Enthalpy Research Articles

A detailed investigation on thermal performance and energy savings of cool roof systems for composite climates of India

ABSTRACT The rising worldwide temperatures leading to a spike in air conditioning to ensure thermal comfort in buildings is the root cause of the increase in energy demand in India's building sector. The roof of a building significantly adds to the heat gained on the top floor, accounting for 50–60% of the total heat gain. One sustainable way to reduce this heat gain is via cool roofing technology. Through examination and dynamic simulations with the Energy-Plus-based Design Builder software tool, this study explores different cool roof solutions. An experimental setup of a Reinforced Cement Concrete (RCC) roof with cement plaster, solar reflective paint, solar reflective tiles, and earthen pots have been created on the institute campus. Recordings were taken during the peak summer days and peak winter days, alongside simulations carried out to determine various factors such as Albedo, Surface Temperatures, Air Temperatures, Diurnal Heat Ingress, and the Building's Thermal Energy Consumption. The experiments have demonstrated that cool roof layers can considerably improve interior thermal comfort by minimizing heat transfer, which maintains a constant temperature over the bottom surface of the roof. By reducing heat gain by 33–71%, they can save energy by 21-26% compared to traditional RCC roof slab.

A sustainable and economical solution for CO2 capture with biobased carbon materials derived from palm kernel shells.

This study investigates the synthesize of activated carbon for carbon dioxide adsorption using palm kernel shell (PKS), a by-product of oil palm industry. The adsorbent synthesis involved a simple two-step carbonization method. Firstly, PKS was activated with potassium oxide (KOH), followed by functionalization with magnesium oxide (MgO). Surface analysis revealed that KOH activated PKS has resulted in a high specific surface area of 1086 m2/g compared to untreated PKS (435 m2/g). However, impregnation of MgO resulted in the reduction of surface area due to blockage of pores by MgO. Thermogravimetric analysis (TGA) demonstrated that PKS-based adsorbents exhibited minimal weight loss of less than 30% up to 500 °C, indicating their suitability for high-temperature applications. CO2 adsorption experiments revealed that PKS-AC-MgO has achieved a higher adsorption capacity of 155.35 mg/g compared to PKS-AC (149.63 mg/g) at 25 °C and 5 bars. The adsorption behaviour of PKS-AC-MgO was well fitted by both the Sips and Langmuir isotherms, suggesting a combination of both heterogeneous and homogeneous adsorption and indicating a chemical reaction between MgO and CO2. Thermodynamic analysis indicated a spontaneous and thermodynamically favourable process for CO2 capture by PKS-AC-MgO, with negative change in enthalpy (- 0.21 kJ/mol), positive change in entropy (2.44 kJ/mol), and negative change in Gibbs free energy (- 729.61 J/mol, - 790.79 J/mol, and - 851.98 J/mol) across tested temperature. Economic assessment revealed that the cost of PKS-AC-MgO is 21% lower than the current market price of commercial activated carbon, indicating its potential for industrial application. Environmental assessment shows a significant reduction in greenhouse gas emissions (381.9 tCO2) through the utilization of PKS-AC-MgO, underscoring its environmental benefits. In summary, the use of activated carbon produced from PKS and functionalised with MgO shows great potential for absorbing CO2. This aligns with the ideas of a circular economy and sustainable development.

Proton Transfer via Arginine with Suppressed pKa Mediates Catalysis by Gentisate and Salicylate Dioxygenase.

Gentisate and salicylate 1,2-dioxygenases (GDO and SDO) facilitate aerobic degradation of aromatic rings by inserting both atoms of dioxygen into their substrates, thereby participating in global carbon cycling. The role of acid-base catalysts in the reaction cycles of these enzymes is debatable. We present evidence of the participation of a proton shuffler during catalysis by GDO and SDO. The pH dependence of Michaelis-Menten parameters demonstrates that a single proton transfer is mandatory for the catalysis. Measurements at variable temperatures and pHs were used to determine the standard enthalpy of ionization (ΔHion°) of 51 kJ/mol for the proton transfer event. Although the observed apparent pKa in the range of 6.0-7.0 for substrates of both enzymes is highly suggestive of a histidine residue, ΔHion° establishes an arginine residue as the likely proton source, providing phylogenetic relevance for this strictly conserved residue in the GDO family. We propose that the atypical 3-histidine ferrous binding scaffold of GDOs contributes to the suppression of arginine pKa and provides support for this argument by employing a 2-histidine-1-carboxylate variant of the enzyme that exhibits elevated pKa. A reaction mechanism considering the role of the proton source in stabilizing key reaction intermediates is proposed.

