International Journal of Chemical Kinetics最新文献

{"title":"The Role of Solvent Polarity on the Synthesis of Ibuprofen Molecule: A Density Functional Approach","authors":"Akash Deep Das, Kuldeep Nagar, Amit Dubey, Soumya Mukherjee","doi":"10.1002/kin.70081","DOIUrl":"https://doi.org/10.1002/kin.70081","url":null,"abstract":"<div>\u0000 \u0000 <p>In the present work, we intend to perform a computational study to explore the effects of solvent polarity for the synthesis of a well-known nonsteroidal anti-inflammatory drug, ibuprofen. For each and every step of ibuprofen synthesis, structure, energetics and spectral analysis are carried out to unveil the most suitable solvent among seven different ones with a wide range of polarity, namely, benzene (<span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <msub>\u0000 <mi>C</mi>\u0000 <mn>6</mn>\u0000 </msub>\u0000 <mi>H</mi>\u0000 </mrow>\u0000 <annotation>${rm C}_6{rm H}$</annotation>\u0000 </semantics></math><span></span><math>\u0000 <semantics>\u0000 <msub>\u0000 <mrow></mrow>\u0000 <mn>6</mn>\u0000 </msub>\u0000 <annotation>$_6$</annotation>\u0000 </semantics></math>), carbon tetrachloride (<span></span><math>\u0000 <semantics>\u0000 <msub>\u0000 <mi>CCl</mi>\u0000 <mn>4</mn>\u0000 </msub>\u0000 <annotation>${rm CCl}_4$</annotation>\u0000 </semantics></math>), tetrahydrofuran (<span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <msub>\u0000 <mi>C</mi>\u0000 <mn>4</mn>\u0000 </msub>\u0000 <mi>H</mi>\u0000 </mrow>\u0000 <annotation>${rm C}_4{rm H}$</annotation>\u0000 </semantics></math><span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <msub>\u0000 <mrow></mrow>\u0000 <mn>10</mn>\u0000 </msub>\u0000 <mi>O</mi>\u0000 </mrow>\u0000 <annotation>$_{10}{rm O}$</annotation>\u0000 </semantics></math>), acetone (<span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <msub>\u0000 <mi>CH</mi>\u0000 <mn>3</mn>\u0000 </msub>\u0000 <mi>COCH</mi>\u0000 </mrow>\u0000 <annotation>${rm CH}_3{rm COCH}$</annotation>\u0000 </semantics></math><span></span><math>\u0000 <semantics>\u0000 <msub>\u0000 <mrow></mrow>\u0000 <mn>3</mn>\u0000 </msub>\u0000 <annotation>$_3$</annotation>\u0000 </semantics></math>), dichloromethane (<span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <msub>\u0000 <mi>CH</mi>\u0000 <mn>2</mn>\u0000 </msub>\u0000 <mi>Cl</mi>\u0000 </mrow>\u0000 <annotation>${rm CH}_2{rm Cl}$</annotation>\u0000 </semantics></math><span></span><math>\u0000 <semantics>\u0000 <msub>\u0000 <mrow></mrow>\u0000 <mn>2</mn>\u0000 </msub>\u0000 <annotation>$_2$</a","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":"58 9","pages":"694-704"},"PeriodicalIF":1.7,"publicationDate":"2026-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148615176","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":"Effect of HBr on Explosion Limits of Stoichiometric Hydrogen-oxygen Mixture","authors":"Chunkan Yu,&nbsp;Peter Glarborg","doi":"10.1002/kin.70076","DOIUrl":"https://doi.org/10.1002/kin.70076","url":null,"abstract":"<p>This work, based on numerical simulations, discusses the effect of HBr as an inhibitor on the explosion limit of stoichiometric hydrogen-oxygen gas mixture in a closed spherical vessel. The numerical simulation solves the complete governing equations for mass, momentum, species and energy. In addition, wall surface reactions are included to describe the destruction of chemically reactive radicals. The in-house <i>INSFLA</i> code is used, which takes into account the differential diffusion and thermal diffusion (Soret effect) to describe the mass transport of species within the system. The inhibitory effect of HBr on all three explosion limits under the considered conditions is analyzed based on sensitivity analysis of the explosion limit with respect to chemical reaction rates and reaction pathway analysis. It is found that the main reason for the inhibition effect is the chain-propagating step HBr+<span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <mi>H</mi>\u0000 <mo>→</mo>\u0000 <mi>Br</mi>\u0000 </mrow>\u0000 <annotation>${rm H}rightarrow{rm Br}$</annotation>\u0000 </semantics></math>+<span></span><math>\u0000 <semantics>\u0000 <msub>\u0000 <mi>H</mi>\u0000 <mn>2</mn>\u0000 </msub>\u0000 <annotation>${rm H}_2$</annotation>\u0000 </semantics></math> which is in effect terminating. However, each of the three explosion limits is governed by different key reactions.