International Journal of Chemical Kinetics最新文献

{"title":"Distinguishing Kinetics and Mechanistic Approaches of Ce(IV) Efficient Oxidation of Cadaverine in HClO4 and H2SO4 Media","authors":"Nada Alqarni","doi":"10.1002/kin.70010","DOIUrl":"https://doi.org/10.1002/kin.70010","url":null,"abstract":"<div>\u0000 \u0000 <p>The kinetics of highly efficient oxidation of cadaverine (CAD) by Ce(IV) in both HClO₄ and H₂SO₄ solutions were examined using UV–Vis absorption spectra at numerous temperatures. The last products of CAD oxidation were recognized as ammonia and 5-aminopentanal, that is, an essential organic compound in both biological and chemical settings. From the obtained data, it's clear that the reactions’ kinetics demonstrated a first-order dependence in [Ce^IV], where they exhibited lower than unit orders with regard to [CAD] over the studied concentration range. In HClO₄ and H₂SO₄, the oxidation reactions showed positive and negative incomplete unit orders in [H⁺], correspondingly. Based on the obtained results, the mechanistic reactions’ pathways were suggested. The reliable rate laws were derived, and the reactions’ rate constants were estimated. In addition, the activation and thermodynamic parameters were calculated and discussed. This study illuminated the role of the oxidant, medium, temperature, and other conditions on the oxidation kinetics and mechanisms of these redox systems.</p>\u0000 </div>","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":"57 11","pages":"674-683"},"PeriodicalIF":1.6,"publicationDate":"2025-08-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129229","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Reactive Molecular Dynamics Simulation of Methane-Oxygen Autoignition at High-Pressure Conditions","authors":"Jonathan Henry Martin,&nbsp;Benjamin Akih-Kumgeh","doi":"10.1002/kin.70009","DOIUrl":"https://doi.org/10.1002/kin.70009","url":null,"abstract":"<div>\u0000 \u0000 <p>An investigation of autoignition using molecular dynamics simulations and ReaxFF force fields is presented. The study is motivated by the fact that combustion at rocket engine conditions of high pressures can involve real gas behavior that is not captured by chemical kinetic models and kinetic solvers based on ideal gas assumptions. Also, the mechanistic reaction pathways at these conditions may not be well known. Molecular dynamics simulations based on reactive force fields can be used to gain insight into combustion under these conditions. However, for such molecular dynamics simulations to yield useful and trustworthy results, they must be able to simulate thermodynamic ensembles that are relevant to practical combustion, such as constant volume adiabatic reactors. They must also be able to reproduce known features from combustion simulations using continuum and statistical chemical kinetic models. These aspects can be verified for small molecular fuel systems, such as methane. In this work, the autoignition of methane-oxygen mixtures at pressures of 200 atm is simulated using non-equilibrium molecular dynamics with the ReaxFF force fields and the LAMMPS software package. To account for difficulties associated with maintaining the internal energy constant, a combination of NVT and NVE ensembles is used to capture the rapid temperature rise associated with autoignition. The evolution of key chemical species is examined and a characteristic ignition delay time is defined for each temperature. The results are contextualized by comparing them to the predictions of two continuum and statistical chemical kinetic models and the Chemkin Pro solver. ReaxFF simulations are found to reproduce the chemical structure of autoigniting reactors. The ignition delay times obtained from the ReaxFF are comparable to those obtained from continuum kinetic models, although the ReaxFF results are characterized by a higher global activation energy. With respect to the final products of the ignition process, ReaxFF predicts CO and OH levels that are comparable with continuum kinetic and equilibrium models. Generally, ReaxFF under predicts the formation of triatomic molecules. This study advances the use of molecular dynamics simulation to study standard combustion problems, such as constant-volume autoignition.