Enthalpy Values Research Articles

CALCULATION OF THERMODYNAMIC TEMPERATURES OF CHEMICAL REACTIONS OF STEPWISE IRON REDUCTION PROCESS FROM HEMATITE BY SOLID CARBON

The results of thermodynamic analysis of chemical reactions of stepwise reduction of iron from hematite by solid carbon are presented. The aims of the work are to obtain our own expressions for calculating the numerical values of Gibbs free energy depending on temperature using tabular values of standard enthalpies of formation and entropies of inorganic substances, as well as graphical dependences of Gibbs energy on temperature using formulas from literary sources and using the obtained expressions. Numerical values of boundary temperatures are obtained, above which chemical reactions of stepwise reduction of iron from hematite by solid carbon can thermodynamically proceed. It has been established that: the reduction of magnetite (Fe3O4) from hematite (Fe2O3) by solid carbon C is thermodynamically possible above the boundary temperature, the numerical value of which, according to the obtained formula, is 270°; the reduction of wustite (FeO) from magnetite (Fe3O4) by solid carbon C is thermodynamically possible above the boundary temperature, the numerical value of which, according to the obtained formula, is 658°C; the reduction of iron (Fe) from wustite (FeO) by solid carbon C is thermodynamically possible above the boundary temperature, the numerical value of which, according to the obtained formula, is 703°C, and according to formulas, taken from literary sources, is 774°C, 690°C, 680°C and 609°C, respectively, for each formula. Despite the fact that thermodynamics allows all these chemical reactions to occur above the certain above-mentioned temperature values, each of the reactions of stepwise reduction of iron from its oxides by solid carbon in a shaft reduction furnace either occurs at higher temperatures, and, which is quite obvious, with a change in the aggregate state of the reacting (initial) substances or at least one of them (given that FeO forms low-melting compounds with SiO2, this will be the reaction of reduction of iron from wustite), or does not occur at all (given that Fe2O3 and Fe3O4 do not form low-melting compounds with SiO2, and their melting temperatures are greater than 1500°C, these will be the reactions of reduction of magnetite from hematite and reduction of wustite from magnetite).

Comparison of extraction process, physicochemical properties, and in vitro digestion characteristics of chia seed mucilage polysaccharide.

The study explored five (acidic, alkaline, heating, ionic liquid, and urea solvent) extraction methods' effects on chia seed mucilage polysaccharide (CSM), an anionic polymeric macromolecule, regarding its physicochemical properties, structure, and digestion behavior. The results showed that extraction parameters have a considerable effect on modulating CSM properties. Significant differences emerged in the predominant chemical compositions: the carbohydrates and protein content ranged from 49.20±0.06% to 85.81±0.03%, and 3.20±0.13% to 14.57±0.30%, respectively. The structural analysis revealed that alkaline heating treatment facilitated the formation of protein-polysaccharide conjugates, resulting in reduced particle size, enhanced ζ-potential, and improved thermal stability (194.72±2.19J/g). The crystallinity of CSM varied, peaking at 42.9±0.22% without pH adjustment and heating. CSM extracted using 6M urea exhibited the lowest protein content, and crystallinity (25.50±0.09%), coupled with the highest gastrointestinal digestion rate and poorest thermal stability (with a carbohydrate degradability of 24.223±1.78% and enthalpy value of 62.82±0.32J/g). The CSM obtained under alkaline heating showed minute particles (201.1±10.35μm), the highest ζ-potential absolute value (20.95±2.28mV), and robust thermal stability (194.72±2.19J/g of enthalpy value), which is ideal for stabilizing emulsions or encapsulating thermolabile substances. Additionally, compared to monovalent cations‑sodium ions, divalent cations‑magnesium ions, is more tend to aggregate the CSM structure, resulting in larger molecular particles and a higher protein content. Elevated ionic concentration further diminished thermal stability. These findings suggest that CSM is a customizable, multi-purpose polymer that can be extracted in various ways based on the end-product requirements.

