Thermodynamic Properties Research Articles

Investigation of electronic, elastic, dynamical, thermodynamic and thermoelectric properties of Cobalt based half-Heusler compounds

Heusler compounds have attracted remarkable attention from scientists over the year by virtue of their peculiarity and suitability in multi-functional applications. In the current study, the structural, elastic, dynamical, thermodynamic and thermoelectric properties of CoMSb (M = V, Nb and Ta) half-Heusler compounds were computed. Projector augmented-wave (PAW) pseudopotentials with PBE exchange correlation functional have been used to obtain the results for the studied compounds. The computed elastic constants satisfy the general stability condition based on the cubic symmetry and endorse the ductile nature of the compounds. The CoVSb compound is predicted to be ferromagnetic half-metallic compound while CoNbSb and CoTaSb are non-magnetic compounds. The dynamical properties revealed the dynamical stability in CoVSb and CoTaSb compounds while the imaginary frequency observed at W⟶L⟶Γ predicts instability in CoNbSb compound. The thermodynamic properties for the compounds were reported. The thermoelectric properties were calculated based on the results obtained from electronic structure using semi-classical Boltzmann theory. The ductile nature and the figure of merit computed predict CoMSb (M = V, Nb and Ta) are relatively good for thermoelectric application.

Thermodynamic stability, electronic structure and mechanical properties of Mo-Re binary alloys: A first-principles calculations

Using first-principles calculations, we have systematically studied thermodynamic stability, electronic structure and mechanical properties of Mo-Re binary alloys. The alloying element Re prefers to occupy the substitution position with a formation energy of 0.10 eV in Mo rather than the tetrahedron/octahedron interstitial position. The charge transfers are obviously present between Re and Mo atoms, which can be confirmed by the Bader charge analysis. The density of states (DOS) demonstrates that the d orbitals of Re and Mo atoms are hybridized, revealing that Re and its adjacent Mo atoms can form the directional bond containing covalent components. On the basis of above studies on the most stable occupancy structure, the mechanical quantities (the elastic constants Cij, bulk modulus B, Young’s modulus E, shear modulus G, Poisson’s ratio v, and B/G) have been analyzed for three Mo-Re alloys with the low Re content, which are Mo127Re1, Mo53Re1 and Mo15Re1, respectively. All these mechanical quantities of both Mo127Re1 and Mo53Re1 alloys are nearly the same as that of perfect Mo, while all these mechanical quantities of Mo15Re1 alloy are obviously larger or smaller than that of perfect Mo. This demonstrates that Mo15Re1 alloy has significantly different mechanical characteristics from Mo127Re1 and Mo53Re1 alloys as well as perfect Mo. These results can provide a significant reference for the application of Mo-Re alloys in future fusion fields.

The thermodynamic properties of diatomic gases. A rigorous analytical approach

The paper reports a closed-form analytical representation of the thermodynamic functions of diatomic molecules in the ground electronic state. For this purpose, analytical formulas for vibrational and rotational partition functions are derived. A rigorous method is proposed for factorizing the vibrational and rotational contributions to the ro-vibrational partition function using an average vibrational quantum number. The behavior of thermodynamic functions as a function of temperature is discussed for carbon monoxide as a test system. The reliability of the analytical method is verified by comparison with experimental data and with the direct summation method, which uses theoretical values of energy levels.

Improving Adsorption Efficiency of Recycled Activated Carbon from Household Water Purifiers through Sonication

