Temperature Dependence Of Heat Capacity Research Articles

Determination of the Thermal Conductivity and Volumetric Heat Capacity of Substance from Heat Flux

The study of nonlinear problems related to heat transfer in a substance is of great practical important. Earlier, this paper’s authors proposed an effective algorithm for determining the volumetric heat capacity and thermal conductivity of a substance based on experimental observations of the dynamics of the temperature field in the object. In this paper, the problem of simultaneous identification of temperature-dependent volumetric heat capacity and thermal conductivity of the substance under study from the heat flux at the boundary of the domain is investigated. The consideration is based on the first boundary value problem for a one-dimensional unsteady heat equation. The coefficient inverse problem under consideration is reduced to a variational problem, which is solved by gradient methods based on the application of fast automatic differentiation. The uniqueness of the solution of the inverse problem is investigated.

Heat capacities and thermodynamic functions of three 1-benzyl-4-aryl-1H-1,2,3-triazoles in the temperature range of (0 – Tm) K

In this paper, we present the results of comprehensive thermodynamic study of some functionally substituted triazoles such as 1-benzyl-4-phenyl-1H-1,2,3-triazole, 1-benzyl-4-(m-tolyl)-1H-1,2,3-triazole and 1-benzyl-4-(4‑tert-butylphenyl)-1H-1,2,3-triazole. The temperature dependences of heat capacities of 1-benzyl-4-(m-tolyl)-1H-1,2,3-triazole and 1-benzyl-4-(4‑tert-butylphenyl)-1H-1,2,3-triazole were measured in a wide temperature range of ∼(5 – 370) K using the adiabatic calorimetry. Those of 1-benzyl-4-phenyl-1H-1,2,3-triazole were determined at the range of ∼(5 – 80) K, supplementing the previous measurements at the more elevated temperatures. The melting parameters and thermal stability (melting temperature, enthalpy of fusion, temperature of thermal destruction) of the compounds were determined using the differential scanning calorimetry. Also, the standard thermodynamic functions (absolute entropies, reduced enthalpies and Gibbs energies) were calculated in the temperature range of (0 – Tm) K.

Refined prediction of thermal transport performance in amorphous silica

Thermal transport in amorphous silica (a-SiO2) and silica aerogel is critically important for thermal protection and microelectronics applications. However, notable disparities exist between the predicted and measured thermal conductivity of a-SiO2. Inspired by the dual-phonon theory proposed by Luo et al. [Nat. Commun. 2020, 11, 2554] for crystalline materials, this work introduces a dual-diffuson transport method for amorphous materials. The criterion based on the thermal diffusivity is employed to differentiate between normal diffusons and phonon-like diffusons. Herein, the thermal conductivity of a-SiO2 is investigated by combining a modified Allen-Feldman (AF) theory with the dual-diffuson transport method. The present method is validated well by the measurement using the transient plane source (TPS) method. In addition, the results indicate that normal diffusons primarily govern the thermal transport in a-SiO2, with only a minor contribution from phonon-like diffusons. The temperature dependence of specific heat capacity and mode linewidth contributes to the positive temperature-dependent thermal conductivity. The quantum effect of specific heat capacity is the primary influencing factor in the temperature range of 100–1000 K, while the mode linewidth becomes dominant at higher temperatures. Finally, a theoretical framework for predicting the solid thermal conductivity of silica aerogel is introduced by including the temperature effect on the inherent thermophysical properties of the backbone. This work uncovers the physical mechanisms underlying temperature-dependent thermal transport in a-SiO2 and silica aerogels.

Phonon spectroscopy and features of low-temperature heat capacity of solid solutions of electrolytes

The kinetic characteristics of thermal frequency phonons in the region of helium temperatures in ceramic samples of the Ce1–xGdxO2–y electrolyte solid solution have been studied. To explain the temperature dependence of the phonon mean free path, we used the previously performed calculations of the energy of vacancy formation in the anion sublattice of a solid solution of zirconium dioxide stabilized by yttrium ZrO2:Y2O3 (YSZ) with a similar crystal structure. It is shown that in the Ce1–xGdxO2–y system under study, the formation of structural defects associated with the presence of vacancies in the anion sublattice with energy Δ = 8.53 K is possible. It has been established that analysis of the temperature dependences of the YSZ heat capacity allows one to trace the degree of disorder (amorphization) of the solid solution depending on its level of stabilization.

