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

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

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

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

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

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

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

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

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

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

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

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.

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

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

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.

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

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

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

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

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)

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

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

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

Using Reaction Mechanism Generator (RMG), we have automatically constructed a detailed mechanism for acetylene pyrolysis, which predicts formation of polycyclic aromatic hydrocarbons (PAHs) up to pyrene. To improve the data available for formation pathways from naphthalene to pyrene, new high‐pressure limit reaction rate coefficients and species thermochemistry were calculated using a combination of

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

The determination of rate constants for consecutive irreversible reactions is a difficult and time‐consuming problem, especially when the research extends up to many subsequent products. Thus, the derivation of proper mathematical expressions would greatly facilitate the determination of these rate constants when only the rate constant of the first consecutive reaction is known. Many authors have dealt

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

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

The redox reaction between dicyanobis(bipyridine)iron(III) and iodide ion follows first‐order kinetics in 10% (v/v) tertiary butyl alcohol‐water. The reaction was found first and zero order in iodide and dicyanobis(bipyridine)iron(III), respectively, at 0.06 M ionic strength and 293 ± 1 K. The thermodynamic parameters of activation such as EA (16.07 kJ mol−1), A (1 × 10−4 M s−1), ΔH# (13.6 kJ mol−1)

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

The vibrational and rotational mode‐specific relaxations of CH3NO2 with 50 kcal/mol of initial internal energy in an argon bath is computed at 300 K at pressures of 10‐400 atm. This work uses archived information from our previously published [J. Chem. Phys. 142, 014303 (2015)] molecular dynamics simulations and employs our previous published [J. Chem. Phys. 151, 034303 (2019)] method for projecting

The pyrolysis of selected C3–C5 allylic hydrocarbons has been studied using a single‐pulse shock tube. A new single‐pulse shock tube has been designed and constructed by recommissioning an existing conventional shock tube. This facility enables the investigation of high‐temperature chemical kinetics with an emphasis on combustion chemistry. The modifications performed on the existing shock tube are

The overall rate constants for H‐abstraction (k H) from tetrahydrofuran and D‐abstraction (k D) from fully deuterated tetrahydrofuran by chlorine atoms in the temperature range of 298‐547 K were determined. In both cases, very weak negative temperature dependences of the overall rate constants were observed, described by the expressions: k H = (1.55 ± 0.13) × 10−10 exp(52 ± 28/T ) cm3 molecule−1 s−1

Electric arc furnace dust contains mainly ZnO, ZnFe2O4, and iron oxides. In this study, chemical composition of ZnO, ZnFe2O4, and Fe2O3 and leaching kinetics of ZnO, ZnFe2O4, and Fe2O3 in HNO3 solutions were investigated. It was seen that the dissolution of ZnO is very fast, therefore the leaching kinetics of ZnO cannot be determined. Kinetic parameters and model equations were derived for the leaching

Cyclopentane and methylcyclopentane oxidation was investigated in a jet‐stirred reactor at atmospheric pressure, over temperatures ranging from 900 to 1250 K, for fuel‐lean, stoichiometric, and fuel‐rich mixtures at a constant residence time of 70 ms. The initial mole fraction of both fuels was kept constant at 1000 ppm. The reactants were highly diluted by a flow of nitrogen to ensure thermal homogeneity

A detailed chemical kinetic model for oxidation of methylamine has been developed, based on theoretical work and a critical evaluation of data from the literature. The rate coefficients for the reactions of CHNH + O CHNH / CHNH + HO, CHNH + H CH + NH, CHNH CHNH, and CHNH + O CHNH + HO were calculated from ab initio theory. The mechanism was validated against experimental results from batch reactors

A combinatorial approach was applied to devise a set of reference Si–C–O–H species that is used to derive group‐additivity values (GAVs) for this class of molecules. The reference species include 62 stable single‐bonded, 19 cyclic, and nine double‐bonded Si–C–O–H species. The thermochemistry of these reference species, that is, the standard enthalpy of formation, entropy, and heat capacities covering

We conducted a simultaneous measurement of the potential of Cu2+, oxidation‐reduction potential (ORP), and the chemiluminescence intensity in the luminol‐H2O2‐KSCN‐CuSO4‐NaOH system. Two types of chemiluminescence were identified: a very faint continuous chemiluminescence and a strong oscillating chemiluminescence. The correlation between the potential of Cu2+ and ORP was measured experimentally for