Objectives:This study evaluated the potential of recycled activated carbon from household water purifiers as an adsorbent for removing methylene blue. It aimed to achieve resource recycling and dyeing wastewater treatment through the sonication modification of recycled activated carbon.Methods:After sieving recycled activated carbon from water purifiers to a particle size of 75-150μm, the material, in this paper referred to as PCB-S, was processed using sonication to enhance its adsorption capacity. The characteristics of PCB-S were analyzed using SEM, XRD and BET analysis. To evaluate its efficacy, adsorption experiments were carried out varying the following parameters: PCB-S dosage (0.05-0.6gL-1), pH (2.0-10.0), initial concentration of methylene blue (100mgL-1), reaction time (1440 min), and temperature (298 K). The data from these experiments were analyzed using first and second-order kinetic models to understand the reaction kinetics, and the adsorption efficiency was further compared using Langmuir and Freundlich isotherm models. Finally, the thermodynamic properties of the adsorption process between PCB-S and methylene blue were studied to determine its endothermic nature and spontaneity.Results and Discussion:The analysis of the surface characteristics of PCB and PCB-S revealed that sonication significantly altered the pore structure of the activated carbon, leading to increases in both the specific surface area and pore volume. XRD analysis, indicated that sonication had no impact on the crystalline or amorphous structure of the activated carbon. PCB-S demonstrated superior porosity and adsorption capabilities compared to PCB. With a dosage of 0.6gL-1, PCB-S was able to remove 65% of methylene blue from the solution. The adsorption kinetics were best described by a pseudo-second-order kinetic model, with the Langmuir adsorption isotherm fitting the data most accurately. The Gibbs free energy (-1.90~-1.32kJ mol-1) and enthalpy change (7.44 kJ mol-1) confirmed that the adsorption reaction was endothermic.Conclusion:This study confirmed that recycled activated carbon from water purifiers exhibits excellent effectiveness as a dye removal adsorbent when subjected to sonication treatment. Therefore, the possibility of utilizing recycled household water purifier filters as adsorbents is expected to contribute to reducing waste disposal costs by promoting resource recycling.

Study on Confined Water in Flexible Graphene/GO Nanochannels.

The structural evolution of flexible nanochannels within a 2D material membrane, influenced by the ingress of water molecules, plays a crucial role in the membrane's filtration and structural stability. However, the experimental observation of nanoscale water is challenging, and current studies mostly focus on rigid nanochannels. Further investigation on the nanoconfined water is urgently needed, considering the flexibility and deformation of the channel. In this work, MD simulations and theoretical analyses are conducted to investigate the water structure and thermodynamic properties when confined within both rigid and flexible graphene/graphene oxide (GO) nanochannels. In free rigid graphene nanochannels, the interlayer distance exhibits a quantized increase with the number of water molecules, along with sudden changes in entropy, potential energy, and free energy of the water molecules. Meanwhile, in flexible graphene nanochannels, the average interlayer space increases linearly with the number of water molecules. In free rigid GO nanochannels, with the increase of oxidation concentration, the quantized increase in the interlayer space gradually diminishes, accompanied by a decrease in both potential energy and free energy. This work provides insights into the configurational evolution of flexible nanochannels within water, offering guidance in fields such as desalination and mass transport of 2D material membranes.

On a conjecture concerning the Fisher–Widom line and the line of vanishing excess isothermal compressibility in simple fluids

In the statistical mechanics approach to liquid-state theory, understanding the role of the intermolecular potential in determining thermodynamic and structural properties is crucial. The Fisher–Widom (FW) line, which separates regions in the temperature vs density plane where the decay of the total correlation function is monotonic or oscillatory, provides insights into the dominance of the attractive or repulsive part of the interactions. Stopper et al. have recently conjectured [J. Chem. Phys. 151, 014501 (2019)] that the line of vanishing excess isothermal compressibility approximates the FW line in simple fluids. Here, we investigate this conjecture using the Jagla potential and also explore the line of vanishing excess pressure. We employ theoretical approximations and Monte Carlo simulations to study one-dimensional and three-dimensional systems. While exact results for the one-dimensional case do not support the conjecture, our Monte Carlo simulations for the three-dimensional fluid validate it. Our findings not only contribute to the understanding of the relationship between the three transition lines but also provide valuable insights into the thermodynamic and structural behaviour of simple fluids.

