The states of alkali occuring in Portland cement clinker were studied. Potassium was added to raw mixture by there kinds ; $K_2SO_4$, $K_2CO_3$ and KOH. In case of $K_2CO_3$ and KOH addition the new state of unstable alkali was found when alkakli content is high and $SO_3$ content is low in the clinker. Unstable state of highly basic free 4K_2O$ causes lowering burnability much more than alkali sulfate especially at the early stage of burning. Lowered burnability by 4K_2O$ became more serious with higher LSF. Unstable free-4K_2O$ which is readily soluble with water reacts with gypsum to form <TES>$Ca(OH)_2$</TEX> and syngenite as soon as water is added. As a results the liberation rate of heat of hydration at the early hydration process(1st peak) was increased.