Search Results (272)

The low water solubility of sulfamethazine (SMT) limits its clinical efficacy, making it crucial to study techniques such as cosolvency to optimize pharmaceutical formulations. This study aimed to thermodynamically evaluate the solubility of SMT in {acetonitrile (MeCN) + ethanol (EtOH)} cosolvent mixtures over a temperature range of 278.15 to 318.15 K in order to understand the molecular interactions that govern this process. SMT solubility in the mixtures was measured using a flask-shaking method. The solid phases were analyzed using differential scanning calorimetry (DSC) to rule out polymorphisms. Using the Gibbs–van’t Hoff–Krug model, we calculated the apparent thermodynamic functions of the solution and mixture from the obtained data. The results showed that solubility increased almost linearly with MeCN fraction and temperature, indicating that MeCN is a more efficient solvent and that the process is endothermic. Thermodynamic analysis revealed that dissolution is an endothermic process with favorable entropy for all compositions. The higher solubility in MeCN is attributed to the lower energetic cost required to form the solute cavity compared to the high energy needed to disrupt the hydrogen bond network of ethanol. This behavior can be explained by an enthalpy–entropy compensation phenomenon. This phenomenon provides an essential physicochemical basis for designing pharmaceutical processes. Full article

This study explores how intermolecular interactions govern the composition of saturated solutions of influence flufenamic acid (FlA) in deep eutectic solvents (DESs). Using choline chloride (ChCl) or menthol (Men) as the HBAs and various polyols as the HBDs, FlA solubility was measured in different DES systems. The experimental values along with intermolecular interactions quantified via COSMOtherm-derived Gibbs free energies were used in the determination of component distributions for varying DES formulations. It was inferred that DES systems primarily consist of molecular complexes (dimers and hetero-pairs) rather than monomers due to their high association propensity. In the case of ChCl-based DESs, the HBA–HBD hetero-pairs are favored and strongly dominate. In contrast, Men-based DESs exhibited a strong attraction to HBDs; however, their self-association led to the predominance of HBD dimers. Solubility of FlA correlated with solute-containing hetero-pairs, peaking at optimal HBA–HBD ratios. These insights support in developing a rationale for DES design for pharmaceutical applications. The conclusions of this study were inferred from a novel crafted physically constrained iterative algorithm that reliably determines molecular composition from the equilibrium constants, overcoming the limitations of conventional numerical solvers in highly associated systems. Full article

The saponin-rich plant extracts are mixtures of various surface-active and non-surface-active compound substances. Their exact composition depends on the type of plant and its part from which they were extracted. In this study, we analyze the wetting properties of the extract obtained by boiling soapwort (Saponaria officinalis L.) roots in water (SE). To this aim, the contact angle measurements of aqueous solutions of SE on apolar (AP) (polytetrafluoroethylene, PTFE), monopolar (MP) (polymethyl methacrylate, PMMA), weak bipolar (WBP) (composites with varying content of cellulose and chitosan), and bipolar solids (BP) (quartz) were determined. The surface tension of the solids used for the contact angle measurements ranged from 20.24 to 47.7 mN/m. Based on the measured contact angles, the relationship between adhesion and surface tension, the cosine of the contact angle and surface tension, the cosine of the contact angle and the reciprocal of the surface tension, as well as the adsorption of the surface-active components of SE at the solid-solution and solid-air interfaces were analyzed. The results indicate that the adsorption of SE components at the hydrophobic solid-solution interface is comparable to that at the solution–air interface. Moreover, the Gibbs free energy of adsorption at the solid-air interface for all solids studied is comparable to that at the solution–air interface. Full article