Proton‐conducting hydrogel electrolytes with tight contact to binder‐free MXene electrodes for high‐performance thermally chargeable supercapacitor

AbstractThermally chargeable supercapacitors (TCSCs) have offered exceptional energy‐converting efficiency for absorbing human epidermal heat and generating and storing electrical energy, which then realize continuous power supply to electronic devices, such as sensors and wearable electronic products, in a wide range of practical significance. Here, we proposed a flexible TCSC by attaching binder‐free Ti3C2Tx MXene@PPy electrodes on both ends of the H3PO4@P(AM‐co‐AA‐co‐AYP K+) hydrogel electrolyte, which exhibits a large thermal power of 35.2 mV K−1 at 50% relative humidity and maximum figure of merit of 2.1. The high performances of the fabricated devices can be attributed to the tunable electrical, thermodynamic, thermoelectric, and mechanical properties of the hydrogel electrolyte by adjusting the acid content and the proportion of zwitterionic compound AYP K+ in the hydrogel, and the high photothermal conversion efficiency and electrochemical performance of the electrodes. Moreover, the stable and outstanding thermofvoltage output (∼200 mV) under different time scenarios of the TCSC makes it possible to drive a strain sensor, accomplishing the objectives of a human activity monitor.

A systematic study of carbon clustering dynamics for explosives

ABSTRACT The carbon clustering mechanism of insensitive explosive is investigated by molecular dynamics. We find that the free carbon gas aggregates to form flexible chain, and the chain changes to graphite-phase particle. A set of thermodynamic properties for carbon clusters are calculated, and five clustering mechanisms are investigated, including the nucleation, deposition, sublimation, diffusion and phase transition effects. We use chemical reaction model to describe the free carbon aggregation, use diffusion/impaction model to describe the deposition/growing process, use heterogeneous equilibrium condition to evaluate the sublimation rate, use Shaw's model to describe the Smoluchowski coagulation and use Arrhenius model to describe the phase transition rate. Based on the microscopic properties, the detonation wave of explosive is simulated by finite difference method. A set of detonation properties are calculated, and the meso-structure of slow reaction zone is obtained.

Thermodynamic Properties and Equations of State for Solid and Liquid Magnesium

Thermodynamic Properties and Equations of State for Solid and Liquid Magnesium

Drying Kinetics and Thermodynamic Properties of Ultrasound Pretreatment Bitter Melon Dried by Infrared

Determination of drying characteristics of ripe and unripe bitter melon in an infrared dryer at 50, 60, and 70°C with airborne ultrasonic pretreatment with a power of 20 kW for 0, 10, and 20 minutes and a frequency of 20 kHz is the purpose of this study. At the end of drying, among the five used models that fit the moisture ratio data, the Midilli and logarithmic models were selected to properly characterize the drying behavior in the infrared dryer with ultrasonic pretreatment of ripe and unripe bitter melon samples. Moisture transfer from bitter melon samples’ ripeness and early maturity was defined using Fick’s diffusion equation. Then, the Arrhenius equation was utilized to determine the effective moisture diffusivity. Also, the activation energy of unripe and ripe bitter melon slices was reduced with the enhancement in the ultrasound pretreatment time. Water activity (aw) amounts of ripe and unripe bitter melon were achieved at various drying temperatures and ultrasound pretreatment. The trends of the experiment indicate a decrease in enthalpy (ΔH) and entropy (ΔS) amounts of bitter melon with enhancing temperature and ultrasonic. The Gibbs free energy (ΔG) increases with enhancing drying temperature and ultrasonic pretreatment. Specific energy consumption decreased with enhancing drying temperature and ultrasound pretreatment duration for both ripe and unripe bitter melon samples.

