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Liquids, Volume 3, Issue 1 (March 2023) – 12 articles

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9 pages, 1468 KiB  
Article
Conformational Dependence of the First Hyperpolarizability of the Li@B10H14 in Solution
by Idney Brandão, Tertius L. Fonseca, Herbert C. Georg, Marcos A. Castro and Renato B. Pontes
Liquids 2023, 3(1), 159-167; https://doi.org/10.3390/liquids3010012 - 20 Feb 2023
Viewed by 1393
Abstract
Using the ASEC-FEG approach in combination with atomistic simulations, we performed geometry optimizations of a Cs conformer of the lithium decahydroborate (Li@B10H14) complex in chloroform and in water, which has been shown to be the most stable in [...] Read more.
Using the ASEC-FEG approach in combination with atomistic simulations, we performed geometry optimizations of a Cs conformer of the lithium decahydroborate (Li@B10H14) complex in chloroform and in water, which has been shown to be the most stable in the gas phase and calculated its first hyperpolarizability. At room temperature, ASEC-FEG calculations show that this conformer is stable only in chloroform. However, it is found that the nonlinear response of the Cs conformer in chloroform is mild, and the result for the hyperpolarizability is markedly decreased in comparison with the result of the C2v conformer. Full article
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27 pages, 13661 KiB  
Article
Investigation of the Impact of High Concentration LiTFSI Electrolytes on Silicon Anodes with Reactive Force Field Simulations
by Heather Cavers, Julien Steffen, Neeha Gogoi, Rainer Adelung, Bernd Hartke and Sandra Hansen
Liquids 2023, 3(1), 132-158; https://doi.org/10.3390/liquids3010011 - 6 Feb 2023
Cited by 1 | Viewed by 2130
Abstract
The initial formation cycles are critical to the performance of a lithium-ion battery (LIB), particularly in the case of silicon anodes, where the high surface area and extreme volume expansion during cycling make silicon susceptible to detrimental side reactions with the electrolyte. The [...] Read more.
The initial formation cycles are critical to the performance of a lithium-ion battery (LIB), particularly in the case of silicon anodes, where the high surface area and extreme volume expansion during cycling make silicon susceptible to detrimental side reactions with the electrolyte. The solid electrolyte interface (SEI) that is formed during these initial cycles serves to protect the surface of the anode from a continued reaction with the electrolyte, and its composition reflects the composition of the electrolyte. In this work, ReaxFF reactive force field simulations were used to investigate the interactions between ether-based electrolytes with high LiTFSI salt concentrations (up to 4 mol/L) and a silicon oxide surface. The simulation investigations were verified with galvanostatic testing and post-mortem X-ray photoelectron spectroscopy, revealing that highly concentrated electrolytes resulted in the faster formation and SEIs containing more inorganic and silicon species. This study emphasizes the importance of understanding the link between electrolyte composition and SEI formation. This ReaxFF approach demonstrates an accessible way to tune electrolyte compositions for optimized performance without costly, time-consuming experimentation. Full article
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14 pages, 476 KiB  
Article
Determination of Abraham Model Solute Descriptors for 62 Additional C10 through C13 Methyl- and Ethyl-Branched Alkanes
by Ramya Motati and William E. Acree, Jr.
Liquids 2023, 3(1), 118-131; https://doi.org/10.3390/liquids3010010 - 1 Feb 2023
Cited by 3 | Viewed by 1827
Abstract
Abraham model solute descriptors are reported for the first time for 62 additional C10 through C13 methyl- and ethyl-branched alkanes. The numerical values were determined using published gas chromatographic retention Kováts retention indices for 157 alkane solutes eluted from a squalane [...] Read more.