Synthesis and Polymerization of the Bio‐Benzoxazine Derived from Resveratrol and Thiophenemethylamine and Properties of its Polymer

AbstractResveratrol and 2‐thiophenemethylamine have been employed in the synthesis of a novel tri‐functional benzoxazine (RES‐th) to develop the bio‐benzoxazine monomer. The chemical structure of the synthesized monomer is confirmed by various characterization technics. The polymerization behavior is monitored by in situ Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). The in situ FTIR results reveal distinct reaction mechanisms for the three oxazine rings presented in RES‐th, with both ether and phenolic Mannich bridge structures observed in the products. The activation energy values of RES‐th are calculated to be 119.05, 120.97, and 119.44 kJ mol−1 by Kissinger, Ozawa, and Starink methods, respectively, which are all based on the heat flow curves at various heating temperatures. The thermal stability and flame retardancy of the resulting polybenzoxazine (poly(RES‐th)) are investigated by thermogravimetric analysis (TGA) and microscale combustion calorimeter (MCC). The values of Td5 and Td10 of polybenzoxazine are found to be 356 °C and 399 °C, respectively, with a char yield of 66.3% at 800 °C. The prepared polybenzoxazine also demonstrates nonflammability characteristics with the values of heat release capacity (HRC) and total heat release rate (THR) of 18.65 J (g K)−1 and 2.69 kJ g−1, respectively. These findings suggest that the thermoset, poly(RES‐th), is a promising candidate for fire‐resistant applications.

Comparative Assessment of Thermal Oils and Water as Working Fluids in Parabolic Trough Collectors for Enhanced Solar Power Generation

Abstract Examining the thermal behavior of specific working fluids, namely Syltherm800 and TherminolVP-1, in parabolic trough collectors (PTCs) is imperative for enhancing power generation. This study addresses a crucial gap by conducting computational fluid dynamics simulations through COMSOL Multiphysics software and experimental tests to explore the advantages of utilizing thermal oils over water as a working fluid in PTCs. Experimental tests were performed on a water-based PTC in Iraq to validate the numerical model, considering various operating conditions such as input temperature (323.15-423.15 K) and mass flow rates (0.00926-0.0556 kg/s). Key parameters including output temperature, thermal efficiency, useful heat, and total heat losses were evaluated. The numerical model was validated against experimental data, showing good agreement with an overall discrepancy of 1.7% for the current experiments and 3.18% for literature results. The results indicated that Syltherm800, particularly with a high mass flow rate, outperformed TherminolVP-1 and water in terms of overall thermal performance. The optimal PTC thermal efficiency was achieved in July with a mass flow rate of 0.0556 kg/s and an input temperature of 348.15 K. The optimal range for PTC thermal efficiency over four months was between 50% and 70%. The endorsement of thermal oils in PTCs is supported by their low vapor pressure, superior thermal stability, and extended lifespan.

On the thermodynamics of Barium Oxyfluoride precursor in YBCO growth via MOD process

Abstract Barium Oxyfluoride plays an important role, as precursor species, in the nucleation and growth of YBa2Cu3O7-δ (YBCO) via the low fluorine Metal Organic Decomposition (MOD low-fluorine) route. In this contribution, we present a study on the thermodynamics of the Oxyfluoride by processing experimental data on the YBCO growth at LaAlO3 (LAO) substrate. The analysis allows one to determine the standard enthalpy and the standard entropy changes for Oxyfluoride formation from Barium oxide and Barium fluoride. To identify the thermodynamically more favorable route to the Oxyfluoride formation in the MOD low-fluorine process, the free energy change for the formation of the precursor, through reactions involving gas water, has been determined. The free energy of formation via fluoride and water indicates higher stability of oxygen rich Oxyfluoride for (P_HF^2)/P_(H_2 O) <10^(-6). In the framework of the nucleation theory the present results are needed to study the effect of precursor composition on film orientation.

