Microwave Inhibition of the Hydrogenation of CO2 for Methane Formation

The complex equilibria associated with the hydrogenation of CO2 to form valuable products are of considerable interest for the remediation of CO2. Due to the potential usefulness of these reactions, alternative methods of driving them more favorably using alternative energy sources, such as microwave radiation, are also of interest. We report here a study of the methanation reaction that yields CH4 , which was studied under microwave and conventional convective heating conditions. An essential part of the science that arises from such studies is characterizing the microwave-specific effects on the reaction. From the determined equilibrium constants, we found that microwave radiation strongly inhibited the formation of CH4. The effective thermodynamic parameters obtained from a van't Hoff plot reflect this inhibition. The enthalpy under microwave conditions is -38.63 kJ/mol, compared to -180.02 kJ/mol under conventional heating methods. Similarly, the free energy across the temperature range is less negative, suggesting a decrease in spontaneity under microwave conditions. We also observed a significant difference in the entropy, with entropy of -52 J/mol under microwave conditions and -206 J/mol under conventional conditions. This is consistent with prior observations that microwaves do not accelerate exothermic reactions. As discussed, this difference may arise from the microwave-driven dissociation of the reactant before CH4 bonds are made. Analysis of this system is of interest in understanding how the microwave inhibits the formation of the products of exothermic reactions. These results are of significance for understanding the broad area of microwave driven heterogeneous catalysis.