International Journal of Chemical Kinetics最新文献_第10页

Measurement and modeling of peroxides half-life: A thermo-kinetic approach 过氧化物半衰期的测量和建模:一种热动力学方法

IF 1.5 4区化学

International Journal of Chemical Kinetics Pub Date : 2023-09-12 DOI: 10.1002/kin.21691

Florin Dan, Pranav Bagaria, Brian Habersberger, Amy Koziol

{"title":"Measurement and modeling of peroxides half-life: A thermo-kinetic approach","authors":"Florin Dan, Pranav Bagaria, Brian Habersberger, Amy Koziol","doi":"10.1002/kin.21691","DOIUrl":"10.1002/kin.21691","url":null,"abstract":"Half-life values of organic peroxides at elevated temperature conditions are important in characterizing the reactivity and are often available in literature or through vendors. However, there is often lack of details/accuracy on methods used to obtain these values, as well as differences in methods across vendors and publications, thus resulting in discrepant reactivity profile. To address this, a method involving calorimetric experiment and thermo-kinetic modeling was developed. The current approach was applied on five peroxides samples to obtain kinetic parameters and estimate their half-life in the temperature range of interest. The measurements were performed by DSC under non-isothermal conditions on the dilute peroxide solutions (∼0.12 M in mineral oil) and the data were kinetically treated according to three model-based and one model-free kinetic equations. A very good agreement was found between the half-life calculated by all kinetic methods, but significant differences were noticed with the kinetic parameters reported in literature. Additionally, the obtained half-life results, based on non-isothermal measurements developed kinetic models, were validated through isothermal calorimetric testing. Given the accuracy and robustness of our results, the current method can be applied to estimate half-life of organic peroxides at elevated temperature conditions.","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":"56 1","pages":"43-58"},"PeriodicalIF":1.5,"publicationDate":"2023-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135826227","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}

引用次数: 0

Thermally activated persulfate oxidation of Basic Fuchsin dye: Effect of different operating parameters, kinetic, and thermodynamic study 碱性品红染料的过硫酸盐热活化氧化:不同操作参数的影响、动力学和热力学研究

IF 1.5 4区化学

International Journal of Chemical Kinetics Pub Date : 2023-08-31 DOI: 10.1002/kin.21690

Naima Habache, Ouahiba Bechiri

{"title":"Thermally activated persulfate oxidation of Basic Fuchsin dye: Effect of different operating parameters, kinetic, and thermodynamic study","authors":"Naima Habache, Ouahiba Bechiri","doi":"10.1002/kin.21690","DOIUrl":"10.1002/kin.21690","url":null,"abstract":"The present paper aims to investigate the efficiency of thermal activation persulfate in eliminating the organic dye “Basic Fuchsin” (BF). In addition, the study attempts to elucidate the effect of different operating parameters, such as persulfate dosage (0.44–4.4 mM), the initial solution pH of (3–10), and temperature (25–50°C), on the process. The effects of various anions and water matrices on BF discoloration were investigated. Thus, the findings revealed that 94.15% of BF can be eliminated using persulfate at a concentration of 4.4 mM and a temperature equal to 50°C. It occurs under the following operating conditions: oxidation time of 60 min, initial pH equal to 6, the pollutant concentration of 10 ppm, and stirring speed equal to 300 rpm. Furthermore, the kinetic study indicated that the degradation of the BF dye using PS followed a first-order pattern with rate constants varying within a range of 15.3 × 10−3–43.2 × 10−3 min−1. Based on the Arrhenius equation, the activation energy of the studied process was determined to be 29 kJ mol−1, suggesting that a moderate activation energy is required for BF discoloration. The results of the thermodynamic study confirm that the oxidation process is non-spontaneous and endothermic. Coexisting inorganic anions delayed BF discoloration to varying degrees, and the inhibitory action followed the following order: carbonate > chloride > sulfate > nitrate. Organic pollutants oxidation by the thermal activation of the persulfate is a simple and effective method for the depollution of waste textile water.","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":"56 1","pages":"30-42"},"PeriodicalIF":1.5,"publicationDate":"2023-08-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42260989","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}

引用次数: 0

Super rapid preparation of biodiesel over highly dispersed K2CO3 supported by LDH LDH负载的高分散K2CO3超快速制备生物柴油

