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Lumped kinetic simulation of hydrodenitrogenation for full‐range middle‐low temperature coal tar Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2021-01-21 Yonghong Zhu; Yong Dan; Chongpeng Du; Feng Tian; Yaqing Liu; Zhihui Sun; Xiaoyong Fan; Dong Li
With the increasingly prominent environmental problems and depletion of light petrochemical resources, the clean utilization of heavy oil has become the research focal area. The hydrodenitrogenation (HDN) experiments and kinetics of full‐range middle‐low temperature coal tar (MLCT) was studied on a fixed‐bed reactor with a Ni‐Mo/γ‐Al2O3 catalyst. Two kinds of three‐lumped kinetic models (K1 and K1
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Ignition delay and chemical–kinetic modeling of undiluted mixtures in a high‐pressure shock tube: Nonideal effects and comparative uncertainty analysis Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2021-01-21 Lisa Zander; Johann Vinkeloe; Neda Djordjevic
High‐pressure shock tube ignition delay data are essential for fuel characterization and for the validation and optimization of chemical–kinetic models. Therefore, it is crucial that realistic measurement conditions are considered in modeling. Furthermore, an accurate uncertainty quantification for experimental data is the basis for evaluation of the predictive reliability of chemical–kinetic models
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Kinetic studies of excited singlet oxygen atom O(1D) reactions with ethanol Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2021-01-17 Hongtao Zhong; Chao Yan; Chu C. Teng; Timothy Y. Chen; Gerard Wysocki; Yiguang Ju
The multichannel reaction of excited singlet oxygen atom with ethanol, O(1D) + C2H5OH (1), was studied in a photolysis flow reactor coupled with mid‐infrared Faraday rotation spectroscopy (FRS) and UV‐IR direct absorption spectroscopy (DAS) at 297 K with reactor pressures of 60, 120, and 150 Torr (bath He). The excited singlet oxygen atom was generated through the photolysis of O3 at 266 nm. The photon
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Reactions of OH and OD radicals with simple thiols and sulfides studied by infrared chemiluminescence of isotopic water products: Reaction OH + CH3SH revisited Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2021-01-13 Nadezhda I. Butkovskaya; Don W. Setser
Vibrational excitation of the H2O, HOD, and D2O product molecules from the reactions of OH and OD radicals with CH3SH, CH3C(O)SH, (CH3)3CSH, H2S, and CH3SCH3 was determined by modeling the infrared emission spectra using a renovated and extended set of model spectroscopic bands. Using the deuterated reactant, CH3SD, it was possible to separate spectra of abstraction from C‐ and S‐sites, which allowed
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Elementary gas‐phase reactions of radical species during chemical vapor deposition of silicon carbide using CH3SiCl3 Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2021-01-11 Noboru Sato; Yuichi Funato; Kohei Shima; Hidetoshi Sugiura; Yasuyuki Fukushima; Takeshi Momose; Mitsuo Koshi; Yukihiro Shimogaki
We established a kinetic model (the UT2017 model) for chemical vapor deposition of silicon carbide (SiC) from methyltrichlorosilane (CH3SiCl3, MTS)/H2, and quantitatively identified CH2SiCl3 as one of the SiC film‐forming species. In a previous study, we established a kinetic model (the UT2014 model), which reproduced the overall decomposition of MTS, but had not validated it in terms of radicals.