Large reversible magnetocaloric effect in rare-earth molybdate RE2(MoO4)3 (RE: Gd and Tb) compounds

We report on the synthesis, structural, DC magnetic susceptibility studies on Gd2(MoO4)3 and Tb2(MoO4)3 polycrystals, prepared by conventional solid-state reaction method. Temperature and magnetic field (H) dependent magnetization and heat capacity measurements have been carried out to estimate the isothermal magnetic-entropy change (−ΔSm) and adiabatic temperature change (ΔTadi) in both rare-earth molybdates. No obvious long-range magnetic ordering can be found down to 2 K in both studied compounds. The estimated maximum value of –ΔSm at 3.5 K for 70 kOe is 31.1 J kg−1 K−1 and 16.7 J kg−1 K−1 in Gd2(MoO4)3 and Tb2(MoO4)3, respectively. Further, the calculated total-adiabatic temperature change for Gd2(MoO4)3 was 12.8 K, and Tb2(MoO4)3 has shown 9.8 K. The difference in the observed magnetocaloric and adiabatic temperature responses of Tb2(MoO4)3 compared to Gd2(MoO4)3 could be attributed to the presence of orbital angular moment of Tb3+ ions and relatively low-value of magnetization. Both the systems show a large magnetocaloric effect (MCE) (−ΔSm ∼ 12 J kg−1 K−1) even in low applied H (<20 kOe) attainable by a permanent magnet. Large magnetocaloric behaviour of Gd2(MoO4)3 and Tb2(MoO4)3 systems at a moderate field change along with very low electrical conductivity and the absence of thermal and magnetic field hysteresis in magnetization make them conducive to their use as promising magnetic refrigerants in the vicinity of liquid-helium temperatures.

Thermodynamic properties of MnV2O6 and Mn2V2O7 at high temperatures

MnV2O6 and Mn2V2O7 are the key compounds during the manganese salt roasting for extracting vanadium from vanadium bearing slag. Thermodynamic properties of MnV2O6 and Mn2V2O7 are dispensable to get insight into the multi-phase reaction mechanism and clarify the phase evolution. In this study, the MnV2O6 and Mn2V2O7 compounds were synthesized through solid-state roasting routes under a nitrogen gas atmosphere, and their crystal structure and thermodynamic properties were determined using X-ray powder diffraction, differential scanning calorimetry, and drop calorimetry. The enthalpy increments of MnV2O6 and Mn2V2O7 were experimentally measured for temperatures ranging from 573 K to 1023 K and 573 K to 1173 K, respectively, using drop calorimetry for the first time. Based on the experimentally measured enthalpy increments, the temperature dependence of the molar heat capacity of MnV2O6 and Mn2V2O7 was then derived. Furthermore, thermodynamic properties such as enthalpy, entropy, and Gibbs free energy were also calculated. Finally, the Gibbs free energy of the chemical reactions during the roasting of vanadium slag was evaluated, and compared with other roasting techniques.

Characterization and Application of Cyrene as a Biomass-Based Solvent for Homogeneous Heck-Coupling Reaction.

Cyrene, a renewable, non-toxic substance having negligible vapor pressure, even at high temperatures, was proposed as a reaction medium for homogeneous Pd-catalyzed Heck-coupling reactions. It was first characterized by its temperature-dependent physicochemical properties, i.e., vapor pressure, density, surface tension, heat capacity, and viscosity, the key parameters of its reaction and process chemistry. Its refractive indices in the function of temperature were also determined. Hereafter, the effect of reaction parameters (Pd source, nature of the base, the water content of the reaction mixture, leaving group (-I, -Br, -Cl, and -OTf of aromatic substrates) on Pd-catalyzed Heck-coupling reaction was investigated using iodobenzene and styrene as model substrates. Subsequently, 4-substituted iodobenzene and styrene derivatives were applied to investigate the effect of electronic parameters on the reaction efficiency and functional group tolerance. To demonstrate the applicability of the system, thirteen stilbene derivatives were isolated with good to high yields and purity (> 95%) using 0.2 mol% of Pd, 1.5 eq. of Et3N as a base, in 1 mL of Cyrene for 2 h at 100 °C.

