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Macroscopic and Microscopic Thermodynamics: From Fundamentals to Present Applications 2.0

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A special issue of International Journal of Molecular Sciences (ISSN 1422-0067). This special issue belongs to the section "Physical Chemistry and Chemical Physics".

Deadline for manuscript submissions: closed (15 June 2023) | Viewed by 17109

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Prof. Dr. José S. Urieta

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Group of Applied Thermodynamics and Surfaces (GATHERS), Universidad de Zaragoza, Zaragoza, Spain
Interests: thermophysical properties; thermodynamic modeling; calorimetry; pressurized fluids; ionic liquids; solubilities; electrochemistry; electrolytes
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Dr. Ana M. Mainar

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Co-Guest Editor

Associate Professor of Physical Chemistry, Universidad de Zaragoza, Zaragoza, Spain
Interests: advanced separation methods; supercritical fluids; process development; thermodynamic properties; biocides; cosmetic; thermodynamics; solvation; fluid mixtures
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Special Issue Information

Dear Colleagues,

As in the case of other “frontier” areas of knowledge, thermodynamics stands out, alongside other sciences, in taking on new challenges in solving problems, and ultimately in the transfer of knowledge. However, for this purpose, it is necessary to identify the fields of interest in which there are demands and to close the communication gaps that currently exist between experimental and theoretical researchers—a mission that is difficult but not impossible.

In recent decades, the incorporation of the molecular point of view of matter—combining laws of classical and statistical thermodynamics with chemical–physical models of the structure of matter and intermolecular forces—has allowed the development of procedures that are very useful to solve a wide variety of problems in fields as diverse as those of chemistry, chemical engineering, materials, energy, and food or health sciences. New possibilities have also arisen due to the increase in computing power and the development of software whose handling is, in many cases, quite affordable.

This Special Issue presents an invitation to researchers in molecular thermodynamics and other related fields to contribute their works; this aims to gather and promote research lines and build bridges between the basic aspects of science and the new developments in technological processes and materials.

Prof. Dr. José S. Urieta
Guest Editors
Dr. Ana M. Mainar
Co-Guest Editor

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Keywords

thermophysical properties
statistical thermodynamics
intermolecular forces
molecular models
applied thermodynamics
phase equilibria
transport across interfaces
process modeling
advanced separation processes

Published Papers (11 papers)

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Research

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22 pages, 4049 KiB

Open AccessArticle

Thermodynamic Behavior of (2-Propanol + 1,8-Cineole) Mixtures: Isothermal Vapor–Liquid Equilibria, Densities, Enthalpies of Mixing, and Modeling

by Beatriz Gimeno, Santiago Martinez, Ana M. Mainar, Jose S. Urieta and Pascual Perez

Int. J. Mol. Sci. 2023, 24(12), 10380; https://doi.org/10.3390/ijms241210380 - 20 Jun 2023

Viewed by 1132

Abstract

Vapor pressures and other thermodynamic properties of liquids, such as density and enthalpy of mixtures, are the key parameters in chemical engineering for designing new process units, and are also essential for understanding the physical chemistry, macroscopic and molecular behavior of fluid systems. In this work, vapor pressures between 278.15 and 323.15 K, densities and enthalpies of mixtures between 288.15 and 318.15 K for the binary mixture (2-propanol + 1,8-cineole) have been measured. From the vapor pressure data, activity coefficients and excess Gibbs energies were calculated via the Barker’s method and the Wilson equation. Excess molar volumes and excess molar enthalpies were also obtained from the density and calorimetric measurements. Thermodynamic consistency test between excess molar Gibbs energies and excess molar enthalpies has been carried out using the Gibbs–Helmholtz equation. Robinson–Mathias, and Peng–Robinson–Stryjek–Vera together with volume translation of Peneloux equations of state (EoS) are considered, as well as the statistical associating fluid theory that offers a molecular vision quite suitable for systems having highly non-spherical or associated molecules. Of these three models, the first two fit the experimental vapor pressure results quite adequately; in contrast, only the last one approaches the volumetric behavior of the system. A brief comparison of the thermodynamic excess molar functions for binary mixtures of short-chain alcohol + 1,8-cineole (cyclic ether), or +di-n-propylether (lineal ether) is also included. Full article

