Progress in Reaction Kinetics and Mechanism (PROG REACT KINET MEC )

Journal description

Now in its 29th Volume, Progress in Reaction Kinetics and Mechanisms is published four times a year. It presents in-depth reviews of topics of current interest. It brings together work from many sources and thus provides a handy source of reference.

Current impact factor: 0.35

Impact Factor Rankings

2015 Impact Factor Available summer 2015
2013 / 2014 Impact Factor 0.351
2012 Impact Factor 0.373
2011 Impact Factor 0.761
2010 Impact Factor 0.45
2009 Impact Factor 0.821
2008 Impact Factor 0.44
2007 Impact Factor 0.375
2006 Impact Factor 0.25
2005 Impact Factor 0.714
2004 Impact Factor 1.15
2003 Impact Factor 0.773
2002 Impact Factor 1.737

Impact factor over time

Impact factor
Year

Additional details

5-year impact 0.41
Cited half-life 0.00
Immediacy index 0.07
Eigenfactor 0.00
Article influence 0.08
Website Progress in Reaction Kinetics and Mechanism website
ISSN 1468-6783
OCLC 42052171
Material type Periodical, Internet resource
Document type Journal / Magazine / Newspaper, Internet Resource

Publications in this journal

  • [Show abstract] [Hide abstract]
    ABSTRACT: Hetero-/homogeneous micro-combustion of fuel-lean hydrogen–air mixtures in the plane channel containing a Pt/γ-Al2O3 catalyst washcoat was investigated numerically with detailed chemical kinetic mechanisms. The main theme of the paper is assessing the relative significance of the H2 gas-phase reaction as compared with catalytic reaction at different plane channel heights H, inlet mass fluxes J, and equivalence ratios  in plane micro-channels. The numerical model of micro-combustion was employed, which included detailed gas-phase and surface catalytic reaction mechanisms, heat transfer mechanisms, and diffusion of multi-component species. In order to sustain micro-combustion of fuel-lean hydrogen–air mixtures over Pt/γ–Al2O3 in the range of operating conditions, the solid wall temperature of the micro-combustors was maintained at 1400 K. In plane micro-channels, as the channel dimension is decreased, the micro-combustion characteristics of hydrogen–air mixtures are significantly impacted due to radical and effective heat losses to the walls. However, the catalytic walls contribute to sustain the H2 gas-phase reaction in the micro-channels by decreasing heat losses to the walls due to the exothermic surface catalytic reaction, which also restrains the H2 gas-phase reaction by extracting radicals owing to typically high absorption rates of the above-mentioned species at the walls. Therefore, the detailed radical chain reaction mechanisms can be significantly changed by the presence of surface catalytic reaction (wall reaction), and the radical accumulation in the gas-phase can be restrained. In the present work, the effects of the above-mentioned three key parameters on the interaction between the surface catalytic and gas-phase reactions are discussed. For fuel-lean hydrogen–air mixtures, in each case, the limiting values of the plane channel height, inlet mass flux, and equivalence ratio beyond which the gas-phase reaction become negligible as compared with the surface catalytic reaction are explored. The computational results indicate that variation of the hydrogen–air inlet mass flux at constant inlet equivalence ratio and plane channel height alters the balance between the diffusive and convective mass fluxes. Finally, the equivalence ratio of the hydrogen–air mixtures significantly effects the contribution of the H2 gas-phase reactions to the entire H2 conversion.
    Progress in Reaction Kinetics and Mechanism 01/2015; 40(1).
  • [Show abstract] [Hide abstract]
    ABSTRACT: The decomposition processes and reactivity of C4F9OCH2O• radical formed from C4F9OCH3(HFE-7100) have been studied by density function theory computational methods. All calculations were performed at B3LYP and mPW1PW91 levels of theory with the 6-311G(d, p) basis set. The calculated barrier heights were further improved by QCISD(T)/6-31G(d)//MP2/6-31G(d) methodology to obtain better rate constants. Five possible pathways were investigated: reaction with O2, reaction with OH radical, C-O bond dissociation, release of H radical and finally rearrangement of the radical and then C-O bond cleavage with energy barriers of 6.35 (6.09) [12.12], 12.85 (16.87) [7.51], 17.05 (21.77) [28.34], 20.3 (20.75) [18.13], 32.60 (31.50) [32.63] and 16.07 (18.73) [20.04] kcal mol-1, respectively (the values in the parentheses for mPW1PW91 and in the brackets for the QCISD(T) method). Rate constants were calculated by utilising canonical transition state theory in the temperature range of 200–400 K and 1 atm pressure, and Arrhenius diagrams were plotted. The results showed that H elimination and H abstraction pathways are dominant for degradation of C4F9OCH2O• radical in the atmosphere. A smooth transition from the reactants to products on the corresponding potential energy surface was confirmed by intrinsic reaction coordinate calculations.
