This paper presents an extension of the Activated Sludge Model No. 2d (ASM2d) including a chemical model able to calculate the pH value in biological processes. The developed chemical model incorporates the complete set of chemical species affecting the pH value to ASM2d describing non-equilibrium biochemical processes. It considers the system formed by one aqueous phase, in which biochemical processes take place, and one gaseous phase, and is based on the assumptions of instantaneous chemical equilibrium under liquid phase and kinetically governed mass transport between the liquid and gas phase. The ASM2d enlargement comprises the addition of every component affecting the pH value and an ion-balance for the calculation of the pH value and the dissociation species. The significant pH variations observed in a sequencing batch reactor operated for enhanced biological phosphorus removal were used to verify the capability of the extended model for predicting the dynamics of pH jointly with concentrations of acetic acid and phosphate. A pH inhibition function for polyphosphate accumulating bacteria has also been included in the model to simulate the behaviour observed. Experimental data obtained in four different experiments (with different sludge retention time and influent phosphorus concentrations) were accurately reproduced.