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Kinetic analysis of the degradation of HDPE+PP polymer mixtures Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2021-01-09 Jhon Briceno; Maria Amélia Lemos; Francisco Lemos
An in depth understanding of the kinetics of the decomposition of plastic mixtures is necessary to enhance chemical recycling approaches, in particular by pyrolysis. The fact that plastic waste is usually composed of mixtures of plastics constitutes a hindrance for secondary recycling but may not be a particular difficulty for tertiary recycling. In this study, an analysis of the thermal degradation
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Oxidation process and kinetics of bromothymol blue by alkaline permanganate Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-12-31 Ahmed F. Al‐Hossainy; Samia M. Ibrahim
Spectrophotometric analysis was applied to check the kinetics of bromothymol blue (BTB) oxidation by alkaline permanganate at constant ionic strength 0.2 mol dm−3. The redox reaction was observed to proceed through two independently distinct, detectable steps. The first step coexists with the formation of intermediate complexes involving transient species relatively quickly of the blue hypomanganate(V)
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Experimental and theoretical studies on the reaction of H atom with C3H6 Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-12-27 Wei‐Yu Chen; Trong‐Nghia Nguyen; Ming‐Chang Lin; Niann‐Shiah Wang; Hiroyuki Matsui
A comprehensive study on the reaction of H + C3H6 has been conducted in order to clarify the temperature and pressure dependence of product branching. Site‐specific rate of addition of a hydrogen atom to the center carbon is measured by a comparative method for the evolutions of H atoms behind reflected shock waves. The rate constant for the addition to the center carbon can be given by ln(k1‐2/cm
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Influence of cationic surfactants and inorganic salts on the enzyme kinetic activity of Mucor javanicus lipase Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-10-26 Santosh K. Verma; Kallol K. Ghosh; Rameshwari Verma; Shekhar Verma
In this article, the enzyme kinetic activity of Mucor javanicus lipase (MJL) has investigated via hydrolysis of p‐nitrophenyl acetate (PNPA) in different pH environment, cationic surfactants, and inorganic salts. The influence of hydrophilicity has been studied in the presence of cationic cetyltrimethylammonium bromide (CTAB), cetyltriphenylphosphonium bromide (CTPB), and cetyldimethylethanolammonium
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Thermal and kinetic study of hydroxyapatite formation by solid‐state reaction Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-12-17 Hamid Reza Javadinejad; Reza Ebrahimi‐Kahrizsangi
Hydroxyapatite (HAP) is one of the most attractive calcium phosphates which is used for different applications. While HAP has been mostly synthesized using wet methods, recently solid‐state synthesis methods have attracted more attention. Many efforts have been made to better understand the solid‐state synthesis mechanism. In this study, the kinetics of the solid‐state reaction between hydroxide calcium
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Mechanistic scrutiny of the oxidations of thiol‐containing drugs cysteamine and d‐penicillamine by cis‐diamminetetrachloroplatinum(IV) Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-12-17 Li Zhou; Tiejian Li; Ying Sun; Hongwu Tian; Cunxiu Gao; Chunli Liu; Lingli Kong; Guimin Zhang; Tiesheng Shi
Cysteamine (CA) and d‐penicillamine (Pen) are the thiol‐containing drugs and good antioxidants. Their reactions with a cisplatin Pt(IV) prodrug cis‐diamminetetrachloroplatinum(IV) (cis‐[Pt(NH3)2Cl4]) were investigated by use of rapid scan, stopped‐flow, and mass spectral techniques. The kinetic traces are biphasic in nature, encompassing a faster reduction of cis‐[Pt(NH3)2Cl4] to cisplatin followed
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Rate constants of CH3O2 + NO2 CH3O2NO2 and C2H5O2 + NO2 C2H5O2NO2 reactions under atmospheric conditions Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-12-17 Nanase Kohno; Jiaru Li; Yosuke Sakamoto; Yoshizumi Kajii
Peroxy (RO2) radicals derived from short‐chain alkanes were detected by an improved technique involving combined fluorescence assay by gas expansion and laser‐induced fluorescence (FAGE‐LIF) and chemical conversion under atmospheric conditions (298 K and 1 bar). The suitability of the system for measuring RO2 kinetics was tested using the CH3O2 + NO2 + M CH3O2NO2 + M reaction. CH3O2 radicals were generated
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Purification, characterization, immobilization and kinetic studies of catalase from a novel source Sechium edule Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-12-17 Nene Takio; Meera Yadav; Mridusmita Barman; Hardeo Singh Yadav
A catalase from a novel source Sechium edule (squash) has been purified to homogeneity using ammonium sulfate fractional precipitation, dialysis, and anion exchange chromatography on Diethylaminoethyl (DEAE) cellulose in sodium acetate buffer pH 6.0. The purity of the enzyme was analyzed by SDS‐PAGE. The molecular weight of the enzyme using the SDS‐PAGE method was found to be 55 kDa with specific activity
