to the termini of the con jugated system with migration of the double bond synony mous with 1 4 addition The most common examples include conjugate addition to 1 3 dienes and to a 3 unsaturated car bonyl compounds... 

Conjugate base (Section 1 13) The species formed from a Brpnsted acid after it has donated a proton... 

Weak acids, of which aqueous acetic acid is one example, cannot completely donate their acidic protons to the solvent. Instead, most of the acid remains undissociated, with only a small fraction present as the conjugate base. 

Acid-base reactions occur when an acid donates a proton to a base. The equilibrium position of an acid-base reaction is described using either the dissociation constant for the acid, fQ, or the dissociation constant for the base, K, . The product of and Kb for an acid and its conjugate base is K (water s dissociation constant). 

Procedures to compute acidities are essentially similar to those for the basicities discussed in the previous section. The acidities in the gas phase and in solution can be calculated as the free energy changes AG and AG" upon proton release of the isolated and solvated molecules, respectively. To discuss the relative strengths of acidity in the gas and aqueous solution phases, we only need the magnitude of —AG and — AG" for haloacetic acids relative to those for acetic acids. Thus the free energy calculations for acetic acid, haloacetic acids, and each conjugate base are carried out in the gas phase and in aqueous solution. 

Specific acid catalysis is observed when a reaction proceeds through a protonated intermediate that is in equilibrium with its conjugate base. Because the position of this equilibrium is a function of the concentration of solvated protons, only a single acid-dependent term appears in the kinetic expression. For example, in a two-step reaction involving rate-determining reaction of one reagent with the conjugate acid of a second, the kinetic expression will be as follows ... 

A kinetic expression which is equivalent to that for general acid catalysis also occurs if a prior equilibrium between reactant and the acids is followed by rate-controlling proton transfer. Each individual conjugate base will appear in the overall rate expression ... 

Addition of nucleophiles sueh as ammonia or alcohols or their conjugate bases to benzynes takes place very rapidly. These nueleophilie additions are believed to involve eapture of the nueleophile, followed by protonation to give the substituted benzene. ... 

These reactions are often promoted by a strong base, which assists the departure of the proton. X is the leaving group. Both El and E2 mechanisms are known, as is a variant designated Elcb, for unimolecular elimination from the conjugate base of the substrate. ... 

To make this more specific let us consider the proton transfer from conjugate base A (site A) to base B (site B),... 

When a Br nsted plot includes acids or bases with different numbers of acidic or basic sites, statistical corrections are sometimes applied in effect, the rate and equilibrium constants are corrected to a per functional group basis. If an acid has p equivalent dissociable protons and its conjugate base has q equivalent sites for proton addition, the statistically corrected forms of the Br insted relationships are... 

The shapes of the titration curves of weak electrolytes are identical, as Figure 2.13 reveals. Note, however, that the midpoints of the different curves vary in a way that characterizes the particular electrolytes. The pV, for acetic acid is 4.76, the pV, for imidazole is 6.99, and that for ammonium is 9.25. These pV, values are directly related to the dissociation constants of these substances, or, viewed the other way, to the relative affinities of the conjugate bases for protons. NH3 has a high affinity for protons compared to Ac NH4 is a poor acid compared to HAc. 

Hydrogen was recognized as the essential element in acids by H. Davy after his work on the hydrohalic acids, and theories of acids and bases have played an important role ever since. The electrolytic dissociation theory of S. A. Arrhenius and W. Ostwald in the 1880s, the introduction of the pH scale for hydrogen-ion concentrations by S. P. L. Sprensen in 1909, the theory of acid-base titrations and indicators, and J. N. Brdnsted s fruitful concept of acids and conjugate bases as proton donors and acceptors (1923) are other land marks (see p. 48). The di.scovery of ortho- and para-hydrogen in 1924, closely followed by the discovery of heavy hydrogen (deuterium) and... 

Hydronium ion, the product that results when the base H20 gains a proton, is called the conjugate acid of the base, and chloride ion, the product that results when the acid HCI loses a proton, is called the conjugate base of the acid. Other common mineral acids such as H2S04 and HNOj behave similarly, as do organic acids such as acetic acid, CH2C02H. 

Strategy In (a), note that in both cases a proton is transferred to a water molecule. The products are an H30+ ion and the conjugate base of the weak acid. In (b) use Table 13.2 to find which weak acid has the larger Ka. In (c) use the equation... 

As pointed out in Section 13.5, anions that are the conjugate bases of weak acids act themselves as weak bases in water They accept a proton from a water molecule, leaving an Oil ion that makes the solution basic. The reactions of the fluoride and carbonate ions are typical ... 

---