Calculated Activation Energy Research Articles

Investigating the dielectric characteristics, electrical conduction mechanisms, morphology, and structural features of mullite via sol-gel synthesis at low temperatures

This research explores the fabrication of mullite precursor powder utilizing the sol-gel process at low temperatures. Silicon tetraethoxide (Si(C2H5O)4) and aluminum nitrate nonahydrate (Al(NO3)3.9H2O) were employed as the sources of SiO2 and Al2O3 oxides, respectively. Various analytical techniques, such as Fourier transform infrared spectroscopy (FTIR), thermogravimetry (TG), dilatometry, differential thermal analysis (DTA), and X-ray powder diffractometer (XRD), were utilized to investigate the formation and crystallization of the amorphous powder. The microstructure of specimens sintered at 1600 °C for 1 h was examined utilizing scanning electron microscopy (SEM). Measurements of hardness (HV) and coefficient of thermal expansion (CTE) were conducted on mullite samples heated to 1600 °C and then cooled, revealing an increase in HV from 888 to 1000 HV as the sintering temperature rose from 1500 to 1600 °C. The CTE of mullite within the temperature range of 50–1300 °C was determined as 5.23 × 10−6/°C. Additionally, the dielectric and electrical characterization of mullite was analyzed utilizing complex impedance spectroscopy at a frequency of 0.1–106 Hz and conductivity measurements over a temperature range of 40–400 °C. The real and imaginary parts of the dielectric permittivity exhibited frequency-dependent and temperature-dependent behaviors. Significantly, the observed variations in the imaginary component of the modulus and impedance maximum frequency point to a relaxation process that is not Debye-type, with calculated activation energies (Ea) consistent across different methods.

The thawing process in gentamicin and polyethylene glycol hydrogel: The impact of selected parameters on the calculation of activation energy using the methods of Belichmaer and Duswalt

AbstractThe subject of the research conducted by differential scanning calorimetry (DSC) was hydrated mixtures of polyethylene glycol and gentamicin (GEN) in a 1:1 (w/w) ratio. In this way, a system with a particularly high ability to form hydrogen bonds was created. It was postulated that studying the effective activation energy (EA) of the thawing process of diverse hydrated polymer mixtures will indirectly allow for an attempt to assess the distribution of water molecules in the examined material in future studies. This article presents a detailed analysis of the impact of selected parameters on the calculation of EA using the Belichmaer and Duswalt methods. The research focused on assessing how the interpolation method affects the accuracy of results obtained from these techniques. The interpolation method was analyzed in terms of its ability to accurately replicate experimental data. By evaluating the impact of the number of points from the DSC curve used in linear interpolation, a standard deviation from the average value of EA was obtained, respectively: 2.4% for the Belichmaer method and 1.9% for the Duswalt method. The article also shows that by using both methods simultaneously, it is possible to detect the moment when additional endothermic and exothermic reaction activity becomes present in the reaction curve. This allowed for the avoidance of the depletion error. Computer modeling and simulations were used to compare the effectiveness of both techniques in various scenarios. The results showed that the choice of interpolation method and taking into account the depletion error significantly affect the accuracy of calculating EA. The computed activation energy via Duswalt method was EA = 363.32 kJ mol−1 with a standard deviation of 7.07 kJ mol−1 and using the Belichmaer method the EA was 364.81 kJ mol−1, with a standard deviation of 9.10 kJ mol−1.

Assessing the accuracy and efficacy of multiscale computational methods in predicting reaction mechanisms and kinetics of SN2 reactions and Claisen rearrangement

