Thermodynamic Parameters Research Articles

DFT calculations of structural, chemical, electronic and thermodynamic properties of Rifampicin and Oxalic Acid

The thermodynamic properties of the compounds contribute to the theoretical analysis of the results of favorable energies that are subject to interaction. In this work, through the DFT study, the comparison of the functionals ωB97XD and B3LYP. Geometry optimization calculations and vibrational frequencies were performed for the individual ions and for the interactions. In all cases, all calculated vibrational frequencies are positive, confirming the optimized geometry obtained as a minimum on the potential energy surface. The calculations were carried out in solvent, considering the solvation effect in methanol using the IEFPCM (Integral Equation Formalism of the Polarizable Continuum Model) method. The present work aims to carry out a theoretical study, for in-depth investigations of structural, electronic and thermodynamic properties. In usability in the calculation of the thermodynamic properties, Rifampicin (RIF) and Oxalic Acid (OXA) and the interaction between RIF-OXA in the protonated form protonated RIF with charge +1 and deprotonated OXA with charge -1. In this context, the most favorable thermodynamic parameters in the interaction calculated RIF+-OXA- the values of ∆EZPVE+BSSE, ∆G298 and ∆H in kcal/mol more favorable are -19.62, -14.81 and -25,77.

Facile synthesis of ZnO/RGO/Fe2O3 using macroalgae Caulerpa taxifolia as green reductor and its application as malachite green removal

This study presents the synthesis of a novel ZnO/rGO/Fe₂O₃ composite using Caulerpa taxifolia as a green reductant for the effective removal of Malachite Green from aqueous solutions. Characterization techniques, including FTIR, SEM, and XRD, confirmed the successful incorporation of ZnO and Fe₂O₃ onto the rGO matrix, enhancing its adsorption properties. The composite achieved an exceptional maximum adsorption capacity of 454.5 mg/g at pH 9, significantly outperforming rGO alone and other adsorbents. The adsorption kinetics followed a pseudo-second-order model, indicating chemisorption as the dominant mechanism, with a high correlation coefficient (R² = 0.999). The adsorption isotherms were best described by the Langmuir model, suggesting monolayer adsorption. Thermodynamic parameters revealed that the process was spontaneous and exothermic, with a Gibbs free energy (ΔGo) of -10.93 kJ/mol at 25 °C. The composite's high adsorption capacity, rapid kinetics, and favorable thermodynamics highlight its potential as an efficient and sustainable adsorbent for dye removal. This research offers a promising approach to water treatment, aligning with environmentally friendly practices and providing a viable solution for mitigating water pollution caused by organic dyes. KEY WORDS: Reduced graphene oxide, Water treatment, Caulerpa taxifolia, Isothermal and kinetic studies, Malachite Green Bull. Chem. Soc. Ethiop. 2025, 39(1), 29-47. DOI: https://dx.doi.org/10.4314/bcse.v39i1.3

Entropically and enthalpically driven self-assembly of a naphthalimide-based luminescent organic π-amphiphile in water.

The self-assembly of π conjugated systems in water has emerged as an efficient method for the development of functional materials for biological applications. But the process is more difficult to understand and to control in water compared to organic solvents due to hydrophobic effects. For π-conjugated molecules, self-assembly in solution generally occurs due to either an enthalpic or entropic gain, but designing π systems that undergo self-assembly via both an entropically and enthalpically favorable process is challenging. Herein, we elucidate in detail the self-assembly of a luminescent naphthalene monoamide-based dipolar π-bolaamphiphile appended with a primary amine and triethylene glycol monomethyl ether (NMI-W) side chain into a vesicular nanostructure. By utilizing a detailed isothermal titration calorimetry (ITC) experiment, we have calculated the thermodynamic parameters associated with the self-assembly of NMI-W in water. Interestingly, the NMI-W shows both entropically and enthalpically favorable robust self-assembly into a vesicular structure, which can encapsulate both hydrophilic and hydrophobic guest molecules. The synergistic effect of dipole-dipole, π-π stacking and hydrophobic interactions of the NMI chromophore is found to be very crucial in driving self-assembly in an aqueous medium as revealed by various experiments and molecular dynamics.

