Dehydration Kinetics Research Articles

Mechanistic origins for the enhanced ethanol dehydration kinetics in H-ZSM-5 by cofeeding n-butanol

Periodic density functional theory (DFT) with dispersion corrections is used to construct a detailed reaction network for dehydration of n-butanol/ethanol mixtures in H-ZSM-5.

Dehydration kinetics of the synthesis of high-nickel cathode materials used in lithium ion batteries

Kinetics of dehydration reactions of cathode precursors such as lithium hydroxide monohydrate (LiOH·H2O) and transition metal hydroxide (NixCoyMnz(OH)2) are identified and modeled using a random pore model (RPM) method.

Stabilizing tetragonal ZrO2 nanocrystallites in solvothermal synthesis.

Phase-pure tetragonal ZrO2 nanoparticles have been prepared under simple solvothermal synthesis conditions using different types of alcohols as solvents and studied using in situ X-ray scattering. The variation of tetragonal/monoclinic phase ratios within the produced powders was directly correlated with the amount of in situ generated water from solvent dehydration during the syntheses. By controlling the dehydration kinetics, either choosing primary alcohols of varying thermal stability or by changing synthesis temperatures, it is possible to selectively tune this tetragonal/monoclinic phase ratio.

Thermal Decomposition Kinetics of Clinochlore at High Temperature and Its Implications

Abstract The dehydration kinetics of clinochlore were performed using a non-isothermal thermogravimetric analysis under a dynamic nitrogen atmosphere at ambient pressure. Clinochlore, with a grain size of 5–10 μm, was analyzed using heating rates of 2, 5, 10, 20, and 40 K/min at temperatures of up to 1260 K. Thermogravimetric data of clinochlore at different heating rates were modeled using the Kissinger method, Flynn-Wall-Ozawa method, and Coats-Redfern method. The dehydration of clinochlore is ascribed to the decomposition of brucite and talc layers. The dehydration temperature of the brucite layer is 730–920 K, which corresponds to a two-dimensional phase boundary model (R2) with an activation energy of 214.94 ± 7.79 kJ/mol and a pre-exponential factor of 12.52 ± 0.62 min−1. The dehydration temperature of the talc-like layer is 960–1140 K, which follows a two-dimensional diffusion model with an apparent activation energy of 419.49 ± 23.62 kJ/mol and a pre-exponential factor of 19.97 ± 1.76 min−1. Combined with the parameters obtained in this study, the fast dehydration of clinochlore can trigger earthquakes in the subduction zone.

Excellent Absorption of LaCoxO3 Over Full Solar Spectrum and Direct Photothermal Energy Storage of Ca(OH)2–LaCoxO3

Abstract: Photothermal conversion is a vital way for solar energy applications. The strong absorption of near Infrared light is essential for excellent photothermal performance. In this study, we demonstrated that nano LaCoxO3 is able to harvest light intensely across the full solar spectrum with high photothermal temperature. A core-shell-like structure of LaCoxO3-coated Ca(OH)2 particles was fabricated and shows excellent photothermal conversion, high kinetics of dehydration and remarkable cycle stability of heat storage and release. The photothermal dehydration-conversion of Ca(OH)2 increases 8.4-fold. Results demonstrate the multifunctionality of LaCoxO3, intensifying light harvesting, high photothermal conversion, good stability, considerable strength, and porous framework favouring the performance of photothermal storage and release cycles. LaCoxO3–Ca(OH)2 composite can simultaneously harvest light and store thermal energy.

Chemical and Thermal Treatment for Drying Cassava Tubers: Optimization, Microstructure, and Dehydration Kinetics.

Perishable commodities like cassava necessitate effective postharvest preservation for various industrial applications. Hence, optimizing pretreatment processes and modeling drying kinetics hold paramount importance. This study aimed to optimize cassava pretreatment using the central composite design of a response surface methodology while also assessing microstructure and dehydration kinetics. Diverse chemical and thermal pretreatments were explored, encompassing sodium metabisulfite concentrations (0-4% w/w), citric acid concentrations (0-4% w/w), and blanching time (0-4 min). The four investigated responses were moisture content, whiteness index, activation energy (Ea), and effective moisture diffusivity (Deff). Employing five established drying models, suitability was appraised after optimal pretreatment conditions were determined. The findings revealed that moisture content ranged from 5.82 to 9.42% db, whereas the whiteness index ranged from 87.16 to 94.23. Deff and Ea ranged from 5.06 × 10-9 to 6.71 × 10-9 m2/s and 29.65-33.28 kJ/mol, respectively. The optimal pretreatment conditions for dried cassava were identified by optimizing the use of 1.31% citric acid, 1.03% sodium metabisulfite, and blanching time for 1.01 min. The microstructure indicated that particular chemical and thermal pretreatment configurations yielded particles in the shape of circular and elliptical granules. The logarithmic model provided the most accurate description of the dehydration kinetics, with the highest R2 value (0.9859) and the lowest χ2, RSME, and SSE values of 0.0351, 0.0015, and 0.0123, respectively.