Blackwater rivers are enriched in humic acids and impoverished in nutrients, sometimes discharging into oceans. Brazil has a coastal zone of about 8700 km, with several blackwater rivers discharging into the Atlantic Ocean, in addition to the Rio Negro of the northern Amazon basin, which is the largest (about 1700 km long) and best-known tropical backwater river. On the other hand, only a few attempts have been made to deal with their hydrochemical composition and how it is related to the hydrochemistry of different water bodies nearby. This paper focuses on a sector of the Atlantic Ocean shore occurring in São Paulo State, enclosing two important Ecological Reserves, i.e., the Restinga State Park of Bertioga and the State Park of Serra do Mar–São Sebastião Nucleus, located at Bertioga and São Sebastião cities, respectively. Physicochemical parameters such as pH and electrical conductivity, as well as the composition of major constituents like sodium, potassium, calcium, magnesium, bicarbonate, chloride, sulfate, nitrate, etc., have been evaluated in two blackwater rivers and one blackwater stream to compare their relative inputs into the Atlantic Ocean. Traditional hydrogeochemical diagrams such as the Piper, Schoeller, Gibbs, van Wirdum, and Wilcox graphs were utilized for investigating the major features of the blackwater’s composition, revealing in some cases that they suffer an accentuated influence of the constituents occurring in the Atlantic Ocean waters, due to backward currents (coastal upwelling or tidal currents). Another highlight of this paper is the measurement of an enhanced concentration of dissolved iron in one blackwater sample analyzed, reaching a value of 1.9 mg/L. Such a finding has also been often reported in the literature for blackwater rivers and streams, as humic and fulvic acids are used to bind Fe³⁺, keeping it in solution. Nowadays, iron in solution has been considered a very important element acting as a natural fertilizer of the coastal ocean because it is an essential nutrient to marine phytoplankton. Full article

In this paper, closed-form expressions for the variation of the expectation of a given function due to changes in the probability measure (probability distribution drifts) are presented. These expressions unveil interesting connections with Gibbs probability measures, information projections, Pythagorean identities for relative entropy, mutual information, and lautum information. Full article

Isobaric vapor-liquid equilibrium (VLE) data for binary mixtures of biomass–derived ethyl levulinate and ethanol were measured using an apparatus comprising a modified Rose-Williams still and a condensation system. Measurements were taken at temperatures ranging from 329.58 K to 470.00 K and pressures of 40.0, 60.0 and 80.0 kPa. The thermodynamic consistency of the VLE data was evaluated using the Redlich-Kister area test, the Fredenslund test and the Van Ness point-to-point test. The data was correlated using three activity coefficient models: Wilson, NRTL and UNIQUAC. The Gibbs energy of mixing of the VLE data was analyzed to verify the suitability of the binary interaction parameters of these models. The activity coefficients and excess Gibbs free energy, calculated from the VLE experimental data and model correlation results, were analyzed to evaluate the models’ fit and the non–ideality of the binary system. The accuracy of the regression results was also assessed based on the root mean square deviation (RMSD) and average absolute deviation (AAD) for both temperature and the vapor phase mole fraction of ethyl levulinate. The results indicate that the NRTL model provided the best fit to the experimental data. Notably, the experimental data showed strong correlation with the predictions of all three models, suggesting their reliability for practical application. Full article

Understanding the adsorption mechanism is essential for developing efficient technologies to capture carbon dioxide from industrial flue gases. In this work, laboratory measurements, density functional theory calculations, and molecular dynamics simulations were employed to study CO₂ adsorption and diffusion behavior in LTA-type zeolites. The CO₂ adsorption isotherms measured in zeolite 5A are best described by the Toth model. Thermodynamic analysis indicates that the adsorption process is spontaneous and exothermic, with an enthalpy change of −44.04 kJ/mol, an entropy change of −115.23 J/(mol·K), and Gibbs free energy values ranging from −9.68 to −1.03 kJ/mol over the temperature range of 298–373 K. The isosteric heat of CO₂ adsorption decreases from 40.35 to 21.75 kJ/mol with increasing coverage, reflecting heterogeneous interactions at Ca²⁺ and Na⁺ sites. The adsorption kinetics follow a pseudo-first-order model, with an activation energy of 2.24 kJ/mol, confirming a physisorption mechanism. The intraparticle diffusion model indicates that internal diffusion is the rate-limiting step, supported by a significant reduction in the diffusion rate. The DFT calculations demonstrated that CO₂ exhibited a −35 kJ/mol more negative adsorption energy in zeolite 5A than in zeolite ITQ-29, attributable to strong interactions with Ca²⁺/Na⁺ cations in 5A that were absent in the pure silica ITQ-29 framework. The molecular dynamics simulations based on molecular force fields indicate that CO₂ diffuses more rapidly in ITQ-29, with a diffusion coefficient measuring 2.54 × 10⁻⁹ m²/s at 298 K, whereas it was 1.02 × 10⁻⁹ m²/s in zeolite 5A under identical conditions. The activation energy for molecular diffusion reaches 5.54 kJ/mol in zeolite 5A, exceeding the 4.12 kJ/mol value in ITQ-29 by 33%, which accounts for the slower diffusion kinetics in zeolite 5A. There is good agreement between experimental measurements and molecular simulation results for zeolite 5A across the studied temperature and pressure ranges. This confirms the accuracy and reliability of the selected simulation parameters and allows for the study of zeolite ITQ under similar simulation conditions. This research provides insights into CO₂ adsorption energetics and diffusion within LTA-type zeolite frameworks, supporting the rational design of high-performance adsorbents for industrial gas separation. Full article

A previously pyrometallurgical process, developed to obtain a Pb-Ag alloy and a slag rich in sulfur from the recycling of a mixture of industrial wastes of jarosite and lead paste, was thermodynamically assessed at 1200 °C. The industrial jarosite sourced from a Mexican zinc hydrometallurgical plant corresponded to an ammonium jarosite with a measurable silver content. The specific heat capacity (Cp) of the ammonium jarosite was obtained from TGA and DSC measurements, as well as the thermodynamic functions of enthalpy, entropy, and Gibbs free energy. The Cp was successfully modeled using polynomial regression, with a second-degree polynomial employed to describe the low-temperature behavior. The thermodynamic data generated were input into the thermodynamic software FactSage 8.2 for modeling of the lead paste–ammonium jarosite-Na₂CO₃-SiC system and represented by stability phase diagrams. The thermodynamic assessment of the pyrometallurgical process predicted compounds formed at high temperatures, showing that a Pb-Ag alloy and a slag rich in Na, S, and Fe (NaFeS₂ and NaFeO₂) were obtained. The compounds formed evidence of the effective sulfur retention in the slag, which is crucial for mitigating SO₂ emissions during high-temperature treatments. The experimental compounds, after solidification, were determined by X-ray diffraction measurements to be Na₂Fe(SO₄)₂ and Na₂(SO₄), which reasonably match the thermodynamic assessment. The heat capacity of the ammonium jarosite provides essential thermodynamic insights into the compositional complexities of industrial waste, which are particularly relevant for thermodynamic modeling and process optimization in pyrometallurgical systems aimed at metal recovery and residue valorization. Full article

Rare earth metals (REMs) are vital for high-tech industries, but their extraction from secondary sources is challenging due to environmental and technical constraints. This study investigates the ion-exchange extraction of light REMs (neodymium, praseodymium, and samarium) from sulfuric and phosphoric acid solutions, modeling industrial leachates from apatite concentrates and phosphogypsum. The study considers the use of anion- and cation-exchange resins with different functional groups for efficient and environmentally safe REM separation. Experimental sorption isotherms were obtained under static conditions at 298 K and analyzed using a thermodynamic model based on the linearization of the mass action equation. Equilibrium constants and Gibbs energy were calculated, which reveals the spontaneity of the processes. Cation-exchange resins demonstrated high selectivity towards individual REMs, while anion-exchange resins were suitable for group extraction. Infrared spectral analysis confirmed the presence of sulfate and phosphate complexes in the resin matrix, clarifying the ion-exchange mechanisms. Thermal effect measurements indicated exothermic sorption on anion-exchange resins with negative entropy and endothermic sorption on cation-exchange resins with positive entropy. The findings highlight the potential of ion-exchange resins for selective and sustainable REM recovery, offering a safer alternative to liquid extraction and enabling the valorization of industrial wastes like phosphogypsum for resource recovery. Full article

This study employs first principles calculations and thermodynamic analyses to investigate the dissociative adsorption of hydrogen on the Fe(110) surface. The results show that the adsorption energies of hydrogen at different sites on the iron surface are −1.98 eV (top site), −2.63 eV (bridge site), and −2.98 eV (hollow site), with the hollow site being the most stable adsorption position. Thermodynamic analysis further reveals that under operational conditions of 25 °C and 12 MPa, the Gibbs free energy change (ΔG) for hydrogen dissociation is −1.53 eV, indicating that the process is spontaneous under pipeline conditions. Moreover, as temperature and pressure increase, the spontaneity of the adsorption process improves, thus enhancing hydrogen transport efficiency in pipelines. These findings provide a theoretical basis for optimizing hydrogen transport technology in natural gas pipelines and offer scientific support for mitigating hydrogen embrittlement, improving pipeline material performance, and developing future hydrogen transportation strategies and safety measures. Full article

Measurements of the surface tension of aqueous solutions of some trisiloxane surfactants containing various polyether groups (HOL7, HOL9, and HOL12) at 293 K, 303 K, and 313 K were performed. The studied surfactants were synthesized by hydrosilylation reaction and their structural analysis was carried out by the ¹H NMR, ¹³C NMR, ²⁹Si NMR, as well as FT-IR techniques. The thermal stability of HOL7, HOL9, and HOL12, as well as their molecular weight distributions, were also studied. On the basis of the obtained experimental results of the surface tension of aqueous solutions of HOL7, HOL9, and HOL12, the activity of the studied surfactants at the water–air interface was determined and discussed in the light of intermolecular interactions. Using the measured values of the surface tension, the Gibbs surface excess concentration, the area occupied by the surfactant molecule in the adsorption layer, and the standard Gibbs free energy of adsorption of the studied surfactants at the water–air interface were also calculated. Based on the obtained thermodynamic parameters of adsorption of the studied surfactants at the water–air interface, temperature, as well as a number of polyether groups in the hydrophilic part of surfactant, impact on particular surfactant adsorption was deduced. In general, the changes in the standard Gibbs free energy of adsorption of the studied surfactants at the water–air interface indicate that their adsorption tendency decreases with decreasing temperature. In addition, that tendency also diminishes as the number of the polyether groups in the hydrophilic part of the surfactant increases. Full article

We survey developments in the use of entropy maximization for applying the Gibbs Canonical Ensemble to finite situations. Biological insights are invoked along with physical considerations. In the game-theoretic approach to entropy maximization, the interpretation of the two player roles as predator and prey provides a well-justified and symmetric analysis. The main focus is placed on the Lagrange multiplier approach. Using natural physical units with Planck’s constant set to unity, it is recognized that energy has the dimensions of inverse time. Thus, the conjugate Lagrange multiplier, traditionally related to absolute temperature, is now taken with time units and oriented to follow the Arrow of Time. In quantum optics, where energy levels are bounded above and below, artificial singularities involving negative temperatures are eliminated. In a biological model where species compete in an environment with a fixed carrying capacity, use of the Canonical Ensemble solves an instance of Eigen’s phenomenological rate equations. The Lagrange multiplier emerges as a statistical measure of the ecological age. Adding a weak inequality on an order parameter for the entropy maximization, the phase transition from initial unconstrained growth to constrained growth at the carrying capacity is described, without recourse to a thermodynamic limit for the finite system. Full article

We study the thermodynamic properties of the generalized non-convex multispecies Curie–Weiss model, where interactions among different types of particles (forming the species) are encoded in a generic matrix. For spins with a generic prior distribution, we compute the thermodynamic limit of the generating functional for the moments of the Boltzmann–Gibbs measure using simple interpolation techniques. For Ising spins, we further analyze the fluctuations of the magnetization in the thermodynamic limit under the Boltzmann–Gibbs measure. It is shown that a central limit theorem (CLT) holds for a rescaled and centered vector of species magnetizations, which converges to either a centered or non-centered multivariate normal distribution, depending on the rate of convergence of the relative sizes of the species. Full article

