Search Results (96)

To ensure the inherent safety of fine chemical nitration processes, the nitration reaction of benzotriazole ketone was selected as the research object. The thermal decomposition and reaction characteristics of the nitration system were studied using a combination of differential scanning calorimetry (DSC), reaction calorimetry (RC1), and accelerating rate calorimetry (ARC). The results showed that the nitration product released 455.77 kJ/kg of heat upon decomposition, significantly higher than the 306.86 kJ/kg of the original material, indicating increased thermal risk. Through process hazard analysis based on GB/T 42300-2022, key parameters such as the temperature at which the time to maximum rate is 24 h under adiabatic conditions (T_D24), maximum temperature of the synthesis reaction (MTSR), and maximum temperature for technical reason (MTT) were determined, and the reaction was classified as hazard level 5, suggesting a high risk of runaway and secondary explosion. Process intensification strategies were then proposed and verified by dynamic calorimetry: the adiabatic temperature increase (ΔT_ad) was reduced from 86.70 °C in the semi-batch reactor to 19.95 °C in the optimized continuous process, effectively improving thermal safety. These findings provide a reliable reference for the quantitative risk evaluation and safe design of nitration processes in fine chemical manufacturing. Full article

Carbon monoxide (CO) is classified as a simple fuel that contains one carbon and one oxygen atom. The oxidation of CO with an oxidizer is relatively unusual, with the oxidation of CO having a slow reaction time. The addition of a small amount of “hydrogenous” species, such as H₂, H₂O, and CH₄, will substantially increase the reaction time. This study numerically investigated and compared the effects of different hydrogenous species addition on the premixed CO/air flames, which act as the initiation of a CO/air flame, on the adiabatic flame temperature, laminar flame speed, and heat release rates at standard conditions (298 K and 1 atm pressure) using San Diego Mechanism. The results showed that the addition of critical hydrogenous species distinguished the difference between dry and wet CO/air oxidation, in which different hydrogenous species have an identical critical value. Adding different hydrogenous species and different addition ratios has an indistinguishable adiabatic flame temperature, while adding CH₄ has a higher laminar flame speed distribution compared with H₂ and H₂O addition, respectively. Furthermore, the laminar flame speed positively correlates with the net heat release rate, which adding CH₄ has a noticeable increase on the net heat release rate. Adding more hydrogenous species makes the reactant more reactive and moves the reaction zone upstream. Finally, the dominant reactions to the heat release rate are identical in different hydrogenous species addition, where R23: CO + O (+M) ⇌ CO₂ (+M) becomes the most contributed reaction. Full article

Sodium-ion batteries (SIBs) share similar working principles with lithium-ion batteries while demonstrating cost advantages. However, the current understanding of their safety characteristics remains insufficient, and the thermal runaway mechanisms of different SIB systems have not been fully elucidated. This study investigated the following two mainstream sodium-ion battery systems: polyanion-type compound (PAC) and layered transition metal oxide (TMO) cathodes. Differential scanning calorimetry (DSC) was employed to evaluate the thermal stability of cathodes and anodes, examining the effects of state of charge (SOC), cycling, and overcharging on electrode thermal stability. The thermal stability of electrolytes with different compositions was also characterized and analyzed. Additionally, adiabatic thermal runaway tests were conducted using an accelerating rate calorimeter (ARC) to explore temperature–voltage evolution patterns and temperature rise rates. The study systematically investigated heat-generating reactions during various thermal runaway stages and conducted a comparative analysis of the thermal runaway characteristics between these two battery systems. Full article

Recent observations have increasingly challenged the conventional understanding of atmospheric NH₃ and its potential sources in remote environments. Laboratory studies suggest that the microdroplet redox generation of NH₃ could offer an alternative explanation. However, key questions remain: (1) Can microdroplet redox generation of NH₃ occur in ambient air? (2) Is it restricted by the presence of specific catalysts? (3) What factors determine the efficiency of ambient NH₃ generation via microdroplet redox reactions? We investigate these questions based on adiabatic-expansion-induced perturbation observations performed in various atmospheres over the last decade. Our results indicate the adiabatic-expansion-induced generation of NH₃ + HNO₃ at ultrafast formation rates, with campaign-dependent stable stoichiometric ratios of HNO₃ to NH₃, as well as highly variable occurrence frequencies and efficiencies. These findings suggest that microdroplet redox reactions are more likely responsible for the generation of NH₃ + HNO₃ than conventional atmospheric NH₃ chemistry. Moreover, our analysis suggests that the line speed of microdroplets may be one of the key factors in determining the occurrence, stoichiometric ratio and efficiency of the redox reaction. Additionally, the presence of sea salt aerosols and low ambient temperature, rather than the specific catalysts, may significantly influence these processes. However, the current observational data do not allow us to derive a functional relationship between the redox reaction rate and these parameters, nor to fully detail the underlying chemistry. Comprehensive and controlled laboratory experiments, similar to our adiabatic-expansion-induced observations but utilizing state-of-the-art highly sensitive analyzers, would be necessary, though such experiments are beyond our current capabilities. Full article

