Mechanism Of Thermal Reaction Research Articles

State-of-the-Art Light-Driven Hydrogen Generation from Formic Acid and Utilization in Enzymatic Hydrogenations.

A concept of combining photocatalytically generated hydrogen with green enzymatic reductions is demonstrated. The developed photocatalytic formic acid (FA) dehydrogenation setup based on Pt(x)@TiO2 shows unprecedented hydrogen generation activity, which is two orders of magnitude higher than reported values of state-of-the-art systems. Mechanistic studies confirm that hydrogen generation proceeds via a photocatalytic pathway, which is entirely different from purely thermal reaction mechanisms previously reported. The viability of the presented approach is demonstrated by the synthesis of value-added compounds 3-phenylpropanal and (2R, 5S)-dihydrocarvone at ambient pressure and room temperature, which should be applicable for many other hydrogenation processes, e.g., for the preparation of flavours and fragrance compounds, as well as pharmaceuticals.

Research on the dynamics and mechanism of thermal cracking of coal-based endothermic hydrocarbon fuels

Thermal cracking of endothermic hydrocarbon fuels (EHF) plays an important role in the endothermic process when the fuel temperature exceeds the supercritical temperature. To gain a deeper understanding of the thermal cracking behavior of EHF, this work discusses the thermal cracking law and reaction mechanism of coal-based EHF at different temperatures through static thermal cracking experiments, and establishes a total molecular reaction dynamics model containing 34 species and 24-step reactions based on product distribution. The results show that in the temperature range of 450℃ to 500℃, the gas phase yield of the fuel increases linearly from 8% to 56%, and the conversion rate reaches up to 96.1%. The kinetic reaction of thermal cracking conforms to the primary kinetic equation, the cracking rate constant k is between 1.08×10-4~7.92×10-4s-1, the activation energy Ea=184.47±11.5kJ∙mol-1, and the precursor factor lnA=21.61±3.0. Gas phase products include hydrogen, methane, ethane, ethylene, propane and butane. Liquid phase products include paraffins, alkyldecahydronaphthalenes and aromatic hydrocarbons. As the cracking depth increases, the degree of fuel branching first increases and then decreases, up to 0.33. Paraffins and alkyldecahydronaphthalenes are gradually converted into olefins, cyclic olefins, benzene, naphthalene, indene, fluorene and pyrene and other compounds. Based on the product distribution, the reaction mechanism of thermal cracking of coal-based EHF is speculated to include single-molecule β-cracking, bimolecular F-S-S, intramolecular H-transfer, cyclization and isomerization mechanisms.

Investigation of kinetics, reaction mechanisms, thermodynamics, and synergetic effects in co-pyrolysis of wood sawdust and linear low-density polyethylene using the thermogravimetric approach.

This study focused on investigating thermal degradation behaviors, kinetics, reaction mechanisms, synergistic effects, and thermodynamic parameters of wood sawdust (WSD), linear low-density polyethylene (LLDPE), and their blends (LW1:3, LW1:1, and LW3:1) during co-pyrolysis in a thermogravimetric analyzer (TGA). Thermal behavior exhibited a LW1:3 blend (25 wt.% LLDPE) showing significant mass loss at lower temperatures (150 to 300°C) compared to the individual feedstocks, such as 150 to 400°C and 300 to 520°C for WSD and LLDPE, respectively. The iso-conversional methods (KAS, FWO, and FM) were used to determine the kinetic parameters (Ea and A), and the activation energy drop was highest for the LW1:3 blend. According to the master plots, the third-order reaction (O3), nucleation (P2/3), and diffusional model (D4) were the predominant reaction mechanisms for the co-pyrolysis of the LW1:3, LW1:1, and LW3:1 blend, respectively. The thermodynamic parameters demonstrate that a small amount of plastic addition into WSD can improve the reactivity of the blend, shorten the reaction time, and cause less energy-intensive reactions. The values of ΔH, ΔG, and ΔS also confirmed the co-pyrolysis process's spontaneity and endothermic nature. The Fourier transforms infrared spectrometer (FTIR) spectra of raw feedstock, blends, and their biochar revealed some of the peaks were shifted, the intensity was reduced, and disappearance can happen when the temperature was increased. Using the experimental and theoretical/predicted activation energies, the parity chart illustrates the synergistic effects of co-pyrolysis of different blends, and the LW1:3 blend has a favorable synergistic impact. These results could be helpful in process optimization and designing an effective reactor system for co-pyrolysis.