This study investigates the application of quantum mechanical (QM) and multiscale computational methods in understanding the reaction mechanisms and kinetics of SN2 reactions involving methyl iodide with NH2OH and NH2O−, as well as the Claisen rearrangement of 8-(vinyloxy)dec-9-enoate. Our aim is to evaluate the accuracy and effectiveness of these methods in predicting experimental outcomes for these organic reactions. We achieve this by employing QM-only calculations and several hybrids of QM and molecular mechanics (MM) methods, namely QM/MM, QM1/QM2, and QM1/QM2/MM methodologies. For the SN2 reactions, our results demonstrate the importance of explicitly including solvent effects in the calculations to accurately reproduce the transition state geometry and energetics. The multiscale methods, particularly QM/MM and QM1/QM2, show promising performance in predicting activation energies. Moreover, we observe that the size of the MM active region significantly affects the accuracy of calculated activation energies, highlighting the need for careful consideration during the setup of multiscale calculations. In the case of the Claisen rearrangement, both QM-only and multiscale methods successfully reproduce the proposed reaction mechanism. However, the activation free energies calculated using a continuum solvation model, based on single-point calculations of QM-only structures, fail to account for solvent effects. On the other hand, multiscale methods more accurately capture the impact of solvents on activation free energies, with systematic error correction enhancing the accuracy of the results. Furthermore, we introduce a Python code for setting up multiscale calculations with ORCA, which is available on GitHub at https://github.com/iranimehdi/pdbtoORCA.

Kinetic Study and Reaction Mechanism of the Gas-Phase Thermolysis Reaction of Methyl Derivatives of 1,2,4,5-Tetroxane.

Tetroxane derivatives are interesting drugs for antileishmaniasis and antimalaric treatments. The gas-phase thermal decomposition of 3,6,-dimethyl-1,2,4,5-tetroxane (DMT) and 3,3,6,6,-tetramethyl-1,2,4,5-tetroxane (acetone diperoxide (ACDP)) was studied at 493-543 K by direct gas chromatography by means of a flow reactor. The reaction is produced in the injector chamber at different temperatures. The resulting kinetics Arrhenius equations were calculated for both tetroxanes. Including the parent compound of the series 1,2,4,5-tetroxane (formaldehyde diperoxide (FDP)), the activation energy and frequency factors decrease linearly with the number of methyl groups. The reaction mechanisms of ACDP and 3,6,6-trimethyl-1,2,4,5-tetroxane (TMT) decomposition have been studied by means of the DFT method with the BHANDHLYP functional. Our calculations confirm that the concerted mechanism should be discarded and that only the stepwise mechanism occurs. The critical points of the singlet and triplet state potential energy surfaces (S- and T-PES) of the thermolysis reaction of both compounds have been determined. The calculated activation energies of the different steps vary linearly with the number of methyl groups of the methyl-tetroxanes series. The mechanism for the S-PES leads to a diradical O···O open structure, which leads to a C···O dissociation in the second step and the production of the first acetaldehyde/acetone molecule. This last one yields a second C···O dissociation, producing O2 and another acetone/acetaldehyde molecule. The O2 molecule is in the singlet state. A quasi-parallel mechanism for the T-PES from the open diradical to products is also found. Most of the critical points of both PES are linear with the number of methyl groups. Reaction in the triplet state is much more exothermic than the singlet state mechanism. Transitions from the singlet ground state, S0 and low-lying singlet states S1-3, to the low-lying triplet excited states, T1-4, (chemical excitation) in the family of methyl tetroxanes are also studied at the CASSCF/CASPT2 level. Two possible mechanisms are possible here: (i) from S0 to T3 by strong spin orbit coupling (SOC) and subsequent fast internal conversion to the excited T1 state and (ii) from S0 to S2 from internal conversion and subsequent S2 to T1 by SOC. From these experimental and theoretical results, the additivity effect of the methyl groups in the thermolysis reaction of the methyl tetroxane derivatives is clearly highlighted. This information will have a great impact for controlling these processes in the laboratory and chemical industries.

Atomistic Modeling of Quaternized Chitosan Head Groups: Insights into Chemical Stability and Ion Transport for Anion Exchange Membrane Applications.

The chemical stability and ion transport properties of quaternized chitosan (QCS)-based anion exchange membranes (AEMs) were explored using Density Functional Theory (DFT) calculations and all-atom molecular dynamics (MD) simulations. DFT calculations of LUMO energies, reaction energies, and activation energies revealed an increasing stability trend among the head groups: propyl trimethyl ammonium chitosan (C) < oxy propyl trimethyl ammonium chitosan (B) < 2-hydroxy propyl trimethyl ammonium chitosan (A) at hydration levels (HLs) of 0 and 3. Subsequently, all-atom MD simulations evaluated the diffusion of hydroxide ions (OH-) through mean square displacement (MSD) versus time curves. The diffusion coefficients of OH- ions for the three types of QCS (A, B, and C) were observed to increase monotonically with HLs ranging from 3 to 15 and temperatures from 298 K to 350 K. Across different HLs and temperatures, the three QCS variants exhibited comparable diffusion coefficients, underlining their effectiveness in vehicular transport of OH- ions.

