Ammonia Equilibrium Chemistry
In aqueous solution, ammonia exists in a pH- and temperature-dependent equilibrium:
The fraction of total ammonia that is unionized (NH₃) is determined by the dissociation constant (pKa) and the water pH:
The pKa of ammonia decreases with increasing temperature (Emerson et al., 1975):
where T is temperature in °C. This means that at higher temperatures, a greater fraction of TAN exists as toxic NH₃. Salinity further reduces pKa (Khoo et al., 1977), increasing the NH₃ fraction in brackish or marine systems.