Abraham model solute descriptors are reported for the first time for 62 additional C10 through C13 methyl- and ethyl-branched alkanes. The numerical values were determined using published gas chromatographic retention Kováts retention indices for 157 alkane solutes eluted from a squalane stationary phase column. The 95 alkane solutes that have known descriptor values were used to construct the Abraham model KRI versus L-solute descriptor correlation needed in our calculations. The calculated solute descriptors can be used in conjunction with previously published Abraham model correlations to predict a wide range of important physico-chemical and biological properties. The predictive computations are illustrated by estimating the air-to-polydimethylsiloxane partition coefficient for each of the 157 alkane solutes. Full article
(This article belongs to the Collection Feature Papers in Solutions and Liquid Mixtures Research)
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26 pages, 1019 KiB  
Article
How Does Heat Propagate in Liquids?
by Fabio Peluso
Liquids 2023, 3(1), 92-117; https://doi.org/10.3390/liquids3010009 - 30 Jan 2023
Cited by 3 | Viewed by 2182
Abstract
In this paper, we proceed to illustrate the consequences and implications of the Dual Model of Liquids (DML) by applying it to the heat propagation. Within the frame of the DML, propagation of thermal (elastic) energy in liquids is due to wave-packet propagation [...] Read more.
In this paper, we proceed to illustrate the consequences and implications of the Dual Model of Liquids (DML) by applying it to the heat propagation. Within the frame of the DML, propagation of thermal (elastic) energy in liquids is due to wave-packet propagation and to the wave-packets’ interaction with the material particles of the liquid, meant in the DML as aggregates of molecules swimming in an ocean of amorphous liquid. The liquid particles interact with the lattice particles, a population of elastic wave-packets, by means of an inertial force, exchanging energy and momentum with them. The hit particle relaxes at the end of the interaction, releasing the energy and momentum back to the system a step forward and a time lapse later, like in a tunnel effect. The tunnel effect and the duality of liquids are the new elements that suggest on a physical basis for the first time, using a hyperbolic equation to describe the propagation of energy associated to the dynamics of wave-packet interaction with liquid particles. Although quantitatively relevant only in the transient phase, the additional term characterizing the hyperbolic equation, usually named the “memory term”, is physically present also once the stationary state is attained; it is responsible for dissipation in liquids and provides a finite propagation velocity for wave-packet avalanches responsible in the DML for the heat conduction. The consequences of this physical interpretation of the “memory” term added to the Fourier law for the phononic contribution are discussed and compiled with numerical prediction for the value of the memory term and with the conclusions of other works on the same topic. Full article
(This article belongs to the Section Physics of Liquids)
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2 pages, 142 KiB  
Editorial
Acknowledgment to the Reviewers of Liquids in 2022
by Liquids Editorial Office
Liquids 2023, 3(1), 90-91; https://doi.org/10.3390/liquids3010008 - 13 Jan 2023
Viewed by 775
Abstract
High-quality academic publishing is built on rigorous peer review [...] Full article
24 pages, 1178 KiB  
Article
Linear Solvation–Energy Relationships (LSER) and Equation-of-State Thermodynamics: On the Extraction of Thermodynamic Information from the LSER Database
by Costas Panayiotou, Ioannis Zuburtikudis, Hadil Abu Khalifeh and Vassily Hatzimanikatis
Liquids 2023, 3(1), 66-89; https://doi.org/10.3390/liquids3010007 - 11 Jan 2023
Cited by 4 | Viewed by 2212
Abstract
There is a remarkable wealth of thermodynamic information in freely accessible databases, the LSER database being a classical example. The LSER, or Abraham solvation parameter model, is a very successful predictive tool in a variety of applications in the (bio)chemical and environmental sector. [...] Read more.