Comprehensive investigation of novel synthesized thiophenytoin derivative (antiepileptic drug) as an environmentally friendly corrosion inhibitor for mild steel in 1 M HCl: Theoretical, electrochemical, and surface analysis perspectives

This study evaluates the potential of N-(2,6-dimethylphenyl)-2-(5-oxo-4,4-diphenyl-4,5-dihydro-1H-imidazol-2-yl)thio)acetamide (AM16), a novel thiophenytoin derivative used as an antiepileptic drug, as a corrosion inhibitor for mild steel in 1.0 M HCl. The research focuses on AM16’s adsorption behavior and corrosion inhibition efficiency. Electrochemical techniques, including potentiodynamic polarization (PDP), electrochemical impedance spectroscopy (EIS), and electrochemical frequency modulation (EFM), were employed to assess the inhibitor’s effectiveness. The results demonstrate that AM16 achieved a corrosion inhibition efficiency of 95.7 %, with its performance improving with increasing concentration. Polarization studies reveal that AM16 acts as a mixed-type inhibitor. The adsorption of AM16 on the steel surface was modeled using the Langmuir adsorption isotherm. Surface analysis via scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS) confirmed the formation of a protective layer. Experimental findings were complemented by density functional theory (DFT)-based calculations. The combined theoretical, experimental, and analytical approaches affirm the efficacy of this molecule as a corrosion inhibitor, achieving a 95.7 % inhibition rate. Polarization studies reveal that the inhibitor acts as a mixed-type inhibitor. Thermodynamic parameters suggest that the molecule chemically adsorbs onto the steel surface, following the Langmuir isotherm.

Stress Evaluation of Ferromagnetic Materials Based on a New Barkhausen Noise Sensor Composed by High Entropy Alloy Magnetic Core

Abstract During the service of ferromagnetic structural steel materials, stress should be evaluated accurately. Although the magnetic Barkhausen noise (MBN) testing has the ability to sense stress, it can be easily interfered with by environment. In this paper, a new MBN sensor is fabricated by selecting FeCoNi(AlMn)0.25 high entropy alloy (HEA) as the case of magnetic core to improve the accuracy of stress evaluation. The process optimization results show that the stability of MBN signal characteristics is the largest when the excitation frequency is 4 Hz and the voltage is 6 V. The signal-to-noise ratio of MBN indicates that the HEA and Ni-Zn ferrite probes have better anti-interference capability. The MBN signal characteristic values peak voltage and root mean square measured by the HEA probe can linearly quantify the stress level with higher efficiency, stability, and accuracy. The underlying reason of high sensitivity of HEA probe to the variation of MBN signals is revealed based on the magnetic properties. The microstructure and the thermodynamic parameters are analyzed to clarify whether the additions of Al and Mn atoms can affect the short-ranged magnetic exchange interaction and lattice distortion, which affects the magnetization behavior of HEA. Finally, the availability of MBN sensor with HEA magnetic core to the stress evaluation on the retired slide rails of car seats is conducted, which demonstrates its great application value.

Band Diagram Insights into the Kinetic and Thermodynamic Engineering of Tandem Photocatalytic Cells.