Aza-Diarylethenes Undergoing Both Photochemically and Thermally Reversible Electrocyclic Reactions.

Exploring novel molecular photoswitches plays a crucial role in the field of photo-functional materials chemistry. In this study, we synthesized aza-diarylethenes with benzothiophene-S,S-dioxide as apart of hexatriene structureand investigated their photochromic properties. Unlike previously reported aza-diarylethenes, which exhibit fast thermally reversible photochromism, the compounds synthesized here exhibited pseudo-photochemically reversible photochromism. Due to their thermal stability, we successfully isolated the colored isomer. X-ray crystallographic analysis revealed for the first time that the colored isomer adopts a closed-ring structure with a bond between carbon and nitrogen atoms. Remarkably, these aza-diarylethenes exhibited not only photochemical ring-closing and ring-opening reactions but also thermal ring-closing and ring-opening reactions, driven by a thermal equilibrium between the open- and closed-ring isomers. This behavior, unprecedented for common diarylethenes, was elucidated through kinetic analysis, revealing an energy-level diagram for the thermal equilibrium between these isomers. Furthermore, 1H NMR spectroscopy revealed that both photochemically and thermally generated closed-ring isomers adopt the same structure, which was well explained based on the reaction mechanism of photochemical and thermal ring-closing reactions. These findings not only advance the field of aza-diarylethenes but also inspire future research in the development of new photoswitches.

Transient simulation of conjugate heat transfer of kerosene with thermal oxidative and surface coking reactions at a supercritical pressure

The regenerative cooling technology in aerospace applications often involves supercritical-pressure heat transfer of a hydrocarbon fuel, in which thermal oxidative reactions of the fuel would lead to surface coke accumulation on the cooling channel wall. In this paper, the long-term transient conjugate heat transfer of kerosene has been numerically investigated in a circular mini tube at a supercritical pressure of 3 MPa. The modified chemical mechanism and kinetics of thermal oxidative and surface coking reactions of kerosene are proposed, which, with an additional surface reaction, are capable of treating large coke deposition in regions with sharp temperature gradients. Transient surface coke accumulation and its effect on heat transfer are handled by a dynamic mesh technique. A series of numerical studies are conducted to elucidate the influences of surface heat flux, dissolved oxygen mass fraction, inlet fuel mass flow rate, and coke layer thermal conductivity on the supercritical-pressure heat transfer and thermal oxidative reactions. The effects of different reaction pathways on surface coke accumulation are analyzed comprehensively, and it is revealed that the oxygen-consuming surface coke deposition is initiated only at the high fuel temperature at around 590 K. The present numerical results would enhance fundamental understanding of the long-term transient heat transfer process of a hydrocarbon fuel at supercritical pressures in the regenerative cooling applications.

Study on the electrical-thermal properties of lithium-ion battery materials in the NCM622/graphite system.