Model chemistry G3(MP2,CC)//B3LYP/6‐311G(d,p) calculations of the potential energy surface for the reaction of phenyl radical (C6H5) with phenylacetylene (C8H6) have been carried out and combined with Rice‐Ramsperger‐Kassel‐Marcus/Master Equation calculations of temperature‐ and pressure‐dependent rate constants. The results showed that the reaction can serve as a viable source for the formation of

This study was undertaken to investigate the comparative substitution behavior of mononuclear trans‐ platinum(II) complexes with symmetric and asymmetric amine ligands. The rate of substitution of the aqua moeities from the complexes trans‐[Pt(NH3)2(H2O)2](ClO4)2 (tPt), trans‐[Pt(NH3)(NH2C2H5)(H2O)2](ClO4)2 (tPt2H2O), trans‐ [Pt(NH3)(NH2C3H7)(H2O)2](ClO4)2 (tPt3H2O), [trans‐Pt(OH2)2(NH2CH3)2](ClO4)2

Liquid‐phase esterification of acetic acid with n‐butanol to n‐butyl acetate is studied in the presence of a polymeric catalyst, that is, poly(o‐methylene p‐toluene sulfonic acid). The performance of the proposed catalyst is compared with the other commercially available homogeneous and heterogeneous catalysts in terms of its activity. Experiments are conducted in an isothermal stirred batch reactor

3‐Carene is an important potential biofuel with properties similar to the jet‐propellant JP‐10. Its thermal decomposition and combustion behavior is to date unknown, which is essential to assess its quality as a fuel. A combined experimental and kinetic modeling study has been conducted to understand the initial decomposition of 3‐carene. The pyrolysis of 3‐carene was investigated in a jet‐stirred

A model of core mechanism of hydrocarbon pyrolysis with good predictive ability is crucial to the development of active cooling technology for advanced aeroengines. In this work, a detailed core kinetic model of pyrolysis of C1–C4 hydrocarbon fuels is developed through the combination of a series of potential energy surfaces and validated against a series of experimental results. The kinetic model

The hydrogen‐abstraction‐C2H2‐addition (HACA) chemistry of naphthalenyl radicals has been studied extensively, but there is a significant discrepancy in product distributions reported or predicted in literature regarding appearance of C14H8 and C14H10 species. Starting from ab initio calculations, a comprehensive theoretical model describing the HACA chemistry of both 1‐ and 2‐naphthalenyl radicals

Herein a well‐sealed and thermostated kinetics assembly is designed and built, which can run stirred at different reaction temperatures. With the reaction assembly above and the volumetric method together, the hydrogen peroxide (H2O2) decomposition reaction kinetics is systematically investigated under a variety of reaction conditions over a copper‐doped buserite‐type layer manganese oxide (referred

In this paper, the kinetic model of colemanite dissolution in gluconic acid solutions was carried out in a batch reactor. The effects of the particle size, reaction temperature, stirring speed, gluconic acid concentration, and solid/liquid ratio on colemanite dissolution were experimentally studied. The empirical parameters were the gluconic acid concentration (0.05‐0.2 M), the temperature (20‐50°C)

Shock tube experiments have been carried out on 2‐methyl‐1‐butene (2M1B), 2‐methyl‐2‐butene (2M2B), and 3‐methyl‐1‐butene (3M1B)—the three isomers of methyl butene compound. Carbon monoxide (CO) time‐histories and ignition delay times are obtained behind reflected shockwaves over the temperature range of 1350‐1630 K and pressures of 8.3‐10.5 atm with stoichiometric mixtures of 0.075% fuel in O2/Ar

The pyrolysis of propane plays an important role in determining the combustion properties of natural gas mixtures and offers insight into the cracking patterns of larger fuels. This work investigates propane pyrolysis behind reflected shock waves with a multiwavelength laser‐absorption speciation technique. Nine laser wavelengths, sensitive to key pyrolysis species, were used to measure absorbance

We report ignition delay time measurements for methyl propanoate (MP) and methyl acrylate (MA), carried out in a high‐pressure shock tube. Experiments were performed behind reflected shock waves across a temperature range of 989‐1 367 K, for fuel‐air mixtures at equivalence ratios of ϕ = 0.5, 1.0, and 2.0, and nominal pressures of 1 and 4 MPa. Ignition delay times were found to decrease with increasing