</p>","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":"58 9","pages":"646-657"},"PeriodicalIF":1.7,"publicationDate":"2026-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/kin.70076","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148615438","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":"Sustainable Remediation of Dye-Contaminated Water: Phragmites australis Leaves (Reed) as a Low-Cost Biosorbent for Brilliant Cresyl Blue","authors":"Romaissa Hadjaissa,&nbsp;Chifaa Ad,&nbsp;Mokhtar Benalia,&nbsp;Nour Elhouda Brichi,&nbsp;Mebrouk Djedid","doi":"10.1002/kin.70070","DOIUrl":"https://doi.org/10.1002/kin.70070","url":null,"abstract":"<div>\u0000 \u0000 <p>This study examines Phragmites australis leaves (LPA) as a biosorbent for removing brilliant cresyl blue (BCB) dye from aqueous solutions. Batch experiments evaluated the effects of pH (2–10), contact time (0–180 min), adsorbent dose (0.05–1 g), initial dye concentration (30 –150 mg/L), and temperature (298-328 K). Maximum BCB removal (&gt;67%) was achieved at pH 8, with an equilibrium time of 30 min and an adsorbent dose of 0.6 g, consistent with the point of zero charge (pHpzc = 6.8). Characterization revealed a porous structure (SEM), an oxygen-rich functional group surface (FTIR), and a specific surface area of 2.4276 ± 0.0467 m²/g (BET). The adsorption kinetics followed the pseudo-second-order model (R² &gt; 0.99), and the equilibrium data were best described by the Freundlich isotherm, with a maximum adsorption capacity of 66.28 mg/g at 318 K. Thermodynamic analysis indicated ΔG &gt; 0 and ΔH &gt; 0, confirming a non-spontaneous and endothermic process. The positive value of ΔS suggests an increase in the randomness/disorder at the solid–liquid interface during the adsorption process. These results demonstrate the potential of Phragmites australis leaves as a cost-effective and eco-friendly biosorbent for dye removal, combining natural abundance with competitive adsorption capacity. Future studies should investigate its performance in continuous-flow systems and real wastewater matrices.</p>\u0000 </div>","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":"58 9","pages":"603-618"},"PeriodicalIF":1.7,"publicationDate":"2026-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148616799","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":"Surfactant Catalysis of Phloroglucinol Oxidation With Pyrosulphate Ion: Piszkiewicz's, Raghavan–Srinivasan's, and Portnoy–Menger Models","authors":"Ikechukwu Ugbaga Nkole,&nbsp;Abhishek Srivastava,&nbsp;Ikenna Benedict Onyeachu,&nbsp;Patricia Ese Umoru","doi":"10.1002/kin.70084","DOIUrl":"https://doi.org/10.1002/kin.70084","url":null,"abstract":"<div>\u0000 \u0000 <p>Phloroglucinol (PGN) oxidation can result in accelerated lipid peroxidation, leading to oxidative stress and cellular damage (including protein carbonylation and DNA damage). Hence, its oxidation in a surfactant environment is investigated to ascertain its reaction character and property kinetically using spectrophotometric method. The PGN oxidation with pyrosulphate ion (S₂O₇²⁻) exposes the possibility of electrostatic, hydrophobic, or hydrophilic behaviour in a micelle host. The investigated kinetic functions expose first-order-kinetics in respect of PGN and S₂O₇²⁻ concentrations, and an equally shared mole ratio between PGN and S₂O₇²⁻ ions. The increment in electrolyte level has no impact on the oxidation rate, and the increase in acid concentration accelerates the oxidation rate, whereas the aggregation of surfactant monomers (cetyltrimethylammonium bromide, CTAB) assists the oxidation rate. The PGN and S₂O₇²⁻ ions binding state (<i>K</i>_B = 0.8445; <i>K</i>_PGN = 0.4633, <i>K</i>_PS = 0.9265; <i>K</i>_B = 0.2849) with the CTAB-micelles is anchored by Piszkiewicz's, Raghavan–Srinivasan's, and Portnoy–Menger models, respectively. The involvement of intermediate species and substrate radicals is deniable and undeniable, accordingly. The thermodynamic feasibility of the oxidation process is verified by the thermodynamic parameters (Δ<i>G</i>  =   + 70.98 kJmol⁻¹, Δ <i>H</i>* =   + 32.69 kJmol⁻¹, and Δ <i>S</i>* =   − 128.05 JK⁻¹mol⁻¹) and non-spontaneity leads the process.