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A simple chemical engine in steady and dynamic situations

Sieniutycz S.

Archives of Thermodynamics

2007

Vol. 28, no. 2

57-84

We transfer to the realm of chemical engines a method of thermodynamic optimization that was developed earlier for thermal machines aimed at maximum production of power. Steady-state model refers to the situation when two reservoirs are infinite, whereas an unsteady model treats a dynamical case with finite upper reservoir and gradually decreasing chemical potential of the active component of fuel. In the considered chemical systems total power output is maximized at constraints which take into account dynamics of mass transport and efficiency of power generation. Methods of dynamic optimization, especially dynamic programming, lead to kinetic limits estimated in form of an optimal function that describes integral power output and extends the reversible chemical work W[rev] to finite rate situations. Optimization results lead to energy limits in chemical systems subject to dissipative effects caused by rates of chemical reaction and transport phenomena. Finite-rate results include irreducible losses caused by mass transfer resistances to the classical work potential. Functions of extremum power, which incorporate a residual minimum of entropy production, are formulated in terms of initial and final states, total duration and (in a discrete process) number of stages.