Abstract The use of De Donder relations is addressed for analysis of reaction schemes to describe the kinetics of overall reactions. These relations provide a simple means of determining the number of kinetic parameters required to calculate the overall reaction rate. These kinetic parameters for gaseous reactions are controlled by quasi-equilibria between the reactants and/or products of the overall reaction with the transition states of the elementary steps, and they are not determined by the properties of the stable reaction intermediates. For surface reaction schemes, one additional kinetic parameter is required for each stable surface species that becomes abundant on the surface. De Donder relations offer a rigorous approach for assessing whether a reaction scheme contains a rate determining step, and they provide a convenient means of deriving a series of rate expressions for cases where specific steps are assumed to be rate determining. In addition, these relations make it possible to calculate the maximum rate at which a given transition state may contribute to the overall reaction rate, providing a necessary condition for assessing the participation in the overall reaction scheme of transition states identified by quantum-chemical calculations.