This study investigates the combustion characteristics of silicon-based time-delay compositions with bismuth(III) oxide (Bi₂O₃), antimony(III) oxide (Sb₂O₃), and lead(II,IV) oxide (Pb₃O₄) to identify formulations with pressure-independent burn rates. Unlike conventional pyrotechnic compositions, silicon-based mixtures offer an improved energy density and reduced sensitivity to pressure variations. The linear combustion rate of the compositions was determined for a wide range of silicon contents and for different compaction pressures. Experimental results show that burn rates range from 8 mm s⁻¹ to 195 mm s⁻¹, depending on the metal oxide type and silicon content. The highest rate (195 mm s⁻¹) was observed for Si/Pb₃O₄ at 30 wt.% silicon, while Si/Sb₂O₃ had the lowest (10 ÷ 35 mm s⁻¹). The calorimetric heat of combustion varied between 1200 J g⁻¹ and 1400 J g⁻¹, with adiabatic combustion temperatures reaching 2200 K, calculated from this heat. DTA and XRD confirmed the condensed-phase combustion, forming reduced metal phases and silicon oxides. SEM and EDS revealed a porous residue structure. This work introduces a novel approach to time-delay compositions using silicon as a primary fuel. It shows that specific silicon oxide–metal systems maintain stable combustion for different loading pressures and advance pyrotechnic formulations for safer and more efficient industrial and defense applications. Full article

Nanothermites as high-energy-density and high-reaction-rate materials have important applications in civil and military fields. Nevertheless, it is difficult to detect all intermediates and products using conventional experimental methods. In this work, the reaction process of core-shell SiO₂@Al nanoparticles under adiabatic conditions was investigated through molecular dynamics simulations using a reactive force field (ReaxFF). In the microcanonical ensemble, the redox reaction of SiO₂@Al nanothermite becomes explosive due to the huge energy release during Al-O bond formation. The gaseous products are mainly the intermediate products Al₅O and Al₄O as well as the final products Al₂O, AlO, Si and Al. Analyses of the steric charge distributions and evolution show that the Coulomb effect causes the number of intermediates Al₅O (0.32|e|) to increase to the maximum, then slowly decrease and remain stable. But the tetrahedral Al₄O cluster is almost charge-neutral, at −0.05|e|, and the number remained almost constant. This work is expected to provide deeper insights into the complex reaction mechanism of nanothermite. Full article

We present the first step toward the quantum computing (QC) formulation of the electron nuclear dynamics (END) method within the variational quantum simulator (VQS) scheme: END/QC/VQS. END is a time-dependent, variational, on-the-flight, and non-adiabatic method to simulate chemical reactions. END represents nuclei with frozen Gaussian wave packets and electrons with a single-determinantal state in the Thouless non-unitary representation. Within the hybrid quantum/classical VQS, END/QC/VQS currently evaluates the metric matrix M and gradient vector V of the symplectic END/QC equations on the QC software development kit QISKIT, and calculates basis function integrals and time evolution on a classical computer. To adapt END to QC, we substitute the Thouless non-unitary representation with Fukutome unitary representation. We derive the first END/QC/VQS version for pure electronic dynamics in multielectron chemical models consisting of two-electron units with fixed nuclei. Therein, Fukutome unitary matrices factorize into triads of one-qubit rotational matrices, which leads to a QC encoding of one electron per qubit. We design QC circuits to evaluate M and V in one-electron diatomic molecules. In log2-log2 plots, errors and deviations of those evaluations decrease linearly with the number of shots and with slopes = −1/2. We illustrate an END/QC/VQS simulation with the pure electronic dynamics of H₂⁺ We discuss the present results and future END/QC/QVS extensions. Full article

