Modeling of gas-phase photodegradation of chloroform and carbon tetrachloride.

The relationship between the irradiance in a photoreactor and the rate of photodegradation of organics is essential in the scaling-up of photoreactors to treat large volumes of air contaminated with organic pollutants. In this study, the analysis is adopted to compare results obtained from two different photoreactors. Initially, the applicability of two light models in calculating the irradiance in two photoreactors was evaluated. Thereafter, kinetic models of ultraviolet (UV) photooxidation of chloroform (CHCl3) and carbon tetrachloride (CCl4) from the archived literature were tested using experimental data under various operating conditions and different irradiances. Sensitivity analyses were conducted using different values of model parameters to determine the significance of each parameter on the photodegradation of the two chlorinated organics. For compounds that undergo photolysis as a primary mode of degradation, the rate of photodegradation at low initial concentrations can be predicted easily by the following equation: d[C]/dt = -2.303Iave, lambdaepsilonlambdaphilambda[C]. Although the photodegradation of chlorinated organic compounds in dry and humid air can be predicted well, it is difficult to predict the Cl* sensitized oxidation occurring at high initial concentrations. A good agreement between the simulated and experimental data provides a sound basis for the design of large-scale reactors.