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

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.

  • Impact factor
    0.37
    Show impact factor history
     
    Impact factor
  • 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: 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: 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 05/2014;
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    ABSTRACT: The effect of nanoparticle size on the kinetics of the water–gas-shift (WGS) reaction using an iron based catalyst used in the Fischer – Tropsch synthesis (FTS) was studied in a continuous spinning basket reactor. A series of iron oxide particles with different particle sizes doped with copper and lanthanum was prepared as the catalyst. A new size-dependent kinetic model for the WGS reaction has been developed by a thermodynamic method. The kinetic parameters of the model were evaluated from experimental results for iron catalysts with different particle sizes. The results show that the parameters of the size-dependent model changed with temperature and particle size. The surface tension energy (σ) of the iron oxide catalyst and the size-independent activation energy for the WGS reaction was calculated from the experimental results. The size-independent activation energy for the WGS reaction is calculated as 4 kJ mol−1 based on haematite particles.
    Progress in Reaction Kinetics and Mechanism 01/2014; 39(2).
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    ABSTRACT: We describe here a mild and efficient method for the nucleophilic ring-opening of epoxides with amines, alcohols and water in the presence of nitromethane as a polar solvent without using any catalyst. The reactions are highly regioselective and afford the products in excellent yields within a short period of time at room temperature. The regioselectivity for this ring opening has been investigated using experimental and theoretical 1H and 13C NMR studies together with activation energy calculations at the B3LYP/6-311+G(2d, p) level of theory. The mechanism of nucleophilic attack has been investigated in terms of a direct attack or a methanol chain attack.
    Progress in Reaction Kinetics and Mechanism 01/2014; 39(1).
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    ABSTRACT: A metallomicelle system comprising an azacrown ether, lanthanum(III) ion and a cationic surfactant was constructed and used as catalyst in the hydrolysis of bis(4-nitrophenyl) phosphate ester (BNPP). The interaction between La(III) and the azacrown ether, and the resulting complex and BNPP, were analysed by fluorescence spectroscopy. The catalytic rate of BNPP hydrolysis was measured kinetically by UV-Vis spectrophotometry. The results indicated that the metallomicelle system exhibited relatively high stability and excellent catalytic function in BNPP hydrolysis, the rate of which, compared with the spontaneous hydrolysis, increased by a factor of ca 2 × 107 due to the catalytic effect of the active species and the local concentration effect of the micelle in the metallomicellar system. The results also showed that the complex, comprising La(III) ion, and the azacrown ether, is the active catalytic species, while the micelles provide a useful catalytic environment for reaction. On the basis of these results, a reaction mechanism for the catalytic hydrolysis of BNPP is proposed.
    Progress in Reaction Kinetics and Mechanism 01/2014; 39(1).
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    ABSTRACT: Biomass-derived glycerol is emerging as a renewable, cheap and versatile feedstock for the production of a variety of chemicals and fuels. In particular, hydrogenolysis of glycerol to other value-added chemicals over heterogeneous catalysts has been extensively studied in the past few years. The most desired products arising from this process are propanediols, i.e. 1,2-propanediol and 1,3-propanediol. Both diols are important industrial chemicals, being especially well-known as monomers for the production of many useful polymers. Although hydrogenolysis of glycerol is a promising new route for the production of propanediols, the design of applicable catalysts for its industrialisation is still a great challenge. In order to guide the rational development of efficient catalysts, several possible reaction mechanisms have been proposed based on experimental and theoretical investigations. A brief review is now presented on the reaction mechanisms for the hydrogenolysis of glycerol to propanediols over heterogeneous catalysts. The possible reaction mechanisms are summarised and classified. The main characteristics and general reaction conditions for each reaction mechanism are highlighted. Furthermore, the developing prospects and future direction of research are suggested.
    Progress in Reaction Kinetics and Mechanism 01/2014; 39(1).
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    ABSTRACT: TiO2 nanotubes were prepared by anodisation of Ti sheets using the conventional electrochemical technique as well as an emerging sonoelectrochemical technique. Scanning electron microscope analysis showed that ultrasoundassisted anodisation yielded more ordered and controllable TiO2 tube banks with higher tube diameter. TiO2 nanotubes prepared using the sonoelectrochemical method were used in the sonophotocatalytic degradation experiments of Congo Red dye and degradation kinetics were obtained. The effects of temperature and the amplitude of ultrasound energy were investigated and a kinetic equation, which also included the effect of ultrasound energy, was developed. The sonophotocatalytic degradation rate was found to be –r dye = kaCdye/(1 + k bC dye). The ultrasound energy did not influence the activation energy. It was observed that the reaction rate accelerated in the presence of ultrasound energy in the course of the experiments. The activation energy of the reaction was calculated to be 56.1 kJ mol–1.
    Progress in Reaction Kinetics and Mechanism 01/2014; 39(3).
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    ABSTRACT: In this study, the catalytic combustion of a volatile organic compound (VOC) namely formaldehyde on manganese oxide catalysts supported on silica or alumina, and on an industrial catalyst, i.e. a mixture of copper oxide and zinc oxide, was studied in the temperature range 125–225 °C. Formaldehyde was used as the aqueous solution. It was found that as the temperature was increased, the combustion of the produced and feed formaldehyde was enhanced whereas methanol combustion decreased. Also, the degree of conversion increased with the percentage of MnO in the catalysts.
