Exothermic Research Articles

Exploration of altered reaction pathways in aging pyrotechnic compositions under seasonal cycles

Since pyrotechnic delays are utilized to control the initiation timing of the metal-rich chemical reactions, precise control of these reactions is desired even when the combustion mixture is subjected to extended storage conditions. However, alterations in physicochemical and geometrical properties, accompanied by changes in thermal behavior, significantly influence the reaction pathways. This study explores the reactions of tungsten (W)-based pyrotechnic compositions subjected to aging. In particular, the work identifies the altered reaction pathways and fundamental causes leading to deterioration in both thermodynamic and physicochemical characteristics due to aging under seasonal cycles. Surface analyses revealed the major aging products as KClO3, WO3, BaO, and Cr2O3, along with three distinct effects of aging: pre-oxidation of metals, a priori decomposition of oxidizers, and surface cracking. Thermal analyses using peak deconvolution techniques described the sub-reactions of the major exothermic reaction, such as chemical reactions #1: (W and KClO4) and #2: (W, KClO4, and BaCrO4) and (WO3 and BaO). Notably, samples aged longer than 2 weeks underwent an additional side reaction, #3: (KClO3 decomposition). The multi-step reaction kinetics obtained from the Friedman method disclosed notably distinct trends in both pristine and aged samples. Among the aging products, KClO3 played a decisive role in altering the Eα-α relationship from a monotonic increase to a convex pattern. The measured decrease in Eα due to the involvement of KClO3 was approximately 30 % (from 464.7 kJ/mol to 272.4 kJ/mol). This demonstrates that KClO3 is critical to performance degradation, as it can release excess oxygen at initiation and decompose at a later stage. This results in incomplete combustion and a decline in thermodynamic performance due to the resulting ad-hoc O/F ratio. Thus, these findings may help in designing the time delay margins and estimating the shelf-life of these compositions.

Mass Velocity Profiles for Non-Ideal Detonation of Mixtures of Nitromethane and Ammonium Perchlorate Overloaded with Aluminum. Measurements and Calculation

Earlier, by comparing the results of mathematical modeling with experimental data on the non-ideal detonation velocities of triple mixtures of nitromethane and ammonium perchlorate with aluminum excess, the rates of exothermic reactions and the consumption degree of components within the detonation wave reaction zone were determined. A quasi-one-dimensional model of steady detonation was used for calculations, in which all components have a common pressure and move with a common mass velocity, and exothermic conversion is carried out in three stages, which include decomposition of nitromethane and ammonium perchlorate and diffusion combustion of aluminum. To confirm the obtained results and the applicability of the relatively simple theoretical model, calculations of the mass velocity profile during detonation of one of the triple mixtures with 17% nitromethane have been carried out. The calculation results are in agreement with the measured mass velocity profile, concerning the shape of the profile, the amplitude and the rate of decrease of the mass velocity along the detonation reaction zone. A possible explanation of a “leaning” of the beginning portion of the mass velocity profile observed in experiments has been proposed, and an estimate of the rise time of the sensor signal is given, taking into account the calculated curvature of the shock front of the detonation wave.

Enthalpy of the Cerium (Ce) Chemi-Ionization Reaction and CeO+, CeC+, and CeCO+ Bond Energies Determined by Energy-Resolved Guided Ion Beam Mass Spectrometry Experiments.

Cerium (Ce) oxide, carbide, and carbonyl cation bond energies and the exothermicity of the Ce chemi-ionization (CI) reaction with atomic oxygen were investigated using guided-ion beam tandem mass spectrometry (GIBMS). The kinetic energy dependent product cross sections for reactions of Ce+ with O2, CO, and CO2 and CeO+ with O2, CO, Xe, and Ar were measured using GIBMS. For the reactions of Ce+ with O2 and CO2, CeO+ is formed through an exothermic reaction, whereas CeO+ formation is endothermic in the reaction with CO. This reaction also forms CeC+ and CeCO+ is formed in the reaction of Ce+ with CO2, both in endothermic processes. Reactions of CeO+ with all four gases led to endothermic collision-induced dissociation as well as exchange reactions to form CeO2+ for the O2 and CO reactants. Bond dissociation energies (BDEs) at 0 K were determined through analyses of the kinetic energy dependent cross sections for all endothermic reactions. We determined that the BDEs of CeO+, CeC+, and CeCO+ are 8.46 ± 0.15, 3.93 ± 0.16, and ≥0.25 ± 0.07 eV, respectively, where the CeO+ BDE is a weighted average of 6 independent 0 K threshold measurements. The CeO+ BDE is combined with the ionization energy (IE) of Ce to determine an exothermicity of 2.91 ± 0.15 eV for the Ce + O → CeO+ + e- chemi-ionization reaction. Combined with neutral BDEs from the literature, the thermochemistry determined here also provides IE(CeO) = 5.03 ± 0.12 eV and IE(CeC) = 6.50 ± 0.16 eV. Theoretical calculations for ground and some excited states were performed for CeO+, CeC+, and CeCO+ to provide insight into the bonding and a comparison with the experimentally determined BDEs for each molecule.