The formation of the four 3-ring systems c-(CH₂)_3−k(SiH₂)_k ($k=0$: cyclopropane, $k=1$: silirane, $k=2$: disilirane, $k=3$: cyclotrisilane) by addition of methylene and silylene to the double bond in ethene, disilene, and silaethene, as well as the elimination of the carbene analogs from the 3-rings, was studied with CAS(4,4) wave functions in both $C_{2v}$ and $C_s$ symmetry. To reveal the charge and spin redistribution during these reactions the CAS(4,4) wave functions were analyzed using the orthogonal valence bond method (OVB). The potential energy curves, different internal coordinates, and the results of the OVB analysis show that, frequently, the addition and elimination reactions follow different minimum energy paths, because they are indeed diabatic reactions. In these cases, there are no energy barriers corresponding to saddle points on the potential energy surfaces but the energy increases during one diabatic reaction until, at a certain point, the system jumps to the other diabatic state and, in the following, the energy decreases. This happens for reactions in $C_{2v}$ symmetry; as soon as the system can change to the lower symmetry, the diabatic states combine to an adiabatic one and the reaction follows a single minimum energy path. Full article

This article theoretically investigates the interaction of a normal shock wave in a flow with chemical reactions under high-temperature conditions. The main novelty of the work is that the thermal effect of chemical reactions is modeled as a function of the temperature. A modified Rankine–Hugoniot model for a shock wave in a flow with chemical reactions has been developed. It is shown that for an exothermic reaction the pressure jump increases with increasing Arrhenius numbers. This is due to the additional energy introduced into the flow as heat is released during the chemical reaction. For endothermic reactions, the opposite trend is observed. The change in the speed of the adiabatic gas flow as it passes through a normal shock wave depending on the type of chemical reaction is clarified. The study provides comparisons between the results of the analytical and numerical solutions of the modified Hugoniot adiabatic equations. Full article

Fired heaters upstream of distillation towers, despite their optimal thermal efficiency, often suffer from performance decline due to fluctuations in fuel composition and unpredictable operational parameters. These heaters have high energy consumption, as fuel properties vary depending on the source of the crude oil. This study aims to optimize the combustion process of a three-gas mixture, mainly refinery gas, by incorporating more stable fuels such as natural gas and liquefied petroleum gas (LPG) to improve energy efficiency and reduce LPG consumption. Using real-time gas chromatography-mass spectrometry (GC-MS) data, we accurately calculate the mass fractions of individual compounds, allowing for more precise burner flow rate determinations. Thermochemical data are used to calculate equilibrium constants as a function of temperature, with the least squares method, while the Newton–Raphson method solves the resulting nonlinear equations. Four key variables ($X_4,X_6,X_8,$ and $X_{11}$), representing $H_2,CO,O_2,$ and $N_2$, respectively, are defined, and a Jacobian matrix is constructed to ensure convergence within a tolerance of 1 ×${10}^{-6}$ over a maximum of 200 iterations, implemented via Python 3.10.4 and the scipy.optimize library. The optimization resulted in a reduction in LPG consumption by over 50%. By tailoring the fuel supply to the specific thermal needs of each processing unit, we achieved substantial energy savings. For instance, furnaces in the hydrocracking unit, which handle cleaner subproducts and benefit from hydrogen’s adiabatic reactions, require much less energy than those in the primary distillation unit, where high-impurity crude oil is processed. Full article

Thermal decomposition (pyrolysis) of coal bottom ash (collected after lignite combustion in coal-fired power plant TEKO-B, Republic of Serbia) was investigated, using the simultaneous TG-DTG techniques in an inert atmosphere, at various heating rates. By using the XRD technique, it was found that the sample (CBA-TB) contains a large amount of anorthite, muscovite, and silica, as well as periclase and hematite, but in a smaller amount. Using a model-free kinetic approach, the complex nature of the process was successfully resolved. Thermodynamic analysis showed that the sample is characterized by dissociation reactions, which are endothermic with positive activation entropy changes, where spontaneity is achieved at high reaction temperatures. The model-based method showed the existence of a complex reaction scheme that includes two consecutive reaction steps and one single-step reaction, described by a variety of reaction models as nucleation/growth phase boundary-controlled, the second/n-th order chemical, and autocatalytic mechanisms. It was established that an anorthite I1 phase breakdown reaction into the incongruent melting product (CaO·Al₂O₃·2SiO₂) represents the rate-controlling step. Autocatalytic behavior is reflected through chromium-incorporated SiO₂ catalyst reaction, which leads to the formation of chromium(II) oxo-species. These catalytic centers are important in ethylene polymerization for converting light olefin gases into hydrocarbons. Adiabatic T_D24 prediction simulations of the process were also carried out. Based on safety analysis through validated kinetic parameters, it was concluded that the tested sample exhibits high thermal stability. Applied thermal treatment was successful in promoting positive changes in the physicochemical characteristics of starting material, enabling beneficial end-use of final products and reduction of potential environmental risks. Full article

