pH is a gerneric term where as pKa is specific. pH is the measurment of [H+] at any desired time whereas pKa is the pH at equilibrium. Ka is the acidic constant (also dissociation constant) of a system and it is given by:
Ka = [H+][A-]/[HA]
at equilibrium.
For an acidic buffer, when an acid is added to the buffer, the conjugate base [A-] reacts with the [H+] and form the acid HA:
A- + H+ -----> HA
conversely, if a base is added to such a buffer, it reacts with the acid and we have:
OH- + HA -----> A- + H
2O
producing it conjugate base and water:
Usually buffers (for an acidic buffer) are made by having both the acid and a salt of the its conjugate base in a solution. A more correct representation would be:
A- + H+ <-----> HA
Analyse the following data:
H
3PO
4/H
2PO
4, pKa = 2.13, e.p.r = 1.1-3.1
CH
3COOH/CH
3COO-, pKa = 4.76, e.p.r. 3.8-5.8
(values taking form my lab manual)(e.p.r. - effective pH range). You will see that both acidic buffer have an effective pH range of 2. Phorphoric acid is triprotic whereas acetic acid is monoprotic - the point is that the effectiveness of a buffer is not determined by the proticity of its acid. I am assuming you are thinking that since a polyprotic acid can donates more H+ therefore it can react with more base? The ability of the buffer to resist change in pH depends on
both the conjugate base and the acid. When you analyse the examples given above, you will see that the conjugate base and acid in both cases have a monoprotic relationship - therefore being a polyprotic acid does not mean that the buffers made form it are "better" (more effective).
Remember:
The buffer's ability to resist to change in pH is maximised when [A-]=[HA]
And the larger the [A-] and [HA] the more effective the buffer is (as more acid or base can be put into the system).