The influence of temperature (T) and ionic strength (I m ) on the stoichiometric (molality scale) acidity constants of nicotinic acid in aqueous solution was investigated by potentiometry (H þ -glass electrode). The background salt used was potassium chloride, and the temperature and ionic strength ranges covered were 283.15 K < T < 318.15 K and 0.05 mol 3 kg À1 < I m < 0.52 mol 3 kg À1 , respectively. Acidity constants at zero ionic strength were derived by means of a DebyeÀH€ uckel type formalism, and their temperature dependence was obtained through a van't Hoff analysis. This led to pK a1 = 2.19 ( 0.06 and pK a2 = 4.86 ( 0.03 at 298.15 K and to the corresponding standard molar enthalpies and entropies of proton dissociation in the temperature range of the experiments, Δ r H m,l °= (4.5 ( 3.5) kJ 3 mol À1 , Δ r S m,l °= À(26.8 ( 11.8) J 3 K À1 3 mol À1 , Δ r H m,2 °= (12.5 ( 2.1) kJ 3 mol À1 , and Δ r S m,2 °= À(51.2 ( 7.0) J 3 K À1 3 mol À1 . These values were compared with previously reported data.