</p></div>","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":"57 11","pages":"662-673"},"PeriodicalIF":1.6,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129221","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ab Initio Study of the Gas- and Liquid-Phase Hydrogen Abstraction From Dimethyl-, Diethyl-, and Ethyl–Methyl Carbonates by \u0000 \u0000 \u0000 H\u0000 ̇\u0000 \u0000 ${dot{mathrm{H}}} $\u0000 and \u0000 \u0000 \u0000 C\u0000 ̇\u0000 \u0000 ${dot{mathrm{C}}} $\u0000 H3 and Subsequent Reactions","authors":"Marwa Saab,&nbsp;Yann Fenard,&nbsp;Guillaume Vanhove,&nbsp;Malte Döntgen,&nbsp;K. Alexander Heufer","doi":"10.1002/kin.70007","DOIUrl":"https://doi.org/10.1002/kin.70007","url":null,"abstract":"&lt;p&gt;Dimethyl-, diethyl, and ethyl–methyl carbonate are important components of lithium batteries. They are used as solvents and comprise the medium through which the lithium ions move between the anode and the cathode during charge and discharge. However, these species are susceptible to decomposition if thermal runaway occurs, forming flammable gases inside the battery, and eventually leading to mechanical failure and ignition with the surrounding air. These events have been reported and are extremely hazardous. To avoid these incidents, it is important to understand the reactivity of carbonates by building chemical kinetic mechanisms based on experimental testing and theoretical calculations. These models are also important when using these species in combustion as additives or replacements to fossil fuels. Because of their high oxygen content, researchers believe that including carbonates in combustion processes would decrease soot and particulate matter emissions. Existing models typically use estimated reaction rate parameters; thus, more accurate rate parameters would benefit existing and new models. In this study, the rate coefficients of H-atom abstraction reactions by &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mover&gt;\u0000 &lt;mi&gt;H&lt;/mi&gt;\u0000 &lt;mo&gt;̇&lt;/mo&gt;\u0000 &lt;/mover&gt;\u0000 &lt;annotation&gt;$dot {mathrm{H}} $&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; and &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mover&gt;\u0000 &lt;mi&gt;C&lt;/mi&gt;\u0000 &lt;mo&gt;̇&lt;/mo&gt;\u0000 &lt;/mover&gt;\u0000 &lt;annotation&gt;$dot{mathrm{C}} $&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; H&lt;sub&gt;3&lt;/sub&gt;, β-scission, isomerization, and internal radical migration reactions are computed from CCSD(T)/aug-cc-pV(D+T)Z//B3LYP-D3BJ/def2-TZVP calculations. Additionally, solvation effects have been investigated to allow for comparison between liquid and gas phase kinetics. Consistent with the literature, H-atom abstraction by &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mover&gt;\u0000 &lt;mi&gt;H&lt;/mi&gt;\u0000 &lt;mo&gt;̇&lt;/mo&gt;\u0000 &lt;/mover&gt;\u0000 &lt;annotation&gt;$dot {mathrm{H}} $&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; is found to be faster than that by &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mover&gt;\u0000 &lt;mi&gt;C&lt;/mi&gt;\u0000 &lt;mo&gt;̇&lt;/mo&gt;\u0000 &lt;/mover&gt;\u0000 &lt;annotation&gt;$dot{mathrm{C}} $&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; H&lt;sub&gt;3&lt;/sub&gt;. At the low-temperature end of the investigated range (300 K), available literature rate coefficients and the present rate coefficients are deviating up to three orders of magnitude. Notably, uncertainties in the imaginary frequency computation are found to contribute most to deviations between the present calculations and combined theoretical and experimental literature dat","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":"57 11","pages":"652-661"},"PeriodicalIF":1.6,"publicationDate":"2025-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/kin.70007","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129193","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Navigating Imidacloprid Insecticide's Destiny: Sorption and Degradation Aspects in Varied Ecological Zones","authors":"Sara Majid,&nbsp;Khuram Shahzad Ahmad,&nbsp;Jehad S. Alhawadi,&nbsp;Ghulam Abbas Ashraf,&nbsp;Mohammad K. Okla","doi":"10.1002/kin.21786","DOIUrl":"https://doi.org/10.1002/kin.21786","url":null,"abstract":"<div>\u0000 \u0000 <p>Sorption profoundly influences the destiny and behavior of agrochemicals in soil and water. The goal of the current study is to use the batch equilibrium technique to examine the adsorption–desorption behavior of the neonicotinoid pesticide imidacloprid in 10 distinct types of Pakistani soils (Ss1–Ss10). Adsorption coefficients (<i>K_d</i>) and associated parameters