    Progress in Reaction Kinetics and Mechanism 01/2015; 40(1).
  • [Show abstract] [Hide abstract]
    ABSTRACT: The solvent effects on the reaction of 1-fluoro-2,4-dinitrobenzene with aniline was studied in various compositions of molecular-molecular solvent mixtures and molecular solvent-2-hydroxyethylammonium formate mixtures as media containing an ionic liquid. A mounting trend with the mole fraction of water in aqueous solution of alcohols up to a maximum at a mole fraction of 0.9 with respect to water was found, but a mild decrease with the mole fraction of ethyl acetate in methanol–ethyl acetate mixtures. A similar increasing trend was observed with increasing methanol, ethanol, 2-propanol and dimethylsulfoxide content in the mixtures containing the ionic liquid. Solvent effect investigations based on linear free energy relationship confirm that polarity has a major effect in molecular-molecular solvent mixtures, whereas polarity and hydrogen–bond acceptor ability were the dominant factors on reaction rate in molecular-ionic solvent mixtures. A nonlinear free energy relationship based on the preferential solvation hypothesis showed differences between the microsphere solvation of the solute and the bulk composition of the solvents. In these mixtures, the intermediate of the reaction was preferentially solvated by the ionic liquid.
    Progress in Reaction Kinetics and Mechanism 01/2015; 40(1).
  • [Show abstract] [Hide abstract]
    ABSTRACT: Electro-oxidation of catechol derivatives has been studied in the presence of N-methylbenzylamine as nucleophile in phosphate buffer (c=0.15 M, pH=7)/ethanol solution using cyclic voltammetry and controlled-potential coulometry (CPC). Voltammetric data indicate that a 1,4-Michael addition of N-methylbenzylamine from its NH group to the electrochemically derived o-quinone via an ECE mechanism has occurred. Moreover, the progress of coulometry confirmed our electrochemical mechanism. The electrochemical synthesis of quinone derivatives has been successfully accomplished using CPC in a two-compartment cell and the products were characterised by FTIR and NMR spectroscopy and elemental analysis.
    Progress in Reaction Kinetics and Mechanism 01/2015; 40(1).
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    ABSTRACT: The thermal stability and decomposition kinetics of riboflavin were investigated by nonisothermal thermogravimetric analysis (TGA) experiments in an inert atmosphere. For kinetic analysis, riboflavin was heated from room temperature to 800 °C with five different heating rates (5,10,15,20 and 30°C min-1). From the thermal decomposition process, it was found that there are two main stages of pyrolysis. In the DTG thermograms, the temperature peaks at maximum weight loss rate changed with varying heating rate. The kinetic parameters of decomposition including apparent activation energy (E a) and lnA (pre-exponential factor) under an inert atmosphere have been evaluated from the model-free isoconversion methods of Kissinger–Akahira–Sunose (KAS), Flynn–Wall–Ozawa (FWO) and Friedman over the whole temperature domain. It was found that values of E a and lnA decrease with increasing conversion (α). The reaction order does not have a significant influence on the process because of the high value of the pre-exponential factor. The apparent activation energy distributions with conversion calculated by these methods ranged between 15.18 and 236.55 kJ mol-1, and varied over a broad range in a complex manner depending on the heating rate.
    Progress in Reaction Kinetics and Mechanism 01/2015; 40(1).
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    ABSTRACT: In the last years, the stability of carbamate pesticides have been studied by our research group in a large amount biomimetic microheterogeneous media such as micelles, reverse micelles. These microheterogeneous media included different surfactants species and hence different self-assembled structures. In particular, the basic hydrolysis of carbofuran and its derivatives have been analyzed in the presence of anionic, cationic, non-ionic and reverse micelles. The obtained results of these physicochemical and kinetic studies as well as a consistent comparison of these results its been reported to summarize in the present review paper.
