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Thermodynamics and Anomalous Properties in Fluids

A special issue of Entropy (ISSN 1099-4300). This special issue belongs to the section "Thermodynamics".

Deadline for manuscript submissions: closed (30 June 2024) | Viewed by 1412

Special Issue Editor


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Guest Editor
Faculty of Chemistry and Chemical Technology, University of Ljubljana, Večna pot 113, SI-1000 Ljubljana, Slovenia
Interests: water; anomalous properties; polymers; electrolytes; computer simulations; analytical theories

Special Issue Information

Dear Colleagues,

Water is the most abundant and, arguably, the most important fluid on Earth. It influences every aspect of our lives, as it drives the biological processes, serving as a universal solvent. In the biosphere, water accounts for more than half of the weight of living cells. Industrially, it is used as a coolant, solvent, and reactant. Water is also one of the most unusual liquids. It is notable for having a very complex phase diagram with many anomalies, such as the negative slope of its liquid–solid boundary. Related to this is the other well-known anomaly, namely, the greater density of water compared with ice and a temperature range where the density of water increases with warming. Water’s thermodynamics and the exact mechanism of water anomalies have been extensively researched and are not completely clear. It is known, however, that strong and heavily angular-dependent interactions, known as hydrogen bonds, play a vital role in water’s thermodynamic properties. They introduce a competition between the orientational order that favors low-density tetrahedral coordination and the configurational order that favors denser coordination. At lower temperatures, the orientational contribution is dominant, whereas at higher temperatures the reverse is true.

Despite significant work and progress in this area, the thermodynamics properties of water and other anomalous liquids are still not well understood. Water, for example, is difficult to model because it forms hydrogen bonds, which can be described by orientation-dependent interactions. These interactions are coupled to each other rigidly and sterically (i.e., when a water molecule rotates, moving one hydrogen bonding arm, it rigidly moves all the other hydrogen bonding arms). This Special Issue aims to emphasize new research results in the application of statistical thermodynamics to entropy and anomalous properties of liquids. Original manuscripts highlighting the various topics in this area, both traditional and novel, are welcome.

Prof. Dr. Tomaž Urbić
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Entropy is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2600 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • theory of the liquid structure
  • anomalous properties
  • liquid–liquid transition
  • supercooled liquids and crystal nucleation
  • entropy changes
  • water
  • liquid polymorphism in soft matter
  • crystallization of anomalous liquids

Published Papers (2 papers)

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Research

8 pages, 648 KiB  
Article
Molecular-Scale Liquid Density Fluctuations and Cavity Thermodynamics
by Attila Tortorella and Giuseppe Graziano
Entropy 2024, 26(8), 620; https://doi.org/10.3390/e26080620 - 24 Jul 2024
Viewed by 180
Abstract
Equilibrium density fluctuations at the molecular level produce cavities in a liquid and can be analyzed to shed light on the statistics of the number of molecules occupying observation volumes of increasing radius. An information theory approach led to the conclusion that these [...] Read more.
Equilibrium density fluctuations at the molecular level produce cavities in a liquid and can be analyzed to shed light on the statistics of the number of molecules occupying observation volumes of increasing radius. An information theory approach led to the conclusion that these probabilities should follow a Gaussian distribution. Computer simulations confirmed this prediction across various liquid models if the size of the observation volume is not large. The reversible work required to create a cavity and the chance of finding no molecules in a fixed observation volume are directly correlated. The Gaussian formula for the latter probability is scrutinized to derive the changes in enthalpy and entropy, which arise from the cavity creation. The reversible work of cavity creation has a purely entropic origin as a consequence of the solvent-excluded volume effect produced by the inaccessibility of a region of the configurational space. The consequent structural reorganization leads to a perfect compensation of enthalpy and entropy changes. Such results are coherent with those obtained from Lee in his direct statistical mechanical study. Full article
(This article belongs to the Special Issue Thermodynamics and Anomalous Properties in Fluids)
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12 pages, 2232 KiB  
Article
The Magnetic Field Freezes the Mercedes–Benz Water Model
by Tomaz Urbic
Entropy 2023, 25(12), 1618; https://doi.org/10.3390/e25121618 - 4 Dec 2023
Viewed by 908
Abstract
In this study, we investigate the impact of magnetic fields on the structural and thermodynamic properties of water. To accomplish this, we employed the Mercedes–Benz (MB) model, a two-dimensional representation of water using Lennard–Jones disks with angle-dependent interactions that closely mimic hydrogen bond [...] Read more.
In this study, we investigate the impact of magnetic fields on the structural and thermodynamic properties of water. To accomplish this, we employed the Mercedes–Benz (MB) model, a two-dimensional representation of water using Lennard–Jones disks with angle-dependent interactions that closely mimic hydrogen bond formation. We extended the MB model by introducing two charges to enable interaction with the magnetic field. Employing molecular dynamics simulations, we thoroughly explored the thermodynamic properties concerning various magnetic flux intensities. As a result, we observed that under a weak magnetic flux, the property of water remained unaltered, while a stronger flux astonishingly led to the freezing of water molecules. Furthermore, our study revealed that once a specific flux magnitude was reached, the density anomaly disappeared, and an increase in flux caused the MB particles to form a glassy state. Full article
(This article belongs to the Special Issue Thermodynamics and Anomalous Properties in Fluids)
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