In this work, we theoretically investigate the impact of kinetic and thermodynamic properties on the performance of photocatalytic cells operating in an unassisted tandem configuration, including electron affinity and ionization energies, recombination rates, and reaction rates. To this end, we present general rules and metrics for identifying and isolating the origin of an observed shift in the onset potential at either the photoanode or the photocathode of these devices. The correlation between kinetic and thermodynamic shifts in the onset potential is demonstrated through the use of band diagrams and key comparable features within readily accessible characterization tools: current-voltage plots are taken both under illumination and in the dark and further coupled with Mott-Schottky plots. To illustrate this conceptual framework, a model system comprised of a p-type doped BiVO4 photocathode and an n-type doped BiVO4 photoanode is employed. By varying each of the aforementioned kinetic and thermodynamic parameters in isolation, the manner in which these various mechanisms shift the onset potential is demonstrated. This work intends to showcase how kinetic and thermodynamic effects are distinctly manifested in these commonly used characterization tools and further proposes thermodynamic band-edge engineering as a potentially useful and largely unexplored avenue for possibly improving tandem cell performance, in addition to the conventional approach of optimizing kinetics.

The first-principles prediction of mechanical, electronic, elastic and thermodynamic properties of Mo2XB2 (X=Nb, Os, Ta)

The mechanical, electronic and elastic properties of Mo2XB2 (X = Nb, Os, Ta) at different pressures (0–50 GPa) were predicted using first-principles calculations. The enthalpy of formation and the elastic constant calculations show that the three transition metal borides are thermodynamically and mechanically stable. The analysis of density of state and band structure reveals that Mo2XB2 (X = Nb, Os, Ta) have metallic and covalent properties. The increase of pressure will increase the elastic modulus of Mo2XB2 (X = Nb, Os, Ta). The elastic modulus of Mo2XB2 (X = Nb, Os, Ta) are anisotropic. Furthermore, the quasi-harmonic Debye model is used to predict thermodynamic parameters at various temperatures (0–1200K) and pressures (0–50 GPa), such as heat capacity at constant pressure, heat capacity at constant volume, coefficient of thermal expansion, Debye temperature, and the Grüneisen parameter.

In−depth insights into the kinetic and thermodynamic parameters of synergistic coffee residue pyrolysis of sugar industry sludge and biochar characterization

In−depth insights into the kinetic and thermodynamic parameters of synergistic coffee residue pyrolysis of sugar industry sludge and biochar characterization

MgO Assisted Catalytic Hydrothermal Carbonization Followed by Pyrolysis of Sunflower Stalks for the Determination of Kinetic and Thermodynamic Parameters

MgO Assisted Catalytic Hydrothermal Carbonization Followed by Pyrolysis of Sunflower Stalks for the Determination of Kinetic and Thermodynamic Parameters

First-Principles Calculations on Relative Energetic Stability, Mechanical, and Thermal Properties of B2-AlRE (RE = Sc, Y, La-Lu) Phases

The relative energetic stability, mechanical properties, and thermodynamic behavior of B2-AlRE (RE = Sc, Y, La-Lu) second phases in Al alloys have been investigated through the integration of first-principles calculations with the quasi-harmonic approximation (QHA) model. The results demonstrate a linear increase in the calculated equilibrium lattice constant a0 with the ascending atomic number of RE, while the enthalpy of formation ΔHf exhibits more fluctuating variations. The lattice mismatch δ between B2-AlRE and Al matrix is closely correlated with the transferred electron et occurring between Al and RE atoms. Furthermore, the mechanical properties of the B2-AlRE phases are determined. It is observed that the calculated elastic constants Cij, bulk modulus BH, shear modulus GH, and Young’s modulus EH initially decrease with increasing atomic number from Sc to Ce and then increase up to Lu. The calculated Cauchy pressure C12-C44, Pugh’s ratio B/G, and Poisson’s ratio ν for all AlRE particles exhibit a pronounced directional covalent characteristic as well as uniform deformation and ductility. With the rise in temperature, the calculated vibrational entropy (Svib) and heat capacity (CV) of AlRE compounds exhibit a consistent increasing trend, while the Gibbs free energy (F) shows a linear decrease across all temperature ranges. The expansion coefficient (αT) sharply increases within the temperature range of 0~300 K, followed by a slight change, except for Al, AlHo, AlCe, and AlLu, which show a linear increase after 300 K. As the atomic number increases, both Svib and CV increase from Sc to La before stabilizing; however, F initially decreases from Sc to Y before increasing up to La with subsequent stability. All thermodynamic parameters demonstrate similar trends at lower and higher temperatures. This study provides valuable insights for evaluating high-performance aluminum alloys.