    Progress in Reaction Kinetics and Mechanism 01/2014; 39(2).
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    ABSTRACT: A quantitative treatment of quenching processes under restricted geometry conditions in the Slow Exchange Limit is presented. The expressions for K SV have been obtained for this limit in some common situations that can arise in studies under restricted geometry conditions, such as an inhomogeneous quencher distribution in the solution, the presence of oxygen in solution, or the case of solutions containing a mixture of receptors. These situations have been considered and incorporated into the treatment.
    Progress in Reaction Kinetics and Mechanism 01/2014; 39(2).
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    ABSTRACT: The quality of predictions of reactivity coming from alternative theoretical approaches as related to the experimental values is examined for the hydrolysis of phenyl N-methylcarbamates. We have combined literature kinetic data for phenyl N-phenylcarbamates with our own kinetic data and have correlated them all with theoretically estimated reactivity indices: i.e. Hirshfeld and NBO atomic charges, the Parr electrophilicity index (ω), and the electrostatic potential at the carbon and oxygen atoms of the reaction centre (VC, VO). The results show that the best correlation coefficients are obtained with the electrostatic potentials VO and VC and the electrophilicity index ω. The variations of electronic structure in the phenolate ions (leaving groups) were also analysed. The results obtained illustrate the accuracy of theoretical description of local properties as provided by the electrostatic potential at the nuclei.
    Progress in Reaction Kinetics and Mechanism 01/2014; 39(1).
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    ABSTRACT: Reactive oxygen species (ROS) are reactive molecules which are produced normally by metabolic reactions. 2,7-Dichlorofluorescein diacetate (DCHF-DA) assay is used to determine intracellular levels of ROS in cancer cells. In the present study, the mechanism and kinetic parameters of this determination are obtained by kinetic Monte Carlo simulation. The values of the rate constants for the suggested mechanism were obtained by simulation. Then, the effect of DCHF-DA concentration on the rate of reaction was studied. According to the results, the product concentration should increase on increasing the DCHF-DA concentration. In addition, the effect of ROS concentration on the rate of reaction was determined.
    Progress in Reaction Kinetics and Mechanism 01/2014; 39(3).
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    ABSTRACT: The absorption of CO2 on 1-butyl-3-methylimidazolium acetate ([Bmim] [Ac]) with different substituents are calculated systematically at the GGA/PW91 level. Three hydrogen bonds are formed between [Ac]− and the cations of 1-n-[Bmim][Ac] ([NBmim]+) and 1-tert-[Bmim][Ac] ([TBmim]+). The interaction between CO2 and [NBmim][Ac] via a C–O bond is much weaker than that with [TBmim][Ac] by its forming an O…O…C…C four-membered ring. The chemisorption of CO2 on the ion pair [NBmim][Ac] is much weaker than that on [TBmim][Ac], as indicated from an absorption energy analysis. The frontier molecular orbitals show the electron density overlap between absorbed CO2 and the [Ac]– in CO2 – [NBmim][Ac] is much weaker than that in [TBmim][Ac]. As a result, the chemisorption of CO2 on [NBmim][Ac] is much weaker than that on [TBmim][Ac]. Ionic liquids based on [NBmim]+ can be used repeatedly, and the adsorbed CO2 would be more easily desorbed.
    Progress in Reaction Kinetics and Mechanism 01/2014; 39(2).
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    ABSTRACT: The interaction of the cis-diaqua-chloro-tris(dimethyl sulfoxide)ruthenium(II) complex with selected nucleosides such as adenosine (L1H) and cytidine (L2H) has been studied spectrophotometrically in aqueous medium as a function of [substrate complex], [ligand] and temperature. The reaction has been monitored at 295 nm where the difference in spectra between the reactant and product is a maximum. At pH 5.0, the interaction with the two nucleosides shows two distinct consecutive steps, i.e., it shows a non-linear dependence on the concentration of the nucleosides: both steps are [ligand] dependent. The rate constants for the processes are: k 1 ∼ 10–3 s–1 and k 2 ∼ 10–5 s–1. The activation parameters were calculated from Eyring plots. Based on the kinetic and activation parameters, an associative interchange mechanism is proposed for the interaction processes. From the temperature dependence of the outer sphere association equilibrium constant, the thermodynamic parameters were also calculated, which gives a negative δG° value for both the steps at all temperatures studied, supporting the spontaneous formation of an outer sphere association complex. The product of the reaction has been characterised by IR and ESI-mass spectroscopic analysis.
    Progress in Reaction Kinetics and Mechanism 01/2014; 39(1).