Фізичні властивості нанокомпозитів ПХТФЕ-ТРГ та ПХТФЕ-ТРГ/SiO2

Polymeric nanocomposites based on polychlorotrifluoroethylene (PCTFE) with a low content of dispersed thermally expanded graphite TRG and modified filler TRG/SiO2, characterized by high electrophysical properties, were obtained. The features of the electronic structure of the composite surface have been investigated. The regularities of changes in the electrophysical properties of the composites depending on the content of fillers and temperature have been established. On the basis of studies and comparative analysis of the thermophysical properties (specific heat capacity cp, temperature coefficient of linear expansion a) of the systems, the influence of the structural morphological state of the components and their concentration, the level of interfacial interaction on the physical properties of nanocomposites have been investigated.It has been established that the modified nanofiller is more active towards the polymer matrix than the unmodified one. The composites exhibit a double effect of the modified nanofiller on the matrix structure, which consists in the formation of a powerful crystal structure in the zones of influence of the nanofiller and amorphization of the polymer matrix in the peripheral zones. It has been found that the amorphization of the matrix results in a decrease in the area of temperature reflexes peaks on the temperature dependences of the specific heat capacity and a change in the absolute value of the temperature coefficient of linear expansion with an increase in the concentration of the modified TRG.

Precise integration boundary element method for solving nonlinear transient heat conduction problems with temperature dependent thermal conductivity and heat capacity

The precise integration boundary element method (PIBEM) is used to solve nonlinear transient heat conduction problems with temperature dependent thermal conductivity and heat capacity in this article. At first, a boundary-domain integral equation can be obtained by using the fundamental solution for steady linear heat conduction problems. Secondly, the domain integrals are converted into boundary integrals by using the radial integration method to get a pure boundary integral equation, which can retain the advantage of dimension reduction of the boundary element method. Then, after discretization, a first-order nonlinear differential equation system in time is obtained, and the precise integration method with predictor-corrector technique is used to solve the system of nonlinear equations. In the end, several numerical examples are presented to verify the accuracy and stability of the presented method. The results obtained by the presented method are less affected by the time step size and satisfactory results can be obtained even for a large time step size.

Large electrocaloric effect across the non-hysteretic electrostructural phase transition in lead-free (Ba0.88Ca0.12)(Ti0.94Sn0.06)O3 ceramics

Structural, dielectric, and electrocaloric properties were investigated in Pb-free ceramic (Ba0.88Ca0.12)(Ti0.94Sn0.06)O3 (BCST), synthesized using solid-state sintering method. Rietveld refinement of room temperature XRD data revealed the existence of pure perovskite tetragonal (P4mm) phase. Temperature-dependent XRD analyses confirmed a structural transition from tetragonal to cubic phase near 380 K. Temperature-dependent dielectric constant (εr) and specific heat capacity (Cp) confirmed the presence of thermal hysteresis in two phase transitions near 233 ± 10 K and 254 ± 10 K, and a non-hysteretic behavior at the Curie temperature (TC∼373 ± 10 K). A comprehensive Raman study corroborated the existence of phase transitions. Electrocaloric properties were determined using indirect method utilizing the non-hysteretic nature across TC. A large adiabatic temperature change of |∆T| = 0.52 K, isotropic entropy change |∆S| = 0.68 J/kg.K, electrocaloric coefficients, |∆T/∆E |= 0.311 K.mm/kV and |∆S/∆E| = 0.41 J.mm/K.kg.kV were obtained at 380 K for an electric field of 16.7 kV/cm. Obtained value of |∆T/∆E| is relatively good, reported among other BaTiO3-based ceramics.