</p>\u0000 </div>","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":"58 9","pages":"705-712"},"PeriodicalIF":1.7,"publicationDate":"2026-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148615177","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":"Simulation Enhancement of CO2 Hydrogenation to Methanol With Water Removal Membrane","authors":"Zongliang Fan,&nbsp;Tengfei Ma,&nbsp;Wenlong Mo,&nbsp;Dongliang Wang,&nbsp;Huairong Zhou,&nbsp;Yong Yang","doi":"10.1002/kin.70074","DOIUrl":"https://doi.org/10.1002/kin.70074","url":null,"abstract":"<div>\u0000 \u0000 <p>The integration of carbon dioxide (CO₂) with green hydrogen (H₂) for methanol synthesis presents a viable alternative to conventional fossil fuel-based production routes under the background of carbon emission reduction. However, the synthesis reaction is thermodynamically limited and the byproduct of H₂O would deactivate catalysts. The water removal membrane is introduced to improve the synthesis process and a coupled multiphase catalytic membrane reaction model has been established to investigate the enhancement of methanol synthesis due to the water removal in CO₂ hydrogenation. Results demonstrate that the selective permeability of water removal membrane both for countercurrent and co-current flow lead to the significant improvement to the CO₂ conversion and methanol yield. The former flow type exhibits higher ΔP_H2O around the outlet of the reaction channel (RC), higher maximum for H₂O concentration in the sweep gas channel (SC), but may cause reverse H₂O permeability around the inlet of RC, while the later flow shows a slightly lower average driving force but a relatively smooth water removal process. The optimization analysis show that the performance of membrane reactor can be significantly improved with the increase of reaction temperature and, pressure or H₂/CO₂. For the membrane reactor with co-current flow at 513 K, 5.5 MPa and 0.015 m/s, CO₂ conversion increase up to 50% and methanol yield up to 56%, which are much higher than that of fixed-bed reactor.</p>\u0000 </div>","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":"58 9","pages":"637-645"},"PeriodicalIF":1.7,"publicationDate":"2026-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148615437","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":"The Rate of the Diels-Alder Cycloaddition Reactions of Benz(a)Anthracene With Tetracyanoethylene and 4-Phenyl-1,2,4-triazoline-3,5-dione in Solution and Solid State","authors":"Dmitry A. Kornilov,&nbsp;Mikhail I. Yagofarov,&nbsp;Timur T. Sadykov,&nbsp;Alina F. Sattarova,&nbsp;Akhat G. Mustafin","doi":"10.1002/kin.70059","DOIUrl":"https://doi.org/10.1002/kin.70059","url":null,"abstract":"<div>\u0000 \u0000 <p>The data on solvent and temperature influence on the rates of Diels-Alder reactions of benz(a)anthracene with tetracyanoethylene and 4-phenyl-1,2,4-triazoline-3,5-dione were experimentally obtained. The activation enthalpies and entropies for these reactions in several organic solvents were determined. For the reaction of benz(a)anthracene with tetracyanoethylene, the equilibrium constants in some solvents were measured as functions of temperature, and the reaction enthalpies and entropies have been calculated. The kinetics of benz(a)anthracene-tetracyanoethylene and benz(a)anthracene-4-phenyl-1,2,4-triazoline-3,5-dione reactions upon crystal grinding in a vibration ball mill was studied. Based on the obtained and literature data, we concluded that, for Diels-Alder reactions, the rate and equilibrium in the solution correlate with the rate and equilibrium in the solid state.