Sustainable polyurethane biocomposite foams by improved microstructure, acoustic characteristics, thermoregulation performance and reduced CO2 emission through phase change material integration

In this research, phase change material (PCM) comprised of energy storage biocomposite materials were improved with raw materials obtained from renewable resources. Modified raw material was synthesized by epoxy castor oil (ECO). After mixing the obtained modified castor oil (MCO) and polyether polyol, PCM of capric acid (CA) was supplemented. To initiate the chemical reaction, a certain amount of methylene diphenyl diisocyanate (MDI) was added to the mixture to provide cross-linking. The physical and chemical properties of the resulting biocomposite foams (BCF) were characterized. According to the results obtained, mixing MCO into polyether raw material increased the number of closed pores in BCF resulting in more CA stored in BCF cells produced. The use of MCO in BCF materials increased the CA integration ratio to 68 wt%. The melting enthalpy value of the novel BCF-PCM composites has been determined as 121.43 J/g. In a warm environment, the PCM additive creates a temperature difference exceeding 6 °C, while in a cold environment, it provides a cooling effect close to 6 °C. A more than 50 % improvement in thermal conductivity was achieved with 68 wt% PCM addition compared to pure BCF. The addition of PCM caused a reduction in tensile stress and strain values to an acceptable level. BCFs with PCM additives exhibit a sound absorption coefficient of 0.9 in narrow frequency ranges, whereas, in broad frequency ranges, this value was more than 0.7. In cold weather conditions, employing BCF-PCM material instead of traditional EPS material with a thickness of 0.1 m has led to at least a 30 % drop in CO2 emissions, no matter the type of fuel used for heating. When opting for BCF-PCM materials, the necessary heat demand was approximately 33 % less compared to using the same thickness of EPS in cold climates.

Experimental and theoretical studies on antioxidant and antibacterial properties of chitosan-gelatin functional composite films loaded with flavonoids

Chitosan-gelatin-flavonoid functional composite films were prepared with chitosan, gelatin, and three flavonoids (Naringenin, Apigenin, and Luteolin). The effect of three flavonoids on physical, antioxidant, and antibacterial properties of functional composite film was investigated from experimental and Density functional theory (DFT) simulations. The tensile strength, thermal stability, water solubility, water vapor permeability, antioxidant activity, and antibacterial activity of chitosan-gelatin-flavonoid functional composite films were improved with flavonoid (Naringenin, Apigenin, and Luteolin) incorporation. The release behavior of Apigenin from functional composite film was much lower than that of Naringenin or Luteolin. ABTS+ radical scavenging ability values of functional composite films followed: Luteolin (69.53 %) > Naringenin (41.39 %) > Apigenin (36.13 %). The antibacterial activities of functional composite films against Staphylococcus aureus followed: Luteolin (52.03 mm) > Apigenin (49.34 mm) > Naringenin (43.15 mm). The total number, location of hydroxyl groups on ring-B, and the unsaturation degree on pyrone ring of flavonoids influenced antioxidant and antibacterial activities of functional composite films. The minimum bond dissociation enthalpy values of flavonoids followed: Luteolin < Apigenin < Naringenin. The interaction energy of Apigenin-chitobiose was stronger than that of Naringenin or Luteolin. These results will shed light on flavonoid selection for functional composite films of food packaging.

Exploring enthalpies of CO2 and N2 adsorption on Zn- and Co-based zeolitic frameworks at varying temperatures and pressures

