Few studies of chemical reactions at interfaces have dealt with experimental approaches that directly measure thermodynamic parameters. Understandably, these data do not resolve molecular configurations and interactions that underpin them. These details can be provided by other in-depth spectroscopic and molecular simulations. Yet, the significance of connecting fundamental thermodynamic parameters of sorption with the molecular-level structure of the interface lies in the ability to predict macroscopic behavior based on surface reactivity. Then, equilibrium and kinetic information at the molecular scale can be used to model macroscopic reactive transport. This contribution will present illustrative examples of how insights from thermodynamic data obtained through experimental approaches, such as operando flow microcalorimetry and isothermal titration calorimetry, have helped advance our understanding of exchange and adsorption reactions at various solid interfaces. Additional data will be shared to illustrate the next developments necessary to rationalize macroscopic thermodynamic data, connect them to molecular-level and computational frameworks, and approach the next frontier in deciphering complex interfaces.

The role of experimental thermodynamics in understanding complex interfaces

ACS Fall 2021

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