Where do you plan to get pKa2 from for a monoprotic acid?
In some cases it will work for triprotic acid, for example it will work for a solution of NaH2PO4, it will also work for Na2HPO4 (but then it requires pKa2 and pKa3). But it works only if the separation of pKa values is large enough and pKa values are not too large nor too small.