    Progress in Reaction Kinetics and Mechanism 02/2015;
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    ABSTRACT: The kinetics and mechanism of nitrogen monoxide (NO) adsorption and oxidation on a tungsten oxide nanocrystalline surface have been studied. First principle calculations were performed within the framework of density functional theory with the ONIOM method at the (B3LYP/LANL2DZ:UFF) level. The activation energy for the rate-determining step of the reaction was determined as 0.45 eV. NBO analysis confirmed that charge transfer has occurred from the adsorbate to the surface. Density of state spectral analysis showed that the Fermi level was shifted to higher values and confirmed the effective interaction between the nanocrystal and adsorbate. HOMO–LUMO analysis showed that crystal band gap was reduced after adsorption. Quantum reactivity indices showed that the chemical hardness was reduced after adsorption which corresponded to the band gap reduction. The electronic chemical potential was shifted to more positive values while the electrophilicity of the surface was reduced after adsorption. These parameters predict that charge transfer has occurred to the surface.
    Progress in Reaction Kinetics and Mechanism 01/2015; 40(1).
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    ABSTRACT: ZnO was grown on Mordenite zeolite, activated carbon and alumina substrates by a liquid deposition method. The photocatalytic activity of the synthesized samples was elucidated using the photodegradation of Acid Blue 92 dyes as a pollutant under UV light irradiation. Supports play a key role in AB92 photodegradation and significantly improve the photocatalytic activity of ZnO. Different supports form additional transport channels and provide a desirable pathway for the charge carriers. The supports effectively construct porous structures with more active sites. Hence, the higher photocatalytic activity of supported catalysts was attributed to the large surface area and charge carrier separation. Bader’s AIM theory showed that the strength and nature of intermolecular interactions between ZnO and various supports is different. All geometry structures optimized with B3LYP/6-31g (d) level theory. The performed local reactivity descriptors determined the reactive sites in molecules demonstrating the mechanism for the enhanced photocatalytic activity of composites. Both experimental and theoretical results confirm that the insertion of ZnO nanoparticles on the supports enhances electron transfer between ZnO and catalyst surface, thus obstructing the charge recombination. The highest photocatalytic activity was observed for ZnO/MOR nanocomposite due to its high surface area, unique structure of MOR and photonic efficiency.
    Progress in Reaction Kinetics and Mechanism 01/2015;
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    ABSTRACT: The adsorption kinetics of adenine and adenosine on a ligand-exchange matrix, carboxymethyl diaminoethane poly(vinyl chloride) in cobalt form (cobalt-CMEDA-PVC), have been studied in a fixed-bed column system. The initial ligand concentrations ranged between 1.25x10-5 and 2.0x10-4 mol L-1. The kinetic studies were carried out spectrophotometrically, in order to determine the rate-controlling step of the adsorption. The kinetic data of the single-component systems were acquired from the breakthrough curves of the ligands on the basis of the equivalent points method. In this study, the homogeneous diffusion model was adapted to a fixed-bed column system to describe the differentiation in the ligand concentration of the effluent, beginning from breakthrough point as a function of time. The results obtained for the adsorption kinetics indicated that the diffusion step plays a significant role in the adsorption kinetics of the ligands, due to the fact that the adsorption performance was strongly affected by the initial concentration of ligands.
    Progress in Reaction Kinetics and Mechanism 01/2015; 40(1).
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    ABSTRACT: The kinetics of the entire process of the SAPO-34 catalyst for the transformation of methanol into olefins in the 400–450 °C range has been established by using the experimental data obtained in an isothermal fixed bed reactor. The model considers the activity change of SAPO-34 zeolite with time on stream. The activity of the catalyst consists of two parts: the stabilisation activity (while methanol is fully transformed) and the deactivation activity (while methanol is not all transformed). According to the activity of the catalyst, this study measured the evolution of each olefin with time on stream respectively.
