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The chemistry involved in free-radical water treatment processes (AOPs) is sufficiently complex that true optimization of the processes is often difficult without the use of kinetic models to allow simulation of the treatment process and optimization via “computer experiments.” Powerful software is now widely available for numerical integration of complex sets of rate equations, such as are encountered in simulations of water treatment using AOPs. However, limited availability of the required rate constants poses a serious barrier to performing meaningful calculations. This problem cannot, in general, be solved by simply using rate constants as optimization parameters in a fit of the experimental data to the chosen equation set. A simpler “semi-empirical” model based on the concept of efficiency was developed, using the work of Hoigne, Bader, and Staehelin during the period 1977-1985 as a starting point. This model was shown to be useful in AOP process optimization, by allowing the identification of reaction steps for which the efficiency can be improved, evaluation of "generic" hydroxyl radical rate constants for complex environmental matrices, and determination of the importance of reactive species other than hydroxyl radical.

Kinetic Modeling of Free-Radical Water Treatment Processes: Pitfalls, Practicality, and the Extension of the Hoigné/ Bader/ Staehelin Model