Methane photolysis is a very important initiation reaction from the perspective of hydrogen production for alternative energy applications. In our recent work, we demonstrated using our recently developed novel method, non-adiabatic excited-state time-dependent $GW$ (TD$GW$) molecular dynamics (MD), how the decomposition reaction of methane into a methyl radical and a hydrogen atom was captured accurately via the time-tracing of all quasiparticle levels. However, this process requires a large amount of photoabsorption energy (PAE ∼$10.2$ eV). Moreover, only one hydrogen atom is produced via a single photon absorption. Transition metal atoms can be used as agents for photochemical reactions, to reduce this optical gap and facilitate an easier pathway for hydrogen production. Here, we explore the photolysis of methane in the presence of a Ni atom by employing TD$GW$-MD. We show two possibilities for hydrogen-atom ejection with respect to the location of the Ni atom, towards the Ni side or away from it. We demonstrate that only the H ejection away from the Ni side facilitates the formation of a hydrogen molecule with the quasiparticle level corresponding to it having an energy close to the negative ionization potential of an isolated H₂ molecule. This is achieved at a PAE of 8.4 eV which is lower compared to that of pristine methane. The results obtained in this work are an encouraging step towards transition metal-mediated hydrogen production via photolysis of hydrocarbons. Full article

It has been found out that Pd-Co-based catalyst, supported on anodized aluminum, possesses very high activity in combustion reactions of C₁–C₆ alkanes and toluene. The catalyst characterization has been made by N₂-pysisorption, XRD, SEM, XPS, FTIR, TEM, and EPR methods. In view of the great interest, methane combustion was investigated in detail. It is ascertained that the complete oxidation of methane proceeds by dissociative adsorption on PdO and formation of hydroxyl and methyl groups, the former being highly reactive, and it undergoes further reaction to oxygen-containing intermediates, whereupon HCHO is one of them. The presence of Co²⁺ cations promotes greatly oxygen adsorption. The dissociative adsorption is favored on neighboring Co²⁺ cations, leading to the formation of bridging peroxides. Further, the oxygen dissociates on the nearest Pd²⁺ cations. According to the results from the experimental data, instrumental methods, and the observed kinetics and DFT model calculations, it can be concluded that the reaction pathway over Pd+Co/anodic alumina support (AAS) catalyst proceeds most probably through Mars–van Krevelen. The obtained data on the kinetics were used for simulation of the methane combustion in a full-scale adiabatic reactor. Full article

This research paper explores the use of machine learning to relate images of flame structure and luminosity to measured NOx emissions. Images of reactions produced by 16 aero-engine derived injectors for a ground-based turbine operated on a range of fuel compositions, air pressure drops, preheat temperatures and adiabatic flame temperatures were captured and postprocessed. The experimental investigations were conducted under atmospheric conditions, capturing CO, NO and NOx emissions data and OH* chemiluminescence images from 27 test conditions. The injector geometry and test conditions were based on a statistically designed test plan. These results were first analyzed using the traditional analysis approach of analysis of variance (ANOVA). The statistically based test plan yielded 432 data points, leading to a correlation for NOx emissions as a function of injector geometry, test conditions and imaging responses, with 70.2% accuracy. As an alternative approach to predicting emissions using imaging diagnostics as well as injector geometry and test conditions, a random forest machine learning algorithm was also applied to the data and was able to achieve an accuracy of 82.6%. This study offers insights into the factors influencing emissions in ground-based turbines while emphasizing the potential of machine learning algorithms in constructing predictive models for complex systems. Full article

Cement-based construction materials, commonly known as “cement concrete”, result from the hydration reaction of cement, which releases heat. Numerous studies have examined the heat of cement hydration and other thermal properties of these materials. However, a significant gap in the literature is the assessment of the impact of the hydration temperature on the material’s strength, particularly compressive strength. This work presents an experimental methodology that consistently estimates the temperature evolution of a mixture used to manufacture concrete or mortar during the first hours of Portland cement hydration. The methodology aims to ensure results that correspond to an infinite medium (adiabatic conditions), where there are no heat losses to the surroundings. Results obtained under adiabatic conditions (simulating an infinite medium) indicate that a ready-made mortar (Portland cement: sand: water; 1:2.5:0.5) can reach temperatures of approximately 100 °C after 48 h of hydration. Under these conditions, compressive strength decreases by up to 20%. Full article