A Novel Method for Combination of Ionic Conductivity and pH-metry Methods for the Determination of the Aqueous Solubility of a New Diisopropylammonium Hydrogenmaleate Crystalline Molecule

Dissociation constant, solubility, and thermodynamic data are very important physicochemical parameters for biological substances and their knowledge is of fundamental importance for the validation of drugs. In addition to their low cost and accessibility, Conductometric and pH-metric methods seem to be particularly suitable for the determination of these parameters given the often weak acidic or basic nature of drugs. These parameters were determined for a new synthesized diisopropylammonium hydrogenmaleate (iPr2NH2-MA) crystalline molecule. Conductometric and pH-metric methods were used for this characterization. The pH-metric method lead to pKa1 = 3.6, pKa2 = 6.7 and pKa3 = 7.5, while the conductometric method made it possible to determine two pKa values which are pKa1 = 3.5 and pKa3 = 7.8. The values of the thermodynamic parameters calculated for the enthalpy change (∆rH0) and the entropy change (∆S) of the iPr2NH2-MA acidic dissociation reaction are of the order of ∆H = 25. 36 ± 0.06 kJ.mol-1 and ∆S = 6.08 ± 0.18 kJ.mol-1.K-1. In addition, the Gibbs free energy change (ΔG) of the molecule decreased as a function of temperature. The solubility varied between 1 and 84 mg mL-1 for pH values comprised between 3.5 and 8.5 and reached its maximum Smax = 84 mg mL-1 at pH 5.6. The dissociation process was found to be is non-spontaneous, endothermic and entropically favorable. These results demonstrated on the one hand the reliability and effectiveness of the Conductometric and pH-metric methods for the characterization of molecules with acidic and/or basic sites, and on the other hand the excellent physical and chemical properties of diisopropylammonium hydrogenmaleate (iPr2NH2-MA) crystalline molecule.

Evolution of carbides and Charpy toughness in a low alloy bainitic steel during step-up aging process

The low alloy bainitic steel used in reactor pressure vessels deteriorates during thermal service while the macroscopic thermodynamic parameters that cause thermal aging remains unknown. In this work, a thermal aging restructuring scheme was proposed by step-up aging the steel from 350 °C to 490 °C, with a total duration of 7500 hours. Samples from varied thickness of the steel were characterized in terms of carbides evolution and Charpy impact toughness at 20 °C. The carbide size and its fraction were statistically analyzed showing partial coarsening and dissolution during aging, while the carbide fraction was found linearly correlated with the impact energy for the first time. The critical transition temperature parameter of the aging process was found to be 470 °C for the steel. The macroscopic thermodynamic parameters, including the thermal aging time and temperature, facilitate a comprehensive understanding of the material degradation mechanism and provide a basis for long-term safety of equipment.

Deciphering the Entropy-Driven Host-Guest Interactions within Single Covalent Organic Frameworks for Trapping of 131I.

By combining dark-field optical microscopy with an in situ thermochemical aqueous solution system, we report a single-particle imaging strategy to investigate the host-guest interactions between covalent organic framework-300 (COF-300) as a representative COF host and a series of linear-chain fatty amines. The thermodynamic parameters, such as dissociation constant, Gibbs free energy changes, enthalpy changes, and entropy changes for the binding events within COF-300 are quantified. Correlation between the hydrophobicity of various amines and other data suggests that the mechanism of the host-guest bindings arises from the entropy-driven noncovalent interactions such as hydrogen bonds and van der Waals forces. These mechanistic insights allow for the rational design and preparation of COF-300-encapsulated n-octylamine with enhanced trapping performance of radioactive 131I-. This study not only provides thermodynamic insights into the host-guest interactions within the COF framework but also establishes a structure-property relationship between fatty amines and energetic magnitude information.

