2011/01/28 by P. D. Gujrati, Gujrati, P. D. · 1 citation
Chemistry · Engineering · Physics and Astronomy · #80 #82 #Advanced Thermodynamics and Statistical Mechanics #Classical Physics (physics.class-ph) #FOS: Physical sciences #Materials Science (cond-mat.mtrl-sci) #Phase Equilibria and Thermodynamics #Statistical Mechanics (cond-mat.stat-mech) #cond-mat.mtrl-sci #cond-mat.stat-mech #msc:80 #msc:82 #physics.class-ph #thermodynamics and calorimetric analyses
paper · pdf · doi:10.48550/arxiv.1101.5623
25 pages; 1 figure; new results
openalex publication_date 2011/01/28 · arxiv created 2011/06/10 · arxiv updated 2011/06/13 · openalex created_date 2016/06/24 · openalex updated_date 2026/07/28
We use rigorous non-equilibrium thermodynamic arguments to prove (i) the residual entropy of any system is bounded below by the experimentally (calorimetrically) determined absolute temperature entropy, which itself is bounded below by the entropy of the corresponding equilibrium (metastable supercooled liquid) state, and (ii) the instantaneous entropy cannot drop below that of the equilibrium state. The theorems follow from the second law and the existence of internal equilibrium and refer to the thermodynamic entropy. They go beyond the calorimetric observations by Johari and Khouri [J. Chem. Phys. 134, 034515 (2011)] and others by extending them to all non-equilibrium systems regardless of how far they are from their equilibrium states. We also discuss the statistical interpretation of the thermodynamic entropy and show that the conventional Gibbs or Boltzmann interpretation gives the correct thermodynamic entropy even for a single sample regardless of the duration of measurements.