On QSAR modeling with novel degree-based indices and thermodynamics properties of eye infection therapeutics

On QSAR modeling with novel degree-based indices and thermodynamics properties of eye infection therapeutics

Computational exploration of strain‐induced in the physical characteristics of inverse‐spinel Li2RuSn4 via density functional theory

AbstractIn this research, the physical properties of the inverse‐spinel Li2RuSn4 compound have been investigated using ab‐initio computational methods within the Wien2k package. The LSDA+mBJ approach was employed to determine the exchange‐correlation potential. The compound was found to exhibit metallic and nonmagnetic behavior in terms of electronic properties. The optical characteristics have been analyzed along xx, yy, and zz directions, revealing an increase in absorption coefficient with rising photon energies, culminating in a prominent peak in the UV domain. The higher intensity in xx and yy directions signify stronger absorption along these axes. The thermodynamic properties of Li2RuSn4, including volume, Debye temperature, Grüneisen parameter, volumetric thermal expansion coefficient, and lattice thermal conductivity were examined. The Debye temperature was found to rise proportionally with tensile strain and decrease with temperature, suggesting that dilatation strain can enhance the mechanical and thermal stability of the compound. The thermoelectric analysis revealed n‐type behavior, with negative Seebeck coefficient values. This research offers valuable insights into the properties of Li2RuSn4, contributing to the understanding of its potential applications.

Thermodynamics assessment of the Erbium-Ruthenium system by combining the Ab-initio and CALPHAD methods

ABSTRACT In the present study, the erbium-ruthenium system was optimised using the CALPHAD approach. The thermodynamic properties and the phase diagram were evaluated. The enthalpies of formation of the intermetallic compounds for the binary system Er-Ru were calculated by ab- initio methods. The liquid phase was treated with the exponential model, while a solution model was applied to represent the HCP (Er, Ru) solid solution. The five intermetallic compounds Er3Ru, Er5Ru2, Er3Ru2, ErRu2, and Er44Ru25 were considered as stoichiometric compounds. The calculations are in good agreement with the phase diagram information and experimental thermodynamic values documented in the literature.

Electronic, elastic, and thermodynamic properties of complex hydrides XAlSiH (X = Sr, Ca, and Ba) intended for hydrogen storage: an ab-initio study

The mechanical and thermodynamic properties of polyanionic hydrides XAlSiH (X = Sr, Ca, and Ba) were evaluated using density functional theory (DFT). The thermal parameters of XAlSiH hydrides, such as the Grüneisen parameter γ, heat capacity, and thermal expansion coefficient, were computed for the first time. The quasi-harmonic Debye model was used to determine these parameters over a range of pressures (0–40 GPa) and temperatures (0–1000 K). The gravimetric hydrogen storage capacities for BaAlSiH, SrAlSiH, and CaAlSiH were found to be 0.52%, 0.71%, and 1.05%, respectively. The hydrogen desorption temperatures for these compounds were also simulated at 748.90 K, 311.57 K, and 685.40 K. Furthermore, semiconducting behavior with an indirect bandgap value between 0.2 and 0.7 eV was exhibited by these compounds using the GGA and LDA approximation, and between 0.7 and 1.2 eV using the mBJ-GGA and mBJ-LDA approximation. Accurate elastic constants for single crystals were obtained from the calculated stress–strain relationships. The elastic constants for the XAlSiH compounds were significantly higher than those for other hydrides. The [001] direction was more compressible than the [100] direction in the hexagonal structure of XAlSiH. A lower bulk modulus than metallic hydrides was exhibited by these materials, indicating that XAlSiH compounds (X = Sr, Ca, and Ba) were highly compressible. The melting temperature for CaAlSiH was higher than that for SrAlSiH and BaAlSiH. Consequently, the decomposition temperature for XAlSiH (X = Sr and Ba) at which hydrogen was released from a fuel cell was lower than that for CaAlSiH. The bonding behavior of CaAlSiH was more directional than that of SrAlSiH and BaAlSiH. Brittle materials were XAlSiH (X = Sr, Ca, and Ba). Our PBE calculations yield linear compressibility and orientation-dependent Young’s modulus. Materials composed of hexagonal XAlSiH (where X represents Sr, Ca, or Ba elements) exhibit anisotropy in Young’s modulus but isotropy in bulk modulus.