Toward better understanding of anharmonic structural, thermodynamic, and elastic properties of CaSiO3 perovskite under extreme conditions via statistical moment method

CaSiO3 perovskite is thought to be the third most abundant minerals in both the Earth’s transition zone and lower mantle but its structural, thermodynamic, and elastic properties have not been well characterized. In this work, for the first time, we apply the statistical moment method (SMM) to determine analytical expressions of thermoelastic quantities such as isothermal and adiabatic elastic moduli, Grüneisen parameter, Young’s and shear moduli, compression wave and shear velocities including the full anharmonic effects of thermal lattice vibrations of perovskite crystals with cubic structure. The theoretical results are applied for numerical calculations for cubic CaSiO3 perovskite, which is a strongly anharmonic system, at temperatures and pressures up to 4000 K and 180 GPa corresponding to the extreme conditions of the Earth’s lower mantle. Our results for temperature and pressure dependences of unit cell volume, thermal expansivity, isochoric and isobaric heat capacities, Grüneisen parameter, isothermal and adiabatic elastic moduli, Young’s and shear moduli, compression wave and shear velocities are important signs of anharmonic effects under high temperatures and pressures. The SMM results are compared with experiments and other calculations. The present study provides an effective theoretical approach for finding the structural, thermodynamic, and elastic properties of strongly anharmonic materials under extreme conditions.

Fragility and Tendency to Crystallization for Structurally Related Compounds.

The present study was designed to investigate the physical stability of three organic materials with similar chemical structures. The examined compounds revealed completely different crystallization tendencies in their supercooled liquid states and were classified into three distinct classes based on their tendency to crystallize. (S)-4-Benzyl-2-oxazolidinone easily crystallizes during cooling from the melt; (S)-4-Benzylthiazolidine-2-thione does not crystallize during cooling from the melt, but crystallizes easily during subsequent reheating above Tg; and (S)-4-Benzyloxazolidine-2-thione does not crystallize either during cooling from the melt or during reheating. Such different tendencies to crystallize are observed despite the very similar chemical structures of the compounds, which only differ in oxide or sulfur atoms in one of their rings. We also studied the isothermal crystallization kinetics of the materials that were shown to transform into a crystalline state. Molecular dynamics and thermal properties were thoroughly investigated using broadband dielectric spectroscopy, as well as conventional and temperature-modulated differential scanning calorimetry in the wide temperature range. It was found that all three glass formers have the same dynamic fragility (m = 93), calculated directly from dielectric structural relaxation times. This result verifies that dynamic fragility is not related to the tendency to crystallize. In addition, thermodynamic fragility predictions were also made using calorimetric data. It was found that the thermodynamic fragility evaluated based on the width of the glass transition, observed in the temperature dependence of heat capacity, correlates best with the tendency to crystallize.

Cooperative Conformational Transitions Underpin the Activation Heat Capacity in the Temperature Dependence of Enzyme Catalysis.