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    ABSTRACT: A theoretical study on the reactivity and regioselectivity of 1,3-dipolar cycloaddition reactions of ethyl diazoacetate (EDA) with ethynes (CH ≡ CX, X = H, CH3, n-But, CF3, CO2Et, C6H5, p-CH3OC6H4 and p-NO2C6H4) has been carried out by means of several theoretical approaches, activation energies, frontier molecular orbital (FMO) theory, conceptual density functional theory reactivity indices and hard and soft acid and base theory. Potential energy surface analysis and intrinsic reaction coordinate calculations show that these cycloadditions follow an asynchronous concerted mechanism with a low or non-polar character, displaying C-regioselectivity. Moreover, the reaction of EDA with electron-deficient alkynes is faster compare to electron-rich ethynes. Reactions of EDA with electron-deficient and electron-rich alkynes are normal electron demand and inverse electron demand cycloadditions, respectively, because of moderate electrophilicity and nucleophilicity of EDA. This result is confirmed by FMO analysis and reactivity indices.
    Progress in Reaction Kinetics and Mechanism 01/2014; 39(3).
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    ABSTRACT: A theoretical study of the effect of substitution on the 1,3-dipolar cycloaddition of benzonitrile oxide was performed using the DFT method at the B3LYP level of theory using 6-311G(d, p) basis sets. Equilibrium molecular geometries and harmonic vibrational frequencies of the reactants, transition state, and product were calculated. The corresponding rate constants and activation parameters were calculated. The results showed good agreement with experimental data. These calculations indicated that the reaction proceeds through an asynchronous mechanism.
    Progress in Reaction Kinetics and Mechanism 01/2014; 39(3).
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    ABSTRACT: The reaction between urea and HO− in alkaline solution was investigated at B3LYP and MP2 levels. The PCM solvent model was used to include the implicit solvent effects. To estimate the specific solvation effects, explicit water molecules were added stepwise to form molecular clusters. The results show that the OH− anion can abstract a proton from urea, forming the urea anion. The calculated energies indicate the hydrogen bonds formed between the reactants and solvent water molecules affect both the potential and thermodynamic energy barriers. The changing trend of the barriers appears to be 1W > 2W > 3W > 0W. A fast equilibrium can be established between the reactants and the products but the reverse reaction is both kinetically and thermodynamically more favourable, suggesting that the concentration of urea anion in alkaline solution would be low, in agreement with known weak acidity. The results of this study suggest that for reaction systems involving strongly polar reactants and solvent, the employment of only implicit solvent model is not enough, and explicit solvent molecules must be included.
    Progress in Reaction Kinetics and Mechanism 01/2014; 39(2).
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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 01/2014; 39(3).
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    ABSTRACT: The kinetics of the interaction of glycyl-L-valine(L1-L′H), glycyl-L-isoleucine (L2-L′H) and glycyl-L-glutamine(L3-L′H) with cis-[Pt(cis-dach)(OH2)2]2+ (dach = 1,2-diaminocyclohexane) have been studied spectrophotometrically as a function of [cis-[Pt(cis-dach)(OH2)2]2+], [ligand], pH and temperature at constant ionic strength, where the complex exists predominantly as the diaqua species and the dipeptides as a zwitterion. The substitution reactions show two consecutive steps: the initial is the ligand-assisted anation and the subsequent step is chelation. The activation parameters for both steps were evaluated using Eyring's equation. The low δH 1≠ and large negative value of δS 1≠ as well as δH 2≠ and δS 2≠ indicate an associative mode of activation for both the aqua ligand substitution processes. The products of the reactions have been characterised using IR and ESI-mass spectroscopic analysis. The title complex is already established as an anticancer drug; but its reactivity with all biomolecules will confirm its therapeutic activity (i.e. its efficacy versus toxicity).
    Progress in Reaction Kinetics and Mechanism 01/2014; 39(2).
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    ABSTRACT: A theoretical study of the kinetics and mechanism of the reaction between methylene and acetone in the gas phase was performed using the density functional theory method at UB3LYP levels of theory using a 6-311G** basis set. Equilibrium molecular geometries and harmonic vibrational frequencies of the reactants, transition states, intermediates and product were calculated. These calculations showed that the reaction proceeds through an asynchronous concerted mechanism. The effect of fluorine substitution on the reaction rate was investigated: the computed activation barrier exhibits a fairly high sensitivity to the nature of substituents at the C7- and C8-positions. Gibbs free energies of activation for all structures were computed.
    Progress in Reaction Kinetics and Mechanism 01/2014; 39(1).
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    ABSTRACT: In order to further the design of efficient artificial nuclease models for hydrolytic cleavage of DNA, the catalytic system made from an unsaturated tetraaza macrocycle and La(III) and Ce(III) ions was constructed and used as catalyst in the cleavage of plasmid PUC19 DNA. The interactions of these catalytic systems with plasmid PUC19 DNA has been investigated by UV-Vis absorption spectroscopy, fluorescence spectroscopy, cyclic voltammetry and gel electrophoresis. The results show that the combination of the catalytic system with DNA involves electrostatic binding through the phosphodiester linkages of DNA. The gel electrophoresis results also showed that supercoiled PUC19 plasmid DNA (cccDNA) was converted to the nicked form of DNA (ocDNA) under a nitrogen atmosphere. On the basis of these results, a mechanism for the catalytic cleavage of DNA is proposed.
    Progress in Reaction Kinetics and Mechanism 01/2014; 39(1).

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