The phenomenon of fire or even explosion caused by thermal runaway of lithium-ion power batteries poses a serious threat to the safety of electric vehicles. An in-depth study of the core-material thermal runaway reaction mechanism and reaction chain is a prerequisite for proposing a mechanism to prevent battery thermal runaway and enhance battery safety. In this study, based on a 24 Ah commercial Li(Ni0.6Co0.2Mn0.2)O2/graphite soft pack battery, the heat production characteristics of different state of charge (SOC) cathode and anode materials, the separator, the electrolyte, and their combinations of the battery were investigated using differential scanning calorimetry. The results show that the reaction between the negative electrode and the electrolyte is the main mode of heat accumulation in the early stage of thermal runaway, and when the heat accumulation causes the temperature to reach a certain critical value, the violent reaction between the positive electrode and the electrolyte is triggered. The extent and timing of the heat production behaviour of the battery host material is closely related to the SOC, and with limited electrolyte content, there is a competitive relationship between the positive and negative electrodes and the electrolyte reaction, leading to different SOC batteries exhibiting different heat production characteristics. In addition, the above findings are correlated with the battery failure mechanisms through heating experiments of the battery monomer. The study of the electro-thermal properties of the main materials in this paper provides a strategy for achieving early warning and suppression of thermal runaway in batteries.

Thermal behavior analysis and reaction mechanism in the preparation of activated carbon by ZnCl2 activation of bamboo fibers

In this study, bamboo powder (BP), bamboo parenchyma cells (PCs), and bamboo fibers (BFs) were used as precursors to prepare activated carbon by ZnCl2 one-step activation to investigate the differences in the pore structures of the three. The results showed that BFs-based activated carbon had a higher specific surface area (2129 m2/g). Subsequently, the activation reaction paths of the BFs-based activated carbon preparation process were analyzed and explored by TGA, XRD, TG-MS-FTIR, EA, and other analytical methods, and the reaction mechanism was inferred. The results showed that the main reaction below 220 °C was the breaking of molecular bonds of oxygen-containing functional groups on hemicellulose, and the pyrolysis by-products at this stage were dominated by small molecules such as H2O, CO2, CH4, CH3OH, and HCHO. The pyrolysis of cellulose and the activation reaction of ZnCl2 were the main reactions between 220 °C and 650 °C. ZnCl2 was a strong dehydrating agent that can form ZnOCl2·2 H2O with intramolecular water molecules, and gradually decompose to form ZnO with the increase in temperature, the main gaseous products in this temperature interval were mainly H2O, CO, CO2, C3H4, and CH4. Above 650 °C, pyrolysis was basically completed and continued to shift to the aromatic structure, with the gaseous products mainly being H2, H2O, CO2, CH4, CO, C3H4, and a small amount of CH3OH and HCHO.

Activation volume and quantum tunneling in the hydrogen transfer reaction between methyl radical and methane: A first computational study.

We present a theory of the effect of quantum tunneling on the basic parameter that characterizes the effect of pressure on the rate constant of chemical reactions in a dense phase, the activation volume. This theory results in combining, on the one hand, the extreme pressure polarizable continuum model, a quantum chemical method to describe the effect of pressure on the reaction energy profile in a dense medium, and, on the other hand, the semiclassical version of the transition state theory, which includes the effect of quantum tunneling through a transmission coefficient. The theory has been applied to the study of the activation volume of the model reaction of hydrogen transfer between methyl radical and methane, including the primary isotope substitution of hydrogen with deuterium (H/D). The analysis of the numerical results offers, for the first time, a clear insight into the effect of quantum tunneling on the activation volume for this hydrogen transfer reaction: this effect results from the different influences that pressure has on the competing thermal and tunneling reaction mechanisms. Furthermore, the computed kinetic isotope effect (H/D) on the activation volume for this model hydrogen transfer correlates well with the experimental data for more complex hydrogen transfer reactions.