    Progress in Reaction Kinetics and Mechanism 01/2015; 40(1).
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    ABSTRACT: Electrochemical oxidation of catechol has been studied in the presence of thioacetamide (TAM) in a phosphate buffer solution (0.2 mol L-1, pH=6.0) at the surface of glassy carbon electrode by means of cyclic voltammetry. After the cyclic voltammetric investigation of the reaction mechanism of TAM with catechol, TAM has been determinated by means of the differential pulse voltammetry technique. The results showed that the cathodic peak current of catechol reduced in the presence of various concentrations of TAM and that catechol can participate in a 1,4-Michael addition reaction with TAM under an EC mechanism. The decreasing of the cathodic current of catechol showed a linear relationship with the TAM concentration that can be used for the determination of TAM with a detection limit less than 3 μmol L-1.
    Progress in Reaction Kinetics and Mechanism 01/2015; 40(1).
  • Progress in Reaction Kinetics and Mechanism 12/2014; 39(4):328-340.
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    ABSTRACT: In this work, using quantum mechanics, the mechanism of reaction between 2-aminopyrimidine with dichloro-[1-methyl-2-(naphthylazo) imidazole] palladium(II) complex was investigated. The reaction produces two five-coordinated intermediates which are converted into final products through two possible pathways (nucleophile-dependent pathway and solvent-dependent pathway). The activation energy and activation Gibbs free energy of two pathways have been calculated and compared with each other and experimental results. These activation energies for the solvent-dependent pathway are greater in comparison with the nucleophile-dependent pathway which demonstrates that the latter is the dominating route and makes the main contribution to the reaction. Considering solvent effects, the activation Gibbs free energy for the rate determining step of the nucleophile-dependent pathway was calculated, which was in good agreement with the experimental value. Although the theoretical activation energy shows a suitable behaviour qualitatively, it is not fully consistent with the experimental value. All of the calculations were performed using a hybrid density functional method (B3LYP) in the solution phase (PCM model).
    Progress in Reaction Kinetics and Mechanism 12/2014; 39(4).
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    ABSTRACT: Methylcyclohexane (MCH) dehydrogenation is an important reforming reaction and is considered as a model naphthene dehydrogenation reaction. An increase in the rate of this reaction with the addition of hydrogen at low pressures has been observed by various researchers in the field. This enhancement in rate is described, in the present study, using the concept of associative adsorption of MCH with hydrogen in Langmuir – Hinshelwood – Hougen – Watson single-site and dual-site surface reaction mechanisms. The various rate equations developed on these bases are tested against the experimental data of Usman over Pt/Al2O3 and the best-fit rate model is presented. An activation energy of 52.0 kJ mol–1 is obtained for the best-fit rate model.
    Progress in Reaction Kinetics and Mechanism 12/2014; 39(4):404-417.
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    ABSTRACT: Electrochemical oxidation of hydroquinones (1a,b) was studied in the presence of 2-acetyl-gamma-butyrolactone (3) as nucleophile in phosphate buffer solution (pH 7.0 and c = 0.15 mol L–1):ethanol (80 : 20), using cyclic voltammetry and controlled potential coulometry. The results indicated that the p-benzoquinone derived from (1a,b) participates in 1,4-Michael addition reaction with 3 via an EC mechanism which produces the relatively new hydroquinone derivatives (5a,b). The electrochemical synthesis of (5a,b) has been successfully performed on carbon rod electrodes in an undivided cell. Furthermore, the observed homogeneous rate constants of the reaction between hydroquinones and 2-acetyl-gamma-butyrolactone were estimated by comparing the experimental cyclic voltammograms curves with those digitally simulated.
    Progress in Reaction Kinetics and Mechanism 12/2014; 39(4).