Improving Proton-Conducting Stability by Regulating Pore Size of MOF Materials through Mixed Grinding.

An effective strategy to improve the proton conductivity of metal-organic frameworks (MOFs) is to regulate the pore size of composite materials. In this work, composite materials of MOF-808@MOG-808-X (X is the mass ratios of MOF-808 to MOG-808) was successfully prepared by grinding and blending. MOF-808@MOG-808-1:2 was optimal for its suitable pore structure, which facilitates the practical construction of hydrogen bonding networks, promotes rapid and stable proton conduction, and enables the proton conductivity, achieving a 1 + 1 > 2 effect. At 353 K and 93% relative humidity (RH), the maximum proton conductivity of MOF-808@MOG-808-1:2 reaches 1.08 × 10-1 S·cm-1. Next, MOF-808@MOG-808-1:2 was blended with chitosan (CS) to obtain composite proton exchange membranes (PEMs), namely, CS@MOF-808@MOG-808-1:2-Y (Y = 5%, 10%, or 15%) with the maximum proton conductivity reaching 1.19 × 10-2 S·cm-1 at 353 K and 93% RH for CS@MOF-808@MOG-808-1:2-10% with additional stability. The conductive mechanisms of the composite materials were revealed by activation energy calculation. This investigation not only proposes a simple grinding-blending method for the development of MOF-doped composite materials for proton conductivity but also provides a producting material basis for future applications of MOFs in proton exchange membrane fuel cells (PEMFCs).

Kinetics of Plasticized Poly(vinyl chloride) Thermal Degradation, Induction, Autocatalysis, Glass Transition, Diffusion

AbstractKinetics of non‐oxidative thermal degradation of poly(vinyl chloride) (PVC) plasticized with di(2‐ethylhexyl)phthalate and epoxidized linseed oil (ELO) were studied using differential scanning calorimetry. PVC thermal degradation autocatalyzed by forming HCl is delayed in the presence of acid scavenging ELO. Direct HCl elimination rates during steady state degradation (induction period) were almost independent on ELO concentration, with rate constants ranging from ≈3.2×10−6 s−1 at 463 K to ≈7.0×10−5 s−1 at 503 K. Activation energy of HCl elimination increased with glass transition temperature (Tg) increase from 136.0 kJ mol−1 at Tg=260.3 K to 141.9 kJ mol−1at Tg=274.2 K. Diffusion coefficients of HCl diffusion in plasticized PVC deduced using Williams‐Landel‐Ferry equation were of the order of 10−4 cm2 sec−1. Calculated activation energy of HCl diffusion in plasticized PVC was ≈30 kJ mol−1. The rate constants of PVC autocatalytic degradation were derived from the experimental data (for the 1st time) using Šesták‐Berggren approach and ranged from 3.2×10−2 sec−1 at 503 K to 4.4×10−3 sec−1 at 463 K. Autocatalysis activation energies ranged from 70.4 kJ mol−1 to 85.1 kJ mol−1 and increased with increase of glass transition temperature. It was established that PVC degradation kinetics was not controlled by HCl diffusion. Compensation effect was observed for initial and catalyzed PVC degradation.

Uniaxial compressive creep tests by spark plasma sintering of 70% theoretical density α-uranium and U-10Zr

Metallic fuels hold numerous advantages over conventional uranium dioxide fuels and are a key component of several liquid metal-cooled advanced reactor concepts including sodium fast reactors. These fuels undergo rapid swelling during early burnup; consequently, they spend most of their reactor lifetime in a porous state. The presence of this porosity alters many of the mechanical properties of the fuel including creep impacting fuel deformation during axial swelling. This work investigates the creep behavior of the porous fuel using a spark plasma sintering technique. Creep tests were performed for the first time on porous α-phase uranium and uranium with 10 wt. % zirconium (U-10Zr) samples. The samples of α-phase uranium and U-10Zr were fabricated from depleted uranium by spark plasma sintering and subjected to uniaxial compressive creep testing. Calculated stress exponents were found to be 2.6±1.6 and 5.7±1.4 for α-U and U-10Zr, respectively, and calculated activation energies were found to be 61.6±1.1kJ/mol for α-U. The creep data were also used to evaluate existing porosity inclusive in creep models.