Unveiling Fluorescence Spectroscopy, Molecular Docking and Dynamic Simulations: Interactions Between Protein and 2, 4-Dinitrophenylhydrazine Schiff Base.

In this study, we aimed to explore the interaction mechanism between bovine serum albumin (BSA) and a Schiff base compound derived from 2,4-dinotrophenyl hydrazine (L) using various spectroscopic techniques. The interaction between BSA and synthesizing molecule can provide insights into binding affinity, conformational changes and potential applications in drug delivery or biochemistry. The interaction between BSA and L was studied by using UV-Vis and fluorescence titration analysis. The fluorescence quenching emission was observed at 343nm, upon addition of L to the buffer solution of BSA. The binding between BSA and ligand is static in nature using fluorescence quenching emission. The thermodynamic parameters were calculated from the temperature-dependent binding constants (i.e., ∆H = -0.318kcal/mol, ∆G = -7.857kcal/mol and ∆S = 0.023kcal/mol), which indicated that the protein-ligand complex formation between L and BSA is mainly due to the electrostatic interactions. The experimental and theoretical results showed excellent agreement with respect to the mechanism of binding and binding constants. The molecular docking and molecular dynamic analysis experiments were performed to establish the interaction between protein and ligand.

A new thermodynamic modeling method for Brayton cycle schemes based on heat flux of the heat source

The supercritical carbon dioxide Brayton cycle is a promising option for power generation. However, the existing models for assessing its performance lack universality for various layouts and rely on challenging-to-acquire thermodynamic parameters at state points (such as the inlet temperature of the turbine). The present study proposes a modular thermodynamic modeling method, making it suitable for various layouts. A parameter-matching method is proposed using the heat flux of the heat source as an input, making it more practical than methods relying on parameters at state points. The method's accuracy is verified with a deviation not exceeding ±1.5%. Subsequently, four typical schemes including simple recuperation, recompression, intercooling, and reheating cycles are analyzed. The effect of heat flux on power generation and thermal efficiency of each scheme is also evaluated. It is found that the simple recuperation cycle is capable of operating effectively within lower thresholds for both maximum pressure and temperature. For maximizing power generation, the intercooling cycle offers an advantage. As for thermal efficiency, the simple recuperation cycle is best suited for heat fluxes under 1.6 MW/m2, while the recompression cycle is recommended for fluxes exceeding this limit. The outcomes can guide the designing and optimization of Brayton cycle schemes.

Rhombohedral phase high-entropy alloy of AlMnCuZnBi as a photo-Fenton catalyst for methyl orange degradation

The formation of solid solutions with five or more elements having nearly equiatomic contributions termed as high entropy alloys (HEA), is recent strategy for the development of new materials. Such alloys have displayed superior properties than the conventional ones. The prepared alloys are generally face- or body-centered cubic structures with a few exceptions for orthorhombic and hexagonal close packed structure. In this, we report the synthesis of HEA of AlMnCuZnBi having rhombohedral crystal structure. The material was prepared by vacuum arc melting route. Both the diffractions (X-ray and electron) confirm its structure. The calculated thermodynamic empirical parameters e.g. ΔSmix, ΔHmix, δ, VEC and Ω even validate the feasibility of this single phase solid solution. The HEA had shown feeble ferromagnetic behaviour. The rhombohedral structured HEA may open up new possibilities for various emerging applications. The proposed HEA acted as a catalyst for photo-Fenton like reaction and could degraded methyl orange dye completely in 170 minutes.