(This article belongs to the Special Issue Macroscopic and Microscopic Thermodynamics: From Fundamentals to Present Applications 2.0)

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18 pages, 7042 KiB

Open AccessArticle

Direct Measurement of the Four-Phase Equilibrium Coexistence Vapor–Aqueous Solution–Ice–Gas Hydrate in Water–Carbon Dioxide System

by Anton Semenov, Rais Mendgaziev, Andrey Stoporev, Vladimir Istomin, Timur Tulegenov, Murtazali Yarakhmedov, Andrei Novikov and Vladimir Vinokurov

Int. J. Mol. Sci. 2023, 24(11), 9321; https://doi.org/10.3390/ijms24119321 - 26 May 2023

Cited by 1 | Viewed by 1388

Abstract

Precise data on the non-variant equilibrium of the four phases (vapor–aqueous solution–ice–gas hydrate) in P–T coordinates are highly desired for developing accurate thermodynamic models and can be used as reference points (similar to the triple point of water). Using the two-component hydrate-forming system CO₂–H₂O, we have proposed and validated a new express procedure for determining the temperature and pressure of the lower quadruple point Q₁. The essence of the method is the direct measurement of these parameters after the successive formation of the gas hydrate and ice phases in the initial two-phase gas–water solution system under intense agitation of the fluids. After relaxation, the system occurs in the same equilibrium state (T = 271.60 K, P = 1.044 MPa), regardless of the initial parameters and the order of crystallization of the CO₂ hydrate and ice phases. Considering the combined standard uncertainties (±0.023 K, ±0.021 MPa), the determined P and T values agree with the results of other authors obtained by a more sophisticated indirect method. Validating the developed approach for systems with other hydrate-forming gases is of great interest. Full article

(This article belongs to the Special Issue Macroscopic and Microscopic Thermodynamics: From Fundamentals to Present Applications 2.0)

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15 pages, 2688 KiB

Open AccessArticle

Excess Enthalpies for Binary Mixtures of the Reactive System Acetic Acid + n-Butanol + n-Butyl Acetate + Water: Brief Data Review and Results at 313.15 K and Atmospheric Pressure

by Alexandra Golikova, Anna Shasherina, Yuri Anufrikov, Georgii Misikov, Maria Toikka, Irina Zvereva and Alexander Toikka

Int. J. Mol. Sci. 2023, 24(6), 5137; https://doi.org/10.3390/ijms24065137 - 07 Mar 2023

Cited by 2 | Viewed by 1211

Abstract

The data on molar excess enthalpies,

H_{m}^{E}

The data on molar excess enthalpies,

H_{m}^{E}

, for the binary mixtures acetic acid + n-butanol, acetic acid + n-butyl acetate and n-butanol + n-butyl acetate at 313.15 K and atmospheric pressure were obtained with use of the C80 isothermal mixing calorimeter (Setaram). The correlation of the data was carried out using the NRTL model and Redlich–Kister equation. A comparative analysis with the literature data on all available binary subsystems of the quaternary system was carried out. Other thermodynamic properties (

C_{p, m}^{E}

S_{m}^{E}

Δ_{m i x} S_{m}

G_{m}^{E}

and

Δ_{m i x} G_{m}

) of the binary systems were estimated using literature data and well-known formulas of classical thermodynamics. Full article

(This article belongs to the Special Issue Macroscopic and Microscopic Thermodynamics: From Fundamentals to Present Applications 2.0)

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11 pages, 942 KiB

Open AccessArticle

Anomalous Concentration Dependence of Surface Tension and Concentration-Concentration Correlation Functions of Binary Non-Electrolyte Solutions

by Carlo Carbone, Eduardo Guzmán and Ramón G. Rubio

Int. J. Mol. Sci. 2023, 24(3), 2276; https://doi.org/10.3390/ijms24032276 - 23 Jan 2023