Investigation of cathode properties of two-dimensional NbS2Cl2 for Li and Na-ion batteries using density functional theory

Exploring novel two-dimensional materials (2D) for electrode and electrochemical storage applications stands as a pivotal pursuit in advancing renewable energy technologies. While recent research has predominantly focused on anode materials, cathode materials have received comparatively lesser attention. This study delves into the potential cathode applications of the novel two-dimensional material NbS2Cl2 using density functional theory. Fundamental properties, encompassing electronic and thermodynamic attributes, were scrutinized to comprehend the material’s characteristics. Our investigation extended to examining the adsorption and diffusion properties of these electrode materials. Comprehensive calculations of mechanical and thermodynamic properties reaffirmed the stability of this system. Upon adsorption of Li/Na atoms, the conducting nature emerged, evident through charge density difference and projected density of states. Our findings notably reveal minimal diffusion barriers of 1.5 eV and 0.35 eV for Li and Na atoms. Moreover, the observed open circuit voltages for adsorbed Li and Na ions were 4.69 V and 2.62 V, respectively. The calculated theoretical capacity for adsorbed Li-ion on 2D-NbS2Cl2 is 400 mAh g−1, while for Na-ion adsorption, it is 353 mAh g−1, awaiting validation through future experimental verifications.

A study on thermophysical properties of binary mixtures of n-hexane with benzene and some alkyl-substituted benzenes within temperature range (293.15–323.15) K: Experimental and modeling approach

The current work reports densities and sound speeds, and related thermodynamic excess properties, namely excess molar volumes and excess isentropic compressibilities, measured at temperatures from (293.15 to 323.15) K and under atmospheric pressure conditions for binary mixtures of n-hexane with benzene, toluene, ethylbenzene, o-xylene, m-xylene, and p-xylene. Redlich-Kister polynomial correlated the thermodynamic excess properties to test the quality of experimental data. Excess properties contributed to understanding molecular interactions between involved molecules and the peculiarities of their packing in the mixture. The Jouyban-Acree model was used to correlate the mixtures' experimental densities, sound speeds, and their related derived properties, namely isobaric thermal expansivities and isentropic compressibilities. The average absolute percentage deviation of the correlated values from the experimental ones was better than 0.036 %, 0.058 %, 0.040 %, and 0.146 % for density, sound speed, isobaric thermal expansivity, and isentropic compressibility, respectively, attesting to the robustness of the Jouyban-Acree correlations. Additionally, the Perturbed Chain Statistical Associating Fluid Theory Equation of State modeled the densities of the current mixtures. Schaaff's Collision Factor Theory and Nomoto's relation were compared for their ability to model the sound speeds of the mixtures. The efficacy of these models was tested by computing the average absolute percentage deviations between experimental and computed values. The modeled densities are reasonably concordant with experimental data, with an overall deviation of 0.02 %. Notably, Nomoto's relation exhibited superior performance over Schaaff's theory in modeling sound speeds of current mixtures, with an overall deviation of 0.33 %. The current findings underline the efficacy and versatility of the used models for thermodynamic modeling in systems of varying complexity.

PρT measurements of 3-aminopropan-1-ol and N-(2-hydroxyethyl)morpholine from (293.15 to 473.15) K and up to 40 MPa and modeling with modified Tait and PC-SAFT equations

New density data has been reported for 3-aminopropan-1-ol (AP) and N-(2-hydroxyethyl)morpholine (NHEM) at temperatures ranging from (293.15–473.15) K at 19 pressures ranging from (0.1–40) MPa. The experimental measurements were carried out using an Anton Paar high-pressure vibrating tube densimeter with a combined expanded uncertainty of 1 kg m−3 at a 95 % confidence level. Contributions considered in the uncertainty analysis included the impurities in the materials used and apparatus specification. In addition, the density and speed of sound at ambient pressure (81.5 kPa) and temperatures (293.15–343.15) K were measured. The experimental density data were correlated with the modified Tait equation. Values of thermal expansion coefficient (αP ) and isothermal compressibility (κT) were calculated. The work is completed with the modeling of the experimental data using the perturbed-chain statistical associating fluid theory equation of state (PC-SAFT EOS). The parameters of the PC-SAFT equation of state, for the pure compounds, were determined by fitting the equation to the liquid PρT experimental data. Thermodynamic properties such as thermal expansion coefficient (αP), isothermal compressibility (κT), isobaric heat capacity (CP), and speed of sound (u) were calculated with the obtain parameters. Good agreement between experimental data and derived properties represented the modeling accuracy with the obtained parameters.

