The strength of a bronsted acid, HA, in aqueous solution is given
in term of the acidity constant, Ka
(which is also known as the acid ionization
constant), where:
and a(X) is the activity of species X. The activity of a pure liquid
is 1, and in dilute solution the approximation a(H2O)
= 1 is made. Also, it is often convenient in dilute solutions,
where the total ion concentration is less than 10-3
moldm-3, to substitute the concentration of a species,
[X], for its activity.
Hence the acidity constant, Ka, can be defined, as
can the pKa.
The acidity constant is usually reported as pKa for convenience, as Ka
can span many orders of magnitude.
It is often the amount of H3O+ that is
present which is the indication of acid strength. This is reported
in terms of its concentration, as pH,
which is defined as -log10[H3O+].
Substances with pKa<0 are classified as strong
acids, as the proton transfer equilibrium lies in favour
of donation to water. Substances with pKa>0 are
known as weak acids, and now the
proton transfer equilibrium lies in favour of protonated HA. The
conjugate bases of strong acids are weak
bases, and the conjugate bases of weak acids are strong
bases.
The weaker the acid, the stronger the conjugate base.
Polyprotic Acids
Polyprotic Acids: These acids
can donate more than one proton. Separate Ka's can
be defined for the succesive loss of each of the protons.
It is harder to remove the second proton, than to remove the first. (ie: second deprotonation require more energy.)
This may be represented by Ka1
< Ka2: which reflects the
more difficult removal of the second proton from what
is then a negatively charged species.
There are two main reasons that the second deprotonation is more
difficult than the first:
- as implied above, there is an attractive electrostatic
interaction which disfavours the removal of the positively charged
proton from the negatively charged anion.
- the removal of another proton produces a doubly negatively
charged species, which will induce more ordering in a surrounding
dipolar solvent than a singly charged species will. This is disfavoured
on entropic grounds.
Solvent levelling
Any acid stronger than H3O+ in water donates
a proton to H2O. Any base stronger than OH-
in water accepts a proton from H2O. Therefore, no acid
stronger than H3O+ and no base stronger
than OH- can survive in H2O. This is the
effect called solvent leveling.
Water is said to have a leveling effect that controls the pH
range achievable in aqueous solution. A pKa<0 implies
an acid which has been leveled, whereas a pKa>14
implies a base which has been leveled. The width of the range
of available pH's is given by the pKw value.
Different solvents have different leveling ranges. Hence, pH's
may be achieved in other solvents which are not possible in aqueous
solution.
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