Many enzymes display non-Arrhenius behavior with curved Arrhenius plots in the absence of denaturation. There has been significant debate about the origin of this behavior and recently the role of the activation heat capacity (ΔCP⧧) has been widely discussed. If enzyme-catalyzed reactions occur with appreciable negative values of ΔCP⧧ (arising from narrowing of the conformational space along the reaction coordinate), then curved Arrhenius plots are a consequence. To investigate these phenomena in detail, we have collected high precision temperature-rate data over a wide temperature interval for a model glycosidase enzyme MalL, and a series of mutants that change the temperature-dependence of the enzyme-catalyzed rate. We use these data to test a range of models including macromolecular rate theory (MMRT) and an equilibrium model. In addition, we have performed extensive molecular dynamics (MD) simulations to characterize the conformational landscape traversed by MalL in the enzyme-substrate complex and an enzyme-transition state complex. We have crystallized the enzyme in a transition state-like conformation in the absence of a ligand and determined an X-ray crystal structure at very high resolution (1.10 Å). We show (using simulation) that this enzyme-transition state conformation has a more restricted conformational landscape than the wildtype enzyme. We coin the term "transition state-like conformation (TLC)" to apply to this state of the enzyme. Together, these results imply a cooperative conformational transition between an enzyme-substrate conformation (ES) and a transition-state-like conformation (TLC) that precedes the chemical step. We present a two-state model as an extension of MMRT (MMRT-2S) that describes the data along with a convenient approximation with linear temperature dependence of the activation heat capacity (MMRT-1L) that can be used where fewer data points are available. Our model rationalizes disparate behavior seen for MalL and previous results for a thermophilic alcohol dehydrogenase and is consistent with a raft of data for other enzymes. Our model can be used to characterize the conformational changes required for enzyme catalysis and provides insights into the role of cooperative conformational changes in transition state stabilization that are accompanied by changes in heat capacity for the system along the reaction coordinate. TLCs are likely to be of wide importance in understanding the temperature dependence of enzyme activity and other aspects of enzyme catalysis.

High-resolution and high-accuracy calorimetry of order–disorder and melting transitions in the n-alkanes n-pentadecane, n-hexadecane, n-heptadecane, n-octadecane, n-nonadecane and n-eicosane

In this work, a Peltier-element-based adiabatic scanning calorimeter was used to investigate, with high-resolution and accuracy, the temperature dependence of the specific heat capacity and specific enthalpy difference of a series of linear alkanes. More specifically, results are reported for the even n-alkanes; namely n-eicosane, n-octadecane, n-hexadecane and for the odd n-alkanes, namely n-nonadecane, n-heptadecane and n-pentadecane. The measurements cover a temperature range from well in the crystalline solid phase across the solid–solid transitions (when present) in to the liquid phase across the melting transition. Accurate transition temperatures and heat of transitions were derived from the direct experimental data in view of the potential use of n-alkanes as phase change materials.

Temperature Dependence of the Specific Heat Capacity Glasses Produced Based on Na&lt;sub&gt;2&lt;/sub&gt;B&lt;sub&gt;4&lt;/sub&gt;O&lt;sub&gt;7&lt;/sub&gt; + Bi&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;3&lt;/sub&gt;

In this work, the temperature dependence of the specific heat capacity of glasses obtained on the basis of the Na2B4O7 + Bi2O3 compound with different concentrations of sodium tetraborate and bismuth oxide in the initial mixture was studied experimentally during cooling. It has been experimentally shown that with a change in the concentration of the initial substances, the specific heat capacity of the sample’s changes, and a shift of the maxima towards low temperatures is observed with an increase in the concentration of bismuth oxide. A physical interpretation of the nature of the maximum on the temperature dependence of the specific heat is given.

Influence of lithium on the temperature dependence of heat capacity and thermodynamic functions changes in AK1 alloy based on high-purity aluminum

The heat capacity of the AK1 alloy based on high-purity aluminum with lithium was determined in the cooling mode using the known heat capacity of the reference aluminum sample. By means of mathematical processing of cooling rate curves of samples from AK1 alloy with lithium and the reference sample, polynomials describing their cooling rates were obtained. Further, the polynomials of the temperature dependence of the heat capacity of alloys, described by a four-member equation, were established using the experimentally found values of the cooling rates of samples from alloys and the standard, taking into account their mass. Using integrals from specific heat capacity, models of temperature dependence of enthalpy, entropy and Gibbs energy changes were established. It was found that the heat capacity of the alloys increases with rising temperature. The addition of lithium when the temperature is up to 600 K significantly increases the heat capacity, and at temperatures above 600 K lithium in amounts of 0.5 wt. % reduces the heat capacity of the initial alloy AK1. It is shown that lithium addition increases the enthalpy and entropy of the initial AK1 alloy and decreases the Gibbs energy value.

