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.

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 k HCl(298 K) = (7.9 ± 1.3) × 10−13 cm3 molecule−1 s−1 with a weak positive temperature dependence, k HBr (298‐460 K) = (1.04 ± 0.2) × 10−11 cm3 molecule−1 s−1, and k HI(298 K) = (3.0 ± 0

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

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

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 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

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

This study reports experimental data and kinetic modeling of acetic acid esterification with n ‐pentanol using sulfated zirconia as a catalyst. Reactions were carried out in an isothermal well‐mixed batch reactor at different temperatures (50‐80°C), n‐pentanol to acid molar ratios (1:1‐3:1), and catalyst loadings (5‐10 wt% in relation to the total amount of acetic acid). The reaction mechanism regarding

Due to increasing demands for ecofriendly processes within the framework of green chemistry, and having shown substantial properties, especially in terms of toxicity, biodegradability, cost, and ease of preparation under ambient conditions, deep eutectic solvents (DESs) have become a suitable candidate as green solvents for reaction media in the past decade. In this work, condensation reaction of some

The kinetic curves for oxidation of dopamine hydrochloride in aqueous solution in the presence of ammonium peroxydisulfate were obtained by UV–vis spectroscopy and potentiometry. It was shown that the reaction follows the first‐order kinetic equation and proceeds at a low rate. The values for the activation energy and the preexponential factor were determined as 75 kJ × mol−1 and 4 × 108 s−1, respectively

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

The hydrogen abstraction reactions from hydrazine and its methyl derivatives by the H atom have been investigated theoretically by using CBS‐QB3//DSD‐BLYP‐D3(BJ)/Def2‐TZVP quantum chemical calculations and transition state theory calculations coupled with various tunneling correction methods. Both the products and transition state energies of the hydrogen abstraction from the amino group were stabilized

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(X 1Σ+) 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(X 1Σ+) → N2() + O(3P) transition, in good agreement with published data. The T ‐ and P ‐dependent rate coefficients

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

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 (k 2) have been combined with the nucleophilicity parameters values of these series of anions

Rate coefficients, k 1(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). k 1(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

Mechanism and kinetics of the thermal pyrolysis of ethyl 2‐furoate were studied in a wide range of conditions (ie, 500‐1500 K and 1‐7600 Torr) using the accurate dual‐level theory CCSD(T)&MP2(FC)//B3LYP/aug‐cc‐pVTZ and state‐of‐the‐art Rice‐Ramsperger‐Kassel‐Marcus based master equation rate model including hindered internal rotation and tunneling treatments. The predicted rate coefficients are found

A new method for calculating low‐pressure strong‐collision rate constants of dissociation and recombination reactions was proposed. The method is based on determining the density of states of the internal degrees of freedom of the reactant molecule by applying the inverse Laplace transform to the respective partition function, which, in turn, is calculated from the thermodynamic properties in the form

The experimental data of six different types of Pt‐containing alumina catalysts are used to study the detailed and rigorous kinetics of the methylcyclohexane dehydrogenation reaction. A large number of kinetic rate equations were formulated using the power law kinetics and the Langmuir‐Hinshelwood‐Hougen‐Watson (LHHW) kinetics, which were tested against the experimental data. For each catalyst, the

Sodium arsenate, the main component of arsenic‐containing solid waste pollutants, causes serious environmental health threats. Crystallization is one of the effective methods for separating and purifying sodium arsenate from arsenic‐alkali residue lixivium. However, the crystallization process is limited for its low observability and the lack of separation and purification data. In this work, a laser

In the current research, biodiesel production was investigated in the presence of solid catalysts of K2CO3/Al2O3 by transesterification of rapeseed oil. The specifications of produced fatty acid methyl esters like viscosity and flash point were studied, and it was noted that they complied with the requirements of ASTM D6751. In addition, the kinetic and thermodynamic parameters were explored considering