A new dual-functional strategy to desensitize and sense the explosive and toxic 1,3,5-trinitro-1,3,5-triazinane by cyclo[n]carbons (n = 10,14,18).

In this work, in order to find new strategy to solve the safe problem of one famous high energy compound 1,3,5-trinitro-1,3,5-triazinane (RDX) under the impact and static electricity environment, cyclo[n]carbons (n = 10, C10; n = 14, C14; n = 18, C18) were employed to construct novel energetic composites (RDX@C10, RDX@C14, RDX@C18) with RDX for the first time. The investigated results showed that C10, C14 and C18 all can form stable composites with RDX through a exothermal process. Three cyclo[n]carbons could not only decrease the impact sensitivity of RDX by decreasing the positive ESP values and transferring the HPV region. But also could reduce the electrostatic sensitivity greatly by decreasing the energy gap, increasing the EHOMO and controlling the active electron-induced process and reaction. Among them, the desensitization effect by C18 and C14 was found to be much better than C10. In addition, three cyclo[n]carbons may be used as new sensors for the detection of RDX, due to the fast recovery time under different lights, and great change in the UV-Vis spectrum. These improvements may provide valuable insights for enhancing the safe performance of high energy compounds with similar structures to RDX, and broaden the application sphere of cyclo[n]carbons. All of the calculations on the structures were carried out by using the Gaussian 09 software at the M06-2X/6-311G(d,p) level. In addition, further calculations on the properties and interactions were performed by using the Multiwfn software.

Sustainable application of modified Luffa cylindrica biomass for removal of trimethoprim in water by adsorption with process optimization.

The present study describes a set of methodological procedures (seldom applied together), including (i) development of an alternative adsorbent derived from abundant low-cost plant biomass; (ii) use of simple low-cost biomass modification techniques based on physical processing and chemical activation; (iii) design of experiments (DoE) applied to optimize the removal of a pharmaceutical contaminant from water; (iv) at environmentally relevant concentrations, (v) that due to initial low concentrations required determination by ultra-performance liquid phase chromatography coupled to mass spectrometry (UPLC-MS/MS). A central composite rotational design (CCRD) was employed to investigate the performance of vegetable sponge biomass (Luffa cylindrica), physically processed (crushing and sieving) and chemically activated with phosphoric acid, in the adsorption of the antibiotic trimethoprim (TMP) from water. The optimized model identified pH as the most significant variable, with maximum drug removal (91.1 ± 5.7%) achieved at pH 7.5, a temperature of 22.5°C, and an adsorbent/adsorbate ratio of 18.6mgµg-1. The adsorption mechanisms and surface properties of the adsorbent were examined through characterization techniques such as scanning electron microscopy (SEM), point of zero charge (pHpzc) measurement, thermogravimetric analysis (TGA), specific surface area, and Fourier-transform infrared spectroscopy (FTIR). The best kinetic fit was obtained by the Avrami fractional-order model. The hypothesis of a hybrid behavior of the adsorbent was suggested by the equilibrium results presented by the Langmuir and Freundlich models and reinforced by the Redlich-Peterson model, which achieved the best fit (R2 = 0.982). The thermodynamic study indicated an exothermic, spontaneous, and favorable process. The maximum adsorption capacity of the material was 2.32 × 102µgg-1 at an equilibrium time of 120min. Finally, a sustainable and promising adsorbent for the polishing of aqueous matrices contaminated by contaminants of emerging concern (CECs) at environmentally relevant concentrations is available for future investigations.