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Simulation of catalytic toluene alkylation with methanol in fixed‐bed reactors Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-12-12 Zong‐Liang Fan; Xin Su; Dong‐Liang Wang; Dong‐Qiang Zhang; Run‐Hao Duan; Yong Yang
Toluene alkylation with methanol could serve as a green “molecular engineering” to produce para‐xylene (PX). However, the conversion and para‐selectivity are the key index to the application of this technology. Based on the reaction network and kinetics, the fixed‐bed models were introduced to analyze and optimize the para‐selectivity at reactor level. After the validation with the experimental results
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Ethyl lactate: a sinister molecule exhibiting high chemical diversity with potential as a “green” solvent Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-11-30 Judith Würmel; Kieran P. Somers; John M. Simmie
A comprehensive study of the properties and reactivity of ethyl(S)‐lactate has been conducted. The conformational landscape, the enthalpy of formation of the ground state, kJ mol−1, the thermochemistry (entropy, specific heat, enthalpy function), adiabatic ionization energy, and the single bond dissociation energies are also mapped out. Unimolecular elimination reactions leading to water and ethyl
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Isopropanol dehydration reaction rate kinetics measurement using H2O time histories Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-11-27 Sean P. Cooper; Clayton R. Mulvihill; Olivier Mathieu; Eric L. Petersen
H2O formation during thermal decomposition of isopropanol was measured behind reflected shock waves at temperatures ranging from 1127 to 1621 K at an average pressure of 1.42 atm using a laser absorption technique. Of the five modern chemical kinetics models used to compare the H2O time histories, the model from Li et al (Combust. Flame 2019;207:171‐185) showed the best overall agreement. Sensitivity
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A detailed chemical kinetic modeling and experimental investigation of the low‐ and high‐temperature chemistry of n‐butylcyclohexane Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-11-26 William J. Pitz; Jinhu Liang; Goutham Kukkadapu; Kuiwen Zhang; Christine Conroy; John Bugler; Henry J. Curran
Chemical kinetic models of gasoline, jet, and diesel fuels and their mixtures with bioderived fuels are needed to assess fuel property effects on efficiency, emissions, and other performance metrics in internal combustion and gas turbine engines. As these real fuels have too many fuel components to be included in a chemical kinetic model, surrogate fuels containing fewer components are used to represent
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Reaction mechanisms of a cyclic ether intermediate: Ethyloxirane Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-09-21 Matthew G. Christianson; Anna C. Doner; Matthew M. Davis; Alanna L. Koritzke; Justin M. Turney; Henry F. Schaefer; Leonid Sheps; David L. Osborn; Craig A. Taatjes; Brandon Rotavera
Oxiranes are a class of cyclic ethers formed in abundance during low‐temperature combustion of hydrocarbons and biofuels, either via chain‐propagating steps that occur from unimolecular decomposition of β‐hydroperoxyalkyl radicals (β‐̇QOOH) or from reactions of HOȮ with alkenes. Ethyloxirane is one of four alkyl‐substituted cyclic ether isomers produced as an intermediate from n‐butane oxidation. While
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Kinetics of ultrasound‐assisted esterification of maleic acid and butanol using heterogeneous catalyst Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-10-07 Aarti Mulay; Virendra K. Rathod
The present research investigates the kinetics of ultrasound‐assisted synthesis of dibutyl maleate using a heterogeneous catalyst (Amberlyst‐15) in solvent‐free system. Reaction parameters were optimized based on conversion by varying the various parameters such as n‐butanol to maleic acid mole ratio, temperature, molecular sieves, catalyst loading, power, and duty cycle. Optimization of parameters
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Kinetics of isopropanol decomposition and reaction with H atoms from shock tube experiments and rate constant optimization using the method of uncertainty minimization using polynomial chaos expansions (MUM‐PCE) Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-09-28 Laura A. Mertens; Jeffrey A. Manion
We have used the single‐pulse shock tube technique with postshock GC/MS product analysis to investigate the mechanism and kinetics of the unimolecular decomposition of isopropanol, a potential biofuel, and of its reaction with H atoms at 918‐1212 K and 183‐484 kPa. Experiments employed dilute mixtures in argon of isopropanol, a radical scavenger, and, for H‐atom studies, two different thermal precursors
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Isomer‐dependent reaction mechanisms of cyclic ether intermediates: cis‐2,3‐dimethyloxirane and trans‐2,3‐dimethyloxirane Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-10-06 Anna C. Doner; Matthew M. Davis; Alanna L. Koritzke; Matthew G. Christianson; Justin M. Turney; Henry F. Schaefer; Leonid Sheps; David L. Osborn; Craig A. Taatjes; Brandon Rotavera
Oxiranes are a class of cyclic ethers formed in abundance during low‐temperature combustion of hydrocarbons and biofuels, either via chain‐propagating steps that occur from unimolecular decomposition of β‐hydroperoxyalkyl radicals (β‐̇QOOH) or from reactions of HȮO with alkenes. The cis‐ and trans‐isomers of 2,3‐dimethyloxirane are intermediates of n‐butane oxidation, and while rate coefficients for