Coumarin-Phosphazenes: Enhanced Photophysical Properties from Hybrid Materials.

Phosphazenes have drawn a great deal of interest over the past 20 years as a potentially useful building block for the fabrication of fluorescent materials. The main objective of this work is to explore novel derivatives produced by coumarins, a class of chemicals well-known for their photophysical importance, and cyclophosphazenes. UV absorbance, fluorescence emission, quantum yield, and lifetime measurements were conducted to comprehend the optical properties. Furthermore, single-crystal X-ray analysis and theoretical calculations were carried out to confirm the structure of the molecule. The obtained findings collectively confirm the commendable optical properties exhibited by the studied compounds. Moreover, a detailed study of the crystal packing arrangement of DPP-Et-Kum-Et compound crystallized in the P21/n monoclinic space group revealed the presence of stacking interactions between the nonplanar conjugated benzene rings of the coumarins and the rigid diphenyl groups attached to the phosphazene ring. The crystal structure of the DPP-Kum-Me-Me compound is mainly based on classical C-H···O intermolecular hydrogen bonding interactions with an average distance of 2.52 Å. Importantly, the calculated absorption spectra of the compounds are in close agreement with the experimental data, further supporting their interesting electronic properties. Given that the DPP-Et-Kum-Et and DPP-Kum-Et compounds have the theoretically lowest band gaps (4.31 and 4.30 eV, respectively), the activation energies of these compounds were determined by an impedance analyzer using dc conductance values measured at different temperatures. The calculated activation energies for DPP-Et-Kum-Et and DPP-Kum-Et are 104.49 and 100.92 meV, respectively. The results demonstrate that both theoretical and experimental calculations are in agreement with each other and that the DPP-Kum-Et compound has the lowest conductivity.

Growth behavior of cristobalite SiO2 coating on 4H–SiC surface via high-temperature oxidation

When SiO2 films undergo oxidation on 4H–SiC, a distinctive crystalline phase, cristobalite, emerges at elevated temperatures. We deeply explored the growth mechanism of the crystallite, focusing on its dependence on the silicon sublimation process (SSO). Activation energy calculations confirmed that the oxidation after SSO above 1350 °C exhibits a lower activation energy. The reduced activation energy suggests the elimination of the solid-phase diffusion process during oxidation. We devised a controllable growth process for the quartz phase to achieve a seamless transition from 0 to 100 % in the area proportion of cristobalite in SiO2. This strategic approach facilitates the precise preparation of oxide layers and holds potential applications in semiconductor device manufacturing.

Garlic Cellulosic Powders with Immobilized AgO and CuO Nanoparticles: Preparation, Characterization of the Nanocomposites, and Application to the Catalytic Degradation of Azo Dyes.

Nanomaterials have attracted specific consideration due to their specific characteristics and uses in several promising fields. In the present study, Chondrilla juncea was employed as a biological extract to facilitate the reduction of copper and silver ions within garlic peel powders. The resulting garlic-CuO and garlic-AgO nanocomposites were characterized using several analytical methods including FTIR, TGA/DTG, SEM, TEM, and XRD analyses. The garlic peel exhibited a rough surface. The nanoparticles were evenly dispersed across its surface. The incorporation of CuO and AgO nanoparticles affected the crystal structure of garlic peel. The establishment of CuO and AgO nanoparticles was evidenced by the highest residual mass values observed for the prepared nanocomposites. The thermogravimetric analysis showed that the prepared nanocomposites had lower thermal stability compared with garlic peel powders. The prepared nanocomposites were used for catalytic degradation of naphthol blue black B and calmagite. The decolorization process depended on the quantity of H2O2, initial concentration of azo dyes, duration of contact, and temperature of the bath. The calculated activation energy (Ea) values for the garlic-CuO nanocomposites were found to be 18.44 kJ mol-1 and 23.28 kJ mol-1 for calmagite and naphthol solutions, respectively. However, those calculated for garlic-AgO nanocomposites were found to be 50.01 kJ mol-1 and 12.44 kJ mol-1 for calmagite and naphthol, respectively.

