Thermo

Group contribution (GC) methods to predict thermochemical properties are eminently important to process design. Following earlier work which presented a GC model in which, for the first time, chemical accuracy (1 kcal/mol or 4 kJ/mol) was accomplished, we here discuss classes of molecules for which the traditional GC approach does not hold, i.e., many results are beyond chemical accuracy. We report new ring-strain-related parameters which enable us to evaluate the heat of formation of alkyl-substituted cycloalkanes. In addition, the definition of the appropriate group size is important to obtain reliable and accurate data for systems in which the electron density varies continuously but slowly between related species. For this and in the case of ring strain, G4 quantum calculations are shown to be able to provide reliable heats of formation which provide the quantitative data which we can use, in the case of absence of experimental data, to establish group and nearest-neighbour interaction parameters to extend the range of applicability of the GC method whilst retaining chemical accuracy. We also found that the strong van der Waals that overlap in highly congested branched alkanes can be qualitatively investigated by applying DFT quantum calculations, which can provide an indication of the GC approach being inappropriate. Full article

In this work, the thermochemical properties of municipal solid waste (MSW) are studied using the torrefaction process as the main method for investigation. Torrefaction experiments were carried out using an electric laboratory furnace, at temperatures of 200, 250, and 300 °C. The residence time was set to 90 min. Proximate and ultimate analysis were performed on the torrefied MSW samples and compared with the properties of the raw MSW samples. In addition, the thermal properties of the obtained torrefied MSW samples were evaluated by thermogravimetric analysis (TGA) and derivative thermogravimetric analysis (DTG). The following could be stated: the obtained results showed that mass and energy yields (MY and EY, respectively) decrease with increasing when torrefaction temperature, while the heating values (HHV) increased under the same conditions (from 24.3 to 25.1 MJ/kg). Elemental analysis showed an increase in carbon content (C), from 45.7 ± 0.9 to 52.8 ± 1.05 wt.%, and decrease in oxygen content (O), from 45.6 ± 0.9 to 39.5 ± 0.8 wt.%, when torrefaction temperature is increased, which is consistent with the general definition of the torrefaction process. In addition, enhancement factors (EFs) and fuel ratios (FRs) were calculated, which ranged from 1.00 to 1.02 and 0.16 to 0.23, respectively. Some anomalies were observed during the thermal analysis, which are assumed to be related to the composition of the selected MSW. This study therefore shows that torrefaction pretreatment can improve the physicochemical properties of raw MSW to a level comparable to coal, and could contribute to a better understanding of the conversion of MSW into a valuable, solid biofuel. Full article

The paper investigates the techniques associated with the exploitation of the second law of thermodynamics as a restriction on the physically admissible processes. Though the exploitation consists of the use of the arbitrariness occurring in the Clausius–Duhem inequality, the approach emphasizes two uncommon features within the thermodynamic analysis: the representation formula, of vectors and tensors, and the entropy production. The representation is shown to be fruitful whenever more terms of the Clausius–Duhem inequality are not independent. Among the examples developed to show this feature, the paper yields the constitutive equation for hypo-elastic solids and for Maxwell–Cattaneo-like equations of heat conduction. The entropy production is assumed to be given by a constitutive function per se and not merely the expression inherited by the other constitutive functions. This feature results in more general expressions of the representation formulae and is crucial for the compact description of hysteretic phenomena. Full article

The evaporation/decomposition behavior of the ionic liquid 1-butyl-3-methylimidazolium chloride (BMImCl) was studied with various techniques, such as thermogravimetry (TG), Knudsen effusion mass loss (KEML), and Knudsen effusion mass spectrometry (KEMS), in order to investigate the competition between the simple evaporation of the liquid as gaseous ion pairs (NIP: neutral ion pair) and the thermal decomposition releasing volatile species. TG/DSC experiments were carried out from 293 to 823 K under both He and N₂ flowing atmospheres on BMImCl as well as on BMImNTf₂ (NTf₂: bis(trifluoromethylsulfonyl)imide). Both ionic liquids were found undergoing a single step of mass loss in the temperature range investigated. However, while the BMImNTf₂ mass loss was found to occur in different temperature ranges, depending on the inert gas used, the TG curves of BMImCl under helium and nitrogen flow were practically superimposable, thus suggesting the occurrence of thermal decomposition. Furthermore, KEML experiments on BMImCl (in the range between 398 and 481 K) indicated a clear dependence of the unit area mass loss rate on the effusion hole diameter, an effect not observed for the ILs with NTf₂ anion. Finally, KEMS measurements in the 416–474 K range allowed us to identify the most abundant species in the vapor phase, which resulted in methyl chloride, butylimidazole, butyl chloride, and methylimidazole, which most probably formed from the decomposition of the liquid. Full article