Core-shell V2O5- Gum ghatti grafted poly (acrylamide-co-methacrylic acid) adsorbent for the removal of methylene blue dye in water: Kinetic, equilibrium and thermodynamic studies

Herein, vanadium pentoxide (V2O5) encapsulated Gum ghatti grafted poly(acrylamide-co- methacrylic acid) adsorbent was synthesized to remove methylene blue dye from water. The materials were characterized by FTIR, TEM, SEM, Raman and XRD analysis. Batch adsorption studies were performed on the materials. Several variables' effects on methylene blue removal, including pH, contact time, initial dye concentration, and adsorbent dosage, were examined. Kinetics and thermodynamic analysis were also carried out for the adsorbent-adsorbate interaction to determine the maximum adsorption and mechanism for adsorption. By using UV-Vis spectrophotometric analysis, the dye concentration was evaluated both before and after adsorption. Langmuir, Freundlich, and Dubini-Radushkevic's isotherm models were used to analyze the adsorption data. Results showed a maximum adsorption efficiency of 92 % at a pH of 9 and 0.2 g as the maximum adsorbent dosage. The study followed the Langmuir isotherm model with a correlation coefficient (R2) of 0.9995. The results from the kinetic studies show a pseudo-second-order mechanism. The negative values of the Gibbs free energy change ΔG° ranging from −10.57 KJmol−1 to −9.64 Kmol−1 within the temperatures of 298 K to 313 K is an indication of a spontaneous process. A negative enthalpy change (ΔH° = −29.05 KJmol−1) shows an exothermic process and a negative entropy change (ΔS° = −0.06 KJmol−1) represents a highly ordered system. ANOVA in Microsoft Excel and other statistical analyses were used to evaluate the effects of time, pH, concentration, dose, temperature, and other factors on the effectiveness of dye adsorption. Importantly, every parameter that was investigated showed statistically significant impacts on the removal of dye (p < 0.05), revealing their important impact on the adsorption process.

The development of exothermic surface reaction between coal and oxygen affected by methane during coal spontaneous combustion in gob

Coal spontaneous combustion (CSC) derives from the exothermic coal-oxygen reaction occurring at coal's surface. However, methane's influence on this process is still unclear in gob environments. To this end, non-isothermal experiments were performed to elucidate methane's impact on the exothermic effect, pore structure evolvement, and surface composite variation in CSC. Our findings indicated that methane inhibited the exothermic effect; however, low methane (<42.9 %) did not significantly reduce the danger of CSC, but increased methane explosion risk. Methane's influence on pore structure can be elevated by a higher temperature, leading to larger pores, greater surface area, and higher pore volumes. X-ray photoelectron spectroscopic analysis revealed an increase in C1s, C-C and C-H bonds with rising methane and a decrease in O1s and oxygen-containing groups. C-O groups were the main structures affected by methane. O1s and oxygen-containing groups remained stable at low (<20 %) and high (>50 %) methane concentrations, because coal lay in oxygen-rich and fuel-rich oxidation states, respectively. Methane's influence on exothermic reaction originates from competitive adsorption. Methane competes with oxygen and other gases for adsorption sites. This changes the surface properties and affects the competitive adsorption between methane and other gases. This study can provide valuable insights for mitigating CSC risk.

Cost-effective walnut shell biosorbent for efficient Cr(VI) removal from water: Batch adsorption and optimization using RSM-BBD

The conversion or recycling of waste materials into usable products is a sustainable and ecologically benign strategy, aligning with sustainable development and circular economy principles. This study presents a straightforward and cost-effective method for transforming walnut shells, commonly found in agricultural waste, into a biosorbent material highly effective in eliminating hexavalent chromium (Cr(VI)) from water. The prepared material underwent several analyses to determine its physical characteristics and surface chemistry, revealing an amorphous structure similar to lignocellulosic materials. Using Response Surface Methodology (RSM-BBD), we accurately forecasted and optimized the Cr(VI) adsorption process, evaluating and enhancing factors such as pH, biosorbent dosage, pollutant concentration, and adsorption time. Significant enhancement in the removal percentage (%R) was achieved, reaching 100 % after optimization. The RSM-BBD model provided high-quality prediction for data fitting (R² = 0.999). Various kinetic models, including PFO, PSO, and IPD models, were employed, with the PSO model providing the best depiction of adsorption. Equilibrium data analysis using the Langmuir, Freundlich, Redlich-Peterson and Temkin models revealed that the Freundlich model and R-P better fit the adsorption isotherm of Cr(VI) on treated walnut shell (WST). Furthermore, examination of Gibbs free energy and enthalpy indicated that the adsorption of Cr(VI) onto walnut shells is a spontaneous and exothermic reaction, resulting in the release of thermal energy.

