Вы находитесь на странице: 1из 4

ACIDOS Y BASES

3.1 Bronsted acids and bases.


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


reaction 3.15:

Вам также может понравиться