We explore the preliminary design of a space habitat thermally controlled using phase change materials (PCMs). The PCM is used to maintain a suitable, habitable temperature inside the habitat by isolating it from the external solar radiation. The system is studied numerically considering only diffusive heat transport (conduction), a scenario with practical application to microgravity or reduced gravity environments. The system dynamics are explored for a wide range of governing parameters, including the length of the PCM cell L, the thermo-optical properties—absorptivity $\alpha$ and emissivity $\epsilon$—at the external boundary of the habitat wall exposed to solar radiation, the eclipse (illumination) fraction ${\tau }_e$ (${\tau }_i$) of the solar cycle, and the PCM used. We find that the thermo-optical properties at the external radiated boundary, characterized by the absorptivity–emissivity ratio $(\alpha /\epsilon )$, play a key role in the system response and largely define the optimal design of the habitat. This optimum balances the heat absorbed and released by the PCM during repeated illumination and eclipse cycles. Full article

The current work investigates the relationship between the shape of an isolator of a concentric rotary piston compressor and the secondary peak pressure developed during each operating cycle. This peak pressure is developed when the piston passes through the isolator cavity, and it is negative for compressor efficiency. The aim of this paper is to identify the isolator cavity shape that minimizes this secondary peak to improve compressor efficiency. This study covers five different cavities that may be used in such compressors. Contrary to our expectations, the conclusion is that the best geometry is the one that can be manufactured with CNC machining. The geometry that can be manufactured with 3D printing also produces a significantly lower secondary peak pressure, but it is not cost-efficient. Another limitation of the 3D printing design is the thin walls that this cavity creates. Very thin walls may cause significant deformation during the compression cycle. The conclusion is that there is a CNC machining design that is cost-efficient and allows for higher compressor performance. Full article

The energy consumption for space cooling is progressively increasing. Integrating renewable energy into space cooling systems is critical for reducing CO₂ emissions from the building sector. The salt-based cooling system is an appealing alternative as it can be charged by solar energy. This system is based on the characteristic of endothermic salts, which generate a considerable cooling effect when dissolved in water. A screening test was performed in this work to evaluate the cooling performance of several endothermic salts. Furthermore, a laboratory-scale system was developed to demonstrate the endothermic salt-based thermal storage and cooling generation system. Temperature decreases up to 12.3 °C were observed in the system containing Potassium Chloride salt. The temperature drop was maintained after the system underwent a charging/discharging cycle; however, the cooling period was shortened. The system demonstrated an inherent low efficiency due to the large volume of water required in the discharging phase, demanding a considerable amount of energy to evaporate the water in the charging phase. As a result, the application of this system will be restricted to the usage of low-grade energy during the charging phase. Full article

One of the modern methods of protecting against building heat losses is active thermal insulation (ATI). In winter conditions, ATI works by supplying heat into the envelope, which increases the temperature in the ATI layer. A low-temperature renewable energy medium feeds the active insulation layer directly, e.g., through solar or geothermal energy. A model for heat transfer through the building envelope with an ATI layer was developed. The numerical simulations verified the simplifying assumptions in the model. A relationship was derived to determine the optimal location of the ATI layer in the envelope. The objective function of the summed costs of the thermal energy supplied to the internal space and the envelope was assumed. We took into account the fact that the unit price of energy supplied to the ATI layer is lower than the price of the energy supplied to the internal space. Based on the results of the measurements carried out in a building facility with the ATI layer installed, the actual savings effects due to the ATI layer were compared to the calculated values. Full article

Using boundary-layer theory, natural convection heat transfer formulas that are accurate over a wide range of Rayleigh numbers (Ra) were developed in the 1970s and 1980s for vertical and downward-facing plates. A comprehensive formula for upward-facing plates remained unsolved because they do not form conventional boundary-layers. From the thermodynamic constraints on heat-engine efficiency, the novel approach presented here derives formulas for natural convection heat transfer from isothermal plates. The union of four peer-reviewed data-sets spanning $1<Ra<{10}^{12}$ has 5.4% root-mean-squared relative error (RMSRE) from the new upward-facing heat transfer formula. Applied to downward-facing plates, this novel approach outperforms the Schulenberg (1985) formula’s 4.6% RMSRE with 3.8% on four peer-reviewed data-sets spanning ${10}^6<Ra<{10}^{12}$. The introduction of the harmonic mean as the characteristic length metric for vertical and downward-facing plates extends those rectangular plate formulas to other convex shapes, achieving 3.8% RMSRE on vertical disk convection from Hassani and Hollands (1987) and 3.2% from Kobus and Wedekind (1995). Full article