Cited by 1 | Viewed by 1292

Abstract

The concentration dependence of the surface tension of several binary mixtures of non-electrolytes has been measured at 298.15 K. The mixtures have been chosen since they presented a so-called “W-shape” concentration dependence of the excess constant pressure heat capacity and high values of the concentration-concentration correlation function. This behavior was interpreted in terms of the existence of anomalously high concentration fluctuations that resemble those existing in the proximities of critical points. However, no liquid-liquid phase separation has been found in any of these mixtures over a wide temperature range. In this work, we have extended these studies to the liquid-air interfacial properties. The results show that the concentration dependence of the surface tension shows a plateau and the mixing surface tension presents a “W-shape” behavior. To the best of our knowledge, this is the first time that this behavior is reported. The weak anomalies of the surface tension near a liquid-liquid critical point suggest that the results obtained cannot be considered far-from-critical effects. The usual approach of substituting the activity by the concentration in the Gibbs equation for the relative surface concentration has been found to lead to large errors and the mixtures to have a fuzzy and thick liquid/vapor interface. Full article

(This article belongs to the Special Issue Macroscopic and Microscopic Thermodynamics: From Fundamentals to Present Applications 2.0)

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12 pages, 4818 KiB

Open AccessArticle

Solubility of Amino Acids in the Eutectic Solvent Constituted by Sodium Acetate Trihydrate and Urea and in Its Mixture with Water

by Cristina Gallego, Héctor Rodríguez and Ana Soto

Int. J. Mol. Sci. 2023, 24(2), 1550; https://doi.org/10.3390/ijms24021550 - 12 Jan 2023

Cited by 2 | Viewed by 2017

Abstract

Industrial fish and aquaculture processing leads to the generation of a huge quantity of by-products, whose accumulation and mismanagement involve serious environmental consequences as well as high economic losses. Taking advantage of these residues as a source of added-value compounds must be a priority in a circular economy. This work is a preliminary study to analyze the possibility of using the eutectic mixture of urea and sodium acetate trihydrate as a solvent for collagen extraction. To that end, the solid–liquid equilibrium of the system was determined in order to define the exact composition and temperature of the eutectic. The solubility in this solvent of the main amino acids that constitute fish collagen was studied at several temperatures and atmospheric pressure. At 308.15 K, solubilities of the major constituents of the target protein, namely L-proline, trans-4-hydroxy-L-proline, and glycine, were 0.19, 0.16, and 0.12 (mass fraction), respectively. These values increased with temperature. Dilution with water (50 wt%) allowed operation at lower temperature and led to an increase in the solubilities. The van ‘t Hoff model was satisfactorily used to correlate the experimental data and to calculate apparent properties of dissolution. All the dissolution processes studied herein are endothermic, non-spontaneous, and enthalpy-driven. Both the eutectic and its mixture with water are promising solvents for the design of an environmentally benign process for collagen extraction. Full article

(This article belongs to the Special Issue Macroscopic and Microscopic Thermodynamics: From Fundamentals to Present Applications 2.0)

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6 pages, 1115 KiB

Open AccessArticle

BioMThermDB 1.0: Thermophysical Database of Proteins in Solutions

by Mina Nikolić, Sandi Brudar, Evangelos Coutsias, Ken A. Dill, Miha Lukšič, Carlos Simmerling and Barbara Hribar-Lee

Int. J. Mol. Sci. 2022, 23(23), 15371; https://doi.org/10.3390/ijms232315371 - 06 Dec 2022

Cited by 1 | Viewed by 1295

Abstract

We present here a freely available web-based database, called BioMThermDB 1.0, of thermophysical and dynamic properties of various proteins and their aqueous solutions. It contains the hydrodynamic radius, electrophoretic mobility, zeta potential, self-diffusion coefficient, solution viscosity, and cloud-point temperature, as well as the conditions for those determinations and details of the experimental method. It can facilitate the meta-analysis and visualization of data, can enable comparisons, and may be useful for comparing theoretical model predictions with experiments. Full article

(This article belongs to the Special Issue Macroscopic and Microscopic Thermodynamics: From Fundamentals to Present Applications 2.0)