Process optimization, thermal hazard evaluation and reaction mechanism of m-xylene nitration using HNO3-Ac2O as nitrating reagent

Nitro-m-xylenes (NMX) was synthesized in semi-batch mode via m-xylene nitration using nitric acid-acetic anhydride (HNO3-Ac2O) as nitrating reagent in this work. The nitration process was optimized by response surface methodology. The yield of NMX could reach 92.40% under the optimal conditions of jacket temperature of 20 °C, 0.15 mol of HNO3 and 0.19 mol of Ac2O. Corresponding large reaction enthalpy (ΔH=240.9 kJ/mol) and adiabatic temperature rise (ΔTad,r =398.1 K) indicated the serious hazards of nitration in a thermal runaway scenario. Pyrolysis of nitration products occurred at about 320–400 °C by differential scanning calorimetry tests. The reaction order of the pyrolysis was determined to be 1.2 by adiabatic kinetic analysis. Thermal risk of the nitration process was assessed to be acceptable and level 1 via the risk matrix and Stoessel criticality diagram analyses, respectively. Furthermore, detailed nitration mechanisms for NO2+ generation and aromatic substitution were presented. The activation free enthalpy and free energy parameters for each step were calculated by density functional theory (DFT). These findings can help understand the exothermic sources of m-xylene nitration and guide the intrinsically safer design and scale-up of the process.

Understanding the Molecular Mechanism of Thermal and LA-Catalysed Diels-Alder Reactions between Cyclopentadiene and Isopropyl 3-Nitroprop-2-Enate.

The molecular mechanism of the Diels-Alder reaction with the participation of cyclopentadiene and isopropyl 3-nitroprop-2-enate was examined based on wb97xd/6-311+G(d) (PCM) quantum chemical calculations. It was found that the type of mechanism for the conversion of addends depends significantly on the reaction conditions. In less-polar environments, a one-step polar mechanism is realised. In more polar solvents, the formation of "extended"-type zwitterionic intermediates is possible. In contrast, in the presence of an LA-type catalyst, the one-step mechanisms are replaced by respective stepwise mechanisms with zwitterionic or heterocyclic intermediates.

Thermal Stability and Outgassing Behaviors of High-nickel Cathodes in Lithium-ion Batteries.

LiNiO2 -based high-nickel layered oxide cathodes are regarded as promising cathode materials for high-energy-density automotive lithium batteries. Most of the attention thus far has been paid towards addressing their surface and structural instability issues brought by the increase of Ni content (>90 %) with an aim to enhance the cycle stability. However, the poor safety performance remains an intractable problem for their commercialization in the market, yet it has not received appropriate attention. In this review, we focus on the gas generation and thermal degradation behaviors of high-Ni cathodes, which are critical factors in determining their overall safety performance. A comprehensive overview of the mechanisms of outgassing and thermal runaway reactions is presented and analyzed from a chemistry perspective. Finally, we discuss the challenges and the insights into developing robust, safe high-Ni cathodes.

Thermal Stability and Outgassing Behaviors of High‐nickel Cathodes in Lithium‐ion Batteries

AbstractLiNiO2‐based high‐nickel layered oxide cathodes are regarded as promising cathode materials for high‐energy‐density automotive lithium batteries. Most of the attention thus far has been paid towards addressing their surface and structural instability issues brought by the increase of Ni content (>90 %) with an aim to enhance the cycle stability. However, the poor safety performance remains an intractable problem for their commercialization in the market, yet it has not received appropriate attention. In this review, we focus on the gas generation and thermal degradation behaviors of high‐Ni cathodes, which are critical factors in determining their overall safety performance. A comprehensive overview of the mechanisms of outgassing and thermal runaway reactions is presented and analyzed from a chemistry perspective. Finally, we discuss the challenges and the insights into developing robust, safe high‐Ni cathodes.

Fabrication and reaction mechanism study of Co(OH)F@Al nanowire arrays: A functional fluorine-containing metastable intermolecular composite