were assessed using the batch equilibrium approach. The findings showed that the best fit to the experimental data was given by the Freundlich isotherm. In view of this, the Ss6 depicted the highest adsorption coefficient (<i>K_d</i>) value (13.30 µg/mL), followed by Ss7 and Ss8. The positive correlation between <i>K_d</i> and soil organic matter decided it as a major affecting parameter for high adsorption. Negative Gibbs free energy values exhibited the weaker physio-sorption between soil and imidacloprid molecules. Minimum half-lives recorded in photolytic and biodegradative experiments were 247 and 28 days, respectively showing the persisting nature of imidacloprid. Results indicated that imidacloprid had a moderate to strong binding to the chosen soils, resulting in increased persistence and less breakdown. Work currently being done can be expanded to further optimize these impermissible methods to provide workable solutions for cleaning up the environment using natural means.</p>\u0000 </div>","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":"57 11","pages":"639-651"},"PeriodicalIF":1.6,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129173","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enhanced Combustion Kinetic Mechanism Reduction via an Improved Binary Genetic Algorithm","authors":"Xinglong Ren,&nbsp;Shengqiang Lin,&nbsp;Xianfa Zhang,&nbsp;Junyu Chen,&nbsp;Chunshi Qi,&nbsp;Wenli Yu,&nbsp;Yonglian Xiong,&nbsp;Bin Yang","doi":"10.1002/kin.70008","DOIUrl":"https://doi.org/10.1002/kin.70008","url":null,"abstract":"<div>\u0000 \u0000 <p>For high-dimensional complex combustion reaction kinetic systems, conventional simplification methods based on elementary reaction approaches (e.g., sensitivity analysis [SA]) struggle to derive compact reduced mechanisms due to the nonlinear characteristics of the kinetic systems, leading to the widespread adoption of graph-based methods in mechanism reduction. To overcome the dual challenges of reducing high-dimensional stiff mechanisms and resolving the inherent limitations of elementary reaction-based simplification methodologies, a novel mechanism reduction framework employing an improved binary genetic algorithm (IBGA) was established. The IBGA operates through binary-encoded particles where each bit corresponds to an elementary reaction: 0 indicates exclusion from the simplified mechanism, while 1 denotes retention. The optimization objective maximizes the number of zero-value bits while preserving critical combustion characteristics. This methodology was implemented for the mechanism reduction of ethylene and dimethyl ether (DME) combustion systems, etc. Results indicate that the IBGA-based approach achieves significant mechanism size reduction while maintaining accuracy. The ethylene mechanism was reduced to 28 reactions, and the DME mechanism to 40 reactions. Furthermore, in order to further validate the performance of the IBGA reduction method, the ethylene mechanism and DME mechanism are also reduced for predicting both ignition delay time and laminar flame speed. The results shown C₂H₄/air reduced mechanism involving 28 species and 56 reactions and DME/air reduced mechanism involving 31 species and 92 reactions are obtained. The obtained simplified mechanisms exhibit enhanced compactness with preserved prediction fidelity for combustion characteristics. A comparative analysis between the IBGA and deep mechanism reduction (DeePMR) methods in reducing high-temperature LLNL butanol isomers’ mechanisms demonstrates that the IBGA significantly shortens the required computational time for reduction while producing more compact mechanisms.</p>\u0000 </div>","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":"57 11","pages":"627-638"},"PeriodicalIF":1.6,"publicationDate":"2025-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129106","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Catalytic Conversion of Biomass-Derived 5-Hydroxymethylfurfural Into 2,5-Bis(hydroxymethyl)furan Using Hierarchically Hortensia-Like α-Ni(OH)2 Without Prereduction","authors":"Shimao Gao,&nbsp;Mengyao Xu,&nbsp;Yufei Huang,&nbsp;Weixing Pan,&nbsp;Aicheng Chen","doi":"10.1002/kin.70006","DOIUrl":"https://doi.org/10.1002/kin.70006","url":null,"abstract":"<div>\u0000 \u0000 <p>Inexpensive hierarchically hortensia-like α-Ni(OH)₂ catalysts without prereduction were introduced to the 5-hydroxymethylfurfural (HMF) hydrogenation to 2,5-bis(hydroxymethyl)furan (BHMF) via