This study investigates the thermodynamics of CO2 and N2 adsorption on zeolitic imidazolate frameworks (ZIFs), focusing on the effects of metal ions under varying temperatures and pressures. Zn- and Co-based ZIFs were synthesized using 2-methylimidazole and characterized by XRD, FT-IR, Raman spectroscopy, and BET isotherms, confirming high microporosity. Gas adsorption experiments were performed at pressures up to 3000 kPa and temperatures between 268 and 323 K. The CO2 adsorption capacities vary from 274 to 157 cm³/g, while N2 ranged from 67 to 29 cm³/g as temperature increased. The synergistic dynamics of temperature and pressure enhanced CO2 diffusion and induced pore structure changes via a gate-opening mechanism. Isosteric enthalpy (ΔHads) values, determined using Freundlich-Langmuir/Clausius-Clapeyron and virial fits, were -22 ± 5 kJ/mol for CO2 and -15 ± 2 kJ/mol for N2, confirming that physisorption is the dominant mechanism. Gibbs free energy (ΔGads) for CO2 ranged from -12 to -18 kJ/mol, and entropy (ΔSads) from -0.01 to -0.03 kJ/mol/K, suggesting spontaneous and thermodynamically favorable CO2 adsorption, though spontaneity decreased with rising temperature. ZIFs containing Zn exhibited high CO2 adsorption capacity, while those with Co showed better CO2 selectivity over N2, highlighting their potential for efficient CO2 capture under various temperature and pressure conditions.

Effect of Adding Konjac Glucomannan on the Physicochemical Properties of Indica Rice Flour and the Quality of Its Product of Instant Dry Rice Noodles

Instant dry rice noodles have a broad market prospect due to their advantages of long shelf life, convenient transportation, and convenient eating, but there are still quality problems such as long rehydration times and poor eating quality. In order to improve the quality of instant dry rice noodles, the effects of konjac glucomannan (KGM) on the gelatinization characteristics, pasting properties, and rheological properties of Indica rice flour and the structure, food quality, and starch digestibility of instant dry rice noodles made of Indica rice flour were studied. The results showed that the starch gelatinization conclusion temperature and endothermic enthalpy of Indica rice flour were reduced by adding ≤ 3% KGM, the peak viscosity, valley viscosity, final viscosity, and setback value of Indica rice flour in the pasting process decreased with the increase in the KGM addition amount, and the pseudoplasticity, viscosity, and elasticity of Indica rice flour paste were reduced by adding &gt; 1% KGM. When the KGM addition amount was 2%, the endothermic enthalpy, final viscosity, and setback value of Indica rice flour were 2.74 J/g, 2379.5 cp, and 961.5 cp, respectively. The instant dry rice noodles made of Indica rice flour had a looser microstructure after adding KGM, and its short-range ordered structure and double helix content were reduced by adding 1~3% KGM. When the KGM addition amount was 2%, the rehydration time of instant dry rice noodles was 290 s, which was shortened by 14.7%, while the texture and sensory quality remained unchanged, and the SDS content was reduced by 16.4% while the RS content was increased by 28.8%. Therefore, the physicochemical properties of Indica rice flour and the quality of its instant dry rice noodles can be improved by adding an appropriate amount of KGM. This study can promote the application of KGM in improving the quality of rice products.

The Confinement Behavior and Mechanistic Insights of Organic Phase Change Material Encapsulated in Wood Morphology Genetic Nanostructures for Thermal Energy Storage.

Wood, a renewable and abundant biomass resource, holds substantial promise as an encapsulation matrix for thermal energy storage (TES) applications involving phase change materials (PCMs). However, practical implementations often reveal a disparity between observed and theoretical phase change enthalpy values of wood-derived composite PCMs (CPCMs). This study systematically explores the confinement behavior of organic PCMs encapsulated in a delignified balsa wood matrix with morphology genetic nanostructure, characterized by a specific surface area of 25.4 ± 1.1 m2/g and nanoscale pores averaging 2.2 nm. Detailed thermal performance evaluations uncover distinct phase change behaviors among various organic PCMs, influenced by the unique characteristics of functional groups and carbon chain lengths. The encapsulation mechanism is primarily dictated by host-guest interactions, which modulate PCM molecular mobility through hydrogen bonding and spatial constraints imposed by the hierarchical pore structure of the wood. Notably, results demonstrate a progressive enhancement of nanoconfinement effects, evidencing a transition from octadecane to stearic acid, further supported by density functional theory (DFT) calculations. This research significantly advances the understanding of nanoconfinement mechanisms in wood-derived matrices, paving the way for the development of high-performance, shape-stabilized composite PCMs that are essential for sustainable thermal energy storage solutions.