Polydopamine-primed FeCo-LDH endowed epoxy resin with enhanced flame retardancy and mechanical properties

The integration of layered double metal hydroxides (LDH) into epoxy resin (EP) for flame retardancy is in line with the principles of environmentally friendly and sustainable development. In this study, polydopamine (PDA)-primed intercalated LDH containing iron and cobalt ions (LDH-DBS@PDA) was prepared, and its chemical composition, structure and morphology were thoroughly characterized. Due to the synergistic flame-retardant properties exhibited by LDH and PDA, as well as the catalytic charring properties of iron and cobalt ions in both condensed and gaseous phases, EP composite with 5 wt% LDH-DBS@PDA achieved a UL-94 V-0 rating with a limiting oxygen index of 30.7 %. Moreover, EP/LDH-DBS@PDA exhibited a significant decrease in total heat release by 48 % and smoke release by 52 %, demonstrating remarkable fire safety performance. Additionally, the existence of LDH-DBS@PDA improved impact strength, tensile strength, and glass transition temperature due to strong interactions between PDA and EP matrix. This work presents a promising strategy for developing highly efficiency flame retardants with excellent compatibility for polymeric materials.

Heat Transfer Performance and Operation Scheme of the Deeply Buried Pipe Energy Pile Group

This paper describes a study on the heat transfer properties of the deeply buried pipeline energy pile group, which is an efficient and convenient geothermal development technology. Through in situ experiments and a simulation algorithm, the research investigated the heat transmission characteristics of the deeply buried pipe energy pile group and optimized different intermittent operation schemes. The findings suggest that prolonged operation of the pile cluster intensifies heat buildup within the pile foundation, thereby adversely affecting the system’s overall heat exchange efficiency. Employing an intermittent operating mode can alleviate this heat accumulation phenomenon, thereby promoting sustained heat exchange performance of the piles over time. To evaluate the comprehensive thermal interaction and energy efficiency ratio of the energy pile heat exchange system, various intermittent operation strategies were compared in the study. Among them, the intermittent operational scheme with a ratio of n = 5 was found to be optimal, with the total average heat transfer rate of the pile set only 0.51% lower than that of the continuous operational mode, but the overall energy efficiency ratio improved by 19.6%. The intermittent operational mode proposed in this study can achieve the goal of saving energy and efficiently extracting geothermal resources, providing theoretical guidance for the extraction and utilization of subsurface geothermal power by energy piles.

Smoke Suppression Properties of Fe2O3 on Intumescent Fire-Retardant Coatings of Styrene–Acrylic Emulsion

The intumescent flame-retardant coatings were prepared using ammonium polyphosphate (APP), pentaerythritol (PER), melamine (MEL), styrene–acrylic emulsion, and iron oxide yellow (FeOOH) as the base material. A cone calorimeter (CCT), smoke density meter (SDA), and scanning electron microscope (SEM) were employed to investigate the smoke suppression and flame retardancy of FeOOH in intumescent fire-retardant coatings. The thermal degradation performance of intumescent fireproofing coatings with varying FeOOH content was investigated through thermogravimetric analysis (TGA). The structure of the carbon slag in the CCT test was analyzed using a scanning electron microscope (SEM). The results of the cone calorimeter (CCT) experiments demonstrated that FeOOH significantly reduced the heat release rate (HRR), total heat release rate (THR), smoke production rate (SPR), and total smoke release rate (TSR) of the coating, while simultaneously increasing the carbon residue rate of the coating. The smoke density analysis (SDA) results demonstrate that adding FeOOH can effectively reduce smoke generation, regardless of whether a pilot flame is used. TGA results demonstrate that FeOOH can enhance the weight of coke residue at elevated temperatures. SEM results indicate that incorporating FeOOH resulted in a more compact coke residue. According to these findings, among all the samples, those containing 2 wt% FeOOH showed low levels of HRR, THR, SPR, and TSR and high levels of SOD, which proves that FeOOH can be used as a smoke inhibitor in flame-retardant coatings.