Kinetic analysis of PA4 thermal degradation: Thermal stability with respect to crystallinity

Polyamide 4 (PA4) has garnered considerable attention due to its fully bio-based origin and biodegradability as a high-performance polyamide. Nevertheless, thermal degradation during the melting process impedes thermal processing, thereby constraining its potential for engineering plastics applications. To clarify the thermal degradation reactions of PA4 amidst intricate physical and chemical transformations, establishing a theoretical foundation for the thermal stability modification, we conducted a comprehensive analysis of PA4 thermal degradation coupled with crystallization, considering kinetics and reaction mechanisms. Calculation of reaction activation energies and mechanism functions revealed that PA4 pyrolysis is a two-stage compound process, with distinct degradation mechanisms attributed to the crystalline and amorphous regions. Additionally, the thermal degradation mechanism of the PA4-CaCl2 composite system at varying crystallinity levels was illustrated. The incorporation of Ca strengthens intermolecular forces in the samples, leading to an increased overall stability. Simultaneously, a notable alteration in the reaction mechanism was observed in the crystalline zone lacking the Ca phase.

Microstructure, martensitic transformation kinetics, and magnetic properties of (Ni50Mn40In10)100−xCox melt-spun ribbons

AbstractThe effect of Co-doping on the structure, microstructure, martensitic phase transformation kinetics, and magnetic properties of the melt-spun (Ni50Mn40In10)1−xCox (x = 1, 2, and 3) Heusler ribbons, named hereafter Co1 (x = 1), Co2 (x = 2), and Co3 (x = 3), was assessed using X-ray diffraction, scanning electron microscope, energy-dispersive spectroscopy, X-ray fluorescence, differential scanning calorimetry, and vibrating sample magnetometer. The XRD results reveal the formation of a 14M martensite structure alongside the face-centered-cubic (fcc) γ phase. The crystallite size ranges between 50 and 98 nm for the 14M martensite and from 9 to 16 nm for the γ phase. The mass fraction of the γ phase lies between 36.4 and 44.2%. Co-doping affects the lattice parameters and the characteristic temperatures (martensite start, martensite finish, austenite start, and austenite finish). The calculated activation energy values for the non-isothermal martensitic transformation kinetics are 257 kJ mol−1 and 135.6 kJ mol−1 for the Co1 and Co2, respectively. The produced ribbons show a paramagnetic behavior. The variation in the coercivity can be related to the crystallite size and mass fraction of the γ phase. The produced ribbons exhibit an exchange bias at room temperature that decreases with increasing the Co content.

Microwave-assisted ammonia decomposition over metal nitride catalysts at low temperatures

The negative environmental impact of fossil fuel-based energy systems has unveiled the need to develop a COx-free sustainable hydrogen (H2) economy. Employing a microwave-assisted route, a ternary metal nitride catalyst (i.e., Co2Mo3N), and a low-temperature-pressure NH3 decomposition process, this study investigated the possibility of developing a distributed H2 production process. This study not only explored lower cost-based catalyst systems but also the use of a microwave reactor to increase the energy efficiency of the process. Results from catalytic NH3 decomposition experiments, performed in microwave reactors on Co2Mo3N catalyst, demonstrated the peak energy efficiency (of ∼0.006 kgH2/kWh) at 400 °C in ambient pressure (with an NH3 conversion >90%) which was around ninety times (∼90 x) more efficient than a conventional system. Activation energy calculation also displayed a 20% less energy requirement for the microwave-based process (∼31 kJ mol−1) than the conventional system (∼37 kJ mol−1), indicating the advantage of the microwave-based process. Further microwave-assisted catalytic measurements and characterization of the Co2Mo3N catalyst, using x-ray diffraction (XRD) technique and scanning electron microscopic (SEM) images, revealed the excellent stability of this material at its peak performance (at 400 °C) and illustrated the potential of using this catalyst for a sustainable, economic, and energy-efficient approach for producing COx-free H2.

