Thermodynamic Efficiency in Dissipative Chemical/Supramolecular Processes

Out-of-equilibrium chemistry is not anymore a prerogative of nature. In recent years, fuel-driven self-assembly became a paradigmatic example of how chemists were able to access the realm of nonequilibrium processes. In the meantime, theoretical physicists achieved a deep understanding of these phenomena, which resulted in rigorous formulations of nonequilibrium thermodynamics for chemical systems. In this work, we crossbreed experimental and theoretical cutting edge research by building a quantitative thermodynamic description for two classes of chemical dissipative processes: energy storage and dissipative synthesis, which boast experimental examples in supramolecular chemistry. The former consists in storing chemical energy in the form of high-energy molecules, whereas the latter in synthesizing molecules by consuming fuel species. As nascent thermodynamics did for heat engines, we treat these systems as chemical engines and develop a quantitative framework for evaluating their efficiency. In doing so, we set the foundation for performance analysis of generic dissipative chemical processes.

This work was funded by the European Research Council project NanoThermo (ERC-2015-CoG Agreement No. 681456).