Entropy generation and heatline visualization of magnetized thermal convection in an irregular enclosure filled with nanofluid and subject to non-uniform heating: FEM-machine learning hybrid approach

This investigation's primary objective is to analyze the fluid dynamics and heat transfer enhancement in an irregular enclosure. Several physical phenomena such as Alumina-water nanofluids, magnetic field, non-uniform heating and amplitude of non-uniform heating are taken into account. A thorough investigation using machine learning algorithms (MLAs) and computational fluid dynamics (CFD) is carried out. Initially, for CFD phase the coupled non-linear dimensionless governing equations of the considered problem are solved numerically by adapting a Finite Element method (FEM) using appropriate boundary conditions. The analysis considers a range of physical parameters, such as the Hartmann number (0–20), nanoparticle volume friction (0–0.04), Ryleigh number (103-105), offset temperature (0.1–1), frequency (1-10) and non-uniform heating amplitude (0.1–1). The numerical results are explicated in the form of streamlines, isotherms, heatlines structures. The impact of these factors on entropy generation is also explored. In addition, three popular MLAs, Random Forest (RF), Artificial Neural Network (ANN) and Support Vector Machine (SVM) were used to save the computational costs. The finding explore Hartmann number and nanoparticle volume friction has decreasing trend on total entropy production and heat transfer rate. The entropy production decreases up to 42.02 % for Hartman number and for nanoparticles it decreases 12.61 %. However, the non-uniform heating amplitude has opposite effect on irreversibility factor. Also, compared to other MLAs, the ANN model demonstrates more accurate predictions. The objective is to propose novel concept for enhancing the performance of cooling systems and optimizing energy utilization across diverse technical domain.

Solubility of codeine phosphate in ethylene glycol + N-methyl-2-pyrrolidone mixtures at different temperatures

ABSTRACT The primary objective of the present study is to systematically investigate the solubility data and thermodynamic properties associated with codeine phosphate within mixtures comprising ethylene glycol (EG) and N-methyl-2-pyrrolidone (NMP) under atmospheric pressure conditions within the temperature range of 293.2–313.2 K. The analysis reveals a discernible positive correlation with both temperature and the ratio of EG. Mathematical models are employed for the purpose of correlating the obtained data, and the reliability of these models is rigorously assessed through the computation of mean relative deviations for back-calculated values. Additionally, the density values of codeine phosphate saturated mixtures are meticulously measured and subsequently correlated utilising the Jouyban-Acree model. Furthermore, the apparent thermodynamic properties governing the solubilisation process of codeine phosphate, including standard enthalpy, entropy and Gibbs free energy, are computed through the application of Gibbs and van’t Hoff equations, and the obtained results are comprehensively documented.

Preparation of bio-based trinity lignin intumescent flame retardant and its effect on burning behavior and heat transfer process of epoxy resin composites

The thermal insulation performance of intumescent coating coated on the surface of steel structure is of great significance to prevent the underlying steel structure from collapse in fire. Bio-based intumescent flame retardants gradually attract many attentions due to its environmental friendliness and rich natural sources. In this study, a new bio-based intumescent flame retardant trinity lignin intumescent flame retardant (TLI) is synthesized, which is added to epoxy resin (EP) to prepare EP/TLI epoxy intumescent coatings. The burning behavior of EP/TLI epoxy intumescent coatings is investigated by thermogravimetric (TG) analysis, limit oxygen index (LOI), vertical burning test and cone calorimeter test. Microscopic morphology of char layer is observed by scanning electron microscopy (SEM). The results show that when the TLI addition content is 20 wt% (EP/TLI-4), LOI reaches 26.5 %, UL-94 is V-0 rating. Compared to pure EP, the peak heat release rate (pHRR) and total heat release (THR) of EP/TLI-4 coating are reduced by 82.20 % and 78.27 %, respectively. The influence of chemical formulations, initial coating thickness and incident heat flux on heat transfer process of EP/TLI epoxy intumescent coatings is also investigated. At the same time, the thermal insulation mechanism of EP/TLI epoxy intumescent coating is presented.

Experimental and Theoretical Study of Heat Transfer in a Chilled Ceiling System

Radiant cooling has been growing in recent years due to energy savings and improved comfort and health. The aim of this study was to reduce energy consumption and provide comfort using a chilled ceiling panel in the zone. In the experimental part of this study, a test room was created to investigate the change in the heat transfer performance of a chilled ceiling panel according to different water temperatures, different water flow rates and different heat source values. As a result of the experimental study, it was found that optimum conditions were achieved with a heat rate of 280 Watts and the lowest supply water temperature of 14 °C, with indoor comfort conditions being achieved with water flow rates of 0.93 m3/h. In the theoretical part of this study, a thermal balance was established for ceiling panel cooling applications. An analytical model of the heat transfer between the cold ceiling panel and the room air was also developed. The convection coefficient, convective heat transfer and total heat transfer coefficient were compared using the values obtained from the experiments and those reported in the literature. It was found that the convection coefficient was within the range reported in the literature, and the radiation heat coefficient was within 99.8% of the literature values.

