I. Strictly; it is generally accepted that pH buffers consist on weak acid with its conjugate base, or on weak base with its conjugate acid.
II. Nonetheless, a solution of trisodium phosphate (Na3PO4) and NaOH, possibly obtained by titration of phosphoric acid with NaOH, has a fairly stable pH by pH = 13.
III. For the 3rd dissociation equilibrium of phosphoric acid, HPO42- + H2O ⇌ PO43- + H3O+; pKa3 = 12.37; Ka3 = [H3O+]·[PO43−]/[HPO42-] = 2.14·10−13 M. This equilibrium is largely displaced to the right by NaOH addition while some OH- is consumed. Trisodium phosphate is basic salt at its own solution, but behaves as acidic with regards to the stronger base NaOH. The pKa3 ± 1 range covers pH = 13, what should favour pH stability.
IV. Phosphorus balance writes: CNa3PO4 ≈ [HPO42-] + [PO43-]; species H2PO4- and H3PO4 can be neglected for the mentioned alkaline solution. Sodium balance is: CNaOH + 3CNa3PO4 = [Na+]. C denotes nominal (i.e. formal) concentrations.
VII. Here Kw/Ka3 = 0.0467 M. For the considered pH = 13, pOH = 14 - pH = 1; so [OH-] = 1.0·10-1 M and Kw/Ka3 + [OH-] = 0.147 M. Hence, 0.1 M ≈ CNaOH + 3CNa3PO4·(1 - 0.1/0.147), or:
0.1 M ≈ CNaOH + 0.959·CNa3PO4
VIII. More generally, pH can be predicted by solving the equation obtained at § VI: