Search Results (21)

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

Today, the machining of heat-resistant alloys based on triple, quad, or penta equilibria high-entropy alloy systems of elements (ternary, quaternary, quinary iron-, titanium-, or nickel-rich alloys), including dual-phase by Gibb’s phase rule, steels of the austenite class, and nickel- and titanium-based alloys, are highly relevant for the airspace and aviation industry, especially for the production of gas turbine engines. Cutting tools in contact with those alloys should withstand intensive mechanical and thermal loads (tense state of 1.38·10⁸–1.54·10⁸ N/m², temperature up to 900–1200 °C). The most spread material for those tools is cutting ceramics based on oxides, nitrides of the transition and post-transition metals, and metalloids. This work considers the wear resistance of the cutting insert of silicon nitride with two unique development coatings — titanium–zirconium nitride coating (Ti,Zr)N and complex quad nitride coating with TiN content up to 70% (Ti,Al,Cr,Si)N with a thickness of 3.8–4.0 µm on which microtextures were produced by the assisted electric discharge machining with the electrode-tool of ø0.25 mm. The microtextures were three parallel microgrooves of R0.13^+0.02 mm at a depth of 0.025₋₀.₀₅. The operational life was increased by ~1.33 when the failure criterion in turning nickel alloy was 0.4 mm. Full article

The phase rule of Gibbs is one of the basic equations in phase equilibria. Although it has been with us for 150 years, discussions, interpretations and extensions have been published. Here, the following new content is provided: (i). the choice of independent components is discussed, and the component rule is introduced, (ii). independent state variables are divided into compositional and non-compositional ones, (iii). the generalized phase rule is derived replacing number two in the original phase rule by the number of independent non-compositional state variables introduced above, (iv). the degree of freedom is decreased by the number of compositional constraints in special points (azeotrope and congruent melting) of phase diagrams, (v). a rule is derived connecting the maximum number of coexisting phases with the dimensions of the phase diagram, (vi). examples show how to apply the phase rule to unary, binary and ternary phase diagrams and their sections, (vii). the same is extended with the discussion of calculable and not calculable phase fractions, (viii). it is shown that the current definition of the degree of freedom is not sufficient in the number of cases, (ix). the current definition of the degree of freedom is extended, (x). the application of the generalized phase rule is demonstrated when other non-compositional state variables are applied for nano-phase diagrams, and/or for phase diagrams under the influence of electric potential difference, external magnetic field, mechanical strain or the gravitational field. Full article

High-entropy alloys (HEAs) are advanced materials characterized by their unique and complex compositions. Characterized by a mixture of five or more elements in roughly equal atomic ratios, these alloys diverge from traditional alloy formulations that typically focus on one or two principal elements. This innovation has paved the way for subsequent studies that have expanded our understanding of HEAs, highlighting the role of high mixing entropy in stabilizing fewer phases than expected by traditional phase prediction methods like Gibbs’s rule. In this review article, we trace the evolution of HEAs, discussing their synthesis, stability, and the influence of crystallographic structures on their properties. Additionally, we highlight the strength–ductility trade-off in HEAs and explore strategies to overcome this challenge. Moreover, we examine the diverse applications of HEAs in extreme conditions and their promise for future advancements in materials science. Full article

The comprehensive topological isomorphism of liquid–vapor, fusibility, and solubility diagrams in the proper sets of variables is proven with the aid of van der Waals equations of the shift in phase equilibrium. Analogues of Gibbs–Konovalov and Gibbs–Roozeboom laws are demonstrated in solubility diagrams of ternary and quaternary systems under crystallization of different types of solid solutions. For the demonstration, the quaternary reciprocal system ${\mathrm{K}}^{+},{\mathrm{NH}}_4^{+}\left|\right|{\mathrm{Cl}}^{-},{\mathrm{Br}}^{-}-{\mathrm{H}}_2\mathrm{O}$ and its ternary subsystems with modeling of the liquid phase within the framework of the classical Pitzer formalism are mainly used. An algorithm for calculating solubility equilibria in these systems is given. Full article

2D numerical modeling algorithms of multi-component, multi-phase filtration processes of mass transfer in frost-susceptible rocks using nonlinear partial differential equations are a valuable tool for problems of subsurface hydrodynamics considering the presence of free gas, free water, gas hydrates, ice formation and phase transitions. In this work, a previously developed one-dimensional numerical modeling approach is modified and 2D algorithms are formulated through means of the support-operators method (SOM) and presented for the entire area of the process extension. The SOM is used to generalize the method of finite difference for spatially irregular grids case. The approach is useful for objects where a lithological heterogeneity of rocks has a big influence on formation and accumulation of gas hydrates and therefore it allows to achieve a sufficiently good spatial approximation for numerical modeling of objects related to gas hydrates dissociation in porous media. The modeling approach presented here consistently applies the method of physical process splitting which allows to split the system into dissipative equation and hyperbolic unit. The governing variables were determined in flow areas of the hydrate equilibrium zone by applying the Gibbs phase rule. The problem of interaction of a vertical fault and horizontal formation containing gas hydrates was investigated and test calculations were done for understanding of influence of thermal effect of the fault on the formation fluid dynamic. Full article

The effect of planar interfaces on nucleation (namely, on the work of critical cluster formation and their shape) is studied both for crystallization and melting. Advancing an approach formulated about 150 years ago by J. W. Gibbs for liquid phase formation at planar liquid–liquid interfaces, we show that nucleation of liquids in the crystal at crystal–vapor planar interfaces proceeds as a rule with a much higher rate compared to nucleation in the bulk of the crystal. Provided the surface tensions crystal–liquid (${\sigma }_{cl}$), liquid–vapor (${\sigma }_{lv}$), and crystal–vapor (${\sigma }_{cv}$) obey the condition ${\sigma }_{cv}={\sigma }_{cl}+{\sigma }_{lv}$, the work of critical cluster formation tends to zero; in the range ${\sigma }_{cv}<{\sigma }_{cl}+{\sigma }_{lv}$, it is less than one half of the work of critical cluster formation for bulk nucleation. The existence of a liquid–vapor planar interface modifies the work of critical cluster formation in crystal nucleation in liquids to a much less significant degree. The work of critical crystal cluster formation is larger than one half of the bulk value of the work of critical cluster formation, reaching this limit at ${\sigma }_{cv}={\sigma }_{cl}+{\sigma }_{lv}$. The shape of the critical clusters can be described in both cases by spherical caps with a radius, R, and a width parameter, h. This parameter, h, is the distance from the cutting plane (coinciding with the crystal–vapor and liquid–vapor planar interface, respectively) to the top of the spherical cap. It varies for nucleation of a liquid in a crystal in the range $(h/R)\le 1$ and for crystal nucleation in a liquid in the range $2\ge (h/R)\ge 1$. At ${\sigma }_{cv}={\sigma }_{cl}+{\sigma }_{lv}$, the ratio $(h/R)$ of the critical cluster for nucleation in melting tends to zero ($(h/R)\to 0$). At the same condition, the critical crystallite has the shape of a sphere located tangentially to the liquid–vapor interface inside the liquid ($(h/R)\cong 2$). We present experimental data which confirm the results of the theoretical analysis, and potential further developments of the theoretical approach developed here are anticipated. Full article

Phospholipid membranes are ubiquitous components of cells involved in physiological processes; thus, knowledge regarding their interactions with other molecules, including tocopherol ester derivatives, is of great importance. The surface pressure–area isotherms of pure α-tocopherol (Toc) and its derivatives (oxalate (OT), malonate (MT), succinate (ST), and carbo analog (CT)) were studied in Langmuir monolayers in order to evaluate phase formation, compressibility, packing, and ordering. The isotherms and compressibility results indicate that, under pressure, the ester derivatives and CT are able to form two-dimensional liquid-condensed (LC) ordered structures with collapse pressures ranging from 27 mN/m for CT to 44 mN/m for OT. Next, the effect of length of ester moiety on the surface behavior of DPPC/Toc derivatives’ binary monolayers at air–water interface was investigated. The average molecular area, elastic modulus, compressibility, and miscibility were calculated as a function of molar fraction of derivatives. Increasing the presence of Toc derivatives in DPPC monolayer induces expansion of isotherms, increased monolayer elasticity, interrupted packing, and lowered ordering in monolayer, leading to its fluidization. Decreasing collapse pressure with increasing molar ratio of derivatives indicates on the miscibility of Toc esters in DPPC monolayer. The interactions between components were analyzed using additivity rule and thermodynamic calculations of excess and total Gibbs energy of mixing. Calculated excess area and Gibbs energy indicated repulsion between components, confirming their partial mixing. In summary, the mechanism of the observed phenomena is mainly connected with interactions of ionized carboxyl groups of ester moieties with DPPC headgroup moieties where formed conformations perturb alignment of acyl chains, resulting in increasing mean area per molecule, leading to disordering and fluidization of mixed monolayer. Full article

A generalization of the original Gibbs phase rule is proposed in order to study the presence of single phases, multiphase coexistence, and multicritical phenomena in lattice spin magnetic models. The rule is based on counting the thermodynamic number of degrees of freedom, which strongly depends on the external fields needed to break the ground state degeneracy of the model. The phase diagrams of some spin Hamiltonians are analyzed according to this general phase rule, including general spin Ising and Blume–Capel models, as well as q-state Potts models. It is shown that by properly taking into account the intensive fields of the model in study, the generalized Gibbs phase rule furnishes a good description of the possible topology of the corresponding phase diagram. Although this scheme is unfortunately not able to locate the phase boundaries, it is quite useful to at least provide a good description regarding the possible presence of critical and multicritical surfaces, as well as isolated multicritical points. Full article

Li₃FeN₂ material was synthesized by the two-step solid-state method from Li₃N (adiabatic camera) and FeN₂ (tube furnace) powders. Phase investigation of Li₃N, FeN₂, and Li₃FeN₂ was carried out. The discharge capacity of Li₃FeN₂ is 343 mAh g⁻¹, which is about 44.7% of the theoretic capacity. The ternary nitride Li₃FeN₂ molar heat capacity is calculated using the formula C_p,m = 77.831 + 0.130 × T − 6289 × T⁻², (T is absolute temperature, temperature range is 298–900 K, pressure is constant). The thermodynamic characteristics of Li₃FeN₂ have the following values: entropy S⁰₂₉₈ = 116.2 J mol⁻¹ K⁻¹, molar enthalpy of dissolution Δ_dH_LFN = −206.537 ± 2.8 kJ mol⁻¹, the standard enthalpy of formation Δ_fH⁰ = −291.331 ± 5.7 kJ mol⁻¹, entropy S⁰₂₉₈ = 113.2 J mol⁻¹ K⁻¹ (Neumann–Kopp rule) and 116.2 J mol⁻¹ K⁻¹ (W. Herz rule), the standard Gibbs free energy of formation Δ_fG⁰₂₉₈ = −276.7 kJ mol⁻¹. Full article

Polyelectrolyte gels have the capacity to absorb large amounts of multivalent species of opposite charge from aqueous solutions of low ionic strength, and release them at elevated ionic strengths. The reversibility offers the possibility to switch between “storage” and “release” modes, useful in applications such as drug delivery. The review focuses on systems where so-called volume phase transitions (VPT) of the gel network take place upon the absorption and release of proteins and self-assembling amphiphiles. We discuss the background in terms of thermodynamic driving forces behind complex formation in oppositely charged mixtures, the role played by cross-links in covalent gels, and general aspects of phase coexistence in networks in relation to Gibbs’ phase rule. We also briefly discuss a gel model frequently used in papers covered by the review. After that, we review papers dealing with collapse and swelling transitions of gels in contact with solution reservoirs of macroions and surfactants. Here we describe recent progress in our understanding of the conditions required for VPT, competing mechanisms, and hysteresis effects. We then review papers addressing equilibrium aspects of core–shell phase coexistence in gels in equilibrium. Here we first discuss early observations of phase separated gels and results showing how the phases affect each other. Then follows a review of recent theoretical and experimental studies providing evidence of thermodynamically stable core–shell phase separated states, and detailed analyses of the conditions under which they exist. Finally, we describe the results from investigations of mechanisms and kinetics of the collapse/swelling transitions induced by the loading/release of proteins, surfactants, and amphiphilic drug molecules. Full article

In general, during long-term museum conservation, ancient bronzes will generate new corrosion products also called the “secondary corrosion” on the surface of the unearthed “primary corrosion” products due to various environmental conditions. In this paper, the corrosion stages of several ancient Chinese bronzes are characterized by using optical microscope (OM), scanning electron microscope (SEM), energy dispersive spectrometer (EDS), X-ray diffraction (XRD) and Raman spectrometer (Raman). It is found that there exist phase transformation relationships in between the “primary corrosion” and the “secondary corrosion” stages (i.e., (1) the crystal lattice type tends to transform from a high symmetry system to a low symmetry system; (2) in case of the same crystal lattice type, the corrosions exhibit an inter-transformation or symbiosis). It is interesting to note that these transformation rules are very consistent with the well-known physical law of “spontaneous symmetry-breaking”, which won the 2008 Nobel Prize in Physics and also has been considered to be general law of nature, in addition to the principle of Gibbs free energy reduction. The significance of this discovery allows us to achieve the predictability and controllability of the bronze corrosion products (i.e., to predict the corrosive trends in advance and control the “second corrosion” by adjusting the conservation conditions. This research provides a novel conservation concept of ancient bronzes. Full article

Adsorption refrigeration has become an attractive technology due to the capability to exploit low-grade thermal energy for cooling power generation and the use of environmentally friendly refrigerants. Traditionally, these systems work with pure fluids such as water, ethanol, methanol, and ammonia. Nevertheless, the operating conditions make their commercialization still unfeasible, especially owing to safety and cost issues as a consequence of the working pressures, which are higher or lower than 1 atm. The present work represents the first thermodynamic insight in the use of mixtures for adsorption refrigeration and aims to assess the performance of a binary system of ammonia and ethanol. According to the Gibbs’ phase rule, the addition of a component introduces an additional degree of freedom, which allows to adjust the pressure of the system varying the composition of the mixture. The refrigeration process was simulated with isothermal- isochoric flash calculations to solve the phase equilibria, described by the Peng-Robinson-Stryjek-Vera (PRSV) equation of state for the vapor and liquid phases and by the ideal adsorbed solution theory (IAST) and the multicomponent potential theory of adsorption (MPTA) for the adsorbed phase. In operating condenser and evaporator, pressure levels around atmospheric pressure can be achieved using an ammonia/ethanol mixture with a mole fraction of ethanol in the range of 0.70−0.75. A good agreement in the predictions of the adsorbed phase composition was also reported using the IAST and the MPTA methods. Full article

Background: During the previous decade a new class of benzamide-based inhibitors of 2-trans enoyl-acyl carrier protein reductase (InhA) of Mycobacterium tuberculosis (Mt) with unusual binding mode have emerged. Here we report in silico design and evaluation of novel benzamide InhA-Mt inhibitors with favorable predicted pharmacokinetic profiles. Methods: By using in situ modifications of the crystal structure of N-benzyl-4-((heteroaryl)methyl) benzamide (BHMB)-InhA complex (PDB entry 4QXM), 3D models of InhA-BHMBx complexes were prepared for a training set of 19 BHMBs with experimentally determined inhibitory potencies (half-maximal inhibitory concentrations IC50exp). In the search for active conformation of the BHMB1-19, linear QSAR model was prepared, which correlated computed gas phase enthalpies of formation (∆∆HMM) of InhA-BHMBx complexes with the IC50exp. Further, taking into account the solvent effect and entropy changes upon ligand, binding resulted in a superior QSAR model correlating computed complexation Gibbs free energies (∆∆Gcom). The successive pharmacophore model (PH4) generated from the active conformations of BHMBs served as a virtual screening tool of novel analogs included in a virtual combinatorial library (VCL) of compounds containing benzamide scaffolds. The VCL filtered by Lipinski’s rule-of-five was screened by the PH4 model to identify new BHMB analogs. Results: Gas phase QSAR model: −log₁₀(IC₅₀^exp) = pIC₅₀^exp = −0.2465 × ∆∆H_MM + 7.95503, R² = 0.94; superior aqueous phase QSAR model: pIC₅₀^exp = −0.2370 × ∆∆G_com + 7.8783, R² = 0.97 and PH4 pharmacophore model: $p{{\mathrm{IC}}_{50}}^{\exp }$ = 1.0013 × p ${{\mathrm{IC}}_{50}}^{\exp }$ − 0.0085, R² = 0.95. The VCL of more than 114 thousand BHMBs was filtered down to 73,565 analogs Lipinski’s rule. The five-point PH4 screening retained 90 new and potent BHMBs with predicted inhibitory potencies IC₅₀^pre up to 65 times lower than that of BHMB1 (IC₅₀^exp = 20 nM). Predicted pharmacokinetic profile of the new analogs showed enhanced cell membrane permeability and high human oral absorption compared to current anti-tuberculotics. Conclusions: Combined use of QSAR models that considered binding of the BHMBs to InhA, pharmacophore model, and ADME properties helped to recognize bound active conformation of the benzamide inhibitors, permitted in silico screening of VCL of compounds sharing benzamide scaffold and identification of new analogs with predicted high inhibitory potencies and favorable pharmacokinetic profiles. Full article

Thermodynamic aspects of the theory of nucleation are commonly considered employing Gibbs’ theory of interfacial phenomena and its generalizations. Utilizing Gibbs’ theory, the bulk parameters of the critical clusters governing nucleation can be uniquely determined for any metastable state of the ambient phase. As a rule, they turn out in such treatment to be widely similar to the properties of the newly-evolving macroscopic phases. Consequently, the major tool to resolve problems concerning the accuracy of theoretical predictions of nucleation rates and related characteristics of the nucleation process consists of an approach with the introduction of the size or curvature dependence of the surface tension. In the description of crystallization, this quantity has been expressed frequently via changes of entropy (or enthalpy) in crystallization, i.e., via the latent heat of melting or crystallization. Such a correlation between the capillarity phenomena and entropy changes was originally advanced by Stefan considering condensation and evaporation. It is known in the application to crystal nucleation as the Skapski–Turnbull relation. This relation, by mentioned reasons more correctly denoted as the Stefan–Skapski–Turnbull rule, was expanded by some of us quite recently to the description of the surface tension not only for phase equilibrium at planar interfaces, but to the description of the surface tension of critical clusters and its size or curvature dependence. This dependence is frequently expressed by a relation derived by Tolman. As shown by us, the Tolman equation can be employed for the description of the surface tension not only for condensation and boiling in one-component systems caused by variations of pressure (analyzed by Gibbs and Tolman), but generally also for phase formation caused by variations of temperature. Beyond this particular application, it can be utilized for multi-component systems provided the composition of the ambient phase is kept constant and variations of either pressure or temperature do not result in variations of the composition of the critical clusters. The latter requirement is one of the basic assumptions of classical nucleation theory. For this reason, it is only natural to use it also for the specification of the size dependence of the surface tension. Our method, relying on the Stefan–Skapski–Turnbull rule, allows one to determine the dependence of the surface tension on pressure and temperature or, alternatively, the Tolman parameter in his equation. In the present paper, we expand this approach and compare it with alternative methods of the description of the size-dependence of the surface tension and, as far as it is possible to use the Tolman equation, of the specification of the Tolman parameter. Applying these ideas to condensation and boiling, we derive a relation for the curvature dependence of the surface tension covering the whole range of metastable initial states from the binodal curve to the spinodal curve. Full article