Even though pKa and pH are related (pKa=pH -log [A-]/[AH]), it is more common to monitor and set pH in emulsion polymerization. The lower the pH the faster the decompositon of potassium or ammonuim persulfates and it is prefered to polymerize at a lower pH because if carboxyilic acids are part of the recipe they tend to be inside the particles instead of polimerizing in the aqueous phase which occurs at a high pH. Also to mantain a constant pH thoughout the reaction, buffer agents are used as part of the recipe.