A model that describes the inward diffusion of an element I into a solid substrate and the simultaneous precipitation of a compound M y I z , with M as the alloying element initially dissolved in the substrate matrix, is presented for the case of nitriding iron-based alloys. The model was developed by coupling the diffusion kinetics and the precipitation (nucleation and growth) kinetics. Additionally, the role of excess nitrogen and the kinetics of ammonia dissociation at the iron surface were incorporated into this coupled model. The model was successfully applied to the case of nitriding an Fe-2.23 at. pct V alloy; the simulation results are in good agreement with the measured data and allow for detailed understanding of the evolution of the nitride precipitates (volume fraction, number density, and size distribution) as a function of both nitriding time and depth in the specimen. The present model exposed the pronounced effects of the precipitation kinetics, of excess nitrogen, and of the surface-reaction kinetics on the overall nitriding kinetics and demonstrated a striking, nonmonotonous change with time of precipitate particle size at a distinct depth in the specimen.