There is a remarkable wealth of thermodynamic information in freely accessible databases, the LSER database being a classical example. The LSER, or Abraham solvation parameter model, is a very successful predictive tool in a variety of applications in the (bio)chemical and environmental sector. The model and the associated database are very rich in thermodynamic information and information on intermolecular interactions, which, if extracted properly, would be particularly useful in various thermodynamic developments for further applications. Partial Solvation Parameters (PSP), based on equation-of-state thermodynamics, are designed as a versatile tool that would facilitate this extraction of information. The present work explores the possibilities of such an LSER–PSP interconnection and the challenging issues this effort is faced with. The thermodynamic basis of the very linearity of the LSER model is examined, especially, with respect to the contribution of strong specific interactions in the solute/solvent system. This is done by combining the equation-of-state solvation thermodynamics with the statistical thermodynamics of hydrogen bonding. It is verified that there is, indeed, a thermodynamic basis of the LFER linearity. Besides the provenance of the sought linearity, an insight is gained on the thermodynamic character and content of coefficients and terms of the LSER linearity equations. The perspectives from this insight for the further development of LSER and related databases are discussed. The thermodynamic LSER–PSP interconnection is examined as a model for the exchange in information between QSPR-type databases and equation-of-state developments and the associated challenges are examined with representative calculations. Full article
(This article belongs to the Special Issue Modeling of Liquids Behavior: Experiments, Theory and Simulations)
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9 pages, 628 KiB  
Review
The Relevance of Cavity Creation for Several Phenomena Occurring in Water
by Giuseppe Graziano
Liquids 2023, 3(1), 57-65; https://doi.org/10.3390/liquids3010006 - 9 Jan 2023
Cited by 1 | Viewed by 1571
Abstract
The solvent-excluded volume effect is an under-appreciated general phenomenon occurring in liquids and playing a fundamental role in many cases. It is quantified and characterized by means of the theoretical concept of cavity creation and its Gibbs free energy cost. The magnitude of [...] Read more.
The solvent-excluded volume effect is an under-appreciated general phenomenon occurring in liquids and playing a fundamental role in many cases. It is quantified and characterized by means of the theoretical concept of cavity creation and its Gibbs free energy cost. The magnitude of the reversible work of cavity creation proves to be particularly large in water, and this fact plays a key role for, among other things, the poor solubility of nonpolar species, the formation of host–guest complexes, and the folding of globular proteins. An analysis of some examples is provided in the present review. Full article
(This article belongs to the Special Issue Modeling of Liquids Behavior: Experiments, Theory and Simulations)
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9 pages, 4020 KiB  
Communication
Density and Dynamic Viscosity of Perfluorodecalin-Added n-Hexane Mixtures: Deciphering the Role of Fluorous Liquids
by Deepika and Siddharth Pandey
Liquids 2023, 3(1), 48-56; https://doi.org/10.3390/liquids3010005 - 4 Jan 2023
Cited by 6 | Viewed by 2031
Abstract
Fluorous solvents are deputed as prominent solvent systems owing to their salient features, unique physical properties, and ecological importance. In this study, the temperature- and composition-dependence of physical properties, density (ρ/g·cm−3), and dynamic viscosity (η/mPa·s), of neat [...] Read more.
Fluorous solvents are deputed as prominent solvent systems owing to their salient features, unique physical properties, and ecological importance. In this study, the temperature- and composition-dependence of physical properties, density (ρ/g·cm−3), and dynamic viscosity (η/mPa·s), of neat perfluorodecalin (PFD) and PFD-added n-hexane mixtures with select compositions are reported. Density follows a linear decrease with temperature and a quadratic increase with the mole fraction of PFD. The sensitivity or dependence of density on temperature increases with an increase in PFD mole fraction. The temperature-dependence of the dynamic viscosity of the investigated mixtures follows the Arrhenius-type expression from which the resultant activation energy of the viscous flow (Ea,η) is determined. Interestingly, the composition-dependence of dynamic viscosity shows exponential growth with an increase in PFD mole fraction. Excess molar volumes (VE) and deviation in the logarithmic viscosities ∆(ln η) of the mixtures are calculated to highlight the presence of strong repulsive interactions between the two mixture components. Full article
(This article belongs to the Special Issue Modeling of Liquids Behavior: Experiments, Theory and Simulations)
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8 pages, 897 KiB  
Communication
Climbing Colloidal Suspension
by Motoyoshi Kobayashi, Takuya Sugimoto, Shunsuke Sato and Ryouichi Ishibashi
Liquids 2023, 3(1), 40-47; https://doi.org/10.3390/liquids3010004 - 2 Jan 2023
Viewed by 4232
Abstract
Mixtures of powder and liquid are ubiquitous in nature as well as industries and exhibit complex flowing and deforming behaviors, including sol to gel transition under shear stress. In order to better understand the characteristic features of this type of mixture, we observed [...] Read more.