the catalytic transfer hydrogenation (CTH) process. Given the catalytic performance evaluated on the hortensia-like α-Ni(OH)₂, the catalyst of Ni(OH)₂-OLA synthesized using an oleylamine-assisted solvothermal method has prospective in the HMF hydrogenation to BHMF. A remarkable 95.96% of the BHMF selectivity with 96.81% of the HMF conversion was obtained on Ni(OH)₂-OLA at 135°C for 5 h under N₂ atmosphere using the ethanol as the hydrogen donor. Based on the kinetic analysis, the lowest activation energy of 39.6 kJ·mol⁻¹ and the highest preexponential factor of 19.1 s⁻¹ could be found on Ni(OH)₂-OLA, which revealed the superior catalytic performance in the HMF hydrogenation to BHMF over Ni(OH)₂-OLA. Moreover, excellent stability and reusability also could be found on Ni(OH)₂-OLA, which indicated that the hortensia-like α-Ni(OH)₂ catalysts have the potential for industrialization. The findings of this study provide an efficient catalyst system with low-cost and high-performance for the HMF hydrogenation via the CTH process.</p>\u0000 </div>","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":"57 10","pages":"615-624"},"PeriodicalIF":1.6,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144894292","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Investigating the Mechanism of Ruthenium (III)-Catalyzed Oxidation of Benzyl Alcohol and 2-Phenyl Ethanol by a Copper (III) Periodate Complex in an Aqueous Alkaline Environment","authors":"Shalini Srivastav,&nbsp;Suresh C. Yadav,&nbsp;Anamika Srivastava,&nbsp;Praveen K. Tandon,&nbsp;Manish Srivastava","doi":"10.1002/kin.70005","DOIUrl":"https://doi.org/10.1002/kin.70005","url":null,"abstract":"<div>\u0000 \u0000 <p>A study was conducted to investigate the oxidation of benzyl alcohol and 2-phenyl ethanol using a copper (III) complex catalyst with ruthenium (III) chloride in an alkaline water-based solution. The researchers maintained a constant ionic strength in the solution throughout the experiment. They found that the rate of the reaction was directly proportional to the concentrations of the oxidant, organic substrate, catalyst, and hydroxyl ions. However, when external sources of periodate ions were added, the reaction rate slowed down. Increasing the ionized potential of the solution had a positive effect on the reaction rate. The researchers calculated various thermal properties, such as activation energy, activation free energy, and activation entropy, to better understand the energetics of the reaction. They used infrared (IR) and nuclear magnetic resonance (NMR) spectroscopy to identify the oxidation products. Based on their experimental findings, they proposed a plausible mechanism to explain all the observed phenomena. This research highlights the use of simple, cost-effective, and environmentally friendly methods for copper oxidation in its +3 state. These methods offer new possibilities for advancements in the field of oxidation reactions.</p>\u0000 </div>","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":"57 10","pages":"607-614"},"PeriodicalIF":1.6,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144894323","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Extending Excitation Time for Detonation Prevention: Mixture Effect in Dimethyl Ether Auto-Ignition","authors":"Lisa Zander,&nbsp;Neda Djordjevic","doi":"10.1002/kin.70004","DOIUrl":"https://doi.org/10.1002/kin.70004","url":null,"abstract":"<p>Undesired detonation development is an obstacle in the development of modern combustion systems based on auto-ignition. Excitation time is one of two time scales that affect detonation development. It describes the time interval, during which heat is released. Extending excitation time decreases the propensity to detonation development by inhibiting the coupling between heat release and pressure waves emerging from reactivity gradients, which are often present in technical systems. As excitation time is mixture-dependent, mitigation of detonation development is possible through mixture tailoring. This work investigates the underlying physico-chemical processes that are responsible for the effect of dilution and equivalence ratio on excitation time. The numerical investigation is performed for dimethyl ether/air mixtures at 15 bar, which feature multistage ignition depending on initial temperature. The resulting nonmonotonous evolution of the heat release rate requires to adapt the analysis methods and utilize a novel excitation time