Dynamic strain aging and negative strain rate sensitivity in coarse-grained Al0.3CoCrFeNi high entropy alloy under hot compression

This study investigates the deformation behavior of coarse-grained (CG) Al0.3CoCrFeNi alloy under hot compression, revealing notable strain rate sensitivity (SRS) and dynamic strain aging (DSA) phenomena. DSA is observed at temperatures between 1223 K and 1373 K, exclusively at lower strain rates (0.5 s−1 – 1 s−1), while higher strain rates (≥5 s−1) exhibit DSA absence. Non-compact {112} slip activation on dislocation forest structures is proposed as the driving force behind DSA. Negative SRS behavior at 1223 K is attributed to Ni–Al cluster-based solid solution strengthening. Activation energy calculations highlight lattice diffusion and partial dislocation constriction as contributors to hot deformation. Consistency is observed in the activation volume (V*) calculation, indicating dislocation forest formation (127–519 b3, b = Bureger's vector), diminishing to 22–46 b3 upon DSA initiation. The alloy displays delayed dislocation hardening/softening transition due to CG's impact on retarding dislocation accumulation. This behavior stems from a higher V* at yielding, prolonging the typical transition observed in fine-grained alloys with lower V*. The study elucidates the intricate interplay of microstructure, strain rate, and deformation mechanisms in CG Al0.3CoCrFeNi.

Osmotic Dehydration Model for Sweet Potato Varieties in Sugar Beet Molasses Using the Peleg Model and Fitting Absorption Data Using the Guggenheim-Anderson-de Boer Model.

This study investigates the applicability of the Peleg model to the osmotic dehydration of various sweet potato variety samples in sugar beet molasses, addressing a notable gap in the existing literature. The osmotic dehydration was performed using an 80% sugar beet molasses solution at temperatures of 20 °C, 35 °C, and 50 °C for periods of 1, 3, and 5 h. The sample-to-solution ratio was 1:5. The objectives encompassed evaluating the Peleg equation's suitability for modeling mass transfer during osmotic dehydration and determining equilibrium water and solid contents at various temperatures. With its modified equation, the Peleg model accurately described water loss and solid gain dynamics during osmotic treatment, as evidenced by a high coefficient of determination value (r2) ranging from 0.990 to 1.000. Analysis of Peleg constants revealed temperature and concentration dependencies, aligning with previous observations. The Guggenheim, Anderson, and de Boer (GAB) model was employed to characterize sorption isotherms, yielding coefficients comparable to prior studies. Effective moisture diffusivity and activation energy calculations further elucidated the drying kinetics, with effective moisture diffusivity values ranging from 1.85 × 10-8 to 4.83 × 10-8 m2/s and activation energy between 7.096 and 16.652 kJ/mol. These findings contribute to understanding the complex kinetics of osmotic dehydration and provide insights into the modeling and optimization of dehydration processes for sweet potato samples, with implications for food processing and preservation methodologies.

Thermo-kinetics study of microalgal biomass in oxidative torrefaction followed by machine learning regression and classification approaches

Solid biofuels derived from microalgae represent a low-cost, high-volume bioproduct opportunity with excellent CO2 biofixation capability, contributing significantly to the attainment of net zero. Oxidative torrefaction also offers a more economical pretreatment to upgrade its solid fuel properties. This study investigates the thermo-kinetics aspect of oxidative torrefaction of microalgae with varying O2 concentrations using thermogravimetric and differential thermal analysis (TGA-DTA). Isoconversional kinetic modeling is applied to mass-loss data and shows average activation energies of 172.57, 174.68, 199.42, and 209.03 kJ‧mol−1 at 0, 3, 12, and 21 % O2 concentrations, respectively. The effect of O2, especially at 12 vol%, significantly reduces the calculated activation energy at lower conversion. DTA also reveals lower heat flow values under oxidative than inert torrefaction. Thermo-kinetics data are then utilized to conduct machine learning approaches. Regression via artificial neural networks shows that the prediction of conversion and heat flow values are predominantly dictated by the temperature, followed by heating rate and O2 concentration. Finally, classification using the k-nearest neighbors algorithm highlights the effects of factors at specific ranges of conversion and heat flow responses. The O2 concentration is significant only at early conversion (X<0.1) and contributes to generally lower heat flow values.