Influence of phosphomolybdate modified with quaternary ammonium salts on enhancing the flame retardancy and antibacterial characteristics of epoxy resin/aluminum diethylphosphinate composites

In this work, we synthesized a series of compounds, denoted as xCTAB@AMP, by incorporating varying different molar fractions of cetyltrimethylammonium bromide (CTAB) into ammonium phosphomolybdate (AMP). The effects of CTAB modification on the surface characteristics, morphology and hygroscopicity of AMP were studied. Moreover, we explored the combined flame-retardant impact between xCTAB@AMP and aluminum diethylphosphinate (ADP) when incorporated into epoxy resin (EP), as well as the resulting composite's mechanical properties, thermal stability and antibacterial properties. The EP composite containing 50 molar percent CTAB-modified AMP (EP/50CTAB@AMP/ADP) demonstrated remarkable flame retardancy, achieving a UL-94 V-0 rating and increasing limiting oxygen index (LOI) to 30.0%. This formulation significantly lowered the peak heat release rate (PHRR) to 452 kW/m2, a 65% reduction to that of EP, and the total heat release (THR) to 68 MJ/m2, a 24% decrease to that of EP. Additionally, compared to EP, the peak smoke production rate (PSPR) of this composite was decreased by 30% (0.28 m2/s), the total smoke production (TSP) was reduced by 25% (30.2 m2), and peak carbon monoxide release rate (PCOP) was diminished by 34% (0.038 g/s). The combination of 50CTAB@AMP and ADP in the EP matrix exhibited an exceptional synergistic flame-retardant effect. Concurrently, the CTAB modification bolstered the interfacial interactions between AMP and the EP matrix, which enhanced the mechanical properties of EP/AMP/ADP composites. As a result, the tensile strength and elongation at break of the EP/50CTAB@AMP/ADP composite increased by 13% and 15%, respectively, compared to the EP/AMP/ADP. Moreover, the 50CTAB@AMP maintained its inherent antibacterial activity, which endowed the EP/50CTAB@AMP/ADP composite with a potent inhibitory effect against Staphylococcus aureus, a common pathogenic bacterium.

Binder-dependent electrochemical properties of high entropy oxide anodes for lithium-ion batteries

High entropy oxide (HEO) materials have recently emerged as promising anodes for lithium-ion batteries (LIBs). In this study, we conduct the first comparative analysis to investigate the influence of various electrode binders on electrochemical properties of (CrMnFeNiCu)3O4 HEO anodes. The organic-solvent-soluble polyvinylidene fluoride and water-soluble polyvinyl formamide, sodium carboxymethyl cellulose, sodium alginate, and sodium polyacrylate (NaPAA) binders are examined. Notably, the NaPAA binder leads to a significant enhancement in the HEO performance. The NaPAA coating on (CrMnFeNiCu)3O4 effectively improves the electrode charge-discharge Coulombic efficiency and mitigates the electrode deterioration. Binder adhesion strength and stability toward electrolyte are assessed. The charge-transfer resistance and apparent Li+ diffusion of the HEO electrodes with various binders, accompanied by the post-cycling analyses, are examined. By employing the NaPAA binder, exceptional electrode capacities of 800 and 495 mAh g–1 are attained at charge-discharge rates of 50 and 2000 mA g–1, respectively, without noticeable capacity degradation after 300 cycles. The thermal reactivity of the lithiated electrodes is investigated using differential scanning calorimetry, and the impact of binders on the electrode exothermic onset temperature and total heat released is studied. Our findings provide valuable insights for enhancing the performance and safety of HEO anodes for LIBs.

Exploring the molecular binding mechanism of 6-fluoro, 4-hydroxy, 2- methyl quinoline with TiO2 nanoparticles: A spectroscopic, thermodynamic, and insights into the solvatochromic effect.