</p>\u0000 </div>","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":"58 8","pages":"470-476"},"PeriodicalIF":1.7,"publicationDate":"2026-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148324012","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":"Polyindole–Silver Oxide Composite as a Persulfate-Enhanced Photocatalyst for Malachite Green Degradation: Kinetic and Mechanistic Insights Under Natural Sunlight and Room-Light Conditions","authors":"Rozina Khattak,&nbsp; Iqra,&nbsp;Bushra Begum,&nbsp;Rizwan Ullah,&nbsp;Rooh Ullah,&nbsp;Ola A. Abu Ali,&nbsp;Samy F. Mahmoud,&nbsp;Mustafa Tuzen","doi":"10.1002/kin.70064","DOIUrl":"https://doi.org/10.1002/kin.70064","url":null,"abstract":"<div>\u0000 \u0000 <p>Polyindole@silver oxide (PIN@Ag₂O or PIN@SO) composites were synthesized via a simple, green-assisted chemical oxidative route and evaluated as photocatalysts for the rapid degradation of malachite green (MG) dye under natural sunlight and ambient light. The synthesized materials were characterized by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy coupled with energy-dispersive X-ray analysis (SEM-EDX), and UV–Vis spectroscopy, confirming the formation of semi-crystalline, porous composites with reduced optical band gaps compared to pristine polyindole. The photocatalytic performance of the PIN@SO composites was investigated in aqueous media in the presence of potassium persulfate (1.6 mM) at neutral and acidic pH. Under natural sunlight, complete degradation of 0.4 mM MG was achieved within approximately 10 min at neutral pH and 7 min under acidic conditions (pH 1) using 0.7 mg of the PIN@SO-3 catalyst. Kinetic analysis revealed that the overall degradation of MG follows a 2.5-order reaction, comprising 0.5 order with respect to MG, second order with respect to persulfate, and zero order with respect to the catalyst, under optimized conditions. The temperature dependence of the reaction was evaluated using Arrhenius and Eyring analyses, revealing an endothermic activation process. Degradation intermediates were identified by gas chromatography-mass spectrometry (GC-MS), and a plausible degradation pathway was proposed based on the observed intermediates and relevant literature, indicating extensive MG breakdown without confirmed complete mineralization. The composites exhibited good stability over five successive reuse cycles with only a minor decrease in activity. Furthermore, the optimized system was successfully applied to a real textile wastewater sample under sunlight, demonstrating substantial dye degradation and practical applicability. While the catalyst synthesis follows an environmentally benign approach, the requirement for acidic conditions and persulfate addition represents a trade-off that should be considered when assessing overall process sustainability.</p>\u0000 </div>","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":"58 8","pages":"530-552"},"PeriodicalIF":1.7,"publicationDate":"2026-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148324222","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":"Structural Design Principles for Minimal-Volume-Change Anodes in Next-Generation Sulfide Solid-State Batteries","authors":"Yuhong Ma,&nbsp;Shiyu Chen,&nbsp;Xizhi Xu,&nbsp;Lanxin Xue,&nbsp;Miao He,&nbsp;Jun Chen,&nbsp;Zhan Xiong,&nbsp;Shen Liu,&nbsp;Zhulong Liu,&nbsp;Chi Zhang,&nbsp;Wei Chen","doi":"10.1002/kin.70061","DOIUrl":"https://doi.org/10.1002/kin.70061","url":null,"abstract":"<div>\u0000 \u0000 <p>Sulfide-based all-solid-state batteries (ASSBs) are regarded as next-generation energy storage systems due to their high safety and energy density. However, the mechanical stress arising from electrode volume changes during cycling, especially at the anode–electrolyte interface, imposes more severe constraints on cycle life and commercial prospects than cathode-related volume variations. This review summarizes the recent progress in low-strain anode materials for sulfide-based ASSBs. We firstly categorize the design strategies and performance characteristics of several low-strain systems, including metal–organic frameworks (MOFs), alloy-based anodes, silicon-based anodes, and composite anodes, with particular emphasis on interfacial optimization and structural stabilization mechanisms. And then, we address the key challenges in translating material innovations into scalable manufacturing processes. By identifying current research bottlenecks and outlining future directions, this review aims to provide theoretical insight and practical guidance for both fundamental studies and industrial applications of low-strain anodes in sulfide-based ASSBs.