Pitzer Seminar in Physical Chemistry: Scaling Down the Laws of Thermodynamics
Seminar: Physical Chemistry | September 19 | 4-5 p.m. | 120 Latimer Hall
Thermodynamics provides a robust conceptual framework and set of laws that govern the exchange of energy and matter. Although these laws were originally articulated for macroscopic objects, it is hard to deny that nanoscale systems, as well, often exhibit thermodynamic-like behavior biomolecular motors convert chemical fuel into mechanical work (like car engines), and individual polymer molecules exhibit hysteresis and dissipation when stretched and contracted (like rubber bands). To what extent can the venerable laws of thermodynamics be scaled down to apply to individual microscopic systems, and what new features emerge there at the nanoscale? I will review recent progress toward answering these questions.
The second law of thermodynamics is traditionally stated in terms of inequalities. For microscopic systems these inequalities can be replaced by stronger equalities, known as fluctuation relations, which relate equilibrium properties to far-from-equilibrium fluctuations. The discovery and experimental validation of these relations has stimulated interest in the feedback control of small systems, the closely related Maxwell demon paradox, and the interpretation of the thermodynamic arrow of time. These developments have led to new tools for the analysis of non-equilibrium experiments and simulations, and they have refined our understanding of irreversibility and the second law.
I will also discuss challenges and open questions, including how to extend fluctuation relations to quantum systems, how to define the volume of a single molecule, and how to properly formulate the first law of thermodynamics for small systems, when the interaction energy between the system and its thermal surroundings cannot be neglected.
Light refreshments will be served at 3:50 at The Coffee Lab