Metastable intermolecular composites (MICs) comprising solid fuels and oxidizers at nano-scale exhibit high energy densities and fast reaction speeds. As most metal and metalloid fuels are passivated by the natural oxide layer on the surface which acts as a reaction barrier, fluorine-containing oxidizers are of particular interest to promote the reactivity through interfacial fluoridation. In this work, cobalt hydroxy fluoride (Co(OH)F) was introduced as a functional fluorine-containing oxidizer, and core-shell structured Co(OH)F@Al nanoarray was fabricated onto a glass substrate. The thermal behavior and reaction mechanism of pure Co(OH)F and Co(OH)F@Al composites were thoroughly investigated, and Co(OH)F@Al was compared with CoO@Al and Co3O4@Al with identical morphology. In the Co(OH)F@Al composite, a pre-ignition reaction was observed which was attributed to the etching of Al2O3 shell by HF and the fluoridation of Al core by HF and CoF2. With the assistance of pre-ignition reaction, Co(OH)F@Al can complete main exothermal reaction before Al melting in a solid-state mechanism, and its peak temperature is around 200 ℃ lower than those of MICs employing CoO and Co3O4 as oxidizers.

Thermal runaway mechanisms and kinetics of benzene nitrification system based on microcalorimetry experiments and ReaxFF molecular dynamics simulation

The thermal runaway reaction mechanisms and kinetics of nitrification process under abnormal conditions remain incompletely understood. In this study. C600 microcalorimetry experiments combined with GC/MS characterization and IR analysis of the intermediates indicated that the secondary thermal runaway of benzene nitrification system was preferentially initiated by the decomposition of nitrobenzene sulfonated by-products rather than that of nitrobenzene products. This was further verified by the ReaxFF MD simulations and DFT calculations of the microscopic decomposition thermal runaway mechanisms of typical product and by-product. Furthermore, the model-free kinetic models were compared and evaluated from the perspective of reaction mechanism. The results showed that although the models of Kissinger, FWO and Friedman could obtain feasible kinetic parameters, Friedman model had a good match with the microscopic kinetics and thermodynamic mechanisms, and could reasonably approximate the intrinsic thermokinetics. Finally, the thermal hazards under adiabatic conditions with different thermal inertia factors (φ) were discussed, the results provide a reference for the optimization of safety and economy.

Co-pyrolysis of oil-based drill cuttings and pinewood sawdust: Thermal behavior, synergistic effect, artificial neural network and empirical reaction model

Evaluation of pyrolysis characteristics is essential to convert the waste into various high-value products. In this study, the co-pyrolysis of oil-based drill cuttings (OBDC) and pinewood sawdust (PS) was conducted to analyze the thermal behavior, synergistic effect, and reaction mechanism. Results showed that co-pyrolysis of OBDC and PS had a positive synergistic effect, and the more the percentage of PS in the blend, the stronger the synergistic effect. The pyrolysis characteristic index D increased from 6.50 × 10-05 to 47.38 × 10-05. The apparent activation energy during the co-pyrolysis of OBDC and PS (mass ratio in 1:1) was evaluated using two model-free methods (FWO and KAS) which were 101.38 kJ/mol and 97.51 kJ/mol, respectively. The pre-exponential factors analysis found that the solid phase surface reaction occurred in the co-pyrolysis at the conversion rate of 0.05–0.35; and the co-pyrolysis underwent a complex reaction at the conversion rate above 0.35. The artificial neural network (ANN) with Logsig-Tansig transfer function and neurons number 11 × 12 × 1 had the best prediction effect on co-pyrolysis. The reaction mechanism function (f(α)) of the co-pyrolysis of OBDC and PS was (1 − α)6.2778α2.3848[−ln(1 − α)]0.3570, indicating that co-pyrolysis was the combined effects of reaction order, accelerating, and nuclei growth and diffusion mechanism.