Improvements in the efficiency of gas turbine engines over the decades have led to increasing turbine inlet temperatures. This, in turn, has resulted in the need to cool the turbine blades themselves to avoid damage to them. While air-cooling and film-cooling methods have been adopted as the primary methods of gas turbine blade cooling, the heat pipe cooling method shows greater potential in terms of temperature uniformity, maximum allowable gas temperature, reliability, and durability. This paper reviews the state-of-the-art research activities on the radial rotating heat pipes (RRHP) potentially applicable to gas turbine cooling. The emergence of the heat-pipe-cooled turbine blade concept, designs, and variants will be described at the beginning. Then the paper will review the literature addressing the heat transfer performance of RRHPs, and the effects on them of rotational forces, working fluid properties, and geometry, as well as operational limits they may be subject to. Additionally, the effects of secondary flow and numerical simulation of RRHPs will be reviewed and discussed. It can be concluded that fundamental studies are still needed for the understanding of the RRHP, as well as the improvement of numerical models. Full article

As renewable energy production is intermittent, its application creates uncertainty in the level of supply. As a result, integrating an energy storage system (ESS) into renewable energy systems could be an effective strategy to provide energy systems with economic, technical, and environmental benefits. Compressed Air Energy Storage (CAES) has been realized in a variety of ways over the past decades. As a mechanical energy storage system, CAES has demonstrated its clear potential amongst all energy storage systems in terms of clean storage medium, high lifetime scalability, low self-discharge, long discharge times, relatively low capital costs, and high durability. However, its main drawbacks are its long response time, low depth of discharge, and low roundtrip efficiency (RTE). This paper provides a comprehensive review of CAES concepts and compressed air storage (CAS) options, indicating their individual strengths and weaknesses. In addition, the paper provides a comprehensive reference for planning and integrating different types of CAES into energy systems. Finally, the limitations and future perspectives of CAES are discussed. Full article

The isobaric heat capacity of solid eutectic mixtures LiCl-KCl-CsCl, LiBr-CsBr and LiBr-KBr-CsBr was investigated from room temperature up to melting point. The molar heat capacity of all mixtures under study was found to be close to the additive sum of that of pure salts. The heat accumulated up to melting temperature is directly dependent on the melting point. Full article

Accurate soil heat transfer models are needed to predict and adapt to a warming arctic. A numerical model to accurately predict temperatures and thaw depths in soils, both with depth and with horizontal distance from features such as cliffs, was developed in Matlab using the finite element method. The model was validated against analytical solutions to simple versions of the problem and experimental temperature data from borehole thermistor strings on the north shore of Alaska. The current model is most useful for short term (on the order of days) predictions of thaw depth and near surface temperatures in homogeneous soils with existing data to allow the calibration of soil thermal parameters. These are exactly the time scales and capabilities that would integrate well with erosional models to predict the erosion during storm events and summer thaw conditions. Comparisons with analytical solutions show the model to be fairly accurate in predictions of temperatures thaw-depth and temperatures, within about 0.25 °C and 0.02 m respectively, for reasonable arctic soil parameters. Differences between predicted temperatures and thaw-depth against borehole data from Barter Island, Alaska are within about 1 °C and 0.5 m respectively. Comparison to commercial software, which does not directly track and move the phase change boundary, shows that this moving-mesh model has much better agreement. The model developed in this work is flexible and can be modified to model a wide variety of problems, but is efficiently set up to take a surface and thaw-boundary profile (not necessarily horizontal) and use soil parameters and surface boundary conditions appropriate to Arctic regions. It has been verified to appropriately model cliffs, which are particularly vulnerable to erosion. Full article

The biomass waste obtained at the end-of-pipe of the extraction industry can be used as fuel for energy production, aiming at cost reduction/waste disposal issues. However, few systematic investigations into the calorific value of these residues are reported in the literature. In this work, the thermochemical properties of solid residues from different biomasses (residues from citrus peels, leaves, flowers, stems, and poultry feathers used for extraction) as potential biomass fuels have been investigated. The heat of combustion (Δ_cH) of the solid residues from citrus (orange, tangerine, lemon, grapefruit, and pomelo), aromatic herbs (rosemary, lavender, thyme, Artemisia vulgaris L. and Ruta chalepensis L.), and poultry feathers biomasses was measured by direct calorimetry. The results were compared with the higher heating values (HHV) calculated using the elemental (CHNOS) and thermogravimetric (TGA) analyses data and with the enthalpy of combustion calculated using the biomass composition predicted by FTIR spectroscopy in tandem with chemometrics. The calculated values match with the corresponding experimental values of Δ_cH. The heat of combustion highlights the energetic features of solid residues for their potential uses as alternative biomass for energy production. This information is essential to evaluate the employment of solid residues as fossil fuel substitutes. Full article