Synergistic effect of ozone treatment with α-amylase on the modification of microstructure and paste properties of japonica rice starch

The objective was to evaluate the synergistic effect of ozonization and α-amylase on modifying the microstructure and paste properties of starch, using 0.00042 g of ozone/100 g of buffer for various durations. Enzymatic susceptibility was increased, achieving maximum values of 12.73 % with an 11.42 % increase in crystallinity and an average particle size of 10.12 μm for 90 min treated japonica rice starch (JR90). The granules exhibited a polyhedral shape and, with increased intensity of combined treatments, formed clusters and lost their original geometry. Apparent viscosity, rheological, and textural parameters were reduced due to the more efficient action of α-amylase on ozonized starch, as confirmed by the low gelatinization enthalpy value (7.61 J/g). Ozone proved effective in opening starch chains, partially gelatinizing granules, homogenizing the enzymatic medium, and increasing the hydrolysis rate of α-amylase in japonica rice starch.

Valorizing brewery industry waste in nanocellulose cryogel-PEG composites for cold chain packaging

Global concerns about food and energy waste call for new sustainable solutions. Phase changing materials (PCM) are promising thermal storage and management materials which have potential to mitigate food waste, yet they often suffer from leakage and non-shape stability. Here, a green shape-stabilized polyethylene glycol 300 (PEG) nanocellulose-based composite was developed using readily available and cost-effective side streams from the brewery industry. Two different routes were examined for the incorporation of PEG into the cellulose nanofiber (CNF) cryogel including adding different dry mass ratios of PEG in the sol stage, with or without physical crosslinking, or adding the PEG after CNF gelation. FTIR and TGA analysis revealed the improved thermal stability of PEG after incorporation into the CNF cryogel. The PEG/CNF composite produced by adding PEG in the gel stage outperformed the other material formulations by demonstrating the highest enthalpy value (93.2 J/g) and the best mechanical properties (Young's modulus of 140 kPa). The package containing the PEG/CNF composite could maintain the meat temperature below 0 °C around 4 times longer than the control package when the cold system was interrupted. Furthermore, the PEG/CNF composite showed a positive effect on the color and drip loss values of frozen meat.

A concise approach for interpreting the removal kinetic of 2,4-D by carbonized peanut shell

The present study displays the adsorption characteristics of dichloro phenoxy acetic acid (2.4-D) on biomass-based peanut shell (BPC) carbon. Experiments were conducted by varying some parameters like concentration, pH, and temperature. 2,4-D adsorption uptake was increased from 0.504 to 3.826 mg/g with rising concentration from 1 µg/mL to 5 µg/mL and giving the highest adsorption at acidic pH. 1.605 mg/g uptake was obtained at pH 2.7. The data were in good harmony with Langmuir, Freundlic, Dubinin-Radushkevich (DR), and Generalized isotherms. The monolayer adsorption capacity was found as 42.62 ± 0.3257 mg/g. The kinetic was governed by the first-order kinetic. Various kinetic models were employed and particle diffusion was predominated for 2,4-D adsorption. Thermodynamics were explained in detail. The mean adsorption energy (E) was shown by the physical sorption, and Gibbs energy was the indicator of the spontaneous nature of the adsorption. Standard enthalpy, entropy, and Gibbs values were recorded as 5.064 ± 139.84, 18.849 ± 0.148, and 0,7414 ± 0.0943 J/mol. The results showed that BPC was an eco-friendly and cost-effective material.