IF 1.5 4区化学

International Journal of Chemical Kinetics Pub Date : 2023-08-17 DOI: 10.1002/kin.21689

Ying Yang, Shuang Tao, Guangtao Li, Aijun Guo, Ying Tang

引用次数: 0

Temperature-dependent kinetics of the gas-phase reactions of Cl atoms with nopinone, ketolimonene, and myrtenal Cl原子与nopinone、酮柠檬烯和桃金娘醛气相反应的温度相关动力学

IF 1.5 4区化学

International Journal of Chemical Kinetics Pub Date : 2023-08-17 DOI: 10.1002/kin.21682

Mariam Fakih, Estelle Roth, Alexandre Tomas, Abdelkhaleq Chakir

{"title":"Temperature-dependent kinetics of the gas-phase reactions of Cl atoms with nopinone, ketolimonene, and myrtenal","authors":"Mariam Fakih, Estelle Roth, Alexandre Tomas, Abdelkhaleq Chakir","doi":"10.1002/kin.21682","DOIUrl":"10.1002/kin.21682","url":null,"abstract":"In this study, the gas phase reaction of chlorine atoms with three first-generation oxidation products of monoterpene: (myrtenal C10H14O, nopinone C9H14O, and ketolimonene C9H14O) were investigated using a relative technique method. These compounds result from the atmospheric oxidation of monoterpene compounds such as α/β – pinene and limonene. Experiments were performed at temperature range 298–353 K and atmospheric pressure in synthetic air bath gas. Cl atoms were generated by UV photolysis of dichloride (Cl2). The reaction was followed using a proton-transfer reaction mass spectrometer (PTR-MS) and/or Fourier-transform infrared spectroscopy (FTIR) to monitor the concentrations of the investigated species simultaneous with several reference compounds as a function of time. The rate constants were obtained and the Arrhenius expressions (cm3 molecule−1 s−1) obtained were established over the temperature range of 298–353 K:knopinone + Cl = (5.0 ± 1.2) × 10−10 exp ( − (406 ± 78) /T)kketolimonene + Cl = (8.88 ± 1.3) × 10−10 exp( − (246 ± 46)/T)kmyrtenal + Cl = (13.5 ± 6.4) × 10−10 exp( − (535 ± 153)/T)Based on rate constants, the atmospheric lifetimes (τ) of targeted compounds with respect to reaction with chlorine atoms were estimated and expected to be less than 1 day. There results led to conclude that the reaction with chlorine atoms can be an effective tropospheric loss pathway mainly in regions presenting relatively high chlorine concentrations.","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":"55 11","pages":"751-759"},"PeriodicalIF":1.5,"publicationDate":"2023-08-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48940455","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}

引用次数: 0

Kinetic regularities of resolution of amines racemates in the acylation reaction with chiral N-protected amino acids esters 手性N-保护氨基酸酯酰化反应中胺外消旋体拆分的动力学规律

IF 1.5 4区化学

International Journal of Chemical Kinetics Pub Date : 2023-08-17 DOI: 10.1002/kin.21681

Stanislav Bakhtin, Marina Sinelnikova

引用次数: 0

An investigation of the catalytic performance of Fe–Mn/Al2O3 nanocatalyst for light olefins production using RSM method and kinetic study 用RSM法和动力学研究Fe–Mn/Al2O3纳米催化剂对轻烯烃生产的催化性能

IF 1.5 4区化学

International Journal of Chemical Kinetics Pub Date : 2023-08-09 DOI: 10.1002/kin.21688

Maryam Arsalanfar

{"title":"An investigation of the catalytic performance of Fe–Mn/Al2O3 nanocatalyst for light olefins production using RSM method and kinetic study","authors":"Maryam Arsalanfar","doi":"10.1002/kin.21688","DOIUrl":"10.1002/kin.21688","url":null,"abstract":"The Fe–Mn/Al2O3 nanocatalysts were manufactured via the sol-gel procedure and were evaluated for Fischer–Tropsch synthesis. The impact of different operational parameters of T, P, and H2/CO ratio on the catalytic performance for light olefins production has been studied using response surface methodology (RSM). Furthermore, the optimization and modeling of selected responses were also carried out via RSM and historical data design type of DOE; and the best process conditions were found to be T = 365°C, H2/CO = 1.50, and P = 1.50 bar. The mechanism of CO hydrogenation reaction over the Fe–Mn/Al2O3 nanocatalysts was also investigated using the non-linear regression method. It was found that the mechanism of the CO hydrogenation reaction is based on the Eley–Rideal type and the best-fitted equation for this mechanism was found to be −rCO = KPCOPH2/1+αPCO. The obtained value of activation energy (85.20 kJ mol−1) affirmed the absence of internal mass transfer limitations. The physico-chemical properties of the samples were investigated by various techniques of XRD, BET, TPR, TGA, and DSC.","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":"56 1","pages":"3-19"},"PeriodicalIF":1.5,"publicationDate":"2023-08-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"44603129","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}