Non-Metallic NH4 + /H+ Co-Storage in Organic Superstructures for Ultra-Fast and Long-Life Zinc-Organic Batteries.

Compared with Zn2+ storage, non-metallic charge carrier with small hydrated size and light weight shows fast dehydration and diffusion kinetics for Zn-organic batteries. Here we first report NH4 + /H+ co-storage in self-assembled organic superstructures (OSs) by intermolecular interactions of p-benzoquinone (BQ) and 2, 6-diaminoanthraquinone (DQ) polymer through H-bonding and π-π stacking. BQ-DQ OSs exhibit exposed quadruple-active carbonyl motifs and super electron delocalization routes, which are redox-exclusively coupled with high-kinetics NH4 + /H+ but exclude sluggish and rigid Zn2+ ions. A unique 4e- NH4 + /H+ co-coordination mechanism is unravelled, giving BQ-DQ cathode high capacity (299 mAh g-1 at 1 A g-1 ), large-current tolerance (100 A g-1 ) and ultralong life (50,000 cycles). This strategy further boosts the capacity to 358 mAh g-1 by modulating redox-active building units, giving new insights into ultra-fast and stable NH4 + /H+ storage in organic materials for better Zn batteries.

Non‐Metallic NH4+/H+ Co‐Storage in Organic Superstructures for Ultra‐Fast and Long‐Life Zinc‐Organic Batteries

AbstractCompared with Zn2+ storage, non‐metallic charge carrier with small hydrated size and light weight shows fast dehydration and diffusion kinetics for Zn‐organic batteries. Here we first report NH4+/H+ co‐storage in self‐assembled organic superstructures (OSs) by intermolecular interactions of p‐benzoquinone (BQ) and 2, 6‐diaminoanthraquinone (DQ) polymer through H‐bonding and π–π stacking. BQ‐DQ OSs exhibit exposed quadruple‐active carbonyl motifs and super electron delocalization routes, which are redox‐exclusively coupled with high‐kinetics NH4+/H+ but exclude sluggish and rigid Zn2+ ions. A unique 4e− NH4+/H+ co‐coordination mechanism is unravelled, giving BQ‐DQ cathode high capacity (299 mAh g−1 at 1 A g−1), large‐current tolerance (100 A g−1) and ultralong life (50,000 cycles). This strategy further boosts the capacity to 358 mAh g−1 by modulating redox‐active building units, giving new insights into ultra‐fast and stable NH4+/H+ storage in organic materials for better Zn batteries.

Comparative analysis of the kinetics of dehydration and dextrinization of potato and corn starch

In order to compare the kinetic characteristics of the heat treatment of starches and solve the question of what has a greater influence on the processes of their dextrinization, the chemical composition or their botanical origin, we carried out research by using methods of thermogravimetry and differential scanning calorimetry. It was shown for the first time that there is a process with heat absorption at 1300C in the temperature range of 25–2000C, in addition to the stages of dehydration of starches, which is not accompanied by a decrease in weight. This endoeffect is well explained by the melting process of the low-molecular amylose fraction of starches. In contrast to literature data, it was also established that the stage of starch decomposition in the temperature range of 200–3500C should be considered as a set of three consecutive processes. It was established that the activation energies of dehydration processes of pre-dehydrated starches are equal to 60 kJ mol–1. The average activation energy аor the stages of destruction of starches is 400–500 kJ mol–1. Such values of the activation energy of starch destruction processes are explained by the presence in their composition of a number of semi-crystalline subcomponents characterized by different thermal stability. When comparing the values of the activation energies of the dehydration and dextrinization processes of the investigated starches, a linear correlation was established for the first time, which testifies to the uniformity of such processes and their independence from the botanical origin of the starches.