Reactive behaviors and mechanisms of cellulose in chemical looping combustions with iron-based oxygen carriers: An experimental combined with ReaxFF MD study

Biomass energy is one of the important and feasible renewable energy resources. Chemical looping combustion (CLC) can meet the requirements of efficient CO2 capture with low energy consumption. The combination of the two factors is intuitive and important for realizing carbon neutral energy processing and conversion. Cellulose is the component with the highest content in biomass. However, there is still a lack of clear understanding of the thermal conversion behavior and microscopic reaction mechanism of cellulose in CLC. In this work, the behaviors and mechanisms of cellulose in CLC with iron-based OCs were studied systematically based on the comprehensive technics of thermo-gravimetric analysis (TGA) experiments, kinetic models and molecular dynamic simulations. The reaction behaviors, kinetic mechanism, and complex reactive networks of cellulose under complex environmental interface conditions of CLC were revealed. Three different stages were revealed for thermal weight loss and reaction behavior of cellulose in CLC via TGA. The effects of different conversion rates and reaction stages on activation energy during CLC were described based on two model-free integration methods. The dynamic evolution of the CLC process was discussed by ReaxFF MD (reactive force field molecular dynamics) simulations. A complex reaction network of cellulose depolymerization and CO2 release in CLC was obtained.

Unexpected Structural Effects on the Onset of Thermal Reactions of Aromatic Hydrocarbons

This work aims to study the reactivity of a broad range of aromatic hydrocarbons to better understand the reactivities of more complex hydrocarbon mixtures. A set of closed-system pyrolysis experiments were conducted on a diverse range of ∼30 polycyclic aromatic hydrocarbons (PAHs) at the thermal onset reaction temperature of 400 °C to understand structural effects on reactivities and shed light on the early events of thermal reaction mechanisms. Thermal transformations, including methyl transfer (alkylation/dealkylation), rearrangement, condensation, molecular growth, and other chemical transformations, are often indicated by dark carbon materials composed of complex mixtures. Thermal transformation was confirmed by phenomenological changes (color and solubility) and chemical analysis using nuclear magnetic resonance, thermogravimetric analysis, gas chromatography, and electron spin resonance. Unsubstituted PAHs (e.g., phenanthrene, anthracene, pyrene, chrysene, etc.) were unaffected by heating at this temperature, with the exception of tetracene and pentacene which readily transformed into dark and insoluble materials. The reactivity of these unsubstituted PAHs is consistent with aromaticity predicted by the Clar theory. On the contrary, most alkyl-substituted PAHs can be transformed into carbon materials at 400 °C; however, alkyl-substituted phenanthrenes (2,7-dimethyl, 2-ethyl, or 7-ethyl) and benzenes (xylenes and pentamethylbenzene) were unreactive. CH2-containing PAH molecules were unreactive if in a five-membered ring (e.g., fluorene and benzofluorene) but became reactive if in a six-membered ring (9,10-dihydroanthracene), likely as a result of aromatization of the latter. The reactivity of the aryl–aryl linkage depends upon the aromatic moieties to which it is connected. While it is unreactive when connecting phenyl groups, such as in p-terphenyl, it is reactive when connecting pyrenes, such as in 1,1′-bispyrene. These results were unexpected and challenge the conventional thinking about hydrocarbon reactivities. Explanations and possible hypotheses are proposed, but more questions remain unanswered to understand the structural effects on reactivities. These findings are conducive to the sustainable use of aromatic hydrocarbons for higher value carbon materials and relevant to numerous pyrolysis studies on oil shale kerogens, biomass, and waste plastics.

Three ionic liquids as ‘‘smart’’ stabilizers for diethyl azodicarboxylate (DEAD)

As a homogeneous system consists of diethyl azodicarboxylate (DEAD) soluble in three ionic liquids (ILs), such as [BMIM][NTf2], [BMIM][BF4], [BMIM][PF6], the catalytic efficiency can be substantially improved. However, their compatibility and stability have not yet been understood. The present study combines Thermal Safety Software (TSS) with Semenov theory in an in-depth analysis of experiment data to elucidate the reaction mechanism of DEAD with solvents effect. The characteristic thermokinetic parameters of DEAD dissolved in these three ILs, which TSS simulated, were high and consistent with the experimental values. Evidence was presented which showed that the thermal decomposition reaction mechanisms were determined as N-order model when DEAD soluble in the three ILs, and the order of the compatibility was: [BMIM][NTf2] > [BMIM][BF4] > [BMIM][PF6]. In this paper, the simulated value of self-accelerating decomposition temperature (SADT) was 48 °C for DEAD soluble in [BMIM][PF6] with a certain proportion, compared with the SADT value 43 °C calculated by Semenov theory. The research presented here confirms that 43 °C is the upper limit standard for the storage and transportation of DEAD, which paves a new avenue to facilitate the industrial process application of DEAD. The study concludes that three ILs are the smart stabilizers for DEAD, ameliorating its catalytic efficiency and thermal stability and laying a foundation for the rational design of catalysts toward green chemistry.