Long-Term Distributed Temperature Sensing Monitoring for Near-Wellbore Gas Migration and Gas Hydrate Formation

Summary Well integrity monitoring has always been a critical component of subsurface oil and gas operations. Distributed fiber-optic sensing is an emerging technology that shows great promise for monitoring processes, both in boreholes and in other settings. In this study, we present a case study of using distributed temperature sensing (DTS) technology to monitor a cemented and plugged well in the Alaska North Slope (ANS). The well was drilled as part of a long-term gas hydrate study, and the downhole DTS data were recorded over a period of approximately 2 years. By applying a temporal gradient and removing instrument instability noise, we reveal subtle (&amp;lt;0.001°C/h) thermal anomalies, which are characterized by brief warming periods followed by longer cooling periods at discrete depths along the borehole. The observed coherent events show an upward trajectory from deeper formations into the overlying permafrost interval, with the thermal anomalies concentrated in relatively coarse-grained sandstone layers. We also observe that the upward migration rate of the DTS anomalies varies with formation lithology and that there is a spatial and temporal correlation between the subsurface events and measured wellhead annular pressures. We interpret that the observed warming events represent the exothermic process of gas hydrate formation that is occurring in association with the upward migration of gas outside the well casing, and this interpretation is confirmed by numerical simulations. These observations demonstrate the ability of suitably processed DTS data to detect subtle processes and highlight the value of DTS technologies for wellbore integrity monitoring.

Effect of Fe-Co catalysis on the temperature field distribution during the growth of 3C-SiC fibers synthesised by microwave heating

Microwave heating produce local hot spots on materials, which result in uneven heating and other issues. Regulate the microwave temperature field using different catalyst combinations such as Fe (NO3)3·9H2O and Co (NO3)2·6H2O. The electromagnetic and temperature field distributions of 3C–SiC fibers and the molecular dynamics of the SiC interfacial growth process and interfacial oxidation reaction during microwave heating in the presence of a catalyst were simulated and calculated respectively. The results show that the combination of Fe and Co at 9 wt% catalyst concentration can effectively improve the electromagnetic loss capability of SiC fibers. The Fe and Co bimetallic catalysed synthesis of 3C–SiC fibers follows a vapor–liquid–solid growth mechanism. The Fe–Si and Fe–Co–Si alloy phases can induce 3C–SiC growth along (111) crystal faces. The simultaneous exothermic reactions provide a highly catalytically active growth environment that facilitates the enhancement of microwave temperature field uniformity. This phenomenon facilitated the synthesis of 3C–SiC fibers.

Multicomponent double Povarov reaction for julolidine: Synthesis and mechanistic insights

Julolidines constitute a class of N-heterocyclic molecules that behave as molecular rotors. Due to their fluorescent properties, they are applied in a wide range of technological fields, such as the production of solar cells, fluorescent biomarkers or bioimaging, and photoconductive materials. In the present work, we developed a methodology for the synthesis of julolidines through the one-pot tandem reaction-based application of multicomponent double Povarov reaction (MCPR) using BF3.OEt2 as the catalyst (25 mol%), star anise oil rich in trans-anethole as the substrate, and water as the solvent in reactions at room temperature. The julolidines were obtained with total yields ranging from 55 to 95 %. A mechanistic study allowed for the conclusion that these MCPRs take place through an ionic mechanism and also that released protons by the reaction between BF3.Et2O and water are involved in the catalytic process. After extracting the products from the reaction medium, the remaining aqueous phase containing the catalyst can be reused for up to six catalytic cycles with a minimal loss of catalytic efficiency. DFT calculations were conducted to investigate the catalytic cycle using BF3.Et2O and ZnCl2 as catalysts. The results indicate that the formation of iminium ions is a prerequisite for the progress of the reaction (MCPR). When BF3.Et2O and water are involved, the reaction proceeds via Brønsted catalysis, and the formation of iminium ions occurs in an exothermic and spontaneous process. However, when the ZnCl2 is used, the process is Lewis catalyzed to form the first iminium ion and is endergonic, shifting the equilibrium towards the reactants and inhibiting the cyclization.