A detailed chemical kinetic model has been developed for supercritical water oxidation (SCWO) of methylamine, CH3NH2, providing insight into the intermediates and final products formed in this process as well as the dominant reaction pathways. The model was adapted from previous mechanisms, with a revision of the peroxyl radical chemistry to include imine formation, which has recently been identified

A nonisothermal two‐dimensional lumped kinetic model of reactive liquid chromatography is formulated and applied to simulate the separation of multicomponent mixtures in a fixed‐bed cylindrical column operating under nonisothermal condition. The axial and radial variations of concentration and temperature as well as reversibility of the chemical reactions are incorporated in the model equations. The

The spin‐forbidden dissociation reaction of the N2O(X1Σ+) ground state has been investigated by both quantum calculations and experiments. Ab initio prediction at the CCSD(T)/CBS(TQ5)//CCSD(T)/aug‐cc‐pVTZ+d level of theory gave the crossing point (MSX) energy at 60.1 kcal/mol for the N2O(X1Σ+) → N2() + O(3P) transition, in good agreement with published data. The T‐ and P‐dependent rate coefficients

This work reports experimental and computational studies of polyurethanes depolymerization from industrial waste through a reaction with potassium hydroxide. A computational study was performed to identify the chemical reaction mechanism, which is more difficult to determine experimentally. Kinetic and thermodynamic parameters of activation process were also obtained by theoretical calculations. An

The second‐order rate constants (k) for reaction of 7‐chloro‐4‐nitrobenzofurazan 1 and 7‐methoxy‐4‐nitrobenzofurazan 2 with a series of nitroalkyl anions and several of para‐substituted phenoxide anions in aqueous solution at 20 °C have been reported. On the basis of the linear novel approach recently designed by Mayr and coworkers, the electrophilicity parameters E at the C‐5 position of the two nitrobenzofurazans

The kinetics of the reactions of 4‐nitrobenzofurazane 1a, 4‐nitrobenzothiadiazole 1b, and 4‐nitrobenzoselenadiazole 1c with a series of 4‐Y‐substituted phenoxide anions 2a‐e (Y = OMe, Me, H, Cl, and CN) in aqueous solution at 20°C were investigated photometrically. The derived second‐order rate constants (k2) have been combined with the nucleophilicity parameters values of these series of anions 2a‐e

Rate coefficients, k1(T), for the gas‐phase reaction of the OH radical with furan‐2,5‐dione (maleic anhydride (MA), C4H2O3), a biomass burning related compound, were measured under pseudo–first‐order conditions in OH using the pulsed laser photolysis–laser‐induced fluorescence method over a range of temperature (283‐374 K) and bath gas pressure (50‐200 Torr; He or N2). k1(T) was found to be independent

Photodegradation of organic pollutants strongly depends on design of metal oxide semiconductor photocatalysts. Graphene, if composited with ZnO, can effectively enhance its photocatalytic performance for the eradication of pollutants from aqueous medium. Here in, ZnO‐rGO is reported as highly active catalyst for degradation of methylene blue. A 200‐mg/L solution of methylene blue dye was completely

Detailed gas‐phase chemical kinetic models are widely used in combustion research, and many new mechanisms for different fuels and reacting conditions are developed each year. Recent works have highlighted the need for error checking when preparing such models, but a useful community tool to perform such analysis is missing. In this work, we present a simple online tool to screen chemical kinetic mechanisms

The adiabatic mechanism of the reaction of trichloroethylene with O(3P), exploring the various O‐atom addition and H‐atom abstraction channels, is theoretically studied at the MP2/6‐311++G(2d, 2p), MP2/aug‐cc‐pVTZ, CCSD/6‐31G(d), G3, and CBS‐QB3 levels of theory. From a kinetic point of view, the addition to the less substituted carbon atom of the double bond is more favorable than the addition to

The 1081 species cyclohexane‐oxidation elementary reaction mechanism of Silke et al. (DOI:10.1021/jp067592d) is reduced in the number of species by a factor using the local self‐similarity tabulation (LS2T) method. Reduced‐species mechanisms of both 20 (R20) and 15 (R15) species are created in the high‐pressure combustion regime typical of diesel engines. To evaluate the performance of R20 and R15