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Trichloroisocyanuric acid (TCCA) and carboxamide interactions in TCCA/NaNO2 triggered nitration of pyrrole and indole in aqueous aprotic media: A kinetic correlation of solvent properties with reactivity Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-09-28 Govardhan Duguta; Bhooshan Muddam; Chinna Rajanna Kamatala; Umesh Kumar Utkoor
This study deals with the trichloroisocyanuric acid (TCCA) interactions with carboxamides like formamide (FMA), N,N′‐dimethyl formamide (DMF), and N,N′‐dimethyl acetamide (DMA) interactions during the nitration of heterocyclic compounds (HC) like pyrrole and indole in the presence of excess of [NaNO2] over the concentrations of all other reactants. All the reactions were performed in aqueous acetonitrile
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Rate constants for the reactions of F atoms with H2 and D2 over the temperature range 220‐960 K Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-11-25 Yuri Bedjanian
The kinetics of the reactions of F atoms with hydrogen and deuterium has been studied in a discharge flow reactor combined with an electron impact ionization quadrupole mass spectrometer at nearly 2 Torr total pressure of helium and in the temperature range 220‐960 K. The rate constant of the reaction F + H2 → HF + H (1) was determined using both relative rate method (using reaction F + Br2 as a reference)
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The role of the diffusion process in bimolecular reactions with neighborhood Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-11-25 José Cândido de Souza Filho; Alejandro López‐Castillo
We performed stochastic and deterministic calculations to study simple bimolecular chemical kinetics with a neighborhood, necessary for solid‐state and viscous medium reactions. Regarding the standard deterministic method using ordinary differential equations (ODEs) to describe a bimolecular reaction with the neighborhood, we established a comparison that indicates, in this method, an implicit diffusion
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Exploring combustion chemistry of 1‐pentene: Flow reactor pyrolysis at various pressures and development of a detailed combustion model Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-11-20 Chuangchuang Cao; Wei Li; Weiye Chen; Hafiz Ahmad; Jiuzhong Yang; Yuyang Li
The pyrolysis of 1‐pentene was investigated in a flow reactor over temperatures of 900–1300 K and pressures of 0.04 and 1 atm using synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV‐PIMS). Pyrolysis products, especially radicals and cyclic compounds, were identified, and their mole fraction profiles were quantified. A detailed kinetic model of 1‐pentene combustion was developed
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A quantitative assessment of the reactivity of the regioisomers of xylenol by investigation of rapid chlorination kinetics in aqueous solution employing hydrodynamic voltammetry complemented by molecular docking with acetylcholinesterase: A two‐pronged approach Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-11-19 Vitthal T. Borkar
Kinetic data is an elegant tool to quantitatively assess structure—reactivity correlation of organic substrates in reactions and is immaculate if endorsed with complementary information. Halogenations of aromatic substrates in aqueous medium are rapid reactions necessitating special techniques for their study. Their rates depend on nature of the reagents, nucleophilicity of the substrates, and steric
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MBMS study on plasma‐assisted low‐temperature oxidation of n‐heptane and iso‐octane in a flow reactor Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-11-18 Handong Liao; Haodong Chen; Zhongkai Liu; Ruzheng Zhang; Feng Zhang; Bin Yang
Nonequilibrium plasma has a great potential in the lean combustion of gasoline engines. However, fundamental studies on plasma‐assisted combustion on gasoline components are limited. In the present study, Low‐temperature oxidation behaviors for n‐heptane and iso‐octane in a plasma flow reactor were investigated. Species measurements were performed at room temperature and low pressure of 40 mbar using
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Prediction of the product channels in the reaction of the methyl radical with fulminic acid Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-11-17 Trong Nghia Nguyen; Hue Minh Thi Nguyen
The reaction of CH3 + HCNO was theoretically studied by both density functional theory and molecular orbital calculations and analyzed by quantum statistical methods. The potential energy surface was constructed at the UCCSD(T)//B3LYP/6‐311++G(3df,2p) + ZPE level. Four entrance channels are opened relating to the interaction of the CH3 radical with each of the four atoms of the HCNO molecule, giving
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Selective hydrogenation of α‐pinene on a nickel supported aluminophosphate catalyst: Process optimization and reaction kinetics Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-11-11 Chen Yang; Benfu Xiang; Lihong Jiang; Fengmei Zhang; Chunbo Liu; Yaming Wang; Yane Zheng; Zhihua Liu; Pei He