Treatments Technology and Mechanisms of East Asia Black Cotton Soil

The East Asia black cotton soil (BCS) cannot be used as embankment filling directly due to its high clay content, liquid limit, plasticity index, and low CBR strength (CBR &lt; 3%). This study evaluates the effects of treating East Asia BCS with lime, volcanic ash, or a combination of both on its engineering properties. Experiments were conducted to analyze the basic physical properties, swelling characteristics, and mechanical properties of the treated soil. Results indicate that lime addition significantly reduces the free swelling rate, improves limit moisture content, increases optimum moisture content, decreases maximum dry density, and enhances CBR value. Although volcanic ash also improves BCS performance, its effects are less pronounced than those of lime. The combined treatment with lime and volcanic ash exhibits superior performance, greatly reducing expansion potential and significantly increasing soil strength. Specifically, a mixture of 3% lime and 15% volcanic ash optimizes the liquid limit, plasticity index, and CBR value to 49.2%, 23.8, and 24.7%, respectively, meeting the JTG D30-2015 requirements and reducing construction costs. The treatment mechanisms involve hydration exothermic reactions, volcanic ash reactions, and semipermeable membrane effects, which collectively enhance the soil’s properties by producing dense, high-strength compounds.

Fabrication of sulfur-based functionalized activated carbon as solid phase extraction adsorbent for selective analysis of selenite in water

Based on the important feature of sulfur with excellent selectivity toward selenite in the presence of selenate, a simple and low-cost adsorbent of solid phase extraction known as sulfur loading activated carbon (SAC-6) was successfully prepared and applied for selenite (Se(IV)) analysis in water. Microstructure and morphological characteristics of SAC-6 had been identified by XRD, TEM, BET and FT-IR. In the static adsorption experiments, Se(IV) could be separated in a wide range of pH values (pH=3–11). The retention process of Se(IV) onto SAC-6 was characterized as spontaneous exothermic reaction. An obvious change of adsorption mechanism occurred in static and dynamic adsorption processes shown that the behaviors followed monolayer and hybrid adsorption. The theoretical maximum adsorption capacity of SAC-6 calculated by Langmuir-Freundlich was 13.48 mg/g. The microcolumn filled with SAC-6 was applied to extract Se(IV) in water solution. The detection limit of Se(IV) analytical procedure was confirmed as 0.27 μg/L within a linear range of 10–1000 μg/L. A good precision with relative standard deviation of 1.34 % (100 μg/L, n = 6) was achieved. The high adaptability and accuracy of SAC-6 microcolumn was validated by analyzing natural water samples and certified reference materials. Our work successfully excavated the application value of the sulfur selectivity, and also provided a new adsorbent for Se(IV) extraction and analysis.

Understanding the thermodynamic effects of chemically reactive working fluids in the Stirling heat pump

Within the realm of sustainable heating technologies, this study examines the performance of a Stirling heat pump employing chemically reactive working fluids in contrast to conventional inert counterparts. Reactive working fluids are energy vectors that enable the conversion of not only thermal but also chemical energy within the heat pump. The investigation spans a wide range of theoretical reactive gaseous mixtures, leveraging the ideal gas mixture thermodynamic model. Each fluid is characterized by an equilibrated chemical reaction, denoted as A2(g)⇄2A(g), and distinguished by a set of reaction coordinates: the standard entropy change of reaction and standard enthalpy change of reaction. The chemical reaction evolution and thermodynamic properties are observed in each transformation, and the overall coefficient of performance (COP) of the system is evaluated and benchmarked against that of comparable inert working fluids. It is observed that the exothermic reaction during isothermal compression significantly increases the thermal energy supplied to the heat sink, as well as the thermal energy density per unit maximum volume, by up to 269 %, compared to an inert gas system. However, for the majority of reactive fluids studied, chemical reactions introduce irreversibility in the internal regenerator due to heat transfer across a finite temperature difference, contrary to the case of inert working fluids, penalizing the COP. Consequently, a reduction of up to 28 % in the COP is observed. Nevertheless, there exists a range of reactive fluids, characterized by reversible heat exchange in the internal regenerator, offering increased thermal energy transfer to the heat sink without compromising the COP.