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11 pages, 282 KiB

Open AccessArticle

Reaction-Diffusion Systems: Self-Balancing Diffusion and the Use of the Extent of Reaction as a Descriptor of Reaction Kinetics

by Miloslav Pekař

Int. J. Mol. Sci. 2022, 23(18), 10511; https://doi.org/10.3390/ijms231810511 - 10 Sep 2022

Cited by 1 | Viewed by 846

Abstract

Self-balancing diffusion is a theoretical concept that restricts the introduction of extents of reactions. This concept is analyzed in detail for general mass- and molar-based balances of reaction-diffusion mixtures, in relation to non-self-balancing cases, and with respect to its practical consequences. Self-balancing is a mathematical restriction on the divergences of diffusion fluxes. Fulfilling this condition enables the proper introduction of the extents of (independent) reactions that reduce the number of independent variables in thermodynamic descriptions. A note on a recent generalization of the concept of reaction and diffusion extents is also included. Even in the case of self-balancing diffusion, such extents do not directly replace reaction rates. Concentration changes caused by reactions (not by diffusion) are properly described by rates of independent reactions, which are instantaneous descriptors. If an overall descriptor is needed, the traditional extents of reactions can be used, bearing in mind that they include diffusion-caused changes. On the other hand, rates of independent reactions integrated with respect to time provide another overall, but reaction-only-related descriptor. Full article

(This article belongs to the Special Issue Macroscopic and Microscopic Thermodynamics: From Fundamentals to Present Applications 2.0)

14 pages, 4572 KiB

Open AccessArticle

Various Approaches to Studying the Phase Transition in an Octamethylcyclotetrasiloxane Crystal: From X-ray Structural Analysis to Metadynamics

by Alexander D. Volodin, Alexander F. Smol’yakov and Alexander A. Korlyukov

Int. J. Mol. Sci. 2022, 23(16), 9073; https://doi.org/10.3390/ijms23169073 - 13 Aug 2022

Viewed by 1699

Abstract

The structure, thermodynamic parameters, and the character of thermal motion in octamethylcyclotetrasiloxane (D4) were investigated using the combination of experimental (single-crystal X-ray diffraction, thermochemistry) and theoretical (density functional theory calculations, ab initio molecular dynamics and metadynamics) methods. Single crystals of D4 were grown in a glass capillary in situ and the structures of high- (238–270 K) and low-temperature (100–230 K) phases were studied in detail. In the temperature interval 230–238 K, a phase transition with rather low enthalpy (−1.04(7) kcal/mol) was detected. It was found that phase transition is accompanied by change of conformation of cyclosiloxane moiety from boat-saddle (cradle) to chair. According to PBE0/6-311G(d,p) calculation of isolated D4, such conformation changes are characterized by a low barrier (0.07 kcal/mol). The character of molecular thermal motion and the path of phase transition were established with combination of periodic DFT calculations, including molecular dynamics and metadynamics. The effect of crystal field led to an increase in the calculated phase transition barrier (4.27 kcal/mol from low- to high-temperature phase and 3.20 kcal/mol in opposite direction). Full article

(This article belongs to the Special Issue Macroscopic and Microscopic Thermodynamics: From Fundamentals to Present Applications 2.0)

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13 pages, 2590 KiB

Open AccessArticle

Friction in Myocardial Anoxia Leads to Negative Excess Entropy Production, Self-Organization, and Dissipative Structures

by Yves Lecarpentier, Victor Claes, Jean-Louis Hébert, Xénophon Krokidis, Olivier Schussler and Alexandre Vallée

Int. J. Mol. Sci. 2022, 23(13), 6967; https://doi.org/10.3390/ijms23136967 - 23 Jun 2022

Cited by 1 | Viewed by 1223

Abstract

Contraction of the heart is caused by actin filaments sliding along myosin filaments. This generates a frictional force inducing wear of the contractile apparatus. We postulated that this process could be exacerbated when the heart was submitted to severe anoxia. Anoxia induced dramatic abnormalities in the molecular properties of actin-myosin crossbridges. We applied the formalism of far-from-equilibrium thermodynamics to the left ventricular papillary muscles (LVPMs) of mammalian rat hearts which had been subjected to a prolonged anoxia (3 h). We showed that when subjected to prolonged anoxia, the heart operated far-from-equilibrium as evidenced by the non-linearity between thermodynamic force (F/T: Frictional force/Kelvin temperature) and thermodynamic flow (v0: myofilament sliding velocity). The rate of entropy production (EPR) was the product of (F/T) and v0. The excess entropy production (EEP) was equal to