</p>\u0000 </div>","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":"58 8","pages":"585-600"},"PeriodicalIF":1.7,"publicationDate":"2026-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148324982","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":"Phenol Adsorption on Commercial Palm Shell Activated Carbon: A Framework for Resolving Multi-Model Paradoxes Through Objective Selection and Mechanistic Reconciliation","authors":"Ufuk Sancar Vural,&nbsp;H. Cahit Sevindir,&nbsp;Abdullah Yinanc","doi":"10.1002/kin.70058","DOIUrl":"https://doi.org/10.1002/kin.70058","url":null,"abstract":"<div>\u0000 \u0000 <p>Conventional adsorption studies frequently encounter a methodological paradox where multiple kinetic and isotherm models provide statistically valid fits while suggesting contradictory physical mechanisms. This study presents a systematic framework to resolve such contradictions and derive a unified mechanistic understanding. Using phenol adsorption on palm shell activated carbon as a case study, we demonstrate a pathway that moves beyond routine model cataloging. The framework integrates: (1) Objective model discrimination using Akaike (AIC) and Bayesian (BIC) Information Criteria, which decisively identified the Pseudo-Second Order model (<i>R</i>² = 0.9992, AICc = −648.2) over the misleadingly high-<i>R</i>² Pseudo-First Order model, establishing chemisorption as rate-limiting; (2) Paradox resolution through the Sips isotherm model, which reconciles excellent Langmuir and Freundlich fits by quantifying surface heterogeneity (n_s = 0.3215 at 25°C) while accounting for high-affinity sites; and (3) Advanced diffusion diagnostics via fractal analysis, revealing concentration-dependent sub-diffusive transport (fractal exponent <i>a</i> decreasing from 0.916 to 0.726). Thermodynamics confirmed strong chemisorption (ΔH° = −68.1 to −104.5 kJ/mol). This work provides a criterial protocol for transforming conflicting adsorption model outputs into coherent, evidence-based mechanisms applicable across diverse adsorbent systems.</p>\u0000 </div>","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":"58 8","pages":"447-456"},"PeriodicalIF":1.7,"publicationDate":"2026-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148324302","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 Effect of Dibenzo-18-Crown-6 Ether Complexes With Group 2 Metal Chlorides on the Kinetics of Ethylbenzene Oxidation","authors":"Ildar N. Zalyaliev,&nbsp;Nikolai V. Ulitin,&nbsp;Yana L. Lyulinskaya,&nbsp;Konstantin A. Tereshchenko,&nbsp;Natalia M. Nurullina,&nbsp;Svetlana N. Tuntseva,&nbsp;Tatyana L. Puchkova,&nbsp;Kharlampii E. Kharlampidi","doi":"10.1002/kin.70066","DOIUrl":"https://doi.org/10.1002/kin.70066","url":null,"abstract":"<div>\u0000 \u0000 <p>A kinetic model of ethylbenzene oxidation catalyzed by dibenzo-18-crown-6 ether complexes with group 2 metal chlorides (Ca, Sr, Ba) was developed and parameterized using experimental data. Kinetic modeling demonstrated that: 1) an increase in the initial catalyst concentration from 1 to 100 mmol/L leads to a monotonic increase in the rate of ethylbenzene hydroperoxide formation (428 K, 1 atm, volume flow rate of air supply to the reactor of 0.018 m³/h, initial ethylbenzene concentration of 8.17 mol/L, initial concentrations of other species are 0), indicating that the formation of ethylbenzene hydroperoxide prevails over its decomposition; 2) catalysts deactivate within 1 h of the ethylbenzene oxidation process; thus, they are not affect subsequent transformations of ethylbenzene hydroperoxide during propylene epoxidation via the Halcon process; 3) among the dibenzo-18-crown-6 ether complexes with group 2 metal chlorides, the complex with Ca chloride at an initial concentration of 5 mmol/L should be recognized as the best catalyst for industrial use (428 K, 1 atm, volume flow rate of air supply to the reactor of 0.018 m³/h, initial ethylbenzene concentration of 8.17 mol/L, initial concentrations of other species are 0), because it provides the same selectivity as that achieved in non-catalytic ethylbenzene oxidation (about 80%) and reduces the time to reach 10% ethylbenzene conversion by a factor of three (from 1.5 h in the non-catalytic process to 0.5 h in the catalytic process).</p>\u0000 </div>","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":"58 8","pages":"564-576"},"PeriodicalIF":1.7,"publicationDate":"2026-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148324091","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}