Reproduction of experimental data for stacked caffeine dimers using various computational methods

Reliable description of stacking interaction of aromatic molecules is important for the understanding structure, stability, and functions of biopolymers. The caffeine molecule is an ideal object for this study as the stacking interactions are the preferential ones for self-associations of this hydrophobic molecule without H-bond donor groups. The analysis of anhydrous caffeine crystal structures revealed five types of caffeine stacking dimers. Geometry optimization of these dimers was performed using two molecular mechanics force fields, ab-initio method Møller Plesset of the second order (MP2), and density functional theory (DFT) with different functionals. The comparison of geometric parameters of the caffeine dimers obtained using different theoretical methods with those in crystals enables us to suggest the methods providing the most reliable stacking characteristics. These methods are: the MP2 with Basis Set Superposition Error correction (MP2/CP), Poltev force field, along with PBE0-DH, SCAN and PBE-D3 functionals of DFT. For the methods, which give the dimer interaction energy close to that obtained by MP2/CP method, the evaluated sublimation enthalpy values are shown to be close to the experimental data. Additionally, MP2/CP, Poltev FF and PBE0-DH functional showed to be the methods that describe well both the energy and geometry of the caffeine stacking dimer.

DFT + U Study of Plutonium Hydrides with Occupation Matrix Control.

The magnetic order of plutonium hydrides (PuHx) has long been a subject of controversy, both experimentally and theoretically. The magnetic, structural, electronic, and thermodynamic properties of PuHx are investigated using Hubbard-corrected density functional theory (DFT + U), with U derived from linear response calculations. To address the issue of electronic metastable states within DFT + U, we employ an occupation matrix control method as well as allowing 5f orbitals to break the structural symmetry. This advanced computational approach establishes that the ground-state magnetic order for PuH2 is antiferromagnetic and that for PuH3 is ferromagnetic, consistent with Faraday and nuclear magnetic resonance experiments. Using the conventional hydrogen-vacancy model for PuHx, the hydrogen-content-induced magnetic transition and anomalous variation of the magnetic moment are successfully reproduced. In particular, the calculated transition point of x matches the experimental findings. Furthermore, the electronic configuration of the Pu atom in PuHx is determined to be 5f5, which is consistent with observations from X-ray photoemission spectroscopy. Our calculated values for enthalpy of formation, heat capacity, and entropy are in good agreement with experimental data, thereby validating the robustness of our theoretical framework.

Thermogravimetric Assessment of Biomass: Unravelling Kinetic, Chemical Composition and Combustion Profiles

Thermogravimetric analysis (TGA) was performed on six samples of pine wood, poplar sawdust and olive residue, and the kinetic parameters were evaluated by using isoconversional models. The hemicellulose, cellulose and lignin contents were also estimated using the Fraser–Suzuki deconvolution method. In addition, a range of thermodynamic parameters and combustion indices was calculated. Significant correlations were found between the kinetic, thermodynamic and combustion parameters. The ignition index showed an inverse relationship with the activation energy, whereas the burnout index correlated with enthalpy values for most samples. Higher heating rates during TGA increased ignition and combustion efficiencies but decreased combustion stability. Differences in behaviour were detected between the olive residues, which had a much higher lignin content (51.2–56.9%), and the woody biomass samples (24.2–29.2%). Moreover, the sample with the highest ash content also exhibited some distinctive characteristics, including the lowest high heating value and ignition index, coupled with the highest activation energy, indicating a less favourable combustion behaviour than the other samples. The particle size of the samples was also found to be critical for both combustion efficiency and safety.

Comparison of the Reaction Characteristics of Different Fuels in the Supercritical Multicomponent Thermal Fluid Generation Process

Supercritical multicomponent thermal fluid technology is a new technology with obvious advantages in offshore heavy oil recovery. However, there is currently insufficient understanding of the generation characteristics of the supercritical multicomponent thermal fluid, which is not conducive to the promotion and application of this technology. In order to improve the economic benefits and applicability of the supercritical multicomponent thermal fluid thermal recovery technology, this article reports on indoor supercritical multicomponent thermal fluid generation experiments and compares the reaction characteristics of different fuels in the supercritical multicomponent thermal fluid generation process. The research results indicate that the main components of the products obtained from the supercritical water–crude oil/diesel reaction are similar. Compared to the supercritical water–crude oil reaction, the total enthalpy value of the supercritical multicomponent thermal fluid generated by the supercritical water–diesel reaction is higher, and the specific enthalpy is lower. When the thermal efficiency of the boiler is the same, the energy equilibrium concentration of crude oil is lower than that of diesel. The feasibility of using crude oil instead of diesel to prepare supercritical multicomponent thermal fluids is analyzed from three aspects: reaction mechanism, economic benefits, and technical conditions. It is believed that using crude oil instead of diesel to prepare supercritical multicomponent thermal fluids has good feasibility.