cis‐Pinane, the hydrogenation product of pinene, is a key chemical intermediate and its production is an important forest chemical process. In this study, α‐pinene was hydrogenated using a nickel‐supported aluminophosphate catalyst (Ni/APO‐PT) in the batch mode of operation. The pore structure of the catalyst was characterized, the process parameters were studied, the hydrogenation process was optimized
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CO hydrogenation over K‐Co‐MoSx catalyst to mixed alcohols: A kinetic analysis Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-11-09 Leila Negahdar; Xiaoying Xi; Feng Zeng; J. G. M. Winkelman; Hero Jan Heeres; Regina Palkovits
Higher alcohol synthesis (HAS) from syngas is one of the most promising approaches to produce fuels and chemicals. Our recent investigation on HAS showed that potassium‐promoted cobalt‐molybdenum sulfide is an effective catalyst system. In this study, the intrinsic kinetics of the reaction were studied using this catalyst system under realistic conditions. The study revealed the major oxygenated products
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A theoretical kinetic study on the reaction of atomic bromine with toluene Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-11-05 Binod Raj Giri; John M. Roscoe; Milán Szőri; Aamir Farooq
The reaction of Br atoms with toluene was investigated by employing various quantum chemical methods and statistical rate theory calculations. Various composite methods such as CBS‐QB3, G3, and G4 were used to obtain the energy profiles of the Br + toluene reaction. Further single‐point calculations of the stationary points were performed at the CCSD(T)/cc‐pV(D,T)Z level of theory using B3LYP/cc‐pVTZ
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Theoretical and kinetic modeling study of chloromethane (CH3Cl) pyrolysis and oxidation Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-11-05 Matteo Pelucchi; Carlo Cavallotti; Alessio Frassoldati; Eliseo Ranzi; Peter Glarborg; Tiziano Faravelli
This work presents a comprehensive kinetic modeling study of the pyrolysis and oxidation of chloromethane. Theoretical calculations were performed for the decomposition reaction CH3Cl + M = CH3 + Cl + M and for a set of relevant H‐abstraction reactions (CH3Cl + R, R = Cl, Ḣ, ȮH, HȮ2, O2, Ö, ĊH3, Ċ2H3, Ċ2H5; CH4 + Cl, C2H6 + Cl, C2H4 + Cl, C2H2 + Cl). Comparison with previous experimental or theoretical
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Estimation of reaction kinetics for aromatic and heterocycles nitration in mixed acids through computational chemistry approach Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-10-30 Pandurang M. Jadhav; Raj K. Pandey; Amol A. Kulkarni
Nitration of aromatic compounds and heterocycles in mixed acid environment is one of the regularly performed large‐scale reactions in the chemical industry. Although the reaction mechanism of nitration of aromatics in mixed acid is well established, the development of a methodology for the evaluation of kinetics of exothermic aromatic nitrations in a simplified and accurate way is necessary. Here we
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Kinetics of 1‐decene hydroformylation in an aqueous biphasic medium using a water‐soluble Rh‐sulfoxantphos catalyst in the presence of a cosolvent Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-10-30 Nitin S. Pagar; Raj M. Deshpande
The kinetics of hydroformylation of 1‐decene has been studied in an aqueous biphasic medium using a water‐soluble Rh‐sulfoxantphos catalyst in the presence of N‐methyl pyrrolidone as a cosolvent at 383‐403 K. The rate was found to be first order, with concentrations of catalyst and olefin and partial order, with concentrations of hydrogen in the liquid phase. The plot of rate versus excess ligand and
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Experimental and computational studies of the mechanism of base‐catalyzed ring opening of 2‐(chloromethyl)oxirane by benzoic acid Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-10-27 Yuliia Bespalko; Marina Sinel'nikova; Elena Shved; Evgeniia Bakhalova
Using methods of chemical kinetics and quantum modeling, we investigated the mechanism by which base catalysts affect the regioselectivity of the ring opening of 2‐(chloromethyl)oxirane by benzoic acid. The model reaction was carried out using 2‐(chloromethyl)oxirane as both reagent and solvent at temperatures of 303‐333 K. Rate constants and activation parameters of the ring opening were determined
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Leaching kinetics of electronic waste for the recovery of copper: Rate‐controlling step and rate process in a multisize particle system Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-10-26 Gloria I. Dávila‐Pulido; Armando Salinas‐Rodríguez; Francisco R. Carrillo‐Pedroza; Adrián A. González‐Ibarra; Juan Méndez‐Nonell; Mitzué Garza‐García
Electronic waste (e‐waste) contains metallic values that can be recovered by hydrometallurgical methods. This investigation addresses the leaching kinetics of e‐waste for the recovery of copper in H2SO4‐H2O2 media with the objective of determining the rate‐controlling step in monosize particle systems. The results are then used to develop a kinetic model for copper dissolution in multisize particle
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Bond additivity corrections for CBS‐QB3 calculated standard enthalpies of formation of H, C, O, N, and S containing species Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-10-26 Cato A.R. Pappijn; Florence H. Vermeire; Ruben Van de Vijver; Marie‐Françoise Reyniers; Guy B. Marin; Kevin M. Van Geem
