In a
solution where both members of an acid–base conjugate pair are dissolved in comparable concentration, their reaction to reach equilibrium proceeds to a lesser extent than in solutions where only one of these is a major species. This is because, for reaction of both the acid and the conjugate base, one product of the reaction to reach equilibrium (highlighted below) is already a major species in solution.
acid + H
2O
conjugate base + H
3O
+conjugate base + H
2O
acid + OH
–
As a result, the equilibrium concentration of H3O+ in a solution where both the acid and the base are major species, is less than in a solution where only the acid of fhe pair was dissolved. Similarly the equilibrium concentration of OH– is lower than it would be in a solution that has only the conjugate base as a major species.
The small extent of reaction of both solutes with water means that the
equilibrium concentrations of both the acid and conjugate base are very well
approximated by the
initial concentrations. Thus calculation of pH of such a solution from p
Ka is very straightforward as the quantities highlighted are known.
At equilibrium:
| Ka = | [conj base][H3O+] |
| [acid] |
From mass balance:
[acid] =
c(acid)
[conjugate base] =
c(conjugate base)
This smaller extent of reaction to reach equilibrium also means that for a solution in which both members of a conjugate pair are major species,
the pH is higher than if only the acid were a major species.
the pH is lower than if only the base were a major species.