So far we have dealt with acids that donate only one proton per molecule. However, this is not the case for polyprotic acids--acids that can donate more than one proton per molecule. Two key features of polyprotic acids are that they lose their protons in a stepwise manner and that each proton is characterized by a different pKa. The factors contributing to the pKa of each acidic proton in a polyprotic species are the same factors that determine the relative acidity of monoprotic acids--the dominant factor is strength of the acid-H bond. Consider, for example, the triprotic acid H3PO4 shown in :
As each proton is lost from phosphoric acid, the phosphorous becomes more electron rich, and less electron withdrawing. Therefore, the loss of each proton strengthens the O-H bond and increases the pKa of the phosphate species. This trend is evident in the pKa data given in . In general, it is true that Ka1, Ka2, Ka3, and so on, for polyprotic acids.
As you may have guessed, calculating the pH of a polyprotic acid solution is not as simple as it is for monoprotic acids. In fact, it is quite a messy problem. However, that mess can be quickly cleaned up by making the assumption, as we did for a mixture of acids, that only the strongest acid (i.e. only the first dissociation) has a significant effect on the pH. Making that assumption turns the problem into one you already know how to solve--calculating the pH of a weak acid solution.