Theory of Space Quantization and the Quantum Level Understanding of the True Logics of the Principles of Thermodynamics and Heat Engines

The recently discovered Topological Theory of Quantum Gravity (TTQG) is basically a Theory of Space Quantization (TSQ) and in this article first of all it has been substantiated that though the laws of thermodynamics, the well-known thermodynamic principles, the operations of heat engines are very much intuitive but they, in their conventional representations, miserably lack the harmony to the quantized ‘space -time’ of the universe. The well-known thermodynamic parameters, e.g., pressure (P), volume (V), heat content (H), internal energy (U), entropy (S), Gibbs free energy (G),....etc. and the related physical variables like ‘time’ (t)and ‘mass’ (m) do exist in the form of ‘quantum’ or ‘packets’(referred as Gravitons in TTQG) and those are continuously being exchanged between the so called ‘thermodynamic systems’ and the ‘space-time’. It has been shown in this article that a ‘thermodynamic system’ and the above said ‘space quantums’ are very much complimentary and ‘part and parcel’ to each other and a quantum level ‘space-time’ rich understanding has been made through the TSQ of the true logic behind the standing of the thermodynamic laws and the operations of the heat engines.

Thermodynamic Justification for the Effectiveness of the Oxidation—Soda Conversion of Ilmenite Concentrates

This article presents the results of a thermodynamic analysis of the oxidation soda conversion reactions of minerals in ilmenite concentrates in the temperature range of 373–2273 K. The thermodynamic parameters of pseudorutile, pseudobrukite, and the new minerals, zhikinite and spessartine, were calculated for the first time. It has been established that the most important criterion relating to the stability of titanium minerals and related elements, as well as the reaction properties of the structural oxides of metals and silicon, is their degree of oxidation. Oxides of silicon (IV) and manganese have the best reactivity in solid-phase oxidizing alkaline environments (VI). Modeling this process scientifically substantiates the mechanism involved in the destruction of minerals in ilmenite concentrates in the low-temperature region in the presence of atmospheric oxygen and sodium oxide of soda ash, which are decomposed through the absorption of heat and the evaporation of moisture during the dehydration of hydrated minerals of iron and manganese and the dehydration of the soda–ilmenite batch. Tests conducted during pilot metallurgical production at the Institute of Metallurgy and Enrichment (PMP of JSC) confirmed the feasibility of processing high-chromium and siliceous rutile leucoxene ilmenite concentrates, which are unsuitable for traditional pyro- and hydro-metallurgical enrichment methods, through single-stage oxidation soda roasting, followed by the leaching of easily soluble sodium salts of iron and associated impurities with water and a dilute hydrochloric acid solution. The proposed energy-saving method ensures the production of high-purity (>98%) synthetic rutile while eliminating the formation of strong deposits on the lining of roasting units.

The Thermodynamic and Kinetic Properties of the dA-rU DNA-RNA Hybrid Base Pair Investigated via Molecular Dynamics Simulations.

DNA-RNA hybrid duplexes play essential roles during the reverse transcription of RNA viruses and DNA replication. The opening and conformation changes of individual base pairs are critical to their biological functions. However, the microscopic mechanisms governing base pair closing and opening at the atomic level remain poorly understood. In this study, we investigated the thermodynamic and kinetic parameters of the dA-rU base pair in a DNA-RNA hybrid duplex using 4 μs all-atom molecular dynamics (MD) simulations at different temperatures. Our results showed that the thermodynamic parameters of the dA-rU base pair aligned with the predictions of the nearest-neighbor model and were close to those of the AU base pair in RNA. The temperature dependence of the average lifetimes of both the open and the closed states, as well as the transition path times, were obtained. The free-energy barrier for a single base pair opening and closing arises from an increase in enthalpy due to the disruption of the base-stacking interactions and hydrogen bonding, along with an entropy loss attributed to the accompanying restrictions, such as torsional angle constraints and solvent viscosity.

Investigation of thermodynamic parameters of the air environment in subway lines with single-track and double-track tunnels

Investigation of thermodynamic parameters of the air environment in subway lines with single-track and double-track tunnels