Reactions of aniline derivatives in dimethyl sulfoxide with phenyl 1‐(2,4‐dinitronaphthyl) ether yield aryl 1‐(2,4‐dinitronaphthyl) amine, which results in substitution of the phenoxy groups at the naphthyl ipso carbon atom. Rate constants were measured spectrophotometrically, and reaction proton transfer was rate limiting. The values of the rate coefficients indicate a rate‐limiting proton transfer

Collision rate constants and third‐body collision efficiencies are calculated for more than 300 alkanes, alcohols, and hydroperoxides, for the bath gases He, Ar, H2, and N2, and from 300 to 2000 K. The data set includes highly branched species and species with as many as 16 nonhydrogen atoms N, and it is analyzed to develop strategies for estimating collision properties more generally. Simple analytic

In this study, ZSM‐5, which is a Mobil‐type five‐type zeolite with well‐defined crystal morphology, is successfully synthesized via a seed‐assisted, liquid‐free method that uses iron ore tailings as a silica source. The ZSM‐5 crystallization kinetics at 423, 433, and 443 K and different synthesis times are investigated to identify the nucleation and crystallization mechanisms of the synthesized ZSM‐5

Kinetics of hydroformylation of camphene was investigated in the presence of [Rh(CO)2(acac)]/P(OPh)3 catalyst in a temperature range of 363–383 K. The influence of parameters such as stirring speed, camphene, catalyst, ligand concentrations, and partial pressures of H2 and CO on the activity and selectivity of the catalyst has been studied. The rate showed a first‐order dependence with respect to catalyst

The objective of this research work was to investigate the kinetics of esterification of acetic acid with n ‐butanol through the variation of experimental parameters. The reaction mixture was catalyzed heterogeneously by a sulfonated catalyst in batch mode of operation. The catalyst was prepared from abundantly available agro‐waste, Cajanus cajan husk by chemical activation process, which produces

The kinetic parameters and enthalpies of the Diels–Alder reactions between cyclopentadiene and 2,3‐dicyano‐1,4‐benzoquinone leading to the formation of two different monoadducts and bisadduct were determined. The stability of adducts is compared. Monoadduct appears to be thermodynamically more stable than the bisadduct. Comparison with the other Diels–Alder reactions studied previously allows us to

Kinetics of the reaction of Cl atoms with methanol has been investigated at 2 Torr total pressure of helium and over a wide temperature range 225‐950 K, using a discharge flow reactor combined with an electron impact ionization quadrupole mass spectrometer. The rate constant of the reaction Cl + CH3OH → products (1) was determined using both absolute measurements under pseudo‐first order conditions

The kinetics of the self‐reaction of BrO radicals has been studied over a wide temperature range (T = 220‐950 K) at 2 Torr total pressure of He using a low‐pressure flow reactor combined with a quadrupole mass spectrometer: BrO + BrO → 2Br + O2 (1a) and BrO + BrO → Br2 + O2 (1b). The overall rate constant for this reaction (defined by d[BrO]/dt = –2k1[BrO]2) was found to be k1 = k1a +k1b = (1.32 ±

The sequestration of carbon dioxide fumes from oxyfuel combustion is used to reduce significantly the carbon dioxide emissions from coal‐fired power plants. Impurities like nitric oxide, present in the fumes, can cause technical difficulties during the capture, the treatment, the transport, and the storage steps of the CO2 fumes. The purpose of this study is to better understand the oxidation of nitric

In this article, a binderless dealuminated HZSM‐5 zeolite (Si/Al = 41.4) was used as a catalyst for the isomerization of a mixture of ethylbenzene and xylene. The experimental results indicated that at low residence times the catalyst is effective to isomerize the ethylbenzene into xylenes. A comprehensive kinetic model considering chemisorption, surface chemical reactions, and diffusional processes

We established a gas‐phase, elementary reaction model for chemical vapor deposition of silicon carbide from methyltrichlorosilane (MTS) and H2, based on the model developed at Iowa State University (ISU). The ISU model did not reproduce our experimental results, decomposition behavior of MTS in the gas phase in an environment with H2. Therefore, we made several modifications to the ISU model. Of the