Remarkable low-temperature dehydration kinetics of rare-earth-ion-doped Ca(OH)2 for thermochemical energy storage

Thermochemical energy storage based on dehydration-hydration of Ca(OH)2/CaO reversible reaction is considered a promising strategy to address the intermittency of solar thermal energy due to its extremely high storage density, possibility of seasonal heat storage, and low cost. However, conventionally-used Ca(OH)2 particles suffer from instabilities and poor multi-cycle performance at high temperature, which limits their applications. Here, we propose rare-earth-ion-doped Ca(OH)2 materials for thermochemical energy storage at reduced dehydration temperature through extensive DFT computational screening. Rare-earth elements, Sc, Y, La, Gd and Lu, -doped Ca(OH)2 exhibit lower decomposition barrier in comparison to the Ca(OH)2 without doping. The Sc-doped Ca(OH)2 shows the significantly reduced onset temperature of ∼326 °C, which is 50 °C lower than that of the pure Ca(OH)2. Importantly, more than 3-fold increase in the dehydration rate and excellent stability during multi-cycles of the compositions at 320 °C is reached by the doping of Sc or Y into Ca(OH)2. The working performance makes this material a practical alternative to realize stable high-density solar thermal energy storage.

Probing pH-Dependent Dehydration Dynamics of Mg and Ca Cations in Aqueous Solutions with Multi-Level Quantum Mechanics/Molecular Dynamics Simulations.

The dehydration of aqueous calcium and magnesium cations is the most fundamental process controlling their reactivity in chemical and biological phenomena, such as the formation of ionic solids or passing through ion channels. It holds particular relevance in light of recent advancements in the development of carbon capture techniques that rely on mineralization for long-term carbon storage. Specifically, dehydration of Ca2+ and Mg2+ is a key step in proposed carbon capture processes aiming to exploit the relatively high concentration of dissolved carbon dioxide in seawater via the formation of carbonate minerals from solvated Ca2+ and Mg2+ cations for sequestration and storage. Nevertheless, atomic-scale understanding of the dehydration of aqueous Ca2+ and Mg2+ cations remains limited. Here, we utilize rare event sampling via density functional theory molecular dynamics and embedded wavefunction theory calculations to elucidate the dehydration dynamics of aqueous Ca2+ and Mg2+. Emphasis is placed on the investigation of the effect pH has on the stability of the different coordination environments. Our results reveal significant differences in the dehydration dynamics of the two cations and provide insight into how they may be modulated by pH changes.

Low-Frequency Raman Spectroscopy: An Exceptional Tool for Exploring Metastability Driven States Induced by Dehydration.

The use of low-frequency Raman spectroscopy (LFRS; ω < 150 cm-1) is booming in the pharmaceutical industry. Specific processing of spectra is required to use the wealth of information contained in this spectral region. Spectra processing and the use of LFRS for analyzing phase transformations in molecular materials are detailed herein from investigations on the devitrification of ibuprofen. LFRS was used to analyze the dehydration mechanism of two hydrates (theophylline and caffeine) of the xanthine family. Two mechanisms of solid-state transformation in theophylline were determined depending on the relative humidity (RH) and temperature. At room temperature and 1% RH, dehydration is driven by the diffusion mechanism, while under high RH (>30%), kinetic laws are typical of nucleation and growth mechanism. By increasing the RH, various metastability driven crystalline forms were obtained mimicking successive intermediate states between hydrate form and anhydrous form achieved under high RH. In contrast, the dehydration kinetics of caffeine hydrate under various RH levels can be described by only one master curve corresponding to a nucleation mechanism. Various metastability driven states were achieved depending on the RH, which can be described as intermediate between forms I and II of anhydrous caffeine.

Key hydraulic traits control the dynamics of plant dehydration in four contrasting tree species during drought.

Trees are at risk of mortality during extreme drought, yet our understanding of the traits that govern the timing of drought-induced hydraulic failure remains limited. To address this, we tested SurEau, a trait-based soil-plant-atmosphere model designed to predict the dynamics of plant dehydration as represented by changes in water potential, against those observed in potted trees of four contrasting species (Pinus halepensis, Populus nigra, Quercus ilex, and Cedrus atlantica) exposed to drought. SurEau was parameterised with a range of plant hydraulic and allometric traits, soil, and climatic variables. We found close correspondence between predicted and observed plant water potential (MPa) dynamics during early phase drought leading to stomatal closure, as well as during latter phase drought leading to hydraulic failure in all four species. A global model's sensitivity analysis revealed that for a common plant size (leaf area) and soil volume, dehydration times from full hydration to stomatal closure (Tclose) was most strongly controlled by leaf osmotic potential (Pi0) and its influence on stomatal closure, in all four species, while maximum stomatal conductance (gsmax) also contributed to Tclose in Q. ilex and C. atlantica. Dehydration times from stomatal closure to hydraulic failure (Tcav) was most strongly controlled by Pi0, the branch residual conductance (gres), and Q10a sensitivity of gres in the three evergreen species, while xylem embolism resistance (P50) was most influential in the deciduous species Populus nigra. Our findings point to SurEau as a highly useful model for predicting changes in plant water status during drought and suggest adjustments made in key hydraulic traits are potentially beneficial to delaying the onset of drought-induced hydraulic failure in trees.

