Positional microstates and probability fields in real systems
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Dennis Tolley
und
Lee D. Hansen
Abstract
A previously published paper provided six examples of spontaneous processes for ideal systems that cannot be explained using classical thermodynamics. These six examples include free expansion of an ideal gas, mixing of ideal gases, diffusion of an ideal solute, mixing of ideal solutes, osmosis with ideal solutions, and free discharge of a concentration battery with ideal solutions. The previous paper demonstrated how energy was not a driving force in any of these examples and then proceeded to develop a positional entropy model, S D, that explains why these spontaneous processes occur. This new paper provides a method for calculating positional entropy, S D, for the same six systems, but for real particles that include nonzero volumes, particles with different volumes, and particles with different particle-particle interactions. The important outcome of this work shows that spontaneous discharge of these six example systems, either for ideal or real particles, is the result of a probability field created by the non-equilibrium distribution of the microstates that exists after the constraints on the system are changed, e.g., by removal of a separating partition or the shorting of a concentration cell. The probability field biases the movement of the particles toward the equilibrium distribution, where the bias is a consequence of an increased probability and not because of a decrease in energy. An additional conclusion of this work shows that the discharge of the probability field to the final equilibrium distribution of positional microstates removes the potential energy in the system but does not violate the law of conservation of energy.
References
1. Tolley, H. D.; Woodfield, B. F.; Hansen, L. D. The Case of the Missing Entropy. Pure Appl. Chem. 2023, 95, 1207–1215. https://doi.org/10.1515/pac-2023-0808.Suche in Google Scholar
2. Gibbs, J. W. Elementary Principles in Statistical Mechanics; Dover Publications: N.Y., 2018; pp. 57–67. Chapter 6.Suche in Google Scholar
3. Planck, M. Treatise on Thermodynamics, 3rd revised edition, translated by A. Ogg from the 7th German edition; Dover Publications: N.Y, 1927. Section 134, pp 103-104 recognizes the need for inclusion of the distribution of matter in a complete development of thermodynamics, but no such development was forthcoming.Suche in Google Scholar
4. Hansen, L. D.; Woodfield, B. F.; Tolley, H. D. The Case of the Disappearing Energy: Potential Energies in Concentration Gradients. Pure Appl. Chem. 2024, 96, 1785–1788. https://doi.org/10.1515/pac-2024-0220.Suche in Google Scholar
Supplementary Material
This article contains supplementary material (https://doi.org/10.1515/pac-2024-0221).
© 2024 IUPAC & De Gruyter
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- Frontmatter
- In this issue
- IUPAC Recommendations
- Definition of materials chemistry (IUPAC Recommendations 2024)
- Research Articles
- Positional microstates and probability fields in real systems
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Artikel in diesem Heft
- Frontmatter
- In this issue
- IUPAC Recommendations
- Definition of materials chemistry (IUPAC Recommendations 2024)
- Research Articles
- Positional microstates and probability fields in real systems
- Synthesis, characterization and antioxidant screening of a 1,10-phenanthroline-based tetraza-macrocyclic ligand and its nickel complex with therapeutic potential and catalytic significance
- Comprehensive evaluation of physical properties and carbon dioxide capacities of new 2-(butylamino)ethanol-based deep eutectic solvents
- Comprehensive evaluation of the impact of ionic liquid incorporation on the optical properties, Urbach energy, thin film morphology, and surface roughness of poly(vinyl chloride) based on ionic materials
- The impact of nanofiller composition and nature on the enhancement of mechanical and rheological properties of poly(lactic acid) (PLA) nanobiocomposite films is achieved by regulating the spacing of organic fillers and PLA crystallinity
- The case of the disappearing energy: potential energies in concentration gradients
- Removal of metaldehyde pesticide from aquatic media using modified cellulose obtained from Populus nigra plant, as potential adsorbent
- New half sandwich complexes of ruthenium(ii) and iridium(iii). Study of their toxicity against Hela