The graphene nanosheet (GNS) is used as a catalyst support for various catalytic reactions. A comprehensive study of functionalized GNS (FGNS)‐supported catalyst for the purpose of hydrocracking (HDC) process provides a guide to exploring the potential applications and discovering their superior properties. In this research, to study the effect of the support on the conversion and selectivity of n‐hexadecane

Rate coefficients for the OH + (CH3)3SiCl (trimethylchlorosilane) gas‐phase reaction were measured over the temperature range 295–375 K using a pulsed laser photolysis laser‐induced fluorescence technique. The room temperature rate coefficient was determined to be k1(295 K) = (2.51 ± 0.13) × 10−13 cm3 molecule–1 s–1. The Arrhenius expression k1(T) = (7.06 ± 2.15) × 10−12 exp[–(992 ± 101)/T] cm3 molecule–1

A new modified walnut shell was prepared by grafting l‐aspartic acid (ASP) to walnut shell (WNS) in the hydrochloric acid solution (1.0 M). The effects of stirring speed, particle size, solid‐liquid ratio, temperature, and modifying agent concentration on grafting yield were studied. The grafting process conditions were optimized, and the grafting yield of WNS reached ∼14 wt%. The kinetics of the grafting

The products of the Cl‐atom‐initiated oxidation of hydroxyacetone (HYAC, CH3C(O)CH2OH) have been examined under conditions relevant to the earth's lower atmosphere. Over the range of temperatures studied (252‐298 K), in the absence of NOx, methylglyoxal (CH3C(=O)CH=O, MGLY) was formed with a primary yield >84% (96 ± 9% at 298 K), while in the presence of elevated NOx, MGLY and formic acid were both

Uncertainty analysis is a useful tool for inspecting and improving detailed kinetic mechanisms because it can identify the greatest sources of model output error. Owing to the very nonlinear relationship between kinetic and thermodynamic parameters and computed concentrations, model predictions can be extremely sensitive to uncertainties in some parameters while uncertainties in other parameters can

Increasing energy demand in the world leads to more electricity generation mainly at fossil fuel power plants. Greenhouse gases are thus produced and mostly emitted to the atmosphere directly, resulting in global warming and climate change. Carbon dioxide is believed to be a main pollutant among greenhouse gases responsible from global warming. Conventional systems using mostly amine solutions to capture

More than 70% of the world's nickel reserves are found in laterite ores. In this research, a laterite ore sample, containing Ni, Co, and Fe, was employed to study the recovery of nickel and cobalt. Thus, the effect of calcination, acid concentration, percent solids, and stirring rate on nickel and cobalt recoveries from an iron‐rich laterite sample was investigated. Optimization with response surface

Levels of the stabilized Criegee Intermediate (sCI), produced via the ozonolysis of unsaturated volatile organic compounds (VOCs), were estimated at two London urban sites (Marylebone Road and Eltham) and one rural site (Harwell) in the UK over the period of 1998-2012. The steady-state approximation was applied to data obtained from the NETCEN (National Environmental Technology Centre) database, and

A comprehensive and hierarchical optimization of a joint hydrogen and syngas combustion mechanism has been carried out. The Kéromnès et al. (Combust Flame, 2013, 160, 995-1011) mechanism for syngas combustion was updated with our recently optimized hydrogen combustion mechanism (Varga et al., Proc Combust Inst, 2015, 35, 589-596) and optimized using a comprehensive set of direct and indirect experimental

Reaction with hydroxyl radicals (OH) is the major pathway for removal of cyclic volatile methyl siloxanes (cVMS) from air. We present new measurements of second-order rate constants for reactions of the cVMS octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) with OH determined at temperatures between 313 and 353 K. Our measurements were made

The bimolecular rate coefficients [Formula: see text] and [Formula: see text] were measured using the relative rate technique at (297 ± 3) K and 1 atmosphere total pressure. Values of (2.7 ± 0.7) and (4.0 ± 1.0) × 10-15 cm3 molecule-1 s-1 were observed for [Formula: see text] and [Formula: see text], respectively. In addition, the products of [Formula: see text] and [Formula: see text] gas-phase reactions