Effect of environmental factors on adsorption of ciprofloxacin from wastewater by microwave alkali modified fly ash

Antibiotics, as emerging persistent pollutants, pose significant threats to human health. The effective and low-cost removal of ciprofloxacin (CIP) from wastewater has become an important research focus. In this study, fly ash (FA) was used as the raw material, and modified fly ash (MFA) was prepared by varying microwave power, alkali concentration, and immersion time to investigate its adsorption characteristics for CIP. Results showed that the optimal preparation conditions for MFA with the most effective adsorption of CIP, using the Box-Behnken response surface methodology, were a microwave power of 480 W, an alkali concentration of 1.5 mol/L, and a modification time of 3 h. Scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction analyses revealed that after modification, the glassy structure of FA is destroyed, the specific surface area is increased, and obvious hydroxyl O–H absorption peaks appear. Both FA and MFA exhibited adsorption processes for CIP that conformed to pseudo-second-order kinetics and the Langmuir equation. Maximum adsorption of CIP (9.61 and 12.67 mg/g) was achieved at pH = 6. With increasing temperature, the adsorption capacity of both FA and MFA for CIP decreased, indicating an exothermic process. The adsorption capacity of CIP decreased with increasing ion concentration, with the impact order of ions being Al3+ > Ca2+ > Na+. The results show that pore filling, electrostatic interaction, ion exchange and complexation are the main ways of CIP adsorption by FA. Microwave alkali modified fly ash is an economical and efficient adsorbent for CIP removal in water, realizing the purpose of “treating waste with waste”. This study provides a scientific basis for controlling CIP treatment in wastewater.

Copper supported Dowex50WX8 resin utilized for the elimination of ammonia and its sustainable application for the degradation of dyes in wastewater

To obtain high efficient elimination of ammonia (NH4+) from wastewater, Cu(II), Ni(II), and Co(II)) were loaded on Dowex-50WX8 resin (D-H) and studied their removal efficiency towards NH4+ from aqueous solutions. The adsorption capacity of Cu(II)-loaded on D-H (D-Cu2+) towards NH4+ (qe = 95.58 mg/g) was the highest one compared with that of D-Ni2+ (qe = 57.29 mg/g) and D-Co2+ (qe = 43.43 mg/g). Detailed studies focused on the removal of NH4+ utilizing D-Cu2+ were accomplished under various experimental conditions. The pseudo-second-order kinetic model fitted well the adsorption data of NH4+ on D-Cu2+. The non-linear Langmuir model was the best model for the adsorption process, producing a maximum equilibrium adsorption capacity (qmax = 280.9 mg/g) at pH = 8.4, and 303 K in less than 20 min. The adsorption of NH4+ onto D-Cu2+ was an exothermic and spontaneous process. In a sustainable step, the resulting D-Cu(II)-ammine composite from the NH4+ adsorption process displayed excellent catalytic activity for the degradation of aniline blue (AB) and methyl violet 2B (MV 2B) dyes utilizing H2O2 as an eco-friendly oxidant.

The Electrochemical Peroxydisulfate-Oxalate Autocatalytic Reaction.

Aqueous solutions containing both the strong oxidant, peroxydisulfate (S2O82-), and the strong reductant, oxalate (C2O42-), are thermodynamically unstable due to the highly exothermic homogeneous redox reaction: S2O82- + C2O42- → 2 SO42- + 2 CO2 (ΔG0 = -490 kJ/mol). However, at room temperature, this reaction does not occur to a significant extent over the time scale of a day due to its inherently slow kinetics. We demonstrate that the S2O82-/C2O42- redox reaction occurs rapidly, once initiated by the Ru(NH3)62+-mediated 1e- reduction of S2O82- to form S2O83•-, which rapidly undergoes bond cleavage to form SO42- and the highly oxidizing radical SO4•-. Theoretically, the mediated electrochemical generation of a single molecule of S2O83•- can initiate an autocatalytic cycle that consumes both S2O82- and C2O42- in bulk solution. Several experimental demonstrations of S2O82-/C2O42- autocatalysis are presented. Differential electrochemical mass spectrometry measurements demonstrate that CO2 is generated in solution for at least 10 min following a 30-s initiation step. Quantitative bulk electrolysis of S2O82- in solutions containing excess C2O42- is initiated by electrogeneration of immeasurably small quantities of S2O83•-. Capture of CO2 as BaCO3 during electrolysis additionally confirms the autocatalytic generation of CO2. First-principles density functional theory calculations, ab initio molecular dynamics simulations, and finite difference simulations of cyclic voltammetric responses are presented that support and provide additional insights into the initiation and mechanism of S2O82-/C2O42- autocatalysis. Preliminary evidence indicates that autocatalysis also results in a chemical traveling reaction front that propagates into the solution normal to the planar electrode surface.