Buildings account for nearly one-third of overall energy consumption in today’s world energy status, in which a considerable part is used for indoor conditioning. Energy efficiency enhancement of buildings components and technologies is a key priority, given the essential need for carbon neutrality and climate change mitigation around the world. Exterior wall insulation is considered as the most effective technology for protecting buildings against continual ambient fluctuations. Proper design and implementation of wall insulation would lead to performance enhancement, energy conservation as well as improved thermal comfort. They can also protect building structures against corrosion and heat fatigue, extending the life of buildings. There are many different types of thermal insulation materials currently on the market, each with its own set of thermal qualities and functionality. This paper aims to examine the qualities, benefits, and drawbacks of several exterior wall insulation technologies, and provide recommendations for how to use various forms of exterior wall insulation in different climates. Full article

Gas hydrate inhibitors, especially those used in offshore environments, are chemicals. These chemicals are synthetic in nature and pose both technical and environmental risks. This study emphasizes the influence of a Plant Extract (PE) on the phase behavior and equilibrium of structure I (SI) gas hydrate and its inhibition efficiency. The PE was screened using a mini flow loop. From the pressure-temperature phase diagram, the various weight percentages of the PE were able to disrupt the thermodynamic equilibrium conditions of the water and gas molecules to lower temperatures and increase pressures, which caused a shift in the equilibrium curve to an unstable hydrate formation zone. The pressure versus time plot as well as the inhibition efficiency plots for the PE and Mono Ethylene Glycol (MEG) were evaluated. Overall, the inhibition efficiency of the PE was higher than that of MEG for 1 wt% (60.53%) and 2 wt% (55.26%) but had the same efficiency at 3 wt% (73.68%). The PE at 1 wt% had the greatest inhibition effect and adjudged the optimum weight percent with a well-regulated phase equilibrium curve. This shows that PE is a better gas hydrate inhibitor than MEG, which is toxic to both human and aquatic life; therefore, it is recommended for field trials. Full article

Ejectors have gained renewed interest in the last decades, especially in heat-driven refrigeration systems, to reduce the load of the compressor. Their performance is usually influenced by many factors, including the working fluid, operating conditions and basic geometrical parameters. Determining the relationships between these factors and accurately predicting ejector performance over a wide range of conditions remain challenging. The objective of this study is to develop fast and efficient models for the design and operation of ejectors using artificial neural networks. To this end, two models are built. The first one predicts the entrainment and limiting compression ratio given 12 input parameters, including the operating conditions and geometry. The second model predicts the optimal geometry given the desired performance and operating conditions. An experimental database of ejectors using five working fluids (R134a, R245fa, R141b, and R1234ze(E), R1233zd(E)) has been built for training and validation. The accuracy of the ANN models is assessed in terms of the linear coefficient of correlation (R) and the mean squared error (MSE). The obtained results after training for both cases show a maximum MSE of less than 10% and a regression coefficient (R) of, respectively, 0.99 and 0.96 when tested on new data. The two models have then a good generalization capacity and can be used for design purposes of future refrigeration systems. Full article

Geothermal energy storage provides opportunities to store renewable energy underground during summer for utilization in winter. Vertically oriented systems have been the standard when employing boreholes as the means to charge and discharge the underground. Horizontally oriented borehole storage systems provide an application range with specific advantages over vertically oriented systems. They are not limited to the surface requirements needed for installation with vertical systems and have the potential to limit storage losses. Horizontal systems can be incorporated into the built environment and utilize underground storage sites below existing infrastructure. An experimental study examines configurations using a mix of renewable energy (photovoltaic panels) and grid energy to charge a storage system during summer for use during winter. A comparison of five different borehole configurations at three different loading temperatures was composed using an experimentally validated numerical model. The horizontal systems studied and analyzed in this work showed improved performance with scale and charging temperature. This paper supports further exploration into specific use cases for horizontal borehole thermal energy storage systems and suggests applications which would take advantage of better performance at scale. Full article