Mixtures of powder and liquid are ubiquitous in nature as well as industries and exhibit complex flowing and deforming behaviors, including sol to gel transition under shear stress. In order to better understand the characteristic features of this type of mixture, we observed the behavior of a mixture of colloidal silica particles and water as a model system under vibration. The mixture showed different states, from powder-like to viscous fluid-like, with increasing content of water. At certain concentrations of silica particles (around 70 wt. %) and under relatively faster vibration (over 17 Hz), we observed that the colloidal suspension of silica particles and water climbed up the wall of a container against gravity. The main purpose of this paper is to report how we can observe the climbing suspension of colloidal silica. The rheological measurements of the climbing suspension demonstrated that the climbing suspension showed shear-thickening behavior, where force chain networks and normal stress differences are considered to develop. Therefore, we speculate that the transient formation and breaking of force networks and normal stress differences under vibration contribute to the occurrence of the climbing suspension. The tunable nature of colloidal suspensions may help to elucidate the climbing mechanism in the future. Full article
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21 pages, 6351 KiB  
Review
Vibrational Raman Spectroscopy of the Hydration Shell of Ions
by Nishith Ghosh, Subhadip Roy, Anisha Bandyopadhyay and Jahur Alam Mondal
Liquids 2023, 3(1), 19-39; https://doi.org/10.3390/liquids3010003 - 27 Dec 2022
Cited by 6 | Viewed by 3835
Abstract
Ionic perturbation of water has important implications in various chemical, biological and environmental processes. Previous studies revealed the structural and dynamical perturbation of water in the presence of ions, mainly with concentrated electrolyte solutions having significant interionic interactions. These investigations highlighted the need [...] Read more.
Ionic perturbation of water has important implications in various chemical, biological and environmental processes. Previous studies revealed the structural and dynamical perturbation of water in the presence of ions, mainly with concentrated electrolyte solutions having significant interionic interactions. These investigations highlighted the need of selective extraction of the hydration shell water from a dilute electrolyte solution that is largely free from interionic interactions. Double-difference infrared (DDIR) and Raman multivariate curve resolution (Raman-MCR), as well as MD simulation, provided valuable insight in this direction, suggesting that the perturbed water mainly resides in the immediate vicinity of the ion, called the hydration shell. Recently, we have introduced Raman difference spectroscopy with simultaneous curve fitting (Raman-DS-SCF) analysis that can quantitatively extract the vibrational response of the perturbed water pertaining to the hydration shell of fully hydrated ions/solute. The DS-SCF analysis revealed novel hydrogen-bond (H-bond) structural features of hydration water, such as the existence of extremely weakly interacting water–OH (νmax ~ 3600 cm−1) in the hydration shell of high-charge-density metal ions (Mg2+, Dy3+). In addition, Raman-DS-SCF retrieves the vibrational response of the shared water in the water–shared-ion pair (WSIP), which is different from the hydration shell water of either the interacting cation and anion. Herein, we discuss the perturbation of water H-bonding in the immediate vicinity of cation, anion, zwitterion and hydrophobes and also the inter-ionic interactions, with a focus on the recent results from our laboratory using Raman-DS-SCF spectroscopy. Full article
(This article belongs to the Special Issue Hydration of Ions in Aqueous Solution)
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12 pages, 463 KiB  
Article
Thermodynamic Analysis of the Solubility of Sulfadiazine in (Acetonitrile 1-Propanol) Cosolvent Mixtures from 278.15 K to 318.15 K
by Carlos Francisco Trujillo-Trujillo, Fredy Angarita-Reina, Mauricio Herrera, Claudia Patria Ortiz, Rossember Edén Cardenas-Torres, Fleming Martinez and Daniel Ricardo Delgado
Liquids 2023, 3(1), 7-18; https://doi.org/10.3390/liquids3010002 - 22 Dec 2022
Cited by 2 | Viewed by 1709
Abstract
Drug solubility is one of the most significant physicochemical properties as it is related to drug design, formulation, quantification, recrystallization, and other processes, so understanding it is crucial for the pharmaceutical industry. In this context, this research presents the thermodynamic analysis of the [...] Read more.
