On the Motive Power of Chemical Transformations in Open Systems

Abstract

The classical basic concepts of cyclic processes and the efficiency of heat engines are used here to conjecture about the laws of thermodynamics for open systems that can exchange matter with a surrounding environment. An ideal chemomechanical elastic bar is envisioned that changes its stiffness while undergoing a chemical transformation which is, in turn, influenced by the axial strain of the bar. Stable equilibrium states are identified as minimizers of the total energy, which is assumed to be nonconvex in type. If the bar is loaded and then alternatively placed in environments at chemical potentials either μ i or μ s >μ i , a reversible cycle analogous to the classical Carnot cycle may be traced. In this case, the environmental “chemical potential” plays the role of the temperature and the “chemical work” the role of heat. For the system, the main form of interaction with the exterior, other than mechanical work, is the exchange of mass of a component at different environmental chemical potentials. It is then possible to obtain an elementary theory of chemical engines in which efficiency estimates (in terms of environmental chemical potentials) and related pertinent issues can be discussed. This model may serve as a basis for analyzing coupled chemo-mechanical processes occurring in materials such as ionized gels for possible applications as actuators, and to interpret complex phenomena in biological systems, such as the chemical kinetics of smooth muscles.