A combined kinetic analysis for thermal characteristics and reaction mechanism based on non-isothermal experiments: The case of poly(vinyl alcohol) pyrolysis

This work aims to implement one efficient combined kinetic approach for determining thermal kinetic triplets and elucidating reaction mechanism for poly(vinyl alcohol). Thermogravimetric pyrolysis profiles were acquired in inert nitrogen atmosphere with 5, 10, 15, and 20 K/min heating rates, and its thermal decomposition behavior was characterized in details. With respect to two main stages identified in whole pyrolysis process, their activation energies varying with conversion extents were computed by applying several model free methods, including FWO, KAS, FR, and advanced isoconversion approaches. Subsequently, the linear CR and non-linear masterplots model fitting methods were to severely figure out the appropriate reaction mechanism functions. Of particular interest is observed that F3/2 and F2 mechanism models were separately deemed to be appropriate for two stages, but they failed in giving good overlapping details with experimental data. Furthermore, a combined kinetic analysis was carefully conducted to obtain kinetics triplets, which includes model independent analysis and thoroughly considers kinetic compensation effect. Thereby, accurate reaction models were separately optimized and reconstructed for two distinct pyrolysis steps by the imported accommodation functions. This work finally provides a precise methodology to gain insight into thermal behavior and decomposition mechanism of poly(vinyl alcohol) , and improve the prediction accuracy of kinetics.

Kinetic study of plasma assisted oxidation of H2 for an undiluted rich mixture

Non-thermal plasma discharges are considered as an assisted method for supporting conventional thermal processes, because the discharge-generated radicals can be used to benefit them. In this regard, plasma assisted combustion has been investigated extensively, and plasma assisted fuel reforming has expanded its horizons to include plasma assisted chemical synthesis, in accord with a global megatrend—electrification. To scientifically advance this area, plasma-chemical kinetic studies must be conducted, and their mechanisms should consider both electron and gas temperatures to describe electron-induced and thermally-induced chemistry, respectively. Here we present a temperature-dependent plasma-chemical kinetic study for the plasma assisted oxidation of an undiluted rich H2/O2 mixture; it represents our continued effort to establish a foundational plasma assisted reaction mechanism for H2/O2 systems. A plasma-chemical kinetic model (KAUSTKin) and a modified plasma-chemical reaction mechanism were used for the zero-dimensional simulation; a temperature-controlled dielectric barrier discharge reactor was employed for the experiment. Non-linear oxidation behavior was observed in a range of 300–850 K for various discharge powers. To unravel the underlying mechanisms, analysis was broken down to a physical effect, described by the reduced electric field (E/N), and a chemical effect originating from the temperature dependence of the plasma assisted oxidation chemistry. We concluded that (i) the oxidation was initiated by the electron impact dissociation of H2, (ii) E/N governed the degree of H2 dissociation (and thus the degree of oxidation), (iii) the key intermediate was HO2, and (iv) a significant increase in the chain termination reaction, H + HO2 → H2 + O2, suppressed the oxidation (especially in the Negative Temperature Coefficient (NTC)-like regime of 600–725 K). The need to improve existing thermal reaction mechanisms for temperatures below 1000 K was emphasized, and a method for temperature-dependent plasma-chemical kinetic studies to provide a novel and complementary tool for this task was demonstrated.