A computed-based model for the alkali concentrations in pore solution of hydrating Portland cement paste is proposed. Experimental data reported in different literatures with thirteen different recipes are analyzed. A 3-D computer-based cement hydration model CEMHYD3D is used to simulate the hydration of these pastes. The models predictions are used as inputs for the alkali partition theory, which is used to derive the alkali binding capacity of C-S-H in hydrating Portland cement paste. A linear relation between the amount of bound-alkali Na+ in C-S-H and its concentration in the pore solution is found, whilst a non-linear relation should be employed for the amount of bound-alkali K+ in C-S-H. New methods for predicting the alkali concentrations in the pore solution of hydrating Portland cement pastes are proposed based on the computer model CEMHYD3D, which is also validated with experimental results