This study investigates the interaction between titanium oxide nanoparticles (TiO2 NPs) and the heterocyclic fluorophore 6-fluoro,4-hydroxy,2-methylquinoline (6-FHMQ), aiming to understand fluorescence quenching mechanisms and thermodynamic characteristics. Spectroscopic techniques including spectrofluorometry (FL) and spectrophotometry (UV-Vis) were used, with a lifetime decay (τ) of 0.18ns for 6-FHMQ measured using time correlated single photon counting (TCSPC). The interaction between 6-FHMQ and TiO2 NPs revealed a mix of static and dynamic fluorescence quenching mechanisms, with increasing quenching constants (Ksv) and a higher bimolecular quenching rate constant (Kq). The dynamic nature was highlighted by a temperature-dependent increase in binding sites from 1 to ~ 2. Spontaneous complexation was affirmed by negative change in free energy (ΔG), with negative change in enthalpy (ΔH) and a positive change in entropy (ΔS) values indicating favorable electrostatic and ionic interactions. The impact of varying TiO2 NP concentrations on 6-FHMQ absorption was analyzed using the Benesi-Hildbrand equation, with a quantum yield of 0.61 determined. By forster resonance energy transfer (FRET) theory, the proximity between 6-FHMQ and TiO2 NPs was found to be less than 70Å. Ground and excited state dipole moments of 6-FHMQ in different solvents were calculated to demonstrate solvent sensing ability and charge transfer properties. Ultimately, this study serves as a testament to the power of scientific innovation in the realms of drug delivery and tissue engineering.

In-Vitro Study of the Binding of Atorvastatin with Adenine using Multi-Spectroscopic Approaches.

Atorvastatin-an oral lipid regulating drug is a competitive inhibitor of 3-hydroxy-3-methylglutaryl coenzyme A reductase (HMG-CoA reductase), which is the rate determining enzyme for cholesterol synthesis. Adenine is a purine nucleobase that is found in deoxyribonucleic acid (DNA) and ribonucleic acid (RNA) to generate genetic information. The binding mechanism of atorvastatin and adenine was studied for the first time utilizing various techniques, including UV-visible spectrophotometry, spectrofluorimetry, synchronous fluorescence spectroscopy (SF), Fourier transform infrared (FTIR), fluorescence resonance energy transfer (FRET), and metal ion complexation. The fluorescence spectra of the complex indicated that atorvastatin is bound to adenine via hydrophobic interaction through a spontaneous binding process, and the fluorescence quenching mechanism was found to be static quenching with a binding constant of 1.4893 × 104 Lmol-1 at 298 K. Various temperature settings were used to investigate thermodynamic characteristics, such as binding forces, binding constants, and the number of binding sites. The interaction parameters, including the standard enthalpy change (ΔHο) and standard entropy change (ΔSο) were calculated using Van't Hoff's equation to be 42.82 kJmol-1 and 208.9 Jmol-1K-1, respectively. The findings demonstrated that the adenine- atorvastatin binding was endothermic. Furthermore, the results of the experiments revealed that some metal ions (K+, Ca+2, Co+2, Cu+2, and Al+3) facilitate the binding interaction between atorvastatin and adenine. Slight changes are observed in the FTIR spectra of adenine, indicating the binding interaction between adenine and atorvastatin.

Mechanism, thermochemistry, and kinetics of formation of PhC(O)H and HOPhC(O)H during unimolecular decomposition of P-PhC(O2•)HPhOH.

