The Carnot Cycle, Reversibility and Entropy

The Carnot cycle and the attendant notions of reversibility and entropy are examined. It is shown how the modern view of these concepts still corresponds to the ideas Clausius laid down in the nineteenth century. As such, they reflect the outmoded idea, current at the time, that heat is motion. It is shown how this view of heat led Clausius to develop the entropy of a body based on the work that could be performed in a reversible process rather than the work that is actually performed in an irreversible process. In consequence, Clausius built into entropy a conflict with energy conservation, which is concerned with actual changes in energy. In this paper, reversibility and irreversibility are investigated by means of a macroscopic formulation of internal mechanisms of damping based on rate equations for the distribution of energy within a gas. It is shown that work processes involving a step change in external pressure, however small, are intrinsically irreversible. However, under idealised conditions of zero damping the gas inside a piston expands and traces out a trajectory through the space of equilibrium states. Therefore, the entropy change due to heat flow from the reservoir matches the entropy change of the equilibrium states. This trajectory can be traced out in reverse as the piston reverses direction, but if the external conditions are adjusted appropriately, the gas can be made to trace out a Carnot cycle in P-V space. The cycle is dynamic as opposed to quasi-static as the piston has kinetic energy equal in difference to the work performed internally and externally.

[1]  James Clerk Maxwell,et al.  The Scientific Letters and Papers of James Clerk Maxwell: Volume 1, 1846-1862 , 1990 .

[2]  J. B. Boyling,et al.  Carathéodory's principle and the existence of global integrating factors , 1968 .

[3]  D. Sheehan,et al.  Challenges to The Second Law of Thermodynamics: Theory and Experiment , 2005 .

[4]  J. Boyling An axiomatic approach to classical thermodynamics , 1972, Proceedings of the Royal Society of London. A. Mathematical and Physical Sciences.

[5]  R. Clausius,et al.  X. On a modified form of the second fundamental theorem in the mechanical theory of heat , 1856 .

[6]  Karl Heinz Hoffmann,et al.  Modeling, Simulation, and Reconstruction of 2-Reservoir Heat-to-Power Processes in Finite-Time Thermodynamics , 2020, Entropy.

[7]  J. Norton The Impossible Process: Thermodynamic Reversibility , 2016 .

[8]  Thermal damping in the compound piston , 2011 .

[9]  D. Sands Thermodynamic entropy and the accessible states of some simple systems , 2007, 0708.1626.

[10]  Wolfgang Muschik,et al.  A simple example for comparing GENERIC with rational non-equilibrium thermodynamics , 2000 .

[11]  T. G. Cowling,et al.  Natural Philosophy of Cause and Chance , 1949, Nature.

[12]  Rudolf Clausius,et al.  The Mechanical Theory of Heat: With Its Applications to the Steam-Engine and to the Physical Properties of Bodies , 2015 .

[13]  D. Sands,et al.  The compound piston: resolution of a thermodynamic controversy by means of kinetic theory , 2010 .

[14]  H. S. Leff,et al.  Entropy, Its Language, and Interpretation , 2007 .