Preparation of Co x Mg y Cu(1- x - y )Fe2O4 nanoparticles and their adsorption mechanism of methyl blue

A facile rapid-combustion process was introduced for preparing magnetic Co x Mg y Cu(1- x - y )Fe2O4 nanoparticles, and to enhance their specific surface area and saturation magnetization, the optimization involved adjusting the element proportion, calcination temperature, and solvent amount. The optimal element proportion of x:y:(1-x-y) for Co x Mg y Cu(1- x - y )Fe2O4 nanoparticles was 0.1:0.7:0.2, and the effects of solvent amount, and calcination temperature were also investigated. The average particle size and specific surface area of Co0.1Mg0.7Cu0.2Fe2O4 nanoparticles calcined at 400 °C with 25 mL absolute alcohol were 17.9 nm and 56.96 m2/g, respectively; while demonstrating a saturation magnetization of 8.5 emu/g. To solve the increasingly severe issue of water pollution, these nanoparticles were employed to efficiently treat dye wastewater containing methyl blue (MB). After fitting kinetic and isotherm models, the adsorption process of magnetic Co0.1Mg0.7Cu0.2Fe2O4 nanoparticles for MB dominated by chemisorption and was a multilayer adsorption process. The adsorption isotherm experiments revealed a remarkable maximum adsorption capacity of methyl blue, reaching 2255.7 mg/g, within the concentration range of MB from 400 to 4000 mg/L. The thermodynamic analysis indicated the spontaneity of the exothermic adsorption process. The studies on the effect of pH also led to satisfying results; while the residual adsorption capacity could still remain 91.2% initial adsorbance after 12 times recycle. The outstanding recycling ability, resistance to ionic strength, and pH resistance distinguished the magnetic Co0.1Mg0.7Cu0.2Fe2O4 nanoparticles among vast adsorbents. These results highlight the significant potential of these nanoparticles for treating dye wastewater.

Optimizing rotary kiln operations for molybdenite concentrate oxidation roasting to produce molybdic trioxide

The effects of the rotational speed (0–10 rpm) and temperature (550–650 °C) of rotary kiln drums on the oxidation roasting of molybdenite (MoS2) concentrate was investigated in this study. Computational predictions indicated that production of MoO2 was more favorable than that of MoO3 up to a certain stage of the oxidation roasting process, after which MoO3 is produced through the consumption of MoO2. Thus, understanding the MoS2–MoO2–MoO3 relationship and its equilibrium is important. A drum rotational speed > 5 rpm significantly increased the S reduction rate and considerably decreased the S content at 60 min to < approx. 5 %. Additionally, the S content at 60 min decreased with decreasing the temperature from 650 to 550 °C due to the MoS2 concentrate exothermic reaction during oxidation roasting. The MoS2 to MoxOy (≈ MoO2+MoO3) conversion rate (%) was generally proportional to the rotational speed and reaction duration. X-ray diffraction analysis indicated that 5–10 rpm and 550–600 °C yielded a higher experimental conversion rate (97–98 %). Furthermore, the MoO2 and MoO3 conversions were separately quantified. Agglomeration was more pronounced without drum rotation and at higher temperatures. Analysis of the reaction kinetics using the unreacted-core model indicated that diffusion through the gas film layer is supported by the 20.9 kJ/mol activation energy obtained from the Arrhenius plot. Consequently, an appropriate drum rotational speed at a relatively low temperature is a prerequisite for producing MoO3 through the oxidation roasting of MoS2 concentrates in a rotary kiln.

Insights on the separation process of the diethyl carbonate plant obtained by ethanol and CO2

This paper presents the techno-economics insights of projects of diethyl carbonate (DEC) production from ethanol and CO2 in which the raw materials are proposed to be obtained from existing plants such as the bioethanol industry. The complete DEC plant was simulated using Aspen Plus®. The exothermic reaction system was modeled in multitubular PFR with CeO2 catalyst and dehydrating agent 2-cyanopyridine (2-CP), achieving an EtOH conversion of 86.04 % and a yield of DEC of 83.34 %. Three different configurations were evaluated in the DEC separation stage aiming to intensify the plant with the use of a sidestream distillation column and reactive distillation column. The integration of the DEC plant with ethanol and sugar biorefineries, offering lower-cost acquisition of raw materials, is the key to making the process economically profitable. The process has the potential to capture 0.088–0.204 kg CO2/kg DEC, demonstrating a promising pathway to extend the life cycle of renewable carbon.