A prerequisite for the generation of detailed fundamental kinetic models is the availability of accurate thermodynamic properties. To address the scarcity of accurate experimental data, theoretical calculations can be used. The accuracy of these quantum chemistry methods for determination of thermodynamic properties can be improved by making use of empirical correction methods, such as the isodesmic
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Glycerol chlorination reaction mechanism Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-10-26 Diogo Nogueira; Ricardo R. Oliveira; Alexandre B. Rocha
A new reaction mechanism for the glycerol chlorination is proposed. This mechanism is based on theoretical calculations within density functional theory combined with polarizable continuum model . Two possibilities were investigated, the first is the SN2 chlorination forming mono‐ and dichlorinated products and the second one is through an ester intermediate formed by glycerol esterification in the
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Combined kinetic analysis of solid‐state reactions: The integral method (ICKA) Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-08-24 M.D. Casal; Gregorio Marbán
In this work, we propose the first Integral method for the Combined Kinetic Analysis (ICKA) of solid‐state reactions typically performed in a thermogravimetric analyzer. The ICKA method prevents the systematic inaccuracies inherent to all the differential methods, including the standard CKA method. Two main achievements have been made for implementing the method: (1) the most accurate approximation
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An experimental and modeling study of the oxidation of n‐heptane, ethylbenzene, and n‐butylbenzene in a jet‐stirred reactor at pressures up to 10 bar Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-08-28 Olivier Herbinet; Benoit Husson; Hervé Le Gall; Frédérique Battin‐Leclerc
In the context of better understanding pollutant formation from internal combustion engines, new experimental speciation data were obtained in a high‐pressure jet‐stirred reactor for the oxidation of three molecules, which are considered in surrogates of diesel fuel, n‐heptane, ethylbenzene, and n‐butylbenzene. These experiments were performed at pressures up to 10 bar, at temperatures ranging from
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Semiclassical transition state theory/master equation kinetics of HO + CO: Performance evaluation Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-09-02 John R. Barker; John F. Stanton; Thanh Lam Nguyen
Previously, master equation (ME) simulations using semiclassical transition state theory (SCTST) and high‐accuracy extrapolated ab initio thermochemistry (HEAT) predicted rate constants in excellent agreement with published experimental data over a wide range of pressure and temperatures ≳250 K, but the agreement was not as good at lower temperatures. Possible reasons for this reduced performance are
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Rate coefficients for the reactions of OH with butanols from 298 K to temperatures relevant for low‐temperature combustion Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-09-07 Samantha L. Sime; Mark A. Blitz; Paul W. Seakins
Rate coefficients for the reactions of OH with n, s, and iso‐butanol have been measured over the temperature range 298 to ∼650 K. The rate coefficients display significant curvature over this temperature range and bridge the gap between previous low‐temperature measurements with a negative temperature dependence and higher temperature shock tube measurements that have a positive temperature dependence
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Mechanistic insights into biomimetic CO2 hydration activity of titania nanoclusters Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-10-13 Manju Verma; Parag A. Deshpande
Anatase TiO2, a widely used semiconductor metal oxide support, was tested for biomimetic carbonic anhydrase activity catalyzing the reversible hydration of CO2 to bicarbonate ions. Owing to superior photocatalytic response of nanoclusters of TiO2 and its apparent role in catalyzing CO2 hydration, (TiO2)15 nanocluster was tested for the reaction using density functional theory calculations. Free energy
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Updated thermochemistry for renewable transportation fuels: New groups and group values for acetals and ethers, their radicals, and peroxy species Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-10-10 Malte Döntgen; Wassja A. Kopp; Florian vom Lehn; Leif C. Kröger; Heinz Pitsch; Kai Leonhard; K. Alexander Heufer
We present new groups and group values for the gas‐phase thermochemistry of ethers, polyethers, and acetals suited for combustion modeling. Our investigation comprises fuel species, their primary radicals, peroxy radicals, and hydroperoxide species. In total, 45 species are used for the parameterization of 14 groups, six of which are newly introduced here. Presently, calculated thermochemistry at the
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Reaction kinetics of a series of alkenes with ClO and BrO radicals: A theoretical study Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-10-05 Parth Gupta; B. Rajakumar