Thermal Decomposition and Kinetic Analysis of Amazonian Woods: A Comparative Study of Goupia glabra and Manilkara huberi

This study presents a detailed analysis of the thermal degradation and kinetic behavior of two Amazonian wood species, Goupia glabra (cupiúba) and Manilkara huberi (maçaranduba), using thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), Fourier-transform infrared spectroscopy (FTIR-ATR), and direct infusion mass spectrometry (DIMS). Wood samples were subjected to controlled heating rates of 20, 40, and 60 °C/min from 25 to 800 °C under an argon atmosphere. TGA revealed moisture evaporation below 120 °C, with hemicellulose degradation occurring between 220 and 315 °C, cellulose decomposition between 315 and 400 °C, and lignin breakdown over a broader range from 180 to 900 °C. The highest rate of mass loss occurred at 363.99 °C for G. glabra and 360.27 °C for M. huberi at a heating rate of 20 °C/min, with shifts to higher temperatures at faster heating rates. Activation energies were calculated using Arrhenius and Kissinger models, yielding values between 53.46–61.45 kJ/mol for G. glabra and 58.18–62.77 kJ/mol for M. huberi, confirming their stable thermal profiles. DSC analysis identified a significant endothermic peak related to moisture evaporation below 100 °C, followed by two exothermic peaks. For G. glabra, the first exothermic peak appeared at 331.45 °C and the second at 466.08 °C, while for M. huberi, these occurred at 366.41 °C and 466.08 °C, indicating the decomposition of hemicellulose, cellulose, and lignin. Enthalpy values for G. glabra were 12,633.37 mJ and 18,652.66 mJ for the first and second peaks, respectively, while M. huberi showed lower enthalpies of 9648.04 mJ and 14,417.68 mJ, suggesting a higher energy release in G. glabra. FTIR-ATR analysis highlighted the presence of key functional groups in both species, with strong absorption bands in the 3330–3500 cm−1 region corresponding to O-H stretching vibrations, indicative of hydroxyl groups in cellulose and hemicellulose. The 1500–1600 cm−1 region, representing aromatic C=C vibrations, confirmed the presence of lignin. Quantitatively, these results suggest a high content of cellulose and lignin in both species. DIMS analysis further identified polyphenolic compounds and triterpenoids in M. huberi, with major ions at m/z 289 and 409, while G. glabra showed steroidal and polyphenolic compounds with a base peak at m/z 395. These findings indicate the significant presence of bioactive compounds, contributing to the wood’s resistance to microbial degradation. This comprehensive thermal and chemical characterization suggests that both species have potential industrial applications in environments requiring high thermal stability.

Symmetrical homologous series of thiadiazole derivatives containing azomethine linkages: synthesis, characterization and mesomorphic properties

Symmetrical homologous series of liquid crystalline thiadiazole Schiff’s-base derivatives derived from 1,4-bis(4’-formylphenoxy)butane and 5-(4’-alkoxyphenyl)-1,3,4-thiadiazole-2-amine have been synthesized. Spectral analysis including FT-IR and 1H–NMR of every individual compound was carried out and were confirmed using elemental analysis. The microscopic textures of prepared compounds and their transition temperatures were observed using a polarizing optical microscope. The enthalpy change data value was measured using differential scanning calorimetry. Smectic and nematic phases were observed on heating as well as cooling cycles. The thermal stability of the prepared compounds was recorded using a thermogravimetric analysis.

