By Harkins W. D.
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Extra resources for The Change of Molecular Kinetic Energy into Molecular Potential Energy The Entropy Principle and Molecular Association
Example text
Rheol. 9 (1999) 17. ] The fundamental role of symmetries in specifying equilibrium systems puts equilibrium thermodynamicson a quite rigorous footing. Beyond-equilibriumthermodynamics is in a fundamental sense less rigorous than its equilibrium counterpart. The relevant variables beyond equilibrium are found by separating fast and slow variables and keeping only the slowest ones. By neglecting the fast variables one should expect to introduce errors determined by the ratio of short to long time scales, which is zero in equilibrium thermodynamics and small but finite in beyond-equilibrium thermodynamics.
Non-Equilib. Thermodyn. 28 (2003) 51; Pasquali & Scriven, J. NonNewtonian Fluid Mech. 120 (2004) 101. 1 and Appendix B. 20 INTRODUCTION I 0 I I 4 2% - Fig. 4 Variables for two subsystems exchanging heat and volume. 4). Use x = (q, v, E l , E z ) , where v is the velocity of the wall. Assume that the subsystems contain the same number of particles ( N I = N2 = N ) , and that their equilibrium thermodynamics is given by the entropy function S ( E ,V, N). The motion of the wall is assumed to be frictionless.
To arrive at a fundamental equation, we need to introduce the variables z for describing a system of interest; the time derivative d x / d t is then assumed to be the sum of a “reversible” and an “irreversible” contribution. Because the “reversible” contribution should be “under mechanistic control,” this term should have a well-understood structure. 2). To obtain a time evolution &eversible from a Hamiltonian, which we can think of as the energy function of the system, we need to associate a vector field with any Hamiltonian.