引用次数: 0

Salt effects on the reactivity for ligand substitution reactions of [Ru(CN)5OH2]3− anion with two naphthalene substituted ligands (nitroso-R-salt and α-nitroso-β-naphthol) in presence of Tetrapropylammonium bromide (Pr4NBr) and Sodium chloride (NaCl) 在四丙基溴化铵（Pr4NBr）和氯化钠（NaCl）存在下，盐对[Ru（CN）5OH2]3−阴离子与两个萘取代配体（亚硝基-R‐盐和α-亚硝基-β-萘酚）的配体取代反应活性的影响

IF 1.5 4区化学

International Journal of Chemical Kinetics Pub Date : 2023-08-02 DOI: 10.1002/kin.21686

Rupal Yadav, Abhishek Srivastava, Ruchi Singh, Radhey Mohan Naik, Shiv Bali Singh Yadav, Pradeep Kumar Pandey

{"title":"Salt effects on the reactivity for ligand substitution reactions of [Ru(CN)5OH2]3− anion with two naphthalene substituted ligands (nitroso-R-salt and α-nitroso-β-naphthol) in presence of Tetrapropylammonium bromide (Pr4NBr) and Sodium chloride (NaCl)","authors":"Rupal Yadav, Abhishek Srivastava, Ruchi Singh, Radhey Mohan Naik, Shiv Bali Singh Yadav, Pradeep Kumar Pandey","doi":"10.1002/kin.21686","DOIUrl":"10.1002/kin.21686","url":null,"abstract":"The kinetics of the ligand exchange reaction between aquapentacyanoruthenate(II) [Ru(CN)5OH2]3− ion and naphthalene substituted ligands [α-nitroso-β-naphthol (αNβN), and nitroso-R-salt (NRS)] has been studied in aqueous salt solutions of sodium chloride (NaCl) or tetrapropylammonium bromide (Pr4NBr) salt. The kinetics was monitored spectrophotometrically at 525 nm corresponding to the λmax of reddish-brown-colored substituted products, [Ru(CN)5(αNβN)]3− or [Ru(CN)5(NRS)]3−. Increasing the ionic strength of the reaction mixture using NaCl, exerted a negative salt effect on the rate of formation of naphthalene-substituted products. At the same time, an increment in the concentration of Pr4NBr imparted a positive salt effect on the reaction. The observed rate constant (kobs) exhibits linear increment with respect to the concentration of NRS or αNβN while remaining invariant with variation in [Ru(CN)5OH2]3−. The computed activation parameters for NRS (∆H# = 24.55 kJ mol−1, Ea = 27.03 kJ mol−1, ∆G# = 87.83 kJ mol−1, and ∆S# = – 212.5 J K−1 mol−1) and αNβN ((∆H# = 17.33 kJ mol−1, Ea = 19.81 kJ mol−1, ∆G# = 87.87 kJ mol−1, and ∆S# = – 236.7 J K−1 mol−1) also support the proposed mechanism.","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":"55 12","pages":"805-814"},"PeriodicalIF":1.5,"publicationDate":"2023-08-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"44616181","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}

引用次数: 0

Nonenzymatic hydrolysis of 1,2:3,4-diepoxybutane: A kinetic study including pH, temperature, and ion effects 1,2:3,4-二环氧丁烷的非酶水解：包括pH、温度和离子效应的动力学研究

IF 1.5 4区化学

International Journal of Chemical Kinetics Pub Date : 2023-08-01 DOI: 10.1002/kin.21683