Drug solubility is one of the most significant physicochemical properties as it is related to drug design, formulation, quantification, recrystallization, and other processes, so understanding it is crucial for the pharmaceutical industry. In this context, this research presents the thermodynamic analysis of the solubility of sulfadiazine (SD) in cosolvent mixtures {acetonitrile + 1-propanol} at 9 temperatures (278.15 K–318.15 K), which is a widely used drug in veterinary therapy, and two solvents of high relevance in the pharmaceutical industry, respectively. The solubility of SD, in cosolvent mixtures {acetonitrile + 1-propanol} is an endothermic process where the maximum solubility was reached in pure acetonitrile at 318.15 K and the minimum in 1-propanol at 278.15 K. Although the solubility parameters of acetonitrile and propanol were similar, the addition of acetonitrile to the cosolvent mixture leads to a positive cosolvent effect on the solubility of DS. As for the thermodynamic functions of the solution, the process is strongly influenced by enthalpy, and according to the enthalpy–entropy compensation analysis, the process is enthalpy-driven in intermediate to rich mixtures in 1-propanol and entropy-driven in mixtures rich in acetonitrile. Full article
(This article belongs to the Special Issue Modeling of Liquids Behavior: Experiments, Theory and Simulations)
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6 pages, 429 KiB  
Article
Application of Solution Calorimetry to Determining the Fusion Enthalpy of an Arylaliphatic Compound at 298.15 K: n-Octadecanophenone
by Mikhail I. Yagofarov, Ilya S. Balakhontsev, Andrey A. Sokolov and Boris N. Solomonov
Liquids 2023, 3(1), 1-6; https://doi.org/10.3390/liquids3010001 - 21 Dec 2022
Viewed by 1603
Abstract
Evaluating the temperature dependence of the fusion enthalpy is no trivial task, as any compound melts at a unique temperature. At the same time, knowledge of the fusion enthalpies under some common conditions, particularly at the reference temperature of 298.15 K, would substantially [...] Read more.
Evaluating the temperature dependence of the fusion enthalpy is no trivial task, as any compound melts at a unique temperature. At the same time, knowledge of the fusion enthalpies under some common conditions, particularly at the reference temperature of 298.15 K, would substantially facilitate the comparative analysis and development of the predictive schemes. In this work, we continue our investigations of the temperature dependence of the fusion enthalpy of organic non-electrolytes using solution calorimetry. As an object of study, n-octadecanophenone, an arylaliphatic compound was chosen. The solvent appropriate for evaluating the fusion enthalpy at 298.15 K from the solution enthalpy of crystal was selected: p-xylene. The heat capacity and fusion enthalpy at the melting temperature were measured by differential scanning calorimetry to derive the fusion enthalpy at 298.15 K from the Kirchhoff’s law of Thermochemistry. An agreement between the independently determined values was demonstrated. This particular result opens a perspective for further studies of the fusion thermochemistry of arylaliphatic compounds at 298.15 K by solution calorimetry. Full article
(This article belongs to the Special Issue Modeling of Liquids Behavior: Experiments, Theory and Simulations)
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