Geochemical modeling of precipitation reactions in the complex matrix of acid mine drainage is fundamental to understanding natural attenuation, lime treatment, and treatment procedures that separate constituents for potential reuse or recycling. The three main dissolved constituents in acid mine drainage are iron, aluminum, and sulfate. During the neutralization of acid mine drainage (AMD) by mixing with clean tributaries or by titration with a base such as sodium hydroxide or slaked lime, Ca(OH)2, iron precipitates at pH values of 2–3 if oxidized and aluminum precipitates at pH values of 4–5 and both processes buffer the pH during precipitation. Mixing processes were simulated using the ion-association model in the PHREEQC code. The results are sensitive to the solubility product constant (Ksp) used for the precipitating phases. A field example with data on discharge and water composition of AMD before and after mixing along with massive precipitation of an aluminum phase is simulated and shows that there is an optimal Ksp to give the best fit to the measured data. Best fit is defined when the predicted water composition after mixing and precipitation matches most closely the measured water chemistry. Slight adjustment to the proportion of stream discharges does not give a better fit.