Bisphenols are one of the main components of bio-oil, produced during the pyrolysis of lignin-containing biomass. Synthetic bisphenols are used in polycarbonate plastics, epoxy resins, and thermal papers. Their mechanism of oxidation is important for the determination of the fire safety of these materials and the possibility of using them as additives in fuels for the decrease and description of ignition delays, as well as for the determination of their health risk assessment in medicine. One representative of bisphenols is p-benzylphenol (p-PhCH2PhOH), which is formed during the fast pyrolysis of lignine-containing biomass. Its thermochemistry of oxidation has been partially studied previously. It is shown that the reaction of chain oxidation of p-PhCH2PhOH is thermochemically favorable at low temperatures. However, these studies consider only two pathways of this reaction: (1) the chain oxidation of RH by RO2• and (2) the tautomerization of R'HO2• to R'O2H with following production of R'O• and OH radicals. At the same time, the reactions of intramolecular rearrangement of RO2•, produced PhC(O)H and •PhOH or HOPhC(O)H and •Ph, are not reported but can be an important part of its oxidation mechanism. The five DFT (M06-2X (i = 1), B3LYP (i = 2), wB97XD (i = 3), M08HX (i = 4), MN15 (i = 5)) approaches with 6-311 + + G(d,p) basis set are used for the determination of standard enthalpies of atomization (ΔraH°(Xi)) of considered compounds (molecules, radicals, and transition states). These values of ΔraH°(Xi) are corrected using the empirical linear calibration dependencies, reported previously. The different calibration dependencies are used for the hydrocarbons (including the aromatics and simple oxygenated derivatives) and for the peroxides. The corrected values of ΔraH°(Xi, CORR) are used according to Hess's law for the determination of ΔfH°(Xi, CORR). The most consistent values of ΔfH°(X, MEAN) are derived from the coordination of the values of ΔfH°(Xi,CORR) using the intersection of their values of standard deviations (3SDi). These values of ΔfH°(X, MEAN), as well as the B3LYP values of S°(X), which are accounting the frequencies correction and internal rotations, as well as their temperature dependencies, are used for the determination of thermochemistry of considered reactions and of the calculation, within transition state theory (TST), of the values of high pressure limits of the rate constant. The values of H°(Xi), S°(Xi), and G°(Xi) are calculated using the Gaussian 16w program. The considered mechanism is prepared using ISIS/Draw package. The temperature dependencies of thermochemical properties and the values of rate constants are determined using the ChemRate program (v.1.5). The optimized structures are visualized using the Chemcraft package.

Evaluation of Thermal Insulation of Vacuum-Insulated Casing to Prevent Uncontrollable Melting of Ice and Borehole Instability in Permafrost

During oil and gas development in permafrost, hot fluids within the wellbore can cause ice melting around wellbore and a decrease in sediment strength, as well as wellbore instability. In the present work, the experimental system for evaluating the insulation effectiveness was established, and the applicability of this experimental system and methodology was verified. It was found that the difference between the experimentally obtained and actual thermal conductivity of the ordinary casings are all within 1.0 W/(m·°C). Meanwhile, the evaluation of insulation effect found that the decrease in fluid temperature, ambient temperature, and vacuum degree can improve its insulation performance. Finally, the numerical simulation was conducted on ice melting and borehole stability during the drilling operation in permafrost. The investigation results demonstrate that the use of vacuum-insulated casings significantly reduces the total heat transferred during the simulation by 86.72% compared to the ordinary casing. The utilization of vacuum-insulated casing reduces the range of ice melting around wellbore to only 16%, which occurs when using ordinary casing. The use of the vacuum-insulated casing resulted in a reduction in the final borehole enlargement rate from 52.1% to 4.2%, and wellbore instability was effectively suppressed.

Does the Oxygen Functionality Really Improve the Thermodynamics of Reversible Hydrogen Storage with Liquid Organic Hydrogen Carriers?

Liquid organic hydrogen carriers (LOHCs) are aromatic molecules that are being considered for the safe storage and release of hydrogen. The thermodynamic properties of a range of aromatic ethers were investigated using various experimental and theoretical methods to assess their suitability as LOHC materials. The absolute vapour pressures were measured for benzyl phenyl ether, dibenzyl ether and 2-methoxynaphthalene using the transpiration method. The standard molar enthalpies and entropies of vaporisation/sublimation were derived from the temperature dependence of the vapour pressures. The combustion energies of benzyl phenyl ether and dibenzyl ether were measured using high-precision combustion calorimetry, and their standard molar enthalpies of formation were derived from these data. High-level quantum chemical calculations were used to calculate the standard molar enthalpies of formation in the gas phase for benzyl phenyl ether, dibenzyl ether and 2-methoxynaphthalene. The latter values agreed very well with the experimental results obtained in this work. The thermodynamic properties of the hydrogenation/dehydrogenation reactions in liquid phase in LOHC systems based on methoxy–benzene, diphenyl ether, benzyl phenyl ether, dibenzyl ether and 2-methoxynaphthalene were derived and compared with the data for similarly structured hydrogen carriers based on benzene, diphenylmethane, 1,2-diphenylethane, 1,3-diphenylpropane and naphthalene. The influence of the oxygen functionality on the thermodynamic properties of the hydrogenation/dehydrogenation reactions was evaluated.