Michał Romański, Jakub Mikołajewski, Franciszek Główka

{"title":"Nonenzymatic hydrolysis of 1,2:3,4-diepoxybutane: A kinetic study including pH, temperature, and ion effects","authors":"Michał Romański, Jakub Mikołajewski, Franciszek Główka","doi":"10.1002/kin.21683","DOIUrl":"10.1002/kin.21683","url":null,"abstract":"1,3-Butadiene is a carcinogenic and mutagenic air pollutant metabolized to butane epoxides, among which 1,2:3,4-diepoxybutane (DEB) exhibits the highest genotoxicity. DEB is also formed by 1,3-butadiene oxidation in the air, producing a direct environmental and occupational exposure. In this paper, we studied the kinetics of the nonenzymatic hydrolysis of DEB at a wide range of pH and temperature, including the catalytic effect of ionic species. The compound degradation involved a general and specific acid-base catalysis of the epoxide ring hydrolysis. DEB had the greatest stability at pH 5–9, when the rates of acid-catalyzed and base-catalyzed hydrolysis are negligible and the neutral hydrolysis predominates. The capability of the buffer anions to accelerate the DEB decay increased in the order H2PO4− < HCO3− < CH3COO− < HPO42− < and CO32−. The Arrhenius equation well described the influence of temperature on the acid-catalyzed, base-catalyzed, and neutral hydrolysis rate constants. According to the obtained hydrolysis model coupled with the found thermodynamic parameters, the half-life of DEB in natural fresh waters spans from 2 days at 30°C to 31 days at 0°C, but in the laboratory waste adjusted to pH 1or 13, the half-life shortens to 2–3 h at 20°C. Therefore, the results of the paper help to assess the risk of exposure to the genotoxic action of DEB.","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":"55 12","pages":"795-804"},"PeriodicalIF":1.5,"publicationDate":"2023-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49493135","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}

引用次数: 0

Kinetics of bis(2-methyl) butylene carbonate by transesterification of dimethyl carbonate with 1,4-butanediol 碳酸二甲酯与1,4-丁二醇酯交换制备碳酸双（2-甲基）丁烯酯的动力学

IF 1.5 4区化学

International Journal of Chemical Kinetics Pub Date : 2023-07-31 DOI: 10.1002/kin.21687

Yanfang Zhao, Tingting Pei, Rihui Liang, Guoliang Zhao, Zhongkai Yang

{"title":"Kinetics of bis(2-methyl) butylene carbonate by transesterification of dimethyl carbonate with 1,4-butanediol","authors":"Yanfang Zhao, Tingting Pei, Rihui Liang, Guoliang Zhao, Zhongkai Yang","doi":"10.1002/kin.21687","DOIUrl":"10.1002/kin.21687","url":null,"abstract":"The kinetic behavior of bis(2-methyl) butylene carbonate (BMBC) by the transesterification of dimethyl carbonate (DMC) with 1,4-butanediol (BDO) was investigated experimentally and theoretically. The Fourier transform infrared spectroscopy (FTIRs) test confirmed that the BMBC was successfully synthesized. The optimum preparation process of BMBC was investigated at atmospheric pressure, where Zn(Ac)2∙2H2O was the best catalyst for this transesterification reaction, and the optimal concentration was 0.3 wt%. The conversion was determined by measuring the amount of methanol produced during the reaction by refractometric method. A kinetic model was proposed according to the experimental results. The results showed that the transesterification reaction was a pseudo-first-order reaction. The apparent activation energy (Ea) significantly decreased with the increase of catalyst concentration from 0.1 wt% to 0.5 wt%. The Ea of the reaction was 102.13, 84.36, and 70.18 kJ mol−1, respectively, when the catalyst concentration was 0.1 wt%, 0.3 wt%, and 0.5 wt%. Furthermore, the parameters of the optimal heating curve in the batch reactor was obtained according to the optimal model.","PeriodicalId":13894,"journal":{"name":"International Journal of Chemical Kinetics","volume":"55 12","pages":"785-794"},"PeriodicalIF":1.5,"publicationDate":"2023-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46488564","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}

引用次数: 0

High-pressure oxidation of n-butane 正丁烷的高压氧化

IF 1.5 4区化学

International Journal of Chemical Kinetics Pub Date : 2023-07-25 DOI: 10.1002/kin.21678

Hamid Hashemi, Jakob M. Christensen, Peter Glarborg, Sander Gersen, Martijn van Essen, Ziyu Wang, Yiguang Ju

引用次数: 0