The implications of a temperature-dependent heat capacity DCp(t) on temperature-dependent gating in thermoTRPs

The implications of a temperature-dependent heat capacity DCp(t) on temperature-dependent gating in thermoTRPs

Thermophysical properties of the biofuel components: A mini-guide to the critical properties, heat capacities, and thermal conductivities

Experimental data on the critical temperature, critical pressure, heat capacity, and thermal conductivity of the compounds involved in the production of biofuels have been compiled and critically evaluated. The compilation contains the critical temperature and critical pressure of 56 compounds, the heat capacity of 63 compounds, and the thermal conductivity of 35 compounds and covers the period from 1886 to September 2023. The recommended values of the critical temperatures and pressures have been determined. The parameters of correlating polynomials for the temperature dependence of heat capacities and thermal conductivities have been obtained. The compounds under consideration are the components of biofuels or platform chemicals. Some methyl and ethyl esters of saturated and unsaturated acids, furanic compounds, levulinic acid and alkyl levulinates, gamma-valerolactone, alpha-angelica lactone, triglycerides, and several alkyl pentanoates are among the compounds studied.

Heat Capacity of Indium or Gallium Sesqui-Chalcogenides.

The chalcogenides of p-block elements constitute a significant category of materials with substantial potential for advancing the field of electronic and optoelectronic devices. This is attributed to their exceptional characteristics, including elevated carrier mobility and the ability to fine-tune band gaps through solid solution formation. These compounds exhibit diverse structures, encompassing both three-dimensional and two-dimensional configurations, the latter exemplified by the compound In2Se3. Sesqui-chalcogenides were synthesized through the direct reaction of highly pure elements within a quartz ampoule. Their single-phase composition was confirmed using X-ray diffraction, and the morphology and chemical composition were characterized using scanning electron microscopy. The compositions of all six materials were also confirmed using X-ray photoelectron spectroscopy and Raman spectroscopy. This investigation delves into the thermodynamic properties of indium and gallium sesqui-chalcogenides. It involves low-temperature heat capacity measurements to evaluate standard entropies and Tian-Calvet calorimetry to elucidate the temperature dependence of heat capacity beyond the reference temperature of 298.15 K, as well as the enthalpy of formation assessed from DFT calculations.

Оценка термодинамических свойств химических соединений в системах Me-Si-O, Fe-Si-B, Fe-Cr-B и в некоторых системах, используемых для получения покрытий

A comparative analysis was performed for evaluating thermodynamic properties of a number of condensed and gas-phase compounds formed in the Me-Si-O, (Me = Al, Ba, Pb, Fe, Cr, Fe, Ni, Mn, Mo), Fe-Cr-B and Fe-Si-B systems, including those with impurities of oxygen, manganese, nickel, molybdenum and aluminium, and in some systems used for coatings production. The data on the enthalpies of the formation and on the coefficients of 1 ÷ 7 equations for the calculation of the temperature dependences of isobaric-isothermal potential, entropy and heat capacity for 84 compounds were obtained. The results of the comparative correlation analysis of thermodynamic properties for a number of condensed and gas-phase compounds formed in the Me-Si-O, (Me = Al, Ba, Pb, Fe, Cr, Fe, Ni, Mn, Mo) and Fe-Cr-B, Fe-Si-B systems, including those with impurities of oxygen, manganese, nickel, molybdenum and aluminium, and in some systems used for coatings were obtained. The correlation dependences of thermodynamic properties had a multiple correlation coefficient – R = 0.98 and standard deviations for heat capacity σ ~ 4.8 % (for gas-phase compounds σ ~ 0.6 %), entropy σ ~ 5.8 %, the enthalpy of formation σ &lt; 8 %, oxide systems σ ~ 3 % and silicates σ ~ 2 %. As a result, the enthalpies of formation and 1 ÷ 7 – coefficients of the equations for calculating the temperature dependences of isobaricisothermal potential, entropy and heat capacity for 84 condensed and gas-phase substances were estimated. The obtained thermodynamic data were tested in the thermodynamic analyses of the formation of compounds in various systems and showed satisfactory agreement with experimental results.