Quantum chemical calculations were used to investigate the mechanism and kinetics of the reaction of XO (X = Cl, Br) radicals with linear C2 to C4 alkenes. Two reaction routes, namely, addition and H‐abstraction, were investigated as part of the XO‐radical initiated degradation of these alkenes. Energies and structural parameters were obtained at the CCSD(T)/CBS//M062x/cc‐pVTZ level of theory, and
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Kinetics of the oxidation of iodide by dicyanobis(phenanthroline)iron(III) in a binary solvent system Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-10-01 Rozina Khattak; Muhammad Sufaid Khan; Shazia Summer; Rizwan Ullah; Humaira Afridi; Zainab Rehman; Summyia Masood; Hamsa Noreen; Raina Aman Qazi; Bushra Begum
Oxidation of the iodide ion is an important facet of the solar cells such as perovskite solar cells and dye‐sensitized solar cells. The rate of reaction undoubtedly depends upon several factors. Such parameters include reaction media, electrolyte, and the nature of solvents, and electrolyte. If these factors are optimized then the rate of the reaction can be controlled and could be used to get the
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Kinetic investigation of the reaction of ethylperoxy radicals with ethanol Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-10-01 S. Kuzhanthaivelan; B. Rajakumar
The thermodynamic and kinetic investigation for the reaction of ethylperoxy radical (CH3CH2OO•) with ethanol (CH3CH2OH) was studied computationally with variational transition state theory. The geometry optimization calculations showed that both the reactants have two conformers. The energetics and thermodynamic properties were calculated using the G4 composite method. The results showed that the abstraction
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Effects of stereoisomeric structure and bond location on the ignition and reaction pathways of hexenes Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-09-30 Cesar L. Barraza‐Botet; Changpeng Liu; John H. Kim; Scott W. Wagnon; Margaret S. Wooldridge
The current work presents new experimental autoignition and speciation data on the two cis‐hexene isomers: cis‐2‐hexene and cis‐3‐hexene. The new data provide insights on the effects of carbon‐carbon double bond location and stereoisomeric structures on ignition delay times and reaction pathways for linear hexene isomers. Experiments were performed using the University of Michigan rapid compression
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Decomposition of 2,6‐diamino‐3,5‐dinitropyrazine‐1‐oxide (LLM‐105): From thermodynamics to kinetics Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-09-28 Qifeng Hou; Shiyao Niu; Can Huang; Xiaoqing Wu; Wengang Qu; Feng Zhang
The mechanism of initial decomposition of energetic compound is crucial to understand the heat release efficiency, impact sensitivity, toxic emission, and so on. In the present study, we progressively explored the thermodynamic and kinetic features of the decomposition of LLM‐105, or 2,6‐diamino‐3,5‐dinitropyrazine‐1‐oxide, a kind of nitro compound in energetic materials using theoretical calculations
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Cover Image, Volume 52, Issue 11 Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-09-25
The cover image is based on the Article Influence of the double bond position in combustion chemistry of methyl butene isomers: A shock tube and laser absorption study by Farhan Arafin et al., https://doi.org/10.1002/kin.21396.
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Kinetic study of the CN radical reaction with 2‐methylfuran Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-07-21 James Lee; Kacee Caster; Trey Maddaleno; Zachery Donnellan; Talitha M. Selby; Fabien Goulay
The gas phase reaction of the ground state cyano‐radical (CN (X2∑+)) with 2‐methylfuran (2‐MF) is investigated in a quasi‐static reaction cell at pressures ranging from 2.2 to 7.6 Torr and temperatures ranging from 304 to 440 K. The CN radicals are generated in their ground electronic state by pulsed laser photolysis of gaseous cyanogen iodide (ICN) at 266 nm. Their concentration is monitored as a
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Study of the reactions of OH with HCl, HBr, and HI between 298 K and 460 K Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-07-24 Victor G. Khamaganov; Vladimir L. Orkin; Igor K. Larin
The reactions between OH radicals and hydrogen halides (HCl, HBr, HI) have been studied between 298 and 460 K by using a discharge flow‐electron paramagnetic resonance technique. The rate constants were found to be kHCl(298 K) = (7.9 ± 1.3) × 10−13 cm3 molecule−1 s−1 with a weak positive temperature dependence, kHBr (298‐460 K) = (1.04 ± 0.2) × 10−11 cm3 molecule−1 s−1, and kHI(298 K) = (3.0 ± 0.3) × 10−11
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Detailed chemomechanistic sensitivity study on the alkoxylation of fatty amines Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-07-31 Pia Müller; Kevin van Eeten; Wyatt Winkenwerder; John van der Schaaf; Ivo Filot
The mechanism of the autocatalytic alkoxylation of fatty amines was elucidated using a combined experimental and theoretical approach. The kinetic parameters of the elementary reaction steps are fitted to the experimental data gained in semibatch for propylene and butylene oxides with dodecylamine. A quality‐of‐fit sensitivity study was conducted to assess the robustness and accuracy of the model.
