Nitrification involves the sequential biological oxidation of reduced nitrogen species such as ammonium‐nitrogen (NH4+‐N) to nitrite‐nitrogen (NO2−‐N) and nitrate‐nitrogen (NO3−‐N). The adequacy of modeling NH4+‐N to NO3−‐N oxidation as one composite biochemical reaction was examined at different relative dynamics of NH4+‐N to NO2−‐N and NO2−‐N to NO3−‐N oxidation. NH4+‐N to NO2−‐N oxidation and NO2−‐N to NO3−‐N oxidation by a mixed nitrifying consortium were uncoupled using selective inhibitors allylthiourea and sodium azide. The kinetic parameters of NH4+‐N to NO2−‐N oxidation (qmax,ns and KS,ns) and NO2−‐N to NO3−‐N oxidation (qmax,nb and KS,nb) were determined by a rapid extant respirometric technique. The stoichiometric coefficients relating nitrogen removal, oxygen uptake and biomass synthesis were derived from an electron balanced equation. NH4+‐N to NO2−‐N oxidation was not affected by NO2−‐N concentrations up to 100 mg NO2−‐N L−1. NO2−‐N to NO3−‐N oxidation was noncompetitively inhibited by NH4+‐N but was not inhibited by NO3−‐N concentrations up to 250 mg NO3−‐N L−1. When NH4+‐N to NO2−‐N oxidation was the sole rate‐limiting step, complete NH4+‐N to NO3−‐N oxidation was adequately modeled as one composite process. However, when NH4+‐N to NO2−‐N oxidation and NO2−‐N to NO3−‐N oxidation were both rate limiting, the estimated lumped kinetic parameter estimates describing NH4+‐N to NO3−‐N oxidation were unrealistically high and correlated. These findings indicate that the use of single‐step models to describe batch NH4+ oxidation yields erroneous kinetic parameters when NH4+‐to‐NO2− oxidation is not the sole rate‐limiting process throughout the assay. Under such circumstances, it is necessary to quantify NH4+‐N to NO2−‐N oxidation and NO2−‐N to NO3−‐N oxidation, independently. © 2000 John Wiley & Sons, Inc. Biotechnol Bioeng 68: 396–406, 2000.