Halogenated benzaldehydes possess unique chemical properties that render them valuable in pharmaceutical synthesis, pesticide formulation, and dye production. However, thorough thermodynamic data for these compounds remain scarce. This study aims to fill this knowledge gap by investigating key physical properties of several halogenated benzaldehydes, namely 4-chlorobenzaldehyde, 4-bromobenzaldehyde, 2,3-dichlorobenzaldehyde, 2,4-dichlorobenzaldehyde, and 2,6-dichlorobenzaldehyde. The physical properties determined in this study include volatility, phase transitions, and water solubility, all of which are crucial for predicting the environmental fate of these compounds. The vapor pressures of both crystalline and liquid phases were measured using a reliable static method, allowing for the determination of standard molar enthalpies, entropies, and Gibbs energies of sublimation and vaporization, as well as their triple points. The melting temperature and molar enthalpy, along with the isobaric molar heat capacity of the crystalline phase, were assessed using differential scanning calorimetry. Water solubility was evaluated at 25 °C through the saturation shake-flask method, complemented by ultra-violet visible spectroscopy. By combining sublimation and solubility data, additional properties such as Gibbs energies of hydration and Henry’s law constants were derived. The experimental results were integrated into existing databases, enhancing the predictive models for properties including melting temperature, vapor pressure, solubility, Gibbs energy of hydration, and Henry’s constant. These findings significantly improve the environmental modeling capabilities, providing valuable insights into the mobility and fate of halogenated benzaldehydes in various environmental contexts. Full article

Water quality is a fundamental parameter for assessing the suitability of surface waters. Likewise, the hydrochemical behavior is critically important to understand for rivers used in irrigation. This study aims to evaluate and characterize the surface water quality of the Voghji River catchment basin for irrigation, as it reveals the hydrochemical origins in the catchment basin. Nine key parameters, including EC, Cl⁻, SO₄²⁻, Ca²⁺, Mg²⁺, Na⁺, K⁺, CO₃²⁻, and HCO₃⁻, were measured at seven sampling points in July and September 2017. The ion concentration patterns in July followed the sequence: Ca²⁺ > Na⁺ > K⁺ > Mg²⁺ and HCO₃⁻ > SO₄²⁻ > Cl⁻ > CO₃²⁻, while in September, they were Ca²⁺ > Na⁺ > Mg²⁺ > K⁺ and HCO₃⁻ > SO₄²⁻ > Cl⁻ > CO₃²⁻. The sequences were almost similar between the two months, with minor differences in cation distribution, particularly between Mg²⁺ and K⁺. Overall, Ca²⁺ and HCO₃⁻ were the dominant ions in the studied surface water samples. The concentrations of K⁺, Na⁺, Mg²⁺, Ca²⁺, Cl⁻, SO₄²⁻, and HCO₃⁻ were found to be well below the FAO irrigation water standards, indicating that the waters of the Voghji River and its tributaries (Achanan, Vachagan, and Geghi) were generally safe for irrigation. However, the FAO threshold value was exceeded only for CO₃²⁻ in the Vachagan River in Kapan Town. The chemical analysis of surface waters in the Voghji River catchment basin revealed dominant Ca²⁺-HCO₃⁻ and mixed Ca²⁺-K⁺-SO₄²⁻-Cl⁻ facies, with key geochemical processes including carbonate and gypsum dissolution, silicate weathering, and cation exchange. Ionic correlations indicated that Na⁺ and Cl⁻ sources were influenced by both natural (e.g., halite dissolution, weathering) and anthropogenic inputs, while Ca²⁺ and Mg²⁺ primarily originated from carbonate dissolution. The Gibbs diagram suggested that rock–water interactions were the primary natural mechanism controlling the water chemistry, with evaporation also playing a significant role. Various indices, including the Kelly index, magnesium adsorption ratio, sodium percentage, sodium adsorption ratio, permeability index, potential salinity, residual sodium carbonate, soluble sodium percentage, and irrigation water quality index, were applied, along with US Salinity Laboratory diagram and Wilcox diagram, to further assess the irrigation suitability. Most indices confirmed the suitability of the waters for irrigation; however, the Achanan River near the mouth and the Voghji River downstream of Kapan Town exhibited moderate salinity levels, underscoring the need for water management to prevent potential soil degradation. Full article