Unexpected Kinetic Solvent Effects Enhance Activity and Selectivity in Biphasic Systems

Biphasic dehydration of fructose to 5-hydroxymethylfurfural (HMF) has shown unprecedented increases in productivity, but a mechanistic understanding is lacking. Herein, we couple fast experimental reaction kinetics, multiscale modeling (phase behavior, classical molecular dynamics(MD), and quantum mechanics/molecular mechanics MD), in situ sampling, and IR and 13C-NMR spectroscopy to elucidate the complex effects of nonpolar extracting organic solvents on the kinetics of fructose dehydration. We show that these organic solvents can reach significant mutual solubility with water at reaction temperatures, enabling the partition of the sugar and catalyst into the extracting phase. In the organic-rich environment, the dehydration of fructose proceeds faster and more selectively than in water due to increased relative abundance of the reactive furanose isomer, enhanced water–catalyst–substrate interactions driven by nanophase separation, and higher product stability stemming from preferential solvation. We demonstrate that these solvent effects impact other critical biphasic reactions in biomass upgrading and provide qualitative principles for solvent selection.

Drug Phase Transformation and Water Redistribution during Continuous Tablet Manufacturing: A Case Study of Carbamazepine Dihydrate.

In recent years, continuous tablet manufacturing technology has been used to obtain regulatory approval of several new drug products. While a significant fraction of active pharmaceutical ingredients exists as hydrates (wherein water is incorporated stoichiometrically in the crystal lattice), the impact of processing conditions and formulation composition on the dehydration behavior of hydrates during continuous manufacturing has not been investigated. Using powder X-ray diffractometry, we monitored the dehydration kinetics of carbamazepine dihydrate in formulations containing dibasic calcium phosphate, anhydrous (DCPA), mannitol, or microcrystalline cellulose. The combined effect of nitrogen flow and vigorous mixing during the continuous mixing stage of tablet manufacture facilitated API dehydration. Dehydration was rapid and most pronounced in the presence of DCPA. The dehydration product, amorphous anhydrous carbamazepine, sorbed a significant fraction of the water released by dehydration. Thus, the dehydration process resulted in a redistribution of water in the powder blend. The unintended formation of an amorphous dehydrated phase, which tends to be much more reactive than its crystalline counterparts, is of concern and warrants further investigation.

Monitoring lesion activity on primary teeth with CP-OCT and SWIR reflectance imaging.

The purpose of this study was to use cross polarization optical coherence tomography (CP-OCT) and short wavelength infrared imaging (SWIR) reflectance imaging to monitor changes in the structure and activity of early occlusal caries on primary teeth over a period of 6 months during intervention with fluoride. Participants (n = 29) aged 6-10 each with two suspected active occlusal lesions on primary teeth completed the study. Fluoride varnish was applied to tooth surfaces every 3-months and participants were instructed to brush twice daily with a fluoride toothpaste. Images were acquired using CP-OCT every 3 months for 6 months. SWIR reflectance images were acquired during forced air-drying of the lesions for 30 s at 0 and 6-months. Most of the 42 lesions appeared initially active at baseline. Only 6 lesions appeared arrested at baseline based on the presence of a highly mineralized transparent surface layer (TSL) in CP-OCT images. At 6 months, 14 of the lesions appeared arrested including the 6 initially arrested lesions and the TSL thickness increased significantly (p < 0.0001). The mean lesion depth (Ld) and the integrated reflectivity over the lesion depth (ΔR) increased significantly (p < 0.05) after 6 months for the 42 lesions analyzed. SWIR reflectance images showed that there was a significantly higher (p < 0.05) delay before changes in intensity were measured for active lesions versus arrested lesions during lesion drying. CP-OCT was able to monitor changes in lesion structure and activity including the formation of a highly mineralized TSL indicative of lesion arrest during nonsurgical intervention. Time-resolved SWIR reflectance imaging also shows that there are differences in the dehydration kinetics between active and arrested lesions. This study demonstrates two independent imaging methods that can be used to monitor changes in lesion activity over time.