\frac{\partial δ^{2} S}{\partial t}

\frac{\partial F}{T} δ

vo; (S: entropy). The tribological system remained stable when EEP was positive and became unstable when EEP became negative, thus characterizing instability of the system and reflecting the occurrence of self-organization and possibly dissipative structures. After 3 h anoxia, re-oxygenation induced significant reversibility. About 20% of the myosin heads did not recover despite re-oxygenation. These results may be of importance in the context of heart transplantation where the delay between the time of sampling from the donor and the time of the graft installation in the recipient should be as short as possible. Full article

(This article belongs to the Special Issue Macroscopic and Microscopic Thermodynamics: From Fundamentals to Present Applications 2.0)

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Review

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20 pages, 731 KiB

Open AccessReview

Detailing Protein-Bound Uremic Toxin Interaction Mechanisms with Human Serum Albumin in the Pursuit of Designing Competitive Binders

by Vida Dehghan Niestanak and Larry D. Unsworth

Int. J. Mol. Sci. 2023, 24(8), 7452; https://doi.org/10.3390/ijms24087452 - 18 Apr 2023

Cited by 1 | Viewed by 1223

Abstract

Chronic kidney disease is the gradual progression of kidney dysfunction and involves numerous co-morbidities, one of the leading causes of mortality. One of the primary complications of kidney dysfunction is the accumulation of toxins in the bloodstream, particularly protein-bound uremic toxins (PBUTs), which have a high affinity for plasma proteins. The buildup of PBUTs in the blood reduces the effectiveness of conventional treatments, such as hemodialysis. Moreover, PBUTs can bind to blood plasma proteins, such as human serum albumin, alter their conformational structure, block binding sites for other valuable endogenous or exogenous substances, and exacerbate the co-existing medical conditions associated with kidney disease. The inadequacy of hemodialysis in clearing PBUTs underscores the significance of researching the binding mechanisms of these toxins with blood proteins, with a critical analysis of the methods used to obtain this information. Here, we gathered the available data on the binding of indoxyl sulfate, p-cresyl sulfate, indole 3-acetic acid, hippuric acid, 3-carboxyl-4-methyl-5-propyl-2-furan propanoic acid, and phenylacetic acid to human serum albumin and reviewed the common techniques used to investigate the thermodynamics and structure of the PBUT–albumin interaction. These findings can be critical in investigating molecules that can displace toxins on HSA and improve their clearance by standard dialysis or designing adsorbents with greater affinity for PBUTs than HSA. Full article

(This article belongs to the Special Issue Macroscopic and Microscopic Thermodynamics: From Fundamentals to Present Applications 2.0)

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28 pages, 2001 KiB

Open AccessReview

Phase Behavior of Ionic Liquid-Based Aqueous Two-Phase Systems

by Lirong Nie, Ziwei Zheng, Mingxia Lu, Shun Yao and Dong Guo

Int. J. Mol. Sci. 2022, 23(20), 12706; https://doi.org/10.3390/ijms232012706 - 21 Oct 2022

Cited by 4 | Viewed by 2569

Abstract

As an environmentally friendly separation medium, the ionic liquid (IL)-based aqueous two-phase system (ATPS) is attracting long-term attention from a growing number of scientists and engineers. Phase equilibrium data of IL-based ATPSs are an important basis for the design and optimization of chemical reactions and separation processes involving ILs. This article provides the recent significant progress that has been made in the field and highlights the possible directions of future developments. The effects of each component (such as salting-out agents and ILs) on the phase behavior of IL-based ATPSs are summarized and discussed in detail. We mainly focus on the phase behavior of ATPSs by using ILs, expecting to provide meaningful and valuable information that may promote further research and application. Full article

(This article belongs to the Special Issue Macroscopic and Microscopic Thermodynamics: From Fundamentals to Present Applications 2.0)

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