The chemical form of the potassium promoter on an iron-alumina catalyst during ammonia synthesis has been studied by two methods, viz, (i) the measurement of the equilibrium constant of the process KNH2 + H2 KH + NH3, and (ii) chemical analysis of the used catalyst. The equilibrium constant measurements gave K723 = (12.9 ± 0.5) × 10−3, ΔHf2980(KNH2) = −119 ± 3 kJ mol−1 and S2980(KNH2) = 109 ± 4 J mol−1 K−1. The chemical analysis showed that no KNH2 is present on the catalyst during synthesis. From these results and with the aid of thermodynamic considerations it is concluded that KNH2, K and K2O are not stable compounds under conditions of ammonia synthesis. X-Ray diffraction showed that part of the potassium reacts with Al2O3, probably leaving part of the potassium in the form of KOH which is quite stable under ammonia synthesis conditions.