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    ABSTRACT: N,N-bis(2-hydroxyl ethyl) Pongamia glabra oil fatty amide (HEPA) was synthesised by the aminolysis of pongamia oil. The structural elucidation of HEPA was carried out by FTIR, 1H NMR and 13C NMR spectroscopy. Physicochemical studies were carried out by standard laboratory methods. Melting point of pongamia glabra oil and HEPA was measured through differential scanning calorimetry. Thermogravimetry/differential thermogravimetry analysis (TG/DTGA) was used to evaluate the thermal and kinetic behaviour of synthesised HEPA in nitrogen atmosphere under non-isothermal conditions with heating rates of 5, 10, 20, and 30 °C min–1. The TG curves of polymers at four heating rates were approximately in the same shape which indicated that mass loss is independent of heating rate. Obtained TGA data were analysed by the means of model-free isoconversional methods using Flynn – Wall – Ozawa and Kissinger – Akahira – Sunoseon applications on the whole range of temperature, and were found to be consistent. It was found that at the end of the decomposition process, the value of activation energy increases.
    Progress in Reaction Kinetics and Mechanism 12/2014; 39(4).
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    ABSTRACT: An aza-crown ether ligand was synthesised and characterised. The chemical composition of the binary complex containing cerium(III) and the ligand was determined by fluorescence spectroscopy. A new metallomicellar system comprising the cerium(III) complex of the ligand and an anionic micelle (n-lauroylsarcosine) was used as catalyst in the hydrolysis of bis(4-nitrophenyl) phosphate ester (BNPP). The catalytic rate of BNPP hydrolysis and the local concentration effect of the micelle were measured kinetically using UV-Vis spectrophotometry. The results indicated, that compared with a cationic metallomicelle system made from the aza-crown ether, lanthanum(III) ion and CTAB cationic surfactant in our previous report, the anionic metallomicelle exhibited a six-fold higher catalytic activity in BNPP hydrolysis at neutral pH and the same other conditions, thus the micelle based on LSS provides a more effective catalytic environment for reaction. A reaction mechanism has been proposed.
    Progress in Reaction Kinetics and Mechanism 09/2014;
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    ABSTRACT: Ni(HCO3)2, with a unique phase and high crystallinity, was synthesised utilising urea hydrolysis. The physicochemical properties of the synthetic samples were characterised by X-ray diffraction, scanning electron microscopy and N2-adsorption – desorption measurements. The heterogeneous Ni(HCO3)2 catalysts presented high catalytic activity in the synthesis reaction of benzoin ethyl ether from benzaldehyde and ethanol. Furthermore, the catalysts could be recycled several times and showed stable activity without structural change. The kinetic parameters were obtained by the half-life law which showed that the reaction was belong first-order. The apparent activation energy was 42.72 kJ mol–1. The reaction mechanism was probed theoretically using the HF/3-21G method, which suggested that benzoin ethyl ether is formed via a series of states i.e. a complex, transition states and intermediates. Especially, the role of C6H5CHOC2H5OH as an intermediate is significant.
    Progress in Reaction Kinetics and Mechanism 09/2014; 39(3).
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    ABSTRACT: Deuterium kinetic isotope effects support a mechanism for the Boyland–Sims oxidation involving a nucleophilic displacement by the amine on the peroxide oxygen.
    Progress in Reaction Kinetics and Mechanism 09/2014; 39(3).
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    ABSTRACT: Biodiesel production by transesterification of soybean oil with methanol was carried out efficiently over modified CaO by using octadecyltrichlorosilane as surface modifier. It was found that the fatty acid methyl esters (FAME) yield was significantly enhanced from 35.4% to 93.5% over modified CaO with a methanol/oil ratio of 15 : 1 at 65 °C after 3 h. Furthermore, good catalytic activity, i.e. 82.8% yield of FAME, remains even with a 2% water-content condition over modified CaO. The higher catalytic activity and good stability of modified CaO should be mainly attributed to the organic layer formed by the modifier over the CaO surface, which promotes the absorption of grease to CaO surface and protects CaO from water at the same time.
    Progress in Reaction Kinetics and Mechanism 09/2014; 39(3).