Influence of meat sample geometry on dehydration dynamics during dry-aging of beef

Meat geometry may impact on the dehydration kinetics during dry-aging influencing the drying rate and, potentially, aspects of meat quality. In this study, three meat geometries (slices, steaks and sections) were prepared from three bovine Longissimuss thoracis et lumborum at 3 days post-mortem and were dry-aged at 2 °C, 75% relative humidity with an airflow of 0.5–2.0 m/s for 22 days (slices), 48 days (sections) and 49 days (steaks). Weights were recorded during dry-aging and drying curves were obtained for the three geometries, with the larger sections showing limited dehydration due to internal resistance to moisture migration from the core to the surface. Seven thin-layer equations were fitted to the dehydration data in order to model the drying kinetics during dry-aging. Thin-layer models described reliably the drying kinetics of the three geometries. In general, reduced k values (h−1) reflected the lower drying rates as thickness increased. The Midilli model provided the best fit for all geometries. Proximate analyses of the three geometries and bloomed colour of sections were measured at the start and the end of the dry-aging period. Moisture loss during dry-aging led to the concentration of protein, fat and ash contents; while no significant differences were found for L*, a* and b* values of sections before and after the dry-aging process. In addition, moisture content, water activity (aw) and LF-NMR measurements were taken at different locations within beef sections to further explore water dynamics during dry-aging.

Effects of solar radiations on stratum corneum hydration: Part I, protective role of skin surface lipids.

This study used Raman spectroscopy to develop a new approach to evaluate the effects of solar radiation on the stratum corneum (SC). The method measures the SC's hydration and dehydration kinetics by calculating the vOH/vCH ratio to monitor the relative water content during the drying process. The study also investigated the role of skin surface lipids (SSLs) in protecting the SC from solar radiation. The SSLs film is a complex mixture of free fatty acids, triglycerides, wax esters, squalene, free and esterified cholesterols, that play a crucial role in the skin's barrier function. The results showed that solar radiation alters the water content and balance within the SC, and SSLs provide protection by acting as an optical filter by absorbing some of the energy of the solar light. This is confirmed by high temperature gas chromatography coupled to mass spectrometry analyses by revealing a decrease in specific lipids after irradiating the SSLs .

Experimental study on the kinetics of magnesiohornblende dehydration and its implications

Abstract Magnesiohornblende dehydration was studied using both high-temperature thermogravimetric analysis and high-pressure differential thermal analysis (HP-DTA). The high-temperature thermogravi-metric analysis results revealed that magnesiohornblende dehydration at high temperatures could be divided into three steps: 848–1058, 1058–1243, and 1243–1473 K, and each step followed an n-order reaction (Fn). The dehydration process is characterized by an oxidation-dehydrogenation mechanism, and the dehydration of the last step can be explained as the direct decomposition of the hydroxyl groups connected to the magnesium ions. The HP-DTA of magnesiohornblende dehydration under pressures of 0.5, 1.0, 2.0, and 3.0 GPa revealed the occurrence of two endothermic peaks, indicating that the dehydration occurs in two steps at high temperature and pressure. Our experimental results reveal that during subduction, the fluid released during the dehydration of magnesiohornblende may trigger earthquakes and cause high electrical conductivity anomalies in the subduction zones.

Dehydration of a crystal hydrate at subglacial temperatures

Water is one of the most important substances on our planet1. It is ubiquitous in its solid, liquid and vaporous states and all known biological systems depend on its unique chemical and physical properties. Moreover, many materials exist as water adducts, chief among which are crystal hydrates (a specific class of inclusion compound), which usually retain water indefinitely at subambient temperatures2. We describe a porous organic crystal that readily and reversibly adsorbs water into 1-nm-wide channels at more than 55% relative humidity. The water uptake/release is chromogenic, thus providing a convenient visual indication of the hydration state of the crystal over a wide temperature range. The complementary techniques of X-ray diffraction, optical microscopy, differential scanning calorimetry and molecular simulations were used to establish that the nanoconfined water is in a state of flux above −70 °C, thus allowing low-temperature dehydration to occur. We were able to determine the kinetics of dehydration over a wide temperature range, including well below 0 °C which, owing to the presence of atmospheric moisture, is usually challenging to accomplish. This discovery unlocks opportunities for designing materials that capture/release water over a range of temperatures that extend well below the freezing point of bulk water.