New thermodynamic insights into pregabalin interactions with H+, Na+, Mg2+, Ca2+, Cu2+, Zn2+: Equilibrium constants, enthalpy changes and sequestering ability

The thermodynamics of the interaction between (S)-(+)-3-aminomethyl-5-methylhexanoic acid (pregabalin) and protons was studied potentiometrically at different temperatures (288.15 ≤ T/K ≤ 310.15), ionic strengths (0.16 ≤ I/mol kg−1(H2O) ≤ 0.97, NaCl), (0.11 ≤ I/mol kg−1(H2O) ≤ 1.11, (C2H5)4NI), (0.10 ≤ I/mol kg−1(H2O) ≤ 1.03, NaClO4, only at T = 298.15 K). The protonation constants at infinite dilution and the corresponding enthalpy change values were determined, as well as their parameters for the dependence on the temperature and ionic strength. The results showed that the protonation reactions are exothermic, and that the entropic contribution is the driving force of the processes.Formation constants of pregabalin (L) with Zn2+, Cu2+, Ca2+, and Mg2+ were determined in NaCl(aq) at different ionic strength values, at 298.15 K. Different speciation models were proposed for the various metal/Pregabalin systems: ZnHL2+, ZnLOH0(aq), CuL+, CuL20(aq), CaL+, CaHL2+, and MgL+, depending on the different acid–base properties of the metals and the possible formation of sparingly soluble species. The modelling of the thermodynamic formation parameters respect to the temperature and ionic strength variation was carried out by using both the Specific Ion Interaction Theory (SIT) and an extended Debye-Hückel type equation.Being Pregabalin an emerging contaminant, it was interesting to investigate its distribution in presence of the investigated metal cations in aqueous solution simulating both biological fluid (urine) and natural water (seawater).

Experimental and numerical investigations on phase change thermal storage foam concrete based on CaCl2∙6H2O/silica aerogel composite phase change material

A new type of phase change thermal storage foam concrete was developed by effectively incorporating a composite phase change material (CPCM) into foam concrete. The CPCM was obtained by using 75 wt% CaCl2∙6H2O as PCM and 25 wt% silica aerogel as carrier, with a phase change temperature of 27.0 °C and an enthalpy value of 110.9 J/g. The mechanical and thermal properties of the obtained phase change thermal storage foam concrete blocks were investigated experimentally, along with a numerical analysis of their heat transfer characteristics. The experimental results demonstrated that after adding CPCM, the thermal performances of foam concrete blocks significantly increased, under the condition of their dry densities and compressive strengths met the specification requirements. Adding 20 wt% CPCM, the enthalpy value, specific heat capacity, thermal conductivity and thermal inertia of foam concrete block respectively reached 37.0 J/g, 1782.0 J/(kg∙K), 0.131 W/(m·K) and 770.9, with appropriate phase change temperature (27.2 °C). Numerical analysis for the heat transfer characteristics of the phase change thermal storage foam concrete wall revealed that optimal thermal insulation and thermal storage performances were achieved when the wall contained 20 wt% CPCM and thickness of 80 mm. In this case, the model exhibited a temperature wave attenuation factor of 6.66, the temperature amplitude of 5.84 K and a decline of 9.87 K for the highest temperature of the wall as well as delay time of 198,000 s, effectively regulating indoor temperature and saving energy. Therefore, the as-prepared phase change thermal storage foam concrete had great potential for application in building energy conservation.