definition. Diluted and off-stoichiometric mixtures feature longer excitation times compared to undiluted stoichiometric mixtures, which is favorable for decreasing the detonation propensity of a mixture. The results demonstrate that excitation time is mainly controlled by reactions that affect reactivity and the production of important intermediate species, which are related to the underlying heat release chemistry. Dilution impacts excitation time by thermal effects, related to the diluent's heat capacity, and chemical effects, such as scavenging of important radicals by third-body collision of the diluent. The current work illuminates which physico-chemical processes extend the excitation time when mixture composition changes, which supports future work on mixture tailoring for mitigation of detonation development.</p>","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":"57 10","pages":"589-606"},"PeriodicalIF":1.6,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/kin.70004","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144894448","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Thermal Decomposition Kinetics and Decomposition Mechanism of (Dinitropyrazolyl)Azoxyfurazanes","authors":"Valery P. Sinditskii,&nbsp;Ludmila Ya. Melnikova,&nbsp;Anastasia D. Smirnova,&nbsp;Nikolay V. Yudin,&nbsp;Alexei A. Konnov,&nbsp;Igor L. Dalinger,&nbsp;Michael S. Klenov","doi":"10.1002/kin.70003","DOIUrl":"https://doi.org/10.1002/kin.70003","url":null,"abstract":"<div>\u0000 \u0000 <p>The decomposition of azoxy derivatives of dinitropyrazole and furazan, the first example in which an azoxy group is coupled to a pyrazole ring nitrogen, has been studied in detail using DSC, TGA, isothermal TGA, and manometry methods. The studies showed that the degradation of azoxy compounds starts with the cleavage of the bond between the N(O) atom of the azoxy group and the furazan cycle. It was found that under conditions of decomposition product removal, this stage can occur without heat release or with heat release without a pronounced peak. The insignificant heat effect of the initial decomposition stage of azoxy compounds makes it difficult to determine the true kinetic parameters using the standard DSC method, as the observed heat effect is actually due to the decomposition of intermediates. At the same time, decomposition under closed conditions can increase the decomposition rate constants by a factor of 10 or more. A possible mechanism for the decomposition of azoxy compounds has been proposed based on the kinetic data obtained and the analysis of the decomposition products.</p>\u0000 </div>","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":"57 10","pages":"571-588"},"PeriodicalIF":1.6,"publicationDate":"2025-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144894311","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Kinetics of Oxidation of Cyclohexane to Cyclohexanone and Cyclohexanol Over CuO–ZnO Catalyst","authors":"Vishal D. Khomane,&nbsp;Nibedita Sanyal,&nbsp;Virendra K. Rathod","doi":"10.1002/kin.70002","DOIUrl":"https://doi.org/10.1002/kin.70002","url":null,"abstract":"<div>\u0000 \u0000 <p>This work describes the oxidation of cyclohexane to cyclohexanone and cyclohexanol using a CuO–ZnO catalyst. It was found that the CuO–ZnO catalyst is more active for the oxidation of cyclohexane using H₂O₂ as an oxidizing agent, and further catalyst was characterized by using XRD, FTIR, and XPS analysis. Various reaction parameters, such as the effect of solvent, reaction time, different oxidizing agents, reaction temperature, H₂O₂ to cyclohexane mole ratio, catalyst loading, and stirring speed, have been studied to analyze the catalytic activity. The optimized catalytic activity obtained an 88.2 % conversion of cyclohexane, 86 % selectivity of cyclohexanone, and 14 % cyclohexanol selectivity. The oxidation of cyclohexane and the determination of the activation energy for the reaction was explored using different kinetic models such as the Eley–Rideal and Langmuir–Hinshelwood–Hougen–Watson models. Langmuir–Hinshelwood–Hougen–Watson competitive associative adsorption mechanism with surface reaction as the rate-limiting step is the best-fitted model.</p>\u0000 </div>","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":"57 9","pages":"553-567"},"PeriodicalIF":1.5,"publicationDate":"2025-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144714744","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}