A new approach of kinetic modeling: Kinetically consistent energy profile and rate expression analysis

Facet-Induced Strong Metal Chloride−Support Interaction over CuCl2/γ-Al2O3 Catalyst to Enhance Ethylene Oxychlorination Performance

“…In the oxidation step, the adsorbed O 2 dissociation has the highest energy barrier, which can be assigned to the RDS. 58 The energy barrier of 5Cu/Al 2 O 3 (110) is 1.13 and 1.23 eV for 5Cu/Al 2 O 3 (100), and it is also in line with the experimental results that showed the oxidation rate on 5Cu/ Al 2 O 3 -P is much faster than on 5Cu/Al 2 O 3 -T (Figure 6). The presence of the Cl vacancy on the catalysts was found to increase the energy barriers of all the steps regardless of the supports, as shown in Figure 7b.…”

“…It is consistent with the experimentally observed lower rate of 5Cu/Al 2 O 3 -T than on 5Cu/Al 2 O 3 -P. In the reduction step, EDC desorption has the highest energy barrier on both catalysts, 0.2 eV on 5Cu/Al 2 O 3 (110) and 0.66 eV on 5Cu/Al 2 O 3 (100), as shown in Figure a. In the oxidation step, the adsorbed O 2 dissociation has the highest energy barrier, which can be assigned to the RDS . The energy barrier of 5Cu/Al 2 O 3 (110) is 1.13 and 1.23 eV for 5Cu/Al 2 O 3 (100), and it is also in line with the experimental results that showed the oxidation rate on 5Cu/Al 2 O 3 -P is much faster than on 5Cu/Al 2 O 3 -T (Figure ).…”

“…The reaction rate can be estimated by the Gibbs free energy based on the transition state theory, and the lower reaction rate is obtained by the higher Gibbs free energy. 58 The Gibbs free energies of the hydrochlorination step on both catalysts are the lowest among the three steps, indicating that it is energetically favorable. It is in good agreement with the study which previously reported that it is a kinetic-irrelevant step in ethylene oxychlorination.…”

“…The Gibbs free energy profile represents the kinetics of each step as well as the whole catalytic cycle. The reaction rate can be estimated by the Gibbs free energy based on the transition state theory, and the lower reaction rate is obtained by the higher Gibbs free energy . The Gibbs free energies of the hydrochlorination step on both catalysts are the lowest among the three steps, indicating that it is energetically favorable.…”

Investigating Reforming Kinetics of a Synthetic Biogas Mixture on Ni: Model Development and Experimental Validation

“…7 Within these elementary kinetic mechanisms, lumped reactions/rate expressions can be identified to devise a modeling framework with a reduced number of kinetic parameters. 8 This involves identification of the most abundant reaction intermediate (MARI) and quasi-equilibrated steps in the elementary reactions. 9 Most of the reactions other than the rds are in quasi-or pseudoequilibrium, with their rate of change being zero.…”