Investigating the potential of ZrO2/MoO3 nanocomposites for efficient hydrogen generation through NaBH4 methanolysis

This work investigates the potential of ZrO2/MoO3 nanocomposites as catalysts for hydrogen production through NaBH4 methanolysis. The samples were prepared by controlled thermal calcination and characterized using various techniques like XRD, FTIR, Raman, SEM, and surface area BET analysis. Rietveld refinements verified the presence of the ZrO2 monoclinic phase with the space group P21/c in all samples and a second orthorhombic MoO3 phase with the space group Pnma. The average crystal size decreased from 44 to 40 nm. FTIR and Raman spectroscopy confirmed the successful preparation of ZrO2/MoO3 nanocomposites. SEM analysis showed ZrO2 particles and MoO3 nanoparticles adhered to the ZrO2 surface, potentially creating a rougher texture. The results confirmed the formation of ZrO2/MoO3 nanocomposites with increasing MoO3 content, leading to an increased surface area of 19–23 m2/g. The catalytic performance evaluation revealed that the sample containing 30 % MoO3 (ZM3) exhibited the highest hydrogen generation rate of 18,451 mL/g. min at 30 °C. The calculated activation energy for ZM3 was 18.78 kJ/mol, suggesting efficient hydrogen generation at moderate temperatures.

Kinetics and thermodynamics in microwave-assisted transesterification of palm oil utilizing sulphonated bio-graphene catalysts for biodiesel production

Enhanced reaction performance is what has piqued interest in using graphene-based catalysts in producing biodiesel. However, in-depth analyses were lacking from a kinetic and thermodynamic standpoint. This means that a well-designed experiment is necessary to determine the effect that the graphene catalysts have on the reaction rates and yields. This work addresses the kinetic and thermodynamic aspects of heterogeneously catalyzed transesterification using sulphonated biomass-derived graphene catalysts, i.e., bGO-SO3H and brGO-SO3H. It was accomplished using the pseudo-first order mechanism and the Eyring-Polanyi equation, with all data fitting satisfactorily in both models at the ideal reaction temperature of 353.15 K, resulting in R2 values of 0.9784 (bGO-SO3H) and 0.9884 (brGO-SO3H). The calculated activation energy (Ea) was determined to be 44.45 and 51.73 kJ mol-1 for bGO- and brGO-SO3H, respectively. Additionally, the Gibbs free energy (ΔG) values were determined at −38.09 and −31.81 kJ mol−1 for bGO- and brGO-SO3H, respectively. Meanwhile, the values for ΔH and ΔS were obtained as 41.69 kJ mol−1 and 225.93 J mol−1 K−1, respectively, and 48.96 kJ mol−1 and 228.72 J mol−1 K−1, respectively. These collective outcomes collectively signify the endothermic nature of the reaction and their spontaneity, particularly under elevated temperature conditions.

Investigation of the Leaching Kinetics of Zinc from Smithsonite in Ammonium Citrate Solution

In this study, the response surface method is used to develop a model for analyzing and optimizing zinc leaching experiments. An investigation into the leaching kinetics of smithsonite in ammonium citrate solution is also conducted. A model of kinetics is studied in order to represent these effects. The experimental data show that an increase in the solution temperature, concentration, and stirring speed has a positive impact on the leaching rate, while an increase in the particle size has a negative impact on it. The optimal experimental conditions consist of a leaching temperature of 70 °C, ammonium citrate concentration of 5 mol/L, particle size of 38 µm, and rotational speed of 1000 rpm. Under these optimal conditions, the leaching rate of zinc from smithsonite is 83.51%. It is speculated that the kinetic model will change when the temperature is higher than 60 °C. When the temperature is lower than 60 °C, the leaching process is under the control of the shrinking core model of the surface chemical reactions. The calculated activation energy of the leaching reaction is equal to 42 kJ/mol. The model of the leaching process can be described by the following equation: 1−1−x1/3=k0⋅(C)0.6181⋅r0−0.5868⋅SS0.6901exp⁡−42/RT]t. This demonstrates that an ammonium citrate solution can be used in the leaching process of zinc in smithsonite as an effective and clean leaching agent.