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Sodium hydroxide does not have a single pKa. Sodium hydroxide consists of two separate ions, Na^+ and OH^-. Na^+ has a pKa of 13.9 [R. M. Smith, A. E. Martell, R. J. Motekaitis, NIST Critical Stability Constants of Metal Complexes Database 46 (Gaithersburg, MD: NIST, 2001).] The hydroxide ion has a pKb (that is the -log(equilibrium constant) for acting as a base) = 1.0. The pKa of OH- is very large because OH- is a terrible acid because the reaction OH- + H2O --> O^2- + H3O+ is very unlikely to happen in water.
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