Valley edge states with opposite chirality in temperature dependent acoustic media

Abstract The valley degree of freedom in phononic crystals and metamaterials holds immense promise for manipulating acoustic and elastic waves. However, the impact of acoustic medium properties on valley edge state frequencies and their robustness to one-way propagation in valley topological phononic crystals remains unexplored. While significant attention has been devoted to scatterer design embedded in honeycomb lattices within acoustic and elastic media to achieve valley edge states and topologically protected nontrivial bandgaps, the influence of variations in acoustic medium properties, such as wave velocity and density affected by environmental temperature, has been overlooked. In this study, we investigate the effect of valley edge states and topological phases exhibited by topological phononic lattices in a temperature-dependent acoustic medium. We observe that a decrease in wave velocity and density, influenced by changing environmental temperature, shifts the topological valley edge states to lower frequencies. Therefore, alongside phononic lattice design, it is crucial to consider the impact of acoustic medium properties on the practical application of acoustic topological insulators. This issue becomes particularly significant when a topological phononic crystal is placed in a wave medium that transitions from incompressible to compressible, where wave velocity and density are no longer constant. Our findings offer a novel perspective on investigating topological insulators in variable acoustic media affected by changing thermodynamic and fluid properties.

Evaluating black wattle bark industrial residue as a new feedstock for bioenergy via pyrolysis and multicomponent kinetic modeling

This work presents an evaluation of the industrial residue from exhausted black wattle bark after the extraction of tannin for use as a new feedstock for biofuel production, without competing with food production. The physicochemical and thermodynamic properties, the influence of temperature on pyrolysis products and multicomponent kinetics were evaluated. Principal component analysis showed that sugars, carboxylic acids, ethers/esters, furans and aldehydes were formed as primary products of pyrolysis at 450 °C. At 550 °C, phenols and mainly ketones were favored, especially acetone and 2,3-butanedione. Pyrolysis at 650 °C favored the production of aldehydes, alcohols, and 1-alkene, polyene and alkane hydrocarbons. After an upgrade, the series of 1-alkenes produced, with carbons C7 to C16, could be suitable for a range of gasoline and jet fuels. Kinetic modeling was based on the deconvolution of the mass loss of three events of the pseudo-components: hemicellulose (DE-HC), cellulose (DE-CL) and lignin (DE-LG). The activation energy for kinetic models Friedman, Flynn-Wall-Ozawa, Kissinger-Akahira-Sunose and Starink presented average values of ∼141.4–149.4 for DE-HC, ∼190.5–200.9 for DE-CL and ∼237.2–252.3 kJ mol−1 for DE-LG. This study encourages using agro-industrial waste to produce second-generation drop-in biofuels and bio-based chemicals, aiming at industrial decarbonization.

Molecular Interaction Studies of Binary Mixtures of Diethyl Oxalate With Butyl Vinyl Ether, Diisopropyl Ether, Anisole and Dibutyl Ether in Terms of Thermodynamic, Transport and Acoustic Properties

Viscosity, the speeds of sound and density were measured in the binary mixtures of diethyl oxalate with butyl vinyl ether, diisopropyl ether, anisole and dibutyl ether at T = 303.15, 308.15 and 313.15 K. The experimental data were used to calculate the excess molar volume ,deviation in viscosity Δη and the acoustical parameters, namely isentropic compressibility (KS), free volume (Vf ), free length (Lf ) and internal pressure (πi). The excess or deviation properties were fitted to the Redlich-Kister polynomials and the results interpreted in terms of the molecular interactions present in mixtures. Theoretical viscosities were calculated using the Grunberg-Nissan, Lobe and Krishnan-Laddha models before their merits were studied in terms of interaction parameters.