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Homogeneous conversion of NOx and NH3 with CH4, CO, and C2H4 at the diluted conditions of exhaust‐gases of lean operated natural gas engines Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-09-25 Steffen Schmitt; Sabrina Schwarz; Lena Ruwe; Jacqueline Horstmann; Franziska Sabath; Lubow Maier; Olaf Deutschmann; Katharina Kohse‐Höinghaus
Understanding gas‐phase reactions in model gas mixtures approximating pre‐turbine heavy‐duty natural gas engine exhaust compositions containing NO, NH3, NO2, CH4, CO, and C2H4 is extremely relevant for aftertreatment procedure and catalyst design and is thus addressed in this work. In a plug‐flow reactor at atmospheric pressure, five different model gas mixtures were investigated in the temperature
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Diels‐Alder reaction rate in the solid state and the evidence of the location of molecular complexes between the reagents on the reaction pathway Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-09-22 Vladimir D. Kiselev; Anastasia O. Kolesnikova; Ildar F. Dinikaev; Alexey A. Shulyatiev; Alexander E. Klimovitskii; Dmitry A. Kornilov
The rate of reactions in the solid phase with uniform grinding of crystals of dienes, anthracene, and 9,10‐dimethylanthracene, with dienophiles, tetracyanoethylene, N‐phenylmaleimide, and 4‐phenyl‐1,2,4‐triazoline‐3,5‐dione, has been studied. It was shown that, despite the high difference in the reaction rates in solution, the rates of these reactions in the solid phase are much closer. For anthra
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Reaction kinetics of a series of alkanes with ClO and BrO radicals: A theoretical study Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-09-17 Parth Gupta; B. Rajakumar
Reactive halogen species (ClO and BrO) play a critical role in the stratospheric ozone depletion. However, the reactivity of these radical moieties with volatile organic compounds is also important in determining the composition of the Earth's atmosphere. In this study, the reactions of BrO and ClO radicals with a series of smaller linear alkanes (CnH2n+2, n = 1,2,3, and 4) were studied using the
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Studies on the reaction between reduced riboflavin and selenocystine Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-09-16 Ilia A. Dereven'kov; Sergei V. Makarov; Pavel A. Molodtsov; Anna S. Makarova
Selenocysteine (Sec) is a crucial component of mammalian thioredoxin reductase (TrxR) where it serves as a nucleophile for disulfide bond rupture in thioredoxin (Trx). Generation of the reduced state of Sec in TrxR requires consecutive two electron transfer steps, namely: (i) from NADPH to flavin adenine dinucleotide, (ii) from reduced flavin to the disulfide bond Cys59‐S‐S‐Cys64, and finally (iii)
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Unraveling chemical structure of laminar premixed tetralin flames at low pressure with photoionization mass spectrometry and kinetic modeling Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-09-16 Yuyang Li; Jiabiao Zou; Wenhao Yuan; Chuangchuang Cao; Yan Zhang; Fei Qi; Jiuzhong Yang
This work reports an investigation on laminar premixed flames of tetralin at 30 Torr and equivalence ratios of 0.7 and 1.7. Measurements of the chemical structure including identification and mole fraction measurements of free radicals, isomers, and polycyclic aromatic hydrocarbons (PAHs) were performed using synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV‐PIMS). A kinetic model
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Kinetics of esterification of the levulinic acid with n‐hexanol, n‐octanol, and 2‐ethylhexanol in the presence of methanesulfonic acid as a catalyst under nonisothermal conditions Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-09-12 Łukasz Hamryszak; Miroslaw Grzesik
The levulinic acid was esterified with alcohol at an alcohol to acid molar ratio of 3:1, 5:1, and 10:1 in the presence of a 0.1 wt% methanesulfonic acid catalyst. During esterification, the temperature was changed linearly from 373 to 428 K and its average change was 4.5 K/min. The authors stated that reactions were of second order and that the activation energy (E) decreased from 61 to 46 kJ/mol in
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Shock‐tube spectroscopic water measurements and detailed kinetics modeling of 1‐pentene and 3‐methyl‐1‐butene Int. J. Chem. Kinet. (IF 1.531) Pub Date : 2020-09-12 Claire M. Grégoire; Charles K. Westbrook; Sulaiman A. Alturaifi; Olivier Mathieu; Eric L. Petersen
To understand the effects of the chemical structure of two C5 alkene isomers on their combustion properties, and to highlight the major chemical reactions occurring during their high‐temperature oxidation, water time histories were measured behind reflected shock waves for the oxidation of 1‐pentene (C5H10‐1) and 3‐methyl‐1‐butene (3M1B) in 99.5% Ar. The experiments were carried out at three different