Eutectic mixtures of nevirapine: Phase diagrams, solid-state characterization, and dissolution studies

Solid-state modifications can improve drug performance. Studies have shown that multicomponent crystals, such as cocrystals and eutectic compositions, have successfully improved the performance of certain drugs, including their solubility. Nevirapine (NEV) is an antiretroviral drug with low aqueous solubility, impacting its bioavailability. This work aimed to study different nevirapine/co-former solid eutectic systems, define their phase diagrams and evaluate their dissolution properties. Caffeine (CAF), Theobromine (TEOB), and Theophylline (THEO) were chosen as co-formers due to their functional groups that can interact with NEV. Aiming to determine both temperature and eutectic composition, phase and Tamman diagrams were obtained using the differential scanning calorimetry (DSC) analysis of the mixtures indifferent NEV-co-former compositions (%w/w). Powder X-ray diffraction (PXRD) and DSC were used to characterize the eutectic materials. To assess the influence of eutectic systems on dissolution properties, we determined the powder dissolution profiles and intrinsic dissolution rates of anhydrous NEV and eutectic systems NEV-CAF and NEV-THEO using different dissolution media (pH 1.2 and pH 6.8). The eutectic compositions were calculated through the phase diagrams, interpolating the curves obtained by linear regression. Thus, the eutectic composition of the NEV-CAF system was determined to be 36.55 % NEV and eutectic temperature at 201.1 °C, while in the NEV-THEO system, the eutectic was obtained in a composition of 71.04 % NEV and eutectic temperature at 217.8 °C. Tamman diagrams were generated using the enthalpy values obtained from the DSC curves, and eutectic compositions were calculated using linear regression. The analysis revealed a eutectic composition of 36.51 % of NEV for the NEV-CAF system, and a eutectic composition of 70.94 % of NEV for the NEV-THEO system. It was not possible to determine the eutectic mass fraction of NEV-TEOB. A comparison of dissolution profiles and intrinsic dissolution rates in different dissolution media showed a significant improvement in the NEV dissolution rate in both eutectic systems. In an acidic medium, NEV dissolved 16 times faster in the NEV-CAF sample and 4 times faster in the NEV-THEO sample compared to pure anhydrous NEV. In a neutral medium, the dissolution profile of NEV was even more favorable in the same eutectic systems, showing that the increase in dissolution is relevant in a wide range of pH. In addition, the intrinsic dissolution rate in the two eutectic systems was higher than that of anhydrous NEV in all employed dissolution mediums. These eutectic systems improve the dissolution rate compared to pure NEV, offering the potential for enhancing the dissolution of poorly water-soluble drugs in the future.

Smoother Semiclassical Dispersion for Density Functional Theory via D3S: Understanding and Addressing Unphysical Minima in the D3 Dispersion Correction Model.

One of the most widely used and computationally efficient models that accounts for London dispersion interactions within density functional theory (DFT) is the D3 dispersion correction model. In this work, we demonstrate that this model can induce the appearance of unphysical minima on the potential energy surface (PES) when the coordination number of atoms changes. Optimizing to these artifactual structures can lead to significant errors in determining the interaction energy between two molecules and in estimating the thermodynamic properties of the system. In several specific examples, such as Kuratowski-type H2-NiKur and H2-PdKur clusters, these local minima exhibited extremely high PES curvature, resulting in incorrect estimations of harmonic frequencies and significant overestimations of zero-point energy and enthalpy values. Although such erroneous behavior of the D3 model is relatively rare, it can occur across a wide range of chemical species, including molecules like the [Li(C6H6)]+ complex and the dispiro(acridan)-substituted pyracene (DSAP) molecule. Our analysis reveals that the root of the problem lies in the definition of the AB atomic-pair dependent C6AB coefficients in the D3 model. To address this issue, we propose a reparameterization of the D3 model by introducing a modified C6AB functional form that now depends on the specific pair of considered atoms. This new model, termed D3-Smooth (or D3S for short), is designed to smooth out the PES associated with the dispersion correction. By doing so, we demonstrate that D3S eliminates unphysical local minima while maintaining the quite satisfactory accuracy of the parent D3 method in interaction energy benchmark sets. For example, the RMS difference between using the D3(BJ) correction to B3LYP and the D3S(BJ) correction across the large MGCDB84 data set of nearly 5000 data points is only 0.12 kJ/mol. Similar results are obtained for every other D3-corrected functional tested. Consistent with this result, no significant improvement could be obtained for the B3LYP-D3S(0) correction by reoptimizing the damping function.