Jesus Moreira

Determination of Kinetic Parameter in a Unified Kinetic Model for the Photodegradation of Phenol by Using Nonlinear Regression and the Genetic Algorithm

Abstract This study reports the kinetic parameter estimation in the photocatalytic degradation of phenol over different TiO2 catalysts by using the Genetic Algorithm (GA) and nonlinear regression. Reaction networks are based on a previously reported unified kinetic model (UKM) of the Langmuir–Hinshelwood type. Nonlinear least-squares fitting and GA are used to find the values for the kinetic constants. The computed parameters were found to predict experimental data for phenol photodegradation at different levels of concentrations. It is shown that both methods render close values for the kinetic constants. This suggests that UKM approach gives the global minimum and as a result, this method provides good and objective parameter estimates with low to moderate cross-correlation among kinetic constants and acceptable 95% Confidence Intervals (CIs). Global optimization by using GA requires extensive computer times of up to 5 minutes. Least square fitting provides the same results with computer times of seconds only. It is then concluded that the UKM approach effectively avoids overparameterization by finding the global optimum when optimizing the kinetic constants.

Diffusion and Equilibrium Adsorption Coefficients of Aromatic Hydrocarbon Species in Capillary Columns

Abstract This study focuses on a mathematical description of elution of aromatic species in a 30 m×0.25 mm×0.25 μm BPX5 capillary column. Experimental studies involve the detection of chemical species at the capillary column outlet. Using the recorded peaks, statistical moments of different orders are calculated for both toluene and naphthalene. Modeling studies involve a laminar flow model with an equilibrium coefficient (Ks) and a solute diffusion coefficient in the stationary phase (Ds). Model validation is developed by performing experiments at different carrier gas velocities and GC oven temperatures. Under the conditions, neither the first statistical moment (M1) nor the second statistical moment (M2) is affected by the carrier gas velocity. Thus, the interface equilibrium coefficients (Ks) and the diffusion coefficients (Ds) solely depend on the solute and the capillary column polymer coating properties. Furthermore, the statistical moments of different orders show that the proposed interface equilibrium based model in the “narrow bore” 30 m×0.25 mm×0.25 μm BPX5 capillary column is adequate for aromatic species such as toluene and naphthalene.